JP4587723B2 - Substrate manufacturing apparatus with organic crystal and substrate manufacturing method with organic crystal - Google Patents

Description

  The present invention relates to a substrate manufacturing apparatus with an organic crystal and a method for manufacturing a substrate with an organic crystal using a temperature difference method for forming a thin-film organic single crystal used for a nonlinear optical material, an electronic material, a light emitting material, etc. on a substrate. It is.

In recent years, it has become clear that organic materials have superior electrical and optical properties compared to inorganic materials, and have attracted attention. For this reason, organic materials have been actively developed in fields such as heat conductive materials, EL (electroluminescence) materials, PHB (photochemical hole burning) materials, photochromic materials, and nonlinear optical materials.
In particular, when an organic material is used as a nonlinear optical material, it has been found that a large nonlinear optical constant is obtained as compared with an inorganic material and that high-speed response is excellent. For this reason, a bulk single crystal for optical wavelength conversion using a second-order nonlinear optical effect of an organic material, an optical wavelength conversion element, an optical modulator, an optical bistable element using a third-order nonlinear optical effect, an optical shutter, Development of various nonlinear optical elements such as optical phase conjugate elements has been actively promoted.

Conventionally, methods for producing single crystals of organic materials include dry methods such as vacuum deposition and molecular beam epitaxy (MBE), and wet methods such as solvent evaporation, melt, and Langmuir Blodget (LB). And are used.
Here, while the dry method is a method with excellent uniformity and controllability of the film thickness, organic materials generally have a low thermal decomposition point and are decomposed by heat. Limited (see, for example, Patent Document 1).
In addition, in the wet method, the organic material is heated to the melting point to be liquid, and then the melt method is performed by cooling and crystallization, and after the organic material (solute) is completely dissolved in a soluble solvent, A solution method is known in which crystallization is performed by controlling the saturation concentration.
There have been many reports on the melt method until now (see, for example, Patent Documents 2 and 3), but it is necessary to raise the temperature to the melting point of the organic material. Since it cannot be used, the materials that can be used are limited.
In the solution method, various conditions can be selected by selecting a solvent to be used. Among them, a slow cooling method, a temperature difference method, and a solvent evaporation method are generally used as a method for producing a bulk single crystal.
The slow cooling method is a method of precipitating crystals by controlling the temperature (cooling) of an unsaturated solution to a saturated state (a supersaturated state depending on the material). In the temperature difference method, the temperature difference between two tanks creates supersaturation necessary for growth, and crystal growth is performed. Further, the solvent evaporation method is a method in which crystals are precipitated by the solution becoming saturated (supersaturated depending on the material) by evaporation of the solvent.

Various manufacturing methods as described above have been proposed for organic single crystals, but it is difficult to use the deposited crystal shapes as they are when considering actual applications. Must be processed into a more suitable shape by cutting or polishing. In particular, when used as an optical element, the flatness of the crystal plane is also important.
From this point, in the technique described in Patent Document 3, it has been reported that crystals are grown in a thin film shape between substrates, but this is an application of the melt method, and as described above, an organic material that decomposes near the melting point. In this case, the material is limited.

Further, 4-dimethylamino-N-methyl-4-stilbazolium tosylate (hereinafter referred to as “DAST”) shown in FIG. 16 was developed in the Nakanishi Laboratory of Tohoku University, and has an extremely large nonlinear optical constant and electro-optics. And has a low dielectric constant peculiar to organic crystals, it has attracted attention such as low voltage, high-speed light modulation and detection, and generation of millimeter waves.
Here, the electro-optic constants of DAST are r ₁₁ = 53 [pm / V] (1.3 μm), 92 [pm / V] (720 nm), and r _{33 of} LiNbO ₃ = 30.8 [pm / V] ( 633 nm), and the dielectric constant of DAST is ε ₁₁ = 5.2, which is smaller than that of LiNbO ₃ , so that there is a possibility of high-speed and low-voltage optical modulation in the optical modulator.
On the other hand, DAST is a material suitable for optical communication wavelength band devices because its transmission characteristics are almost flat in the 0.8 to 1.6 μm band.
Regarding the production of DAST crystals, a lot of methods for producing a bulk crystal from a solution (solution method) have been reported by Sasaki Laboratory, Osaka University, etc. (see, for example, Patent Document 4).
Sasaki et al. Disclosed a method for controlling the aspect ratio of the crystal form by controlling the concentration of the solution in the technique described in Patent Document 5, but the aspect ratio is 3 to 25, and the aspect ratio is the same under the same conditions. The ratio fluctuation is large and the controllability is not good.

  Further, it is very difficult to apply the obtained crystal without processing. In addition, it is extremely difficult to set a crystal to an arbitrary thickness (crystal shape) by controlling a temperature parameter or the like in a bulk crystal production method from a solution.

