JP4853706B2 - Imprint mold and manufacturing method thereof - Google Patents

Description

  The present invention is applied to the manufacturing process of various products such as semiconductor devices, optical components such as optical waveguides and diffraction gratings, recording devices such as hard disks and DVDs, biochips such as DNA analysis, and displays such as diffusion plates and light guide plates. The present invention relates to an imprint mold that can be used for pattern formation using a printing method and a method for manufacturing the same.

<Background Technology 1: Photolithography>
Conventionally, a method of optically transferring a pattern has been used to form a pattern that requires fine processing, such as a semiconductor device manufacturing process.
As an example, a photomask having a pattern made of an opaque material such as chromium formed on a part of a transparent substrate such as glass is prepared, and this is directly applied on a semiconductor substrate (hereinafter referred to as a sensitive substrate) coated with a resist. Alternatively, the pattern of the photomask is transferred to the sensitive substrate by placing it indirectly or by irradiating light from the back surface of the photomask to selectively expose the resist in the light transmitting portion. This technique is generally called a photolithography method.
Further, in the current semiconductor device manufacturing process, a method of optically reducing a mask pattern and transferring the pattern onto a semiconductor substrate has become mainstream.

However, in these pattern forming methods, the size and shape of the pattern to be formed greatly depend on the wavelength of light to be exposed. For example, in the manufacture of advanced semiconductor devices in recent years, the exposure wavelength used for photolithography is 150 nm or more, while the minimum line width is 65 nm or less, reaching the resolution limit due to the light diffraction phenomenon.
In order to increase the resolution of the resist, super-resolution technology such as proximity effect correction (OPC), phase shift mask, and modified illumination is used, but the mask pattern is faithfully transferred onto the semiconductor substrate. It has become difficult to do.

  Furthermore, in the case of reduced projection exposure, alignment accuracy is required not only in the horizontal direction of the substrate but also in the vertical direction, so precise stage control (X, Y, Z, θ) of the photomask and semiconductor substrate is necessary. Therefore, there has been a drawback that the cost of the apparatus becomes high.

  In addition to the manufacture of semiconductor devices, as long as photolithography is used in various pattern formations such as displays, recording media, biochips, optical devices, etc. The problem of the required apparatus cost similarly exists, and the mask pattern cannot be faithfully transferred.

<Background Technology 2: Thermal Imprint>
Against this background, SYChou et al. Proposed a technique called imprint method (or nanoimprint method) that is very simple but suitable for mass production and can transfer a much finer pattern faithfully than conventional methods. (See Non-Patent Documents 1 and 2, for example).
Although there is no strict distinction between the imprint method and the nanoimprint method, the nanometer-order method used for manufacturing semiconductor devices and diffraction gratings is called the nanoimprint method, and other micrometer-order methods are imprinted. Often called the law. Hereinafter, all are referred to as an imprint method.

Next, a conventional imprint method proposed by SYChou et al. Will be described with reference to FIGS.
First, a silicon substrate 101 having a silicon oxide film 102 formed on the surface is prepared, and the silicon oxide film 102 on the silicon substrate 101 is finally converted into a negative / positive reversal image of a pattern to be transferred to a transfer target such as a semiconductor substrate. A corresponding pattern is formed. For patterning the silicon oxide film 102, for example, a normal electron beam lithography technique can be used. In this way, a mold 100 having irregularities corresponding to a negative / positive reversal image of a pattern to be transferred onto the surface of a semiconductor substrate or the like is formed (FIG. 6A).

Next, a thermoplastic resist material such as PMMA is applied on the silicon substrate 111 on which a pattern is to be formed, thereby forming a resist layer 112 (FIG. 6B). Next, the silicon substrate 111 on which the resist layer 112 is formed is heated to a temperature equal to or higher than the glass transition temperature (Tg) of the resist (about 120 to 200 ° C.) to soften the resist layer 112.
Next, the mold 100 and the silicon substrate 111 are overlapped so that the uneven surface side of the mold faces the coated surface side of the resist layer of the silicon substrate 111 and pressure-bonded with a pressure of about 5 to 20 MPa (FIG. 6C). .
Next, in a state where the mold 100 is pressure-bonded to the silicon substrate 111, the temperature is lowered to a glass transition temperature or lower (about 100 ° C. or lower) of the resist to cure the resist layer 112, and the mold is detached. As a result, a pattern corresponding to the concavo-convex pattern of the mold 100 is formed on the resist layer 112 on the silicon substrate 111 (FIG. 6D).
Next, since a portion corresponding to the convex portion of the mold 100 remains as a thin residual film on the silicon substrate 111, this is removed by O ₂ RIE (reactive ion etching using oxygen gas) (FIG. 6 (e)). )).

