WO2017090577A1 - Dispositif luminescent - Google Patents

Dispositif luminescent Download PDF

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Publication number
WO2017090577A1
WO2017090577A1 PCT/JP2016/084528 JP2016084528W WO2017090577A1 WO 2017090577 A1 WO2017090577 A1 WO 2017090577A1 JP 2016084528 W JP2016084528 W JP 2016084528W WO 2017090577 A1 WO2017090577 A1 WO 2017090577A1
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WIPO (PCT)
Prior art keywords
light emitting
layer
transition metal
emitting device
gas barrier
Prior art date
Application number
PCT/JP2016/084528
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English (en)
Japanese (ja)
Inventor
森　孝博
Original Assignee
コニカミノルタ株式会社
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Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Priority to JP2017552415A priority Critical patent/JP6773048B2/ja
Priority to CN201680068450.1A priority patent/CN108293279B/zh
Publication of WO2017090577A1 publication Critical patent/WO2017090577A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • 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
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers

Definitions

  • the present invention relates to a light emitting device, and more particularly to a light emitting device that can be miniaturized when carried.
  • organic electroluminescent element (hereinafter also referred to as “organic EL element”) using electroluminescence of organic material (hereinafter also referred to as “EL”) can emit light at a low voltage of several V to several tens V. It is a thin film type complete solid-state device and has many excellent features such as high brightness, high luminous efficiency, thinness, and light weight. For this reason, it is applied as a backlight for various displays, display boards such as signboards and emergency lights, and surface light emitters such as illumination light sources.
  • a flexible organic EL element using a resin base material having a thin and light gas barrier layer has attracted attention, and is applied as a light source having a curved surface and a high design property.
  • Patent Document 1 a method in which a gas barrier layer is formed on a glass substrate and then peeled and transferred to a resin base material has been studied.
  • the light-emitting device currently being studied is only a prototype for verifying flexibility, and no specific configuration as a practical device has been presented. Therefore, a specific configuration of the light emitting device that suppresses the deterioration of the light emitting device has been demanded.
  • the present invention has been made in view of the above-described problems and situations, and a problem to be solved is to provide a light-emitting device that can be miniaturized when being carried.
  • the present inventor has a gas barrier layer between a resin base material and an organic light emitting element of an organic light emitting element sandwiched between two resin base materials in the process of examining the cause of the above problem, etc.
  • the present invention has found that the above-mentioned problems can be solved when the radius of curvature of the curved surface formed by the organic light-emitting element is in the range of 1.0 to 10.0 mm when folded or rolled up when carried. It came.
  • a light emitting device in which a light emitting surface side resin base material, an organic light emitting element, and a back surface side base material are laminated in this order, and between the light emitting surface side resin base material and the organic light emitting element or between the organic light emitting element and the back surface side base At least one of the materials has a gas barrier layer containing an inorganic material as a main component, and the light emitting device is supported on a support member with a fixed portion and a movable portion.
  • a light-emitting device having a curved surface portion having a radius of curvature of a curved surface formed by the movable portion of the light-emitting element in a range of 1.0 to 10.0 mm.
  • the light emitting surface side resin bases face each other with a gap of less than 2 mm, and the curved surface formed by the movable part of the organic light emitting element has its light emitting surface bent outward.
  • C / L is 0.3 or more, and the part B with respect to the minimum curvature radius Ar of the part A 2.
  • the gas barrier layer is a region containing the non-transition metal M1 and the transition metal M2 at least in the thickness direction, and the value of the atomic ratio of the transition metal M2 to the non-transition metal M1 (M2 / M1) is Item 6.
  • the light emitting device according to any one of Items 1 to 5, wherein the mixed region in the range of 0.02 to 49 has a thickness of 5 nm or more continuously in the thickness direction.
  • the gas barrier layer includes the mixed region between a region containing the transition metal M2 as a main component of the metal and a region containing the non-transition metal M1 as a main component of the metal. 7.
  • transition metal is selected from niobium (Nb), tantalum (Ta), and vanadium (V).
  • the above-described means of the present invention can provide a light emitting device that can be miniaturized when being carried.
  • An example of a cross-sectional view of a light emitting part of a light emitting device of the present invention An example of a schematic diagram illustrating a light-emitting device having a folded configuration An example of a schematic diagram illustrating a light-emitting device having a folded configuration An example of a schematic diagram illustrating a light-emitting device having a folded configuration An example of a schematic diagram illustrating a light-emitting device having a bent form Conceptual diagram showing the thickness change of the adhesive during winding and withdrawal Conceptual diagram showing the thickness change of the adhesive during winding and withdrawal Conceptual diagram showing the thickness change of the adhesive during winding and withdrawal Conceptual diagram showing the thickness change of the adhesive during winding and withdrawal
  • An example showing the preferred shape of the support member Example of graph for explaining element profile and mixed region when composition distribution of non-transition metal and transition metal is analyzed by XPS method Diagram explaining the peeling method Diagram explaining the peeling method Diagram explaining the peeling method Diagram explaining the peeling method Diagram explaining the peeling method Diagram explaining the peeling method
  • the light emitting device of the present invention is a light emitting device in which a light emitting surface side resin base material, an organic light emitting element, and a back surface side base material are laminated in this order, and between the light emitting surface side resin base material and the organic light emitting element, or At least one of the organic light-emitting element and the back-side base material has a gas barrier layer mainly composed of an inorganic material, and the light-emitting device is supported by having a fixed part and a movable part on a support member. Furthermore, the curved surface formed by the movable portion of the organic light emitting element when carried has a curved surface portion having a radius of curvature in the range of 1.0 to 10.0 mm. This feature is a technical feature common to the inventions according to claims 1 to 12.
  • the light emitting surface side resin bases face each other with a gap of less than 2 mm, and the curved surface formed by the movable portion of the organic light emitting element emits light.
  • a portion A whose surface is bent outward, and a portion B whose light emitting surface is bent inward, wherein the portion A and the portion B exist continuously via an inflection point of curvature, and
  • C / L is 0.3 or more and the minimum of the part A
  • the ratio value (Br / Ar) of the minimum curvature radius Br of the part B to the curvature radius Ar is preferably in the range of 0.4 to 1.1.
  • the light emitting surface side resin when carrying, the light emitting surface side resin has a winding form, and the back side base material is installed on a rigid supporting member via a sheet-like member having viscoelasticity.
  • the base is wound outside and the winding outer end of the light emitting device is fixed so that the position does not shift relatively, and the winding inner is relatively positioned.
  • the movable part is variable.
  • the total thickness of the gas barrier layer is preferably in the range of 20 to 1000 nm.
  • the curved surface formed by the movable portion of the organic light emitting element has a curved radius within a range of 1.0 to 5.0 mm.
  • the gas barrier layer is a region containing the non-transition metal M1 and the transition metal M2 at least in the thickness direction, and has an atomic ratio of the transition metal M2 to the non-transition metal M1. It is preferable that a mixed region having a value (M2 / M1) in the range of 0.02 to 49 has 5 nm or more continuously in the thickness direction. As a result, even if the gas barrier layer is a thin layer, an extremely high gas barrier property can be obtained. Therefore, by making the gas barrier layer thinner, it is possible to achieve both better bending durability and gas barrier property. Is obtained.
  • the gas barrier layer includes the mixed region between a region containing the transition metal M2 as a metal main component and a region containing the non-transition metal M1 as a metal main component. It is preferable to have
  • the entire region in the thickness direction in the gas barrier layer is a mixed region containing the transition metal and the non-transition metal. Thereby, a very high gas barrier property is obtained.
  • composition of the mixed region is represented by the chemical composition formula (1)
  • relational formula (2) is satisfied. Thereby, better gas barrier properties can be obtained.
  • the non-transition metal is preferably silicon.
  • the transition metal is preferably selected from niobium (Nb), tantalum (Ta), and vanadium (V). This combination of metal elements provides the best gas barrier properties.
  • the light-emitting device of the present invention preferably includes an organic EL element.
  • ⁇ 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 light emitting device of the present invention is a light emitting device in which a light emitting surface side resin base material, an organic light emitting element, and a back surface side base material are laminated in this order, and between the light emitting surface side resin base material and the organic light emitting element, or At least one of the organic light-emitting element and the back-side base material has a gas barrier layer mainly composed of an inorganic material, and the light-emitting device is supported by having a fixed part and a movable part on a support member. Furthermore, the curved surface formed by the movable portion of the organic light emitting element when carried has a curved surface portion having a radius of curvature in the range of 1.0 to 10.0 mm.
  • the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 ⁇ 10 ⁇ 3 cm 3 / (m 2 ⁇ 24 h ⁇ atm) or less
  • water vapor transmission rate (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)) measured by a method according to JIS K 7129-1992 % RH) is preferably a high gas barrier property of 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • FIG. 1 is an example of a cross-sectional view of a light emitting portion of a light emitting device of the present invention.
  • the light emitting device has a light emitting portion L in which the light emitting surface side resin base material 2, the organic light emitting element 3 and the back surface side base material 4 are laminated in this order.
  • the organic light emitting element 3 may be, for example, an organic EL element, has an organic functional layer unit 7 including at least a light emitting layer via two electrodes 6, and is sealed with a sealing member 8.
  • the light emitting surface side resin base material 2 or the base material 4 may have a hard coat layer on both sides, and may have an adhesive layer as an intermediate layer, and a protective film on the outermost layer via an adhesive layer.
  • the organic functional layer unit has a hole transport layer, an electron transport layer, and the like in addition to the light emitting layer.
  • This light-emitting device has a curved surface portion in which the radius of curvature of the curved surface formed by the movable portion of the organic light-emitting element 7 when carried is in the range of 1.0 to 10.0 mm.
  • the curvature radius Ar of the part A or the curvature radius Br of the part B is less than 1.0, the base material itself deteriorates due to repeated bending, which is not preferable. Further, if the curvature radius exceeds 10.0 mm, it is not suitable as a small light emitting device.
  • the fixed portion refers to a portion where the light emitting device is fixed on the support member and the positional relationship between the light emitting device and the support member does not change
  • the movable portion refers to the light emitting device not fixed on the support member.