In the DAST thin film crystal production, M. Thakur et al. Reported a thin film crystal having a thickness of 3 to 4 μm and 1 cm ² (for example, see Non-Patent Document 1).
However, in this improved shear method, since the thickness of the crystal is controlled only by the weight, only a relatively thin crystal of about several μm can be produced.
Furthermore, DAST has a melting point (about 260 ° C.) and a thermal decomposition point (about 290 ° C.) that are close to each other, causing thermal decomposition near the melting point and containing many impurities. Reported by Gunter et al. (For example, see Non-Patent Document 2), and it is known that it is difficult to produce a single crystal using a melt method.
P.P. Gunter et al. Reported that a thin DAST crystal having a thickness of 11 mm ² and a thickness of 40 μm in a quartz cell was produced as a Flow Cell Method (see, for example, Non-Patent Document 3), but the crystal production position and crystal orientation were controlled. It is not what has been done.
As described above, there has been no report of producing a DAST thin film crystal with controlled position and orientation.
From the above, it has been found that a new method is required to grow a large single crystal by controlling the position and orientation on the crystal growth substrate.
Japanese Patent Laid-Open No. 7-10698 JP-A-5-170600 JP-A-6-186600 JP 2002-29899 A JP 2004-83345 A "APPLIED PHYSICS LETTERS" VOLUME 74, NUMBER 5, February 1, 1999, p. 635 “ADVANCED MATERIALS No. 7”, August 1996, p. 592 “CR Physique” Savine Manetta, Peter Gunter, March 1, 2002, p. 449-462

  As described above, there has been no report that a DAST crystal has a desired thickness and is controlled in position and orientation to produce a thin film single crystal.

  The present invention has been made in view of the above points, and the object of the present invention is that any temperature difference method can be used even if an organic material is unstable to heat and cannot be crystallized by the melt method. Providing a substrate manufacturing apparatus with an organic crystal suitable for the production of a large, high-quality substrate with an organic crystal by controlling the thickness and position and orientation, and controlling the position and orientation with an arbitrary thickness, An object of the present invention is to provide a method for producing a substrate with an organic crystal capable of producing a large-sized, high-quality substrate with an organic crystal.

In order to solve the above-mentioned problems, the invention according to claim 1 is a substrate with an organic crystal for producing a film-like organic crystal on a crystal production substrate by using a temperature difference method for controlling the temperature of a solution in which the organic crystal is dissolved. In the manufacturing apparatus, a temperature adjustment module that adjusts a temperature of a crystal manufacturing substrate in which a seed crystal is arranged in a crystal manufacturing region, and a predetermined interval is placed between the crystal manufacturing substrate and the crystal manufacturing substrate. A cell module that forms a sealed space; a holding means that is disposed on the temperature adjustment module and that detachably holds the crystal production substrate and the cell module; and a supply that passes through the cell module and communicates with the sealed space parts and through the respective discharge portions connected to the flow path and a circulating means for circulating the solution between the sealed space and the solution holding portion, the crystal formation substrate is Wherein the recess on the downstream side of the solution for serial seed crystal is formed.

According to a second aspect of the present invention, there is provided a substrate manufacturing apparatus with an organic crystal for manufacturing a film-like organic crystal on a crystal manufacturing substrate by using a temperature difference method for controlling a temperature of a solution in which the organic crystal is dissolved. A temperature adjustment module that adjusts the temperature of the crystal production substrate in which the seed crystal is disposed, and a cell module that is placed on the crystal production substrate and forms a sealed space having a predetermined interval between the crystal production substrate And a holding means disposed on the temperature adjustment module for detachably holding the crystal production substrate and the cell module, and connected to a supply unit and a discharge unit that penetrate the cell module and communicate with the sealed space, respectively. Circulation means for circulating the solution between the inside of the sealed space and the solution holding unit through the formed flow path, and the cell module has an outer peripheral part of the sealed space. An annular sealing member made of an elastic material placed on the crystal production substrate, a cell substrate disposed so as to press the sealing member, and an adjusting means for adjusting the predetermined interval. was it it said.

According to a third aspect of the present invention, there is provided a method for producing a substrate with an organic crystal in which a film-like organic crystal is produced on a crystal production substrate by using a temperature difference method for controlling a temperature of a solution in which the organic crystal is dissolved. A seed crystal is placed on the cell module, the cell module is held on the crystal production substrate so that the seed crystal is located in the sealed space and at a predetermined interval, and communicates with the sealed space through the cell module. The solution is circulated between the sealed space and the solution holding unit through flow paths connected to the supply unit and the discharge unit, respectively, and a recess is formed on the downstream side of the solution with respect to the seed crystal as the crystal production substrate. A substrate on which is formed is used .

According to a fourth aspect of the present invention, there is provided an organic crystal-attached substrate manufacturing method for manufacturing a film-like organic crystal on a crystal manufacturing substrate by using a temperature difference method for controlling a temperature of a solution in which the organic crystal is dissolved. A seed crystal is placed on the cell module, the cell module is held on the crystal production substrate so that the seed crystal is located in the sealed space and at a predetermined interval, and communicates with the sealed space through the cell module. The solution is circulated between the inside of the sealed space and the solution holding unit through flow paths respectively connected to the supply unit and the discharge unit to form an outer peripheral part of the sealed space as the cell module. A module comprising an annular seal member placed on the crystal production substrate and made of an elastic body, a cell substrate disposed so as to press the seal member, and an adjusting means for adjusting the predetermined interval. Characterized by using Lumpur.

According to a fifth aspect of the present invention, there is provided an organic crystal-attached substrate manufacturing method for manufacturing a film-like organic crystal on a crystal manufacturing substrate by using a temperature difference method for controlling a temperature of a solution in which the organic crystal is dissolved. A seed crystal is placed on the cell module, the cell module is held on the crystal production substrate so that the seed crystal is located in the sealed space and at a predetermined interval, and communicates with the sealed space through the cell module. The solution is circulated between the sealed space and the solution holding unit via flow paths connected to the supply unit and the discharge unit, respectively, and the crystal growth is performed after the surface of the seed crystal is dissolved at the start of crystal production. It is characterized by making it.

