JP6217197B2 - Vapor deposition mask, metal mask with resin layer, and method of manufacturing organic semiconductor element - Google Patents

Description

  The present invention relates to a deposition mask, a metal mask with a resin layer, and a method for manufacturing an organic semiconductor element.

  Conventionally, in the manufacture of an organic EL element, the organic layer or cathode electrode of the organic EL element is formed of, for example, a metal in which a large number of minute slits are arranged in parallel at minute intervals in a region to be deposited. A vapor deposition mask was used. When using this vapor deposition mask, the vapor deposition mask is placed on the surface of the substrate to be vapor-deposited and held by a magnet from the back side, but the rigidity of the slit is extremely small, so when holding the vapor deposition mask on the substrate surface In this case, the slits are easily distorted, which has been an obstacle to increasing the definition of the products with high definition or increasing the slit length.

  Various studies have been made on the vapor deposition mask for preventing the distortion of the slit. For example, Patent Document 1 covers a base plate that also serves as a first metal mask having a plurality of openings, and covers the openings. There has been proposed a vapor deposition mask having a second metal mask having a large number of fine slits in the region and a mask tension holding means for positioning the second metal mask on the base plate in a state where the second metal mask is pulled in the longitudinal direction of the slit. That is, a vapor deposition mask in which two kinds of metal masks are combined has been proposed. According to this vapor deposition mask, it is said that the slit accuracy can be ensured without causing distortion in the slit.

  Recently, with the increase in size of products using organic EL elements or the increase in substrate size, there is an increasing demand for deposition masks, which are used in the manufacture of deposition masks made of metal. Metal plates are also getting bigger. However, with the current metal processing technology, it is difficult to accurately form a slit in a large metal plate, and even if the slit portion can be prevented from being distorted by the method proposed in Patent Document 1 above, Cannot cope with high definition of slits. Further, in the case of a vapor deposition mask made of only metal, the mass increases with an increase in size, and the total mass including the frame also increases, resulting in trouble in handling.

JP 2003-332057 A

  The present invention has been made in view of such circumstances, and a vapor deposition mask that can satisfy both high definition and light weight even when the size is increased, and a metal mask with a resin layer for producing the vapor deposition mask And a method for manufacturing an organic semiconductor element using the vapor deposition mask.

In order to solve the above problems, the present invention provides a metal mask provided with slits and a plurality of openings arranged vertically and horizontally corresponding to a pattern to be deposited on the surface of the metal mask and overlapping the slit. And a resin layer constituting the resin mask, the stress σ _x (Z) calculated by the following formula (1) is 0.01 MPa to 5 MPa. It is characterized by that.
σ _x (Z) = E · z / R (1)
However, in Formula (1),
E is Young's modulus (MPa)
z is 1/2 (mm) of the thickness of the resin layer constituting the resin mask
R is a radius of curvature (mm). When the resin layer constituting the resin mask bends without a radius of curvature, R calculated by the following equation (2) is used.
R = L ² / 3δ (2)
However, in Formula (2),
L is the length of the resin layer constituting the resin mask (mm)
δ represents the amount of deflection (mm), respectively.

Another invention for solving the above problems is a metal mask with a resin layer, which is formed by vapor deposition at a position where the metal mask provided with a slit is located on the surface of the metal mask and overlaps the slit. Resin layer on one side of a metal mask provided with slits, which is used to manufacture a vapor deposition mask in which a plurality of rows of resin masks corresponding to patterns are arranged in rows and columns. The resin layer is characterized in that the stress σ _x (Z) calculated by the following formula (1) is 0.01 MPa to 5 MPa.
σ _x (Z) = E · z / R (1)
However, in Formula (1),
E is Young's modulus (MPa)
z is 1/2 (mm) of the thickness of the resin layer constituting the resin mask
R is a radius of curvature (mm). When the resin layer constituting the resin mask bends without a radius of curvature, R calculated by the following equation (2) is used.
R = L ² / 3δ (2)
However, in Formula (2),
L is the length of the resin layer constituting the resin mask (mm)
δ represents the amount of deflection (mm), respectively.

Another invention for solving the above-described problems is a method for manufacturing an organic semiconductor element using a vapor deposition method. In the manufacture of the organic semiconductor element, a vapor deposition mask is formed on a metal frame in which a through hole is formed. Is used, and the vapor deposition mask welded and fixed to the metal frame is positioned on the surface of the metal mask and overlaps the slit. And a resin mask in which openings corresponding to a pattern to be deposited are arranged in a plurality of rows vertically and horizontally, and the resin layer constituting the resin mask is calculated by the following equation (1) The applied stress σ _x (Z) is 0.01 MPa to 5 MPa.
σ _x (Z) = E · z / R (1)
However, in Formula (1),
E is Young's modulus (MPa)
z is 1/2 (mm) of the thickness of the resin layer constituting the resin mask
R is a radius of curvature (mm). When the resin layer constituting the resin mask bends without a radius of curvature, R calculated by the following equation (2) is used.
R = L ² / 3δ (2)
However, in Formula (2),
L is the length of the resin layer constituting the resin mask (mm)
δ represents the amount of deflection (mm), respectively.

  According to the vapor deposition mask, the metal mask with a resin layer, and the method for producing an organic semiconductor element of the present invention, both high definition and light weight can be satisfied even when the size is increased.

(A) is the front view seen from the metal mask side of the vapor deposition mask of this embodiment, (b) is an expanded sectional view of the vapor deposition mask of this embodiment. It is explanatory drawing of the method for calculating a stress. (A), (b) is the front view seen from the metal mask side of the vapor deposition mask of this embodiment. It is a schematic sectional drawing which shows the relationship between a shadow and the thickness of a metal mask. It is a partial schematic sectional drawing which shows the relationship between the slit of a metal mask, and the opening part of a resin mask. It is a partial schematic sectional drawing which shows the relationship between the slit of a metal mask, and the opening part of a resin mask. It is process drawing for demonstrating an example of the manufacturing method of the vapor deposition mask of this embodiment. It is process drawing for demonstrating another example of the manufacturing method of the vapor deposition mask of this embodiment.