  • the organic light emitting element 3 is preferably sandwiched between the two base materials 2 and 4, more preferably the two base materials have the same thickness and the same elastic modulus. It can be expected that the stress applied to the organic light emitting element 3 located at the center of bending is brought close to zero when the light emitting device is bent because the two base materials have the same thickness and the same elastic modulus. it can.
  • the total thickness of the light emitting device is preferably in the range of 20 to 200 ⁇ m. More preferably, it is within the range of 30 to 150 ⁇ m, and further preferably within the range of 30 to 100 ⁇ m. It is considered that by reducing the thickness, the stress applied to the organic light emitting element 1 when bent can be further reduced.
  • the total thickness of the gas barrier layer 5 is preferably in the range of 20 to 1000 nm from the viewpoint of achieving both the gas barrier property and the bending resistance of the gas barrier layer.
  • Such a light emitting device makes it possible to reduce the size of the light emitting device when carried.
  • Preferred embodiments include a light-emitting device that is folded and a light-emitting device that is rolled up when carried.
  • Light-emitting device having a folded form When the light emitting device having a folded configuration is carried, the light emitting surface side resin bases face each other with a gap of less than 2 mm, and the curved surface formed by the movable portion of the organic light emitting element is bent outward.
  • the ratio value (Br / Ar) of the minimum curvature radius Br is preferably in the range of 0.4 to 1.1.
  • the movable portion in the case of a light-emitting device having a folded configuration, usually has a plurality of curved surfaces, and therefore the radius of curvature of the portion A and the portion B uses the minimum radius of curvature.
  • the minimum curvature radii of the part A and the part B are the minimum ones among the curvature radii of a plurality of curved surfaces of the organic light emitting element when bent.
  • FIGS. 2A to 2C are examples of schematic diagrams illustrating a light-emitting device having a folded configuration.
  • FIG. 2A shows a state where the light emitting devices supported by the support housing 10 and the support housing 11 as two support members are bent.
  • the bent light emitting device 1 has a portion A where the light emitting surface is bent outward and a portion B where the light emitting surface is bent inward via an inflection point.
  • a portion where the light emitting portion L is supported by the support housing 10 and the support housing 11 is a fixed portion, and a portion A and a portion B are movable portions.
  • FIG. 2C shows a state when the light emitting device 1 is opened.
  • the hinge portion 12 having the hinge portion 12 between the support housings 10 and 11 has a function of protecting the light emitting device together with the support housings 10 and 11.
  • the hinge portion 12 does not need to be in contact with the light emitting portion L.
  • the present invention has a portion A in which the light emitting surface is bent outward and a portion B in which the light emitting surface is bent inward.
  • C / L is 0.3 or more, and the minimum curvature of the part A, where L is the length of the part and C is the protruding length of the loop formed by the movable part from the support member
  • the ratio value (Br / Ar) of the minimum curvature radius Br of the part B to the radius Ar is preferably in the range of 0.4 to 1.1. More preferably, it is in the range of 0.6 to 1.1, and still more preferably in the range of 0.8 to 1.05.
  • the configuration in which the curvature when the light emitting surface is bent inward and the curvature when the light emitting surface is bent outward is approximate is the method for maximizing the minimum curvature. It is.
  • the light emission part L is being fixed on the support member with high rigidity.
  • the light emitting portion L other than the hinge portion 12 needs to be fixed to the support housing as a support member. The hinge portion is not fixed to the support housing so that it can be folded freely.
  • the B part is preferably substantially circular, and the C / L is more preferably 0.35 or more because the minimum curvature radius of the part A is not too small with respect to the minimum curvature radius of the part B.
  • the above is more preferable.
  • the upper limit of C / L may be adjusted so that the value of Br / Ar falls within the range of the present invention.
  • the protruding length C from the support member means the length of A + B in FIGS. 2A to 2C.
  • C is the average value.
  • the stress on the light emitting part L of the light emitting device applied to the part A and the part B can be reduced.
  • the length of the hinge part 12 is preferably within a range of 4 to 17 mm.
  • the minimum curvature radius of the part A is larger than the minimum curvature radius of the part B, it is preferable to have means for adjusting the minimum curvature radii of the part A and the part B.
  • the value of the ratio of the minimum curvature radius Br of the part B to the minimum curvature radius Ar of the part A is within the above range.
  • it can be adjusted by pressing from behind the light emitting device using a member constituting a hinge portion that supports the bent portion of the light emitting device from behind.
  • the respective minimum curvature radii are: As the light emitting device is designed to approach 1.0 mm, the damage to the movable part due to repeated folding increases. However, even in an apparatus having such a design, by having a movable part that falls within the scope of the present invention, an effect of improving folding durability can be obtained with respect to an apparatus having a movable part outside the scope of the present invention.
  • the back side resin base material is installed on a rigid support member having a winding form through a sheet-like member having viscoelasticity, and the light emitting surface side resin base material is wound outward.
  • the outer end of the light emitting device is fixed so that the position does not relatively shift (hereinafter also referred to as a fixed end), and the inner side of the winding is a movable part.
  • the end portion is preferably a free end whose position can be relatively changed. That is, it is preferable that a part of the back side substrate of the light emitting unit of the light emitting device is fixed on a support member having high rigidity.
  • the support member has high rigidity capable of supporting the light emitting portion.
  • FIG. 3 is an example of a schematic diagram illustrating a light emitting device having a winding form.
  • the back-side base material of the light-emitting portion L is installed on a rigid support member 21 via a sheet-like adhesive 22 having viscoelasticity, and the light-emitting surface-side resin base material It is structured to wind around the winding member 24 in the housing 23 with the outer side facing out.
  • the end part far from the winding shaft outside the winding of the light emitting device 1 is a fixed part fixed so as not to be relatively displaced. For example, it is fixed to the control unit 26.
  • the winding inner side is a movable part whose position can change relatively.
  • the positional relationship between the light emitting portion L and the support member 21 is shifted due to the winding diameter difference.
  • one end of the light emitting portion L of the light emitting device is fixed to the support member.
  • the other end of the light emitting portion L is a movable portion whose relative position can be changed with respect to the support member, so that stress can be reduced even if the radius of curvature formed by the movable portion of the light emitting portion L is reduced. .
  • the stress caused by winding is taken up because the adhesive deforms and absorbs due to shear elongation due to shearing elongation. Is considered to be difficult to be transmitted to the light emitting device.
  • the winding is performed as the inside of the light emitting device, the above-described elongation relationship is reversed, and the free end may not be fixed on the support member.
  • the sheet-like pressure-sensitive adhesive 22 not only supports the light emitting portion L on the support member 21 but also has viscoelasticity because it has a function of absorbing the deviation generated at the time of winding.
  • an acrylic or silicon adhesive can be used as the adhesive having viscoelasticity.
  • the magnitude of the deviation between the support member 21 and the light emitting portion L that occurs during winding increases as the winding proceeds.
  • the thickness of the adhesive after winding is constant. Therefore, it is preferable that the adhesive on the free end side is thicker than the adhesive on the fixed end side.
  • FIGS. 4A to 4D are conceptual diagrams showing changes in the thickness of the adhesive during winding and withdrawal.
  • a light emitting part L having a length of 100 mm and a thickness of 60 ⁇ m is installed on a support member having a thickness of 100 ⁇ m via a pressure-sensitive adhesive having a thickness of 100 ⁇ m, and this is wound around a radius of 5 mm.
  • the positions of the support member and the light-emitting device at the free end are shifted by about 3 mm, and the thickness of the adhesive is considered to be about 70% of the original.
  • the drawing at the time of winding is a schematic diagram in which the free end is flat for comparison.
  • the thickness of the pressure-sensitive adhesive is inclined to increase the free end side, and the pressure-sensitive adhesive is formed so that the thickness of the pressure-sensitive adhesive is constant during winding.
  • the stress concerning the light emitting part L can be reduced, which is preferable.
  • FIG. 4D it may be in a form in which the free ends of the organic light emitting element and the adhesive can be aligned at the time of winding.
  • the support member has a shape in which the edge is bent and the planar shape is maintained when being pulled out.
  • FIG. 5 is an example showing a preferable shape of the support member in the winding form.
  • the support member maintains a flat surface in the wound state, and has a shape in which the edge bends as shown in the drawing when pulled out in the direction of the arrow.
  • a metal plate such as a steel plate as the support member in order to increase rigidity.
  • the gas barrier layer according to the present invention has a mixed region containing a non-transition metal M1 and a transition metal M2 at least in the thickness direction, and has an atomic ratio of the transition metal M2 to the non-transition metal M1 in the mixed region.
  • the gas barrier layer is characterized in that a region having a value (M2 / M1) in the range of 0.02 to 49 has a thickness of 5 nm or more continuously in the thickness direction.
  • a region A containing a transition metal of Group 3 to Group 11 as the main component a of metal and a non-transition metal of Group 12 to Group 14 as the main component b of metal is a preferable embodiment to have a mixed region containing a compound derived from the main component a and the main component b between the B region to be contained.
  • the mixed region is formed over the entire region in the layer.
  • transition metal, non-transition metal, and oxygen are preferably contained.
  • the mixed region preferably includes at least one of a mixture of a transition metal oxide and a non-transition metal oxide, or a composite oxide of a transition metal and a non-transition metal. More preferably, a composite oxide of a transition metal and a non-transition metal is contained.
  • composition of the mixed region is represented by the following chemical composition formula (1), it is preferable that at least a part of the mixed region satisfies the condition defined by the following relational formula (2).
  • the “region” means a plane that is substantially perpendicular to the thickness direction of the gas barrier layer (that is, a plane parallel to the outermost surface of the gas barrier layer), and the gas barrier layer has a constant or arbitrary thickness. This is a three-dimensional range (region) between two opposing surfaces formed when divided by 1. The composition of components in the region changes gradually even if the composition is constant in the thickness direction. It may be what you do.
  • the “constituent component” refers to a compound constituting a specific region of the gas barrier layer and a metal or non-metal simple substance.
  • the “main component” in the present invention refers to a component having the maximum content as an atomic composition ratio.
  • metal main component refers to a metal component having the maximum content as an atomic composition ratio among the metal components in the constituent components.
  • the “mixture” refers to a product in which the constituent components of the regions A and B are mixed without being chemically bonded to each other.
