TW201222809A - Organic electro-luminescent device - Google Patents

Abstract

The invention provides an organic electro-luminescent device which has a first film; an organic electro-luminescent element disposed on the first film; and a protective film covering the organic electro-luminescent element. The protective film contains silicon atoms, oxygen atoms and carbon atoms. A distribution curve of silicon, a distribution curve of oxygen and a distribution curve of carbon obtained from the protective film meet the following conditions: (i) the ratio of number of the silicon atoms being the second greatest value among the ratio of the number of the silicon atoms, the ratio of the number of the oxygen atoms and the ratio of the number of the carbon atoms in 90% or more of the region of the gas barrier layer in the thickness direction of the protective film; (ii) the distribution curve of carbon having at least one extremum; and (ii) the difference between the maximum value and the minimum value of the ratio of the number of the carbon atoms in the distribution curve of carbon being 5 atom% or more.

Description

201222809 VI. Description of the Invention: [Technical Field] The present invention relates to an organic EL device, a lighting device, a planar light source, and a display device. [Prior Art] The organic electroluminescence (Electro Luminescence is abbreviated as EL, which is called "electric field emission") has a structure in which a plurality of thin film layers are laminated. The flexibility of the element itself can be imparted by appropriately setting the thickness or material of each film. When such an organic EL element is provided on a flexible film, the entire device in which the organic EL element is mounted can be a flexible device. The organic EL element is deteriorated by exposure to outside air. Therefore, the organic EL element is generally hermetically sealed by a specific sealing member. However, in the invention described in Patent Document 1, the organic EL element is formed to cover the organic EL element with a protective film immediately after the formation of the organic EL element, in order to prevent such deterioration. . Patent Document 1 discloses a protective film composed of Si〇2, SiNx, Si〇xNy, MgF, Ini, p〇1y paraxylylene or the like. [Problems to be Solved by the Invention] However, the protective film is resistant to oxygen and moisture, that is, gas barrier properties are insufficient. Since the protective film is provided and the organic EL element is also deteriorated, it is necessary to carry out the transport step and the sealing step necessary for providing the sealing member in a vacuum environment or an inert gas atmosphere in 323547 4 201222809. Therefore, in order to manufacture an organic EL device, complicated steps such as gas substitution or vacuum replacement are required, and there is a problem that the manufacturing apparatus is enlarged. Further, since the above protective film has a low gas barrier property at the time of bending, it is not suitable for a method of producing an organic EL device by a method of affinity (ro 11 to ro 11). Accordingly, an object of the present invention is to provide an organic EL device which has high gas barrier properties and is provided with a protective film which can suppress a decrease in gas barrier properties due to bending. (Means for Solving the Problem) The present invention relates to an organic EL device comprising: a first film, an organic EL element provided on the first film, and a protective film covering a surface opposite to the first film of the organic EL element . The protective film contains ruthenium (anthracene atom), oxygen (oxygen atom), and carbon (carbon atom), and represents a ratio of the atomic weight (number) of the total amount of the atom, the oxygen atom, and the carbon atom, respectively. , the ratio of the amount (number of oxygen atoms) (the atomic ratio of oxygen) and the amount (number) of carbon atoms (atomic ratio of carbon) and the aforementioned protective film from the thickness direction (film thickness direction) of the protective film The relationship between the distance of the surface on one side and the enthalpy distribution curve, the oxygen distribution curve, and the carbon distribution curve satisfy the following conditions: (i) In a region of 90% or more in the thickness direction (film thickness direction) of the protective film, 矽In the ratio of the ratio of the number of atoms, the ratio of the number of oxygen atoms, and the ratio of the number of carbon atoms, the ratio of the number of bismuth is the second largest value; (ii) the aforementioned carbon distribution curve has at least one extreme value; and (iii) the aforementioned carbon The difference (absolute value) between the maximum value and the minimum value of the ratio of the number of carbon atoms in the distribution curve is 5 atom% (at%) or more. 5 323 547 201222809 The organic EL device may further include a second film which is disposed opposite to the first film and which seals the organic EL element together with the first film. An organic EL element and a protective film are disposed between the second film and the first film. In other words, the present invention relates to an organic EL device having a second film which is disposed on the first film and is sealed with the first film while being interposed between the first film and the protective film. The aforementioned organic EL element. Furthermore, the present invention relates to a method of producing an organic EL device, comprising the steps of forming an organic EL element on a first film, and forming a protective film covering a surface opposite to the first film of the organic EL element. . The protective film formed contains a chopping atom, an oxygen atom and a carbon atom, and represents a ratio of the number of the atoms of the stone atom, the ratio of the number of oxygen atoms, and the number of carbon atoms to the total amount of the stone atom, the oxygen atom and the broken atom, respectively. The ratio of the ratio of the distance to the surface of the protective film in the thickness direction of the protective film, the oxygen distribution curve, and the carbon distribution curve satisfy the following conditions: (i) in the thickness direction of the protective film In the region of more than 90%, the ratio of the number of germanium atoms, the ratio of the number of oxygen atoms, and the ratio of the number of atoms to the atomic ratio, the ratio of the number of turns is the second largest value; (ii) the aforementioned carbon profile has at least one And (iii) the difference between the maximum value and the minimum value of the ratio of the number of carbon atoms in the carbon distribution curve is 5 atom% or more. The method may further include bonding the second film to the first film so that the organic EL element and the protective film are disposed between the second film and the first film after the step of forming the protective film. Step 6 323547 201222809. In other words, the method of the present invention may further include: after the step of forming the protective film, the organic EL element and the protective film are interposed between the first film and the second film; and the second film is bonded to the first film. step. At this time, the second film was bonded to the first film in an air atmosphere. Further, the method may further include the steps of: winding the first film together with the organic EL element and the protective film into a roll shape after the step of forming the protective film, and storing the wound first film, the organic EL element, and the protective film . In this case, the first film, the organic EL element, and the protective film which are taken up may be stored in an air atmosphere. In another aspect, the present invention relates to an illumination device, a surface light source device, and a display device having the foregoing organic EL device. (Effect of the Invention) According to the present invention, the organic EL device can be covered with a protective film having high gas barrier properties and having a low gas barrier property at the time of bending. Therefore, after the protective film is formed, the organic EL element is sealed by a sealing member or the like, and deterioration of the organic EL element can be suppressed. [Embodiment] Hereinafter, a preferred embodiment of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. The organic EL device of the present embodiment includes a first thin film, an organic EL element provided on the first thin film, and a protective film formed by covering the organic EL element. The protective film covers the entire surface opposite to the first film of the organic EL element. The organic EL device mounted in the organic EL device can be roughly classified into the following three types of components: 7 323 547 201222809. In other words, the organic EL element can be roughly divided into (1) an element that emits light toward the support substrate on which the organic EL element is mounted, and a light-emitting element; (II) emits light toward the opposite side of the support substrate; And (III) a double-sided illumination type element that emits light toward the support substrate while emitting light toward the opposite side of the support substrate. The organic EL element mounted on the organic EL device of the present embodiment may be any type of element. The organic EL device further has a second film as necessary. The second thin film system and the first thin film are disposed on the first thin film between the organic EL device and the protective film. The organic EL element and the protective film are sealed by the first film and the second film. Hereinafter, first, an organic EL device in which a second film is not provided will be described with reference to Fig. 1 . Thereafter, referring to Figs. 3 and 4, an organic EL device in which a second film is further provided will be described. Fig. 1 is a cross-sectional view showing the organic EL cracking of the present embodiment. The organic EL device 13 of the embodiment shown in Fig. 1 includes a first thin film, an organic EL element 2 mounted on the first thin film, and a protective film 3 for protecting the organic rainbow element 2. The protective film 3 has high gas barrier properties because it satisfies the conditions (丨), (Η), and (丨丨丨) described later, and further, it is possible to suppress the decrease in gas barrier properties during bending. The film 3 is formed on the organic EL element, and even if the organic device 13 is wound into a parent shape, the protective film can maintain high gas barrier properties, and the organic EL device that is wound up can be stored in the gas barrier property. Great production. Even if the protective film is bent, it can maintain high gas barrier properties, so it is suitable for = 323547 8 201222809. It is used as a manufacturing method for organic EL devices. When the second film described later is bonded, it can be bonded by a roll-to-roll method. Furthermore, this fit can also be carried out in an atmospheric environment. (Protective film) Description About the protective film. One of the features of the organic EL device of the present embodiment is the protective film 3. The protective film contains a halogen atom, an oxygen atom and a carbon atom. By measuring the ratio of the number of germanium atoms to the total amount of germanium atoms, oxygen atoms, and carbon atoms by changing the distance from the surface on one side of the protective film in the thickness