JP5915696B2 - Manufacturing method of substrate with single particle film etching mask - Google Patents

Description

The present invention relates to a single particle film etching mask suitably used for the production of a fine structure (an antireflective body, a nanoimprint mold master, etc.), a method for producing the same, and a fine structure using the single particle film etching mask. Manufacturing method and fine structure obtained by the manufacturing method, as well as nanoimprint mold, nanoimprint apparatus, nanoimprint product obtained by the apparatus, and injection mold, injection molding apparatus, obtained by the apparatus It relates to injection molded products.

Glasses, telescopes, microscopes, cameras, display components, optical instruments for analysis, optical lenses used in industrial optical instruments, etc. have long been used for technology that directly applies anti-reflection processing, and the amount of light taken up by processing on the objective lens has increased. In addition, it has been attempted to improve visibility (antireflection) by processing on an eyepiece lens, or to improve optical performance by processing on other internal lenses and lens groups.

Conventionally, a dry method (vacuum film forming method) has been performed as an antireflection processing method for non-planar surfaces such as lenses. The dry method is a method in which a surface of an object is multilayer-coated mainly using metal or metal oxide by vapor deposition or sputtering. This method has high film thickness accuracy and can perform antireflection processing that exhibits a very high antireflection effect, but has a drawback of low productivity and high cost.

On the other hand, as an antireflection technique different from the dry method, a method of controlling the refractive index with fine protrusions formed on the surface is also known. Specifically, by setting the pitch of the fine protrusions to be equal to or smaller than the wavelength of the incident light, optical scattering is eliminated, and the refractive index of the material forming the protrusions is continuously changed in the depth direction of the surface, so that Fresnel This is to suppress reflection. In order to prevent the refractive index from changing rapidly, the height of the fine protrusion is preferably about 0.4 times or more the target wavelength. This method has improved wavelength dependency and angle dependency compared to the dry method described above. (Nonpatent literature 1-5).
Optica Acta, Vol. 29, 993 (1982) Applied Optics, Vol.32, 2582 (1993) Journal of the Optical Society of America A, Vol.12, 333 (1995) Applied Optics, Vol.26, 1142 (1987) Applied Optics, Vol. 36, 1556 (1997)

In order to create such a fine structure that gives an antireflection effect, X-ray lithography (Patent Document 1), interference exposure method (Non-Patent Document 1, Non-Patent Document 4), electron beam lithography (Patent Document 2), etc. There is a method of combining the etching after creating the pattern. In particular, in order to create a fine structure on a non-planar surface such as a lens or a diffusion film, a pattern is drawn with high accuracy on a curved surface using X-ray lithography as in Patent Document 3 and Patent Document 4, Describes a method for producing submicron periodic microstructures.
JP 56-26438 JP 2001-272505 A JP 2006-195289 A JP 2006-330085 A

Further, as one method for forming such a fine concavo-convex pattern, there is a method in which a single particle film composed of a single layer of resin, metal or the like is disposed on a substrate as an etching mask and the substrate surface is etched. According to this method, the single particle film itself is etched while acting as an etching mask, and is finally scraped off. As a result, it is possible to obtain a substrate on which conical fine protrusions are formed at positions corresponding to the respective particles.

As a method for forming such a single particle film etching mask, Patent Document 5 describes that only a first particle layer electrostatically bonded to a substrate is immersed in a suspension of colloidal particles after that. There has been proposed a method in which an etching mask made of a single particle film is provided on a substrate by removing the remaining second and higher particle layers (particle adsorption method). Patent Document 6 discloses a method of forming a single particle film on a sheet-like substrate and transferring the single particle film to a substrate. At this time, as a method of forming a single particle film on the substrate on the sheet, a binder layer is formed on the substrate on the sheet, a particle dispersion is applied thereon, and then the binder layer is softened by heating. Thus, a method is described in which only the first particle layer is embedded in the binder layer, and excess particles are washed away.
JP 58-120255 A JP-A-2005-279807

However, in the methods described in Patent Documents 3 and 4 for creating a pattern in a curved surface, it is necessary to prepare an X-ray source, the apparatus becomes large, the X-ray irradiation field is limited, and from the viewpoint of exposure There are problems such as the need to handle X-rays carefully. Further, patterning by electron beam drawing has a problem that it takes a very long time and is expensive to obtain an optical element having a practical area. In the interference exposure method, it is not easy to eliminate the influence of vibration of the apparatus and air.

On the other hand, the method using a single particle film etching mask can pattern a large area safely, inexpensively and easily. However, in the methods described in Patent Documents 5 and 6, the particles constituting the single particle film are partially clustered to form two or more layers, or a defect portion where no particles exist is likely to occur. It is difficult to obtain a single particle film in which each particle is closely packed in two dimensions with high accuracy. In this way, in the conventional method using a single particle film as an etching mask, conical fine protrusions are formed at positions corresponding to the respective particles. The arrangement accuracy cannot be increased, and it is difficult to obtain a high antireflection effect.

In addition, in a method that requires a resist resin such as an interference exposure method or X-ray lithography, there arises a problem that thickness unevenness occurs when the resin is coated on an uneven surface having a curved surface or a step. If thickness unevenness occurs, the resist thickness varies locally, which is not preferable because the uniformity of the fine structure after dry etching is lost. In particular, when a resist resin is coated on the surface of a fine structure such as a microlens array or a diffraction grating, a phenomenon occurs in which the resin is thick on the concave portion of the fine structure and the resin is thin on the convex portion. In such a state, it is difficult to obtain a uniform one even if a conical fine protrusion is formed on the surface of a fine structure such as a microlens array or a diffraction grating.

The present invention has been made in view of the above circumstances. A single particle film etching mask on a curved surface in which each particle constituting a single particle film is two-dimensionally closely packed and arranged with high accuracy, a method for manufacturing the same, It is an object of the present invention to provide a manufacturing method of a fine structure on a curved surface using a particle film etching mask and a highly accurate fine structure on a curved surface obtained by the manufacturing method. Furthermore, a mold for nanoimprint or injection molding by using a fine structure, a nanoimprint or injection molding apparatus comprising the nanoimprint or injection mold, and a highly accurate nanoimprint or injection molded product obtained by the apparatus. Offering is an issue.

As a result of intensive studies, the present inventors have dripped a dispersion liquid in which particles are dispersed in a solvent onto the liquid surface in the water tank, and then volatilizes the solvent, whereby the particles are densely packed in a two-dimensional close-packed manner. A non-planar single particle film and a single particle film etching mask arranged on a non-planar substrate with high precision can be manufactured by transferring the single particle layer onto a substrate including a curved surface or a step. The present inventors have found that this can be done and have completed the present invention.

The manufacturing method of the non-planar single particle film and the single particle film etching mask of the present invention includes a dropping step of dropping a dispersion liquid in which particles are dispersed in a solvent onto a liquid surface in a water tank, and volatilizing the solvent. A single particle film forming step of forming a single particle film made of the particles, and a transition step of transferring the single particle film onto a non-planar substrate including a curved surface and a step.
The manufacturing method of the microstructure of the present invention includes a dropping step of dropping a dispersion liquid in which particles are dispersed in a solvent onto a liquid surface in a water tank, and forming a single particle film made of the particles by volatilizing the solvent. A single particle film forming step, a transition step of transferring the single particle film onto a non-planar substrate including a curved surface or a step, and an etching step of performing vapor phase etching of the substrate using the single particle film as an etching mask. It is characterized by having.