1. Deposition mask Hereinafter, the deposition mask of the present invention will be described in detail with reference to the drawings.

  Fig.1 (a) is the front view seen from the metal mask side of the vapor deposition mask concerning embodiment of this invention, FIG.1 (b) is an expanded sectional view of the vapor deposition mask concerning embodiment of this invention. .

  In this figure, in order to emphasize the slits provided in the metal mask and the openings provided in the vapor deposition mask, the ratio to the whole is greatly described.

  As shown in FIG. 1, a vapor deposition mask 100 according to an embodiment of the present invention includes a metal mask 10 provided with slits 15 and a surface of the metal mask 10 (in the case shown in FIG. A configuration is adopted in which a resin mask 20 is stacked, which is positioned on the lower surface of the mask 10 and has a plurality of rows and columns of openings 25 corresponding to the pattern to be deposited. Each will be described in detail below.

(Resin mask)
The resin mask 20 is made of a resin, and as shown in FIG. 1, a plurality of openings 25 corresponding to a pattern to be deposited and formed are arranged in rows and columns at positions overlapping with the slits 15. Further, in the present embodiment, an example in which the openings are arranged in a plurality of rows in the vertical and horizontal directions is described. However, the openings 25 may be provided at positions that overlap with the slits, and the slits 15 are vertically arranged. In the case where only one row is arranged in the horizontal direction or the horizontal direction, the opening 25 may be provided at a position overlapping the slit 15 in the one row.

Here, the resin layer constituting the resin mask 20 is characterized in that the stress σ _x (Z) calculated by the following equation (1) is 0.01 MPa to 5 MPa.
σ _x (Z) = E · z / R (1)

In the formula (1), E is Young's modulus (MPa), z is 1/2 (mm) of the thickness of the resin layer constituting the resin mask, and R is the radius of curvature (mm). When the resin layer to be formed bends without having a radius of curvature, R calculated by the following equation (2) is used.
R = L ² / 3δ (2)
However, in Formula (2), L has shown the length (mm) of the resin layer which comprises a resin mask, and (delta) has shown the deflection amount (mm), respectively.

When the resin mask 20 is formed, the stress σ _x (Z) calculated by the above formula (1) of the resin layer constituting the resin mask 20 is set to 0.01 MPa to 5 MPa, whereby the vapor deposition mask 100 is manufactured. Can prevent the resin mask 20 from sagging in the use stage of the vapor deposition mask 100, or the resin mask 20 from being deformed by being bent or stretched, and is a highly accurate and high-definition vapor deposition mask. It can be.

Here, when the stress σ _x (Z) is smaller than 0.01 MPa, the resin layer constituting the resin mask 20 has almost no stress, and follows this when the metal mask 10 is deformed slightly. There is a risk that sagging of the resin mask 20 may occur. On the other hand, when the stress σ _x (Z) is greater than 5 MPa, a considerable amount of stress is stored in the resin constituting the resin mask 20, such as bending and expansion / contraction at the manufacturing stage and use stage of the vapor deposition mask. Deformation is likely to occur, and there is a possibility that a highly accurate and high-definition deposition mask cannot be obtained.

FIG. 2 is a diagram for explaining a method of calculating the stress σ _x (Z).

Hereinafter, a method for calculating the stress σ _x (Z) in the present embodiment will be specifically described with reference to FIG.

First, a metal plate (for example, size 150 mm square) is prepared, a resin is applied to one surface thereof, and dried and cured to form a resin layer. In this state, since the stress σ _x (Z) of the resin layer cannot be measured, the metal plate is removed by etching. Thereafter, the resin layer is cut into a predetermined size (for example, width = 15 mm × length = 50 mm).

Here, when the stress σ _x (Z) of the resin layer is large, the resin layer is completely curled as shown in FIG. In this case, the resin layer has a radius of curvature. Then, the stress σ _x (Z) of the resin layer can be calculated by measuring the radius of curvature of the resin layer and substituting it into the equation (1). As a method for measuring the radius of curvature, any method can be used as long as the length can be measured by either a ruler or a laser displacement meter.

On the other hand, when the stress σ _x (Z) of the resin layer is small, the resin layer does not curl as shown in FIG. In this case, the resin layer does not have a curvature radius. When the resin layer does not have a radius of curvature, one end of the resin layer is fixed, the amount of deflection δ is measured, and the radius of curvature is calculated using equation (2). The stress σ _x (Z) can be calculated. Alternatively, the stress σ _x (Z) of the resin layer can be obtained after calculating the concentrated load applied to the tip of the resin layer from the deflection amount δ and calculating the moment applied to the fixed end. The method of measuring the deflection amount δ may be any method that can measure the length with either a ruler or a laser displacement meter.

In the type of the resin layer constituting the resin mask 20, a conventionally known resin material may be appropriately selected and used on condition that the stress σ _x (Z) described above is within a predetermined range. It is possible to form a high-definition opening 25 by laser processing or the like, and it is preferable to use a lightweight material that has a small dimensional change rate and moisture absorption rate over time and heat. Examples of such materials include polyimide resin, polyamide resin, polyamideimide resin, polyester resin, polyethylene resin, polyvinyl alcohol resin, polypropylene resin, polycarbonate resin, polystyrene resin, polyacrylonitrile resin, ethylene vinyl acetate copolymer resin, ethylene- Examples thereof include vinyl alcohol copolymer resin, ethylene-methacrylic acid copolymer resin, polyvinyl chloride resin, polyvinylidene chloride resin, cellophane, and ionomer resin. Among the materials exemplified above, a resin material having a thermal expansion coefficient of 16 ppm / ° C. or less is preferable, a resin material having a moisture absorption rate of 1.0% or less is preferable, and a resin material having both conditions is particularly preferable. .

