JP2010094845A - Method of manufacturing pattern forming body, and method of manufacturing mold for nano-printing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a pattern forming body capable of reducing deposition of a chipping or the like onto an irregular pattern part and corrosion thereof. <P>SOLUTION: This method of manufacturing the pattern forming body includes a protection layer forming process for preparing a body to be worked having the irregular pattern part on a surface, and for forming a protection layer comprising a chromium material containing chromium nitride, as a main component, at least on the irregular pattern part, and a working process for working a portion of the body to be worked other than the irregular pattern part protected by the protection layer, and the problem to be solved is solved by the method. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a method for manufacturing a pattern forming body with less adhesion such as chipping to an uneven pattern portion and corrosion.

  In recent years, photomasks have been miniaturized, and phase masks and imprint templates using high-precision photomask manufacturing techniques have been developed. When manufacturing a phase mask or an imprint template, a high-precision pattern is usually produced on a substrate, and then processing such as cutting, polishing, and chamfering is performed to obtain a mask or template having a desired shape. Conventionally, when processing such as cutting is performed, there is a problem that chipping or the like occurs and adheres to the uneven pattern portion.

  In order to solve such a chipping problem, the surface on which the uneven pattern portion is formed is protected with an adhesive tape or a resist. For example, Patent Document 1 describes a method for cutting a semiconductor wafer protective tape, in which a protective tape (adhesive tape) is attached to the surface of a semiconductor wafer, and then the semiconductor wafer is cut using a cutter. . Patent Document 2 describes a printed board manufacturing method in which a through groove for cutting is formed in advance on a substrate material, and then a resist is applied to cut the substrate material.

  However, the method for protecting the concavo-convex pattern portion using an adhesive tape or a resist has the following problems. In other words, when processing such as cutting, it is necessary to firmly fix the workpiece so that it does not shake, but since a flexible resin or the like is usually used for adhesive tape, resist, etc., cutting with high precision There was a problem that it could not be performed. Furthermore, when peeling an adhesive tape or a resist from the uneven | corrugated pattern part, there also existed a problem that the one part remained on the surface of an uneven | corrugated pattern part. These problems are more prominent as the size of the uneven pattern becomes finer.

Further, Patent Document 3 describes a method in which processing such as polishing is performed on the glass substrate before the uneven pattern portion is formed on the glass substrate, and the processed portion is covered with chromium or the like. According to this method, it is possible to coat fine glass protrusions generated in the processed part by performing processing such as polishing, and chipping or the like caused by breakage of the fine glass protrusions in the subsequent process is caused on the glass substrate. It can be prevented from adhering. That is, the focus is on preventing chipping from occurring after processing.
Such a method can certainly prevent the occurrence of chipping from the processed portion after processing such as polishing. However, since the surface on which chipping adhesion is to be prevented is not protected, there is a problem that chipping or the like that occurs during processing cannot be prevented from adhering to the glass substrate that is the workpiece.

  Furthermore, Patent Document 4 discloses that the end face of the photomask is a mirror surface to reduce chipping and foreign matter, but it has not been possible to completely suppress chipping and the like.

  Thus, when performing processing such as cutting, polishing, and chamfering on a workpiece having a concavo-convex pattern portion, it is difficult to perform processing such as cutting with high accuracy and sufficiently suppress adhesion such as chipping. There was a problem.

JP 2004-25402 A Japanese Patent Laid-Open No. 11-145580 Japanese Patent Publication No. 61-40100 JP-A-1-167758

  The present invention has been made in view of the above circumstances, and a main object of the present invention is to provide a method for manufacturing a pattern forming body with less adhesion and corrosion such as chipping to an uneven pattern portion.

  In order to solve the above problems, the present invention provides a workpiece having a concavo-convex pattern portion on the surface, and forms a protective layer mainly composed of a chromium-based material containing chromium nitride on at least the concavo-convex pattern portion. And a processing step for processing a portion of the workpiece other than the concavo-convex pattern portion protected by the protective layer.

According to the present invention, since chromium nitride is excellent in adhesion, the protective layer can be made less peeled off. For this reason, it can suppress that the said uneven | corrugated pattern part surface is exposed by peeling etc. of the said protective layer. As a result, it is possible to reduce problems such as adhesion of chipping generated during processing such as cutting to the uneven pattern portion and corrosion of the uneven pattern portion generated during etching.
In addition, since chromium nitride is excellent in denseness, the protective layer can have few pinholes. For this reason, problems, such as corrosion of the uneven | corrugated pattern part which arise at the time of an etching process, can be made small.
Furthermore, since chromium nitride is excellent in peelability, the protective layer can be easily removed with a stripping solution. For this reason, problems, such as adhesion of the residue of the protective layer to the uneven pattern portion, can be reduced.

