WO2012046742A1 - Dispositif électroluminescent organique - Google Patents

Dispositif électroluminescent organique Download PDF

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Publication number
WO2012046742A1
WO2012046742A1 PCT/JP2011/072890 JP2011072890W WO2012046742A1 WO 2012046742 A1 WO2012046742 A1 WO 2012046742A1 JP 2011072890 W JP2011072890 W JP 2011072890W WO 2012046742 A1 WO2012046742 A1 WO 2012046742A1
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film
organic
protective film
distribution curve
ratio
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PCT/JP2011/072890
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English (en)
Japanese (ja)
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小野　善伸
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住友化学株式会社
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/311—Flexible OLED

Definitions

  • the present invention relates to an organic EL device, a lighting device, a planar light source, and a display device.
  • An organic EL (Electro Luminescence) element has a structure in which a plurality of thin films are stacked. Flexibility can be imparted to the element itself by appropriately setting the thickness and material of each thin film.
  • the entire apparatus on which the organic EL element is mounted can be a flexible apparatus.
  • the organic EL element deteriorates when exposed to the outside air. Therefore, the organic EL element is usually hermetically sealed by a predetermined sealing member. However, the organic EL element may deteriorate even after the organic EL element is formed and before the sealing member is provided. In order to prevent this deterioration, in the invention described in Patent Document 1, the organic EL element is covered with a protective film immediately after the organic EL element is formed.
  • Patent Document 1 discloses a protective film made of SiO 2 , SiN x , SiO x Ny, MgF, In 2 O 3 , polyparaxylylene, or the like.
  • the protective film does not have sufficient characteristics to block oxygen and moisture, that is, gas barrier properties, and even if a protective film is provided, the organic EL element deteriorates.
  • the protective film is not suitable for a method of manufacturing an organic EL device by, for example, a roll-to-roll method.
  • an object of the present invention is to provide an organic EL device having a protective film that has a high gas barrier property and suppresses a decrease in the gas barrier property due to bending.
  • the present invention provides an organic EL device comprising: a first film; an organic EL element provided on the first film; and a protective film that covers a surface of the organic EL element opposite to the first film.
  • the protective film contains silicon (silicon atoms), oxygen (oxygen atoms), and carbon (carbon atoms), and the ratio of the number (number) of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (silicon atoms) Ratio), the ratio of oxygen atom quantity (number) (oxygen atom ratio), and the ratio of carbon atom quantity (number) (carbon atom ratio), and the protection in the thickness direction (film thickness direction) of the protective film.
  • a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve, each representing a relationship with the distance from one surface of the film are as follows: (I) Of the ratio of the number of silicon atoms, the ratio of the number of oxygen atoms, and the ratio of the number of carbon atoms in the region of 90% or more in the thickness direction (film thickness direction) of the protective film, The ratio is the second largest value, (Ii) the carbon distribution curve has at least one extreme value; and (iii) the difference (absolute value) between the maximum value and the minimum value of the ratio of the number of carbon atoms in the carbon distribution curve is 5 atomic% (at %) Or more, Meet.
  • the organic EL device may further include a second film that is disposed to face the first film and seals the organic EL element together with the first film.
  • An organic EL element and a protective film are disposed between the second film and the first film.
  • the present invention is arranged on the first film with the organic EL element and the protective film interposed between the first film, and seals the organic EL element together with the first film.
  • the present invention relates to an organic EL device having a second film to be stopped.
  • this invention includes the process of forming an organic EL element on a 1st film, and the process of forming the protective film which covers the surface on the opposite side to the said 1st film of an organic EL element, and organic EL.
  • the invention relates to a method of manufacturing a device.
  • the formed protective film contains silicon atoms, oxygen atoms and carbon atoms, and the ratio of the number of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms, the ratio of the number of oxygen atoms and the number of carbon atoms.
  • a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve representing the relationship between the ratio and the distance from one surface of the protective film in the thickness direction of the protective film are as follows: (I) In the region of 90% or more in the thickness direction of the protective film, the ratio of the number of silicon is the second among the ratio of the number of silicon atoms, the ratio of the number of oxygen atoms, and the ratio of the number of carbon atoms. A large value, (Ii) the carbon distribution curve has at least one extreme value; and (iii) the difference between the maximum value and the minimum value of the ratio of the number of carbon atoms in the carbon distribution curve is 5 atomic% or more. Meet.
  • the second film is formed so that the organic EL element and the protective film are disposed between the second film and the first film.
  • the process of bonding to 1 film may further be included.
  • the organic EL element and the protective film are interposed between the first film and the second film on the first film.
  • the process of bonding a film may be included. In this case, the second film may be bonded to the first film under an air atmosphere.
  • the first film is wound into a roll together with the organic EL element and the protective film, and the wound first film, organic EL element, and protective film are stored.
  • the process may further be included.
  • the wound first film, organic EL element, and protective film may be stored in an air atmosphere.
  • the present invention relates to an illumination device, a surface light source device, and a display device having the organic EL device.
  • the organic EL element can be covered with a protective film that has a high gas barrier property and is unlikely to deteriorate even when bent. Therefore, after forming a protective film, it can suppress that an organic EL element deteriorates by sealing an organic EL element with a sealing member etc.
  • the organic EL device includes a first film, an organic EL element provided on the first film, and a protective film formed so as to cover the organic EL element.
  • a protective film covers the whole surface on the opposite side to the 1st film of an organic EL element.
  • Organic EL elements mounted on organic EL devices can be broadly classified into the following three types of elements. That is, the organic EL element (I) emits light toward a support substrate on which the organic EL element is mounted, a so-called bottom emission type element, and (II) emits light toward the opposite side of the support substrate. And so-called top emission type elements, and (III) a dual emission type element that emits light toward the support substrate and emits light toward the opposite side of the support substrate. .
  • the organic EL element mounted on the organic EL device according to this embodiment may be any type of element.
  • the organic EL device further includes a second film as necessary.
  • This 2nd film is arrange
  • the organic EL element and the protective film are sealed with the first film and the second film.
  • FIG. 1 is a cross-sectional view schematically showing the organic EL device of this embodiment.
  • the organic EL device 13 according to the embodiment shown in FIG. 1 includes a first film 1, an organic EL element 2 mounted on the first film 1, and a protective film 3 that protects the organic EL element 2.
  • the protective film 3 has high gas barrier properties by satisfying conditions (i), (ii), and (iii) described later, and can further suppress a decrease in gas barrier properties when bent.
  • the protective film can maintain a high gas barrier property even when the organic EL device 13 is rolled up, and the gas barrier property is high.
  • the wound organic EL device can be stored in an air atmosphere. Since a high gas barrier property can be maintained even if the protective film is bent, a roll-to-roll method can be suitably applied as a method for manufacturing an organic EL device.
  • the bonding can be performed by a roll-to-roll method. Furthermore, this bonding can also be performed in an air atmosphere.
  • the protective film contains silicon atoms, oxygen atoms, and carbon atoms.
  • the ratio of the number of silicon atoms (the atomic ratio of silicon), the ratio of the number (quantity) of oxygen atoms (the atomic ratio of oxygen) and the ratio of the number of carbon atoms (carbon) to the total amount of silicon atoms, oxygen atoms and carbon atoms.
