KR100832763B1 - Organic el device and process for producing the same, and organic el display panel - Google Patents

Abstract

An organic electroluminescent element has the laminated structure which consists of an organic film containing the light emitting layer at least between a positive electrode and a negative electrode, the positive hole transport layer adjacent to the positive electrode side of the said light emitting layer, and the electron carrying layer adjacent to the negative electrode side of the said light emitting layer, The said laminated body At least one of the organic films constituting the structure contains a metal element having reactivity with oxygen or water.

Organic EL

Description

Organic EL element, its manufacturing method, and organic EL display panel {ORGANIC EL DEVICE AND PROCESS FOR PRODUCING THE SAME, AND ORGANIC EL DISPLAY PANEL}

Field of technology

BACKGROUND OF THE INVENTION Field of the Invention The present invention generally relates to organic electroluminescent devices (hereinafter referred to as organic EL devices), and more particularly to organic EL devices having a long lifetime.

Background

The organic EL device has characteristics such as self-luminous, high-speed response, and is expected to be applied to flat display devices and the like.

Since the report of stacked devices in which a hole transporting organic film and an electron transporting organic film are laminated (CW Tang and SA VanSlyke, Applied Physics Letters vol. 51, 913 (1987)), organic EL devices emit large-area light emitting at low voltage of 10V or less. Attention is drawn to the device. This conventional organic EL device exhibits green light emission.

1 shows a configuration of a typical stacked organic EL element 10.

Referring to FIG. 1, the organic EL element 10 is formed on a transparent substrate 11 such as glass supporting a transparent electrode 11A such as ITO (In ₂ O ₃ · SnO ₂ ), and the hole transporting organic film A hole transport layer 12 comprising a light emitting layer 13, an emission layer 13, and an electron transport layer 14 formed of the electron transporting organic film. The electrode 15, such as Al, is formed on the electron transport layer 14. do.

Therefore, as shown in FIG. 1, the DC drive power supply 16 is formed, the negative voltage is applied to the electrode 15 which contacts the said electron carrying layer 14 from the said DC drive power supply 16, and the said hole transport layer 12 By applying a constant voltage to the electrode (11A) to contact the electrode), holes are injected into the light emitting layer 13 through the hole transport layer 12, and electrons are injected through the electron transport layer 14, the light emitting layer 13 By recombination of electrons and holes in the air, desired light emission is generated at a wavelength corresponding to the energy gap of the light emitting layer 13 in the light emitting layer 13.

Among these light emitting layers 13, a hole transporting layer or an electron transporting layer may also have a function as in the case of the two-layer type device by Tang and VanSlyke described above. Moreover, in order to obtain the organic electroluminescent element of high luminous efficiency, as a structure of a light emitting layer, in addition to the single film | membrane formed from one type of material, the pigment | dye doping film which doped a small amount of highly fluorescent dye pigment | dye in host material which is a main component is proposed. (CW Tang, SA Van Slyke, and CH Chen, Applied Physics Letters vol. 65, 3610 (1989)).

Patent Document 1: Japanese Patent Application Laid-Open No. 7-138739

Patent Document 2: Japanese Patent Application Laid-Open No. 8-120442

Patent Document 3: Japanese Patent Application Laid-Open No. 11-92915

Patent Document 4: Japanese Patent Application Laid-Open No. 9-256142

Patent Document 5: Japanese Unexamined Patent Publication No. 2003-313654

Disclosure of the Invention

At present, various element structures and organic materials have been proposed as organic EL elements, and luminances of about 1000 cd / m ² are realized at a driving voltage of 10V.

However, this luminance value is at the start of driving, and continuous driving of the organic EL element results in a decrease in light output over time and an increase in the driving voltage. Eventually, a high driving voltage causes a short circuit inside the element, resulting in an organic EL. The device is destroyed.

Such rapid deterioration of the organic EL element is known to be particularly remarkable when impurities such as oxygen and water are present in the organic EL element. Therefore, the display device using the conventional organic EL element is organic EL as shown in FIG. The display area which consists of arrangement | positioning of the element 10 is covered with the airtight cover 17, and dry nitrogen etc. are enclosed inside the said airtight cover 17, and deterioration of organic material is suppressed.

