JP2010240864A - Method for producing imprinting member and imprinting member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To propose a method for producing an imprinting member, in which a highly accurate and correct engraved groove can be formed by a few treatment steps and which is suitable for mass production and to propose the imprinting member. <P>SOLUTION: The method for producing the imprinting member comprises the steps of: depositing an amorphous DLC (diamond-like carbon) film containing 12-30 atomic% hydrogen and the balance of carbon on the surface of a base material; and irradiating the surface of the DLC film directly with a laser beam to form the engraved groove consisting of a geometrical pattern or the like. The imprinting member can transfer a groove shape onto a synthetic resin layer correctly and highly accurately and is suitable for low-cost mass production. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a technique for performing ultra-fine pattern microfabrication performed in the industrial field such as an optical device, a magnetic recording device, and a culture device and nano-processing that is a transfer technique thereof, and a novel imprint member manufacturing method and imprint Propose printed material.

  In recent years, nanoimprint technology in the field of semiconductor processing products with high-precision processing of integrated circuits, optical devices such as optical waveguides and light guide plates, magnetic recording devices such as pattern media, and cell culture devices in regenerative medicine Has attracted attention, and energetic research on this technology is being conducted.

  The nanoimprint method is characterized in that a nanometer (nm) to micrometer (μm) scale structure can be processed easily and at low cost. As the nanoimprint method, a thermal cycle method (thermal imprint method) and a photocuring method (photoimprint method) are well known. Among them, the former thermal cycle system is a technique in which a thermoplastic resin is used as a resin material to be transferred, and a mold is pressed against a resin softened by heating to a glass transition temperature or higher.

  On the other hand, the latter photocuring method is a technique for transferring a pattern of a mold to a resin by using a photosensitive resin as a resin material and curing the resin by irradiating ultraviolet rays while the mold is pressed.

  The nanoimprint method has recently been actively researched and developed because the equipment cost is low in place of the photolithography technique and the engraving method for the mold base material by electron beam irradiation and ion beam irradiation. It has become like this.

(1) For example, in Patent Document 1, a surface of a silicon support is coated with a SiC film by a CVD method, and then the surface is finely processed by plasma etching, and further, Ti, Ni, A method of improving the wettability of the work surface by forming a metal thin film such as Pt by electroplating and anodizing the metal thin film is disclosed.
(2) Patent Document 2 discloses a technique for improving the releasability from a resin by coating concavo-convex surfaces of a quartz substrate with TiO ₂ having a photocatalytic function by a PVD method as a mold for photo-curing nanoimprint. .
(3) Patent Document 3 discloses a technique in which a DLC film is formed on the surface of a stamper (pressing die) used in the thermal / optical nanoimprint method to improve the transfer system.
(4) Patent Document 4 discloses a technique in which the wettability of the surface is improved by forming a DLC film in which fluorine is injected on the surface of a finely processed SiO ₂ film.
(5) In Patent Document 5, after anodizing the surface of an Al substrate and the like, impregnating benzoyl peroxide and methyl methacrylate monomer in fine voids generated on the surface of the anodized film, A technique for solidifying and then dissolving and removing only the anodic oxide film with an alkaline aqueous solution is disclosed. In addition, according to this technology, an organic solid material composed of benzoyl peroxide and methyl methacrylate monomer can be left in an amorphous state on the surface of the Al base material, and a method using this can also be adopted. It is.
(6) Patent Document 6 discloses a technique in which fine irregularities are formed on the surface of a roll base material by a thermal / optical nanoimprint method, and the surface is continuously transferred onto the surface of the resin by the rotation of the roll.

