WO2020178924A1

WO2020178924A1 - Vapor deposition device and display apparatus manufacturing method

Info

Publication number: WO2020178924A1
Application number: PCT/JP2019/008213
Authority: WO
Inventors: 真伸水崎; 敏明大下
Original assignee: シャープ株式会社
Priority date: 2019-03-01
Filing date: 2019-03-01
Publication date: 2020-09-10

Abstract

This vapor deposition device (3) is provided with a vapor deposition source (1) having: a case (4) that has an opening (4K) and in which a mixture of a first vapor deposition material (71) and a second vapor deposition material (72) is housed; and a top plate (5) that is attached to the opening in an airtight manner and that is provided with a first nozzle (5S) and second nozzles (5N). A coating layer (41) containing a siloxane group is at least partially formed on the inner surface of the case and/or the inner surface of the top plate.

Description

Manufacturing method of thin-film deposition equipment and display equipment

The present invention relates to a method for manufacturing a vapor deposition device and a display device.

Patent Document 1 discloses that in an organic EL display device, a red light emitting layer and a green light emitting layer are formed by a vapor deposition method using a mixed material containing a low molecular material and a high molecular material as a plurality of types of vapor deposition materials. Has been done. Further, Patent Document 2 discloses a vapor deposition apparatus for co-evaporating a mixed material containing a plurality of types of vapor deposition materials.

Japanese Patent Laid-Open Publication "JP 2012-028764" International Publication No. 2012/10533 Pamphlet

However, when the vapor deposition process is performed by using the premix type mixed material containing a plurality of types of vapor deposition materials as described above, the mixing ratio of the vapor deposition materials varies while the vapor deposition process is repeated. It was also found that the ratio of each vapor deposition material in the vapor deposition film after vapor deposition may be different from the ratio of each vapor deposition material in the mixed material introduced into the vapor deposition source before vapor deposition.

The present invention has been made in view of the above problems, and an object thereof is to prevent the mixing ratio of each vapor deposition material from varying during repeated vapor deposition processing in co-evaporation of a plurality of vapor deposition materials. An object of the present invention is to provide a method for manufacturing a vapor deposition device and a display device.

In order to solve the above problems, a vapor deposition device according to one embodiment of the present invention has an opening on an upper side, a housing in which a mixture of a plurality of kinds of evaporation materials is accommodated, and the opening of the housing. Attached in an airtight manner, and a top plate provided with a plurality of nozzles for ejecting vapor deposition particles obtained by vaporizing the plurality of types of vapor deposition materials, and a vapor deposition source having, and the inner surface of the casing and the top plate. A coating layer containing a siloxane group is formed on at least a part of at least one of the inner surfaces.

In order to solve the above problems, a method for manufacturing a display device according to one embodiment of the present invention includes a housing having an opening on an upper side and containing a mixture of a plurality of kinds of evaporation materials; A top plate, which is attached to the opening in an airtight manner and has a plurality of nozzles for ejecting vapor deposition particles obtained by vaporizing the plurality of types of vapor deposition materials, and a vapor deposition source having: A vapor deposition apparatus in which a coating layer containing a siloxane group is formed on at least a part of at least one of the inner surfaces of the top plate, the vapor deposition material accommodating step of accommodating the plurality of types of vapor deposition materials in the housing, and A temperature raising step of raising the temperature of the housing to a temperature higher than the vaporization temperature of each of the plurality of types of vapor deposition materials, a vapor deposition substrate loading step of loading the vapor deposition substrate into the vapor deposition apparatus, and the vapor deposition substrate to the vapor deposition substrate described above. It includes a co-deposited step of co-depositing a plurality of types of vapor-deposited materials and a step of carrying out the vapor-deposited substrate from the vapor deposition apparatus.

According to one embodiment of the present invention, there is provided a vapor deposition device and a method for manufacturing a display device capable of suppressing a change in a mixing ratio of vapor deposition materials during repeated vapor deposition processing in co-evaporation of a plurality of types of vapor deposition materials. can do.

FIG. 3 is a partial perspective view showing a schematic configuration of a main part of the vapor deposition device according to the first embodiment. FIG. 2 is a partial cross-sectional view showing a schematic configuration of a main part of the vapor deposition device shown in FIG. 1. (A) is a plan view showing a schematic configuration of an upper surface of a top plate according to the first embodiment, and (b) is a cross-sectional view schematically showing the housing and the top plate according to the first embodiment. FIG. 3 is a diagram showing an example of vibration of the vibration device according to the first embodiment. FIG. 6 is a diagram showing another example of vibration of the vibrating device according to the first embodiment. It is a flowchart which shows the formation process of the coating layer shown in FIG. FIG. 4 is a cross-sectional view showing a part of the process of forming the coating layer shown in FIG. 2. FIG. 6 is a cross-sectional view showing another part of the process of forming the coating layer shown in FIG. 2. It is a flowchart which shows the formation process of the vapor deposition film shown in FIG. (A) is a top view which shows the schematic structure of the upper surface of the top plate used in Example 3, and FIG. (b) simplifies and shows the housing and top plate of the vapor deposition source used in Example 3. It is a sectional view. 6 is another plan view showing the schematic configuration of the top surface of the top plate according to Embodiment 1. FIG. 5 is a partial cross-sectional view showing a schematic configuration of a main part of the vapor deposition device according to Embodiment 2. FIG.

[Embodiment 1]
FIG. 1 is a partial perspective view showing a schematic configuration of a main part of a vapor deposition device 3 according to this embodiment. FIG. 2 is a partial cross-sectional view showing a schematic configuration of a main part of the vapor deposition device 3 shown in FIG. 2 shows a vertical cross section of the vapor deposition device 3 in which the vapor deposition source 1, the deposition preventive plate 6, and the tube portion 7 are extracted from the vapor deposition device 3. Further, for convenience of illustration, the thickness of the coating layer 41 is exaggerated in FIG. For convenience of illustration, in FIG. 2, the housing 4, the top plate 5, and the deposition preventive plate 6 are shown separated from each other, but the housing 4, the top plate 5, and the deposition protection plate 6 are actually airtight. It is in close contact. Further, in FIGS. 1 and 2, the number of nozzles is omitted for convenience of illustration.

As shown in FIG. 1, the vapor deposition device 3 includes a vapor deposition source 1 that ejects vapor deposition particles, and a vapor deposition rate detecting crystal resonator 2 that detects the vapor deposition rate of the vapor deposition particles. The vapor deposition apparatus forms (deposits) a vapor deposition film 61 on a substrate 52, which is a film formation substrate, as a vapor deposition film 61 by simultaneously vapor depositing (co-evaporating) a plurality of types of vapor deposition materials.

The vapor deposition source 1 has an opening 4K (upper side opening) on the upper side, a housing 4 in which the vapor deposition material is housed, a top plate 5 that covers the opening 4K, and a vibrating device 11. ing. The housing 4 may be a crucible or a vapor deposition boat. The top plate 5 is airtightly attached to the opening 4K of the housing 4. The top plate 5 is provided with a plurality of nozzles that eject (discharge) the vapor deposition material housed in the housing 4 as vapor deposition particles.

The housing 4 contains a mixture of a plurality of types of vapor deposition materials (mixed material) as the vapor deposition material. Specifically, the housing 4 contains a mixture of a plurality of types of vapor deposition materials having different characteristics as the vapor deposition material. The vaporized materials having different characteristics have different skeleton structures and different molecular weights, densities, vaporization temperatures (sublimation temperature when the vaporized material is a liquid material, evaporation temperature when the vaporized material is a liquid material), and the like. Therefore, the housing 4 accommodates a premix type vapor deposition material including the first vapor deposition material 71 and the second vapor deposition material 72 having a molecular weight larger than that of the first vapor deposition material 71. Examples of such a premix type vapor deposition material include a mixture of two kinds of organic materials for OLED (organic light emitting diode) used as a host material in the green light emitting layer and the red light emitting layer.

