JP5565327B2 - Vapor deposition equipment - Google Patents

Description

  The present invention relates to a vapor deposition apparatus.

  In display displays and light-emitting elements of various information industrial devices, the use of organic electroluminescence elements (hereinafter abbreviated as organic EL elements) has progressed because they are thin and excellent in visibility and impact resistance. Yes. The organic EL element has a configuration including an organic layer sandwiched between a pair of electrodes on a substrate. The organic layer is formed by laminating a plurality of layers having different functions, and includes, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

  The organic layer of such an organic EL element is formed by, for example, a vapor deposition method. In general, film formation by vapor deposition is performed by storing an organic material, which is a film formation material, in a container such as a crucible and evaporating the organic material by heating each container in a vacuum state.

Here, the light emitting layer of the organic layer has a configuration in which an organic compound (dopant) serving as a color former is dispersed in an organic compound (host) serving as a light emitting agent. However, the content of the dopant in the light emitting layer is very small, and it is difficult to uniformly disperse the dopant in the light emitting layer.
Thus, for example, Patent Document 1 discloses an apparatus for uniformly depositing a dopant on a substrate by installing a point source for vaporizing a small amount of dopant in the center of a ring-shaped deposition source that vaporizes a large amount of host. Yes.
For example, Patent Document 2 discloses a device that provides a shielding plate between a host material vapor deposition source and a guest material (dopant) vapor deposition source and a substrate, and rotates the substrate and the shielding plate.

JP 2000-313952 A JP 2003-193217 A

  However, the devices disclosed in Patent Documents 1 and 2 are assumed to be used for a fixed substrate. Therefore, for example, when it is applied to a substrate transported by a roll-to-roll apparatus or the like, there is a problem that uniform vapor deposition is difficult.

  This invention is made | formed in view of the said subject, The objective is to provide the vapor deposition apparatus which can co-evaporate uniformly with respect to the board | substrate conveyed.

In order to solve the above problems, the present invention provides:
In a deposition apparatus for depositing a thin film on a substrate in a vacuum vessel,
In the vacuum vessel,
Transport means for transporting the substrate;
A plurality of linear vapor deposition sources arranged side by side along the transport direction so as to extend in an orthogonal direction perpendicular to the transport direction of the substrate, and jetting a film forming material as vapor to the substrate;
A plurality of point vapor deposition source portions arranged side by side along the transport direction and ejecting a film-forming material having a concentration lower than that of the film-forming material ejected from the plurality of linear vapor deposition sources to the substrate; ,
With
Each of the point vapor deposition source units includes a point vapor deposition source capable of reciprocating along the orthogonal direction,
The point vapor deposition source reciprocates in the orthogonal direction in a movement range wider than the width of the substrate and ejects steam,
Co-deposition is performed such that vapors ejected from the plurality of linear deposition sources and the plurality of point-like deposition sources overlap each other .
Moreover, in a vapor deposition apparatus for vapor-depositing a thin film on a substrate in a vacuum vessel,
In the vacuum vessel,
Transport means for transporting the substrate;
A plurality of linear vapor deposition sources arranged side by side along the transport direction so as to extend in an orthogonal direction perpendicular to the transport direction of the substrate, and jetting a film forming material as vapor to the substrate;
A plurality of point vapor deposition source portions arranged side by side along the transport direction and ejecting a film-forming material having a concentration lower than that of the film-forming material ejected from the plurality of linear vapor deposition sources to the substrate; ,
With
Each of the point vapor deposition source portions includes a plurality of point vapor deposition sources fixedly installed along the orthogonal direction,
The plurality of point-like vapor deposition sources are switched at a predetermined timing to sequentially eject steam,
Co-deposition is performed such that vapors ejected from the plurality of linear deposition sources and the plurality of point-like deposition sources overlap each other .

According to the present invention, a plurality of linear vapor deposition sources that are arranged side by side along the transport direction so as to extend in an orthogonal direction orthogonal to the transport direction of the substrate, and jet the film forming material as vapor to the substrate; A plurality of point-like vapor deposition source units that are arranged side by side along the transport direction and eject a film-forming material having a lower concentration than a film-forming material ejected from a plurality of linear vapor deposition sources to the substrate as vapor. Each of the point vapor deposition source sections includes a point vapor deposition source that can reciprocate along the orthogonal direction, and the point vapor deposition source reciprocates in the orthogonal direction within a range of movement wider than the width of the substrate and vapor. The vapor deposition is performed such that the vapors ejected from the plurality of linear vapor deposition sources and the plurality of point vapor deposition source portions overlap each other .
Further, according to the present invention, a plurality of linear vapor deposition sources that are arranged side by side along the transport direction so as to extend in an orthogonal direction orthogonal to the transport direction of the substrate, and eject the film forming material as vapor to the substrate. And a plurality of point-like vapor deposition source portions that are arranged side by side along the transport direction and eject a film-forming material having a concentration lower than that of the film-forming material ejected from the plurality of linear vapor deposition sources to the substrate, Each of the point vapor deposition source units includes a plurality of point vapor deposition sources fixedly installed along the orthogonal direction, and the plurality of point vapor deposition sources are switched at a predetermined timing to sequentially eject steam, Co-deposition is performed such that the vapors ejected from the plurality of linear deposition sources and the plurality of point-like deposition sources overlap each other.
For this reason, since a very small amount of film forming material can be controlled by a plurality of point-like vapor deposition sources, co-deposition can be performed uniformly on the substrate to be conveyed.

It is a schematic perspective view which shows an example of an organic electroluminescent panel. It is a schematic sectional drawing in alignment with the II-II line of FIG. It is a top view which shows the board | substrate and two types of vapor deposition sources in the vapor deposition apparatus of 1st Embodiment. It is a perspective view which shows the board | substrate and two types of vapor deposition sources of the vapor deposition apparatus of FIG. It is a figure for demonstrating the effect | action by the reciprocating movement of a point vapor deposition source part. It is a figure which shows the locus | trajectory in the reciprocating movement of a point vapor deposition source part. It is a figure for showing the modification of the movement range of a point vapor deposition source part. It is a figure for showing the modification of the installation method of a linear vapor deposition source and a dotted vapor deposition source part. It is a figure for showing the state provided with the shielding board in the linear vapor deposition source. It is a top view which shows the board | substrate and two types of vapor deposition sources in the vapor deposition apparatus of 2nd Embodiment.

  Embodiments of the present invention will be described below with reference to the drawings. However, the scope of the invention is not limited to the illustrated examples.

[First Embodiment]

(1. Organic EL device)
First, the organic EL element will be described.

