KR100501906B1 - Method for forming barrier layer on anode in organic light emitting device and organic light emitting device comprising barrier layer on anode - Google Patents

Abstract

The present invention relates to a method of forming an anode barrier layer on an anode electrode surface of an organic light emitting device by an atomic layer deposition method and an organic light emitting device including an anode barrier layer formed by an atomic layer deposition method. A method of forming an anode barrier layer according to the present invention comprises the steps of: placing a substrate on which an anode layer is formed in a reaction chamber; Injecting a precursor comprising the elements constituting the anode barrier layer into the chamber; Maintaining the temperature in the chamber above room temperature and inducing a surface chemical reaction between the precursors to form an anode barrier layer with a thickness of 2 nm or less. According to the present invention, by using the surface chemical reaction of the precursors containing the thin film constituent elements, the insulating film having a large band gap is deposited on the anode while controlling to less than 1 angstrom thickness, and can be deposited precisely without pinholes. It is effective to increase efficiency.

Description

Anode barrier layer forming method of organic light emitting device and organic light emitting device including an anode barrier layer TECHNICAL FIELD AND ORGANIC LIGHT EMITTING DEVICE AND ORGANIC LIGHT EMITTING DEVICE COMPRISING BARRIER LAYER ON ANODE}

According to the present invention, a method of forming an insulating film as an anode barrier within a few mono layers on the surface of an anode of an organic light emitting device using surface chemical reaction between precursors including an element of an inorganic insulating film having a large band gap such as oxide or nitride. And to an organic light emitting device comprising an anode barrier layer in this manner.

In the high information age of the 21st century, the research and development of new futuristic display devices is of paramount importance. In particular, technologies related to the development of materials such as semiconductors and displays along with the ubiquitous revolution have become a key issue. In particular, organic electroluminescence (OEL or Organic Light Emitting Diode); OLED) is attracting attention.

Organic light emitting devices are well known as flat panel displays capable of implementing a roll-type display technology, which is a next-generation display device, and are currently being used as LCD backlights or portable display devices based on glass substrates. The organic light emitting device is a device in which electrons and holes generate electron-hole pairs, and light is generated through a process in which they fall to the ground state. In addition, the organic light emitting device has all three primary colors of light even at a low driving voltage of less than 10V, the organic monomolecule is excellent in achieving high resolution and natural colors, and in the case of organic polymers, large area displays can be manufactured at low cost. This has the advantage of being flexible, and having a fast response time.

Looking at the structure of the organic light emitting device, as an injection type thin film device made of a light emitting layer and a transport layer, carrier injection type light emitting device in which all carriers that contribute to light emission are injected from an external electrode, and carrier injection and carrier movement are easier than anything else. One material is needed. Among the electrodes, a high work function electrode (anode) is used as a hole injection electrode and a low work function electrode (cathode) is used as an electron injection electrode. In order to increase the efficiency of the OLED, the work function of these electrodes must be well aligned with the energy of the molecular orbital of the organic light emitting layer. If not, insert another layer having a band gap between the electrode and the light emitting layer to improve the light emitting efficiency. It is widely known that it can increase. In addition, it is known that it is important to control not only the work function of each metal but also the amount of hole and electron injection so that light is emitted from the light emitting layer without losing these carriers.

Among the electrode materials, a metal such as magnesium (Mg), indium (In), calcium (Ca), aluminum (Al), or an alloy thereof is mainly used as a cathode. In the case of the cathode, many studies have been conducted to increase the efficiency of the organic light emitting device by using a multi-layer structure of a metal thin film having a low work function or an easy structure for electron injection, whereas the research on the anode and the anode surface barrier layer has only recently been performed. It is active in various fields such as treatment.

The work function of the anode affects the efficiency of injecting holes into the organic layer. K. Sugiyama et al. Reported that the work function changes as the ITO is affected by the chemical composition of the anode according to the surface treatment. (Journal of Applied Physics Vol. 87, pp. 295, 2000). On the other hand, SM Tadayyon et al. Provided a high work function ITO by depositing a metal layer having a high work function such as Au or Pt on the ITO thin film (J. Vac. Sci. Technol. A. 17 (4) Jul. Pp. 773).