The vapor deposition source 1 vaporizes a vapor deposition material containing a first vapor deposition material 71 and a second vapor deposition material 72 (specifically, a mixture of the first vapor deposition material 71 and the second vapor deposition material 72) from the plurality of nozzles. Eject as particles. As a result, the vapor deposition source 1 simultaneously attaches the first vapor deposition material 71 and the second vapor deposition material 72 to the substrate 52. Thus, the vapor deposition film 61 (co-evaporation film) containing the first vapor deposition material 71 and the second vapor deposition material 72 as constituent components is formed.

In addition, in order to manufacture a display device that performs color display as a device provided with the vapor-deposited film 61, it is necessary to separately paint light emitting layers having different emission colors for each pixel. At this time, in order to achieve high definition, an FMM (Fine Metal Mask) provided with a highly accurate mask opening is used as a vapor deposition mask (not shown). The vapor-deposited particles ejected from the plurality of nozzles are formed on the substrate 52 as a thin-film deposition film 61 having a predetermined pattern through a mask opening of a thin-film deposition mask (not shown).

The vapor deposition source 1 includes a first nozzle 5S and a second nozzle 5N as the plurality of nozzles. The first nozzle 5S is a nozzle arranged near the crystal unit 2. The second nozzle 5N is a nozzle arranged at a position farther from the crystal unit 2 than the first nozzle 5S. The first nozzle 5S is, for example, formed so as to be inclined toward the crystal oscillator 2. Since the first nozzle 5S is formed so as to be inclined toward the crystal oscillator 2, the vapor-deposited particles can be more reliably adhered to the crystal oscillator 2. However, the orientation of the first nozzle 5S is not limited to this.

3A is a plan view showing a schematic configuration of the top surface of the top plate 5, and FIG. 3B is a sectional view showing the housing 4 and the top plate 5 in a simplified manner. 3(a) and 3(b), for convenience of illustration, the first nozzle 5S is not shown, and the number of holes 5K is omitted.

The total area of the holes 5K of the first nozzle 5S and the second nozzle 5N on the upper surface of the top plate 5, which is the area of the upper opening hole of the vapor deposition source 1, is 1/20 to 1/8 of the area of the upper surface of the top plate 5. It is desirable that it is within the range of. If the area ratio of the upper openings is less than 1/20, vapor deposition may take too long. Further, if the area ratio of the upper opening holes is larger than 1/8, when the vapor deposition source 1 is vibrated, the vapor deposition material which is not vaporized particles may fly out from the holes 5K as it is.

Also, when the evaporation source 1 is heated, the temperature rises earlier on the outer edge side (that is, the peripheral edge side) than on the center side of the evaporation source 1. Therefore, as shown in FIG. 3A, the holes 5K having an area ratio of 50% or more and 80% or less on the top surface of the top plate 5 are closer to the center of the top plate 5 in a plan view (specifically, It is desirable that the top plate 5 is located within a distance of 1/2 from the center point C on the upper surface of the top plate 5 to the outer edge of the top plate 5. In other words, a region surrounded by a line connecting the points P on the upper surface of the top plate 5 at a distance ½ of the distance between the center point C of the top plate 5 and the outer edge of the top plate 5. It is desirable that the total area of the holes 5K in the inside occupies 50% or more and 80% or less of the total area of the holes 5K on the upper surface of the top plate 5. The holes 5K may be provided so as to straddle the above line, but for simplicity, the holes 5K having an area ratio of 50% or more and 80% or less are, for example, 50% of the total area of the holes 5K. Above, the number of holes 5K corresponding to an area of 80% or less is shown. When the area ratio of the holes 5K existing in the above region is set to 100%, for example, the film thickness change of the formed vapor deposition film 61 becomes remarkable. If the area ratio of the holes 5K existing in the above region is 50% or more and 80%, such a problem does not occur. Therefore, by setting the holes 5K as described above, the first vapor deposition material 71 and the second vapor deposition material 72 are not uniformly distributed (mixed) on the peripheral side of the vapor deposition source 1 due to a rapid temperature rise. It is possible to prevent the vapor deposition from proceeding as it is.

The inner surface of the housing 4 and the inner surface of the top plate 5 (in other words, the surface on which the coating layer 41 is formed) have low reactivity with the vapor deposition material housed in the housing 4 and are made of a material to which the vapor deposition material does not adhere. It is preferably formed of a base material. Specifically, the inner surface of the housing 4 and the inner surface of the top plate 5 are at least one metal selected from the group consisting of, for example, molybdenum (Mo), tungsten (W), tantalum (Ta), and niobium (Nb). Alternatively, it is preferably formed of an alloy thereof or at least one ceramic material (inorganic insulating material) selected from the group consisting of silicon oxide (SiOx), silicon nitride (SiNx), and aluminum nitride (AlN).

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that the deposition material adheres to the inside of the deposition source (specifically, the inner surface of the casing or the inner surface of the top plate). We have come to the conclusion that it is the largest factor in the fluctuation of the ratio.

That is, the inner surface of the vapor deposition source is oxidized by oxygen in the air under high temperature treatment, and then hydrated by moisture (steam) in the air, or reacted with carbon dioxide in the air to be carboxylated. By doing so, at least one of a hydroxyl group and a carboxyl group is formed on the inner surface of the vapor deposition source. The vapor deposition material contained in the vapor deposition source chemically reacts with at least one of the hydroxyl group and the carboxyl group and chemically bonds with the inner surface of the vapor deposition source to form an adhered substance. This deposit is difficult to remove.

In particular, when a mixture of a plurality of types of vapor deposition materials is housed in a housing such as a pit or a vapor deposition boat and left for a certain period of time, for example, the vapor deposition material having a large molecular weight moves below the housing and above the housing. The distribution of the vapor deposition material is biased in the housing because there are many vapor deposition materials with small molecular weights. Therefore, the ratio of each vapor deposition material attached to the inner surface of the vapor deposition source is not constant. Further, when the vapor deposition process is repeated, the vaporized vapor deposition material adheres and sticks to the inner surface of the vapor deposition source. Due to the uneven distribution of the vapor deposition material in the vapor deposition source, the amount of the vapor deposition material sticking to the inner surface of the deposition source is uneven, and the amount of each vapor deposition material adhering to the vapor deposition source due to the difference in the vaporization temperature of each vapor deposition material There is a difference in.

Then, when the vapor deposition source is heated and the vapor deposition film is formed with the distribution of the vapor deposition material in the vapor deposition source biased in this way, a mixed film of the vapor deposition materials is not formed, but extremely. Two layers of respective vapor deposition materials are formed, or the ratio of one vapor deposition material becomes extremely higher than that of the other vapor deposition material. In this case, recombination of holes and electrons in the light emitting layer (EML) becomes difficult to occur, and problems such as a decrease in quantum efficiency of the light emitting element, an increase in driving voltage, and a decrease in life of the light emitting element occur.

Therefore, in the present embodiment, in order to prevent the mixing ratio of each vapor deposition material from changing while the vapor deposition process is repeated in the co-evaporation of a plurality of types of vapor deposition materials, in order to prevent the vapor deposition material from adhering to the vapor deposition source 1. It is important to suppress.

