KR102102913B1 - Method for Manufacturing Organic Emitting Display Device and Display Device Applying the Same - Google Patents

Abstract

The present invention relates to a method of manufacturing an organic light emitting display device that improves reliability and improves lifespan while reducing costs by varying a method of forming a thin film laminate for encapsulation of an organic light emitting device. In the method of manufacturing an organic light emitting display device including at least one pair of an inorganic film and an organic film stacked barrier to seal the organic light emitting device array, the step of forming the inorganic film closest to the organic light emitting device array includes the organic light emitting device array On the substrate, trimethylaluminum (Al ₂ (CH ₃ ) ₆ ) is supplied, and ozone (O ₃ ) gas is used as a reaction gas for a first time (t1), so that the first aluminum oxide film (Al ₂ O ₃ ) is Forming; And supplying trimethylaluminum (Al ₂ (CH ₃ ) ₆ ) on the first aluminum oxide film, and using ozone (O ₃ ) gas as a reaction gas for a second time (t2> t1) longer than the first time. , It comprises a step of forming a _second aluminum oxide film (Al ₂ O ₃ ).

Description

Method of manufacturing an organic light emitting display device and an organic light emitting display device using the same {Method for Manufacturing Organic Emitting Display Device and Display Device Applying the Same}

The present invention relates to an organic light emitting display device, and in particular, by manufacturing a thin film laminate for encapsulation of an organic light emitting device, the manufacturing method of an organic light emitting display device with improved cost and improved reliability and lifetime It relates to a method and an organic light emitting display device using the same.

With the advent of the full-fledged information age, the display field for visually displaying electrical information signals is rapidly developing. Accordingly, research is being conducted to develop performance of thinning, lightening, and low power consumption for various flat display devices.

Typical examples of such a flat panel display device are a liquid crystal display device (LCD), a plasma display panel device (PDP), a field emission display device (FED), and an electroluminescent display device. (Electro Luminescence Display device: ELD), Electro-Wetting Display device (EWD), and Organic Light Emitting Display device (OLED).

These flat panel display devices commonly include a flat panel display panel for realizing an image. The flat panel display panel is a structure in which a pair of substrates with unique light emitting materials or polarizing materials interposed therebetween.

Among them, an organic light emitting display device is a device that displays an image using an organic light emitting diode, which is a self-emission type element.

Hereinafter, a general organic light emitting device will be described.

A general organic light emitting device includes, on a substrate, first and second electrodes that face each other, and a light emitting layer formed therebetween, as a basic configuration, and emits light based on a driving current flowing between the first electrode and the second electrode. . Here, in the light emitting layer, holes and electrons recombine to generate light.

In addition, a hole transport layer between the first electrode and the light emitting layer for easy hole transport from the first electrode to the light emitting layer, and an electron transport layer between the second electrode and the light emitting layer for easy electron transport from the second electrode to the light emitting layer. Can be formed.

In some cases, the hole transport layer may further include a hole injection layer adjacent to the first electrode, and the electron transport layer may further include an electron injection layer adjacent to the second electrode. Each hole injection layer may be formed integrally with the hole transport layer or may be formed of another layer, and the electron injection layer may also be formed integrally with the electron transport layer or as a separate layer.

Here, the components of the layers included between the first electrode and the second electrode are organic substances, and these organic substance layers are formed by vaporizing the components of the layer and sequentially depositing them on the substrate.

In addition, the organic light emitting display device using the above-described organic light emitting device has an advantage that it can be thinned. However, the organic light emitting display device has deterioration due to internal factors such as deterioration of the electrode and the light emitting layer due to oxygen, and deterioration due to reaction between the light emitting layer and the interface, while easily deteriorating due to external factors such as external moisture, oxygen, and ultraviolet rays. Since there are disadvantages, packaging and encapsulation of an organic light emitting display device is very important.

In an organic light emitting display device, a method of encapsulating a method of sealing a sealant on an edge with a substrate on which an organic light emitting layer is formed and a counter substrate, and a method of sealing an organic light emitting layer on a substrate on which an organic light emitting layer is formed are alternately stacked and sealed. There is this.

In recent years, since convenience and thinning are possible, a method of encapsulating and laminating thin and organic films alternately is preferred.

The general organic light emitting display device has the following problems.

