WO2009096250A1 - Organic light-emitting diode, method for manufacturing organic light-emitting diode, manufacturing device for manufacturing organic light-emitting diode, and plasma processing device - Google Patents

Abstract

An organic layer is protected in the process of manufacturing an organic light-emitting diode. An organic layer (51) is continuously formed on ITO (50) on a substrate by deposition (step a in Fig. 2). A cathode layer (52) and a hydrogen-adsorbing layer (53) are formed by sputtering (step b and step c in Fig. 2), and part of the organic layer (51) is removed by etching (step d in Fig. 2). A side portion of the cathode layer (52) is formed by sputtering (step e in Fig. 2), the hydrogen-adsorbing layer (53) is formed by sputtering (step f in Fig. 2), and finally a sealing film (54) is formed by CVD (step g in Fig. 2). The hydrogen-adsorbing layer (53) adsorbs hydrogen gas used in the process of manufacturing the organic light-emitting diode. Thus, the organic layer (51) can be prevented from deteriorating.

Description

Organic light emitting diode, method for manufacturing organic light emitting diode, manufacturing apparatus for manufacturing organic light emitting diode, and plasma processing apparatus

The present invention relates to an organic light emitting diode, a method for manufacturing an organic light emitting diode, a manufacturing apparatus for manufacturing an organic light emitting diode, and a plasma processing apparatus, and particularly relates to a method for manufacturing an organic diode for protecting an organic layer.

In recent years, an organic EL display using an organic electroluminescence (EL) element that emits light using an organic compound has attracted attention. This organic EL element has features such as self-emission, fast reaction speed, and low power consumption, so it does not require a backlight and is expected to be applied to, for example, a display unit of a portable device. Has been.

The organic EL element is formed on a glass substrate and has a structure in which an organic layer is sandwiched between an anode (anode) and a cathode layer (cathode). Among these layers, the organic layer is easily deteriorated. For example, when moisture or oxygen is mixed from the outside, hydrogen and an organic substance react to generate hydrogen gas. For this reason, conventionally, a method for protecting an organic layer from external moisture or the like by forming a sealing film on the organic EL element and sealing the organic EL element has been proposed (for example, patents). Reference 1).

JP 2000-223264 A

However, the sealing film is a barrier layer that protects the entire organic element so that moisture or the like existing outside does not penetrate to the organic layer, and is formed before the sealing film is formed or while the sealing film is being formed. It is not possible to protect the organic layer from hydrogen generated in the water.

On the other hand, the manufacturing process of the organic EL element includes a process of using a gas containing hydrogen. For example, in the step of dry etching the organic layer, the etching rate of the organic layer can be increased by including hydrogen in the gas to be converted into plasma. In the step of forming the sealing film by PE-CVD (Plasma Enhanced-Chemical Vapor Deposition), a silicon compound is formed on the object to be processed by converting the silane (SiH ₄ ) gas containing hydrogen into plasma at high frequency. Thus, a thin film with high sealing properties can be formed.

In this way, when hydrogen is used before forming the sealing film or in the process of forming the sealing film, the hydrogen passes through the metal electrode (cathode) laminated on the organic layer and enters the organic layer. Mixed. For the cathode, silver Ag having a small work function and the highest reflectance in the visible light region is generally used to facilitate electron injection into the organic layer. However, since hydrogen has a small atomic radius, It passes through silver Ag. For this reason, the hydrogen gas used in the dry etching of the organic layer and the PE-CVD process of the sealing film reaches the organic layer through the cathode, gasifies in the organic layer, and the boundary between the organic layer and the cathode It becomes a bubble in the part. As a result, a gap is formed between the organic layer and the cathode, and conduction is lost in the gap portion, and the portion does not emit light, thereby causing unevenness in the light emission state of the organic display. From the above, there has been a demand for a technique that protects the organic layer from the used hydrogen and does not deteriorate the organic EL element while ensuring the freedom to use hydrogen in the manufacturing process of the organic EL element.

Therefore, in order to solve the above problem, the present invention provides a method for manufacturing an organic light emitting diode that protects an organic layer in the manufacturing process of an organic EL element.

That is, in order to solve the above-described problem, according to an aspect of the present invention, an organic layer stacked on an object to be processed, an electrode including an anode and a cathode formed with the organic layer interposed therebetween, and the organic An organic light emitting diode comprising a layer and a sealing film for sealing the electrode from the outside, wherein a hydrogen adsorption layer having a property of adsorbing hydrogen is provided between the organic layer and the sealing film An organic light emitting diode is provided.

According to this, a hydrogen adsorption layer having a characteristic of adsorbing hydrogen is provided between the organic layer of the organic light emitting diode and the sealing film. Thereby, the hydrogen gas used in the organic film etching process or the sealing film forming process is adsorbed on the hydrogen adsorption layer while passing through the hydrogen adsorption layer. For this reason, hydrogen is confined in the hydrogen adsorption layer and cannot reach the organic layer. As a result, hydrogen gas becomes bubbles in the organic layer, and a gap is formed between the organic layer and the cathode, and a phenomenon in which the cathode is peeled off from the organic layer can be avoided. Thereby, the light emitted by the combination of electrons and holes in the organic layer can be efficiently reflected on the cathode side and output from the anode side. As a result, it is possible to use hydrogen gas in the manufacturing process of the organic EL element, for example, to achieve a high etching rate in the etching process of the organic layer and to have a high sealing performance in the film forming process of the sealing film. It is possible to manufacture a high-performance organic light-emitting diode that can maintain the light emission intensity while enabling the formation of a sealing film.