In the present embodiment, at least a part of at least one of the inner surface of the housing 4 and the inner surface of the top plate 5 is covered with a coating layer 41 using a siloxane compound as a material (coating material). Specifically, the coating layer 41 according to the present embodiment is made of a material including a siloxane-based compound, and includes a siloxane (—Si—O—Si—) group (siloxane unit), and is a structural unit derived from the siloxane-based compound. have. Therefore, the coating layer 41 contains a siloxane group. Therefore, the coating layer 41 containing a siloxane group is formed on at least a part of at least one of the inner surface of the housing 4 and the inner surface of the top plate 5. The coating layer 41 can be formed by chemically reacting a siloxane compound with the above-mentioned base material, and is introduced into at least a part of at least one of the inner surface of the housing 4 and the inner surface of the top plate 5 by a chemical modification method. To be done.

The inner surface of the top plate 5 is an inner surface of the first nozzle 5S and the second nozzle 5N provided on the top plate 5 (specifically, the inner surface of these nozzles defining the holes 5K of these nozzles). May include. In the example shown in FIG. 2, the coating region coated with the coating layer 41 (the surface on which the coating layer 41 is formed) includes the corner 4b formed by the side surface 4a and the bottom surface 4c on the inner surface of the housing 4. In addition, in the example shown in FIG. 2, the covering region defines the holes 5K on the inner surface of the top plate 5, the inner surfaces of the first nozzles 5S and the second nozzles 5N, and the lower surface 5b around the holes 5K. including.

In addition, in FIG. 2, the case where the coating region covered with the coating layer 41 is provided on at least a part of the inner surfaces (that is, the surfaces of the inner walls) of the housing 4 and the top plate 5 is taken as an example. It is shown in the figure. However, the present embodiment is not limited to this, and the bottom surface of the housing 4 or the side surface of the housing 4 may be used as at least a part of at least one of the inner surface of the housing 4 and the inner surface of the top plate 5. Alternatively, the covering region may be provided on any of the inner surfaces of the first nozzle 5S and the second nozzle 5N of the top plate 5.

“Siloxane compound” is a general term for silicic acid organic compounds having a skeleton of a siloxane unit in which silicon (Si), which is an inorganic component, and —O— groups having polarity are alternately bonded.

When the vapor deposition material is, for example, an organic material for OLED as described above, a π-conjugated organic material having a low polarity is used as the vapor deposition material. Si, which is an inorganic component in siloxane, does not adsorb organic materials (organic compounds). Further, the —O— group in the siloxane also has a large electronegativity and polarity due to the influence of unpaired electrons, and is not compatible with the organic material for OLED.

The siloxane-based compound is not particularly limited, but is, for example, at least one compound selected from the group consisting of a compound represented by the following structural formula (1) and a compound represented by the following structural formula (2). Is mentioned. In the structural formula (1) below, R1 and R2 each independently represent an alkyl group or an alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 to 24 (desirably, 4 to 18). Indicates. In the structural formula (2), R3 and R4 each independently represent an alkyl group or an alkylene group having 2 to 6 carbon atoms, and m is an integer of 1 to 24 (preferably 4 to 18). Indicates.

In the coating layer 41, the siloxane compound preferably has an epoxy group like the compound represented by the structural formula (1) or (2). The epoxy group has high reactivity with the base material forming the inner surface of the housing 4 and the inner surface of the top plate 5, and the surface of the base material can be chemically modified.

The inner surface of the housing 4 and the inner surface of the top plate 5 (specifically, the surface of the base material forming these inner surfaces) are oxygen (O ₂ ), carbon dioxide (CO ₂ ), water vapor (H ₂ O), and By reacting with at least one gas of hydrocarbons, at least a part of the surface thereof is oxidized, hydroxylated or carboxylated. The surface of the base material is reacted with, for example, carbon dioxide or hydrocarbon in the air under high temperature heat treatment (for example, about 200° C. or lower) to bond carbon molecules to at least a part of the surface of the base material. .. As an example, when the surface of the base material reacts with carbon dioxide under the high-temperature heat treatment, for example, a carboxyl group is formed on at least a part of the surface of the base material. The surface of the base material forms an oxide film by being oxidized by oxygen or carbon dioxide in the air, for example. This oxide film reacts with moisture (water vapor) in the air, or, as will be described later, at least a part of at least one of the inner surface of the housing 4 and the inner surface of the top plate 5 (that is, coated with the coating layer 41). The surface of the substrate on at least part of at least one of the inner surface of the housing 4 and the inner surface of the top plate 5 (in other words, the inner surface of the housing 4 and A hydroxyl group is formed on at least a part of at least one of the inner surfaces of the top plate 5 on which the coating layer 41 is formed).

In the present embodiment, as will be described later, at least a part of at least one of the inner surface of the housing 4 and the inner surface of the top plate 5, which is the surface on which the coating layer 41 is formed, is immersed in weakly basic water. At least a hydroxyl group among the above-mentioned hydroxyl group and carboxyl group is formed on the formation surface of the coating layer 41. When the base material comes into contact with the siloxane-based compound, the hydroxyl group or the carboxyl group reacts with, for example, an epoxy group in the siloxane-based compound, and the surface of the base material is siloxane-crosslinked with the siloxane-based compound. As a result, at least a part of the inner surface of the housing 4 and the inner surface of the top plate 5 is coated with the coating layer 41 having a siloxane group on the surface.

As described above, for example, when the base material is W (tungsten), the surface of W reacts with at least one gas of O ₂ , CO ₂ , H ₂ O, and hydrocarbons to generate, for example, WC. (OH) or WCOOH. Therefore, for example, when WC(OH) is bonded to the epoxy group of the siloxane compound represented by the structural formula (1) or (2), —CH(OH)CH ₂ OCW is formed, and the surface of the substrate is A component having a siloxane unit (siloxane bond) bonded to the epoxy group in the siloxane compound represented by the structural formula (1) or (2) via —CH(OH)CH ₂ OC— A coating layer 41 including (structural unit) is formed.

Alternatively, as described above, for example, when the base material is AlN, AlN becomes Al(OH) ₃ when contacted with water, for example. Next, when Al(OH) ₃ is bonded to the epoxy group of the siloxane compound represented by the structural formula (1) or (2), —CH(OH)CH ₂ OAl(OH) ₂ is formed. Then, as the reaction proceeds further, —(CH(OH)CH ₂ O) ₃ Al is formed. As a result, the epoxy group in the siloxane compound represented by the structural formula (1) or (2) is bonded to the surface of the base material via —(CH(OH)CH ₂ O) ₃ —. A coating layer 41 containing a component (structural unit) having a siloxane unit (siloxane bond) is formed. Examples of the ceramic material made of AlN include “Shapal (registered trademark)” manufactured by Tokuyama Corporation, but the present embodiment is not limited to this.

Further, as shown in FIGS. 1 and 2, the vapor deposition source 1 includes deposition

preventive plates

6 and 8 for preventing the vapor deposition particles from flying to the film formation unnecessary region, and an angle limiting plate 9 for limiting the flight angle of the vapor deposition particles.・ 10 and more are provided. The deposition-preventing

plates

6 and 8 are provided on each end of the housing 4 in the direction orthogonal to the scanning direction of the vapor deposition source 1 (in other words, the arrangement direction of the first nozzle 5S and the second nozzle 5N). .. The

angle limiting plates

9 and 10 are provided on each end of the housing 4 in the scanning direction of the vapor deposition source 1 (in other words, the direction orthogonal to the arrangement direction of the first nozzles 5S and the second nozzles 5N). ..