  • the atomic ratio of each atom is measured while changing the distance from one surface of the protective film in the thickness direction (thickness direction) of the protective film, whereby the relationship between the atomic ratio of each atom and the distance from the surface of the protective film Can be obtained silicon distribution curve, oxygen distribution curve and carbon distribution curve, respectively.
  • the silicon atomic ratio is the second largest value among the silicon atomic ratio, oxygen atomic ratio, and carbon atomic ratio.
  • the carbon distribution curve has at least one extreme value.
  • the difference (absolute value) between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more.
  • condition (i) means that the following formula (1) or the following formula (2) is satisfied in a region of 90% or more in the thickness direction of the protective film.
  • the organic EL device may have another layer that does not satisfy at least one of the conditions (i) to (iii).
  • the protective film or other layer may further contain nitrogen atoms, aluminum atoms, and the like.
  • the gas barrier property of the protective film is lowered. It is preferable that the region satisfying the above formula (1) or (2) occupies 90% or more of the thickness of the protective film. This ratio is more preferably 95% or more, and still more preferably 100%.
  • the carbon distribution curve needs to have at least one extreme value as the condition (ii).
  • the carbon distribution curve preferably has two extreme values, and more preferably has three or more extreme values.
  • the gas barrier property is lowered when the obtained protective film is bent.
  • the distance in the thickness direction between adjacent extreme values of the carbon distribution curve is preferably 200 nm or less, and more preferably 100 nm or less.
  • the extreme value means a maximum value or a minimum value in a distribution curve obtained by plotting an atomic ratio of an element with respect to a distance from the surface of the protective film in the thickness direction of the protective film.
  • the maximum value is a point where the value of the atomic ratio of the element changes from increasing to decreasing with the change of the distance from the surface of the protective film, and the atomic ratio value of the element at that point.
  • the atomic ratio of an element at a point where the atomic ratio of the element at a position where the distance from the surface of the protective film in the thickness direction of the protective film from the point is further changed by 20 nm is reduced by 3 at% or more.
  • the minimum value is a point where the value of the atomic ratio of the element changes from decreasing to increasing with a change in the distance from the surface of the protective film, and compared with the value of the atomic ratio of the element at that point,
  • the atomic ratio of the element at the point where the value of the atomic ratio of the element at a position where the distance from the surface in the thickness direction of the protective film from the point is further changed by 20 nm further increases by 3 at% or more.
  • the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve needs to be 5 at% or more.
  • the difference between the maximum value and the minimum value of the atomic ratio of carbon is more preferably 6 at% or more, and further preferably 7 at% or more. If this difference is less than 5 at%, the gas barrier property of the protective film is lowered when the second film is bent.
  • the upper limit of the difference is not particularly limited, but is usually about 30 at%.
  • the oxygen distribution curve of the protective film preferably has at least one extreme value, more preferably has at least two extreme values, and more preferably has at least three extreme values.
  • the oxygen distribution curve has an extreme value, the gas barrier property tends to be less likely to occur due to the bending of the protective film.
  • the oxygen distribution of the protective film has at least three extreme values, the protective film in the thickness direction of each protective film between one extreme value of the oxygen distribution curve and the extreme value adjacent to the extreme value.
  • the difference in distance from the surface is preferably 200 nm or less, and more preferably 100 nm or less.
  • the difference between the maximum value and the minimum value of the oxygen atomic ratio in the oxygen distribution curve of the protective film is preferably 5 at% or more, more preferably 6 at% or more, and further preferably 7 at% or more. If this difference is equal to or greater than the lower limit, the gas barrier property tends to be less likely to occur due to the bending of the protective film.
  • the upper limit of this difference is not particularly limited, but is usually about 30 at%.
  • the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve of the protective film is preferably less than 5 at%, more preferably less than 4 at%, and even more preferably less than 3 at%. If this difference is less than the upper limit, the gas barrier property of the protective film tends to be particularly high.
  • Oxygen carbon distribution curve difference between maximum and minimum values Expresses the relationship between the distance from the surface of the layer in the thickness direction of the protective film and the ratio of the total amount of oxygen atoms and carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atomic ratio of oxygen and carbon)
  • the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon is preferably less than 5 at%, more preferably less than 4 at%, and more preferably less than 3 at%. Further preferred. If this difference is less than the upper limit, the gas barrier property of the protective film tends to be particularly high.
  • the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve are obtained by combining X-ray photoelectron spectroscopy (XPS) measurement with rare gas ion sputtering such as argon. It can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while being exposed.
  • XPS depth profile measurement in which surface composition analysis is sequentially performed while being exposed.
  • a distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).
  • the etching time generally correlates with the distance from the surface of the protective film in the thickness direction of the protective film.
  • the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time adopted in the XPS depth profile measurement is Can be adopted.
  • an argon (Ar +) rare gas ions sputter method using the adopted as an etching ion species the etching rate (etching rate) was 0.05 nm / sec ( It is preferable to set the value in terms of SiO 2 thermal oxide film.
  • the protective film is substantially uniform in the film surface direction (direction parallel to the main surface (surface) of the protective film).
  • the protective film is substantially uniform in the film surface direction
  • “the protective film is substantially uniform in the film surface direction” means that an oxygen distribution curve and a carbon distribution curve are measured at any two measurement points on the film surface of the protective film by XPS depth profile measurement.
  • the oxygen carbon distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement points is the same, and the maximum value of the carbon atomic ratio in each carbon distribution curve The difference from the minimum value is the same as each other, or the difference is within 5 at%.
  • the carbon distribution curve is preferably substantially continuous.
  • “the carbon distribution curve is substantially continuous” means that a portion in which the atomic ratio of carbon in the carbon distribution curve changes discontinuously is not included. Specifically, this is because the distance (x, unit: nm) from the surface of the layer in the thickness direction of the protective film calculated from the etching rate and etching time, and the atomic ratio of carbon (c, unit: at) %) In relation to the following formula (F1): ⁇ 1.0 ⁇ (dc / dx) ⁇ 1.0 (F1) It means that the condition represented by is satisfied.
  • the protective film according to the present embodiment only needs to include at least one film that satisfies all of the above conditions (i) to (iii), and the protective film includes a film that satisfies all of the above conditions (i) to (iii). Two or more layers may be provided. When the protective film includes two or more such films, the materials of the plurality of films may be the same or different.
  • silicon atoms and oxygen in the protective film when the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the condition expressed by the formula (1), silicon atoms and oxygen in the protective film
  • the atomic ratio of the silicon atom content to the total amount of atoms and carbon atoms is preferably 25 to 45 at%, more preferably 30 to 40 at%.
  • the atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the protective film is preferably 33 to 67 at%, more preferably 45 to 67 at%.
  • the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the protective film is preferably 3 to 33 at%, and more preferably 3 to 25 at%.
  • silicon in the protective film when the silicon atomic ratio, oxygen atomic ratio, and carbon atomic ratio satisfy the condition expressed by the above formula (2), silicon in the protective film
  • the atomic ratio of the content of silicon atoms with respect to the total amount of atoms, oxygen atoms and carbon atoms is preferably 25 to 45 at%, more preferably 30 to 40 at%.
  • the atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the protective film is preferably 1 to 33 at%, more preferably 10 to 27 at%.
  • the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the protective film is preferably 33 to 66 at%, and more preferably 40 to 57 at%.
