WO2011070841A1 - 有機el素子の製造方法 - Google Patents
有機el素子の製造方法 Download PDFInfo
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- WO2011070841A1 WO2011070841A1 PCT/JP2010/067220 JP2010067220W WO2011070841A1 WO 2011070841 A1 WO2011070841 A1 WO 2011070841A1 JP 2010067220 W JP2010067220 W JP 2010067220W WO 2011070841 A1 WO2011070841 A1 WO 2011070841A1
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Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
- H10K71/441—Thermal treatment, e.g. annealing in the presence of a solvent vapour in the presence of solvent vapors, e.g. solvent vapour annealing
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/851—Division of substrate
Definitions
- the present invention relates to a method for producing an organic EL element produced by a roll-to-roll method.
- organic EL elements organic electroluminescence elements
- a first electrode (anode) made of a transparent conductive film such as ITO (Indium tin oxide) is provided on a transparent substrate such as a glass substrate, and an organic functional layer including at least a light emitting layer thereon, and aluminum
- the second electrode (cathode) made of, for example, is provided in this order, and the first electrode (anode) and the second electrode (cathode) are connected to an external circuit or an internal drive at the periphery of the organic EL element.
- a first electrode (anode) side extraction electrode and a second electrode (cathode) side extraction electrode for connection to the circuit are formed.
- An organic EL element emits light when a very thin thin film (organic functional layer) of an organic compound including a fluorescent or phosphorescent light emitting layer is sandwiched between a first electrode (anode) and a second electrode (cathode) and a current is passed.
- This is a current-driven light-emitting element.
- the organic substance is an insulator, but by making the thickness of the organic layer very thin, current can be injected and it can be driven as an organic EL element. It can be driven at a low voltage of 10 V or less, and it is possible to obtain high-efficiency light emission.
- a dry process method and a wet process method are known.
- vapor deposition is performed under a high vacuum to form a thin film.
- a high vacuum condition 10 ⁇ 4 Pa or less, the operation is complicated and the cost is high. It is not always preferable from the viewpoint of production.
- the wet process method various wet methods such as an extrusion coating method, a dip coating method, a spin coating method, an ink jet method, and a printing method can be employed.
- an extrusion coating method a dip coating method
- a spin coating method an ink jet method
- a printing method a printing method
- it since it can be formed under atmospheric pressure, there is an advantage that the cost can be reduced.
- a coating solution is prepared to form a thin film, there is a feature that unevenness is hardly generated even in a large area. Therefore, it is a thin film forming method that is actively used because of its great merit in terms of cost and manufacturing technology. This can be said to be very advantageous in terms of cost and manufacturing technology, especially for lighting applications of organic EL elements.
- a single-wafer method using a single-wafer base material and a roll-to-roll method using a strip-like flexible base material are known.
- the single wafer method has a limit in increasing the production efficiency
- the roll-to-roll method has a high possibility of increasing the production efficiency, and therefore, a method using a wet process method is being studied.
- a plurality of first electrodes are formed on a strip-shaped flexible substrate by a roll-to-roll method, and a hole transport layer forming coating solution and a light emitting layer are formed on these first electrodes by a wet coating method.
- a method of forming a hole transport layer and a light emitting layer by sequentially applying a coating solution in a pattern such as an ink jet method is known (for example, see Patent Document 1).
- this method makes it difficult to increase the production efficiency, and induces non-uniform film thickness called drying unevenness.
- an organic electroluminescence panel with a roll-to-roll method As a method for producing an organic electroluminescence panel with a roll-to-roll method to increase production efficiency and a uniform film thickness without drying unevenness, it is a strip-like flexible film that is continuously conveyed and the first electrode is patterned.
- a manufacturing method is known in which a coating solution for forming an organic functional layer is applied onto a resin film by a wet coating method over the entire surface such as a die coating method (see, for example, Patent Document 2).
- the first electrode since the first electrode is patterned, if the coating liquid for forming the organic functional layer is applied to the entire surface by the wet coating method, the organic function is caused by the presence of a step in the gap between the first electrode and the first electrode. Since uneven coating occurs in the layer, it causes light emission unevenness. This phenomenon is particularly likely to occur at the edge of the electrode.
- the organic EL device manufacturing method that uses a low viscosity coating solution to form a thin organic functional layer with a small wet film thickness is susceptible to steps.
- the gap portion of the first electrode it has been found that there is coating unevenness due to the unstable coating film that seems to be caused by the step.
- an organic EL having at least a first electrode, an organic functional layer including at least a light emitting layer, a second electrode, and a sealing member on a strip-shaped flexible substrate.
- An object of the present invention is to provide a method for producing an organic EL device having high production efficiency and stable performance quality by a production method using a roll-to-roll method.
- an organic EL element having a first electrode, at least one organic functional layer, and a second electrode on a strip-shaped flexible substrate
- the flexible substrate is conveyed.
- a method for manufacturing an organic EL element comprising: forming a structure of a plurality of organic EL elements; and cutting the organic EL elements into individual organic EL elements to manufacture the organic EL elements.
- an organic EL device having at least a first electrode, an organic functional layer including at least a light-emitting layer, and a second electrode on a strip-like flexible substrate can be produced with a roll-to-roll method. It is possible to provide a method for producing an organic EL element that is high and has stable performance quality.
- FIG. 3 is a schematic diagram after the cathode buffer layer (electron injection layer) forming step shown in FIG. 2.
- FIG. 5 is a schematic flow diagram showing patterning of a hole transport layer in the hole transport layer forming step shown in FIG. 4.
- FIG. 1 is a schematic diagram showing a configuration of an organic EL element.
- 1A is a plan view of the organic EL element 1
- FIG. 1B is a cross-sectional view taken along the line AA ′ of the organic EL element 1, and FIG. It is B 'sectional drawing.
- the organic EL element 1 has a first electrode 12, an organic functional layer 13, and a second electrode 14 formed on a flexible substrate 11 to form an organic EL structure 20.
- the organic EL structure 20 has a configuration in which the sealing member 16 is laminated on the upper surface of the organic EL structure 20 with the sealing agent 15 interposed therebetween.
- the organic functional layer 13 includes a plurality of organic layers such as a hole transport layer 103, a light emitting layer 104, an electron transport layer 105, and a cathode buffer layer (electron injection layer) 106, for example.
- the organic EL structure 20 has an upper surface portion including the organic functional layer 13 covered with a sealing member 16, and the first electrode 12 is formed on the upper portion of the sealing member 16 in the drawing. A part of the second electrode 14 is exposed at a lower portion of the sealing member 16 in the figure.
- the organic functional layer 13 emits light by supplying current from the exposed portions of the first and second electrode sealing members 16 at the upper and lower portions in the drawing.
- first electrode lead portion 12a The portion of the first electrode 12 exposed at the top of the sealing member 16 is referred to as a first electrode lead portion 12a.
- second electrode 14 exposed at the bottom of the sealing member 16 is the second electrode lead-out. This will be referred to as part 14a.
- the organic functional layer 13 includes a hole transport layer, a light emitting layer, an electron transport layer, and a cathode buffer layer (electron injection layer).
- a gas barrier film (not shown) may be provided between the first electrode (anode) 12 and the flexible substrate 11.
- a discontinuous portion 17 may be provided in a part of the first electrode (anode) 12 so as to be orthogonal to the transport direction. This is because when the first electrode (anode) 12 formed continuously is formed into a plurality of organic EL elements, the first electrode (anode) is exposed from the cut surface when separated and cut into individual organic EL elements. There is a concern about short circuit. In consideration of the short circuit, it is desirable to form the discontinuous portion 17 so as to separate the exposed first electrode (anode).
- the layer configuration of the organic EL element shown in the figure is an example, but the following configuration is given as an example of another typical layer configuration between the first electrode (anode) and the second electrode. It is done.
- FIG. 2 is a schematic diagram showing an example of a manufacturing process for manufacturing the organic EL element shown in FIG. 1 by a roll-to-roll method using a strip-like flexible base material.
- the manufacturing process 2 includes a strip-shaped flexible substrate supplying process 201, a first electrode forming process 202, a hole transport layer forming process 203, a light emitting layer forming process 204, an electron transport layer forming process 205, It has a cathode buffer layer (electron injection layer) forming step 206, a second electrode forming step 207, a sealing step 208, and a recovery step 209.
- a cutting device for obtaining individual organic EL elements from a strip-shaped flexible substrate having a plurality of organic EL elements may be used, or a strip-shaped apparatus having a plurality of organic EL elements may be used.
- a winding device When a winding device is used, after winding and collecting in a roll shape, a plurality of organic EL elements produced on a strip-shaped flexible substrate in another process are cut as individual organic EL elements. It doesn't matter.
- the roll-to-roll method uses a strip-shaped flexible base material wound in a roll shape as shown in the figure, and sequentially produces a first electrode forming step 202 to a sealing step 208 to produce an organic EL element.
- FIG. 3 is a schematic diagram up to the supplying step shown in FIG. 2 and the first electrode forming step.
- 201 indicates a supply process of the strip-shaped flexible substrate 3, and 202 indicates a first electrode formation process.
- a feeding device (not shown) for feeding out a strip-like flexible substrate 3a wound in a roll shape is used, and the strip-like flexibility is continuously applied to the first electrode forming step 202 of the next step.
- the substrate 3 is fed out through the transport roller 201b.
- the belt-like flexible substrate 3 is provided with an alignment mark (not shown) used for positioning such as patterning of an organic functional layer including a hole transport layer described later.
- the first electrode step 202 uses a first electrode forming device 202a, a first accumulator 202b, a second accumulator 202c, a first electrode cutting device 202d1, a third accumulator 202d, and a winding device 202e. Yes.
- the first electrode forming apparatus 202a includes a vapor deposition apparatus 202a1 having an evaporation source container 202a2. In the case of the invention according to claim 1 or 2, the first electrode excision device 202d1 (details will be described later) is not used.