The deposition-inhibiting plate 6 of the deposition-inhibiting

plates

6 and 8 adjacent to the crystal oscillator 2 is provided between the first nozzle 5S and the crystal oscillator 2, and is connected to the crystal oscillator 2 through the first nozzle 5S. A tube portion 7 having a first conduction opening 7K capable of inducing vapor-deposited particles is provided. The first nozzle 5S side of the tube portion 7 is connected to the deposition preventing plate 6. The adhesive plate 6 is provided with a second conduction opening 6K that communicates with the first conduction opening 7K of the pipe portion 7. The inner surfaces of the pipe portion 7 and the protective plate 6 are each coated with the coating layer 41. The inner surfaces of the tube portion 7 and the deposition preventing plate 6 are the inner surface of the tube portion 7 defining the first conduction opening 7K, the inner surface of the deposition preventing plate 6 defining the second conduction opening 6K, and , The surface of the deposition-inhibiting plate 6 on the side of the first nozzle 5S.

The vibrating device 11 is a vibration-type stirring device that vibrates the housing 4 (that is, the vapor deposition source 1) to cause the vapor deposition material in the housing 4 to flow and stir. In other words, the vibrating device 11 is a kinetic energy supply device (vapor deposition material flowing device) that applies kinetic energy to the vapor deposition material in the housing 4 to flow (move) the vapor deposition material. By applying vibration to the housing 4, the vibrating device 11 applies kinetic energy to the vapor-deposited material in the housing 4 to cause the vapor-deposited material to flow (exercise).

The vibration device 11 applies, for example, at least one of horizontal vibration, vertical vibration, and tilt vibration to the vapor deposition source 1, so that the vapor deposition material in the housing 4 has horizontal vibration, vertical vibration, and At least one vibration of tilt vibration is applied.

Here, the lateral vibration means vibration that moves the vapor deposition source 1 or the vapor deposition material in the horizontal direction. The vertical vibration means a vibration that moves the vapor deposition source 1 or the vapor deposition material in a direction perpendicular to the horizontal direction. The tilt vibration indicates a vibration that tilts the vapor deposition source 1 with respect to the horizontal direction. It is desirable that the vertical vibration can move the vapor deposition source 1 by a distance of 1/10 or more of the vertical length of the vapor deposition source 1 (that is, the length between the upper end and the lower end of the vapor deposition source 1). Further, it is desirable that the tilt vibration can tilt the vapor deposition source 1 in the horizontal direction within a range of, for example, ± 45 °.

The vibration conditions such as the type and combination of vibrations, the number of vibrations of each vibration per unit time, and the vibration time of each vibration are not particularly limited, and the first vapor deposition material 71 and the second vapor deposition material 72 are sufficiently uniform. It may be set appropriately so that it is mixed.

Since the housing 4, the top plate 5, and the deposition preventive plate 6 are airtightly adhered to each other, the vibration device 11 applies the above vibration to the vapor deposition source 1 together with the deposition preventive plate 6.

The configuration of the vibration device 11 is not particularly limited as long as it can apply at least one vibration of lateral vibration, vertical vibration, and tilt vibration to the vapor deposition source 1. The vibration exciter 11 includes, for example, a drive unit including a motor (XYθ drive motor) such as a stepping motor (pulse motor), rollers, gears, an XYZ stage, etc., and a drive control unit such as a motor drive control unit. The vapor deposition source 1 may be moved by driving the drive unit by the drive control unit. In addition, for example, a reciprocating motion in the lateral direction may be performed by a moving mechanism including a linear guide and a ball screw or a moving mechanism including a piston. The tilt vibration may be performed. Further, the vibration device 11 may be a shaker, a vibration device using an electromagnet or the like, or a vibration device using ultrasonic waves.

4 and 5 are diagrams showing an example of vibration of the vibration device 11. As described above, the vibration device 11 only needs to be able to apply at least one of lateral vibration, vertical vibration, and tilt vibration to the vapor deposition source 1, but as shown in FIGS. More preferably, at least one of tilt vibration and lateral vibration and vertical vibration can be applied to the vapor deposition source 1. For example, as shown in FIG. 4, vertical vibration is performed after tilt vibration, or, as shown in FIG. 5, vertical vibration is performed after horizontal vibration, so that the first vapor deposition material 71 and the second vapor deposition material 72 are more effectively separated from each other. It can be mixed efficiently and uniformly. Note that the lateral vibration, the vertical vibration, and the tilt vibration may be performed by repeating at least two types of vibration in a fixed order or simultaneously.

<Process of forming coating layer 41>
Next, the process of forming the coating layer 41 will be described below with reference to FIGS. 6 to 8.

In the following, a case where at least a hydroxyl group is formed on the surface of the base material on a part of the inner surface of the housing 4 by step S3 will be described as an example. However, as described above, it is sufficient that a carboxyl group or a hydroxyl group is formed on the surface where the coating layer 41 is formed, and in step S3, at least one of the carboxyl group and the hydroxyl group may be formed. In the case where a carboxyl group is formed on the surface of the base material on a part of the inner surface of the housing 4 in step S3, the surface of the base material on a part of the inner surface of the housing 4 is formed with the weakly basic water shown in FIG. As described above, it may be reacted with carbon dioxide, for example, before immersing in 22 or without the step of immersing in weakly basic water 22 shown in FIG. 7.

FIG. 6 is a flow chart showing a forming process of the coating layer 41 shown in FIG. 7 and 8 are cross-sectional views each showing a part of the process of forming the coating layer 41 shown in FIG.

First, as shown in FIG. 6, the surface of the housing 4 is washed with an organic solvent (step S1). As the organic solvent, for example, acetone, ethanol, isopropyl alcohol or the like can be used. Step S1 is a step of cleaning the surface of the housing 4. Therefore, instead of cleaning with an organic solvent, the housing 4 may be cleaned by adopting another method such as burning off contaminants by ignition at 50 to 350 ° C. If the surface of the housing 4 is clean, step S1 may be omitted.

Next, as shown in FIG. 7, the uncoated region of the surface of the housing 4 that is not covered with the coating layer 41 is sealed with the sealing material 20 (step S2). Step S2 is a step for preventing the formation of the hydroxyl group and the coating layer 41 in the non-covered area. Therefore, step S2 may be omitted when the prevention is performed by another method or when the coating layer 41 is formed on the entire inner surface of the housing 4. Further, it is not necessary to seal all of the non-coated area, and a part of the non-coated area which is soaked in at least one of the weakly basic water and the solution 24 containing the siloxane compound used in step S5 described later is used. , It is enough if it is sealed.

The sealing material 20 is a material that does not chemically react with the weakly basic water 22 and the solution 24 in the uncoated region. Further, the sealing material 20 is a material capable of shielding the uncoated region from the weakly basic water 22 and the solution 24. As the sealing material 20, for example, an acrylic sealing material or a methacrylic sealing material may be used. Further, as the solvent for dissolving the siloxane compound used in the solution 24, for example, acetone, ethanol, NMP (N-methyl-2-pyrrolidone) and the like are used.

Then, as shown in FIG. 7, by pouring weakly basic (about pH 8 to 9) water 22 into the housing 4 and allowing it to stand overnight (12 hours or more), the coating layer on the inner surface of the housing 4 is removed. At least a hydroxyl group is formed in the coating region forming 41 (step S3). The weakly basic water 22 is, for example, an aqueous potassium hydrogen carbonate solution having a concentration of 10 ⁻⁴ mol/L. Even if step S3 is not performed, the surface of the housing 4 is somewhat hydroxylated by the moisture in the air. Therefore, step S3 can be omitted. However, performing step S3 can increase the density of hydroxyl groups in the coating region. Therefore, it is preferable to perform step S3 in order to increase the density of the coating layer 41 formed in step S5. Instead of the weakly basic water 22, neutral water or a strongly basic aqueous solution such as an aqueous potassium hydroxide solution may be used. However, when neutral water is used, the reaction rate of forming a hydroxyl group is slow. Moreover, when a strongly basic aqueous solution is used, side reactions other than the formation of hydroxyl groups are likely to occur. For this reason, it is preferable to use weakly basic water 22.