  • the thickness of the protective film is preferably 5 to 3000 nm, more preferably 10 to 2000 nm, and particularly preferably 100 to 1000 nm. When the thickness of the protective film is within these numerical ranges, more excellent gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties are obtained, and a decrease in gas barrier properties due to bending tends to be more effectively suppressed.
  • the total thickness of the plurality of films is usually 10 to 10000 nm, preferably 10 to 5000 nm, more preferably 100 to 3000 nm, More preferably, it is 200 to 2000 nm.
  • a superior gas barrier property such as oxygen gas barrier property and water vapor barrier property can be obtained, and a decrease in gas barrier property due to bending tends to be more effectively suppressed. is there.
  • the protective film is preferably a layer formed by a plasma chemical vapor deposition method.
  • the protective film formed by the plasma chemical vapor deposition method is a plasma in which the first film and the organic EL element provided thereon are disposed on a pair of film forming rolls and discharged between the pair of film forming rolls. More preferably, the layer is formed by a plasma enhanced chemical vapor deposition method for generating methane. When discharging between the pair of film forming rolls, it is preferable to reverse the polarity of the pair of film forming rolls alternately.
  • the film forming gas used for such plasma chemical vapor deposition preferably includes an organosilicon compound and oxygen.
  • the oxygen content in the film forming gas is preferably less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas.
  • the protective film is preferably a layer formed by a continuous film forming process. Details of a method for forming a protective film using such a plasma chemical vapor deposition method will be described in a method for manufacturing a protective film described later.
  • a protective film is formed so that the organic EL element previously formed on the 1st film may be covered with a 1st film.
  • plasma chemical vapor deposition plasma chemical vapor deposition
  • This plasma chemical vapor deposition method may be a plasma chemical vapor deposition method using a Penning discharge plasma method.
  • the first film is disposed on the surface and discharged between a pair of film forming rolls to generate plasma.
  • the other film forming roll is formed while forming a protective film on the first film and the organic EL element existing on one film forming roll during film formation.
  • a protective film can be simultaneously formed on the first film and the organic EL element existing on the upper film.
  • a film having the same structure can be simultaneously formed at a double film formation rate.
  • An apparatus that can be used when manufacturing a protective film by such plasma chemical vapor deposition is not particularly limited, and includes at least a pair of film forming rolls and a plasma power source, and the pair of film forming rolls. It is preferable that the device is capable of discharging in between. For example, by using the manufacturing apparatus shown in FIG. 2, it is possible to manufacture a protective film by a roll-to-roll method using a plasma chemical vapor deposition method.
  • FIG. 2 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing the protective film according to the present embodiment.
  • the same or corresponding elements are denoted by the same reference numerals, and overlapping descriptions are omitted as appropriate.
  • the manufacturing apparatus shown in FIG. 2 includes a feed roll 701, transport rolls 21, 22, 23, and 24, a pair of film forming rolls 31 and 32 disposed opposite to each other, a gas supply pipe 41, and a plasma generation power source. 51, magnetic field generators 61 and 62 installed inside the film forming rolls 31 and 32, and a winding roll 702.
  • a vacuum chamber (not shown).
  • This vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by such a vacuum pump.
  • each film forming roll has a plasma generation power source so that a pair of film forming rolls (film forming roll 31 and film forming roll 32) can function as a pair of counter electrodes.
  • 51 is connected.
  • a discharge is generated in the space between the film forming roll 31 and the film forming roll 32, and thereby plasma is generated in the space between the film forming roll 31 and the film forming roll 32.
  • the material and design may be changed as appropriate so that they can also be used as electrodes.
  • the pair of film forming rolls are preferably arranged so that their central axes are substantially parallel on the same plane.
  • a pair of film-forming rolls (film-forming rolls 31 and 32) are arranged, and a protective film is formed on each film-forming roll, so that the film is formed on one film-forming roll.
  • the film formation rate can be doubled.
  • the films having the same structure can be stacked, it is possible to at least double the number of extreme values in the carbon distribution curve. According to such a manufacturing apparatus, it is possible to form a protective film on the surface of the first film 1 and the organic EL element by the CVD method, and the first film 1 and the organic EL are formed on the film forming roll 31.
  • the film component While depositing the film component on the surface of the element, the film component can also be deposited on the surface of the first film 1 and the organic EL element on the film forming roll 32. Therefore, a protective film can be efficiently formed on the surfaces of the first film 1 and the organic EL element.
  • magnetic field generators 61 and 62 are provided inside the film forming roll 31 and the film forming roll 32.
  • the magnetic field generators 61 and 62 are fixed so as not to rotate even if the film forming roll rotates.
  • the diameters of the film forming rolls 31 and 32 are preferably substantially the same from the viewpoint of forming a thin film more efficiently.
  • the diameters of the film forming rolls 31 and 32 are preferably 5 to 100 cm from the viewpoint of discharge conditions, chamber space, and the like.
  • the first film is disposed on a pair of film forming rolls (film forming roll 31 and film forming roll 32) so that the surfaces of the first film face each other.
  • the first film existing between the pair of film-forming rolls is generated when the plasma is generated by performing discharge between the film-forming roll 31 and the film-forming roll 32.
  • the film component is deposited on the surface of the first film and the organic EL element on the film forming roll 31 by the CVD method, and further, the first component is formed on the film forming roll 32.
  • Film components can be deposited on the surface of the film and the organic EL element. Therefore, it is possible to efficiently form a gas barrier layer on the surfaces of the first film and the organic EL element.
  • the winding roll 702 is not particularly limited as long as it can wind the first film 1 on which the protective film is formed, and is appropriately selected from commonly used rolls.
  • the gas supply pipe 41 only needs to be able to supply or discharge the raw material gas or the like at a predetermined speed.
  • a power source of a normal plasma generating apparatus can be used as appropriate.
  • the plasma generating power supply 51 supplies power to the film forming roll 31 and the film forming roll 32 connected to the power supply 51, and makes it possible to use these as counter electrodes for discharge.
  • a power source such as an AC power source
  • a power source that can alternately reverse the polarity of a pair of film forming rolls is used. Is preferred.
  • the plasma generation power source 51 can set the applied power to 100 W to 10 kW and the AC frequency to 50 Hz to 500 kHz in order to perform plasma CVD more efficiently.
  • the magnetic field generators 61 and 62 normal magnetic field generators can be used as appropriate.
  • a base material sent out from the feed roll in addition to the first film and the organic EL element, a base material having a protective film previously formed thereon can be used. As described above, the protective film can be further thickened by forming the protective film in multiple times.
  • the manufacturing apparatus shown in FIG. 2 for example, by appropriately adjusting the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roll, and the film transport speed Can be a protective film.
  • the manufacturing apparatus shown in FIG. 2 By using the manufacturing apparatus shown in FIG. 2 to generate a discharge between a pair of film-forming rolls (film-forming rolls 31 and 32) while supplying a film-forming gas (such as a raw material gas) into the vacuum chamber,
  • a film-forming gas such as a raw material gas
  • the film gas is decomposed by plasma, and a protective film is formed on the surface of the first film on the film forming roll 31 and on the surface of the first film on the film forming roll 32 by the plasma CVD method. Is done.
  • the first film 1 is conveyed by the delivery roll 701, the film formation roll 31, and the like, respectively. Therefore, the first film 1 is formed by a roll-to-roll continuous film formation process.