In this way, a resist pattern is formed using the imprint method.
This method is called a thermal imprint method or a thermal nanoimprint method because it involves a thermal cycle of temperature rise and cooling.

<Thermal Imprint: Issues>
However, the conventional pattern formation method using the thermal imprint method has problems to be solved in terms of overlay position accuracy, mold strength and durability. That is, as described above, the pattern forming method using the imprint method requires an extremely high pressure of about 5 to 15 MPa when the mold and the substrate are pressure-bonded. It is extremely difficult to maintain the horizontal positional accuracy between the substrate and the substrate.
Further, when the number of times of transfer is increased at such a high pressure, there arises a problem that the mold is broken. Furthermore, since it involves a thermal cycle, the positional accuracy deteriorates due to the difference in thermal expansion coefficient between the substrate to be transferred and the mold material, and there arises a problem that the processing time is long for temperature rise and cooling. That is, it can be said that the fundamental problem of thermal imprinting is two points of high press pressure and high temperature.

<Background Technology 3: Optical Imprint>
In order to solve such a problem, a pattern forming method by an imprint method as described below has been proposed (for example, see Patent Document 1).
Specifically, as shown in FIG. 7A, a mold 120 having a concavo-convex shape on the surface is produced by etching a substrate made of a light-transmitting material such as quartz with an electron beam lithography method or the like. Next, as shown in FIG. 7 (b), a low-viscosity liquid photocurable resin composition (resist 112) to be transferred is applied on the silicon substrate, and as shown in FIG. 7 (c). Next, the mold 120 is pressure-bonded to the photocurable resin composition (resist 112). The pressing pressure at this time may be as small as about 0.01 to 5 MPa. In this state, light is irradiated from the back surface of the mold 120 to cure the photocurable resin composition (resist 112). As shown in FIG. 7D, the thin residual film of the photocurable resin (resist 112) to which the pattern of the mold 120 has been transferred is removed by the O ₂ RIE method or the like. Thereby, as shown in FIG.7 (e), the resin pattern is obtained.

According to this method, since the resin is cured by a photoreaction, there is no thermal cycle (it may be at room temperature), the processing time can be greatly shortened, and the positional accuracy is not degraded by the thermal cycle. Moreover, since the photocurable resin composition is a liquid having a low viscosity, the pattern can be transferred without pressing the mold to the photocurable resin composition with a high pressure as in thermal imprinting.
Therefore, a decrease in positional accuracy and mold damage due to the press pressure are dramatically reduced. That is, optical imprinting can be said to be a technology that solves the high pressing pressure and high temperature that are the fundamental problems of thermal imprinting.
However, compared to the thermoplastic resin used for thermal imprinting, the photo-curable resin used for optical imprinting is less expensive and less expensive, so it can be used according to the application and product. It is necessary to use imprint and optical imprint properly.

<Background Technology 4: Imprint Release Technology (Wet)>
In these imprint methods (Background Technology 2 and Background Technology 3), the releasability between the mold and a resin pattern such as a resist formed on the substrate is extremely important. In imprinting, when the mold and the resin are separated after pressing, a phenomenon in which the resin is partially deformed or peeled off with the mold due to adhesion and friction between the mold and the resin is observed. FIG. 8 shows this state, and all or part of the resin resist 132 remains on the mold 130 side, and an appropriate pattern is not formed on the silicon substrate 131 (FIGS. 8B to 8D). This is because the surface energy of the mold or resin is large (= weak hydrophobicity = small contact angle).

Therefore, in order to avoid such separation of the substrate and the resin, it is necessary to form a fluoropolymer having a small surface energy on the mold surface as a release agent to improve the releasability between the mold and the resin on the substrate (for example, non (See Patent Documents 2 and 3 and Patent Document 2). FIG. 9 shows the method. As a general release agent, a silane coupling agent solution is allowed to act on the OH group of the silicon oxide film on the mold surface to form a film with a low surface energy (called a release layer) on the mold surface. is doing.
In FIG. 9, first, the mold 140 is immersed in a fluororesin-containing silane coupling solution 143 for several minutes using a mold release agent (FIG. 9B), and then an atmosphere having a temperature of 30 to 150 ° C. and a humidity of 85% or more (constant temperature and constant temperature). The reaction between the mold and the release agent proceeds by leaving it in the wet chamber 144) for about 10 minutes to 1 day (FIG. 9C). Finally, by rinsing with a fluorine-based inert solvent, alcohol, purified water, or the like, a mold 146 having a release layer 145 chemically bonded to the surface can be obtained (FIG. 9D). This release layer can reduce the adhesive force between the mold and the resin.

