JP4787094B2 - Method for manufacturing light emitting device - Google Patents

Description

    The present invention relates to a method for manufacturing an electroluminescence light-emitting device (electroluminescence light-emitting device, hereinafter sometimes abbreviated as “light-emitting device”) used for a planar light source or a display element.

    In the electroluminescence light emitting device, the light emitting layer is made of an organic compound or the like. Attention has been drawn to the fact that a large-area display element can be realized by low-voltage driving.

Tang et al. Proposed a structure in which organic compounds having different carrier transport properties are stacked and holes and electrons are injected in a balanced manner from the anode electrode layer and the cathode electrode layer, respectively, in order to increase the efficiency of the device. Then, the film thickness of the organic layer was set to 200 nm or less, and an emission luminance of 1000 cd / m ² and an external quantum efficiency of 1% were realized with an applied voltage of 10 V or less (for example, Non-Patent Document 1).

    In developing such a high-efficiency element, a technique for injecting electrons from the cathode electrode layer and holes from the anode electrode layer into the organic layer without an energy barrier is recognized as an important element.

    In Kido et al., The hole injection layer is formed of a mixed film of a metal oxide and an organic compound. This lowers the drive voltage of the device and adjusts the thickness of the hole injection layer to greatly reduce the risk of electrical shorting between the cathode electrode layer and the anode electrode layer without increasing the drive voltage. (Patent Document 1).

However, the above configuration has a problem that the luminance half-life is shortened (Patent Document 2). Therefore, an object of the present invention is to improve the reliability of a light emitting device having a mixed layer of a metal oxide and an organic compound without reducing productivity.
Appl. Phys. Lett. 51, 913 (1987). JP 2005-123095 A Japanese Patent Laid-Open No. 2005-166641 JP 2000-68068 A Japanese Patent Laid-Open No. 11-8065

In the present invention, after forming a mixed layer containing an organic compound and a metal oxide, the mixed layer is exposed to a nitrogen (N ₂ ) gas atmosphere without being exposed to an oxygen-containing gas atmosphere, and then to an oxygen-containing gas atmosphere. The above-mentioned problem is solved by forming a subsequent laminated film in vacuum or under reduced pressure without exposure. Here, the gas atmosphere containing oxygen refers to a gas atmosphere containing oxygen atoms such as oxygen gas, NO ₂ gas, N ₂ O gas, and the like. By exposing the mixed layer containing the organic compound and the metal oxide to a nitrogen gas atmosphere after forming, the film quality is improved and the reliability is improved without reducing the productivity.

    In the present invention, an anode is formed, a mixed layer having an organic compound and a metal oxide is formed on the anode, the mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then the mixed A hole transport layer is formed without exposing the layer to a gas atmosphere containing oxygen, a light emitting layer is formed on the hole transport layer, and a cathode is formed on the light emitting layer.

    According to the present invention, an anode is formed, a first mixed layer having an organic compound and a metal oxide is formed on the anode, and the first mixed layer is not exposed to a gas atmosphere containing oxygen, and a nitrogen gas is formed. A second mixed layer containing an organic compound and a metal oxide is formed without exposing the first mixed layer to an oxygen-containing gas atmosphere, and the second mixed layer contains oxygen. Without exposing to a gas atmosphere, exposing to a nitrogen gas atmosphere, and then forming a hole transport layer without exposing the second mixed layer to a gas atmosphere containing oxygen, and forming a light emitting layer on the hole transport layer A cathode is formed on the light emitting layer.

    Further, the present invention provides an anode, a hole transport layer is formed on the anode, a light emitting layer is formed on the hole transport layer, an electron transport layer is formed on the light emitting layer, and the electron transport A mixed layer having an organic compound and a metal oxide is formed on the layer, the mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then the mixed layer is exposed to a gas atmosphere containing oxygen. The cathode is formed without.

    Further, the present invention provides an anode, a hole transport layer is formed on the anode, a light emitting layer is formed on the hole transport layer, an electron transport layer is formed on the light emitting layer, and the electron transport Forming a first mixed layer having an organic compound and a metal oxide on the layer; exposing the first mixed layer to a nitrogen gas atmosphere without exposing the first mixed layer to an oxygen-containing gas atmosphere; Forming a second mixed layer having an organic compound and a metal oxide without exposing the layer to an oxygen-containing gas atmosphere, and exposing the second mixed layer to a nitrogen gas atmosphere without exposing the layer to an oxygen-containing gas atmosphere; Then, a cathode is formed without exposing the second mixed layer to a gas atmosphere containing oxygen.

    The anode, the hole transport layer, the light emitting layer, the mixed layer, the first mixed layer, the second mixed layer, the electron transport layer, the electron injection layer, and the cathode are preferably formed in a vacuum or under reduced pressure.

    After the heat treatment is performed on the anode, the mixed layer or the first mixed layer may be formed, and then the light emitting layer and the cathode may be formed. The heat treatment is desirably performed in vacuum or under reduced pressure.

    An electron injection layer may be formed between the mixed layer or the second mixed layer and the electron transport layer, and then a cathode may be formed. The electron injection layer is formed in a vacuum or under reduced pressure.

    After the mixed layer, the first mixed layer, and the second mixed layer are exposed to a nitrogen gas atmosphere, the nitrogen gas may be exhausted and again exposed to the nitrogen gas atmosphere.

    The mixed layer, the first mixed layer, and the second mixed layer may be exposed to a nitrogen gas atmosphere by blowing nitrogen gas.

    The present invention also includes forming a cathode, forming a mixed layer having an organic compound and a metal oxide on the cathode, exposing the mixed layer to a nitrogen gas atmosphere without exposing to a gas atmosphere containing oxygen, An electron transport layer is formed without exposing the mixed layer to a gas atmosphere containing oxygen, a light emitting layer is formed on the electron transport layer, and an anode is formed on the light emitting layer.

    According to the present invention, a cathode is formed, a first mixed layer having an organic compound and a metal oxide is formed on the cathode, and the first mixed layer is not exposed to a gas atmosphere containing oxygen, and a nitrogen gas is formed. A second mixed layer containing an organic compound and a metal oxide is formed without exposing the first mixed layer to an oxygen-containing gas atmosphere, and the second mixed layer contains oxygen. Without exposing to a gas atmosphere, exposing to a nitrogen gas atmosphere, then forming the electron transport layer without exposing the second mixed layer to a gas atmosphere containing oxygen, forming a light emitting layer on the electron transport layer, A hole transport layer is formed on the light emitting layer, and an anode is formed on the hole transport layer.

    Further, the present invention forms a cathode, forms a mixed layer having an organic compound and a metal oxide on the cathode, exposes the mixed layer to a nitrogen gas atmosphere without exposing to a gas atmosphere containing oxygen, An electron injection layer is formed without exposing the mixed layer to a gas atmosphere containing oxygen, an electron transport layer is formed on the electron injection layer, a light emitting layer is formed on the electron transport layer, and a positive electrode is formed on the light emitting layer. A hole transport layer is formed, and an anode is formed on the hole transport layer.

  According to the present invention, a cathode is formed, a first mixed layer having an organic compound and a metal oxide is formed on the cathode, and the first mixed layer is not exposed to a gas atmosphere containing oxygen, and a nitrogen gas atmosphere Then, a second mixed layer having an organic compound and a metal oxide is formed without exposing the first mixed layer to a gas atmosphere containing oxygen, and the second mixed layer is formed of a gas containing oxygen. Without exposing to an atmosphere, exposing to a nitrogen gas atmosphere, and then forming an electron injection layer without exposing the second mixed layer to a gas atmosphere containing oxygen, forming an electron transport layer on the electron injection layer, A light emitting layer is formed on the electron transport layer, and an anode is formed on the light emitting layer.

  The present invention also includes forming a cathode, forming an electron transport layer on the cathode, forming a light emitting layer on the electron transport layer, forming a hole transport layer on the light emitting layer, and forming the hole transport layer. A mixed layer having an organic compound and a metal oxide is formed thereon, the mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then the mixed layer is exposed to a gas atmosphere containing oxygen. Without forming an anode.

  The present invention also includes forming a cathode, forming an electron transport layer on the cathode, forming a light emitting layer on the electron transport layer, forming a hole transport layer on the light emitting layer, and forming the hole transport layer. A first mixed layer having an organic compound and a metal oxide is formed thereon, the first mixed layer is exposed to a nitrogen gas atmosphere without being exposed to a gas atmosphere containing oxygen, and then the first mixed layer is formed. Forming a second mixed layer having an organic compound and a metal oxide without exposing to a gas atmosphere containing oxygen, exposing the second mixed layer to a nitrogen gas atmosphere without exposing to the gas atmosphere containing oxygen, Next, an anode is formed without exposing the second mixed layer to a gas atmosphere containing oxygen.

    The anode, the hole transport layer, the light emitting layer, the mixed layer, the first mixed layer, the second mixed layer, the electron transport layer, the electron injection layer, and the cathode are preferably formed in a vacuum or under reduced pressure.

    After the mixed layer, the first mixed layer, and the second mixed layer are exposed to a nitrogen gas atmosphere, the nitrogen gas may be exhausted and exposed again to the nitrogen gas atmosphere.

    A method for manufacturing a light-emitting device, characterized in that nitrogen gas is blown onto the mixed layer, the first mixed layer, and the second mixed layer to expose them to a nitrogen gas atmosphere.

    According to the present invention, an anode is formed, a first mixed layer having an organic compound and a metal oxide is formed on the anode, and the first mixed layer is not exposed to a gas atmosphere containing oxygen, but a nitrogen gas atmosphere Next, a hole transport layer is formed without exposing the first mixed layer to a gas atmosphere containing oxygen, a light emitting layer is formed on the hole transport layer, and an electron transport layer is formed on the light emitting layer. Forming a second mixed layer having an organic compound and a metal oxide on the electron transport layer, and exposing the second mixed layer to a nitrogen gas atmosphere without exposing to a gas atmosphere containing oxygen, Next, a cathode is formed without exposing the second mixed layer to a gas atmosphere containing oxygen.

    The first mixed layer may be formed after heat-treating the anode, and then the hole transport layer may be formed. The heat treatment is desirably performed in vacuum or under reduced pressure.

    An electron injection layer may be formed between the second mixed layer and the electron transport layer, and then a cathode may be formed.

    The anode, the hole transport layer, the light emitting layer, the mixed layer, the first mixed layer, the second mixed layer, the electron transport layer, the electron injection layer, and the cathode are preferably formed in a vacuum or under reduced pressure.

    According to the present invention, a cathode is formed, a first mixed layer having an organic compound and a metal oxide is formed on the cathode, and the first mixed layer is not exposed to a gas atmosphere containing oxygen, and a nitrogen gas atmosphere Then, an electron transport layer is formed without exposing the first mixed layer to a gas atmosphere containing oxygen, a light emitting layer is formed on the electron transport layer, and a hole transport layer is formed on the light emitting layer. Forming a second mixed layer having an organic compound and a metal oxide on the hole transport layer, and exposing the second mixed layer to a nitrogen gas atmosphere without exposing to a gas atmosphere containing oxygen; Next, an anode is formed without exposing the second mixed layer to a gas atmosphere containing oxygen.

    Forming a cathode, forming a first mixed layer having an organic compound and a metal oxide on the cathode, exposing the first mixed layer to a nitrogen gas atmosphere without exposing to a gas atmosphere containing oxygen; Forming an electron injection layer without exposing the first mixed layer to an oxygen-containing gas atmosphere, forming an electron transport layer on the electron injection layer, forming a light emitting layer on the electron transport layer, A hole transport layer is formed on the light emitting layer, a second mixed layer having an organic compound and a metal oxide is formed on the hole transport layer, and the second mixed layer is placed in a gas atmosphere containing oxygen. The anode is formed without exposing to a nitrogen gas atmosphere and then exposing the second mixed layer to a gas atmosphere containing oxygen.

    After the first mixed layer is exposed to a nitrogen gas atmosphere, the nitrogen gas is exhausted, and again exposed to the nitrogen gas atmosphere. After the second mixed layer is exposed to the nitrogen gas atmosphere, the nitrogen gas is exhausted and again You may expose to nitrogen gas atmosphere.

    The first mixed layer and the second mixed layer may be exposed to a nitrogen gas atmosphere by blowing nitrogen gas.

    The anode, the hole transport layer, the light emitting layer, the mixed layer, the first mixed layer, the second mixed layer, the electron transport layer, the electron injection layer, and the cathode are preferably formed in a vacuum or under reduced pressure.

    When providing a mixed layer on both the anode side and the cathode side, the first mixed layer includes a third mixed layer having an organic compound and a metal oxide, and a fourth mixed layer having an organic compound and a metal oxide. It is good also as what laminated | stacked. The second mixed layer may be a stack of a fifth mixed layer having an organic compound and a metal oxide and a sixth mixed layer having an organic compound and a metal oxide.

    At this time, a third mixed layer is formed, the third mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then the third mixed layer is exposed to a gas atmosphere containing oxygen. Without forming a fourth mixed layer, exposing the fourth mixed layer to a nitrogen gas atmosphere without exposing the fourth mixed layer to an oxygen-containing gas atmosphere, and then exposing the fourth mixed layer to an oxygen-containing gas atmosphere. The next layer may be formed.

    In addition, a fifth mixed layer is formed, the fifth mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then the fifth mixed layer is not exposed to a gas atmosphere containing oxygen. A sixth mixed layer is formed, the sixth mixed layer is exposed to a nitrogen gas atmosphere without being exposed to a gas atmosphere containing oxygen, and then the sixth mixed layer is not exposed to a gas atmosphere containing oxygen. These layers may be formed.

    After the third mixed layer is exposed to a nitrogen gas atmosphere, the nitrogen gas is exhausted and again exposed to the nitrogen gas atmosphere. After the fourth mixed layer is exposed to the nitrogen gas atmosphere, the nitrogen gas is exhausted and again You may expose to nitrogen gas atmosphere.

    After the fifth mixed layer is exposed to a nitrogen gas atmosphere, the nitrogen gas is exhausted and again exposed to the nitrogen gas atmosphere. After the sixth mixed layer is exposed to the nitrogen gas atmosphere, the nitrogen gas is exhausted and again You may expose to nitrogen gas atmosphere.

    The third mixed layer and the fourth mixed layer may be exposed to a nitrogen gas atmosphere by blowing nitrogen gas.

    The fifth mixed layer and the sixth mixed layer may be exposed to a nitrogen gas atmosphere by blowing nitrogen gas.

    In the present invention, an anode is formed, a first light emitting unit having a light emitting layer is formed on the anode, and a layer having an electron donating substance and an electron transporting substance is formed on the first light emitting unit. Forming a mixed layer having an organic compound and a metal oxide on the layer having the electron-donating substance and the electron-transporting substance, and exposing the mixed layer to a nitrogen gas atmosphere without exposing the mixed layer to a gas atmosphere containing oxygen. Next, a second light emitting unit is formed without exposing the mixed layer to a gas atmosphere containing oxygen, and a cathode is formed on the second light emitting unit.