As the anode of the OLED, a metal electrode having a high work function may be used in addition to the transparent electrode. In this case, when the emitted light is emitted toward the opposite side of the substrate, that is, toward the upper side (cathode), instead of toward the lower transparent substrate, TA Beierlein et al. As various techniques relating to the structural transformation of the anode; 1) using Ti / Al anode electrode on quartz substrate and depositing ITO on top of it; 2) using Al electrode as anode on silicon substrate and depositing InNO _x on top of it; 3) silicon A technique of depositing Al-Cu / Ni / NiO _x on a substrate in turn and depositing V ₂ O ₅ as a final anode conversion layer has been reported. (US 6501217) All of these techniques are intended to effectively inject hole carriers from the anode electrode by converting the anode itself or by inserting another intermediate layer between the anode and the hole injection layer.

As another conventional technique related to an anode barrier layer (buffer layer or anode converting layer), a method of forming a metal thin film on an electrode such as ITO with a thickness of 1 nm or less and (C. Qiu et al Dig. Of SID 2002, pp. 1262), Ga ₂ O ₃ , TiO ₂ , SnO ₂ , Tb ₄ O ₇ , ZnO, Y ₂ O ₃ , Pr ₂ O ₃ and other inorganic thin films have been reported to form a thermal deposition method. (C. Qui, et al, Eurodisplay, 2002, p631). In addition to the Al by vacuum deposition it may be reported to leave the introduction of Al ₂ O ₃ barrier layer on the ITO by Kane generate Al ₂ O ₃ in the air (Kurisaka Y. et al, Jpn. J. Appl. Phys. Vol. 37 (1998) pp. L872-L875). In addition, ZB Deng et al. Reported the results of improving the efficiency of organic light emitting diodes by depositing several Angstroms of SiO ₂ on the ITO by electron beam deposition. (Appl. Phys. Lett. Vol. 74, No. 15, pp. 2227-2229)

The introduction of the buffer layer or barrier layer on the anode as described above is by physical vapor deposition or vapor chemical vapor deposition such as thermal evaporation, and it is not easy to control the thickness in several angstroms, There is a limit in improving the reproducibility and the life of the device because the characteristics and surface characteristics are not excellent. Particularly, when the anode inorganic buffer layer according to the prior art is deposited by thermal evaporation, the melting point must be low, so that a material having a high melting point, such as aluminum oxide or silicon oxide, cannot be deposited. In this case as well, it is difficult to realize thin film deposition with excellent characteristics. In addition, when the chemical vapor deposition method is used because of the high deposition temperature is limited to the use of a substrate such as plastic, there is a problem that the thickness control is not easy.

The present invention provides a method of forming an anode barrier layer that can solve various problems as described above, excellent in surface properties and electrical properties, can be formed at low temperatures, and also can be implemented in plastic substrates, organic light-emitting comprising an anode barrier layer An object thereof is to provide a device and a flat panel display device using the same.

In order to achieve the above object, the present inventors have made intensive studies, and the present invention is focused on the fact that the above problems can be solved when the anode barrier layer is formed by using a surface chemical reaction such as atomic layer deposition. To complete.

This invention is comprised as follows.

Placing the substrate on which the anode layer is formed in a reaction chamber; Injecting a precursor into the chamber, the precursor comprising an element constituting an anode barrier layer; The method provides a method of forming an anode barrier layer on an anode electrode of an organic light emitting device, the method comprising maintaining a temperature in the chamber at or above room temperature and inducing a surface chemical reaction between the precursors to form an anode barrier layer. .

The present invention also provides an organic electroluminescent device comprising a substrate, an anode layer and a cathode layer, comprising a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, formed between the anode layer and the cathode layer, An organic electroluminescent device comprising an anode barrier layer formed by a surface chemical reaction between an anode layer and a hole injection layer is provided.

The present invention also provides a flat panel display device comprising an anode barrier layer formed according to a surface deposition reaction.

In the present specification, the term "flat display element" includes all display elements manufactured using a glass substrate, a plastic substrate, or a silicon substrate. For example, an organic light emitting diode, a field emission device, and a liquid crystal display device. , Digital paper, and so on. In the present embodiment, an organic light emitting diode (OLED) is used as the flat panel display.

As the substrate used for forming the anode barrier layer on the anode electrode of the organic light emitting device according to the present invention, a silicon, glass or plastic substrate may be used, and the anode electrode may be a transparent or opaque anode electrode.

According to the present invention, as a method of forming the anode barrier layer, since the surface chemical reaction between precursors including the elements of the insulating thin film as the anode layer is used, dozens in several angstroms do not cause physical damage on the electrode surface. It is possible to control deposition in Angstrom thickness. Therefore, since the injection of the holes is effectively performed and the thin film is uniformly formed, the element of the anode can be prevented from diffusing into the organic layer, thereby improving the characteristics of the device.