When forming a thin film barrier layer of an inorganic film and an organic film for sealing, the inorganic film thin film is mainly deposited as a single film on a substrate on which an organic light emitting device is formed by sputtering. In this case, the formed inorganic film thin film is formed at a time by supplying a single reaction gas, and is formed to a thickness of approximately 500 mm 2 to 1000 mm 2 (50 nm to 100 nm).

In addition, such an inorganic film thin film is formed of a component of AlOx, but the inorganic film thin film of a single component has poor reliability and tends to have poor barrier properties. For example, when the film uniformity is poor, pin holes or defects may occur. That is, the inorganic film thin film formed of a single reaction gas is vulnerable to moisture, and thus it is difficult to completely block moisture over time. For example, the inorganic film thin film of the AlOx component formed by the sputtering method has a moisture permeability of about 2.3 x 10 ^-2 g / m2 · day or higher and has a large value.

In this case, in order to effectively prevent moisture permeation, several inorganic films must be further applied to the thin film stacked barrier. Due to this, the organic film is also stretched together due to the structure of the thin film stacked barrier in which the organic film and the inorganic film are alternately formed, thereby increasing the thickness of the entire thin film barrier. Increases, making it difficult to slim the organic light emitting display device.

In addition, in the active matrix type organic light-emitting display device, there is a problem such as defective lighting after formation of a single-film inorganic film. In the process of forming the inorganic film, it is presumed that oxidation occurs in the thin film transistor of the pad portion. do.

The present invention has been devised to solve the above problems, and the method of forming a thin film laminate for encapsulation of an organic light emitting device is different, thus reducing costs, improving reliability, and improving the life of the organic light emitting display. It is an object of the present invention to provide a method for manufacturing a device.

The manufacturing method of the organic light emitting display device of the present invention for achieving the above object is the production of an organic light emitting display device including an inorganic film and an organic film on the substrate, and a barrier in which one or more pairs of organic films are alternately stacked. In the method, the step of forming the inorganic film closest to the organic light-emitting device array is to supply trimethylaluminum (Al ₂ (CH ₃ ) ₆ ) on a substrate including the organic light-emitting device array, and for a first time t1. Forming a first aluminum oxide film (Al ₂ O ₃ ) using ozone (O ₃ ) gas as a reaction gas; And supplying trimethylaluminum (Al ₂ (CH ₃ ) ₆ ) on the first aluminum oxide film, and using ozone (O ₃ ) gas as a reaction gas for a second time (t2> t1) longer than the first time. , It comprises a step of forming a _second aluminum oxide film (Al ₂ O ₃ ) It has a feature.

Here, the first time is 0.1 second to 1 second, and the second time is preferably 1 second to 5 seconds.

In addition, the ratio of oxygen to aluminum (O / Al) between the first aluminum oxide film and the second aluminum oxide film is lower than that of the second aluminum oxide film. In this case, the oxygen to aluminum ratio of the first aluminum oxide film is 1.60 or more.

If there are two or more inorganic films on the barrier that seals the organic light emitting device array, the step of forming the inorganic film on the organic film may include trimethylaluminum (Al ₂ (CH ₃ ) ₆ ) on the first aluminum oxide film. It can be made by forming a single aluminum oxide film (Al ₂ O ₃ ) by supplying, and using ozone (O ₃ ) gas as the reaction gas for the second time or longer.

In some cases, when there are two or more inorganic films on the barrier that seals the organic light emitting device array, the step of forming inorganic films on the organic films may include trimethylaluminum (Al ₂ (CH ₃ ) ₆ ) may be supplied, and the ozone gas and H ₂ O gas or the ozone gas and H ₂ O ₂ gas may be used as reaction gases to form an aluminum oxide film.

On the other hand, when there are two or more inorganic films of the barrier sealing the organic light emitting device array, the step of forming inorganic films on each organic film may be performed in the same manner as the method of forming the inorganic film closest to the organic light emitting device array. have.

Further, the first aluminum oxide film is preferably 5nm to 19nm, and the second aluminum oxide film is preferably 20nm to 45nm.

In addition, the first and second aluminum oxide films may be formed by atomic layer deposition, respectively, after carrying the substrate into the same chamber.

On the other hand, the formation of the first and second aluminum oxide films may be performed by supplying the trimethylaluminum, the first purge, the ozone gas supply, and the second purge in one cycle.

Here, the formation of the first and second aluminum oxide films may be performed by heating the temperature of the substrate to 50 ° C to 150 ° C.