However, in such a structure, even if intrusion of impurities from the outside after the display device is assembled can be prevented, deterioration due to impurities introduced into the organic material at the time of manufacturing the organic EL element cannot be prevented.

The present invention provides a method for producing an organic EL device which can suppress the influx of impurities into the device structure at the time of manufacturing an organic EL device, thereby realizing a long device life, and an organic EL produced by such a manufacturing method. Provided is an element.

According to 1 aspect of this invention,

As a manufacturing method of the organic electroluminescent element which consists of a board | substrate and the laminated structure which consists of an organic film formed on the said board | substrate, and contains an at least a hole transport layer, a light emitting layer, and an electron carrying layer,

A deposition step of depositing each organic film constituting the laminated structure,

At least a part of the deposition step is provided in the vicinity of the substrate, where a method of producing an organic EL device is performed in a state where a metal element having reactivity with oxygen or water is present.

According to another aspect of the present invention,

An organic EL device having a laminated structure composed of an organic film, comprising at least a light emitting layer, a hole transporting layer adjacent to the positive electrode side of the light emitting layer, and an electron transporting layer adjacent to the negative electrode side of the light emitting layer, between the positive electrode and the negative electrode.

At least one of the organic films constituting the organic film laminate structure is provided with an organic EL device containing a metal element having reactivity with oxygen or water.

According to the present invention, when depositing each organic film constituting the laminated structure, a metal element having a reactivity with oxygen or water is present in the vicinity of the substrate where the organic film is deposited, and otherwise flows into the laminated structure. Impurities, such as oxygen and water, are removed at the time of manufacture of an organic EL element, and the removed impurity does not return to a laminated structure. The organic EL device produced in this way has the characteristic of containing the said metal element in the laminated structure, and has the outstanding element life.

Other objects and features of the present invention will become apparent from the following detailed description of the invention, which is made with reference to the drawings.

Brief description of the drawings

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the structure of the conventional organic electroluminescent element.

2 is a diagram illustrating a configuration of a conventional organic EL display panel.

3 is a view showing the configuration of a vacuum vapor deposition apparatus used in the present invention.

4 is a diagram showing the configuration of an organic EL device according to a first embodiment of the present invention.

5 is a view showing a method for manufacturing an organic EL device according to the first embodiment of the present invention.

6 is a view showing a method for manufacturing an organic EL device according to a second embodiment of the present invention.

7 is a diagram showing the configuration of an organic EL display panel according to a third embodiment of the present invention.

Best Mode for Carrying Out the Invention

[First Embodiment]

3 shows a configuration of a vacuum deposition apparatus 20 used in the present invention.

Referring to FIG. 3, the vacuum deposition apparatus 20 is typically 1 × 10 ^{-4 to} 1 × 10 ^-5 from an exhaust port 21A connected to a high vacuum exhaust system such as a rotary pump, cryopump or turbomolecular pump. It has the vacuum chamber 21 exhausted by the pressure of Pa, The board | substrate holder 21B which hold | maintains the to-be-processed substrate W is formed in the said vacuum chamber 21, and in the said vacuum chamber 21, the said A cell 21C holding an organic raw material is formed to face the substrate W on the substrate holder 21.

Shutter mechanism 21D cooperates with the said cell 21C, and the heating mechanism 21F which energizes and heats Ti wire 21E is provided in the vicinity of the said board | substrate W. As shown in FIG.

The vacuum chamber 21 is also provided with a substrate loading / unloading port 21H having a gate valve 21G.

In operation, the cell 21C is heated to a predetermined temperature, the shutter mechanism 21D is opened, and a desired organic film or the like is placed on the surface of the substrate W on the substrate holder 21B. The film is deposited.

At that time, in the vacuum vapor deposition apparatus 20 of FIG. 3, Ti atom is discharge | released from the Ti wire 21E to the said vacuum chamber 21 by driving the said heating mechanism 21F. The released Ti atoms are oxygen or water released into the vacuum chamber 21 accompanying the evaporation of organic raw materials from the cell 21C, or oxygen or water remaining in the vacuum chamber 21, moreover, the vacuum chamber 21. It reacts with oxygen or water adhering to the wall surface of the substrate to inactivate it. That is, the Ti atom acts as a getter metal element.

4 shows the configuration of an organic EL element 40 according to the first embodiment of the present invention manufactured using the vacuum vapor deposition apparatus 20 of FIG.