- the first accumulator 202b has a plurality of lower conveyance rollers 202b1 and a plurality of upper conveyance rollers 202b2, and is arranged for speed adjustment between the supply step 201 and the first electrode forming apparatus 202a.
- the second accumulator 202c and the third accumulator 202d have a plurality of lower transport rollers 202c1 and 202d2 and a plurality of upper transport rollers 202c2 and 202d3.
- the first electrode excision device 202d1, the first electrode forming device 202a, and the winding It is arranged for speed adjustment with the take-off device 202e.
- the first electrode is formed on the strip-shaped flexible substrate 3 continuously supplied from the supplying step 201 by the first electrode forming apparatus 202a.
- the thickness of the first electrode is preferably 100 nm to 200 nm.
- the first electrodes are continuous without gaps in the transport direction (the flow direction of application) of the strip-shaped flexible substrate 3. It is preferable that it is formed.
- the belt-shaped flexible substrate on which the first electrode is laminated via the transport roller 202e1 is temporarily wound and temporarily stored by the winding device 202e. After the primary storage, it is sent to the hole transport layer forming step 203 (see FIG. 4). In addition, when not winding up and storing, it is continuously sent to the hole transport layer forming step 203 (see FIG. 2).
- the supply process 201 and the first electrode formation process 202 are preferably performed in a vacuum environment.
- the 1st electrode formation process is formed with a vapor deposition method is shown in this figure, there is no limitation in particular about a formation method, For example, sputtering method etc. can be used.
- FIG. 4 is a schematic diagram of the hole transport layer forming step shown in FIG.
- the hole transport layer forming step 203 includes a feeding unit 203a, a coating unit 203b, a drying unit 203c, a pattern forming unit 203d, an accumulator 203e, and a winding unit 203f.
- a hole transport layer forming coating solution is applied to the entire upper surface of the first electrode of the strip-shaped flexible substrate 3 formed up to the first electrode, and passes through the drying section 203c.
- the pattern transporting layer 203d is formed on the extraction electrode portion of the first electrode and around the first electrode. Is removed and patterned. After the hole transport layer has been patterned, it can be wound up and stored. Further, it may be transferred to the light emitting layer forming step 204 (see FIG. 2).
- the hole transport layer forming step 203 in this figure is arranged in an atmospheric pressure environment.
- the first electrode is already formed, and the strip-shaped flexible base material 3a wound in a roll wound around the winding core is supplied via the transport roller 203a1.
- An accumulator 203a2 and an antistatic means 203a3 can be disposed between the feeding unit 203a and the coating unit 203b as necessary.
- the accumulator 203a2 has a plurality of lower conveyance rollers 203a21 and a plurality of upper conveyance rollers 203a22, and is arranged for speed adjustment in the application unit 203b.
- the antistatic means 203a3 has a non-contact type antistatic device 203a31 and a contact type antistatic device 203a32.
- Examples of the non-contact type antistatic device 203a31 include a non-contact type ionizer.
- the type of ionizer is not particularly limited, and the ion generation method may be either an AC method or a DC method.
- An AC type, a double DC type, a pulsed AC type, and a soft X-ray type can be used, but the AC type is particularly preferable from the viewpoint of precise static elimination.
- Air or N 2 is used as the injection gas required when using the AC type, but it is preferable to use N 2 with sufficiently high purity. From the viewpoint of in-line operation, the blower type or the gun type is selected.
- a static eliminating roll or a conductive brush connected to the ground is used as the contact-type antistatic device 203a32.
- the static elimination roll as the static eliminator is grounded and removes the surface charge by rotatingly contacting the neutralized surface.
- Such static elimination rolls include rolls made of elastic plastic or rubber mixed with conductive materials such as carbon black, metal powder, and metal fibers in addition to rolls made of metal such as aluminum, copper, nickel, and stainless steel. used.
- an elastic material is preferable in order to improve contact with the belt-like flexible substrate 3a.
- the conductive brush connected to the earth include a neutralizing bar or a neutralizing yarn structure having a brush member made of conductive fibers arranged in a line or a linear metal brush.
- the neutralization bar is not particularly limited, but a corona discharge type is preferably used.
- a corona discharge type is preferably used.
- SJ-B manufactured by Keyence Corporation is used.
- static elimination yarn usually a flexible yarn is preferably used.
- 12/300 ⁇ 3 manufactured by Naslon can be cited as an example.
- the non-contact type antistatic device 203a31 is used on the surface side of the hole transport layer formed on the strip-like flexible substrate 3a, and the contact type antistatic device 203a32 is on the back side of the strip-like flexible substrate 3a. It is preferable to use for.
- the coating unit 203b uses a wet coating machine 203b1 and a backup roll 203b2 that holds the strip-shaped flexible substrate 3 on which the first electrode (anode) is formed.
- the coating liquid for forming a hole transport layer by the wet coater 203b1 is applied on the entire surface of the strip-shaped flexible substrate 3 on which the first electrode (anode) is formed.
- the thickness of the hole transport layer is about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
- the first electrode can be taken out even in a full-coat type coating including the first electrode.
- a slit coating type in which the electrode portion is not applied from the beginning is also possible. In the case of the slit coating type, the pattern forming portion 203d is unnecessary, which is desirable.
- the drying unit 203c has a drying device 203c1 and a heat treatment device 203c2, and heats the hole transport layer from the back surface side of the strip-shaped flexible substrate 3a by the back surface heat transfer method.
- the heat treatment conditions for the hole transport layer in the heat treatment apparatus 203c2 the smoothness of the hole transport layer is improved, the residual solvent is removed, the hole transport layer is cured, and the glass transition temperature of the hole transport layer is considered. Therefore, it is preferable to perform the back surface heat transfer type heat treatment at ⁇ 30 to + 30 ° C. and at a temperature not exceeding the decomposition temperature of the organic compound constituting the hole transport layer.
- the pattern forming unit 203d has a wiping device 203d1.
- the wiping device 203d1 has an alignment mark detector (not shown) that detects an alignment mark (not shown) attached to the belt-like flexible base material 3a formed up to the hole transport layer.
- the wiping device 203d1 uses a solvent (good solvent) that dissolves the hole transport layer based on information from an alignment mark detector (not shown).
- the hole transport layer on the extraction electrode of the first electrode (anode) is wiped off with the impregnated member.
- a method for wiping and removing the organic functional layer using a member impregnated with a solvent (good solvent) is not particularly limited, and for example, a method as described in JP-T-2007-515756 can be used. The method for removing the organic functional layer is not limited to this.
- the solvent (good solvent) that dissolves the hole transport layer is not particularly limited as long as it is a solvent that dissolves the hole transport material forming the hole transport layer.
- the hole transport material forming the hole transport layer is polyethylene dioxythiophene (PEDOT: PSS), water, isopropanol, and the like can be given.
- the accumulator 203e has a plurality of lower conveyance rollers 203e1 and a plurality of upper conveyance rollers 203e2, and is arranged for speed adjustment between the pattern forming unit 203d and the winding device 203f.
- the light emitting layer forming step 204 (see FIG. 2) and the electron transport layer forming step 205 (see FIG. 2) have the same configuration as the hole transport layer forming step 203 shown in FIG. Omitted, the outline of the light emitting layer formation and the electron transport layer formation will be described.
- the light emitting layer forming coating solution is applied to the entire surface by a wet coater on the strip-like flexible substrate 3 on which the patterned hole transport layer is formed.
- a wet coater it is possible to use a wet coater of the same type as the wet coater used to coat the hole transport layer forming coating solution.
- An alignment mark detector (not shown) is provided on the light emitting layer formed by drying in the drying section and heat treatment, and an alignment mark (not shown) attached to the belt-like flexible substrate 3 by a solvent coating device. And the light emitting layer is wiped off with a member impregnated with a solvent (good solvent) that dissolves the light emitting layer in accordance with the patterned hole transport layer based on information from an alignment mark detector (not shown).
- the solvent to be used is not particularly limited as long as the material constituting the light emitting layer is dissolved.
- the material constituting the light emitting layer uses a dicarbazole derivative (CBP) as a host material and an iridium complex (Ir (ppy) 3 ) as a dopant material, toluene, anisole, cyclohexanone, and the like can be given.
- CBP dicarbazole derivative
- Ir (ppy) 3 iridium complex
- a coating liquid for forming an electron transport layer is formed on the entire surface by a wet coater on the strip-shaped flexible substrate 3 on which the patterned light emitting layer is formed.
- a wet coater it is possible to use a wet coater of the same type as the wet coater used to coat the hole transport layer forming coating solution.
- An alignment mark (not shown) attached to the belt-like flexible base material 3 is detected by an alignment mark detector (not shown) on the electron transport layer formed by drying and heat treatment in the drying section. Based on information from an alignment mark detector (not shown), the electron transport layer is wiped off with a member impregnated with a solvent (good solvent) that dissolves the electron transport layer in accordance with the patterned light emitting layer.
- the solvent to be used is not particularly limited as long as the material constituting the electron transport layer is dissolved.
- the material constituting the electron transport layer is 2- (4-biphenylyl) -5- (p-tertbutylphenyl) -1,3,4-oxadiazole (tBu-PBD). If present, ethyl lactate and the like can be mentioned.
- FIG. 5 is a schematic view of a forming process starting from the cathode buffer layer (electron injection layer) forming process shown in FIG.
- this figure shows the case where the cutting apparatus is used for the collection step, and the band-shaped flexible substrate 3 on which the electron transport layer is formed is used.
- the cathode buffer layer (electron injection layer) forming step 206 includes a feeding portion 206a of the strip-shaped flexible base material 3a formed up to the electron transport layer wound up in a roll shape, and includes an evaporation source container 206c.
- a vapor deposition device 206b and an accumulator 206d are used.
- the accumulator 206d has a plurality of lower conveyance rollers 206d1 and a plurality of upper conveyance rollers 206d2, and is disposed between the feeding unit 206a and the vapor deposition device 206b, and the feeding unit 206a and the vapor deposition device 206b. It is arranged for speed adjustment.