When the microstructure of the present invention is an antireflective body, the height is 50 nm or more and the aspect ratio is 0.4 or more on at least one surface on the non-planar substrate including the curved surface and the step, which is manufactured by the manufacturing method. Conical fine protrusions are formed, and it is suitable as an original plate for producing an antireflection body, nanoimprint or injection molding mold. In addition, when the microstructure of the present invention is not an antireflective body, it is manufactured by the above manufacturing method, and at least one surface on the non-planar substrate including the curved surface and the step is conical, cylindrical, hemispherical, or these shapes. It is characterized by forming a structure having both, and uses other than the antireflection structure, that is, a super water-repellent structure, a super hydrophilic structure, a fine polished surface structure, a bioadhesion prevention structure, an antifouling surface structure, a MEMS separator structure, and these It is suitable as a master for producing a mold for structure nanoimprint or injection molding.
The method for producing a mold for nanoimprinting or injection molding according to the present invention includes a transfer step of transferring the fine protrusions of the fine structure to a metal layer.
The transfer step is preferably a step of peeling the metal layer after forming a metal layer on a non-planar surface on which the fine protrusions of the microstructure are formed.
The non-planar mold for nanoimprinting or injection molding of the present invention is manufactured by the above manufacturing method.
The nanoimprint or injection molding apparatus of the present invention comprises the non-planar mold for nanoimprint or injection molding.
The nanoimprint or injection-molded product of the present invention is manufactured by the nanoimprint or injection-molding apparatus.
The single particle film of the present invention is formed on a substrate having a part or all of a surface having a pitch or size in a plane direction of 0.1 μm to 10000 μm in a non-planar part such as a curved surface or a step. A single-particle film closely packed in dimension,
The deviation D (%) in the arrangement of particles defined by the following formula (1) is 10% or less.
D (%) = | B−A | × 100 / A (1)
(In formula (1), A represents the average particle diameter of the particles, and B represents the average pitch between the particles in the single particle film.)

The fine structure of the present invention is a fine structure prepared by vapor phase etching using the single particle film etching mask, and has a structure displacement D defined by the following formula (2): '(%) Is 10% or less.
D ′ (%) = | C−A | × 100 / A (2)
(In the formula (2), A represents the average particle diameter of the particles, and C represents the average pitch of the structural arrangement in the fine structure.)
A non-planar mold for nanoimprinting or injection molding according to the present invention is a non-planar mold for nanoimprinting or injection molding characterized in that it is produced by electroforming using the fine structure, and is defined by the following formula (3): The arrangement deviation D ′ ′ (%) of the structure to be formed is 10% or less.
D ′ ′ (%) = | EA− × 100 / A (3)
(In Formula (3), A represents the average particle diameter of the particles, and E represents the average pitch of the structural arrangement in the non-planar mold for nanoimprint or injection molding.)
The nanoimprint or injection-molded product of the present invention is a nanoimprint or injection-molded product produced by the nanoimprint or injection molding method using the non-planar mold for nanoimprint or injection molding, and represented by the following formula (4): The arrangement deviation D ′ ′ ′ (%) of the defined structure is 10% or less.
D ′ ′ ′ (%) = | FA− × 100 / A (4)
(In formula (4), A represents the average particle diameter of the particles, and F represents the average pitch of the structural arrangement in the nanoimprint or injection-molded product.)

According to the present invention, each particle constituting a single particle film is two-dimensionally closely packed, and a single particle film etching mask arranged with high precision can be formed on a non-planar surface including a curved surface or a step, and the single particle film A manufacturing method of a fine structure using an etching mask and a highly accurate fine structure obtained by the manufacturing method can be provided. Furthermore, it is possible to provide a nanoimprint mold corresponding to a non-planar surface using a fine structure, a nanoimprint apparatus including the nanoimprint mold, and a nanoimprint object obtained by the apparatus and capable of corresponding to a non-planar surface.

Hereinafter, the present invention will be described in detail, but the non-planar single particle film of the present invention and an etching mask using the same are the same manufacturing method.
[Single particle film etching mask]
As shown in FIG. 1, the single particle film etching mask of the present invention is an etching mask comprising a single particle film in which a large number of particles P are two-dimensionally closely packed, and is defined by the following formula (1). The deviation D (%) of the arrangement is 10% or less.
D [%] = | B−A | × 100 / A (1)
In the formula (1), A is the average particle diameter of the particles P constituting the single particle film, and B is the average pitch between particles in the single particle film. | B−A | indicates the absolute value of the difference between A and B.

Here, the average particle diameter A of the particles is the average primary particle diameter of the particles constituting the single particle film, and is obtained by fitting the particle size distribution obtained by the particle dynamic light scattering method to a Gaussian curve. It can obtain | require by a conventional method from the peak obtained.

The shape of the particles of the present invention is preferably a true sphere. This is because it is necessary to avoid the generation of lattice defects as much as possible in order to produce a close-packed two-dimensional crystal. However, if the particles are almost the same size, a polyhedron (a shape such as a cube or a star) or an atypical body (one that is neither a sphere nor a polyhedron) is prepared as a single particle film and placed in the process of the present invention. It is possible.

On the other hand, the pitch between particles is the distance between the vertices of two adjacent particles, and the average pitch B is an average of these. If the particles are spherical, the distance between the vertices of adjacent particles is equal to the distance between the centers of the adjacent particles.
Specifically, the average pitch B between particles in the single particle film etching mask is obtained as follows.
First, an atomic force microscope image or a scanning electron microscope image is obtained for a randomly selected region in a single particle film etching mask and a square region with a side having a fine structure of 30 to 40 wavelengths. For example, in the case of a single particle film using particles having a particle size of 300 nm, an image of a region of 9 μm × 9 μm to 12 μm × 12 μm is obtained. Then, this image is waveform-separated by Fourier transform to obtain an FFT image (fast Fourier transform image). Next, the distance from the zero-order peak to the primary peak in the profile of the FFT image is obtained. The reciprocal of the distance thus obtained is the average pitch B1 in this region. Such a process is similarly performed for a total of 25 or more regions having the same area selected at random, and average pitches B1 to B25 in each region are obtained. The average value of the average pitches B1 to B25 in the 25 or more regions thus obtained is the average pitch B in the equation (1). In this case, the regions are preferably selected at least 1 mm apart, more preferably 5 mm to 1 cm apart.
At this time, the variation in pitch between particles in each image can be evaluated from the area of the primary peak in the profile of the FFT image.

In the single particle film etching mask in which the deviation D of the particle arrangement is 10% or less, each particle is two-dimensionally closely packed and the interval between the particles is controlled, and the arrangement accuracy is high. Therefore, by using such a single particle film etching mask and forming conical fine protrusions at positions corresponding to the respective particles on the substrate, a highly accurate fine uneven pattern can be obtained. Since such two-dimensional close-packing is based on the principle of self-organization described later, it includes some lattice defects. However, since such grating defects in two-dimensional close-packing create a variety of filling orientations, especially in the case of antireflection applications, the reflection characteristics such as diffraction gratings are reduced to provide a uniform antireflection effect. Help give.
The fine structure having a fine uneven pattern formed of such conical fine protrusions on the surface is suitably used as a high-performance anti-reflection body such as an anti-reflection film. It is also suitably used as an original plate (master) for producing a nanoimprint or injection molding mold. By transferring the original plate to obtain a mold for nanoimprint or injection molding, and using this mold, a high-performance antireflection body can be stably mass-produced at a low cost.

When a fine uneven pattern is formed on a substrate to produce an antireflective body or the above-described original plate, the average particle diameter A obtained by the particle dynamic light scattering method is used as the particles constituting the single particle film etching mask. The one of 3 to 380 nm is used. Since the average particle diameter A of the particles and the diameter of each circular bottom surface of the conical microprotrusions formed are almost the same value, by using particles having an average particle diameter A of 380 nm or less smaller than the lower limit wavelength of visible light The diameter of the circular bottom surface of the formed conical fine protrusion is also 380 nm or less, so that optical scattering can be suppressed and a fine uneven pattern suitable for antireflection use can be formed. In addition, by using a particle having an average particle diameter (A) of 3 nm or more, a sufficient distance can be secured in a space where the refractive index is inclined through which incident light passes, and a quenching effect by a so-called sub-wavelength grating can be obtained satisfactorily. Can do.

The particles constituting the single particle film etching mask preferably have a particle size variation coefficient (standard deviation divided by average value) of 20% or less, more preferably 10% or less. % Or less is more preferable. If particles having a small variation coefficient of particle size, that is, particles having a small particle size variation are used in this way, in the manufacturing process of a single particle film etching mask, which will be described later, it becomes difficult to generate a defect portion where particles are not present, and an alignment shift D It is easy to obtain a single particle film etching mask having a thickness of 10% or less. From the single particle film etching mask having no defect portion, an antireflection film which gives a uniform refractive index gradient effect to incident light is easily obtained, which is preferable.