JP 2008-47797 A JP 2007-144959 A JP 2006-32423 A JP 2007-320142 A JP 2008-229869 A JP 2007-289999 A

The present invention aims to solve the following problems of the above-described conventional technology.
(1) In the thermal imprinting method, a thermoplastic resin is heated and softened, and then a mold press is performed. Therefore, the transfer accuracy is lowered due to the occurrence of thermal strain caused by the difference in thermal expansion coefficient between the mold and the substrate.
(2) In the photoimprint method, a shrinkage phenomenon occurs when the photosensitive resin that has received ultraviolet rays is cured, and the transfer accuracy is reduced due to a difference in expansion coefficient between the photosensitive resin and the substrate.
(3) In the thermal and optical imprint method, a process of pressing a mold engraved with fine irregularities and patterns against a resin and transferring it is essential. For this reason, the accuracy and accuracy of engraving on the mold influence the quality of the product, but the engraving process takes a long time and the productivity is poor.
(4) Metal, silicon (Si) as a metalloid, silicon carbide (SiC) as a nonmetal, etc. are used as the mold base material. In contrast, this leads to a decline in productivity.
(5) When a thin film such as SiC is produced by a method such as CVD or PVD, if the SiC thin film is engraved, it may be greatly deformed during engraving due to residual stress in the film. The film is peeled off and cracked and cannot be used as a mold.
(6) For surface treatment methods such as CVD, PVD, electroplating, and anodizing, all of these require a lot of time, and sometimes use chemicals that cause environmental pollution. Costs and environmental measures costs will increase.
(7) In the technology that forms a porous anodic oxide film on the surface of an Al base, fills the voids with an organic substance, and dissolves and removes only the oxide film, control the void shape and size of the oxide film. Is impossible and has limited applications. In addition, since this method uses an alkaline solution by dissolving and removing the oxide film including an anodizing agent, an environmental pollution countermeasure is indispensable and the cost increases.

  As a result of diligent research to solve the above-described problems of the prior art, the inventors have come up with the following solution. That is, the present invention relates to a DLC film comprising a deposited layer of amorphous carbon hydrogen solids mainly composed of carbon and hydrogen on a smooth inorganic (metal, glass, quartz, ceramics, etc.) or organic (synthetic resin) surface. After that, the surface of this DLC film is directly irradiated with a laser beam heat source to form engraving grooves made of engineering patterns such as fine irregularities and geometric patterns. In this method, a prototype corresponding to a conventional mold (stamper) is created and used as an imprint member.

In the present invention,
(1) The DLC film engraved with an engineering pattern contains 13 to 30 atomic% of hydrogen vapor-deposited from a hydrocarbon-based gas using a high-frequency / high-voltage pulse superposition type plasma CVD apparatus, and the remainder is A film in which amorphous carbon hydrogen solid particles made of carbon are deposited,
(2) The DLC film has a thickness of 3 to 50 μm.
(3) The DLC film has a residual stress value of 1.0 GPa or less and a hardness of about Hv 700 to 3000.
(4) The surface roughness of the DLC film in which the laser beam engraving groove is formed is Ra: 0.1 μm or less,
(5) polishing and smoothing the surface of the DLC film prior to laser beam irradiation;
(6) The engraving groove is formed by irradiating the surface of the DLC film with any one laser beam heat source selected from a CO ₂ laser, a YAG laser, an Ar laser, an excimer laser, and a semiconductor laser. There is,
(7) The base material is at least one selected from metal / alloy (including Si) synthetic resin, glass, quartz, ceramics, sintered carbon, and metal carbide.
(8) The substrate has a surface roughness of Ra ≦ 0.1 μm, Rz ≦ 0.5 μm,
It is desirable to employ the above solution.

The present invention also comprises a substrate and a DLC film that is a deposited layer of amorphous carbon hydrogen solid particles formed on the surface of the substrate. The surface of the DLC film is directly irradiated with a laser beam heat source. An imprint member comprising a laser beam engraving groove having an engineering pattern formed by engraving.
In addition, said (1)-(7) is one of the solution means applied as it is also about this imprint member.

According to the present invention, the following effects can be expected.
(1) The engraved groove with an engineered pattern engraved with a laser beam heat source is formed directly on a hard and wear-resistant DLC film. Since it can be accurately maintained over a long period of time, it can be used as an imprinting member in the engraved state, and its life is long.
(2) Since the laser beam engraving groove is directly engraved on the DLC film by a laser beam heat source, the number of steps is less than that of the conventional process, and the production efficiency is high.
(3) Since the engraved grooves formed directly on the surface of the DLC film are obtained by irradiation with a laser beam heat source, the processing speed is high and the accuracy and accuracy of the groove shape are excellent.
(4) The engraving groove is easily formed by directly irradiating the DLC film with a laser beam, and the DLC film in the irradiated portion is volatilized into the atmosphere as a gas such as CO ₂ or H ₂ O. Therefore, accurate and beautiful sculpture can be made without the presence of fine molten mass.
(5) Since the DLC film formed on the surface of the imprint member can be easily decomposed and gasified by heating to 700 ° C. or higher after use, industrial waste is less generated and waste processing is simple. There is little environmental pollution.
(6) Since the surface of the imprint member is formed of a DLC film having excellent corrosion resistance against acids, alkalis, and organic solvents, the imprint member is not altered or the engraved pattern is not deformed.
(7) Since the surface of the imprint member is coated with the DLC film, the chemical stability of the member is high, and it can be applied to bioengineering and medical fields.
(8) The DLC film used in the present invention is composed of amorphous carbon hydrogen solid fine particles containing 13 to 30 atomic% of hydrogen, and since the residual stress is 1 GPa or less, a thick film can be formed. Even when engraving with a high aspect ratio is performed, the DLC film is not deformed and the engraving groove is not deformed.
(9) The DLC film formed on the surface of the imprint member can be easily formed with or without electrical conductivity, and the shape of the object to be processed (member) is a sheet shape. In addition to plate shapes, prisms and cylinders (roll shapes) can be freely laminated so that they can be applied in a wide range of industrial fields.
(10) According to the method of the present invention, a DLC film engraved with an engineered pattern can be used as a mold (stamper), especially on the surface of various synthetic resin sheets and plates having a lower hardness than the DLC film. The engraving shape can be directly stamped and transferred.
(11) The DLC film used in the present invention, for example, has a property of increasing to about Hv: 27000 when heated to 300 ° C. at a normal temperature and having a Hv of about 1400, so that it can be used in a high temperature environment. Is also durable enough.