  • a protective film covering the organic EL element is formed on the surface.
  • the source gas in the film forming gas used for forming the protective film is appropriately selected according to the material of the protective film to be formed.
  • the source gas for example, an organosilicon compound containing silicon can be used.
  • the source gas may contain monosilane as a silicon source in addition to the organosilicon compound.
  • the source gas is, for example, hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, At least one organosilicon compound selected from the group consisting of phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane including.
  • organosilicon compounds hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the resulting gas barrier layer.
  • organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.
  • the film forming gas may contain a reactive gas in addition to the source gas.
  • a gas that reacts with the raw material gas to form an inorganic compound such as oxide or nitride can be appropriately selected and used.
  • a reaction gas for forming an oxide for example, oxygen or ozone can be used.
  • the reaction gas for forming the nitride for example, nitrogen or ammonia can be used. These reaction gases are used alone or in combination of two or more. For example, when oxynitride is formed, a reaction gas for forming an oxide and a reaction gas for forming a nitride can be combined.
  • a carrier gas may be used as necessary in order to supply a source gas into the vacuum chamber.
  • a discharge gas may be used as necessary in order to generate plasma discharge.
  • a carrier gas and a discharge gas known ones can be used as appropriate.
  • a rare gas such as helium, argon, neon, and xenon, or hydrogen can be used as the carrier gas or the discharge gas.
  • the ratio of the source gas and the reactive gas is greater than the ratio of the amount of the reactive gas that is theoretically necessary to completely react the source gas and the reactive gas. However, it is preferable not to make the ratio of the reaction gas excessive.
  • a thin film (protective film) satisfying all the above conditions (i) to (iii) can be formed particularly efficiently.
  • the deposition gas contains an organosilicon compound and oxygen
  • the amount of oxygen in the deposition gas is less than or equal to the theoretical oxygen amount required to fully oxidize the entire amount of the organosilicon compound in the deposition gas. Is preferred.
  • a gas containing hexamethyldisiloxane organosilicon compound: HMDSO: (CH 3 ) 6 Si 2 O :) as a source gas and oxygen (O 2 ) as a reaction gas is used as a film forming gas
  • organosilicon compound: HMDSO: (CH 3 ) 6 Si 2 O :) as a source gas
  • oxygen (O 2 ) as a reaction gas
  • a film-forming gas containing hexamethyldisiloxane (HMDSO, (CH 3 ) 6 Si 2 O) as a source gas and oxygen (O 2 ) as a reaction gas is reacted by plasma CVD to form a silicon-oxygen-based material.
  • HMDSO hexamethyldisiloxane
  • O 2 oxygen
  • the following reaction formula (3) in the film-forming gas (CH 3 ) 6 Si 2 O + 12O 2 ⁇ 6CO 2 + 9H 2 O + 2SiO 2 (3)
  • the reaction represented by this occurs and silicon dioxide is formed.
  • the amount of oxygen necessary to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol.
  • a uniform silicon dioxide film can be formed when 12 moles or more of oxygen is contained in 1 mole of hexamethyldisiloxane and completely reacted in the film forming gas.
  • the oxygen amount is set to a stoichiometric ratio of 12 with respect to 1 mol of hexamethyldisiloxane so that the reaction of the above formula (3) does not proceed completely. It is preferable to make it less than a mole.
  • the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount (flow rate) of oxygen in the reaction gas
  • the molar amount (flow rate) is 12 times the molar amount (flow rate) of the raw material hexamethyldisiloxane
  • the reaction does not proceed completely, and oxygen is compared to the stoichiometric ratio. It is thought that the reaction is often completed only when a large excess is supplied.
  • the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material. Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. .
  • the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane. It is preferable that the amount is more than 0.5 times.
  • the pressure in the vacuum chamber (degree of vacuum) can be adjusted as appropriate according to the type of source gas, but is preferably in the range of 0.1 Pa to 50 Pa.
  • an electrode drum connected to the plasma generating power supply 51 (in this embodiment, the film forming rolls 31 and 32 are installed).
  • the conveyance speed (line speed) of the first film can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably 0.1 to 100 m / min. More preferably, it is 5 to 20 m / min.
  • line speed is less than the lower limit, wrinkles due to heat tend to occur in the film, and when the line speed exceeds the upper limit, the thickness of the protective film formed tends to be thin.
  • the first film can be wound into a roll together with the organic EL element and the protective film and stored until the second film described later is bonded.
  • This storage step is performed, for example, in a vacuum, in an inert gas atmosphere, or in an air atmosphere. In view of simplicity of the process, an inert gas atmosphere or an air atmosphere is preferable, and an air atmosphere is more preferable. Even when the storage step is performed in an inert gas atmosphere or an atmospheric atmosphere, the gas barrier property of the protective film wound up in a roll is not easily lowered, and the protective film has a high gas barrier property. Deterioration of the organic EL element can be suppressed.
  • FIG. 3 shows a form in which a top emission type organic EL element is provided as an example
  • FIG. 4 shows a form in which a bottom emission type organic EL element is provided.
  • FIG. 3 is a cross-sectional view schematically showing the organic EL device of this embodiment.
  • the organic EL element 2 is mounted on the first film 1, and the protective film 3 is formed so as to cover the organic EL element 2.
  • the second film 11 is disposed on the first film 1 with the organic EL element 2 and the protective film 3 interposed between the second film 11 and the first film 1.
  • the second film 11 seals the organic EL element 2 together with the first film 1.
  • the 1st film 1 and the 2nd film 11 are bonded together via the contact bonding layer 4 provided between them.
  • the organic EL element 2 of the present embodiment shown in FIG. 3 is a top emission type element, and emits light toward the second film 11. Therefore, the second film 11 needs to be formed by a member that transmits light.
  • the first film 1 corresponding to the support substrate in the present embodiment may be formed of an opaque member that does not transmit light.
  • the first film 1 a plastic film or a metal film can be used, and a metal film is preferable. Since the metal film has a higher gas barrier property than a plastic film or the like, the gas barrier property of the organic EL device can be improved.
  • the metal film for example, a thin plate of Al, Cu or Fe and a thin plate of an alloy such as stainless steel can be used.
  • the second film 11 a film having a high gas barrier property is preferably used.
  • the 2nd film 11 is provided on the main surface by the side of the organic EL element 2 of the base material 6 of the base material 6, and is comprised from the gas barrier layer 5 which has high gas barrier property.
  • the gas barrier layer 5 may be composed of alternately stacked organic layers and inorganic layers, or the same thin film as the protective film 3 described above may be used as the gas barrier layer 5.
  • the gas barrier layer 5 is preferably a film similar to the thin film described as the protective film. That is, the second film 11 preferably has a predetermined base material 6 and a thin film similar to the above-described protective film formed on the base material 6 as the gas barrier layer 5.
  • FIG. 4 is a cross-sectional view schematically showing an organic EL device 13 according to another embodiment of the present invention.
  • the organic EL device 13 of the embodiment shown in FIG. 4 is different from the embodiment shown in FIG. 3 in the organic EL element and the first film 1. That is, the organic EL element 2 of the present embodiment is a bottom emission type element, and emits light toward the first film 1 corresponding to the support substrate. Therefore, the 1st film 1 needs to be a film which shows a light transmittance.
