WO2017047346A1 - Dispositif électronique et procédé d'étanchéification de dispositif électronique - Google Patents

Dispositif électronique et procédé d'étanchéification de dispositif électronique Download PDF

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Publication number
WO2017047346A1
WO2017047346A1 PCT/JP2016/074751 JP2016074751W WO2017047346A1 WO 2017047346 A1 WO2017047346 A1 WO 2017047346A1 JP 2016074751 W JP2016074751 W JP 2016074751W WO 2017047346 A1 WO2017047346 A1 WO 2017047346A1
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Prior art keywords
layer
transition metal
gas barrier
electronic device
sealing
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PCT/JP2016/074751
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English (en)
Japanese (ja)
Inventor
真人 奥山
礼子 小渕
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コニカミノルタ株式会社
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Priority to CN201680053520.6A priority Critical patent/CN108029164B/zh
Priority to JP2017539804A priority patent/JP6737279B2/ja
Priority to KR1020187007027A priority patent/KR102004107B1/ko
Publication of WO2017047346A1 publication Critical patent/WO2017047346A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity

Definitions

  • the present invention relates to an electronic device and an electronic device sealing method. More specifically, the present invention relates to an electronic device including a sealing layer having high gas barrier performance, and an electronic device sealing method using the sealing layer.
  • An electronic device particularly an organic electroluminescence device (hereinafter also referred to as an organic EL device or an organic EL element) is formed with a sealing layer that covers the element in order to prevent deterioration of organic materials and electrodes used due to moisture. Is done.
  • the sealing layer for the organic EL device has a water vapor transmission rate (WVTR) of 10 ⁇ 5 to 10 ⁇ 6 g / m 2 ⁇ 24 h in an environment of 25 ⁇ 0.5 ° C. and 90 ⁇ 2% RH. It is said that a very high gas barrier property is required.
  • gas barrier films using a vapor phase film forming apparatus have been manufactured as a gas barrier substrate.
  • gas barrier films in the order of 10 ⁇ 3 g / m 2 ⁇ 24 h are manufactured by a physical vapor deposition (PVD) film forming apparatus such as a sputtering method.
  • PVD physical vapor deposition
  • a laminated gas barrier film has been studied.
  • Group A including tantalum (Ta), niobium (Nb), etc.) oxide, nitride, oxynitride, and Group B (boron (B), aluminum (Al), silica (Si) ), Titanium (Ti), tantalum (Ta), etc.) oxide, nitride, oxynitride, and the like are stacked and formed by sputtering or the like, and a technique for obtaining a stacked gas barrier film is disclosed.
  • the gas barrier performance is not sufficient, and only a gas barrier film of 10 ⁇ 2 g / m 2 ⁇ 24 h is obtained.
  • Patent Document 2 discloses a silicon nitride (SiN) film (thickness: 2 ⁇ m) formed by a CVD (chemical vapor deposition) film forming method and a polysilazane coating film (thickness: 500 nm).
  • SiN silicon nitride
  • CVD chemical vapor deposition
  • polysilazane coating film thinness: 500 nm.
  • a combined sealing film has been proposed.
  • the polysilazane coating film is formed only by coating and drying, and uses only the moisture absorption capability, the initial performance has an apparent water vapor blocking function due to the moisture absorption capability, but after the moisture absorption capability is saturated Will lose its water vapor blocking function and only have a limited effect.
  • a process requiring a long deposition time is required for forming a 2 ⁇ m thick SiN film, and the required gas barrier property cannot be satisfied only by a 2 ⁇ m thick SiN film.
  • an electronic device including a sealing layer having a gas barrier property that minimizes the time of exposure to high temperature and ultraviolet (UV) and satisfies the required performance, and an electronic device sealing method using the sealing layer is necessary.
  • the present invention has been made in view of the above-described problems and situations, and a solution to the problem is an electronic device including a sealing layer having high gas barrier performance, and sealing of an electronic device using the sealing layer. Is to provide a method.
  • the sealing layer of the electronic device includes a first gas barrier layer containing an oxide of a specific metal (M1) and A stack of second gas barrier layers containing an oxide of a specific metal (M2), or a gas barrier layer containing a composite oxide of the metal (M1) and the metal (M2).
  • An electronic device having a functional element and a sealing layer for sealing the functional element on a base material, wherein the sealing layer contains an oxide of a non-transition metal (M1) of Groups 12 to 14 Or a non-transition layer of the first gas barrier layer and the second gas barrier layer containing an oxide of a transition metal (M2) disposed in contact with the first gas barrier layer.
  • An electronic device comprising a gas barrier layer containing a composite oxide of a metal (M1) and the transition metal (M2) or a region containing the composite oxide.
  • transition metal (M2) is selected from niobium (Nb), tantalum (Ta), and vanadium (V). .
  • An electronic device sealing method for forming a functional element and a sealing layer for sealing the functional element on a base material, wherein the sealing layer is a non-transition of at least one layer of Group 12-14 Lamination of a first gas barrier layer containing an oxide of metal (M1) and a second gas barrier layer containing an oxide of transition metal (M2) arranged in contact with the first gas barrier layer Or a gas barrier layer containing a composite oxide of the non-transition metal (M1) and the transition metal (M2) or a region containing the composite oxide by a vapor deposition method or a coating method.
  • An electronic device sealing method comprising forming the electronic device.
  • a second gas barrier layer containing an oxide of the transition metal (M2) is formed on the first gas barrier layer containing an oxide of the non-transition metal (M1) by a vapor deposition method.
  • Item 10 The method for sealing an electronic device according to Item 8 or 9, wherein the method is formed.
  • the first gas barrier layer containing the non-transition metal (M1) oxide contains polysilazane and a modified polysilazane, and the polysilazane modified is coated with a coating liquid containing polysilazane.
  • the present invention is an electronic device including a sealing layer having a high gas barrier property applicable to an organic EL element, and the sealing layer includes an oxide of a non-transition metal (M1) of Groups 12 to 14 A stack of a first gas barrier layer containing and a second gas barrier layer containing an oxide of a transition metal (M2) disposed in contact with the first gas barrier layer, It is a gas barrier layer containing a transition metal (M1) and a composite oxide of the transition metal (M2), or a region containing the composite oxide.
  • M1 non-transition metal
  • M2 transition metal
  • the non-transition metal (M1) and the transition metal (M 1) and the transition metal ( M2) and a region in which the composition is present simultaneously are formed, and the region is a region containing a metal oxide having a composition in which oxygen is deficient with respect to the stoichiometric composition. It is considered that a region having a high-density bond is formed and a high gas barrier property is expressed.
  • the gas barrier layer containing the composite oxide of the non-transition metal (M1) and the transition metal (M2), or the region containing the composite oxide for example, Si (or SiO x ) and Nb (or NbO x ) is simultaneously sputtered as a sputtering target (also referred to as co-deposition or co-sputtering), oxygen is introduced as a reactive gas, and a composite oxide of Si and Nb is formed in a stoichiometric manner.
  • the obtained composite oxide is considered to have a structure having a Si—Nb bond.
  • the composite oxide having a high-density bond between metals As a result, when the oxygen-deficient composition is satisfied so that the relational expression (1) is satisfied with respect to the composite oxide having the stoichiometric composition, the composite oxide having a high-density bond between metals. It is presumed that the gas barrier layer containing or a region containing the complex oxide exhibits high gas barrier properties.
  • 1 is a schematic cross-sectional view showing an electronic device including a sealing layer according to an embodiment of the present invention.
  • 1 is a schematic cross-sectional view showing an electronic device including a sealing layer according to an embodiment of the present invention.
  • 1 is a schematic cross-sectional view showing an electronic device including a sealing layer according to an embodiment of the present invention.
  • the cross-sectional schematic diagram which shows the electronic device which comprises the sealing layer which has the organic polymer layer and gas barrier layer which concern on another embodiment of this invention.
  • the cross-sectional schematic diagram which shows the electronic device which comprises the sealing layer which has the organic polymer layer and gas barrier layer which concern on another embodiment of this invention.
  • a graph for explaining the element profile and the composite composition region when the composition distribution of the non-transition metal (M1) and the transition metal (M2) in the thickness direction of the sealing layer is analyzed by the XPS method.
  • Schematic diagram of evaluation device for WVTR measurement Schematic sectional view showing an example of a vacuum ultraviolet light irradiation apparatus applicable to the formation of a sealing layer according to the present invention
  • the electronic device of the present invention is an electronic device having a functional element and a sealing layer for sealing the functional element on a base material, wherein the sealing layer is a non-transition metal of group 12-14 ( A stack of a first gas barrier layer containing an oxide of M1) and a second gas barrier layer containing an oxide of a transition metal (M2) disposed in contact with the first gas barrier layer; Or a gas barrier layer containing a composite oxide of the non-transition metal (M1) and the transition metal (M2) or a region containing the composite oxide.
  • This feature is a technical feature common to the claimed invention.
  • the non-transition metal (M1) is formed on a part of the laminate of the first gas barrier layer and the second gas barrier layer in the thickness direction.
  • a region containing a composite oxide of the transition metal (M2) is preferable from the viewpoint of forming a sealing layer having a high gas barrier property.
  • the gas barrier layer or region containing the composite oxide has M1 as a non-transition metal, M2 as a transition metal, O as oxygen, and N as nitrogen, (M1) (M2) x O y N
  • M1 (M2) M1 (M2) x O y N
  • M1 (M2) M1 (M2) x O y N
  • the relational expression (1) represents that the region containing the composite oxide has a composition in which oxygen is deficient with respect to the stoichiometric composition.
  • the layer containing the non-transition metal (M1) is preferably a layer containing polysilazane or a modified polysilazane from the viewpoint of uniformly sealing the functional element, and the transition metal ( M2) is preferably selected from niobium (Nb), tantalum (Ta), and vanadium (V) from the viewpoint of further improving gas barrier properties by forming the composite oxide.
  • the functional element has an organic functional layer including a pair of electrodes and at least one light emitting layer between the electrodes.
  • An electronic device sealing method of the present invention is a method for sealing an electronic device in which a functional element and a sealing layer for sealing the functional element are formed on a substrate, and the sealing layer includes at least 1st gas barrier layer containing oxide of non-transition metal (M1) of Group 12-14 of 1 layer, and oxide of transition metal (M2) arrange
  • a second gas barrier layer containing an oxide of the transition metal (M2) is formed on the first gas barrier layer containing an oxide of the non-transition metal (M1) by a vapor deposition method. From the viewpoint of efficiently forming the gas barrier layer or region containing the composite oxide with high productivity.
  • the first gas barrier layer containing the oxide of the non-transition metal (M1) contains polysilazane and a modified polysilazane, and the modified polysilazane is coated with a coating liquid containing polysilazane.