Referring to FIG. 4, the organic EL element 40 is formed on a glass substrate 41 carrying an ITO electrode pattern 41A (positive electrode), and is typically 140 nm on the ITO electrode pattern 41A. Formed by the film thickness of

A hole injection layer 42 composed of commercially available 2-TNTA (4,4 ', 4 "-tris (2-naphthylphenylamino) triphenylamine) represented by Chemical formula formed of a film thickness of 10 nm

A hole transport layer 43 composed of commercially available α-NPD (N, N'-dinaphthyl-N, N'-diphenyl [1,1'-biphenyl] -4,4'-diamine) On the hole transport layer 43, typically formed with a film thickness of 20 nm

A light emitting layer 44 composed of commercially available CBP (4,4'-bis (9-carbazolyl)-(biphenyl)), and a film thickness of typically 10 nm on the light emitting layer 44 Formed chemical formula

A hole block layer 45 made of BAlq commercially available from SynTec GmbH Wolfen, and a film thickness of 20 nm is typically formed on the hole block layer 45

An electron transport layer 46 made of commercially available Alq ₃ , a LiF electron injection layer 47 formed on the electron transport layer 46 with a film thickness of typically 0.5 nm, and the LiF electron injection layer 47 ) Is formed of an Al electrode 48 formed to a thickness of 100 nm, the hole transport layer 42

A concentration of 0.1% by an acceptor composed of F4TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinomimethane) commercially available from Tokyo Kasei Co., Ltd. Doped with. In addition, the light emitting layer 44 is represented by the chemical formula

It is doped at a concentration of 10% by tbppy (1,3,6,8-tetrabiphenylpyrene).

The organic EL element 40 in FIG. 4 emits light at a driving voltage of 4 V or more and emits blue light.

Next, the manufacturing method of the organic electroluminescent element of FIG. 4 using the vacuum vapor deposition apparatus 20 of FIG. 3 is demonstrated.

5 is a flowchart for explaining a method for manufacturing the organic EL element 40 in FIG.

Referring to FIG. 5, for a substrate which is first ultrasonically cleaned using water, acetone, and isopropyl alcohol, in which the ITO electrode pattern 41A is formed to a thickness of 150 nm in step 1, and thus treated, UV ozone treatment or oxygen plasma treatment is performed. Next, in step 2, this is introduced into the vacuum chamber 21 of the vacuum deposition apparatus 20 as the substrate W to be processed. In the case of performing the UV ozone treatment, UV irradiation is performed on the substrate in the air for 20 minutes.

Further, in the next step 3, the vacuum chamber 21C is decompressed to a high vacuum of 1 × 10 ^-4 -10 ^-5 pa, and in step 4, the cell 21C is closed with the shutter 21D of FIG. 4 closed. ) Is heated using a resistance heater or an electron beam to dehydrate the organic raw material held in the cell 21.

In addition, in step 4, the heating mechanism 21F is driven to heat the Ti wire 21E, and Ti atoms are released into the vacuum chamber 21. As a result, oxygen and water released in the vacuum chamber 21 by the dehydration of the organic raw material in step 4 are trapped by Ti atoms to form inert Ti oxide or hydroxide, and the inner wall of the vacuum chamber 21 or the like. It is fixed, and it returns to an organic raw material again, and it is suppressed that it is absorbed in the organic film formed on the to-be-processed substrate W. FIG.

In addition, in step 6, the shutter 21D is opened, and the vapor deposition cell 21C is heated to form a hole injection layer 42, a hole transport layer 43, and a light emitting layer on the substrate in accordance with the configuration of FIG. 44, the hole block layer 45, the electron transport layer 46, the electron injection layer 47, and the Al electrode layer 48 are formed in order by vacuum vapor deposition. For this reason, in the vacuum chamber 21, the some vapor deposition cell 21C which hold | maintained each raw material is formed. In this vapor deposition step, the substrate temperature of the substrate W to be processed is set to room temperature.

