KR100971503B1 - Method of preparing passivation layer using electron cyclotron resonance plasma in organic device - Google Patents

Abstract

The present invention relates to a method for manufacturing a protective film of an organic device using an ECR plasma, and more particularly, adsorbing an organometallic source on the surface of the organic device; Injecting an inert gas to remove unsorbed organometallic sources; Injecting a source containing oxygen and an electron cyclotron resonance (ECR) plasma to react with a metal in the organometallic source to form a metal oxide layer on the surface of the organic device, wherein the ECR plasma is generated from 100 W to 500 W To; And injecting an inert gas to remove a residual organometallic source that does not form a metal oxide layer.

The manufacturing method is performed using an ECR plasma, and can be deposited at low temperature without damaging an organic device, and the protective film thus formed exhibits excellent film density and hydrophobicity to prevent permeation of oxygen, moisture, or impurities penetrating into the device from the outside. In addition to suppressing the lifespan of organic devices such as nonvolatile polymer memory devices (PoRAM) and organic light emitting devices (OLEDs), the present invention is preferably applied to devices having large structures.

 PoRAM, OLED, Moisture, Oxygen, Metal Oxides, Polymer Memory

Description

METHODS OF PREPARING PASSIVATION LAYER USING ELECTRON CYCLOTRON RESONANCE PLASMA IN ORGANIC DEVICE}

The present invention relates to a method for manufacturing a protective film of an organic device using an ECR plasma, and more particularly, by using an ECR plasma, it is possible to deposit at a low temperature without damaging the organic device, and thus the protective film has excellent film density. The present invention relates to a method for manufacturing an organic device protective film, which exhibits hydrophobicity and suppresses permeation of oxygen, moisture, or impurities that penetrate into the device from the outside to increase the life of the organic device, and is also suitably applicable to devices having a large step structure. will be.

Polymers are easy to process and mass-produce, lightweight, and inexpensive, making them versatile.

Among them, conductive polymers have the advantages of plastics and the characteristics of metals or semiconductors, and are used as core materials in various fields from daily necessities to high-tech industrial products.

Such conductive polymers are used instead of metals in various devices, and typically include non-volatile polymer memory devices (PoRAM) or organic light emitting diodes (OLEDs). And the like.

PoRAM has a simple structure in which a polymer layer is inserted between a pair of electrodes on a substrate, and multiple layers can be stacked on a single chip, thereby making a large capacity memory. In addition, the PoRAM not only has a very simple process and an operation speed of several tens of nanoseconds, but also has low power consumption and low manufacturing cost.

OLED is a display that displays characters and images by using an organic light emitting device that emits light when current flows. It has high brightness and high definition characteristics, has a wide viewing angle, can be formed into a thin film structure, and has a fast response speed. The OLED has a very simple structure in which organic layers such as an electron transport layer, a light emitting layer, a hole transport layer, etc. are sequentially stacked between a pair of electrodes on a substrate, and an organic compound or a polymer is used as the organic layer.

Such PoRAM or OLED is relatively weak in heat, and in particular, there is a disadvantage in that deterioration is easily caused by external factors such as external moisture, oxygen, ultraviolet rays, and device manufacturing conditions. The external oxygen and moisture have a critical effect on the life of the device, so the packaging of the device is very important, and a passivation layer (passivation layer) is formed on the surface of the device for the packaging.

Non-volatile memory using a polymer is an electrical device that operates using a conductive polymer as a material, and is relatively weak to heat, and is particularly deteriorated through a combination of moisture and oxygen. Accordingly, there is a need for a technology that must prevent the phenomenon of deterioration of the properties of the polymer device due to the penetration of oxygen and moisture for stable current transfer of the electron flow.

In addition, the formation of a high step coverage protective film layer that can isolate the unit device to solve the mutual interference and noise (Cross Talking) problem of the electrode wiring of several nanometers is essential for the implementation of the nonvolatile polymer memory device At the same time, the protective film is a metal oxide film and must be a material that prevents the penetration of moisture or oxygen and must be deposited at low temperatures.

In order for polymer-based PoPRAM devices to replace flash memory, it is necessary to develop new materials with stable current transfer characteristics, new processes, and new concept device structures. In addition, it is necessary to solve various problems such as technical difficulties in the current transfer characteristics of a circuit having a tera-bit density and mutual interference and noise (Cross Talking) problem between neighboring unit cells. .