Next, the water 22 is discharged from the inside of the housing 4 to completely dry the housing 4 (step S4). When step S3 is omitted, step S4 is also omitted.

Next, as shown in FIG. 8, the above solution 24 is poured into the housing 4 and left to stand for about 10 hours while keeping the temperature at 30 ° C. or higher. As a result, the coating layer 41 is formed on the covered area of the inner surface of the housing 4 (step S5). Then, the solution 24 is discharged from the housing 4.

Next, the sealing material 20 is removed (step S6). When step S2 is omitted, step S6 is also omitted. Note that step 6 may be performed after step 7 described below or after step S8.

Next, the housing 4 is washed with an organic solvent (step S7), and the housing 4 is completely dried (step S8). In step S7, at least the surface of the coating layer 41 is cleaned, preferably in addition, the uncoated area after the sealing material 20 is peeled off. The same organic solvent as the organic solvent in step S1 can be used as the organic solvent in step S7.

By the above steps, it is possible to form the coating layer 41 in a desired coating region on the inner surface of the housing 4. The coating layer 41 may be formed only on the side surface 4a or may be formed only on the bottom surface 4c. Further, it may be formed only on a part of at least one of the side surface 4a and the bottom surface 4c. Further, the top plate 5, the tube portion 7, and the adhesion-preventing plate 6 can also be formed with the coating layer 41 in a desired coating region by the same method as described above. The coating layer 41 formed on at least a part of the inner surface of any one or more of the housing 4, the top plate 5, the adhesion-preventing plate 6, and the tube portion 7 is included in the technical scope of the present invention. .. Further, a method for manufacturing a vapor deposition apparatus including the above-mentioned forming step of the coating layer 41 or a forming step obtained by modifying the coating layer 41 is included in the technical scope of the present invention.

Since the coating layer 41 is firmly bonded to the housing 4 by a siloxane bond, the coating layer 41 is difficult to peel off from the housing 4. Therefore, the risk that the peeled coating layer 41 contaminates the vapor deposition material is low. Further, the coating layer 41 formed on the inner surfaces of the top plate 5, the adhesive plate 6, and the pipe portion 7 is also difficult to peel off.

<Formation process of vapor deposition film 61>
Next, as a vapor deposition film manufacturing method, a process of forming the vapor deposition film 61 will be described below with reference to FIGS. 1, 2, 4, 5, and 9. Note that, in the following, the case where the vapor deposition material is a mixed material of the first vapor deposition material 71 and the second vapor deposition material 72 will be described as an example, but the mixed material includes three or more types of vapor deposition materials. You may stay.

FIG. 9 is a flow chart showing a process of forming the vapor deposition film 61 shown in FIG.

As shown in FIG. 9, first, as a vapor deposition material, a mixed material containing a first vapor deposition material 71 and a second vapor deposition material 72 in a predetermined content ratio is prepared (step S11). Next, the mixed material is supplied into the housing 4 of the vapor deposition source 1 and housed in the housing 4 (step S12, vapor deposition material storage step).

Next, by vibrating the vapor deposition source 1 by the vibrating device 11 as shown in FIG. 4 or FIG. 5, the mixed material accommodated in the housing 4 is made to flow and stirred in the housing 4 (step S13, Deposited material stirring process). As a result, the first vapor deposition material 71 and the second vapor deposition material 72 are uniformly mixed.

Next, the housing 4 is heated to a temperature higher than the vaporization temperature (sublimation temperature or evaporation temperature) of the first vaporized material 71 and the second vaporized material 72, respectively, to raise the temperature of the mixed material (step S14, rise). Warming process). As a result, the first thin-film deposition material 71 and the second thin-film deposition material 72 are vaporized (sublimation when the vapor deposition material is a liquid material, evaporation when the vapor deposition material is a liquid material), respectively, and are shown in FIGS. 1 and 2. The vapor deposition particles are caused to fly from the first nozzle 5S and the second nozzle 5N.

Next, the substrate 52 is loaded into the vapor deposition apparatus 3 (step S15, deposition target substrate loading step).

Subsequently, while monitoring the vapor deposition rate by the vapor deposition particles attached to the crystal oscillator 2, the first vapor deposition material 71 and the second vapor deposition material 72 are co-evaporated on the substrate 52 to form a film at the same time (step S16, co-deposition). Deposition process). As a result, a co-deposited film of the first vapor deposition material 71 and the second vapor deposition material 72 is formed on the substrate 52 as the vapor deposition film 61 having a predetermined pattern.

After that, the vapor-deposited substrate 52 on which the co-evaporation is deposited is carried out from the vapor deposition apparatus 3 (step S17, step of carrying out the substrate to be vapor-deposited).

The steps S15 to S17 are repeated until, for example, a predetermined number of substrates 52 are vapor-deposited or the mixed material contained in the housing 4 becomes a predetermined amount or less. When the vapor deposition is performed on a predetermined number of substrates 52 or the amount of the mixed material contained in the housing 4 becomes less than the predetermined amount, the process returns to step S11, and the mixed material remaining in the housing 4 is the housing. 4 is mixed with the newly supplied mixed material. Note that step S13 may be performed at least between steps S12 and S14, but if necessary, after the substrate 52 after vapor deposition is carried out in step S17, the substrate in step S15 is then carried out. It may be performed before the carry-in of 52 is performed, or may be performed at a desired timing between steps S15 and S17. Depending on the type of the stirring device (vibration device 11 in this embodiment), for example, step S13 may be performed at the same time as the vapor deposition process of step S16.

According to the present embodiment, at least a part of at least one of the inner surface of the housing 4 and the inner surface of the top plate 5 is covered with the coating layer 41 containing the siloxane-based compound that does not interact with the organic material. It is possible to prevent the vapor-deposited material from adhering to the region (covered region) covered with the coating layer 41 on the inner surface of the housing 4 and the inner surface of the top plate 5. This can prevent a change in the mixing ratio of the first vapor deposition material 71 and the second vapor deposition material 72 due to the deposition of the vapor deposition material on the inner surface of the housing 4 or the inner surface of the top plate 5, and can be used for film formation. It is possible to reduce the amount of vapor deposition material that is not retained. In addition, cleaning is facilitated, and it is possible to prevent a decrease in vapor deposition rate and a decrease in vapor deposition rate detection accuracy.

Further, according to the present embodiment, as described above, the vapor deposition source 1 is vibrated to cause the vapor deposition material to flow in the housing 4, so that the first vapor deposition material 71 and the second vapor deposition material 72 in the housing 4 are formed. Of the first evaporation material 71 and the second evaporation material 72 in the mixed material of the first evaporation material 71 and the second evaporation material 72 introduced into the housing 4 can be kept uniform. (In other words, the mixing ratio of the first vapor deposition material 71 and the second vapor deposition material 72) and the content ratio of the first vapor deposition material 71 and the second vapor deposition material 72 forming the vapor deposition film 61 formed on the substrate 52. , Are almost equal. Further, the first vapor deposition material 71 and the second vapor deposition material 72 are not unevenly distributed in the vapor deposition film 61, and the vapor deposition film 61 can be uniformly mixed.