  As shown in FIGS. 1 and 2, the organic EL element 100 has a configuration in which an anode 102, an organic layer 103, and a cathode 104 are sequentially provided on a support substrate 101. The upper surface which becomes the non-light-emitting surface of the organic EL element 100 is covered with a glass cover 105, and the state in which the organic EL element 100 is covered with the glass cover 105 in this way is called an organic EL panel. The glass cover 105 is filled with nitrogen gas 106 and a water catching agent 107 is provided.

The organic layer 103 between the anode 102 and the cathode 104 can be configured as long as it includes at least a light emitting layer. As typical layer configurations of the organic layer 103, for example, the following (i) to ( The structure of v) is mentioned.
(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode

(1-1. Light emitting layer)
The light emitting layer in this embodiment is formed by forming a film by a vacuum vapor deposition method using a vapor deposition apparatus 10 described later.
The light emitting layer is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer. The portion that emits light may be within the layer of the light emitting layer or at the interface between the light emitting layer and the adjacent layer.
The thickness of the light emitting layer is not particularly limited, but from the viewpoint of the uniformity of the film to be formed, the application of unnecessary high voltage during light emission, and the improvement of the stability of the emission color with respect to the drive current. It is preferable to adjust to a range of 40 nm to 200 nm, and more preferably to a range of 50 nm to 150 nm.
The light emitting layer preferably contains a phosphorescent blue light emitting dopant, a green light emitting dopant and a red light emitting dopant, and a host compound.
Hereinafter, each luminescent dopant and host compound will be described.

前記一般式（Ａ）において、Ｒａは水素原子、脂肪族基、芳香族基または複素環基を表し、Ｒｂ、Ｒｃは各々水素原子または置換基を表し、Ａ１は芳香族環または芳香族複素環を形成するのに必要な残基を表し、ＭはＩｒまたはＰｔを表す。

また、前記一般式（Ｂ）において、Ｒａは水素原子、脂肪族基、芳香族基または複素環基を表し、Ｒｂ、Ｒｃ、Ｒｂ_１、Ｒｃ_１は各々水素原子または置換基を表し、Ａ１は芳香族環または芳香族複素環を形成するのに必要な残基を表し、ＭはＩｒまたはＰｔを表す。

また、前記一般式（Ｃ）において、Ｒａは水素原子、脂肪族基、芳香族基または複素環基を表し、Ｒｂ、Ｒｃは各々水素原子または置換基を表し、Ａ１は芳香族環または芳香族複素環を形成するのに必要な残基を表し、ＭはＩｒまたはＰｔを表す。 (1-1-1. Blue emitting dopant)
The blue light-emitting dopant preferably has at least one partial structure selected from the following general formulas (A) to (C).

In the general formula (A), Ra represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, Rb and Rc each represents a hydrogen atom or a substituent, and A1 represents an aromatic ring or an aromatic heterocyclic ring. Represents the residues necessary to form and M represents Ir or Pt.

In the general formula (B), Ra represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, Rb, Rc, Rb ₁ and Rc ₁ each represent a hydrogen atom or a substituent, and A1 represents It represents a residue necessary for forming an aromatic ring or an aromatic heterocyclic ring, and M represents Ir or Pt.

In the general formula (C), Ra represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, Rb and Rc each represents a hydrogen atom or a substituent, and A1 represents an aromatic ring or an aromatic group. It represents a residue necessary for forming a heterocyclic ring, and M represents Ir or Pt.

The structures of the general formulas (A) to (C) are partial structures, and a ligand corresponding to the valence of the central metal is necessary for the structure itself to be a light-emitting dopant of a completed structure.
In the general formulas (A) to (C), M represents Ir or Pt, and Ir is particularly preferable. Moreover, the tris body which becomes a complete structure with three partial structures of general formula (A)-(C) is preferable.

Hereinafter, although the compound which has the partial structure of the said general formula (A)-(C) of the light emission dopant which concerns on this embodiment is illustrated, it is not limited to these.
In the present embodiment, the following compounds (1-1) to (1-10) may be mentioned as compounds suitably used as the blue light-emitting dopant.

(1-1-2. Green light emitting dopant)
In the present embodiment, examples of the compound suitably used as the green light emitting dopant include the following compounds.

(1-1-3. Red light emitting dopant)
In the present embodiment, examples of the compound suitably used as the red light emitting dopant include the following compounds.

(1-1-4. Host compound)
The host compound is preferably a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1, and more preferably a compound having a phosphorescence quantum yield of less than 0.01. Moreover, in the compound contained in a light emitting layer, it is preferable that the mass ratio in the layer is 20 mass% or more.
As a host compound, a host compound may be used independently or may be used in combination of multiple types.
The light emitting host compound used in the present embodiment is not particularly limited in terms of structure, but is typically a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative. A compound having a basic skeleton such as an oligoarylene compound, or a carboline derivative or a diazacarbazole derivative (herein, a diazacarbazole derivative is at least one carbon atom of a hydrocarbon ring constituting a carboline ring of a carboline derivative) Represents the one substituted with a nitrogen atom).

一般式（ａ）において、Ｘは、ＮＲ′、Ｏ、Ｓ、ＣＲ′Ｒ″またはＳｉＲ′Ｒ″を表し、Ｒ′、Ｒ″は各々水素原子または置換基を表す。Ａｒは芳香環を表す。ｎは０から８の整数を表す。
Ｘとして好ましく用いられるのは、ＮＲ′またはＯであり、Ｒ′としては芳香族炭化水素基、芳香族複素環基が特に好ましい。
一般式（ａ）において、Ａｒで表される芳香環としては、芳香族炭化水素環または芳香族複素環が挙げられる。また、該芳香環は単環でもよく、縮合環でもよく、更に未置換でも、後述するような置換基を有していてもよい。
Ａｒで表される芳香環として好ましく用いられるのは、カルバゾール環、カルボリン環、ジベンゾフラン環、ベンゼン環であり、特に好ましく用いられるのは、カルバゾール環、カルボリン環、ベンゼン環である。上記の中でも、置換基を有するベンゼン環が好ましく、特に好ましくは、カルバゾリル基を有するベンゼン環が好ましい。
ここで、一般式（ａ）において、Ａｒで表される芳香環が有してもよい置換基は、Ｒ′、Ｒ″で、各々表される置換基と同義である。
また、一般式（ａ）において、ｎは０〜８の整数を表すが、０〜２であることが好ましく、特にＸがＯ、Ｓである場合には１または２であることが好ましい。
また、本発明に用いるホスト化合物は、低分子化合物でも、繰り返し単位をもつ高分子化合物でもよく、ビニル基やエポキシ基のような重合性基を有する低分子化合物（蒸着重合性発光ホスト）でもよい。 As the light emitting host compound used in the light emitting layer according to this embodiment, a compound represented by the following general formula (a) is preferable.