- the cathode buffer layer (electron injection layer) forming step 206 the electron transport layer (not shown, corresponding to the electron transport layer 105 in FIG. 1) continuously supplied from the feeding portion 206a through the transport roller 206a1 is formed.
- An alignment mark (not shown) attached to the strip-shaped flexible substrate 3 is read by a detection device (not shown) and taken out to a position determined by the vapor deposition device 206b according to information of the detection device (not shown).
- a cathode buffer layer (electron injection layer) (not shown, corresponding to the electron injection layer 107 in FIG. 1) is formed on the already formed electron transport layer as a mask pattern.
- the thickness of the cathode buffer layer (electron injection layer) is preferably in the range of 0.1 nm to 5 ⁇ m.
- the second electrode forming step 207 uses a vapor deposition apparatus 207a having an evaporation source container 207b and an accumulator 207c.
- the accumulator 207c has a plurality of lower conveyance rollers 207c1 and a plurality of upper conveyance rollers 207c2, and is disposed between the cathode buffer layer (electron injection layer) formation step 206 and the second electrode formation step 207.
- the cathode buffer layer (electron injection layer) forming step 206 and the second electrode forming step 207 are provided for speed adjustment.
- the cathode buffer layer (electron injection layer) continuously supplied from the cathode buffer layer (electron injection layer) formation step 206 is attached to the already formed belt-like flexible substrate 3.
- An alignment mark (not shown) is read by a detection device (not shown), and an extraction electrode (not shown, extraction electrode 12a in FIG. 1) is placed at a position determined by the vapor deposition device 207a according to information of the detection device (not shown).
- a cathode buffer layer (electron injection layer) (not shown, FIG. 1) that has already been formed is provided on a second electrode (cathode) (not shown, corresponding to the second electrode (cathode) 14 in FIG. 1).
- the sheet resistance as the second electrode (cathode) is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
- an organic EL device having a configuration of base material / first electrode (anode) / hole transport layer / light emitting layer / cathode buffer layer (electron injection layer) / second electrode (cathode) is completed.
- the first electrode excision device 207d3 is used to align with the alignment mark (not shown) attached to the strip-shaped flexible substrate 3.
- One electrode is excised to form a discontinuity (not shown) in the first electrode. Examples of the excision method include removal of the first electrode by a laser, but are not limited thereto.
- the formation of the discontinuous portion is not limited to the second electrode forming step 7, but in view of the influence on the application due to the discontinuity of the first electrode (anode), the application at the application portion 203b (see FIG. 4). It is desirable to be performed between the end and before the formation of the sealing member in the sealing step 208 (see FIG. 5).
- the accumulator 207d and the accumulator 208e have a plurality of lower conveyance rollers 207d1 and 208e1 and a plurality of upper conveyance rollers 207d2 and 208e2, and form a first electrode excision device 207d3, a vapor deposition device 207a, and a second electrode (cathode). It is provided for speed adjustment with step 207.
- the cathode buffer layer (electron injection layer) forming step 206 and the second electrode (cathode) forming step 207 are shown as a vapor deposition apparatus.
- the cathode buffer layer (electron injection layer) and the second electrode (cathode) are shown.
- the formation method of, for example, dry process sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma polymerization method, plasma CVD.
- a laser CVD method, a thermal CVD method, or the like can be used.
- the cathode buffer layer (electron injection layer) can be a wet coating method.
- the sealing step 208 includes a sealing member supply step 208b, and uses a sealant coating device 208a, a bonding device 208c, and an accumulator 208e.
- the sealing member 208b1 is sent from the sealing member supply step 208b.
- an alignment mark (not shown) is attached to the sealing member 208b1 at the same position as the alignment mark (not shown) attached to the strip-shaped flexible substrate 3a in which the second electrode is already formed. Yes.
- an alignment mark (not shown) attached to the strip-like flexible base material 3a where the second electrode has already been formed is read by a detection device (not shown), and the detection device (not shown) According to the information, the sealant coating device 208a is coated on the organic EL element at the upper part and the periphery thereof except for the extraction electrode (not shown, corresponding to the extraction electrode 12a and the extraction electrode 14a in FIG. 1).
- an alignment mark (not shown) and a sealing member 208b1 attached to the strip-shaped flexible base material 3a having a plurality of organic EL elements formed by applying a sealing agent by the bonding device 208c. Together with the alignment mark (not shown), the organic EL element is tightly sealed. At this stage, an organic EL element is manufactured. Since a plurality of organic EL elements produced at this stage are continuously connected, they are cut into individual organic EL elements in the recovery step 209.
- the collection step 209 uses a cutting device 209a, an accumulator 209b, and a collection box 209c.
- the accumulator 209b has a plurality of lower transport rollers 209b1 and a plurality of upper transport rollers 209b2, and is arranged for speed adjustment between the sealing step 208 and the recovery step 209.
- an alignment mark (not shown) attached to the strip-like flexible base material 3 on which a plurality of organic EL elements are formed or an alignment mark (not shown) of the sealing member 208b1 is detected (not shown). And is cut and punched in accordance with information from a detection device (not shown), and collected as an individual organic EL element 6 in a collection box 209c.
- Reference numeral 209d denotes a skeleton wound in a roll shape in which an organic EL element is punched.
- the cut organic EL element 6 has the same configuration as the organic EL element shown in FIG.
- FIG. 6 is a schematic flow diagram showing the patterning of the hole transport layer in the hole transport layer forming step shown in FIG. 4 of the invention according to claim 1 or 2.
- the patterning of the hole transport layer formed on the entire surface of the belt-like flexible substrate on which the first electrode (anode) is formed will be described with reference to the flowchart.
- Step 1 shows the strip-shaped flexible base material 11 on which the first electrode (anode) 12 continuous in the first electrode forming step 202 (see FIG. 2) is formed.
- the right side is a schematic cross-sectional view taken along the line CC ′ of the drawing shown in Step 1.
- Step 2 shows the strip-shaped flexible substrate 11 on which the hole transport layer 103 is formed in the hole transport layer forming step 203 (see FIG. 2).
- the hole transport layer is formed on the entire surface except for both ends of the strip-shaped flexible substrate including the first electrode (anode) 12.
- the right side is a schematic cross-sectional view along the line DD 'in the drawing shown in Step 2.
- Step 3 is a member that is impregnated with a solvent (good solvent) that dissolves the hole transport layer 103 on the take-out electrode of the first electrode (anode) by the wiping device 203d1 (see FIG. 4) of the pattern forming unit 203d.
- 103 shows a state in which 103 has been wiped away (part indicated by hatching in the figure).
- the right side is a schematic cross-sectional view along the line EE ′ in the drawing shown in Step 3.
- Step 4 shows a state in which the hole transport layer 103 on the extraction electrode 12a of the first electrode (anode) 12 is wiped and removed by the wiping device 203d1 (see FIG. 4) of the pattern forming unit 203d.
- the extraction electrode 12a of the anode (first electrode) 12 is exposed.
- the right side is a schematic cross-sectional view along the line FF ′ in the drawing shown in Step 4.
- the light emitting layer is formed on the hole transport layer 5 according to the flow of Step 1 to Step 4, and the electron transport layer is similarly formed on the light emitting layer according to the flow of Step 1 to Step 4.
- Step 1 the first electrode excision device 202d1 disposed between the second accumulator 202c and the third accumulator 202d in FIG. A one-electrode discontinuity is produced.
- Step 2 and the following steps are performed using the first electrode (anode) 12a having the first electrode discontinuity obtained in the first electrode forming step 202 (see FIG. 2). Therefore, in each step, it becomes the 1st electrode which has the 1st electrode discontinuity part.
- the first electrode is not patterned and is continuously manufactured, so that it is affected by deformation in the transport direction (coating direction) of the belt-shaped substrate and step differences. Without effect, the coating film was stabilized.
- a resin film is mentioned as a strip
- 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, poly Cycloolefin resins such as ether imide, polyether ketone imide, polyamide, fluororesin, nylon,
- PET polyethylene ter
- a gas barrier film When using a resin film, it is preferable that a gas barrier film is formed on the surface of the resin film as necessary.
- the gas barrier film include an inorganic film, an organic film, or a hybrid film of both.
- the water vapor permeability is 0.01 g / m 2 / day or less.
- a high barrier film having an oxygen permeability of 0.1 ml / m 2 ⁇ day ⁇ MPa or less and a water vapor permeability of 10 ⁇ 5 g / m 2 / day or less is preferable.
- the material for forming the barrier film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
- silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
- the method for forming the gas barrier film is not particularly limited.
- 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 particularly preferable.
- first electrode 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.
- electrode substances include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
- conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
- an amorphous material such as IDIXO (In 2 O 3 .ZnO) that can form a transparent conductive film may be used.
- a coatable substance such as an organic conductive compound can be used.
- 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 the pattern accuracy is not so required. (About 100 ⁇ m or more), a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered.
- the transmittance be greater than 10%, and the sheet resistance as the first electrode (anode) is preferably several hundred ⁇ / ⁇ or less.
- the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
- a hole injection layer may be present between the first electrode and the light emitting layer or the hole transport layer.
- the hole injection layer is a layer provided between the electrode and the organic layer in order to lower the driving voltage and improve the luminance of light emission.
- the organic EL element and the forefront of industrialization June 30, 1998, NTS
- the details are described in Chapter 2 “Electrode Materials” (pages 123 to 166) of the second volume of “published by the company”.
- the details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like.
- copper phthalocyanine is used.
- Examples thereof include a phthalocyanine buffer layer, an oxide buffer layer typified by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
- 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.
- triazole derivatives for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives,
- Examples include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
- the above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.
- aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminoph
- a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
- inorganic compounds such as p-type-Si and p-type-SiC can be used as the hole injection material and the hole transport material.
- JP-A-11-251067 J. Org. Huang et. al.