  • the “compound derived from the main component a and the main component b” refers to the composite compound formed by the reaction between the main component a and the main component b themselves and the main component a and the main component b.
  • a “composite oxide” will be described as a specific example of the composite compound.
  • the “composite oxide” is a compound (oxide) formed by chemically bonding the constituent components in the regions A and B to each other.
  • a complex formed by physically bonding the constituent components of the regions A and B to each other by intermolecular interaction or the like is also included in the “composite oxide” according to the present invention.
  • Transition metal-containing region A region
  • the A region which is a transition metal-containing region refers to a region containing a transition metal as the main component a of the metal.
  • 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, Rh, 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.
  • Nb, Ta, and V, which are Group 5 elements, are preferably used from the viewpoint of easy binding to the non-transition metal (M1) contained in the gas barrier layer, based on various examination results. it can.
  • the transition metal (M2) is a Group 5 element (particularly Nb) and the non-transition metal (M1), which will be described in detail later, is Si
  • a significant gas barrier property improvement effect can be obtained.
  • the transition metal (M2) is particularly preferably Nb or Ta from which a compound with good transparency can be obtained.
  • the thickness of the region A is preferably in the range of 2 to 50 nm, more preferably in the range of 4 to 25 nm, and more preferably in the range of 5 to 15 nm from the viewpoint of achieving both gas barrier properties and optical characteristics. More preferably it is.
  • Non-transition metal-containing region B region
  • the B region which is a non-transition metal-containing region, refers to a region containing a non-transition metal as a metal main component b.
  • the “compound” here, that is, the “non-transition metal compound” means a compound containing a non-transition metal, for example, a non-transition metal oxide.
  • the non-transition metal (M1) is preferably a non-transition metal selected from Group 12 to Group 14 metals of the long-period periodic table.
  • the non-transition metal is not particularly limited, and any metal of Group 12 to Group 14 can be used alone or in combination. Examples thereof include Si, Al, Zn, In, and Sn. . Especially, it is preferable that Si, Sn, or Zn is included as the non-transition metal (M1), Si is more preferable, and Si alone is particularly preferable.
  • the thickness of the region B is preferably in the range of 10 to 1000 nm, more preferably in the range of 20 to 500 nm, and more preferably in the range of 50 to 300 nm from the viewpoint of achieving both gas barrier properties and productivity. More preferably it is.
  • the mixed region according to the present invention includes a non-transition metal (M1) selected from Group 12 to Group 14 metals of a long-period periodic table and a transition metal selected from Group 3 elements to Group 11 metals.
  • M1 non-transition metal
  • M2 is contained in the mixed region in which the value (M2 / M1) of the atomic ratio of the transition metal M2 to the non-transition metal M1 is in the range of 0.02 to 49. This is a region having 5 nm or more continuously in the vertical direction.
  • the mixed region may be formed as a plurality of regions having different chemical compositions of the constituent components, or may be formed as a region in which the chemical compositions of the constituent components are continuously changed. .
  • the region other than the mixed region of the gas barrier layer may be a region such as a non-transition metal (M1) oxide, nitride, oxynitride, or oxycarbide, or a transition metal (M2) oxide. It may be a region of nitride, oxynitride, oxycarbide, or the like.
  • M1 non-transition metal
  • M2 transition metal
  • Oxygen deficient composition In the present invention, it is preferable that a part of the composition contained in the mixed region has a non-stoichiometric composition (oxygen deficient composition) in which oxygen is lost.
  • the oxygen deficient composition is defined by the following relational expression (2) when at least a part of the composition of the mixed region is expressed by the following chemical composition formula (1). It is defined as satisfying the condition.
  • the oxygen deficiency index indicating the degree of oxygen deficiency in the mixed region
  • the minimum value obtained by calculating (2y + 3z) / (a + bx) in the certain mixed region is used.
  • composition represented by the chemical composition formula (1) is simply referred to as the composition of the composite region.
  • the composition of the composite region 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 which is the formula (1).
  • the composition of the composite region may partially include a nitride structure, and it is more preferable to include a nitride structure from the viewpoint of gas barrier properties.
  • the maximum valence of the non-transition 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.
  • the composition of the composite region including a part of the nitride
  • (2y + 3z) / (a + bx) 1.0.
  • 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 performing the weighted average according to the existence ratio is adopted as the values of a and b of each “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 mixed 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.
  • the mixed region is a region satisfying 0.1 ⁇ x ⁇ 10.
  • a thickness of 5 nm or more more preferably include a region satisfying 0.2 ⁇ x ⁇ 5 at a thickness of 5 nm or more, and a region satisfying 0.3 ⁇ x ⁇ 4 to a thickness of 5 nm or more. It is further preferable to contain.
  • the thickness of the mixed region where good gas barrier properties can be obtained is 5 nm or more as a sputtering thickness in terms of SiO 2 in the XPS analysis method described later, and this thickness is 8 nm or more. Preferably, it is 10 nm or more, more preferably 20 nm or more.
  • the thickness of the mixed region is not particularly limited from the viewpoint of gas barrier properties, but is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less from the viewpoint of optical characteristics. preferable.
  • a gas barrier layer having a mixed region having a specific configuration as described above exhibits a very high gas barrier property that can be used as a gas barrier layer for an electronic device such as an organic EL element.
  • composition analysis by XPS and measurement of the thickness of the mixed region About the composition distribution in the gas barrier layer according to the present invention, the composition distribution in the A region and the B region, the thickness of each region, and the like, X-ray photoelectron spectroscopy (abbreviation: XPS) described in detail below. It can obtain
  • XPS X-ray photoelectron spectroscopy
  • the element concentration distribution curve (hereinafter referred to as “depth profile”) in the thickness direction of the gas barrier layer according to the present invention is the element concentration of the non-transition metal M1 (for example, silicon), the transition metal M2 ( For example, the element concentration of niobium, oxygen (O), nitrogen (N), carbon (C) element concentration, etc. can be measured by combining X-ray photoelectron spectroscopy measurement with rare gas ion sputtering such as argon. It can be created by sequentially performing surface composition analysis while exposing the interior from the surface of the barrier layer.
  • the non-transition metal M1 for example, silicon
  • the transition metal M2 for example, the element concentration of niobium, oxygen (O), nitrogen (N), carbon (C) element concentration, etc.
  • rare gas ion sputtering such as argon. It can be created by sequentially performing surface composition analysis while exposing the interior from the surface of the barrier layer.
  • 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 gas barrier layer in the thickness direction of the gas barrier layer in the layer thickness direction, As the “distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer”, the distance from the surface of the gas barrier 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 QUANTERASXM 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).
  • Quantification 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, 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 atomic ratio of the transition metal (M2) / non-transition metal (M1) is , 0.02 to 49 is obtained, this is defined as a mixed region, and its thickness is obtained.
  • the thickness of the mixed region represents the sputter depth in XPS analysis in terms of SiO 2 .
  • the thickness of the mixed region when the thickness of the mixed region is 5 nm or more, it is determined as “mixed region”. From the viewpoint of gas barrier properties, there is no upper limit of the thickness in the mixed region, but from the viewpoint of optical properties, it is preferably in the range of 5 to 100 nm, more preferably in the range of 8 to 50 nm. Preferably, it is in the range of 10 to 30 nm.
  • FIG. 6 is an example of a graph for explaining the element profile and the mixed region when the composition distribution of the non-transition metal and the transition metal in the thickness direction of the gas barrier layer is analyzed by the XPS method.
  • elemental analysis of non-transition metal (M1), transition metal (M2), O, N, and C is performed in the depth direction from the surface of the gas barrier layer (the left end portion of the graph), and the horizontal axis represents spattering.
  • the B region which is an elemental composition having a non-transition metal (M1, for example, Si) as the main component of the metal is shown, and on the left side, the transition metal (M2, for example, niobium) is the main component of the metal.
  • a region which is an elemental composition is shown.
  • the mixed region is a region where the value of the atomic ratio of transition metal (M2) / non-transition metal (M1) is indicated by an element composition within the range of 0.02 to 49, and a part of A region and B region Is a region that overlaps with a part of the region and has a thickness of 5 nm or more.
  • transition metal-containing region formation of region A
  • transition metal (M2) include Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce, and the like from the viewpoint of obtaining good gas barrier properties as described above.
  • Nb, Ta, and V which are Group 5 elements, can be preferably used because they are likely to be bonded to the non-transition metal (M1) contained in the gas barrier layer.
  • the formation of the layer containing the transition metal (M2) oxide is not particularly limited.
  • a conventionally known vapor deposition method using an existing thin film deposition technique can be used to make the mixed region efficient. It is preferable from a viewpoint of forming.
  • 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.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • 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 any of DC (direct current) sputtering, DC pulse sputtering, AC (alternating current) sputtering, and 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. Furthermore, by introducing oxygen, nitrogen, carbon dioxide and carbon monoxide into the process gas, thin films of non-transition metal (M1) and transition metal (M2) composite oxides, nitride oxides, oxycarbides, etc. are formed. can do. Examples of 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 sputtering method may be a multi-source simultaneous sputtering method using a plurality of sputtering targets including a transition metal (M2) alone or its oxide.
  • M2 transition metal
  • 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
  • JP The methods and conditions described in JP 2013-047361 A can be referred to as appropriate.
  • 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 gas concentration during the film forming. Examples include one or more conditions selected from the group consisting of supply amount, degree of vacuum during film formation, and power during film formation.
  • These film formation conditions preferably oxygen partial pressure
  • a mixed region made of a complex oxide having an oxygen deficient composition can be formed. That is, by forming the gas barrier layer using the co-evaporation method as described above, almost all regions in the thickness direction of the formed gas barrier layer can be mixed regions.
  • a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixed region.
  • what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method, for example, in order to control the thickness of a mixing area
  • the method for forming the B region containing the non-transition metal (M1) is not particularly limited, and for example, a vapor deposition method can be used by a known method.
  • 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 assisted 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.
  • PVD physical vapor deposition
  • a method of forming by a wet coating method using a polysilazane-containing coating solution containing Si as a non-transition metal is also a preferable method.