  • the first film 1 of this embodiment is not particularly limited as long as it is a light transmissive film.
  • the second film 11 contains silicon, oxygen, and carbon in the same manner as the second film 11. It is preferable to have the gas barrier layer 8.
  • the first film 1 includes a base material 7 and a second gas barrier layer 8 provided on the base material 7.
  • the second gas barrier layer 8 has high gas barrier properties by satisfying the conditions (i) to (iii), and can further suppress a decrease in gas barrier properties when bent.
  • the base material of the first film or the second film described above includes a colorless and transparent resin film or resin sheet.
  • the resin used for such a substrate include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefin; Resin; Polycarbonate resin; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; and Polyimide resin.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • Resin Polycarbonate resin
  • Polystyrene resin Polyvinyl alcohol resin
  • Saponified ethylene-vinyl acetate copolymer Polyacrylonitrile resin
  • Acetal resin and Polyimide resin.
  • polyester-based resins and polyolefin-based resins are preferable, and PET and PEN are particularly preferable from the viewpoint of high heat resistance, low coefficient of linear expansion, and low manufacturing cost.
  • These resin may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the thickness of the base material can be appropriately set in consideration of, for example, stability when a protective film is produced on the first film.
  • the thickness of the substrate is preferably in the range of 5 to 500 ⁇ m from the viewpoint that the film can be conveyed even in a vacuum.
  • the gas barrier layer is formed by the plasma CVD method, the protective film is formed while discharging through the base material of the first film. Therefore, the thickness of the base material of the first film is more preferably 50 to 200 ⁇ m. Preferably, the thickness is 50 to 100 ⁇ m.
  • the substrate it is preferable to subject the substrate to a surface activation treatment for cleaning the surface.
  • a surface activation treatment include corona treatment, plasma treatment, and flame treatment.
  • the first film and / or the second film may further include a primer coat layer, a heat-sealable resin layer, an adhesive layer, and the like as necessary.
  • the primer coat layer can be formed using a primer coat agent that can improve the adhesion between the substrate or the gas barrier layer and the substrate.
  • the heat-sealable resin layer can be appropriately formed using a normal heat-sealable resin.
  • the adhesive layer can be appropriately formed using a normal adhesive, and a plurality of first or second films may be bonded to each other by such an adhesive layer.
  • a double-sided light emitting organic EL element may be provided in place of the bottom emission organic EL element.
  • an additional film may be further bonded to the first film and / or the second film.
  • Additional films include a protective film that protects the surface of the organic EL device, an antireflection film that prevents reflection of external light incident on the organic EL device, a light extraction film that has an effect of increasing the light extraction efficiency, and a phase of light.
  • the additional film is bonded to one side or both sides of the first film and / or the second film.
  • the adhesive layer is a layer that adheres the first film and the second film in a state where the organic EL element is disposed between them.
  • the adhesive used for the adhesive layer preferably has a high gas barrier property.
  • the light transmittance of the adhesive layer 4 is preferably high. In this case, from the viewpoint of light extraction efficiency, the absolute value of the difference in refractive index between the layer in contact with the adhesive layer 4 and the adhesive layer 4 is preferably small.
  • a curable adhesive such as a thermosetting adhesive and a photocurable adhesive is suitable.
  • thermosetting resin adhesives examples include epoxy adhesives and acrylate adhesives.
  • the epoxy adhesive examples include an adhesive containing an epoxy compound selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenoxy resin.
  • acrylate adhesive for example, a monomer as a main component selected from acrylic acid, methacrylic acid, ethyl acrylate, butyl acrylate, 2-hexyl acrylate, acrylamide, acrylonitrile, hydroxyl acrylate, and the like, and copolymerizable with the main component And an adhesive containing a simple monomer.
  • photo-curable adhesive examples include radical adhesives and cationic adhesives.
  • radical adhesives include adhesives containing epoxy acrylate, ester acrylate, ester acrylate, and the like.
  • cationic adhesives examples include adhesives containing epoxy resins, vinyl ether resins, and the like.
  • FIG. 5 schematically shows an apparatus for manufacturing an organic EL device.
  • the first film 1 and the second film 11 are bonded together, and an additional film 820 is bonded to the second film 11.
  • an organic EL element and a protective film are formed in advance.
  • the unwinding roll 500 sends out the 1st film 1 in which the organic EL element and the protective film were previously formed on it.
  • the unwinding roll 510 sends out the second film 11.
  • the adhesive agent is apply
  • the first film 1 and the second film 11 supplied via the transport roll 513 are bonded via the first adhesive layer by the first bonding rolls 511 and 512, and further for the first adhesive layer.
  • the first adhesive layer is cured (solidified) by the curing device 611.
  • an adhesive is applied by a second adhesive layer coating device 620 provided on the downstream side of the curing device 611, and a second adhesive layer is further formed.
  • the second bonding rolls 521 and 522 cause the second film 11 and the additional film 820 fed from the unwinding roll 520 and supplied via the transporting roll 523 to pass through the second adhesive layer.
  • the second adhesive layer is cured (solidified) by the curing device 621 for the second adhesive layer.
  • the formed organic EL device is wound up by a winding roll 530.
  • the additional film for example, the above-described film is used.
  • one additional film is bonded, but two or more additional films may be bonded sequentially.
  • the order of bonding is appropriately changed according to the stacking order of the organic EL devices.
  • a protective film that has excellent gas barrier properties and suppresses deterioration of the gas barrier property due to bending is formed in advance on the organic EL device.
  • the step of bonding the films can be performed in any atmosphere.
  • the step of bonding the second film in a vacuum, an inert gas atmosphere, or an air atmosphere can be performed.
  • an inert gas atmosphere or an air atmosphere is preferable, and an air atmosphere is more preferable. This is because a device for manufacturing the organic EL device is not complicated, and the organic EL device can be manufactured by a simple process.
  • the first film is once wound up, and the roll of the laminate having the first film, the organic EL element, and the protective film is stored.
  • the wound roll of the laminate can be stored in an arbitrary atmosphere.
  • the laminate can be stored in a vacuum, an inert gas atmosphere, or an air atmosphere.
  • the said laminated body containing a 1st film in inert gas atmosphere or air
  • Organic EL device (Organic EL device) Next, the configuration of the organic EL element will be described.
  • the organic EL element is formed on the first film before the step of bonding the first film and the second film.
  • the organic EL element is composed of a pair of electrodes composed of an anode and a cathode, and a light emitting layer provided between the electrodes.
  • a predetermined layer may be provided between the pair of electrodes as necessary.
  • the light emitting layer is not limited to one layer, and a plurality of layers may be provided.
  • Examples of the layer provided between the cathode and the light emitting layer include an electron injection layer, an electron transport layer, and a hole blocking layer.
  • the layer in contact with the cathode is referred to as an electron injection layer, and the layer excluding this electron injection layer is referred to as an electron transport layer.
  • the electron injection layer has a function of improving the electron injection efficiency from the cathode.
  • the electron transport layer has a function of improving electron injection from the layer in contact with the surface on the cathode side.
  • the hole blocking layer has a function of blocking hole transport. When the electron injection layer and / or the electron transport layer has a function of blocking hole transport, these layers may also serve as the hole blocking layer.