- a so-called p-type hole transport material described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. These materials are preferably used to obtain a light emitting element with higher efficiency.
- the film thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
- This hole transport layer may have a single layer structure composed of one or more of the above materials.
- a hole transport layer having a high p property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like. It is preferable to use such a hole transport layer having a high p property because an organic EL element with lower power consumption can be produced.
- the light emitting layer refers to a blue light emitting layer, a green light emitting layer, and a red light emitting layer.
- the light emitting layer There is no restriction
- blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting layer blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting from the order close to the anode.
- a white element can be manufactured by forming a light emitting layer in multiple layers.
- the light emitting layer includes at least three or more layers having different emission spectra having emission maximum wavelengths in the range of 430 nm to 480 nm, 510 nm to 550 nm, and 600 nm to 640 nm, respectively. If it is three or more layers, there will be no restriction
- a layer having an emission maximum wavelength in the range of 430 nm to 480 nm is referred to as a blue light emitting layer
- a layer in the range of 510 nm to 550 nm is referred to as a green light emitting layer
- a layer in the range of 600 nm to 640 nm is referred to as a red light emitting layer.
- the blue light emitting layer may be used by mixing a blue light emitting compound having a maximum wavelength of 430 nm to 480 nm and a green light emitting compound having a maximum wavelength of 510 nm to 550 nm.
- the material used for the light emitting layer is not particularly limited, and examples thereof include various materials as described in Toray Research Center, Inc., latest trends in flat panel displays, current status of EL displays and latest technological trends, pages 228-332.
- the light emitting layer preferably contains a known host material and a known dopant material (a phosphorescent compound (also referred to as a phosphorescent compound)) in order to increase the light emission efficiency of the light emitting layer.
- the host material is a material contained in the light emitting layer, the mass ratio in the layer is 20% or more, and the phosphorescence quantum yield of phosphorescence emission is 0.1 at room temperature (25 ° C.). Is defined as less than material.
- the phosphorescence quantum yield is preferably less than 0.01.
- a plurality of host materials may be used in combination. By using a plurality of types of host materials, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. In addition, by using a plurality of dopant materials, it is possible to mix different light emission, thereby obtaining an arbitrary emission color. White light emission is possible by adjusting the kind of dopant material and the doping amount, and it can also be applied to illumination and backlight.
- a material that has a hole transporting ability and an electron transporting ability, prevents the emission of light from becoming longer, and has a high Tg (glass transition temperature) is preferable.
- Known host materials include, for example, Japanese Patent Application Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, and 2002-334786. Gazette, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645 No. 2002-338579, No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No.
- the host compound in each layer is the same compound because it is easy to obtain a uniform film property over the entire organic layer. It is more preferable that the light emission energy is 2.9 eV or more because it is advantageous in efficiently suppressing energy transfer from the dopant material and obtaining high luminance.
- Phosphorescence emission energy refers to the peak energy of 0-0 band of phosphorescence emission measured by measuring the photoluminescence of a deposited film of 100 nm on a substrate with a host compound.
- the host material has a phosphorescence energy of 2.9 eV or more and a Tg of 90 ° C. or more in consideration of deterioration of the organic EL element over time (decrease in luminance and film properties) and market needs as a light source.
- phosphorescence emission energy is 2.9 eV or more and Tg is 90 ° C. or more.
- Tg is more preferably 100 ° C. or higher.
- a dopant material (phosphorescent compound (phosphorescent compound)) is a material in which light emission from an excited triplet is observed, and is a material that emits phosphorescence at room temperature (25 ° C.). The rate is a material of 0.01 or more at 25 ° C. When used in combination with the host material described above, an organic EL element with higher luminous efficiency can be obtained.
- the dopant material phosphorescent compound (phosphorescent compound)
- phosphorescent compound preferably has a phosphorescence quantum yield of 0.1 or more.
- the phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 version, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence quantum yield used in the present invention only needs to achieve the phosphorescence quantum yield in any solvent.
- the dopant material There are two types of light emission of the dopant material in principle.
- One is an energy transfer type in which recombination of carriers occurs on the host material to which carriers are transported to generate an excited state of the host material, and this energy is transferred to the dopant material to obtain light emission from the dopant material.
- the other is a carrier trap type in which the dopant material becomes a carrier trap, and recombination of carriers occurs on the dopant material, and light emission from the phosphorescent compound is obtained.
- the condition is that the excited state energy of the dopant material is lower than the excited state energy of the host material.
- the dopant material can be appropriately selected from known materials used for the light emitting layer of the organic EL element.
- the dopant material is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, a platinum compound (platinum complex compound), or a rare earth complex. Among them, the most preferable is an iridium compound.
- the maximum phosphorescence wavelength of the dopant material is not particularly limited. In principle, the emission wavelength obtained by selecting a central metal, a ligand, a substituent of the ligand, etc. can be changed. I can do it.
- the color emitted from the material used for the light emitting layer of the organic EL element is shown in FIG. 4.16 on page 108 of the “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured at ⁇ 1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.
- the light emitting layer formed by drying is a layer that emits light by recombination of electrons and holes injected from the electrode or electron injection layer and hole transport layer, and the light emitting part is within the layer of the light emitting layer. Even the interface between the light emitting layer and the adjacent layer may be used.
- 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.
- 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.
- any material can be selected and used from the conventionally known compounds, such as nitro-substituted fluorene derivatives and diphenylquinone derivatives.
- a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
- a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
- Metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq 3 ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) Aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metals of these metal complexes are In, Mg Metal complexes replaced with Cu, Ca, Sn, Ga, or Pb can also be used as the electron transport material.
- metal-free or metal phthalocyanine or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material.
- the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transporting material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc., like the hole injection layer and the hole transporting layer. Can also be used as an electron transporting material.
- the film thickness of the electron transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 nm to 200 nm.
- the electron transport layer may have a single layer structure composed of one or more of the above materials.
- the cathode buffer layer (electron injection layer) is made of a material having a function of transporting electrons and is included in the electron transport layer in a broad sense.
- the cathode buffer layer (electron injection layer) is a layer provided between the electrode and the organic layer in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and its forefront of industrialization (November 30, 1998) “Published by TS Co., Ltd.)”, Chapter 2, “Electrode Materials” (pages 123 to 166) in the second volume.
- cathode buffer layer (electron injection layer) The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc.
- a metal buffer layer typified by lithium fluoride, an alkali metal compound buffer layer typified by lithium fluoride, an alkaline earth metal compound buffer layer typified by magnesium fluoride, an oxide buffer layer typified by aluminum oxide, etc.
- the buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 ⁇ m, depending on the material.
- the electron transport layer is provided adjacent to the light emitting layer side of the cathode buffer layer.
- An electron transport layer having a high n property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, JP-A-2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like. It is preferable to use such an electron transport layer having a high n property because an element with lower power consumption can be manufactured.
- Electrode As the second electrode, a material having a 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.
- 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.
- 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 the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
- the emission luminance is advantageously improved.
- the conductive transparent material mentioned in the description of the first electrode is formed thereon, so that a transparent or translucent second electrode ( A cathode) can be manufactured, and by applying this, an element in which both the first electrode (anode) and the second electrode (cathode) are transmissive can be manufactured.
- the sealant examples include a liquid sealant and a thermoplastic resin.
- the liquid sealant include acrylic acid oligomer, methacrylic acid oligomer photo-curing and thermosetting sealant having a reactive vinyl group, moisture-curing sealant such as 2-cyanoacrylate, Examples thereof include epoxy-based heat- and chemical-curing type (two-component mixed) sealing agents, cationic curing type ultraviolet curing epoxy resin sealing agents, and the like. It is preferable to add a filler to the liquid sealant as necessary. The addition amount of the filler is preferably 5 to 70% by volume in consideration of adhesive strength.
- the size of the filler to be added is preferably 1 ⁇ m to 100 ⁇ m in consideration of the adhesive strength, the thickness of the sealant after bonding and bonding, and the like.
- the kind of filler to be added is not particularly limited, and examples thereof include soda glass, non-alkali glass, or silica, titanium dioxide, antimony oxide, titania, alumina, zirconia, tungsten oxide, and other metal oxides.
- thermoplastic resin a thermoplastic resin having a melt flow rate of JIS K 7210 specified in a range of 5 to 20 g / 10 min is preferable, and a thermoplastic resin of 6 to 15 g / 10 min or less is preferably used. This is because if a resin having a melt flow rate of 5 (g / 10 min) or less is used, the gap caused by the step of the lead electrode of each electrode cannot be completely filled, and a resin of 20 (g / 10 min) or more cannot be filled. This is because if used, the tensile strength, stress cracking resistance, workability and the like are lowered.
- thermoplastic resins are preferably formed into a film and bonded to a flexible sealing member (a strip-shaped flexible sealing member or a single-sheet flexible sealing member).
- the laminating method can be made by using various generally known methods such as wet laminating method, dry laminating method, hot melt laminating method, extrusion laminating method, and thermal laminating method.
- the thermoplastic resin is not particularly limited as long as it satisfies the above numerical values.
- low density polyethylene which is a polymer film described in the new development of functional packaging materials (Toray Research Center, Inc.).
- HDPE linear low density polyethylene
- LLDPE linear low density polyethylene
- CPP unstretched polypropylene
- OPP OPP
- ONy PET, cellophane
- PVA polyvinyl alcohol
- PVA polyvinyl alcohol
- OV stretched vinylon
- EVOH ethylene-vinyl acetate copolymer
- EVOH ethylene-propylene copolymer
- an ethylene-acrylic acid copolymer an ethylene-methacrylic acid copolymer
- PVDC vinylidene chloride
- the flexible sealing member examples include a material in which a barrier layer is formed on a support made of a flexible resin film such as polyethylene terephthalate or nylon by a vapor deposition method or a coating method, or a material using a metal foil as the barrier layer.
- the barrier layer include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO 2 , Al 2 O 3 , GeO, NiO, CaO, BaO, and Fe 2 O 3. , Y 2 O 3 , TiO 2 and other metal oxides deposited on the material.