    In the present invention, an anode is formed, a first light emitting unit having a light emitting layer is formed on the anode, and a layer having an electron donating substance and an electron transporting substance is formed on the first light emitting unit. Forming a first mixed layer having an organic compound and a metal oxide on the layer having the electron donating substance and the electron transporting substance, and exposing the first mixed layer to a gas atmosphere containing oxygen. First, a second mixed layer is formed without exposing the first mixed layer to a gas atmosphere containing oxygen, and then exposing the second mixed layer to a gas atmosphere containing oxygen. Then, a second light emitting unit is formed without exposing the second mixed layer to a gas atmosphere containing oxygen, and a cathode is formed on the second light emitting unit.

    According to the present invention, a cathode is formed, a first light emitting unit having a light emitting layer is formed on the cathode, and a layer having an electron donating substance and an electron transporting substance is formed on the first light emitting unit. Forming a mixed layer having an organic compound and a metal oxide on the layer having the electron-donating substance and the electron-transporting substance, and exposing the mixed layer to a nitrogen gas atmosphere without exposing the mixed layer to a gas atmosphere containing oxygen. Next, a second light emitting unit is formed without exposing the mixed layer to a gas atmosphere containing oxygen, and an anode is formed on the second light emitting unit.

  According to the present invention, a cathode is formed, a first light emitting unit having a light emitting layer is formed on the cathode, and a layer having an electron donating substance and an electron transporting substance is formed on the first light emitting unit. Forming a first mixed layer having an organic compound and a metal oxide on the layer having the electron donating substance and the electron transporting substance, and exposing the first mixed layer to a gas atmosphere containing oxygen. First, a second mixed layer is formed without exposing the first mixed layer to a gas atmosphere containing oxygen, and then exposing the second mixed layer to a gas atmosphere containing oxygen. Then, a second light emitting unit is formed without exposing the second mixed layer to a gas atmosphere containing oxygen, and an anode is formed on the second light emitting unit.

    After the mixed layer is exposed to a nitrogen gas atmosphere, the nitrogen gas may be exhausted and again exposed to the nitrogen gas atmosphere.

    The mixed layer may be exposed to a nitrogen gas atmosphere by blowing nitrogen gas.

    The light emitting unit may be formed after heat-treating the anode. The heat treatment is desirably performed in vacuum or under reduced pressure.

    The light emitting unit has a light emitting layer. An electron transport layer and a hole transport layer may be formed. An electron injection layer may be formed between the cathode and the electron transport layer. A hole injection layer may be formed between the anode and the hole transport layer.

    Further, after the first mixed layer and the second mixed layer are exposed to a nitrogen gas atmosphere, the nitrogen gas may be exhausted and again exposed to the nitrogen gas atmosphere.

    The first mixed layer and the second mixed layer may be exposed to a nitrogen gas atmosphere by blowing nitrogen gas.

    The anode, the light emitting unit, the mixed layer, the first mixed layer, the second mixed layer, and the cathode are preferably produced in a vacuum or under reduced pressure.

    When exposed to a nitrogen gas atmosphere, it is better to carry out at room temperature without heating. It is considered that when heated, the characteristics are likely to change, and the characteristics of the light emitting device are likely to vary. The amount of water contained in the nitrogen gas is 40 ppm or less, preferably 3 ppm or less.

Ogawa et al. Formed a hole-injecting CuPc organic film, and then performed a first gas rinsing process with nitrogen gas, and then a _second gas rinsing process with NO ₂ gas to infiltrate the NO ₂ gas into the CuPc organic film. (Patent Document 3). However, in the present invention, after the mixed layer is formed, the mixed layer is exposed to a nitrogen gas atmosphere without being exposed to a gas atmosphere containing oxygen, and then a laminated film is formed without being exposed to a gas atmosphere containing oxygen. Therefore, it is completely different from Patent Document 3 in which the first gas rinsing process is performed with nitrogen gas, and then exposed to a gas atmosphere containing oxygen.

Kuribayashi et al., When forming organic electroluminescence of the three primary colors on the same substrate, can be manufactured in a vacuum, in a reduced pressure space or in a dry nitrogen atmosphere without being exposed to the air throughout the entire process (patented) Reference 4). Specifically, Kuribayashi et al. Disclosed that the hole injection layer, the light emitting layer, and the Alq ₃ layer stack are formed in a vacuum or in a reduced pressure space without being exposed to the atmosphere. Is disclosed. However, after forming the mixed layer, it is disclosed that the mixed layer is exposed to a nitrogen gas atmosphere without being exposed to an oxygen-containing gas atmosphere, and then the subsequent laminated film is formed without being exposed to an oxygen-containing gas atmosphere. Absent.

    By forming the mixed layer and then exposing the mixed layer to a nitrogen gas atmosphere without exposing it to an oxygen-containing gas atmosphere, and then forming a subsequent laminated film without exposing it to an oxygen-containing gas atmosphere. Without lowering, it is possible to improve the light emission luminance life without deteriorating the characteristics of the light emitting device.

    Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention can be implemented in many different modes, and those skilled in the art can easily understand that the modes and details can be variously changed without departing from the spirit and scope of the present invention. Is done. Therefore, the present invention is not construed as being limited to the description of this embodiment mode.

(Embodiment 1)
Here, a light emitting device having an anode, a cathode, a light emitting layer provided between the anode and the cathode, and a mixed layer having an organic compound and a metal oxide provided between the anode and the light emitting layer In the manufacturing method of, exposure to a nitrogen gas atmosphere after formation of the mixed layer will be described.

    An anode 2 is formed to 10 to 1000 nm on the substrate 1 (FIG. 1A). As the substrate 1, for example, quartz, glass, plastic, or the like can be used. Note that other materials may be used as long as they function as a support in the manufacturing process of the light-emitting device.

  The anode 2 has a function of injecting holes into the light emitting layer, and various metals, alloys, electrically conductive compounds, and mixed metals thereof can be used. For example, aluminum (Al), silver (Ag), gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co ), Copper (Cu), palladium (Pd), lithium (Li), cesium (Cs), magnesium (Mg), calcium (Ca), strontium (Sr), titanium (Ti), or other conductive metals, or Aluminum-silicon (Al-Si), aluminum-titanium (Al-Ti), alloys thereof such as aluminum-silicon-copper (Al-Si-Cu), or nitrides of metal materials such as titanium nitride (TiN), ITO (Indium tin oxide), ITO containing silicon oxide (ITSO), indium oxide mixed with zinc oxide (ZnO) A metal compound such as (indium zinc oxide) can be used.

    Usually, the anode is preferably formed of a material having a large work function (such as a work function of 4.0 eV or more) so that holes can be injected. However, since the mixed layer 3 is formed on the anode 2 in contact with the present invention, the anode 2 is not limited to a material having a high work function, and a material having a low work function can also be used.

    After depositing the above material on the substrate 1 by sputtering or CVD, the anode 2 is formed using photolithography and etching.

    Here, before the mixed layer 3 is formed, heat treatment is performed to remove moisture contained in the substrate 1 and the anode 2 (FIG. 1B). The heat treatment can be performed at 100 to 200 ° C., for example, 150 ° C., for example, in vacuum or under reduced pressure. From this heat treatment, each layer is formed in vacuum or under reduced pressure without being exposed to the atmosphere.

    Next, a mixed layer 3 of an organic compound and a metal oxide is formed in a vacuum or under reduced pressure (FIG. 1C). As a result, it is possible to prevent the anode 2 and the cathode 7 from being short-circuited due to the unevenness formed on the surface of the anode 2 or the influence of foreign matter remaining on the electrode surface. The film thickness of the mixed layer 3 is desirably 60 nm or more. Moreover, it is more preferable that it is 120 nm or more. Even if the thickness is increased, the driving voltage of the light emitting device is not increased. Further, there is no increase in power consumption.

    As the metal oxide, an oxide of a transition metal is desirable. Specifically, zirconium oxide, hafnium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, titanium oxide, manganese oxide, and rhenium oxide are preferable.

As an organic compound, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (abbreviation: NPB), 4,4′-bis [N- (3-methylphenyl) -N-phenyl Amino] biphenyl (abbreviation: TPD), 4,4 ′, 4 ″ -tris (N, N-diphenylamino) triphenylamine (abbreviation: TDATA), 4,4 ′, 4 ″ -tris [N- ( 3-methylphenyl) -N-phenylamino] triphenylamine (abbreviation: MTDATA), 4,4′-bis {N- [4- (N, N-di-m-tolylamino) phenyl] -N-phenylamino } Biphenyl (abbreviation: DNTPD), 1,3,5-tris [N, N-di (m-tolyl) amino] benzene (abbreviation: m-MTDAB), 4,4 ′, 4 ″ -tris (N— Carbazolyl) triphenylamine (abbreviation: Or organic material having an arylamino group such as CTA), phthalocyanine _{(abbreviation:} H 2 Pc), copper phthalocyanine (abbreviation: CuPc), or vanadyl phthalocyanine (abbreviation: VOPc), and the like can also be used.

  In addition, an organic material represented by the following general formula (1) can also be suitably used. Specific examples thereof include 3- [N- (9-phenylcarbazol-3-yl) -N-phenylamino]. -9-phenylcarbazole (abbreviation: PCzPCA1), 3,6-bis [N- (9-phenylcarbazol-3-yl) -N-phenylamino] -9-phenylcarbazole (abbreviation: PCzPCA2), and the like. it can. An organic compound having this structure has excellent thermal stability and good reliability.

（式中、Ｒ^１およびＲ^３は、それぞれ同一でも異なっていてもよく、水素、炭素数１〜６のアルキル基、炭素数６〜２５のアリール基、炭素数５〜９のヘテロアリール基、アリールアルキル基、炭素数１〜７のアシル基のいずれかを表し、Ａｒ^１は、炭素数６〜２５のアリール基、炭素数５〜９のヘテロアリール基のいずれかを表し、Ｒ^２は、水素、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基のいずれかを表し、Ｒ^４は、水素、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、下記一般式（２）で示される置換基のいずれかを表し、一般式（２）で示される置換基において、Ｒ^５は、水素、炭素数１〜６のアルキル基、炭素数６〜２５のアリール基、炭素数５〜９のヘテロアリール基、アリールアルキル基、炭素数１〜７のアシル基のいずれかを表し、Ａｒ^２は、炭素数６〜２５のアリール基、炭素数５〜９のヘテロアリール基のいずれかを表し、Ｒ^６は、水素、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基のいずれかを表す。）

(In the formula, R ¹ and R ³ may be the same or different from each other; hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 25 carbon atoms, a heteroaryl group having 5 to 9 carbon atoms, Ar ¹ represents any of an arylalkyl group and an acyl group having 1 to 7 carbon atoms, Ar ¹ represents any of an aryl group having 6 to 25 carbon atoms and a heteroaryl group having 5 to 9 carbon atoms, and R ² represents Any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms, R ⁴ is hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, Represents any of the substituents represented by the general formula (2), and in the substituent represented by the general formula (2), R ⁵ is hydrogen, an alkyl group having 1 to 6 carbon atoms, or an aryl having 6 to 25 carbon atoms. Group, C5-C9 heteroaryl group, arylalkyl group, charcoal Represents an acyl group having 1 to 7, Ar ² is an aryl group having 6 to 25 carbon atoms, represents any heteroaryl group having 5 to 9 carbon atoms, ^{R 6} is hydrogen, a carbon number 1 Represents an alkyl group having ˜6 or an aryl group having 6 to 12 carbon atoms.)

As a synthesis method of the carbazole derivative, various reactions can be applied. For example, the method shown to the following reaction scheme (A-1) and reaction scheme (A-2) is mentioned. However, the synthesis method of the carbazole derivative used in the present invention is not limited to this.

    An organic material represented by any one of the following general formulas (3) to (6) can also be suitably used. Specific examples of the organic compound represented by any one of the following general formulas (3) to (6) include N- (2-naphthyl) carbazole (abbreviation: NCz), 4,4′-di (N-carbazolyl). Biphenyl (abbreviation: CBP), 9,10-bis [4- (N-carbazolyl) phenyl] anthracene (abbreviation: BCPA), 3,5-bis [4- (N-carbazolyl) phenyl] biphenyl (abbreviation: BCPBi) 1,3,5-tris [4- (N-carbazolyl) phenyl] benzene (abbreviation: TCPB) and the like.

式中Ａｒ^３は炭素数６〜４２の芳香族炭化水素基を表し、ｎは１〜３の自然数を表し、Ｒ^１１、Ｒ^１２は水素、または炭素数１〜４のアルキル基、または炭素数６〜１２のアリール基を表す。

In the formula, Ar ³ represents an aromatic hydrocarbon group having 6 to 42 carbon atoms, n represents a natural number of 1 to 3, R ¹¹ and R ¹² are hydrogen, an alkyl group having 1 to 4 carbon atoms, or a carbon number Represents 6-12 aryl groups.

ただし、式中Ａｒ^４は炭素数６〜４２の１価の芳香族炭化水素基を表し、Ｒ^２１、Ｒ^２２は水素、または炭素数１〜４のアルキル基、または炭素数６〜１２のアリール基を表す。

In the formula, Ar ⁴ represents a monovalent aromatic hydrocarbon group having 6 to 42 carbon atoms, R ²¹ and R ²² are hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Represents a group.

ただし、式中Ａｒ^５は炭素数６〜４２の２価の芳香族炭化水素基を表し、Ｒ^３１〜Ｒ^３４は水素、または炭素数１〜４のアルキル基、または炭素数６〜１２のアリール基を表す。

However, wherein Ar ⁵ represents a divalent aromatic hydrocarbon group having 6 to 42 carbon ^atoms, R 31 ^{to R 34} is hydrogen or an alkyl group having 1 to 4 carbon atoms or aryl having 6 to 12 carbon atoms, Represents a group.

ただし、式中Ａｒ^６は炭素数６〜４２の３価の芳香族炭化水素基を表し、Ｒ^４１〜Ｒ^４６は水素、または炭素数１〜４のアルキル基、または炭素数６〜１２のアリール基を表す。

In the formula, Ar ⁶ represents a trivalent aromatic hydrocarbon group having ⁶ to 42 carbon atoms, R ^{41 to} R ⁴⁶ are hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Represents a group.

    Aromatic hydrocarbons such as anthracene, 9,10-diphenylanthracene (abbreviation: DPA), 2-tert-butyl-9,10-di (2-naphthyl) anthracene (abbreviation: t-BuDNA), tetracene, rubrene, and pentacene Can also be used.

    A compound having a large steric hindrance may be added to the mixed layer 3 by a co-evaporation method or the like. Thereby, crystallization of the mixed layer 3 can be prevented. As a compound having a large steric hindrance (that is, having a structure having a spatial extension unlike a planar structure), 5,6,11,12-tetraphenyltetracene (abbreviation: rubrene) is preferable. However, other than this, hexaphenylbenzene, diphenylanthracene, t-butylperylene, 9,10-di (phenyl) anthracene, coumarin 545T, or the like may be used. In addition, dendrimers and the like are also effective.

    The mixed layer 3 can be produced by the co-evaporation method of the metal oxide and the organic compound described above. It can also be formed by a wet method, a droplet discharge method, or the like. However, it is necessary not to be exposed to a gas atmosphere containing oxygen. In the case of forming by vapor deposition, a pattern is formed by providing a mask of metal or the like between the vapor deposition source and the substrate. In the mixed layer 3, the organic compound and the metal oxide are desirably in a weight ratio of 95: 5 to 20:80, more preferably 90:10 to 50:50.