In the general formula (a), X represents NR ′, O, S, CR′R ″ or SiR′R ″, R ′ and R ″ each represent a hydrogen atom or a substituent. Ar represents an aromatic ring. N represents an integer of 0 to 8.
NR ′ or O is preferably used as X, and R ′ is particularly preferably an aromatic hydrocarbon group or an aromatic heterocyclic group.
In the general formula (a), examples of the aromatic ring represented by Ar include an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The aromatic ring may be a single ring or a condensed ring, and may be unsubstituted or may have a substituent as described later.
The aromatic ring represented by Ar is preferably a carbazole ring, carboline ring, dibenzofuran ring or benzene ring, and particularly preferably used are a carbazole ring, carboline ring or benzene ring. Among these, a benzene ring having a substituent is preferable, and a benzene ring having a carbazolyl group is particularly preferable.
Here, in the general formula (a), the substituent that the aromatic ring represented by Ar may have is the same as the substituent represented by R ′ and R ″.
In the general formula (a), n represents an integer of 0 to 8, preferably 0 to 2, and particularly preferably 1 or 2 when X is O or S.
The host compound used in the present invention may be a low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). .

As the host compound, a compound having a hole transporting ability and an electron transporting ability, which prevents emission of longer wavelengths and has a high Tg (glass transition temperature) is preferable.
In the present embodiment, in the case of having a plurality of light emitting layers, the host compound may be different for each light emitting layer, but the same compound is preferable because excellent driving life characteristics are obtained.
In addition, the host compound preferably has a lowest excited triplet energy (T1) larger than 2.7 eV because higher luminous efficiency can be obtained. The lowest excited triplet energy as used in the present invention refers to the peak energy of an emission band corresponding to the transition between the lowest vibrational bands of a phosphorescence emission spectrum observed at a liquid nitrogen temperature after dissolving a host compound in a solvent.
In the present embodiment, a compound having a glass transition point of 90 ° C. or higher is preferable, and a compound having a glass transition temperature of 130 ° C. or higher is preferable because excellent driving life characteristics can be obtained.
Here, the glass transition point (Tg) is a value obtained by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).
In the organic EL device of the present embodiment, since the host material is responsible for carrier transport, a material having carrier transport capability is preferable. Carrier mobility is used as a physical property representing carrier transport ability, but the carrier mobility of an organic material generally depends on the electric field strength. Since a material with high electric field strength dependency easily breaks the balance of hole and electron injection / transport, it is preferable to use a material with low mobility electric field strength dependency as the intermediate layer material and the host material.
In the present embodiment, examples of the compound suitably used as the host compound include the following compounds.

(1-2. Injection layer: electron injection layer, hole injection layer)
The injection layer can be provided as necessary, and may exist between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer.
An injection layer is a layer provided between an electrode and an organic layer in order to lower drive voltage and improve light emission luminance. For example, “Organic EL element and its forefront of industrialization (November 30, 1998, NTS Corporation) Issue) ”, Chapter 2, Chapter 2,“ Electrode Materials ”(pages 123-166), which is described in detail, and has a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer). .
Specific examples of the anode buffer layer (hole injection layer) include a phthalocyanine buffer layer typified by copper phthalocyanine, an oxide buffer layer typified by vanadium oxide, an amorphous carbon buffer layer, polyaniline (emeraldine), and polythiophene. And a polymer buffer layer using the conductive polymer.
Specifically, the cathode buffer layer (electron injection layer) is a metal buffer layer typified by strontium or aluminum, an alkali metal compound buffer layer typified by lithium fluoride, or an alkaline earth typified by magnesium fluoride. Examples thereof include a metal compound buffer layer and an oxide buffer layer typified by aluminum oxide.
The buffer layer (injection layer) is preferably a very thin film, and although it depends on the material used, the film thickness is preferably in the range of 0.1 nm to 5 μm.

(1-3. Blocking layer: hole blocking layer, electron blocking layer)
The blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film. There is a hole blocking layer described on page 237 of “Organic EL devices and their forefront of industrialization” (published on November 30, 1998 by NTT).
The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer as needed.
The hole blocking layer provided in the organic EL device of this embodiment is preferably provided adjacent to the light emitting layer.
On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed.
The thicknesses of the hole blocking layer and the electron blocking layer are not particularly limited, but are preferably 3 nm to 100 nm, and more preferably 5 nm to 30 nm.

(1-4. Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.
The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
What is preferably used as the hole transport material is a hole transport material that has a so-called p-type semiconductor property because a light emitting element with higher efficiency can be obtained.
Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5 nm-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

(1-5. Electron transport layer)
The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.
Conventionally, when a single electron transport layer and a plurality of layers are used, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the light emitting layer on the cathode side is injected from the cathode. It has a function of transmitting the generated electrons to the light emitting layer, and may be either organic or inorganic.
The electron transport material preferably used as the electron transport material is an n-type semiconductor material doped with impurities because an element with lower power consumption can be obtained.
Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

(1-6. Support substrate)
The support substrate 101 applied to the organic EL element 100 of the present embodiment is not particularly limited in the type of glass, plastic, and the like, and may be transparent or opaque. When light is extracted from the support substrate 101 side, the support substrate is preferably 101 transparent. Examples of the transparent support substrate 101 preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate 101 is a resin film that can give flexibility to the organic EL element 100.
Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Can be mentioned. An inorganic or organic film or a hybrid film of both may be formed on the surface of the resin film, and the water vapor permeability measured by a method according to JIS K 7129-1992 is 0.01 g / m ^2. It is preferably a barrier film of day · atm or less, and further, the oxygen permeability measured by a method according to JIS K 7126-1992 is 10 ⁻³ g / m ² / day or less, water vapor permeability. Is preferably a high barrier film of 10 ⁻³ g / m ² / day or less, and the water vapor permeability and oxygen permeability are both 10 ⁻⁵ g / m ² / day or less, Further preferred.
As a material for forming the barrier film, any material may be used as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and layers made of organic materials. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.
The method for forming the barrier film is not particularly limited. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the molecular beam epitaxy method, the cluster ion beam method, the ion plating method, the plasma polymerization method, the atmospheric pressure plasma. A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is also preferable.
Examples of the opaque support substrate 100 include a metal substrate such as aluminum and stainless steel, an opaque resin film, and a ceramic substrate.