According to the present invention, it is possible to produce a thin film crystal by performing crystal growth in a sealed space (hereinafter referred to as “between micro gaps”) in a crystal production apparatus / method from a solution. In addition, large crystals can be obtained by performing crystal growth while supplying a solution to the crystals even between minute gaps. Further, by using a seed crystal, it is possible to specify a crystal growth portion and a crystal orientation. In addition, crystal growth can be performed using a low supersaturated solution in which crystals due to natural nuclei are unlikely to occur, and crystal growth (miscellaneous crystals) other than the growth site can be suppressed. In addition, by forming a recess in the downstream area from the position where the seed crystal is arranged, and increasing the distance between the crystal production substrate and the cell module, the flow of the solution can be improved even when miscellaneous crystals are generated. Crystal growth can be performed without hindrance. Further, by changing the distance between the crystal production substrate and the cell module, non-uniformity of the solution flow accompanying crystal growth can be eliminated, and a large crystal can be produced efficiently. In addition, fine defects (scratches) may be generated on the surface of the seed crystal due to operations during preparation and installation of the seed crystal. The structural defect on the seed crystal surface greatly affects the crystal structure (crystal quality) of the crystal growth portion. Therefore, by dissolving the crystal surface before the crystal growth (melt back), defects on the crystal surface are removed, and a crystal with few structural defects can be obtained.

  The organic crystal-attached substrate manufacturing apparatus of the present invention is an organic crystal-attached substrate manufacturing apparatus that forms a film-like organic crystal on a crystal-prepared substrate by using a temperature difference method for controlling the temperature of a solution in which the organic crystal is dissolved. Forming a sealed space between the temperature adjustment module on which the crystal production substrate having the seed crystal disposed in the crystal production region is placed and the crystal production substrate placed on the crystal production substrate. A cell module, one end fixed to the temperature control module and the other end detachably holding the cell module, and a flow path formed in the cell module and connected to a supply unit and a discharge unit communicating with the sealed space, respectively And a circulating means for circulating the solution between the sealed space and the solution holding part.

  The method for producing a substrate with an organic crystal of the present invention is a method for producing a substrate with an organic crystal in which a film-like organic crystal is produced on a crystal production substrate by using a temperature difference method for controlling the temperature of a solution in which the organic crystal is dissolved. The seed crystal is arranged on the crystal production substrate, and the cell module is placed on the crystal production substrate so that the seed crystal is located in the sealed space and at a predetermined interval. It is characterized in that the solution is circulated between the sealed space and the solution holding unit through flow paths respectively connected to the supply unit and the discharge unit communicating with the space.

  By producing an organic crystal in a minute gap formed by the crystal production substrate and the cell substrate, the thickness of the organic crystal obtained is the distance between the gaps formed by both substrates, and the planarity is also improved.

  As both substrates, a quartz substrate, a resin substrate such as polyimide or polyethylene, glass, silicon, or the like can be used. The surface shapes of both substrates are not particularly limited, and may be, for example, a circle, a rectangle, or an ellipse.

  The distance between the gaps formed by the two substrates can be arbitrarily determined, and is not particularly limited. However, considering application to an optical device such as an optical modulator, it is 300 nm to 800 μm, and particularly in a waveguide type optical device. Is preferably 1 μm to 100 μm.

As the organic substance, any organic material having a large nonlinear optical constant as compared with inorganic materials such as KH ₂ PO ₄ and LiNbO _{3 that} have been used in the past can be used. For example, 4-dimethylamino-N— Methyl-4-stilbazolium tosylate (DAST), 2-methyl-4-nitroaniline (MNA), metanitroaniline (mNA), 3-methyl-4-nitropyridine-1-oxide (POM), urea 2-methyl-3- (2-methoxyphenyl) -2-propenoate (CMP methyl), L-arginine phosphate monohydrate (LAP), 4- (N, N dimethylamino) -3-acetamidonitrobenzene (DAN), 3,5-dimethyl-1- (4-nitrophenyl) pyrazole (DMNP), 4'-nitrobenzylidene- - acetamino-4-methoxyaniline (MNBA), and the like. Here, 4-dimethylamino-N-methyl-4-stilbazolium tosylate is preferable because it has a very large nonlinear optical constant and electro-optical constant and has a low dielectric constant specific to organic crystals. .

  Examples of the solvent include various organic substances such as methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, chloroform, dichloromethane, 1,2-dichloroethane, dimethyl ether, acetate ester, hexane, cyclohexane, acetonitrile, toluene, and the like. A solvent having a large change in solubility with respect to temperature and having no association with a solute may be selected according to the substance. In the case of 4-dimethylamino-N-methyl-4-stilbazolium tosylate, methanol is one of the most suitable solvents.