Next, the mixed layer 3 is exposed to a nitrogen gas atmosphere at room temperature without being exposed to a gas atmosphere containing oxygen (FIG. 1D). In FIG. 1D, nitrogen (N ₂ ) is schematically indicated by a circle. 3, 5, 6, and 8, nitrogen (N ₂ ) is schematically indicated by a circle. Nitrogen gas is introduced into the chamber in which the substrate 1 on which the mixed layer 3 is formed is set. The nitrogen gas is desirably one from which moisture is removed as much as possible, and is 40 ppm or less, preferably 3 ppm or less. Nitrogen gas is introduced at a flow rate of 1 to 500 sccm so that the pressure in the chamber is 1 × 10 ⁻¹ to 1 × 10 ⁶ Pa. The mixed layer 3 is exposed to a nitrogen gas atmosphere by being left for 1 to 24 hours while maintaining the pressure in the chamber. Alternatively, nitrogen gas may be sprayed onto the mixed layer 3. In this case, it is not necessary to leave for 1 to 24 hours, and it may be sprayed for 10 to 180 minutes. After the exposure to the nitrogen gas atmosphere, the nitrogen gas in the chamber may be removed and vacuum or reduced pressure may be applied, and the exposure to the nitrogen gas atmosphere may be performed again as described above. Thereby, the lifetime of the light emitting device can be improved.

Next, without exposing the mixed layer 3 to a gas atmosphere containing oxygen, the hole transport layer 4 is formed in a thickness of 5 to 50 nm by a vapor deposition method or the like in a vacuum or under reduced pressure (FIG. 2A). The hole transport layer 4 is a layer having a function of transporting holes, for example, a layer made of a compound of an aromatic amine (that is, having a benzene ring-nitrogen bond) such as NPB, TPD, TDATA, MTDATA, BSPB. is there. The substances mentioned here are mainly substances having a hole mobility of 1 × 10 ^{−6 to} 10 cm ² / Vs. Note that other than these substances, any substance that has a property of transporting more holes than electrons may be used. The hole transport layer 4 is not limited to a single layer, and may be a stack of two or more layers made of the above substances.

Next, the light-emitting layer 5 is formed to 5 to 100 nm by a vapor deposition method or the like in vacuum or under reduced pressure (FIG. 2A). There is no particular limitation on the light emitting layer 5. The layer functioning as the light emitting layer is roughly divided into two modes. One is a host-guest type layer in which the light-emitting material is dispersed in a layer made of a material (host material) having an energy gap larger than that of the light-emitting substance (dopant material) that becomes the emission center, and the other is light emission. It is a layer which comprises a light emitting layer only with material. The former is a preferable structure because concentration quenching hardly occurs. As a light-emitting substance serving as a luminescent center, 4-dicyanomethylene-2-methyl-6- (1,1,7,7-tetramethyljulolidyl-9-enyl) -4H-pyran (abbreviation: DCJT), 4 -Dicyanomethylene-2-t-butyl-6- (1,1,7,7-tetramethyljulolidyl-9-enyl) -4H-pyran, perifrantene, 2,5-dicyano-1,4-bis ( 10-methoxy-1,1,7,7-tetramethyljulolidyl-9-enyl) benzene, N, N′-dimethylquinacridone (abbreviation: DMQd), coumarin 6, coumarin 545T, tris (8-quinolinolato) aluminum (Abbreviation: Alq ₃ ), 9,9′-bianthryl, 9,10-diphenylanthracene (abbreviation: DPA) and 9,10-bis (2-naphthyl) anthracene (abbreviation: DN) A), 2,5,8,11-tetra-t-butylperylene (abbreviation: TBP) and the like.

Bis [2- (3,5-bis (trifluoromethyl) phenyl) pyridinato-N, C ^{2 ′} ] iridium (III) picolinate (abbreviation: Ir (CF ₃ ppy) 2 (pic)), bis [2- ( 4,6-difluorophenyl) pyridinato-N, C ^{2 ′} ] iridium (III) acetylacetonate (abbreviation: FIr (acac)), bis [2- (4,6-difluorophenyl) pyridinato-N, C ^{2 ′} Phosphorescent substances such as iridium (III) picolinate (FIr (pic)), tris (2-phenylpyridinato-N, C ^{2 ′} ) iridium (abbreviation: Ir (ppy) ₃ ) are also used as dopant materials. be able to.

Examples of the host material include anthracene derivatives such as 9,10-di (2-naphthyl) -2-tert-butylanthracene (abbreviation: t-BuDNA), 4,4′-bis (N-carbazolyl) biphenyl (abbreviation: Carbazole derivatives such as CBP), tris (8-quinolinolato) aluminum (abbreviation: Alq ₃ ), tris (4-methyl-8-quinolinolato) aluminum (abbreviation: Almq ₃ ), bis (10-hydroxybenzo [h] -quinolinato ) Beryllium (abbreviation: BeBq ₂ ), bis (2-methyl-8-quinolinolato) -4-phenylphenolato-aluminum (abbreviation: BAlq), bis [2- (2-hydroxyphenyl) pyridinato] zinc (abbreviation: Znpp) _2), bis [2- (2-hydroxyphenyl) benzoxazolato] zinc (abbreviation ZnBOX) can be used and metal complexes such as. Examples of a material that can form the light-emitting layer 5 with only a light-emitting substance include tris (8-quinolinolato) aluminum (abbreviation: Alq ₃ ), 9,10-bis (2-naphthyl) anthracene (abbreviation: DNA), bis (2-methyl-8-quinolinolato) -4-phenylphenolato-aluminum (abbreviation: BAlq).

The electron transport layer 6 is formed on the light-emitting layer 5 in a vacuum or under reduced pressure by a vapor deposition method or the like (FIG. 2A). The electron transport layer 6 is a layer having an excellent function of transporting electrons, such as tris (8-quinolinolato) aluminum (abbreviation: Alq ₃ ), tris (5-methyl-8-quinolinolato) aluminum (abbreviation: Almq ₃ ), bis. (10-hydroxybenzo [h] -quinolinato) beryllium (abbreviation: BeBq ₂ ), bis (2-methyl-8-quinolinolato) -4-phenylphenolato-aluminum (abbreviation: BAlq), quinoline skeleton or benzoquinoline skeleton A layer made of a metal complex having In addition, bis [2- (2-hydroxyphenyl) benzoxazolate] zinc (abbreviation: ZnBOX), bis [2- (2-hydroxyphenyl) -benzothiazolate] zinc (abbreviation: Zn (BTZ) ₂ ), etc. A metal complex having an oxazole-based or thiazole-based ligand can also be used. In addition to metal complexes, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis [5 -(P-tert-butylphenyl) -1,3,4-oxadiazol-2-yl] benzene (abbreviation: OXD-7), 3- (4-tert-butylphenyl) -4-phenyl-5 (4-Biphenylyl) -1,2,4-triazole (abbreviation: TAZ), 3- (4-tert-butylphenyl) -4- (4-ethylphenyl) -5- (4-biphenylyl) -1,2 , 4-triazole (abbreviation: p-EtTAZ), bathophenanthroline (abbreviation: BPhen), bathocuproin (abbreviation: BCP), and the like can also be used. The substances described here are mainly substances having an electron mobility of 1 × 10 ^{−6 to} 10 cm ² / Vs. Note that a substance other than those described above may be used as the electron transport layer 6 as long as it has a property of transporting more electrons than holes. Further, the electron transport layer 6 is not limited to a single layer, and two or more layers made of the above substances may be stacked.

    A cathode 7 is formed on the electron transport layer 6 in a vacuum or under reduced pressure by a vapor deposition method or the like to form a light emitting device (FIG. 2A). A metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a low work function (work function of 3.8 eV or less) can be used. Specific examples of such a cathode material include elements belonging to Group 1 or Group 2 of the periodic table of elements, that is, alkali metals such as lithium (Li) and cesium (Cs), and magnesium (Mg), calcium (Ca), Examples thereof include alkaline earth metals such as strontium (Sr) and alloys containing them (Mg: Ag, Al: Li). However, by providing a layer (electron injection layer, not shown) excellent in the function of injecting electrons between the cathode 7 and the light emitting layer 5 so as to be laminated with the cathode 7, the work function is small or large. Various conductive materials can be used as the cathode 7 including the materials mentioned as the material of the anode 2 such as Al, Ag, ITO, ITO containing silicon.

Note that as a layer having an excellent function of injecting electrons, an alkali metal or alkaline earth metal compound such as lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF ₂ ), or the like is used. be able to. In addition, a material containing an electron transporting property containing an alkali metal or an alkaline earth metal, for example, a material containing magnesium (Mg) in Alq ₃ can be used.

    The mixed layer 3, the hole transport layer 4, the light emitting layer 5, and the electron transport layer 6 can be formed by a vapor deposition method. As other methods, it can also be formed by a wet method such as a droplet discharge method or a spin coating method. However, the mixed layer 3 and the layer stacked thereon need to be formed without being exposed to a gas atmosphere containing oxygen. Moreover, you may form using the different film-forming method for each electrode or each layer.

    Since the light emitting device may be deteriorated by moisture or the like, a passivation film may be formed or sealed as follows.

Here, a silicon oxide film containing nitrogen is formed as a passivation film 8 by 10 to 1000 nm by plasma CVD, sputtering, or the like. In the case of using a silicon oxide film containing nitrogen, a silicon oxynitride film manufactured from SiH ₄ , N ₂ O, NH ₃ by a plasma CVD method, or a silicon oxynitride film manufactured from SiH ₄ , N ₂ O, Alternatively, a silicon oxynitride film formed from a gas obtained by diluting SiH ₄ and N ₂ O with Ar may be formed.

Alternatively, a silicon oxynitride silicon nitride film formed from SiH ₄ , N ₂ O, and H ₂ may be used. Of course, the passivation film is not limited to a single layer structure, and another insulating layer containing silicon may be used as a single layer structure or a laminated structure. A multilayer film of a carbon nitride film and a silicon nitride film, a multilayer film of styrene polymer, a silicon nitride film, or a diamond-like carbon film may be formed instead of the silicon oxide film containing nitrogen.

    Subsequently, sealing is performed in order to protect from substances that promote deterioration such as water (FIG. 2B). Here, the counter substrate 11 is used for sealing, and is bonded with an insulating sealing material so that the external connection portion is exposed. A space between the counter substrate 11 and the substrate 1 may be filled with an inert gas such as dry nitrogen, or a sealing material or a light-transmitting resin 9 is applied over the entire surface, whereby the counter substrate 11 is formed. You may stick together. It is preferable to use an ultraviolet curable resin or the like for the sealing material. The sealing material may contain a desiccant 10 or particles 10 for keeping the gap between the substrates constant. Then, a flexible wiring board is affixed on an external connection part. Since this light-emitting device is exposed to a nitrogen gas atmosphere without being exposed to oxygen or moisture after the mixed layer 3 is formed, the lifetime can be improved.

    Up to the above, the anode 2 was formed on the substrate 1 and the mixed layer 3 was formed on the anode 2. However, the cathode 7 is formed on the substrate 1, the electron transport layer 6 is formed on the cathode 7, the light emitting layer 5 is formed on the electron transport layer 6, the hole transport layer 4 is formed on the light emitting layer 5, The present invention can also be applied to a light emitting device in which the mixed layer 3 is formed on the hole transport layer 4 and the anode 2 is formed on the mixed layer 3 (FIG. 21).

    After the mixed layer 3 is formed, the anode 2 is formed without being exposed to a gas atmosphere containing oxygen without being exposed to a nitrogen gas atmosphere in which moisture is reduced as much as possible at room temperature.

    As the method for exposing the mixed layer 3 to a nitrogen gas atmosphere, the above-described method can be used. Further, after the mixed layer 3 is exposed to a nitrogen gas atmosphere, the nitrogen gas may be exhausted and again exposed to the nitrogen gas atmosphere. The mixed layer 3 may be exposed to a nitrogen gas atmosphere by blowing nitrogen gas.

    In this case, the substrate 1, the cathode 7, the electron transport layer 6, the light emitting layer 5, the hole transport layer 4, the mixed layer 3, and the anode 2 described above can be used. Further, as described above, this light-emitting device can be manufactured by a vapor deposition method or the like in a vacuum or under reduced pressure.

    Further, an electron injection layer may be formed between the cathode 7 and the electron transport layer 6.

(Embodiment 2)
In this embodiment, a structure different from the structure described in Embodiment 1 will be described. In the structure shown in this embodiment mode, the mixed layer 3 is provided so as to be in contact with the cathode.

    FIG. 3A illustrates an example of a structure of the light-emitting device. A positive hole transport layer 4, a light emitting layer 5, an electron transport layer 6, a first layer 15, and a mixed layer 3 are laminated between the anode 2 and the cathode 7. As the anode 2, the cathode 7, the hole transport layer 4, the light emitting layer 5, the electron transport layer 6, and the mixed layer 3, those described in Embodiment 1 can be used.

    The first layer 15 is an electron injection layer, and includes an electron donating substance and an electron transporting substance. The electron donating substance contained in the first layer 15 is preferably an alkali metal or alkaline earth metal and oxides or salts thereof. Specifically, lithium, cesium, calcium, lithium oxide, calcium oxide, barium oxide, cesium carbonate, and the like can be given. As the electron transporting substance, those described in the compounds that can be used for the electron transporting layer of Embodiment 1 can be used. The first layer 15 is formed with a thickness of 1 to 100 nm by vapor deposition or the like.

After the first layer 15 is formed, the mixed layer 3 is formed as described in Embodiment 1 in vacuum or under reduced pressure. After that, the mixed layer 3 is exposed to a nitrogen gas atmosphere at room temperature without being exposed to a gas atmosphere containing oxygen (FIG. 3B). The water content in the nitrogen gas is 40 ppm or less, preferably 3 ppm or less. Nitrogen gas is introduced into the chamber in which the substrate 1 on which the mixed layer 3 is formed is set. Nitrogen gas is introduced at a flow rate of 1 to 500 sccm so that the pressure in the chamber is 1 × 10 ⁻¹ to 1 × 10 ⁶ Pa.

    The mixed layer 3 is exposed to a nitrogen gas atmosphere by being left for 1 to 24 hours while maintaining the pressure in the chamber. Alternatively, nitrogen gas may be sprayed onto the mixed layer 3. In this case, it is not necessary to leave for 1 to 24 hours, and it may be sprayed for 10 to 180 minutes.

    After the exposure to the nitrogen gas atmosphere, the nitrogen gas in the chamber may be removed and a vacuum or reduced pressure may be applied, and then the exposure may be performed again to the nitrogen gas atmosphere as described above. Thereby, the lifetime of the light emitting device can be improved.

    Thereafter, the cathode 7 is formed in a vacuum or under reduced pressure without exposing the mixed layer 3 to a gas atmosphere containing oxygen, whereby the light emitting device is completed. Further, the passivation film 8 may be formed as in the first embodiment, and subsequently sealed to protect it from a substance that promotes deterioration such as water.

    Up to the above, the anode 2 was formed on the substrate 1, and the mixed layer 3 and the cathode 7 were formed above the anode 2. However, the cathode 7 is formed on the substrate 1, the mixed layer 3 is formed on the cathode 7, the first layer 15 is formed on the mixed layer 3, and the electron transport layer 6 is formed on the first layer 15. The present invention can also be applied to a light emitting device in which the light emitting layer 5 is formed on the electron transport layer 6, the hole transport layer 4 is formed on the light emitting layer 5, and the anode 2 is formed on the hole transport layer 4 ( FIG. 22).