<Background Technology 5: Imprint Release Technology (Dry)>
Further, as a release processing method different from the background art 4, a method of forming a release layer on the mold surface by plasma processing of the mold has been proposed (see, for example, Patent Document 3). FIG. 10 illustrates this method. According to this, in the vacuum chamber 153, plasma 154 is generated using F atomic gas such as CHF ₃ , C ₃ F ₈ , CH ₂ F ₂ , CH ₃ F as a raw material, and the mold 150 is placed therein. (FIG. 10 (b)), a mold 156 having a release layer (surface treatment layer) 155 containing fluorine atoms on the surface can be obtained (FIG. 10 (c)). According to this method, the mold release property of the mold and the resin is better than the release treatment method of Background Art 4.

<Background Technology 6>
On the other hand, in order to improve mold releasability, a mold is disclosed in which the surface layer of the mold is made of a material containing silicon. Furthermore, in order to improve the steel properties of the mold, a mold is shown in which the material containing silicon, for example, the material of the mold body having a surface layer made of silicon, silicon carbide, or silicon oxide is made of a material containing diamond ( For example, see Patent Document 4).

However, in such a mold, silicon and its compounds are suitable as a release layer, but they are all naturally oxidized in the air, that is, oxygen is chemisorbed on the mold surface layer, so that it is hydrophobic. That is, it is not possible to obtain sufficient release properties. In addition, although it is stated that diamond is used for the mold body, a surface layer made of silicon and a silicon compound is indispensable in order to increase the releasability. Not mentioned.
JP 2000-194142 A JP 2002-283354 A JP 2003-77807 A JP 2004-311713 A Appl.Phys.Lett., Vol.67, p.3314 (1995) A thorough explanation of nanoimprint technology Electric Journal Published November 22, 2004 P20-38 J. Photopolym. Sci. Technol., Vol.14 (2001) pp.457-462 J. Taniguchi et al. JJAP Vol. 41 (2002) pp. 41944197, Measurement of Adhesive Force Between Mold and Photocurable Resin in Imprint Technology

However, even if a release layer is formed on the mold surface by the methods as described in Background Art 4 and 5, there is a problem that this release layer has low durability.
For this reason, when imprinting is repeatedly performed, the release layer is gradually peeled off from the mold surface, and the mold release property between the mold and the resin is lowered. Specifically, although depending on imprint conditions such as thermal imprint and optical imprint, generally, mold releasability between the mold and the resin is lowered after about 10 to 100 times, and the resin adheres to the mold.
Such adhesion of the resin becomes a defect of the transfer pattern, and a transfer pattern faithful to the mold pattern cannot be obtained. Moreover, since the mold with the resin filled in the pattern groove becomes a defect in the mold pattern, it cannot be repeatedly used for imprinting thereafter (for example, see Non-Patent Document 4).

  An object of the present invention is to form a highly durable release layer on a mold used in an imprint method, and to perform the imprint transfer repeatedly so that adhesion of the resin to the mold does not occur and a method for producing the same Is to provide.

In order to achieve the above-mentioned object, an invention according to claim 1 is an imprint mold having a surface layer on which a concavo-convex pattern is formed, and transferring the concavo-convex pattern shape to a transfer object by an imprint method. The surface layer on which the concavo-convex pattern is formed is composed of a nanocrystal diamond film, the surface of the nanocrystal diamond film is terminated with a hydrogen atom or a halogen atom, and the halogen atom is fluorine or chlorine. .
The invention according to claim 2 is an imprint mold having a surface layer on which a concavo-convex pattern is formed, and transferring the concavo-convex pattern shape to a transfer object by an imprint method, which is laminated on a mold support substrate. is a nano-crystal diamond film, the uneven pattern is formed on the nano-crystal diamond film that, the surface of the nano-crystal diamond film is terminated with hydrogen atom or a halogen atom, said halogen atom is a fluorine or chlorine It is characterized by.

