JP4059657B2 - Manufacturing method of three-dimensional photonic crystal - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a three-dimensional photonic crystal used for an optical functional element, and in particular, a three-dimensional photonic crystal composed of a plurality of dielectric materials (photonic materials) having sufficiently different refractive indexes is particularly efficient. The present invention relates to a method for producing a three-dimensional photonic crystal that can be obtained.
[0002]
[Prior art]
In recent years, it is a microstructure formed of two or more kinds of dielectric materials having different refractive indexes (dielectric constants), and more specifically has a crystal grain size of about 1 μm to 100 μm, and it is periodic The three-dimensional photonic crystals arranged in a column have attracted attention because they have a photonic band gap (PBG) that can control the propagation of light. That is, using this photonic band gap, it is expected that a three-dimensional photonic crystal is applied to an optical functional element such as a duplexer, an optical waveguide, an optical delay element, or a laser.
Therefore, as a method for obtaining a three-dimensional photonic crystal having such a fine structure, the following manufacturing method has been proposed.
(1) A method of laminating silica or polymer beads.
(2) A method using a self-organized structure such as a polymer.
(3) Self-cloning method using CVD process.
(4) A method of three-dimensionally dry-etching a semiconductor material from three axial directions.
(5) A method of laminating wafers by fusing.
(6) A method of laminating a polysilicon layer.
(7) A method of forming a composition distribution in a polymer by photopolymerizing a medium composed of two kinds of photosensitive agents.
(8) A stereolithography method in which a polymerizable monomer is three-dimensionally photocured.
[0003]
However, these proposed methods have low production efficiency and cannot be used as practical manufacturing methods.
For example, the above-mentioned (1) method of laminating beads and (2) the method of using a self-organized structure such as a polymer not only has low production efficiency, but also has a problem that the three-dimensional structure that can be formed is excessively limited. There is.
In addition, the above-mentioned (3) self-cloning method, (4) dry etching method, (5) wafer fusion method, and (6) polysilicon lamination method require an expensive semiconductor process and have low production efficiency. Moreover, there is a problem that the range of materials that can be used is narrow.
Further, the above-mentioned method (7) of forming a composition distribution in a polymer has a problem that it is difficult to increase the refractive index ratio between regions having different refractive indexes, and the production efficiency is low.
Further, the above-described (8) stereolithography also has a problem that production efficiency is extremely low while the three-dimensional structure that can be formed is excessively limited.
[0004]
Therefore, in JP-A-2001-42144, an inorganic oxide particle-dispersed sol is applied to the surface of a substrate using a dropping method (casting method) or the like and then dried under a vapor pressure of a solvent of 50 to 760 mmHg. A method for producing a photonic crystal in which inorganic oxide particles having an average particle diameter of 0.05 to 1 μm are arranged in a layer form is disclosed.
Japanese Patent Application Laid-Open No. 2001-191025 discloses a step of forming a polymer-containing layer mainly composed of a polymer material, and fine particles in a solvent capable of swelling the polymer material in the polymer-containing layer. A step of contacting the dispersed fine particle dispersion to form a polymer-particle composite, a step of filling a gap between the particles of the polymer-particle composite with a predetermined substance, and a polymer-particle composite A method for producing a porous body comprising a step of removing fine particles by heat treatment or chemical treatment is disclosed, and the produced porous body can be applied to the production of photonic crystals, separation membranes, and the like. Proposed.
[0005]
JP-A-2001-72414 discloses a photonic crystal gel obtained by pouring a metal alkoxide partially hydrolyzed solution into a micromold produced by a photolithography method and aging it. Manufacturing methods have been proposed.
Japanese Patent Application Laid-Open No. 2001-83347 includes a porous body having three-dimensionally continuous through holes, and a region formed in the porous body and filled with a photosensitive substance. There has been proposed a method for manufacturing a three-dimensional structure in which regions filled with a substance are arranged with an average period of 0.1 to 2 μm so as to form a photonic band gap.
[0006]
Furthermore, Japanese Patent Laid-Open No. 2001-91911 has a periodic structure equivalent to the wavelength of an electromagnetic wave made of a dielectric material, and is provided with means for disturbing periodicity at least at one location of the periodic structure. A functional material having a one-dimensional structure to a three-dimensional structure, characterized in that means for disturbing periodicity can be controlled from the outside. For example, when creating a photonic crystal as a functional material having a two-dimensional structure, it is proposed to use an inkjet method as an example.
[0007]
[Problems to be solved by the invention]
However, the manufacturing method disclosed in Japanese Patent Application Laid-Open No. 2001-42144 is basically intended for a single type of structure composed of inorganic oxide particles, and has a three-dimensional structure having two regions with sufficiently different refractive indexes. It has been difficult to produce photonic crystals. Moreover, the drying conditions of inorganic oxide particle dispersion | distribution sol were severe, and the problem that the usable solvent seed | species was restrict | limited too much was also seen.
Therefore, depending on the disclosed manufacturing method, it has been substantially difficult to efficiently manufacture a photonic crystal composed of a plurality of dielectric materials having sufficiently different refractive indexes.