  • the hole blocking layer has a function of blocking hole transport can be confirmed, for example, by fabricating a device that allows only the hole current to flow and reducing the current value.
  • Examples of the layer provided between the anode and the light emitting layer include a hole injection layer, a hole transport layer, and an electron block layer.
  • the layer in contact with the anode is called a hole injection layer, and the layers other than the hole injection layer are positive. It is called a hole transport layer.
  • the hole injection layer has a function of improving the hole injection efficiency from the anode.
  • the hole transport layer has a function of improving hole injection from a layer in contact with the surface on the anode side.
  • the electron blocking layer has a function of blocking electron transport. When the hole injection layer and / or the hole transport layer have a function of blocking electron transport, these layers may also serve as the electron block layer.
  • the electron blocking layer has a function of blocking electron transport can be confirmed, for example, by producing an element that allows only an electron current to flow and reducing the current value.
  • the electron injection layer and the hole injection layer may be collectively referred to as a charge injection layer, and the electron transport layer and the hole transport layer may be collectively referred to as a charge transport layer.
  • anode / light emitting layer / cathode b) anode / hole injection layer / light emitting layer / cathode c) anode / hole injection layer / light emitting layer / electron injection layer / cathode d) anode / hole injection layer / light emitting layer / Electron transport layer / cathode e) anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode f) anode / hole transport layer / light emitting layer / cathode g) anode / hole transport layer / light emitting layer / Electron injection layer / cathode h) anode / hole transport layer / light emitting layer / electron transport layer / cathode i) anode / hole transport layer / light emitting layer / electron transport layer
  • the organic EL element of the present embodiment may have two or more light emitting layers.
  • structural unit A when the laminate sandwiched between the anode and the cathode is referred to as “structural unit A”, the configuration of an organic EL element having two light emitting layers is obtained. And the layer structure shown in the following q).
  • the two (structural unit A) layer structures may be the same or different.
  • Examples of the configuration of the organic EL device having three or more light emitting layers include the layer configuration shown in the following r).
  • x represents an integer of 2 or more
  • (Structural unit B) x is a stacked layer of the structural units B stacked in x stages. Represents the body.
  • a plurality of (structural unit B) layer structures may be the same or different.
  • the charge generation layer is a layer that generates holes and electrons by applying an electric field.
  • Examples of the charge generation layer include vanadium oxide and indium tin oxide (Indium).
  • a thin film containing Tin Oxide (abbreviation ITO), molybdenum oxide, and the like can be given.
  • the order of the layers to be laminated, the number of layers, and the thickness of each layer can be appropriately set in consideration of the light emission efficiency and the element lifetime.
  • an electrode exhibiting light transmittance is used as the anode.
  • an electrode exhibiting light transmittance a thin film of metal oxide, metal sulfide, metal, or the like can be used, and an electrode having high electrical conductivity and light transmittance is preferable.
  • indium oxide, zinc oxide, tin oxide, ITO, indium zinc oxide (Indium A thin film containing Zinc Oxide (abbreviation IZO), gold, platinum, silver, copper, or the like is used.
  • a thin film made of ITO, IZO, or tin oxide is preferable.
  • the method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
  • an organic transparent conductive film such as polyaniline or a derivative thereof and polythiophene or a derivative thereof may be used.
  • the thickness of the anode is appropriately set in consideration of required characteristics and process simplicity, and is, for example, 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, and more preferably 50 nm to 500 nm.
  • the hole injection material constituting the hole injection layer includes oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide, phenylamine compounds, starburst amine compounds, phthalocyanines, amorphous carbon, polyaniline And polythiophene derivatives.
  • Examples of the method for forming the hole injection layer include film formation from a solution containing a hole injection material.
  • a hole injection layer can be formed by applying a solution containing a hole injection material by a predetermined application method to form a film, and solidifying the formed solution.
  • the solvent used for film formation from a solution is not particularly limited as long as it dissolves the hole injection material.
  • Chlorine solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as tetrahydrofuran, toluene and xylene
  • aromatic hydrocarbon solvents such as acetone, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate, and water.
  • coating methods spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset Examples thereof include a printing method and an ink jet printing method.
  • the thickness of the hole injection layer is appropriately set in consideration of required characteristics and process simplicity, and is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
  • ⁇ Hole transport layer> As the hole transport material constituting the hole transport layer, polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, Triphenyldiamine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof, polyarylamine or derivative thereof, polypyrrole or derivative thereof, poly (p-phenylenevinylene) or derivative thereof, and poly (2,5-thienylenevinylene) or Examples thereof include derivatives thereof.
  • hole transport materials include polyvinyl carbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having aromatic amine compound groups in the side chain or main chain, polyaniline or derivatives thereof, polythiophene or derivatives thereof, poly Polymeric hole transport materials such as arylamines or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, and poly (2,5-thienylene vinylene) or derivatives thereof are preferred. More preferable hole transport materials are polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in a side chain or a main chain.
  • the low molecular hole transport material is preferably used by being dispersed in a polymer binder.
  • the method for forming the hole transport layer is not particularly limited, but in the case of a low molecular hole transport material, film formation from a mixed solution containing a polymer binder and a hole transport material can be exemplified.
  • molecular hole transport materials include film formation from a solution containing a hole transport material.
  • the solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material.
  • Chlorine solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as tetrahydrofuran, toluene and xylene
  • aromatic hydrocarbon solvents such as ketone solvents such as acetone and methyl ethyl ketone, and ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate.
  • the polymer binder combined with the hole transport material does not extremely impede charge transport, and that absorption with respect to visible light is weak.
  • the polymer binder is selected from, for example, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.
  • the thickness of the hole transport layer varies depending on the material used, and is appropriately set so that the drive voltage and the light emission efficiency are appropriate.
  • the hole transport film must have at least a thickness that does not cause pinholes. If the hole transport film is too thick, the drive voltage of the device increases. Therefore, the thickness of the hole transport layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.
  • the light emitting layer is usually formed of an organic substance (light emitting material) that mainly emits fluorescence and / or phosphorescence, or the organic substance and a dopant that assists the organic substance.
  • the dopant is added, for example, to improve the luminous efficiency or to change the emission wavelength.
  • the organic substance contained in the light emitting layer may be a low molecular compound or a high molecular compound.
  • the light emitting layer preferably contains a polymer compound.
  • the light emitting layer preferably contains a high molecular compound having a polystyrene-reduced number average molecular weight of 10 3 to 10 8 .
  • Examples of the light emitting material constituting the light emitting layer include the following dye materials, metal complex materials, polymer materials, and dopant materials.
  • dye-based materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds. Pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, oxadiazole dimers, pyrazoline dimers, quinacridone derivatives, and coumarin derivatives.
  • Metal complex materials examples include rare earth metals such as Tb, Eu, and Dy, and a central metal selected from Al, Zn, Be, Ir, Pt, and the like, oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, and the like.
  • a metal complex having a ligand selected from a quinoline structure and the like can be given.
  • Metal complex materials include, for example, metal complexes that emit light from triplet excited states such as iridium complexes and platinum complexes, aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazolyl zinc complexes, benzothiazole zinc complexes, azomethyl zinc Selected from complexes, porphyrin zinc complexes, and phenanthroline europium complexes.
  • Polymer material As polymer materials, polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, the above dye materials or metal complex light emitting materials are polymerized. Materials etc. can be mentioned.