In the present invention, the processing steps include a cutting step for cutting the workpiece, a polishing step for polishing the workpiece, a chamfering step for chamfering corners of the workpiece, and etching the workpiece. It is preferable that the method includes at least one of the etching steps to be processed. Even when processing that causes chipping such as the cutting step, the polishing step, and the chamfering step is performed, the effect of the present invention that the adhesion such as chipping can be reduced is more effectively exhibited. Because you can.
In addition, since the protective layer contains chromium nitride which is a material having excellent adhesion and denseness and has few peeling, pinholes, etc., even when the etching process is performed, unevenness This is because the effect of the present invention that the corrosion of the pattern portion can be reduced can be more effectively exhibited.

  In this invention, it is preferable that the ratio (the number of nitrogen atoms / the number of chromium atoms) of chromium atoms and nitrogen atoms contained in the chromium-based material is 0.2 or more. Since chromium nitride is excellent in adhesion, denseness, and peelability, the ratio of chromium atom and nitrogen atom (number of nitrogen atoms / number of chromium atoms) contained in the chromium-based material is within the above-described range, so that the above protection is achieved. This is because the layer can be made more excellent in adhesion, denseness, and peelability, and an uneven pattern portion with less defects such as adhesion and corrosion to the uneven pattern portion can be formed. .

  The present invention provides a method for producing a mold for nanoimprint, which uses the above-described method for producing a patterned body.

  According to the present invention, since the above-described method for manufacturing a pattern forming body is used, it is possible to reduce adhesion and corrosion such as chipping to the uneven pattern portion. For this reason, the mold for nanoimprint manufactured by the manufacturing method of the present invention can have a concavo-convex pattern portion with less foreign matter and high dimensional accuracy.

In the present invention, the processing step includes a pedestal forming step in which the periphery of the concavo-convex pattern portion protected by the protective layer is made concave by etching and the region including the concavo-convex pattern portion is made convex. Is preferred.
By performing a pedestal forming step and forming a convex shape (mesa structure) projecting from the surrounding area including the concavo-convex pattern portion, the mold for nanoimprint manufactured by the manufacturing method of the present invention is combined with the concavo-convex pattern portion and others. This is because the contact with the member can be more easily performed. Moreover, it is because it can form with sufficient precision even if the convex shape of the said uneven | corrugated pattern part is a complicated shape by forming by an etching.

  The present invention has an effect that it is possible to obtain a pattern forming body with less adhesion and corrosion such as chipping to the uneven pattern portion.

The present invention relates to a method for producing a pattern forming body and a method for producing a mold for nanoimprinting using the same.
Hereinafter, the manufacturing method of the pattern formation body of this invention and the manufacturing method of the mold for nanoimprint are demonstrated in detail.

A. First, the manufacturing method of the pattern formation body of this invention is demonstrated.
In the method for producing a pattern formed body of the present invention, a workpiece having a concavo-convex pattern portion is prepared on the surface, and a protective layer mainly composed of a chromium-based material containing chromium nitride is formed on at least the concavo-convex pattern portion. The method includes a protective layer forming step and a processing step of processing a portion of the workpiece other than the concavo-convex pattern portion protected by the protective layer.

  The manufacturing method of such a pattern formation body of this invention is demonstrated using drawing. FIG. 1 is a schematic cross-sectional view showing an example of a method for producing a pattern forming body of the present invention. In the method of manufacturing the pattern forming body shown in FIG. 1, first, a quartz workpiece 1 having a concavo-convex pattern portion on the surface is prepared (FIG. 1 (a)), and the concavo-convex pattern portion of the workpiece 1 is prepared. A protective layer forming step (FIG. 1B) is performed in which a protective layer 2 made of chromium nitride is formed on the surface on which is formed by sputtering. Next, as a processing step for processing the portion of the workpiece 1 other than the concavo-convex pattern portion protected by the protective layer 2, a cutting step for cutting the workpiece 1 in the cross-sectional direction using a diamond cutter 3 (FIG. 1 (c)), a polishing step (FIG. 1 (d)) for polishing a cross section generated by cutting, a chamfering step (FIG. 1 (e)) for chamfering a corner of the workpiece 1; I do. Finally, the protective layer 2 is removed and washed to obtain the pattern forming body 10 (FIG. 1 (f)).