[0008]
In addition, in the production method disclosed in Japanese Patent Application Laid-Open No. 2001-191025, the type of usable polymer substance and the type of solvent are excessively selected, while fine particles having a fine period suitable for a photonic crystal are used. It was difficult to arrange them uniformly. In addition, it is not easy to remove such fine particles uniformly. Furthermore, it was virtually impossible to uniformly fill the porous material obtained by removing the fine particles in this way with a predetermined substance.
Therefore, it has been substantially difficult to efficiently manufacture a photonic crystal from a plurality of dielectric materials having sufficiently different refractive indexes depending on the disclosed manufacturing method.
[0009]
In addition, in the production method disclosed in Japanese Patent Application Laid-Open No. 2001-72414, it is difficult to uniformly fill a micromold with a partially hydrolyzed solution of metal alkoxide, and thus the obtained photonic crystal gel In addition to variations in optical properties, there were also problems with low production efficiency. In addition, it is not easy to form the micromold to be used, and there are problems that the types of constituent materials are limited and the manufacturing cost increases.
Therefore, it has been substantially difficult to efficiently manufacture a photonic crystal from a plurality of dielectric materials having sufficiently different refractive indexes depending on the disclosed manufacturing method.
[0010]
Also in the manufacturing method disclosed in Japanese Patent Application Laid-Open No. 2001-83347, it is difficult to uniformly fill a photosensitive material into a porous body having three-dimensionally continuous through-holes. Not only did the optical properties of the original structure vary, but the production efficiency was still low. Moreover, the formation of the porous body itself to be used is not easy, and there are problems that the types of constituent materials are limited and the manufacturing cost is increased.
Therefore, it has been substantially difficult to efficiently manufacture a photonic crystal from a plurality of dielectric materials having sufficiently different refractive indexes depending on the disclosed manufacturing method.
[0011]
In addition, the manufacturing method disclosed in Japanese Patent Laid-Open No. 2001-91911 is basically intended to create a periodic structure made of a single type of dielectric material, and the periodicity is disturbed in the middle of the periodic structure. Since it is necessary to provide a means and control from the outside, it has been substantially difficult to efficiently produce a photonic crystal from a plurality of dielectric materials having sufficiently different refractive indexes.
[0012]
Accordingly, the inventors of the present invention have made extensive studies in order to solve the above-described problems. As a result, two or more dielectric materials (photonic materials) having sufficiently different refractive indexes are used, and are used in the horizontal direction and the vertical direction. It has been found that a three-dimensional photonic crystal can be efficiently produced by pattern printing in the direction.
That is, the present invention provides a method for efficiently and inexpensively manufacturing a three-dimensional photonic crystal having a periodic structure made of a dielectric material (photonic material) having a sufficiently different refractive index by a pattern printing method. For the purpose.
[0013]
[Means for Solving the Problems]
  According to the present invention, the first photonic material and the second photonic material having a refractive index lower than the refractive index of the first photonic material are alternately arranged on the substrate. Pattern printing and forming a first two-dimensional photonic crystal layer;
  Pattern printing so that the first photonic material and the second photonic material are alternately arranged on the first two-dimensional photonic crystal layer, and stacking the second two-dimensional photonic crystal layer; ,
  A method for producing a three-dimensional photonic crystal characterized in that the above-described problems can be solved..
That is, in carrying out the method for producing a three-dimensional photonic crystal of the present invention, the first photonic material and the second photonic material are subjected to pattern printing in which an inkjet method or a screen printing method is combined with an offset printing method. A method for producing a three-dimensional photonic crystal using the first photonic material and the second photonic material after pattern printing on an offset printing plate by an inkjet method or a screen printing method, The first photonic material and the second photonic material are transferred from the offset printing plate to the substrate. If implemented in this way, a printing pattern of about 30 μm, for example, printed by an ink jet method or a screen printing method can be made into a fine printing pattern of 10 μm or less by utilizing the repelling phenomenon that occurs on the offset printing plate. Therefore, even a three-dimensional photonic crystal having a finer periodic structure can be efficiently manufactured.
[0014]
In carrying out the method for producing a three-dimensional photonic crystal according to the present invention, the first photonic material and the second photonic material are mixed with an ink jet method, a screen printing method, an offset printing method, a perforated filter method, or It is preferable to perform pattern printing by at least one printing method of the thermal head method.
When implemented in this way, since a specific pattern printing method is used, for example, even a three-dimensional photonic crystal having a fine periodic structure of 30 μm or less can be efficiently manufactured.
[0016]
Further, in carrying out the method for producing a three-dimensional photonic crystal of the present invention, a patterned hole is formed on a substrate by using a pattern printing in which an inkjet method or a screen printing method and the perforated filter method are combined. After providing the perforated plate, it is preferable to pattern-print the first photonic material and the second photonic material through the perforated plate by an ink jet method or a screen printing method.
When implemented in this way, even with a printing pattern of, for example, about 30 μm printed by an ink jet method or a screen printing method, a finer printing of, for example, 10 μm or less using a perforated plate having a fine periodic structure It can be a pattern.