direction (film thickness direction) of the protective film (stone) The ratio of the atomic ratio of oxygen atoms (the atomic ratio of oxygen atoms) (the atomic ratio of oxygen) and the ratio of the number of carbon atoms (atomic ratio of carbon) can be obtained by indicating the atomic ratio of each atom and the distance from the surface of the protective film. The relationship between the distribution curve, the oxygen distribution curve and the carbon distribution curve. These curves obtained from the protective film of the present embodiment satisfy the following conditions (i), (ii), and (iii). (i) In the region of 90% or more in the thickness direction of the protective film, the atomic ratio of ytterbium, the atomic ratio of oxygen, and the atomic ratio of carbon are the second largest value. (ii) The carbon distribution curve has at least one extreme value. The difference (absolute value) between the maximum value and the minimum value of the atomic ratio of carbon in the (Hi) carbon distribution curve is 5 at% or more. In other words, the condition of (i) means that the following formula (丨) or the following formula (2) is satisfied in a region of 9% or more of the thickness direction of the protective film. (Atomic ratio of oxygen) >(Atomic ratio of bismuth)> (Atomic ratio of carbon)···〇) (Atomic ratio of carbon)>(Atomic ratio of 矽)> (Atomic ratio of oxygen)· (2) 323547 9 201222809 The organic EL device may have other layers that do not satisfy at least any of the above conditions (1) to (iii) in addition to the above protective film. The protective film or the layer of the pot may further contain a nitrogen atom, an aluminum atom or the like. When the atomic ratio of Shixi, the atomic ratio of oxygen, and the atomic ratio of carbon do not satisfy the condition, the gas barrier properties of the protective film are lowered. It is preferable that the region satisfying the above formula (1) or (2) is m or more inclusive of the thickness of the protective film. This ratio is preferably 95% or more preferably 100%. In the protective film of the present embodiment, the β carbon distribution curve is required to have one extreme value as the above condition (ii). In the case of such protection, it is preferred that the curve has at least two extreme values, more preferably three or more. 4 = the carbon distribution curve does not have an extreme value, and the obtained protective film has a low gas barrier property when bent. . When the carbon distribution curve has at least three extreme values, it is preferable that the carbon distribution curve is adjacent to the extremum_thickness direction and the distance nm is less than 100 nm. In the present specification, the extreme value is plotted against the atomic ratio of the element at the distance from the thickness of the protective film to the surface of the protective film, and the extreme value in the obtained distribution curve is large or small. The so-called maximum value is in the above distribution curve, as the distance from the surface of the protective film changes, the value of the atomic ratio of the element changes from an increase to a point of decrease, and the atomic ratio of the element at this point is The point at which the distance from the surface of the protective film in the thickness direction of the protective film is further changed by 2 〇 nm, and the atomic ratio of the element at a point where the atomic ratio of the element is decreased by 3 at% or more. The so-called minimum value varies with the distance from the surface of the protective film, and the value of the atomic ratio of the element changes from decreasing to increasing point and compared with the atomic ratio of the element at this point, from which point the protective film 323547 10 The thickness direction is set from the surface of the protective film to the value of the atomic ratio of the elements = the distance further changes the position ratio from 0 nm. In the protection of the original embodiment, the atomic ratio of the carbon of the distribution curve is: in the above condition (iii), it must be on carbon. The protective enthalpy is preferably 妒, the difference between the large value and the minimum value is 5 cents or more, and the difference is 6 atom% or more, more preferably the maximum value and the minimum value of the atomic ratio of ash, and the protection is performed when the second film is bent. Gland 7 at% or more. When the difference is less than 5 at%, there is no particular limitation, but generally the gas barrier property is lowered. The above difference (oxygen distribution curve, extreme value) is about 3G at%. In order to have at least one extreme value, it is better to have at least two extreme values, and the best value is better. The cloth curve has three extreme values when it has an extreme value. When the value of oxygen gas is lowered, the oxygen distribution is at least 3 extremes, and the oxidization distribution has at least 3 extreme values, and an extreme value is adjacent to the extreme value of the protective film. The difference in the distance between the thickness direction and the surface of the protective film is preferably 2 〇〇 nm or less, more preferably 100 rnn or less. (Oxygen distribution curve, difference between maximum value and minimum value) The difference between the maximum value and the minimum value of the atomic ratio of oxygen in the oxygen distribution curve of the protective film is preferably 5 at% or more, more preferably 6 at% or more, most Good for 7 & find = on. When the difference is at least the above lower limit, there is a tendency that the gas barrier properties due to the bending of the protective film are less likely to occur. The upper limit of this difference is not particularly limited' but is generally around 30 at%. The difference between the maximum atomic ratio of 矽 in the 矽 distribution curve of the protective film and the minimum value of 323547 11 201222809 is preferably less than 5 at%, more preferably less than 3, and most preferably less than 3a. If the difference is the aforementioned If the upper limit is not reached, the gas barrier property of the protective film becomes a special tendency. (oxygen carbon distribution curve, the difference between the maximum value and the minimum value) "in the thickness direction of the protective film from the surface of the layer, the total amount of oxygen atoms and carbon atoms relative to the stone atom, oxygen atom and The difference between the maximum value and the minimum value of the sum of the atomic ratios of oxygen and carbon in the oxygen-carbon distribution curve of the ratio of the carbon atom to the ratio of the atomic ratio of oxygen to carbon (the atomic ratio of oxygen to carbon) is preferably less than jat%. Jiawei is not up to (10), and the best is less than 3at%. When the difference does not reach the above upper limit, the gas barrier properties of the protective film tend to be particularly high. The Shixi distribution curve, oxygen distribution curve, carbon distribution curve and oxygen-carbon distribution curve are combined by X-ray photoelectron spectroscopy (XPS: Xray Ph〇t〇e i (5) tr〇n

The measurement of Spectroscopy and the rare gas ion sputtering of argon and the like were carried out by sequentially performing surface composition analysis on the inside of the sample, and the measurement was performed by so-called xps depth profile measurement. The distribution curve obtained by such XPS depth profile measurement is, for example, such that the vertical axis represents the atomic ratio of each element (unit: at%) and the horizontal axis represents the etching time (sputter time). The etching time is roughly related to the distance from the thickness direction of the protective film to the surface of the protective film. Therefore, the "distance from the surface on one side of the gas barrier layer in the thickness direction of the protective film" can be calculated from the relationship between the etching rate and the etching time used in the xps depth profile measurement. The distance from the surface of the gas barrier layer. In the sputtering method used for such XPS depth profile measurement, argon (ar〇 is used as the rare gas ion sputtering method of the etching ion species, and the etching rate (etching rate) is preferably 〇. 5 nm/sec. (Si〇2 thermal enthalpy equivalent value) 323547 12 201222809 From the viewpoint of forming a uniform and excellent gas barrier on the entire film surface, it is preferable that the protective film is substantially in the direction of the film (the direction of the layer (surface)) In the present specification, the term "substantially-oriented direction" means that when an oxygen distribution curve, a carbon component, and a distribution curve are produced at a measurement position of any two of the film faces of the protective film by XPS depth profile measurement, The values obtained by the distribution curves at any two of the measurement sites are the same as each other, and the difference between the maximum value and the minimum value of the carbon atoms in the two carbon lines of the respective carbon distributions is equal to each other by 5 at . 4 b "The carbon distribution curve is preferably substantially continuous. In the present specification, the clock carbon distribution curve is calculated from the curve in which the carbon atom ratio of the month is not continuously changed. In the thickness direction of the protective film away from this = The distance between the surface (X, unit: nm) and the atomic ratio of carbon & unit: 'in the following mathematical formula (10): ° -i.〇s(dc/dx) m"(F1 As long as at least the layer is satisfied, the above conditions are satisfied: 丨; to: factory) The 'protective film system can also have two layers of all ^ 2 〇 film. The protective film has two or more layers of the film. Capture, the 4th layer of the film (four) can be