  • polysilazane applicable to the formation of the B region is a polymer having a silicon-nitrogen bond in the structure, and includes SiO 2 , Si 3 made of Si—N, Si—H, NH, or the like.
  • N is 4 and both of the intermediate solid solution SiO x N preceramic inorganic polymers, such as y.
  • the relatively Polysilazanes that can be modified to silicon oxide, silicon nitride, or silicon oxynitride at low temperatures are preferred.
  • Examples of such polysilazane include compounds having a structure represented by the following general formula (1).
  • R 1 , R 2 and R 3 each represent 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 of the B region constituting the resulting gas barrier layer as a thin film.
  • the organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the adhesion to an adjacent substrate is improved and it may be hard.
  • the ceramic film made of polysilazane can be tough, and even when the film thickness is increased, the generation of cracks is preferred.
  • perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.
  • Perhydropolysilazane is presumed to have a structure in which a linear structure and a ring structure centered on a 6- or 8-membered ring coexist.
  • the molecular weight of polysilazane is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and is a liquid or solid substance, and varies depending on the molecular weight.
  • Mn number average molecular weight
  • These polysilazane compounds are commercially available in the form of a solution dissolved in an organic solvent, and commercially available products can be used as they are as coating solutions containing polysilazane compounds.
  • polysilazanes that are ceramicized at a low temperature include silicon alkoxide-added polysilazanes obtained by reacting the above polysilazanes with silicon alkoxides (Japanese Patent Laid-Open No. 5-238827), and glycidol-added polysilazanes obtained by reacting glycidol (specially No. 6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (Japanese Patent Laid-Open No. 6-240208), and a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (Japanese Patent Laid-Open No. 6-299118). No.
  • acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (JP-A-7- 1969 6 No.), and the like.
  • polysilazane examples include, for example, paragraphs (0024) to (0040) of JP2013-255910A, paragraphs (0037) to (0043) of JP2013-188942A, JP Paragraphs (0014) to (0021) of 2013-151123, Paragraphs (0033) to (0045) of JP2013-052569A, Paragraphs (0062) to (0075) of JP2013-129557A. ), And the contents described in paragraphs (0037) to (0064) of JP2013-226758A can be applied.
  • Suitable organic solvents include, for example, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, ethers such as aliphatic ethers and alicyclic ethers. it can.
  • hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran.
  • organic solvents may be selected according to the purpose such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of organic solvents may be mixed.
  • the concentration of polysilazane in the coating liquid containing polysilazane varies depending on the film thickness of the target gas barrier layer and the pot life of the coating liquid, but is preferably about 0.2 to 35% by mass.
  • an amine or metal catalyst can be added to the coating liquid containing polysilazane in order to promote modification to silicon oxide, silicon nitride, or silicon oxynitride.
  • a polysilazane solution containing a catalyst such as NAX120-20, NN120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, SP140 manufactured by AZ Electronic Materials Co., Ltd. as a commercial product is used. be able to.
  • these commercial items may be used independently and may be used in mixture of 2 or more types.
  • the addition amount of the catalyst is adjusted to 2% by mass or less with respect to polysilazane in order to avoid excessive silanol formation by the catalyst, decrease in film density, increase in film defects, and the like. It is preferable.
  • the coating liquid containing polysilazane can contain an inorganic precursor compound in addition to polysilazane.
  • the inorganic precursor compound other than polysilazane is not particularly limited as long as a coating liquid can be prepared.
  • compounds other than polysilazane described in paragraphs “0110” to “0114” of JP2011-143577A can be appropriately employed.
  • An organometallic compound of a metal element other than Si can be added to the coating liquid containing polysilazane.
  • an organometallic compound of a metal element other than Si By adding an organometallic compound of a metal element other than Si, the replacement of N atom and O atom of polysilazane is promoted in the coating and drying process, and the composition can be changed to a stable composition close to SiO2 after coating and drying. .
  • metal elements other than Si 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), Examples include potassium (K), calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), and the like.
  • Al, B, Ti and Zr are preferable, and among them, an organometallic compound containing Al is preferable.
  • 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.
  • 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).
  • 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 metal element in the polysilazane-containing layer constituting the gas barrier film according to the present invention is preferably 0.05 to 10 mol%, more preferably 100 mol% of silicon (Si). Is 0.5 to 5 mol%.
  • the modification treatment is a treatment in which polysilazane is imparted with energy and part or all thereof is converted to silicon oxide or silicon oxynitride.
  • a known method based on the conversion reaction of polysilazane can be selected, and examples thereof include known plasma treatment, plasma ion implantation treatment, ultraviolet irradiation treatment, vacuum ultraviolet irradiation treatment and the like.
  • 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 gas barrier layer is formed by providing a coating film of a polysilazane-containing coating liquid of a coating method on a substrate and applying a vacuum ultraviolet irradiation treatment in which a vacuum ultraviolet ray (VUV) having a wavelength of 200 nm or less is irradiated to perform a modification treatment.
  • VUV vacuum ultraviolet ray
  • a rare gas excimer lamp is preferably used.
  • an excimer lamp (single wavelength of 172 nm, 222 nm, 308 nm, for example, manufactured by USHIO INC., Manufactured by M.D. Can be mentioned.
  • the treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in polysilazane, and the bonding of atoms is an action of only a photon called a photon process.
  • a silicon oxide film or a silicon oxynitride film is formed at a relatively low temperature (about 200 ° C. or lower) by proceeding an oxidation reaction with active oxygen or ozone while directly cutting.
  • the thickness of the B region is not particularly limited, but is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm.
  • the mixed region forming method is preferably a method of forming the mixed region between the A region and the B region by appropriately adjusting each forming condition when forming the A region and the B region.
  • the B region is formed by the above-described vapor deposition method, for example, the ratio of the non-transition metal (M1) and oxygen in the deposition raw material, the ratio of the inert gas and the reactive gas during the deposition, Mixing by adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation Regions can be formed.
  • a film forming raw material type (polysilazane type or the like) containing the non-transition metal (M1), a catalyst type, a catalyst content, a coating film thickness, and a drying temperature.
  • a mixed region can be formed by adjusting one or more conditions selected from the group consisting of time, reforming method, and reforming conditions.
  • the ratio of the transition metal (M2) and oxygen in the deposition material for example, the ratio of the inert gas and the reactive gas during the deposition, A mixed region by adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation Can be formed.
  • the formation conditions of the method of forming the A region and the B region can be adjusted as appropriate.
  • a desired thickness can be obtained by controlling the deposition time.
  • a method of directly forming a mixed region of a non-transition metal and a transition metal is also preferable.
  • 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 of a non-transition metal (M1) and a transition metal (M2).
  • M1 non-transition metal
  • M2 transition metal
  • M2 non-transition metal
  • M2 a composite of a non-transition metal
  • M2 transition metal
  • M2 a composite of a non-transition metal
  • M2 transition metal
  • the co-sputtering method in the present invention is multi-source simultaneous sputtering using a plurality of sputtering targets including a single non-transition metal (M1) or its oxide and a single transition metal (M2) or its oxide. May be.
  • M1 non-transition metal
  • M2 single transition metal
  • 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 mixed region.
  • what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method, for example, in order to control the thickness of a mixing area
  • the gas barrier layer according to the present invention is formed by forming a gas barrier layer as a layer to be peeled through a release layer on a substrate such as glass, as in the peeling method described in JP-A-2015-173249,
  • the peelable layer can be transferred to a plastic film to function as a gas barrier film.
  • it can transfer to electronic devices, such as an organic electroluminescent (EL) element, and can also function as a sealing layer.
  • EL organic electroluminescent
  • Such a method for forming a gas barrier layer makes it easy to manage the cleanliness of the process of forming a thin gas barrier layer or sealing layer in a light, thin, or flexible electronic device. It is preferable from the viewpoint of improving the yield.
  • a first step of forming a release layer with a thickness of 0.1 nm or more and less than 10 nm on a substrate and a layer to be peeled including a first layer in contact with the release layer are formed on the release layer.
  • a gas barrier layer by a peeling method comprising: a second step of: separating a part of the peeling layer and the first layer; and a third step of separating the peeling layer and the layer to be peeled. It is preferable to form as a layer to be peeled.
  • a step of forming a starting point of peeling may be provided between the second step and the third step.
  • 7A to 7F are diagrams for explaining a peeling method.
  • a peeling layer 103 with a thickness of less than 10 nm is formed over a manufacturing substrate 101, and then, as a second step, a layer to be peeled 105 is formed on the peeling layer 103 (FIG. 7A).
  • a layer to be peeled 105 is formed on the peeling layer 103 (FIG. 7A).
  • an example in which an island-shaped release layer is formed is shown, but the present invention is not limited thereto.
  • the layer to be peeled 105 may be formed in an island shape.
  • the layer to be peeled 105 when the layer to be peeled 105 is peeled from the manufacturing substrate 101, peeling occurs in the interface between the manufacturing substrate 101 and the peeling layer 103, the interface between the peeling layer 103 and the layer to be peeled 105, or the peeling layer 103.
  • Select material In this embodiment, the case where separation occurs at the interface between the separation layer 105 and the separation layer 103 is illustrated; however, the present invention is not limited to this depending on the combination of materials used for the separation layer 103 and the separation layer 105. Note that in the case where the layer to be peeled 105 has a stacked structure, a layer in contact with the peeling layer 103 is particularly referred to as a first layer.
  • the thickness of the peeling layer 103 is, for example, less than 10 nm, preferably 8 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less.
  • the thickness of the release layer 103 may be, for example, 0.1 nm or more, preferably 0.5 nm or more, more preferably 1 nm or more.
  • a thicker release layer 103 is preferable because a uniform film can be formed.
  • the thickness of the release layer 103 is preferably 1 nm or more and 8 nm or less. In this embodiment, a tungsten film with a thickness of 5 nm is used.
  • the thickness of the release layer 103 is desirably as described above over the entire layer.
  • the peeling layer 103 may have a region with the above thickness at least in part.
  • the release layer 103 may have a region with the above-described thickness in a region of 50% or more of the release layer, more preferably in a region of 90% or more of the release layer. That is, in one embodiment of the present invention, part of the peeling layer 103 may have a region with a thickness of less than 0.1 mm or a region with a thickness of 10 nm or more.