In the case of using the resin material, for example, a polyimide resin, in order to set the stress σ _x (Z) of the resin layer to a predetermined range, the temperature and time when the polyimide resin is cured, the atmospheric gas, What is necessary is just to control an air volume etc. suitably.

  The thickness of the resin mask 20 is not particularly limited, but when vapor deposition is performed using the vapor deposition mask of the present invention, a vapor deposition portion that is insufficient for the pattern to be vapor deposited, that is, a film thinner than the target vapor deposition film thickness. The resin mask 20 is preferably as thin as possible in order to prevent the deposition portion that is thick, so-called shadows from occurring. However, when the thickness of the resin mask 20 is less than 3 μm, defects such as pinholes are likely to occur, and the risk of deformation and the like increases. On the other hand, if it exceeds 25 μm, shadows may occur. Considering this point, the thickness of the resin mask 20 is preferably 3 μm or more and 25 μm or less. By setting the thickness of the resin mask 20 within this range, it is possible to reduce the risk of defects such as pinholes and deformation, and to effectively prevent the generation of shadows. In particular, when the thickness of the resin mask 20 is 3 μm or more and 10 μm or less, more preferably 4 μm or more and 8 μm or less, it is possible to more effectively prevent the influence of shadows when forming a high-definition pattern exceeding 300 ppi. .

  The shape and size of the opening 25 formed in the resin mask 20 are not particularly limited, and may be any shape and size corresponding to the pattern to be deposited. Further, as shown in FIG. 1A, the horizontal pitch P1 and the vertical pitch P2 of the adjacent openings 25 can be set as appropriate according to the pattern to be deposited. Accordingly, when the openings are formed by laser irradiation, the pitches P1 and P2 may be appropriately designed.

  There are no particular limitations on the positions where the openings 25 are provided and the number of openings 25, and one opening may be provided at a position overlapping the slit 15, or a plurality of openings 25 may be provided in the vertical direction or the horizontal direction. For example, as shown in FIG. 3A, when the slit extends in the vertical direction, two or more openings 25 overlapping the slit 15 may be provided in the horizontal direction.

  The cross-sectional shape of the opening 25 is not particularly limited, and the end faces facing each other of the resin mask forming the opening 25 may be substantially parallel to each other. However, as shown in FIG. It is preferable that the cross-sectional shape has a shape that expands toward the vapor deposition source. In other words, it is preferable to have a tapered surface that expands toward the metal mask 10 side. By setting the cross-sectional shape of the opening 25 to the configuration, it is possible to prevent a shadow from being generated in the pattern to be deposited when vapor deposition is performed using the vapor deposition mask of the present invention. The taper angle θ can be appropriately set in consideration of the thickness of the resin mask 20 and the like, but the angle between the bottom end of the bottom of the resin mask and the top of the top of the opening of the resin mask is the same. It is preferably within the range of 25 ° to 65 °. In particular, within this range, an angle smaller than the vapor deposition angle of the vapor deposition machine to be used is preferable. Further, in FIG. 1B, the end face 25a forming the opening 25 has a linear shape, but is not limited to this, and has an outwardly convex curved shape. The entire shape of the opening 25 may be a bowl shape. The opening 25 having such a cross-sectional shape is subjected to multi-stage laser irradiation that appropriately adjusts the laser irradiation position and laser irradiation energy or changes the irradiation position in stages when the opening 25 is formed. It can be formed by doing.

  In the present invention, since the resin mask 20 is used as the configuration of the vapor deposition mask 100, when the vapor deposition is performed using the vapor deposition mask 100, very high heat is applied to the opening 25 of the resin mask 20. Further, gas may be generated from the end face 25a (see FIG. 1) that forms the opening 25 of the resin mask 20, and there is a possibility that the degree of vacuum in the vapor deposition apparatus is reduced. Therefore, in consideration of this point, it is preferable that a barrier layer 26 is provided on the end face 25a forming the opening 25 of the resin mask 20, as shown in FIG. By forming the barrier layer 26, it is possible to prevent gas from being generated from the end face 25 a that forms the opening 25 of the resin mask 20.

  As the barrier layer 26, an inorganic oxide, an inorganic nitride, a metal thin film layer, or a vapor deposition layer can be used. As the inorganic oxide, an oxide of aluminum, silicon, indium, tin, or magnesium can be used, and as the metal, aluminum or the like can be used. The thickness of the barrier layer 26 is preferably about 0.05 μm to 1 μm.

  Furthermore, the barrier layer preferably covers the deposition source side surface of the resin mask 20. The barrier property is further improved by covering the deposition source side surface of the resin mask 20 with the barrier layer 26. In the case of inorganic oxides and inorganic nitrides, the barrier layer is preferably formed by various PVD methods and CVD methods. In the case of a metal, it is preferably formed by a vacuum deposition method. The surface on the vapor deposition source side of the resin mask 20 referred to here may be the entire surface on the vapor deposition source side of the resin mask 20, and is exposed from the metal mask on the surface on the vapor deposition source side of the resin mask 20. It may be only the part which is.

(Metal mask)
The metal mask 10 is made of metal, and when viewed from the front of the metal mask 10, the metal mask 10 is vertically positioned at a position where it overlaps with the opening 25, in other words, at a position where all the openings 25 arranged in the resin mask 20 can be seen. A plurality of rows of slits 15 extending in the horizontal direction or the horizontal direction are arranged. In FIG. 1, slits 15 extending in the vertical direction of the metal mask 10 are continuously arranged in the horizontal direction. Further, in the present embodiment, an example is described in which the slits 15 are arranged in a plurality of rows of slits 15 extending in the vertical direction or the horizontal direction, but the slits 15 are arranged in one row in the vertical direction or the horizontal direction. May be arranged only.