In addition, after sealing an organic EL element with a sealing film, a sealing film barriers an organic layer from external moisture. Therefore, the hydrogen adsorption layer functions to protect the organic layer from hydrogen generated before the organic EL element is sealed with the sealing film. Further, for example, when a hydrogen adsorption layer is formed of a metal such as titanium Ti, titanium Ti does not decompose hydrogen confined therein into other substances unless the temperature is about 400 ° C. On the other hand, since it is unthinkable to use an organic display at a high temperature of about 400 ° C., after completion of the production of the organic EL element, the hydrogen adsorption layer is used during the production of the organic EL element in the stage of using the organic EL element. While adsorbing the generated hydrogen, it can be present in the organic EL element without any badness.

The hydrogen adsorption layer may be provided between the cathode and the sealing film. According to this, an organic layer, a cathode, a hydrogen adsorption layer, and a sealing film are sequentially formed on the substrate. That is, the cathode contacts the organic layer. As a result, the characteristics of the organic EL element can be maintained as in the conventional case by using silver Ag having the highest reflectivity for visible light and a small work function for the cathode.

On the other hand, according to such a configuration, a hydrogen adsorption layer is provided between the cathode and the sealing film. Thereby, the hydrogen gas used in the manufacturing process of the organic EL element is adsorbed on the hydrogen adsorption layer and cannot reach the organic layer. As a result, in the manufacturing process of the organic EL element, for example, the hydrogen gas deteriorates the organic layer while taking advantage of the use of the hydrogen gas such as formation of a sealing film having a high etching rate and a high sealing property. Overcoming the drawbacks of using hydrogen gas, a high performance organic light emitting diode having high emission intensity can be produced.

The hydrogen adsorption layer may be provided between the organic layer and the cathode. According to this, the organic layer, the hydrogen adsorption layer, the cathode, and the sealing film are sequentially formed on the substrate. That is, the hydrogen adsorption layer is in contact with the organic layer. For example, when silver Ag is used for the cathode and titanium Ti is used for the hydrogen adsorption layer, titanium Ti has a small work function and good reflectivity like silver Ag, so that the characteristics of the organic EL element should be maintained. Can do.

In addition to this, the hydrogen adsorption layer adsorbs the hydrogen gas used in the manufacturing process of the organic EL element. Thereby, hydrogen can be shut off from the organic layer. As a result, an organic light-emitting diode that maintains high performance by using a material with a low work function and good reflectivity while ensuring a high etching rate and formation of a sealing film with high sealing performance can be obtained. Can be manufactured.

The hydrogen adsorption layer may be provided on the cathode as part or all of the cathode. Here, an example in which the hydrogen adsorption layer is provided on a part of the cathode includes a case where the hydrogen adsorption layer is formed between the cathodes. As an example in which the hydrogen adsorption layer is provided on all the cathodes, there is a case where the hydrogen adsorption layer is formed as a cathode. Also by this, the hydrogen adsorption layer can block hydrogen from the organic layer by adsorbing the hydrogen gas used in the manufacturing process of the organic EL element. This overcomes the drawbacks of using hydrogen gas, which deteriorates the organic layer, while taking advantage of the advantages of using hydrogen gas, such as improving the etching rate, in the manufacturing process of organic EL elements. A high-performance organic light-emitting diode having high emission intensity can be manufactured.

In order to solve the above-described problem, according to another aspect of the present invention, an organic layer laminated on an object to be processed, an electrode including an anode and a cathode formed with the organic layer interposed therebetween, An organic light emitting diode comprising an organic layer and a sealing film for sealing the electrode from the outside, wherein the cathode is provided between the organic layer and the sealing film and has a property of adsorbing hydrogen An organic light emitting diode mixed with a hydrogen adsorbent is provided.

According to this, a cathode in which a hydrogen adsorbent having a characteristic of adsorbing hydrogen is mixed between the organic layer and the sealing film is provided. Thereby, the hydrogen gas used in the manufacturing process of the organic EL element is adsorbed by the hydrogen adsorbent mixed in the cathode when passing through the cathode, and is confined in the cathode. As a result, overcoming the drawbacks of using hydrogen gas, which deteriorates the organic layer, while taking advantage of the use of hydrogen gas, such as improving the etching rate, in the manufacturing process of organic EL elements. A high-performance organic light-emitting diode having high emission intensity can be manufactured.

The hydrogen adsorbing layer or the hydrogen adsorbing material described above is composed of titanium (Ti), zirconium (Zr), palladium (Pd), vanadium (V), tantalum (Ta), an element having the property of adsorbing hydrogen. It may be formed including any of a lanthanum element and an alkaline earth metal.

In addition, the hydrogen adsorption layer or the hydrogen adsorbent may be LaNi ₅ , CaCu ₅ , MgZn ₂ , ZrNi ₂ , ZrCr ₂ , TiFe, TiCo, Mg ₂ Ni, Mg ₂ Cu, It may be formed including any of Ti—V, V—Nb, and Ti—Cr.

In order to solve the above problem, according to another aspect of the present invention, after an organic layer is laminated on a workpiece, a cathode is formed on the organic layer, and the organic layer and the cathode are further formed. An organic light emitting diode manufacturing method for forming a sealing film that seals the outside from the outside, wherein the organic light emitting diode forms a hydrogen adsorbing layer having a property of adsorbing hydrogen between the organic layer and the sealing film A manufacturing method is provided.

According to this, the hydrogen gas used in the manufacturing process of the organic EL element is adsorbed on the hydrogen adsorption layer and blocked from the organic layer. This overcomes the drawbacks of using hydrogen gas, which deteriorates the organic layer, while taking advantage of the advantages of using hydrogen gas, such as improving the etching rate, in the manufacturing process of organic EL elements. A high-performance organic light-emitting diode having high emission intensity can be manufactured.

At this time, the hydrogen adsorption layer may be formed after the cathode is formed on the organic layer and before the sealing film is formed.

Further, the hydrogen adsorption layer may be formed after the organic layer is laminated on the object to be processed and before the cathode is formed.

