JPWO2014126063A1 - ORGANIC ELECTROLUMINESCENT ELEMENT AND METHOD FOR PRODUCING ORGANIC ELECTROLUMINESCENT ELEMENT - Google Patents

Abstract

A flexible substrate and at least a silicon atom, an oxygen atom, and a carbon atom provided on the flexible substrate, and an atomic ratio of the silicon atom, the oxygen atom, and the carbon atom satisfies a specific condition A barrier layer, a planarization layer provided on the barrier layer, a pair of electrodes, and an organic functional layer having at least one light emitting layer between the electrodes. Furthermore, it is solid-sealed by the sealing resin layer and the sealing member.

Description

  The present invention relates to an organic electroluminescence element using a transparent electrode and a method for producing the organic electroluminescence element.

  An organic electroluminescence element (organic electroluminescence element; organic EL element) using electroluminescence (hereinafter referred to as EL) of an organic material has an organic material layer or a photoelectric conversion layer sandwiched between two electrodes. Have In the organic EL element, emitted light generated in the organic material layer (light emitting layer) passes through the electrode and is extracted outside. Therefore, in these electronic devices, at least one of the two electrodes needs to be configured by a transparent electrode.

  On the other hand, as a form of a thin and lightweight organic EL element, a structure in which a flexible base is used and solid-sealed is known (for example, see Patent Document 1 and Patent Document 2). In this configuration, it is essential to form a barrier layer on a flexible substrate. However, the surface of the barrier layer has fine irregularities, and there is a problem that the element is easily short-circuited in the pressure / heating process of solid sealing.

As a method for improving the smoothness of the transparent electrode, a technique for smoothing the surface of the barrier layer on the flexible substrate is known (for example, see Patent Document 3). Patent Document 3 discloses a technique for smoothing the surface according to CVD conditions when forming a vapor deposition barrier film.
Moreover, the technique of smoothing the surface of a barrier layer with an organic-inorganic hybrid polymer is disclosed (for example, refer patent document 4).

JP 2002-216950 A International Publication No. 2010/001831 Pamphlet JP 2012-084353 A JP 2002-46208 A

However, when the surface of the barrier layer is smoothed, the adhesiveness between the sealing member after solid sealing and the base material is weakened, which causes element failure due to film peeling. Moreover, in order to suppress film peeling, there is a method of sufficiently proceeding the curing reaction of the resin used for solid sealing. However, when a resin-made flexible base material is used, the base material is damaged by heat or the like for advancing the curing reaction. That is, in an organic electroluminescence element using a flexible substrate, it is difficult to accelerate the curing of the resin by increasing the curing conditions.
For this reason, in an organic electroluminescent element, the improvement of reliability is calculated | required by preventing the short circuit resulting from the unevenness | corrugation of a base material, the film | membrane of a solid sealing, etc. peeling.

  In order to solve the above-described problems, the present invention provides an organic electroluminescence element capable of improving reliability.

The organic electroluminescence device of the present invention includes a flexible substrate, a barrier layer provided on the flexible substrate, a planarization layer provided on the barrier layer, a pair of electrodes, and an interelectrode The organic functional layer having at least one light emitting layer. Furthermore, it is solid-sealed by the sealing resin layer and the sealing member.
The barrier layer has at least silicon atoms, oxygen atoms, and carbon atoms, the distance from the surface of the layer in the thickness direction of the barrier layer, and the silicon atoms relative to the total amount of silicon atoms, oxygen atoms, and carbon atoms. Silicon distribution curve, oxygen distribution curve and carbon showing the relationship between the quantity ratio (silicon atomic ratio), oxygen atom quantity ratio (oxygen atomic ratio) and carbon atom quantity ratio (carbon atomic ratio), respectively. In the distribution curve, the following conditions (i) to (iii):
(I) In a region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the layer, the following formula (1):
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (1)
Or in the region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the layer, the following formula (2):
(Atomic ratio of carbon)> (Atomic ratio of silicon)> (Atomic ratio of oxygen) (2)
Satisfying the condition represented by
(Ii) the carbon distribution curve has at least one extreme value;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more.

  The organic electroluminescence device manufacturing method of the present invention includes a step of forming a barrier layer on a flexible substrate by a plasma CVD method, a step of forming a planarization layer on the barrier layer, And a step of forming a pair of electrodes and an organic functional layer having at least one light emitting layer between the electrodes, and a step of applying a sealing resin layer and solid-sealing with a sealing member.