Particle materials include metals such as Al, Au, Ti, Pt, Ag, Cu, Cr, Fe, Ni, Si, metal oxides such as SiO2, Al2O3, TiO2, MgO2, and CaO2, polystyrene, polymethyl methacrylate, etc. In addition to these organic polymers, one or more of semiconductor materials, inorganic polymers, and the like can be employed.

[Method of manufacturing single particle film etching mask]
Such a single particle film etching mask is disposed on at least one surface of a non-planar substrate including a curved surface or a step which is an object to be etched, and is based on the so-called LB method (Langmuir-Blodget method). It can be formed on the substrate by the method used. Specifically, a dropping step of dropping a dispersion in which particles are dispersed in a solvent onto the liquid surface in the water tank, a single particle film forming step of forming a single particle film made of particles by volatilizing the solvent, And a transfer step of transferring the particle film onto a non-planar substrate including a curved surface or a step.
A preferred method for producing a single particle film etching mask will be specifically described below with an example.

(Drip process and single particle film formation process)
First, a dispersion liquid is prepared by adding particles having a hydrophobic surface to a hydrophobic organic solvent composed of one or more of volatile solvents such as chloroform, methanol, ethanol, and methyl ethyl ketone. On the other hand, a water tank (trough) is prepared, and water is added thereto as a liquid for developing particles on the liquid surface (hereinafter sometimes referred to as lower layer water).
And a dispersion liquid is dripped at the liquid level of lower layer water (drip process). Then, the solvent as the dispersion medium is volatilized, and the particles are developed in a single layer on the liquid surface of the lower layer water, so that a two-dimensional close-packed single particle film can be formed (single particle film forming step). ).
Thus, when a hydrophobic particle is selected as the particle, it is necessary to select a hydrophobic particle as the solvent. On the other hand, in that case, the lower layer water needs to be hydrophilic, and water is usually used as described above. By combining in this way, as will be described later, self-organization of particles proceeds and a two-dimensional close packed single particle film is formed. However, hydrophilic particles and solvents may be selected. In that case, a hydrophobic liquid is selected as the lower layer water.

The particle concentration of the dispersion dropped into the lower layer water is preferably 1 to 10% by mass. Further, the dropping rate is preferably 0.001 to 0.01 ml / second. If the concentration of the particles in the dispersion and the amount of dripping are in such a range, the particles are partially agglomerated in a cluster to form two or more layers, defective portions where no particles are present, and the pitch between particles is A tendency of spreading and the like is suppressed, and a single particle film in which each particle is two-dimensionally closely packed with high accuracy is more easily obtained.

As the particles having hydrophobic surfaces, among the previously exemplified particles, particles made of organic polymers such as polystyrene and having a hydrophobic surface may be used. It may be used after making it hydrophobic with an agent. As the hydrophobizing agent, for example, a surfactant, a metal alkoxysilane, or the like can be used.

The method of using a surfactant as a hydrophobizing agent is effective for hydrophobizing a wide range of materials, and is suitable when the particles are made of metal, metal oxide, or the like.
As the surfactant, cationic surfactants such as brominated hexadecyltrimethylammonium and brominated decyltrimethylammonium, and anionic surfactants such as sodium dodecyl sulfate and sodium 4-octylbenzenesulfonate can be suitably used. Moreover, alkanethiol, a disulfide compound, tetradecanoic acid, octadecanoic acid, etc. can also be used.

Such a hydrophobizing treatment using a surfactant may be performed in a liquid by dispersing particles in a liquid such as an organic solvent or water, or may be performed on particles in a dry state.
When performed in a liquid, for example, in a volatile organic solvent composed of one or more of chloroform, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, ethyl ethyl ketone, toluene, hexane, cyclohexane, ethyl acetate, butyl acetate and the like. Then, the particles to be hydrophobized may be added and dispersed, and then the surfactant may be mixed and further dispersed. If the particles are dispersed in advance in this way and then a surfactant is added, the surface can be more uniformly hydrophobized. Such a hydrophobized dispersion can be used as it is as a dispersion for dripping onto the surface of the lower layer water in the dropping step.

If the particles to be hydrophobized are in the form of an aqueous dispersion, a surfactant is added to the aqueous dispersion, the surface of the particles is hydrophobized with an aqueous phase, and then an organic solvent is added to make the hydrophobized treatment. An oil phase extraction method is also effective. The dispersion thus obtained (a dispersion in which particles are dispersed in an organic solvent) can be used as it is as a dispersion for dropping onto the liquid surface of the lower layer water in the dropping step. In order to improve the particle dispersibility of this dispersion, it is preferable to appropriately select and combine the type of organic solvent and the type of surfactant. By using a dispersion having a high particle dispersibility, the particles can be prevented from agglomerating in clusters, and a single particle film in which each particle is two-dimensionally closely packed with high accuracy can be obtained more easily. For example, when chloroform is selected as the organic solvent, it is preferable to use brominated decyltrimethylammonium as the surfactant. In addition, a combination of ethanol and sodium dodecyl sulfate, a combination of methanol and sodium 4-octylbenzenesulfonate, a combination of methyl ethyl ketone and octadecanoic acid, and the like can be preferably exemplified.
The ratio of the particles to be hydrophobized and the surfactant is preferably such that the mass of the surfactant is 1/3 to 1/15 times the mass of the particles to be hydrophobized.
In addition, in such a hydrophobizing treatment, it is effective in terms of improving particle dispersibility to stir the dispersion during the treatment or to irradiate the dispersion with ultrasonic waves.

The method of using a metal alkoxysilane as a hydrophobizing agent is effective when hydrophobizing particles such as Si, Fe, and Al and oxide particles such as AlO2, SiO2, and TiO2, but is not limited to these particles. Basically, it can be applied to particles having a hydroxyl group on the surface.
As the metal alkoxysilane, monomethyltrimethoxysilane, monomethyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxy Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3methacryloxy Propyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (amino Ethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyl Examples include trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

When using a metal alkoxysilane as a hydrophobizing agent, the alkoxysilyl group in the metal alkoxysilane is hydrolyzed to a silanol group, and the silanol group is dehydrated and condensed to a hydroxyl group on the particle surface to effect hydrophobicity. Therefore, the hydrophobization using metal alkoxysilane is preferably performed in water. Thus, when hydrophobizing in water, it is preferable to stabilize the dispersion state of the particles before hydrophobization by using a dispersant such as a surfactant, for example. Since the hydrophobizing effect of the alkoxysilane may be reduced, the combination of the dispersant and the metal alkoxysilane is appropriately selected.

As a specific method for hydrophobizing with a metal alkoxysilane, first, particles are dispersed in water, and this is mixed with a metal alkoxysilane-containing aqueous solution (an aqueous solution containing a hydrolyzate of metal alkoxysilane), and from room temperature. The reaction is carried out for a predetermined time, preferably 6 to 12 hours, with appropriate stirring in the range of 40 ° C. By carrying out the reaction under such conditions, the reaction proceeds moderately and a dispersion of sufficiently hydrophobized particles can be obtained. When the reaction proceeds excessively, the silanol groups react with each other to bond the particles, the particle dispersibility of the dispersion decreases, and the resulting single particle film has particles partially agglomerated in clusters 2 It tends to be more than a layer. On the other hand, when the reaction is insufficient, the surface of the particles is not sufficiently hydrophobized, and the resulting single particle film tends to have a wide pitch between the particles.

Moreover, since metal alkoxysilanes other than amines are hydrolyzed under acidic or alkaline conditions, it is necessary to adjust the pH of the dispersion to acidic or alkaline during the reaction. Although there is no restriction | limiting in the adjustment method of pH, Since the effect of silanol group stabilization is acquired besides the acceleration | stimulation of hydrolysis according to the method of adding 0.1-2.0 mass% concentration acetic acid aqueous solution, it is preferable. .
The ratio of the particles to be hydrophobized and the metal alkoxysilane is preferably in the range where the mass of the metal alkoxysilane is 1/10 to 1/100 times the mass of the particles to be hydrophobized.