  • the manufacturing substrate 101 a substrate having heat resistance that can withstand at least a processing temperature in the manufacturing process is used.
  • a glass substrate, a quartz substrate, a sapphire substrate, a semiconductor substrate, a ceramic substrate, a metal substrate, a resin substrate, a plastic substrate, or the like can be used.
  • a large glass substrate is preferably used as the manufacturing substrate 101 in order to improve mass productivity.
  • the third generation 550 mm ⁇ 650 mm
  • the third generation 600 mm ⁇ 720 mm, or 620 mm ⁇ 750 mm
  • the fourth generation (680 mm ⁇ 880 mm, or 730 mm ⁇ 920 mm)
  • the fifth generation (1100 mm ⁇ 1300 mm
  • 6th generation (1500 mm ⁇ 1850 mm
  • 7th generation (1870 mm ⁇ 2200 mm
  • 8th generation (2200 mm ⁇ 2400 mm
  • 9th generation 2400 mm ⁇ 2800 mm, 2450 mm ⁇ 3050 mm
  • 10th generation 2950 mm ⁇ 3400 mm
  • a glass substrate or a glass substrate larger than this can be used.
  • an insulating film such as a silicon oxide film, a silicon oxynitride film, a silicon nitride film, or a silicon nitride oxide film is formed as a base film between the manufacturing substrate 101 and the separation layer 103. It is preferable because contamination from the glass substrate can be prevented.
  • the separation layer 103 includes an element selected from tungsten (W), molybdenum (Mo), titanium, tantalum, niobium, nickel, cobalt, zirconium, zinc, ruthenium, rhodium, palladium, osmium, iridium, and silicon, and the element.
  • An alloy material or a compound material containing the element can be used.
  • the crystal structure of the layer containing silicon may be any of amorphous, microcrystalline, and polycrystalline.
  • a metal oxide such as aluminum oxide, gallium oxide, zinc oxide, titanium dioxide, indium oxide, indium tin oxide, indium zinc oxide, or In—Ga—Zn oxide may be used. It is preferable to use a refractory metal material such as tungsten, titanium, or molybdenum for the separation layer 103 because the degree of freedom in the formation process of the separation layer 105 is increased.
  • the peeling layer 103 is formed by, for example, sputtering, CVD (Chemical Vapor Deposition) (plasma CVD, thermal CVD, MOCVD (Metal Organic CVD), etc.), ALD (Atomic Layer Deposition), coating (spin coating, (Including a droplet discharge method, a dispensing method, and the like), a printing method, a vapor deposition method, and the like.
  • CVD Chemical Vapor Deposition
  • CVD Chemical Vapor Deposition
  • MOCVD Metal Organic CVD
  • ALD Atomic Layer Deposition
  • coating spin coating, (Including a droplet discharge method, a dispensing method, and the like), a printing method, a vapor deposition method, and the like.
  • the separation layer 103 has a single-layer structure, it is preferable to form a tungsten film, a molybdenum film, or a film containing a mixture of tungsten and molybdenum.
  • a film containing tungsten oxide or oxynitride, a film containing molybdenum oxide or oxynitride, or a film containing an oxide or oxynitride of a mixture of tungsten and molybdenum may be formed.
  • the mixture of tungsten and molybdenum corresponds to, for example, an alloy of tungsten and molybdenum.
  • the surface of a film containing tungsten is subjected to thermal oxidation treatment, oxygen plasma treatment, nitrous oxide (N 2 O) plasma treatment, treatment with a solution having strong oxidizing power such as ozone water, and the like to form tungsten oxide.
  • a containing film may be formed.
  • Plasma treatment and heat treatment may be performed in oxygen, nitrogen, nitrous oxide alone, or a mixed gas atmosphere of the gas and other gases.
  • tungsten film with a thickness of less than 10 nm by using a tungsten film with a thickness of less than 10 nm, it is possible to easily perform separation with a small separation force in the third step, so that the plasma treatment or the heat treatment is not performed. Good. This is preferable because it can simplify the peeling process and the manufacturing process of the apparatus.
  • a gas barrier layer in contact with the peeling layer 103 is prepared. Furthermore, you may produce a functional element on a gas barrier layer.
  • FIG. 7B corresponds to a cross-sectional view taken along alternate long and short dash line A1-A2 in FIG. 7C.
  • FIG. 7C is a plan view seen from the substrate 109 (not shown) side.
  • the bonding layer 107 is preferably disposed so as to overlap with the peeling layer 103 and the peeled layer 105. 7B and 7C, the end portion of the bonding layer 107 is preferably not positioned outside the end portion of the release layer 103.
  • a starting point of peeling is formed by irradiation with laser light (step of forming a starting point of peeling) (FIGS. 7B and 7D).
  • Laser light is applied to a region where the bonding layer 107 in a cured state, the peeled layer 105, and the peeling layer 103 overlap (see arrow P1 in FIG. 7B).
  • the laser light may be irradiated from either side of the substrate, but it is preferable to irradiate from the side of the manufacturing substrate 101 provided with the release layer 103 in order to suppress the scattered light from being irradiated to the functional element or the like. .
  • a material that transmits the laser light is used for the substrate on the laser light irradiation side.
  • At least the first layer (the layer included in the layer to be peeled 105 and in contact with the peeling layer 103) is cracked (to cause film cracking or cracking), thereby removing a part of the first layer, A starting point can be formed (see the region enclosed by the dotted line in FIG. 7D).
  • the first layer not only the first layer but also other layers of the layer to be peeled 105, the peeling layer 103, and part of the bonding layer 107 may be removed.
  • the formation method of the starting point of peeling is not ask
  • the force for separating the layer to be peeled 105 and the peeling layer 103 is concentrated on the starting point of peeling, so that the starting point of peeling is formed near the end rather than the central part of the cured bonding layer 107.
  • a starting point of peeling in the form of a solid line or a broken line by continuously or intermittently irradiating a laser beam in the vicinity of the end of the bonding layer 107 because the peeling becomes easy.
  • laser used to form the starting point of peeling there is no particular limitation on the laser used to form the starting point of peeling.
  • a continuous wave laser or a pulsed laser can be used.
  • Laser light irradiation conditions frequencies, power density, energy density, beam profile, and the like are appropriately controlled in consideration of the thickness, material, and the like of the manufacturing substrate 101 and the separation layer 103.
  • the layer to be peeled 105 and the manufacturing substrate 101 are separated from the starting point of the peeling (FIGS. 7E and 7F).
  • the layer 105 to be peeled can be transferred from the manufacturing substrate 101 to the substrate 109.
  • the manufacturing substrate 101 may be fixed to an adsorption stage, and the layer to be peeled 105 may be peeled from the manufacturing substrate 101.
  • the substrate 109 may be fixed to the suction stage and the manufacturing substrate 101 may be peeled from the substrate 109.
  • the bonding layer 107 formed outside the separation starting point remains on at least one of the manufacturing substrate 101 and the substrate 109.
  • FIG. 7E and 7F show the example which remains on both sides, it is not restricted to this.
  • the layer to be peeled 105 and the manufacturing substrate 101 may be separated from the starting point of peeling by a physical force (a process of peeling with a human hand or a jig, a process of separating while rotating a roller, or the like).
  • the manufacturing substrate 101 and the layer to be peeled 105 may be separated by infiltrating a liquid such as water into the interface between the peeling layer 103 and the layer to be peeled 105.
  • the liquid can be easily separated by permeating between the peeling layer 103 and the peeled layer 105 by capillary action.
  • static electricity generated at the time of peeling can be prevented from adversely affecting the functional elements included in the layer to be peeled 105 (such as a semiconductor element being destroyed by static electricity).
  • the liquid may be sprayed in the form of mist or steam.
  • pure water, an organic solvent, or the like can be used, and a neutral, alkaline, or acidic aqueous solution, an aqueous solution in which a salt is dissolved, or the like may be used.
  • the bonding layer 107 or the like that does not contribute to adhesion between the layer to be peeled 105 and the substrate 109 remaining on the substrate 109 after peeling may be removed. By removing, it is possible to suppress adverse effects on the functional elements in the subsequent steps (mixing of impurities, etc.), which is preferable. For example, unnecessary resin can be removed by wiping, washing, or the like.
  • a peeling starting point is formed by laser light irradiation, and the peeling layer 103 and the layer to be peeled 105 are easily peeled, and then peeling is performed. Thereby, the yield of a peeling process can be improved.
  • the gas barrier film according to the present invention as described above has excellent gas barrier properties, transparency, and bending resistance. Therefore, the gas barrier film according to the present invention is a gas barrier used for electronic devices such as packages such as electronic devices, photoelectric conversion elements (solar cell elements), organic electroluminescence (EL) elements, liquid crystal display elements, and the like. It can be used for various applications such as a conductive film and an electronic device using the same.
  • electronic devices such as packages such as electronic devices, photoelectric conversion elements (solar cell elements), organic electroluminescence (EL) elements, liquid crystal display elements, and the like. It can be used for various applications such as a conductive film and an electronic device using the same.
  • an organic electroluminescent element organic EL element
  • LCD liquid crystal display element
  • PV solar cell
  • the electronic device body is preferably an organic EL element.
  • a plastic film is preferably used as the light emitting surface side resin base material and the back surface side base material used in the present invention.
  • the plastic film used is not particularly limited in material, thickness and the like as long as it can hold an organic light emitting element, a gas barrier layer, and the like, and can be appropriately selected.
  • Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide.
  • Resin cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring
  • thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.
  • the thickness of the resin substrate is preferably about 10 to 100 ⁇ m, more preferably 15 to 50 ⁇ m.
  • the back substrate has a high rigidity from the viewpoint of stably supporting the light emitting device.
  • the charge injection layer is a layer provided between the electrode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance.
  • the details are described in Volume 2, Chapter 2, “Electrode Materials” (pages 123-166) of “November 30, 1998, NTS Co., Ltd.”. There is.
  • a charge injection layer generally, if it is a hole injection layer, it exists between a transparent anode and a light emitting layer or a hole transport layer, and if it is an electron injection layer, it exists between a cathode and a light emitting layer or an electron transport layer. Can be made.
  • the details of the hole injection layer are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, etc.