  The width W of the slit 15 is not particularly limited, but is preferably designed to be at least shorter than the pitch between the adjacent openings 25. Specifically, as shown in FIG. 1A, when the slit 15 extends in the vertical direction, the horizontal width W of the slit 15 is shorter than the pitch P1 of the openings 25 adjacent in the horizontal direction. It is preferable to do. Similarly, although not illustrated, when the slit 15 extends in the horizontal direction, the width in the vertical direction of the slit 15 is preferably shorter than the pitch P2 of the openings 25 adjacent in the vertical direction. On the other hand, the vertical length L when the slit 15 extends in the vertical direction is not particularly limited, and the vertical length of the metal mask 10 and the opening 25 provided in the resin mask 20 are not limited. What is necessary is just to design suitably according to a position.

  Further, the slits 15 extending continuously in the vertical direction or the horizontal direction may be divided into a plurality of pieces by the bridge 18 as shown in FIG. FIG. 3B is a front view of the vapor deposition mask 100 as viewed from the metal mask 10 side. A plurality of slits 15 extending continuously in the vertical direction shown in FIG. The example divided | segmented into (slit 15a, 15b) is shown. The width of the bridge 18 is not particularly limited, but is preferably about 5 μm to 20 μm. By setting the width of the bridge 18 within this range, the rigidity of the metal mask 10 can be effectively increased. The arrangement position of the bridge 18 is not particularly limited, but the bridge 18 is preferably arranged so that the divided slits overlap with the two or more openings 25.

  The cross-sectional shape of the slit 15 formed in the metal mask 10 is not particularly limited, but, as with the opening 25 in the resin mask 20, as shown in FIG. It is preferable to have a shape having

  The material of the metal mask 10 is not particularly limited, and any conventionally known material can be appropriately selected and used in the field of the evaporation mask, and examples thereof include metal materials such as stainless steel, iron-nickel alloy, and aluminum alloy. . Among them, an invar material that is an iron-nickel alloy can be suitably used because it is less deformed by heat.

  Further, when vapor deposition is performed on the substrate using the vapor deposition mask 100 of the present invention, a metal mask 10 is used when it is necessary to place a magnet or the like behind the substrate and attract the vapor deposition mask 100 in front of the substrate by magnetic force. Is preferably made of a magnetic material. The magnetic metal mask 10 is pure iron, carbon steel, W steel, Cr steel, Co steel, KS steel, MK steel, NKS steel, Cunico steel, Al-Fe alloy, iron nickel alloy, iron nickel alloy. Invar and the like can be mentioned. When the material forming the metal mask 10 is not a magnetic material, the metal mask 10 may be magnetized by dispersing the magnetic powder in the material.

  The thickness of the metal mask 10 is not particularly limited, but is preferably about 5 μm to 100 μm. Considering prevention of shadow during vapor deposition, the thickness of the metal mask 10 is preferably thin. However, when the thickness is smaller than 5 μm, the risk of breakage and deformation increases and handling may be difficult. However, in the present invention, since the metal mask 10 is integrated with the resin mask 20, even when the thickness of the metal mask 10 is as thin as 5 μm, the risk of breakage and deformation can be reduced. It can be used if it is 5 μm or more. When the thickness is greater than 100 μm, shadows may be generated, which is not preferable.

  FIG. 4 is a partial schematic cross-sectional view for explaining the relationship between the generation of shadows and the slit 15 of the metal mask 10.

  Hereinafter, the relationship between the occurrence of shadows and the thickness of the metal mask 10 will be described in detail with reference to FIGS. 4 (a) to 4 (c). As shown in FIG. 4A, when the thickness of the metal mask 10 is thin, the vapor deposition material released from the vapor deposition source toward the vapor deposition target is the inner wall surface of the slit 15 of the metal mask 10 or the metal mask. 10 passes through the slit 15 of the metal mask 10 and the opening 25 of the resin mask 20 without colliding with the surface on the side where the resin mask 20 is not provided. Thereby, it becomes possible to form a vapor deposition pattern with a uniform film thickness on the vapor deposition object. That is, the occurrence of shadows can be prevented. On the other hand, as shown in FIG. 4B, when the thickness of the metal mask 10 is thick, for example, when the thickness of the metal mask 10 exceeds 100 μm, a part of the vapor deposition material released from the vapor deposition source. Cannot collide with the inner wall surface of the slit 15 of the metal mask 10 or the surface of the metal mask 10 where the resin mask 20 is not formed, and cannot reach the deposition target. As the amount of the vapor deposition material that cannot reach the vapor deposition target increases, an undeposited portion having a thickness smaller than the target vapor deposition thickness is generated on the vapor deposition target.

  In order to sufficiently prevent the generation of shadows, it is preferable that the cross-sectional shape of the slit 15 is a shape that expands toward the vapor deposition source, as shown in FIG. With such a cross-sectional shape, even if the thickness of the entire deposition mask is increased for the purpose of preventing distortion that may occur in the deposition mask 100 or improving durability, it is emitted from the deposition source. The deposited material can reach the deposition object without colliding with the surface of the slit 15 or the inner wall surface of the slit 15. More specifically, the angle formed by the straight line connecting the lower bottom tip of the slit 15 of the metal mask 10 and the upper bottom tip of the slit 15 of the metal mask 10 and the bottom surface of the metal mask 10 is 25 ° to 65 °. It is preferable to be within the range. In particular, within this range, an angle smaller than the vapor deposition angle of the vapor deposition machine to be used is preferable. With such a cross-sectional shape, even if the thickness of the metal mask 10 is relatively thick for the purpose of preventing distortion that may occur in the vapor deposition mask 100 or improving durability, the metal is released from the vapor deposition source. The vapor deposition material can reach the vapor deposition object without colliding with the inner wall surface of the slit 15. As a result, the occurrence of shadows can be more effectively prevented. In the form shown in FIG. 4C, the slit 15 of the metal mask 10 has a shape that widens toward the vapor deposition source side, and the end faces that face the opening of the resin mask 20 are substantially parallel. However, in order to more effectively prevent the occurrence of shadows, the slits of the metal mask 10 and the opening 25 of the resin mask 20 both have a shape in which the cross-sectional shape expands toward the deposition source side. It is preferable.