More specifically, the hole injection layer 42 is formed by depositing 2TNATA and F4-TCNQ at a rate of 0.1 nm / sec and 0.0001 nm / sec, respectively, and the hole transport layer 43 is α-NPD of 0.1. It is formed by depositing at a rate of nm / second. The light emitting layer 44 is formed by depositing CBP and tbppy at rates of 0.09 nm / sec and 0.01 nm / sec, respectively. The hole block layer 45 is formed by depositing BAlq at a rate of 0.1 nm / second, and the electron transport layer 46 is formed by depositing Alq ₃ at a rate of 0.1 nm / second. Further, the LiF electron injection layer 47 and the Al electrode are formed by depositing LiF and Al at a rate of 0.01 nm / sec and 1 nm / sec, respectively.

The heating process of the Ti wire 21E in the step 5 is stopped just before the start of the step 6, so that in the vapor deposition step of the step 6, no emission of Ti atoms from the Ti wire 21E occurs, The Ti atom released in the vacuum chamber 21 in step 5 immediately before is still present in the vacuum chamber 21, and traps oxygen or moisture present in the vicinity of the surface of the substrate W to be treated, and burns it. Activate it. For this reason, even if the high temperature raw material particles discharged from the deposition cell 21C are cooled while flying in the space in the vacuum chamber 21 to the vicinity of the surface of the substrate W to be processed, the inflow of oxygen or water into the raw material particles can be maintained. It is effectively suppressed.

In the present embodiment, the organic EL device according to Comparative Example 1 having the same structure as that shown in FIG. 4 is omitted in step 5 of FIG. 5, that is, the step of discharging the Ti atoms into the vacuum chamber 21. Formed. In this embodiment, as Comparative Example 2, an organic EL device having the same structure as that shown in FIG. 4 was formed by omitting the step 4 of FIG. 5, that is, the dehydration step of the organic raw material and the step 5 of FIG. 5. .

The organic EL element 40 according to the present Example, the organic EL element according to Comparative Example 1, and the organic EL element according to Comparative Example 2 thus obtained were driven at a driving voltage of 7 V and a driving current density of 15 mA / cm 2. In this case, the high luminescence efficiency was obtained immediately after the start of driving in any of the devices. The organic EL device of the present embodiment is shown in Table 1 below when the relative luminance of the drive immediately after the start of driving for 200 hours is compared. In 40, the relative luminance is 0.71, while in Comparative Example 1, it is decreased to 0.64, and in Comparative Example 2, it is known that it is reduced to 0.38.

Luminous Efficiency (cd / A) 15mA / ㎠ Relative luminance 0H 200H Comparative Example 1 3.15 One 0.64 Comparative Example 2 2.42 One 0.38 Example 3.30 One 0.71

As a result of Table 1, when the heat treatment of the raw material was not performed at the time of formation by the vacuum deposition method of each organic layer constituting the organic EL device as in Comparative Example 2, oxygen and moisture in the raw material flowed into the device and the organic EL When the heat treatment is performed only, as in Comparative Example 1, which causes a fatal effect on the life of the device, the lifetime of the organic EL device is improved, but the oxygen or moisture remaining in the vacuum chamber in addition to the dehydration treatment as in the present embodiment is obtained. In the case of carrying out the inactivation treatment, it is meant that further improvement in life is realized. In particular, the organic EL device of the present embodiment has a longer life compared to Comparative Example 1 by exhausting the vacuum chamber 21 in a high vacuum state by a high performance pump only by heating the organic raw material in step 4 of FIG. 5. Even if it does, the oxygen and moisture which escaped cannot remain in the vacuum tank 21, and this shows that this flows into the organic electroluminescent element on the to-be-processed substrate W. As shown in FIG.

In addition, in the present invention, since the Ti releasing step of step 5 is performed immediately before the deposition step in step 6, the inflow of Ti into each layer constituting the organic EL element 40 cannot be avoided, and in fact, the result of XPS analysis It is confirmed that Ti is contained in the organic EL element 40. However, the results in Table 1 above show that the presence of Ti does not adversely affect the luminescence properties of the organic EL element when comparing the luminous efficiency immediately after the start of driving. Not only that, it shows that a desirable effect of improving the luminous efficiency up to 3.30 cd / A is obtained by the reduction of impurities. Note that in the organic EL devices of Comparative Examples 1 and 2, step 5 is omitted, so that Ti is not contained in the device structure. Nevertheless, it can be seen that in these devices, the luminous efficiency immediately after the start of driving is only 3.15 cd / A and 2.42 cd / A, respectively.