After the reaction for a predetermined time, one or more of the above-mentioned volatile organic solvents are added to the dispersion, and the particles hydrophobized in water are subjected to oil phase extraction. At this time, the volume of the organic solvent to be added is preferably in the range of 0.3 to 3 times the dispersion before addition of the organic solvent. The dispersion thus obtained (a dispersion in which particles are dispersed in an organic solvent) can be used as it is as a dispersion for dropping onto the liquid surface of the lower layer water in the dropping step. In such a hydrophobizing treatment, it is preferable to carry out stirring, ultrasonic irradiation, etc. in order to improve the particle dispersibility of the dispersion during the treatment. By increasing the particle dispersibility of the dispersion, it is possible to suppress the aggregation of particles in a cluster shape, and it becomes easier to obtain a single particle film in which each particle is two-dimensionally closely packed with high accuracy.

In order to further improve the accuracy of the formed single particle film, the dispersion before dropping onto the liquid surface is microfiltered with a membrane filter or the like, and aggregated particles (from a plurality of primary particles) present in the dispersion are used. Secondary particles) are preferably removed. If the microfiltration is performed in advance as described above, it is difficult to generate a portion where two or more layers are formed or a defective portion where particles are not present, and it is easy to obtain a single particle film with high accuracy. Assuming that a defect portion having a size of several to several tens of μm exists in the formed single particle film, a surface pressure sensor that measures the surface pressure of the single particle film in a transition step described later in detail, Even if an LB trough device having a movable barrier that compresses the single particle film in the liquid surface direction is used, such a defective portion is not detected as a difference in surface pressure, and a highly accurate single particle film etching mask is obtained. Things get harder.

Furthermore, such a single particle film forming step is preferably performed under ultrasonic irradiation conditions. When the single particle film formation process is performed while irradiating ultrasonic waves from the lower layer water to the water surface, the close packing of particles is promoted, and a single particle film in which each particle is two-dimensionally close packed with high accuracy is obtained. It is done. At this time, the ultrasonic output is preferably 1 to 1200 W, and more preferably 50 to 600 W. Moreover, although there is no restriction | limiting in particular in the frequency of an ultrasonic wave, For example, 28 kHz-5 MHz are preferable, More preferably, they are 700 kHz-2 MHz. In general, when the vibration frequency is too high, energy absorption of water molecules starts and a phenomenon in which water vapor or water droplets rise from the surface of the water occurs, which is not preferable for the LB method of the present invention. In general, when the frequency is too low, the cavitation radius in the lower layer water is increased, bubbles are generated in the water, and rise toward the water surface. When such bubbles accumulate under the single particle film, the flatness of the water surface is lost, which is inconvenient for the implementation of the present invention. In addition, standing waves are generated on the water surface by ultrasonic irradiation. If the output is too high at any frequency, or if the wave height of the water surface becomes too high due to the tuning conditions of the ultrasonic transducer and transmitter, the single particle film will be destroyed by the water surface wave, so care must be taken.

If the frequency of the ultrasonic wave is appropriately set in consideration of the above, close-packing of particles can be effectively promoted without destroying the single particle film being formed. In order to perform effective ultrasonic irradiation, the natural frequency calculated from the particle size of the particles should be used as a guide. However, when the particle diameter is small, for example, 100 nm or less, the natural frequency becomes very high, and it is difficult to apply ultrasonic vibration as calculated. In such a case, the calculation is performed assuming that the natural vibration corresponding to the mass of the particle dimer, trimer,... Can be reduced. Even when ultrasonic vibration corresponding to the natural frequency of the aggregate of particles is applied, the effect of improving the particle filling rate is exhibited. The ultrasonic irradiation time may be sufficient to complete the rearrangement of particles, and the required time varies depending on the particle size, ultrasonic frequency, water temperature, and the like. However, under normal production conditions, it is preferably performed for 10 seconds to 60 minutes, more preferably 3 minutes to 30 minutes.
Advantages obtained by ultrasonic irradiation include the effect of destroying the soft agglomerates of particles that tend to occur when preparing a nanoparticle dispersion, in addition to the closest packing of particles (to make the random array 6-way closest) This also has the effect of repairing some of the point defects, line defects, or crystal transitions.

The formation of the single particle film described above is due to self-organization of particles. The principle is that when the particles are aggregated, surface tension acts due to the dispersion medium existing between the particles. As a result, the particles do not exist at random, but a two-dimensional close packed structure is automatically used. It is to form. In other words, the close-packing by surface tension can be said to be arrangement by lateral capillary force.
In particular, when three particles, such as colloidal silica, which are spherical and have a highly uniform particle size, come together and come into contact with each other in a floating state on the water surface, the surface of the particle group is minimized so as to minimize the total length of the waterline. Tension acts, and as shown in FIG. 1, the three particles P are stabilized in an arrangement based on an equilateral triangle indicated by T in the figure. If the water line is at the top of the particle group, that is, if the particles P are submerged below the liquid surface, such self-organization does not occur and a single particle film is not formed. Therefore, when one of the particles and the lower layer water is hydrophobic, it is important to make the other hydrophilic so that the particles do not dive under the liquid surface.
As the lower layer water, it is preferable to use water as described above. When water is used, relatively large surface free energy acts, and the close-packed arrangement of particles once generated is stable on the liquid surface. It becomes easy to sustain.

(Transition process)
Next, the single particle film formed on the liquid surface by the single particle film forming step is transferred to a non-planar substrate including a curved surface or a step in a single layer state (transfer step). The non-planar substrate partially or entirely includes a non-planar shape such as a curved surface, an inclination, and a step. In addition, there are uneven portions such as curved surfaces, slopes and steps on the non-planar substrate, and the pitch or size of these uneven portions in the planar direction is 0.1 μm to 10000 μm. That is, the unevenness may be a periodic structure or a non-periodic (random) structure. For example, a microlens array, a diffraction grating, an anti-glare surface (an uneven surface of several μm to several tens of μm in the horizontal direction is the surface) Processed)). A common feature is that when a resist resin or the like is applied by a spin coating method or the like, the resin has a non-planar structure with a size such that the resin is thick in the concave and convex portions and the resin is thin in the convex portions. For example, when a resin is coated on a large concavo-convex structure such as a magnifying glass, it can be considered that the construction is almost flat, and as described above, the uneven coating thickness locally generated by the concavo-convex shape is not significant. The size of the unevenness of the non-planar structure targeted by the present invention refers to the size that makes uniform coating difficult depending on the shape.

On the other hand, even when viewed from the fine particles, such a concavo-convex structure is sufficiently varied, but the single particle film of the present invention can cover the surface with a single layer while following the shape. The single particle film of the present invention follows the shape of the uneven substrate surface while maintaining a two-dimensional close-packed state even if the substrate is not flat, and deforms the surface shape to completely cover it. Is possible. When following the concavo-convex shape, it is considered that a slip phenomenon occurs on the grain crystal plane in the single particle film, and the shape is freely deformed from two dimensions to three dimensions. The specific method for transferring the single particle film onto the substrate is not particularly limited. For example, the single particle film is lowered from above while keeping the hydrophobic non-planar substrate substantially parallel to the single particle film. A method in which the single particle film is transferred to the substrate by the affinity between the single particle film and the substrate, both of which are in contact with the membrane and transferred to the substrate, and transferred to the substrate; There is a method of transferring the single particle film onto the substrate by arranging the substrate in a substantially horizontal direction and gradually lowering the liquid surface after forming the single particle film on the liquid surface. According to these methods, a single particle film can be transferred onto a non-planar substrate without using a special apparatus. It is preferable to adopt a so-called LB trough method in that it can be easily transferred onto a non-planar substrate while maintaining the filled state.