FIG. 1 is a schematic view showing an embodiment of a substrate manufacturing apparatus with an organic crystal to which the method for manufacturing a substrate with an organic crystal of the present invention is applied.
(Constitution)
The apparatus shown in FIG. 1 uses a temperature difference method for controlling the degree of supersaturation of a solution by controlling the temperature of the temperature adjustment module 150 and the temperature adjustment module 100 to produce an organic crystal on a crystal production substrate 101. An attached substrate manufacturing apparatus, which is mounted on the crystal manufacturing substrate 101, and a temperature adjustment module (for example, a Peltier element) 100 that adjusts the temperature of the crystal manufacturing substrate 101 in which the seed crystal 120 is arranged in the crystal manufacturing region. A cell substrate 103 that forms a sealed space (hereinafter referred to as “micro gap”) 301 having a predetermined interval with the crystal production substrate 101, and the crystal production substrate 101 and the cell substrate 103 that are arranged on the temperature adjustment module 100. A holding means 200 for detachably holding, a supply unit 113 that passes through the cell substrate 103 and communicates with the minute gap 301, and a drain. Through the flow path 105, 106 which are respectively connected to part 114 and a circulation means 152 for circulating the solution 112 between the minute gap 301 and the solution holding portion 130.

A fluorine member is provided on the micro gap 301 side of the cell substrate 103, and the seed crystal 120 is 4-dimethylamino-N-methyl-4-stilbazolium tosylate (DAST).
The holding means 200 includes a base 201 on which the crystal production substrate 101 and the cell substrate 103 are placed, a frame-like member (may be plate-like) 153 placed on the cell substrate 103, and a frame-like member Fixing screws 154a and 154b for fixing the frame-like member 153 by being screwed to the base 201 through through holes formed on both sides of the 153 are provided. In order to take out the crystal production substrate 101 and the cell substrate 103 after the crystal production, the fixing screws 154a and 154b may be removed. It is preferable that a recess for facilitating the alignment of the crystal production substrate 101 is formed on the opposing surfaces of the frame member 153 and the base 201.
The frame-like member 153 is provided with a supply unit 113 and a discharge unit 114. For example, a hollow screw is used for the supply unit 113, and one end (the left end in the drawing) of the liquid feeding tube 106 as a flow path is inserted and connected to the through hole. An O-ring for maintaining airtightness is disposed at the tip (in this case, the lower end) of the hollow screw for the supply unit 113. Similarly, a hollow screw is used for the discharge portion 114, and one end (in this case, the left end) of the liquid supply tube 105 as a flow path is inserted and connected to the through hole. An O-ring for maintaining airtightness is disposed at the tip (in this case, the lower end) of the hollow screw for the discharge portion 114.

The circulation means 152 has a liquid feeding tube 106 whose one end is connected to the supply unit 113, a liquid feeding pump 104 whose discharge side is connected to the other end of the liquid feeding tube 106, and a supply port on the suction side of the liquid feeding pump 104. A connected solution holding unit 130 and a liquid feeding tube 105 having one end connected to the discharge unit 114 and the other end connected to the discharge port of the solution holding unit 130 are provided.
The solution holding unit 130 holds the temperature adjustment module 150 that adjusts the temperature of the solution 112, the reservoir 151 that is disposed on the temperature adjustment module 150 and stores the solution, and the temperature of the solution 112 in the reservoir 151 is constant. And a constant temperature bath 108.

Next, the organic crystal 120 is disposed in a crystal growth portion (the minute gap 301) constituted by the crystal production substrate 101 and the cell substrate 103. The crystal production substrate 101 and the cell substrate 103 are placed on the base 201. The frame-like member 153 is fixed with fixing screws 154a and 154b. The liquid feeding tube 105 is connected to the solution holding unit 130, and the liquid feeding tube 106 is connected to the liquid feeding pump 104. The liquid feeding pump 104 is operated to supply the solution 112 in which the organic crystals are dissolved into the minute gap 301 and circulate it to perform crystal growth. The seed crystal 120 becomes a crystal having a thickness between the crystal production substrate 101 and the cell substrate 103, and finally a thin film-like substrate with an organic crystal is obtained. A temperature difference (ΔT = T1−T2> 0) between the temperature (T1) of the thermostatic chamber 108 holding the solution 112 and the temperature (T2) of the temperature adjustment module 100 of the micro gap 301 which is a crystal production unit. By giving, the difference of the supersaturation degree (sigma) of a solution is given and only the seed crystal 120 in the microgap 301 can be selectively grown.
(Supersaturation σ = (C−Ce) / Ce Ce: saturation concentration, C: solution concentration)
When the DAST solution having a concentration of 20 mg / ml in which DAST is dissolved in methanol is used as the solution in the reservoir 151, the temperature of the reservoir 151 is set to 35 ° C., and the temperature of the temperature adjustment module 100 is set to 20 ° C. In this case, since the DAST solution is unsaturated at 35 ° C. from the solubility curve of DAST in methanol in FIG. 17, no crystal precipitation occurs in the reservoir 151. Further, at 20 ° C., the crystal in the crystal growth part (the minute gap 301) grows due to the supersaturated state.

2A is a cross-sectional view showing an embodiment of the crystal production substrate and the cell substrate shown in FIG. 1, and FIG. 2B is a cross-sectional view taken along the line IIb-IIb in FIG. FIG. 2C is an enlarged view of the seed crystal shown in FIG.
As shown in FIG. 2A, the solution 112 (see FIG. 1) is supplied in the direction of the arrow P3 into the minute gap 301, and the solution 112 is discharged in the direction of the arrow P4. The seed crystal 120 is fixed to the crystal production substrate 101 with an adhesive (for example, an epoxy-based adhesive or a hot-melt adhesive).
As shown in FIG. 2B, the solution flows in the direction of arrows P5 to P7 in the minute gap 301 (laminar flow). In the drawing, the planar shape of the minute gap 301 is a hexagon, but the present invention is not limited to this, and may be any one of an ellipse, an oval, and a polygon.
As shown in FIG. 2C, the preferential growth direction (maximum growth direction) of the seed crystal 120 is the arrow P8 direction, which is opposite to the direction in which the solution flows (arrows P5 to P7). Yes.