Further, the hydrogen adsorption layer may be formed on the cathode as a part or all of the cathode.

In order to solve the above problem, according to another aspect of the present invention, after an organic layer is laminated on a workpiece, a cathode is formed on the organic layer, and the organic layer and the cathode are further formed. A manufacturing apparatus for manufacturing an organic light emitting diode using a method for manufacturing an organic light emitting diode for forming a sealing film for sealing the outside from the outside, wherein hydrogen is adsorbed between the organic layer and the sealing film A manufacturing apparatus for manufacturing an organic light emitting diode using a method for manufacturing an organic light emitting diode that forms a hydrogen adsorption layer having characteristics is provided.

In order to solve the above problems, according to another aspect of the present invention, there is provided a plasma processing apparatus for generating plasma from a gas supplied into a processing container and processing an object to be processed with the generated plasma. And a gas supply source for supplying a gas into the processing container, and generating plasma from the gas supplied from the gas supply source. Then, a plasma processing apparatus is provided that forms a hydrogen adsorption layer having a characteristic of adsorbing a cathode and hydrogen by the generated plasma.

According to these, the hydrogen gas used in the manufacturing process of the organic EL element is adsorbed on the hydrogen adsorption layer and blocked from the organic layer. This overcomes the drawbacks of using hydrogen gas, which deteriorates the organic layer, while taking advantage of the advantages of using hydrogen gas, such as improving the etching rate, in the manufacturing process of organic EL elements. A high-performance organic light-emitting diode having high emission intensity can be manufactured.

As described above, according to the present invention, it is possible to provide a method for manufacturing an organic light emitting diode that protects an organic layer in the process of manufacturing an organic EL element.

It is a schematic block diagram of the substrate processing apparatus concerning 1st Embodiment of this invention and each modification. It is a figure for demonstrating the organic EL element manufacturing process concerning 1st Embodiment. It is a longitudinal cross-sectional view of process module PM1 which performs 6 layer continuous film-forming processing concerning 1st Embodiment and each modification. It is a figure for demonstrating the film | membrane formed by 6 layer continuous film-forming processing. It is a longitudinal cross-sectional view of the sputtering processing apparatus (process module PM4) concerning 1st Embodiment and each modification. It is a longitudinal cross-sectional view of the RLSA plasma CVD processing apparatus (process module PM3) concerning 1st Embodiment and each modification. It is a figure for demonstrating the organic EL element manufacturing process concerning the modification 1. FIG. It is the figure which showed the laminated structure of the organic EL element concerning another modification. It is the figure which showed the laminated structure of the organic EL element concerning another modification. It is the figure which showed the laminated structure of the organic EL element concerning another modification. It is the figure which showed the experimental result corresponding to 1st Embodiment or a modification.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings. In the following description and the accompanying drawings, the same reference numerals are given to the constituent elements having the same configuration and function, and redundant description is omitted. In this specification, 1 mTorr is (10 ⁻³ × 101325/760) Pa, and 1 sccm is (10 ⁻⁶ / 60) m ³ / sec.

First, a substrate processing apparatus 10 according to an embodiment of the present invention will be described with reference to FIG. In the present embodiment, a process of manufacturing an organic light emitting diode using the substrate processing apparatus 10 will be described.

The substrate processing apparatus 10 according to the present embodiment is a cluster type manufacturing apparatus having a plurality of processing containers, and includes a load lock chamber LLM, a transfer chamber TM (Transfer Module), a preprocessing chamber CM, and four process modules PM (Process). Module) 1 to PM4.

The load lock chamber LLM is a vacuum transfer chamber in which a glass substrate (hereinafter referred to as “substrate”) G transferred from the atmospheric system is held in a reduced pressure state in order to transfer the glass substrate G to a transfer chamber TM in a reduced pressure state. Note that indium tin oxide (ITO) is formed in advance as an anode on the substrate G carried into the load lock chamber LLM from the atmospheric system.

In the transfer chamber TM, an articulated transfer arm Arm that can bend, stretch and turn is arranged. The substrate G is first transferred from the load lock chamber LLM to the pretreatment chamber CM using the transfer arm Arm, then transferred to the process module PM1, and further transferred to the other process modules PM2 to PM4. In the pretreatment chamber CM, contaminants (mainly organic matter) adhering to the surface of ITO as an anode formed on the substrate G are removed.

(Manufacturing process of organic light emitting diode)
In the four process modules PM1 to PM4, each process is executed to manufacture an organic light emitting diode. First, in the process module PM1, six organic layers 51 are continuously formed on the surface of the ITO 50 of the substrate by vapor deposition (step a in FIG. 2). Next, the substrate G is transferred to the process module PM4, and a metal electrode (cathode layer 52) is formed on the organic layer 51 of the substrate G by sputtering (step b in FIG. 2). Next, the hydrogen adsorption film 53 is formed by sputtering while changing the target in the process module PM4 (step c in FIG. 2). Next, the substrate G is transferred to the process module PM2, and a part of the organic layer 51 is removed by etching (step d in FIG. 2). Next, the substrate G is transferred again to the process module PM4, the side of the cathode layer 52 is formed by sputtering (step e in FIG. 2), and the target is changed in the process module PM4 to form the hydrogen adsorption film 53. It is formed by sputtering (step f in FIG. 2), and finally transferred to the process module PM3, and a sealing film 54 is formed by CVD (step g in FIG. 2).