Therefore, even a three-dimensional photonic crystal having a finer periodic structure can be efficiently manufactured.
[0017]
In carrying out the method for producing a three-dimensional photonic crystal of the present invention, it is preferable to use an ionizing radiation curable resin or a thermosetting resin as the photonic material.
If implemented in this way, a three-dimensional photonic crystal having excellent mechanical properties and heat resistance can be efficiently produced.
[0018]
In carrying out the method for producing a three-dimensional photonic crystal of the present invention, it is possible to use photonic materials having different refractive index differences of 0.01 or more as the first photonic material and the second photonic material. preferable.
When implemented in this way, a three-dimensional photonic crystal having a large photo band gap can be efficiently produced.
[0019]
Further, in carrying out the method for producing a three-dimensional photonic crystal of the present invention, when forming the first two-dimensional photonic crystal layer, the marker is printed at the same time, and the second two-dimensional It is preferable to form a photonic crystal layer.
When implemented in this way, the positional deviation between the first two-dimensional photonic crystal layer and the second two-dimensional photonic crystal layer is reduced, and a photo band gap can be formed reliably.
[0020]
Moreover, when implementing the manufacturing method of the three-dimensional photonic crystal of this invention, it is preferable to further include the process of performing the planarization process on the surface of a 1st two-dimensional photonic crystal layer.
When implemented in this way, the surface of the first two-dimensional photonic crystal layer is flattened, so that the misalignment between the first two-dimensional photonic crystal layer and the second two-dimensional photonic crystal layer As a result, the photo band gap can be formed reliably. Further, when the surface of the first two-dimensional photonic crystal layer is flattened, a flat three-dimensional photonic crystal can be formed as a whole, and uniform optical characteristics can be exhibited.
In performing the planarization treatment, it is also preferable to directly polish the surface of the first two-dimensional photonic crystal layer, or to provide a planarization layer and polish the surface indirectly. It is also preferable to flatten the surface of the first two-dimensional photonic crystal layer.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
  The embodiment of the present invention is a method for producing a three-dimensional photonic crystal using a pattern printing method including the following steps.
(1)A step of preparing a photonic material having a relatively high refractive index and a photonic material having a relatively low refractive index (hereinafter referred to as a preparation step).
(2)A step of pattern-printing the first and second photonic materials on the substrate so as to be alternately arranged to form a first two-dimensional photonic crystal layer (hereinafter referred to as a printing step).
(3)A step of pattern printing so that the first and second photonic materials are alternately arranged on the first two-dimensional photonic crystal layer and laminating the second two-dimensional photonic crystal layer (hereinafter, a lamination step) Called.)
That is, the first embodiment of the present invention uses pattern printing in which the first photonic material and the second photonic material are combined with an inkjet method or a screen printing method and an offset printing method in the printing process. The first photonic material and the second photonic material are subjected to pattern printing on an offset printing plate by an ink jet method or a screen printing method, and then the first photonic material and the second photonic material are offset. It is characterized by transferring from a printing plate to a substrate.
In the second embodiment of the present invention, in the printing process, the first photonic material and the second photonic material are subjected to pattern printing in which an ink jet method or a screen printing method and a perforated filter method are combined. After using the perforated plate patterned on the substrate, the first photonic material and the second photonic material are pattern printed by the ink jet method or the screen printing method through the perforated plate. It is characterized by that.
The third embodiment of the present invention is characterized in that, in the printing step, the marker is printed at the same time, and the second two-dimensional photonic crystal layer is formed using the marker as a mark.
Furthermore, the fourth embodiment of the present invention further includes a step of performing a planarization process on the surface of the first two-dimensional photonic crystal layer.
  Although the structure of the three-dimensional photonic crystal is not particularly limited, for example, a three-dimensional structure as shown in FIG. 1 is preferable.
[0022]
1. Preparation process
(1) Photonic material
▲ 1 ▼ Type
The type of photonic material is not particularly limited. For example, acrylic resin, vinyl acetate resin, silicone resin, polyester resin, polycarbonate resin, epoxy resin, phenol resin, urethane resin, polyimide resin, olefin resin, halogen One kind or a combination of two or more kinds, such as a fluorinated hydrocarbon resin, an acetal resin, and a cellulose derivative.
Of these photonic materials, it is preferable to use an ionizing radiation curable resin or a thermosetting resin. With such a photonic material, a three-dimensional photonic crystal having excellent mechanical properties and heat resistance can be efficiently produced.
In addition, for the purpose of crosslinking these photonic materials or improving heat resistance, it is also preferable to add a crosslinking agent, a curing agent, an antioxidant, an ultraviolet absorber or the like.
Furthermore, it is also preferable to add metal oxide particles such as silica, zirconia, alumina, and titania to these photonic materials in order to adjust the refractive index and heat resistance.
[0023]
(2) Refractive index
Also, the refractive index of the photonic material is not particularly limited, and as long as the refractive index value is different, a photonic material having a relatively high refractive index and a photonic material having a relatively low refractive index are used. , Each can be used.