(1-7. Sealing)
Examples of the sealing means used for sealing the organic EL element 100 include a method in which a sealing member, an electrode, and the support substrate 101 are bonded with an adhesive.
The sealing member which consists of glass, a polymer, a metal, etc. should just be arrange | positioned so that the organic EL element 100 may be covered, and a sealing member may be concave plate shape or flat plate shape. Sand blasting, chemical etching, or the like is used for processing into a concave shape. Moreover, the transparency and electrical insulation of the sealing member are not particularly limited.
Since the organic EL element 100 can be thinned, a polymer film or a metal film (metal foil) can be preferably used. Furthermore, the polymer film preferably has an oxygen permeability of 10 ⁻³ g / m ² / day or less and a water vapor permeability of 10 ⁻³ g / m ² / day or less. Moreover, it is more preferable that both the water vapor permeability and the oxygen permeability are 10 ⁻⁵ g / m ² / day or less.
Examples of the adhesive include a photocurable adhesive, a thermosetting adhesive, a moisture curable adhesive, a heat and chemical curable adhesive (mixed with two components), a hot melt adhesive, and an ultraviolet curable adhesive.
In addition, since the organic EL element 100 may be deteriorated by heat treatment, an element that can be adhesively cured from room temperature to 80 ° C. is preferable. A desiccant may be dispersed in the adhesive. The adhesive can be formed on the sealing member by coating with a dispenser, screen printing, lamination, or the like.

In addition, it is also preferable to coat the electrode and the organic layer on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and form an inorganic or organic layer in contact with the support substrate to form a sealing film. it can. In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of the element such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like is used. it can. Furthermore, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials. The method for forming these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster-ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.
In the gap between the sealing member and the organic EL element, it is preferable to inject an inert gas such as nitrogen and argon, or an inert liquid such as fluorinated hydrocarbon and silicon oil in the gas phase and the liquid phase. A vacuum can also be used. Moreover, a hygroscopic compound can also be enclosed inside.

(1-8. Protective film, protective plate)
In order to increase the mechanical strength of the element, a protective film or a protective plate may be provided outside the sealing film or the sealing film on the side facing the support substrate with the organic layer interposed therebetween. In particular, when sealing is performed by the sealing film, the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate. As a material that can be used for this, the same material as that used for the sealing member can be used.

(1-9. Anode)
As the anode 102 in the organic EL element 100, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such an electrode substance include conductive transparent materials such as metals such as Au, CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not required (about 100 μm or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1000 nm, preferably 10 nm to 200 nm.

(1-10. Cathode)
As the cathode 104 in the organic EL element 100, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as a cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 nm to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the emission luminance is advantageously improved.
Moreover, after producing the said metal by the film thickness of 1 nm-20 nm to a cathode, the transparent or semi-transparent cathode can be produced by producing the electroconductive transparent material quoted by description of the anode on it, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

(2. Method for producing organic EL element)
Next, a manufacturing method of the organic EL element 100 having the above configuration will be described.
Note that as described above, the organic layer 103 can be configured as long as it includes at least a light-emitting layer. Here, as an example, an anode buffer layer and a hole transport layer are provided between the anode 102 and the cathode 104. A method for manufacturing the organic EL element 100 including the organic layer 103 including a layer, a light emitting layer, a hole blocking layer, an electron transport layer, and a cathode buffer layer will be described.

  First, a desired electrode material, for example, a thin film made of a material for an anode is formed on a suitable support substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 nm to 200 nm, thereby producing an anode. To do.

Next, an organic compound thin film of an anode buffer layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and a cathode buffer layer, which are organic EL element materials, is sequentially formed thereon.
As a method for forming the light emitting layer in the organic compound thin film, a vacuum vapor deposition method using a vapor deposition apparatus 10 described later is used.
In addition, as a method for forming each layer other than the light emitting layer, a vapor deposition method, a wet process (spin coating method, cast method, ink jet method, printing method, LB method (Langmuir-Blodget method), spray method, printing method, slot type A known method such as a coater method is used, but from the viewpoint that a homogeneous film is easily obtained and pinholes are not easily generated, a vacuum deposition method, a spin coating method, an ink jet method, a printing method, a slot type coater. The method is particularly preferred. Further, different film forming methods may be applied for each layer.

  After forming these layers, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 50 nm to 200 nm, and a cathode is provided. Thus, a desired organic EL element 100 is obtained.

  In addition, it is also possible to reverse the production order and produce the cathode, the cathode buffer layer, the electron transport layer, the hole blocking layer, the light emitting layer, the hole transport layer, the anode buffer layer, and the anode in this order. When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 V to 40 V with the anode as + and the cathode as-. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

(3. Vapor deposition equipment)
Next, the vapor deposition apparatus 10 will be described.
As described above, the vapor deposition apparatus 10 is suitably used, for example, when the light emitting layer of the organic layer 103 in the organic EL element 100 is formed, and a plurality of vapor deposition apparatuses 10 are provided for the substrate K transported in vacuum. This is a vacuum vapor deposition apparatus that performs co-evaporation with vapor released from the vapor deposition source.
Here, the substrate K indicates a laminated body manufactured until the light emitting layer of the organic EL element 100 is formed. Specifically, the substrate K is, for example, a substrate in which the anode 102 is provided on the support substrate 101, a substrate in which the anode 102 and the hole injection layer are provided on the support substrate 101, the anode 102 on the support substrate 101, the positive electrode. For example, a hole injection layer and a hole transport layer are provided.
Further, the substrate K in the present embodiment is formed in a thin and long band shape, but is used in a form wound in a roll shape. The width, length, and the like of the substrate K are appropriately set according to the size of the organic EL panel to be manufactured.
In the following description, the transport direction of the substrate K is the X direction, and the direction orthogonal to the transport direction of the substrate K (the width direction of the substrate K) is the Y direction.

  As shown in FIGS. 3 and 4, the vapor deposition apparatus 10 includes a vacuum vessel 1, a conveying means 2, linear vapor deposition sources 3 </ b> A and 3 </ b> B, point vapor deposition source units 4 </ b> A and 4 </ b> B, film thickness monitors 7 and 7, and film thickness monitors 8. , 8 and so on.

(3-1. Vacuum container)
The vacuum container 1 includes, for example, a container body having an open top surface and a lid (not shown) that closes the opening, and the film is accommodated in the substrate K and each evaporation source by removing the lid. The materials P1 to P4 are taken in and out.
In addition, a vacuum pump 11 is connected to the vacuum vessel 1, and the inside of the vacuum vessel 1 is evacuated by the vacuum pump 11 during vapor deposition so that a vacuum state is maintained.
The degree of vacuum varies depending on the type of film forming material, but is, for example, 10 ⁻² to 10 ⁻⁷ Pa.