  According to the organic electroluminescence device of the present invention, the barrier layer is provided on the flexible substrate, and the planarization layer is provided on the barrier layer. As the barrier layer, an inorganic film containing silicon atoms, oxygen atoms and carbon atoms having the above-described structure is formed. This barrier layer has high thermal conductivity, and heat dissipation by this barrier layer is good, so even when the resin curing conditions are increased during solid sealing, damage to the flexible substrate due to heat, etc. is suppressed. can do. For this reason, in the case of solid sealing, the hardening conditions of an adhesive layer can be made high and the adhesiveness of a base material and a sealing member can be improved. Furthermore, by providing a planarizing layer on the barrier layer, the unevenness of the barrier layer can be planarized, and a short circuit of the element in the solid sealing pressure / heating process can be suppressed. Therefore, the reliability of the organic electroluminescence element can be improved.

  ADVANTAGE OF THE INVENTION According to this invention, the organic electroluminescent element which can improve reliability can be provided.

It is a figure which shows schematic structure of the organic electroluminescent element of 1st Embodiment. It is a figure which shows a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve. It is the figure which expanded the carbon distribution curve shown in FIG. It is a figure which shows the refractive index distribution of a barrier layer. It is a figure which shows the structure of the manufacturing apparatus of a barrier layer. It is a figure which shows schematic structure of the organic electroluminescent element of 2nd Embodiment.

Hereinafter, embodiments of the present invention will be described in the following order based on the drawings.
1. Organic electroluminescence device (first embodiment: bottom emission type)
2. Organic electroluminescence device (second embodiment: reverse stacking configuration)
3. Method for manufacturing organic electroluminescence element (third embodiment)

<1. Organic Electroluminescence Element (First Embodiment: Bottom Emission Type)>
Hereinafter, specific embodiments of the organic electroluminescence element of the present invention (hereinafter referred to as organic EL element) will be described.
In FIG. 1, the schematic block diagram (sectional drawing) of the organic EL element of 1st Embodiment is shown. As shown in FIG. 1, the organic EL element 10 includes a base material 11, a barrier layer 12, a planarizing layer 13, a first electrode 14, an organic functional layer 15, a second electrode 16, a sealing resin layer 17, and a sealing material. A stop member 18 is provided. In the organic EL element 10 shown in FIG. 1, an organic functional layer 15 including a light emitting layer and a second electrode 16 serving as a cathode are laminated on a first electrode 14 serving as an anode. The structure is solid-sealed by the layer 17 and the sealing member 18. Among these, the 1st electrode 14 used as an anode is comprised as a translucent electrode. In such a configuration, only a portion where the organic functional layer 15 is sandwiched between the first electrode 14 and the second electrode 16 becomes a light emitting region in the organic EL element 10. The organic EL element 10 is configured as a bottom emission type in which generated light (hereinafter, referred to as emitted light h) is extracted from at least the substrate 11 side.

  Further, in the organic EL element 10, a sealing member 18 is bonded to one surface of the base material 11 via a sealing resin layer 17 that covers the first electrode, the organic functional layer 15, and the second electrode 16. By doing so, it is solid-sealed. In the solid sealing of the organic EL element 10, uncured resin material is applied to a plurality of locations on the bonding surface of the sealing member 18 or on the planarization layer 13 and the second electrode 16 of the substrate 11. The base material 11 and the sealing member 18 are pressed and integrated with each other in a heated state with the resin material interposed therebetween.

  Below, about the organic EL element 10 of this example, the base material 11, the barrier layer 12, the planarization layer 13, the 1st electrode 14 and the 2nd electrode 16, the organic functional layer 15, the sealing resin layer 17, and the sealing member 18 are shown. The detailed configuration will be described in this order. In addition, in the organic EL element 10 of this example, translucency means that the light transmittance in wavelength 550nm is 50% or more.

[Base material]
The base material 11 applied to the organic EL element 10 is not particularly limited as long as it is a flexible base material that can impart flexibility to the organic EL element 10. An example of the flexible base material is a transparent resin film.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Is mentioned.

[Barrier layer]
A barrier layer 12 is preferably provided on the surface of the substrate 11. In particular, when the substrate 11 is made of a resin film, it is preferable that a film made of an inorganic material or an organic material, or a barrier layer 12 combining these films is formed on the surface of the resin film. Such a barrier layer 12 has a water vapor permeability (25 ± 0.5 ° C., relative humidity 90 ± 2% RH) measured by a method according to JIS-K-7129-1992, 0.01 g / (m ² · 24 hours) or less. Further, the oxygen permeability measured by a method according to JIS-K-7126-1987 is 10 ⁻³ ml / (m ² · 24 hours · atm) or less, and the water vapor permeability is 10 ⁻⁵ g / (m ² · 24 hours) or less.

  As a material for forming the barrier layer 12 as described above, a material having a function of suppressing intrusion of elements such as moisture and oxygen that cause deterioration of the resin film is used. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Furthermore, in order to improve the brittleness of the barrier film, it is more preferable to have a laminated structure of these inorganic layers and layers (organic layers) made of an organic material. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

  The method for forming the barrier film is not particularly limited. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the molecular beam epitaxy method, the cluster ion beam method, the ion plating method, the plasma polymerization method, the atmospheric pressure plasma weighting. A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used. In particular, the atmospheric pressure plasma polymerization method described in JP-A-2004-68143 can be preferably used.