In the following, first, as shown in step a of FIG. 2, for the step of forming the organic layer 51 on the ITO 50 by vapor deposition, refer to FIG. 3 showing the internal configuration of the process module PM1 that executes this step. While explaining. Thereafter, this step is performed for the step of forming the cathode layer 52 by sputtering (step b and step e in FIG. 2) and the step of forming the hydrogen adsorption layer 53 (step c and step f in FIG. 2). A description will be given with reference to FIG. 5 showing the internal configuration of the module PM4. Finally, the step of forming the sealing film 54 by CVD (step g in FIG. 2) will be described with reference to FIG. 6 showing the internal configuration of the process module PM3 that executes this step. Since the etching process in the process module PM2 shown in the process d of FIG. 2 is processed using a general etching apparatus, the description thereof is omitted here.

(Process module PM1: Organic film formation process)
As schematically shown in FIG. 3, the process module PM <b> 1 has a first processing container 100 and a second processing container 200, and has six layers in the first processing container 100. The organic film is continuously formed.

The first processing container 100 has a rectangular parallelepiped shape, and has a sliding mechanism 110, six blowing mechanisms 120a to 120f, and seven partition walls 130 therein. A gate valve 140 capable of loading and unloading the substrate G by opening and closing is provided on the side wall of the first processing container 100.

The sliding mechanism 110 includes a stage 110a, a support 110b, and a sliding mechanism 110c. The stage 110a is supported by the support 110b and electrostatically adsorbs the substrate G carried in from the gate valve 140 by a high voltage applied from a high voltage power source (not shown). The slide mechanism 110c is mounted on the ceiling of the first processing container 100 and is grounded, and the substrate G is slid in the longitudinal direction of the first processing container 100 together with the stage 110a and the support 110b. The substrate G is moved in parallel slightly above each blowing mechanism 120.

The six blowing mechanisms 120a to 120f are all the same in shape and structure, and are arranged in parallel at equal intervals. The blowing mechanisms 120a to 120f have a hollow rectangular shape inside, and blow out organic molecules from an opening provided at the upper center. Lower portions of the blowing mechanisms 120a to 120f are connected to connecting pipes 150a to 150f penetrating the bottom wall of the first processing vessel 100, respectively.

A partition wall 130 is provided between each blowing mechanism 120. The partition wall 130 partitions each blowing mechanism 120 to prevent organic molecules blown from the opening of each blowing mechanism 120 from being mixed into organic molecules blown from the neighboring blowing mechanism 120.

The second processing container 200 contains six vapor deposition sources 210a to 210f having the same shape and structure. The vapor deposition sources 210a to 210f store organic materials in the storage portions 210a1 to 210f1, respectively, and vaporize each organic material by raising the temperature of each storage portion to about 200 to 500 ° C. Vaporization includes not only a phenomenon in which a liquid changes into a gas but also a phenomenon in which a solid changes directly into a gas without passing through a liquid state (that is, sublimation).

The vapor deposition sources 210a to 210f are connected to the connecting pipes 150a to 150f at the upper portions thereof. The organic molecules vaporized in each evaporation source 210 pass through each connection pipe 150 without being attached to each connection pipe 150 from the opening of each blowing mechanism 120 by keeping each connection pipe 150 at a high temperature. It is discharged into the processing container 100. Note that the second processing vessel 200 is depressurized to a desired vacuum level by an exhaust mechanism (not shown) in order to keep the inside of the second processing container 200 at a predetermined vacuum level.

Valves 220a to 220f are attached to each connecting pipe 150. When each valve 220 is closed, a space in the vapor deposition source 210 storing each organic material and an internal space of the first processing container are formed. When the valves 220 are opened and the valves 220 are opened, the spaces communicate with each other. In the present embodiment, each valve 220 is released into the atmosphere, but may be provided in the second processing container 200.

Among the organic molecules blown out from each blowing mechanism 120, first, the organic molecules blown out from the blowing mechanism 120a adhere to the ITO (anode) on the substrate G that travels above the blowing mechanism 120a at a certain speed. As shown in FIG. 4, the first hole transport layer is formed on the substrate G. Subsequently, when the substrate G sequentially moves from the blowing mechanism 120b to the blowing mechanism 120f, the organic molecules blown from the blowing mechanisms 120b to 120f are deposited on the substrate G, respectively, so that the organic layers (second layer to sixth layer) are deposited. Layer) are formed in order. In this way, the organic layer 51 shown in step a of FIG. 2 is formed.

(Process module PM4: Metal electrode deposition step)
In the process module PM4 schematically showing the longitudinal section in FIG. 5, the metal electrode (cathode layer) 52 shown in the process b of FIG. 2 and the process e of FIG. 2 and the process c and FIG. The hydrogen adsorption layer 53 shown in step 2 of f is formed.

The plasma processing apparatus in the process module PM4 includes a processing container 500 and a lid 505. The processing vessel 500 has a bottomed cubic shape with an upper portion opened. A lid 505 is fitted on the ceiling surface of the processing container 500. The processing container 500 and the lid 505 are sealed by an O-ring 510 disposed on the contact surface between the processing container 500 and the lid 505, thereby forming a processing chamber S in which plasma processing is performed. The processing container 500 and the lid 505 are made of, for example, a metal such as aluminum and are electrically grounded. The lid body 505 is provided with a recess 505a at substantially the center.

The processing container 500 is provided with a stage 515 (mounting table) on which a glass substrate (hereinafter referred to as “substrate”) G is mounted. Stage 515 is made of, for example, aluminum nitride.

An electrode 520 is embedded in the concave portion 505 a of the lid body 505. A high frequency power source 530 is connected to the electrode 520 via a matching unit 525 from the outside, and plasma is generated from the gas supplied into the processing container 500 by the high frequency power output from the high frequency power source 530. It has become.

A target 535 is attached to the lower surface of the electrode 520 at a position facing the substrate G placed on the stage 515. The material of the target 535 is determined by the type of thin film formed on the substrate G. In the present embodiment, for example, when forming the cathode layer 52 shown in steps b and e of FIG. 2, silver Ag, which is a metal having the highest reflectivity and a low work function, is used. When forming the hydrogen adsorption layer 53 shown in the steps c and f, titanium Ti, which is a metal having a property of adsorbing hydrogen, is used.