    After the mixed layer 3 is formed, the first layer is formed without being exposed to a gas atmosphere containing oxygen, without being exposed to a nitrogen gas atmosphere with a reduced amount of water at room temperature, and then being exposed to a gas atmosphere containing oxygen. To do.

    As the method for exposing the mixed layer 3 to a nitrogen gas atmosphere, the above-described method can be used. Further, after the mixed layer 3 is exposed to a nitrogen gas atmosphere, the nitrogen gas may be exhausted and again exposed to the nitrogen gas atmosphere. The mixed layer 3 may be exposed to a nitrogen gas atmosphere by blowing nitrogen gas.

    As the substrate 1, the cathode 7, the mixed layer 3, the first layer 15, the electron transport layer 6, the light emitting layer 5, the hole transport layer 4, and the anode 2, those described above can be used. Further, as described above, this generator can be manufactured by a vapor deposition method or the like in a vacuum or under reduced pressure.

    A hole injection layer may be formed between the hole transport layer 4 and the anode 2.

(Embodiment 3)
In this embodiment mode, a mixed layer is provided so as to be in contact with the anode and the cathode.

    FIG. 4 shows an example of the structure of the light emitting device. A structure in which a first mixed layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, a first layer 15, and a second mixed layer 3 are laminated between the anode 2 and the cathode 7. It has become. As each layer, those shown in Embodiment Modes 1 and 2 can be used. Further, the organic compound and the metal oxide used for the first mixed layer and the second mixed layer may be the same or different.

After the first mixed layer 3 and the second mixed layer 3 are formed in vacuum or under reduced pressure, the mixed layer 3 is not exposed to a gas atmosphere containing oxygen as shown in the first and second embodiments. Exposure to a nitrogen gas atmosphere at room temperature (FIGS. 5A and 5B). The water content in the nitrogen gas is 40 ppm or less, preferably 3 ppm or less. Nitrogen gas is introduced into the chamber in which the substrate 1 on which the mixed layer 3 is formed is set. The nitrogen gas is preferably one from which moisture has been removed as much as possible. Nitrogen gas is introduced at a flow rate of 1 to 500 sccm so that the pressure in the chamber is 1 × 10 ⁻¹ to 1 × 10 ⁶ Pa.

    The mixed layer 3 is exposed to a nitrogen gas atmosphere by being left for 1 to 24 hours while maintaining the pressure in the chamber. Alternatively, nitrogen gas may be sprayed onto the mixed layer 3. In this case, it is not necessary to leave for 1 to 24 hours, and it may be sprayed for 10 to 180 minutes.

    After the exposure to the nitrogen gas atmosphere, the nitrogen gas in the chamber may be removed and a vacuum or reduced pressure may be applied, and then the exposure may be performed again to the nitrogen gas atmosphere as described above. Thereafter, the hole transport layer 4 and the cathode 7 are formed in a vacuum or under reduced pressure without exposing the mixed layer to a gas atmosphere containing oxygen, whereby a light emitting device is manufactured. Thereby, the lifetime of the light emitting device can be improved.

    Up to this point, the anode 2 has been formed on the substrate 1 and the cathode 7 has been formed above the anode 2. However, the cathode 7 is formed on the substrate 1, the first mixed layer 3 is formed on the cathode 7, the first layer 15 is formed on the first mixed layer 3, and the electrons are formed on the first layer 15. The transport layer 6 is formed, the light emitting layer 5 is formed on the electron transport layer 6, the hole transport layer 4 is formed on the light emitting layer 5, and the second mixed layer 3 is formed on the hole transport layer 4. The present invention can also be applied to a light emitting device in which the anode 2 is formed on the second mixed layer 3 (FIG. 23).

    After the first mixed layer 3 is formed, the first layer 15 is formed without being exposed to a nitrogen gas atmosphere at room temperature without being exposed to a gas atmosphere containing oxygen, and then being exposed to a gas atmosphere containing oxygen. After the second mixed layer 3 is formed, the anode 2 is formed without being exposed to a nitrogen gas atmosphere without being exposed to a gas atmosphere containing oxygen, and then being exposed to a gas atmosphere containing oxygen.

    As the method for exposing the first and second mixed layers 3 to a nitrogen gas atmosphere, the above-described method can be used. Further, after the mixed layer is exposed to a nitrogen gas atmosphere, the nitrogen gas may be exhausted and again exposed to the nitrogen gas atmosphere. The mixed layer may be exposed to a nitrogen gas atmosphere by blowing nitrogen gas. The water content in the nitrogen gas is 40 ppm or less, preferably 3 ppm or less.

    Further, as described above, this light-emitting device can be manufactured by a vapor deposition method or the like in a vacuum or under reduced pressure.

(Embodiment 4)
The mixed layer 3 is formed by a method different from the method shown in the first to third embodiments. Here, a method of forming the mixed layer 3 in multiple steps without forming the mixed layer 3 at once will be described.

    As shown in FIGS. 1A and 1B, an anode 2 is formed on a substrate 1. After the anode 2 is heat-treated in vacuum or under reduced pressure to remove moisture and the like, the first mixed layer 17a is formed, for example, 10 to 30 nm in vacuum or under reduced pressure. After that, without exposure to a gas atmosphere containing oxygen, exposure is performed at room temperature to a nitrogen gas atmosphere in which the amount of water is reduced as much as shown in the above embodiment (FIG. 6A).

    Next, without exposing the first mixed layer 17a to a gas atmosphere containing oxygen, the second mixed layer 17b is formed in a vacuum or under reduced pressure, for example, 10 to 30 nm. Thereafter, the mixed layer 3 is formed by exposure to a nitrogen gas atmosphere in which the amount of moisture is reduced as much as possible at room temperature without being exposed to a gas atmosphere containing oxygen by the method described in the above embodiment (FIG. 6B). . The first mixed layer or the second mixed layer is left to stand for 1 to 24 hours while keeping the inside of the chamber at a constant pressure as shown in the above embodiment, or exposed to the nitrogen gas atmosphere. You may spray on the 1st mixed layer or the 2nd mixed layer.

    In addition, after the first mixed layer or the second mixed layer is exposed to a nitrogen gas atmosphere, the nitrogen gas in the chamber is removed and vacuum or reduced pressure is applied, and then the nitrogen gas atmosphere is again exposed as described above. Good.

    Next, without exposing the second mixed layer 17b to a gas atmosphere containing oxygen, a hole transport layer or the like is formed in a vacuum or under reduced pressure to manufacture a light emitting device. Thereby, the lifetime of the light emitting device can be improved.

    The present invention can also be applied to the case where the mixed layer 3 is provided in contact with the cathode. That is, after the first layer (electron injection layer) 15 is formed, the first mixed layer is formed, exposed to a nitrogen gas atmosphere, the second mixed layer is formed, exposed to the nitrogen gas atmosphere, and the cathode is formed. It will be. Needless to say, this embodiment can be applied to the structure described in the above embodiment.

    Further, the anode 2 is formed on the substrate 1, the hole transport layer is formed on the anode 2, the light emitting layer is formed on the hole transport layer, the electron transport layer is formed on the light emitting layer, and the electron transport layer is formed. The first mixed layer 3 is formed on the first layer, and the first mixed layer 3 is formed on the first layer. The first mixed layer 3 is exposed to a nitrogen gas atmosphere with a reduced amount of water at room temperature to form the second mixed layer. The present invention can also be applied to a light emitting device in which the cathode 7 is formed by exposure to a nitrogen gas atmosphere whose amount is reduced as much as possible.

    Also, a cathode 7 is formed on the substrate 1, a first mixed layer 3 is formed on the cathode 7, exposed to a nitrogen gas atmosphere at room temperature, a second mixed layer is formed, exposed to a nitrogen gas atmosphere, 1 layer 15, the electron transport layer 6 is formed on the first layer 15, the light emitting layer 5 is formed on the electron transport layer 6, the hole transport layer 4 is formed on the light emitting layer 5, The present invention can also be applied to a light emitting device in which the anode 2 is formed on the hole transport layer 4.

    Also, a cathode 7 is formed on the substrate 1, an electron transport layer 6 is formed on the cathode 7, a light emitting layer 5 is formed on the electron transport layer 6, and a hole transport layer 4 is formed on the light emitting layer 5. The first mixed layer 3 is formed on the hole transport layer 4 and exposed to a nitrogen gas atmosphere at room temperature. The second mixed layer is formed and exposed to a nitrogen gas atmosphere with a reduced amount of water at room temperature. The present invention can also be applied to a light emitting device that forms the anode 2.

(Embodiment 5)
In this embodiment, structures that are different from the structures described in the above embodiments are described. A light-emitting device having a structure in which a plurality of light-emitting units are stacked (hereinafter also referred to as a tandem light-emitting device) will be described. That is, a plurality of light emitting units are provided between the anode and the cathode. FIG. 7 shows a tandem light emitting device in which two light emitting units are stacked. A plurality of light emitting units are connected in series via a charge generation layer, and a mixed layer having an organic compound and a metal oxide is applied to the charge generation layer.

    In FIG. 7, a first light emitting unit 22 and a second light emitting unit 24 are stacked between an anode 20 and a cathode 21. A charge generation layer 23 is formed between the first light emitting unit 22 and the second light emitting unit 24.

  The materials described in the above embodiments can be used for the anode 20 and the cathode 21.

    The first light-emitting unit 22 and the second light-emitting unit 24 have a structure in which a hole transport layer, a light-emitting layer, and an electron transport layer are stacked from the anode 20 side, and the anode, the hole transport layer, the light-emitting layer, It has a laminated structure of an electron transport layer, a charge generation layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode. Here, the hole transport layer and the electron transport layer are not essential components, and may be provided as necessary. Further, a hole injection layer, an electron injection layer, or the like may be provided as necessary. The materials used for the light-emitting unit can be those described in the above embodiment modes.

    The charge generation layer 23 is formed by combining the mixed layer including the organic compound and the metal oxide described in the above embodiment and the layer including an electron donating substance and an electron transporting substance. You may form combining a mixed layer and a transparent conductive film. Since the mixed layer has a high visible light transmittance, the light transmittance of the light emitted from the first light emitting unit and the second light emitting unit is high, and the external extraction efficiency can be improved.

    The electron donating substance is preferably an alkali metal or alkaline earth metal and oxides or salts thereof. Specifically, lithium, cesium, calcium, lithium oxide, calcium oxide, barium oxide, cesium carbonate, and the like can be given. As the electron transporting substance, a substance that can be used for the electron transporting layer can be used.

    An anode 20 and a first light emitting unit 22 are formed on a substrate, and then a layer 25 having an electron donating substance and an electron transporting substance is formed by a vapor deposition method or the like in vacuum or under reduced pressure. Next, a mixed layer 26 containing an organic compound and a metal oxide is formed by a co-evaporation method or the like in a vacuum or under reduced pressure (FIG. 8A).

    After that, according to the method described in the above embodiment mode, the substrate is exposed to a nitrogen gas atmosphere in which the amount of moisture is reduced as much as possible at room temperature without being exposed to a gas atmosphere containing oxygen (FIG. 8B). Thereby, the lifetime of the light emitting device can be improved.

    Next, the second light emitting unit 24 is formed in a vacuum or under reduced pressure without being exposed to a gas atmosphere containing oxygen, and the cathode 21 is formed to complete the light emitting device shown in FIG. For the sealing, the method of the above embodiment can be used.

    In addition, the mixed layer 26 can be formed by being divided into a large number of times as shown in the fourth embodiment.

    Although the light-emitting device having two light-emitting units has been described in this embodiment mode, the material of the present invention can also be applied to a light-emitting device in which three or more light-emitting units are stacked. For example, a light emitting element in which three light emitting units are stacked is stacked in the order of a first light emitting unit, a first charge generating layer, a second light emitting unit, a second charge generating layer, and a third light emitting unit. However, the mixed layer containing the organic compound and the metal oxide may be included only in any one of the charge generation layers, or may be included in all the charge generation layers. Note that this embodiment can be combined with any of the other embodiments as appropriate.

    The first light emitting unit 22 and the second light emitting unit 24 may have a structure of an electron transport layer, a light emitting layer, and a hole transport layer, respectively.

    Further, a cathode is formed, a first light emitting unit having a light emitting layer is formed on the cathode, a mixed layer having an organic compound and a metal oxide is formed on the first light emitting unit, and the mixed layer A layer having an electron-donating substance and an electron-transporting substance without being exposed to a nitrogen gas atmosphere with a reduced amount of water at room temperature, and then exposed to a gas atmosphere containing oxygen. The present invention can also be applied to a light-emitting device that is formed and a second light-emitting unit is formed on a layer having the electron-donating substance and the electron-transporting substance, and an anode is formed on the second light-emitting unit.

(Embodiment 6)
In this embodiment, an example of a manufacturing process of a light-emitting device disclosed in the present invention and a multi-chamber manufacturing apparatus used at that time will be described. Here, after the substrate is loaded and the film formation process of the mixed layer, the light emitting layer, and the like are continuously performed, the sealing process is performed after being combined with the counter substrate that is loaded separately from the substrate.

    The light-emitting device manufacturing apparatus shown in FIG. 9 includes a transfer chamber 101 (attached with a transfer robot 111 for transferring a substrate, a counter, and a metal mask), a substrate connected to the transfer chamber through a gate valve, Mask stock chamber 102, pretreatment chamber 103, first vapor deposition chamber 104, second vapor deposition chamber 105, third vapor deposition chamber 106, fourth vapor deposition chamber 110, CVD chamber 107, and sealing glass stock chamber 108 And a sealing chamber 109.

    First, the substrate and the metal mask for vapor deposition are loaded in the substrate / mask stock chamber 102. The substrate / mask stock chamber 102 allows the substrate to be taken in and out of the chamber.

    The substrate / mask stock chamber has an elevator structure, and each stage of the elevator structure also serves as a substrate or a mask. A total of 10 to 15 sheets can be stored in total including the substrate and the mask. The substrate here has an anode formed outside the chamber.

    On the other hand, the counter substrate is loaded in the sealing glass stock chamber 108. The sealed glass stock chamber has an elevator structure, and pretreatment (typically, desiccant application for absorbing moisture inside and outside the panel, and formation of a sealing material for application to the substrate) The counter substrate having been finished) is stored.

    In this manufacturing apparatus, the film forming process is finished for all the substrates that have been input. This is called “evaporation mode”. After this vapor deposition mode is completed, a “sealing mode” in which bonding with the counter substrate is performed is entered.

Hereinafter, the vapor deposition mode will be described. First, the transfer chamber 101, the pretreatment chamber 103, the first vapor deposition chamber 104, the second vapor deposition chamber 105, the third vapor deposition chamber 106, the fourth vapor deposition chamber 110, and the CVD chamber 107 are, for example, 1 × 10 ^−5. Evacuate to high vacuum to ~ ^1x10-6 Pa. During the deposition mode, the transfer chamber is always kept at a high vacuum. The vapor deposition material set in each vapor deposition chamber is preheated at a temperature 30 ° C. lower than the respective evaporation start temperature. Preferably, the preheating time is 12 hours or longer. This is intended to remove water adhering to the vapor deposition material.