(Barrier layer: composition)
The barrier layer 12 applied to the organic EL element 10 preferably includes an inorganic film having a refractive index distribution in the thickness direction and having one or more extreme values in the refractive index distribution. The barrier layer 12 is made of a material containing silicon, oxygen, and carbon, and has a laminated structure including a plurality of layers having different silicon, oxygen, and carbon contents.
The barrier layer 12 has a relationship between the distance from the surface of the barrier layer 12 (interface of the planarization layer 13) in the film thickness direction and the ratio (atomic ratio) of the atomic weight of each element (silicon, oxygen, or carbon). Each element has a characteristic distribution curve.

In addition, the atomic ratio of silicon, oxygen, or carbon is represented by the ratio [(Si, O, C) / (Si + O + C)] of silicon, oxygen, or carbon to the total amount of each element of silicon, oxygen, and carbon.
The silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve indicate the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon at a distance from the surface of the barrier layer 12. In addition, a distribution curve showing the relationship between the distance from the surface of the barrier layer 12 (interface on the first electrode 14 side) in the film thickness direction and the ratio (atomic ratio) of the total atomic weight of oxygen and carbon is represented by oxygen carbon. The distribution curve.

The barrier layer 12 may further contain nitrogen in addition to silicon, oxygen, and carbon. By containing nitrogen, the refractive index of the barrier layer 12 can be controlled. For example, the refractive index of SiO ₂ is 1.5, whereas the refractive index of SiN is about 1.8 to 2.0. For this reason, nitrogen is contained in the barrier layer 12. By forming SiON in the barrier layer 12, a preferable refractive index value of 1.6 to 1.8 can be obtained. Thus, the refractive index of the barrier layer 12 can be controlled by adjusting the nitrogen content.

When the barrier layer 12 contains nitrogen, the distribution curve of each element (silicon, oxygen, carbon, or nitrogen) constituting the barrier layer 12 is as follows.
In the case of containing nitrogen in addition to silicon, oxygen and carbon, the atomic ratio of silicon, oxygen, carbon or nitrogen is the ratio of silicon, oxygen, carbon or nitrogen to the total amount of each element of silicon, oxygen, carbon and nitrogen [(Si, O, C, N) / (Si + O + C + N)].
The silicon distribution curve, oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve are the atomic ratio of silicon, the atomic ratio of oxygen, the atomic ratio of carbon, and the atomic ratio of nitrogen at a distance from the surface of the barrier layer 12, respectively. Indicates.

(Relationship between element distribution curve and refractive index distribution)
The refractive index distribution of the barrier layer 12 can be controlled by the amount of carbon and the amount of oxygen in the thickness direction of the barrier layer 12.
FIG. 2 shows an example of the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve of the barrier layer 12. 3 shows an enlarged carbon distribution curve from the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve shown in FIG. 2 and 3, the horizontal axis indicates the distance [nm] from the surface of the barrier layer 12 in the film thickness direction. The vertical axis represents the atomic ratio [at%] of silicon, oxygen, carbon, or nitrogen with respect to the total amount of each element of silicon, oxygen, and carbon.
In addition, the detail of the measuring method of a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and a nitrogen distribution curve is mentioned later.

  As shown in FIG. 2, the atomic ratio of silicon, oxygen, carbon, and nitrogen changes depending on the distance from the surface of the barrier layer 12. In particular, with respect to oxygen and carbon, the atomic ratio varies greatly depending on the distance from the surface of the barrier layer 12, and each distribution curve has a plurality of extreme values. In addition, the oxygen distribution curve and the carbon distribution curve are correlated, and the oxygen atomic ratio decreases at a distance where the carbon atomic ratio is large, and the oxygen atomic ratio increases at a distance where the carbon atomic ratio is small.

  FIG. 4 shows a refractive index distribution curve of the barrier layer 12. In FIG. 4, the horizontal axis indicates the distance [nm] from the surface of the barrier layer 12 in the film thickness direction. The vertical axis represents the refractive index of the barrier layer 12. The refractive index of the barrier layer 12 shown in FIG. 4 is a measured value of the distance from the surface of the barrier layer 12 in the film thickness direction and the refractive index of the barrier layer 12 with respect to visible light at this distance. The refractive index distribution of the barrier layer 12 can be measured using a known method, for example, a spectroscopic ellipsometer (ELC-300 manufactured by JASCO Corporation) or the like.