In addition, when forming the first and second aluminum oxide films, the pressure in the chamber is maintained at 1 Torr to 2 Torr.

In addition, the organic light emitting display device of the present invention for achieving the same object is made of a method of manufacturing the above-described organic light emitting display device.

The manufacturing method of the organic light emitting display device of the present invention as described above has the following effects.

In the thin film barrier having an alternating organic-inorganic film for sealing the organic light emitting display device, the inorganic gas is formed by dividing the film into two films with different reaction gas supply times.

Therefore, the first film shortens the supply time of the ozone reactant gas and supplies only the minimum amount sufficient to react with trimethylaluminum, thereby forming an aluminum oxide film to prevent defects in the portion exposed to the inorganic film in contact with the organic light emitting array for the first time. In addition, the second film is formed of an aluminum oxide film having a relatively higher metal content than the first film by growing the thickness so as to have sufficient barrier function by increasing the supply time of the ozone reactant gas.

Thus, by forming the aluminum oxide film with two films, the first film prevents damage by ozone radicals, and the second film has a unique inorganic film barrier function that covers pinholes or defects with a sufficient thickness.

Also, when forming the first and second films, no other materials are required, and by using the atomic layer deposition equipment, it is possible to form a double aluminum oxide film by varying the time of supply of the reactive gas, so that when ozone gas is used as the reactive gas , In order to solve the damage caused by the ozone radical, it is possible to solve the problem damage without requiring equipment or materials for forming a separate film.

As a result, the method of manufacturing the organic light emitting display device of the present invention can reduce the number of layers of the entire stacked barrier, so that a sufficient barrier property is obtained when the structure of the conventional stacked barrier is 3.5 pairs, but the organic light emitting display device of the present invention provides 2.5. Even when reduced to a pair or 1.5 pairs, excellent barrier properties can be obtained. That is, by reducing the number of layers included in the barrier, it is possible to reduce the overall thickness of the barrier to be entered when sealing the thin film, thereby enabling thinning of the organic light emitting display device.

1A and 1B are cross-sectional views showing an organic light emitting display device including a method of manufacturing the organic light emitting display device of the present invention.
2 is a cross-sectional view showing the formation of an inorganic film laminate in the method of manufacturing the organic light emitting display device of the present invention.
3 is a view showing equipment used for forming an inorganic film laminate in a method of manufacturing an organic light emitting display device of the present invention.
4 is a flow chart showing a method of forming an inorganic film laminate of a method of manufacturing an organic light emitting display device of the present invention.
5 is a cross-sectional view showing an organic light emitting display device of the present invention according to a first embodiment to which the method of forming an inorganic film laminate of FIG. 4 is applied
6 is a cross-sectional view showing an organic light emitting display device of the present invention according to a second embodiment to which the method of forming the inorganic film laminate of FIG. 4 is applied
7 is a photograph showing a cell defect due to TFT damage generated when forming a single-film inorganic film
8A and 8B are photographs showing states of each pixel when the organic light emitting display device is turned on after the formation of the first aluminum oxide film and the second aluminum oxide film of the inorganic film laminate.

Hereinafter, a method of manufacturing the organic light emitting display device of the present invention and an organic light emitting display device manufactured by applying the same will be described in detail with reference to the accompanying drawings.

1A and 1B are cross-sectional views showing an organic light emitting display device including a method of manufacturing the organic light emitting display device of the present invention.

As shown in FIG. 1A, in the organic light emitting diode display device, an organic light emitting device array 200 is formed on a substrate 100, and thus the organic light emitting device array 200 is sealed to protect it from moisture and outside air. The multilayer barrier 3000 is formed by including at least one pair of the inorganic layer 300 and the organic layer 400.

In the drawing, the inorganic film 300 is positioned below and above the organic film 400. In the illustrated example, the stacked barrier 3000 is formed in 1.5 pairs. The laminated barrier may be mainly formed of n.5 pairs (n is a natural number), and preferably, the uppermost layer is an inorganic film 300. When the thin film in contact with the outside air is an organic film, the organic film may be vulnerable to moisture permeation, so that the inorganic film 300 is the top layer of the laminated barrier.

In addition, the inorganic layer 300 and the organic layer 400 are alternately configured. Here, the inorganic film 300 is sized to sufficiently cover a region where the organic film 400 is formed, thereby preventing external air from directly contacting the organic film 400 in any case.