  • the gas barrier layer or region containing the composite oxide can be formed with high accuracy and stability, and the gas barrier property is excellent in optical characteristics such as transmittance. From the viewpoint of obtaining a high sealing layer, this is a preferred embodiment.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the electronic device of the present invention is an electronic device having a functional element and a sealing layer for sealing the functional element on a base material, wherein the sealing layer is a non-transition metal of group 12-14 ( A stack of a first gas barrier layer containing an oxide of M1) and a second gas barrier layer containing an oxide of a transition metal (M2) disposed in contact with the first gas barrier layer; Or a gas barrier layer containing a composite oxide of the non-transition metal (M1) and the transition metal (M2) or a region containing the composite oxide.
  • the “sealing layer” is sometimes referred to as a “gas barrier layer”, but in this case, they are substantially the same layer.
  • the functional element according to the present invention is not particularly limited, but preferably refers to an element made of an organic material such as an organic EL element, an organic thin film solar cell, a liquid crystal display device, a touch panel, and the like.
  • a functional element is preferably an organic EL element.
  • the organic EL element which is a preferable example of the functional element according to the present invention is preferably composed of a pair of electrodes and an organic functional layer having at least one light emitting layer between the electrodes.
  • the gas barrier property of the sealing layer that seals the organic EL element is 10 ⁇ 5 to 10 ⁇ 6 g /% in terms of water vapor permeability (WVTR) in an environment of 25 ⁇ 0.5 ° C. and 90 ⁇ 2% RH.
  • WVTR water vapor permeability
  • a very high gas barrier property of m 2 ⁇ 24 h is required.
  • the high gas barrier property is achieved by providing a first gas barrier layer containing an oxide of a non-transition metal (M1) of Groups 12 to 14 and a transition disposed in contact with the first gas barrier layer.
  • non-transition metal (M1) in the present invention refers to a metal other than a transition metal and belonging to Groups 12 to 14 of the long-period periodic table, and “transition metal (M2)” Means a metal belonging to Groups 3-11.
  • FIG. 1 is a schematic cross-sectional view showing an electronic device including a sealing layer according to an embodiment of the present invention.
  • the 1A includes a pair of electrodes 2 and an organic functional layer 3 having at least one light emitting layer between the electrodes as a functional element on a substrate 1.
  • the electrode 2 and the organic functional layer 3 may be formed on both surfaces of the base material as well as the form in which the organic functional layer 3 is disposed on one surface of the base material.
  • a sealing layer 4 is formed on the organic functional layer 3 so as to cover the organic functional layer 3 and a part of the substrate 1.
  • the sealing layer 4 has a first gas barrier layer 5 containing an oxide of a non-transition metal (M1) and a second gas barrier layer 6 containing an oxide of a transition metal (M2), and the gas A region 7A (hereinafter also referred to as a composite composition region) containing a composite oxide of a non-transition metal (M1) and a transition metal (M2) exists at the interface between the barrier layer 5 and the gas barrier layer 6.
  • the sealing layer 4 has a three-layer structure including the gas barrier layer 5, the gas barrier layer 6, and the region 7A.
  • the sealing layer 4 may further include a plurality of regions 7A that are composite composition regions.
  • the layer order of the first gas barrier layer 5 and the second gas barrier layer 6 may be in any order.
  • a pair of electrodes 2 and an organic functional layer 3 having at least one light-emitting layer between the electrodes are formed on a substrate 1, and the non-transition metal ( And a gas barrier layer 7B (also referred to as a composite composition gas barrier layer in the present application) composed of a composite oxide of M1) and the transition metal (M2).
  • the gas barrier layer 7B shown here is sputtered simultaneously with a non-transition metal (M1) oxide and the transition metal (M2) oxide as a sputtering target by co-evaporation described later, and oxygen is introduced as a reactive gas.
  • the gas barrier layer is formed under the condition that oxygen is insufficient compared to the stoichiometric composition when the composite oxide of the non-transition metal (M1) and the transition metal (M2) is formed.
  • the substrate 1 is a moisture-permeable substrate such as a resin film, it is at least one surface of the substrate, preferably both surfaces.
  • 1 shows an embodiment having a gas barrier layer 8.
  • FIG. 2 is a schematic cross-sectional view showing an electronic device including an organic polymer layer and a sealing layer according to another embodiment of the present invention.
  • An electronic device 10 shown in FIG. 2A is formed by forming an organic functional layer 3 having a pair of electrodes 2 and at least one light emitting layer between the electrodes on a base material 1, and on the organic functional layer 3,
  • the organic polymer layer 9 is formed so as to cover all of the organic functional layer 3 and a part of the substrate 1 and then sealed with the sealing layer 4.
  • the sealing layer 4 has a first gas barrier layer 5 containing an oxide of a non-transition metal (M1) and a second gas barrier layer 6 containing an oxide of a transition metal (M2), and the layer A region 7A (composite composition region) containing a composite oxide of a non-transition metal (M1) and a transition metal (M2) exists at the interface between 5 and the layer 6.
  • an organic polymer layer 9 and a sealing layer 4 are further laminated as an upper layer.
  • the sealing layer 4 has a gas barrier layer 7B (composite composition gas barrier layer) composed of a composite oxide of the non-transition metal (M1) and the transition metal (M2).
  • a gas barrier layer 7B composite composition gas barrier layer
  • M1 non-transition metal
  • M2 transition metal
  • the organic polymer layer 9 and the sealing layer 4 are similarly laminated.
  • composition content and layer thickness can be determined by the following composition analysis by XPS.
  • the composite composition region referred to in the present invention refers to the first gas barrier layer containing an oxide of the non-transition metal (M1) and the transition metal (when the composition distribution in the thickness direction of the sealing layer is analyzed by the XPS method.
  • the non-transition metal (M1) and the transition metal (M2) coexist in the interface region with the second gas barrier layer containing the oxide of M2), and the transition metal (M2) / non-transition metal (described later)
  • the value of the atomic ratio of M1) is defined as a region having a thickness in the range of 0.02 to 49 and a thickness of 5 nm or more.
  • the element concentration distribution (hereinafter referred to as depth profile) in the thickness direction of the sealing layer according to the present invention includes a non-transition metal (M1) distribution curve (for example, a silicon distribution curve), a transition metal (M2). ) Distribution curves (for example, niobium distribution curves), oxygen (O), nitrogen (N), carbon (C) distribution curves, etc. are measured by X-ray photoelectron spectroscopy (XPS) and noble gases such as argon.
  • XPS X-ray photoelectron spectroscopy
  • XPS X-ray photoelectron spectroscopy
  • noble gases such as argon
  • a distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio of each element (unit: atom%) and the horizontal axis as the etching time (sputtering time).
  • the etching time is generally correlated with the distance from the surface of the sealing layer in the thickness direction of the sealing layer in the layer thickness direction, As the “distance from the surface of the sealing layer in the thickness direction of the sealing layer”, the distance from the surface of the sealing layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement Can be adopted.
  • etching rate is 0.05 nm / It is preferable to set to sec (SiO 2 thermal oxide film conversion value).
  • ⁇ Analyzer QUANTERA SXM manufactured by ULVAC-PHI ⁇ X-ray source: Monochromatic Al-K ⁇ ⁇ Sputtering ion: Ar (2 keV)
  • Depth profile Measurement is repeated at a predetermined thickness interval with a SiO 2 equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).
  • the background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area.
  • Data processing uses MultiPak manufactured by ULVAC-PHI.
  • the analyzed elements are non-transition metal M1 (for example, silicon (Si)), transition metal M2 (for example, niobium (Nb)), oxygen (O), nitrogen (N), and carbon (C).
  • the composition ratio is calculated from the obtained data, the non-transition metal M1 and the transition metal M2 coexist, and the value of the number ratio of transition metal M2 / non-transition metal M1 is 0.02 to 49.
  • the range was determined, this was defined as the composite composition region, and the thickness was determined.
  • the thickness of the composite composition region represents the sputter depth in XPS analysis in terms of SiO 2 .
  • a composite composition region is determined when the thickness of the composite composition region is 5 nm or more. From the viewpoint of gas barrier properties, there is no upper limit of the thickness of the composite composition region, but from the viewpoint of optical properties and productivity, it is preferably in the range of 5 to 200 nm, more preferably 8 to 100 nm. Within the range, more preferably within the range of 10 to 60 nm.
  • FIG. 3 shows a schematic graph of the element profile when the composition distribution of the non-transition metal M1 and the transition metal M2 in the thickness direction of the sealing layer including the composite composition region is analyzed by the XPS method.
  • FIG. 3 shows the elemental analysis of M1, M2, O, N, and C in the depth direction from the surface of the sealing layer (the left end of the graph), and the horizontal axis indicates the sputtering depth (film thickness: nm). It is the graph which showed the content rate (atom%) of M1 and M2 on the vertical axis
  • the element composition of the second gas barrier layer containing the oxide of transition metal (M2), the element composition of the composite composition region, and the oxide of non-transition metal (M1: Si in the figure) from the left side.
  • the element composition profile in one gas barrier layer is shown, and the composite composition region is a region having a value of the number ratio of M2 / M1 in the range of 0.02 to 49 and a thickness of 5 nm or more.
  • Substrate As the substrate according to the present invention, specifically, application of glass or a resin film is preferable, and when flexibility is required, a resin film is preferable.
  • Preferred resins include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, and cellulose acylate resin.
  • the base material is preferably made of a material having heat resistance. Specifically, a base material having a linear expansion coefficient of 15 ppm / K or more and 100 ppm / K or less and a glass transition temperature (Tg) of 100 ° C. or more and 300 ° C. or less is used.
  • the base material satisfies the requirements for use as a laminated film for electronic parts and displays. That is, when using the sealing layer which concerns on these uses for these uses, a base material may be exposed to the process of 150 degreeC or more.
  • the linear expansion coefficient of the base material exceeds 100 ppm / K, the substrate dimensions are not stable when flowing through the temperature process as described above, and the barrier performance deteriorates due to thermal expansion and contraction. Or, the problem that it cannot withstand the thermal process is likely to occur. If it is less than 15 ppm / K, the film may break like glass and the flexibility may deteriorate.
  • Polyolefin for example, ZEONOR (registered trademark) 1600: 160 ° C, manufactured by Nippon Zeon Co., Ltd.
  • polyarylate PAr: 210 ° C
  • polyethersulfone PES: 220 ° C
  • polysulfone PSF: 190 ° C
  • cycloolefin copolymer COC: Compound described in JP-A No. 2001-150584: 162 ° C.
  • polyimide for example, Neoprim (registered trademark): 260 ° C.
  • the substrate is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.
  • the light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.
  • the above-mentioned base material may be an unstretched film or a stretched film.
  • the said base material can be manufactured by a conventionally well-known general method. Regarding the method for producing these base materials, the items described in paragraphs “0051” to “0055” of International Publication No. 2013/002026 can be appropriately employed.
  • the surface of the substrate may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and the above treatments are performed in combination as necessary. It may be. Moreover, you may perform an easily bonding process to a base material.
  • the base material may be a single layer or a laminated structure of two or more layers.
  • the respective substrates may be the same type or different types.