It is a figure which compares the conventional imprint process process (a), (b) and the process process (c) of this invention. (A) is an imprint method using a thermoplastic resin, (b) is an imprint method using a photosensitive resin, and (c) is an embodiment of the present invention in which laser beam engraving is directly performed on a DLC film. This is an imprint method. It is an operation process figure of the imprint method concerning the present invention. (A) is a cross section of the DLC film when the Rz value of the roughness of the substrate surface is large, and (b) is a cross section of the DLC film coated on the substrate surface where both the Ra value and the Rz value are small. 1 is a schematic view of a plasma CVD apparatus for coating a DLC film. It is an enlarged SEM image (linear engraving) of the surface of the DLC film engraved with a laser beam heat source. It is the expansion SEM image (pocket type engraving) of the DLC film surface engraved by the laser beam heat source. It is a basic diagram which shows the measuring method of the residual stress of a DLC film. It is a sample for evaluating adhesiveness by the form of the scratch wrinkles remaining on the DLC film surface after the scratch test. It is explanatory drawing which shows the process of transferring engraving on the surface of a synthetic resin with the roller which forms a laser beam engraving groove | channel on the DLC film surface.

FIG. 1 shows a comparison between a conventional imprint method using a thermoplastic resin and a conventional imprint method using a photosensitive resin, and the method of the present invention in which the DLC film surface according to the present invention is directly engraved by laser beam irradiation. It is. In this figure, in the process of the imprint method of the thermal cycle type (a), a process of heating the thermoplastic resin layer on the surface of the substrate and a pressure transfer process using a mold to the resin layer are required. On the other hand, in the optical imprint method of FIG. 1B, in addition to the pressure transfer process using a mold to the photosensitive resin layer, an ultraviolet irradiation process is essential. In addition, both methods require a separate process for fine engraving on the mold, and it can be seen that a very large number of man-hours, time, and costs are required to perform all the processes.
On the other hand, since the method according to the present invention of (c) consists only of a process of engraving by direct laser beam irradiation on the surface of the DLC film coated on the substrate surface, the process is very simple, The economic effect is enormous.

  FIG. 2 shows representative processing steps for carrying out the method of the present invention. In this example, a substrate made of metal, ceramics or the like having a smooth surface is cleaned by an operation such as washing or degreasing, and then a DLC film is formed on the cleaned substrate surface. Thereafter, a method of manufacturing an imprint member by directly forming a laser beam engraving groove having an engineering pattern using a laser beam heat source on the surface of the DLC film is shown.

Hereinafter, it will be specifically described according to the processing steps shown in FIG.
(1) A substrate that can be used as an imprint member;
As the substrate that can be used in the present invention, the following are preferably used.
(A) Metallic: A desired film is formed on a metal such as Cr, Mo, Ti, Ta, W or Si and an alloy thereof, or an electroplating method, a CVD method, a PVD method or the like on these metals or alloys. What
(b) Organic: various synthetic resins
(c) Ceramics: carbides such as WC, TiC, TaC, SiC, MoC, TaC, etc., or the surface of the base material coated with the carbide by a groove film forming method such as a CVD method,
(d) other inorganic materials: those sintered carbon, ceramics, glass, inorganic materials containing SiO _2, such as quartz, or these inorganic materials coated by the PVD method,
(E) the surface of the substrate coated with a thermal spray coating;

  The base material completely removes oils and fats, fine foreign matters, dust and the like by degreasing, washing with water, and the like. In particular, the surface of the metal substrate is preferably adjusted to a surface roughness Ra ≦ 0.1 μm and Rz ≦ 5.0 μm by grinding or polishing and further polishing or electrolytic polishing as necessary. This is because if the surface roughness of these base materials is rough, fatal defects occur in the DLC film formed on the surface.