The vapor deposition may be performed by ejecting vapor deposition particles from the vapor deposition source 1 toward the substrate 52 with the vapor deposition device 3 and the substrate 52 fixed, and a vapor deposition mask (not shown) fixed to the substrate 52. Good. Further, the vapor deposition is performed by ejecting vapor deposition particles from the vapor deposition source 1 toward the substrate 52 while moving or rotating at least one of the vapor deposition device 3 and the substrate 52 with a vapor deposition mask (not shown) fixed to the substrate 52. May be done. Of course, a vapor deposition mask having a smaller area than the substrate 52 is used as the vapor deposition mask, and the substrate 52, the vapor deposition mask, and the vapor deposition apparatus 3 are in a state where the relative positions of the vapor deposition mask and the vapor deposition source 1 of the vapor deposition apparatus 3 are fixed. You may perform scan vapor deposition or step vapor deposition by relatively moving.

The vapor deposition apparatus 3 is suitably used for manufacturing an organic EL (electroluminescence) display device using, for example, an OLED. A method of manufacturing a display device (for example, an organic EL display device) according to this embodiment includes the above-described vapor deposition film manufacturing method (in other words, steps S11 to S17). Further, the manufacturing method of the display device according to the present embodiment can be traced back to a step of manufacturing the vapor deposition device 3 including a step of forming the coating layer 41 as a step of preparing the vapor deposition device 3 (in other words, the vapor deposition device 3). 3), or as maintenance of the vapor deposition source 1, the step of forming the coating layer 41 on the vapor deposition source 1 is included. Therefore, at least a part of at least one of the inner surface of the housing 4 and the inner surface of the top plate 5 shown in steps S1 to S8 before at least step S12 is used in the method for manufacturing the display device according to the present embodiment. In addition, the step of forming the coating layer 41 made of a material containing a siloxane-based compound (coating layer forming step) is included. The coating layer forming step may be performed before step S12, may be performed before step S11, and may be performed in parallel with step S11 or after step S11. .. In addition, the method of manufacturing the organic EL display device according to the present embodiment includes, for example, a step of forming a first electrode (not shown) on the substrate 52, and an organic layer including at least a light emitting layer on the first electrode. A step of forming the second electrode on the organic layer and a step of forming the second electrode on the organic layer are included, and at least the light emitting layer is formed by the vapor deposition film manufacturing method.

Next, the effects of the vapor deposition device 3 according to this embodiment will be described below with reference to examples and comparative examples. However, the following examples are merely examples, and the present embodiment is not limited to the following examples.

[Example 1]
First, as a mixture of a plurality of types of vapor deposition materials (organic compounds), Alq ₃ (tris (8-quinolinolate) aluminum) represented by the following structural formula (3) and FL-3 (represented by the following structural formula (4)). Three kinds of mixed materials of spiro-(di-(phenyl)-di-(di-3-methylphenyl)amine) were adjusted by changing the content ratio (mixing ratio) of each material.

Alq ₃ is an electron transporting vapor deposition material, and its molecular weight is 459. FL-3 is a hole transporting vapor deposition material, and its molecular weight is 862. Therefore, the molecular weight ratio of both is Alq ₃ :FL-3≈1.0:1.9. Further, the content ratio (Alq ₃ :FL-3) of Alq ₃ and FL-3 in the above-mentioned mixed material is (30:70), (50:50), (70: 30) three conditions.

Next, the above three types of mixed materials having different weight ratios were housed in the housing 4 of the vapor deposition device 3 shown in FIG. 1 having the top plate 5 shown in FIGS. 1 and 3A and 3B. In the vapor deposition source 1 of the vapor deposition apparatus 3, as shown in FIG. 2, the inner surface of the housing 4 and the inner surface of the top plate 5 are made of AlN, and the inner surface of the housing 4 and the first nozzle 5S are formed. An vapor deposition source in which the inner surface of the top plate 5 including the inner surface of the second nozzle 5N was chemically modified (coated) with the siloxane compound represented by the structural formula (1) was used.

Next, as shown in FIG. 4, the vapor deposition source 1 was subjected to tilt vibration at 1 Hz for 5 minutes and then vertical vibration at 1 Hz for 5 minutes by the vibration exciter 11. The tilt vibration and the vertical vibration were alternately repeated three times each. Then, it was heated to 250 ° C. in a vacuum, and the mixed material was deposited on the substrate 52 so as to have a film thickness of 25 nm to form a thin-film deposition film.

After vapor deposition, the ratio of organic compounds in the vapor deposited film was measured by liquid chromatography. As a result, as shown in Table 1, even though the molecular weight ratios of the two kinds of organic materials differ by 1.5 times or more, the content ratio of Alq ₃ and FL-3 in the mixed material before vapor deposition, There was no difference in the content ratio of Alq ₃ and FL-3 in the subsequent vapor deposition film.

[Comparative Example 1]
Vapor deposition having the same structure as in Example 1 except that the coating layer 41 was not formed on the inner surface of the housing 4 and the inner surface of the top plate 5 and that the vibration source 11 did not vibrate the vapor deposition source 1. The same operation as in Example 1 was performed using the apparatus 3. As a result, a vapor deposition film for comparison was formed on the substrate 52.

After vapor deposition, the content ratio of the organic compound in the vapor deposited film was measured by the same method as in Example 1. As a result, as shown in Table 2, when the content ratio of Alq ₃ having a relatively small molecular weight in the mixed material before vapor deposition is high, the content ratio of Alq ₃ in the vapor deposition film after vapor deposition is considerably high. The uneven distribution of each material was confirmed.

[Example 2]
First, as a mixture of a plurality of kinds of vapor deposition materials (organic compounds), Alq _{3 represented} by the structural formula (3) and M-MTDATA(4,4′,4″-) represented by the structural formula (5) below. Three kinds of mixed materials of tris[phenyl(m-tolyl)amino]triphenylamine) were adjusted by changing the content ratio (mixing ratio) of each material.

As described above, Alq ₃ is an electron transporting vapor deposition material, and its molecular weight is 459. M-MTDATA is a hole transporting vapor deposition material, and its molecular weight is 788. Therefore, the molecular weight ratio of the two is Alq ₃ :M-MTDATA≈1.0:1.7. The content ratio of Alq ₃ and M-MTDATA (Alq ₃ : M-MTDATA) in the mixed material is _{3 of} (30:70), (50:50), and (70:30) in weight ratio. It was a condition.

Next, the above three types of mixed materials having different weight ratios were housed in the housing 4 of the vapor deposition device 3 shown in FIG. 1 having the top plate 5 shown in FIGS. 3(a) and 3(b). In the vapor deposition source 1 of the vapor deposition apparatus 3, as shown in FIG. 2, the inner surface of the housing 4 and the inner surface of the top plate 5 are made of AlN, and the inner surface of the housing 4 and the first nozzle 5S are formed. An vapor deposition source in which the inner surface of the top plate 5 including the inner surface of the second nozzle 5N was chemically modified (coated) with the siloxane compound represented by the structural formula (1) was used.

Next, as shown in FIG. 4, the vapor deposition source 1 was subjected to lateral vibration at 1 Hz for 10 minutes by the vibrating device 11, and then subjected to vertical vibration at 1 Hz for 10 minutes. The lateral vibration and the vertical vibration were alternately repeated three times each. After that, the film was heated to 200° C. in a vacuum, and the mixed material was vapor-deposited on the substrate 52 so as to have a film thickness of 25 nm, thereby forming a vapor deposition film.

After vapor deposition, the content ratio of the organic compound in the vapor deposited film was measured by the same method as in Example 1. As a result, as shown in Table 3, the content ratio of Alq ₃ and M-MTDATA in the mixed material before vapor deposition and the vapor deposition were 2 There was no difference in the content ratio of Alq ₃ and M-MTDATA in the subsequent vapor deposition film. It was also confirmed that the same effect can be obtained when lateral vibration is performed instead of tilt vibration.