According to the present invention, since chromium nitride is excellent in adhesion as compared with a material such as chromium, the inclusion of such chromium nitride makes the protective layer less peeled or chipped. it can. For this reason, when the said protective layer is provided in the surface in which the said uneven | corrugated pattern part of the said to-be-processed object was formed, the said protective layer peels off partially and the surface of the said uneven | corrugated pattern part is rarely exposed. Can be. For this reason, it is possible to reduce the adhesion of chipping to the concave / convex pattern portion that occurs during processing such as cutting.
In addition, since exposure of the surface of the concavo-convex pattern portion due to partial peeling of the protective layer can be suppressed, there are few problems such as corrosion of the concavo-convex pattern portion due to contact with the etchant during etching processing It can be.

Further, since chromium nitride is excellent in denseness as compared with a material such as chromium, the inclusion of such chromium nitride makes it possible to reduce the number of pinholes in the protective layer. As a result, it is possible to reduce problems such as corrosion of the concavo-convex pattern portion caused by the etchant entering from the pinhole of the protective layer during the etching process.
In addition, since the protective layer can have few pinholes, chipping generated during processing such as cutting can be prevented from entering the pinholes and adhering to the uneven pattern portion.

  Furthermore, chromium nitride is excellent in releasability compared with materials such as chromium, and therefore can be easily removed with a stripping solution. For this reason, problems, such as adhesion of the residue of the protective layer to the uneven pattern portion, can be reduced.

  As described above, by providing a protective layer containing chromium nitride having excellent adhesion, denseness, and peelability on at least the concave / convex pattern portion of the workpiece, chipping to the concave / convex pattern portion and a residue of the protective layer are provided. It is possible to suppress changes in shape due to adhesion of foreign substances such as, corrosion, and the like. That is, by providing the protective layer containing chromium nitride, the pattern forming body manufactured by the manufacturing method of the present invention can have a concavo-convex pattern portion with less foreign matter and high dimensional accuracy.

The manufacturing method of the pattern formation body of this invention has at least the said protective layer formation process and a process process.
Hereinafter, the manufacturing method of the pattern formation body of this invention is demonstrated for every process.

1. Protective layer formation process The protective layer formation process in this invention is demonstrated. The protective layer forming step in the present invention is a step of preparing a workpiece having a concavo-convex pattern portion on the surface and forming a protective layer mainly composed of a chromium-based material containing chromium nitride on at least the concavo-convex pattern portion. is there.

(1) To-be-processed body First, the to-be-processed body used for this process is demonstrated. The workpiece used in this step has a concavo-convex pattern portion on the surface.

  About the light transmittance of the to-be-processed body used for this process, it may have a light transmittance and may not have a light transmittance, but the pattern formation body obtained by this invention For example, in the case of a template or a phase mask for optical imprinting, it is preferable that the workpiece has light transparency. On the other hand, when the pattern formed body obtained by this step is, for example, a thermal imprint template, it may not have light transmittance.

The material of the workpiece varies depending on the application of the pattern forming body, and examples thereof include glass such as quartz and soda lime glass; silicon (Si), gallium nitride (GaN), and gallium arsenide (GaAs). Semiconductors: metals such as nickel (Ni) and aluminum (Al); ceramics such as silicon nitride (SiN), silicon oxide (SiO ₂ ) and silicon carbide (SiC); diamond, diamond-like carbon (DLC) and cubic nitriding Examples thereof include boron (CBN). Among these, quartz and silicon (Si) are more preferable, and quartz is particularly preferable from the viewpoint that processing with finer dimensions is possible. Such a material is also preferable because of excellent adhesion of chromium nitride.

  Although the cross-sectional shape of the said uneven | corrugated pattern part changes with uses of the pattern formation body obtained, For example, rectangular shape, semicircle shape, etc. can be mentioned. For example, when using a pattern formation body as a phase mask, it is preferable to form an uneven | corrugated pattern part so that the cross-sectional shape of an uneven | corrugated pattern part may become a rectangular shape, for example. Further, for example, when the pattern forming body is used as an imprint template for forming a microlens, for example, the concavo-convex pattern portion may be formed so that the cross-sectional shape of the concavo-convex pattern portion is semicircular. preferable.

  In this step, the pattern size of the concavo-convex pattern portion is preferably small, and specifically, the pattern size is preferably nano-order. This is because by providing a protective layer, which will be described later, processing such as cutting can be performed with high accuracy even when the pattern size is small. The pattern size of the concavo-convex pattern portion is, for example, preferably in the range of 10 nm to 1000 nm, particularly in the range of 20 nm to 500 nm. In addition, when the cross-sectional shape of an uneven | corrugated pattern part is a rectangular shape, it is preferable that the width | variety of the recessed part exists in the range of said pattern size. Moreover, when the cross-sectional shape of the uneven | corrugated pattern part is semicircle shape, it is preferable that the diameter of a semicircle-shaped recessed part exists in the range of said pattern size.