(3-2. Conveying means)
The transport means 2 is installed above the inside of the vacuum vessel 1 and transports the roll-shaped substrate K by a technique called a roll-to-roll system.
Specifically, the transport unit 2 includes an unwinding unit 21 disposed at the upstream end of the transport path and a winding unit 22 disposed at the downstream end of the transport path. The substrate K is fed out and conveyed, and the substrate K that has been conveyed is wound up by the winding unit 22.
The substrate K is transported at a constant speed between the unwinding unit 21 and the winding unit 22 while maintaining a constant tension, and while being transported from the unwinding unit 21 to the winding unit 22, Co-evaporation is performed by the vapors ejected from the linear deposition sources 3A and 3B and the point-like deposition sources 4A and 4B installed in the.
In addition, the conveyance speed of the board | substrate K is set to 1 m / min, for example.

(3-3. Linear evaporation source)
The linear vapor deposition sources 3A and 3B are also called line sources, and are arranged in parallel along the X direction so as to extend in the Y direction near the bottom surface inside the vacuum vessel 1.
The linear vapor deposition sources 3A and 3B eject the film-forming materials P1 and P2 as vapor from the lower surface side of the substrate K to the substrate K being transported.
Specifically, each of the linear vapor deposition sources 3A and 3B is a long container extending in the Y direction, and has a long vapor jet 31 extending in the Y direction on the upper surface thereof. .
The linear deposition sources 3A and 3B are formed of, for example, a refractory metal such as tantalum or tungsten, and film-forming materials P1 and P2 to be deposited on the surface (lower surface) of the substrate K are accommodated therein. Yes. Further, the linear vapor deposition sources 3A and 3B are provided with a heater 32 for heating the linear vapor deposition sources 3A and 3B. The heater 32 is energized according to the control of a heater control unit (not shown). Then, the linear vapor deposition sources 3A and 3B are heated to a certain temperature.
Thereby, the film-forming materials P1 and P2 evaporate or sublimate, and the vapor is released from the respective vapor ejection ports 31 to the substrate K.
When the substrate K passes above the linear vapor deposition sources 3A and 3B in the X direction, the film forming materials P1 and P2 are uniformly deposited in the Y direction. Then, as the substrate K is transported, thin films of film forming materials P1 and P2 are formed on the entire lower surface of the substrate K.
In addition, the linear vapor deposition sources 3A and 3B may be configured such that, for example, a plurality of point vapor deposition sources are arranged in a line in addition to the above configuration.

(3-4. Point vapor deposition source)
The point vapor deposition sources 4A and 4B are arranged side by side along the X direction on the upstream side of the linear vapor deposition sources 3A and 3B.
In the present embodiment, each of the point vapor deposition source units 4A and 4B includes one point vapor deposition source that can reciprocate along the Y direction. The point deposition source is also referred to as a point source.
The point vapor deposition source portions 4A and 4B eject the film-forming materials P3 and P4 as vapor from the lower surface side of the substrate K to the substrate K being transported. Because of the shape of the point vapor deposition source portions 4A and 4B, a small amount of film forming material can be efficiently evaporated.
Specifically, the point vapor deposition source parts 4A and 4B are point-like containers having a vapor jet port 41 on the upper surface thereof. Similarly to the linear vapor deposition sources 3A and 3B, the point vapor deposition source portions 4A and 4B are formed of, for example, a refractory metal such as tantalum or tungsten, and vapor deposited on the surface (lower surface) of the substrate K therein. Film forming materials P3 and P4 are accommodated. Further, the spot vapor deposition source sections 4A and 4B are provided with a heater 42 for heating the spot vapor deposition source sections 4A and 4B, and the heater 42 is controlled by a heater control section (not shown). The point vapor deposition source sections 4A and 4B are heated to a certain temperature.
As a result, the film forming materials P3 and P4 evaporate or sublimate, and vapor is ejected from the vapor ejection port 41 to the substrate K.

As described above, each of the point vapor deposition source portions 4A and 4B is configured to be reciprocally movable in the Y direction. Specifically, each of the point vapor deposition source units 4A and 4B is provided with a drive mechanism 43 that is driven by control of a drive control unit (not shown), and reciprocates in the Y direction according to the drive of the drive mechanism 43. .
Thereby, each of the spot-like vapor deposition source units 4A and 4B ejects steam while reciprocating in the Y direction.
As shown in FIG. 5 (a), this is for improving the defect in the point vapor deposition source part that the deposition amount on the substrate K is increased at a position where the distance from the vapor jet port 41 is shorter. In addition, by reciprocating the point vapor deposition source portions 4A and 4B, as shown in FIG. 5 (b), it is possible to eliminate unevenness in the width direction (Y direction) of the substrate K and to perform uniform vapor deposition. Yes.

  At this time, the moving speed of the point vapor deposition source units 4A and 4B is set to be, for example, 5 times the transport speed of the substrate K. If the moving speed is within this range, for example, as shown in FIG. 6, the dotted vapor deposition source sections 4A and 4B draw a constant locus (broken line in FIG. 6) with respect to the width direction of the substrate K. Thus, the film-forming materials P3 and P4 are vapor-deposited, and uniform vapor-deposition can be performed without any unevenness with respect to the conveyance speed of the substrate K.

Further, the linear deposition sources 3A and 3B and the spot deposition sources 4A and 4B are formed by the film deposition materials P1 to P4 released from the linear deposition sources 3A and 3B and the spot deposition sources 4A and 4B. It is preferable that they are arranged close enough to overlap each other on the substrate K.
For example, the distance between the linear vapor deposition source 3A and the linear vapor deposition source 3B, the distance between the linear vapor deposition source 3B and the point vapor deposition source part 4A, and the distance between the point vapor deposition source part 4A and the point vapor deposition source part 4B. Are set to 5 mm, the film-forming materials P1 to P4 can overlap each other on the substrate K, and uniform co-evaporation can be performed.

The film thickness monitors 7 and 7 are, for example, quartz resonators, and are respectively installed at the end of the linear deposition source 3A and the end of the linear deposition source 3B.
The ends where the film thickness monitors 7 and 7 are installed in the linear vapor deposition sources 3A and 3B have a structure capable of ejecting vaporized vapor. The film thickness monitors 7 and 7 are connected to the film thickness monitors 7 and 7, respectively. Measure the thickness of the deposited material.
A monitor control unit (not shown) is connected to the film thickness monitors 7 and 7. The monitor control unit converts the film thickness measured by the film thickness monitors 7 and 7 into a film formation speed, and controls the heater. Feedback to the department. Therefore, when there is a change in the film forming speed, the output of the heater 32 is controlled, whereby the evaporation amounts of the film forming materials P1 and P2 from the linear vapor deposition sources 3A and 3B are kept constant, and The film speed is also kept constant.