  FIGS. 5A to 5D are partial schematic sectional views showing the relationship between the slit of the metal mask and the opening of the resin mask. In the illustrated embodiment, the slit 15 of the metal mask and the opening of the resin mask are shown. The cross-sectional shape of the entire opening formed by the step 25 is stepped. As shown in FIG. 5, the occurrence of shadows can be effectively prevented by making the cross-sectional shape of the entire opening into a stepped shape that expands toward the vapor deposition source side.

  Therefore, in the vapor deposition mask of the present invention, it is preferable that the cross-sectional shape of the entire opening formed by the slit of the metal mask and the opening 25 of the resin mask is stepped.

  As shown in FIGS. 5A and 5C, the slits 15 of the metal mask and the cross-sectional shapes of the resin mask 20 may have substantially parallel end faces as shown in FIG. 5A. In addition, only one of the slit 15 of the metal mask and the opening of the resin mask may have a cross-sectional shape that expands toward the deposition source side. As described above, in order to more effectively prevent the occurrence of shadows, the slit 15 of the metal mask and the opening 25 of the resin mask are formed as shown in FIG. 1B or FIG. As shown in FIG. 5, it is preferable that both have a cross-sectional shape that expands toward the vapor deposition source side.

  The width of the flat portion (reference numeral (X) in FIG. 5) in the step-like cross section is not particularly limited, but when the width of the flat portion (X) is less than 1 μm, the width of the slit of the metal mask Due to the interference, the effect of preventing shadows tends to be reduced. Therefore, considering this point, the width of the flat portion (X) is preferably 1 μm or more. The preferable upper limit value is not particularly limited, and can be appropriately set in consideration of the size of the opening of the resin mask, the interval between adjacent openings, and the like, and is about 20 μm as an example.

  5A to 5D show an example in which one opening 25 overlapping the slit 15 is provided in the horizontal direction when the slit extends in the vertical direction. 2, when the slit extends in the vertical direction, two or more openings 25 overlapping the slit 15 may be provided in the horizontal direction. In FIG. 6, both the slit 15 of the metal mask and the opening 25 of the resin mask have a cross-sectional shape that expands toward the deposition source side, and the opening 25 that overlaps the slit 15 extends in the lateral direction. Two or more are provided.

2. Manufacturing method of vapor deposition mask, and metal mask with resin layer (first manufacturing method)
FIG. 7 is a process diagram for explaining an example of the manufacturing method of the vapor deposition mask of the present embodiment. Note that (a) to (e) are all cross-sectional views.

As shown to Fig.7 (a), the metal plate 60 with the resin layer in which the resin layer 67 is provided in the one surface of the metal plate 61 is prepared. Here, the preparation method of the metal plate 60 with a resin layer is not particularly limited. For example, the metal plate 60 with a resin layer may be provided by providing a resin layer on the surface of the metal plate. However, even when the resin layer is provided by any method, the resin constituting the resin layer needs to have the stress σ _x (Z) described above of 0.01 MPa to 5 MPa. .

  As a method of providing the resin layer on the surface of the metal plate, for example, the metal plate 60 with a resin layer can be obtained by applying a coating liquid containing a resin that becomes the resin layer to the metal plate and drying it.

  Next, a metal mask 68 with a resin layer is formed on the metal plate 61 in the metal plate with a resin layer 60 by forming a slit that penetrates only the metal plate. This step in the present method is not particularly limited and may be any step as long as a desired slit can be formed only in the metal mask. The metal mask 68 with a resin layer said in this specification means that the slit was formed in the metal plate of the said metal plate 60 with a resin layer, and this is the metal mask with a resin layer of this invention.

  7B to 7D show an example of a process for forming the metal mask 68 with a resin layer of the present invention. As shown in FIG. 7B, a resist material 62 is applied to the surface of the metal plate 60 with the resin layer where the resin layer 67 is not provided, and the resist material is used using a mask 63 in which a slit pattern is formed. Is masked, exposed and developed. Thus, a resist pattern 64 is formed on the surface of the metal plate 67 as shown in FIG. Then, using the resist pattern 64 as an etching resistant mask, only the metal plate 60 is etched, and the resist pattern is washed and removed after the etching is completed. Thereby, as shown in FIG.7 (d), the metal mask 66 (metal mask 68 with a resin layer) by which the slit 65 was formed only in the metal plate 67 can be obtained.

  There is no particular limitation on the masking method of the resist material, and the resist material 62 may be applied only on the surface side where the resin layer 67 of the metal plate 60 with the resin layer is not provided as shown in FIG. A resist material 62 may be applied to both surfaces of the metal plate 60 with a resin layer (not shown). Moreover, the dry film method which bonds a dry film resist on the surface in which the resin layer 67 of the metal plate 60 with a resin layer is not provided, or both surfaces of the metal plate 60 with a resin layer can also be used. The coating method of the resist material 62 is not particularly limited. When the resist material 62 is coated only on the surface side of the metal plate 60 with the resin layer where the resin layer 67 is not provided, a spin coating method or a spray coating method is used. Can be used. On the other hand, when using a long sheet-like metal plate 60 with a resin layer, it is preferable to use a dip coating method or the like that can apply a resist material by a roll-to-roll method. In the dip coating method, the resist material 62 is applied to both surfaces of the metal plate 60 with a resin layer.

  As the resist material, it is preferable to use a resist material having good processability and desired resolution. Further, the etching material used in the etching process is not particularly limited, and a known etching material may be appropriately selected.