However, more specifically, in the case of a photonic material having a high refractive index, the refractive index is preferably set to a value in the range of 1.4 to 1.7, and in the case of a photonic material having a low refractive index, The refractive index is preferably set to a value within the range of 1.3 to 1.6.
Note that the refractive index of the photonic material can be measured using a refractometer under the measurement conditions of a temperature of 25 ° C. with reference to the sodium D-line.
[0024]
(2) Solvent
It is also preferable to provide the photonic material in the form of a solution because pattern printing is performed by an inkjet method or the like. In this case, examples of the solvent for dissolving the photonic material include water, alcohol, and petroleum hydrocarbons. , Aromatic hydrocarbons, halogenated hydrocarbons, etc., alone or in combination of two or more.
[0025]
2. Printing process, curing process and lamination process
The printing process is a process of pattern printing the first and second photonic materials having sufficiently different refractive indexes, and the printing method is not particularly limited. It is preferable to employ a pattern printing method capable of printing a fine pattern, such as an ink printing method, an offset printing method, a perforated filter method, or a thermal head method.
[0026]
The curing step is a step (including a drying step) of curing the first and second photonic materials printed with a pattern, respectively, and depends on the type of the first and second photonic materials to be used. It is preferable to implement as follows.
(1) Drying photonic materials
In the case of using the solution-type first and second photonic materials, it is possible to remove the solvent contained by carrying out natural drying in a room temperature atmosphere after pattern printing. However, it is usually preferable to sufficiently remove such a solvent by heat treatment.
In the case of performing heat treatment for drying, it is preferable to use a heating means such as a thermostatic bath, an electric furnace, a steam oven, an infrared heating furnace or the like.
Furthermore, when performing heat processing, while setting the heating temperature to the value within the range of 25-300 degreeC, for example, it is preferable to make the heating time into the value within the range of 1 minute-100 hours.
The photonic material used in the present invention is usually a resin and often contains water or an organic solvent. In that case, the heating temperature is set to a value within the range of 50 to 150 ° C. In addition, the heating time is more preferably set to a value within the range of 10 minutes to 2 hours.
[0027]
(2) Curing of ionizing radiation curable resin
When the ionizing radiation curable resin is cured, X-rays, ultraviolet rays, visible rays, infrared rays, etc. can be used as the ionizing radiations. However, since the handling is easier, it is more preferable to use ultraviolet rays and visible rays. preferable.
When ionizing radiation is used, it is preferable to use, for example, a xenon lamp, a mercury lamp, sunlight, an incandescent bulb, or a fluorescent lamp as the light source.
Further, when ionizing radiation is used, the irradiation amount is not particularly limited. For example, when ultraviolet rays and visible light are used, the irradiation amount is 40 to 200 W / cm, and the irradiation time is 0.1 to 0.1. More preferably, the range is 60 minutes.
[0028]
(3) Curing of thermosetting resin
In the case of curing the thermosetting resin, it is preferable to heat and cure using a heating means such as a thermostatic bath, an electric furnace, a steam oven, or an infrared heating furnace.
Moreover, when making it harden | cure, for example, while making the heating temperature into the value within the range of 25-300 degreeC, it is preferable to make the heating time into the value within the range of 1 minute-100 hours.
However, since the photonic material used in the present invention is a resin, the heating temperature is usually set to a value in the range of 50 to 150 ° C., and the heating time is set to a value in the range of 10 minutes to 2 hours. More preferably.
[0029]
Next, the lamination process will be described. In this lamination process, the first and second photonic materials are alternately disposed both in the horizontal direction and in the vertical direction in relation to the first two-dimensional photonic crystal layer. Is positioned at a predetermined position, and then printed with a pattern, and a second two-dimensional photonic crystal layer is stacked at a predetermined position on the first two-dimensional photonic crystal layer.
The pattern printing method for forming the second two-dimensional photonic crystal layer is not particularly limited. For example, an inkjet method, a screen printing method, an offset printing method, a perforated filter, which will be described later, is used. Or the thermal head method is preferably used as appropriate.
[0030]
(1) Inkjet method
FIG. 2 shows an outline of a method for forming a three-dimensional photonic crystal using an ink jet method.
As an example, the inkjet apparatus 5 shown in FIG. 2 employs a charge modulation method, and includes a first solution or a second solution 12 including first and second photonic materials having sufficiently different refractive indexes. Ink bottle 10 for containing, supply pump 14 for supplying these first solution or second solution 12 to nozzle 18, pressure regulating valve 16 provided in the middle of pipeline 13, nozzle 18 A piezoelectric element 20 electrically connected to the high-frequency power source 22, a charging electrode 24 electrically connected to the character signal generator 26, a pair of deflection electrodes 28 electrically connected to the power source 30, It is preferable that the gutter 34 and the recovery pump 36 are basically configured.
The following description is based on the case where the first solution or the second solution containing the first and second photonic materials is used. It is also possible to use first and second photonic materials.
[0031]
Then, by adopting such a configuration of the ink jet device 5, the first solution or the second solution 12 contained in the ink bottle 10 is supplied to the nozzle 18 through the pipeline 13 using the supply pump 14. Can be supplied to.