A protective member 540 formed of the same material as that of the target 535 is attached to the periphery of the target 535 so as to protect the inner wall of the lid 505 from an ion attack.

The processing vessel 500 is provided with a gas introduction pipe 545 that penetrates the side wall thereof. The gas introduction pipe 545 is connected to a gas supply source 555 via a gas line 550. The gas supply source 555 is provided with a plurality of valves V, a mass flow controller MFC, and an argon gas supply source 555a. By controlling the opening and closing of the valve V and the opening of the mass flow controller MFC, the argon gas is supplied to the gas line. Then, the gas is supplied to the processing chamber S from the gas introduction pipe 545. Note that other inert gases such as krypton (Kr) and xenon (Xe) can be used instead of argon gas.

A vacuum pump (not shown) is connected to the processing container 500 via an exhaust pipe 560 that penetrates the wall opposite to the wall where the gas introduction pipe 545 is provided. The pressure is reduced to a vacuum level.

With this configuration, in the process module PM4, the high frequency output from the high frequency power source 530 is introduced into the processing chamber S from the electrode 520, and plasma is generated from the argon gas supplied into the processing chamber S by the introduced high frequency electric field energy. Generated. Among the generated plasma, positively charged argon ions fly toward the target 535 by colliding with the target 535 by maintaining the potential on the electrode 520 side at a negative potential.

When silver Ag, which is the material of the target 535, is used due to this collision, silver Ag atoms jump out of the target 535 and are deposited on the substrate G placed at the opposing position, so that the cathode layer 52 of silver Ag. Is formed (step b and step e in FIG. 2). Further, when titanium Ti is used as the material of the target 535, titanium Ti atoms are ejected from the target 535 and deposited on the substrate G placed at the opposite position, so that the hydrogen adsorption layer 53 of titanium Ti is formed. A film is formed (step c and step f in FIG. 2).

(Process module PM2: Organic film etching process)
Etching treatment of the organic layer 51 shown in step d of FIG. 2 between the sputtering treatment step shown in steps b and c of FIG. 2 and the sputtering treatment step shown in steps e and f of FIG. There is a process. Therefore, after the sputtering process shown in step c of FIG. 2 is completed, the substrate G is once transferred into the process module PM2. In the process module PM2, the organic layer other than the organic layer 51 laminated below the cathode layer 52 is scraped off by the plasma generated from the etching gas using the cathode layer 52 and the hydrogen adsorption layer 53 as a mask (dry etching). Thereby, only the organic layer 51 located below the cathode layer 52 remains on the substrate as shown in step d of FIG.

In the process of dry etching the organic layer 51 described above, hydrogen may be included in the gas to be converted into plasma in order to increase the etching rate of the organic layer 51. However, the organic layer 51 is easily deteriorated, and when moisture or oxygen is mixed from the outside, hydrogen and the organic substance react to generate gas. For this reason, in the process of this embodiment, the hydrogen adsorption layer 53 is formed in advance. According to this, when the gas containing hydrogen is turned into plasma and the organic layer 51 is etched by the plasma, the hydrogen adsorbing layer 53 adsorbs hydrogen, whereby the hydrogen can be shut off from the organic layer 51.

(Process module PM3: Sealing film forming step)
Next, a film forming process of a sealing film formed on the organic EL element will be described. The substrate G is again transported to the process module PM4, and as described above, the substrate G is transported into the process module PM3 through the sputtering process of step e and step f of FIG. 2, and its longitudinal section is schematically shown in FIG. A film forming process is performed by the illustrated RLSA (Radial Line Slot Antenna) plasma CVD apparatus.

The RLSA plasma CVD apparatus has a cylindrical processing container 600 having an open ceiling surface. A shower plate 605 is fitted into the opening on the ceiling surface. The processing container 600 and the shower plate 605 are sealed by an O-ring 610 disposed on the contact surface between the processing container 600 and the shower plate 605, thereby forming a processing chamber U in which plasma processing is performed. For example, the processing container 300 is made of a metal such as aluminum, and the shower plate 305 is made of a metal such as aluminum or a dielectric, and is electrically grounded.

At the bottom of the processing container 600, a stage (mounting table) 615 for mounting the wafer W is installed via an insulator 620. A high frequency power source 625b is connected to the stage 615 via a matching unit 625a, and a predetermined bias voltage is applied to the inside of the processing container 600 by the high frequency power output from the high frequency power source 625b. The stage 615 is connected to a high voltage DC power supply 630b via a coil 630a, and the substrate G is electrostatically attracted by a DC voltage output from the high voltage DC power supply 630b. A cooling jacket 635 for supplying cooling water to cool the wafer W is provided inside the stage 615.

The shower plate 605 is covered with a cover plate 640 at the top thereof. A radial line slot antenna 645 is provided on the upper surface of the cover plate 640. The radial line slot antenna 645 is provided between a slot plate 645a on a disk in which a number of slots (not shown) are formed, an antenna body 645b on the disk holding the slot plate 645, a slot plate 645a, and an antenna body 645b. And a slow phase plate 645c formed of a dielectric such as alumina (Al ₂ O ₃ ). The radial line slot antenna 645 is provided with a microwave generator 655 via a coaxial waveguide 650.

A vacuum pump (not shown) is attached to the processing container 600, and the processing chamber U is decompressed to a desired degree of vacuum by discharging the gas in the processing container 600 through the gas discharge pipe 660. Yes.

The gas supply source 665 includes a plurality of valves V, a plurality of mass flow controllers MFC, an ammonia (NH ₃ ) gas supply source 665a, an argon (Ar) gas supply source 665b, and a silane (SiH ₄ ) gas supply source 665c. . The gas supply source 665 supplies a gas having a desired concentration to the inside of the processing container 600 by controlling the opening / closing of each valve V and the opening of each mass flow controller MFC.