    Next, after the substrate / mask stock chamber 102 is evacuated, the mask is transferred to each deposition chamber. When the above preparation is completed, the substrate is transferred to the pretreatment chamber 103. In the pretreatment chamber 103, the substrate is heated in a vacuum or under reduced pressure by a lamp heater or the like. The substrate heating may be performed in the substrate / mask stock chamber 102.

    Next, the substrate is transferred from the pretreatment chamber 103 to the fourth vapor deposition chamber 110 via the transfer chamber 101, and after the alignment process using the mask and the CCD camera is completed, a mixed layer is formed. In the fourth vapor deposition chamber 110, an organic compound and a metal oxide are evaporated from a fixed vapor deposition source, and a film is formed on a substrate placed above. During the deposition, the substrate is rotated, which improves the in-plane distribution of the film thickness formed on the substrate.

Next, the substrate is transferred to the CVD chamber 107 via the transfer chamber 101 without being exposed to a gas atmosphere containing oxygen. The CVD chamber 107 is evacuated to high vacuum until the substrate is transferred to the CVD chamber 107. After transporting the substrate, a high-purity nitrogen gas with a reduced water content is supplied to the CVD chamber at 1 to 500 sccm, for example. Even if the nitrogen gas is supplied, the pressure in the CVD chamber becomes constant if the CVD chamber is exhausted by the turbo booster pump. The pressure is preferably 1 × 10 ⁻¹ to 1 × 10 ⁶ Pa. The substrate is blown with nitrogen gas for 10 to 180 minutes and exposed to nitrogen gas, and then the supply of nitrogen gas is stopped.

    After exhausting the nitrogen gas and evacuating the CVD chamber, the substrate may be exposed to the nitrogen gas by supplying the nitrogen gas again. When nitrogen gas is not sprayed onto the substrate, the nitrogen gas may be kept in the above pressure while being supplied into the CVD chamber and exposed to a nitrogen gas atmosphere for 1 to 24 hours.

In the CVD chamber 107, a CVD film can be formed on the entire surface of the substrate. Plasma treatment using a plurality of gases is also possible. By utilizing this, for example, a silicon nitride film, a silicon oxide film or the like as a protective film can be formed on the cathode. Further, as a pretreatment for the substrate, plasma treatment using a plurality of kinds of gases (for example, Ar + O ₂ plasma treatment) may be performed.

    Next, the substrate is transferred to the second vapor deposition chamber 105 through the transfer chamber 101 without exposing the mixed layer to a gas atmosphere containing oxygen. After the alignment process, a hole transport layer is formed.

    Next, the substrate is transferred to the first vapor deposition chamber 104 via the transfer chamber 101. The mechanism of the vapor deposition chamber and the film forming method are the same as those of the other vapor deposition chambers. Here, after the light emitting layer is formed, the electron transport layer is formed. The light emitting layer may be formed by co-evaporation of a host material and a dopant material. Further, switching from the light emitting layer to the electron transport layer can be smoothly performed by simply closing the vapor deposition source shutter attached to the vapor deposition source.

    Next, the substrate is transferred to the third vapor deposition chamber 106 via the transfer chamber 101. Here, a cathode is formed. The mechanism of the vapor deposition chamber and the film forming method are the same as those of the other vapor deposition chambers.

    The substrate that has undergone the necessary processing as described above is returned to the starting substrate / mask stock chamber 102 again via the transfer chamber 101. Although a series of processes necessary for obtaining a light emitting monochrome panel is shown here, the present invention is not particularly limited.

    When the same processing is completed for all the substrates that have been input and the mask is recovered from each vapor deposition chamber to the substrate / mask stock chamber 102, the vapor deposition mode ends, and the manufacturing apparatus continues to enter the sealing mode.

    Hereinafter, the sealing mode will be described. First, the transfer chamber 101, the substrate / mask stock chamber 102, and the sealing glass stock chamber 108 are pressurized with nitrogen gas to atmospheric pressure. For the transfer chamber and the substrate / mask stock chamber, this process may be performed immediately after the end of the deposition mode. In addition, with respect to the sealing glass stock chamber, deterioration of the sealing material and the desiccant can be suppressed by setting the counter substrate that has been subjected to the pretreatment immediately before sealing. After the setting, the moisture concentration in the transfer chamber in the sealing mode can be reduced by performing the pressurization process with the exhaust gas / nitrogen gas in the sealing glass stock chamber a plurality of times. Furthermore, the defoaming of the sealing material formed in the opposite direction can be performed.

    Next, the substrate is transferred from the substrate / mask stock chamber 102 and the counter substrate is transferred from the sealing glass stock chamber 108 to the sealing chamber 109 via the transfer chamber 101. In the sealing chamber, the end portions of the substrates are aligned with each other, and after the alignment processing of the substrate and the counter substrate is completed, the substrates and the counter substrate are bonded and pressed to perform sealing. Further, UV irradiation is performed from the counter substrate side (lower side) to cure the sealing material (here, UV curable resin). At this time, it is possible to selectively irradiate only the seal material portion with a light shielding mask.

    By the sealing process described above, the substrate and the counter substrate become an integrated panel. This panel is transferred from the sealing chamber 109 to the substrate / mask stock chamber 102 via the transfer chamber 101. Thereafter, the same processing is performed for the next substrate and the counter substrate. Finally, the panel is stored in the substrate / mask stock chamber, and the sealing mode ends. After completion of the sealing mode, the completed panel may be taken out from the substrate / mask stock chamber.

(Embodiment 7)
In this embodiment mode, a light-emitting device of the present invention will be described with reference to FIGS. Note that an example of manufacturing an active matrix light-emitting device is described in this embodiment mode.

    First, after the first base insulating layer 51a and the second base insulating layer 51b are formed over the substrate 50, a semiconductor layer is further formed over the second base insulating layer 51b. (Fig. 10 (A))

    As a material of the substrate 50, glass, quartz, plastic (polyimide, acrylic, polyethylene terephthalate, polycarbonate, polyacrylate, polyethersulfone, or the like) can be used. These substrates may be used after being polished by CMP or the like, if necessary. In this embodiment, a glass substrate is used.

    The first base insulating layer 51a and the second base insulating layer 51b prevent an element such as an alkali metal or an alkaline earth metal in the substrate 50 that adversely affects the characteristics of the semiconductor film from diffusing into the semiconductor layer. Provided for this purpose. As a material, silicon oxide, silicon nitride, silicon oxide containing nitrogen, silicon nitride containing oxygen, or the like can be used. In this embodiment mode, the first base insulating layer 51a is formed using silicon nitride, and the second base insulating layer 51b is formed using silicon oxide. In this embodiment mode, the base insulating layer is formed of the first base insulating layer 51a and the second base insulating layer 51b. However, the base insulating layer may be formed of a single layer or a multilayer of two or more layers. It doesn't matter. In addition, it is not necessary to provide a base insulating layer as long as the diffusion of impurities from the substrate does not matter.

    The semiconductor layer formed subsequently is obtained by laser crystallization of an amorphous silicon film in this embodiment mode. An amorphous silicon film is formed to a thickness of 25 to 100 nm (preferably 30 to 60 nm) over the second base insulating layer 51b. As a manufacturing method, a known method such as a sputtering method, a low pressure CVD method or a plasma CVD method can be used. After that, heat treatment is performed at 500 ° C. for 1 hour to dehydrogenate.

    Subsequently, the amorphous silicon film is crystallized using a laser irradiation apparatus to form a crystalline silicon film. An excimer laser is used in the laser crystallization of this embodiment. The oscillated laser beam is processed into a linear beam spot using an optical system and irradiated to an amorphous silicon film to form a crystalline silicon film, which is used as a semiconductor layer.

    As other crystallization methods of the amorphous silicon film, there are a method of performing crystallization only by heat treatment and a method of performing heat treatment using a catalyst element that promotes crystallization. Examples of elements that promote crystallization include nickel, iron, palladium, tin, lead, cobalt, platinum, copper, and gold. By using such an element, crystallization is performed at a lower temperature and in a shorter time than when crystallization is performed only by heat treatment. Therefore, there is little damage to the glass substrate. When crystallization is performed only by heat treatment, the substrate 50 may be a quartz substrate resistant to heat.

    Subsequently, in order to control the threshold value in the semiconductor layer as required, a small amount of impurity addition, so-called channel doping is performed. In order to obtain a required threshold value, N-type or P-type impurities (phosphorus, boron, etc.) are added by an ion doping method or the like.

    After that, as shown in FIG. 10A, the semiconductor layer is processed into a predetermined shape, and an island-shaped semiconductor layer 52 is obtained. Processing is performed by applying a photoresist to the semiconductor layer, exposing a predetermined mask shape, baking, forming a resist mask on the semiconductor layer, and etching using the mask.

    Subsequently, a gate insulating layer 53 is formed so as to cover the semiconductor layer 52. The gate insulating layer 53 is formed of an insulating layer containing silicon with a film thickness of 40 to 150 nm using a plasma CVD method or a sputtering method. In this embodiment mode, silicon oxide is used.

    Next, the gate electrode 54 is formed over the gate insulating layer 53. The gate electrode 54 may be formed of an element selected from tantalum, tungsten, titanium, molybdenum, aluminum, copper, chromium, and niobium, or an alloy material or a compound material containing the element as a main component. Alternatively, a semiconductor film typified by a polycrystalline silicon film doped with an impurity element such as phosphorus may be used. Further, an AgPdCu alloy may be used.

    Further, although the gate electrode 54 is formed as a single layer in this embodiment mode, a stacked structure of two or more layers such as tungsten in the lower layer and molybdenum in the upper layer may be used. Even in the case where the gate electrode is formed as a stacked structure, the materials described in the preceding stage may be used. Moreover, the combination may be selected as appropriate. The gate electrode 54 is processed by etching using a mask using a photoresist.

    Subsequently, a high concentration impurity is added to the semiconductor layer 52 using the gate electrode 54 as a mask. Thus, the thin film transistor 70 including the semiconductor layer 52, the gate insulating layer 53, and the gate electrode 54 is formed. Here, the LDD region 57 may be provided in addition to the source region 55 and the drain region 56 by using low-speed ion doping or high-speed ion doping.

  Note that there is no particular limitation on the manufacturing process of the thin film transistor, and it may be changed as appropriate so that a transistor with a desired structure can be manufactured.

    In this embodiment mode, a top-gate thin film transistor using a crystalline silicon film crystallized by laser crystallization is used; however, a bottom-gate thin film transistor using an amorphous semiconductor film can also be used. It is. As the amorphous semiconductor, not only silicon but also silicon germanium can be used. When silicon germanium is used, the concentration of germanium is preferably about 0.01 to 4.5 atomic%.

    Alternatively, a microcrystalline semiconductor film (semi-amorphous semiconductor) in which crystals of 0.5 nm to 20 nm can be observed in an amorphous semiconductor may be used. Microcrystals capable of observing 0.5 nm to 20 nm crystals are also called so-called microcrystals (μc).

Semi-amorphous silicon (also referred to as SAS) that is a semi-amorphous semiconductor can be obtained by glow discharge decomposition of a silane-based gas. A typical one is SiH ₄ , and in addition, Si ₂ H ₆ , SiH ₂ Cl ₂ , SiHCl ₃ , SiCl ₄ , SiF _{4, and the} like can be used. The formation of the SAS can be facilitated by diluting the above gas with one or plural kinds of rare gas elements selected from hydrogen, hydrogen and helium, argon, krypton, and neon. It is preferable to dilute the silane-based gas within a range of a dilution rate of 10 to 1000 times. The reaction generation of the film by glow discharge decomposition may be performed at a pressure in the range of 0.1 Pa to 133 Pa. The power for forming the glow discharge may be high frequency power of 1 MHz to 120 MHz, preferably 13 MHz to 60 MHz. The substrate heating temperature is preferably 300 ° C. or less, and a substrate heating temperature of 100 to 250 ° C. is suitable.

The SAS thus formed has a Raman spectrum shifted to a lower wavenumber than 520 cm ⁻¹ , and diffraction peaks of (111) and (220), which are considered to be derived from the Si crystal lattice in X-ray diffraction, are observed. Is done. Hydrogen or halogen is contained in at least 1 atomic% or more to terminate dangling bonds (dangling bonds). Impurities of atmospheric components such as oxygen, nitrogen, and carbon in the film are desirably 1 × 10 ²⁰ cm ⁻¹ or less, and in particular, the oxygen concentration is 5 × 10 ¹⁹ cm ⁻³ or less, preferably 1 × 10 ¹⁹ cm. ^-3 or less.

    Further, this SAS may be further crystallized with a laser.

    Subsequently, an insulating film (hydrogenated film) 59 is formed of silicon nitride so as to cover the gate electrode 54 and the gate insulating layer 53. After the insulating film (hydrogenated film) 59 is formed, heating is performed at 480 ° C. for about 1 hour to activate the impurity element and hydrogenate the semiconductor layer 52.

    Subsequently, a first interlayer insulating layer 60 covering the insulating film (hydrogenated film) 59 is formed. As a material for forming the first interlayer insulating layer 60, silicon oxide, acrylic, polyimide, siloxane, a low dielectric constant material, or the like may be used. In this embodiment mode, the silicon oxide film is formed as the first interlayer insulating layer. (Fig. 10 (B))

    Next, a contact hole reaching the semiconductor layer 52 is opened. The contact hole can be formed by performing etching using a resist mask until the semiconductor layer 52 is exposed, and can be formed by either wet etching or dry etching. Note that etching may be performed once depending on conditions, or etching may be performed in a plurality of times. In addition, when etching is performed a plurality of times, both wet etching and dry etching may be used. (Fig. 10 (C))

    Then, a conductive layer covering the contact hole and the first interlayer insulating layer 60 is formed. The conductive layer is processed into a desired shape, and the connection portion 61a, the wiring 61b, and the like are formed. This wiring may be a single layer of aluminum, copper, an alloy of aluminum, carbon, and nickel, an alloy of aluminum, carbon, and molybdenum, or a laminated structure of molybdenum, aluminum, molybdenum, titanium, and aluminum from the substrate side. A structure such as titanium, titanium, titanium nitride, aluminum, or titanium may be used. (Figure 10 (D))

    Thereafter, a second interlayer insulating layer 63 is formed so as to cover the connection portion 61a, the wiring 61b, and the first interlayer insulating layer 60. As a material for the second interlayer insulating layer 63, a coating film of acrylic, polyimide, siloxane or the like having self-flatness can be suitably used. In this embodiment mode, siloxane is used as the second interlayer insulating layer 63. (Fig. 10 (E))

    Subsequently, an insulating layer may be formed of silicon nitride or the like on the second interlayer insulating layer 63 (not shown). This is formed to prevent the second interlayer insulating layer 63 from being etched more than necessary in the subsequent etching of the pixel electrode. Therefore, when the ratio of the etching rate between the pixel electrode and the second interlayer insulating layer is large, it may not be provided. Subsequently, a contact hole that penetrates through the second interlayer insulating layer 63 and reaches the connection portion 61a is formed.

  Then, a light-transmitting conductive layer is formed so as to cover the contact hole and the second interlayer insulating layer 63 (or insulating layer), and then the light-transmitting conductive layer is processed to form the anode 64. . Here, the anode 64 is in electrical contact with the connecting portion 61a.