Further, the supply amount of the first solution or the second solution 12 is controlled by the pressure regulating valve 16 of the pipeline 13, and the first solution or the second solution 12 is pressurized and injected from the nozzle 18. Is possible.
In addition, it is preferable that the viscosity of the first solution and the second solution 12 to be ejected can be easily adjusted using an organic solvent or an aqueous solvent. With such first solution and second solution 12, clogging in the nozzle 18 can be efficiently prevented.
[0032]
Next, the piezoelectric element 20 applies a predetermined pressure to the first solution or the second solution 12 ejected from the nozzle 18 so that the first solution or the second solution 12 is made into a fine droplet. it can. That is, the piezoelectric element 20 operates in response to a high-frequency signal from the high-frequency power source 22 and applies pressure by synchronizing excitation and vibration frequencies from the direction intersecting the injection direction. The solution or the second solution 12 can be discontinuous microdroplets.
Further, the first solution or the second solution 12 in the form of fine droplets can be charged with a predetermined charge amount corresponding to the print signal from the character signal generator 26 using the charging electrode 24. . Therefore, the jet direction of the charged first solution or second solution 12 is controlled by the pair of deflection electrodes 28, and fine pattern printing can be performed in a non-contact manner on a predetermined portion of the substrate 32.
Further, when the first solution or the second solution 12 has an excellent affinity for the base material 32, ink dripping or the like can be efficiently prevented, and as a result, printing with high resolution can be performed. It becomes possible to do.
When the charging by the charging electrode 24 is insufficient, the first solution or the second solution 12 is recovered by the gutter 34 without being sprayed onto the base material 32, and is further recovered by the recovery pump 36. Thus, the ink bottle 10 is returned.
[0033]
In addition, although the above description is based on the case where it uses for the inkjet apparatus by a charge modulation system, when implementing the inkjet method, a diffusion system (divergence system), an electromechanical conversion system, an electrothermal conversion system, electrostatic attraction It is also possible to use an ink jet apparatus such as a method, a discharge method (spark jet), an electric permeable method, a hot-melt ink method, and an ink mist method.
In addition, pattern printing of the first solution and the second solution respectively including the first and second photonic materials can be performed simultaneously by providing a plurality of nozzles, or alternatively, the first solution It is also preferable to pattern-print the second solution after pattern printing.
In any case, according to the ink-jet method, the first and second photonic materials are each printed at predetermined positions on the base material, and are made of the first and second photonic materials having sufficiently different refractive indexes. The alternating pattern can be formed with relatively high accuracy not only in the horizontal direction but also in the vertical direction.
[0034]
(2) Screen printing method
FIG. 3 shows an outline of a method for forming a three-dimensional photonic crystal using a screen printing method.
First, as shown in FIG. 3A, after the base material 32 is placed below the screen 40 constituting the screen printing apparatus 41, the squeegee 39 is moved downward while being pressed horizontally. Thus, the first solution dropped on the screen 40 is pattern-printed only on a predetermined portion of the substrate 32 to form a pattern 42 made of the first photonic material.
Next, as shown in FIG. 3B, the base material 32 coated with the screen 40 or the first solution is moved by a predetermined pitch, and exposed to the gap between the patterns 42 made of the first photonic material. The second solution is subjected to pattern printing on the substrate 32 by the screen printing device 41 to form the pattern 44 made of the second photonic material, and the first two-dimensional photonic crystal layer 48 is formed.
Next, alignment between the screen 40 and the substrate 32 having the first two-dimensional photonic crystal layer 48 is performed. Thereafter, on the first two-dimensional photonic crystal layer 48, the first solution and the second solution respectively containing the first and second photonic materials having different refractive indexes are further alternately arranged. -Pattern printing is performed by the printing apparatus 41, and a second two-dimensional photonic crystal layer (not shown) is laminated.
Then, by adopting the screen printing method in this way, the first solution and the second solution are respectively pattern-printed at predetermined locations on the substrate, and the first and second refractive indexes are sufficiently different from each other. The alternating pattern made of photonic material can be formed with relatively high accuracy not only in the horizontal direction but also in the vertical direction.
The above description of the screen printing method is based on the case where the first solution or the second solution respectively containing the first and second photonic materials is used, but either or both of them are used. In both cases, it is also possible to use solvent-free first and second photonic materials.
[0035]
(3) Offset printing method
FIG. 4 shows an outline of a method for forming a three-dimensional photonic crystal using the offset printing method.
First, as shown in FIG. 4A, an offset printing plate 45 is prepared in which a lipophilic portion 46 and a hydrophilic portion 47 are formed in a pattern. The offset printing plate 45 includes a so-called waterless flat plate in which a photocurable resin layer having fine openings is laminated on a silicone plate.
Next, on the offset printing plate 45, for example, a first solution containing a hydrophilic first photonic material is roll-coated. By applying in this way, the first solution is applied only to the hydrophilic portion, and the first solution is repelled in the lipophilic portion. Accordingly, in this state, the pattern 42 made of the first photonic material is formed on the offset printing plate 45 by pressing the substrate 32 using, for example, a pressure roll (not shown). be able to.