In the 矽 distribution curve, the “J ^ b knives curve and the carbon distribution curve”, when the original rtt ratio of 矽 and the atomic ratio of carbon satisfy the conditions shown in formula (1), the two θ, the content is relative to the dream atom. The atomic ratio of w I of the oxygen atom and the carbon atom is preferably from 25 to 45 at%, more preferably from 3 〇 to 4 〇 323547 13 201222809 at %. The content of oxygen atoms in the protective film is relative to the ruthenium atom, the oxygen atom and The atomic ratio of the total amount of carbon atoms is preferably from 33 to 67 at%, more preferably from 45 to 67 at%, and the atomic ratio of the content of carbon atoms in the protective film to the total of the ruthenium atom, the oxygen atom and the carbon atom is preferably Preferably, it is 3 to 33 at%, more preferably 3 to 25 at%. In the Shishi distribution curve, the oxygen distribution curve, and the carbon distribution curve, the atomic ratio of the stone, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the foregoing. In the case of the formula (2), the atomic ratio of the content of the ruthenium atom in the protective film to the total amount of the ruthenium atom, the oxygen atom and the carbon atom is preferably 25 to 45 at%, more preferably 30 to 40 at%. Atom of the content of oxygen atoms in the protective film relative to the total amount of germanium atoms, oxygen atoms and carbon atoms The ratio is preferably from 1 to 33 at%, more preferably from 1 to 27 at%, and the atomic ratio of the content of carbon atoms in the protective film to the total of the ruthenium atom, the oxygen atom and the carbon atom is preferably from 33 to 66 at. %, more preferably 40 to 57 at%. The thickness of the film is preferably from 5 to 3 〇〇〇 nm, more preferably from 1 〇 to 2,000 Å, and particularly from 1 〇〇 to 1 〇〇〇 nm. When the thickness of the protective film is such a value: gas 2 亇 - more excellent oxygen gas barrier property, water vapor barrier property, etc. can be obtained, and the tendency of the gas barrier property due to bending is more effectively suppressed. When the product is composed of a plurality of layers, the thickness of the plurality of layers is generally 10 to 1 〇〇〇〇 nm, preferably 10 to 50 Å, ^ to nm, preferably When the value of the protective film is in the numerical range (4), more excellent oxygen can be obtained; gas barrier properties such as water vapor barrier property can be more effectively suppressed, and 323547 14 201222809 can be more effectively suppressed. The tendency of the gas barrier property to decrease. The protective film is preferably a protective film formed by a chemical vapor phase growth method of the canister: a layered film and a layered film , Good enough to make the first thin film provided thereon of an organic EL element disposed heteroaryl - on the one pair of 1 percent _ «" _ = Zhao depends on the, in the layer formed. Discharge between a pair of film-forming rolls = growth method The film is intimately interacted with (4). It is preferable to use the amount of money that is used in the production of such money, and it is preferable to make the occupational body t 4 . The film-forming wind recognizes that the 'Zhuang Ma will become the theoretical oxygen meter that is necessary for the complete oxidation of the gas. (4) The continuous formation of the compound of the cerium compound. It is better to describe in the detailed method of forming a method of protecting 臈 by the method of forming a guarantor by the law. <Manufacturing Method of Protective Film> Next, an organic group element which is first formed on the first film will be described with respect to the side where the protective enamel is produced. The protective film is formed in a pre-formed manner. The method of forming the protective film on the organic film 1 to cover the first film is from the viewpoint of gas barrier properties to the surface of the first film and the first film (plasma CVD). This plasma chemical vapor phase growth method ^ electric 襞 chemical vapor phase growth method discharge electropolymerization method of plasma chemical vapor growth, / 'for Penning (Penning) in the electropolymerization chemical vapor growth method 吝 a ' _ The plasma between the film forming rolls generates plasma, and is preferably a plurality of rolls, and the pair of film forming rolls are respectively arranged to discharge between the forming rolls using a pair of film forming rolls. Plasma. In this case, the film is formed by a pair of film-forming rolls, and the film is formed by a film-forming roll which is described later in the vapor phase. 15 201222809 When forming a film, it can be present in one of the film forming rolls. In the first film and the organic EL element, the protective film is formed on the film, and the protective film is simultaneously formed on the first film and the organic EL element which are present on the other film forming roll. Thereby, not only the protective film can be efficiently produced, but also a film having the same structure can be simultaneously formed at a film formation rate of twice. As a result, at least the extreme value in the carbon distribution curve is at least multiplied, and the protective film which satisfies the above conditions (i) to (iii) can be efficiently formed. From the viewpoint of productivity, it is preferred to form a protective film on the surfaces of the first film and the organic EL element by a roll-to-roll method. The apparatus used for producing the protective film by such a plasma chemical vapor phase growth method is not particularly limited, but it is preferable to provide at least one pair of film forming rolls and an electropolymerization source, which can form a film on the aforementioned pair. A device for discharging between rollers. For example, by using the manufacturing apparatus shown in Fig. 2, a protective film can be produced by a roll-to-roll method while using an electrification chemical vapor deposition method. Hereinafter, a method of manufacturing a protective film will be described in more detail with reference to Fig. 2'. Fig. 2 is a schematic view showing an example of a manufacturing device for making the protection of the present embodiment appropriately used. In the following descriptions and ^, the same symbols are given to the same elements, and the appropriate explanations are given. The manufacturing equipment shown in Figure 2 is equipped with: Sending a pro? 〇1; transport, 22, 23, 24 'oppositely arranged one pair of film formation 31, corpus supply tube 41; plasma generating power source 51; magnetic field generating device installed inside _ Μ and = 6 卜 62; take the pro 7 〇 2 32 source 51; magnetic field agricultural device, arranged in the vacuum omitted 323547 16 201222809. The vacuum chamber is connected to the vacuum i omitted from the drawing, and the air pump appropriately adjusts the pressure in the vacuum chamber. θ. True In the manufacturing apparatus of Fig. 2, the film forming rolls which function as a pair of counter electrodes for "pair 31 and dirty 32" are respectively connected to the electric (four) green power source 51. By supplying electric power from the = power source 51, it is possible to make a discharge between the film forming roller 32 and the film forming roller 32, and it is possible to generate electricity between the film forming roller 31 and the forming film 32. It is also possible to use the alloy 31 and the alloy 32 as the electrode. The material can be appropriately changed and the design can be used as the electrode. One of the film forming rolls (film forming rolls 31 and 32) is preferably arranged such that their central axes are substantially parallel on the same plane. In this way, it is configured (for 31 and 32) to form a protective film on each of the film forming rolls, which doubles the film formation rate when filming on a film forming roll. . Further, the film of the structure of the phase 3 can be formed to form a film, so that the value of the extreme value in the carbon distribution curve can be minimized. According to this manufacturing apparatus, a protective film can be formed on the surface of the i-th film and the organic EL element by the method (10), and the composition of the film and the organic EL element can be stacked on the film forming roller 31 while advancing. - Step on the film forming roller 32 also on the first film! And a film component is deposited on the surface of the organic EL element. Therefore, a protective film can be efficiently formed on the surfaces of the first film 1 and the organic EL element. Magnetic field generating devices 61 and 62 are provided inside the film forming roller 31 and the film forming roller 32. The magnetic field generating devices 61 and 62 are fixed in such a manner that they do not rotate themselves even if the film forming roller rotates. As for the film forming spokes 31 and the film forming roll 32, a general Xingkun can be suitably used. 323547 17 201222809 Film-forming roll 31 and *古, - preferably heart 'from the viewpoint of forming a film more efficiently, the chamber R μ, the direct view of the rolls 31 and 32, from the discharge condition, the special point of view, It is preferably 5 to 100 cm. In the opposite device, the first thin surfaces are made into a thin film. The filming roller of the funeral mountain (filming pro 31 and film formation (10)) is placed on the first! 32 Λ Λ , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , . That is, if the film composition is deposited on the first film and the organic EL element on the film forming roller 31, the film is formed on the film forming roller 32 and the organic EL element | LΑ 社弟一厚膜卜# Stacked film ingredients. Therefore, the gas barrier layer can be efficiently formed on the surface of the first film and the yak. The transfer roller 7Q1 and the transport roller 2, 22, 23, and 24 are suitably used. Generally, the take-up roll 702 is not particularly limited as long as it can take up the first film 1 on which the protective film can be wound, and is appropriately used from the general The static tube 41 can supply or discharge the raw material and P at a specific speed. The plasma generating power source 51 can appropriately use the power source of the general electropolymer generating device. The plasma generating power source 51 is connected to the battery. These film forming rolls 31 and Difficulty 32 supply electric power, and these can be used as electrons to the electrodes. The plasma generating power source 51 can perform plasma CVD more efficiently. A power source (AC power source, etc.) that alternately reverses polarity, and the power generation source 51 is more preferably configured to perform electric t CVD more efficiently, so that the applied power is set to 1 〇 to 1 〇kw, The frequency of the alternating current is 50 Hz to 500 kHz. The magnetic field generating devices 61 and 62 are appropriately 323547 18 201222809. A general magnetic field generating device is used. The substrate sent from the sending parent can be used in addition to the first film and the organic EL element. Pre-formed on it, etc. The substrate of the protective film is formed by dividing the protective film into a plurality of times to further thicken the protective film. By using the manufacturing apparatus shown in Fig. 2, the type of the material gas and the plasma generating device can be appropriately adjusted. The protective film is formed by the electric power of the electrode drum, the pressure in the vacuum chamber, the diameter of the film forming roller, and the transport speed of the film. By using the manufacturing apparatus shown in Fig. 2, the film forming gas (raw material gas, etc.) is supplied to the vacuum. In the chamber, a discharge is generated between the pair of deposition rollers (film formation rollers 31 and 32), and the film formation gas (raw material gas or the like) is decomposed by the plasma to form the first film on the film formation roller 31. On the surface and the surface of the first film on the film forming roll 32, a protective film is formed by a plasma CVD method. When the film is formed as described above, the first film 1 is transported by the feed roller 701 and the film forming roller 31, respectively. A protective film covering the organic EL element is formed on the surface of the first film 1 by a roll-to-roll continuous film forming process. The raw material gas system in the film forming gas for forming the protective film can be protected by the formation. The material of the film is appropriately selected. As the raw material gas system, for example, an organic ruthenium compound containing ruthenium may be used. The raw material gas system may contain, in addition to the organic ruthenium compound, monodecane as a ruthenium source. The feed gas system contains, for example, hexamethylene dioxane, 1, 1, 3, 3-tetradecyldioxane, vinyltrimethylnonane, decyltrimethyldecane, hexamethylene dioxane, decyl decane, dimethyl decane, tridecyl decane, diethyl decane , propyl decane, phenyl decane, vinyl triethoxy decane, vinyl trimethoxy decane, tetradecyl decane, tetraethoxy decane, phenyl 19 323547 201222809 At least one organic ruthenium compound selected from the group consisting of triethoxy zephyr