Hereinafter, with reference to the accompanying drawings will be described the present invention in more detail through the organic light emitting device manufactured according to an embodiment of the present invention.

1 is a diagram schematically showing a cross section of one conventional organic light emitting device. The anode electrode 120, the hole injection layer 140, the hole transport layer 160, the light emitting layer 180, the electron transport layer 200, the electron injection layer on the transparent substrate 100 made of a glass substrate or a protective film formed plastic, etc. 220 and cathode electrode 240 are stacked in order.

2 illustrates a cross section of an organic light emitting diode according to an exemplary embodiment of the present invention, in which an anode barrier layer 110 is formed on an anode electrode 120. The type of the substrate 100 used in the present invention is not particularly limited and may be various. For example, a glass substrate or a plastic substrate may be used. Although not shown in the drawings, in the case of the top emission, a protective film capable of passing light such as a glass protective film instead of a metal protective film may be used, and an opaque substrate such as silicon or metal foil may be used as the substrate.

The anode electrode 120 may mainly use a transparent oxide electrode such as ITO, ZnO: Al, or a metal thin film having a high work function such as Au in the case of a top emission.

The anode barrier layer 110 according to the present invention includes aluminum oxide (Al ₂ O ₃ ), silicon oxide (SiO ₂ ), hafnium oxide (HfO ₂ ), zirconium oxide (ZrO ₂ ), tantalum oxide (Ta ₂ O ₅ ) , Titanium oxide (TiO ₂ ), zinc oxide (ZnO), niobium oxide (Nb ₂ O ₅ ), yttrium oxide (Y ₂ O ₅ ), silicon nitride (Si ₃ N ₄ ), silicon oxynitride (SiON) Inorganic insulating films such as aluminum nitride (AlN) and aluminum oxynitride (AlON) may be used as a single film, or two or more layers may be formed in multiple layers.

The hole injection layer 140 serves to supply holes supplied from the anode electrode 120 to the hole transport layer 160, and the hole transport layer 160 is a TPD, a diamine derivative, and a polyconductive polymer. (9-vinylcarbazole) and the like can be used.

The electron transport layer 200 may use an oxadiazole derivative, or the like. The combination of the transport layers enhances the quantum efficiency (Photons Out Per Charge Injected), and the two-stage injection process through the transport layer without directly injecting carriers. Through this, the driving voltage can be lowered. In addition, when the electrons and holes injected into the light emitting layer 180 are moved to the opposite electrode through the light emitting layer 180, it is possible to control recombination by blocking the opposite transport layer. Through this, the luminous efficiency can be improved.

The light emitting layer 180 is composed of high molecular organic EL materials such as Alq ₃ , anthracene, and other monomolecular organic light emitting layers, poly (p-phenylenevinylene) (PPV), polythiophene (PT), or derivatives thereof. The thin film of the light emitting layer (EML, 180) for the charge emission at a low driving voltage is being studied.

The electron transport layer 200 and the electron injection layer 220 are formed on the opposite side of the hole injection layer 140 and the hole transport layer 160 with the light emitting layer 180 interposed therebetween, and the anode electrode 120 of the organic light emitting device Holes are injected into the light emitting layer 180 through the transport layer 140, and electron-holes are paired in the light emitting layer 180 by injecting electrons into the light emitting layer 180 through the electron injection layer. As it is extinguished, light is emitted by radiating energy.

The cathode electrode 240 may be a metal having a low work function, such as Ca, Mg, or Al, as an electrode for electron injection, and a buffer layer such as LiF or CsF may be used for easier electron injection. . The reason why the metal having the low work function is used as the electron injection electrode is to lower the barrier formed between the cathode electrode 240 and the light emitting layer 180 to obtain a high current density in electron injection. Because it can. Therefore, while Ca having the lowest work function shows high efficiency, Al has a relatively high work function and thus has low efficiency. However, Ca has a problem of being easily oxidized by oxygen or moisture in the air, and Al has a stable property in air.