  FIG. 3 schematically shows a cross section when DLC is formed on the ground or ground-polished substrate (sprayed coating) surface. FIG. 3A shows a state in which there is a protrusion 35 protruding on the surface of the DLC film or a protrusion 33 reaching near the surface because the Rz value is high even though the Ra value is low. is there. When a DLC film coated on such a rough surface is engraved with a laser beam, it is easily affected by the projections 33 and 35 and a good engraved surface cannot be obtained. On the other hand, FIG. 3B shows that the Ra value and the Rz value are both low, and that the DLC film coated on such a surface is a film that is not affected by the underlayer. FIG. 3B Then, the height of the protrusion 33 showing the Rz value is less than about 50% of the DLC film thickness. Therefore, the engineering pattern is preferably engraved by irradiating the DLC film in such a state with a laser beam. Here, 31 shown is a metallic substrate, 32 is a surface roughness indicated by Ra, 33 is a surface roughness indicated by Rz, 34 is a DLC film, and 35 is indicated by Rz that could not be coated with a DLC film. It is a projection of roughness.

  In addition, even if a metal film (Mo, Cr, etc.) or carbide (SiC, MoC, etc.) is coated by CVD or PVD, if the surface roughness of the substrate is large, the coating Since the surface of the film inevitably becomes rough, it is important to finish it with a smooth surface. In this respect, sheets and films made of synthetic resin, glass, quartz plates, etc., are almost the same as those already smoothed in each manufacturing process, and in this case, smoothing can be omitted.

(2) DLC film coating formation treatment;
This process is a process for forming a DLC film on the substrate surface. In general, methods for forming a DLC film include methods such as an ion deposition method, an arc ion plating method, a plasma booster method, and a high frequency / high voltage pulse superposition type plasma CVD method (hereinafter simply referred to as “plasma CVD method”). However, as a result of various experiments conducted by the inventors, it was confirmed that the “plasma CVD method” is suitable for forming a thick DLC film suitable for the purpose of the present invention. The apparatus will be described.

  FIG. 4 is a schematic diagram showing an example of a plasma CVD apparatus for carrying out the DLC film coating forming method suitable for the object of the present invention. The plasma CVD apparatus according to the illustrated example mainly includes a grounded reaction vessel 41, a high voltage pulse generating power source 44 for applying a high voltage pulse in the reaction vessel 41, an object to be treated (hereinafter referred to as “plate making roll”). In addition to a plasma generating power source 45 for generating hydrocarbon gas plasma around 42, a high-voltage pulse and a high-frequency voltage are simultaneously applied to the conductor 43 and the plate-making roll 42. A superimposing device 46 is disposed between the high voltage pulse generating power source 44 and the plasma generating power source 45. The conductor 43 and the plate-making roll 42 are connected to the superimposing device 46 through a high voltage introduction unit 49.

  This plasma CVD apparatus includes a gas introducing device (not shown) for introducing an organic gas for film formation into the reaction vessel 41 and a vacuum device (not shown) for evacuating the reaction vessel 41, respectively. It is connected to the reaction vessel 41 via valves 47a and 47b.

  In order to form a DLC thin film on the surface of the object to be processed using this plasma CVD apparatus, first, the object to be processed (base material) 42 is set at a predetermined position in the reaction vessel 41 and the vacuum apparatus is operated. After the air in the reaction vessel 41 is discharged and deaerated, an organic hydrocarbon gas is introduced into the reaction vessel 41 by a gas introduction device.

  Next, high frequency power from the plasma generating power supply 45 is applied to the object to be processed 42. In addition, since the reaction container 41 is in an electrically neutral state by the ground wire 48, the workpiece 42 exhibits a relatively negative potential. For this reason, positive ions in the plasma are generated around the object 42 to be negatively charged.

  Next, when a high voltage pulse (negative high voltage pulse) from the high voltage pulse generator 44 is applied to the object to be processed 42, positive ions in the plasma of the organic hydrocarbon gas are applied to the surface of the object to be processed 42. Attracted adsorption. By such an operation, a DLC film is formed on the surface of the object to be processed. The inventors estimate that this phenomenon is formed through the following processes (a) to (d). .