FIG. 2 schematically shows an outline of the LB trough method. In this method, the substrate 11 is preliminarily immersed in the lower layer water 12 in the water tank, and the above-described dropping step and single particle film forming step are performed in this state to form the single particle film F (see FIG. 2 (a)). Then, after the step of forming the single particle film, the non-planar substrate 11 is pulled upward, so that the single particle film F can be transferred while following the shape of the non-planar substrate 11 (FIG. 2B). Here, since the single particle film F is already formed in a single layer state on the liquid surface by the single particle film forming step, the temperature condition (temperature of the lower layer water) of the transition step and the pulling speed of the non-planar substrate 11 are increased. Even if there are some fluctuations, there is no fear that the single particle film F will collapse and become multi-layered in the transfer step. In addition, the temperature of lower layer water is normally about 10-30 degreeC depending on the environmental temperature which fluctuates with a season or weather.

At this time, as a water tank, a surface pressure sensor based on a Wilhelmy plate (not shown) for measuring the surface pressure of the single particle film F and a single particle film F are compressed in a direction along the liquid surface. When the LB trough device having the movable barrier is used, the single-particle film F having a larger area can be transferred onto the non-planar substrate 11 more stably. According to such an apparatus, the single particle film F can be compressed to a preferable diffusion pressure (density) while measuring the surface pressure of the single particle film F, and at a constant speed toward the non-planar substrate 11. Can be moved. Therefore, the transition from the liquid surface of the single particle film F to the non-planar substrate 11 proceeds smoothly, and troubles such as the fact that only the single particle film F having a small area can be transferred onto the non-planar substrate are less likely to occur. A preferable diffusion pressure is 5 to 80 mNm-1, more preferably 10 to 40 mNm-1. With such a diffusion pressure, it is easy to obtain a single particle film F in which each particle is two-dimensionally closely packed with higher accuracy. Further, the speed for pulling up the non-planar substrate 11 is preferably 0.5 to 20 mm / min. The temperature of lower layer water is 10-30 degreeC normally as above-mentioned. Note that the LB trough device can be obtained as a commercial product.

The material of the non-planar substrate including the curved surface and the step can be appropriately selected according to the application, for example, semiconductors such as silicon and gallium arsenide, metals such as aluminum, iron and copper, glass, quartz glass, mica, Examples thereof include metal oxides such as sapphire (Al2O3), polymer materials such as polyethylene terephthalate (PET), polyethylene naphthalate, and triacetyl cellulose. In addition, the surface of the non-planar substrate may be coated with another material or chemically altered. For example, when the microstructure obtained by the subsequent etching process is used as an antireflection body as it is, a transparent body such as glass, quartz glass, or a polymer material having transparency is preferable as the substrate material. In the case of using it as an original plate of a nanoimprint mold for producing a prevention body, a material that is widely used as an etching object, such as quartz glass and silicon, is preferable as the material of the non-planar substrate.

A single particle film etching mask can be formed on a non-planar substrate by such a transition process, but after the transition process, fixing for fixing the formed single particle film etching mask on the non-planar substrate is performed. You may perform a process. By fixing the single particle film on the non-planar substrate, it is possible to suppress the possibility that particles move on the non-planar substrate during an etching process described later, and it is possible to perform etching more stably and with high accuracy. In particular, such a possibility increases when the final stage of the etching process in which the diameter of each particle gradually decreases.

As a method of the fixing step, there are a method using a binder and a sintering method.
In the method using a binder, a binder solution is supplied to the single particle film side of the non-planar substrate on which the single particle film etching mask is formed, and this is infiltrated between the single particle film etching mask and the non-planar substrate.
The amount of the binder used is preferably 0.001 to 0.02 times the mass of the single particle film etching mask. In such a range, the particles can be sufficiently fixed without causing the problem that the binder is too much and the binder is clogged between the particles, and the accuracy of the single particle film etching mask is adversely affected. When a large amount of the binder solution has been supplied, after the binder solution has permeated, the excess of the binder solution may be removed by using a spin coater or tilting the non-planar substrate.
As the binder, metal alkoxysilanes, general organic binders, inorganic binders and the like exemplified above as the hydrophobizing agent can be used. After the binder solution has permeated, heat treatment may be appropriately performed depending on the type of the binder. . When using a metal alkoxysilane as a binder, it is preferable to heat-process at 40-80 degreeC on the conditions for 3 to 60 minutes.

When the sintering method is employed, the non-planar substrate on which the single particle film etching mask is formed may be heated to fuse each particle constituting the single particle film etching mask to the non-planar substrate. . The heating temperature may be determined according to the material of the particle and the material of the non-planar substrate, but particles having a particle size of 1 μmφ or less start an interfacial reaction at a temperature lower than the original melting point of the material, so the relatively low temperature side The sintering is complete. If the heating temperature is too high, the fusion area of the particles increases, and as a result, the shape as a single particle film etching mask may change, which may affect the accuracy. In addition, if heating is performed in air, the substrate and each particle may be oxidized. Therefore, in the etching process described later, it is necessary to set etching conditions in consideration of the possibility of such oxidation. Become.

Thus, the method for producing a single particle film etching mask includes a dropping step of dropping a dispersion liquid in which particles are dispersed in a solvent onto a liquid surface in a water tank, and a single particle film made of particles by volatilizing the solvent. Since it has a single particle film formation process to be formed and a transfer process to transfer the formed single particle film onto a non-planar substrate, it can handle single layer accuracy, ease of operation, and large area. Furthermore, it has excellent reproducibility and is superior to the so-called particle adsorption method described in, for example, the liquid thin film method described in Nature, Vol. 361, 7 January, 26 (1993) or the patent document 1 Can also handle industrial production levels.

[Microstructure and its manufacturing method]
Thus, by subjecting the substrate provided with the single particle film etching mask on one side to vapor phase etching and surface processing (etching process), a large number of conical fine protrusions can be formed on one side of the substrate. Specifically, when the vapor phase etching is started, first, as shown in FIG. 3A, the etching gas passes through the gaps between the particles P constituting the single particle film F and reaches the surface of the substrate 11. A groove is formed in the portion, and a cylinder 11 'appears at a position corresponding to each particle P. When the gas phase etching is continued, the particles P on each cylinder 11 ′ are gradually etched to become smaller, and at the same time, the groove of the substrate 11 becomes deeper (FIG. 3B). Finally, each particle P disappears by etching, and at the same time, many conical fine protrusions are formed on one surface of the substrate 11 (FIG. 3C).

The fine structure C thus obtained is an optical lens, a microlens array, a diffraction grating, an uneven plastic body, an uneven lighting fixture, a light diffusion film surface or a light diffusion plate surface, various display windows, uneven surfaces. It can be used as an antireflection body applied to the surface of a certain road / traffic sign or an optical material constituting a signboard, and can also be used as a master plate for a nanoimprint mold for producing such an antireflection body.
In the microstructure for antireflection use, it is preferable to form the diameter of the circular bottom surface of each conical microprojection to 3 to 380 nm from the viewpoint of suppressing optical scattering and sufficiently exhibiting the antireflection effect. For that purpose, as described above, particles having an average particle diameter A of 3 to 380 nm may be used as the particles constituting the single particle film etching mask. Further, the height of each conical fine protrusion is preferably 100 nm or more, and the aspect ratio (height / diameter of the circular bottom) is preferably 0.5 or more. With such a height and aspect ratio, a sufficient refractive index gradient effect is obtained at the portion where the conical microprojections are formed, and effective Fresnel reflection of incident light entering from the conical microprojections side is effective. Can be suppressed.
The height of the preferable conical fine protrusion is at least 50 nm or more, preferably 152 nm or more, more preferably 500 nm or more. As described above, when the height of the fine protrusion is set to 0.4 times or more of the target wavelength, an excellent antireflection effect can be obtained, so that it is 0.4 times the wavelength lower limit of 380 nm of visible light. It preferably has a height of 152 nm or more. On the other hand, when the microstructure is used as it is for an antireflective body, the upper limit of the preferred aspect ratio is 10, and when it is used as a master for a nanoimprint or injection mold, the upper limit of the preferred aspect ratio is Is 5.0.

Etching gases used for vapor phase etching include, for example, Ar, SF6, F2, CF4, C4F8, C5F8, C2F6, C3F6, C4F6, CHF3, CH2F2, CH3F, C3F8, Cl2, CCl4, SiCl4, BCl2, BCl3, BC2 , Br2, Br3, HBr, CBrF3, HCl, CH4, NH3, O2, H2, N2, CO, CO2 and the like, but are not limited to these in order to carry out the gist of the present invention. One or more of these can be used depending on the particles constituting the single particle film etching mask, the material of the substrate, and the like.