The film thickness monitors 8 and 8 are, for example, quartz resonators, and move so as to follow the point vapor deposition source unit 4A and the point vapor deposition source unit 4B, respectively, and adhere to the film thickness monitors 8 and 8, respectively. Measure the film thickness of the material.
A monitor control unit (not shown) is connected to the film thickness monitors 8 and 8. The monitor control unit converts the film thickness measured by the film thickness monitors 8 and 8 into a film formation speed, and controls this with a heater. Feedback to the department. Therefore, when there is a change in the film forming speed, the output of the heater 42 is controlled, whereby the evaporation amounts of the film forming materials P3 and P4 from the point vapor deposition source parts 4A and 4B are kept constant, The film forming speed is also kept constant.

  In addition, it is good also as installing a shutter (illustration omitted) between the board | substrate K and four vapor deposition sources. Such a shutter opens and closes based on an instruction signal from a control device (not shown). Specifically, the shutter is closed until the measured values by the film thickness monitors 7, 7, 8, 8 reach a desired constant value, and the shutter is opened when the desired constant value is reached. When the shutter is opened, vapor deposition starts.

The film forming materials P1 and P2 are ejected from the linear vapor deposition source 3A and the linear vapor deposition source 3B, respectively. Specifically, the film forming materials P1 and P2 are, for example, organic materials that exist in a high concentration in the light emitting layer, and include the blue light emitting dopant and the host compound described above.
Further, the film forming materials P3 and P4 are ejected from the point vapor deposition source part 4A and the point vapor deposition source part 4B, respectively. Specifically, the film forming materials P3 and P4 are, for example, organic materials present in the light emitting layer at a lower concentration than the film forming materials P1 and P2, and include the above-described green light emitting dopant and red light emitting dopant. .

(3-5. Deposition method)
Next, a vapor deposition method using the vapor deposition apparatus 10 will be described.
The vapor deposition apparatus 10 of this embodiment is an apparatus that performs co-vapor deposition on a long substrate K transported by a roll-to-roll method using two types of vapor deposition sources.
When performing vapor deposition, first, the vacuum pump 11 is operated and the inside of the vacuum vessel 1 is evacuated.
When the linear vapor deposition sources 3A and 3B and the point vapor deposition source units 4A and 4B are heated to a certain temperature by the heaters 32 and 42, the linear vapor deposition sources 3A and 3B and the point vapor deposition source units 4A and 4B The film forming materials P1 to P4 accommodated inside are heated to a predetermined temperature and evaporated or sublimated to generate a vapor flow. The vapor flow escapes from the vapor ejection ports 31 and 41 and is conveyed upward. A thin film by co-evaporation is formed on the surface (lower surface) of the substrate K.

At this time, the film forming materials P1 and P2 are uniformly deposited in the Y direction on the lower surface of the substrate K by being emitted from the linear deposition sources 3A and 3B.
On the other hand, the film-forming materials P3 and P4 having a lower concentration than the film-forming materials P1 and P2 are efficiently deposited on the lower surface of the substrate K by being emitted from the point-like deposition source parts 4A and 4B.
Further, since the point vapor deposition source portions 4A and 4B reciprocate in the Y direction, the film forming materials P3 and P4 are also uniformly deposited on the lower surface of the substrate K.
In addition, since the moving speed of the point vapor deposition source units 4A and 4B is set to be 5 times the transport speed of the substrate K, the occurrence of unevenness in the X direction of the substrate K is suppressed, Co-deposited uniformly.

As described above, according to the present embodiment, in the vapor deposition apparatus 10 for vapor-depositing and forming a thin film on the substrate K in the vacuum vessel 1, the conveyance means 2 for conveying the substrate K in the vacuum vessel 1 and the Y direction. A plurality of linear vapor deposition sources 3A and 3B which are arranged in parallel along the X direction so as to extend, and eject film forming materials P1 and P2 as vapor to the substrate K, and are arranged side by side along the X direction. Point deposition source sections 4A and 4B that eject film deposition materials P3 and P4 having a concentration lower than that of the film deposition materials P1 and P2 ejected from the linear deposition sources 3A and 3B to the substrate K as vapor. In addition, co-evaporation is performed by vapor ejected from the linear deposition sources 3A and 3B and the point deposition sources 4A and 4B.
For this reason, since a small amount of film forming materials P3 and P4 can be controlled by the point vapor deposition source sections 4A and 4B, it is possible to perform co-vapor deposition uniformly on the transported substrate K.
That is, by using a combination of the linear vapor deposition sources 3A and 3B and the point vapor deposition source portions 4A and 4B, it is possible to perform co-vapor deposition uniformly on the substrate K being transported.

In particular, according to the present embodiment, the point vapor deposition source sections 4A and 4B can reciprocate in a direction (Y direction) orthogonal to the transport direction of the substrate K, and release vapor while reciprocating in the Y direction. It is supposed to be.
For this reason, unevenness in the Y direction of the point vapor deposition source parts 4A and 4B is eliminated, and the co-deposition can be performed more uniformly on the substrate K being transported.
Therefore, it is possible to perform vapor deposition with high material efficiency without increasing the size of the vapor deposition apparatus 10 itself.

  The embodiments to which the present invention can be applied are not limited to the above-described embodiments, and can be appropriately changed without departing from the spirit of the present invention.

For example, as shown in FIG. 7, the movement range in the Y direction of the point vapor deposition source portions 4A and 4B may be made wider than the width of the substrate K.
By doing so, control is performed such that the point vapor deposition source units 4A and 4B are moved at a constant speed while facing the substrate K, decelerated and stopped outside the substrate K, and acceleration is started in the opposite direction. Can be performed. Therefore, there is no unevenness in the central portion and both end portions in the width direction of the substrate K, and vapor deposition can be performed more uniformly.

Further, for example, as shown in FIG. 8, the vapor outlets 31 of the linear vapor deposition sources 3 </ b> A and 3 </ b> B and the vapor jet outlets 41 of the point vapor deposition source units 4 </ b> A and 4 </ b> B are inclined with respect to the substrate K. It is also good to do. At this time, an angle formed by a line perpendicular to the vapor ejection direction from the linear vapor deposition sources 3A and 3B and a line perpendicular to the vapor ejection direction from the point vapor deposition source sections 4A and 4B is smaller than 180 degrees. To do.
By doing in this way, the film-forming materials P3 and P4 ejected from the point vapor deposition sources 4A and 4B and the film-forming materials P1 and P2 ejected from the linear vapor deposition sources 3A and 3B overlap each other. It can be enlarged compared with the case where it is not inclined.