  • examples of materials that emit blue light include distyrylarylene derivatives, oxadiazole derivatives, and polymers thereof, polyvinylcarbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives. .
  • polymer materials such as polyvinyl carbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives are preferred.
  • Examples of materials that emit green light include quinacridone derivatives, coumarin derivatives, and polymers thereof, polyparaphenylene vinylene derivatives, and polyfluorene derivatives. Of these, polymer materials such as polyparaphenylene vinylene derivatives and polyfluorene derivatives are preferred.
  • Examples of materials that emit red light include coumarin derivatives, thiophene ring compounds, and polymers thereof, polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives. Of these, polymer materials such as polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives are preferred.
  • the material that emits white light may be a mixture of the materials that emit light in the above-described blue, green, or red colors, or a component (monomer) that forms a material that emits light in each color may be mixed and polymerized. It may be a polymer material to be formed. A plurality of light emitting layers formed using materials that emit light of each color may be stacked to form an element that emits white light as a whole.
  • Dopant material examples include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, and phenoxazone.
  • the thickness of the light emitting layer is usually about 2 nm to 200 nm.
  • a method for forming the light emitting layer a method of applying a solution containing a light emitting material, a vacuum deposition method, a transfer method, or the like can be used.
  • the solvent used for film formation from a solution include the same solvents as those described above used for forming a hole injection layer from a solution.
  • coating methods such as coating methods, spray coating methods, and nozzle coating methods
  • printing methods such as gravure printing methods, screen printing methods, flexographic printing methods, offset printing methods, reversal printing methods, and inkjet printing methods.
  • a printing method such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an ink jet printing method is preferable in that pattern formation and multicolor coating are easy.
  • a vacuum deposition method can be used in the case of a low molecular compound exhibiting sublimability.
  • a method of forming a light emitting layer only at a desired portion by laser transfer or thermal transfer can also be used.
  • an electron transport material constituting the electron transport layer a commonly used material can be used, such as an oxadiazole derivative, anthraquinodimethane or a derivative thereof, benzoquinone or a derivative thereof, naphthoquinone or a derivative thereof, anthraquinone or a derivative thereof, Tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, and polyfluorene or Examples thereof include derivatives thereof.
  • electron transport materials include oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, and poly Fluorene or its derivatives are preferred, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline Is more preferable.
  • the method for forming the electron transport layer is not particularly limited.
  • a vacuum deposition method from powder, or film formation from a solution or a molten state can be exemplified
  • film formation from a solution or a melt state can be exemplified. be able to.
  • a polymer binder may be used in combination. Examples of the method for forming an electron transport layer from a solution include the same film formation method as the method for forming a hole injection layer from a solution described above.
  • the thickness of the electron transport layer varies depending on the material used, and is appropriately set so that the drive voltage and the light emission efficiency are appropriate.
  • the electron transport layer needs to have at least a thickness that does not generate pinholes, and if it is too thick, the drive voltage of the device increases. Accordingly, the thickness of the electron transport layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
  • ⁇ Electron injection layer> As a material constituting the electron injection layer, an optimum material is appropriately selected according to the type of the light emitting layer. As a material constituting the electron injection layer, an alloy containing one or more kinds of metals selected from alkali metals, alkaline earth metals, alkali metals and alkaline earth metals, oxides of alkali metals or alkaline earth metals, halides, Mention may be made of carbonates and mixtures of these substances.
  • alkali metals, alkali metal oxides, halides, and carbonates include lithium, sodium, potassium, rubidium, cesium, lithium oxide, lithium fluoride, sodium oxide, sodium fluoride, potassium oxide, potassium fluoride , Rubidium oxide, rubidium fluoride, cesium oxide, cesium fluoride and lithium carbonate.
  • alkaline earth metal, alkaline earth metal oxides, halides and carbonates include magnesium, calcium, barium, strontium, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, barium oxide, fluoride Examples thereof include barium, strontium oxide, strontium fluoride and magnesium carbonate.
  • the electron injection layer may be composed of a laminate in which two or more layers are laminated.
  • An example of a laminate of electron injection layers is LiF / Ca.
  • the electron injection layer is formed by vapor deposition, sputtering, printing, or the like.
  • the thickness of the electron injection layer is preferably about 1 nm to 1 ⁇ m
  • a material for the cathode is preferably a material having a low work function, easy electron injection into the light emitting layer, and high electrical conductivity.
  • a material having a high visible light reflectivity is preferable as the cathode material in order to reflect light emitted from the light emitting layer to the anode side at the cathode.
  • the material of the cathode for example, alkali metal, alkaline earth metal, transition metal, and Group 13 metal of the periodic table can be used.
  • cathode materials include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like. And an alloy containing two or more metals selected from these metals, one or more selected from the above metals, and one selected from gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin Alloys with seeds or more, or graphite or graphite intercalation compounds are used.
  • alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.
  • a transparent conductive electrode made of a conductive metal oxide, a conductive organic material, or the like can be used as the cathode.
  • the conductive metal oxide include indium oxide, zinc oxide, tin oxide, ITO, and IZO
  • examples of the conductive organic substance include polyaniline or a derivative thereof and polythiophene or a derivative thereof.
  • the cathode may be composed of a laminate in which two or more layers are laminated. In some cases, the electron injection layer is used as a cathode.
  • the thickness of the cathode is appropriately designed in consideration of required characteristics and process simplicity, and is, for example, 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, more preferably 50 nm to 500 nm.
  • Examples of the method for producing the cathode include a vacuum deposition method, a sputtering method, and a lamination method in which a metal thin film is thermocompression bonded.
  • the above organic EL device can be used as a lighting device, a surface light source device, or a display device by adding predetermined components.
  • a protective film was formed directly on the base material on which the organic EL element was not formed using the manufacturing apparatus shown in FIG. That is, a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 ⁇ m, width: 350 mm, manufactured by Teijin DuPont Films, trade name “Teonex Q65FA”) was used as a base material, and this was mounted on a feed roll 701. . And while applying a magnetic field between the film-forming roll 31 and the film-forming roll 32 and supplying electric power to each of the film-forming roll 31 and the film-forming roll 32, Was discharged to generate plasma.
  • PEN film thickness: 100 ⁇ m, width: 350 mm
  • Teijin DuPont Films trade name “Teonex Q65FA”
  • a film-forming gas (mixed gas of hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (which also functions as a discharge gas) as a source gas) is supplied to the formed discharge region under the following conditions
  • a thin film was formed by plasma CVD, and a protective film was formed on the substrate.
  • ⁇ Film formation conditions Supply amount of source gas: 50 sccm (Standard Cubic Centimeter per Minute converted to zero and 1 atm. The same applies hereinafter) Supply amount of oxygen gas: 500 sccm Degree of vacuum in the vacuum chamber: 3Pa Applied power from the power source for plasma generation: 0.8 kW Frequency of power source for plasma generation: 70 kHz Film conveyance speed: 0.5 m / min.
  • the thickness of the protective film formed on the base material was 0.3 ⁇ m.
  • the water vapor permeability of the substrate on which the protective film is formed is 3.1 ⁇ 10 ⁇ 4 g / (under conditions of a temperature of 40 ° C., a low humidity side humidity of 0% RH, and a high humidity side humidity of 90% RH. m 2 ⁇ day), which was below the detection limit under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side.