Although not shown, the organic light emitting device array includes a TFT array including thin film transistors formed for each pixel, a first electrode connected to the thin film transistor of each pixel, an organic material layer including a light emitting layer, and a second electrode. In some cases, a protective film covering the second electrode is formed before the inorganic film 300 is formed. In this case, the protective film can be formed of a silicon insulating film such as SiNx.

In addition, the first electrode and the second electrode may have different reflectivity or transparency depending on top emission or bottom emission depending on the emission direction.

In addition, the TFT array may be omitted in some cases, and may be classified into an active method or a passive method depending on the presence or absence of the TFT array.

The organic film 400 may be formed to a relatively thicker thickness than the inorganic film 300, and its components may be selected from the group of, for example, epoxy-based resin, acrylic-based resin, thermosetting polyimide, and polyethylene. have.

Meanwhile, the main material of the inorganic film 300 is an aluminum oxide film (Al ₂ O ₃ ). Hereinafter, a method of forming the inorganic film will be described in detail with reference to the drawings.

In addition, in FIG. 1B, in the organic light emitting display device of the present invention, a pair of organic films 400 and an inorganic film 300 are further formed compared to the example disclosed in FIG. 1A. An inorganic film was formed.

In this case, the materials and functions of the internal organic film 400 and the inorganic film 300 are the same as those disclosed in FIG. 1A, and descriptions of the same content are omitted.

2 is a cross-sectional view showing the formation of an inorganic film laminate in a method of manufacturing an organic light emitting display device of the present invention.

2, the inorganic film of the organic light emitting display device of the present invention is a double film formed by varying the supply time of the reaction gas.

In the method of forming the inorganic film, first, on the substrate 100 including the organic light emitting element array 200, trimethylaluminum (Al ₂ (CH ₃ ) ₆ ) (TMA) is supplied as a main raw material gas, and primarily, The first aluminum oxide film (Al ₂ O ₃ ) 310 is formed by using ozone (O ₃ ) gas as the reaction gas for 1 hour (t1). Here, the first time is 0.1 second to 1 second, which is a very short period of time to enter the general inorganic film formation, and the reaction with the trimethylaluminum component is minimal, so that the aluminum oxide film component is so thin that the organic light emitting device array 200 is covered very thinly. The first aluminum oxide film 310 is formed.

For example, the first aluminum oxide film 310 is formed to a thickness of about 5nm to 19nm.

Here, the equipment is purged for a certain time after TMA supply and after ozone gas supply, respectively.

Subsequently, on the first aluminum oxide film 310, trimethylaluminum (Al ₂ (CH ₃ ) ₆ ) is supplied as a main raw material gas, and ozone (O) is generated for a second time (t2> t1) longer than the first time. ₃ ) A second aluminum oxide film (Al ₂ O ₃ ) 320 is formed using gas as a reaction gas.

Here, the second time for supplying the reaction gas of the ozone component secondarily is about 1 second to 5 seconds, and is longer than the first time, so that a sufficient barrier function as an inorganic film on the first aluminum oxide film 310 is performed. 2 An aluminum oxide film 320 is formed.

At this time, the thickness of the second aluminum oxide film 320 is formed to a thickness of about 20 nm to 45 nm, and in any case, it is formed to be thicker than the thickness of the first aluminum oxide film 310.

On the other hand, the first aluminum oxide film 310 and the second aluminum oxide film 320 have different supply times of ozone gas as a reaction gas, and thus the degree of reaction with trimethylaluminum is different, and thus, the thickness of the deposited film is different. Not only are they different, but the oxygen to aluminum component ratio included in the aluminum oxide film is different.

Since the second aluminum oxide film 320 supplied the reaction gas in a sufficient time, the reaction degree to be formed with the aluminum oxide film is excellent, so that a pure aluminum oxide film is formed, and in this case, oxygen vs. oxygen of the second aluminum oxide film 320 The ratio of aluminum (O / Al) is lower than the ratio of oxygen to aluminum in the first aluminum oxide film 310.

In addition, when the aluminum content is substantially increased from the content of the entire aluminum oxide film, the barrier property is improved and the function of preventing moisture permeation is improved.