  For example, as shown in FIG. 9, it is good also as providing the shielding board 33 which shields a part of vapor | steam ejection port 31 of linear vapor deposition source 3A, 3B. By doing in this way, it can deposit on a substrate K conveyed with a concentration gradient.

[Second Embodiment]
Next, a second embodiment of the present invention will be described focusing on differences from the first embodiment.
In addition, about the structure similar to 1st Embodiment, the same code | symbol is attached | subjected and the description is abbreviate | omitted.

As shown in FIG. 10, the vapor deposition apparatus 20 of the present embodiment includes point vapor deposition source portions 9A and 9B arranged side by side along the X direction on the upstream side of the linear vapor deposition sources 3A and 3B. Each of the vapor deposition source portions 9A and 9B includes a plurality of point vapor deposition sources 9a,..., 9b.
The plurality of point-like vapor deposition sources 9a,..., 9b,... Are controlled by a timing control unit (not shown), are switched at a predetermined timing, and sequentially emit steam. In this case, since the amount of ejection from each vapor deposition source can be controlled by time, even when the distance between the vapor ejection port 91 of the vapor deposition source and the substrate K is reduced, the time during which the vapor is ejected is shortened. This makes it possible to reduce the deposition amount. Furthermore, material use efficiency can be improved by shortening the distance.
At this time, the linear vapor deposition sources 3A and 3B and the point vapor deposition source portions 9A and 9B are film deposition materials P1 to P4 emitted from the linear vapor deposition sources 3A and 3B and the point vapor deposition source portions 9A and 9B. Are preferably arranged close enough to overlap each other on the substrate K.
For example, the distance between the linear vapor deposition source 3A and the linear vapor deposition source 3B, the distance between the linear vapor deposition source 3B and the point vapor deposition source part 9A, and the distance between the point vapor deposition source part 9A and the point vapor deposition source part 9B. Are set to 5 mm, the film-forming materials P1 to P4 can overlap each other on the substrate K, and uniform co-evaporation can be performed.

As described above, according to the present embodiment, the same effects as those of the first embodiment can be obtained, and each of the point vapor deposition source sections 9A and 9B is fixedly installed along the Y direction. .., 9b..., And the plurality of point deposition sources 9a..., 9b. Therefore, it is possible to perform co-evaporation uniformly in the Y direction on the substrate K to be transported.
Therefore, vapor deposition with good material efficiency can be performed without increasing the size of the vapor deposition apparatus 20 itself.

  In addition, the number of the plurality of point-like vapor deposition sources 9a,..., 9b... Is not particularly limited, and the vapor deposition is performed uniformly with no unevenness at the center and both ends in the width direction of the substrate K. Therefore, it is appropriately set according to the width of the substrate K.

Also in the present embodiment, the vapor outlet 31 of the linear vapor deposition sources 3A and 3B and the vapor jet 91 of the point vapor deposition sources 9A and 9B are inclined with respect to the substrate K, and at this time, the line The angle formed between the line perpendicular to the vapor ejection direction from the vapor deposition sources 3A and 3B and the line perpendicular to the vapor ejection direction from the point vapor deposition sources 9A and 9B is set to be smaller than 180 degrees. It's also good.
By doing in this way, the part which the film-forming material P3, P4 ejected from the point-like vapor deposition source part 9A, 9B and the film-formation material P1, P2 ejected from the linear vapor deposition source 3A, 3B overlap. It can be enlarged compared with the case where it is not inclined.

[Example]
Hereinafter, the vapor deposition apparatus of the present invention will be specifically described by way of examples, including comparative examples.

<Production of organic EL panel>
Example 1
After patterning a support substrate in which ITO (indium tin oxide) was deposited to a thickness of 110 nm on a glass substrate having a thickness of 0.7 mm as an anode, the transparent support substrate with the ITO transparent electrode attached thereto was isopropyl alcohol. The substrate was ultrasonically cleaned with, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes, and then the transparent support substrate was fixed to a substrate holder of a vacuum deposition apparatus.
After reducing the pressure to 1 × 10 ⁻⁴ Pa using a commercially available vacuum deposition apparatus, the following compound HT-1 was deposited at a deposition rate of 0.1 nm / second while moving the transparent support substrate, and a positive 20 nm thickness was obtained. A hole transport layer was provided.

Next, using the vapor deposition apparatus shown in FIGS. 3 and 4, while moving the support substrate at a conveyance speed of 1 m / min, the following compound A-1 (green light emitting dopant), compound A-2 (red light emitting dopant), Compound A-3 (blue light-emitting dopant) and compound H-1 (host compound), compound A-1 and A-2 are each 0.2% by weight, regardless of film thickness, using a point source. Vapor deposition was carried out at a deposition rate of 0.02 nm · m / min so as to achieve a concentration, and compounds A-3 and H-1 were vapor deposited using a line source so that they were 35 wt% and 94.6 wt%, respectively. Evaporation was performed at a fixed speed, and co-evaporation was performed to a thickness of 70 nm to form a light emitting layer.

  In addition, the rate measurement of each evaporate was implemented using the quartz oscillator. The vapor deposition rate was measured using a vibrator installed at the end so that vaporized vapor could be injected from the end of the line source. Moreover, the evaporation rate of the point source was measured by installing a vibrator that moved to follow the point source. The line source and point source can monitor the evaporation rate during the vapor deposition, and when the evaporation rate fluctuates, the evaporation rate is kept constant by feeding back to the crucible temperature. Film formation was performed.

Thereafter, using a commercially available vacuum deposition apparatus, the following compound ET-1 was deposited to a film thickness of 30 nm to form an electron transport layer, and KF was further formed to a thickness of 2 nm as a cathode buffer layer. Furthermore, aluminum 110nm was vapor-deposited and the cathode was formed.

Subsequently, the non-light-emitting surface of the organic EL element was covered with a glass cover to produce an organic EL panel having the configuration shown in FIGS.
The sealing operation with the glass cover was performed in a glove box (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more) in a nitrogen atmosphere without bringing the organic EL element into contact with the atmosphere. The glass cover was filled with nitrogen gas and provided with a water catching agent.

(Example 2)
In Example 2, the vapor deposition apparatus shown in FIG. 9 was used, and the vapor outlet of the line source was covered with a shielding plate, so that the concentration of Compound H-1 was changed from 64.6% to 94.6% by weight. An organic EL device was fabricated in the same manner as in Example 1 except that a light emitting layer was formed by applying a concentration gradient so that Compound A-3 was 35% to 5% by weight linearly with respect to the film thickness. Produced.
Subsequently, the non-light-emitting surface of the produced organic EL element was covered with a glass cover to produce an organic EL panel.