    The material of the anode 64 is aluminum (Al), silver (Ag), gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe). Conductivity of cobalt (Co), copper (Cu), palladium (Pd), lithium (Li), cesium (Cs), magnesium (Mg), calcium (Ca), strontium (Sr), titanium (Ti), etc. Or metal alloys such as aluminum-silicon (Al-Si), aluminum-titanium (Al-Ti), aluminum-silicon-copper (Al-Si-Cu), or titanium nitride (TiN) A conductive film as shown in Embodiment Mode 1, such as a metal compound such as nitride, ITO, ITO containing silicon oxide (ITSO), or IZO, is formed. Door can be.

    Further, the electrode for extracting light may be formed of a conductive film having transparency, and an ultrathin film of metal such as Al or Ag is used in addition to a metal compound such as ITO, ITSO, or IZO. When light emission is extracted from the cathode, a material with high reflectivity (Al, Ag, etc.) can be used for the anode. In this embodiment mode, ITSO is used as the anode 64 (FIG. 11A).

    Next, an insulating layer made of an organic material or an inorganic material is formed so as to cover the second interlayer insulating layer 63 (or insulating layer) and the anode 64. Subsequently, the insulating layer is processed so that a part of the anode 64 is exposed, and a partition wall 65 is formed. As the material of the partition wall 65, a photosensitive organic material (acrylic, polyimide, or the like) is preferably used, but it may be formed of an organic material or an inorganic material that does not have photosensitivity. Alternatively, a black pigment or dye such as titanium black or carbon nitride may be dispersed in the material of the partition wall 65 using a dispersing agent or the like, and the partition wall 65 may be blackened and used for the black matrix. It is desirable that the end surface of the partition wall 65 facing the anode has a curvature and has a tapered shape in which the curvature continuously changes (FIG. 11B). Thereafter, the substrate is heated in vacuum or under reduced pressure to remove moisture and the like.

    Next, a mixed layer containing an organic compound and a metal oxide is formed in a vacuum or under reduced pressure so as to cover the anode 64 exposed from the partition wall 65. This mixed layer is a layer having the structure described in Embodiment 1. In this embodiment, DNTPD is used as an organic compound, molybdenum trioxide is used as a metal compound, and molybdenum trioxide is 10 to 80 wt% with respect to DNTPD. It forms by co-evaporation so that it may become. Needless to say, the mixed layer may be formed using other materials described in Embodiment Mode 1.

    After that, the mixed layer is exposed to a nitrogen gas atmosphere at room temperature without being exposed to a gas atmosphere containing oxygen by the method described in the above embodiment. Nitrogen gas is introduced into the chamber in which the substrate is set. The nitrogen gas is desirably one from which moisture is removed as much as possible in the above embodiment.

Subsequently, without exposing the mixed layer to a gas atmosphere containing oxygen, NPB is formed to have a film thickness of 10 to 100 nm as a layer excellent in the function of transporting holes, and coumarin 6 is added to Alq ₃ as a light emitting layer in a weight ratio of 1: 0. 005, thickness 35～100Nm, as the electron transport layer is deposited in vacuum or under reduced pressure so that the Alq ₃ film thickness 10 to 100 nm. As a result, a light emitting laminate 66 composed of a mixed layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode 64.

    Subsequently, a cathode 67 that covers the light-emitting stacked body 66 is formed (FIG. 11C). Thus, a light emitting device 93 in which an organic layer including a light emitting layer is sandwiched between the anode 64 and the cathode 67 can be manufactured, and light emission can be obtained by applying a higher voltage to the anode than the cathode. As an electrode material used for forming the cathode 67, a material similar to the material of the anode can be used. In this embodiment, aluminum is used as the cathode. Thus, the light emitting device is completed.

Thereafter, a silicon oxide film containing nitrogen is formed as a passivation film by a plasma CVD method. In the case of using a silicon oxide film containing nitrogen, a silicon oxynitride film manufactured from SiH ₄ , N ₂ O, NH ₃ by a plasma CVD method, or a silicon oxynitride film manufactured from SiH ₄ , N ₂ O, Alternatively, a silicon oxynitride film formed from a gas obtained by diluting SiH ₄ and N ₂ O with Ar may be formed.

Alternatively, a silicon oxynitride silicon film formed from SiH ₄ , N ₂ O, and H ₂ by a plasma CVD method may be used as the passivation film. The passivation film is not limited to a single layer structure, and another insulating layer containing silicon may be used as a single layer structure or a laminated structure. Further, a multilayer film of carbon nitride film and silicon nitride film, a multilayer film of styrene polymer, a silicon nitride film, or a diamond-like carbon film may be formed instead of the silicon oxide film containing nitrogen.

    Subsequently, the display portion is sealed in order to protect the light emitting device from a substance that promotes deterioration such as water. In the case where the counter substrate is used for sealing, bonding is performed with an insulating sealing material so that the external connection portion is exposed. The space between the counter substrate and the element substrate may be filled with an inert gas such as dry nitrogen, or a sealing material may be formed on the entire surface of the pixel portion, thereby bonding the counter substrate. It is preferable to use an ultraviolet curable resin or the like for the sealing material. The sealing material may contain a desiccant or particles for keeping the gap between the substrates constant. Then, a flexible wiring board is affixed on an external connection part.

    One example of the structure of the light-emitting device manufactured as described above will be described with reference to FIG. In addition, even if the shapes are different, parts showing similar functions are denoted by the same reference numerals, and explanations thereof are omitted. In the present embodiment, the thin film transistor 70 having an LDD structure is connected to the light emitting device 93 through the connection portion 61a.

    12A shows a structure in which the anode 64 is formed of a light-transmitting conductive film, and light emitted from the light-emitting stacked body 66 is extracted to the substrate 50 side. Reference numeral 94 denotes a counter substrate, which is fixed to the substrate 50 using a sealing material after the light emitting device 93 is formed. By filling and sealing the light-transmitting resin 88 between the counter substrate 94 and the element, the light-emitting device 93 can be prevented from being deteriorated by moisture. Further, it is desirable that the resin 88 has a hygroscopic property. Further, if a desiccant 89 having high translucency is dispersed in the resin 88, the influence of moisture can be further suppressed, which is a more desirable form.

    In FIG. 12B, both the anode 64 and the cathode 67 are formed of a light-transmitting conductive film, and light can be extracted to both the substrate 50 and the counter substrate 94. Further, in this configuration, by providing the polarizing plate 90 outside the substrate 50 and the counter substrate 94, it is possible to prevent the screen from being seen through, and visibility is improved. A protective film 91 may be provided outside the polarizing plate 90.

    There is no particular limitation on the arrangement of transistors, light-emitting elements, and the like in the pixel portion. For example, they can be arranged as shown in the top view of FIG. In FIG. 13, the first electrode of the first transistor 1001 is connected to the source signal line 1004, and the second electrode is connected to the gate electrode of the second transistor 1002. The first electrode of the second transistor is connected to the current supply line 1005, and the second electrode is connected to the electrode 1006 of the light emitting element. Part of the gate signal line 1003 functions as a gate electrode of the first transistor 1001.

  Note that either an analog video signal or a digital video signal may be used for the light-emitting device of the present invention having a display function. When a digital video signal is used, the video signal is classified into one using a voltage and one using a current. At the time of light emission, a video signal input to a pixel has a constant voltage and a constant current, and a video signal having a constant voltage has a constant voltage applied to the light emitting device and emits light. Some currents flow through the device. In addition, the video signal having a constant current includes a constant voltage applied to the light emitting device and a constant current flowing in the light emitting device. A constant voltage applied to the light emitting device is constant voltage driving, and a constant current applied to the light emitting device is constant current driving. In constant current driving, a constant current flows regardless of the resistance change of the light emitting device. In the light emitting device and the driving method thereof according to the present invention, either a voltage driving method or a current driving method may be used, and either constant voltage driving or constant current driving may be used.

    The light emitting device of the present invention manufactured by the above manufacturing method has improved light emission lifetime without deterioration of characteristics. Further, this embodiment can be used in combination with the above embodiment.

(Embodiment 8)
In this embodiment mode, the appearance of a panel including the light-emitting device of the present invention will be described with reference to FIGS. 14 is a top view of a panel in which a transistor and a light-emitting element formed over a substrate are sealed with a sealant formed between a counter substrate 4006 and FIG. 14B is a cross-sectional view taken along line A- in FIG. Corresponds to the sectional view of A ′. The structure of the light-emitting device mounted on this panel is the structure shown in Embodiment Mode 7.

    A sealant 4005 is provided so as to surround the pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004 which are provided over the substrate 4001. A counter substrate 4006 is provided over the pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004. Therefore, the pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004 are sealed together with the filler 4007 by the substrate 4001, the sealant 4005, and the counter substrate 4006.

    The pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004 provided over the substrate 4001 include a plurality of thin film transistors. In FIG. 14B, the thin film transistor 4008 included in the signal line driver circuit 4003 is provided. And a thin film transistor 4010 included in the pixel portion 4002.

    In addition, the light-emitting device 4011 is electrically connected to the thin film transistor 4010.

    The lead wiring 4014 corresponds to a wiring for supplying a signal or a power supply voltage to the pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004. The lead wiring 4014 is connected to the connection terminal 4016 via the lead wirings 4015a and 4015b. The connection terminal 4016 is electrically connected to a terminal included in a flexible printed circuit (FPC) 4018 through an anisotropic conductive film 4019.

    Note that as the filler 4007, in addition to an inert gas such as nitrogen or argon, an ultraviolet curable resin or a thermosetting resin can be used, and polyvinyl chloride, acrylic, polyimide, epoxy resin, silicon resin, polyvinyl butyral, Alternatively, ethylene vinylene acetate can be used.

    Note that the light-emitting device of the present invention includes in its category a panel in which a pixel portion having a light-emitting element is formed and a module in which an IC is mounted on the panel.

    The light-emitting device of the present invention having such a configuration is a light-emitting device that can suppress the occurrence of dark spots without causing an increase in driving voltage or power consumption.

    This embodiment can be used in combination with the above embodiment.

(Embodiment 9)
In this embodiment mode, pixel circuits and protection circuits included in the panel and module described in Embodiment Mode 8 and operations thereof will be described. Note that the cross-sectional views shown in FIGS. 10 and 11 are cross-sectional views of the driving TFT 1403 and the light emitting device 1405.

  In the pixel shown in FIG. 15A, a signal line 1410 and power supply lines 1411 and 1412 are arranged in the column direction, and a scanning line 1414 is arranged in the row direction. The pixel further includes a switching TFT 1401, a driving TFT 1403, a current control TFT 1404, a capacitor element 1402, and a light emitting device 1405.

    The pixel shown in FIG. 15C is different from the pixel shown in FIG. 15A except that the gate electrode of the driving TFT 1403 is connected to the power supply line 1412 arranged in the row direction. It is a configuration. That is, the pixels shown in FIGS. 15A and 15C show the same equivalent circuit diagram. However, in the case where the power supply line 1412 is arranged in the column direction (FIG. 15A) and in the case where the power supply line 1412 is arranged in the row direction (FIG. 15C), each power supply line has a different layer. It is formed of a conductive film. Here, attention is paid to the wiring to which the gate electrode of the driving TFT 1403 is connected, and FIGS. 15A and 15C are separately shown in order to show that the layers for producing these are different.

    As a feature of the pixel shown in FIGS. 15A and 15C, a driving TFT 1403 and a current control TFT 1404 are connected in series in the pixel, and the channel length L (1403) and channel width W (1403) of the driving TFT 1403 are connected. ), The channel length L (1404) and the channel width W (1404) of the current control TFT 1404 satisfy L (1403) / W (1403): L (1404) / W (1404) = 5 to 6000: 1. It is good to set to.

    Note that the driving TFT 1403 operates in a saturation region and has a role of controlling a current value flowing to the light emitting device 1405, and the current control TFT 1404 operates in a linear region and has a role of controlling current supply to the light emitting device 1405. . Both TFTs preferably have the same conductivity type in terms of manufacturing process, and in this embodiment mode, they are formed as n-channel TFTs. The driving TFT 1403 may be a depletion type TFT as well as an enhancement type. In the light-emitting device having the above structure, since the current control TFT 1404 operates in a linear region, a slight change in Vgs of the current control TFT 1404 does not affect the current value of the light-emitting device 1405. That is, the current value of the light emitting device 1405 can be determined by the driving TFT 1403 operating in the saturation region. With the above structure, it is possible to provide a light-emitting device in which luminance unevenness of a light-emitting element due to variation in TFT characteristics is improved and image quality is improved.

    In the pixels shown in FIGS. 15A to 15D, the switching TFT 1401 controls input of a video signal to the pixel. When the switching TFT 1401 is turned on, a video signal is input into the pixel. Then, the voltage of the video signal is held in the capacitor element 1402. Note that FIGS. 15A and 15C illustrate a structure in which the capacitor 1402 is provided; however, the present invention is not limited to this, and the capacity for holding a video signal can be covered by a gate capacity or the like. In this case, the capacitor 1402 is not necessarily provided.

    The pixel shown in FIG. 15B has the same pixel structure as that shown in FIG. 15A except that a TFT 1406 and a scanning line 1415 are added. Similarly, the pixel illustrated in FIG. 15D has the same pixel structure as that illustrated in FIG. 15C except that a TFT 1406 and a scanning line 1415 are added.

    The TFT 1406 is controlled to be turned on or off by a newly arranged scanning line 1415. When the TFT 1406 is turned on, the charge held in the capacitor element 1402 is discharged, and the current control TFT 1404 is turned off. That is, the arrangement of the TFT 1406 can forcibly create a state in which no current flows through the light emitting device 1405. Therefore, the TFT 1406 can be called an erasing TFT. Accordingly, the configurations of FIGS. 15B and 15D can improve the duty ratio because the lighting period can be started simultaneously with or immediately after the start of the writing period without waiting for signal writing to all the pixels. It becomes possible.

  In the pixel shown in FIG. 15E, a signal line 1410, a power supply line 1411 are arranged in the column direction, and a scanning line 1414 is arranged in the row direction. In addition, the pixel includes a switching TFT 1401, a driving TFT 1403, a capacitor element 1402, and a light emitting device 1405. The pixel illustrated in FIG. 15F has the same pixel structure as that illustrated in FIG. 15E except that a TFT 1406 and a scanning line 1415 are added. Note that the duty ratio can also be improved by the arrangement of the TFT 1406 in the structure of FIG.

    As described above, various pixel circuits can be employed. In particular, in the case where a thin film transistor is formed from an amorphous semiconductor film, it is preferable to increase the semiconductor film of the driving TFT 1403. Therefore, it is preferable that the pixel circuit be a top emission type in which light from the light emitting laminate is emitted from the sealing substrate side.

    Such an active matrix light-emitting device is considered to be advantageous because it can be driven at a low voltage because a TFT is provided in each pixel when the pixel density is increased.

    In this embodiment mode, an active matrix light-emitting device in which each pixel is provided with each TFT has been described; however, a passive matrix light-emitting device can also be formed. A passive matrix light-emitting device has a high aperture ratio because a TFT is not provided for each pixel. In the case of a light-emitting device in which light emission is emitted to both sides of a light-emitting stack, transmittance using a passive matrix light-emitting device is increased.