As shown in FIGS. 3 and 4, there is a correlation between the atomic ratio of carbon and the refractive index of the barrier layer 12. Specifically, in the barrier layer 12, the refractive index of the barrier layer 12 increases at a position where the atomic ratio of carbon increases. Thus, the refractive index of the barrier layer 12 changes according to the atomic ratio of carbon. That is, the refractive index distribution curve of the barrier layer 12 can be controlled by adjusting the distribution of the atomic ratio of carbon in the film thickness direction in the barrier layer 12.
In addition, since the carbon atomic ratio and the oxygen atomic ratio are correlated as described above, the refractive index distribution curve of the barrier layer 12 is controlled by controlling the oxygen atomic ratio and the distribution curve. Can do.

  By providing the barrier layer 12 having an extreme value in the refractive index distribution, reflection and interference occurring at the interface of the substrate 11 can be suppressed. For this reason, the light transmitted through the organic EL element 10 is emitted without being affected by total reflection or interference by the action of the barrier layer 12. Therefore, the amount of light is not reduced, and the light extraction efficiency of the organic EL element 10 is improved.

(Conditions for each element's distribution curve)
In the barrier layer 12, the atomic ratio of silicon, oxygen and carbon, or the distribution curve of each element preferably satisfies the following conditions (i) to (iii).

(I) In a region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the barrier layer 12, the following formula (1):
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (1)
The condition represented by is satisfied.
Alternatively, in a region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the barrier layer 12, the following formula (2):
(Atomic ratio of carbon)> (Atomic ratio of silicon)> (Atomic ratio of oxygen) (2)
The condition represented by is satisfied.

(Ii) The carbon distribution curve has at least one local maximum and local minimum.

(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more.

  The organic EL element 10 has a barrier layer 12 that satisfies all of the above conditions (i) to (iii). Further, two or more barrier layers 12 that satisfy all of the above conditions (i) to (iii) may be provided. When two or more barrier layers 12 are provided, the materials of the plurality of thin film layers may be the same or different. When two or more barrier layers 12 are provided, the barrier layer 12 may be formed on one surface of the substrate 11 or may be formed on both surfaces of the substrate 11.

  The refractive index of the barrier layer 12 can be controlled by the atomic ratio of carbon or oxygen as in the correlation shown in FIGS. For this reason, the refractive index of the barrier layer 12 can be adjusted to a preferable range by the above conditions (i) to (iii).

(Carbon distribution curve)
The barrier layer 12 needs to have at least one extreme value in the carbon distribution curve. In such a barrier layer 12, it is more preferable that the carbon distribution curve has at least two extreme values, and it is even more preferable that the carbon distribution curve has at least three extreme values. Furthermore, it is preferable that the carbon distribution curve has at least one maximum value and one minimum value.

When the carbon distribution curve has no extreme value, the light distribution of the obtained barrier layer 12 is insufficient. For this reason, it becomes difficult to eliminate the light angle dependency of the organic EL element 10 obtained through the first electrode 14.
Further, when the barrier layer 12 has three or more extreme values, one extreme value of the carbon distribution curve and another extreme value adjacent to the extreme value are a film from the surface of the barrier layer 12. The difference in the distance in the thickness direction is preferably 200 nm or less, and more preferably 100 nm or less.

(Extreme value)
In the barrier layer 12, the extreme value of the distribution curve is the maximum or minimum value of the atomic ratio of the element to the distance from the surface of the barrier layer 12 in the film thickness direction of the barrier layer 12, or the refractive index corresponding to the value. It is a measured value of the distribution curve.

  In the barrier layer 12, the maximum value of the distribution curve of each element is a point where the value of the atomic ratio of the element changes from increasing to decreasing when the distance from the surface of the barrier layer 12 is changed. In addition, from this point, the atomic ratio value of the element at a position where the distance from the surface of the barrier layer 12 is further changed by 20 nm is reduced by 3 at% or more.

  In the barrier layer 12, the minimum value of the distribution curve of each element is that the atomic ratio value of the element changes from decreasing to increasing when the distance from the surface of the barrier layer 12 is changed. In addition, from this point, the value of the atomic ratio of the element at the position where the distance from the surface of the barrier layer 12 is further changed by 20 nm is increased by 3 at% or more.

In the carbon distribution curve of the barrier layer 12, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is preferably 5 at% or more. In such a barrier layer 12, the absolute value of 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. When the difference between the maximum value and the minimum value of the atomic ratio of carbon is less than the above range, the refractive index difference in the refractive index distribution curve of the obtained barrier layer 12 becomes small and the light distribution becomes insufficient.
There is a correlation between the amount of carbon distribution and the refractive index, and when the absolute value of the maximum value and the minimum value of the preferable carbon atom is 7 at% or more, the absolute value of the difference between the maximum value and the minimum value of the obtained refractive index is It becomes 0.2 or more.