Above all, in order to suppress the isolation of the device and the deterioration of the properties of the conductive polymer itself, the insulating film which prevents the penetration of oxygen and moisture is deposited to have a high coverage in the structure having a large step, and at low temperature without applying heat to the polymer, the underlying structure. Deposition is necessary.

In order to prevent deterioration characteristics of organic devices including polymers, the organic insulating polymer and organic or polymer thin films are laminated to prevent penetration of external oxygen and moisture of the organic devices or to encapsulate the organic devices in a substrate. External moisture and oxygen were blocked to prevent deterioration of the organic device. However, there is always a problem that the reliability and satisfaction of practical use is minimized because the efficiency is limited in preventing the penetration of water and oxygen.

In the case of PoRAM or OLED, a method of sealing a device by encapsulating a strong hygroscopic material such as CaO ₂ or BaO ₂ as a protective film is used. This technique is disadvantageous because it uses a capsule, which is inflexible, takes up as much space as the volume of the capsule and is expensive.

In addition, a method of blocking an element from moisture by covering an inorganic or organic insulating layer to cover the entire substrate of PoRAM or OLED has been proposed. In the case of the inorganic or organic insulating layer, a silicon oxide film or a silicon oxide film may be formed using ion beam deposition, electron beam deposition, plasma beam deposition, chemical vapor deposition, or the like. A method of encapsulating an element by forming an inorganic insulating film such as silicon nitride and forming a lipophilic polymer such as polysiloxane and polytetrafluethtylene thereon.

DS Wuu et al. Proposed that SiN thin films can be deposited on plastic substrates to prevent oxygen and moisture by using Plasma enhanced chemical vapor deposition (PECVD), a PVD method (DS Wuu, WC Lo, CC Chiang, HB). Lin, LS Chang, RH Horng, CL Huanc, YJ Gao, Water and oxygen permeation of silicon nitride films prepared by plasma-enhanced chemical vapor deposition, Surface & Coatings Technology 198 (2005) 114-117).

However, this deposition method is difficult to apply to devices having a high aspect ratio because of low step coverage in the case of PVD or PECVD. In addition, in the case of CVD, since the device is deposited by heating to a high temperature, deterioration of the polymer occurs due to device properties including organic materials such as polymers, which is not suitable.

Therefore, there is a need for a new deposition method at a low temperature that is deposited to have a high step coverage in a large stepped structure and does not apply heat to the underlying polymer.

As a new method of forming a protective film, an atomic layer deposition method (hereinafter referred to as ALD) has been proposed. The ALD can solve the difficulties that cannot be solved by the conventional PVD or CVD deposition method, and in addition, since both sides can be deposited, it is also possible to add an advantage that double-sided display is possible when the transparent protective film is deposited. And while conventional deposition methods use a multilayer film, ALD can deposit a film having a low density and impurities with a single film, thereby improving efficiency in the manufacturing process.

U.S. Patent No. 5,496,597 proposes to form an inorganic insulating thin film as a protective film using ALD. In addition, US Patent Nos. 2001/0052752 and 2002/0003403 manufacture protective films using ALD to protect devices from oxygen or moisture at low temperatures.

However, there is always a problem that the reliability and satisfaction of practical use is minimized because the efficiency is limited in preventing the penetration of water and oxygen.

Korean Patent Laid-Open Publication No. 2003-64599 discloses a plasma including a precursor constituting a protective film, and performs plasma enhanced atomic layer deposition (PEALD) through a surface chemical reaction between the precursors. The protective film of OLED is manufactured.

In addition, Yun et al. Manufactures a protective film by flowing N ₂ gas in the PEALD process so that a small amount of nitrogen is contained in the protective film (Sun Jin Yun, Young-Wook Ko, Jung Wook Lim, passivation of organic light-emitting diodes). with aluminum oxide thin films grown by plasma-enhanced atomic layer deposition, Applied Physics Letters Vol. 85 No. 21 pp. 4896-4898 (2004)).

In addition, a method of changing the material of the protective film or forming the protective film in the form of a multilayer thin film has been proposed.

Korean Patent Registration No. 10-0540179 proposes a mixed inorganic thin film in which two or more inorganic materials are mixed as an inorganic thin film having excellent moisture and oxygen penetration prevention properties for application to an organic device.

As described above, various attempts have been made to manufacture the protective film, but the reliability and satisfaction in practical use are not so high because the efficiency is limited in preventing the penetration of water and oxygen. Moreover, when the metal oxide is included in the protective film, there is a problem in that the oxide easily contacts with moisture.