    In the light-emitting device of the present invention further including the pixel circuit as described above, a material suitable for the configuration and required performance of the light-emitting device can be used as the electrode of the light-emitting device, and the light-emitting device having the above characteristics. It can be a device.

    Next, the case where a diode is provided as a protective circuit in the scan line and the signal line will be described using the equivalent circuit illustrated in FIG.

    In FIG. 16, switching TFTs 1401 and 1403, a capacitor element 1402, and a light emitting device 1405 are provided in the pixel portion 1500. The signal line 1410 is provided with diodes 1561 and 1562. Similarly to the switching TFT 1401 or 1403, the diodes 1561 and 1562 are manufactured based on the above embodiment mode and include a gate electrode, a semiconductor layer, a source electrode, a drain electrode, and the like. The diodes 1561 and 1562 operate as diodes by connecting a gate electrode and a drain electrode or a source electrode.

    Common potential lines 1554 and 1555 connected to the diodes 1561 and 1562 are formed in the same layer as the gate electrode. Therefore, in order to connect to the source electrode or the drain electrode of the diode, it is necessary to form a contact hole in the gate insulating layer.

  The diodes 1563 and 1564 provided in the scanning line 1414 have the same configuration.

    Thus, according to the present invention, the protection diode provided in the input stage can be formed simultaneously. Note that the position where the protective diode is formed is not limited to this, and the protective diode can be provided between the driver circuit and the pixel.

    The light-emitting device of the present invention having such a protection circuit has high reliability because the light-emitting device can be driven stably for a long time, and the above structure makes it possible to further increase the reliability as the light-emitting device. Become.

(Embodiment 10)
As an electronic apparatus having the light emitting device of the present invention in which the module as shown in the above embodiment is mounted, a camera such as a video camera / digital camera, a goggle type display (head mounted display), a navigation system, and sound reproduction Device (car audio component, etc.), computer, game machine, portable information terminal (mobile computer, mobile phone, portable game machine, electronic book, etc.), image playback device (specifically Digital Versatile Disc (equipment) with recording medium) DVD) and the like, and a device provided with a display capable of displaying the image. Specific examples of these electronic devices are shown in FIGS.

  FIG. 17A illustrates a television receiver, a personal computer monitor, and the like. A housing 3001, a display portion 3003, a speaker portion 3004, and the like are included. The display portion 3003 is provided with an active matrix display device. The display portion 3003 includes a light-emitting device and a TFT using the manufacturing method of the present invention for each pixel. By having the light emitting device of the present invention, a television with little characteristic deterioration and a long light emission life can be obtained.

  FIG. 17B illustrates a mobile phone, which includes a main body 3101, a housing 3102, a display portion 3103, a voice input portion 3104, a voice output portion 3105, operation keys 3106, an antenna 3108, and the like. The display portion 3103 is provided with an active matrix display device. The display portion 3103 includes a light emitting device and a TFT using the manufacturing method of the present invention for each pixel. By having the light-emitting device of the present invention, a cellular phone with a long light emission life can be obtained with little deterioration in characteristics.

  FIG. 17C illustrates a computer, which includes a main body 3201, a housing 3202, a display portion 3203, a keyboard 3204, an external connection port 3205, a pointing mouse 3206, and the like. The display portion 3203 is provided with an active matrix display device. The display portion 3203 includes a light-emitting device and a TFT using the manufacturing method of the present invention for each pixel. By having the light emitting device of the present invention, a computer with little characteristic deterioration and a long light emission lifetime can be obtained.

    FIG. 17D illustrates a mobile computer, which includes a main body 3301, a display portion 3302, a switch 3303, operation keys 3304, an infrared port 3305, and the like. The display portion 3302 is provided with an active matrix display device. The display portion 3302 has a light-emitting device and a TFT using the manufacturing method of the present invention for each pixel. By having the light emitting device of the present invention, a mobile computer with little characteristic deterioration and a long light emission lifetime can be obtained.

    FIG. 17E illustrates a portable game machine including a housing 3401, a display portion 3402, speaker portions 3403, operation keys 3404, a recording medium insertion portion 3405, and the like. The display portion 3402 is provided with an active matrix display device. The display portion 3402 includes a light emitting device and a TFT using the manufacturing method of the present invention for each pixel. By having the light emitting device of the present invention, a portable game machine with little characteristic deterioration and a long light emission life can be obtained.

    FIG. 18A illustrates a flexible display, which includes a main body 3110, a pixel portion 3111, a driver IC 3112, a receiving device 3113, a film battery 3114, and the like. The receiving device can receive a signal from the infrared communication port 3107 of the mobile phone. The pixel portion 3111 is provided with an active matrix display device. The pixel portion 3111 includes a light emitting device and a TFT using the manufacturing method of the present invention for each pixel. By having the light emitting device of the present invention, a flexible display with little characteristic deterioration and a long light emission lifetime can be obtained.

    FIG. 18B illustrates an ID card manufactured by applying the present invention, which includes a support body 5541, a display portion 5542, an integrated circuit chip 5543 incorporated in the support body 5541, and the like.

    The display portion 5542 is provided with an active matrix display device. The display portion 5542 is provided with an active matrix display device. The display portion 5542 includes a light-emitting device and a TFT using the manufacturing method of the present invention for each pixel. By having the light emitting device of the present invention, it is possible to obtain an ID card with little characteristic deterioration and a long light emission life.

    As described above, the applicable range of the present invention is so wide that it can be used for electronic devices in various fields.

    Here, a mixed layer is formed using DNTPD as an organic compound, molybdenum trioxide as a metal oxide, and rubrene, which is a highly sterically hindered substance, and then exposed to a nitrogen gas atmosphere, and then a hole transport layer, a light emitting layer, and an electron transport The time change of the luminance of the light emitting device in which the layer, the electron injection layer, and the cathode were formed and the light emitting device manufactured without being exposed to the nitrogen gas atmosphere were examined.

    An anode 2 made of ITO was formed on the glass substrate 1, and then heated at 150 ° C. for 30 minutes under reduced pressure (FIGS. 1A and 1B). Next, DNTPD, molybdenum trioxide, and rubrene were co-evaporated under reduced pressure to form a mixed layer 3 having a thickness of 120 nm (FIG. 1C). DNTPD, molybdenum trioxide, and rubrene were mixed at DNTPD: molybdenum trioxide: rubrene = 1: 0.5: 0.02 (mass ratio). Thereafter, the mixed layer 3 was exposed to a nitrogen gas atmosphere at room temperature overnight under atmospheric pressure without being exposed to a gas atmosphere containing oxygen (FIG. 1D). The water content in the nitrogen gas was about 0.5 ppm.

Next, without exposing the mixed layer 3 to a gas atmosphere containing oxygen, NPB was formed by a 10 nm deposition method as the hole transport layer 4 under reduced pressure (FIG. 19). The light emitting layer 5 was formed by vapor deposition using Alq ₃ as a host material and DMQd as a dopant material (FIG. 19). Alq ₃ and DMQd were adjusted to be Alq ₃ : DMQd = 1: 0.003 (mass ratio).

The electron transport layer 6 was formed by forming Alq ₃ at 37.5 nm under reduced pressure by a vapor deposition method. Next, 1 nm of CaF ₂ was formed in vacuum as the electron injection layer 16 and 200 nm of Al was formed under reduced pressure as the cathode 7 to manufacture the light emitting device 1 (FIG. 19).

    On the other hand, as a comparative example, a light-emitting device 2 in which a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode were formed without forming the mixed layer 3 and then exposing to a nitrogen gas atmosphere was produced. The light emitting device 2 was manufactured under the same conditions as the light emitting device 1 except that the mixed layer 3 was not exposed to the nitrogen gas atmosphere.

FIG. 20 shows the results of measuring the temporal change in the light emission luminance of the light emitting devices 1 and 2 manufactured in this example. In FIG. 20, 1 indicates the light emitting device 1, and 2 indicates the light emitting device 2. The horizontal axis represents elapsed time (hour), and the vertical axis represents emission luminance. The light emission luminance is shown as a relative value with respect to the initial luminance when the initial luminance is 100. Note that this measurement was performed by a method in which a current having a constant current density was continuously supplied to the light emitting device and the luminance of the light emitting device was measured every arbitrary time. As the current density, a value at an initial luminance of 3000 cd / m ² was used.

    If the time when the luminance is 70 compared to the initial luminance (100) is the light emission lifetime, the light emission lifetime of the light-emitting device 2 is 530 hours, but the light emission lifetime of the light-emitting device 1 is 710 hours. It was. Therefore, by exposing the mixed layer 3 to a nitrogen gas atmosphere, the light emission lifetime was improved about 1.3 times.

4A and 4B illustrate a method for manufacturing a light-emitting device of the present invention. 4A and 4B illustrate a method for manufacturing a light-emitting device of the present invention. 4A and 4B illustrate a method for manufacturing a light-emitting device of the present invention. 4A and 4B illustrate a method for manufacturing a light-emitting device of the present invention. 4A and 4B illustrate a method for manufacturing a light-emitting device of the present invention. 4A and 4B illustrate a method for manufacturing a light-emitting device of the present invention. 4A and 4B illustrate a method for manufacturing a light-emitting device of the present invention. 4A and 4B illustrate a method for manufacturing a light-emitting device of the present invention. 4A and 4B illustrate a device used for manufacturing a light-emitting device of the present invention. 4A and 4B illustrate a method for manufacturing a light-emitting device of the present invention. 4A and 4B illustrate a method for manufacturing a light-emitting device of the present invention. FIG. 6 illustrates a light-emitting device. FIG. 6 illustrates a pixel portion of a light-emitting device. FIG. 6 illustrates a light-emitting device. 3A and 3B each illustrate a pixel circuit of a light-emitting device. 4A and 4B each illustrate a protection circuit of a pixel circuit of a light-emitting device. 4A and 4B each illustrate an electronic device or the like to which a light-emitting device manufactured according to the present invention can be applied. 4A and 4B each illustrate an electronic device or the like to which a light-emitting device manufactured according to the present invention can be applied. 4A and 4B illustrate a method for manufacturing a light-emitting device of the present invention. The figure explaining the reliability of the light-emitting devices 1 and 2 of an Example. 4A and 4B illustrate a method for manufacturing a light-emitting device of the present invention. 4A and 4B illustrate a method for manufacturing a light-emitting device of the present invention. 4A and 4B illustrate a method for manufacturing a light-emitting device of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Mixed layer 4 Hole transport layer 5 Light emitting layer 6 Electron transport layer 7 Cathode 8 Passivation film 9 Resin 10 Desiccant or particle 11 Substrate 15 First layer 16 Electron injection layer 17a First mixed layer 17b First 2 mixed layer 20 anode 21 cathode 22 first light emitting unit 23 charge generating layer 24 second light emitting unit 25 layer 26 having electron donating substance and electron transporting substance mixed layer 50 substrate 51a insulating layer 51b insulating layer 52 semiconductor Layer 53 gate insulating layer 54 gate electrode 55 source region 56 drain region 57 LDD region 59 insulating film 60 insulating layer 61a connecting portion 61b wiring 63 insulating layer 64 anode 65 partition 66 light emitting laminate 67 cathode 70 thin film transistor 88 resin 89 desiccant 90 polarization Plate 91 Protective film 93 Light emitting device 94 Counter substrate 101 Transfer chamber 102 Substrate / mask stock Chamber 103 Pretreatment chamber 104 First deposition chamber 105 Second deposition chamber 106 Third deposition chamber 107 CVD chamber 108 Sealing glass stock chamber 109 Sealing chamber 110 Fourth deposition chamber 111 Transfer robot 1001 Transistor 1002 Transistor 1003 Gate signal line 1004 Source signal line 1005 Current supply line 1006 Electrode 1401 Switching TFT
1402 Capacitor element 1403 Driving TFT
1404 Current control TFT
1405 Light Emitting Device 1406 TFT
1410 Signal line 1411 Power supply line 1412 Power supply line 1414 Scanning line 1415 Scanning line 1500 Pixel portion 1554 Common potential line 1555 Common potential line 1561 Diode 1562 Diode 1563 Diode 1564 Diode 3001 Case 3003 Display portion 3004 Speaker portion 3101 Main body 3102 Case 3103 Display Unit 3104 audio input unit 3105 audio output unit 3106 operation key 3107 infrared communication port 3108 antenna 3110 main body 3111 pixel unit 3112 driver IC
3113 Receiving device 3114 Film battery 3201 Main body 3202 Case 3203 Display unit 3204 Keyboard 3205 External connection port 3206 Pointing mouse 3301 Main unit 3302 Display unit 3303 Switch 3304 Operation key 3305 Infrared port 3401 Display unit 3403 Speaker unit 3404 Operation key 3405 Recording Medium insertion portion 4001 Substrate 4002 Pixel portion 4003 Signal line driver circuit 4004 Scan line driver circuit 4005 Sealant 4006 Counter substrate 4007 Filler 4008 Thin film transistor 4010 Thin film transistor 4011 Light emitting device 4014 Wiring 4015a Wiring 4015b Wiring 4016 Connection terminal 4018 FPC
4019 Anisotropic conductive film 4020 Drive circuit 5541 Support body 5542 Display unit 5543 Integrated circuit chip 5544 Integrated circuit 5545 Integrated circuit 5551 Display unit 5552 Body 5553 Antenna 5554 Audio output unit 5555 Audio input unit 5556 Operation switch 5557 Operation switch 5557

Claims (26)