Next, separately, an offset printing plate 45 in which a lipophilic portion 46 and a hydrophilic portion 47 are similarly formed in a pattern is prepared. Since the second solution containing only the lipophilic second photonic material is roll-coated thereon so that the second solution is applied only to the lipophilic portion, the second solution is repelled in the hydrophilic portion. It will be scratched. Therefore, in this state, by pressing the base material 32 on the offset printing plate 45, the pattern 44 made of the second photonic material is formed in the gap between the patterns 42 made of the first photonic material. Can do.
By repeating this offset printing operation, an alternating pattern composed of the first photonic material and the second photonic crystal having sufficiently different refractive indexes is formed not only in the horizontal direction but also in the vertical direction with relatively high accuracy. can do.
Note that the above description of offset printing is based on the use of the first solution or the second solution containing the first and second photonic materials, respectively. It is also possible to use solvent-type first and second photonic materials.
[0036]
(4) Perforated filter method
FIG. 5 shows an outline of a method for forming a three-dimensional photonic crystal using a perforated filter method.
First, as shown in FIG. 5A, after placing the perforated filter 50 on the base material 32, the first solution is dropped in the direction of the arrow only at the desired location of the base material 32. As shown in FIG. 5B, printing for forming the pattern 42 made of the first photonic material is performed.
Next, as shown in FIG. 5C, the substrate coated with the screen or the first solution is moved by a predetermined pitch, and the substrate exposed in the gap of the pattern 42 made of the first photonic material. The second solution is pattern-printed on the material 32 through the perforated filter 50 to form the first two-dimensional photonic crystal layer 48.
Next, on the first two-dimensional photonic crystal layer 48, using a perforated filter so that the first solution and the second solution containing photonic materials having different refractive indexes are alternately arranged, a pattern is formed. A second two-dimensional photonic crystal layer (not shown) is stacked by printing.
Therefore, by using the perforated filter in this way, the alternating pattern composed of the first photonic material and the second photonic crystal having different refractive indexes can be relatively accurately detected not only in the horizontal direction but also in the vertical direction. Can be formed. Note that the above description of the perforated filter method is based on the use of the first solution or the second solution containing the first and second photonic materials, respectively. It is also possible to use solvent-free first and second photonic materials.
[0037]
(5) Thermal head method
FIG. 6 shows an outline of a method for forming a three-dimensional photonic crystal using the thermal head device 70.
As shown in FIG. 6, a thermal head 64 is provided below a sublimable ink film 63 composed of a sublimable ink 60 made of a first photonic material formed from a first solution and a support film 62. Then, while controlling the temperature by a CPU (Central Processing Unit) 68, the switch 66 of the thermal head 64 is turned on to generate heat, and only the sublimation ink 60 at a desired location is heated via the support film 62. By doing so, the sublimation ink 60 as a photonic crystal raw material is pattern-printed on the base material 32.
Next, a thermal head is placed below a sublimable ink film (not shown) composed of a sublimable ink made of the second photonic material formed from the second solution and a support film. Then, while controlling the temperature by the CPU, the thermal head switch is turned on to generate heat, and by heating only the sublimation ink at a desired location, the sublimation ink composed of the second photonic crystal is printed on the pattern, A first two-dimensional photonic crystal layer (not shown) is formed.
Next, on the first two-dimensional photonic crystal layer, a sublimable ink film composed of a sublimable ink made of the first solution containing the first photonic material and a support film, and a first film A substrate having a first two-dimensional photonic crystal layer, each prepared with a sublimable ink composed of a second solution containing two photonic materials and a film for sublimable ink composed of a support film Are aligned. Thereafter, a desired position of the sheet containing the sublimation ink is heated by the thermal head, the alternating pattern printing made of the first photonic material and the second photonic material is printed, and the second two-dimensional photonic crystal layer is laminated. .
As described above, according to the thermal head method, the alternating pattern composed of the first photonic material and the second photonic crystal having different refractive indexes can be formed with high accuracy not only in the horizontal direction but also in the vertical direction. Can do.
[0038]
(6) Combination method 1
In addition, when pattern printing is performed on the first and second photonic materials, it is also preferable to combine an offset printing method with an inkjet method or a screen printing method.
That is, an ink jet method or a screen printing method is used when roll-coating the offset printing plate described above in the offset printing method. For example, when the first solution containing the hydrophilic first photonic material is applied, the first solution is applied to the hydrophilic portion only with high accuracy by using an inkjet method or a screen printing method. Can do.
On the other hand, even if the first solution is partially applied to the lipophilic part, the first solution is completely repelled by the lipophilic part.
Therefore, by pressing the substrate on the offset printing plate in this state, the pattern made of the first photonic material can be formed with high accuracy, for example, even with a diameter pattern of 10 μm or less. Can do.
Then, by repeating the operation described above in the offset printing method in combination with the ink jet method or the screen printing method, an alternating pattern composed of the first photonic material and the second photonic crystal can be used not only in the horizontal direction but also in the vertical direction. It can also be formed with extremely high accuracy in the direction.