The vapor phase etching is performed by anisotropic etching in which the etching rate in the vertical direction is larger than the horizontal direction of the substrate. As an etching apparatus that can be used, a reactive ion etching apparatus, an ion beam etching apparatus, or the like that can perform anisotropic etching and can generate a bias electric field of about 20 W at the minimum can generate plasma. There are no particular restrictions on specifications such as system, electrode structure, chamber structure, and frequency of the high-frequency power source.

In order to perform anisotropic etching, the etching rate of the single particle film etching mask and the substrate must be different, and the etching selectivity (etching rate of the substrate / etching rate of the single particle film etching) is preferably 1 or more. Etching conditions (particle material constituting the single particle film etching mask, substrate material, etching gas type, bias power, antenna power, gas flow rate, etc. are preferably 2 or more, more preferably 3 or more. It is preferable to set pressure, etching time, and the like.

For example, when gold particles are selected as the particles constituting the single particle film etching mask, a glass substrate is selected as the substrate, and these are combined, if an etching gas that is reactive with glass such as CF4 or CHF3 is used. The etching rate of the gold particles becomes relatively slow, and the glass substrate is selectively etched.
When colloidal silica particles are selected as the particles constituting the single particle film etching mask, a PET substrate is selected as a substrate, and these are combined, a relatively soft PET substrate is obtained by using an inert gas such as Ar as an etching gas. Can be selectively physically etched.
When the electric field bias is set to several tens to several hundreds W, the positively charged particles in the etching gas in the plasma state are accelerated and incident on the substrate at a high speed almost vertically. Therefore, when a gas having reactivity with the substrate is used, the reaction rate of the physicochemical etching in the vertical direction can be increased.
Depending on the combination of the material of the substrate and the type of etching gas, isotropic etching by radicals generated by plasma also occurs in parallel in gas phase etching. Etching with radicals is chemical etching, and isotropically etches in any direction of the object to be etched. Since radicals have no electric charge, the etching rate cannot be controlled by setting the bias power, and the operation can be performed with the concentration (flow rate) of the etching gas in the chamber. In order to carry out anisotropic etching with charged particles, a certain level of gas pressure must be maintained, so as long as a reactive gas is used, the influence of radicals cannot be made zero. However, a method of slowing the reaction rate of radicals by cooling the substrate is widely used, and since there are many devices equipped with the mechanism, it is preferable to use them.

In addition, when the obtained fine structure is used as an antireflection body, or used as a master of a nanoimprint or injection molding mold for producing the antireflection body, the shape of the formed protrusion is a cone. It needs to be in the shape. However, in the actual etching process, as shown in FIG. 3, the side surface (side wall) of the cone is etched in the process of changing the shape of the protrusion from the columnar shape to the conical shape. The conical microprotrusion has a large side wall inclination, and the vertical cross-sectional shape of the groove between adjacent cones tends to be U-shaped instead of V-shaped. If it becomes such a shape, sufficient refractive index gradient effect cannot be exhibited, and suppression of Fresnel reflection of incident light may be insufficient. Therefore, in this etching step, it is preferable to improve the aspect ratio while protecting the side wall formed by etching, such as by using a so-called Bosch method, so that the shape of the protrusions approaches an ideal conical shape.

That is, C4F8, C5F8, C2F6, C3F6, C4F6, CHF3, CH2F2, CH3F, C3F8 and other chlorofluorocarbon-based etching gases are decomposed in a plasma state and then polymerized by combining the decomposition products. It is known to form a deposited film made of a material such as Teflon (registered trademark) on the surface of an object to be etched. Since such a deposited film has etching resistance, it acts as an etching protective film. Further, when the substrate is a silicon substrate and the etching gas used has a high etching selectivity with respect to silicon, it is formed by etching by introducing O2 as part of the etching gas. The sidewalls can be modified to a protective film of SiO2. Further, by using a mixed gas of CH4 and H2 as an etching gas, conditions for obtaining a hydrocarbon-based etching protective film can be set.
Therefore, it is preferable to perform the etching process while forming an etching protective film by appropriately selecting the type of etching gas as described above in terms of forming a more ideal conical fine protrusion.

When the average pitch C of the arrangement of the conical microprotrusions is obtained in the same manner as the method for obtaining the average pitch B between the particles in the single particle film etching mask described above, The pitch C is substantially the same value as the average pitch B of the used single particle film etching mask. Further, the average pitch C of the array corresponds to the average value of the diameters d of the circular bottom surfaces of the conical fine protrusions. Further, when an alignment shift D ′ (%) defined by the following formula (2) is obtained for this fine structure, the value is also 10% or less.
D ′ [%] = | C−A | × 100 / A (2)
However, in Formula (2), A is an average particle diameter of the particle | grains which comprise the used single particle film etching mask.

[Nanoimprint or injection mold and its manufacturing method]
When manufacturing a nanoimprint or injection mold by using the microstructure as a master for a nanoimprint or injection mold, for example, a non-planar surface including a curved surface or a step formed by conical microprojections of the microstructure is formed on the surface. After forming the metal layer, the metal layer is peeled to transfer the conical fine protrusions of the fine structure to the metal layer (transfer process). As a result, a non-planar metal layer having conical fine protrusions on the surface is obtained, which can be used as a mold for nanoimprinting or injection molding.

As a method of forming a metal layer on a non-planar surface on which a conical fine protrusion of a fine structure is formed, a plating method is preferable. Specifically, first, nickel, copper, gold, silver, platinum, titanium, cobalt, Not required by one or more metals selected from tin, zinc, chromium, gold / cobalt alloy, gold / nickel alloy, solder, copper / nickel / chromium alloy, tin / nickel alloy, nickel / palladium alloy, nickel / cobalt / phosphorus alloy, etc. A method of increasing the thickness of the metal layer by performing electrolytic plating or vapor deposition and then performing electrolytic plating with one or more metals selected from these metals is preferable.

The thickness of the metal layer formed by electroless plating or vapor deposition is preferably 10 nm or more, more preferably 100 nm or more. However, the conductive layer generally requires a thickness of 50 nm. When the film thickness is set in this way, the unevenness of the current density in the surface to be plated can be suppressed in the subsequent electrolytic plating process, and a nanoimprint or injection molding mold having a uniform thickness can be easily obtained.
In the subsequent electrolytic plating, it is preferable that the thickness of the metal layer is finally increased to 10 to 3000 μm, and then the metal layer is peeled off from the original plate. Although there is no restriction | limiting in particular in the current density in electroplating, Since generation | occurrence | production of a bridge | bridging can be suppressed and a uniform metal layer can be formed, and such a metal layer can be formed in a comparatively short time, it is 0.03-10A. / M 2 is preferred.
Moreover, from the viewpoint of wear resistance as a mold for nanoimprint or injection molding and reworkability at the time of peeling / bonding, the material of the metal layer is preferably nickel, and electroless plating or vapor deposition performed first, followed by electrolysis performed It is preferable to employ nickel for both plating.

[Nanoimprint or injection molding equipment and nanoimprint or injection molding]
According to the nanoimprint or injection molding apparatus provided with the non-planar mold for nanoimprint or injection molding thus manufactured, the conical microprojections are formed with high accuracy, and the nanoimprint or injection molded product (microstructure) suitable for the antireflection body. Body) can be mass-produced stably with good reproducibility.
There is no particular limitation on the method of the nanoimprint or injection molding apparatus. The nanoimprint non-planar mold is pressed against a heated and softened thermoplastic resin base material, and then the base material is cooled before being used for nanoimprinting. A thermal imprint system that transfers a fine pattern formed on a non-planar mold for nanoimprinting onto the substrate by separating the non-planar mold from the substrate. The fine pattern formed on the non-planar mold for nanoimprinting is released by pressing the planar mold and then irradiating ultraviolet rays to cure the photocurable resin and then separating the non-planar mold for nanoimprinting from the substrate. Light (UV) imprint method to transfer to the substrate, molten resin is injected and injected into the non-planar mold at high pressure, A non-planar mold was released through the step of cooling each nonplanar molds, injection molding method for transferring a fine pattern formed on the non-planar mold for injection molding the molding material surface, it can be adopted a known method such as.
A thermal imprinting nanoimprinting apparatus is schematically configured to include a non-planar mold for nanoimprinting provided with pressing means, and a temperature control means for controlling the temperature of the substrate, and the optical imprinting nanoimprinting apparatus includes pressing means. And a non-planar mold for nanoimprinting, and an ultraviolet irradiation means for irradiating the substrate with ultraviolet rays. In addition, the injection molding apparatus sets a closed mold in the injection molding machine, and performs the mold clamping, the melting of the plastic material, the pressure injection into the cavity of the closed mold, and the cooling process by the injection molding machine. It is comprised roughly by providing a mechanism.