(Comparative Example 1)
Comparative Example 1 was the same as Example 1 except that the light emitting layer was formed using a point source of the vapor deposition apparatus shown in FIGS. Thus, an organic EL element was produced.
Subsequently, the non-light-emitting surface of the produced organic EL element was covered with a glass cover to produce an organic EL panel.

(Comparative Example 2)
In Comparative Example 2, an organic EL element was produced in the same manner as in Example 1 except that the light emitting layer was formed using a point source moving range of the vapor deposition apparatus shown in FIGS. did.
Subsequently, the non-light-emitting surface of the produced organic EL element was covered with a glass cover to produce an organic EL panel.

(Comparative Example 3)
Comparative Example 3 emits light using a vapor deposition apparatus shown in FIGS. 3 and 4 in which the distance between the line source and the point source is large and each source is installed so that the ejected vapors do not overlap each other. An organic EL device was produced in the same manner as in Example 1 except that the layer was formed.
Subsequently, the non-light-emitting surface of the produced organic EL element was covered with a glass cover to produce an organic EL panel.

<Evaluation of organic EL panel>
The organic EL panels produced in Examples 1 and 2 and Comparative Examples 1 to 3 described above were evaluated using the following method. The evaluation results are shown in Table 1.

(Concentration evaluation by TOF-SIMS)
As a concentration measurement by TOF-SIMS, a time-of-flight secondary ion mass spectrometer TRIFT2 manufactured by Physical Electronics was used, and an ion of an accelerating voltage of 25 kV was used as a primary ion (beam current was 2 nA). The concentration of each material from the side end to the cathode side end was measured.
As a result of the measurement, the evaluation was evaluated as ◯ if it was within ± 5% of the set value, and X in other ranges.

(Evaluation of uneven brightness and chromaticity)
As an evaluation of luminance unevenness and chromaticity unevenness, the produced organic EL panel was driven at a constant current value of 25 A / m ² , and the light emitting surface was observed from the front to observe luminance unevenness and chromaticity unevenness.
As a result of the observation, when there was no luminance unevenness and chromaticity unevenness, it was evaluated as ◯, and when there was luminance unevenness and chromaticity unevenness, it was evaluated as x.

(Evaluation of chromaticity fluctuation range)
As the evaluation of the chromaticity variation range was calculated in CIE1931 chromaticity coordinates in front luminance ^{300cd / m 2 ~1500cd / m 2} , x, the variation of the y values maximum distance ΔE (the following equation).
ΔE = (Δx ² + Δy ² ) ^1/2
As a result of the calculation, the case where the fluctuation maximum distance ΔE of the organic EL panel was less than 0.01 was evaluated as ◯, and the evaluation was made as x in other regions.

<Result>

In Comparative Example 1, the luminance of the central portion of the support substrate is high, and the luminance decreases as it approaches the end portion. Therefore, the evaluation of luminance / chromaticity unevenness is x. In Comparative Example 1, since the maximum fluctuation distance ΔE was 0.06, the evaluation of the chromaticity fluctuation range is x.
In Comparative Example 2, the luminance unevenness occurred due to the width of the support substrate, and thus the evaluation of the luminance / chromaticity unevenness was x. In Comparative Example 2, since the maximum variation distance ΔE was 0.1, the evaluation of the chromaticity variation range is x.
In Comparative Example 3, both the luminance and chromaticity are lower than those of the other Comparative Examples and Examples, and the product specifications are not satisfied. Therefore, the evaluation of luminance / chromaticity unevenness is x. In Comparative Example 3, since the maximum fluctuation distance ΔE was 0.05, the evaluation of the chromaticity fluctuation range is x.

DESCRIPTION OF SYMBOLS 10, 20 Vapor deposition apparatus 1 Vacuum container 11 Vacuum pump 2 Conveying means 21 Unwinding part 22 Winding part 3A, 3B Linear vapor deposition source 31 Vapor outlet 32 Heater 33 Shielding plates 4A, 4B Point vapor deposition source part 41 Vapor outlet 42 Heater 43 Drive mechanism 7, 7 Film thickness monitor 8, 8 Film thickness monitor 9A, 9B Point vapor deposition source section 9a ..., 9b ... Point vapor deposition source 91 Vapor outlet K Substrate P1-P4 Film deposition material

Claims (4)

In a deposition apparatus for depositing a thin film on a substrate in a vacuum vessel,
In the vacuum vessel,
Transport means for transporting the substrate;
A plurality of linear vapor deposition sources arranged side by side along the transport direction so as to extend in an orthogonal direction perpendicular to the transport direction of the substrate, and jetting a film forming material as vapor to the substrate;
A plurality of point vapor deposition source portions arranged side by side along the transport direction and ejecting a film-forming material having a concentration lower than that of the film-forming material ejected from the plurality of linear vapor deposition sources to the substrate; ,
With
Each of the point vapor deposition source units includes a point vapor deposition source capable of reciprocating along the orthogonal direction,
The point vapor deposition source reciprocates in the orthogonal direction in a movement range wider than the width of the substrate and ejects steam,
The vapor deposition apparatus characterized in that co-vapor deposition is performed such that vapors ejected from the plurality of linear vapor deposition sources and the plurality of point vapor deposition source units overlap each other . In a deposition apparatus for depositing a thin film on a substrate in a vacuum vessel,
In the vacuum vessel,
Transport means for transporting the substrate;
A plurality of linear vapor deposition sources arranged side by side along the transport direction so as to extend in an orthogonal direction perpendicular to the transport direction of the substrate, and jetting a film forming material as vapor to the substrate;
A plurality of point vapor deposition source portions arranged side by side along the transport direction and ejecting a film-forming material having a concentration lower than that of the film-forming material ejected from the plurality of linear vapor deposition sources to the substrate; ,
With
Each of the point vapor deposition source portions includes a plurality of point vapor deposition sources fixedly installed along the orthogonal direction,
The plurality of point-like vapor deposition sources are switched at a predetermined timing to sequentially eject steam,
The vapor deposition apparatus characterized in that co-vapor deposition is performed such that vapors ejected from the plurality of linear vapor deposition sources and the plurality of point vapor deposition source units overlap each other. The vapor jet outlet of the linear vapor deposition source and the vapor jet outlet of the dotted vapor deposition source section are inclined with respect to the substrate,
The angle formed by a line perpendicular to the vapor ejection direction from the linear vapor deposition source and a line perpendicular to the vapor ejection direction from the point vapor deposition source section is smaller than 180 degrees. The vapor deposition apparatus according to 1 or 2 . The vapor deposition apparatus according to any one of claims 1 to 3 , further comprising a shielding plate that shields a part of a vapor jet port of the linear vapor deposition source.

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