(A) ionization of the introduced hydrocarbon gas (neutral particles called radicals also exist),
(B) Ions and radicals changed from the hydrocarbon gas collide impactively with the surface of the object 42 to which a negative voltage is applied,
(C) C—H having a low binding energy is cut by the energy at the time of collision, and then activated C and H are polymerized by repeating the polymerization reaction to form an amorphous state mainly composed of carbon and hydrogen. Vapor deposition of solid carbon hydrogen particles
(D) When the reaction of (c) above occurs, a DLC film consisting of a deposited layer (film) of solid matter (fine particles) mainly composed of amorphous carbon and hydrogen is formed on the surface of the object to be processed. It becomes.

  Note that in the plasma CVD apparatus, ion implantation of metal or the like is performed on the object 42 by changing the output power of the high voltage pulse generation power supply 44 as shown in the following (a) to (d). Can do. For example, when the object to be processed is metallic, it is possible to improve the adhesion of the DLC film formed on the surface by implanting ions such as Ti, Si, Cr, Nb, and C.

(A) When ion implantation is focused on: 10 to 40 kV
(B) When performing both ion implantation and film formation: 5 to 20 kV
(C) When only film formation is performed: several hundred V to several kV
(D) When performing sputtering or the like intensively: several hundred V to several kV]
(E) In the high voltage pulse generation source 44, it is also possible to repeat a pulse width of 1 μmsec to 10 msec and a pulse number of 1 to a plurality of times.
(F) The output frequency of the high frequency power of the plasma generating power supply 45 can be changed in the range of several tens of kilohertz to several GHz.

  As the film-forming organic gas introduced into the reaction vessel 41 of this plasma CVD processing apparatus, hydrocarbon gases as shown in the following (a) to (b) are used alone or in combination of two or more. .

(I) Gas phase state at room temperature (18 ° C.) CH ₄ , CH ₂ CH ₂ , C ₂ H ₂ , CH ₃ CH ₂ CH ₃ , CH ₃ CH ₂ CH ₂ CH ₃
(B) Liquid phase at normal temperature C ₆ H ₅ CH ₃ , C ₆ H ₅ CH ₂ CH, C ₆ H ₄ (CH ₃ ) ₂ , CH ₃ (CH ₂ ) ₄ CH ₃ , C ₆ H ₁₂ ,
C ₆ H ₄ Cl

  The gas introduced into the reaction vessel 41 in the gas phase at normal temperature can be introduced into the reaction vessel 41 as it is, but the compound in the liquid phase is heated to gasify it. A DLC film can be formed by supplying gas (vapor) into the reaction vessel 41.

A ratio of carbon and hydrogen content constituting the DLC film;
Although the DLC film is hard and excellent in wear resistance, a large residual stress is generated at the time of film formation, so that the DLC film lacks flexibility. For this reason, if a local micro defect occurs in the DLC film, or if a slight engraving shape difference occurs locally during engraving with a laser, the DLC film easily peels off due to residual stress. It is important to reduce the residual stress.

  As a countermeasure, in the present invention, attention is paid to the ratio of carbon to hydrogen forming the DLC film, and in particular, by controlling the hydrogen content to 13 to 30 atomic% of the whole, the DLC film can be flexible with wear resistance. Decided to give sex. Specifically, the hydrogen content contained in the DLC film was 13 to 30 atomic%, and the balance was the carbon content. Note that the formation of the DLC film having such a composition can be achieved by mixing compounds having different hydrogen and hydrogen content ratios in the hydrocarbon-based gas for film formation.

  Since the surface hardness of the DLC film having such a hydrogen content is in the range of Hv: 700 to 3000 in terms of micro Vickers hardness, compared with the DLC film formed on tool steel or the like, It is flexible and can withstand a certain degree of deformation.

  The thickness of the DLC film formed on the substrate surface by the method described above is suitably in the range of 3 to 50 μm. This is because when the film thickness is 3 μm or less, the aspect ratio of the laser beam engraving groove engraved by the laser beam heat source cannot be increased, and the substrate surface is easily affected by “swells” or slight deformation. Because it becomes. Moreover, there is a possibility that the laser beam engraving groove completely penetrates the DLC film and reaches the base material due to a slight deviation in engraving processing accuracy by the laser beam heat source and a difference in the absorption rate of the laser generated locally in the DLC film. Because there is. On the other hand, in order to form a film thicker than 50 μm, it takes a long time, resulting in an increase in production cost, and there is a risk of a decrease in bonding force with the base material due to an increase in residual stress accompanying the growth of the DLC film. It is possible.