  • the water vapor transmission rate under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side after bending the substrate together with the protective film under the condition of a curvature radius of 8 mm is below the detection limit. It was confirmed that even when the protective film was bent, the decrease in gas barrier properties was sufficiently suppressed.
  • XPS depth profile measurement was performed on the protective film on the substrate under the following conditions to obtain a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve.
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): 10 nm
  • X-ray photoelectron spectrometer Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific Irradiation X-ray: Single crystal spectroscopy AlK ⁇ X-ray spot and size: 800 ⁇ 400 ⁇ m oval.
  • the obtained silicon distribution curve, oxygen distribution curve and carbon distribution curve are shown in FIG. Regarding the obtained silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen-carbon distribution curve, the atomic ratio (atomic concentration) and the distance from the surface of the protective film (atomic concentration) and the relationship between the etching time and the ratio (atomic concentration).
  • nm is shown in the graph of FIG. “Distance (nm)” described on the horizontal axis of the graph of FIG. 7 is a value obtained by calculation from the etching time and the etching rate.
  • the obtained carbon distribution curve has a plurality of distinct extreme values, and the difference between the maximum value and the minimum value of the atomic ratio of carbon is 5 at. %, And in the region of 90% or more in the thickness direction of the protective film, the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the conditions represented by the above formula (1). It was confirmed.
  • Reference Example A2 The base material on which the protective film having a thickness of 0.3 ⁇ m obtained in Reference Example A1 was formed was further attached to the feed roll 701, and a protective film was newly formed on the surface of the protective film. Except this, it carried out similarly to Reference Example A1, and obtained the base material (A) in which the protective film was formed.
  • the thickness of the protective film on the base material (PEN film) in the base material (A) on which the protective film was formed was 0.6 ⁇ m.
  • the base material (A) on which the protective film was formed was mounted on the feed roll 701, and a protective film was newly formed on the surface of the protective film. Except this, it carried out similarly to Reference Example A1, and obtained the base material (B) in which the protective film was formed.
  • the thickness of the protective film of the base material (B) on which the protective film was formed was 0.9 ⁇ m.
  • the water vapor permeability of the base material (B) on which the protective film is formed is 6.9 ⁇ 10 ⁇ 4 g / g under the conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side, and a humidity of 90% RH on the high humidity side. (M 2 ⁇ day), which was a value below the detection limit under conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side.
  • the water vapor transmission rate under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side after bending the substrate together with the protective film under the condition of a curvature radius of 8 mm is below the detection limit. It was confirmed that even when the protective film was bent, the decrease in gas barrier properties was sufficiently suppressed.
  • a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve and an oxygen carbon distribution curve were prepared by the same method as in Reference Example A1.
  • the obtained result is shown in FIG. Regarding the silicon distribution curve, oxygen distribution curve, carbon distribution curve and oxygen-carbon distribution curve, the relationship between the atomic ratio (atomic concentration) and etching time, as well as the atomic ratio (atomic concentration) and the distance (nm) from the surface of the protective film.
  • the relationship is also shown in the graph of FIG. “Distance (nm)” indicated on the horizontal axis of the graph of FIG. 9 is a value obtained by calculation from the etching time and the etching rate.
  • the obtained carbon distribution curve has a plurality of distinct extreme values, and the difference between the maximum value and the minimum value of the atomic ratio of carbon is 5 at. %, And in the region of 90% or more in the thickness direction of the protective film, the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the conditions represented by the above formula (1). It was confirmed.
  • Reference Example A3 A base material on which a protective film was formed was obtained in the same manner as in Reference Example A1, except that the supply amount of the source gas was 100 sccm.
  • the thickness of the protective film on the substrate was 0.6 ⁇ m.
  • the water vapor permeability of the substrate on which the protective film is formed is 3.2 ⁇ 10 ⁇ 4 g / (m 2) under the conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side, and a humidity of 90% RH on the high humidity side. Day), which was below the detection limit under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side.
  • the water vapor transmission rate under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side after bending the substrate together with the protective film under the condition of a curvature radius of 8 mm is below the detection limit. It was confirmed that even when the protective film was bent, the decrease in gas barrier properties was sufficiently suppressed.
  • a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve were prepared by the same method as in Reference Example A1.
  • the obtained silicon distribution curve, oxygen distribution curve and carbon distribution curve are shown in FIG. Regarding the obtained silicon distribution curve, oxygen distribution curve, carbon distribution curve and oxygen-carbon distribution curve, the atomic ratio (atomic concentration) and the distance from the surface of the protective film (nm) as well as the relationship between the atomic ratio (atomic concentration) and etching time. 11 is also shown in the graph of FIG.
  • the “distance (nm)” described on the horizontal axis of the graph of FIG. 11 is a value obtained by calculation from the etching time and the etching rate.
  • the obtained carbon distribution curve has a plurality of distinct extreme values, and the difference between the maximum value and the minimum value of the atomic ratio of carbon is 5 at. %, And in the region of 90% or more in the thickness direction of the protective film, the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the conditions represented by the above formula (1). It was confirmed.
  • the thickness of the protective film on the substrate was 100 nm. Further, the water vapor permeability of the substrate on which the protective film is formed is 1.3 g / (m 2 ⁇ day) under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side. The gas barrier property was insufficient.
  • a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve were prepared by the same method as in Reference Example A1.
  • the obtained silicon distribution curve, oxygen distribution curve and carbon distribution curve are shown in FIG. Regarding the obtained silicon distribution curve, oxygen distribution curve, carbon distribution curve and oxygen-carbon distribution curve, the atomic ratio (atomic concentration) and the distance from the surface of the protective film (nm) as well as the relationship between the atomic ratio (atomic concentration) and etching time.
  • the graph of FIG. “Distance (nm)” described on the horizontal axis of the graph of FIG. 13 is a value obtained by calculation from the etching time and the etching rate. As is clear from the results shown in FIGS. 12 and 13, it was confirmed that the obtained carbon distribution curve did not have an extreme value.
  • the protective film used in the organic EL device according to the present invention has a sufficient gas barrier property, and even when bent, it can sufficiently suppress a decrease in the gas barrier property. It is.

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  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne un élément électroluminescent (EL) organique, comprenant un premier film, un élément EL organique disposé sur le premier film, et une couche de protection recouvrant l'élément EL organique. Le film de protection contient un atome de silicium, un atome d'oxygène, et un atome de carbone. La courbe de répartition de silicium, la courbe de répartition d'oxygène, et la courbe de répartition de carbone, obtenues à partir de la couche de protection, satisfont aux conditions suivantes : (i) entre le rapport du nombre d'atomes de silicium, le rapport du nombre d'atomes d'oxygène, et le rapport du nombre d'atomes de carbone, le rapport du nombre d'atomes de silicium est le deuxième plus grand dans une région représentant 90 % ou plus dans la direction de l'épaisseur de la couche de protection ; (ii) la courbe de répartition de carbone présente au moins une valeur extrême ; et (iii) la différence entre la valeur maximum et la valeur minimum du rapport du nombre d'atomes de carbone est supérieure ou égale à 5 % atomiques dans la courbe de répartition de carbone.
PCT/JP2011/072890 2010-10-08 2011-10-04 Dispositif électroluminescent organique WO2012046742A1 (fr)

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