  • the thickness of the substrate according to the present invention (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m.
  • a resin film it is preferably a resin film substrate with a gas barrier layer (FIG. 1C).
  • the gas barrier layer may be formed with an inorganic film, an organic film, or a hybrid film of both on the surface of the film substrate, and measured by a method in accordance with JIS K 7129-1992, 25 ⁇ 0. It is preferably a gas barrier film having a water vapor permeability of 0.01 g / m 2 ⁇ 24 h or less in an environment of 5 ° C. and 90 ⁇ 2% RH, and moreover, by a method based on JIS K 7126-2006. The measured oxygen permeability under an environment of 85 ° C.
  • RH is 1 ⁇ 10 ⁇ 3 mL / m 2 ⁇ 24 h ⁇ atm or less, and the water vapor permeability is 1 ⁇ 10 ⁇ 3 g / m 2 ⁇ 24 h.
  • the following high gas barrier films are preferred.
  • the material for forming the gas barrier layer may be any material as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
  • the gas barrier layer is not particularly limited.
  • an inorganic material is sputtered (for example, magnetron cathode sputtering, flat plate magnetron sputtering, bipolar AC Reactive sputtering methods such as flat-plate magnetron sputtering, 2-pole AC rotating magnetron sputtering, etc.), vapor deposition methods (for example, resistance heating vapor deposition, electron beam vapor deposition, ion beam vapor deposition, plasma assisted vapor deposition, etc.), thermal CVD methods, catalytic chemistry Layer formation by chemical vapor deposition such as vapor phase epitaxy (Cat-CVD), capacitively coupled plasma CVD (CCP-CVD), photo CVD, plasma CVD (PE-CVD), epitaxial growth, atomic layer deposition It is preferable to do.
  • Cat-CVD vapor phase epitaxy
  • CCP-CVD capacitively coupled plasma CVD
  • PE-CVD plasma CVD
  • epitaxial growth atomic layer deposition
  • an inorganic gas barrier layer is formed.
  • the inorganic gas barrier layer can also be formed by a metallization technique such as metal plating on a resin base material or adhesion of a metal foil and a resin base material.
  • the inorganic gas barrier layer may include an organic layer containing an organic polymer. That is, the inorganic gas barrier layer may be a laminate of an inorganic layer containing an inorganic material and an organic layer.
  • the organic layer can be polymerized using, for example, an electron beam device, a UV light source, a discharge device, or other suitable device, for example, by applying an organic monomer or oligomer to a resin substrate to form a layer. And it can form by bridge
  • Examples of the method for applying the organic monomer or organic oligomer include roll coating (for example, gravure roll coating) and spray coating (for example, electrostatic spray coating).
  • roll coating for example, gravure roll coating
  • spray coating for example, electrostatic spray coating
  • laminated body of an inorganic layer and an organic layer the laminated body of the international publication 2012/003198, international publication 2011/013341, etc. are mentioned, for example.
  • the thickness of each layer may be the same or different.
  • the layer thickness of the inorganic layer is preferably in the range of 3 to 1000 nm, more preferably in the range of 10 to 300 nm.
  • the layer thickness of the organic layer is preferably in the range of 100 nm to 100 ⁇ m, more preferably in the range of 1 to 50 ⁇ m.
  • the sealing layer according to the present invention can be preferably applied to a functional element whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air.
  • Examples of the functional element according to the present invention include, for example, an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like. From the viewpoint that the effect of the present invention can be obtained more efficiently, an organic EL element or a solar cell is preferable, and an organic EL element is particularly preferable.
  • an organic EL element or a solar cell is preferable, and an organic EL element is particularly preferable.
  • the functional element is preferably an organic functional layer having a pair of electrodes on a substrate and at least one light emitting layer between the electrodes, and constitutes an organic EL element.
  • Organic EL element comprising an organic functional layer having a pair of electrodes according to the present invention and at least one light emitting layer between the electrodes is, for example, an anode, One organic functional layer group, a light emitting layer, a second organic functional layer group, and a cathode are laminated.
  • the first organic functional layer group includes, for example, a hole injection layer, a hole transport layer, an electron blocking layer, and the like
  • the second organic functional layer group includes, for example, a hole blocking layer, an electric transport layer, and an electron injection layer.
  • Etc Each of the first organic functional layer group and the second organic functional layer group may be composed of only one layer, or the first organic functional layer group and the second organic functional layer group may not be provided.
  • the organic EL element may have a non-ode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode (ii) Anode / hole injection transport layer / light emitting layer / hole blocking layer / electron injection transport layer / cathode (iii) Anode / Hole injection / transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron injection transport layer / cathode (iv) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / Cathode (v) Anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode (vi) Anode / hole injection layer / hole transport layer / electron blocking Layer / light emitting layer / hole blocking layer / electron transporting layer / electron injecting layer / cathode Furthermore, the organic
  • JP2013-157A No. 634, JP 2013-168552 A, JP 2013-177361 A, JP 2013-187411 A, JP 2013-191644 A, JP 2013-191804 A, JP 2013-225678 A.
  • the sealing layer according to the present invention is a layer that exhibits gas barrier properties
  • the functional element according to the present invention is a base material.
  • a first gas barrier layer and a transition containing an oxide of a non-transition metal (M1) selected from metals of Group 12 to Group 14 of the long-period periodic table It is a laminate of a second gas barrier layer containing an oxide of metal (M2) or a gas barrier layer containing a composite oxide of the non-transition metal (M1) and transition metal (M2). Or a region containing the complex oxide.
  • the oxygen permeability measured by a method in accordance with JIS K 7126-2006 is 1 ⁇ 10 ⁇ 3 mL / m 2 ⁇ 24 h ⁇ atm or less, measured by a method according to JIS K 7129-1992
  • the water vapor permeability in an environment of 25 ⁇ 0.5 ° C. and 90 ⁇ 2% RH is 1 ⁇ 10
  • the non-transition metal (M1) oxide and transition metal (M2) selected from the group 12 to group 14 metals The oxygen deficient region of the oxide is continuously present in the thickness direction of the sealing layer with a thickness of a predetermined value or more (specifically, 5 nm or more) (this is referred to as “composite composition region” in this specification). It is preferable to be configured as follows.
  • the region other than the composite composition region of the sealing layer is, for example, an oxide and transition metal of a non-transition metal (M1) that does not fall within the composite composition region ( M2) oxide layer (may be an oxygen-deficient region or a stoichiometric region).
  • M1 non-transition metal
  • M2 oxygen-deficient region or a stoichiometric region
  • the non-transition metal (M1) selected from the Group 12 to Group 14 metals is not particularly limited, and any of the Group 12 to Group 14 metals can be used alone or in combination. Examples thereof include Si, Al, Zn, In, and Sn. Especially, it is preferable that a non-transition metal (M1) contains Si, Sn, or Zn, it is more preferable that Si is included, and it is especially preferable that it is Si alone.
  • the transition metal (M2) is not particularly limited, and any transition metal can be used alone or in combination.
  • the transition metal refers to a Group 3 element to a Group 11 element in the long-period periodic table, and the transition metal includes Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y , Zr, Nb, Mo, Tc, Ru, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W , Re, Os, Ir, Pt, and Au.
  • Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce, and the like can be cited as transition metals (M2) that can provide good gas barrier properties.
  • M2 transition metals
  • Nb, Ta, and V, which are Group 5 elements, are considered to be preferably used because they are likely to be bonded to the non-transition metal (M1) contained in the sealing layer. be able to.
  • the transition metal (M2) is a Group 5 element (particularly Nb) and the above-mentioned non-transition metal (M1) is Si, a significant gas barrier property improvement effect can be obtained. This is presumably because the bond between Si and the Group 5 element (particularly Nb) is particularly likely to occur. Furthermore, from the viewpoint of optical properties, the transition metal (M2) is particularly preferably Nb and Ta, which are compounds with good transparency.
  • the gas barrier layer used for the sealing layer is formed by sputtering an inorganic material containing a non-transition metal (M1) or a transition metal (M2) (for example, magnetron cathode sputtering, flat magnetron sputtering, bipolar AC flat magnetron sputtering).
  • M1 non-transition metal
  • M2 transition metal
  • vapor deposition eg, resistance heating vapor deposition, electron beam vapor deposition, ion beam vapor deposition, plasma assisted vapor deposition
  • thermal CVD catalytic chemical vapor deposition (Cat-CVD), capacitively coupled plasma CVD method (CCP-CVD), photo CVD method, plasma CVD method (PE-CVD), epitaxial growth method, atomic layer growth method, etc.
  • Cat-CVD catalytic chemical vapor deposition
  • CCP-CVD capacitively coupled plasma CVD method
  • PE-CVD plasma CVD method
  • epitaxial growth method atomic layer growth method, etc.
  • a method for forming a gas barrier layer containing a composite oxide of a non-transition metal (M1) and a transition metal (M2) it is preferable to use a known co-evaporation method.
  • a co-evaporation method a co-sputtering method is preferable.
  • the co-sputtering method employed in the present invention is, for example, a composite target made of an alloy containing both a non-transition metal (M1) and a transition metal (M2), or a composite oxide of a metal (M1) and a transition metal (M2).
  • the co-sputtering method in the present invention is multi-source simultaneous sputtering using a plurality of sputtering targets including a single metal (M1) or its oxide and a single transition metal (M2) or its oxide.
  • M1 single metal
  • M2 single transition metal
  • Good With respect to a method for producing these sputtering targets and a method for producing a thin film made of a composite oxide using these sputtering targets, for example, JP 2000-160331 A, JP 2004-068109 A, JP Reference can be made to the descriptions in Japanese Patent Application Laid-Open No. 2013-047361.
  • the film forming conditions for carrying out the co-evaporation method include the ratio of the transition metal (M2) and oxygen in the film forming raw material, the ratio of the inert gas to the reactive gas during the film forming, and the film forming process.
  • One or two or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum during film formation, and the power during film formation are exemplified, and these film formation conditions (preferably oxygen content)
  • these film formation conditions preferably oxygen content
  • a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the composite composition region.
  • a co-evaporation method for example, in order to control the thickness of a composite composition area
  • the non-transition metal is M1
  • the transition metal is M2
  • oxygen is O
  • nitrogen is N
  • the composition of the compound in the composite composition region of the sealing layer is (M1) (M2) x O y when a N z, it is preferable to satisfy the following relation (1).
  • the composition of the composite oxide of the non-transition metal (M1) and the transition metal (M2) according to the present invention is represented by (M1) (M2) x O y N z .
  • the composite oxide may partially include a nitride structure.
  • the maximum valence of the metal (M1) is a
  • the maximum valence of the transition metal (M2) is b
  • the valence of O is 2
  • the valence of N is 3.
  • This formula means that the total number of bonds of non-transition metal (M1) and transition metal (M2) is equal to the total number of bonds of O and N.
  • non-transition metal (M1) And the transition metal (M2) are bonded to either O or N.