In this way, ammonia gas and argon gas are supplied to the upper side of the processing chamber U from the gas introduction pipe 675 that passes through the shower plate 605 through the first flow path 670a, and argon gas and silane gas are supplied to the second flow path 670a. The first gas is supplied downward from the integrated gas pipe 680 through the flow path 670b.

According to such a configuration, plasma is generated from various gases by the microwave incident from the microwave generator 655 into the processing chamber U through the slot of the radial line slot antenna 645 and the shower plate 605, and the generated plasma As a result, a silicon oxynitride (H: SiNx) film having high sealing properties is formed. In this way, the sealing film 54 is formed so as to cover the organic EL element so that moisture existing outside does not penetrate to the organic layer 51.

However, in the film forming process of the sealing film 54, hydrogen is contained in the processing gas (ammonia gas NH ₃ , silane gas SiH ₄ ). The hydrogen may pass through the cathode layer 52 laminated on the organic layer 51.

For example, for the cathode layer 52, silver Ag having a small work function and the highest reflectance in the visible light region is generally used in order to facilitate the injection of electrons into the organic layer 51. Since the radius is small, it passes through silver Ag. For this reason, if the hydrogen adsorption layer 53 does not exist, the hydrogen gas used in the film forming process of the sealing film 54 reaches the organic layer 51 through the cathode layer 52 and reacts with the organic substance in the organic layer 51. And gasify. As a result, hydrogen gas becomes bubbles at the boundary between the organic layer 51 and the cathode layer 52, and a gap is generated between the organic layer 51 and the cathode layer 52. As a result, continuity is lost in the gap portion, and the portion does not emit light, resulting in unevenness in the light emission state of the organic display.

However, in the organic light emitting diode according to this embodiment, as described above, the hydrogen adsorption layer 53 exists between the cathode layer 52 and the sealing film 54. The hydrogen gas used in the process of forming the sealing film 54 is adsorbed to the hydrogen adsorption layer 53 while passing through the hydrogen adsorption layer 53, and is thereby confined in the hydrogen adsorption layer 53, and reaches the organic layer 51. Can't reach. As a result, hydrogen gas becomes bubbles in the organic layer 51, and a gap is generated between the organic layer 51 and the cathode layer 52, and a phenomenon in which the cathode layer 52 is peeled off from the organic layer 51 can be avoided. As a result, it is possible to form the sealing film 54 having a high sealing performance in the film forming process of the sealing film 54, while preventing the conduction from being interrupted, thereby maintaining the light emission intensity satisfactorily. Light emitting diodes can be manufactured.

In particular, in the first embodiment, since the organic layer 51 and the cathode layer 52 have a laminated structure adjacent to each other, by using silver Ag having the highest reflectivity in visible light and a small work function for the cathode layer 52, The characteristics of the organic EL element can be maintained as before.

On the other hand, according to this configuration, the hydrogen adsorption layer 53 is provided between the cathode layer 52 and the sealing film 54. Thereby, hydrogen gas used in the manufacturing process of the organic EL element is confined in the hydrogen adsorption layer 53 by being adsorbed on the hydrogen adsorption layer 53 and cannot reach the organic layer 51. As a result, in the manufacturing process of the organic EL element, the hydrogen gas that the hydrogen gas deteriorates the organic layer 51 while utilizing the advantage of using the hydrogen gas that the formation of the sealing film 54 having a high sealing property is used. Overcoming the drawbacks when used, it is possible to produce a high performance organic light emitting diode with high emission intensity.

(Modification 1)
Next, a modification of the first embodiment will be described. In the first embodiment, the organic layer 51, the cathode layer 52, the hydrogen adsorption layer 53, and the sealing film 54 are sequentially formed on the substrate G. However, in the manufacturing process of the organic light emitting diode according to Modification 1 shown in FIG. 7, the hydrogen adsorption layer 53 is provided between the organic layer 51 and the cathode layer 52. According to this, the organic layer 51, the hydrogen adsorption layer 53, the cathode layer 52, and the sealing film 54 are sequentially formed on the substrate G, and the hydrogen adsorption layer 53 is in contact with the organic layer 51.

Also in this case, when the organic layer 51 is etched by adding hydrogen to the gas to be converted into plasma, the hydrogen adsorbing layer 53 adsorbs hydrogen, so that the hydrogen can be shut off from the organic layer 51. Also in the film forming process of the sealing film 54, hydrogen can be blocked from the organic layer 51 by the hydrogen adsorption layer 53 adsorbing the hydrogen gas used at the time of forming the sealing film 54. As a result, a hydrogen gas that deteriorates the organic layer 51 is used while taking advantage of the hydrogen gas that forms a sealing film having high sealing properties or improves the etching rate. Overcoming drawbacks at times, it is possible to produce high performance organic light emitting diodes with high emission intensity.

(Other variations)
As another modification, for example, the hydrogen adsorption layer 53 may be provided on the cathode layer 52 as a part or all of the cathode layer 52. An example in which the hydrogen adsorption layer 53 is provided in a part of the cathode layer 52 will be described in detail. As shown in FIG. 8A, the hydrogen adsorption layer 53 is sandwiched by the cathode layer 52 so that the cathode layer 52 is sandwiched. The case where it forms between is mentioned. According to this, when hydrogen passes through the cathode layer 52, the hydrogen is adsorbed on the hydrogen adsorption layer 53. Thereby, hydrogen can be shut off from the organic layer 51.

An example in which the hydrogen adsorption layer 53 is provided on the entire cathode layer 52 will be described in detail. As shown in FIG. 8B, the hydrogen adsorption layer 53 is formed as the cathode layer 52. . According to this, the hydrogen adsorption layer 53 functions as a cathode and also functions as a member that adsorbs hydrogen gas used in the manufacturing process of the organic EL element. Thereby, hydrogen can be shut off from the organic layer 51.