For example, the oxygen to aluminum ratio (O / Al) of the first aluminum oxide film is about 1.60 or more, and the oxygen to aluminum ratio of the second aluminum oxide film is less than 1.60. That is, when the oxygen to aluminum ratios included in the first and second aluminum oxide films 310 and 320 are different from each other, and this is photographed with an atomic force microscope, the interfacial interface between the films can be observed. That is, it is possible to distinguish between the first and second aluminum oxide films.

On the other hand, like the first aluminum oxide film 310, when the second aluminum oxide film 320 is formed, the equipment is purged for a period of time after TMA supply and ozone gas supply.

In addition, the formation of the first and second aluminum oxide films 310 and 320 is performed after the substrate is brought into the same chamber, and the supply time of ozone gas as a reaction gas is changed, respectively, and atomic layer deposition is performed. Is made of

Meanwhile, when the first and second aluminum oxide films 310 and 320 are formed, the gaseous ozone gas component not used for the reaction may be degassed to the outside through a purge process after the third aluminum oxide film 330 is formed.

3 is a view showing equipment used for forming an inorganic film laminate in a method of manufacturing an organic light emitting display device of the present invention.

As shown in FIG. 3, equipment used for forming an inorganic film includes a chamber 1000 into which a substrate 2000 on which an organic light emitting element array is formed, and a TMA supply unit 700 and a reactive gas supply unit 720.

Here, the reaction gas has different supply times when forming the first aluminum oxide film and the second aluminum oxide film, and is supplied after the TMA is supplied into the chamber 1000 in the TMA supply unit 700 and after purging is performed.

Meanwhile, the substrate 2000 on which the organic light emitting device array is formed may have a top surface thereof as a second electrode or a protective film of the organic light emitting device, and in some cases, a stack of one or more inorganic films / organic films may be already formed.

In addition, the substrate 2000 on which the organic light emitting element array is formed may be carried into the chamber 1000 even as a single unit, or as shown, a plurality of carriers 600 may be stacked and supplied.

In addition, although not shown, a heater or the like may be included in the chamber 1000 to control the temperature of the substrate 2000 on which the organic light emitting element array is formed inside the chamber 1000, and the control device thereof is the chamber 1000. On the outside can be further configured.

The formation of the inorganic film of the above-described double layer is performed after the substrate 2000 on which the organic light emitting element array is formed is carried into the chamber 1000, and after evacuating the inside of the chamber, TMA supply, secondary purge, reaction gas supply, 2 A vapor deposition process using primary purge as one cycle is performed. During the deposition process, the substrate 2000 is heated by heating to a temperature of 50 ° C to 150 ° C.

In addition, the supply of the TMA and the supply of the reaction gas are made in a state maintained at 1 Torr to 2 Torr, respectively. When the supply amount is increased or the supply time is increased, the thickness of the aluminum oxide film formed may increase. In the present invention, the lower layer of the double layer shortens the supply time of the reaction gas, and the upper layer is relatively long to form a double layer of aluminum oxide films having slightly different properties. That is, the first aluminum oxide film is made thin to prevent surface oxidation of the exposed pad portion, etc., and the second aluminum oxide film is formed to a certain thickness or more with good covering power and good moisture permeability.

4 is a flowchart illustrating a method of forming an inorganic film laminate in a method of manufacturing an organic light emitting display device of the present invention.

As shown in FIG. 4, in the formation of the inorganic film laminate (including the first and second aluminum oxide films), first, primary trimethylaluminum (TMA) is supplied as a main raw material gas into the chamber 1000 (100S). Here, the supplied trimethylaluminum (TMA) is atomically deposited as a seed on a substrate 2000 including the organic light emitting device array 200.

Subsequently, the TMA of the residual component not adsorbed on the substrate 2000 including the organic light emitting element array 200 is discharged to the first purge 110S.

Subsequently, ozone gas is supplied as a reaction gas for a first time t1 of about 0.1 second to 1 second (120S).

When the reaction gas is supplied, the trimethylaluminum component adsorbed on the substrate and ozone gas react to form a thin first aluminum oxide film 310. The first aluminum oxide film 310 is formed to cover the upper portion of the organic light emitting diode array 200.

Subsequently, the unreacted ozone gas is discharged to the second purge 130S.

Subsequently, by supplying (140S) trimethylaluminum (TMA) into the chamber 1000 as a source gas on the substrate 2000 on which the first aluminum oxide film 310 is formed, the first aluminum oxide film 310 is provided. An atomic layer is deposited on the substrate 2000 including the TMA component as a seed layer.