(Oxygen distribution curve)
The barrier layer 12 preferably has an oxygen distribution curve having at least one extreme value. In particular, the barrier layer 12 more preferably has an oxygen distribution curve having at least two extreme values, and more preferably at least three extreme values. Furthermore, it is preferable that the oxygen distribution curve has at least one maximum value and one minimum value.

When the oxygen distribution curve has no extreme value, the light distribution of the obtained barrier layer 12 is insufficient. For this reason, it becomes difficult to eliminate the light angle dependency of the organic EL element 10 obtained through the first electrode 14.
Further, when the barrier layer 12 has three or more extreme values, one extreme value of the oxygen distribution curve and another extreme value adjacent to the extreme value are a film from the surface of the barrier layer 12. The difference in the distance in the thickness direction is preferably 200 nm or less, and more preferably 100 nm or less.

  In the oxygen distribution curve of the barrier layer 12, the absolute value of the difference between the maximum value and the minimum value of the oxygen atomic ratio is preferably 5 at% or more. In such a barrier layer 12, the absolute value of the difference between the maximum value and the minimum value of the oxygen atomic ratio is more preferably 6 at% or more, and further preferably 7 at% or more. If the difference between the maximum value and the minimum value of the atomic ratio of oxygen is less than the above range, the light distribution is insufficient from the refractive index distribution curve of the obtained barrier layer 12.

(Silicon distribution curve)
The barrier layer 12 preferably has an absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve of less than 5 at%. Moreover, in such a barrier layer 12, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon is more preferably less than 4 at%, and further preferably less than 3 at%. When the difference between the maximum value and the minimum value of the atomic ratio of silicon is not less than the above range, the light distribution is insufficient from the refractive index distribution curve of the obtained barrier layer 12.

(Total amount of oxygen and carbon: oxygen carbon distribution curve)
In the barrier layer 12, the ratio of the total amount of oxygen atoms and carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms is defined as an oxygen-carbon distribution curve.
In the oxygen-carbon distribution curve, the barrier layer 12 preferably has an absolute value of a difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon of less than 5 at%, more preferably less than 4 at%. Particularly preferably, it is less than 3 at%.
When the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon is not less than the above range, the light distribution becomes insufficient from the refractive index distribution curve of the obtained barrier layer 12.

(XPS depth profile)
The silicon distribution curve, oxygen distribution curve, carbon distribution curve, oxygen carbon distribution curve, and nitrogen distribution curve described above are measured by X-ray photoelectron spectroscopy (XPS) and rare gas ion sputtering such as argon. By using together, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by 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).

In the element distribution curve with the horizontal axis as the etching time, the etching time generally correlates with the distance from the surface in the film thickness direction of the barrier layer 12. For this reason, when measuring the XPS depth profile, the distance from the surface of the barrier layer 12 calculated from the relationship between the etching rate and the etching time is adopted as the “distance from the surface of the barrier layer 12 in the film thickness direction”. be able to.
For XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and an etching rate (etching rate) is set to 0.05 nm / sec (SiO ₂ thermal oxide film equivalent value). It is preferable to do.

  Moreover, the barrier layer 12 is substantially in the film surface direction (a direction parallel to the surface of the barrier layer 12) from the viewpoint of forming a layer having a uniform and excellent light distribution over the entire film surface. Are preferably uniform. That the barrier layer 12 is substantially uniform in the film surface direction means that the number of extreme values of the distribution curves of the elements at the respective measurement points is the same at any two points on the film surface of the barrier layer 12, and The absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the distribution curve is the same as each other, or the difference between the maximum value and the minimum value is within 5 at%.

(Substantially continuous)
In the barrier layer 12, the carbon distribution curve is preferably substantially continuous. The carbon distribution curve being substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, the distance (x, unit: nm) from the surface of the barrier layer 12 calculated from the etching rate and etching time, and the atomic ratio of carbon (C, unit: at%) are expressed by the following formula ( F1):
(DC / dx) ≦ 0.5 (F1)
The condition represented by is satisfied.

(Silicon atomic ratio, oxygen atomic ratio)
In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, in the region where the silicon atomic ratio, the oxygen atomic ratio, and the carbon atomic ratio are 90% or more of the thickness of the barrier layer 12, the above formula (1) is satisfied. It is preferable to satisfy the conditions represented. In this case, the atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the barrier layer 12 is preferably 25 to 45 at%, and preferably 30 to 40 at%. Is more preferable.

The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the barrier layer 12 is preferably 33 to 67 at%, and more preferably 45 to 67 at%. .
Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the barrier layer 12 is preferably 3 to 33 at%, more preferably 3 to 25 at%. .