FIGS. 3A and 3B are diagrams showing the relationship between the preferential growth orientation of the seed crystal and the flow of the solution.
FIG. 3A shows the case where the preferential growth direction (arrow P9 direction) of the seed crystal 120 is 90 degrees with respect to the solution flow (arrow P10), and the preferential growth direction (arrow P11 direction) of the seed crystal 120 is the solution flow. In the case of 135 degrees with respect to (the direction of arrow P12), the preferred growth direction of seed crystal 120 (in the direction of arrow P13) is 180 degrees with respect to the flow of the solution (in the direction of arrow P14). When the arrow P15 direction is 225 degrees with respect to the solution flow (arrow P16 direction), the preferential growth direction (arrow P17 direction) of the seed crystal 120 is 270 degrees with respect to the solution flow (arrow P18 direction). In each case, the solution is supplied in the preferential growth direction. In particular, when the preferential growth direction (arrow P13 direction) of the seed crystal 120 is 180 degrees with respect to the flow of the solution (arrow P14 direction). Maximum priority growth is preferably carried out.
On the other hand, as shown in FIG. 3B, when the preferential growth direction of the seed crystal 120 (arrow P19 direction) is 315 degrees with respect to the flow of the solution (arrow P20 direction), the preferential growth direction of the seed crystal 120 When the (arrow P21 direction) is 0 degrees with respect to the solution flow (arrow P22 direction), the preferential growth direction (arrow P23 direction) of the seed crystal 120 is 45 degrees with respect to the solution flow (arrow P24 direction). However, there is a shortage of solution supply in the preferred growth direction.
Organic crystals often have different growth rates depending on the crystal orientation, and the crystals can be efficiently grown by arranging them so that the solution is supplied in the direction of the highest growth rate. The orientation through which the solution flow passes (the preferential growth orientation of the seed crystal 120 within the range of 90 to 325 degrees with respect to the solution flow) may be sufficient, and in particular, the preferential crystal orientation of the seed crystal 120 faces the solution flow. It is most preferable to arrange them as follows.

4A is a cross-sectional view showing another embodiment of the crystal production substrate and the cell substrate shown in FIG. 1, and FIG. 4B is a cross-sectional view taken along line IVb-IVb in FIG. 4A. .
4 (a) and 4 (b) is different from the embodiment shown in FIGS. 3 (a) and 3 (b) in that the microgap 301 of the crystal production substrate 101 has no difference with respect to the seed crystal 120. A point-shaped protrusion 400 is formed on the downstream side of the solution so as to be held in contact with the side surface of the seed crystal 120.
By forming the protrusion 400 on the crystal production substrate 101 in this manner (three-dimensional structure), the seed crystal 120 does not move from the arrangement position (installation position) in the solution flowing in the directions of arrows P25 to P29. As a result, a substrate with an organic crystal having a high-quality, large-size organic crystal is obtained.

FIG. 5A is a transverse sectional view showing another embodiment of the crystal production substrate and the cell substrate shown in FIG. 1, and FIG. 5B is a sectional view taken along the line Vb-Vb in FIG. .
The difference between the embodiment shown in FIGS. 5A and 5B and the embodiment shown in FIGS. 4A and 4B is that the seed crystal is formed on the downstream side of the seed crystal 120 of the crystal production substrate 101. The difference is that a stepped portion 500 having a notch in the shape of a dogleg shape that is held so as to be in contact with the side surface is formed.
By forming the stepped portion 500 on the crystal production substrate 101 in this manner (three-dimensional structure), the seed crystal 120 does not move from the arrangement position (installation position) in the solution flowing in the directions of arrows P30 to P34. As a result, a substrate with an organic crystal having a high-quality, large-size organic crystal is obtained.
Here, in order to prevent the seed crystal 120 from moving from the installation position (arrangement position) in the flow of the solution, a three-dimensional structure for fixing the seed crystal to the crystal production substrate 101 or the cell substrate 103 is configured. . As long as the solution supply to the crystal is not hindered, the structure may be a convex part or a concave part.
The structure may be such that the crystal production substrate 101 is processed as shown, or may be composed of a resin or the like that is resistant to solvents.

6A is a cross-sectional view showing another embodiment of the crystal production substrate and the cell substrate shown in FIG. 1, and FIG. 6B is a cross-sectional view taken along the line VIb-VIb of FIG. 6A. .
The difference between the embodiment shown in FIGS. 6A and 6B and the embodiment shown in FIGS. 2A and 2B is that a seed crystal 120 is provided between the crystal production substrate 101 and the cell substrate 103. It is the point provided with the cyclic | annular spacer 600 inserted | pinched together.
In this case, the distance between the crystal production substrate 101 and the cell substrate 103 can be the thickness of the seed crystal 120.
For example, silicone rubber is used for the spacer 600.
By using the spacer 600 in this way, the seed crystal 120 does not move from the arrangement position (installation position) in the solution flowing in the directions of the arrows P35 to P39. As a result, a substrate with an organic crystal having a high-quality, large-size organic crystal is obtained.