Subsequently, TMA of the component not adsorbed to the substrate 2000 is discharged to the third purge 150S.

Subsequently, ozone gas is supplied as a reaction gas for a second time t2 of about 1 second to 5 seconds (160S). In this process, the supply time of the supplied ozone gas is increased, and the TMA component reacts sufficiently, so that the formed second aluminum oxide film 320 has a relatively higher metal content than the first aluminum oxide film 310 and also increases in thickness. do. Accordingly, the barrier properties of the second aluminum oxide film 320 are superior to that of the first aluminum oxide film 310. That is, even if there is a pinhole or a defect in the first aluminum oxide film 310, the second aluminum oxide film 320 covers it and compensation is possible.

Subsequently, the unreacted component of the TMA and the reaction gas is discharged to the fourth purge 170S.

Here, the first and second aluminum oxide films 310 and 320 are respectively composed of the main raw material TMA supply, the primary purge, the supply of ozone gas as the reaction gas, and the order of the secondary purge in one cycle, respectively, and the reaction gas supply time By adjusting the, the thickness of the first and second aluminum oxide films 310 and 320 can be adjusted.

In the above-described formation of the inorganic film laminate, the formation of the first and second aluminum oxide films 310 and 320 may be performed by heating the temperature of the substrate 2000 to 50 ° C to 150 ° C. In this case, when forming the first to second aluminum oxide films 310 and 320, the pressure in the chamber is preferably maintained at 1 Torr to 2 Torr.

On the other hand, through the above-described inorganic film stack forming process, after forming an inorganic film made of a double aluminum oxide film on the substrate on which the organic light emitting device array is formed, the substrate 100 is again carried out of the chamber 1000 After that, an organic film may be formed through a separate device.

In addition, the stacked barrier formed by alternating the inorganic film and the organic film of the above-described triple film forming method can omit the glass-based counter substrate, which has been a means of encapsulation, so that the entire organic light emitting display device can be made thinner to the extent possible. There are possible advantages. In particular, until recently, in the thin film barrier method, the inorganic film of the method in which the organic / inorganic film was stacked was formed by a single reaction gas supply, but there was a problem in that the thin film transistor on the pad side side was defective in lighting due to an oxidation problem. , The inorganic film is formed with a first film for preventing oxidation and a second film having barrier function by varying the reaction gas supply time, so that the problem of lighting failure can be solved.

In addition, since the barrier property is excellent, it is possible to prevent sufficient moisture permeation of 1.5 or 2.5 pairs of organic / inorganic films, so that when the organic light emitting display device is flexible, the thinning property is excellent, and the bending radius of the device Can be reduced.

5 is a cross-sectional view illustrating an organic light emitting display device of the present invention according to a first embodiment to which the method of forming an inorganic film laminate of FIG. 4 is applied.

As shown in FIG. 5, in the organic light emitting diode display according to the first exemplary embodiment of the present invention, only the inorganic layer 300a adjacent to the organic light emitting element array is formed of a double layer, and then the inorganic layers 300b formed on the upper side are It is formed of a single layer inorganic film.

Here, the inorganic film 300a formed to sufficiently cover the organic light emitting diode array 200 is 1 second to 5 seconds with the first aluminum oxide film 310 formed by supplying a reaction gas of ozone gas for 0.1 second to 1 second. It consists of a second aluminum oxide film 320 formed by supplying a reaction gas of ozone gas during.

Subsequently, an organic layer 400 is formed on the inorganic layer 300a.

In this way, the inorganic film 300b after forming the first pair of stacked barrier layers of the inorganic film 300a and the organic film 400 covering the organic light emitting device array 200 forms the second aluminum oxide film 320 described above. By supplying a reaction gas of ozone gas for about 2 to 6 seconds under conditions similar to those described above, an inorganic film 300b is formed of a single aluminum oxide film.

In this case, the reaction gas used for the single layer inorganic film 300b that does not directly cover the organic light emitting element array 200 may be ozone gas, or ozone gas and H ₂ O gas or ozone gas and H ₂ O _Two gases may be used in parallel.

In addition, the single layer inorganic film 300b is formed to a thickness of about 30 nm to 60 nm, and may be formed on each organic film 400.

In this case, the inorganic film 300b formed after the first pair of inorganic films 300a / organic films 400 are stacked may form a single aluminum oxide film having a high metal content, thereby enhancing the moisture permeation prevention function from outside air. .