and octadecyl cycline. In the organic chemistry of the above, hexamethyldioxane and 113,3-tetramethyl one are preferred from the viewpoints of the rationality of the compound and the gas barrier properties of the obtained gas barrier layer. Oxane. These organic hydrazine compounds may be used alone or in combination of two or more. The film forming gas system may contain a reaction gas in addition to the material gas. The reaction gas system can be suitably selected by using a gas which reacts with a material gas to form an inorganic compound such as an oxide or a nitride. The reaction gas system for forming an oxide may use, for example, oxygen or ozone. As the reaction gas for forming the nitride, for example, nitrogen or ammonia can be used. These reaction gas systems may be used alone or in combination of two or more. For example, when an oxynitride is formed, a reaction gas for forming an oxide and a reaction gas for forming a nitride may be combined. In order to supply the material gas into the vacuum chamber, the film forming gas system may use a carrier gas if necessary. In order to generate a plasma discharge, a film forming gas system may use a discharge gas if necessary. Such a carrier gas and a gas system for discharge can be suitably used. A rare gas such as helium, argon, neon or krypton or hydrogen may be used as the carrier gas or the gas for discharge. When the film forming gas contains the material gas and the reaction gas, the ratio of the material gas to the reaction gas is preferably a ratio of the amount of the reaction gas which is theoretically necessary to completely react the material gas with the reaction gas, and the ratio of the reaction gas is not excessive. . By appropriately controlling the ratio of the reaction gas, a film (protective film) which satisfies the above conditions (i) to (Hi) can be formed particularly efficiently. When the film forming gas contains an organic cerium compound and oxygen, the amount of oxygen in the cerium gas is preferably 323547 20 201222809. The amount of oxygen required for complete oxidation of the organic cerium compound in the film forming body is below. Hereinafter, as the film forming gas, hexamethyldioxane (organoquinone compound, HMDS 〇, (CH3) 6 ""cyanide and oxygen as a reaction gas (G2)) as a raw material may be used. The gas, the production of sulphur, (4) protection, for example, in more detail, the appropriate ratio of the raw material gas to the gas of the film forming gas, etc., and the hexamethylene dioxane as a raw material gas ( HMDS〇,

When a ♦-oxygen protective film is produced by reacting with oxygen as a reactive gas ((4), (4), it is represented by the following reaction formula (3) in the film forming gas. Reaction, formation of cerium oxide, (CH〇6Si2〇' -1 B (1) ' duj2 + 9H2 〇 + Ui 〇 2 (3) 〇 In this ^, in order to make hexamethyl bis(tetra) burn 1 mole complete oxidation The amount of oxygen is 12 moles. Therefore, in the film forming gas, when the hexamethyl _ Meng Wei 1 Moer* contains 12 moles or more of oxygen to completely react, the oxygen-cutting is performed. 'There is no possibility of forming a protective film that fully satisfies the above j = to (in). Therefore, when forming a solid-hearted film, in order to make the upper-relative Hi/() formula Good; Mo Er.,: Money 1 Mo, oxygen less than stoichiometric] Shi Xi oxygen, inter-production! The reaction in the tCVD chamber is the supply of hexamethyl-membrane of the raw material: oxygen: gas supply The part is supplied to the film-forming area and the second part of the oxygen is burned; the amount of the ear (flow rate) is the raw material of the hexagram; the reaction is not completely entered into the 1 2 times the molar amount (flow rate) 'actually - 仃, presumably mostly compared Supplying the heart than the non-stoichiometric 32354721 201 222 809 ^ opposite end of the primary reaction. For example, in order to completely oxidize ruthenium oxide by CVD, the amount of oxygen (flow rate) of oxygen is also 2 G times or more of the molar amount (flow rate) of the hexamethylene hexahydrate. Therefore, it is preferred that the amount of oxygen (flow rate) of oxygen is less than 12 times the stoichiometric ratio of the molar content of the hexamethyl oxazepine of the raw material (more preferably 1 time) The carbon atoms and hydrogen atoms in the Sj borrowing & lysing gas containing hexa-f-octyl-oxygen and methyl-oxygen are taken into the protective film. As a result, the above conditions (1) can be completely satisfied. (111) U_° Thereby, the excellent barrier property of the obtained protective film and the amount of moles of gas (flow rate) relative to the hexamethyl group of the film forming gas can be exhibited ( When the flow rate is too small, carbon atoms and hydrogen atoms which are not oxidized are excessively taken into the protective film. At this time, the transparency of the protective film is lowered, and it is difficult to use the organic EL device and the organic thin film solar cell. The transparency is a flexible substrate for a necessary device. From this point of view, L is the amount of oxygen (flow rate) relative to the amount of ', thiol-7oxygen in the film forming gas. Preferably, the amount of 莫·1 times more than the hexamethylene oxides (flow rate) is more than 0. More preferably, it is more than 0. The pressure in the vacuum chamber (vacuum degree) may be appropriately adjusted depending on the type of the material gas, etc., but is preferably in the range of 〇·1 Pa to 5 〇 Pa. In this electric f CVD method' In order to discharge between the film forming rolls 31 and 32, the electric power applied to the electric shock drum connected to the plasma generating power source 51 (in the present embodiment, the film forming rolls 31 and 32) can be based on the type of the material gas. And the pressure in the vacuum chamber is appropriately adjusted, but it is preferably 〇323547 22 201222809: when the force is less than the above lower limit, there are many particles which are likely to be generated, and when the filming force exceeds the above upper limit, the film formation is performed. The generated heat is increased due to the heat on the surface of the heat. If the temperature rises excessively and the base melts, it is possible to produce a limb in the material. The film is lightly known by the heat film formation, and it is feared that the electricity (4) 1 generates a large current discharge. The transport speed (linear velocity) of the type and U thin may be appropriately adjusted depending on the pressure of the in-cavity of the material gas, etc., but preferably 〇.1 to

Phi & good is G·5 to 2Gm/min. When the linear velocity is less than the above-mentioned next one, the film tends to cause wrinkles due to heat, and if the linear velocity is too high, the thickness of the protective film formed at the upper limit tends to be thin. After the protective film is formed as described above, the second film can be bonded to the second film, which can be described later, and the first film can be wound into a roll shape together with the organic EL element and the protective film. It is carried out in a vacuum, in an inert gas atmosphere or in an atmospheric environment. The ease of the steps is preferably in the inert gas turbulence or in the atmospheric environment, more preferably in the atmosphere. Therefore, even if the step of the official is carried out in an inert gas atmosphere or in an atmospheric environment, the gas barrier property of the protective film wound up in a state of being reported is not easily lowered, and since the gas barrier property of the protective film is high, the organic film can be suppressed. Degradation of the EL element. An organic EL device in which a second film is provided on a protective film will be described with reference to Figs. 3 and 4 . Fig. 3 shows an example in which an organic EL element having a top emission type is provided as an example, and Fig. 4 shows a form in which an organic EL element having a bottom emission type is provided. Fig. 3 is a view schematically showing a cross section of the organic EL device of the present embodiment 23 323547 201222809. In the organic EL device 13 of the embodiment shown in Fig. 3, the organic EL element 2 is mounted on the first film 1, and a protective film 3 is formed to cover the organic EL element 2. The organic thin element 11 and the protective film 3 are interposed between the second thin film 11 and the second thin film, and are disposed on the jth thin film j. The second film 11 is post-sealed to the first film 1 and the organic EL element 2. The first film 1 and the second film 11 are bonded together via the adhesive layer 4 provided between them. The organic germanium element 2 of the present embodiment shown in Fig. 3 is a 70-piece of the top emission type, and emits light toward the second thin film 11. Therefore, the second film U must be formed by a member that transmits light. On the other hand, in the first embodiment, the i-th film i prepared for the substrate can be formed by an opaque member. For the first film 1, a plastic film or a metal film can be used. Preferably, the metal film and the metal film have a high resistance compared to a plastic film, etc., and the gas barrier property of the organic EL device. As the metal thin film, a thin plate of 歹'b〇1 or Fe and a thin plate of an alloy other than _# can be used. For the film 2, a film having a high gas barrier property can be suitably used. For example, in the present embodiment, the second film u is formed by placing the substrate 6 on the main surface of the substrate on the side of the organic EL element 2. , a gas barrier layer with a barrier property of rolling, a gas barrier layer, an organic layer which is alternately laminated, and a helmet machine; i: resistance::r, the film described above is the same as the film of the protective film 3, The gas barrier layer 5 is preferably a film. That is, the second film 11 is preferably formed from the substrate 321547 24 201222809 which has the same ease of manufacture and gas barrier properties as the protective layer, and has a specific substrate 6 and is formed as a gas barrier layer 5 on the substrate 6. And the same film as the above protective film. By sealing the organic EL element 2 with the first film 1 and the second film, it is possible to realize an organic device which is flexible and has sufficient durability and gas barrier properties. In particular, when the metal film is used for the i-th film i, both the i-th film and the second film π exhibit high gas barrier properties, so that an organic EL device having higher durability and gas barrier properties can be realized. Fig. 4 is a cross-sectional view schematically showing an organic EL device 13 according to another embodiment of the present invention. The organic germanium device 13 of the embodiment shown in Fig. 4 differs from the organic EL device and the i-th film (1) of the embodiment shown in Fig. 3. In other words, the organic EL element 2 of the present embodiment is a bottom emission type element that emits light toward the i-th film i corresponding to the support substrate. Therefore, the 1st / film 1 must be a film that exhibits light transmittance. The first film of this embodiment! The film which exhibits light transmittance is not particularly limited, but from the viewpoint of gas barrier properties, similarly to the second film u, it is preferable to have the second gas barrier layer 8 containing stone, oxygen and carbon. In the present embodiment, the first thin layer 1 is composed of a substrate 7 and a second gas