Forming the anode,
A mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the anode by a co-evaporation method , and the mixed layer has a thickness of 60 nm or more, and the organic compound having the arylamine group The molybdenum oxide has a weight ratio of 95: 5 to 20:80,
The mixed layer is exposed to a nitrogen gas atmosphere without being exposed to a gas atmosphere containing oxygen, and then a hole transport layer is formed without exposing the mixed layer to a gas atmosphere containing oxygen, and the moisture content in the nitrogen gas is 40 ppm. And
Forming a light emitting layer on the hole transport layer;
Forming a cathode on the light emitting layer;
A method for manufacturing a light-emitting device, wherein the anode, the mixed layer, the hole transport layer, the light-emitting layer, and the cathode are manufactured in a vacuum or under reduced pressure . Forming the anode,
A first mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the anode by a co-evaporation method , and the thickness of the first mixed layer is 10 to 30 nm. The weight ratio of the organic compound having an amine group and the molybdenum oxide is 95: 5 to 20:80,
The first mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then the first mixed layer is exposed to a gas atmosphere containing oxygen and an organic compound having an arylamine group and molybdenum oxide The second mixed layer is formed by a co-evaporation method , the thickness of the second mixed layer is 10 to 30 nm, and the organic compound having an arylamine group and the molybdenum oxide are in a weight ratio. 95: 5 to 20:80, the water content in the nitrogen gas is 40 ppm or less,
Exposing the second mixed layer to a nitrogen gas atmosphere without exposing to a gas atmosphere containing oxygen, and then forming a hole transport layer without exposing the second mixed layer to a gas atmosphere containing oxygen; The moisture content in the gas is 40 ppm or less,
Forming a light emitting layer on the hole transport layer;
Forming a cathode on the light emitting layer;
A method for manufacturing a light emitting device , wherein the anode, the first mixed layer, the second mixed layer, the hole transport layer, the light emitting layer, and the cathode are manufactured in a vacuum or under reduced pressure . Forming the anode,
Forming a hole transport layer on the anode;
Forming a light emitting layer on the hole transport layer;
Forming an electron transport layer on the light emitting layer;
A mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the electron transport layer by a co-evaporation method , and the thickness of the mixed layer is 60 nm or more, and the organic layer having the arylamine group is formed. The compound and the molybdenum oxide are in a weight ratio of 95: 5 to 20:80,
The mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then a cathode is formed without exposing the mixed layer to a gas atmosphere containing oxygen. The water content in the nitrogen gas is 40 ppm or less. The
The anode, the hole transport layer, the emission layer, the electron transport layer, a method for manufacturing a light emitting device comprising that you prepared in the mixed layer and the vacuum in the cathode or reduced pressure. Forming the anode,
Forming a hole transport layer on the anode;
Forming a light emitting layer on the hole transport layer;
Forming an electron transport layer on the light emitting layer;
A first mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the electron transport layer by a co-evaporation method , and the thickness of the first mixed layer is 10 to 30 nm, The organic compound having an arylamine group and the molybdenum oxide have a weight ratio of 95: 5 to 20:80,
The first mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then the first mixed layer is exposed to a gas atmosphere containing oxygen and an organic compound having an arylamine group and molybdenum oxide The second mixed layer is formed by a co-evaporation method , the thickness of the second mixed layer is 10 to 30 nm, and the organic compound having an arylamine group and the molybdenum oxide are in a weight ratio. 95: 5 to 20:80, the water content in the nitrogen gas is 40 ppm or less,
The second mixed layer is exposed to a nitrogen gas atmosphere without being exposed to a gas atmosphere containing oxygen, and then a cathode is formed without exposing the second mixed layer to a gas atmosphere containing oxygen. the amount is Ri der below 40ppm,
The anode, the hole transport layer, the emission layer, the electron transport layer, and the first mixed layer, characterized that you prepared in the second mixed layer and the vacuum in the cathode or reduced pressure A method for manufacturing a light-emitting device.   The method for manufacturing a light-emitting device according to claim 1, wherein the mixed layer is formed after heat treatment is performed on the anode.   3. The method for manufacturing a light-emitting device according to claim 2, wherein the first mixed layer is formed after the anode is subjected to heat treatment.   4. The method for manufacturing a light-emitting device according to claim 3, wherein an electron injection layer is formed between the mixed layer and the electron transport layer.   5. The method for manufacturing a light-emitting device according to claim 4, wherein an electron injection layer is formed between the first mixed layer and the electron transport layer. Forming the cathode,
A mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the cathode by a co-evaporation method , and the mixed layer has a thickness of 60 nm or more, and the organic compound having the arylamine group The molybdenum oxide has a weight ratio of 95: 5 to 20:80,
The mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then an electron injection layer is formed without exposing the mixed layer to a gas atmosphere containing oxygen, and the moisture content in the nitrogen gas is 40 ppm or less. And
Forming an electron transport layer on the electron injection layer;
Forming a light emitting layer on the electron transport layer;
Forming a hole transport layer on the light emitting layer;
Forming an anode on the hole transport layer;
A method for manufacturing a light emitting device, wherein the cathode, the mixed layer, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, and the anode are manufactured in a vacuum or under reduced pressure . Forming the cathode,
A first mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the cathode by a co-evaporation method , and the thickness of the first mixed layer is 10 to 30 nm. The weight ratio of the organic compound having an amine group and the molybdenum oxide is 95: 5 to 20:80,
The first mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then the first mixed layer is exposed to a gas atmosphere containing oxygen and an organic compound having an arylamine group and molybdenum oxide The second mixed layer is formed by a co-evaporation method , the thickness of the second mixed layer is 10 to 30 nm, and the organic compound having an arylamine group and the molybdenum oxide are in a weight ratio. 95: 5 to 20:80, the water content in the nitrogen gas is 40 ppm or less,
The second mixed layer is exposed to a nitrogen gas atmosphere without being exposed to a gas atmosphere containing oxygen, and then an electron injection layer is formed without exposing the second mixed layer to a gas atmosphere containing oxygen. The amount of water in is 40 ppm or less,
Forming an electron transport layer on the electron injection layer;
Forming a light emitting layer on the electron transport layer;
Forming a hole transport layer on the light emitting layer;
Forming an anode on the hole transport layer;
The cathode, the first mixed layer, the second mixed layer, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, and the anode are produced in a vacuum or under reduced pressure. A method for manufacturing a light-emitting device. Forming the cathode,
Forming an electron transport layer on the cathode;
Forming a light emitting layer on the electron transport layer;
Forming a hole transport layer on the light emitting layer;
A mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the hole transport layer by a co-evaporation method , and the thickness of the mixed layer is 60 nm or more, and has the arylamine group. The organic compound and the molybdenum oxide have a weight ratio of 95: 5 to 20:80,
The mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then an anode is formed without exposing the mixed layer to a gas atmosphere containing oxygen, and the moisture content in the nitrogen gas is 40 ppm or less. The
The cathode, the electron transport layer, the emission layer, the hole transport layer, a method for manufacturing a light emitting device comprising that you prepared in vacuum or under reduced pressure the mixture layer and the anode. Forming the cathode,
Forming an electron transport layer on the cathode;
Forming a light emitting layer on the electron transport layer;
Forming a hole transport layer on the light emitting layer;
A first mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the hole transport layer by a co-evaporation method , and the thickness of the first mixed layer is 10 to 30 nm. The organic compound having an arylamine group and the molybdenum oxide are in a weight ratio of 95: 5 to 20:80,
The first mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then the first mixed layer is exposed to a gas atmosphere containing oxygen and an organic compound having an arylamine group and molybdenum oxide The second mixed layer is formed by a co-evaporation method , the thickness of the second mixed layer is 10 to 30 nm, and the organic compound having an arylamine group and the molybdenum oxide are in a weight ratio. 95: 5 to 20:80, the water content in the nitrogen gas is 40 ppm or less,
The second mixed layer is exposed to a nitrogen gas atmosphere without being exposed to a gas atmosphere containing oxygen, and then an anode is formed without exposing the second mixed layer to a gas atmosphere containing oxygen. the amount is Ri der below 40ppm,
The cathode, the electron transport layer, the emission layer, the hole transport layer, the first mixed layer, characterized that you prepared in the second mixed layer and vacuum or reduced pressure under the anode A method for manufacturing a light-emitting device. According to claim 1,3,9 or 11, the mixed layer after exposure to the nitrogen gas atmosphere by evacuating the nitrogen gas, a method for manufacturing a light emitting device characterized by exposing to a nitrogen gas atmosphere again. According to claim 2, 4, 10 or 12, the first mixed layer after exposure to the nitrogen gas atmosphere by evacuating the nitrogen gas, exposed to a nitrogen gas atmosphere again,
Wherein the second mixed layer after exposure to a nitrogen gas atmosphere, and evacuating the nitrogen gas, a method for manufacturing a light emitting device characterized by exposing to a nitrogen gas atmosphere again. 12. The method for manufacturing a light-emitting device according to claim 1, wherein the mixed layer is exposed to the nitrogen gas atmosphere by blowing nitrogen gas onto the mixed layer. According to claim 2, 4, 10 or 12, the method for manufacturing a light emitting device, wherein the exposure to the first mixed layer and the second said nitrogen gas atmosphere by spraying nitrogen gas to a mixed layer of. Forming the anode,
A first mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the anode by a co-evaporation method , and the thickness of the first mixed layer is 10 to 30 nm. The weight ratio of the organic compound having an amine group and the molybdenum oxide is 95: 5 to 20:80,
The first mixed layer is exposed to a nitrogen gas atmosphere without being exposed to an oxygen-containing gas atmosphere, and then a hole transport layer is formed without exposing the first mixed layer to an oxygen-containing gas atmosphere. The moisture content in the gas is 40 ppm or less,
Forming a light emitting layer on the hole transport layer;
Forming an electron transport layer on the light emitting layer;
A second mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the electron transport layer by a co-evaporation method , and the thickness of the second mixed layer is 10 to 30 nm, The organic compound having an arylamine group and the molybdenum oxide have a weight ratio of 95: 5 to 20:80,
The second mixed layer is exposed to a nitrogen gas atmosphere without being exposed to a gas atmosphere containing oxygen, and then a cathode is formed without exposing the second mixed layer to a gas atmosphere containing oxygen. the amount is Ri der below 40ppm,
The anode, the first mixed layer, the hole transport layer, the emission layer, the electron transport layer, characterized that you prepared in the second mixed layer and the vacuum in the cathode or under reduced pressure of A method for manufacturing a light-emitting device.   The method for manufacturing a light-emitting device according to claim 17, wherein the first mixed layer is formed after heat treatment is performed on the anode.   The method for manufacturing a light-emitting device according to claim 17, wherein an electron injection layer is formed between the second mixed layer and the electron transport layer. Forming the cathode,
A first mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the cathode by a co-evaporation method , and the thickness of the first mixed layer is 10 to 30 nm. The weight ratio of the organic compound having an amine group and the molybdenum oxide is 95: 5 to 20:80,
The first mixed layer is exposed to a nitrogen gas atmosphere without being exposed to a gas atmosphere containing oxygen, and then an electron injection layer is formed without exposing the first mixed layer to a gas atmosphere containing oxygen. The amount of water in is 40 ppm or less,
Forming an electron transport layer on the electron injection layer;
Forming a light emitting layer on the electron transport layer;
Forming a hole transport layer on the light emitting layer;
A second mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the hole transport layer by a co-evaporation method , and the thickness of the second mixed layer is 10 to 30 nm. The organic compound having an arylamine group and the molybdenum oxide are in a weight ratio of 95: 5 to 20:80,
The second mixed layer is exposed to a nitrogen gas atmosphere without being exposed to a gas atmosphere containing oxygen, and then an anode is formed without exposing the second mixed layer to a gas atmosphere containing oxygen. the amount is Ri der below 40ppm,
The cathode, the first mixed layer, the electron injection layer, the electron transport layer, the emission layer, the hole transport layer, you manufactured in vacuum or under reduced pressure the second mixed layer and the anode of A method for manufacturing a light-emitting device. According to claim 17 or 20, the first mixed layer after exposure to the nitrogen gas atmosphere by evacuating the nitrogen gas, exposed to a nitrogen gas atmosphere again,
Wherein the second mixed layer after exposure to a nitrogen gas atmosphere, and evacuating the nitrogen gas, a method for manufacturing a light emitting device characterized by exposing to a nitrogen gas atmosphere again. According to claim 17 or 20, the method for manufacturing a light emitting device, wherein the exposure to the first mixed layer and the second said nitrogen gas atmosphere by spraying nitrogen gas to a mixed layer of. Forming the anode,
Forming a first light emitting unit having a light emitting layer on the anode;
Forming a layer having an electron donating substance and an electron transporting substance on the first light emitting unit;
A mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the layer having the electron donating substance and the electron transporting substance by a co-evaporation method , and the thickness of the mixed layer is 60 nm. The weight ratio of the organic compound having an arylamine group and the molybdenum oxide is 95: 5 to 20:80,
The mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then a second light-emitting unit is formed without exposing the mixed layer to a gas atmosphere containing oxygen. 40 ppm or less,
Forming a cathode on the second light emitting unit;
The anode, the first light emitting unit, the layer having the electron donating substance and the electron transporting substance, the mixed layer, the second light emitting unit, and the cathode are produced in a vacuum or under reduced pressure. A method for manufacturing a light-emitting device. Forming the anode,
Forming a first light emitting unit having a light emitting layer on the anode;
Forming a layer having an electron donating substance and an electron transporting substance on the first light emitting unit;
A first mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the layer having the electron donating substance and the electron transporting substance by a co-evaporation method , and the first mixing is performed. The film thickness of the layer is 10 to 30 nm, and the organic compound having an arylamine group and the molybdenum oxide are 95: 5 to 20:80 by weight ratio,
The first mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then the first mixed layer is exposed to a gas atmosphere containing oxygen and an organic compound having an arylamine group and molybdenum oxide The second mixed layer is formed by a co-evaporation method , the thickness of the second mixed layer is 10 to 30 nm, and the organic compound having an arylamine group and the molybdenum oxide are in a weight ratio. 95: 5 to 20:80, the water content in the nitrogen gas is 40 ppm or less,
Forming the second light emitting unit without exposing the second mixed layer to a nitrogen gas atmosphere without exposing the second mixed layer to a gas atmosphere containing oxygen, and then exposing the second mixed layer to a gas atmosphere containing oxygen; The moisture content in nitrogen gas is 40 ppm or less,
Forming a cathode on the second light emitting unit;
The anode, the first light emitting unit, the layer having the electron donating substance and the electron transporting substance, the first mixed layer, the second mixed layer, the second light emitting unit, and the cathode are vacuumed. A method for manufacturing a light-emitting device, which is manufactured in the middle or under reduced pressure . Forming the cathode,
Forming a first light emitting unit having a light emitting layer on the cathode;
A mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the first light-emitting unit by a co-evaporation method , and the thickness of the mixed layer is 60 nm or more, and the arylamine group The organic compound having a weight ratio of molybdenum oxide to the molybdenum oxide is 95: 5 to 20:80,
The mixed layer is exposed to a nitrogen gas atmosphere without being exposed to a gas atmosphere containing oxygen, and then a layer having an electron donating substance and an electron transporting substance is formed without exposing the mixed layer to a gas atmosphere containing oxygen. The water content in the nitrogen gas is 40 ppm or less,
Forming a second light-emitting unit on the layer having the electron-donating substance and the electron-transporting substance;
Forming an anode on the second light emitting unit;
The cathode, the first light emitting unit, the mixed layer, the layer having the electron donating substance and the electron transporting substance, the second light emitting unit and the anode are produced in a vacuum or under reduced pressure. A method for manufacturing a light-emitting device. Forming the cathode,
Forming a first light emitting unit having a light emitting layer on the cathode;
A first mixed layer having an organic compound having an arylamine group and molybdenum oxide is formed on the first light emitting unit by a co-evaporation method , and the thickness of the first mixed layer is 10 to 30 nm. And the organic compound having an arylamine group and the molybdenum oxide are 95: 5 to 20:80 in a weight ratio,
The first mixed layer is not exposed to a gas atmosphere containing oxygen, but is exposed to a nitrogen gas atmosphere, and then the first mixed layer is exposed to a gas atmosphere containing oxygen and an organic compound having an arylamine group and molybdenum oxide The second mixed layer is formed by a co-evaporation method , the thickness of the second mixed layer is 10 to 30 nm, and the organic compound having an arylamine group and the molybdenum oxide are in a weight ratio. 95: 5 to 20:80, the water content in the nitrogen gas is 40 ppm or less,
Exposing the second mixed layer to a nitrogen gas atmosphere without exposing the second mixed layer to an oxygen-containing gas atmosphere, and then exposing the second mixed layer to an oxygen-containing gas atmosphere; A moisture content in the nitrogen gas is 40 ppm or less,
Forming a second light-emitting unit on the layer having the electron-donating substance and the electron-transporting substance;
Forming an anode on the second light emitting unit;
The cathode, the first light emitting unit, the first mixed layer, the second mixed layer, the layer having the electron donating substance and the electron transporting substance, the second light emitting unit and the anode are vacuumed. A method for manufacturing a light-emitting device, which is manufactured in the middle or under reduced pressure .

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