An object of the present invention for solving the above problems is to be deposited at a low temperature, excellent film density and hydrophobicity to suppress the permeation of oxygen, moisture or impurities penetrating into the device from the outside to extend the life of the organic device The present invention provides a method of manufacturing an organic device protective film that can be applied to a device having a large step structure as well as to increase.

The present invention to achieve the above object

a) adsorbing an organometallic source on the surface of the organic device;

b) injecting an inert gas to remove unsorbed organometallic sources;

c) injecting an oxygen-containing source and an electron cyclotron resonance (ECR) plasma to react with a metal in the organometallic source to form a metal oxide layer on the surface of the organic device, wherein the ECR plasma is 100 W to 500 W Occurs in; And,

d) injecting an inert gas to remove residual organometallic sources that do not form a metal oxide layer;

It provides a method of manufacturing a protective film of an organic device comprising a.

Preferably, the organic device may include a nonvolatile polymer memory device (PoRAM) and an organic light emitting device (OLED) including at least one polymer layer.

In the manufacturing method according to the present invention, it is possible to deposit at low temperature without damaging the organic device by using ECR plasma, and the protective film thus formed exhibits excellent film density and hydrophobicity to penetrate oxygen, moisture or In addition to suppressing the permeation of impurities to increase the life of the organic device, the present invention is preferably applied to devices having a large step structure.

The organic device to be applied in the present invention may be a nonvolatile polymer memory device (PoRAM) and an organic light emitting device (OLED) including at least one polymer layer.

The nonvolatile polymer memory device and the organic light emitting device have a relatively simple structure in which a pair of electrodes are formed on a substrate, and a polymer layer is present as an organic layer between the electrodes.

An element having such a structure forms a protective film (passivation layer) to suppress the permeation of oxygen, moisture, or impurities that penetrate into the element from the outside. Although the protective layer is formed using a conventional chemical vapor deposition method or a physical vapor deposition method as the protective film, since these methods are accompanied by damage due to high temperature or plasma, there is a problem in that the device to be protected is rather deteriorated or destroyed.

Accordingly, the present invention suggests forming a protective film using an atomic layer deposition method, and in particular, in order to lower the deposition temperature, it is possible to deposit a uniform film while significantly lowering the deposition temperature by exposing to an ECR plasma during the deposition process. This is expected as a measure to prevent damage to the polymer substrate which may be caused by the conventional plasma atomic layer deposition method.

ECR plasma has the following advantages over RF plasma or DC plasma.

First, it is possible to generate plasma at low pressures and to operate at a wide range of pressures. This is because the atomic layer deposition method is deposited by a self limited mechanism (membrane limited mechanism) does not require a high degree of vacuum, and thus the application of ECR plasma is more positive because it can simplify the vacuum equipment required for high vacuum.

Secondly, it has a high ionization rate and a wide range of ion energy. This facilitates the decomposition of reactive gases introduced during atomic layer deposition and enables the formation of thin films with few impurities and high density.

Third, the low-temperature deposition is possible through high ion energy, and the generation area of the ECR plasma is designed to be remote from the substrate, thereby minimizing damage to the organic device (polymer material) by the plasma.

The protective layer of the nonvolatile polymer memory (PoRAM) device

a) adsorbing an organometallic source on the surface of the organic device;

b) injecting an inert gas to remove unsorbed organometallic sources;

c) injecting an oxygen-containing source and an electron cyclotron resonance (ECR) plasma to react with a metal in the organometallic source to form a metal oxide layer on the surface of the organic device, wherein the ECR plasma is 100 W to 500 W Occurs in; And,

d) injecting an inert gas to remove residual organometallic sources that do not form a metal oxide layer.

Each step will be described in more detail below.

a) adsorption of organometallic sources

In step a), first, the organic device for forming a protective film is loaded in the chamber, and then the chamber is maintained at a process temperature of 60 to 250 ° C. Subsequently, a heated organometallic source for forming a protective film is injected into the chamber loaded with the device to adsorb the organometallic source on the surface of the device.

The organic device may be a nonvolatile polymer memory device and an organic light emitting device including at least one polymer layer.