  As a method for forming the concavo-convex pattern portion on the surface of the workpiece, any method can be used as long as it can have a desired concavo-convex shape. For example, the surface of the workpiece can be formed using photolithography or the like. It may be formed by cutting a part, or may be formed by laminating another member (for example, Cr) on the surface of the workpiece by vapor deposition or the like. Of these, the former is preferred in the present invention. This is because the problem of peeling does not occur.

(2) Protective layer Next, the protective layer used in this step will be described. The protective layer used in this step is formed on at least the concavo-convex pattern portion.

(A) Material As a material constituting the protective layer, any material having a chromium-based material containing chromium nitride as a main component may be used.
Here, the main component means that the protective layer is included to such an extent that the function as a chromium-based material can be exhibited when the protective layer is used as a protective layer for protecting the uneven pattern portion during processing such as etching or cutting. Specifically, it means that 80% by mass or more is contained in the protective layer.
In this step, it is preferable that the content of the chromium-based material in the protective layer is 90% by mass or more. When the content of the chromium-based material in the protective layer is in the above-described range, the protective layer that protects the concavo-convex pattern portion as described above sufficiently exhibits the function as the chromium-based material. Because you can.

  The material constituting the protective layer used in this step is not particularly limited as long as it contains the above-mentioned chromium-based material as a main component, but can contain a material other than the above-mentioned chromium-based material as necessary.

The chromium-based material used in this step is made of a compound containing chromium such as chromium, chromium nitride, chromium oxide, chromium carbide, chromium carbonitride and the like, and contains at least chromium nitride.
Here, the reason for containing chromium nitride is that chromium nitride is excellent in adhesion, and the protective layer can be made less peeled or chipped. Further, as a result, it is possible to reduce problems such as chipping adhesion to the uneven pattern portion during cutting and corrosion of the uneven pattern portion during etching.
Further, since chromium nitride is excellent in denseness, the protective layer can be made to have few pinholes by including chromium nitride. As a result, problems such as corrosion of the concavo-convex pattern portion during etching can be reduced.
Furthermore, since chromium nitride is excellent in releasability, the protective layer can be easily removed with a stripping solution by including chromium nitride. For this reason, it is possible to reduce problems such as adhesion of the residue of the protective layer to the uneven pattern portion.
As described above, by including chromium nitride, the pattern forming body manufactured by the manufacturing method of the present invention has an uneven pattern portion with less defects such as adhesion to the uneven pattern portion and corrosion. Because you can.

The content of chromium nitride contained in such a chromium-based material is appropriately set according to the adhesion and peelability with the workpiece, the processing method in the processing step, etc. The ratio of the chromium atom to the nitrogen atom (the number of nitrogen atoms / the number of chromium atoms) contained in the chromium-based material is preferably 0.2 or more, and particularly preferably within the range of 0.3 to 1. In particular, it is preferably in the range of 0.4 to 1.
By including chromium nitride so that the ratio of chromium atoms to nitrogen atoms in the chromium-based material is within the above range, the protective layer should be more excellent in adhesion, denseness and peelability. This is because it is possible to form a concavo-convex pattern portion with less defects such as adhesion such as chipping to the concavo-convex pattern portion and corrosion.
For the measurement of the ratio of the number of atoms, a general elemental analyzer such as X-ray photoelectron spectroscopy (XPS) can be used.

(B) Protective layer The method for forming the protective layer in this step is not particularly limited as long as it is a method capable of forming a desired protective layer. In some cases, a CVD method such as a plasma CVD method, a thermal CVD method, and a photo CVD method; a PVD method such as a sputtering method and an ion plating method can be used, and a sputtering method is particularly preferable. This is because a uniform protective layer can be obtained.

  Although it does not specifically limit as hardness of the protective layer formed by this process, For example, it is preferable that it is in the range of 3-10 in Mohs hardness, and especially in the range of 5-8 in Mohs hardness.

  The thickness of the protective layer formed in this step is not particularly limited as long as the workpiece can be processed with high accuracy, but it is, for example, in the range of 10 nm to 200 nm, particularly in the range of 50 nm to 150 nm. Is preferred. This is because if the protective layer is thinner than the above range, the workpiece may not be protected, and if it is thicker than the above range, it tends to break due to film stress.

  The formation position of the protective layer formed in this step may be any place as long as it is formed on at least the concave / convex pattern portion of the workpiece, and the workpiece on the side opposite to the surface on which the concave / convex pattern portion is formed. A similar protective layer may be formed on other surfaces such as the surface.