In addition, although the above description of the inkjet method or the screen printing method is based on the case where the first solution or the second solution containing the first and second photonic materials, respectively, Both can also use solvent-free first and second photonic materials.
[0039]
(7) Combination method 2
It is also preferable to combine the ink jet method and the perforated filter method when pattern printing is performed on the first solution and the second solution.
That is, the ink jet method is used in the above-described application in the perforated filter method. For example, when the first solution containing the first photonic material is applied through a perforated filter, the first solution is sprayed on the desired hole with high accuracy by using an inkjet method. As a result, it can be applied to the substrate with extremely high accuracy. On the other hand, even if the first solution is partially sprayed in the vicinity of the specific hole, the first solution wraps around the specific hole and only through the hole, Can reach the substrate.
Then, by repeating the above-described operation in the perforated filter method, the alternating pattern composed of the first photonic material and the second photonic crystal can be obtained not only in the horizontal direction but also in the vertical direction with extremely high accuracy. Even a diameter pattern of 10 μm or less can be reliably formed.
The above description of the ink jet method is based on the use of the first solution or the second solution containing the first and second photonic materials, respectively. It is also possible to use solvent-type first and second photonic materials.
[0040]
(8) Combination method 3
It is also preferable to combine any of the ink jet methods described above with a photolithography method (including a lift-off method).
That is, a photo-curable material is used as a photonic material, and after pattern printing by any one of the above-described pattern printing methods or a combination thereof, pattern exposure is performed through a photomask or the like, and then an unexposed portion is developed. It is also preferable to make the pattern finer.
When implemented in this way, for example, even a three-dimensional photonic crystal having a fine periodic structure of 5 μm or less can be efficiently manufactured.
[0041]
(9) Positioning
Further, it is important to perform alignment after forming the first two-dimensional photonic crystal layer and then pattern printing to form the second two-dimensional photonic crystal layer. This is because if the positions of the first two-dimensional photonic crystal layer and the second two-dimensional photonic crystal layer are shifted, a photo band may not be formed in the three-dimensional photonic crystal.
Therefore, when forming the first two-dimensional photonic crystal layer, it is preferable that the marker is printed at the same time, and the second two-dimensional photonic crystal layer is formed using the marker as a mark. For example, a registration mark or scale is printed adjacent to the first two-dimensional photonic crystal layer, and the registration mark or scale is used as a mark.
It is preferable to appropriately adjust the nozzle position in the ink jet method, the screen position in the screen printing method, the position of the offset plate in the offset printing method, and the position of the perforated filter in the perforated filter method.
[0042]
In addition, it is preferable that alignment is performed accurately by further including a planarization step of planarizing the surface of the first two-dimensional photonic crystal layer. For example, it is preferable that the surface of the first two-dimensional photonic crystal layer is directly directly subjected to chemical polishing or physical polishing, or a flattening layer is once formed and then subjected to chemical polishing or physical polishing.
That is, when a pattern is printed in the vertical direction in order to form the second two-dimensional photonic crystal layer, the surface unevenness of the first two-dimensional photonic crystal layer affects the second two-dimensional photonic crystal layer. When forming a pattern of layers, misalignment may occur. Therefore, a planarization layer is provided to eliminate the influence of surface irregularities of the first two-dimensional photonic crystal layer, and the second two-dimensional photonic crystal layer is formed on the pattern of the first two-dimensional photonic crystal layer. These patterns are preferably formed by accurately aligning the patterns.
[0043]
【Example】
Hereinafter, although the manufacturing method of the photonic crystal of this invention is demonstrated in detail based on an Example, it cannot be overemphasized that this invention is not limited by description of these Examples.
[0044]
[Example 1]
1. Creation of three-dimensional photonic crystal
(1) Preparation process
35 parts by weight of methyl acrylate, 30 parts by weight of ethyl methacrylate, and 35 parts by weight of urethane acrylate (weight average molecular weight: 4500) are respectively accommodated in a container, mixed uniformly, and the refractive index after curing is 1. A mixed solution of 57 was prepared. Next, 2 parts by weight of benzoyl peroxide was added to 100 parts by weight of the mixed liquid, and further mixed uniformly to obtain a first photonic material. Further, 40 parts by weight of toluene was added to 100 parts by weight of vinyl acetate polymer (weight average molecular weight: 28000) having a refractive index of 1.45 to obtain a second photonic material (solution).
[0045]
(2) Printing process
Next, the first photonic material and the second photonic material were pattern-printed so that the adjacent pitch was 20 μm by an inkjet method so as to be alternately arranged on the substrate. Then, it put into a 100 degreeC thermostat in nitrogen atmosphere for 1 hour, and formed the 1st two-dimensional photonic crystal layer.
[0046]
(3) Lamination process
Next, the inkjet apparatus was aligned so that further pattern printing of the first photonic material and the second photonic material could be performed alternately on the first two-dimensional photonic crystal layer. In this state, pattern printing was performed by an inkjet method so that the adjacent pitch was 20 μm, and then the film was placed in a constant temperature bath at 100 ° C. for 1 hour in a nitrogen atmosphere to form a second two-dimensional photonic crystal layer.