  The etching method for the metal plate 61 is not particularly limited. For example, a spray etching method in which an etching material is sprayed from a spray nozzle at a predetermined spray pressure, an immersion etching method or an etching material is dropped into an etching solution filled with the etching material. A wet etching method such as a spin etching method or a dry etching method using gas, plasma, or the like can be used.

  Next, laser is irradiated from the metal mask 66 side of the metal plate with resin layer 68 through the slit 65, and openings 69 corresponding to the pattern to be deposited on the resin layer 67 are formed in a plurality of rows and columns to form the resin mask 70. . The laser device used here is not particularly limited, and a conventionally known laser device may be used. Thereby, the vapor deposition mask 80 as shown in FIG.7 (e) is obtained. In the specification of the present application, the pattern formed by vapor deposition means a pattern to be produced using the vapor deposition mask. For example, when the vapor deposition mask is used for forming an organic layer of an organic EL element, the organic The shape of the layer.

(Second manufacturing method)
FIG. 8 is a process diagram for explaining another example of the deposition mask manufacturing method of the present embodiment. Note that (a) to (e) are all cross-sectional views.

  In the first manufacturing method shown in FIG. 7, the etching pattern 64 used as an etching mask when the metal mask 66 is formed is removed. However, without removing the etching pattern 64, FIG. 8D and FIG. As shown in e), it may be left as it is. The other steps, that is, FIGS. 8A to 8C are the same as those in FIG. 7 and will not be described here.

  In the first and second manufacturing methods, after the metal mask 66 (metal mask with resin layer 68) is formed, that is, between (d) and (e) in FIGS. You may fix the metal mask 68 with a resin layer to the flame | frame containing. In this way, by fixing to the frame before forming the opening 69 of the resin mask 70 that finally regulates the pattern shape to be deposited, the mounting error that occurs when the deposition mask is fixed to the frame is made zero. be able to. In the conventionally known method, since the metal mask whose opening is determined is fixed while being pulled with respect to the frame, the accuracy of the opening position coordinate is lowered.

  Further, when the opening 69 is provided in the resin layer of the metal mask 68 with the resin layer fixed to the frame by a laser processing method, a pattern for vapor deposition, that is, a pattern corresponding to the opening 69 to be formed is provided in advance. A reference plate is prepared, and this reference plate is attached to the surface of the metal mask with resin layer 68 on the side where the metal mask 66 is not provided, and corresponds to the pattern of the reference plate from the metal mask 66 side. Laser irradiation may be performed. According to this method, the opening 69 can be formed in the resin layer 67 in a so-called facing-off state in which laser irradiation is performed while looking at the pattern of the reference plate bonded to the metal mask 68 with the resin layer. A resin mask 70 having a high-definition opening 69 with extremely high dimensional accuracy can be formed. Moreover, since this method forms the opening 69 in a state of being fixed to the frame, it can be a vapor deposition mask that is excellent not only in dimensional accuracy but also in positional accuracy.

  In the case of using the above method, it is necessary that the pattern of the reference plate can be recognized by a laser irradiation device or the like through the resin layer 67 from the metal mask 66 side. When the resin layer 67 has a certain thickness, it is necessary to use a transparent one. However, as described later, a preferable thickness in consideration of the influence of shadow, for example, a thickness of about 3 μm to 25 μm In this case, the reference plate pattern can be recognized even with a colored resin layer.

  The method for bonding the resin layer and the reference plate is not particularly limited. For example, when the metal mask 66 is a magnetic body, a magnet or the like is disposed behind the reference plate, and the resin layer 67 and the reference plate are bonded. Can be attached by attracting. In addition, it can also be bonded using an electrostatic adsorption method or the like. Examples of the reference plate include a TFT substrate having a predetermined pattern and a photomask.

  According to the first and second manufacturing methods, it is possible to manufacture a deposition mask that can satisfy both high definition and light weight even when the size is increased, with a high yield. Moreover, according to one embodiment of the present invention, the positional accuracy between the frame and the vapor deposition mask 100 can be improved. Further, by forming the opening 69 using a reference plate, the opening 69 can be made extremely excellent in dimensional accuracy.

  In the vapor deposition mask according to the embodiment of the present invention, a resin mask 70 and a metal mask 66 are laminated. Comparing the mass of the vapor deposition mask 100 with the mass of a vapor deposition mask made of only a conventionally known metal on the assumption that the thickness of the entire vapor deposition mask is the same, one of the metal materials of the conventional vapor deposition mask is known. The mass of the vapor deposition mask 100 of the present embodiment is reduced by the amount that the portion is replaced with the resin material. In addition, in order to reduce the weight by using a vapor deposition mask made of only metal, it is necessary to reduce the thickness of the vapor deposition mask. However, if the vapor deposition mask is thin, When the size is increased, the vapor deposition mask may be distorted or the durability may be reduced. On the other hand, according to the vapor deposition mask of this embodiment, even when the thickness of the entire vapor deposition mask is increased in order to satisfy the distortion and durability when it is enlarged, the presence of the resin mask 70 is sufficient. Further, the weight can be reduced as compared with a vapor deposition mask formed of only metal.

Moreover, since the vapor deposition mask of this embodiment can obtain the resin mask 70 by irradiating the resin layer 67 capable of forming a high-definition opening with a laser as compared with a metal material, the high-definition opening In addition to being able to manufacture the vapor deposition mask 100 having 69, the resin mask constituting the vapor deposition mask of the present embodiment has a predetermined stress σ _x (Z), and thus may be further curved or deformed. Therefore, a highly accurate and high-definition resin mask can be obtained.

(Slimming process)
In the above manufacturing method, a slimming process may be performed between or after each process. This step is an optional step, and is a step of optimizing the thickness of the metal mask 66 and the thickness of the resin mask 70. The preferable thickness of the metal mask 66 and the resin mask 70 may be set as appropriate within the above-described preferable range, and detailed description thereof is omitted here.