  • the maximum valence of each element is set to The composite valence calculated by weighted averaging with the existence ratio is adopted as the values of a and b of the “maximum valence”.
  • the remaining bonds of the non-transition metal (M1) and the transition metal (M2) have the possibility of bonding to each other, and the metals of the non-transition metal (M1) and the transition metal (M2) When they are directly bonded, it is considered that a denser and higher-density structure is formed than when bonded between metals via O or N, and as a result, gas barrier properties are improved.
  • the composite composition region is a region where the value of x satisfies 0.02 ⁇ x ⁇ 49 (0 ⁇ y, 0 ⁇ z). This is defined as a region in which the value of the number ratio of transition metal (M2) / non-transition metal (M1) is in the range of 0.02 to 49 and the thickness is 5 nm or more. It is the same definition as that. In this region, since both the non-transition metal (M1) and the transition metal (M2) are involved in the direct bonding between the metals, a composite composition region that satisfies this condition exists in a thickness of a predetermined value or more (5 nm). This is considered to contribute to the improvement of gas barrier properties.
  • the composite composition region is a region that satisfies 0.1 ⁇ x ⁇ 10 because the closer the abundance ratio of the non-transition metal (M1) and the transition metal (M2) is, the more likely it is to contribute to the improvement of gas barrier properties.
  • Is preferably 5 nm or more, more preferably a region satisfying 0.2 ⁇ x ⁇ 5 is included at a thickness of 5 nm or more, and a region satisfying 0.3 ⁇ x ⁇ 4 is 5 nm or more. More preferably, it is included.
  • the thickness of the composite composition region that provides good gas barrier properties is 5 nm or more as the sputtering thickness in terms of SiO 2 , and this thickness is preferably 8 nm or more, preferably 10 nm or more. It is more preferable that it is 20 nm or more.
  • the sealing layer having the configuration as described above exhibits a very high gas barrier property that can be used as a sealing layer for an electronic device such as an organic EL element.
  • a sealing layer was formed by using an oxygen-deficient composition film of a compound (oxide) of a non-transition metal (M1) alone, or a transition metal (M2)
  • a sealing layer is formed by using an oxygen-deficient composition film of a compound (oxide) alone
  • the gas barrier property tends to improve as the degree of oxygen deficiency increases. It did not lead to improvement.
  • a layer containing an oxide of a non-transition metal (M1) and a layer containing an oxide of a transition metal (M2) are stacked, and the non-transition metal (M1) and the transition metal (M2) are formed. It was found that when a composite composition region that exists at the same time is formed and the composite composition region is an oxygen deficient composition, the gas barrier property is further improved as the degree of oxygen deficiency increases.
  • a composite composition region made of a composite oxide is formed at the stack interface. Is formed.
  • the abundance ratio of each metal element (M1 or M2) in the metal elements included in the composite composition region is formed with a certain degree of inclination with respect to the thickness direction of the composite composition region.
  • the oxygen-deficient composition of the composite oxide of the non-transition metal (M1) and the transition metal (M2) is formed in the composite composition region described above, but the thickness is limited to about 20 nm at the maximum. It will be a thing.
  • the thickness of the region in which (M1) / ⁇ (M1) + (M2) ⁇ is in the range of 0.1 to 0.9, which is highly effective in improving gas barrier properties, is only formed to about 10 nm.
  • the gas barrier property that can be reached by the laminated structure is limited, and even when the layer thickness of each layer in the laminated structure is increased, the thickness is hardly changed.
  • the present inventor has determined that 0.02 ⁇ x ⁇ which is a preferable condition for both of the aforementioned non-transition metal (M1) and transition metal (M2) to participate in the direct bonding between metals.
  • the critical thickness at which the effect of improving the gas barrier property is observed by changing the thickness of the oxygen-deficient composition of the composite oxide of non-transition metal (M1) and transition metal (M2) that satisfies 49 It was.
  • the thickness was 5 nm or more, a very significant improvement in gas barrier properties was observed, and the present invention was completed.
  • the method for sealing an electronic device includes a first gas barrier layer containing at least one oxide of a non-transition metal (M1) of Group 12-14. And a laminate of a second gas barrier layer containing an oxide of a transition metal (M2) disposed in contact with the first gas barrier layer, or the non-transition metal (M1) and the transition metal (M1) (The electronic device is sealed with a gas barrier layer containing the composite oxide of M2) or a sealing layer formed by vapor phase film-forming or coating method on the region containing the composite oxide.
  • M1 non-transition metal
  • M2 transition metal
  • a first gas barrier layer containing an oxide of the non-transition metal (M1) is preferably formed on the functional element side, and the oxide of the transition metal (M2) is contained.
  • the second gas barrier layer is preferably formed on the first gas barrier layer containing the non-transition metal (M1) oxide by a vapor deposition method.
  • the first gas barrier layer containing an oxide of the non-transition metal (M1) contains polysilazane and a modified polysilazane, and the modified polysilazane is coated with a coating liquid containing polysilazane. And it is preferable to form by irradiating with vacuum ultraviolet light.
  • first gas barrier layer containing oxide of non-transition metal (M1) and second gas barrier layer containing oxide of transition metal (M2) First gas barrier Formation of the layer containing the oxide of the non-transition metal (M1) as a layer and the layer containing the oxide of the transition metal (M2) as a second gas barrier layer are not particularly limited. It is preferable to use a conventionally known vapor deposition method using an existing thin film deposition technique from the viewpoint of efficiently forming a composite composition region.
  • the vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, and ion assist vapor deposition, plasma CVD (chemical vapor deposition), and ALD. Examples thereof include a chemical vapor deposition (CVD) method such as an (Atomic Layer Deposition) method. Especially, since it becomes possible to form a film without damaging the organic functional layer and it has high productivity, it is preferably formed by a physical vapor deposition (PVD) method, more preferably by a sputtering method. preferable.
  • bipolar sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more.
  • the target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used.
  • a reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can also be used.
  • a metal oxide film can be formed at a high film formation speed, which is preferable.
  • the inert gas used for the process gas He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used.
  • Ar is preferably used.
  • a thin film of a non-transition metal (M1) and transition metal (M2) composite oxide, nitride oxide, oxycarbide, or the like is formed. be able to.
  • film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, which can be appropriately selected according to the sputtering apparatus, the material of the film, the layer thickness, and the like.
  • the layer thickness of the first gas barrier layer and the second gas barrier layer is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm.
  • gas barrier layer containing composite oxide of non-transition metal (M1) and transition metal (M2) A composite oxide of non-transition metal (M1) and transition metal (M2) The gas barrier layer to be contained can be formed by employing a co-evaporation method using a non-transition metal (M1) oxide and the transition metal (M2) oxide as a sputtering target.
  • the film formation conditions for carrying out the co-evaporation method include the ratio of the non-transition metal (M1) and transition metal (M2) to oxygen in the film formation raw material, and the ratio of inert gas and reactive gas during film formation.
  • examples include one or more conditions selected from the group consisting of the ratio, the gas supply amount during film formation, the degree of vacuum during film formation, and the power during film formation.
  • a thin film made of a complex oxide having an oxygen deficient composition can be formed by adjusting the oxygen partial pressure. That is, by forming the sealing layer using the co-evaporation method as described above, most of the region in the thickness direction of the formed sealing layer can be a composite composition region.
  • a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the composite composition region.
  • a co-evaporation method for example, in order to control the thickness of a composite composition area
  • a method for producing a sputtering target and a method for producing a thin film made of a composite oxide using these sputtering targets are disclosed in, for example, JP 2000-160331 A and JP 2004-2004 A. Descriptions such as 068109 and JP2013-043761A can be referred to as appropriate.
  • the layer containing the non-transition metal (M1) according to the present invention contains Si as described above. More preferably, Si alone is particularly preferable.
  • the layer containing the non-transition metal (M1) is a layer containing polysilazane or a modified polysilazane, and the polysilazane modified body is a coating liquid containing polysilazane. It is preferable that the layer is formed by coating on the functional element according to the above and irradiating with vacuum ultraviolet light because a gas barrier sealing layer having excellent optical characteristics such as transmittance can be obtained. .
  • the number of layers to be formed is not particularly limited, and may be at least one layer, and may be a plurality of layers.
  • the reforming treatment is preferably a vacuum ultraviolet light irradiation treatment.
  • the modification treatment such as irradiation with vacuum ultraviolet light, the sealing layer exhibits gas barrier properties.
  • a coating solution containing polysilazane can be applied by a known wet coating method and subjected to a modification treatment to form a layer that becomes a part of the sealing layer.
  • the “polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond in the structure and serving as a precursor of silicon oxynitride, and one having a structure of the following general formula (1) is preferably used. .
  • each of R 1 , R 2 , and R 3 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.
  • perhydropolysilazane in which all of R 1 , R 2 and R 3 are hydrogen atoms is particularly preferred from the viewpoint of the denseness as a film of the resulting sealing layer.
  • Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and the commercially available product can be used as a polysilazane-containing coating solution as it is.
  • Examples of commercially available polysilazane solutions include NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials.
  • paragraphs “0024” to “0040” of JP2013-255910A, paragraphs “0037” to “0043” of JP2013-188942A, and JP2013-2013A are known. No. 151123, paragraphs “0014” to “0021”, JP 2013-052569 A paragraphs “0033” to “0045”, JP 2013-129557 A paragraphs “0062” to “0075”, JP 2013 It can be adopted with reference to paragraphs “0037” to “0064” of Japanese Patent No. 226758.
  • the coating liquid containing polysilazane is performed in a nitrogen atmosphere, for example, in a glove box in order to suppress deterioration of the electronic device due to oxygen or water vapor.
  • Any appropriate method can be adopted as a method of applying the coating liquid containing polysilazane. Specific examples include spin coating, roll coating, flow coating, ink jet, spray coating, printing, dip coating, cast film formation, bar coating, and gravure printing.
  • After applying the coating solution it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed.
  • the formation method refer to paragraphs “0058” to “0064” of JP-A-2014-151571, paragraphs “0052” to “0056” of JP-A-2011-183773, etc., which are conventionally known. Can do.
  • the modification treatment refers to a conversion reaction of polysilazane to silicon oxide or silicon oxynitride.
  • the reforming process is performed under a nitrogen atmosphere such as in a glove box or under reduced pressure.
  • a known method based on the conversion reaction of polysilazane can be selected.
  • a conversion reaction using plasma, ozone, or ultraviolet light that can be converted at a low temperature is preferable.
  • Conventionally known methods can be used for plasma and ozone.
  • a layer containing a non-transition metal (M1) is formed by providing a coating film of a polysilazane-containing liquid and irradiating it with vacuum ultraviolet light (also referred to as VUV) having a wavelength of 200 nm or less. It is preferable to do.
  • VUV vacuum ultraviolet light
  • the layer thickness is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm.
  • the entire layer may be a modified layer, but the thickness of the modified layer subjected to the modification treatment is preferably 1 to 50 nm, and more preferably 1 to 10 nm.