  In the present invention, when the base material is a non-electric conductive synthetic resin plate or sheet or film thereof, in order to directly coat the surface of the base material with the DLC film, these are attached to a metal plate or the like. Then, the DLC film can be formed on the surface of these synthetic resin bodies in the same manner as the metal electrode. Further, in the plasma CVD apparatus shown in FIG. 4, it is possible to form a DLC film on the surface of the non-electric conductor by controlling the pulse waveform to only positive.

  When a DLC film having a large thickness (for example, 10 μm or more) is formed, sometimes a plurality of minute circular protrusions (for example, Rz ≦ 1.0 μm) are generated on the surface. In such a case, as shown in FIG. 2, a smooth surface (for example, Ra ≦ 0...) Is obtained by performing bubbling (polishing) or the like to remove the circular protrusion as required. It is preferable to finish to 1 μm).

(3) Laser beam engraving processing on the DLC film;
(A) Overview of laser beam engraving This process is performed by directly irradiating the surface of the DLC film with a laser beam after finishing the coating formation process of the DLC film on the substrate surface. It is a process of engraving a pattern.

In this step, a commercially available laser processing light source such as a CO ₂ laser, a YAG laser, an Ar laser, a semiconductor laser, or an excimer laser can be used as the laser light source. It is recommended that the resulting engineering pattern engraving be performed automatically by a computer with a pre-programmed computer, but depending on the size of the engraving groove (width and depth), a laser beam condensing lens, etc. Can be adjusted manually.

The DLC film is heated by irradiation with a laser beam heat source. However, since the heating is performed locally, heat does not conduct to the non-irradiated part, and the DLC component is CO only at the local part of the heating part. ₂ and gas such as H ₂ O will diffuse. As a result, a molten residue does not remain particularly around the laser beam engraving groove, and a precise and accurate engraving groove pattern can be formed on the DLC film surface.

  5 and 6 show SEM images of the appearance of the DLC film engraved with the laser beam by the method of the present invention. As the heat source of the laser beam in the illustrated example, the heat source having the following specifications is used, but it may have a relatively low output as compared with that applied to metal or ceramic engraving.

Laser output: 50W ~ 1KW
Pulse frequency: 10000 Mz to 50000 Hz
Progression speed: 0.1 to 300 mm / min

(B) Residual stress of DLC film suitable for engraving according to the present invention Residual stress is inevitably generated in a DLC film in a solid phase deposited from a hydrocarbon gas in a gas phase. Since the DLC film containing a large residual stress has a larger residual stress as the film thickness increases, the residual stress eventually becomes larger than the adhesion strength of the film, and the DLC film is peeled off. Currently, many types of apparatuses have been developed as a method for forming a DLC film. One of the application conditions is a limit film thickness determined by the residual stress of the DLC film.

  In particular, in the case of a DLC film having a relatively large thickness, even if the film can be formed, residual stress is concentrated in the concave portion obtained by engraving with a laser beam, and the DLC film is locally broken, Since it will peel, it is very important to determine the allowable value of the residual stress of the DLC film.

  For these reasons, the inventors conducted a test for evaluating the residual stress of the DLC film by the following method. As shown in FIG. 5, evaluation of the residual stress of the DLC film is performed on one surface of a strip-shaped thin quartz substrate (size: width 5 mm × length 50 mm × thickness 0.5 mm) with one end of the test piece fixed. The DLC film is formed, and the displacement (δ) of the quartz substrate before and after the film formation is measured to determine the residual stress of the film. Specifically, the residual stress (σ ) Was calculated.

Ｅ：基板のヤング率＝７６．２ＧＰａ
ｖ：基板のポアソン比＝０．１４
ｂ：基板の厚さ＝０．５ｍｍ
ｌ：ＤＬＣ膜が形成された基板の長さ
δ：変位量
ｄ：ＤＬＣの膜厚

E: Young's modulus of substrate = 76.2 GPa
v: Poisson's ratio of substrate = 0.14
b: substrate thickness = 0.5 mm
l: length of substrate on which DLC film is formed δ: displacement d: film thickness of DLC

  Table 1 summarizes the residual stress values of various DLC films obtained by the above method. As is apparent from this result, the residual stress of the DLC film formed by the arc ion plating method, the ionized vapor deposition method or the like is 10 to 18 GPa, whereas the DLC film obtained by the plasma CVD method is The residual stress was in the range of 0.30 to 0.98 GPa and was a very low residual stress value.

  In this test, when the maximum formation thickness of the DLC film was tried, a film having a thickness of 50 μm could be formed by the plasma CVD method although the film formation time was increased. However, in other film formation, it is difficult to form a film having a thickness of 3 μm or more.