FIG. 7 is a schematic view showing another embodiment of the organic crystal-attached substrate manufacturing apparatus to which the organic crystal-attached substrate manufacturing method of the present invention is applied.
The difference from the apparatus shown in FIG. 1 is that the temperature adjustment module is divided into a temperature adjustment module 100a on the upstream side of the solution for the seed crystal 10 and a temperature adjustment module 100b on the downstream side, and the temperature adjustment module 100a on the upstream side. The temperature (Tb) of the temperature adjustment module 100b on the downstream side of the temperature (Ta) is increased (Ta <Tb).
The organic crystal-attached substrate manufacturing apparatus shown in FIG. 7 uses separate temperature control modules 100a and 100b on the upstream side and the downstream side of the seed crystal 120 with respect to the flow direction of the solution 112 (arrow P40, 41 direction). The degree of supersaturation of the solution 112 on the downstream side of the crystal production substrate 101 can be reduced, and generation and growth of unnecessary crystals (miscellaneous crystals) can be suppressed.

8A is a cross-sectional view showing another embodiment of the crystal production substrate and the cell substrate shown in FIG. 1, and FIG. 8B is a cross-sectional view taken along the line VIIIb-VIIIb of FIG. 8A. .
The difference between the embodiment shown in FIGS. 8A and 8B and the embodiment shown in FIGS. 6A and 6B is that a recess is formed on the downstream side of the solution with respect to the seed crystal 120 of the crystal production substrate 101. 800 is formed.
In this way, by increasing the distance between the crystal production substrate 101 and the cell substrate 103 on the downstream side of the seed crystal 120 with respect to the solution flow direction (arrow P42 to P46 direction), the miscellaneous crystal on the downstream side. Can prevent clogging.

FIG. 9A is a schematic view showing another embodiment of the cell module used in the organic crystal-attached substrate manufacturing apparatus shown in FIG. 1, and FIG. 9B is a line IXb-IXb in FIG. 9A. It is sectional drawing.
FIG. 10A is a diagram showing a state in which the space between the crystal production substrate and the cell substrate of the cell module shown in FIG. 9A is widened, and FIG. 10B is a diagram of FIG. It is Xb-Xb sectional view taken on the line.
The difference between the apparatus shown in FIGS. 9A and 9B and the apparatus shown in FIG. 1 is that the cell module is placed on the crystal production substrate 101 so as to form the outer periphery of the minute gap 301 and is elastic. An annular seal member 900 made of a body, a cell substrate 103 arranged so as to press the seal member 900, and micrometers 205a and 205b as adjusting means for adjusting a predetermined interval are provided.
As the crystal grows, the flow of the solution 112 (see FIG. 1) (in the direction of arrows P47 to P51) is suppressed by the grown crystal itself, and the cross section of the flow path of the solution 112 becomes narrow. Therefore, by increasing the distance between the crystal production substrate 101 and the cell substrate 103 stepwise or steplessly (FIGS. 10A and 10B), the flow path of the solution 112 is secured, and the solution 112 The flow can be kept constant, and stable crystal growth can be performed. The sealing member 900 between the crystal production substrate 101 and the cell substrate 103 is a member whose thickness changes with pressure (for example, silicone rubber), and the minute gap 301 is accurately formed by an adjusting means having a micrometer function. It is possible to control the interval. The seal member 900 only needs to be resistant to the solution 112, and Viton (trade name) or the like may be used.

FIG. 11 is a diagram showing the shape and orientation of a DAST crystal as a seed crystal.
In the figure, a DAST crystal is shown together with coordinate axes. The DAST crystal 120 belongs to the monoclinic system, the space group Ce, and the point group m (SR Marder, JW Perry, CP Yakimysyn, Chem. Mater., 6, 1137 (1994)), The crystal shape is a rhomboid plate. Arrow P55 is the highest priority growth direction.
The a-axis and b-axis of the crystal lie on a rhombus diagonal, and can be distinguished by the angle of the (001) plane 1102. As shown in the figure, (001 plane) 1102 is a flat plane, and (00-1) plane 1101 is a tilted plane. Further, the [100] direction can be distinguished by the direction of the inclined surface from the flat surface of the (00-1) surface 1101.

12A, 12B, and 12C are schematic views of the growth anisotropy of the DAST crystal.
It has been reported that the growth rate of the DAST crystal 120 in methanol is higher in the [100] direction than in the [-100] direction and faster in the [001] direction than in the [00-1] direction (Science Technical Report EMD2001). -44 (2001-08)).