barrier layer provided on the substrate 7. As described above, the second gas barrier layer 8 has a gas barrier property of 1% by satisfying the conditions (1) to (ill), and the step of suppressing the decrease in gas barrier properties during bending can be suppressed. By sealing the organic EL element 2 by the first film 1 and the second film, it is possible to realize an organic layer which is flexible and has both sufficient durability and gas barrier properties. The substrate of the first film or the second film described above may, for example, be a resin film or a resin sheet which is opaque to 323547 25 201222809. The resin used for such a substrate is, for example, a poly-branched resin such as polyethylene terephthalate (PET) and polyethylene naphthalate (PE); polyethylene (PE), polypropylene (PP) And a polysulfonated resin such as a cyclic polyolefin; a polyamide resin; a polycarbonate resin; a polystyrene resin; a polyvinyl alcohol resin; an alkali compound of an ethylene-vinyl acetate copolymer; A resin; an acetal resin; and a polyamidene resin. Among these resins, polyester resin and polyolefin resin are preferable, and PET and PEN are preferable from the viewpoints of high heat build-up, small linear expansion ratio, and low production. These resins may be used alone or in combination of two or more. The thickness of the substrate can be appropriately set, for example, in consideration of the stability at the time of producing the ruthenium film on the first film. The thickness of the substrate is preferably in the range of 5 to 5 Å/m from the viewpoint of transporting the film even in many cases. When the gas barrier layer is formed by the two plasma CVD methods, the protective film is formed by discharging the substrate of the i-th film, so that the thickness of the substrate of the second film is preferably more than 50 _, more preferably 50 to 1. 〇〇/zm. For the adhesion of the substrate 'from the protective film or to the gas barrier layer', it is preferred to carry out a surface active treatment for cleaning the surface. Such surface paint removal treatments include, for example, corona treatment, electropolymerization treatment, and flame treatment. Further, the first film and/or the second film may further include a bottom heat insulating resin layer and an adhesive layer. The undercoat layer can be formed using a primer which can be raised and adhered or adhered to the substrate. The heat-sealing resin layer can be formed by suitably using a heat-sealing resin. Adhesive Jianguang # can be formed by the use of a general adhesive, or by this kind of adhesive sword 26

3235^7 S 201222809 Adhesive layers of the first or second film are in contact with each other. In the organic EL device of the embodiment shown in Fig. 4, a ^ type organic EL device may be provided instead of the bottom emission type organic EL device. ^ In the embodiment shown in Figs. 3 and 4, an additional film may be further bonded to the film and/or the second film. The additional shots are, for example, a protective film that protects the surface of the organic EL device, an anti-reflection (four) film that prevents reflection of light outside the effect soap H, and a phase and polarizing film that enhances the light of the light:::: The optical thinness of the composition has a single layer of a plurality of thin layers or a second film selected from the above; = a film attached to the home (adhesive layer) is preferably a layer having a high resistance. The light emitted from the adhesive for the adhesive layer can be adhered; the light is visible from the organic EL element 2 as the adhesive layer 4; the organic device which is emitted toward the outside is followed by the adhesive layer 4^ = ^4, from the point of view of light extraction efficiency, the smaller is better. Absolute value of the difference in refractive index of the adhesive layer 4: For the adhesive: the adhesive of the layer is suitably a hardenable adhesive such as a thermosetting adhesive and a curable adhesive. Examples of the thermosetting resin adhesive include an epoxy adhesive, an acid ester adhesive, and the like. Ping 323547 27 201222809 Epoxy adhesives include, for example, F-type epoxy resins, benzophenone A-type epoxy resins, and double agents. The adhesion of the epoxy compound of the epoxy compound of (4) may, for example, be carried out by hydrazine, ethyl acrylate, butyl acrylate-methacryl: dilute nitrile and ___ A monomer-based adhesive that is copolymerized. _ w The photocurable adhesive may, for example, be a self-adhesive or the like. For example, the epoxy resin-based resin (for example, the method for producing an organic EL device) is described below with reference to Fig. 5, which is a schematic diagram showing the production of organic rainbow. In the apparatus shown in the figure of the apparatus, the first film 1 and the second film U are bonded together, and the additional film 820 is further bonded to the second thin (four). An organic EL element and a protective film are formed in advance on the i-th film i. The take-up roll 5GG feeds the second film u by taking out the first film roll 510 which is formed on the organic EL element riding film in advance. The adhesive film is applied to the first film 1 which is fed out of the light 500 by the application layer 610 for the first adhesive layer to form the first! Squatting on the floor. Thereafter, the i-th film i and the second film 11 that transports the light 513 323 547 28 201222809 are bonded to each other via the first adhesive layer by the first bonding roller 51 512, and are further used by the first adhesive layer. The curing device 611 hardens (cures) the first adhesive layer. On the second film 11, an adhesive is applied to the coating device 62 for the second adhesive layer provided on the downstream side of the curing device 611 to further form a second adhesive layer. Then, the second film 11 and the additional film 820 fed through the take-up roll 520 and supplied via the transfer roller 523 are bonded together via the second adhesive layer by the second bonding rolls 521 and 522, and further 2 The curing device 621 for the adhesive layer hardens (cures) the second adhesive layer. Thereafter, the formed organic EL device is taken up by a take-up roll 53. As the additional film, for example, the aforementioned film can be used. In the present embodiment, one sheet of the additional film is bonded, but two or more sheets may be bonded in sequence: force: When the film is bonded to three or more films, the order of bonding may be in the order of lamination of the organic device. And change it as appropriate. Before the organic thin element is sealed by the second film, the protection of the gas barrier property caused by the gas barrier property is preliminarily formed on the H, and (4) the feed material is thinned (4), and the money is fed by any driver. For example, it is possible to bond the second film to the ring W, or the atmosphere or the atmosphere in a vacuum medium, and more preferably, the device which is preferably an inert gas ring device does not record. There are (4) sets. (4) Simple steps to manufacture the organic EL device f 2 map and the fifth (four) show the solid surface. Once the first _ is taken, the storage of the film with the first film 4, the organic EL element and the layer of the film is not limited to this. In addition, a protective film can also be formed. 323547 29 201222809 The second film is continuously bonded directly. The organic EL element is protected by a protective film which is excellent in gas barrier properties and can suppress a decrease in gas barrier properties due to bending. Therefore, the roll of the laminated body which is wound up can be stored in an arbitrary environment. For example, the laminate may be stored in a vacuum, in an inert gas atmosphere, or in an atmospheric environment. Among them, it is preferable to store the layered body containing the first film in an inert gas atmosphere or in an atmosphere, and it is more preferable to store the layered body in an atmosphere. The storage device is not complicated, and the laminate can be easily stored. (Organic EL Element) Next, the configuration of the organic EL element will be described. The organic EL device is formed on the first film before the step of bonding the first film and the second film. The organic EL element is composed of an electrode composed of an anode and a cathode, and a light-emitting layer provided between the electrodes. In addition to the luminescent layer between the electrodes of a pair, a specific layer is provided as necessary. The light-emitting layer is sometimes not limited to one layer but is provided with a plurality of layers. The layer provided between the cathode and the light-emitting layer may, for example, be an electron injecting layer, an electron transporting layer, a hole blocking layer or the like. When a layer of both the electron injecting layer and the electron transporting layer is provided between the cathode and the light emitting layer, the layer connected to the cathode is referred to as an electron injecting layer, and the layer excluding the electron injecting layer is referred to as an electron transporting layer. The electron injecting layer has a function of improving the efficiency of electron injection from the cathode. The electron transport layer has a function of improving electron injection from a layer connecting the cathode side surfaces. The hole barrier layer has the function of blocking the transport of holes. When the electron injecting layer and/or the electron transporting layer have a function of blocking the transport of holes, these layers also serve as a hole blocking layer. 30 323547 201222809 The hole barrier layer has a component that blocks the flow of the work of the hole (Haii) current, which can be reduced according to the current value. For example, the layer provided between the anode and the light-emitting layer can be, for example, a hole ς In: There is == electronic barrier layer. When a layer of both electrical and electrical electrical reading layers is disposed between the anode and the light-emitting layer, the anode is connected to the anode: a hole injection layer, and the layer other than the hole injection layer is called a hole-transporting hole. The in-layer system has the ability to improve the efficiency of hole injection from the anode. The hole transport layer has a function of improving hole injection from a layer connected to the anode side surface. The electric barrier layer has the function of blocking electron transport. When the hole injection layer and/or the hole transport layer have the function of blocking electron transfer, the layers also serve as an electron blocking layer. The electron blocking layer has a function of blocking electron transport, for example, a member s which produces only an electron current flowing, which can be confirmed by a decrease in the current value thereof. Sometimes the electron injection layer and the hole injection layer are collectively referred to as a charge injection layer, and sometimes the electron transport layer and the hole transport layer are charge transport layers. An example of the layer constitution of the organic EL device of the present embodiment can be obtained. a) anode/light-emitting layer/cathode b) anode/hole injection layer/light-emitting layer/cathode c) anode/hole injection layer/light-emitting layer/electron injection layer/cathode d) anode/hole injection layer/light-emitting layer/ Electron transport layer / cathode e) Anode / hole injection layer / luminescent layer / electron transport layer / electron injection layer / cathode 323547 31 201222809 f) anode / hole transport layer / luminescent layer / cathode g) anode / hole transport layer / luminescent layer / electron injection layer / cathode h) anode / hole transport layer / luminescent layer / electron transport layer / cathode 1) anode / hole transport layer / luminescent layer / electron transport layer / electron injection layer / cathode j) anode / hole injection layer / hole transport layer / light-emitting layer / cathode k) anode / hole injection layer / hole transport layer / light-emitting layer / electron injection layer / cathode l) anode / hole injection layer / hole transport layer / luminescent layer / electron transport layer / cathode m) anode / hole injection layer / hole transport layer / luminescent layer / electron transport layer / electron injection layer / cathode a η) anode / luminescent layer / electron injection layer / cathode 〇) !