The invention according to claim 3, and characterized the material of the mold support substrate, silicon, nickel, chromium, iron, tantalum, metals containing either tungsten or oxides thereof, nitrides, that the carbide To do .
The invention according to claim 4 is the method for producing an imprint mold according to claim 1 , wherein after the nanocrystal diamond film is formed on the surface layer of the mold on which the concavo-convex pattern is formed, hydrogen atoms or A release layer is formed by performing plasma treatment with a source gas containing a halogen atom, wherein the halogen atom is fluorine or chlorine.

The invention of claim 5, wherein, there is provided a method of imprint mold production according to claim 2, by forming a nanocrystalline diamond film on the mold support substrate, an uneven pattern on the nano-crystal diamond film After the formation, a release layer is formed by performing plasma treatment with a source gas containing hydrogen atoms or halogen atoms , wherein the halogen atoms are fluorine or chlorine.

According to the imprint mold of the present invention and the manufacturing method thereof, the durability of the mold release layer is improved in the imprint method, so that the occurrence of adhesion of the resin to the mold is greatly increased even in repeated imprint processes. Can be suppressed. Furthermore, it is possible to greatly reduce the occurrence of mold pattern breakage due to resin adhesion.
Accordingly, it is possible to reduce transfer pattern defects and extend the life of the mold, and it can be expected that a good transfer pattern is formed and the cost is greatly reduced in the imprint method.

FIG. 1 is a cross-sectional view showing a method for manufacturing an imprint mold according to an embodiment of the present invention. As a first example, a method for forming a diamond film and performing plasma treatment after pattern formation is shown.
First, a mold material 160 shown in FIG. 1A has a concavo-convex shape on the surface of a mold material using a metal such as silicon, nickel, chromium, iron, tantalum, and tungsten, and oxides, nitrides, and carbides thereof. A pattern is formed.
In FIG. 1B, a diamond film 161 is formed on the pattern surface of the mold material 160. Then, a hydrogen plasma treatment 162 is further performed to form a release layer 163 (FIGS. 1C and 1D).

As is well known, diamond has the hardest physical property among substances, so that it can obtain mechanical resistance superior to other materials. Further, the surface of the diamond film becomes hydrophobic because oxygen atoms are not chemisorbed on the surface layer in the air, that is, not oxidized, like silicon or metal and their compounds. The friction coefficient is very small. Therefore, it has the property that other substances that come into contact are difficult to be adsorbed. Therefore, the durability of the release layer in imprinting can be improved by forming a diamond film on the surface of the mold material.
In addition, a layer in which oxygen atoms are not chemically adsorbed on the surface of the mold material 160 can be obtained, and removal of the oxide film on the surface is unnecessary, so that the surface can be easily hydrogenated and formed on the surface. It is possible to obtain an excellent hydrophobic and chemically stable mold surface due to the C—H bond having a strong binding energy.

  In addition, a release layer can be formed on the diamond film surface by performing a halogenated plasma treatment instead of the hydrogen plasma. In this case, an excellent hydrophobic and chemically stable mold surface due to the C—F or C—Cl bond having a strong binding energy generated on the diamond surface can be obtained.

Since the mold surface layer only needs to be a diamond film, the diamond film may be formed on the surface of the mold on which the mold pattern has been formed, or the diamond film may be formed after the diamond film is formed on the mold support substrate. It is good also as a mold pattern by patterning.
FIG. 2 shows an example of this. First, a diamond film 171 is formed on a mold support substrate 174 (FIG. 2A), and this diamond film 171 is patterned to form a surface pattern (FIG. 2B). Then, this is subjected to plasma treatment 172 to form a release layer 173 (FIGS. 2C and 2D).

  In addition, by making the diamond film particularly a nanocrystal diamond film, it is possible to obtain a very flat surface and easily obtain a nanometer rule pattern in order to construct the film from nano-sized crystal grains. It becomes possible.

Examples according to the present invention will be described below.
In the present invention, the imprinting method and the molding material are not limited. In the following examples, a case where a Si mold for thermal imprinting is manufactured will be described as an example.
A method for producing the mold of this example is shown in FIG. A 4-inch silicon wafer was prepared as a substrate 181 as a mold base (FIG. 3A). This substrate 181 is coated with an electron beam resist (ZEP520 / manufactured by Zeon Corporation) 182 with a thickness of 200 nm (FIG. 3 (b)), a line pattern of 100 to 400 nm is drawn with an electron beam drawing apparatus, and then organic development is performed. A resist pattern was formed (FIG. 3C). The conditions at this time were a drawing dose of 100 μC / cm ² and a development time of 2 minutes.