FIGS. 13 (a)-(d) show schematic diagrams of DAST crystal growth versus solution flow. FIG. 13A is a plan view when the flow of the solution and the maximum crystal growth direction are in a relationship of 180 degrees, and FIG. 13B is a side view of FIG. 13A. FIG. 13C is a plan view when the flow of the solution and the maximum growth direction of the crystal are 0 degrees, that is, in the same direction, and FIG. 13D is a side view of FIG. 13A to 13D, the seed crystal 120 has the same size.
The DAST crystal has a fast uptake of molecules into the crystal in the a-axis [100] direction (the crystal growth rate is fast). For this reason, in the direction of fast crystal growth, the solution concentration around the crystal is lower than in other portions. Reduction of the solution concentration around the crystal prevents crystal growth.
Usually, the non-uniform solution concentration is uniformed with time by natural diffusion, but when the crystal growth rate is high, the uniformization by diffusion cannot catch up. Further, as in this embodiment, natural diffusion is more easily suppressed in a minute gap environment. Therefore, by efficiently supplying the solution (that is, molecules constituting the crystal) to the maximum growth direction of the crystal, the crystal can be efficiently grown.
That is, the crystal growth portion 1300 obtained by arranging the seed crystal 120 such that the maximum growth direction (direction of arrow P56) is 180 degrees with respect to the solution flows P57 to P59 (FIGS. 13A and 13B). ) And a crystal growth portion 1301 (FIG. 13C, FIG. 13D) obtained by arranging the seed crystal 120 so that the maximum growth direction (arrow P60 direction) is 0 degrees with respect to the solution flow P61 to P63. )) Clearly shows that the crystal growth portion 1300 is larger than the crystal growth portion 1301.

14A to 14E are explanatory views for explaining the relationship between the (001) plane of the DAST crystal and the flow of the solution.
In FIG. 14A, coordinate axes and the DAST crystal 120 are shown. 1100 is the (00-1) plane, 1101 is the (001) plane, and the direction of arrow P66 is the maximum growth direction.
The growth rate of the DAST crystal 120 is higher in the [001] direction than in the [00-1] direction. Therefore, as shown in FIGS. 14B and 14C, the (001) plane is brought into contact with the crystal production substrate 101 and the maximum growth direction (arrow P67) is fixed to be 180 degrees with respect to the flow of the solution. In this case, since the growth rate in the [00-1] direction is slower than the growth in the [100] direction (a axis), it takes time until the (00-1) plane reaches the cell substrate 103. Therefore, crystal growth can be efficiently performed without hindering the flow of the solution (in the direction of arrow P68) (a thin film crystal having a large aspect ratio in the [100] (a-axis) direction is obtained).
However, as shown in FIGS. 14D and 14E, the (00-1) plane is brought into contact with the crystal production substrate 101 and the maximum growth direction (arrow P69 direction) is 180 degrees with the solution flow (arrow P70). When the DAST crystal 120 is fixed as described above, the (001) plane having a high growth rate grows with respect to the (00-1) plane, so that the cell substrate 103 is reached in a short time, and the solution is uniform. Is obstructed (in the direction of arrow P70).

FIGS. 15A to 15D are explanatory views for explaining the relationship between the DAST crystal fixed to the crystal production substrate on which the pattern is formed and the flow of the solution.
When the DAST crystal 120 is fixed to the crystal production substrate 101 in which the (001) plane is formed with a pattern (concave portion), it can be produced in a crystal shape reflecting the structure of the crystal production substrate 101.
That is, as shown in FIGS. 15A and 15B, the (001) plane is brought into contact with the crystal production substrate 101 on which the pattern 1500 (concave portion) is formed, and the maximum growth direction (direction of arrow P71) is the flow of the solution. When the DAST crystal 120 is fixed so as to be 180 degrees (in the direction of arrow P72), the DAST crystal 1501 including the volume of the pattern (concave portion) 1500 is obtained.
Further, as shown in FIGS. 15C and 15D, the (001) plane is in contact with the crystal production substrate 101 on which a pattern (concave portion) 1502 smaller than the pattern 1500 is formed, and the maximum growth direction (direction of arrow P73). When the DAST crystal 120 is fixed so as to be 180 degrees with the flow of the solution (in the direction of the arrow P74), the DAST crystal 1503 including the volume of the pattern (concave portion) 1502 is obtained.

It is the schematic which shows one Example of the board | substrate preparation apparatus with an organic crystal to which the board | substrate preparation method with an organic crystal of this invention is applied. (A) is the cross-sectional view which shows one Example of the crystal production board | substrate and cell substrate which were shown in FIG. 1, (b) is the IIb-IIb sectional view taken on the line of (a), (c) is (b) 2 is an enlarged view of the seed crystal shown in FIG. (A), (b) is a figure which shows the relationship between the preferential growth direction of a seed crystal, and the flow of a solution. (A) is the cross-sectional view which shows the other Example of the crystal production board | substrate and cell substrate which were shown in FIG. 1, (b) is the IVb-IVb sectional view taken on the line of (a). (A) is the cross-sectional view which shows the other Example of the crystal production board | substrate and cell substrate which were shown in FIG. 1, (b) is the Vb-Vb sectional view taken on the line of (a). (A) is the cross-sectional view which shows the other Example of the crystal production board | substrate and cell substrate which were shown in FIG. 1, (b) is VIb-VIb sectional view taken on the line of (a). It is the schematic which shows the other Example of the board | substrate preparation apparatus with an organic crystal to which the board | substrate manufacturing method with an organic crystal of this invention is applied. (A) is the cross-sectional view which shows the other Example of the crystal production board | substrate and cell substrate which were shown in FIG. 1, (b) is the VIIIb-VIIIb sectional view taken on the line of (a). (A) is the schematic which shows the other Example of the cell module used for the board | substrate preparation apparatus with an organic crystal shown in FIG. 1, (b) is the IXb-IXb sectional view taken on the line of (a). (A) is a figure which shows the state which expanded the space | interval between the crystal production board | substrate of a cell module shown to Fig.9 (a), and a cell substrate, (b) is the Xb-Xb sectional view taken on the line of (a). It is. It is a figure which shows the shape and orientation of a DAST crystal as a seed crystal. (A), (b), (c) is the schematic of the growth anisotropy of a DAST crystal. (A)-(d) shows a schematic representation of DAST crystal growth with respect to solution flow. (A)-(e) is explanatory drawing for demonstrating the relationship between the (001) plane of a DAST crystal, and the flow of a solution. (A)-(d) is explanatory drawing for demonstrating the relationship between the DAST crystal fixed to the crystal production substrate in which the pattern was formed, and the flow of a solution. It is a figure which shows the molecular structure of 4-dimethylamino-N-methyl-4-stilbazolium tosylate. It is a solubility curve with respect to methanol of 4-dimethylamino-N-methyl-4-stilbazolium tosylate.