  For example, when a metal plate 60 with a resin layer having a certain thickness is used, when the metal plate 60 with a resin layer and the metal mask 68 with a resin layer are conveyed during the manufacturing process, the above manufacturing method is used. When carrying the vapor deposition mask 100 manufactured by the above, excellent durability and transportability can be imparted. On the other hand, in order to prevent the occurrence of shadows and the like, the thickness of the vapor deposition mask 100 obtained by the production method of the present invention is preferably an optimum thickness. The slimming process is a useful process for optimizing the thickness of the vapor deposition mask 100 while satisfying durability and transportability during or after the manufacturing process.

  The slimming of the metal plate 61 to be the metal mask 66 and the metal mask 66, that is, the optimization of the thickness of the metal mask is performed on the side of the metal plate 61 that does not contact the resin layer 67 between or after the above-described steps. Alternatively, it can be realized by etching the surface of the metal mask 66 that is not in contact with the resin layer 67 or the resin mask 70 using an etching material that can etch the metal plate 61 or the metal mask 66.

  The same applies to the slimming of the resin layer 67 to be the resin mask 70 and the resin mask 70, that is, the optimization of the thickness of the resin layer 67 and the resin mask 70. An etching material that can etch the material of the resin layer 67 or the resin mask 70 is used for the surface of the layer 67 that does not contact the metal plate 61 or the metal mask 66 or the surface of the resin mask 70 that does not contact the metal mask 66. This can be realized by etching. In addition, after forming the vapor deposition mask 100, both the metal mask 66 and the resin mask 70 can be etched to optimize the thickness of both.

  In the slimming process, the etching material for etching the resin layer 67 or the resin mask 70 may be appropriately set according to the resin material of the resin layer 67 or the resin mask 70, and is not particularly limited. For example, when a polyimide resin is used as the resin material of the resin layer 67 or the resin mask 70, an alkaline aqueous solution in which sodium hydroxide or potassium hydroxide is dissolved, hydrazine, or the like can be used as the etching material. Commercially available etching materials can be used as they are, and TPE3000 manufactured by Toray Engineering Co., Ltd. can be used as the polyimide resin etching material.

3. Next, a method for manufacturing an organic semiconductor element of the present invention will be described. The method for producing an organic semiconductor element of the present invention includes a step of forming a vapor deposition pattern by a vapor deposition method using a vapor deposition mask with a metal frame, and the following vapor deposition mask with a metal frame is used in the step of forming the organic semiconductor element. It is characterized in that

  An organic semiconductor device manufacturing method according to an embodiment having a step of forming a vapor deposition pattern by a vapor deposition method using a vapor deposition mask with a metal frame includes an electrode formation step of forming an electrode on a substrate, an organic layer formation step, and a counter electrode formation A vapor deposition pattern is formed on the substrate by a vapor deposition method using a vapor deposition mask with a metal frame in each arbitrary step. For example, when the vapor deposition method using the vapor deposition mask with a metal frame is applied to the organic layer forming step, a vapor deposition pattern of the organic layer is formed on the substrate. In addition, the manufacturing method of the organic-semiconductor element of this invention is not limited to these processes, It is applicable to the arbitrary processes of the conventionally well-known organic-semiconductor element using a vapor deposition method.

The vapor deposition mask with a metal frame of one embodiment used in the method for manufacturing an organic semiconductor element is a vapor deposition mask with a metal frame in which the vapor deposition mask is welded and fixed to a metal frame in which a through hole is formed. The vapor deposition mask welded and fixed to the metal mask provided with slits, and the openings corresponding to the pattern to be vapor deposited are positioned on the surface of the metal mask and overlapped with the slits arranged in multiple rows vertically and horizontally And a resin layer constituting the resin mask, the stress σ _x (Z) calculated by the following formula (1) is 0.01 MPa to 5 MPa. Features.
σ _x (Z) = E · z / R (1)

In the formula (1), E is Young's modulus (MPa), z is 1/2 (mm) of the thickness of the resin layer constituting the resin mask, and R is the radius of curvature (mm). When the resin layer to be formed bends without having a radius of curvature, R calculated by the following equation (2) is used.
R = L ² / 3δ (2)
However, in Formula (2), L has shown the length (mm) of the resin layer which comprises a resin mask, and (delta) has shown the deflection amount (mm), respectively.

  As the vapor deposition mask constituting the vapor deposition mask with a metal frame, the vapor deposition mask 100 manufactured by the manufacturing method of the present invention described above can be used as it is, and detailed description thereof is omitted here. According to the vapor deposition mask manufactured by the manufacturing method of the present invention described above, sagging occurs in the vapor deposition mask when being fixed to a metal frame by welding or when an organic semiconductor element is actually manufactured. In addition, deformation due to bending, expansion and contraction, etc. can be prevented, and a highly precise vapor deposition mask with a metal frame can be obtained with little or no dimensional variation in the opening. Therefore, an organic semiconductor element having a high-definition pattern can be formed using the vapor deposition mask with the metal frame. As an organic semiconductor element manufactured with the manufacturing method of this invention, the organic layer, light emitting layer, cathode electrode, etc. of an organic EL element can be mentioned, for example. In particular, the method for producing an organic semiconductor element of the present invention can be suitably used for producing R, G, and B light emitting layers of organic EL elements that require high-definition pattern accuracy.

(Examples and Comparative Examples)
In selecting the resin layer constituting the resin mask, 13 types of samples A to M of the metal plate with the resin layer in which the resin layer was provided on the metal plate were prepared.

Next, the stress σ _x (Z) of each resin layer constituting each of the samples A to M was measured by the method described above. Note that the stress σ _x (Z) was measured in two directions, the longitudinal direction (MD direction) and the lateral direction (TD direction).

  Next, the evaluation of whether or not the resin layer in each of the samples A to M can be used as a vapor deposition mask is made up of two types: (1) the amount of variation in the opening position of the resin layer, and (2) the amount of sag between the metal / resin-resin layer. We evaluated by item.