Next, a Si pattern having a depth of 50 nm was formed by Si dry etching using an ICP dry etching apparatus (FIG. 3D). The Si etching conditions were C ₄ F ₈ flow rate 30 sccm, O ₂ flow rate 30 sccm, Ar flow rate 50 sccm, pressure 2 Pa, ICP power 500 W, and RIE power 130 W. Finally, the resist was peeled off by O ₂ plasma ashing (conditions: O ₂ flow rate 500 sccm, pressure 30 Pa, RF power 1000 W), and a Si mold 180 before forming a release layer was produced (FIG. 3E).

  Next, the steps of diamond film formation and release layer formation are shown in FIG. A diamond film 191 made of nanocrystals was formed on the surface of the Si mold 190 of FIG. 4A (= FIG. 3E) by microwave plasma chemical vapor deposition (MPCVD) (FIG. 4B). . The film formation conditions were a total flow rate of 500 sccm (methane 50 sccm, hydrogen 445 sccm, nitrogen 5 sccm), a reaction pressure of 77 Torr, and a microwave power of 2 kW. The substrate temperature was 750 ° C. At this time, the film thickness was about 10 nm. Subsequently, the plasma was treated for 10 minutes under the same conditions as described above, except that the hydrogen flow rate was 500 sccm (FIG. 4C).

  As a result, a Si mold 196 having a diamond film made of nanocrystals and a release layer (hydrogen-terminated surface) 193 on the Si pattern was completed (FIG. 4D). When this surface structure was analyzed by vibration spectroscopy, a C—H structure was confirmed on the surface of the nanocrystal diamond film. In addition, it was confirmed that a similar release layer could be formed by treatment with radio frequency (RF) plasma instead of the microwave plasma (FIG. 4 (e1)).

Next, an example in which a Si mold for thermal imprinting was produced by another surface treatment method will be described. Until the production of the diamond film made of nanocrystals, a Si mold was produced under the same conditions as in the production method described in Example 1 (FIG. 4B). Next, a release layer was formed by fluorine plasma treatment using an ICP dry etching apparatus (FIG. 4C). The plasma treatment conditions were CF ₄ gas 35 sccm, reaction pressure 30 mTorr, high frequency power 300 W, and treatment time 5 minutes.

Thereby, a Si mold having a diamond film made of nanocrystals and a release layer (fluorine-terminated surface) on the Si pattern was completed (FIG. 4D). When this surface structure was analyzed by X-ray photoelectron spectroscopy (XPS), a C—F structure was confirmed (FIG. 4 (e2)). Further, changes to the _{CF 4, C 2 F 6,} C 3 F 8, C 4 F 8, CHF 3, CH 2 F 2, CH 3 F, F2, BF 3, NF 3, ClF 3, PF 3, SF _6. It was also confirmed that a release layer could be formed using any one of the gases ₆ and SiF ₄ , or a mixed gas containing one of them.

Next, a Si mold for thermal imprinting was produced by another surface treatment method. Until the production of the diamond film made of nanocrystals, a mold was produced under the same conditions as in the production method described in Example 1 (FIG. 4B). Next, a release layer was formed by chlorine plasma treatment using an ICP dry etching apparatus (FIG. 4C). The plasma treatment conditions were Cl ₂ gas 35 sccm, reaction pressure 30 mTorr, high frequency power 300 W, and treatment time 5 minutes.

As a result, a Si mold having a nanocrystal diamond film and a release layer (chlorine terminated surface) on the Si pattern was completed (FIG. 4D). When this surface structure was analyzed by X-ray photoelectron spectroscopy (XPS), a C—Cl structure was confirmed (FIG. 4 (e3)). It was also confirmed that the release layer could be formed by using any one gas of CCl ₄ and CHCl ₃ or a mixed gas containing any of them instead of Cl ₂ .

  Next, an example in which a diamond mold for thermal imprinting is produced by another method will be described. The manufacturing method is shown in FIG. A 4-inch silicon wafer was prepared as the mold support substrate 204, and a diamond film 201 made of nanocrystals was formed on the surface of the Si wafer by microwave plasma chemical vapor deposition (MPCVD) (FIG. 5A). The film formation conditions were a total flow rate of 500 sccm (methane 50 sccm, hydrogen 445 sccm, nitrogen 5 sccm), a reaction pressure of 77 Torr, and a microwave power of 2 kW. The substrate temperature was 750 ° C. At this time, the film thickness was about 100 nm.