(3) Others In this step, after forming the protective layer, a soft layer may be provided on the protective layer. This is because by providing the soft layer, it is possible to prevent the fragments of the protective layer from scattering even when the protective layer is cracked or the like. Although it does not specifically limit as a material of the said soft layer, For example, a commercially available adhesive tape, a resist, etc. can be mentioned. In addition, it is thought that by providing a soft layer, the precision of processing, such as a cutting | disconnection, will worsen compared with the case of only a protective layer, However, It is thought that it has the following advantages by providing a protective layer and a soft layer.

  That is, since a protective layer is provided between the soft layer and the work piece, when the soft layer is peeled from the work piece, a part of the soft layer remains in the uneven pattern portion of the work piece. Can be prevented. Furthermore, by adopting a two-layer structure of a protective layer and a soft layer, even if the thickness of each layer is reduced, chipping is less likely to adhere to the concavo-convex pattern portion, and further, the thickness of each layer is reduced. Thus, processing such as cutting can be performed with high accuracy.

2. Processing Step Next, the processing step in the present invention will be described. The processing step in the present invention is a step of processing a portion of the workpiece other than the uneven pattern portion protected by the protective layer.

  Such processing steps include a cutting step for cutting the workpiece, a polishing step for polishing the workpiece, a chamfering step for chamfering corners of the workpiece, and processing the workpiece by etching. And an etching process to be performed.

In the present invention, it is preferable that the processing step includes at least one of the cutting step, the polishing step, the chamfering step, and the etching step. Even in the case of performing processing that causes chipping such as the cutting step, polishing step, and chamfering step, it is possible to reduce adhesion of chipping and the like to the uneven pattern portion, and thus the effect of the present invention. It is because it can exhibit more effectively.
Further, since the protective layer contains chromium nitride, which is a material with excellent denseness, even when the etching process is performed, the corrugated pattern portion can be less corroded. It is because it can be exhibited effectively.

The cutting step is not particularly limited as long as it is a step of cutting the workpiece, and specifically, a step of cutting the workpiece in the cross-sectional direction, and forming a mesa structure on the workpiece. In order to do this, a step of countersinking can be cited. Especially in this invention, it is preferable that the said cutting process is a process of cut | disconnecting a to-be-processed body in a cross-sectional direction.
As a method for cutting the workpiece, a general cutting method can be used, and is not particularly limited, and specific examples include a method using a diamond cutter.

In the polishing step, the place for polishing is not particularly limited as long as it is a part of the workpiece other than the uneven pattern part protected by the protective layer. The cut surface etc. which arose by the process can be mentioned.
As an abrasive used for polishing the workpiece, a general abrasive can be used, and is not particularly limited. Specifically, diamond, cubic boron nitride, silicon carbide , Aluminum oxide, silica, alumina, cerium oxide, and diamond slurry. Since the method for polishing the workpiece is the same as a general polishing method, description thereof is omitted here.

  In the chamfering step, the method for chamfering the corner of the workpiece is not particularly limited, and a general method can be used. Specific examples include buffing.

In the etching step, a general method can be used as a method of etching the workpiece. Specifically, a resist formed in a pattern having an opening at a location to be etched is formed on the workpiece, and then the workpiece is brought into contact with an etchant using the resist formed in a pattern as a mask. In addition, in the case where the protective layer is formed at a location where etching is desired, after the resist is formed in a pattern, the protective layer in the region to be etched is removed by etching. A method of etching the workpiece can be used.

The resist may be formed by any method that can form a resist in a pattern, and a general resist forming method such as a photolithography method can be used.
The etchant is not particularly limited as long as it can dissolve the workpiece without dissolving the resist, and a wet etchant in solution, a dry etchant such as a reactive gas, or the like can be used. It is appropriately set according to the material of the workpiece.

  The method for etching the protective layer may be any method that can remove the protective layer with high accuracy. For example, when the protective layer is made of the chromium-based material, the protective layer is formed in a pattern. A method of etching with a ceric ammonium nitrate solution or the like using the formed resist as a mask can be mentioned.

3. Others In the present invention, a removal step for removing the protective layer is usually performed after the processing step. As a method for removing the protective layer, when the protective layer is made of the chromium-based material, a ceric ammonium nitrate solution or the like can be used as a stripping solution. Moreover, in this invention, you may perform a washing | cleaning process as needed before and after each process mentioned above.

4). Pattern Formed Body The pattern formed body obtained by the present invention is not particularly limited as long as it has a concavo-convex pattern portion on the surface. For example, an imprint template used for optical imprint or thermal imprint It can be used as a phase mask or the like.

B. Next, a method for producing a nanoimprint mold of the present invention will be described. The method for producing a mold for nanoimprinting according to the present invention is characterized by using the method for producing a pattern forming body.