- a material of the metal foil for example, a metal material such as aluminum, copper, or nickel, or an alloy material such as stainless steel or an aluminum alloy can be used, but aluminum is preferable in terms of workability and cost.
- the film thickness is about 1 to 100 ⁇ m, preferably about 10 ⁇ m to 50 ⁇ m.
- a film such as polyethylene terephthalate or nylon may be laminated in advance.
- a resin film for the flexible sealing member it is preferable to have a thermoplastic adhesive resin layer on the side in contact with the liquid sealing agent.
- the water vapor permeability of the flexible sealing member is preferably 0.01 g / m 2 ⁇ day or less, and the oxygen permeability is preferably 0.1 ml / m 2 ⁇ day ⁇ MPa or less.
- the water vapor permeability is a value measured mainly by the MOCON method by a method based on JIS K7129B method (1992), and the oxygen permeability is a value measured mainly by the MOCON method by a method based on JIS K7126B method (1987). is there.
- the Young's modulus of the flexible sealing member is 1 ⁇ 10 ⁇ 3 GPa in consideration of adhesion between the flexible sealing member, the first pressure-bonding member and the second pressure-bonding member, prevention of spreading of the sealant, and the like. It is preferably ⁇ 80 GPa, and the thickness is preferably 10 ⁇ m to 500 ⁇ m.
- the external extraction efficiency at room temperature of light emission of the organic EL element produced by the method for producing a functional thin film of the present invention is preferably 1% or more, more preferably 5% or more.
- the external extraction quantum efficiency (%) the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element ⁇ 100.
- a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination.
- the ⁇ max of light emission of the organic EL element is preferably 480 nm or less.
- the organic EL device produced by the method for producing a functional thin film of the present invention preferably uses the following method in combination in order to efficiently extract light generated in the light emitting layer.
- An organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1), and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said that there is no.
- Measures for improving the light extraction efficiency include, for example, a method of forming irregularities on the transparent substrate surface to prevent total reflection at the transparent substrate and the air interface (US Pat. No. 4,774,435).
- a method for improving efficiency by providing a substrate with a light condensing property JP-A-63-314795.
- a method of forming a reflective surface on the side surface of an element Japanese Patent Laid-Open No. 1-220394.
- a method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between a substrate and a light emitter Japanese Patent Laid-Open No. 62-172691).
- Japanese Patent Laid-Open No. 2001-202827 A method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter. There is a method of forming a diffraction grating between any one of the substrate, the transparent electrode layer, and the light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951).
- an organic EL element is produced by the method for producing a functional thin film of the present invention
- a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitting layer, or a substrate, a transparent electrode layer or a light emitting layer can be suitably used.
- the low refractive index layer When a low refractive index medium is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.
- the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.
- the thickness of the low refractive index medium is preferably at least twice the wavelength in the medium.
- the method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency.
- This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction or second-order diffraction.
- the introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. The light extraction efficiency does not increase so much. However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.
- the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the organic functional layer where light is generated.
- the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.
- the arrangement of the diffraction grating is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.
- a structure on a microlens array for example, is provided on the light extraction side of the substrate.
- the luminance in a specific direction can be increased by condensing light in a specific direction, for example, the front direction with respect to the element light emitting surface.
- the microlens array quadrangular pyramids having a side of 30 ⁇ m and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate.
- One side is preferably 10 ⁇ m to 100 ⁇ m. If it becomes smaller than this, the effect of diffraction will generate
- the condensing sheet it is possible to use, for example, an LED backlight of a liquid crystal display device that has been put into practical use.
- a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.
- the shape of the prism sheet for example, the substrate may be formed with a triangle stripe having a vertex angle of 90 degrees and a pitch of 50 ⁇ m, or the vertex angle is rounded, and the pitch is randomly changed. The shape may be other shapes.
- a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
- Example 1 Preparation of strip-shaped flexible substrate> A polyethylene naphthalate film (Teijin-DuPont film, hereinafter abbreviated as PEN) having a thickness of 125 ⁇ m, a width of 200 mm, and a length of 500 m was prepared.
- PEN polyethylene naphthalate film
- the alignment mark was previously provided in the same position of both surfaces of the flexible base material in the strip
- the first electrode is continuously formed by sputtering with 120 nm thick ITO (indium tin oxide) under a vacuum environment condition of 5 ⁇ 10 ⁇ 1 Pa. did.
- the surface tension of the coating solution for forming the hole transport layer was 40 mN / m (manufactured by Kyowa Interface Chemical Co., Ltd .: surface tension meter CBVP-A3).
- the roll-shaped PEN on which the prepared first electrode is formed is subjected to a charge removal treatment, and then a hole transport layer is formed on the entire upper surface of PEN (except 10 mm at both ends).
- the coating solution for coating was applied by the wet coating method using an extrusion coating machine under the following conditions so that the thickness after drying was 30 nm. After coating, drying and heat treatment were performed in the drying section under the following conditions to form a hole transport layer.
- the conveyance speed was 3 m / min.
- the conveyance speed was measured with a laser Doppler velocimeter LV203 manufactured by Mitsubishi Electric Corporation.
- a non-contact type antistatic device was used on the first electrode formation side, and a contact type antistatic device was used on the back side.
- a non-contact type antistatic device a flexible AC ionizing bar MODEL4100V manufactured by Hugle Electronics Co., Ltd. was used.
- the contact type antistatic device was a conductive guide roll ME-102 manufactured by Miyako Roller Kogyo Co., Ltd.
- the coating conditions for the hole transport layer forming coating solution are as follows: the temperature during coating of the hole transport layer forming coating solution is 25 ° C., and the atmospheric pressure is N 2 gas environment with a dew point temperature of ⁇ 20 ° C. or lower. And it was performed with a cleanliness class of 5 or less (JIS B 9920).
- Drying and Heating treatment conditions for the coating film for forming the hole transport layer are as follows. After the coating liquid for forming the hole transport layer is applied, the drying device and the heat treatment device shown in FIG. Then, after removing the solvent at a height of 100 mm from the slit nozzle type discharge port toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 120 ° C., a temperature of 150 ° C. is continuously applied by a heat treatment apparatus. The back surface heat transfer system heat treatment was performed to form a hole transport layer.
- the alignment mark attached to the PEN is detected, and the hole transport layer formed on the PEN according to the position of the alignment mark, the extraction electrode portion of the first electrode, and the first electrode
- the hole transporting layer was wiped off using a method described in JP-T-2007-515756 with a member impregnated with pure water which is a good solvent for the hole transporting layer in an unnecessary part around .
- the coating solution for forming the light emitting layer is extruded at a temperature of 25 ° C. on the entire upper surface of PEN (except 10 mm at both ends). It apply
- the conveyance speed was 3 m / min.
- a non-contact type antistatic device was used on the hole transport layer side, and a contact type antistatic device was used on the back side.
- a non-contact type antistatic device a flexible AC ionizing bar MODEL4100V manufactured by Hugle Electronics Co., Ltd. was used.
- the contact type antistatic device was a conductive guide roll ME-102 manufactured by Miyako Roller Kogyo Co., Ltd.
- the application conditions for the light-emitting layer are as follows: the application temperature of the application liquid for forming the light-emitting layer is 25 ° C., an atmospheric pressure of N 2 gas environment with a dew point temperature of ⁇ 20 ° C. or less, and a cleanliness class 5 or less (JIS B 9920).
- Drying and Heating Treatment Conditions Drying and heating treatment conditions for the light emitting layer forming coating film were applied to the light emitting layer forming coating solution, and then used for drying and heating treatment of the hole transport layer coating film shown in FIG.
- the same apparatus as the apparatus and the heat treatment apparatus is used.
- the drying apparatus the height is 100 mm from the slit nozzle type discharge port toward the film formation surface, the discharge air speed is 1 m / s, the width of the wide air speed is 5%, and the temperature is 60 ° C.
- the back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. by a heat treatment apparatus to form a light emitting layer.
- the alignment mark attached to the PEN is detected according to the flow shown in FIG. 6, and the light emitting layer formed on the PEN according to the position of the alignment mark, the extraction electrode portion of the first electrode, and the periphery of the hole transport layer
- the light emitting layer was wiped off using a method described in JP-T-2007-515756 with a member impregnated with toluene, which is a good solvent, in the unnecessary portion.
- the roll-shaped PEN on which the prepared light emitting layer is formed is charged and removed, and then the electron transport layer forming coating solution is applied to the entire upper surface of PEN (however, excluding 10 mm at both ends) at a temperature of 25 ° C. It apply
- a non-contact type antistatic device was used on the light emitting layer side, and a contact type antistatic device was used on the back side.
- a non-contact type antistatic device a flexible AC ionizing bar MODEL4100V manufactured by Hugle Electronics Co., Ltd. was used.
- the contact type antistatic device was a conductive guide roll ME-102 manufactured by Miyako Roller Kogyo Co., Ltd.
- Coating conditions for the electron transport layer are as follows: the temperature during coating of the electron transport layer forming coating solution is 25 ° C., an atmospheric pressure of N 2 gas environment with a dew point temperature of ⁇ 20 ° C. or less, and a cleanliness class 5 or less. (JIS B 9920).
- Drying and Heating Treatment Conditions Drying and heating treatment conditions for the electron transport layer forming coating are applied to the electron transport layer forming coating solution and then used for drying and heating the hole transport layer coating shown in FIG.
- the drying apparatus and the same apparatus as the heat treatment apparatus are used.
- the height from the slit nozzle type discharge port to the film forming surface is 100 mm
- the discharge air speed is 1 m / s
- the width of the wide air speed is 5%
- the temperature is 150 ° C.
- heat treatment by a back surface heat transfer method was performed at a temperature of 100 ° C. by a heat treatment apparatus to form an electron transport layer.
- the alignment mark attached to the PEN is detected, and on the electron transport layer formed on the PET according to the position of the alignment mark, on the extraction electrode portion of the first electrode and on the light emitting layer.