  • the illuminance of the vacuum ultraviolet light on the coating surface received by the polysilazane layer coating film is preferably in the range of 30 to 200 mW / cm 2 , and in the range of 50 to 160 mW / cm 2 . It is more preferable that By setting the illuminance of the vacuum ultraviolet light to 30 mW / cm 2 or more, the reforming efficiency can be sufficiently improved, and when it is 200 mW / cm 2 or less, the rate of damage to the coating film is extremely suppressed, It is preferable because damage to the device can be reduced.
  • the electronic device of the present invention from the viewpoint of forming the region containing the composite oxide, it is not necessary to irradiate the polysilazane layer coating film with an excessive amount of vacuum ultraviolet light, and it is not necessary to irradiate vacuum ultraviolet light. However, since a high gas barrier property can be obtained, damage to the functional element can be reduced.
  • the amount of irradiation energy of vacuum ultraviolet light on the polysilazane layer coating surface is preferably in the range of 0.01 to 0.9 J / cm 2 , and 0.05 to 0.5 J / Cm 2 is more preferable from the viewpoint of reducing damage to the device.
  • the vacuum ultraviolet light source Since vacuum ultraviolet light is absorbed by oxygen, the efficiency in the vacuum ultraviolet light irradiation process is likely to decrease. Therefore, it is preferable to perform the irradiation with vacuum ultraviolet light in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration at the time of vacuum ultraviolet light irradiation is preferably in the range of 10 to 10,000 ppm, more preferably in the range of 50 to 5000 ppm, further preferably in the range of 80 to 4500 ppm, and most preferably in the range of 100 to 1000 ppm. is there.
  • a heat treatment can also be used for the reforming treatment.
  • the heating conditions are preferably in the range of 50 to 300 ° C., more preferably in the range of 70 to 200 ° C., preferably 0.005 to 60 minutes, more preferably 0.01 to 10 minutes.
  • condensation is performed and a modified product can be formed.
  • the heat treatment for example, a method of heating a coating film by contacting a substrate with a heating element such as a heat block, a method of heating an atmosphere with an external heater such as a resistance wire, an infrared region such as an IR heater
  • a heating element such as a heat block
  • an external heater such as a resistance wire
  • an infrared region such as an IR heater
  • the temperature of the coating film during the heat treatment is preferably adjusted as appropriate within a range of 50 to 250 ° C, and more preferably within a range of 50 to 120 ° C.
  • the heating time is preferably within a range of 1 second to 10 hours, and more preferably within a range of 10 seconds to 1 hour.
  • the coating liquid for forming the layer containing the non-transition metal (M1) contains at least an additive element (selected from the group consisting of elements of Group 2 to Group 14 of the long-period periodic table) 1 element) can be contained.
  • additive elements include aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), gallium (Ga), indium (In), chromium (Cr), iron (Fe), magnesium (Mg) ), Tin (Sn), nickel (Ni), palladium (Pd), lead (Pb), manganese (Mn), lithium (Li), germanium (Ge), copper (Cu), sodium (Na), potassium (K ), Calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), germanium (Ge) and the like. .
  • the layer containing the non-transition metal (M1) according to the present invention is preferably formed by applying and drying a coating liquid containing polysilazane and an aluminum compound or polysilazane and a boron compound.
  • Examples of the aluminum compound applicable to the present invention include aluminum isopoloxide, aluminum-sec-butyrate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate, aluminum tri-n- Examples include butyrate, aluminum tri-sec-butylate, aluminum ethyl acetoacetate / diisopropylate, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monoaluminum-t-butylate, aluminum trisethylacetoacetate, aluminum oxide isopropoxide trimer, etc. be able to.
  • Examples of the boron compound include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tri-tert-butyl borate and the like.
  • aluminum compounds are preferred.
  • Specific commercial products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate / diisopropylate), ALCH-TR (aluminum trisethyl acetoate).
  • Acetate aluminum chelate M (aluminum alkyl acetoacetate / diisopropylate), aluminum chelate D (aluminum bisethylacetoacetate / monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) Ken Fine Chemical Co., Ltd.), Preneact (registered trademark) AL-M (acetoalkoxyaluminum diisopropylate, Ajinomoto Fine Chemical Co., Ltd.) It is possible.
  • the temperature is preferably raised to 30 to 100 ° C. and maintained for 1 minute to 24 hours with stirring.
  • the content of the additive element in the layer containing the non-transition metal (M1) is preferably 0.1 to 20 mol% with respect to 100 mol% of silicon (Si). More preferably, it is 0.5 to 10 mol%.
  • thermosetting resin As such a resin sealing material, it is preferable to use a thermosetting resin.
  • thermosetting adhesive for example, a resin mainly composed of a compound having an ethylenic double bond at the end or side chain of a molecule and a thermal polymerization initiator can be used. More specifically, a thermosetting adhesive made of an epoxy resin, an acrylic resin, or the like can be used. Moreover, according to the bonding apparatus and hardening processing apparatus which are used by the manufacturing process of an organic EL element, you may use a fusion type thermosetting adhesive.
  • photo-radically polymerizable resins mainly composed of various (meth) acrylates such as polyester (meth) acrylate, polyether (meth) acrylate, epoxy (meth) acrylate, polyurethane (meth) acrylate, epoxy, vinyl ether, etc.
  • photo-radically polymerizable resins mainly composed of various (meth) acrylates such as polyester (meth) acrylate, polyether (meth) acrylate, epoxy (meth) acrylate, polyurethane (meth) acrylate, epoxy, vinyl ether, etc.
  • examples thereof include a cationic photopolymerizable resin mainly composed of a resin and a thiol / ene addition type resin.
  • an epoxy resin-based photo-cationic polymerizable resin having a low shrinkage of the cured product, a small outgas, and excellent long-term reliability is preferable.
  • a resin sealing material a chemically curable (two-component mixed) resin can be used.
  • Hot melt polyamide, polyester, and polyolefin can also be used.
  • a cationic curing type ultraviolet curing epoxy resin can be used.
  • the organic material which comprises an organic EL element may deteriorate with heat processing. For this reason, it is preferable to use a resin sealing material that can be adhesively cured from room temperature to 80 ° C.
  • Organic polymer layer In the present invention, at least one organic polymer layer on the substrate, a laminate of the first gas barrier layer and the second gas barrier layer, or the non-transition metal (M1) ) And a gas barrier layer containing a composite oxide of the transition metal (M2) improves the adhesion between the base material and the sealing layer, the organic functional layer and the sealing layer, and is used This is a preferred embodiment from the viewpoint of preventing damage and defects of the layer due to mechanical or thermal stress on the sealing layer due to environmental fluctuations and suppressing deterioration of gas barrier properties.
  • Examples of the resin used in the organic polymer layer according to the present invention include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicone resin, and alkyl titanate. Can be used alone or in combination of two or more.
  • a polymerizable composition containing the following polymerizable compound, a silane coupling agent, and a polymerization initiator may be formed into a layer and then cured.
  • the polymerizable composition can be formed by applying the polymerizable composition on the substrate and the organic EL element.
  • Arbitrary appropriate methods may be employ
  • the formation method refer to paragraphs “0058” to “0064” of JP-A-2014-151571, paragraphs “0052” to “0056” of JP-A-2011-183773, etc., which are conventionally known. Can do.
  • the coating is performed in a nitrogen atmosphere, without solvent, or with a low content of hydrophilic solvent.
  • An ink jet method using the composition can be preferably applied.
  • the ink jet method can be adopted with reference to the technical contents described in International Publication No. 2014/176365, International Publication No. 2015/100375, International Publication No. 2015/112454, and the like.
  • the organic polymer layer is formed using YIELDjet (registered trademark) Platform manufactured by Kateeva.
  • a vapor phase film forming method such as a known flash vapor deposition method can be used.
  • a polymerizable composition containing a polymerizable compound, a silane coupling agent, and a polymerization initiator may be volatilized by heating in a reduced pressure atmosphere to form a deposited film on a substrate, an electrode layer, or an organic functional layer. preferable.
  • a base material and an organic functional layer formed thereon are installed in a vacuum apparatus, and the polymerizable composition is placed in a heating boat installed in the vacuum apparatus, and the polymerization is performed under a reduced pressure of about 10 Pa.
  • the vapor-deposited film can be formed to have a desired layer thickness while heating the composition to about 200 ° C. and covering the base material and the organic functional layer.
  • the obtained deposited film is irradiated with ultraviolet rays using a high-pressure mercury lamp or the like in a vacuum environment to cure the deposited polymerizable composition to form an organic polymer layer.
  • the polymerizable compound used in the present invention is a compound having an ethylenically unsaturated bond at the terminal or side chain, or a compound having epoxy or oxetane at the terminal or side chain. Of these, compounds having an ethylenically unsaturated bond at the terminal or side chain are preferred. Examples of the compound having an ethylenically unsaturated bond at the terminal or side chain include a (meth) acrylate compound, an acrylamide compound, a styrene compound, maleic anhydride and the like, and a (meth) acrylate compound is preferable.
  • (meth) acrylate compound As the (meth) acrylate compound, (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and the like are preferable.
  • styrene compound styrene, ⁇ -methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxystyrene, 4-carboxystyrene and the like are preferable.
  • silane coupling agent examples include halogen-containing silane coupling agents (2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane).
  • Silane epoxy group-containing silane coupling agents [2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxy Cyclohexyl) propyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, etc.], amino Group-containing silane coupling agent (2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- [N- (2-aminoethyl) amino] ethyltrimethoxysi
  • (Meth) acryloyl group-containing silane coupling agents (2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3- Methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, etc.).
  • the silane coupling agent ((meth) acryloyl group containing silane coupling agent) containing a (meth) acryloyl group is used preferably.
  • acryloyl group-containing silane coupling agents include 1,3-bis (acryloyloxymethyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (methacryloyloxymethyl). ) -1,1,3,3-tetramethyldisilazane, 1,3-bis ( ⁇ -acryloyloxypropyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis ( ⁇ -methacryloyl) Oxypropyl) -1,1,3,3-tetramethyldisilazane, acryloyloxymethylmethyltrisilazane, methacryloyloxymethylmethyltrisilazane, acryloyloxymethylmethyltetrasilazane, methacryloyloxymethylmethyltetrasilazane, acryloyloxymethylmethylpolysilazane , Methacryloyloxymethyl Rumethylpolysilazane
  • silane coupling agent used in the present invention the compounds shown below are preferably used.
  • the synthesis method of the silane coupling agent reference can be made to JP-A-2009-67778.
  • the polymerizable composition in the present invention usually contains a polymerization initiator.
  • a polymerization initiator When a polymerization initiator is used, its content is preferably 0.1 mol% or more, more preferably 0.5 to 2 mol% of the total amount of compounds involved in the polymerization. By setting it as such a composition, the polymerization reaction via an active component production
  • photopolymerization initiators are Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819, etc.) commercially available from BASF Japan.
  • Darocur series eg, Darocur TPO, Darocur 1173, etc.