Next, an electron beam resist (ZEP520 / Nippon Zeon) is coated on the diamond film 201 made of nanocrystals to a thickness of 200 nm, a line pattern of 100 to 400 nm is drawn with an electron beam drawing apparatus, and then a resist pattern 207 is formed by organic development. (FIG. 5B), and a surface pattern is formed on the diamond film 201 (FIG. 5C). The conditions at this time were a drawing dose of 100 μC / cm ² and a development time of 2 minutes. Here, in order to obtain a higher selection ratio, an inorganic resist such as a silicon nitride film can be used as a hard mask as the resist layer.

Subsequently, the plasma was introduced into a microwave plasma CVD apparatus, and microwave plasma treatment 202 was applied for 10 minutes under the same conditions as those for producing the diamond film made of nanocrystals with 500 sccm of hydrogen and others (FIG. 5D).
As a result, a diamond mold 206 having a diamond film 201 made of nanocrystals patterned on the mold support substrate 204 and a release layer (hydrogen-terminated surface) 203 was completed (FIG. 5E). When this surface structure was analyzed by vibration spectroscopy, a C—H structure was confirmed on the surface of the nanocrystal diamond film. In addition, it was confirmed that a similar release layer could be formed by treatment with radio frequency (RF) plasma instead of the microwave plasma (FIG. 5 (f1)).

Next, a diamond mold for thermal imprinting was produced by another surface treatment method. Until the production of the diamond film made of nanocrystals, a mold was produced under the same conditions as in the production method described in Example 4 (FIG. 5C). Next, a release layer was formed by fluorine plasma treatment using an ICP dry etching apparatus (FIG. 5D). The plasma treatment conditions were CF ₄ gas 35 sccm, reaction pressure 30 mTorr, high frequency power 300 W, and treatment time 5 minutes.

As a result, a diamond mold 206 having a diamond film 201 made of nanocrystals patterned on the mold support substrate 204 and a release layer (fluorine-terminated surface) 203 was completed (FIG. 5E). When this surface structure was analyzed by X-ray photoelectron spectroscopy (XPS), a C—F structure was confirmed (FIG. 5 (f2)). Further, changes to the _{CF 4, C 2 F 6,} C 3 F 8, C 4 F 8, CHF 3, CH 2 F 2, CH 3 F, F 2, BF3, NF 3, ClF 3, PF 3, SF _6. It was also confirmed that a release layer could be formed using any one of the gases ₆ and SiF ₄ , or a mixed gas containing one of them.

Next, a diamond mold for thermal imprinting was produced by another surface treatment method. Until the production of the diamond film made of nanocrystals, a mold was produced under the same conditions as in the production method described in Example 4 (FIG. 5C). Next, a release layer was formed by chlorine plasma treatment using an ICP dry etching apparatus (FIG. 5D). The plasma treatment conditions were Cl ₂ gas 35 sccm, reaction pressure 30 mTorr, high frequency power 300 W, and treatment time 5 minutes.

As a result, a diamond mold having a nanocrystal diamond film patterned on the Si support substrate and a release layer (chlorine-terminated surface) was completed (FIG. 5E). When this surface structure was analyzed by X-ray photoelectron spectroscopy (XPS), a C-Cl structure was confirmed (FIG. 5 (f3)). It was also confirmed that the release layer could be formed by using any one gas of CCl ₄ and CHCl ₃ or a mixed gas containing any of them instead of Cl ₂ .

  Next, thermal imprinting was repeatedly performed using the Si molds produced in Examples 1 to 3 and the diamond molds produced in Examples 4 to 6, and the mold releasability was lowered and the mold pattern was durable. I examined the sex. In addition, as a general mold release agent for comparison, a decrease in mold release and durability of the mold pattern are similarly applied to Si molds that have been dipped with a fluorine-based surface treatment agent EGC-1720 (Sumitomo 3M). I investigated.

  A silicon substrate was used as a transfer substrate to be imprinted, and a thermoplastic resin PMMA (polymethyl methacrylate) was coated on the silicon substrate to a thickness of 300 nm. The thermal imprinting conditions for one time were a substrate and mold heating temperature of 140 ° C., a press pressure of 15 MPa, a press holding time of 1 minute, and a substrate cooling temperature of 30 ° C.