The organometallic source is one organometallic precursor selected from a metal consisting of Al, Ti, Si, Zr, Hf, La, Ta, Mg, and a combination thereof, and is composed of a ligand having a coordination bond with the metal. . Preferably, the organometallic source may be one selected from the group consisting of chlorides, hydroxides, oxyhydroxides, nitrates, carbonates, acetates, oxalates, citrates, and combinations thereof including metals, but is not limited thereto. It doesn't happen.

Preferably, the organometallic precursor including the metal may be M (OH) x, MClx, M (OC ₂ H ₅ ) x, M (i-OC ₄ H ₉ ) x, M (n-butoxide) x, M (t-OC ₄ H ₉ ) x, M (OCH ₃ ) x, M (n-OC ₃ H ₇ ) x _-5 , M (O-iPr) x (where M = Al, Ti, Si, Zr, Hf , La, Ta, Mg or a combination thereof, 3 ≦ x ≦ 5) and a combination thereof may be used.

Typically, the organometallic precursor containing Al may be Al (OH) ₂ , Al (i-OPr) ₃ and the like, the organometallic precursor containing Ti is Ti (MPD) (TMHD) ₂ , Ti (i- OPr) ₂ (TMHD) ₂ , Ti (DMAE) ₄ , Ti (i-OPr) ₄ , Ti (O) (TMHD) ₂ , Ti (i-OPr) ₂ (AcAc) ₂ , Ti (DEPD) (TMHD) ₂ , Ti (DMPD) (TMHD) ₂ , and the like (MPD = methylpentanediol, TMHD = tetramethylheptanedionate, DMAE = dimethylaminoethoxide, DEPD = diethylpentanediol, DMPD = dimethylpentanediol). In addition, as the organometallic precursor containing Si, silicon tetraethoxide (TEOS) is most widely used. And organometallic precursors comprising Zr include Zr (i-OPr) ₄ , Zr (TMHD) (i-OPr) ₃ , Zr (TMHD) ₂ (i-OPr) ₂ , Zr (TMHD) ₄ , Zr (DMAE) ₄ , Zr (METHD) _4, etc. (where METHD = methoxyethoxytetramethylheptanedionate). In addition, the organometallic precursor containing Hf may be Hf ([N (CH ₃ ) (C ₂ H5)] ₃ [OC (CH ₃ ) ₃ ]), and the like. The organometallic precursor including La may be La (TMHD). ₃ , La (TMHD) ₃ -Lewis base is possible. In addition, the organometallic precursor including Ta may be Ta (i-OPr) ₅ , Ta (i-OPr) ₄ (TMHD), Ta (i-OPr) ₄ (DMAE), Ta (DMAE) _5, and the like. The organometallic precursor including Mg (OH) ₂ is possible.

The temperature of the chamber is carried out at a temperature of 250 ° C. or less, preferably 60 to 250 ° C. in order to deposit so as not to affect the conductive polymer present in the organic device. If the temperature in the chamber exceeds the above range, deterioration of the conductive polymer present in the organic device occurs, which makes it impossible to drive the device.

In addition, the pressure in the chamber is maintained at a process pressure of 1 mTorr to 10,000 mTorr.

The process temperature and the process pressure may be the process temperature and the process pressure maintained in subsequent processes, but the process temperature and the process pressure may be changed as necessary.

b) inert gas purge step

In step b), an inert gas is purged into the chamber to remove the organometallic source that has not been adsorbed in step a).

The inert gas may be one selected from the group consisting of Ar, N ₂ , and mixtures thereof, and the purge of these inert gases may cause impurities in the precursor or other chambers that are only physically adsorbed to the surface of the organic device to be removed from the chamber. Discharge.

At this time, in the part where the purging is large in the chamber, the adsorbed organometallic precursor is removed to reduce the uniformity of the protective film. On the contrary, the part that is not properly purged has impurities and the composition of the protective film becomes uneven, so the purging is sufficiently performed. .

c) metal oxide layer formation step using ECR plasma

In step c), a source containing oxygen and an electron cyclotron resonance (ECR) plasma are injected into the reactor and reacted with the metal in the organometallic source to form a metal oxide layer on the surface of the organic device.

The source containing oxygen may be O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , N ₂ O, NH ₃ , CH ₃ OH, C ₂ H ₅ OH, C ₃ H ₇ OH or a mixture thereof. The oxygen may react with an organometallic source adsorbed on the surface of the organic device to form a metal oxide layer on the surface of the device.

At this time, the distance between the organic device and the source injection port is preferably as close as possible to increase the adsorption of the organometallic precursor and to facilitate the formation of a thin film.