  • Quantacure PDO eg, Ezacure TZM, Ezacure TZT, Ecure TZT, Ecure TZT, Ecure TZT, Ecure Etc.
  • a polymerizable composition containing a silane coupling agent, a polymerizable compound, and a polymerization initiator is cured with light (for example, ultraviolet rays), electron beams, or heat rays, but is preferably cured with light. .
  • light for example, ultraviolet rays
  • electron beams or heat rays
  • the hydrolysis reaction of the silane coupling agent proceeds, the polymerizable composition is effectively cured, and the film is formed without damaging the base material or the organic functional layer. Can do.
  • the light to be irradiated is usually ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp.
  • the radiation energy is preferably 0.1 J / cm 2 or more, 0.5 J / cm 2 or more is more preferable.
  • a (meth) acrylate compound is employed as the polymerizable compound, polymerization inhibition is caused by oxygen in the air, so that it is preferable to reduce the oxygen concentration or oxygen partial pressure during polymerization.
  • the oxygen concentration during polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less.
  • the oxygen partial pressure during polymerization is reduced by the decompression method, the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. Further, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of 0.5 J / cm 2 or more under a reduced pressure condition of 100 Pa or less.
  • the organic polymer layer according to the present invention is preferably smooth and has high film hardness.
  • the smoothness of the organic layer is preferably less than 1 nm as average roughness (Ra value) of 1 ⁇ m square, and more preferably less than 0.5 nm.
  • the polymerization rate of the monomer is preferably 85% or more, more preferably 88% or more, still more preferably 90% or more, and particularly preferably 92% or more.
  • the polymerization rate here means the ratio of the reacted polymerizable group among all the polymerizable groups (for example, acryloyl group and methacryloyl group) in the monomer mixture.
  • the polymerization rate can be quantified by an infrared absorption method.
  • the layer thickness of the organic polymer layer is not particularly limited, but if it is too thin, it is difficult to obtain the uniformity of the layer thickness, and if it is too thick, cracks are generated due to external force and gas barrier properties are lowered. From this viewpoint, the thickness of the organic layer is preferably 50 to 2000 nm, more preferably 200 to 1500 nm.
  • the surface of the organic polymer layer is required to be free of foreign matters such as particles and protrusions. For this reason, it is preferable that the organic polymer layer is formed in a clean room.
  • the degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less. Higher hardness of the organic layer is preferred. When the hardness of the organic layer is high, the inorganic layer is formed smoothly and as a result, the barrier ability is improved.
  • the hardness of the organic layer can be expressed as a microhardness based on the nanoindentation method.
  • the microhardness of the organic layer is preferably 100 N / mm or more, and more preferably 150 N / mm or more.
  • Lamination of organic polymer layer and sealing layer can be performed by sequentially and repeatedly forming the organic polymer layer and the sealing layer according to a desired layer configuration.
  • a high gas barrier property can be exhibited, which is preferable (see FIGS. 2A and 2B).
  • a protective layer made of a polysiloxane modified layer or the like may be formed on the outermost layer of the sealing layer according to the present invention on the side where the sealing layer is formed with respect to the substrate.
  • the polysiloxane modified layer is formed by applying a coating solution containing polysiloxane by a wet coating method and drying, and then subjecting the dried coating film to a modification treatment by heating, irradiation with ultraviolet light, irradiation with vacuum ultraviolet light, etc. It can be formed by performing the modification treatment.
  • As the vacuum ultraviolet light it is preferable to use VUV used in the above-described polysilazane modification treatment.
  • paragraphs “0028” to “0032” of JP2013-151123A, paragraphs “0050” to “0064” of JP2013-086501, and JP2013 are known.
  • paragraphs “0063” to “0081”, and JP-A-2013-226673, paragraphs “0119” to “0139” can be employed.
  • Example 1 ⁇ Production of evaluation device> According to the so-called Electrical Calcium Test method (for example, see US Pat. No. 8,664,963), which is known as a method for measuring water vapor transmission rate (WVTR) using the change in the electrical resistance value of the Ca thin film. A device for evaluation imitating an electronic device was produced.
  • Electrical Calcium Test method for example, see US Pat. No. 8,664,963
  • WVTR water vapor transmission rate
  • Fig. 4 shows the configuration of the evaluation device.
  • a glass plate having a thickness of 0.7 mm and a size of 50 mm ⁇ 50 mm was used as the substrate.
  • the Ca vapor deposition layer was UV cleaned on one side of the 50 mm ⁇ 50 mm non-alkali glass plate (thickness 0.7 mm).
  • Ca was vapor-deposited by the size of 14 mm x 20 mm through the mask in the center of the glass plate using the vacuum vapor deposition apparatus made from an EILS technology.
  • the thickness of the Ca vapor deposition layer was 80 nm.
  • the mask was replaced, and aluminum was deposited to a thickness of 200 nm with the pattern shown in FIG. 4 to form an electrode.
  • covered with the aluminum electrode was 10 mm x 20 mm.
  • the organic polymer layer was formed by a known flash vapor deposition method. The following mixture was used as a raw material for the organic polymer layer.
  • 1,9-nonanediol diacrylate 75 parts by weight Trimethylolpropane triacrylate 14 parts by weight Phenoxyethyl acrylate 6 parts by weight 2,4,6-trimethylbenzophenone 5 parts by weight
  • the pressure during flash deposition was 3 Pa, and the conditions for UV curing treatment was 2 J / cm 2 .
  • a mask was used to form the organic polymer layer, and it was formed in the center of the glass plate so as to have a size of 26 mm ⁇ 26 mm.
  • the thickness of the organic polymer layer was 1 ⁇ m in the size of the central part 22 mm ⁇ 22 mm covering the Ca deposition range, and the layer thickness was gradually reduced outside the central part 22 mm ⁇ 22 mm.
  • sealing layer gas barrier layer
  • a magnetron sputtering apparatus manufactured by Canon Anelva: Model EB1100 was used as a vapor phase method / sputtering apparatus.
  • the following targets were used, and Ar and O 2 were used as process gases, and film formation was performed by an RF method or a DC method using a magnetron sputtering apparatus.
  • the sputtering power source power was 5.0 W / cm 2 unless otherwise specified, and the film forming pressure was 0.4 Pa. Further, the oxygen partial pressure was adjusted under each film forming condition. It should be noted that, after film formation using a glass substrate in advance, data on the layer thickness change with respect to the film formation time was obtained under each film formation condition, and after calculating the layer thickness formed per unit time, the set layer thickness The film formation time was set so that
  • the base material was moved between the film forming apparatuses while maintaining the reduced pressure state.
  • ⁇ target> T1 A commercially available polycrystalline silicon target was used.
  • T2 A commercially available oxygen-deficient niobium oxide target was used. The composition was Nb 12 O 29 .
  • T3 A commercially available metal Nb target was used.
  • T4 A commercially available metal Ta target was used.
  • T5 Si and Nb powder pulverized so that Si was 80 atomic% and Nb was 20 atomic% were mixed, and hot-pressed in an Ar atmosphere to perform sintering. After the sintered mixed material was mechanically molded, bonding was performed on a copper back plate to obtain a target.
  • T6 50% by mass of Nb 2 O 5 powder and 50% by mass of SiO 2 powder, mixed with a ball mill using distilled water as a dispersant, and granulated the resulting slurry using a spray dryer, An oxide mixed powder having a particle size of 20 to 100 ⁇ m was obtained.
  • a copper backing plate having a diameter of 6 inches (1 inch is 2.54 cm) was used as a target holder. Then, the oxide mixed powder is a backing plate surface portion to be sprayed, roughened by sandblasting using Al 2 O 3 abrasive grains was in a state of the rough surface.
  • Ni—Al (mass ratio 8: 2) alloy powder was plasma sprayed in a reducing atmosphere (using a Metco sprayer), and an undercoat made of Ni—Al (mass ratio 8: 2) with a layer thickness of 50 ⁇ m. Then, the above oxide mixed powder was plasma sprayed on the undercoat in a reducing atmosphere to prepare a target.
  • the obtained target is an oxygen deficient target containing Si at a ratio of 40 atomic% and Nb at a ratio of 60 atomic%.
  • T1 was used as a target, and sputtering was performed by an RF method.
  • the sputtering power source power was 4.0 W / cm 2 and the oxygen partial pressure was 20%.
  • the film formation time was set so that the layer thickness was 100 nm.
  • T1-2 Performed in the same manner as T1-1 except that the film formation time was set so that the layer thickness was 90 nm.
  • T1-3 Performed in the same manner as T1-1 except that the film formation time was set so that the layer thickness was 200 nm.
  • T1-4 Performed in the same manner as T1-1 except that the film formation time was set so that the layer thickness was 40 nm.
  • T2-1 A film was formed by DC method using T2 as a target.
  • the oxygen partial pressure was 12%.
  • the film formation time was set so that the layer thickness was 10 nm.
  • T2-2 Performed in the same manner as T2-1 except that the film formation time was set so that the layer thickness was 5 nm.
  • T3-1 Two-component simultaneous sputtering was performed by DC method using T1 and T3.
  • the oxygen partial pressure was 18%.
  • the composition of the barrier layer the power supply power at T1 and the power supply power at T3 were adjusted so that the atomic ratio of Si and Nb was the same.
  • the film formation time was set so that the layer thickness was 50 nm.
  • T4-1 Two-component simultaneous sputtering was performed by DC method using T1 and T4.
  • the oxygen partial pressure was 18%.
  • the composition of the barrier layer the power supply power at T1 and the power supply power at T4 were adjusted so that the atomic ratio of Si and Ta was the same.
  • the film formation time was set so that the layer thickness was 50 nm.
  • T5-1 A film was formed by DC method using T5 as a target.
  • the oxygen partial pressure was 18%.
  • the film formation time was set so that the layer thickness was 50 nm.
  • T6-1 A film was formed by DC method using T6 as a target.
  • the oxygen partial pressure was 10%.
  • the film formation time was set so that the layer thickness was 50 nm.
  • T6-2 Performed in the same manner as T6-1 except that the film formation time was set so that the layer thickness was 30 nm.
  • composition distribution profile in the thickness direction of the sealing layer was measured by XPS analysis.
  • the XPS analysis conditions are as follows.
  • the composition of the sealing layer can be represented by (Si) (Nb) x O y N z from the data obtained from the XPS composition analysis.
  • Si as a non-transition metal
  • Nb as a transition metal coexist in the interface region between the first layer and the second layer
  • the transition metal Nb / Si A region where the value x of the atomic number ratio in the range of 0.02 ⁇ x ⁇ 49 was defined as a “composite composition region”, and the presence / absence of the region and its thickness (nm) were measured and listed in the table.
  • the sealing layer was formed as a composite oxide layer of Si, which is a non-transition metal, and Nb (or Ta), which is a transition metal, and the thickness (nm) of the region is listed in the table. did.