Furthermore, as shown in FIG. 8C, a cathode layer 52 doped with a hydrogen adsorbent 55 having a property of adsorbing hydrogen may be provided between the organic layer 51 and the sealing film 54. Also by this, when the hydrogen gas used in the manufacturing process of the organic EL element passes through the cathode layer 52, the hydrogen gas is adsorbed on the hydrogen adsorbing material 55 doped in the cathode layer 52, thereby causing the hydrogen gas to enter the cathode layer 52. The hydrogen can be shut off from the organic layer 51 by confinement.

As described above, even when the hydrogen adsorption layer 53 is provided on the cathode layer 52 as a part or the whole of the cathode layer 52 as shown in FIGS. The hydrogen gas deteriorates the organic layer 51 while taking advantage of the use of hydrogen gas, such as the improvement of the etching rate when etching 51 and the formation of the sealing film 54 having high sealing performance become possible. Overcoming the drawbacks of using hydrogen gas, a high performance organic light emitting diode with high emission intensity can be produced.

In addition, after the organic EL element is sealed with the sealing film 54, external moisture cannot be reached to the organic layer 51 because it is blocked by the sealing film 54. Therefore, the hydrogen adsorption layer 53 functions to protect the organic layer 51 from hydrogen generated before the organic EL element is sealed with the sealing film 54.

Also, for example, when the hydrogen adsorption layer 53 is formed of titanium Ti, the titanium Ti does not decompose the hydrogen trapped inside it into other substances unless the temperature is about 400 ° C. Here, since it is unthinkable to use an organic display at a high temperature of about 400 ° C., the hydrogen adsorbing layer 53 produces an organic EL element at the stage of using the organic EL element after the production of the organic EL element is finished. The hydrogen generated inside can be adsorbed in the organic EL element without any adverse effects.

(Hydrogen adsorption material)
In addition, as an example of the hydrogen adsorption layer 53 or the hydrogen adsorbent 55 described above, titanium (Ti), zirconium (Zr), palladium (Pd), vanadium (V), an element having a characteristic of adsorbing hydrogen, Examples include materials containing tantalum (Ta), a lanthanum element, and an alkaline earth metal.

Examples of the hydrogen adsorption layer 53 or the hydrogen adsorbent 55 include LaNi ₅ , CaCu ₅ , MgZn ₂ , ZrNi ₂ , ZrCr ₂ , TiFe, TiCo, MgCo, Mg ₂ Ni, and Mg as alloys having characteristics of adsorbing hydrogen. ₂ Materials including Cu, Ti—V, V—Nb, and Ti—Cr.

(Experiment to prove the action and effect of the hydrogen adsorption layer)
In order to prove the operation and effect of the hydrogen adsorption layer 53 described above, the inventor conducted an experiment described below. As process conditions, the inventors controlled the microwave output from the microwave generator 655 of the RLSA plasma CVD apparatus in FIG. 6 to 2.5 kW. The inventor set the pressure in the processing chamber U to 10 Pa, and the gap between the ceiling surface and the stage 615 to 90 mm. Further, the inventor supplied argon gas and hydrogen gas from the upper stage, and set the flow rates thereof to 200 sccm and 10 sccm, respectively. Further, the inventor controls the temperature of the stage 615 to 70 ° C., electrostatically attracts the substrate G, supplies 5 Torr helium (He) gas to the back surface of the substrate to cool it, and sets the temperature in the processing chamber to 45 ° C. Set. Further, Alq3 (3 tris (8-hydroxyquinoline) aluminum) was used as the light emitting material of the organic layer 51, silver Ag was used as the cathode layer 52, and titanium Ti was used as the hydrogen adsorption layer 53.

The four patterns shown in FIG. 9 were considered as the experimental model. That is, model 0 is a conventional model, and is a stacked structure of organic EL elements in which a silver Ag electrode is formed as a cathode layer 52 on an organic layer 51. Model 1 is a stacked structure of organic EL elements according to the first embodiment. Model 2 is a stacked structure of organic EL elements according to Modification 1. Model 3 is a stacked structure of organic EL elements according to other modified examples. In the case of model 0, the thickness of each layer is 100 nm for the organic layer 51 and 150 nm for the cathode layer 52. In the case of model 1, the thickness is 100 nm for the organic layer 51, 100 nm for the cathode layer 52, and 50 nm for the hydrogen adsorption layer 53. In the case of 2, the organic layer 51 was 100 nm, the hydrogen adsorption layer 53 was 50 nm, and the cathode layer 52 was 100 nm. In the case of Model 3, the organic layer 51 was 100 nm and the hydrogen adsorption layer 53 was 150 nm.

(Model 0)
As a result of the experiment, the inventor confirmed that hydrogen gas was bubbled at the boundary between the organic layer 51 and the cathode layer 52 in the model 0 experiment. This is proof that hydrogen gas reaches the organic layer 51 through the cathode layer 52 made of silver Ag and reacts with the organic substance in the organic layer 51 to gasify. Conductivity is lost in the existing portion, and the portion does not emit light, resulting in unevenness in the light emission state of the organic display.

(Models 1 to 3)
On the other hand, the inventors confirmed that no bubbles exist in the organic layer 51 in the experiments of Models 1 to 3. This proves that hydrogen gas is trapped in the hydrogen adsorbing layer 53 or the hydrogen adsorbing material 55 by being adsorbed on the hydrogen adsorbing layer 53 or the hydrogen adsorbing material 55 and cannot reach the organic layer 51. As a result, a high performance organic light emitting diode with good emission intensity maintained.