% pole / luminescent layer / electron transport layer / cathode / cathode 2 layers of adjacent Ρ) anode / luminescent layer / electron transport layer / electron injection layer (here The mark "/" indicates that the mark "/" is used to laminate the mark. The same applies to the following.) The organic EL element of === may have two or more light-emitting layers. Any one of the layer configurations of the above a) to p) is assumed to be "structural unit A" _ hair = for example, the following. The layer shown = the same as 7 (a) secret village, can also be phase Q) anode / (construction single) / charge generation layer / (structural unit A) / cathode 323547 32 201222809 The structure of the organic EL element having three or more light-emitting layers when the charge-generating layer is referred to as "structural unit B" is, for example, a layer configuration as shown in the following r). The symbol "X" indicates an integer of 2 or more, and (structural unit Β) indicates a layer body composed of a structural unit of the layer -x segment. The layer constitutions having a plurality of (structural unit 亦可) may be the same or different. The so-called charge generating layer generates a layer of holes and electrons by applying an electric field. The charge generating layer may, for example, be a film containing cerium oxide, indium tin oxide (ITO), IT_ Tin Oxide (ITO0), and molybdenum oxide. The order of the layers, the number of layers, and the thickness of each layer may be considered to be luminous efficiency. In the following, the material and the formation method of each layer constituting the organic EL element are described in more detail. <Anode> When the light emitted from the light-emitting layer is emitted through the anode and emitted to the external organic EL element An electrode for exhibiting light transmittance can be used for the anode, and a film of metal oxide, metal sulfide, or metal can be used as the electrode for exhibiting light transmittance, and an electrode having high conductivity and light transmittance is suitable. In other words, a film composed of indium oxide, zinc oxide, tin oxide, antimony 0, indium zinc oxide (Indium Zinc Oxide: ΙΖ0), gold, platinum, silver, or copper may be used. a film made of ΙΤ0, ΙΖ0, or tin oxide. Examples of the method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, etc. Polyaniline or a polyaniline may be used as the anode. A derivative, and an organic transparent conductive film such as polythiophene or a derivative thereof, etc. 323547 33 201222809 The film thickness of the anode is appropriately set as required for the characteristics and the ease of the steps, for example, 1 Onm to 10 # m ' is preferable. 20 nm to 1 &quot; m, preferably 50 nm to 500 nm. <Pore injection layer> The hole injection material constituting the hole injection layer may, for example, be an oxide such as yttrium oxide, molybdenum oxide, yttrium oxide or aluminum oxide. a phenylamine compound, a startburst amine burst, a phthalocyanine system, an amorphous carbon, a polyaniline, a polythiophene derivative, etc. The film forming method of the layer may be, for example, a film formation of a solution containing a hole injecting material. For example, a solution containing a hole injecting material is applied to a film by a specific coating method, and further cured by a curing method. The film-forming solution is formed into a hole injection layer. The solvent used for film formation from the solution is not particularly limited as long as it can dissolve the hole injection material, and examples thereof include gas-mold, di-methane, and second gas. Ethyl chloride solvent; ether solvent such as tetrahydrofuran; aromatic (iv) solvent such as toluene and diphenylbenzene; solvent such as acetone and methyl ethyl ketone; acetonitrile acetate such as butyl hydrazine and ethyl acetate Ethyl cel losolve acetate), such as an ester solvent, water, etc. The coating method may, for example, be a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, or a roll coating method. , bar coating method, dip coating method, nozzle coating method, screen printing method, flexographic printing method, offset printing method, inkjet printing method, etc. The thickness of the hole/main entrance layer is considered. The characteristics and the ease of the steps are appropriately set by 323547 34 201222809, etc., for example, 1 nm to 1 #m, preferably 2 nm to 500 // m, more preferably 5 nm to 200 nm. <Cell Transport Layer> The hole transport material constituting the hole transport layer may, for example, be a polyvinyl-based or a derivative thereof, a polysilane or a derivative thereof, or have a side chain or a main chain. a polysiloxane, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, or a polyphenylene oxide derivative, Polyaniline or its derivative, poly. Cephene or a derivative thereof, a polyarylamine or a derivative thereof, a polypyrrole or a derivative thereof, a poly(P-phenylenevinylene) or a Biological, or poly(2,5-thienylene vinylene) or a derivative thereof. The medium-transporting material is preferably polyvinyl carbazole or a derivative thereof, poly-Wei or a derivative thereof, an aromatic amine in a side chain or a main chain, and a stone oxide reduction material and a woven material. a polymer such as a contact substance, (tetra) phenanthrene or a derivative thereof, a base amine or a derivative thereof, a poly(p-stabilized vinyl group) or a derivative thereof, and a poly(2'5-(tetra) phenyl group) Hole feeding material. Better hole transport Raw s Μ W W 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其The low-molecular hole has the molecular bond of the aromatic amine. (4) Materials (4) Good film-dispersing method for dispersing in the high-porosity transport layer. For example, there is no special hole-wheeling material, for example, _ 'low-powered sub-adhesive agent and hole 323547 35 201222809 The film formation of the mixed material of the material is formed by a solution of a polymer hole transporting material, for example, a solution containing a hole transporting material. The solvent to be used for film formation from a solution is not particularly limited as long as it can dissolve the hole transporter, and examples thereof include a gas solvent such as chloroform, dioxane and di-ethane, and a solvent such as tetrahydrofuran; Aromatic hydrocarbon-based solvents such as benzene and hydrazine; ketone-based solvents such as propyl ketone and methyl ethyl ketone; and ester solvents such as butyl acetate and ethyl acetate. 9. A method of forming a film by a solution, for example, a coating method similar to the method of the above-described hole injection layer. The polymer binder combined with the hole transporting material is preferably incapable of hindering charge transport or weak absorption of visible light. The polymer binder is derived from, for example, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polystyrene, and polyoxyalkylene. The thickness of the hole transport layer varies depending on the material to be used, and is appropriately set to an appropriate value in accordance with the driving voltage and the luminous efficiency. The hole transport film system must have at least a thickness that does not cause pin holes, and if it is too thick, the driving voltage of the device becomes high. Therefore, the thickness of the hole transport layer is, for example, 1 nm to 1 β m', preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm. <Light-emitting layer> The light-emitting layer is generally formed mainly of an organic substance (light-emitting material) that emits glory and/or light, or an organic substance and a dopant that assists the same. The inclusions are added, for example, to increase the luminescence rate or to change the luminescence wavelength. The organic substance in the light-emitting layer 3 may be a low molecular compound or a high molecular compound. Generally, a polymer compound having a low solubility in a solvent and a high molecular weight is suitable for use in the coating method, so the light-emitting layer is preferably high. Molecular compound. The light-emitting layer is preferably a polymer compound having a number average molecular weight of from 1 to 3 to 1 inclusive of polystyrene. Examples of the light-emitting material constituting the light-emitting layer include the following pigment-based materials, metal-based compound materials, polymer-based materials, and dopant materials. (Pigmentary Material) The dye-based material may, for example, be a derivative of Cyclafamine, a tetraphenylbutadiene derivative compound, a diphenylamine derivative, or a xylophone. An oxadiaz〇ie derivative, a pyrazoloquinoline derivative, a distyrylbenzene derivative, a di(styryl)distyrylarylene derivative, Pyrrole (pyrr〇ie) derivative, thiophene ring compound, pyridine ring derivative, perin〇ne bamboo organism, perylene bamboo organism, 嗟Hg〇thi〇phene a derivative, an oxadiazole dimer, a pyrazoline dimer, a quinacraidone derivative, a cumin derivative, or the like. (Metal complex material) The metal complex material is, for example, a rare earth metal such as Tb, Eu or Dy, or a central metal selected from Al, Zn, Be, Ir, Pt or the like, and oxadiazole and ruthenium. A metal complex of a selected ligand such as thiadiazole, phenyl acridine, phenyl benzimidazole, and quinoline structure. The metal complex-based material may, for example, be a metal complex having a luminescence excited by a triplet state, such as a silver complex or a complex compound, an aluminum quinolinol complex, and cumene quinolol.铍 合 323 547 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 ° ^Non-rotop (polymer material), == can be, for example, poly(p-phenylene)-derived p乙lyacetylene street organism, poly-glycosyl-wow derivative # μ W (P〇lynU〇rene) Derivatives of luminescence (4) Polymerization (4) or metal mismatched dilute base ^^'^^ material shot her beta phenyl hydrazine bio phenyl heart This: two: raw: phenylene = two: =: poly card derivative, poly hair green mosquito material can be mentioned, for example, (four) pin organisms, and such polymers, poly (sugar derivatives and poly derivatives). Its _ vinyl) (Voice, Shin-Bei) Touching Molecular Materials For the materials of the stupid base = color light, for example, the polymer plugging and stimuli derivatives of the polymer, and the polythene extensions Derivatives, poly: poly (p-phenylene extension. base):: polymer materials and so on. Bio-(4) 义何生物和聚代衍 The white light material can also be the above-mentioned blue, green or red hair 323547 38 201222809, or can be mixed to form a material of various colors of light.