(1) Evaluation Method for Opening Position Variation of Resin Layer First, an evaluation method for the opening position variation of the resin layer will be described.
A mask frame having a square opening with an effective portion of 150 mm was prepared.
-Tensile tension was applied to the metal mask with a resin layer having various stresses from the vertical / horizontal directions and fixed by welding. The metal mask has an opening area of 70 mm × 120 mm (only the resin layer).
A rectangular pattern of 30 μm × 500 μm was irradiated to the resin layer surface a plurality of times with a YAG laser (1 J / cm ² ) having a wavelength of 355 nm to form two rows and columns of openings. The long side gap was 5 μm, and the short side gap was 50 μm. The opening state at that time was observed with a microscope.
-The bridge part on one side (gap of 50 μm on the short side) was cut with a laser. The opening position variation at this time was observed on a microscope image monitor and evaluated by visual observation and measurement of the variation amount.

(2) Evaluation method of sagging amount between metal / resin-resin layer Next, an evaluation method of sagging amount between metal / resin-resin layer will be described.
A mask frame having a square opening with an effective portion of 150 mm was prepared.
-Tensile tension was applied to the metal mask with a resin layer having various stresses from the vertical / horizontal directions and fixed by welding. The metal mask has a metal slit processing area of 70 mm × 120 mm.
・ The amount of sagging of the resin layer was visually inspected.
-With the resin surface facing up, surface irregularities in the direction perpendicular to the slit were measured with a depth of focus meter.
-From the measurement data, the slack of the resin layer was evaluated by the peak value of the periodic fluctuation.

Table 1 summarizes the stress σ _x (Z) of the resin layer of each sample and the above two evaluation results.

  In Table 1, regarding the amount of change in the opening position of the resin layer, “small” means 1 μm or less, “medium” means 1 to 5 μm, and “large” means 5 μm or more. Also, in the slack amount between the metal / resin-resin layer, “small” means 2 μm or less and no wrinkle before tension is applied, and “medium” is 2 to 12 μm and tension is applied. “Large” means that there is a wrinkle even after a tension of 12 μm or more is applied.

From the above results, it can be seen that Samples D to J having a stress σ _x (Z) of 0.01 MPa to 5 MPa have obtained good judgment, and in particular, Sample F having a stress σ _x (Z) of 0.02 MPa to 4 MPa. It can be seen that ~ I is good.

DESCRIPTION OF SYMBOLS 100 ... Deposition mask 10, 66 ... Metal mask 15 ... Slit 18 ... Bridge 20, 70 ... Resin mask 25 ... Opening 60 ... Metal plate 61 with a resin layer ... Metal plate 62 ... Resist material 64 ... Resist pattern 67 ... Resin layer 68 ... Metal mask with resin layer 80 ... Vapor deposition mask

Claims (3)

A metal mask provided with slits and a resin mask which is located on the surface of the metal mask and in which a plurality of openings corresponding to a pattern to be deposited and deposited in a position overlapping the slits are arranged in rows and columns are stacked. A vapor deposition mask,
The resin layer constituting the resin mask has a stress σ _x (Z) calculated by the following equation (1) of 0.01 MPa to 5 MPa.
σ _x (Z) = E · z / R (1)
However, in Formula (1),
E is Young's modulus (MPa)
z is 1/2 (mm) of the thickness of the resin layer constituting the resin mask
R is a radius of curvature (mm). When the resin layer constituting the resin mask bends without a radius of curvature, R calculated by the following equation (2) is used.
R = L ² / 3δ (2)
However, in Formula (2),
L is the length of the resin layer constituting the resin mask (mm)
δ represents the amount of deflection (mm), respectively. A metal mask provided with slits and a resin mask which is located on the surface of the metal mask and in which a plurality of openings corresponding to a pattern to be deposited and deposited in a position overlapping the slits are arranged in rows and columns are stacked. Used to produce a vapor deposition mask,
A resin layer is provided on one surface of a metal mask provided with a slit,
The metal mask with a resin layer, wherein the resin layer has a stress σ _x (Z) calculated by the following formula (1) of 0.01 MPa to 5 MPa.
σ _x (Z) = E · z / R (1)
However, in Formula (1),
E is Young's modulus (MPa)
z is 1/2 (mm) of the thickness of the resin layer constituting the resin mask
R is a radius of curvature (mm). When the resin layer constituting the resin mask bends without a radius of curvature, R calculated by the following equation (2) is used.
R = L ² / 3δ (2)
However, in Formula (2),
L is the length of the resin layer constituting the resin mask (mm)
δ represents the amount of deflection (mm), respectively. A method of manufacturing an organic semiconductor element using a vapor deposition method,
For the production of the organic semiconductor element, a metal frame with a metal frame in which a vapor deposition mask is fixed by welding to a metal frame in which a through hole is formed, is used.
The vapor deposition mask fixed by welding to the metal frame is
A metal mask provided with slits and a resin mask which is located on the surface of the metal mask and in which a plurality of openings corresponding to a pattern to be deposited and deposited in a position overlapping the slits are arranged in rows and columns are stacked. A vapor deposition mask,
The method for producing an organic semiconductor element, wherein the resin layer constituting the resin mask has a stress σ _x (Z) calculated by the following formula (1) of 0.01 MPa to 5 MPa.
σ _x (Z) = E · z / R (1)
However, in Formula (1),
E is Young's modulus (MPa)
z is 1/2 (mm) of the thickness of the resin layer constituting the resin mask
R is a radius of curvature (mm). When the resin layer constituting the resin mask bends without a radius of curvature, R calculated by the following equation (2) is used.
R = L ² / 3δ (2)
However, in Formula (2),
L is the length of the resin layer constituting the resin mask (mm)
δ represents the amount of deflection (mm), respectively.

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