  • each evaluation device After measuring the initial resistance value between the electrodes of each evaluation device, each evaluation device was stored in a 60 ° C./90% RH environment while being connected to the measuring apparatus, and the change in resistance value with time was measured. . The time when the resistance value was 1.1 times the initial resistance value was determined, and the rank of gas barrier properties was determined according to the following evaluation index, and listed in the table.
  • Example 2 ⁇ Production of Electronic Device 201> ⁇ Preparation of substrate>
  • resin base material a 100 ⁇ m-thick polyethylene terephthalate film (Lumirror (registered trademark) (U48), manufactured by Toray Industries, Inc.) with easy adhesion treatment on both surfaces was used.
  • a UV curable resin manufactured by Aika Kogyo Co., Ltd., product number: Z731L was applied on a resin base material so that the dry layer thickness was 0.5 ⁇ m, and then dried at 80 ° C., and then under high pressure in air. Curing was performed using a mercury lamp under the condition of an irradiation energy amount of 0.5 J / cm 2 .
  • a clear hard coat layer having a thickness of 2 ⁇ m was formed on the surface of the resin base on the side where the gas barrier layer is to be formed as follows.
  • a UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied to a resin substrate so as to have a dry layer thickness of 2 ⁇ m, dried at 80 ° C., and then using a high-pressure mercury lamp in the air. Then, curing was performed under the condition of an irradiation energy amount of 0.5 J / cm 2 . In this way, a resin substrate with a clear hard coat layer was obtained.
  • this resin substrate with a clear hard-coat layer is only used as a base material for convenience.
  • the coating solution was applied to the surface of the base material on which the functional layer was to be formed by spin coating so that the dry layer thickness was 250 nm, and dried at 80 ° C. for 2 minutes.
  • vacuum ultraviolet irradiation treatment was performed on the dried coating film using a vacuum ultraviolet irradiation apparatus having an Xe excimer lamp having a wavelength of 172 nm under the irradiation energy of 6 J / cm 2 .
  • the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume.
  • the stage temperature for installing the sample was set to 80 ° C. This operation was repeated once to form two gas barrier layers by the coating modification method.
  • the base material having gas barrier properties thus prepared was cut into a size of 50 mm ⁇ 50 mm, and this was used as a base material to form a bottom emission type organic electroluminescence element (organic EL element) by the method shown below. Produced.
  • Organic functional layer Preparation of organic EL element> An anode, a lead-out wiring, an organic functional layer, and a cathode were sequentially formed on the gas barrier layer of the base material. Each layer was formed in such a shape that a light emitting region of 30 mm ⁇ 30 mm was obtained at the center of the substrate.
  • An ITO layer having a thickness of 150 nm was formed as a positive electrode by high-frequency sputtering, and an aluminum layer having a thickness of 300 nm was formed as an extraction wiring.
  • a hole injection layer (copper phthalocyanine (CuPc), thickness 30 nm) / hole transport layer (NPD, thickness 100 nm) / fluorescent blue light emitting layer (thickness 30 nm) / electron transport layer ( Aluminum quinolate (Alq 3 , thickness 30 nm) / electron injection layer (lithium fluoride, thickness 1 nm) was formed in this order, and an aluminum layer having a thickness of 200 nm was formed as a cathode.
  • CuPc copper phthalocyanine
  • NPD hole transport layer
  • NPD hole transport layer
  • thickness 30 nm / electron transport layer
  • Aluminum quinolate (Alq 3 , thickness 30 nm) / electron injection layer lithium fluoride, thickness 1 nm
  • ⁇ Formation of sealing layer> (Formation of organic polymer layer)
  • a mask was used to form the organic polymer layer, and the organic polymer layer was formed in the center of the substrate so as to have a size of 38 mm ⁇ 38 mm.
  • the thickness of the organic polymer layer was 2 ⁇ m in the size of the central part 34 mm ⁇ 34 mm covering the light emitting region, and the layer thickness was gradually reduced outside the central part 34 mm ⁇ 34 mm.
  • a gas barrier layer having a thickness of 200 nm was formed using film formation conditions: T1-3.
  • the film formation was performed such that the film formation range was larger than the organic polymer layer formation range and the electrode contact portion was not covered.
  • an organic polymer layer and a gas barrier layer were formed one layer at a time to obtain a sealing layer.
  • the sealing layer of the electronic device 201 does not have a composite composition region.
  • An electronic device 202 of a comparative example was obtained in the same manner as the electronic device 201 except that the gas barrier layer was formed as follows.
  • the sealing layer of the electronic device 202 does not have a composite composition region.
  • Formation of gas barrier layer A commercially available batch type plasma CVD apparatus was used. The substrate was set in a vacuum apparatus and evacuated to the 10 ⁇ 4 Pa level, and then a 50 nm silicon nitride layer was formed by plasma CVD using silane and nitrogen as source gases.
  • the gas barrier layer was formed in the same manner as the electronic device 201 except that a gas barrier layer having a thickness of 50 nm was formed under the same film forming conditions as T1-4 and T2-1 in the same manner as the evaluation device 105.
  • the electronic device 203 was obtained.
  • the sealing layer of the electronic device 203 had two 22 nm composite composition regions in the thickness direction.
  • the minimum value of (2y + 3z) / (a + bx) in the two composite composition regions was 0.65, respectively, indicating an oxygen deficient composition.
  • Each electronic device was wound around a metal roller having a diameter of 75 mm and left in a constant temperature and humidity chamber under high temperature and high humidity (temperature 60 ° C., relative humidity 90%). Each electronic device was taken out from the constant temperature and humidity chamber at regular time intervals and allowed to emit light at room temperature to confirm the presence or absence of dark spots. This operation is continued until the dark spot area ratio in the light emitting region reaches 1%, and the time from the standing in a constant temperature and humidity chamber until the dark spot area ratio reaches 1% is evaluated as a gas barrier property. did. The longer the time, the higher the gas barrier property.
  • the time until the dark spot area ratio reaches 1% was 50 hours for the electronic device 201 of the comparative example and 200 hours for the electronic device 202 of the comparative example, whereas the electronic device of the present invention was 203 was 1500 hours and was very good.
  • the sealing layer and the sealing method of the present invention are efficient, showing extremely high gas barrier performance even in a thin layer. It turned out that it is a proper sealing layer and sealing method.
  • Example 3 In the same manner as in Example 1, an evaluation device having a Ca thin film was produced. Similarly, an organic polymer layer was also formed.
  • Gas barrier layer 1 formation of a non-transition metal (M1) -containing layer
  • a polysilazane containing Si was used as the non-transition metal (M1), and a non-transition metal (M1) -containing layer was formed by a coating / modification method.
  • the formation conditions are shown in Table 2 by combining the following coating conditions P-1 to P-4 and reforming conditions V-1 to V-5.
  • P-1 a dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials, NN120-20), and an amine catalyst (N, N, N, N′-tetramethyl-1,6-diamino) Hexane (TMDAH)) and 20% by weight dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) in a ratio of 4: 1 (mass ratio) and further dried layer thickness For adjustment, it was diluted appropriately with dehydrated dibutyl ether to prepare a coating solution.
  • the other part is masked so that it is applied to the central part of the evaluation device in a range of 36 mm ⁇ 36 mm, and the coating liquid is dried to a thickness of 100 nm by spin coating under a nitrogen atmosphere in the glove box. And then dried at 80 ° C. for 10 minutes.
  • P-2 The same as P-1, except that the dry layer thickness was 250 nm.
  • P-3 The same as P-1, except that the dry layer thickness was 40 nm.
  • P-4 A dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and ALCH (aluminum ethyl acetoacetate diisopropylate) with Al atoms relative to Si atoms 100 The mixture was mixed at a ratio such that the number was 1 and appropriately diluted with dehydrated dibutyl ether to adjust the dry layer thickness to prepare a coating solution. Subsequently, it was applied by the same method as P-1 so that the dry layer thickness was 80 nm, and dried at 80 ° C. for 10 minutes.
  • V-1 A sample on which a non-transition metal (M1) -containing layer was formed was placed in the vacuum ultraviolet irradiation apparatus shown in FIG. 5 having a Xe excimer lamp with a wavelength of 172 nm, and vacuum was applied under the condition of irradiation energy of 5.0 J / cm 2. An ultraviolet irradiation treatment was performed. At this time, nitrogen and oxygen were supplied into the chamber, and the oxygen concentration in the irradiation atmosphere was adjusted to 0.1% by volume. The stage temperature for installing the sample was set to 80 ° C.
  • reference numeral 101 denotes an apparatus chamber, which is supplied with appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) and exhausted from a gas discharge port (not shown). Water vapor can be substantially removed from the inside, and the oxygen concentration in the chamber can be maintained at a predetermined concentration.
  • Reference numeral 102 denotes an Xe excimer lamp (excimer lamp light intensity: 130 mW / cm 2 ) having a double tube structure that irradiates vacuum ultraviolet light of 172 nm
  • reference numeral 103 denotes an excimer lamp holder that also serves as an external electrode.
  • Reference numeral 104 denotes a sample stage.
  • the sample stage 104 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 101 by a moving means (not shown).
  • the sample stage 104 can be maintained at a predetermined temperature by a heating means (not shown).
  • Reference numeral 105 denotes a sample on which a polysilazane compound coating layer is formed. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the surface of the sample coating layer and the excimer lamp tube surface is 3 mm.
  • Reference numeral 106 denotes a light-shielding plate, which prevents the application layer of the sample from being irradiated with vacuum ultraviolet rays during aging of the Xe excimer lamp 102.
  • the energy irradiated on the surface of the sample coating layer in the vacuum ultraviolet light irradiation step was measured using a 172 nm sensor head using a UV integrating photometer: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics.
  • the sensor head is installed in the center of the sample stage 104 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 101 is vacuum ultraviolet light. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as that in the irradiation step, and measurement was performed by moving the sample stage 104 at a speed of 0.5 m / min.
  • an aging time of 10 minutes was provided after the Xe excimer lamp was turned on, and then the sample stage was moved to start the measurement.
  • the moving speed of the sample stage was adjusted to adjust the irradiation energy amount to 5.0 J / cm 2 .
  • the vacuum ultraviolet light irradiation was performed after aging for 10 minutes.
  • V-2 The same as V-1, except that the irradiation energy was 3.5 J / cm 2 .
  • V-3 The same as V-1 except that the irradiation energy was 1.0 J / cm 2 .
  • V-4 Same as V-1 except that the irradiation energy was 0.5 J / cm 2 .
  • V-5 Vacuum ultraviolet light irradiation treatment was not performed.
  • Formation of gas barrier layer 2 transition metal (M2) -containing layer or (M2) non-containing layer
  • M2 transition metal
  • sputtering apparatus a magnetron sputtering apparatus (manufactured by Canon Anelva: model EB1100) was used.
  • each of the following T1 to T4 targets used in Example 1 is used, and Ar and O 2 are used as process gases, and film formation is performed by an RF method or a DC method using a magnetron sputtering apparatus. It was.