- the electron transport layer was wiped off by using a method described in JP-T-2007-515756 with a member impregnated with ethyl lactate, which is a good solvent, in the surrounding unnecessary portion.
- cathode buffer layer (electron injection layer)
- An alignment mark attached to the roll-shaped PEN on which the first electrode is formed is detected, and 5 ⁇ is deposited on the electron transport layer according to the position of the alignment mark and on the periphery excluding the extraction electrode of the first electrode by a vapor deposition apparatus.
- a cathode buffer layer (electron injection layer) having a thickness of 0.5 nm was formed by using LiF as a material for forming a cathode buffer layer (electron injection layer) layer under a vacuum environment condition of 10 ⁇ 4 Pa, using a vapor deposition method. Were laminated.
- Second electrode (Formation of second electrode) Subsequently, an alignment mark attached to the PEN is detected, and a vacuum of 5 ⁇ 10 ⁇ 4 Pa is formed on the cathode buffer layer (electron injection layer) formed according to the position of the alignment mark in accordance with the size of the first electrode. Then, aluminum is used as the second electrode forming material, a mask pattern is formed by vapor deposition so as to have an extraction electrode, a second electrode having a thickness of 100 nm is laminated, and organic EL element No. 1 is stacked. 101 was produced.
- Coating agent coating An alignment mark attached to the PEN of the produced organic EL element is detected, and an ultraviolet curable type is formed around the light emitting region and the light emitting region except for the end portions of the extraction electrodes of the first electrode and the second electrode according to the position of the alignment mark.
- a liquid sealant epoxy resin system
- the coating was applied at a thickness of 30 ⁇ m.
- the belt-like sheet sealing member shown below is prepared by stacking the sealant coating surface of the organic EL element at a position excluding the ends of the first electrode and the lead electrode of the second electrode by the roll laminator method. After press-bonding with a pressure of 0.1 MPa in an atmospheric pressure environment, a high-pressure mercury lamp with a wavelength of 365 nm is irradiated for 1 minute at an irradiation intensity of 5 to 20 mW / cm 2 and a distance of 5 to 15 mm, and bonded and bonded. The organic EL elements were continuously connected.
- a PET film manufactured by Teijin / DuPont was used as a sealing member, and a belt-shaped sheet sealing member having a two-layer structure using an aluminum foil as a barrier layer was prepared.
- the thickness of PET was 50 ⁇ m, and the thickness of the aluminum foil of the barrier layer was 30 ⁇ m.
- formation of the barrier layer of PET film was implemented by the well-known lamination method.
- Example 2 An organic EL element was formed in the same manner as in Example 1 except that the first electrode discontinuity was formed in the first electrode formation step before coating. The intervals between the first electrode discontinuities were changed to 1, 2, 3, and 5 mm, respectively. About each obtained organic EL element, it evaluated according to the evaluation rank shown below, and a result is shown in Table 1.
- Samples Nos. 102 and 103 are sample Nos. That do not form discontinuous portions. As in 101, there was no influence of uneven light emission.
- the first electrode before coating is desirably free of gaps (steps) in the direction of substrate transport from the viewpoint of coating stability, but the interval between the discontinuous portions (gap) of the first electrode is 2 mm or less, preferably 1 mm. If it is set to the following, since the influence of light emission unevenness is small, the first electrode can be discontinuous before coating. By forming the discontinuous portion on the first electrode before coating, cleaning becomes possible before coating, and there is a concern about the influence of dust (increased leakage current, increased dark spot) due to the formation of the discontinuous portion after coating. Will disappear.
Abstract
Description
(1)第1電極自体の段差有無によるによる凹凸。
(2)第1電極パターニング時に発生する端部(エッジ)の盛り上がりによる凹凸(段差による凹凸の増加)。
(3)第1電極形成基材を加熱処理した場合、第1電極の有無による収縮差に起因する凹凸(第1電極形成後に、基材の乾燥や塗布後の塗布膜の乾燥や活性化処理のために加熱処理の機会が多く、基材の凹凸の増加させる原因になっている。)がある。
(2)第1電極(陽極)/発光層/電子輸送層/第2電極(陰極)
(3)第1電極(陽極)/正孔輸送層/発光層/正孔阻止層/電子輸送層/第2電極(陰極)
(4)第1電極(陽極)/正孔輸送層(正孔注入層)/発光層/正孔阻止層/電子輸送層/陰極バッファ層(電子注入層)/第2電極(陰極)
(5)第1電極(陽極)/陽極バッファ層(正孔注入層)/正孔輸送層/発光層/正孔阻止層/電子輸送層/陰極バッファ層(電子注入層)/第2電極(陰極)
有機EL素子を構成している各層については後に説明する。
帯状の可撓性基材としては樹脂フィルムが挙げられる。樹脂フィルムとしては、例えば、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)等のポリエステル、ポリエチレン、ポリプロピレン、セロハン、セルロースジアセテート、セルローストリアセテート、セルロースアセテートブチレート、セルロースアセテートプロピオネート(CAP)、セルロースアセテートフタレート(TAC)、セルロースナイトレート等のセルロースエステル類又はそれらの誘導体、ポリ塩化ビニリデン、ポリビニルアルコール、ポリエチレンビニルアルコール、シンジオタクティックポリスチレン、ポリカーボネート、ノルボルネン樹脂、ポリメチルペンテン、ポリエーテルケトン、ポリイミド、ポリエーテルスルホン(PES)、ポリフェニレンスルフィド、ポリスルホン類、ポリエーテルイミド、ポリエーテルケトンイミド、ポリアミド、フッ素樹脂、ナイロン、ポリメチルメタクリレート、アクリル或いはポリアリレート類、アートン(商品名JSR社製)或いはアペル(商品名三井化学社製)といったシクロオレフィン系樹脂等が挙げられる。
樹脂フィルムを使用する場合、樹脂フィルムの表面にはガスバリア膜が必要に応じて形成されることが好ましい。ガスバリア膜としては無機物、有機物の被膜又はその両者のハイブリッド被膜が挙げられる。ガスバリア膜の特性としては、水蒸気透過度が0.01g/m2/day以下であることが好ましい。更には、酸素透過度0.1ml/m2・day・MPa以下、水蒸気透過度10-5g/m2/day以下の高バリア性フィルムであることが好ましい。