In addition, in the case of such a structure, the first and second aluminum oxide films have different film properties by giving a time difference when forming the inorganic film 300a in contact with the organic light emitting device array for the first time, and then the inorganics formed on each organic film 400 The film 300b is a single layer and is formed of a film having good barrier properties. That is, the first thin film transistor pad is prevented from being damaged by forming a first aluminum oxide film having a low metal content by supplying a reaction gas only for a very specific time only when the first inorganic film 300a corresponding to the vulnerable portion of the thin film transistor pad side is formed. , In the second aluminum oxide film 320 of the remaining inorganic film 300a and the inorganic film 300b of a single layer, excellent barrier properties are maintained. Thereby, the number of layers of the entire stacked barrier can be reduced, and when sufficient barrier properties are obtained when the structure of the conventional stacked barrier is 3.5 pairs, excellent barrier properties can be obtained even if it is reduced to 2.5 or 1.5 pairs.

6 is a cross-sectional view illustrating an organic light emitting display device of the present invention according to a second embodiment to which the method of forming an inorganic film laminate of FIG. 4 is applied.

As shown in FIG. 6, the organic light emitting display device of the present invention according to the second embodiment of the present invention applies the above-described formation of the inorganic film 300a of the double layer on every organic film 400, and the first embodiment The structure of the inorganic film 300a closest to the organic light emitting element array is the same.

Commonly in both embodiments, the reason why the inorganic film 300a closest to the organic light emitting device array formed at the bottom is used as a double layer is because, during the initial inorganic film formation process, pads are generated due to the reaction gas supplied during the inorganic film formation. Since the oxidation phenomenon of the thin film transistor constituting the part is severe, the first aluminum oxide film is formed by supplying a reaction gas for a short time to prevent this.

In addition, in FIGS. 5 and 6, the organic light emitting array 200 has an inorganic film 300a / organic film 400 / inorganic film 300a / organic film 400 / inorganic film 300a in total in the order of 2.5. Although a pair of laminated barriers is formed, in the present invention, there is a function of preventing damage when forming the first aluminum oxide film of the first inorganic film 300a to be formed, and preventing moisture permeation from the second aluminum oxide film formed thereafter. The function is good, and the number of inorganic films 300a can be reduced to 3 or less. That is, even if the stacked barriers are formed in 1.5 pairs or 2.5 pairs, in the general stacked barrier, when a single layered inorganic film / organic film stacked structure is provided, there is a film reduction effect compared to a structure in which 3.5 pairs are required.

7 is a photograph showing cell defects due to TFT damage generated when forming a single layer inorganic film.

For example, as shown in FIG. 7, when forming the inorganic layer of the barrier laminate, when supplying ozone gas as a reaction gas for about 3 to 10 seconds after supplying TMA, oxidation is performed on the GIP (Gate In Panel) or the pad portion A phenomenon may occur, and thus a defect may occur in the thin film transistor, resulting in cell failure.

Since the method of manufacturing an organic light emitting display device of the present invention forms a first aluminum oxide film by supplying only a minimum amount of a reaction gas that reacts with TMA for a first time to form a first aluminum oxide film, the actual first aluminum oxide film is formed in a chamber. As a reaction gas, there is little residual of ozone, oxidation can be prevented, and pinholes or defects that may be caused by the thin formation of the first aluminum oxide film again form a second aluminum oxide film of sufficient thickness to sufficiently cover It is to form a functional inorganic film.

8A and 8B are photographs showing states of each pixel when the organic light emitting display device is turned on after forming the first aluminum oxide film and the second aluminum oxide film of the inorganic film laminate.

8A shows the state of W, R, G, and B pixels immediately after forming the first aluminum oxide film, and FIG. 8B shows the state of W, R, G, and B pixels immediately after forming the second aluminum oxide film. The state was observed.

In any case, it was confirmed that normal lighting occurred, which is expected as a result obtained by preventing the oxidation phenomenon of the GIP or the pad portion when forming the first aluminum oxide film, confirming that the reliability of the laminated barrier of the present invention is obtained.