The organic light emitting device according to the present invention may be formed to emit light upward. In order to emit light upward, organic light emitting devices having two structures are possible. One is a structure in which an organic light emitting device is formed on a opaque substrate such as Si by laminating a cathode electrode, an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, a hole injection layer, and an anode barrier layer and an anode electrode. Another is a structure in which a thin layer of the upper metal electrode (cathode) is deposited to be as transparent as possible, and then the transparent electrode is deposited thereon. The description of the stacked film of the organic light emitting device emitting light to the top is the same as the description of the stacked film of the organic light emitting device emitting light to the lower as described in FIG. Let's do it.

The surface chemical reaction in the method of forming the anode barrier layer according to the present invention may be atomic layer deposition or the like, and representative examples of the atomic layer deposition method include a traveling wave reactor type including a showerhead method and a traveling wave reactor type. Plasma-enhanced atomic layer deposition. In the case of the plasma enhanced atomic layer deposition method, it is divided into a remote plasma atomic layer deposition method and a direct plasma atomic layer deposition method according to a plasma generator. The anode barrier layer according to the present invention may use any of these atomic layer deposition methods, and one of them may be used or two or more thereof may be used in combination. The anode barrier layer may be formed using a mixed deposition method in which two or more of the traveling type and the direct plasma type are used in combination. Precursors for forming the anode barrier layer can be variously formed, such as organometallic precursors, chloride precursors, coordination compound precursors. For nitrides, ammonia, ammonia plasma, nitrogen plasma, and the like are used. For example, alcohol such as methanol, ethanol isopropyl alcohol, water or ozone (O ₃ ) can be used, and in the case of plasma deposition, oxygen, water or alcohol plasma can be used.

For example, in the case of alumina, which has a large band gap and is effective as an anode barrier layer, aluminum precursor is mainly used as a stable and relatively inexpensive trimethyl aluminum or triethyl aluminum. It is also possible to use metal compounds. In some cases, aluminum chloride may be used, but in this case, since the growth temperature is relatively high, it is difficult to use the plastic substrate. As the oxygen precursor, water or alcohol, ozone, or the like may be used in the case of the traveling wave type, and oxygen or water plasma may be used in the case of the plasma enhanced type. In this case, since the film is dense even at the time of several angstrom deposition, it is possible to prevent impurity migration from the anode, so that a thin film having excellent characteristics can be obtained.

When forming a titanium oxide barrier layer, organic precursors, such as titanium isopropoxide, a titanium chloride, etc. can be used as a titanium precursor, and water or an oxygen plasma can be used as an oxygen precursor. In the case of forming the silicon oxide barrier layer, film deposition is possible using a chloride source or an organic precursor and water. Other barrier layers, which are not mentioned, can also be deposited with each precursor using several angstroms of atomic layer deposition.

Figure 3 shows a manufacturing process diagram related to the Al ₂ O ₃ barrier layer manufacturing method of an embodiment of forming an anode barrier layer in accordance with the present invention.

Placing the anode-formed substrate in a reactor; Injecting an Al-precursor with the carrier gas to form an anode barrier layer into the reactor; Inert gas into the reactor; Injecting H ₂ O into the reactor; And repeating the five step process of placing the inert gas in the reactor several times or tens of times until an anode barrier layer of the desired thickness is formed. For effective hole injection, it is desirable to form a thickness of 2 nm or less. The deposition thickness of the Al ₂ O ₃ layer formed by such an atomic layer deposition method varies depending on how many times one cycle of the process is performed. At this time, the deposition time according to one cycle is different depending on the conditions, such as the injection amount of the precursor, and the injection amount of the precursor may depend on the size of the substrate. In the case of the Al ₂ O ₃ layer, several angstrom thicknesses can be obtained by repeating the above-described series of steps less than 10 or 20 times. Using similar methods, silicon oxide (SiO ₂ ), hafnium oxide (HfO ₂ ), zirconium oxide (ZrO ₂ ), tantalum oxide (Ta ₂ O ₅ ), titanium oxide (TiO ₂ ), zinc oxide (ZnO), niobium Oxide (Nb ₂ O ₅ ), yttrium oxide (Y ₂ O ₅ ), silicon nitride (Si ₃ N ₄ ), silicon oxynitride (SiON), aluminum nitride (AlN), aluminum oxynitride (AlON), etc. Various barrier layers can be implemented.