A method for producing such a nanoimprint mold of the present invention will be described with reference to the drawings. 2 and 3 are schematic process diagrams illustrating an example of a method for producing a nanoimprint mold of the present invention. As illustrated in FIG. 2, in the method for manufacturing a mold for nanoimprinting of the present invention, first, a quartz workpiece 1 having a concavo-convex pattern portion on the surface is prepared (FIG. 2A), and the workpiece 1 is prepared. A protective layer forming step (FIG. 2B) is performed in which a protective layer 2 made of chromium nitride is formed by sputtering on the surface on which the concave / convex pattern portion is formed and the surface on the opposite side.
Next, as shown in FIG. 2C, as a processing step for processing a portion of the workpiece 1 other than the uneven pattern portion protected by the protective layer 2, the uneven pattern portion protected by the protective layer is processed. After forming a resist 4 having an opening around it, the protective layer 2 is removed by etching by using a ceric ammonium nitrate solution 5 as an etchant.
Next, as shown in FIG. 2 (d), the workpiece 1 is etched by using hydrofluoric acid 6 as an etchant (FIG. 2 (e)), and then the resist 4 is peeled to remove the irregularities. A region including the pattern portion is assumed to have a convex shape (mesa structure) (FIG. 2 (f)). In addition, the said FIG.2 (c)-(f) shows a base formation process. In the present invention, since the protective layer containing chromium nitride having high adhesion is formed in the protective layer forming step described above, infiltration of hydrofluoric acid into the concavo-convex pattern portion can be prevented.
Thereafter, as shown in FIG. 3A, a diamond cutter 3 is used to cut the workpiece 1 in the cross-sectional direction, and a polishing step to polish the cross-section generated by the cutting (FIG. 3B). Then, a chamfering process (FIG. 3C) for chamfering the corner of the workpiece 1 is performed.
Finally, the protective layer 2 is removed and washed to obtain the nanoimprint mold 20 (FIG. 3D).

  According to the present invention, since the above-described method for manufacturing a pattern forming body is used, it is possible to reduce adhesion and corrosion such as chipping to the uneven pattern portion. For this reason, the mold for nanoimprint manufactured by the manufacturing method of the present invention can have a concavo-convex pattern portion with less foreign matter and high dimensional accuracy.

  The method for producing a mold for nanoimprinting of the present invention includes the protective layer forming step and the processing step.

1. Protective layer formation process The protective layer formation process in this invention is a process of forming the protective layer which has as a main component the chromium system material containing chromium nitride on the said uneven | corrugated pattern part at least.
In addition, about the protective layer formed by this process, since it is the same as that of the content described in the term of the said "A. manufacturing method of a pattern formation body", description here is abbreviate | omitted.

(1) Workpiece The workpiece used in this step may be any material that can be used for forming a nanoimprint mold, and can be appropriately set according to the use of the nanoimprint mold.

The pattern size of the concavo-convex pattern portion of such a workpiece is set according to the use of the nanoimprint mold, and specifically, the line width of the concavo-convex pattern is within the range of 10 nm to 1000 nm. In particular, it is preferably within a range of 10 nm to 80 nm, and particularly preferably within a range of 20 nm to 70 nm. This is because if the line width of the fine pattern is larger than the above range, the influence of chipping is small, and the effect of the present invention cannot be effectively exhibited. Moreover, it is because manufacture is difficult when the said line | wire width is smaller than the said range.
Further, the aspect ratio (height / line width) of the fine pattern is preferably 0.5 or more, more preferably in the range of 0.5 to 10, particularly in the range of 1 to 4. It is preferable that This is because when the aspect ratio is within the above range, when other members are processed using the nanoimprint mold manufactured by the manufacturing method of the present invention, processing can be performed with high accuracy.

  Regarding the light transmittance of the workpiece used in this step, the material of the workpiece, the cross-sectional shape, and the method of forming the concavo-convex pattern portion, refer to the above-mentioned section “A. Manufacturing method of pattern forming body”. Since it can be the same as that of the to-be-processed object of description, description here is abbreviate | omitted.

(2) Others This step is a step of preparing a workpiece having a concavo-convex pattern portion on the surface and forming a protective layer on the surface on which the concavo-convex pattern portion of the workpiece is formed. Then, after forming the protective layer, a soft layer may be formed on the protective layer.
This is because by providing the soft layer, it is possible to prevent the fragments of the protective layer from scattering even when the protective layer is cracked or the like.
In addition, about such a soft layer, since it can be made to be the same as that of the content described in the above-mentioned item of "A. Manufacturing method of a pattern formation body", description here is abbreviate | omitted.