Explanation of symbols

100, 150 Temperature adjustment module 101 Crystal production substrate 103 Cell substrate 104 Liquid feed pump 105, 106 Flow path 108 Constant temperature bath 112 Solution 113 Supply unit 114 Discharge unit 120 Seed crystal (DAST crystal)
130 Solution Holding Unit 151 Reservoir 152 Circulating Means 153 Frame-Shaped Members 154a, 154b Fixing Screw 200 Holding Means 301 Sealed Space (Micro Gap)

Claims (5)

In an organic crystal-attached substrate manufacturing apparatus for manufacturing a film-like organic crystal on a crystal manufacturing substrate by using a temperature difference method for controlling the temperature of a solution in which the organic crystal is dissolved,
A temperature adjustment module for adjusting the temperature of the crystal production substrate in which the seed crystal is arranged in the crystal production region;
A cell module which is placed on the crystal production substrate and forms a sealed space having a predetermined interval with the crystal production substrate;
Holding means disposed on the temperature adjustment module and detachably holding the crystal production substrate and the cell module;
A circulation unit that circulates the solution between the sealed space and the solution holding unit through flow paths connected to a supply unit and a discharge unit that penetrate the cell module and communicate with the sealed space, respectively. The substrate for producing an organic crystal is characterized in that the crystal production substrate has a recess formed on the downstream side of the solution with respect to the seed crystal . In an organic crystal-attached substrate manufacturing apparatus for manufacturing a film-like organic crystal on a crystal manufacturing substrate by using a temperature difference method for controlling the temperature of a solution in which the organic crystal is dissolved,
A temperature adjustment module for adjusting the temperature of the crystal production substrate in which the seed crystal is arranged in the crystal production region;
A cell module which is placed on the crystal production substrate and forms a sealed space having a predetermined interval with the crystal production substrate;
Holding means disposed on the temperature adjustment module and detachably holding the crystal production substrate and the cell module;
A circulation unit that circulates the solution between the sealed space and the solution holding unit through flow paths connected to a supply unit and a discharge unit that penetrate the cell module and communicate with the sealed space, respectively. ,
The cell module is an annular seal member made of an elastic body placed on the crystal production substrate so as to form an outer peripheral portion of the sealed space, and a cell substrate arranged to press the seal member; the features and organic crystal substrate with manufacturing apparatus you that an adjusting means for adjusting a predetermined distance. In a method for producing a substrate with an organic crystal, which produces a film-like organic crystal on a crystal production substrate by using a temperature difference method for controlling the temperature of a solution in which the organic crystal is dissolved,
A seed crystal is arranged on the crystal production substrate, the cell module is held on the crystal production substrate so that the seed crystal is located in a sealed space and at a predetermined interval, and the cell module is penetrated to form the sealed The solution is circulated between the sealed space and the solution holding unit through flow paths respectively connected to a supply unit and a discharge unit communicating with the space, and the solution for the seed crystal is downstream of the crystal preparation substrate. A method for producing a substrate with an organic crystal, comprising using a substrate having a recess formed on a side thereof. In a method for producing a substrate with an organic crystal, which produces a film-like organic crystal on a crystal production substrate by using a temperature difference method for controlling the temperature of a solution in which the organic crystal is dissolved,
A seed crystal is arranged on the crystal production substrate, the cell module is held on the crystal production substrate so that the seed crystal is located in a sealed space and at a predetermined interval, and the cell module is penetrated to form the sealed The solution is circulated between the inside of the sealed space and the solution holding unit through flow paths connected to a supply unit and a discharge unit communicating with the space, and an outer peripheral portion of the sealed space is formed as the cell module. An annular sealing member made of an elastic body placed on the crystal production substrate, a cell substrate arranged to press the sealing member, and an adjusting means for adjusting the predetermined interval A method for producing a substrate with an organic crystal, comprising using a module . In a method for producing a substrate with an organic crystal, which produces a film-like organic crystal on a crystal production substrate by using a temperature difference method for controlling the temperature of a solution in which the organic crystal is dissolved,
A seed crystal is arranged on the crystal production substrate, the cell module is held on the crystal production substrate so that the seed crystal is located in a sealed space and at a predetermined interval, and the cell module is penetrated to form the sealed The solution is circulated between the sealed space and the solution holding unit through channels connected to the supply unit and the discharge unit communicating with the space, respectively, and the surface of the seed crystal is dissolved at the start of crystal production. wherein the organic crystal substrate with a manufacturing method you that crystal growth occurs from.

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