A component that emits white light. (Dop material) Mixture of materials of various colors of light (monomer) 'This ruthene derivative derivative material can be, for example, money organism, coumarin derivative, Hongrong , anthrone derivatives, squaric acid rust, porphyrin derivatives, styrene pigments, tetracene imitation organisms, py pyridones (pyraz〇i〇ne) derivatives, decacyclic ( Decacyclene) derivatives, and phenex xaz〇ne derivatives. The thickness of the luminescent layer is generally from about 2 nm to about 2 Å. <Method of Forming Light Emitting Layer> The film forming method of the light emitting layer is a method of applying a solution containing a light emitting material, a vacuum deposition method, a transfer method, or the like. The solvent to be used for film formation from the solution may, for example, be the same solvent as the solvent used for forming the hole injection layer from the solution. Examples of the method of applying the solution containing the luminescent material include a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a stick honey method, a roll coating method, a wire bar coating method, and a dipping coating method. Coating methods such as a method, a slit coating method, a capillary coating method, a spray coating method, and a nozzle coating method, and a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, and a reverse printing method And printing methods such as inkjet printing. In terms of pattern formation and ease of coloring of a plurality of colors, printing methods such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an inkjet printing method are preferred. When the sublimation property of 39 323547 201222809 is shown as a low molecular compound, vacuum evaporation can be used. A method of forming a light-emitting layer only for a desired portion can also be used by laser-transfer or thermal transfer. <Electron transport layer> The electron transport material constituting the electron transport layer can be a commonly used material, for example, an oxadiazole derivative, anthraquinone dimethane or a derivative thereof, and benzene brewing i ( Benzoquinone) or a derivative thereof, naphthoquinone or a derivative thereof, anthraquinone or a derivative thereof, tetracyanoanthraquinone dimethane or a derivative thereof, a fluorenone derivative , diphenyl dicyanoethylene or a derivative thereof, a diphenoquinone derivative, or a metal complex of 8-hydroxyquinoline or a derivative thereof, Or a derivative thereof, polyquinoxaline or a derivative thereof, polyg or a derivative thereof, or the like. Among these, the electron transporting material is preferably an oxadiazole derivative, a benzene styrene or a derivative thereof, hydrazine or a derivative thereof, or a metal complex of 8-hydroxyquinoline or a derivative thereof, polyquinoline. Or a derivative thereof, polyquinoxaline or a derivative thereof, and polydi or a derivative thereof, more preferably 2_(4-biphenylt-butylphenyl)-1,3,4-anthracene Oxazole, benzoquinone, anthracene, tris(8-quinolinol) aluminum, and polyquinoline. The film formation method of the electron transport layer is not particularly limited. When it is a low-molecular electron transporting material, for example, a vacuum vapor deposition method of a powder, or a film formation in a molten liquid or a molten state, when it is a polymer electron transporting material, the life can be = 323547 40 201222809 For example, from a solution Or film formation in a fused state. When a film is formed from a solution or a molten state, a polymer binder may be used in combination. The method of forming the electron transporting layer from the solution is, for example, a film forming method similar to the method of forming a hole in the hole injection layer from the solution. The thickness of the electron transporting layer is different depending on the optimum value of the material to be used, and it is preferable to set a value such that the driving voltage and the luminous efficiency are moderate. The electron transport layer must have at least a thickness that does not cause pinholes, and if it is too thick, the driving voltage of the components becomes high. Therefore, the thickness of the electron transporting layer is, for example, from 1 nm to 1 // m ', preferably from 2 nm to 500 nm, more preferably from 5 nm to 200 nm. <Electron Injection Layer> The material constituting the electron injection layer is appropriately selected depending on the kind of the light-emitting layer. The material constituting the electron injecting layer may, for example, be an alloy containing a metal of a metal test group, a metal containing one or more types selected from a metal and a test group metal, an oxide of an alkali metal or an alkaline earth metal, a halide, or a carbonic acid. a compound, a mixture of such substances, and the like. Examples of the alkali metal, the metal oxide, the compound, and the carbonate include, for example, a clock, a sodium, a potassium, an H oxidation clock, a fluorination clock, a sodium oxide, a sodium fluoride: potassium, cerium oxide, and fluorination- , cerium oxide, gasification planer, oxide of carbonated metal, self-oxidation, turtle: strontium, barium, magnesium oxide, magnesium fluoride, acid town, etc. == lock, _, oxidation recording side, and carbon formation, and the electron injection may be a laminate of two or more layers, and may be, for example, LiF/Ga. E-notes 2. Recording, _ method or printing method. The electron injection layer 323547 41 201222809 film thickness should be about 1 nm to the left and right. <Cathode> The material of the cathode is preferably a material having a small work function and electrons which are easily injected into the light-emitting layer and have high conductivity. The organic EL element having light-removed light from the anode side is such that the light emitted from the light-emitting layer is reflected toward the anode side at the cathode, and the material of the cathode is preferably a material having a high conductivity. The material of the cathode can be used, for example, metals such as metals, soils of the soil tester, transition metals, and metals of the third group of the periodic table, such as fun, sodium, potassium, cesium, cesium, strontium, samarium, Metals such as Shao, Zhu, Rui, Ci, Ji, Marriage, Yi, Peng, Pin, Qian, Qi, and other alloys containing two or more metals selected from the above, and more than one or more selected from the metal and gold, silver , overturned, copper, fierce, chin, ming, nickel, niobium and tin selected more than one type of alloy, or graphite or graphite intercalation compounds. Examples of the alloy include, for example, a town-silver alloy, a town-in-law alloy, a bismuth alloy, an indium-silver alloy, a lithium-aluminum alloy, a lithium-magnesium alloy, a lithium-indium alloy, and a bismuth-salt alloy. As the cathode, a transparent conductive electrode made of a conductive metal oxide, a conductive material, or the like can be used. Specific examples of the conductive metal oxide include indium oxide, oxidized sugar, tin oxide, (10), and (10). Examples of the conductive organic substance include polyaniline or a derivative thereof, a polystimene or a derivative. The cathode may also be formed by laminating two or more layers. Sometimes an electron injection layer can also be used as the cathode. The thickness of the cathode is determined by considering the characteristics and the ease of the steps, and the like: for example, 1 〇 nm to 10 Å, preferably 2 〇 nm to _, and most preferably 50 nm leather 500 nm. The method for producing the cathode can be, for example, a vacuum distillation method, a lining method, and a lamination method of a hot-pressed metal film of 323547 42 201222809. The above organic EL device can be used as a lighting device, a surface light source device, or a display device by adding a specific constituent element. (Example) (Reference Example A1) Using the manufacturing apparatus shown in Fig. 2, a protective crucible was directly formed on a substrate on which an organic germanium element was not formed. That is, using a biaxially stretched film of polyacetate ethyl vinegar (PEN thin, thickness: 1 inch in m, width: 35 inches, manufactured by Teijin DuPont Film Co., Ltd., trade name "Teonex Q65FA") The material is placed on the transfer roller 7Q, and then a magnetic field is applied between the film formation roller 31 and the film formation roller 32, and the electric power is supplied to the film formation roller 31 and the film formation roller 32, respectively. The rollers 32 are discharged to generate plasma. By supplying a service body (hexamethyldiazepine oxygenOmDSO as a material gas) and a gas mixture (as a function of a discharge gas) in the discharge region formed by the following conditions, by the following conditions The plasma CVD method performs film formation to form a protective film on a substrate. <Film formation conditions> Supply amount of raw material gas: 50 seem (zero degree, converted to lapm

Standard Cubic Centimeter per Minute, the same as below) Oxygen supply: 500 seem Vacuum in vacuum chamber: 3Pa Applied power from plasma generation power supply: 0. 8Kw Frequency of self-generating power supply: 70 kHz Film transport Speed: 〇.5m / min 43 323547 201222809 The thickness of the smear film formed on the substrate is 〇.3em. l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l (m2 · day), which is a value below the detection limit in a condition of a temperature of 40 ° C, a humidity on a low humidity side, and a humidity of 100% RH on a high humidity side. Further, the water vapor opacity under the condition that the substrate is bent with the protective film at a temperature of 40 ° C, the humidity at the low humidity side is 10% RH, and the humidity at the high humidity side is less than the detection limit, with a radius of curvature of 8 mm. The value is such that even if the protective film is bent, the reduction in gas barrier properties can be sufficiently suppressed. Regarding the protective film on the substrate, the xps depth rim measurement, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve were measured under the following conditions. Etching ion species: argon (Ar+) etching rate (si〇2 thermal oxide film conversion value): 〇〇5nm/sec etching interval (Si〇2 conversion value): i〇nm X-ray photoelectron spectroscopy device: The coffee Fisher Scientific company Model name "VG Theta Probe" Irradiation X-ray. Early crystal spectroscopy A1 κ α X-ray focus and its size: 800 j uu&gt;&lt;4〇〇/zm ellipse will get the 矽 distribution curve, gas eight + The latex cloth curve and the carbon distribution curve are shown in Fig. 6, respectively. Regarding the obtained 少 distribution curve, oxygen distribution curve and carbon distribution curve, the relationship between the atomic ratio (brow 2 *, the concentration of the item) and the etching time, and the atomic ratio (atomic concentration) and the separation (four) (f) t 323547 44 201222809