  • materials used for the hole injection layer include: , Porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyarylalkane derivatives, triarylamine derivatives, carbazole derivatives, Indolocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, polyvinylcarbazole, aromatic amines introduced into the main chain or side chain Child material or oligomer, polysilane, a conductive polymer or oligomer
  • Examples of the triarylamine derivative include benzidine type represented by ⁇ -NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), and MTDATA (4,4 ′, 4 ′′).
  • Examples include a starburst type represented by -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine), a compound having fluorene or anthracene in the triarylamine-linked core.
  • hexaazatriphenylene derivatives such as those described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as a hole transport material.
  • JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like Specific examples of materials preferably used for the electron injection layer are as follows. Metals represented by strontium and aluminum, alkali metal compounds represented by lithium fluoride, sodium fluoride, potassium fluoride, etc., alkali metal halide layers represented by magnesium fluoride, calcium fluoride, etc. Examples thereof include an alkaline earth metal compound layer typified by magnesium, a metal oxide typified by molybdenum oxide and aluminum oxide, and a metal complex typified by lithium 8-hydroxyquinolate (Liq).
  • Metals represented by strontium and aluminum alkali metal compounds represented by lithium fluoride, sodium fluoride, potassium fluoride, etc.
  • the transparent electrode in this invention is a cathode
  • organic materials such as a metal complex
  • the electron injection layer is preferably a very thin film, and depending on the constituent material, the layer thickness is preferably in the range of 1 nm to 10 ⁇ m.
  • the light emitting layer constituting the organic functional layer unit preferably includes a phosphorescent light emitting compound as a light emitting material.
  • This light emitting layer is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer and holes injected from the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. Alternatively, it may be the interface between the light emitting layer and the adjacent layer.
  • Such a light emitting layer is not particularly limited in its configuration as long as the light emitting material contained satisfies the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting intermediate layer between the light emitting layers.
  • the total thickness of the light emitting layers is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because a lower driving voltage can be obtained.
  • the sum total of the thickness of a light emitting layer is the thickness also including the said intermediate
  • each light emitting layer is preferably adjusted within the range of 1 to 50 nm, more preferably within the range of 1 to 20 nm.
  • the plurality of stacked light emitting layers correspond to the respective emission colors of blue, green, and red, there is no particular limitation on the relationship between the thicknesses of the blue, green, and red light emitting layers.
  • the light emitting layer as described above is prepared by using a known method such as a vacuum evaporation method, a spin coating method, a casting method, an LB method (Langmuir Blodget, Langmuir Blodgett method), an ink jet method, or the like. Can be formed.
  • a plurality of light emitting materials may be mixed, and a phosphorescent light emitting material and a fluorescent light emitting material (also referred to as a fluorescent dopant or a fluorescent compound) may be mixed and used in the same light emitting layer.
  • the structure of the light-emitting layer preferably includes a host compound (also referred to as a light-emitting host) and a light-emitting material (also referred to as a light-emitting dopant compound), and emits light from the light-emitting material.
  • ⁇ Host compound> As the host compound contained in the light emitting layer, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. Further, the phosphorescence quantum yield is preferably less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in a light emitting layer.
  • a known host compound may be used alone, or a plurality of types of host compounds may be used.
  • a plurality of types of host compounds it is possible to adjust the movement of charges, and the efficiency of the organic electroluminescent device can be improved.
  • a plurality of kinds of light emitting materials described later it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.
  • the host compound used in the light emitting layer may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). )
  • host compounds applicable to the present invention include, for example, JP-A Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002 -75645, 2002-338579, 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002 36 No. 227, No. 2002-231453, No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-260861, No. 2002-280183. No. 2002, No. 2002-299060, No.
  • a phosphorescent compound also referred to as a phosphorescent compound, a phosphorescent material, or a phosphorescent dopant
  • a fluorescent compound both a fluorescent compound or a fluorescent material
  • a phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C.
  • a preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.
  • the phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7.
  • the phosphorescence quantum yield in the solution can be measured using various solvents, but when using a phosphorescent compound in the present invention, the phosphorescence quantum yield is 0.01 or more in any solvent. Should be achieved.
  • the phosphorescent compound can be appropriately selected from known compounds used in the light emitting layer of a general organic EL device, and preferably a group 8-10 metal in the periodic table of elements is used. It is a complex compound to be contained, more preferably an iridium compound, an osmium compound, a platinum compound (platinum complex compound) or a rare earth complex, and most preferably an iridium compound.
  • At least one light emitting layer may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compound in the light emitting layer varies in the thickness direction of the light emitting layer. It may be an embodiment.
  • preferred phosphorescent compounds include organometallic complexes having Ir as a central metal. Furthermore, a complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond is preferable.
  • the phosphorescent compound described above (also referred to as a phosphorescent metal complex) is described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, pp. 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), European Journal of It can be synthesized by applying the methods described in Organic Chemistry, Vol. 4, pages 695 to 709 (2004) and references in these documents.
  • Fluorescent compounds include, for example, coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes. Stilbene dyes, polythiophene dyes, rare earth complex phosphors, and the like.
  • the hole transport layer is composed of a hole transport material having a function of transporting holes.
  • the hole injection layer and the electron blocking layer also have a function of a hole transport layer.
  • the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport material has characteristics of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
  • triazole derivatives oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives
  • Examples include stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, and thiophene oligomers.
  • hole transport material those described above can be used, but in addition, porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds can be used, and in particular, aromatic tertiary amines. It is preferable to use a compound.
  • aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (abbreviation: TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1 -Bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis (4-di-p -Tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p
  • the hole transport material may be formed by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, and an LB method (Langmuir Brodget, Langmuir Brodgett method). Thus, it can be formed by thinning.
  • the layer thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the hole transport layer may have a single layer structure composed of one or more of the above materials.
  • the p property can be increased by doping impurities into the material of the hole transport layer.
  • Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175 and J.P. Appl. Phys. 95, 5773 (2004), and the like.
  • the electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer.
  • the electron transport layer can be provided as a single layer structure or a stacked structure of a plurality of layers.
  • an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer is used as an electron transporting material. What is necessary is just to have the function to transmit.
  • any one of conventionally known compounds can be selected and used. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as a material for the electron transport layer. It can. Furthermore, a polymer material in which these materials are introduced into a polymer chain, or a polymer material having these materials as a polymer main chain can also be used.
  • metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (abbreviation: Alq 3 ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8- Quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (abbreviation: Znq), etc., and the central metal of these metal complexes
  • a metal complex in which In, Mg, Cu, Ca, Sn, Ga, or Pb is replaced can also be used as the material for the electron transport layer.
  • the electron transport layer can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, and an LB method.
  • the thickness of the electron transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the electron transport layer may have a single structure composed of one or more of the above materials.
  • blocking layer examples include a hole blocking layer and an electron blocking layer, which are provided as necessary in addition to the constituent layers of the organic functional layer unit described above. For example, it is described in JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization (published by NTT Corporation on November 30, 1998)” on page 237. Hole blocking (hole block) layer and the like.
  • the hole blocking layer has a function of an electron transport layer in a broad sense.
  • the hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved.
  • the structure of an electron carrying layer can be used as a hole-blocking layer as needed.
  • the hole blocking layer is preferably provided adjacent to the light emitting layer.
  • the electron blocking layer has a function of a hole transport layer in a broad sense.
  • the electron blocking layer is made of a material that has the ability to transport holes and has a very small ability to transport electrons. By blocking holes while transporting holes, the probability of recombination of electrons and holes is improved. Can be made.
  • the structure of a positive hole transport layer can be used as an electron blocking layer as needed.
  • the layer thickness of the hole blocking layer applied to the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.
  • anode in the organic EL element a material having a work function (4 eV or more, preferably 4.5 eV or more) of a metal, an alloy, an electrically conductive compound, or a mixture thereof is preferably used.
  • electrode substances include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • the anode may be formed by depositing a thin film of these electrode materials by vapor deposition or sputtering, and a pattern having a desired shape may be formed by photolithography, or when pattern accuracy is not so high (about 100 ⁇ m or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
  • a wet film forming method such as a printing method or a coating method can be used.
  • the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness of the anode depends on the material, it is usually selected within the range of 10 nm to 1 ⁇ m, preferably 10 to 200 nm.
  • the cathode is an electrode film that functions to supply holes to the organic functional layer unit, and a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof is used. Specifically, gold, aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum 1 mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO, ZnO And oxide semiconductors such as TiO 2 and SnO 2 .
  • the cathode can be produced by using these conductive materials and forming a thin film by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • a cathode having good light transmittance may be selected and configured.
  • the organic EL device is a sealing member for shielding a transparent conductive film (TF) including a transparent anode, a cathode, and an organic functional layer unit formed between the cathode and the transparent anode from the outside air. It is preferable to have a structure for sealing.
  • TF transparent conductive film
  • sealing means used in the present invention include a method of bonding a sealing material and a constituent member of the organic EL element by forming a sealing resin layer with an adhesive. As long as it is arranged so as to cover the display area of the organic EL element, it may be in the form of a concave plate or a flat plate. Further, transparency and electrical insulation are not particularly limited.
  • the sealing material used for sealing include a glass plate, a polymer plate / film, and a metal plate / film.
  • the glass plate include soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
  • a polymer film and a metal film can be preferably used because the organic EL element can be thinned.
  • the polymer film is JIS K
  • the oxygen permeability measured by a method according to 7126-1987 is 1 ⁇ 10 ⁇ 3 cm 3 / ( m 2 ⁇ 24 h ⁇ atm)
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured by a method according to JIS K 7129-1992 is 1 ⁇ 10 ⁇ 3 g / (M 2 ⁇ 24h) or less is preferable.
  • sealing member For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.
  • the adhesive for forming the sealing resin layer include acrylic acid oligomers, photocuring and thermosetting adhesives having reactive vinyl groups of methacrylic acid oligomers, and moisture curing such as 2-cyanoacrylates.
  • examples thereof include an adhesive such as a mold.
  • hot-melt type polyamide, polyester, and polyolefin can be mentioned.
  • a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • an organic EL element may deteriorate by heat processing, what can be adhesive-hardened in the temperature range from room temperature to 80 degreeC is preferable.