  As a method for evaluating the deterioration of mold releasability, as a method for evaluating the durability of the mold pattern by repeating the thermal imprinting of this condition up to 200 times, examining the number of times the transfer pattern starts to adhere to the mold, The number of times mold destruction occurred was examined.

  As a result of the experiment, in the general Si mold, the transfer pattern was adhered to the mold by thermal imprinting 40 to 60 times. However, the Si mold of Examples 1 to 3 and Examples 4 to 6 were used. In the diamond mold, no adhesion to the mold occurred even after 200 thermal imprints. From this, it was proved that there is almost no decrease in adhesion force in the mold of this example as compared with a general Si mold.

  As for the destruction of the mold pattern, the general Si mold occurred at the 48th time, but the mold pattern destruction did not occur even when the Si mold and the diamond mold of this example were repeated 200 times or more. From this, it can be seen that the mold of this example also has better mold pattern durability than the general Si mold.

  By the way, considering this result, it is considered that there is a considerable correlation between the mold release property and the durability of the mold pattern. In other words, in order to improve mold releasability, it is necessary not only to reduce the adhesion of the surface but also to increase the rigidity of the mold pattern. To increase the durability of the mold pattern, the rigidity of the mold pattern must be increased. In addition to increasing, it is considered necessary to reduce the adhesion of the surface.

It is sectional drawing which shows the manufacturing process of the mold by embodiment of this invention. It is sectional drawing which shows the manufacturing process of the mold by embodiment of this invention. It is sectional drawing which shows the manufacturing process of the mold by embodiment of this invention. It is sectional drawing which shows the manufacturing process of the mold by embodiment of this invention. It is sectional drawing which shows the manufacturing process of the mold by embodiment of this invention. It is sectional drawing which shows the manufacturing process of the mold by a prior art. It is sectional drawing which shows the manufacturing process of the mold by a prior art. It is sectional drawing which shows the manufacturing process of the mold by a prior art. It is sectional drawing which shows the manufacturing process of the mold by a prior art. It is sectional drawing which shows the manufacturing process of the mold by a prior art.

Explanation of symbols

150, 160, 170, 180, 190, 200 ... mold, 153 ... vacuum chamber, 154, 162, 172, 192, 202 ... plasma, 155, 163, 173, 193, 203 ... release layer, 161 , 171, 191, 201... Diamond film, 156, 166, 176, 196, 206... Molds that have undergone mold release treatment, 174, 204.

Claims (5)

It has a surface layer on which a concavo-convex pattern is formed, and is an imprint mold for transferring the concavo-convex pattern shape to a transfer object by an imprint method,
The surface layer on which the uneven pattern is formed is a nanocrystal diamond film,
The surface of the nanocrystal diamond film is terminated with hydrogen atoms or halogen atoms,
The halogen atom is fluorine or chlorine;
An imprint mold characterized by the above. It has a surface layer on which a concavo-convex pattern is formed, and is an imprint mold for transferring the concavo-convex pattern shape to a transfer object by an imprint method,
It has a nanocrystal diamond film laminated on a mold support substrate, and an uneven pattern is formed on the nanocrystal diamond film ,
The surface of the nanocrystal diamond film is terminated with hydrogen atoms or halogen atoms,
The halogen atom is fluorine or chlorine;
An imprint mold characterized by the above.   3. The imprint according to claim 2, wherein the material of the mold support substrate is a metal including any one of silicon, nickel, chromium, iron, tantalum, and tungsten, or an oxide, nitride, or carbide thereof. Mold. It is a manufacturing method of the mold for imprints according to claim 1 ,
After forming a nanocrystal diamond film on the surface layer of the mold on which the concavo-convex pattern is formed, a release layer is formed by performing plasma treatment with a source gas containing hydrogen atoms or halogen atoms ,
The halogen atom is fluorine or chlorine;
A method for producing an imprint mold, wherein: It is a manufacturing method of the mold for imprints according to claim 2 ,
The nanocrystalline diamond film is formed on the mold support substrate, wherein after forming an uneven pattern on the nano-crystal diamond film, a release layer was formed by performing a plasma treatment with a raw material gas containing hydrogen atom or a halogen atom ,
The halogen atom is fluorine or chlorine;
A method for producing an imprint mold, wherein:

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