(Barrier layer thickness)
The thickness of the barrier layer 12 is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, and particularly preferably in the range of 100 to 1000 nm. When the thickness of the barrier layer 12 is out of the above range, the light distribution of the barrier layer 12 becomes insufficient.
When the barrier layer 12 is formed from a plurality of layers, the total thickness of the barrier layer 12 is in the range of 10 to 10000 nm, preferably in the range of 10 to 5000 nm, and in the range of 100 to 3000 nm. More preferably, it is particularly preferably in the range of 200 to 2000 nm.

(Primer layer)
The barrier layer 12 may include a primer coat layer, a heat-sealable resin layer, an adhesive layer, and the like between the substrate 11. The primer coat layer can be formed using a known primer coat agent that can improve the adhesion between the substrate 11 and the barrier layer 12. Moreover, a heat-sealable resin layer can be suitably formed using well-known heat-sealable resin. Further, the adhesive layer can be appropriately formed using a known adhesive, and the plurality of barrier layers 12 may be adhered by such an adhesive layer.

(Manufacturing method of barrier layer)
In the organic EL element 10, the barrier layer 12 is preferably a layer formed by a plasma chemical vapor deposition (plasma CVD) method. As the barrier layer 12 formed by the plasma chemical vapor deposition method, a plasma chemical vapor deposition method in which the substrate 11 is disposed on a pair of film forming rolls and plasma is generated by discharging between the pair of film forming rolls. More preferably, the layer is formed by the method. The plasma enhanced chemical vapor deposition method may be a plasma chemical vapor deposition method using a Penning discharge plasma method. Moreover, when discharging between a pair of film-forming rolls, it is preferable to reverse the polarity of a pair of film-forming rolls alternately.

  When generating plasma in the plasma chemical vapor deposition method, it is preferable to generate plasma discharge in the space between the plurality of film forming rolls. In particular, it is more preferable to use a pair of film forming rolls, dispose the base material 11 on each of the pair of film forming rolls, and generate plasma by discharging between the pair of film forming rolls.

  In this way, the base material 11 is arranged on a pair of film forming rolls, and a film is formed on the base material 11 existing on one film forming roll by discharging between the film forming rolls. it can. At the same time, it is possible to form a film on the substrate 11 on the other film forming roll. For this reason, the film-forming rate can be doubled and a thin film can be manufactured efficiently. Furthermore, a film having the same structure can be formed on each substrate 11 on a pair of film forming rolls.

In the plasma chemical vapor deposition method, a film forming gas containing an organosilicon compound and oxygen is preferably used. 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 barrier layer 12 is preferably a layer formed by a continuous film forming process.

(Barrier layer production equipment)
As described above, the barrier layer 12 is preferably formed on the surface of the substrate 11 by a roll-to-roll method from the viewpoint of productivity. An apparatus capable of manufacturing the barrier layer 12 by plasma enhanced chemical vapor deposition is not particularly limited, but includes at least a pair of film forming rolls and a plasma power source, and can discharge between the film forming rolls. It is preferable that the device is.

  For example, when the manufacturing apparatus 30 shown in FIG. 5 is used, it is also possible to manufacture by a roll-to-roll method using a plasma chemical vapor deposition method. Hereinafter, the manufacturing method of the barrier layer 12 will be described with reference to FIG. FIG. 5 is a schematic view showing an example of a manufacturing apparatus suitable for manufacturing the barrier layer 12.

  The manufacturing apparatus 30 shown in FIG. 5 includes a delivery roll 31, transport rolls 32, 33, 34, 35, film formation rolls 36, 37, a gas supply pipe 38, a plasma generation power source 39, and a film formation roll 36. And 37, and magnetic field generators 41 and 42 installed inside 37, and a winding roll 43. In the manufacturing apparatus 30, at least film forming rolls 36 and 37, a gas supply pipe 38, a plasma generation power source 39, and magnetic field generation apparatuses 41 and 42 are disposed in a vacuum chamber (not shown). Furthermore, in the manufacturing apparatus 30, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be adjusted by the vacuum pump.

  In the manufacturing apparatus 30, each film forming roll is connected to the plasma generation power source 39 so that the pair of film forming rolls (the film forming roll 36 and the film forming roll 37) can function as a pair of counter electrodes. It is connected. For this reason, in the manufacturing apparatus 30, it is possible to discharge to the space between the film forming roll 36 and the film forming roll 37 by supplying power from the plasma generating power source 39. Plasma can be generated in the space between the film forming roll 37. When the film forming roll 36 and the film forming roll 37 are used as electrodes, the material and design of the film forming roll 36 and the film forming roll 37 may be changed so that they can be used as electrodes. Further, in the manufacturing apparatus 30, the pair of film forming rolls (film forming rolls 36 and 37) are preferably arranged so that the central axes are substantially parallel on the same plane. By arranging the pair of film forming rolls (film forming rolls 36 and 37) in this way, the film forming rate can be doubled and a film having the same structure can be formed. For this reason, it is possible to at least double the extreme value in the carbon distribution curve. Then, according to the manufacturing apparatus 30, it is possible to form the barrier layer 12 on the surface of the film 40 by the CVD method, while depositing a film component on the surface of the film 40 on the film forming roll 36, and further, Since the film component can be deposited on the surface of the film 40 also on the film forming roll 37, the barrier layer 12 can be efficiently formed on the surface of the film 40.