[0047]
2. Evaluation of three-dimensional photonic crystals
The three-dimensional photonic crystal obtained in this way was laminated with almost no misalignment between the first two-dimensional photonic crystal layer and the second two-dimensional photonic crystal layer.
Therefore, according to the manufacturing method of the present invention, it was confirmed that a three-dimensional photonic crystal composed of a plurality of dielectric materials having sufficiently different refractive indexes can be obtained efficiently.
[0048]
[Example 2]
Example 1 except that after the first two-dimensional photonic crystal layer is formed, the first two-dimensional photonic crystal layer is planarized by CMP (Chemical Mechanical Polishing). A three-dimensional photonic crystal was manufactured.
As a result, in the obtained three-dimensional photonic crystal, the first two-dimensional photonic crystal layer and the second two-dimensional photonic crystal layer were stacked without any displacement.
Therefore, according to the manufacturing method of another aspect of the present invention, it was confirmed that a three-dimensional photonic crystal composed of a plurality of dielectric materials (photonic materials) having sufficiently different refractive indexes can be obtained with high accuracy.
[0049]
[Brief description of the drawings]
FIG. 1 is a diagram for explaining a structural example of a three-dimensional photonic crystal.
FIG. 2 is a diagram provided for explaining a method of forming a three-dimensional photonic crystal using an ink jet method.
FIG. 3 is a diagram for explaining a method of forming a three-dimensional photonic crystal using a screen printing method.
FIG. 4 is a diagram provided for explaining a method of forming a three-dimensional photonic crystal using an offset printing method.
FIG. 5 is a diagram for explaining a method of forming a three-dimensional photonic crystal using a perforated filter method.
FIG. 6 is a diagram for explaining a method of forming a three-dimensional photonic crystal using a thermal head method.
[0050]
[Explanation of sign]
5: Inkjet device
32: Base material
41: Screen printing device
42: Pattern (first photonic material)
44: Pattern (second photonic material)
45: Offset printing plate
50: Perforated filter
63: Film for sublimation ink
64: Thermal head

Claims (6)

A first photonic material and a second photonic material having a refractive index lower than the refractive index of the first photonic material are pattern-printed on the substrate so as to be alternately arranged, Forming a two-dimensional photonic crystal layer of
A pattern is printed on the first two-dimensional photonic crystal layer so that the first photonic material and the second photonic material are alternately arranged, and a second two-dimensional photonic crystal layer is stacked. And a step of performing
A method for producing a three-dimensional photonic crystal using pattern printing in which the first photonic material and the second photonic material are combined with an inkjet method or a screen printing method and an offset printing method, The first photonic material and the second photonic material are subjected to pattern printing on the offset printing plate by an inkjet method or a screen printing method, and then the first photonic material and the second photonic material are offset. 3. A method for producing a three-dimensional photonic crystal, comprising transferring from a printing plate to the substrate . A first photonic material and a second photonic material having a refractive index lower than the refractive index of the first photonic material are pattern-printed on the substrate so as to be alternately arranged, Forming a two-dimensional photonic crystal layer of
A pattern is printed on the first two-dimensional photonic crystal layer so that the first photonic material and the second photonic material are alternately arranged, and a second two-dimensional photonic crystal layer is stacked. And a step of performing
A method for producing a three-dimensional photonic crystal using pattern printing in which the first photonic material and the second photonic material are combined with an ink jet method or a screen printing method and a perforated filter method, After providing the patterned perforated plate on the base material, the first photonic material and the second photonic material are printed by the ink jet method or the screen printing method through the perforated plate. A method for producing a three-dimensional photonic crystal. A first photonic material and a second photonic material having a refractive index lower than the refractive index of the first photonic material are pattern-printed on the substrate so as to be alternately arranged, Forming a two-dimensional photonic crystal layer of
A pattern is printed on the first two-dimensional photonic crystal layer so that the first photonic material and the second photonic material are alternately arranged, and a second two-dimensional photonic crystal layer is stacked. And a step of performing
When forming the first two-dimensional photonic crystal layer, a marker is simultaneously printed and formed, and the second two-dimensional photonic crystal layer is formed using the marker as a mark. Original photonic crystal manufacturing method. A first photonic material and a second photonic material having a refractive index lower than the refractive index of the first photonic material are pattern-printed on the substrate so as to be alternately arranged, Forming a two-dimensional photonic crystal layer of
A pattern is printed on the first two-dimensional photonic crystal layer so that the first photonic material and the second photonic material are alternately arranged, and a second two-dimensional photonic crystal layer is stacked. And a step of performing
A method for producing a three-dimensional photonic crystal, further comprising a step of performing a planarization process on a surface of the first two-dimensional photonic crystal layer . The method for producing a three-dimensional photonic crystal according to any one of claims 1 to 4 , wherein an ionizing radiation curable resin or a thermosetting resin is used as the photonic material. The tertiary according to any one of claims 1 to 5 , wherein a photonic material having a difference in refractive index of 0.01 or more is used as the first photonic material and the second photonic material. Original photonic crystal manufacturing method.

Images