第1電極(陽極)としては、仕事関数の大きい(4eV以上)金属、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが好ましく用いられる。この様な電極物質の具体例としてはAu等の金属、CuI、インジウムチンオキシド(ITO)、SnO2、ZnO等の導電性透明材料が挙げられる。又、IDIXO(In2O3・ZnO)等非晶質で透明導電膜を作製可能な材料を用いてもよい。或いは、有機導電性化合物のように塗布可能な物質を用いることも可能である。第1電極(陽極)はこれらの電極物質を蒸着やスパッタリング等の方法により、薄膜を形成させ、フォトリソグラフィー法で所望の形状のパターンを形成してもよく、或いはパターン精度をあまり必要としない場合は(100μm以上程度)、上記電極物質の蒸着やスパッタリング時に所望の形状のマスクを介してパターンを形成してもよい。この第1電極(陽極)より発光を取り出す場合には、透過率を10%より大きくすることが望ましく、又第1電極(陽極)としてのシート抵抗は数百Ω/□以下が好ましい。更に膜厚は材料にもよるが、通常10~1000nm、好ましくは10~200nmの範囲で選ばれる。
第1電極と発光層又は正孔輸送層の間、正孔注入層(陽極バッファ層)を存在させてもよい。正孔注入層とは、駆動電圧低下や発光輝度向上のために電極と有機層間に設けられる層のことで、「有機EL素子とその工業化最前線(1998年11月30日エヌ・ティー・エス社発行)」の第2編第2章「電極材料」(123-166頁)に詳細に記載されている。陽極バッファ層(正孔注入層)は、特開平9-45479号公報、同9-260062号公報、同8-288069号公報等にもその詳細が記載されており、具体例として、銅フタロシアニンに代表されるフタロシアニンバッファ層、酸化バナジウムに代表される酸化物バッファ層、アモルファスカーボンバッファ層、ポリアニリン(エメラルディン)やポリチオフェン等の導電性高分子を用いた高分子バッファ層等が挙げられる。
正孔輸送層とは、正孔を輸送する機能を有する正孔輸送材料からなり、広い意味で正孔注入層、電子阻止層も正孔輸送層に含まれる。正孔輸送層は単層又は複数層設けることが出来る。正孔輸送材料としては、正孔の注入又は輸送、電子の障壁性の何れかを有するものであり、有機物、無機物の何れであってもよい。例えば、トリアゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体及びピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、オキサゾール誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、アニリン系共重合体、又導電性高分子オリゴマー、特にチオフェンオリゴマー等が挙げられる。
発光層とは青色発光層、緑色発光層、赤色発光層を指す。発光層を積層する場合の積層順としては、特に制限はなく、又各発光層間に非発光性の中間層を有していてもよい。本発明においては、少なくとも1つの青発光層が、全発光層中最も陽極に近い位置に設けられていることが好ましい。又、発光層を4層以上設ける場合には、陽極に近い順から、例えば青色発光層/緑色発光層/赤色発光層/青色発光層、青色発光層/緑色発光層/赤色発光層/青色発光層/緑色発光層、青色発光層/緑色発光層/赤色発光層/青色発光層/緑色発光層/赤色発光層のように青色発光層、緑色発光層、赤色発光層を順に積層することが、輝度安定性を高める上で好ましい。発光層を多層にすることで白色素子の作製が可能である。
ホスト材料としては、正孔輸送能、電子輸送能を有しつつ、且つ発光の長波長化を防ぎ、尚且つ高Tg(ガラス転移温度)である材料が好ましい。公知のホスト材料としては、例えば、特開2001-257076号公報、同2002-308855号公報、同2001-313179号公報、同2002-319491号公報、同2001-357977号公報、同2002-334786号公報、同2002-8860号公報、同2002-334787号公報、同2002-15871号公報、同2002-334788号公報、同2002-43056号公報、同2002-334789号公報、同2002-75645号公報、同2002-338579号公報、同2002-105445号公報、同2002-343568号公報、同2002-141173号公報、同2002-352957号公報、同2002-203683号公報、同2002-363227号公報、同2002-231453号公報、同2003-3165号公報、同2002-234888号公報、同2003-27048号公報、同2002-255934号公報、同2002-260861号公報、同2002-280183号公報、同2002-299060号公報、同2002-302516号公報、同2002-305083号公報、同2002-305084号公報、同2002-308837号公報、同2007-59119号公報、同2007-251096号公報、同2007-250501号公報等に記載の化合物が挙げられる。
ドーパント材料(リン光性化合物(リン光発光性化合物))とは、励起三重項からの発光が観測される材料であり、室温(25℃)にてリン光発光する材料であり、リン光量子収率が、25℃において0.01以上の材料である。先に説明したホスト材料と合わせ使用することで、より発光効率の高い有機EL素子とすることが出来る。
電子輸送層とは電子を輸送する機能を有する材料からなり、広い意味で電子注入層、正孔阻止層も電子輸送層に含まれる。電子輸送層は単層又は複数層設けることが出来る。
陰極バッファ層(電子注入層)とは、電子を輸送する機能を有する材料からなり広い意味で電子輸送層に含まれる。陰極バッファ層(電子注入層)とは、駆動電圧低下や発光輝度向上のために電極と有機層間に設けられる層のことで、「有機EL素子とその工業化最前線(1998年11月30日エヌ・ティー・エス社発行)」の第2編第2章「電極材料」(123~166頁)に詳細に記載されている。陰極バッファ層(電子注入層)は、特開平6-325871号公報、同9-17574号公報、同10-74586号公報等にもその詳細が記載されており、具体的にはストロンチウムやアルミニウム等に代表される金属バッファ層、フッ化リチウムに代表されるアルカリ金属化合物バッファ層、フッ化マグネシウムに代表されるアルカリ土類金属化合物バッファ層、酸化アルミニウムに代表される酸化物バッファ層等が挙げられる。上記バッファ層(注入層)はごく薄い膜であることが望ましく、素材にもよるがその膜厚は0.1nm~5μmの範囲が好ましい。
第2電極としては、仕事関数の小さい(4eV以下)金属(電子注入性金属と称する)、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが用いられる。この様な電極物質の具体例としては、ナトリウム、ナトリウム-カリウム合金、マグネシウム、リチウム、マグネシウム/銅混合物、マグネシウム/銀混合物、マグネシウム/アルミニウム混合物、マグネシウム/インジウム混合物、アルミニウム/酸化アルミニウム(Al2O3)混合物、インジウム、リチウム/アルミニウム混合物、希土類金属等が挙げられる。これらの中で、電子注入性及び酸化等に対する耐久性の点から、電子注入性金属とこれより仕事関数の値が大きく安定な金属である第二金属との混合物、例えば、マグネシウム/銀混合物、マグネシウム/アルミニウム混合物、マグネシウム/インジウム混合物、アルミニウム/酸化アルミニウム(Al2O3)混合物、リチウム/アルミニウム混合物、アルミニウム等が好適である。陰極はこれらの電極物質を蒸着やスパッタリング等の方法により薄膜を形成させることにより、作製することが出来る。又、陰極としてのシート抵抗は数百Ω/□以下が好ましく、膜厚は通常10nm~5μm、好ましくは50~200nmの範囲で選ばれる。尚、発光した光を透過させるため、有機EL素子の第1電極(陽極)又は第2電極(陰極)の何れか一方が、透明又は半透明であれば発光輝度が向上し好都合である。
封止剤としては、液状封止剤と熱可塑性樹脂とが挙げられる。液状封止剤としては、アクリル酸系オリゴマー、メタクリル酸系オリゴマーの反応性ビニル基を有する光硬化及び熱硬化型封止剤、2-シアノアクリル酸エステルなどの湿気硬化型等の封止剤、エポキシ系などの熱及び化学硬化型(二液混合)等の封止剤、カチオン硬化タイプの紫外線硬化型エポキシ樹脂封止剤等を挙げることが出来る。液状封止剤には必要に応じてフィラーを添加することが好ましい。フィラーの添加量としては、接着力を考慮し、5~70体積%が好ましい。又、添加するフィラーの大きさは、接着力、貼合圧着後の封止剤厚み等を考慮し、1μm~100μmが好ましい。添加するフィラーの種類としては特に限定はなく、例えばソーダガラス、無アルカリガラス或いはシリカ、二酸化チタン、酸化アンチモン、チタニア、アルミナ、ジルコニアや酸化タングステン等の金属酸化物等が挙げられる。
可撓性封止部材としてはポリエチレンテレフタレート、ナイロンなどの可撓性樹脂フィルムからなる支持体へ蒸着法やコーティング法でバリア層を形成した材料又はバリア層として金属箔を用いた材料が挙げられる。バリア層としては例えばIn、Sn、Pb、Au、Cu、Ag、Al、Ti、Ni等の金属、MgO、SiO、SiO2、Al2O3、GeO、NiO、CaO、BaO、Fe2O3、Y2O3、TiO2等の金属酸化物を蒸着した材料が挙げられる。又、金属箔の材料としては、例えばアルミニウム、銅、ニッケルなどの金属材料や、ステンレス、アルミニウム合金などの合金材料を用いることが出来るが、加工性やコストの面でアルミニウムが好ましい。膜厚は、1~100μm程度、好ましくは10μm~50μm程度が望ましい。又、製造時の取り扱いを容易にするために、ポリエチレンテレフタレート、ナイロンなどのフィルムを予めラミネートしておいてもよい。可撓性封止部材に樹脂フィルムを使用する場合、液状封止剤と接触する側に熱可塑性接着性樹脂層を有することが好ましい。
〈帯状の可撓性基材の準備〉
厚さ125μm、幅200mm、長さ500mのポリエチレンナフタレートフィルム(帝人・デュポン社製フィルム、以下、PENと略記する)を準備した。尚、帯状の可撓性基材には、予めアライメントマークを可撓性基材の両面の同じ位置に設けた。
図3に示す装置を使用し、5×10-1Paの真空環境条件で厚さ120nmのITO(インジウムチンオキシド)をスパッタリング法により、第1電極を連続的に形成し一旦巻き取り1時間保管した。
ポリエチレンジオキシチオフェン・ポリスチレンスルホネート(PEDOT/PSS、Bayer社製 Bytron P AI 4083)を純水で65%、メタノール5%で希釈した溶液を正孔輸送層形成用塗布液として準備した。正孔輸送層形成用塗布液の表面張力は40mN/m(協和界面化学社製:表面張力計CBVP-A3)であった。
図4に示す装置を使用し、準備された第1電極が形成されたロール状のPENを帯電除去処理した後、PENの上全面(但し、両端の10mmは除く)に、正孔輸送層形成用塗布液をエクストルージョン塗布機を使用した湿式塗布方式により乾燥後の厚みが30nmになるように以下に示す条件で塗布した。塗布後、乾燥部で以下に示す条件により乾燥・加熱処理を行い、正孔輸送層を形成した。尚、搬送速度は、3m/分とした。搬送速度は、三菱電機(株)製 レーザドップラ速度計LV203で測定した。
正孔輸送層形成用塗布液の塗布条件としては、正孔輸送層形成用塗布液の塗布時の温度は25℃、露点温度-20℃以下のN2ガス環境の大気圧下で、且つ清浄度クラス5以下(JIS B 9920)で行った。
正孔輸送層形成用塗膜の乾燥及び加熱処理条件としては、正孔輸送層形成用塗布液を塗布した後、図4示す乾燥装置及び加熱処理装置を使用し、乾燥装置ではスリットノズル形式の吐出口から成膜面に向け高さ100mm、吐出風速1m/s、幅手の風速分布5%、温度120℃で溶媒を除去した後、引き続き、加熱処理装置により温度150℃で裏面伝熱方式の熱処理を行い、正孔輸送層を形成した。
図6に示すフローに従って、PENに付けられたアライメントマークを検出し、アライメントマークの位置に従ってPENの上に形成された正孔輸送層の上、第1電極の取り出し電極部分の上及び第1電極の周囲の不要の部分に、正孔輸送層に対して良溶媒である純水を含浸した部材で特表2007-515756号に記載されている方法を用いて、正孔輸送層を拭き取り除去した。
ジカルバゾール誘導体(CBP) 1.00質量%
イリジウム錯体(Ir(ppy)3) 0.05質量%