The relationship is shown in the R chart in Figure 7. π #β" described on the horizontal axis of the graph of Fig. 7 is a value obtained by calculation from the etching time and the etching rate. From Fig. 6 and the seventh solid a _ , the results shown in the figure clearly confirm that the obtained carbon = a plurality of distinct extreme values, and the difference between the maximum value and the minimum value of the carbon atom ratio is 5 at% to μ, ^ ^ ^ ^ Upper 'and the 90°/〇 above the thickness direction of the protective film, the sand shield. /1N ratio, the atomic ratio of oxygen and the atomic ratio of carbon satisfy the conditions shown in the formula (1) . (Reference Example A2) It is preferable that the protective film of the thickness G. 3#m obtained in Reference Example A1 is sent to (4) 701, and a new right ridge or spear is formed on the surface of the protective film. This is the same as the reference example Α1. Thus, a substrate (A) forming a film is obtained. The substrate of the substrate (A) having the protective film formed thereon (the thickness of the protective film of the film is 〇. 1. The substrate (A) having the protective film formed thereon is attached to the delivery roller 701, and formed on the surface of the protective film. A new protective film was obtained in the same manner as in Reference Example A1, and a substrate (8) having a protective film was formed. The thickness of the protective film of the substrate on which the protective film substrate (B) was formed was 〇. 9 fm The water vapor permeability of the substrate (B) forming the protective crucible is 6.9xl 〇 -4 g / (m2) in the condition of temperature 40 C, humidity on the low humidity side (10) RH, and humidity on the high humidity side 90% RH. • Day), which is the value below the detection limit in the condition of temperature 4 (rc, humidity 10% RH on the low humidity side, and humidity 1〇〇% RH on the high humidity side. Further, the base is made with a radius of curvature of 8 mm. The temperature after the material is bent together with the protective film 40 Ϊ, the humidity on the low humidity side is 10% RH, and the humidity on the high humidity side is 100% RH. The water vapor permeability is below the detection limit 323547 45 201222809 value 'confirm even bending protection In the case of a film, the gas barrier property can be sufficiently suppressed. For the substrate (B) on which the protective film is formed, the enthalpy is divided. The curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen-carbon distribution curve were produced in the same manner as in the method of Reference Example A1, and the obtained results are shown in Fig. 8. Regarding the enthalpy distribution curve, the oxygen distribution curve, and the carbon distribution Curve and oxycarbon distribution curve, the relationship between the combined atomic ratio (atomic concentration) and #刻时间, and the relationship between the atomic ratio (atomic concentration) and the distance from the surface of the protective film (nm) are shown in the graph of Fig. 9. The "distance (nm)" described on the horizontal axis of the graph of Fig. 9 is a value calculated from the etching time and the etching rate. The carbon distribution curve is clearly confirmed from the results shown in Figs. 8 and 9. Having a plurality of distinct extreme values, the difference between the maximum and minimum values of the carbon atom ratio is 5 at% or more, and in the region of more than 90% of the thickness direction of the protective film, the atomic ratio of bismuth, the atomic ratio of oxygen, and carbon The atomic ratio of the above formula (1) is satisfied. (Reference Example A3) A substrate having a protective film was obtained in the same manner as in Reference Example A1 except that the supply amount of the material gas was l〇〇SCCH1. Substrate The thickness of the protective enamel is 0.6. The water vapor permeability of the substrate on which the protective film is formed is at a temperature of 4 〇 (:, humidity on the low humidity side is 0% RH, and humidity on the humidity side is 90% RH). 3. 2xl0_4g/(m2 · day), in the condition of temperature 40 ° C, humidity of 1低% rh on the low humidity side, humidity 100% RH on the high humidity side, the value below the detection limit. The condition of 8 mm makes the substrate and the protective film bend together at a temperature of 4 〇. (:, humidity on the low humidity side is 10% RH, humidity on the high humidity side is 100% RH conditions 46 323547 201222809 Water vapor permeability is detected When the protective film is bent, it is confirmed that the decrease in gas barrier properties can be sufficiently suppressed even when the protective film is bent. With respect to the protective film formed on the substrate, the Shishi distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen-carbon distribution curve were produced in the same manner as in the method of Reference Example A1. The obtained enthalpy distribution curve, oxygen distribution curve and carbon distribution curve are shown in Fig. 10. The relationship between the atomic ratio (atomic concentration) and the etching time, and the atomic ratio (atomic concentration) and the distance from the surface of the protective film (nm) The relationship is shown in the chart of the figure. The "distance (nm)" described on the horizontal axis of the graph of the first diagram is a value obtained by calculating the etching time and the etching speed. It is clearly confirmed from the results shown in Figs. 10 and 11 that the obtained carbon distribution curve has a plurality of distinct extreme values, and the difference between the maximum value and the minimum value of the carbon atom ratio is 5 at% or more, and in the protective film. In the region of 90% or more in the thickness direction, the atomic ratio of ruthenium, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the conditions shown in the formula (1). (Reference Example 1) On the surface of a biaxially stretched polyethylene naphthalate film (ΡΕΝ film, thickness · 10 〇 em, width: 350 mm, manufactured by Teijin DuPont Film Co., Ltd., trade name "Teonex Q65FA") Using a ruthenium target, a protective film made of ruthenium oxide was formed by a reactive sputtering method in an oxygen-containing environment to obtain a substrate having a protective film to be compared. The thickness of the protective film on the substrate was 1 〇〇 #m. Further, the water vapor permeability of the substrate on which the protective film is formed is 1 in the condition of temperature 4 (rc, humidity on the low humidity side 1 〇 0 / 〇 47 323547 201222809 RH, humidity on both humidity sides 1 〇〇 % 仙) 3 g / (m2 • day), the gas barrier property is insufficient. Regarding the substrate on which the protective film is formed, the enthalpy distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen-carbon distribution curve are obtained by the method of Reference Example A1. The same method is used to prepare the obtained cloth curve, oxygen distribution curve and carbon distribution curve in Fig. 12. Regarding the obtained enthalpy distribution curve, oxygen distribution curve, carbon distribution curve and oxygen-carbon distribution curve, merge atoms The relationship between the ratio (atomic concentration) and the time of the last name, and the relationship between the atomic ratio (atomic concentration) and the distance (nm) from the surface of the protective film are shown in the graph of Fig. 13. The horizontal axis of the graph of Fig. 13 "Distance (nm)" is a value obtained by calculating the etching time and the etching rate. It is clearly confirmed from the results shown in Fig. 12 and Fig. 13 that the obtained carbon distribution curve does not have an extreme value. Availability) ^ as explained above The ruthenium film used in the organic EL element card of the present invention has sufficient gas barrier properties, and can sufficiently suppress the decrease in gas barrier properties even when it is bent. [Schematic Description] Fig. 1 shows an implementation Fig. 2 is a cross-sectional view showing an organic EL device according to an embodiment of the present invention. Fig. 4 is a cross-sectional view showing an organic EL device according to an embodiment. Fig. 5 is a conceptual view showing an embodiment of an apparatus for manufacturing an organic EL device. 48 323547 201222809 Fig. 6 shows the 矽 distribution of the protective film obtained in Reference Example A1. A graph of a curve, an oxygen distribution curve, and a carbon distribution curve. Fig. 7 is a graph showing a enthalpy distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen-carbon distribution curve of the protective film obtained in Reference Example A1. A graph showing the enthalpy distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen-carbon distribution curve of the protective film obtained in Reference Example A2. Fig. 9 is a view showing the protective film obtained in Reference Example A2. A graph of the enthalpy distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen-carbon distribution curve. Fig. 10 is a graph showing the enthalpy distribution curve, the oxygen distribution curve, and the carbon distribution curve of the protective film obtained in Reference Example A3. The graph shows the enthalpy distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen-carbon distribution curve of the protective film obtained in Reference Example A3. Fig. 12 shows the 矽 distribution of the protective film obtained in Reference Comparative Example A1. A graph of a curve, an oxygen distribution curve, and a carbon distribution curve. Fig. 13 is a graph showing a enthalpy distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen-carbon distribution curve of the protective film obtained in Reference Comparative Example A1. DESCRIPTION OF SYMBOLS 1 First film 2 Organic EL element 3 Protective film 4 Adhesive layer 5 Gas barrier layer 6 Substrate of second film 49 323547 201222809 7 8 11 13 2 Bu 22, 23, 24 31 ' 32 41 51 61 ' 62 500, 510, 520, 51, 512, 513, 523, 521, 522, 530, 610, 620, 611, 621, 701, 702, 820, substrate of the first film, second gas barrier layer, second film, organic EL device, transport roller, a pair of film forming roller gases for Feed tube Plasma generating power source Magnetic field generating device Roll-out roll 1st bonding roll Transfer roll 2nd bonding roll Take-up roll Coating device Hardening device Feed roller Take-up roll Additive film 50 323547

Claims (1)

201222809 VII. Patent application range: 1. An organic EL device comprising: a first film, an organic EL element provided on the first film, and a surface covering a surface opposite to the first film of the organic EL element; The protective film contains a crushed atom, an oxygen atom, and a carbon atom, and represents a ratio of the ratio of the number of atoms of the atomic atom to the total amount of the atomic atom, the oxygen atom, and the carbon atom, the ratio of the number of oxygen atoms, and the ratio of the number of carbon atoms. The enthalpy distribution curve, the oxygen distribution curve, and the carbon distribution curve in relation to the distance from the surface on one side of the protective film in the thickness direction of the protective film satisfy the following conditions: (i) in the thickness direction of the protective film In more than 90% of the regions, among the ratio of the number of dream atoms, the ratio of the number of oxygen atoms, and the ratio of the number of carbon atoms, the ratio of the number of germanium atoms is the second largest value; (ii) the aforementioned carbon distribution curve has at least one pole. And (iii) the difference between the maximum value and the minimum value of the ratio of the number of carbon atoms in the carbon distribution curve is 5 atom% or more. 2. The organic EL device according to the first aspect of the invention, wherein the organic EL device further includes: facing the first thin film, and sealing the second organic EL device together with the first thin film In the film, the organic 1 323 547 201222809 EL element and the protective ruthenium are disposed between the second film and the first film. 3. A method for manufacturing an organic armor 窨 + a., comprising: a step of forming an organic EL element on the first film, and forming a ^ ^ ^ into an organic EL element; The step of holding the film on the opposite side of the first film of the organic germanium element is described as a protective film. , i 胥矽 atom, oxygen atom and carbon atom, ^ represents the ratio of the number of the atomic atoms of the four atoms to the atomic, 氡 atom and carbon atom (four), the ratio of the number of oxygen atoms and the number of carbon atoms, and The enthalpy distribution curve, the oxygen distribution curve, and the broken distribution curve of the relationship between the distances of the surfaces on the side of the protective film in the thickness direction of the shaft retention satisfy the following conditions: (i) go% in the thickness direction of the protective film In the above region, among the ratio of the number of dream atoms, the ratio of the number of oxygen atoms, and the ratio of the number of broken atoms, the ratio of the number of germanium atoms is the second largest value; (ii) the carbon distribution curve has at least one pole. And (iii) the difference between the maximum value and the minimum value of the ratio of the number of carbon atoms in the carbon distribution curve is 5 atom% or more. 4. The method according to claim 3, further comprising: after the step of forming the protective film, the organic EL element and the protection are disposed between the second film and the first film The step of bonding the second film to the first film as a film. 5. The method of claim 4, wherein the second film is bonded to the first film in an air atmosphere. 2 323547 201222809 6. The claim of claim 3, 5, further includes: forming the above-mentioned protection = method 'the film and the above-mentioned secret element and the above =, the first one of the above-mentioned storage _, the above-mentioned organic and the step of protecting the film, β π, and the method according to the sixth aspect of the invention, wherein the ith film is protected by the underlying storage. Organic EL element and the first embodiment A lighting device having the organic ELM as described in the above aspect. Regarding the first or second light source device, the money has the organic EL device as described in Patent Item 2. Item 10. The display device of claim 10, which has the organic EL device as described in the patent application. Or 2,323,547 3