2. Processing Step The processing step in the method for manufacturing a mold for nanoimprinting of the present invention is a step of processing a portion of the workpiece other than the concavo-convex pattern portion protected by the protective layer.

As such a processing step, the cutting step, the polishing step, the chamfering step, and the concave and convex pattern portions protected by the protective layer are etched to form a concave shape, and the region including the concave and convex pattern portions is formed. An etching process such as a pedestal forming process having a convex shape (mesa structure) can be given.
In the present invention, it is preferable that the processing step includes the pedestal forming step. The mold for nanoimprint produced by the production method of the present invention is used by bringing the concavo-convex pattern portion into contact with another member. Therefore, by performing such a pedestal forming step and making the region including the concavo-convex pattern portion a convex shape (mesa structure) protruding from the periphery, the concavo-convex pattern portion and the other member can be more easily brought into contact with each other. This is because it can be made possible. Moreover, it is because it can form with sufficient precision even if the convex shape of the said uneven | corrugated pattern part is a complicated shape by forming by an etching.
The cutting step, the polishing step, the chamfering step, and the etching step are the same as the contents described in the above section “A. Pattern forming body”, and thus description thereof is omitted here.

  The pedestal forming step in this step is a step in which the periphery of the concavo-convex pattern portion protected by the protective layer is etched to make it concave, and the region including the concavo-convex pattern portion is made convex.

A general etching method can be used as a method for etching the periphery of the concavo-convex pattern portion to form a concave shape. Specifically, a resist having an opening around the concavo-convex pattern portion is used. An example is a method in which a workpiece is formed on a workpiece, and then the workpiece is etched with an etchant using a resist formed in a pattern as a mask.
Further, when the protective layer is formed around the concavo-convex pattern portion which is an area to be etched, after forming the resist in a pattern, the protective layer in the area to be etched is removed by etching, A method of etching a workpiece can be used.

  In the pedestal forming step, the method for forming the resist in a pattern and the method for etching the protective layer may be the same as the contents described in the section “A. Method for producing pattern formed body”. it can.

In the pedestal forming step, the etchant used for etching the workpiece may be any etchant that can etch the workpiece with a desired accuracy, and may be a wet etchant or a dry etchant. In the case where the workpiece is made of quartz, hydrofluoric acid can be preferably used.
This is because by using hydrofluoric acid, quartz that can be easily finely processed can be processed with high accuracy.
In addition, as described above, since the protective layer contains chromium nitride and has less peeling, pinholes, etc., even when a highly corrosive etchant such as hydrofluoric acid is used, the concavo-convex pattern This is because the portion can be effectively prevented from being corroded.

  In the pedestal formation step, the height of the concavo-convex pattern portion formed in a convex shape (mesa structure), that is, the distance from the bottom surface etched into a concave shape to the top surface of the concavo-convex pattern portion, It is appropriately set according to the use and the like, and can be the same as that of a general nanoimprint mold.

3. Method for Producing Nanoimprint Mold The method for producing a nanoimprint mold of the present invention includes at least the protective layer forming step and the processing step, and usually includes a removing step for removing the protective layer.
About such a removal process, it can be made to be the same as that of the content described in the term of the above-mentioned "A. manufacturing method of a pattern formation body."

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

  Hereinafter, the present invention will be described more specifically with reference to examples.

[Reference Examples 1-5]
1. Formation of protective film Using reactive gases such as argon gas, oxygen gas, nitrogen gas, mixed gas (argon gas: nitrogen gas = 1: 1), and carbon dioxide gas, chromium is deposited on a silicon substrate (Si substrate) by sputtering. A film was formed. Elemental analysis was performed on the protective film having a thickness of 100 nm thus obtained.
As a result, by sputtering chromium using the above-described reaction gas, a chromium film (Cr), a chromium oxide film (Cr ₂ O ₃ ), chromium nitride (CrN), chromium and a chromium nitride film (Cr: CrN), respectively. It was confirmed that a chromium oxide + chromium carbide film (Cr ₂ O ₃ : Cr ₃ C ₂ ≈4: 3) was obtained.
Based on the above confirmation test, chromium is synthesized by sputtering using argon gas, oxygen gas, nitrogen gas, mixed gas (argon gas: nitrogen gas = 1: 1), and carbon dioxide as the reaction gas. A film was formed on top. In this way, a protective film having a thickness of 100 nm was formed on the synthetic quartz substrate.

2. Evaluation of protective film About the obtained protective film, (1) peelability, (2) pinhole number (denseness), and (3) adhesiveness were evaluated.