Further, inside the film forming roll 36 and the film forming roll 37, magnetic field generators 41 and 42 fixed so as not to rotate even when the film forming roll rotates are provided, respectively.
Furthermore, as the film forming roll 36 and the film forming roll 37, known rolls can be used. As the film forming rolls 36 and 37, it is preferable to use rolls having the same diameter from the viewpoint of forming a thin film more efficiently. The diameters of the film forming rolls 36 and 37 are preferably in the range of 5 to 100 cm from the viewpoint of discharge conditions, chamber space, and the like.

  Moreover, in the manufacturing apparatus 30, the film 40 is arrange | positioned on a pair of film-forming roll (The film-forming roll 36 and the film-forming roll 37) so that the surface of the film 40 may oppose, respectively. By disposing the film 40 in this manner, each surface of the film 40 existing between the pair of film-forming rolls when the plasma is generated by discharging between the film-forming roll 36 and the film-forming roll 37. At the same time, the barrier layer 12 can be formed. That is, according to the manufacturing apparatus 30, the film component can be deposited on the surface of the film 40 on the film forming roll 36 and further the film component can be deposited on the film forming roll 37 by the CVD method. The barrier layer 12 can be efficiently formed on the surface of the film 40.

  Moreover, a well-known roll can be used as the sending roll 31 and the conveyance rolls 32, 33, 34, 35 used for the manufacturing apparatus 30. The winding roll 43 is not particularly limited as long as the film 40 on which the barrier layer 12 is formed can be wound, and a known roll can be used.

  As the gas supply pipe 38, a pipe capable of supplying or discharging the raw material gas at a predetermined speed can be used. Further, as the plasma generation power source 39, a power source of a known plasma generation apparatus can be used. The plasma generating power source 39 supplies power to the film forming rolls 36 and 37 connected thereto, and enables the film forming rolls 36 and 37 to be used as counter electrodes for discharging. As the plasma generating power source 39, it is preferable to use an AC power source or the like capable of alternately reversing the polarity of the film forming roll, because it is possible to perform plasma CVD more efficiently. In addition, since it becomes possible to perform plasma CVD more efficiently, the power source 39 for plasma generation that can set the applied power to 100 W to 10 kW and set the AC frequency to 50 Hz to 500 kHz is provided. More preferably, it is used. As the magnetic field generators 41 and 42, known magnetic field generators can be used. Furthermore, as the film 40, in addition to the base material 11 applicable to the organic EL element 10 described above, the base material 11 on which the barrier layer 12 is formed in advance can be used. Thus, by using the base material 11 on which the barrier layer 12 is formed in advance as the film 40, the thickness of the barrier layer 12 can be increased.

  As described above, using the manufacturing apparatus 30 shown in FIG. 5, for example, 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 conveyance speed By adjusting the barrier layer 12, the barrier layer 12 can be manufactured. That is, by using the manufacturing apparatus 30 shown in FIG. 5 and discharging a film forming gas (raw material gas or the like) between the pair of film forming rolls (film forming rolls 36 and 37) while supplying it into the vacuum chamber, The film forming gas (raw material gas or the like) is decomposed by plasma, and the barrier layer 12 is formed on the surface of the film 40 on the film forming roll 36 and on the surface of the film 40 on the film forming roll 37 by the plasma CVD method. . In film formation, the barrier layer 12 is formed on the surface of the film 40 by a roll-to-roll continuous film formation process by transporting the film 40 by the delivery roll 31 and the film formation roll 36, respectively. It is formed.

(Raw material gas)
The source gas in the film forming gas used for forming the barrier layer 12 can be appropriately selected and used depending on the material of the barrier layer 12 to be formed. As the source gas, for example, an organosilicon compound containing silicon can be used. Examples of organosilicon compounds include hexamethyldisiloxane, 1.1.3.3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, and propyl. Examples thereof include silane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1.1.3.3-tetramethyldisiloxane should be used from the viewpoint of properties such as film formation and light distribution of the resulting barrier layer 12. Is preferred. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

  In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and a nitride are formed. Can be used in combination with the reaction gas for

  As the film forming gas, a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber. Further, as a film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As the carrier gas and the discharge gas, a known gas can be used. For example, a rare gas such as helium, argon, neon, or xenon, or hydrogen can be used.