In addition, the inorganic film thin film of the AlOx component formed by the atomic layer deposition method of the present invention has a moisture permeability lower than about 10 ^-4 g / m2 · day, and its value is significantly lower than that of the inorganic film single thin film structure. As the prevention function is improved, as illustrated in FIG. 5, deterioration of the organic light emitting display device can be prevented even if only 1.5 pairs of the stacked barriers are used. In this case, it is possible to slim the device, so it is easy to apply it to a device in which a thin film of the entire device thickness is a key, such as a flexible display.

On the other hand, the present invention described above is not limited to the above-described embodiments and the accompanying drawings, it is possible that various substitutions, modifications and changes are possible within the scope without departing from the technical spirit of the present invention. It will be obvious to those with ordinary knowledge.

100: substrate 200: organic light emitting device array
300: inorganic film 300a: inorganic film laminate
300b: inorganic film single layer 310: first aluminum oxide film
320: second aluminum oxide film 400: organic film
700: TMA supply 720: ozone gas supply
740: H ₂ O gas supply unit 2000: a substrate including an organic light emitting device array
3000: laminated barrier

Claims (13)

In the manufacturing method of the organic light emitting display device including an inorganic film and an organic film on the substrate to seal the array of organic light-emitting element and a barrier in which one or more pairs are alternately stacked,
The step of forming the inorganic film closest to the organic light emitting diode array is
On the substrate including the organic light-emitting device array, trimethylaluminum (Al ₂ (CH ₃ ) ₆ ) is supplied, and ozone (O ₃ ) gas is used as a reaction gas for a first time (t1) to form a first aluminum oxide film. Forming (Al ₂ O ₃ ); And
On the first aluminum oxide film, trimethylaluminum (Al ₂ (CH ₃ ) ₆ ) is supplied, and ozone (O ₃ ) gas is used as a reaction gas for a second time (t2> t1) longer than the first time, And forming a _second aluminum oxide film (Al ₂ O ₃ ) having an oxygen to aluminum (O / Al) ratio lower than that of the first aluminum oxide film. According to claim 1,
The first time is 0.1 second to 1 second, and the second time is 1 second to 5 seconds. delete According to claim 1,
The oxygen to aluminum ratio (O / Al) of the first aluminum oxide film is 1.60 or more,
A method of manufacturing an organic light emitting display device, characterized in that the oxygen to aluminum ratio (O / Al) of the second aluminum oxide film is less than 1.60. According to claim 1,
When there are two or more inorganic films of the barrier sealing the organic light emitting element array,
The step of forming an inorganic film on the organic film,
On the first aluminum oxide film, trimethylaluminum (Al ₂ (CH ₃ ) ₆ ) is supplied, and ozone (O ₃ ) gas is used as a reaction gas for the second time or longer, and a single aluminum oxide film ( Al ₂ O ₃ ) is formed to form a method of manufacturing an organic light emitting display device. According to claim 1,
When there are two or more inorganic films of the barrier sealing the organic light emitting element array,
The step of forming an inorganic film on each organic film,
On the first aluminum oxide film, trimethylaluminum (Al ₂ (CH ₃ ) ₆ ) is supplied, and the ozone gas and H ₂ O gas or the ozone gas and H ₂ O ₂ gas are used as reaction gases, and aluminum oxide is used. A method of manufacturing an organic light emitting display device, comprising forming a film. According to claim 1,
When there are two or more inorganic films of the barrier sealing the organic light emitting element array,
The step of forming an inorganic film on each organic film,
A method of manufacturing an organic light emitting display device, characterized in that it is performed in the same way as the method of forming the inorganic film closest to the organic light emitting element array. According to claim 1,
The first aluminum oxide film is 5nm to 19nm, the second aluminum oxide film is a method of manufacturing an organic light emitting display device, characterized in that 20nm to 45nm. According to claim 1,
The first and second aluminum oxide films, the method of manufacturing an organic light emitting display device, characterized in that each made by atomic layer deposition (Atomic layer deposition) method after bringing the substrate into the same chamber. The method of claim 9,
The first and second aluminum oxide films are formed by making the order of supply of the trimethylaluminum, first purge, supply of the ozone gas, and second purge into one cycle, respectively. . The method of claim 10,
The first and second aluminum oxide films are formed by heating the substrate at a temperature of 50 ° C to 150 ° C. The method of claim 10,
When forming the first and second aluminum oxide films, the pressure in the chamber is maintained at 1 Torr to 2 Torr. An organic light emitting display device comprising the method of manufacturing any one of claims 1, 2 and 4 to 12.

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