  • a desiccant may be dispersed in the adhesive.
  • Application of the adhesive to the sealing material may use a commercially available dispenser, or may be printed like screen printing.
  • a display element a display device that is a device including a display element, a light-emitting element, and a light-emitting device that is a device including a light-emitting element have various forms or have various elements. I can do it.
  • a display element As an example of a display element, a display device, a light emitting element, or a light emitting device, an EL element (an EL element including an organic substance and an inorganic substance, an organic EL element, an inorganic EL element), an LED (white LED, red LED, green LED, blue LED, etc.) ), Transistor (transistor that emits light in response to current), electron-emitting device, liquid crystal device, electronic ink, electrophoretic device, grating light valve (GLV), plasma display panel (PDP), MEMS (micro electro mechanical system) ), Digital micromirror device (DMD), DMS (digital micro shutter), IMOD (interference modulation) element, electrowetting element, piezoelectric ceramic display, carbon nanotube, etc.
  • an EL element an EL element including an organic substance and an inorganic substance, an organic EL element, an inorganic EL element
  • an LED white LED, red LED, green LED, blue LED, etc.
  • Transistor Trans
  • An example of a display device using an EL element is an EL display.
  • a display device using an electron-emitting device there is a field emission display (FED) or a SED type flat display (SED: Surface-conduction Electro-emitter Display).
  • FED field emission display
  • SED SED type flat display
  • a display device using a liquid crystal element there is a liquid crystal display (a transmissive liquid crystal display, a transflective liquid crystal display, a reflective liquid crystal display, a direct view liquid crystal display, a projection liquid crystal display) and the like.
  • An example of a display device using electronic ink or an electrophoretic element is electronic paper.
  • Example 1 Production of organic EL element >> [Production of Organic EL Element 1]
  • the organic EL element 1 was produced according to the following method.
  • Step 1-1 Preparation of resin base material
  • a resin base material a polyethylene terephthalate film having a thickness of 23 ⁇ m and easily bonded on both sides (Teijin DuPont Films, KFL12W # 23, hereinafter abbreviated as PET) is used. The following hard coat was formed on both sides.
  • a clear hard coat layer having an antiblock function was formed on the surface opposite to the surface on which the gas barrier layer of PET was formed. Specifically, a UV curable resin (manufactured by Aika Kogyo Co., Ltd., product number: Z731L) was applied so that the dry film thickness was 0.5 ⁇ m, then dried at 80 ° C., and then in air, a high-pressure mercury lamp was cured under the condition of an irradiation energy amount of 0.5 J / cm 2 .
  • a UV curable resin manufactured by Aika Kogyo Co., Ltd., product number: Z731L
  • a clear hard coat layer having a thickness of 2 ⁇ m was formed on the surface on which the gas barrier layer was to be formed.
  • UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied so as to have a dry film thickness of 2 ⁇ m, dried at 80 ° C., and then a high-pressure mercury lamp in air. It was used and cured under conditions of an irradiation energy amount of 0.5 J / cm 2 .
  • the resin base material was produced (Hereafter, the same base material is used about all the preparation examples.).
  • an adhesive layer having an adhesive made of a heat-resistant acrylic resin having a thickness of 20 ⁇ m is used as a support film, and a thickness of 75 ⁇ m.
  • a PET film was bonded and pressure-bonded with a nip roll to obtain a resin base material with a support film.
  • Step 1-2 Formation of CVD gas barrier layer
  • a gas barrier layer was formed on the resin substrate by the following plasma CVD method.
  • a gas barrier layer made of silicon oxide and having a thickness of 200 nm was formed on a resin substrate according to the following film formation conditions.
  • ⁇ Film formation conditions Feed rate of raw material gas (hexamethyldisiloxane, HMDSO): 30 sccm (Standard Cubic Centimeter per Minute) Supply amount of oxygen gas (O 2 ): 300 sccm Degree of vacuum in the vacuum chamber: 3Pa Applied power from the power source for plasma generation: 0.5 kW Frequency of power source for plasma generation: 13.56 MHz Conveying speed of flexible resin substrate: 0.4 m / min (Step 1-3: Formation of coating gas barrier layer) A dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH) )) And a dibutyl ether solution (NAX120-20, manufactured by AZ Electronic Materials Co., Ltd.) containing
  • a roll-to-roll type coating apparatus capable of successively performing coating surface side protective film peeling, coating, drying, excimer modification treatment, and coating surface side protective film bonding was used.
  • the coating solution was applied on the base material using a die coater so that the thickness after drying was 250 nm and dried at 80 ° C. in a dryer zone.
  • a vacuum ultraviolet ray irradiation treatment was performed on the dried coating film continuously in a vacuum ultraviolet ray irradiation zone having an Xe excimer lamp having a wavelength of 172 nm under the condition that the irradiation energy was 6.0 J / cm 2.
  • a barrier layer was formed.
  • the irradiation atmosphere was replaced with nitrogen heated to 60 ° C., and the oxygen concentration was set to 0.1% by volume or less. Up to this point, there was no contact of the transport roll or the like on the coating surface.
  • This process was further repeated twice to form three layers of a coating gas barrier layer having a thickness of 250 nm.
  • a self-adhesive OPP film (Futamura Chemical Co., Ltd., FSA010M) was bonded as a protective film to the coated surface, and then wound up.
  • the water vapor permeability of the gas barrier film substrate 1 was measured using the Ca method.
  • the measurement conditions were 40 ° C. and 90% RH.
  • the water vapor transmission rate obtained was 8.2 ⁇ 10 ⁇ 6 g / (m 2 ⁇ 24 h).
  • thermosetting sheet-like adhesive epoxy resin
  • Ca was vapor-deposited in the center of the glass plate with a size of 20 mm ⁇ 20 mm through a mask.
  • the thickness of Ca was 80 nm.
  • the glass plate on which Ca has been deposited is taken out into the glove box, placed so that the sealing resin layer surface of the gas barrier film to which the sealing resin layer is bonded and the Ca deposition surface of the glass plate are in contact with each other, and adhered by vacuum lamination. . At this time, heating at 110 ° C. was performed. Further, the adhered sample was placed on a hot plate set at 110 ° C. with the glass plate facing down, and cured for 30 minutes to produce an evaluation cell.
  • a sample using a quartz glass plate having a thickness of 0.2 mm was used instead of the gas barrier film sample as a comparative sample.
  • a black and white transmission densitometer TM-5 manufactured by Konica Minolta was used for transmission density measurement.
  • the transmission density was measured at any four points in the evaluation cell, and the average value was calculated.
  • Step 1-4 Formation of transparent anode
  • a transparent anode composed of a silver thin film was formed according to the following method.
  • the external size of the organic EL element 1 is 60 mm ⁇ 150 mm, and the size of the light emitting portion is 40 mm ⁇ 130 mm.
  • the gas barrier film base material 1 was fixed to a base material holder of a commercially available vacuum deposition apparatus, and a resistance heating boat made of tungsten was charged with silver (Ag), and attached to the first vacuum chamber of the vacuum deposition apparatus.
  • the resistance heating boat containing silver was energized and heated.
  • a transparent anode made of silver having a thickness of 15 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second, and a transparent conductive film 1 was produced.
  • Step 1-5 Organic functional layer unit to cathode formation
  • the compound HT-1 shown below was deposited at a deposition rate of 0 while moving the formed transparent conductive film 1 to the transparent anode. Evaporation was performed at a rate of 1 nm / second, and a 20 nm hole transport layer (HTL) was provided.
  • Compound A-3 blue light-emitting dopant
  • Compound A-1 green light-emitting dopant
  • Compound A-2 red light-emitting dopant
  • Compound H-1 host compound shown below
  • the vapor deposition rate is changed depending on the film formation region so that is linearly from 35% by mass to 5% by mass with respect to the film thickness.
  • the deposition rate was changed depending on the film formation region so that the concentration was at a deposition rate of 0.0002 nm / second and the compound H-1 was at a deposition rate of 0.002 nm / second so that the concentration would be 6% by mass to 94.6% by mass.
  • a light emitting layer was formed by co-evaporation so that the total layer thickness was 70 nm.
  • the following compound ET-1 was vapor-deposited with a film thickness of 30 nm to form an electron transport layer, and further potassium fluoride (KF) was formed with a thickness of 2 nm to form an organic functional layer unit. Subsequently, aluminum 110nm was vapor-deposited and the cathode was formed.
  • KF potassium fluoride
  • the compound HT-1, compounds A-1 to A-3, compound H-1 and compound ET-1 are the compounds shown below.
  • Step 1-6 Sealing step
  • the gas barrier film base material 1 used for the production of the transparent conductive film 1 is used as a sealing base material, and a thermosetting adhesive (as a sealing resin layer on one side of the sealing base material ( A sealing member in which an epoxy resin) was bonded to a thickness of 20 ⁇ m was used to superimpose the sample up to the cathode.
  • a thermosetting adhesive as a sealing resin layer on one side of the sealing base material ( A sealing member in which an epoxy resin) was bonded to a thickness of 20 ⁇ m was used to superimpose the sample up to the cathode.
  • the sealing resin layer forming surface of the sealing member and the organic functional layer unit surface of the organic EL element were overlapped so that the end portions of the transparent anode and the lead electrode of the cathode were exposed.
  • the laminate is placed in a decompression device, and the sample formed between the superposed resin base material and the cathode and the sealing member are pressed under a decompression condition of 0.1 MPa at 90 ° C. Hold for a minute. Subsequently, the laminate was returned to the atmospheric pressure environment and further heated at 90 ° C. for 30 minutes to cure the adhesive.
  • the sealing step is an atmospheric pressure with a cleanness measured in accordance with JIS B 9920, class 100, dew point temperature of ⁇ 80 ° C. or less, and oxygen concentration of 0.8 ppm or less in a nitrogen atmosphere with a moisture content of 1 ppm or less. Went under.
  • the description regarding formation of the extraction wiring from a transparent anode and a cathode is abbreviate
  • an organic EL element 1 which is a white light emitting device having a total thickness of about 75 ⁇ m was produced.
  • the organic EL element 2 was produced according to the following method.
  • Step 2-1 Preparation of resin base material
  • the same as the organic EL element 1 was used.