  • the sputtering power source power was 5.0 W / cm 2 unless otherwise specified, and the film forming pressure was 0.4 Pa. Further, the oxygen partial pressure was adjusted under each film forming condition. It should be noted that, after film formation using a glass substrate in advance, data on the layer thickness change with respect to the film formation time was obtained under each film formation condition, and after calculating the layer thickness formed per unit time, the set layer thickness The film formation time was set so that
  • ⁇ target> T1 A commercially available polycrystalline silicon target was used.
  • T2 A commercially available oxygen-deficient niobium oxide target was used. The composition was Nb 12 O 29 .
  • T3 A commercially available metal Nb target was used.
  • T4 A commercially available metal Ta target was used.
  • T1-1 A film was formed by RF method using T1 as a target.
  • the sputtering power source power was 4.0 W / cm 2 and the oxygen partial pressure was 20%.
  • the film formation time was set so that the layer thickness was 100 nm.
  • T1-2 Performed in the same manner as T1-1 except that the film formation time was set so that the layer thickness was 10 nm.
  • T2-1 A film was formed by DC method using T2 as a target.
  • the oxygen partial pressure was 12%.
  • the film formation time was set so that the layer thickness was 10 nm.
  • T2-2 Performed in the same manner as T2-1 except that the film formation time was set so that the layer thickness was 5 nm.
  • T2-3 Performed in the same manner as T2-1 except that the film formation time was set so that the layer thickness was 2 nm.
  • T3-1 A film was formed by DC method using T3 as a target.
  • the oxygen partial pressure was 20%.
  • the film formation time was set so that the layer thickness was 10 nm.
  • T4-1 A film was formed by DC method using T4 as a target.
  • the oxygen partial pressure was 20%.
  • the film formation time was set so that the layer thickness was 10 nm.
  • composition distribution profile in the thickness direction of the sealing layer was measured by XPS analysis used in Example 1.
  • the analyzed elements are Si, Nb, Ta, Al, O, N, and C.
  • each evaluation device After measuring the initial resistance value between the electrodes of each evaluation device, each evaluation device was stored in an 85 ° C./85% RH environment while being connected to the measuring apparatus, and the change in resistance value with time was measured. . The time when the resistance value was doubled from the initial resistance value was determined, and the gas barrier property rank was determined according to the following evaluation index.
  • Example 4 ⁇ Production of Electronic Device 401> [Preparation of substrate]
  • a 100 ⁇ m thick polyethylene terephthalate film roll (Lumirror (registered trademark) (U48), manufactured by Toray Industries, Inc.) with easy adhesion treatment on both surfaces was used.
  • a UV curable resin manufactured by Aika Kogyo Co., Ltd., product number: Z731L was applied on a resin base material so that the dry layer thickness was 0.5 ⁇ m, and then dried at 80 ° C., and then under high pressure in air. Curing was performed using a mercury lamp under the condition of an irradiation energy amount of 0.5 J / cm 2 .
  • a clear hard coat layer having a thickness of 2 ⁇ m was formed on the surface of the resin base on the side where the gas barrier layer is to be formed as follows.
  • a UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied to a resin substrate so as to have a dry layer thickness of 2 ⁇ m, dried at 80 ° C., and then using a high-pressure mercury lamp in the air. It was cured under conditions of irradiation energy 0.5 J / cm 2 Te. In this way, a resin base roll with a clear hard coat layer was obtained.
  • this resin substrate with a clear hard-coat layer is only used as a base material for convenience.
  • the first gas barrier layer is formed on the surface of the base roll on which the clear hard coat layer having a thickness of 2 ⁇ m is formed using the CVD film forming apparatus described in Examples of Japanese Patent Application Laid-Open No. 2015-131473 using the condition a4. Formed.
  • Second gas barrier layer (coating reforming method)>
  • a sheet was cut out from the base roll on which the first gas barrier layer was formed.
  • the second gas barrier layer was formed as follows by laminating on the first gas barrier layer.
  • a dibutyl ether solution of 20% by mass of perhydropolysilazane manufactured by AZ Electronic Materials Co., Ltd., NAX120-20
  • a coating solution was prepared by appropriately diluting with dibutyl ether.
  • the coating solution was applied to the surface of the base material on which the functional layer was to be formed by spin coating so that the dry layer thickness was 250 nm, and dried at 80 ° C. for 2 minutes.
  • vacuum ultraviolet light irradiation treatment was performed on the dried coating film under a condition of irradiation energy of 6 J / cm 2 using a vacuum ultraviolet light irradiation apparatus having a Xe excimer lamp with a wavelength of 172 nm.
  • the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume.
  • the stage temperature for installing the sample was set to 80 ° C. This operation was repeated once to form two gas barrier layers by the coating modification method.
  • the base material having gas barrier properties thus prepared was cut into a size of 50 mm ⁇ 50 mm, and this was used as a base material to form a bottom emission type organic electroluminescence element (organic EL element) by the method shown below. Produced.
  • An anode, a lead-out wiring, an organic functional layer, and a cathode were sequentially formed on the gas barrier layer of the base material. Each layer was formed in such a shape that a light emitting region of 30 mm ⁇ 30 mm was obtained at the center of the substrate.
  • An ITO layer having a thickness of 150 nm was formed as a positive electrode by high-frequency sputtering, and an aluminum layer having a thickness of 300 nm was formed as an extraction wiring.
  • a hole injection layer (copper phthalocyanine (CuPc), thickness 30 nm) / hole transport layer (NPD, thickness 100 nm) / fluorescent blue light emitting layer (thickness 30 nm) / electron transport layer ( Aluminum quinolate (Alq 3 , thickness 30 nm) / electron injection layer (lithium fluoride, thickness 1 nm) was formed in this order, and an aluminum layer having a thickness of 200 nm was formed as a cathode.
  • CuPc copper phthalocyanine
  • NPD hole transport layer
  • NPD hole transport layer
  • thickness 30 nm / electron transport layer
  • Aluminum quinolate (Alq 3 , thickness 30 nm) / electron injection layer lithium fluoride, thickness 1 nm
  • a layer having a thickness of 100 nm was formed on the organic polymer layer using the coating condition: P-1 and the modification condition: V-2.
  • the layer formation was performed by making the film formation range larger than the organic polymer layer formation range and masking so as not to cover the electrode contact portion.
  • a layer having a thickness of 100 nm was formed on the non-transition metal (M1) -containing layer using the film formation condition: T1-1.
  • the film was formed using a mask so that the film formation range was the same size as the non-transition metal (M1) -containing layer.
  • the sealing layer of the electronic device 401 does not have a composite composition region.
  • the sealing layer of the electronic device 402 does not have a composite composition region.
  • An organic polymer layer is formed, and a non-transition metal (M1) -containing layer having a thickness of 40 nm is formed thereon using coating conditions: P-3 and modifying conditions: V-2, and further formed thereon Condition: A transition metal (M2) -free layer having a thickness of 5 nm was formed using T2-2.
  • An electronic device 403 of the present invention was obtained in the same manner as the electronic device 401 except that this was repeated twice to form a sealing layer.
  • the sealing layer of the electronic device 403 had two composite composition regions of 18 nm in the thickness direction.
  • the minimum value of (2y + 3z) / (a + bx) in the two composite composition regions was 0.66, respectively, indicating an oxygen deficient composition.
  • Each electronic device was wound around a metal roller having a diameter of 75 mm and left in a constant temperature and humidity chamber under high temperature and high humidity (temperature 85 ° C., relative humidity 85%).
  • Each electronic device was taken out from the constant temperature and humidity chamber at regular time intervals and allowed to emit light at room temperature to confirm the presence or absence of dark spots. This operation is continued until the dark spot area ratio in the light emitting region reaches 1%, and the time from the standing in a constant temperature and humidity chamber until the dark spot area ratio reaches 1% is evaluated as a gas barrier property. did. The longer the time, the higher the gas barrier property.
  • the time until the dark spot area ratio reached 1% was 100 hours for the electronic device 201 of the comparative example.
  • the electronic device 402 of the comparative example was 120 hours. Although the number of sealing layers was increased with respect to the electronic device 401, performance was hardly improved. This is considered to be due to the insufficient durability of the sealing layer at a temperature of 85 ° C. and a relative humidity of 85%.
  • the electronic device 403 of the present invention was 1000 hours and was very good.
  • the sealing layer and the sealing method of the present invention show extremely high gas barrier performance even in a thin layer, and It turned out that it is an efficient sealing layer and sealing method which has high durability under high temperature, high humidity.
  • the electronic device of the present invention is an electronic device having a sealing layer having high gas barrier performance, and the sealing layer is particularly preferably used for organic EL element applications.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

Le problème abordé par la présente invention est de pourvoir à un dispositif électronique qui comporte une couche d'étanchéité présentant de hautes performances de barrière aux gaz, et un procédé d'étanchéification du dispositif électronique à l'aide de la couche d'étanchéité. Ce dispositif électronique comporte, sur un matériau de base, un élément fonctionnel et une couche d'étanchéité qui étanchéifie l'élément fonctionnel. Le dispositif électronique est caractérisé en ce que la couche d'étanchéité est un corps stratifié, qui est configuré à partir d'une première couche barrière aux gaz contenant l'oxyde d'un non-métal de transition des groupes 12-14 (M1), et d'une seconde couche barrière aux gaz contenant l'oxyde d'un métal de transition (M2) disposée en contact avec la première couche barrière aux gaz, ou la couche d'étanchéité est une couche barrière aux gaz contenant l'oxyde composite du non-métal de transition (M1) et du métal de transition (M2), ou la couche d'étanchéité comporte une région contenant l'oxyde composite.
PCT/JP2016/074751 2015-09-16 2016-08-25 Dispositif électronique et procédé d'étanchéification de dispositif électronique WO2017047346A1 (fr)

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CN201680053520.6A CN108029164B (zh) 2015-09-16 2016-08-25 电子器件及电子器件的密封方法
JP2017539804A JP6737279B2 (ja) 2015-09-16 2016-08-25 電子デバイス及び電子デバイスの封止方法
KR1020187007027A KR102004107B1 (ko) 2015-09-16 2016-08-25 전자 디바이스 및 전자 디바이스의 밀봉 방법

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KR102053996B1 (ko) * 2018-09-27 2019-12-09 한양대학교 산학협력단 배리어, 배리어 제조방법, 배리어를 포함하는 디스플레이, 및 배리어를 포함하는 디스플레이의 제조방법

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CN1482840A (zh) * 2002-09-13 2004-03-17 统宝光电股份有限公司 封装保护结构
JP2008214677A (ja) * 2007-03-01 2008-09-18 Toyota Central R&D Labs Inc バリア膜及びバリア膜の製造方法
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JP6737279B2 (ja) 2020-08-05
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CN108029164A (zh) 2018-05-11
KR20180039708A (ko) 2018-04-18
CN108029164B (zh) 2020-01-10
JPWO2017047346A1 (ja) 2018-06-28
KR102004107B1 (ko) 2019-07-25

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