  When the surface of the DLC film formed on the test piece after the residual stress measurement is irradiated with a laser beam, the film formed by the plasma CVD method according to the present invention is shown in FIGS. Although engraving as shown in Fig. 6 was possible, the DLC film having a large residual stress value peeled off immediately after engraving.

<Example 1>
In this example, the relationship between the adhesion of the DLC film and the substrate is clarified.
(1) Kind of base material The following six kinds were used as a base material of the example of the present invention.
(A) Cr plating film (10 μm thick electroplated on stainless steel plate)
(B) Si film (thickness 1.0 mm)
(C) Glass plate (thickness 1.0 mm)
(D) Quartz plate (thickness 1.0 mm)
(E) Epoxy resin plate (thickness 2 mm)
The following metal plate was used as the base material of the comparative example.
(F) Ni plate ((thickness 0.5mm)
(G) Cu plate ((thickness 0.5 mm)

  The dimensions of the test pieces were 10 mm wide × 30 mm long, and the test pieces forming the DLC film were finished with a surface roughness of Ra: 0.05 μm and Rz: 0.09 μm. .

(2) Formation method and film thickness of DLC film The DLC film was formed to have a thickness of 10 μm for all the test pieces using the plasma CVD apparatus shown in FIG.

(3) DLC film adhesion test method and evaluation A scratch test defined in ISO20502 was performed, and the occurrence of scratches generated on the surface of the DLC film was visually or observed with a magnifying glass. Moreover, in the evaluation, from the scratch test result of the DLC film formed on the substrate surface, a photograph of the state of occurrence of scratches as shown in FIG. 8 is recorded, and the adhesion strength of the DLC film is evaluated based on the photograph. Created standards for In this evaluation standard, evaluation 1 is a scratch wrinkle exhibited by the DLC film having the best adhesion, and is such that no clear wrinkle is observed. On the other hand, evaluation 4 shows the scratches of the DLC film having the lowest adhesion, and many DLC films are observed to be peeled off at the periphery of the heel. Evaluations 2 and 3 are standards showing an adhesion strength intermediate between Evaluation 1 and Evaluation 4, and all are distinguished by the degree of peeling of the DLC film around the scratch ridge.

(4) Test results The test results are shown in Table 2. As is clear from this result, the evaluation of the adhesion strength of the DLC film formed on the surface of the Ni plate and the Cu plate (Nos. 7 and 8) of the comparative example all showed 4, and a lot of DLC was found around the scratches. Peeling of the film was observed. On the other hand, most of the DLC films (Nos. 1 to 6) formed on the base material test piece according to the present invention were evaluated 1, and it was confirmed that good DLC film adhesion was obtained. It was.

<Example 2>
In this example, a surface of a structural carbon steel (SS400) was coated with an electric Cr plating film with a thickness of 10 μm, and then a DLC film obtained by changing the hydrogen content was formed on the surface. The content and resistance to bending deformation of the substrate and subsequent changes in corrosion resistance will be clarified.

(1) Properties of the test substrate and DLC film As test specimens, a Cr film was formed on the surface of SS400 steel (dimensions 15 mm wide x 70 mm long x 1.2 mm thick) by electroplating to a thickness of 10 μm. The coated one was used. A DLC film having a hydrogen content of 5 to 30 atomic% and the balance being a carbon component was coated on the entire surface of the test piece with a thickness of 5 μm by the plasma CVD method shown in FIG.

(2) Test method and conditions The test piece on which the DLC film was formed was subjected to bending deformation of 180 ° from the center (U-bend shape), and the surface of the DLC film at the bent part was observed with a 20 times magnifier. The presence or absence of “cracking”, “peeling” and “lifting” was investigated. In addition, the observed bending test piece was immersed in a 5% HCl aqueous solution and allowed to stand at room temperature (20 ° C.) for 48 hours, and the presence or absence of metal ions eluted in the HCl aqueous solution was examined by visual observation and chemical analysis.

(4) Test results The test results are summarized in Table 3. As is clear from this result, when the DLC film (Nos. 1 and 2) having a low hydrogen content is deformed by 180 °, it generates fine cracks and is in a state of locally rising. Was observed and found to be inflexible. On the other hand, when the test piece after the bending test was immersed in a 5% HCl aqueous solution, the HCl aqueous solution changed from colorless to yellow due to elution of Fe and Cr from the metal substrate in the cracked or lifted DLC film test specimen. As a precaution, chemical analysis of the yellowed HCl aqueous solution confirmed the presence of iron and chromium.