As described above, the present invention is based on the discovery that even if a metal element such as Ti is contained in the organic EL element, the light emission characteristics are not adversely affected. By using such a getter metal element, the luminous efficiency is high and the deterioration with time is small. An organic EL element and an organic EL display panel using the same are provided.

In addition, the said metal is not limited to Ti, The same result can be obtained also in Si, Al, and Cr.

Moreover, this invention is not limited to the said organic electroluminescent element of the said specific material system, For example, to the conventional green electroluminescent organic electroluminescent element shown in FIG. It is also effective for improving device life.

In addition, the heating of the Ti wire 21E in the vacuum vapor deposition apparatus 20 of FIG. 3 not only supplies electricity directly to the wire itself, but also winds this Ti wire on high melting point metal wires, such as W, and such high melting point metals. It is also possible to carry out by energizing a wire. In addition, the Ti wire 21E may be heated by any other means. For example, it is also possible to use a large metal ribbon or the like instead of the wire 21E.

In addition to the above configuration, it is also possible to form a large exposed surface of the getter metal in the vacuum chamber 21 and to capture oxygen and water liberated in the vacuum chamber 21 by the exposed surface.

Second Embodiment

6 is a flowchart showing a method for manufacturing an organic EL device according to a second embodiment of the present invention. However, the same reference numerals are given to the parts described earlier in the drawings, and description thereof is omitted.

In step 6 of FIG. 5, all the layers 42-48 are formed on the ITO electrode pattern 41A in FIG. 4 in sequence, but in the process according to the present embodiment of FIG. 6, after the Ti emission process of step 5 In step 61, the heating of the Ti wire 41E is stopped, and only the hole injection layer 42 is used for the cell holding 2-TNATA and F4-TCNQ by the vacuum deposition apparatus 20 of FIG. 3. It is formed by opening the shutter of the cell being held. After that, the Ti releasing process is executed again in step 62.

In addition, in the next step 63, the Ti emission process is terminated, the shutter of the cell holding α-NPD is opened to form the hole transport layer 43, and the same process is then repeated alternately, thereby stacking the structure of FIG. Form in order.

In the organic EL element formed in this way, since the Ti atom is discharged immediately before the formation of each organic layer and impurities such as oxygen and water in the vicinity of the surface of the substrate W, in particular, in the vacuum chamber 21 are removed, the organic EL element It is possible to further reduce the concentration of impurities introduced in the air.

As a result of this process, in the organic EL device manufactured by the present embodiment, there is shown a characteristic Ti concentration distribution in which the Ti concentration is increased in the vicinity of the interface between one layer and the next layer.

As described above, in the present invention, the metal used as the getter is not limited to Ti, and other metals such as Si, Al, Cr, and the like may be used, and the light emission characteristics of the organic EL device may be reduced even when such metal is used. There is no deterioration.

Third Embodiment

7 shows the configuration of a full color organic EL display panel 60 according to a third embodiment of the present invention.

Referring to FIG. 7, the organic EL display panel 60 is formed on the glass substrate 61 carrying the ITO electrode pattern 61A, the organic EL element 60R emitting red light, and the organic EL element emitting green light. 60G and an array of display elements consisting of repetition of the organic EL element 60B emitting blue light, wherein each of the organic EL elements 60R, 60G, 60B uses the vacuum deposition apparatus 20 of FIG. 5 is formed by the process shown in FIG. 6.

More specifically, the red organic EL device 60R has a hole injection layer 62R made of α-NPD having a thickness of 50 nm on the ITO electrode pattern 61A, and has a chemical formula.

And the electron transport layer (64R) and the red light-emitting layer (63R) containing a concentration of 1wt% DCJTB, consisting of Alq ₃ having a thickness of 30㎚, consisting of Alq ₃ having a thickness of 30㎚ represented by a thickness of 0.5㎚ The getter metal element which has a laminated structure which consists of the electron injection layer 65R which consists of LiF, and the Al electrode layer 66R, and consists of any one of Ti, Si, Al, and Cr is especially in each organic layer 62R-64R. It is contained in high concentration in the interface of a layer.

Similarly, the green organic EL element 60G is formed on the ITO electrode pattern 61A with a hole injection layer 62G made of α-NPD having a thickness of 50 nm, and a green light emitting layer made of Alq ₃ having a thickness of 50 nm. 63G, an electron injection layer 64G made of LiF having a thickness of 0.5 nm, and a laminated structure made of Al electrode layer 65G. Among the organic layers 62G and 63G, any one of Ti, Si, Al, and Cr was used. One getter metal element is contained at a high concentration, particularly at the interface between the layer and the layer.