As described above, since the above-described single particle film etching mask is one in which the particles constituting the single particle film are two-dimensionally closely packed and arranged with high precision, It is possible to manufacture a fine structure such as an accurate antireflection body, a nanoimprint, or a non-planar mold for injection molding. In particular, when a master of a non-planar mold for nanoimprint or injection molding is manufactured, a non-planar mold for nanoimprint or injection molding is manufactured using this, and a nanoimprint or injection molding apparatus equipped with the same is used for reflection. Nanoimprints such as prevention bodies or injection-molded products (microstructures) can be stably mass-produced with good reproducibility, which is industrially suitable.

[Example 1]
A 5.0% by mass aqueous dispersion (dispersion) of spherical colloidal silica having an average particle size of 298.2 nm and a particle size variation coefficient of 6.7% was prepared. The average particle size and the coefficient of variation of the particle size were determined from the peak obtained by fitting the particle size distribution obtained by the particle dynamic light scattering method using Zetasizer Nano-ZS manufactured by Malvern Instruments Ltd to a Gaussian curve.
Next, this dispersion was filtered through a membrane filter having a pore size of 1.2 μmφ, and an aqueous solution of a hydrolyzate of phenyltriethoxysilane having a concentration of 1.0 mass% was added to the dispersion that passed through the membrane filter, and the mixture was heated at about 40 ° C. for 3 hours. Reacted. At this time, the dispersion and the aqueous hydrolysis solution were mixed so that the mass of phenyltriethoxysilane was 0.02 times the mass of the colloidal silica particles.
Next, methyl ethyl ketone having a volume 4 times the volume of the dispersion was added to the dispersion after completion of the reaction and stirred sufficiently to extract the hydrophobized colloidal silica in the oil phase.

The thus obtained hydrophobized colloidal silica dispersion having a concentration of 0.91% by mass includes a surface pressure sensor for measuring the surface pressure of the single particle film and a movable barrier for compressing the single particle film in the direction along the liquid surface. Was added dropwise at a dropping rate of 0.01 ml / sec to the liquid surface (water used as the lower layer water, water temperature 25 ° C.) in the water tank (LB trough device). In addition, a microlens array (made of silicon, lens pitch of 4.2 μm, lens height of 1.0 μm, substrate thickness of 0.5 mm, chip size of 10 × 10 mm) as a non-planar substrate in advance in the lower layer water of the aquarium. Soaked in.
Thereafter, ultrasonic waves (output 100 W, frequency 1500 kHz) are irradiated from the lower layer water toward the water surface for 10 minutes to promote the two-dimensional closest packing of the particles, while volatilizing methyl ethyl ketone, which is the solvent of the dispersion, A single particle film was formed.
Next, this single particle film was compressed by a movable barrier until the diffusion pressure became 25 mNm-1, the microlens array was pulled up at a speed of 3 mm / min, and transferred onto one side of the substrate.
Next, a 1% by mass monomethyltrimethoxysilane hydrolyzate as a binder is infiltrated onto the microlens array on which the single particle film is formed, and then the surplus hydrolyzate is treated with a spin coater (3000 rpm) for 1 minute. Removed. Then, this was heated at 100 degreeC for 10 minute (s), the binder was made to react, and the silicon substrate with the single particle film | membrane etching mask which consists of colloidal silica was obtained.
As shown in FIG. 4, the method according to the present invention was able to satisfactorily produce a single particle film even in the concave portion of the microlens array.

On the other hand, for this single particle film etching mask, a region of 10 μm × 10 μm is selected at random, and an atomic force microscope image of that portion is obtained. Then, this image is subjected to waveform separation by Fourier transform, and FFT is performed. I got a statue. Next, the distance from the 0th order peak to the 1st order peak in the profile of the FFT image was obtained, and the reciprocal thereof was also obtained. This reciprocal is the average pitch B1 between particles in this region.
Such a process was similarly performed for a total of 25 10 μm × 10 μm regions, and average pitches B1 to B25 in each region were obtained, and an average value thereof was calculated to obtain an average pitch B in Equation (1). At this time, each region was set so that adjacent regions were separated from each other by about 5 mm to 1 cm.
As shown in Table 1, the calculated average pitch B was 302.3 nm.
Therefore, when the average particle diameter A = 298.2 nm and the average pitch B = 302.3 nm are substituted into the equation (1), the deviation D of the particle arrangement in the single particle film etching mask of this example is shown in Table 1. As shown in the figure, it was 1.37%.

Next, vapor phase etching was performed on the substrate with a single particle film etching mask using a mixed gas of SF6: CH2F2 = 25: 75 to 75:25. Etching conditions were an antenna power of 1500 W, a bias power of 50 to 300 W, and a gas flow rate of 30 to 50 sccm. The obtained fine structure has a vertical cross-sectional shape as schematically shown in FIG. 8, and the average height h of the conical fine protrusions measured from the atomic force microscope image is 380 nm. The average pitch C (average diameter d of the circular bottom surface) of the array of conical microprojections obtained by the same method as that performed was 301.5 nm, and the aspect ratio calculated from these was 1.26.
The average height h of the conical fine protrusions was determined as follows. First, an atomic force microscope image was obtained for one 5 μm × 5 μm region randomly selected in the microstructure, and then a profile along the diagonal direction of the image was prepared. And the average value of the unevenness which appeared there was calculated | required. Such a process was similarly performed on a total of 25 randomly selected 5 μm × 5 μm regions, and an average value in each region was obtained. An average height h was obtained by further averaging the average values in the 25 regions thus obtained. On each diagonal line, 23 ± 2 protrusions are included.
The deviation D ′ of the arrangement of the conical microprojections according to the expression (2) was determined for this microstructure, and it was 1.11%.
As shown in FIG. 5, the method according to the present invention was able to satisfactorily produce a fine protrusion structure even in the concave portion of the microlens array.

The obtained microstructure is used as a master for a mold for nanoimprinting, Ni electroless plating is performed on the surface on which conical fine protrusions are formed, a Ni layer having a thickness of 50 nm is formed, and then an electrode jig is attached. Electrolytic Ni plating (using nickel sulfamate bath) was performed at a current density of 8 A / m3. The final Ni layer thickness was adjusted to about 250 μm. After plating, the Ni layer was gently peeled from the microstructure to obtain a nanoimprint mold made of Ni.

[Example 2]
Except for using a diffraction grating as a non-planar substrate (made of silicon, line / space = 2.4 μm / 1.2 μm, uneven height 2.2 μm, substrate thickness 0.5 mm, chip size 10 × 10 mm) A colloidal silica single particle film was formed on the substrate by exactly the same operation as in the example, and the deviation D of the particle arrangement was determined to be 3.68%. As shown in FIG. 7, the method according to the present invention was able to satisfactorily produce a single particle film even in the concave portion of the diffraction grating. Conical microprotrusions were created in the subsequent dry etching step, and the deviation D ′ in the arrangement of conical microprotrusions was determined to be 3.50%. As shown in FIG. 8, the method according to the present invention was able to satisfactorily create a fine protrusion structure even in the concave portion of the diffraction grating.