  On the other hand, the DLC film test piece having a hydrogen content of 13 to 30 atomic% shows a healthy state even when bent at 180 °, and even when the bent test piece is immersed in a 5% HCl aqueous solution. The color tone of the aqueous solution did not change. From these results, it was found that the DLC film containing 13 to atomic% of hydrogen does not generate defects due to bending deformation, and the DLC film itself has no pinholes and has excellent environmental barrier properties.

The technique for forming a fine engraving groove by irradiating a laser beam to a DLC film according to the present invention can be applied not only as an imprint member manufacturing technique but also for engraving printing intaglio and letterpress. It can also be used as a technique for forming a lubricating oil passage by forming a DLC film on a sliding part such as a bearing or shaft of a mechanical device and then processing a spiral groove on the film with a laser beam heat source. .
Furthermore, the member formed by forming the laser beam engraving groove on the surface of the DLC film according to the method of the present invention is expected to be used in the following industrial fields.

(1) Electronic display related: surface non-reflective structure, Fourier lens, diffuser plate, color filter, high brightness front light, alignment film, Fresnel lens, substrate liquid crystal (2) Optical media related: DVD pickup, demultiplexing grating, high Density magnetic disk, single mold optical waveguide, multimode optical waveguide, optical interconnection, optical backplane (3) Life science-related: Microbe detection chip, cell culture sheet, fingerprint sensor array, protein chip, microfilter, blood test chip, Nanopillar (4) Semiconductor / electronic circuit, etc .: polymer electrolyte membrane, sheet mold, non-slip flooring material, high-density printed circuit board, fuel cell separator, micro concentrating solar cell, organic semiconductor laser resonator

  FIG. 9 shows an example of engraving and transferring onto a soft synthetic resin sheet surface by a roller covering the DLC film as an application example of the DLC film formed with the laser beam engraving groove according to the present invention. is there.

31 Base material 32 Surface roughness (Ra)
33 Surface roughness (Rz)
34 DLC film 35 Roughness indicated by Rz that could not be covered with DLC film 41 Reaction vessel 42 Roll (object to be processed)
43 conductor 44 high voltage pulse generation source 45 plasma generation source 46 superimposing devices 47a and 48b valve 48 ground wire 49 high voltage introduction terminal

Claims (10)

A DLC film composed of a deposited layer of amorphous carbon hydrogen solids mainly composed of carbon and hydrogen is coated on the surface of the substrate, and then the surface of the DLC film is directly irradiated with a laser beam heat source. The manufacturing method of the imprint member characterized by forming the engraving groove | channel which consists of engineering patterns, such as a fine unevenness | corrugation and a geometrical pattern. The DLC film comprises amorphous carbon hydrogen solid fine particles containing 13 to 30 atomic% of hydrogen vapor-deposited from a hydrocarbon gas using a high-frequency / high-voltage pulse superposition type plasma CVD apparatus, with the balance being carbon. The method for producing an imprint member according to claim 1, wherein the film is a deposited film. The method for manufacturing an imprint member according to claim 1, wherein the DLC film has a thickness of 3 to 50 μm. The method for manufacturing an imprint member according to any one of claims 1 to 3, wherein the DLC film has a residual stress value of 1.0 GPa or less and a hardness of about Hv 700 to 3000. The method for producing an imprint member according to claim 1, wherein the surface roughness of the DLC film is Ra: 0.1 μm or less. The method for producing an imprint member according to claim 1, wherein the surface of the DLC film is polished and smoothed prior to laser beam irradiation. The engraving groove is formed by irradiating the surface of the DLC film with any one laser beam heat source selected from a CO ₂ laser, a YAG laser, an Ar laser, an excimer laser, and a semiconductor laser. The manufacturing method of the imprint member of any one of Claims 1-6 characterized by the above-mentioned. 8. The substrate according to claim 1, wherein the substrate is one or more selected from metal / alloy (including Si) synthetic resin, glass, quartz, sintered carbon, ceramics, and metal carbide. The manufacturing method of the imprint member of Claim 1. The said base material has the surface roughness of Ra <= 0.1micrometer and Rz <= 0.5micrometer, The manufacturing method of the imprint member of any one of Claims 1-8 characterized by the above-mentioned. It consists of a base material and a DLC film that is a deposition layer of amorphous carbon hydrogen solid particles coated on the surface. The surface of the DLC film is directly engraved by irradiating a laser beam heat source. An imprint member comprising a laser beam engraving groove made of an engineered pattern.

Images