The metal oxide layer formed at this time is a monolayer of atomic layer units, and includes a metal oxide layer including one selected from metals consisting of Al, Ti, Si, Zr, Hf, La, Ta, Mg, and combinations thereof. Is formed.

As the single layer of atomic layer unit is formed as described above, even if the step is severe by each component of the organic device to form the protective film, the protective film can be uniformly formed.

The ECR plasma is formed in the chamber to increase the reactivity between the organometallic precursor and the source containing oxygen, thereby lowering the deposition temperature of the metal oxide layer. In addition, the ions formed by the ECR plasma can strike the substrate to increase the film density and improve the deposition rate. By applying ECR plasma during the atomic layer deposition, it is possible to manufacture the protective film at a relatively low temperature of 250 ° C. or lower, preferably 60 to 250 ° C., rather than the high temperature required by other chemical vapor deposition or physical vapor deposition. Prevents deterioration of the protective film that occurs.

At this time, the ECR plasma is controlled by 100 W to 500 W. If the plasma power is less than the above range, it is difficult to generate sufficient plasma, and even if it exceeds the above range, there is no great advantage in effect and thus it is uneconomical, so it is properly performed within the above range.

In particular, in step c), a 2.45 GHz micro is applied to generate a resonance between the circular motion and the microwave to form an electron cyclotron resonance (ECR) plasma in a quartz bell jar. Plasma formed in the quartz bell jar is spread on the substrate 20 to 30cm away through it to use only the ion energy without plasma damage.

The ECR plasma thus formed has the advantage of increasing the reactivity of the precursor and the reaction gas, thereby lowering the deposition temperature. In addition, the ions formed by the ECR plasma may strike the substrate to increase the film density and improve the deposition rate.

d) inert gas purge step

In step d), an inert gas is injected to remove residual organometallic sources that do not form a metal oxide layer in step c).

The inert gas may be one selected from the group consisting of Ar, N _2, and a mixture of these gases, and impurities in the organometallic precursor or other chambers present on or around the surface of the organic device may be purged through these inert gases. Drain out of the chamber.

In this step, since the impurity and the like remain in the part where the purging is not performed properly, the composition of the protective film becomes uneven, so that purging is sufficiently performed.

As mentioned above, since the metal oxide layer formed through the steps a) to d) is a monolayer of atomic layer units, in order to ensure a minimum thickness to serve as a protective film, d) the step is carried out at least once, preferably for 100 to 1000 times.

More preferably, the step is performed until the metal oxide layer has a thickness of 1 to 300 nm. This is because the atomic layer deposition method according to the present invention has an advantage that the thickness of the protective film is very easy because the thickness increases linearly with the cycle.

In this case, the metal oxide layer constituting the protective film is a heterogeneous material by using the same material to form a metal oxide layer of a single material into a single thin film, or by using an organometallic precursor different from the one previously used when the steps a) to d) are repeated. It can be used in the form of a multilayer thin film.

The metal oxide layer of the multilayer thin film form can be easily formed by changing only the organometallic precursor injected during the atomic layer deposition method.

The passivation film formed on the organic device through these steps is manufactured using atomic layer deposition to facilitate thickness control, improve step coverage, and smoothly form a surface.

In addition, it is possible to deposit a uniform film while significantly lowering the deposition temperature by exposure to ECR plasma during deposition, it is possible to manufacture a protective film having a single thin film or a multi-layered thin film by the same or different types of organometallic precursor.

Furthermore, the accelerated ions through ECR plasma treatment penetrate deep into the deposited film, and the surface roughness (RMS) measured by atomic force microscope (AFM) is less than 0.5 nm, resulting in excellent surface properties as well as hydrophobicity. It prevents the invasion of oxygen, moisture or impurities from the outside to improve the life characteristics of the organic device.

This method is preferably applied to organic devices such as nonvolatile polymer memory devices (PoRAM) and organic electroluminescent devices (OLEDs) comprising at least one polymer layer. In addition, the manufacturing of the protective film according to the present invention can be easily applied to the field of flexible display using a polymer substrate.

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited to the examples.

( Example  One)

The device was placed on a substrate heated to 60 ° C., and the precursor of Ti heated to 40 ° C., that is, TDMAT, was adjusted for 20 seconds and injected into the chamber to be adsorbed onto the surface of the device. Then, the Ar gas, which is an inert gas, was adjusted to 5 seconds. It was injected into and purged. At this time, the device was used to deposit PVN (poly-vinylcarbazole) at 6 nm on a Si substrate.