(1) Peelability The etching time (time required for the film to disappear) when etched with a stripping solution (manufactured by Inktec, MRE-2000 (main component: ceric ammonium nitrate)) was measured. Table 1 shows.
Further, the evaluation results of the etching time evaluated according to the following criteria are shown in Table 1 below.
○: Less than 150 seconds Δ: 150 seconds to 1000 seconds ×: more than 1000 seconds

(2) Number of pinholes (denseness)
The surface of the protective film was measured using a defect inspection apparatus Magics manufactured by Lasertec. The number of fine pinholes obtained is shown in Table 1 below. In addition, as a measurement, the hole of 1 micrometer or more which exists in the range of 50 mm square was measured as the number of pinholes.
Table 1 below shows the evaluation results of the number of pinholes evaluated according to the following criteria.
○: Number of pinholes is 0-1
Δ: 2 to 10 pinholes
X: 11 or more pinholes

(3) Adhesiveness After repeating the cold heat test (JAS cold heat B test (left at 80 ° C. and −20 ° C. for 2 hours)) for 10 cycles, the protective film was evaluated according to the following criteria. .
○: No peeling △: Partial peeling ×: Completely peeling

(4) Summary As shown in Table 1, it was confirmed that the protective film made of chromium nitride was excellent in (1) peelability, (2) number of pinholes (denseness), and (3) adhesion.

[Examples 1 to 25 and Comparative Examples 1 and 2]
Fine processing was performed on a 6-inch square, 6.35 mm thick quartz substrate, and an uneven pattern portion was formed on the surface of the quartz substrate. Next, a protective layer having a composition ratio shown in Table 2 below is formed by a sputtering method so as to cover the surface of the concavo-convex pattern portion so as to have a film thickness of 100 nm, and then a resist having openings around the concavo-convex pattern portion is formed. Formed. Next, after etching the protective layer exposed with an etching solution (Mek-2000, manufactured by Inktec, main component: ceric ammonium nitrate), the quartz substrate was etched with hydrofluoric acid. The region including the portion became a convex shape that was approximately 20 μm higher than the surrounding area, and then the resist was removed and washed.
Then, it cut | disconnected in the magnitude | size of 60 mm x 60 mm with the diamond cutter. Thereafter, the cut surface was polished by buffing. Next, the protective layer was removed with a stripping solution (manufactured by Inktec, MRE-2000 (main component: ceric ammonium nitrate), and further washed with sulfuric acid to prepare a pattern forming body.
The composition ratio of the formed protective layer was elementally analyzed by XPS. The results are shown in Table 2 below.

[Evaluation]
The convex / concave pattern surface of the pattern formed body obtained in the examples and comparative examples is inspected using a defect inspection apparatus Magics manufactured by Lasertec Co., Ltd., and measurement of foreign matters and defects (pinholes, scratches). Went. The results are shown in Table 2 below.
In addition, about the foreign material and the defect, the thing of the size of 70 nm or more was measured. Moreover, the result of having measured the 25 mm square area of the said uneven | corrugated pattern part surface as a measurement area is shown.

From Table 2, it can be confirmed that the foreign matter / defects can be reduced by setting the ratio of nitrogen atom N and Cr atom (number of nitrogen atoms / number of chromium atoms) to 0.2 or more in the protective layer. It was.
In addition, as shown in the comparative example, it is confirmed that when a pattern forming body is formed using a protective layer that does not contain nitrogen atoms, that is, a protective layer that does not contain chromium nitride, there are many foreign matters / defects. did it.

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

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Workpiece 2 ... Protective layer 3 ... Diamond cutter 10 ... Pattern formation body 20 ... Nanoimprint mold

Claims (5)

A protective layer forming step of preparing a workpiece having a concavo-convex pattern portion on a surface and forming a protective layer mainly composed of a chromium-based material containing chromium nitride on at least the concavo-convex pattern portion;
A processing step for processing a portion of the workpiece other than the uneven pattern portion protected by the protective layer;
A method for producing a pattern-formed body, comprising:   The processing step includes a cutting step for cutting the workpiece, a polishing step for polishing the workpiece, a chamfering step for chamfering corners of the workpiece, and an etching step for processing the workpiece by etching. The method for producing a pattern forming body according to claim 1, comprising at least one of the following steps.   The ratio of the chromium atom and the nitrogen atom (the number of nitrogen atoms / the number of chromium atoms) contained in the chromium-based material is 0.2 or more. Production method.   The manufacturing method of the mold for nanoimprints using the manufacturing method of the pattern formation body in any one of Claim 1- Claim 3.   5. The pedestal forming step, wherein the processing step includes a pedestal forming step in which a periphery of the concavo-convex pattern portion protected by the protective layer is made concave by etching, and a region including the concavo-convex pattern portion is made convex. Manufacturing method of nanoimprint mold.

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