As another embodiment of the present invention, as described above, in addition to the use of each single film such as oxide and nitride, a multilayer structure thereof may be formed. That is, a dual structure such as TiO ₂ / SiO ₂ and a sandwich structure such as Al ₂ O ₃ / TiO ₂ / Al ₂ O ₃ may be controlled to a thickness within 1 angstrom. In this case, a single anode barrier layer may be deposited by using two or more atomic layer deposition methods, and a multilayer anode barrier layer may be deposited by using two or more atomic layer deposition methods in combination. 4 illustrates a multilayer structure in which a SiO ₂ layer 300 is formed by a traveling atomic layer deposition method formed on a SiO ₂ layer 400 by a remote plasma method, and FIG. 5 illustrates Al ₂ O by a traveling atomic layer deposition method. _The multilayer structure in which the SiO ₂ layer 300 is formed by the traveling atomic layer deposition method on the _three layers 500 is shown. FIG. 6 illustrates the atomic layer deposition method of the traveling atomic layer deposition method on the Al ₂ O ₃ layer 600 by the remote plasma method. Shows a multilayer structure in which the SiO ₂ layer 300 is formed. As such, it is possible to form various anode barrier layers by various atomic layer deposition methods using various reaction precursors.

The organic light emitting device manufactured according to this method can be very usefully used as a flat panel display device.

Hereinafter, the present invention will be described in more detail according to embodiments of the present invention.

The following example is an example of a traveling wave type atomic layer deposition method in which a 12 "x 14" substrate is placed, and the amount of each precursor and carrier gas varies depending on the size and structure of the reactor.

Example 1: Al ₂ O ₃ Formation of the anode barrier layer

The substrate, in which the ITO film was formed of the anode layer, was placed in a chamber of atomic layer deposition equipment where the temperature was maintained at 250 degrees and the pressure was maintained at 15 millitorr (mTorr). Into the chamber was injected trimethyl aluminum [Al (CH ₃ ) ₃ ] vapor at a temperature of 16 degrees with 100 sccm of nitrogen gas as a carrier gas into the chamber for 0.55 seconds. Carrier gas was injected at 0.8 sc for 0.88 seconds. Al precursor reactants were adsorbed on the surface of the anode.

Then, the gas valve of the chamber was opened and nitrogen was injected again to remove all of the molecules not adsorbed on the anode surface of the Al precursor reactant. Thereafter, the gas valve of the chamber was opened and H ₂ O gas was injected for 1.43 seconds with a carrier gas of 100 sccm. The gas valve of the chamber was then opened and nitrogen was injected at 100 sccm for 3 seconds to remove the volatile reaction product between the Al-precursor containing H ₂ O molecules and H ₂ O.

This series of steps was repeated three times to form an aluminum oxide anode barrier layer having a thickness of three angstroms, five times to five angstroms, and ten times to ten angstroms.

After repeating the above procedure five times, the work function of the ITO membrane was measured and found to be 4.80 eV. This was an increase compared to the 4.75 eV work function value before forming the anode barrier layer.

Example 2: TiO ₂  Formation of the anode barrier layer

The substrate on which the ITO film was formed was placed in a chamber of an atomic layer deposition apparatus where the temperature was maintained at 250 degrees and the pressure was maintained at 15 millitorr (mTorr). Into the chamber was injected titanium tetraisoprooxide [Ti (OiPr) ₄ ] vapor, which was maintained at 60 degrees with nitrogen gas as a carrier gas of 200 sccm, into the chamber for 1 second. The injection amount of carrier gas was 200 sccm. Ti precursor reactant was adsorbed on the surface of the anode.

Thereafter, the gas valve of the chamber was opened, and 200 sccm of nitrogen was again injected for 1 second to remove all of the molecules that were not adsorbed on the anode surface of the Ti precursor reactant. Thereafter, the gas valve of the chamber was opened, and H ₂ O gas maintained at a temperature of 18 degrees was injected with a carrier gas of 200 sccm for 1.45 seconds. Then, the gas valve of the chamber was opened and 200 sccm of nitrogen was injected for 3 seconds to remove the volatile reaction product between the Ti-precursor containing H ₂ O molecules and H ₂ O.

This series of steps was repeated 33 times to form an anode barrier layer of TiO ₂ component 5 angstroms thick and 47 repeats 7 angstroms thick.

After repeating the above procedure 47 times, the work function value of ITO was measured and found to be 4.90 eV. It was confirmed that the work function was increased compared to the value before forming the anode barrier layer.

In the case of TiO ₂ , the deposition rate is low, so that the above process should be repeated 30 to 80 times in order to obtain a thickness of several angstroms. If oxygen plasma is used, the deposition rate is higher, and the number of depositions can be reduced to less than half. In any case, it is desirable that the thickness of the barrier layer not exceed 2 nm for effective hole injection.