As described above, according to the present embodiment and the modification thereof, for example, when using hydrogen gas for forming a sealing film having a high etching rate or a high sealing property in the manufacturing process of the organic EL element The organic light emitting diode having high light emission intensity and high performance can be manufactured by overcoming the drawbacks of using hydrogen gas that hydrogen gas deteriorates the organic layer 51 while taking advantage of the above.

Note that the size of the substrate G may be 730 mm × 920 mm or more, for example, a G4.5 substrate size of 730 mm × 920 mm (diameter in the chamber: 1000 mm × 1190 mm) or 1100 mm × 1300 mm (diameter in the chamber: 1470 mm × 1590 mm) G5 substrate size. Further, the target object on which the element is formed is not limited to the substrate G having the above size, and may be a silicon wafer of 200 mm or 300 mm, for example.

In the above embodiment, the operations of the respective units are related to each other, and can be replaced as a series of operations in consideration of the relationship between each other. And by replacing in this way, embodiment of an organic light emitting diode can be made into embodiment of the manufacturing method of an organic light emitting diode.

The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but it goes without saying that the present invention is not limited to such examples. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the claims, and these are naturally within the technical scope of the present invention. Understood.

For example, the hydrogen adsorbing layer or the hydrogen adsorbing material according to the present invention is not limited to an organic EL element. For example, a liquid organic metal is mainly used as a film forming material, and the vaporized film forming material is heated to 500 to 700 ° C. It may be used for an organic metal element formed by MOCVD (Metal Organic Chemical Vapor Deposition) in which a thin film is grown on an object to be processed by being decomposed on the object to be processed.

Further, the manufacturing apparatus for forming a hydrogen adsorption layer using the method for manufacturing an organic light emitting diode according to the present invention is not limited to the sputtering apparatus of FIG. 6, and the above-described RLSA type microwave plasma processing apparatus, It may be a coupled parallel plate type plasma processing apparatus, an inductively coupled plasma (ICP) plasma processing apparatus, or a plasma CVD processing apparatus such as an electron cyclotron system (ECR).

Explanation of symbols

10 Substrate processing equipment 50 ITO
51 Organic Layer 52 Cathode Layer 53 Hydrogen Adsorption Layer 54 Sealing Film 55 Hydrogen Adsorbent G Substrate PM1 to PM4 Process Module

Claims (13)

An organic light emitting diode comprising: an organic layer laminated on an object to be processed; an electrode composed of an anode and a cathode formed with the organic layer sandwiched therebetween; and a sealing film for sealing the organic layer and the electrode from the outside Because
An organic light emitting diode in which a hydrogen adsorption layer having a characteristic of adsorbing hydrogen is provided between the organic layer and the sealing film. The hydrogen adsorption layer is
The organic light emitting diode according to claim 1, which is provided between the cathode and the sealing film. The hydrogen adsorption layer is
The organic light emitting diode according to claim 1, which is provided between the organic layer and the cathode. The hydrogen adsorption layer is
The organic light emitting diode according to claim 1, wherein the organic light emitting diode is provided on the cathode as a part or all of the cathode. An organic light emitting diode comprising: an organic layer laminated on an object to be processed; an electrode composed of an anode and a cathode formed with the organic layer sandwiched therebetween; and a sealing film for sealing the organic layer and the electrode from the outside Because
The organic light-emitting diode in which the cathode is provided between the organic layer and the sealing film, and a hydrogen adsorbent having a property of adsorbing hydrogen is mixed therein. The hydrogen adsorption layer or the hydrogen adsorbent is
The organic light emitting diode according to claim 1, comprising any one of titanium (Ti), zirconium (Zr), palladium (Pd), vanadium (V), tantalum (Ta), a lanthanum element and an alkaline earth metal. . The hydrogen adsorption layer or the hydrogen adsorbent is
_{2. The} composition according to claim 1, comprising any one of LaNi ₅ , CaCu ₅ , MgZn ₂ , ZrNi ₂ , ZrCr ₂ , TiFe, TiCo, Mg ₂ Ni, Mg ₂ Cu, Ti—V, V—Nb, and Ti—Cr. Organic light emitting diode. An organic light emitting diode manufacturing method comprising: forming an organic layer on a workpiece; forming a cathode on the organic layer; and forming a sealing film for sealing the organic layer and the cathode from the outside. And
A method of manufacturing an organic light emitting diode, wherein a hydrogen adsorption layer having a characteristic of adsorbing hydrogen between the organic layer and the sealing film is formed. The method of manufacturing an organic light emitting diode according to claim 8, wherein the hydrogen adsorption layer is formed after the cathode is formed on the organic layer and before the sealing film is formed. The method for producing an organic light emitting diode according to claim 8, wherein the hydrogen adsorption layer is formed after the organic layer is laminated on the object to be processed and before the cathode is formed. The method for producing an organic light emitting diode according to claim 8, wherein the hydrogen adsorption layer is formed on the cathode as a part or all of the cathode. A method for producing an organic light-emitting diode is used, in which an organic layer is laminated on an object to be processed, a cathode is formed on the organic layer, and a sealing film for sealing the organic layer and the cathode from the outside is formed. A manufacturing apparatus for manufacturing an organic light emitting diode,
The manufacturing apparatus which manufactures an organic light emitting diode using the manufacturing method of the organic light emitting diode which forms the hydrogen adsorption layer which has the characteristic to adsorb | suck hydrogen between the said organic layer and the said sealing film. A plasma processing apparatus that generates plasma from a gas supplied into a processing container and processes an object to be processed with the generated plasma,
A mounting table for mounting the object to be processed on which the organic layer is formed;
A gas supply source for supplying gas into the processing container,
A plasma processing apparatus for generating a plasma from a gas supplied from the gas supply source and forming a hydrogen adsorbing layer having a characteristic of adsorbing a cathode and hydrogen by the generated plasma.

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