Further, the blue organic EL element 60B has a hole injection layer 62B made of α-NPD having a thickness of 50 nm on the ITO electrode pattern 61A, and the chemical formula is

A blue light emitting layer 63B containing tppy represented by a concentration of 10 wt% and consisting of CBP having a thickness of 20 nm,

An electron injection layer 66B composed of a BCP represented by BCP and having a thickness of 10 nm, an electron transport layer 65B made of Alq ₃ having a thickness of 50 nm, and LiF having a thickness of 0.5 nm. And a getter metal element composed of any one of Ti, Si, Al, and Cr in each of the organic layers 62B to 65B in a high concentration at the interface between the layer and the layer. It is contained.

In addition, all the organic EL elements on the substrate 61 are covered by an airtight cover 68, and an inert gas such as dry nitrogen gas is filled in the airtight cover 68.

In the organic electroluminescent display panel of such a structure, the lifetime of each organic electroluminescent display element is long by use of the said getter metal element, and the practical lifetime is obtained also as a whole display panel.

As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to this specific embodiment, A various deformation | transformation and a change are possible within the summary described in a claim.

Industrial availability

According to the present invention, when depositing each organic film constituting the laminated structure, a metal element having a reactivity with oxygen or water is present in the vicinity of the substrate where the organic film is deposited, and otherwise flows into the laminated structure. Impurities, such as oxygen and water, are removed at the time of manufacture of an organic EL element, and the removed impurity does not return to a laminated structure. The organic EL device produced in this way has the characteristic of containing the said metal element in the laminated structure, and has the outstanding element life.

Claims (15)

As a manufacturing method of the organic electroluminescent element which consists of a board | substrate, and the laminated structure which consists of an organic film formed on the said board | substrate, and contains an at least a hole transport layer, a light emitting layer, and an electron carrying layer, A deposition step of depositing each organic film constituting the laminated structure, At least a part of the deposition process is performed in the presence of a metal element having a reactivity to oxygen or water in the vicinity of the substrate, Prior to the deposition step, a step of releasing the metal element in the vicinity of the substrate,  And the step of releasing the metal element is performed in advance of the step of depositing each organic film constituting the laminated structure. The method of claim 1, The metal element contains any one of Ti, Si, Al, and Cr. delete The method of claim 1, The process of releasing the metal element is finished before the start of the deposition process. The method of claim 1, The step of releasing the metal element includes a step of heating a medium containing the metal element. delete delete An organic EL device having a laminated structure composed of an organic film, comprising at least a light emitting layer, a hole transporting layer adjacent to the positive electrode side of the light emitting layer, and an electron transporting layer adjacent to the negative electrode side of the light emitting layer, between the positive electrode and the negative electrode. At least one of the organic films constituting the laminated structure contains a metal element having reactivity with oxygen or water, The organic element according to claim 1, wherein the metal element increases in concentration in the vicinity of the interface between one layer and the next layer in the laminated structure. The method of claim 8, The metal element is any one of Ti, Si, Al, and Cr. delete The method of claim 8, The said organic metal element is contained in all the organic films which comprise the said laminated structure. With a transparent substrate, An array consisting of a plurality of organic EL elements formed on the transparent substrate, An organic EL display panel comprising an airtight cover formed on the transparent substrate so as to cover the plurality of organic EL elements and partitioning a space filled with an inert gas. Each organic EL element has a laminated structure consisting of an organic film comprising at least a light emitting layer, a hole transporting layer adjacent to the positive electrode side of the light emitting layer, and an electron transporting layer adjacent to the negative electrode side of the light emitting layer, between the positive electrode and the negative electrode, At least one of the organic films constituting the laminated structure contains a metal element having reactivity with oxygen or water, The organic EL display panel in which the metal element increases in concentration in the vicinity of the interface between one layer and the next layer in the laminated structure. The method of claim 12, The metal element is any one of Ti, Si, Al, and Cr. delete The method of claim 12, The said metal element is contained in all the organic films which comprise the said laminated structure, The organic electroluminescence display panel.

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