[Example 3]
By performing the same operation as in Example 1 by using the vapor deposition device 3 having the same structure as in Example 1 except that the coating layer 41 was not formed on the inner surface of the housing 4 and the inner surface of the top plate 5. A vapor deposition film was formed on the substrate 52.

After the vapor deposition, the ratio of the organic compound in the vapor deposited film was measured by the same method as in Example 1. As a result, as shown in Table 4, in the content ratio of the content ratio of Alq ₃ and FL-3 in the mixed material prior to the deposition, the Alq ₃ and FL-3 in the deposited film after deposition, slightly There was a change in. This is because the coating layer 41 was not formed on the inner surface of the housing 4 and the inner surface of the top plate 5, so that the vapor deposition material adhered inside the vapor deposition source 1 (in particular, Alq ₃ having a relatively small molecular weight was It is considered that this is because the amount of Alq ₃ and FL-3 contained in the obtained vapor deposited film slightly changed due to the deposition of a larger amount of FL-3 than that of FL-3). However, compared with Comparative Example 1, the amount of change was small, and even if the content ratio of Alq ₃ having a small molecular weight in the mixed material before vapor deposition was high, uneven distribution of each material was suppressed.

[Example 4]
10A is a plan view showing a schematic configuration of the upper surface of the top plate 5 used in Example 3, and FIG. 10B is a housing 4 of the vapor deposition source 1 used in Example 3. FIG. 3 is a sectional view showing the top plate 5 in a simplified manner. In addition, in FIG. 10A and FIG. 10B, the number of holes 5K is omitted for convenience of illustration. Further, for convenience of illustration, although the number of holes 5K is different between FIG. 10A and FIG. 10B, it goes without saying that the number of holes 5K is actually the same.

In this example, the three types of mixed materials having different weight ratios, which were prepared in the same manner as in Example 1, were replaced with the top plate 5 shown in FIGS. It was housed in the same casing 4 of the vapor deposition device 3 as in Example 1 except that the holes 5K shown in (a) and (b) had top plates 5 provided at equal intervals. In the vapor deposition source 1 of the vapor deposition apparatus 3, as in the first embodiment, the inner surface of the housing 4 and the inner surface of the top plate 5 are made of AlN, and the inner surface of the housing 4 and the first nozzle 5S and An evaporation source was used in which the inner surface of the top plate 5 including the inner surface of the second nozzle 5N was chemically modified (coated) with the siloxane compound represented by the structural formula (1).

Next, the vapor deposition source 1 was subjected to lateral vibration under the same conditions as in Example 2 by the vibrating device 11, and then vertical vibration was applied under the same conditions as in Example 2. The lateral vibration and the vertical vibration were alternately repeated three times each, as in Example 2. Then, as in Example 1, a vapor-deposited film was formed by heating to 250 ° C. in a vacuum and depositing the mixed material on the substrate 52 so as to have a film thickness of 25 nm.

After the vapor deposition, the ratio of the organic compound in the vapor deposited film was measured by the same method as in Example 1. As a result, as shown in Table 5, when the content ratio of Alq ₃ having a relatively small molecular weight is as high as 70%, the content ratio of Alq _{3 in} the vapor deposition film after vapor deposition is Alq ₃ in the mixed material before vapor deposition. _It was slightly higher than the content ratio of ₃ . Therefore, it was confirmed that it is also important that the location of the hole 5K is near the center of the top plate 5 in plan view.

<Modification>
FIG. 11 is another plan view showing a schematic configuration of the top surface of the top plate 5. The shape of the top plate 5 is not particularly limited, and for example, as shown in FIG. 11, it may be formed in a circular shape in a plan view. Also in this case, like the top plate 5 shown in FIG. 3A, the total area of the holes 5K of the first nozzles 5S and the second nozzles 5N on the top surface of the top plate 5 is 1 of the area of the top surface of the top plate 5. It is desirable to be in the range of /20 to 1/8. Further, on the top surface of the top plate 5, the holes 5K having an area ratio of 50% or more and 80% or less are within a range of a distance of 1/2 from the center point C of the top surface of the top plate 5 to the outer edge of the top plate 5 ( It is desirable to be located in the area surrounded by the line connecting the points P).

[Embodiment 2]
FIG. 12 is a partial cross-sectional view showing a schematic configuration of a main part of the vapor deposition device 3 according to this embodiment. Note that, in FIG. 12, for convenience of illustration, the same components as those shown in FIG. 2 are illustrated in the same method as in FIG. 2. Further, in the present embodiment, differences from the first embodiment will be described, and members having the same functions as the members described in the first embodiment will be designated by the same reference numerals and the description thereof will not be repeated.

As shown in FIG. 12, the vapor deposition device 3 according to the present embodiment is provided with a rotary stirring device 81 instead of the vibration device 11 as the stirring device (kinetic energy supply device). It has the same configuration as the vapor deposition device 3 according to the first embodiment. The stirring device 81 directly stirs the vapor deposition material in the housing 4 to give kinetic energy to the vapor deposition material in the housing 4 to cause the vapor deposition material to flow (exercise).

The stirrer 81 includes, for example, a magnetic stirrer 82 and a stirrer 83 using a magnet. The magnetic stirrer 82 is arranged outside the housing 4. The stirring bar 83 is arranged in the housing 4. The stirring device 81 uses a magnetic stirrer 82 to rotate the stirrer 83 using magnetic force to stir and flow the vapor-deposited material in the housing 4.

Note that, in FIG. 12, the stirring device 81 is illustrated as an example in which the magnetic stirrer 82 and the stirrer 83 are provided, but the stirring device 81 includes, for example, a stirring rod and a stirring rod. It may be a stirrer (mechanical stirrer) having a rotating motor. Further, instead of the stirring rod, for example, a screw type stirring blade or a plurality of pedal-shaped stirring blades may be provided in the vapor deposition source 1.

Note that, also in the present embodiment, the stirring conditions such as the rotation speed and the stirring time are not particularly limited and may be appropriately set so that the first vapor deposition material 71 and the second vapor deposition material 72 are mixed sufficiently uniformly.

In any case, according to the present embodiment, the vapor deposition material is agitated and made to flow in the housing 4, so that the distribution of the first vapor deposition material 71 and the second vapor deposition material 72 in the housing 4 is made uniform. The mixing ratio of the first vapor deposition material 71 and the second vapor deposition material 72 that can be held and introduced into the housing 4, and the first vapor deposition material 71 and the second vapor deposition that form the vapor deposition film formed on the substrate 52. The mixing ratio with the material 72 can be made substantially equal. Further, the first vapor deposition material 71 and the second vapor deposition material 72 are not unevenly distributed in the vapor deposition film, and a uniformly mixed vapor deposition film can be formed.

The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and embodiments obtained by appropriately combining the technical means disclosed in the different embodiments. Is also included in the technical scope of the present invention. Further, new technical features can be formed by combining the technical means disclosed in each embodiment.