トルエン 98.95質量%
発光層形成用塗布液の表面張力は25℃で28mN/m(協和界面化学社製:表面張力計CBVP-A3を使用)であった。
準備された正孔輸送層が形成されたロール状のPENを帯電除去処理した後、PENの上全面(但し、両端の10mmは除く)に、発光層形成用塗布液を温度25℃でエクストルージョン塗布機を使用した湿式塗布方式により乾燥膜厚が50nmになるように以下の塗布条件で塗布した。塗布後、乾燥部で以下に示す条件により乾燥・加熱処理を行い、発光層を形成した。尚、搬送速度は、3m/分とした。搬送速度は、三菱電機(株)製 レーザドップラ速度計LV203で測定した。
発光層の塗布条件としては、発光層形成用塗布液の塗布時の温度は25℃、露点温度-20℃以下のN2ガス環境の大気圧下で、且つ清浄度クラス5以下(JIS B 9920)で行った。
発光層形成用塗膜の乾燥及び加熱処理条件としては、発光層形成用塗布液を塗布した後、図4に示す正孔輸送層塗膜の乾燥及び加熱処理に使用した乾燥装置及び加熱処理装置と同じ装置を使用し、乾燥装置ではスリットノズル形式の吐出口から成膜面に向け高さ100mm、吐出風速1m/s、幅手の風速分布5%、温度60℃で溶媒を除去した後、引き続き、加熱処理装置により温度150℃で裏面伝熱方式の熱処理を行い、発光層を形成した。
図6に示すフローに従ってPENに付けられたアライメントマークを検出し、アライメントマークの位置に従ってPENの上に形成された発光層の上、第1電極の取り出し電極部分の上及び正孔輸送層の周囲の不要の部分に、発光層に対して良溶媒であるトルエンを含浸した部材で特表2007-515756号に記載されている方法を用いて、発光層を拭き取り除去した。
2-(4-ビフェニリル)-5-(p-ターシャルブチルフェニル)-1,3,4-オキサジアゾール(tBu-PBD) 1質量%
乳酸エチル 99質量%
電子輸送層形成用塗布液の表面張力は25℃で29mN/m(協和界面化学社製:表面張力計CBVP-A3を使用)であった。
準備された発光層が形成されたロール状のPENを帯電除去処理した後、PENの上全面(但し、両端の10mmは除く)に、電子輸送層形成用塗布液を温度25℃でエクストルージョン塗布機を使用した湿式塗布方式により乾燥膜厚が30nmになるように以下の塗布条件で塗布した。塗布後、乾燥部で以下に示す条件により乾燥・加熱処理を行い、電子輸送層を形成した。尚、搬送速度は、3m/分とした。搬送速度は、三菱電機(株)製 レーザドップラ速度計LV203で測定した。
電子輸送層の塗布条件としては、電子輸送層形成用塗布液の塗布時の温度は25℃、露点温度-20℃以下のN2ガス環境の大気圧下で、且つ清浄度クラス5以下(JIS B 9920)で行った。
電子輸送層形成用塗膜の乾燥及び加熱処理条件としては、電子輸送層形成用塗布液を塗布した後、図4に示す正孔輸送層塗膜の乾燥及び加熱処理に使用した乾燥装置及び加熱処理装置と同じ装置を使用し、乾燥装置ではスリットノズル形式の吐出口から成膜面に向け高さ100mm、吐出風速1m/s、幅手の風速分布5%、温度150℃で溶媒を除去した後、引き続き、加熱処理装置により温度100℃で裏面伝熱方式の熱処理を行い、電子輸送層を形成した。
図6に示すフローに従って、PENに付けられたアライメントマークを検出し、アライメントマークの位置に従ってPETの上に形成された電子輸送層の上に、第1電極の取り出し電極部分の上及び発光層の周囲の不要の部分に、電子輸送層に対して良溶媒である乳酸エチルを含浸した部材で特表2007-515756号に記載されている方法を用いて、電子輸送層を拭き取り除去した。
図5に示される工程を使用し、以下に示す条件で電子輸送層の上に順次陰極バッファ層(電子注入層)、第2電極、封止部材を形成し、断裁し有機EL素子を作製し試料No.101とした。
第一電極が形成されたロール状のPENに付けられたアライメントマークを検出し、アライメントマークの位置に従って電子輸送層の上及び第1電極の取り出し電極を除いた周辺とに、蒸着装置で5×10-4Paの真空環境条件にて陰極バッファ層(電子注入層)層形成材料としてLiFを用い、蒸着法にてマスクパターン成膜し、厚さ0.5nmの陰極バッファ層(電子注入層)を積層した。
引き続き、PENに付けられたアライメントマークを検出し、アライメントマークの位置に従って形成された陰極バッファ層(電子注入層)の上に第1電極の大きさに合わせ5×10-4Paの真空下にて第2電極形成材料としてアルミニウムを使用し、取り出し電極を有するように蒸着法にてマスクパターン成膜し、厚さ100nmの第2電極を積層し有機EL素子No.101を作製した。
有機EL素子No.101作製の際陰極バッファ層(電子注入層)の形成の前に、準備されたパターン化された電子輸送層が形成されたロール状のPENに付けられたアライメントマークを検出し、アライメントマークの位置に従って、所定の位置にYAGレーザー(第2高調波:波長=532nm)を用いて、第1電極及び第1電極上に形成された有機機能層を0.5mm及び4.0mm幅に除去して第1電極不連続部を形成した。以降は有機EL素子No.101と同様にして、有機EL素子No.102(0.5mm)及び103(4.0mm)を作製した。
作製した有機EL素子のPENに付けられたアライメントマークを検出し、アライメントマークの位置に従って第1電極及び第2電極の引き出し電極の端部を除いて発光領域及び発光領域の周辺に紫外線硬化型の液状封止剤(エポキシ樹脂系)を使用し、厚さ30μmで塗設した。
この後、以下に示す帯状シート封止部材を準備した有機EL素子の封止剤塗設面に第1電極及び第2電極の引き出し電極の端部を除いた位置にロールラミネータ法により積重し、大気圧環境化にて押圧0.1MPaでロール圧着した後、波長365nmの高圧水銀ランプを、照射強度5~20mW/cm2、距離5~15mmで1分間照射し固着させ貼合し、複数の有機EL素子が連続的に繋がった状態とした。
封止部材として、PETフィルム(帝人・デュポン社製)を使用し、アルミ箔をバリア層に使用した2層構成の帯状シート封止部材を準備した。PETの厚さ50μm、バリア層のアルミ箔の厚さを30μmとした。尚、PETフィルムのバリア層の形成は公知のラミネート法により実施した。
準備した複数の有機EL素子が連続的に繋がった状態のものを個別の有機EL素子の大きさにPENに付けられたアライメントマークを検出し、アライメントマークの位置に従って断裁した。
塗布前に第1電極形成工程で第1電極不連続部を形成する以外は実施例1と同じ様に有機EL素子を形成した。第1電極不連続部の間隔は、それぞれ1、2、3、及び5mmに変えた。得られた各有機EL素子について、以下に示す評価ランクに従って評価し、結果を表1に示す。
定電圧電源を用いて、有機EL素子に5V印加し、発光面の中央部の6箇所の輝度差を目視で観察した。
◎:輝度差が全くない
○:6箇所中、1箇所の輝度が異なる
△:6箇所中、2箇所以上4箇所未満の輝度が異なる
×:6箇所中、4箇所以上の輝度が異なる
3 帯状の可撓性基材
3a ロール状に巻かれた帯状の可撓性基材
11 可撓性基材
12 第1電極(陽極)
12a 第1電極引き出し部
13 有機機能層
103 正孔輸送層
104 発光層
105 電子輸送層
106 陰極バッファ層(電子注入層)
14 第2電極(陰極)
14a 第2電極引き出し部
15 封止剤
16 封止部材
17 不連続部
20 有機EL構造体
2 製造工程
201 供給工程
202 第1電極形成工程
202a 第1電極形成装置
202d1 第1電極切除装置
203 正孔輸送層形成工程
203b 塗布部
203b 乾燥部
203d パターン形成部
203d1 拭き取り装置
204 発光層形成工程
205 電子輸送層形成工程
206 陰極バッファ層(電子注入層)形成工程
207 第2電極形成工程
207d3 第1電極切除装置
208 封止工程
209 回収工程
Claims (3)
- 帯状の可撓性基材の上に第1電極と、少なくとも1層の有機機能層と、第2電極とを有し構成される有機EL素子の製造方法において、該可撓性基材の搬送方向に連続して形成されている該第1電極上に、該有機機能層の少なくとも一層を塗布により連続形成し、更に、該有機機能層上に該第2電極を形成することにより搬送方向に複数の有機EL素子の構造体とした後、個々の有機EL素子に断裁して有機EL素子を製造することを特徴とする有機EL素子の製造方法。
- 前記有機機能層を塗布により連続形成した後に、前記複数の有機EL素子の構造体の間の前記第1電極の部位を加工して、不連続化することを特徴とする請求項1に記載の有機EL素子の製造方法。
- 前記第1電極の所定の部位を0.5mm~2mmの間隔に不連続化加工した後、前記有機機能層の少なくとも一層を塗布により連続形成することを特徴とする請求項1に記載の有機EL素子の製造方法。
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WO2016006243A1 (ja) * | 2014-07-10 | 2016-01-14 | 株式会社Joled | 有機el素子 |
JP2016054173A (ja) * | 2014-09-02 | 2016-04-14 | 日本放送協会 | 有機電界発光素子 |
EP3355374A4 (en) * | 2015-09-22 | 2019-05-15 | Kolon Industries, Inc. | FLEXIBLE DEVICE AND MANUFACTURING METHOD THEREFOR |
EP3618575A4 (en) * | 2017-04-25 | 2021-01-20 | Sumitomo Chemical Company, Limited | MANUFACTURING PROCESS OF AN ORGANIC ELECTRONIC DEVICE |
US11121350B2 (en) | 2017-04-26 | 2021-09-14 | Sumitomo Chemical Company, Limited | Electrode-attached substrate, laminated substrate, and organic device manufacturing method |
US11183645B2 (en) | 2015-05-11 | 2021-11-23 | Nippon Hoso Kyokai | Organic thin film and method for manufacturing organic thin film, organic electroluminescence element, display device, illumination device, organic thin film solar cell, thin film transistor, and coating composition |
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EP2770803A4 (en) * | 2011-10-19 | 2015-08-19 | Nitto Denko Corp | METHOD AND DEVICE FOR PREPARING AN ORGANIC ELECTROLUMINIC SCENE ELEMENT |
WO2015037237A1 (ja) * | 2013-09-13 | 2015-03-19 | パナソニック株式会社 | 有機発光装置、およびその製造方法 |
KR102637650B1 (ko) * | 2016-11-30 | 2024-02-15 | 엘지디스플레이 주식회사 | 유기 화합물과 이를 포함하는 유기발광다이오드 및 유기발광 표시장치 |
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EP3618575A4 (en) * | 2017-04-25 | 2021-01-20 | Sumitomo Chemical Company, Limited | MANUFACTURING PROCESS OF AN ORGANIC ELECTRONIC DEVICE |
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