Subsequently, the reaction gas O ₂ gas was adjusted to 5 seconds to form an ECR plasma at 300 W while being injected into the chamber, and reacted with the first injected TDMAT while spreading evenly in the chamber.

Thereafter, Ar gas, which is an inert gas, was also adjusted to 5 seconds and injected into the chamber to purge.

500 cycles of the above cycle was carried out to form a TiO ₂ protective film on the surface of the organic device.

(Comparative Example 1)

In the same manner as in Example 1, an RF plasma was generated instead of the ECR plasma to form a TiO ₂ protective film on the surface of the organic device.

Experimental Example 1

FIG. 1 is a cross-sectional transmission electron micrograph showing damage of a PVK material when TiO ₂ protective film is deposited using RF plasma in Comparative Example 1. FIG.

As can be seen in Figure 1, the interface between the PVK and TiO ₂ is not smooth, and despite the formation of 20 nm thick PVK before the TiO ₂ process it can be seen that the etching to 6 nm under the influence of RF plasma. In order to prevent this problem, ECR plasma should be introduced, and PVK etching by ECR plasma could not be observed.

Experimental Example 2

FIG. 2 is an atomic force microscope (AFM) image showing surface roughness of a PVK treated with a reactive material without RF and an ECR plasma method.

Referring to FIG. 2, the surface roughness was observed to be very high and uneven as observed by etching the PVK by the RF plasma. In the case of the ECR plasma, there is no significant difference with the roughness of the PVK treated without the plasma. .

The AFM image also shows that the ECR plasma does not damage the polymer material.

FIG. 1 is a cross-sectional transmission electron micrograph showing damage of a PVK material when TiO ₂ protective film is deposited using RF plasma in Comparative Example 1. FIG.

FIG. 2 is an AFM image showing the surface roughness of PVK treated with only reactive materials without RF plasma and ECR plasma.

Claims (12)

a) adsorbing an organometallic source comprising a metal ligand on the surface of the organic device; b) injecting an inert gas to remove unsorbed organometallic sources; c) injecting an oxygen-containing source and an electron cyclotron resonance (ECR) plasma to react with a metal in the organometallic source to form a metal oxide layer on the surface of the organic device, wherein the ECR plasma is 100 W to 500 W Occurs in; And, d) injecting an inert gas to remove residual organometallic sources that do not form a metal oxide layer, The organometallic source is a method of manufacturing a protective film of an organic device is an organometallic precursor (precursor) selected from a metal consisting of Al, Ti, Si, Zr, Hf, La, Ta, Mg and combinations thereof. delete The method of claim 1, The organometallic precursor is a chloride, hydroxide, oxyhydroxide, nitrate, carbonate, acetate, oxalic acid containing one metal selected from metals consisting of Al, Ti, Si, Zr, Hf, La, Ta, Mg and combinations thereof. A method for producing a protective film for an organic device, which is one selected from the group consisting of salts, citrate salts, and combinations thereof. The method of claim 1, Step a) is carried out at 60 to 250 ° C protective film manufacturing method of an organic device. The method of claim 1, The inert gas of the step b) and d) is a protective film manufacturing method of an organic device that is one selected from the group consisting of Ar, N ₂ and their mixture gas. The method of claim 1, Sources containing oxygen of step c) are O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , N ₂ O, NH ₃ , CH ₃ OH, C ₂ H ₅ OH, C ₃ H ₇ OH and these Method for producing a protective film of an organic device is one selected from the group consisting of a mixture of gas. The method of claim 1, Method of manufacturing a protective film of an organic device to perform the steps a) to d) for 100 to 1000 times. The method of claim 1, The protective film is a protective film manufacturing method of an organic device having a thickness of 1 to 300 nm. The method of claim 1, The protective film has a surface roughness (RMS) measured by AFM is less than 0.5 nm method of manufacturing a protective film of an organic device. The method of claim 1, The protective film is a protective film manufacturing method of an organic device that is hydrophobic. The method of claim 1, The protective film is a protective film manufacturing method of an organic device having a form of a single thin film or a multilayer thin film. The method of claim 1, The organic device is a nonvolatile polymer memory device (PoRAM) or an organic light emitting device (OLED) comprising at least one polymer layer.

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