As described above, in the case of forming the anode barrier layer according to the present invention, it was found that the work function of the anode layer was improved to improve the surface properties, and the thickness of the atomic layer could be adjusted to have a desired thickness according to the number of depositions. It was confirmed that it was possible to prepare a thin film.

Although the technical spirit of the present invention has been described in detail according to the above-described preferred embodiment, it should be noted that the above embodiment is only for the description and not for the limitation. In addition, those skilled in the art will understand that various embodiments are possible within the scope of the technical idea of the present invention.

As described above, according to the anode barrier layer forming method of the present invention, by using the surface chemistry of the precursors including the thin film constituent elements, an insulating film having a large band gap can be deposited on the anode while controlling to less than 1 angstrom thickness. By precisely depositing without pinholes, there is an effect of increasing the efficiency of the organic light emitting device. It is also possible to form barrier layers in very relaxed conditions without physical and chemical damage to ITO or other anode metal surfaces, and to improve the properties of the device by preventing impurities from the anode from moving to the organic layer.

In addition, the organic light emitting device according to the present invention is characterized in that oxygen or metal from an anode electrode such as ITO is uniformly controlled and grown by atomic layer deposition by an atomic layer deposition method using a surface chemical reaction. For example, in the case of gold (Au), it is possible to form a variety of ultra-thin films having excellent properties for preventing diffusion.

In addition, since the anode barrier layer according to the present invention is deposited through a low temperature process, the anode barrier layer may be implemented on the anode formed on the plastic substrate, and the holes may be effectively injected into the light emitting layer, thereby increasing the efficiency of the device and improving the lifetime. .

1 is a cross-sectional view of an organic light emitting device having a conventional general multilayer structure.

2 is a cross-sectional view of an organic light emitting device including an anode layer according to an embodiment of the present invention.

Figure 3 is a manufacturing process for explaining a method of forming an aluminum oxide anode barrier layer of an embodiment of the present invention.

4 through 6 are cross-sectional views of a multilayered anode barrier layer in which various barrier layers are fabricated using various atomic layer deposition methods.

Explanation of symbols on the main parts of the drawings

100 substrate 110 anode barrier layer

120: anode electrode 140: hole injection layer

160: hole transport layer 180: light emitting layer

200: electron transport layer 220: electron injection layer

240: cathode electrode 260: protective metal can

270: direction of light

300: SiO ₂ layer by the traveling atomic layer deposition method

400: SiO ₂ layer by remote plasma method

500: Al ₂ O ₃ layer by the traveling atomic layer deposition method

600: Al ₂ O ₃ layer by remote plasma method

Claims (6)

In the method of forming an anode barrier layer on the anode of the organic light emitting device, Placing the substrate on which the anode layer is formed in a reaction chamber; Injecting a precursor comprising the elements constituting the anode barrier layer into the chamber; And Maintaining the temperature in the chamber at or above room temperature and inducing a surface chemical reaction between the precursors to form an anode barrier layer with a thickness of 2 nm or less. The method of claim 1, The anode barrier layer Monolayer selected from the group consisting of aluminum oxide, silicon oxide, hafnium oxide, zirconium oxide, tantalum oxide, titanium oxide, zinc oxide, niobium oxide, yttrium oxide, silicon nitride, silicon oxynitride, aluminum nitride, aluminum oxynitride Or a multilayer structure. The method according to claim 1 or 2, The surface chemical reaction A method of forming an anode barrier layer, characterized in that it is one or more selected from among a traveling wave reactor atomic layer deposition method including a showerhead method, a remote plasma atomic layer deposition method, and a direct plasma atomic layer deposition method. In the organic electroluminescent device comprising a substrate, an anode layer, a cathode layer, It comprises a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer sequentially stacked between the anode layer and the cathode layer, An organic electroluminescent device comprising an anode barrier layer formed by a surface chemical reaction between the anode layer and the hole injection layer. The method of claim 4, wherein The anode barrier layer One selected from the group consisting of aluminum oxide, silicon oxide, hafnium oxide, zirconium oxide, tantalum oxide, titanium oxide, zinc oxide, niobium oxide, yttrium oxide, silicon nitride, silicon oxynitride, aluminum nitride, aluminum oxynitride Or an organic electroluminescent device comprising a single layer or a multilayer structure. A flat panel display device comprising an organic light emitting device comprising an anode barrier layer formed according to claim 1.