[Comparative Example 1; particle adsorption method]
A 2.5% by mass aqueous dispersion (dispersion) of spherical colloidal silica having the same average particle size and coefficient of variation in particle size as in Example 1 was prepared.
Subsequently, this dispersion was filtered through a membrane filter having a pore size of 1.2 μmφ in the same manner as in Example 1, and the dispersion that passed through the membrane filter had a concentration of 3.5% by mass of 2- (3,4 epoxycyclohexyl) ethyltrimethoxy. An aqueous solution of silane hydrolyzate was added and reacted at about 30 ° C. for 24 hours to modify the surface of the colloidal particles (dispersion (1)).
On the other hand, an aqueous solution of hydrolyzate of 3-aminopropyltriethoxysilane having a concentration of 1.0% by mass is a microlens array (made of silicon, lens pitch 4 μm, lens height 2 μm, substrate thickness 0.5 mm, chip size 10 × 10 mm). After spin coating at 2000 rpm on the top, the substrate was heated at 80 ° C. for 20 minutes to react the silane coupling agent with the substrate surface.
Subsequently, the dispersion liquid (1) was dropped on the glass substrate after the reaction at a dropping rate of 0.01 ml / second, spin-coated at 2000 rpm, and dried to place the particles on the substrate surface.
Next, the substrate on which the particles are placed is heated at 120 ° C. for 4 hours, and the first layer particles are selectively reacted with the substrate from the substrate surface, and the excess particles of the second layer or more are removed by an ultrasonic cleaning device. The microlens array with a single particle film etching mask made of colloidal silica was removed.

With respect to the single particle film etching mask thus formed, the average pitch B was obtained in the same manner as in Example 1, and the deviation D of the particle arrangement was further obtained. Further, the primary peak area (relative value) in the profile of the FFT image was also obtained. The results are shown in Table 1. Further, the substrate with this single particle film etching mask was subjected to vapor phase etching in the same manner as in Example 1 to obtain a microstructure having a large number of conical microprojections formed on one side of the substrate.

For the microstructure thus obtained, the average height h of the conical microprojections obtained in the same manner as in Example 1 was 397 nm, and the average pitch C of the array of conical microprojections (the average diameter d of the circular bottom surface) was At 375.4 nm, the aspect ratio calculated from these was 1.06.
Further, the displacement D ′ of the arrangement of the conical fine protrusions according to the expression (2) was determined for this fine structure, and it was 25.8%.

[Comparative Example 2: Liquid thin film method]
An aqueous dispersion (dispersion liquid) of spherical colloidal silica having the same average particle diameter and coefficient of variation of the particle diameter as that of Example 1 was prepared, and this dispersion liquid was filtered through a membrane filter having a pore diameter of 1.2 μmφ as in Example 2. . Next, after adjusting the concentration of colloidal silica to 5.5%, this dispersion is placed between a pair of parallel flat plates (area 1 × 1 cm) arranged in a substantially horizontal direction so that the gap (interval) is about 1 mm. Injected into. Then, the upper flat plate (made of glass) was translated (slided) at a speed of 5 to 50 mm per minute to form a single particle film on the lower flat plate (the microlens array). At this time, the microlens array was heated to about 60 ° C. by a heater, and the external atmosphere (experimental environment) was controlled at a constant temperature and humidity of 23 ° C. and a humidity of 50%.
Next, a 1% by mass monomethyltrimethoxysilane hydrolyzate as a binder is infiltrated onto the microlens array on which the single particle film is formed, and then the surplus hydrolyzate is treated with a spin coater (3000 rpm) for 1 minute. Removed. Then, this was heated at 100 degreeC for 10 minute (s), the binder was made to react, and the microlens array board | substrate with a single particle film etching mask which consists of colloidal silica was obtained.

For the single particle film etching mask thus formed, the average pitch B was determined in the same manner as in Example 2, and the deviation D of the particle arrangement was determined. Further, the substrate with this single particle film etching mask was subjected to vapor phase etching in the same manner as in Example 1 to obtain a fine structure having a large number of conical fine protrusions formed on one side of the substrate.

For the microstructure thus obtained, the average height h of the conical microprojections obtained in the same manner as in Example 2 was 431 nm, and the average pitch C of the array of conical microprojections (the average diameter d of the circular bottom surface) was At 407.1 nm, the aspect ratio calculated from these was 1.06. Further, the displacement D ′ of the alignment according to the expression (2) was determined for this microstructure, and it was 36.5%.

[Comparative Example 3; Electron beam drawing method]
Known Documents Report of Osaka Prefectural Industrial Technology Research Institute Report No. 20 (2006) “Preparation of antireflection structure” Antireflection microstructure processing on diffraction grating. A resist (ZEP520 positive electron beam resist made by Nippon Zeon Co., Ltd.) is applied on the diffraction grating to a thickness of 300 nm, and a square pattern is drawn with an electron beam drawing device with a period of 0.35 μm (acceleration voltage 50 kV, current value 750 pA), development After dissolving and removing the resist at the drawing portion, chromium is deposited with a thickness of 25 nm by an electron beam deposition apparatus, and the resist is removed (lifted off) with a stripping solution to create a reverse pattern of chromium. The quartz pattern thus obtained is used as a mask for dry etching of quartz to produce an antireflection structure composed of fine protrusions.
According to this known document, a chrome pattern could be formed on the entire surface without any problem when the depth of the diffraction grating was 0.5 μm or 1.0 μm, but when the depth was 2.0 μm or more, the end of the convex portion of the diffraction grating Causes lift-off failure. In order to perform lift-off, it is necessary that the resist film thickness is larger than the chromium film thickness. However, since the resist film thickness is reduced at the end of the convex portion, this condition is not satisfied when the depth of the diffraction grating is 2.0 μm or more. (See FIG. 9). As for the antireflection structure after etching, it has been confirmed that a production failure occurs at the end of the convex portion in a diffraction grating having a depth of 2.0 μm or more.

[Comparative Example 4]
Publicly-known literature Osaka Prefectural Industrial Technology Research Institute report No. 20 separate volume (2006) “Preparation of antireflection structure” The resist was coated on the microlens array described in Example 1. As a result, a coating thickness distribution as shown in FIG. 6 was generated. The thickness of the microlens array convex portion was about 220 nm, and the thickness of the concave portion was about 450 nm. When a fine protrusion structure was prepared by the same operation as in Comparative Example 3, a defective formation of a protrusion occurred in the recess.

It is a top view which shows typically a single particle film etching mask. It is the schematic which shows an example of the manufacturing method of a single particle film etching mask. It is explanatory drawing explaining the manufacturing method of a microstructure. 1 is a longitudinal sectional view schematically showing a single particle film obtained in Example 1. FIG. 1 is a longitudinal sectional view schematically showing a fine structure obtained in Example 1. FIG. 6 is a longitudinal sectional view schematically showing a resist layer obtained in Comparative Example 4. FIG. 3 is a longitudinal sectional view schematically showing a single particle film obtained in Example 2. FIG. 6 is a longitudinal sectional view schematically showing a microstructure obtained in Example 2. FIG. 10 is a longitudinal sectional view schematically showing a resist layer obtained in Comparative Example 3. FIG.

P particle F single particle film C microstructure 11 substrate

Claims (4)

A method of manufacturing a substrate with a single particle film etching mask comprising a non-planar substrate and an etching mask fixed on the substrate,
The etching mask is composed of a single particle film in which particles are two-dimensionally closely packed, and after a single particle film is formed on the substrate by the LB method , a binder solution is supplied to the single particle film side of the substrate. The substrate and the particles are fixed;
The method for manufacturing a substrate with a single particle film etching mask, wherein the mass of the binder is 0.001 to 0.02 times the mass of the etching mask.
The binder is a single particle film production method of the substrate with an etching mask according to claim 1 is a metal alkoxysilanes. 3. The single particle film etching according to claim 1, wherein the single particle film is a single particle film having a deviation D (%) of the particle arrangement defined by the following formula (1) of 10% or less. Manufacturing method of substrate with mask.
D (%) = | B−A | × 100 / A (1).
(In formula (1), A represents the average particle diameter of the particles, and B represents the average pitch between the particles in the single particle film.) The method for manufacturing a substrate with a single particle film etching mask according to any one of claims 1 to 3 , wherein the particle arrangement includes lattice defects that provide a variety of packing orientations in close-packing.

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