1 Vapor Deposition Source 2 Quartz Resonator 3 Vapor Deposition Device 4 Housing 4a Side 4c Bottom 4K Open 5 Top 5S First Nozzle (Nozzle)
5N Nozzle 2 (Nozzle)
6.8 Anti-adhesion plate 6K Second conduction opening 7 Pipe section 7K First conduction opening 11 Vibration device (stirring device, kinetic energy supply device)
24 Solution containing siloxane-based compound 41 Coating layer 52 Substrate (deposited substrate)
61 Vapor Deposition Film 71 First Vapor Deposition Material 72 Second Vapor Deposition Material 81 Stirrer (Kinetic Energy Supply Device)
82 Magnetic stirrer 83 Stirrer

Claims

A casing having an opening on the upper side and containing a mixture of a plurality of types of vapor deposition materials, and vapor deposition particles formed by vaporizing the plurality of types of vapor deposition materials while being airtightly attached to the openings of the casing. A top plate provided with a plurality of nozzles for discharging, and a vapor deposition source having
A vapor deposition apparatus, wherein a coating layer containing a siloxane group is formed on at least a part of at least one of the inner surface of the housing and the inner surface of the top plate.
The vapor deposition apparatus according to claim 1, wherein at least a part of at least one of the inner surface of the housing and the inner surface of the top plate includes a bottom surface of the housing.
The vapor deposition apparatus according to claim 1 or 2, wherein at least a part of at least one of the inner surface of the housing and the inner surface of the top plate includes a side surface of the housing.
At least a part of at least one of the inner surface of the housing and the inner surface of the top plate includes the inner surface of the plurality of nozzles provided on the top plate. The vapor deposition apparatus according to the section.
Crystal oscillator for vapor deposition rate detection,
A conduction opening that is provided between a first nozzle, which is a part of the plurality of nozzles, and the crystal oscillator, and that is capable of guiding the vapor deposition particles from the first nozzle to the crystal oscillator. And a pipe part having
An anti-adhesion plate for preventing the vapor deposition particles from flying to a film formation unnecessary region,
The first nozzle side of the pipe portion is connected to the deposition preventing plate,
The vapor deposition apparatus according to any one of claims 1 to 4, wherein the inner surface of the tube portion and the inner surface of the deposition preventive plate are covered with the coating layer.
The vapor deposition apparatus according to any one of claims 1 to 5, wherein the material of the coating layer contains a siloxane compound having an epoxy group.
The siloxane compound has the structural formula (1)

(In the formula, R1 and R2 each independently represent an alkyl group or an alkylene group having 2 to 6 carbon atoms, and n represents an integer of 1 to 24)
And a structural formula (2)

(In the formula, R3 and R4 each independently represent an alkyl group or an alkylene group having 2 to 6 carbon atoms, and m represents an integer of 1 to 24)
7. The vapor deposition apparatus according to claim 6, which is at least one compound selected from the group consisting of compounds represented by:
At least a part of at least one of the inner surface of the housing and the inner surface of the top plate is chemically bonded to the epoxy group,
The said coating layer has a siloxane group on the surface, The vapor deposition apparatus of Claim 6 or 7 characterized by the above-mentioned.
At least a part of at least one of the inner surface of the housing and the inner surface of the top plate is formed of at least one metal selected from the group consisting of molybdenum, tungsten, tantalum, and niobium, or an alloy thereof. The vapor deposition device according to any one of claims 1 to 8.
At least a part of at least one of the inner surface of the housing and the inner surface of the top plate is formed of at least one ceramic material selected from the group consisting of silicon oxide, silicon nitride, and aluminum nitride. The vapor deposition device according to any one of claims 1 to 8.
The mixture of a plurality of types of vapor deposition materials is a mixture of a plurality of types of vapor deposition materials including a first vapor deposition material and a second vapor deposition material having a larger molecular weight than the first vapor deposition material. 11. The vapor deposition device according to any one of 10 to 10.
The mixture of the plurality of kinds of vapor deposition materials has the structural formula (3).

And a compound represented by structural formula (4) or structural formula (5)

The vapor deposition apparatus according to any one of claims 1 to 11, which is a mixture of the compound represented by
13. The kinetic energy supply device for applying kinetic energy to the plurality of types of vapor deposition materials in the housing to flow the plurality of types of vapor deposition materials, according to any one of claims 1 to 12. The vapor deposition apparatus described.
The vapor deposition device according to claim 13, wherein the kinetic energy supply device is a stirring device that fluidizes and agitates the plurality of types of vapor deposition materials in the housing.
The vapor deposition apparatus according to claim 13 or 14, wherein the kinetic energy supply apparatus is a vibration type agitation apparatus that agitates the vapor deposition material in the housing by vibrating the vapor deposition source.
The kinetic energy supply device includes a lateral vibration that moves the vapor deposition source in a horizontal direction with respect to the vapor deposition source, a vertical vibration that moves the vapor deposition source in a direction perpendicular to the horizontal direction, and a horizontal vibration that moves the vapor deposition source in a horizontal direction. 16. The vapor deposition apparatus according to claim 15, wherein at least one vibration of tilt vibration that is inclined with respect to is added.
The vapor deposition apparatus according to claim 13, wherein the kinetic energy supply apparatus is a stirring apparatus that directly stirs and flows the plurality of types of vapor deposition materials in the housing.
The vapor deposition apparatus according to claim 17, wherein the kinetic energy supply device includes a stirrer arranged in the housing.
A casing having an opening on the upper side and containing a mixture of a plurality of types of vapor deposition materials, and vapor deposition particles formed by vaporizing the plurality of types of vapor deposition materials while being airtightly attached to the openings of the casing. A top plate provided with a plurality of nozzles for discharging, and a coating layer containing a siloxane group is formed on at least a part of at least one of the inner surface of the housing and the inner surface of the top plate. In the vapor deposition apparatus which is, in the housing, a vapor deposition material accommodation step of accommodating the plurality of types of vapor deposition materials,
A temperature raising step of raising the temperature of the casing to a temperature higher than the vaporization temperature of each of the plurality of types of vapor deposition materials,
A vapor deposition substrate loading step of loading the vapor deposition substrate into the vapor deposition apparatus,
A co-deposition step of co-depositing the plurality of types of deposition materials on the deposition target substrate,
And a step of unloading the vapor deposition substrate from the vapor deposition apparatus, the method for manufacturing a display device.
The method according to claim 19, further comprising a stirring step of flowing and stirring the plurality of kinds of vapor deposition materials accommodated in the housing after the vapor deposition material accommodation step and before the temperature raising step. The method of manufacturing the display device described.
In the stirring step, with respect to the vapor deposition source, a horizontal vibration that moves the vapor deposition source in a horizontal direction, a vertical vibration that moves the vapor deposition source in a direction perpendicular to the horizontal direction, and the vapor deposition source with respect to the horizontal direction. The method of manufacturing a display device according to claim 20, wherein at least one vibration of tilting vibration is added.
The method for manufacturing a display device according to claim 20, wherein, in the stirring step, the plurality of kinds of vapor deposition materials accommodated in the housing are stirred by a stirrer arranged in the housing.
Before the vapor deposition material accommodation step,
By immersing at least a part of at least one of the inner surface of the housing and the inner surface of the top plate in weakly basic water, at least a part of at least one of the inner surface of the housing and the inner surface of the top plate. A step of forming at least a hydroxyl group out of a hydroxyl group and a carboxyl group,
A step of drying at least a part of at least one of the inner surface of the housing and the inner surface of the top plate;
By immersing at least a part of at least one of the inner surface of the housing and the inner surface of the top plate in a solution containing a siloxane compound, at least one of at least one of the inner surface of the housing and the inner surface of the top plate. A step of forming a coating layer containing a siloxane group,
The method for manufacturing a display device according to any one of claims 19 to 22, further comprising a step of cleaning the surface of the coating layer and then drying the surface.
The method for manufacturing a display device according to claim 23, wherein the coating layer is formed by the chemical reaction of the siloxane compound with the hydroxyl group.
25. The method for manufacturing a display device according to claim 23, wherein in the step of cleaning the surface of the coating layer and then drying the surface, the surface of the coating layer is cleaned using an organic solvent.
The display device manufacturing method according to claim 25, wherein the organic solvent contains acetone.