  • Step 2-2 Formation of coating gas barrier layer 1
  • a dibutyl ether solution containing 20% by mass of perhydropolysilazane manufactured by AZ Electronic Materials Co., Ltd., NN120-20
  • an amine catalyst N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH)
  • a dibutyl ether solution NAX120-20, manufactured by AZ Electronic Materials Co., Ltd.
  • NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.
  • a roll-to-roll type coating apparatus capable of successively performing coating surface side protective film peeling, coating, drying, excimer modification treatment, and coating surface side protective film bonding was used.
  • the coating solution was applied on the base material using a die coater so that the thickness after drying was 250 nm and dried at 80 ° C. in a dryer zone.
  • a vacuum ultraviolet ray irradiation treatment was performed on the dried coating film continuously in a vacuum ultraviolet ray irradiation zone having an Xe excimer lamp having a wavelength of 172 nm under the condition that the irradiation energy was 6.0 J / cm 2.
  • a gas barrier layer 1 was formed.
  • the irradiation atmosphere was replaced with nitrogen heated to 60 ° C., and the oxygen concentration was set to 0.1% by volume or less. Up to this point, there was no contact of the transport roll or the like on the coating surface.
  • the coated surface was wound up without attaching a protective film.
  • Step 2-3 Formation of transition metal-containing layer
  • a niobium oxide layer which is a transition metal-containing layer, was formed on the coating gas barrier layer obtained in step 2-2 using a roll-to-roll magnetron sputtering apparatus.
  • a commercially available oxygen deficient niobium oxide target was used as a target, and sputtering was performed by a DC pulse method.
  • the power density was 4.0 kW / cm 2
  • the TS distance was 100 mm
  • the film forming pressure was 0.2 Pa
  • argon and oxygen were used as process gases
  • the oxygen ratio was 10%.
  • the conveyance speed was adjusted so that the film thickness was 15 nm.
  • Step 2-4 Formation of coating gas barrier layer 2
  • a coating solution was prepared in the same manner as the coating gas barrier layer 1 except that the solid content was 4% by mass. Also, the coating gas barrier layer 1 was formed in the same manner as the coating gas barrier layer 1 except that the thickness after drying was 110 nm.
  • a self-adhesive OPP film manufactured by Futamura Chemical Co., Ltd., FSA010M was bonded to the coated surface as a protective film, and then wound up.
  • the water vapor permeability of the gas barrier film substrate 2 was measured using the Ca method.
  • the measurement conditions were set to 40 ° C. and 90% RH as in the measurement of the gas barrier film substrate 1.
  • the water vapor transmission rate obtained was 6.8 ⁇ 10 ⁇ 6 g / (m 2 ⁇ 24 h).
  • composition profile in the thickness direction of the gas barrier was analyzed by the XPS method. Confirm that a mixed region containing Si and Nb is formed at the interface 1 between the coating gas barrier layer 1 and the transition metal-containing layer and at the interface 2 between the transition metal-containing layer and the coating gas barrier layer 2. did. Further, when the minimum value of the oxygen deficiency in the mixed region was obtained using the relational expression (2), it was 0.57 at the interface 1 and 0.60 at the interface 2.
  • composition distribution profile in the thickness direction of the gas barrier layer was measured by XPS analysis.
  • the XPS analysis conditions are as follows.
  • the composition of the gas barrier 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 number ratio of atoms in the range of 0.02 ⁇ x ⁇ 50 was defined as a “mixed region”, and the presence / absence of the region and its thickness (nm) were measured and listed in the table.
  • the gas barrier 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.
  • Step 2-5 Formation of transparent anode
  • the same procedure as in the organic EL element 1 was performed except that the gas barrier film substrate 2 was used.
  • Step 2-6 Formation of organic functional layer unit to cathode
  • the same procedure as in the organic EL element 1 was performed except that the gas barrier film substrate 2 was used.
  • Step 2-7 Sealing step
  • an organic EL element 2 which is a white light emitting device having a total thickness of about 73 ⁇ m was produced.
  • Both the organic EL element 1 and the organic EL element 2 had good initial light emission state and no dark spots were generated. Also, no dark spots were generated after storage for 100 hours in an environment of 85 ° C. and 85% RH.
  • Example 2 Evaluation assuming a light emitting device in a folded form was performed.
  • a light emitting device simulating a folded light emitting device as shown in FIGS. 2A and 2B was created.
  • a device having a hinge part to be peeled is a type (1) (FIG. 2A), and a device having no hinge part at a bent part is a type (2) (FIG. 2B).
  • Eight types of light-emitting devices were produced by changing the radius of curvature of the part B to the values shown in Table 1.
  • the length of the hinge part is 16 mm. In the case of the type (2) which is a device having no hinge part, the minimum curvature radius of the part B was less than 1 mm.
  • the light emitting device of the present invention was good with almost no dark spots due to folding.
  • a light emitting device using a gas barrier film having a mixed region of transition metal and non-transition metal in the gas barrier layer showed good results.
  • Example 3 Evaluation was made assuming a light-emitting device in a winding form.
  • a steel sheet having a thickness of 100 ⁇ m is used as a supporting member, the organic EL element produced above is bonded to the steel sheet, the organic EL element is placed outside, and a winding shaft having a radius of 8 mm is wound in the longitudinal direction.
  • Four types of devices simulating a light emitting device in a winding form were prepared.
  • the type (3) apparatus has a short side 10 mm width on the side far from the take-up shaft attached to a steel sheet with a thermosetting adhesive (epoxy resin, 100 ⁇ m thickness), 90 ° C. for 30 minutes. Curing was performed to obtain a fixed portion (fixed end). The other part was bonded using a 100 ⁇ m thick acrylic adhesive sheet (manufactured by Nitto Denko Corporation), and the short side near the take-up shaft was a free end (see FIG. 4A. The right end is the fixed end) .
  • thermosetting adhesive epoxy resin, 100 ⁇ m thickness
  • the light-emitting devices 11 to 14 were prepared by combining the organic EL element and the device type, and the light-emitting state was confirmed by performing light-up after 100 winding and rewinding of each light-emitting device. The results are shown in Table 2.
  • the light-emitting device of the present invention maintained a good light-emitting state even when it was wound and rewound, and no dark spot was generated.
  • the light emitting device of the comparative example having no movable part linear dark spots, which are thought to be caused by gas barrier layer cracks, formed by stretching the organic EL element by winding were frequently generated.
  • the light-emitting device of the present invention can be miniaturized when being carried, and can be used in various applications such as electronic devices such as packages for electronic devices, photoelectric conversion elements (solar cell elements), organic EL elements, liquid crystal display elements, and the like. Can be used.

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  • Electroluminescent Light Sources (AREA)

Abstract

L'invention a pour objet de fournir un dispositif luminescent permettant une miniaturisation lorsqu'il est porté. Le dispositif luminescent de l'invention est tel que sont stratifiés dans l'ordre un matériau de base en résine côté face luminescente, un élément luminescent organique, et un matériau de base côté face arrière, et possède une couche barrière au gaz ayant une matière organique pour composant principal entre ledit matériau de base en résine côté face luminescente et ledit élément luminescent organique, et/ou entre ledit élément luminescent organique et ledit matériau de base côté face arrière. Ce dispositif luminescent est soutenu à l'aide d'une partie fixe et d'une partie mobile sur un élément de soutien. En outre, ce dispositif luminescent possède une partie face courbe dont le rayon de courbure d'une face courbe sur laquelle est formée ladite partie mobile dudit élément luminescent organique, lors du port, est compris à l'intérieur d'une plage de 1,0 à 10,0mm.
PCT/JP2016/084528 2015-11-24 2016-11-22 Dispositif luminescent WO2017090577A1 (fr)

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JP2011020334A (ja) * 2009-07-15 2011-02-03 Dainippon Printing Co Ltd ガスバリア性シート、ガスバリア性シートの製造方法、封止体、及び装置
JP2013232320A (ja) * 2012-04-27 2013-11-14 Konica Minolta Inc 電子デバイスおよびその製造方法
JP2014120479A (ja) * 2012-12-17 2014-06-30 Universal Display Corp フレキシブル有機電子デバイスの製造
JP2015064570A (ja) * 2013-08-30 2015-04-09 株式会社半導体エネルギー研究所 表示装置およびその作製方法
JP2015152922A (ja) * 2014-02-12 2015-08-24 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． 巻き取り可能な表示装置
JP2015173249A (ja) * 2013-11-06 2015-10-01 株式会社半導体エネルギー研究所 剥離方法及び発光装置
WO2016125477A1 (fr) * 2015-02-04 2016-08-11 シャープ株式会社 Dispositif d'affichage et son procédé de production

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JP3880497B2 (ja) * 2002-09-27 2007-02-14 Ｎｅｃインフロンティア株式会社 Ｌａｎ通信システム
KR102039496B1 (ko) * 2013-08-19 2019-11-04 삼성디스플레이 주식회사 접이식 표시 장치

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010106590A1 (fr) * 2009-03-17 2010-09-23 シャープ株式会社 Dispositif d'affichage
JP2011020334A (ja) * 2009-07-15 2011-02-03 Dainippon Printing Co Ltd ガスバリア性シート、ガスバリア性シートの製造方法、封止体、及び装置
JP2013232320A (ja) * 2012-04-27 2013-11-14 Konica Minolta Inc 電子デバイスおよびその製造方法
JP2014120479A (ja) * 2012-12-17 2014-06-30 Universal Display Corp フレキシブル有機電子デバイスの製造
JP2015064570A (ja) * 2013-08-30 2015-04-09 株式会社半導体エネルギー研究所 表示装置およびその作製方法
JP2015173249A (ja) * 2013-11-06 2015-10-01 株式会社半導体エネルギー研究所 剥離方法及び発光装置
JP2015152922A (ja) * 2014-02-12 2015-08-24 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． 巻き取り可能な表示装置
WO2016125477A1 (fr) * 2015-02-04 2016-08-11 シャープ株式会社 Dispositif d'affichage et son procédé de production

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TW201733093A (zh) 2017-09-16
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CN108293279A (zh) 2018-07-17
JP6773048B2 (ja) 2020-10-21
CN108293279B (zh) 2019-12-31

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