  When the film forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the amount of the reactive gas that is theoretically necessary to completely react the raw material gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessively higher than the ratio of. If the ratio of the reaction gas is excessive, the light distribution of the barrier layer 12 cannot be obtained sufficiently. Moreover, when the film-forming gas contains an organosilicon compound and oxygen, the amount is preferably less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film-forming gas.

Hereinafter, as an example, a case where hexamethyldisiloxane (organosilicon compound: HMDSO: (CH ₃ ) ₆ Si ₂ O :) is used as a source gas and oxygen (O ₂ ) is used as a reaction gas will be described.
When a silicon-oxygen-based thin film is produced by reacting a film-forming gas containing hexamethyldisiloxane as a source gas and oxygen as a reaction gas by plasma CVD, the following reaction formula (1):
_{(CH 3) 6 Si 2 O} + 12O 2 → 6CO 2 + 9H 2 O + 2SiO 2 ··· (1)
The following reaction occurs and silicon dioxide is produced. In this reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. For this reason, when 12 mol or more of oxygen is contained in 1 mol of hexamethyldisiloxane in the film forming gas and completely reacted, a uniform silicon dioxide film is formed. For this reason, the incomplete reaction is performed by controlling the gas flow rate ratio of the raw material to a flow rate equal to or lower than the theoretical reaction raw material ratio. That is, the amount of oxygen needs to be less than 12 moles of the stoichiometric ratio with respect to 1 mole of hexamethyldisiloxane.

  In the actual reaction in the plasma CVD chamber, since the raw material hexamethyldisiloxane and the reactive gas oxygen are supplied from the gas supply unit to the film formation region, the molar amount (flow rate) of the reactive gas oxygen is the raw material. Even if the molar amount (flow rate) is 12 times the molar amount (flow rate) of hexamethyldisiloxane, the reaction cannot actually proceed completely. That is, it is considered that the reaction is completed only when the oxygen content is supplied in a large excess compared to the stoichiometric ratio. For example, in order to obtain silicon oxide by complete oxidation by CVD, 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.

  For this reason, it is preferable that the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that are not completely oxidized are taken into the barrier layer 12 to form a desired barrier layer 12. It becomes possible to do.

  If the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is too small, unoxidized carbon atoms and hydrogen atoms are excessively taken into the barrier layer 12. , The transparency of the barrier layer 12 decreases. For this reason, like the organic EL element 10, it cannot be used for a flexible substrate that requires transparency. From such a viewpoint, the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is more than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane. Preferably, the amount is more than 0.5 times.

(Degree of vacuum)
Although the pressure (degree of vacuum) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5 Pa-100 Pa.

(Deposition roll)
In the plasma CVD method described above, the electric power applied to the electrode drum connected to the plasma generating power source 39 in order to discharge between the film forming rolls 36 and 37 depends on the type of source gas, the pressure in the vacuum chamber, and the like. Can be adjusted accordingly. For example, a range of 0.1 to 10 kW is preferable. If the applied power is less than the lower limit, particles tend to be easily generated. On the other hand, when the upper limit is exceeded, the amount of heat generated during film formation increases, the temperature of the substrate surface during film formation rises, and the substrate 11 loses heat and wrinkles occur during film formation.
In this example, the electrode drum is installed on the film forming rolls 36 and 37.

  The conveyance speed (line speed) of the film 40 can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, and the like, but is preferably in the range of 0.25 to 100 m / min. A range of 5 to 20 m / min is more preferable. When the line speed is less than the lower limit, wrinkles due to heat tend to occur in the film, whereas when the line speed exceeds the upper limit, the thickness of the formed barrier layer 12 tends to be thin.

(Smooth layer)
A smooth layer may be formed between the substrate 11 and the barrier layer 12. The smooth layer is provided in order to flatten the rough surface of the base material 11 on which protrusions and the like exist, or to fill the unevenness and pinholes generated in the barrier layer 12 with the protrusions on the base material 11. Such a smooth layer is basically formed by curing a photosensitive resin.

  Examples of the photosensitive resin used for forming the smooth layer include a resin composition containing an acrylate compound having a radical-reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, Examples thereof include resin compositions in which polyfunctional acrylate monomers such as urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate are dissolved. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl. Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycy Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene Glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propion Oxide modified pentaerythritol triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2, 4-to Limethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with acrylate, γ-methacryloxypropyltrimethoxysilane, Examples thereof include 1-vinyl-2-pyrrolidone and the like. Said reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.

The photosensitive resin composition contains a photopolymerization initiator.
Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichloro. Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoy Methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azide Benzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (O-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxy , Michler's ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide And combinations of photoreducing dyes such as eosin and methylene blue and reducing agents such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more. .

The smooth layer is not particularly limited, but is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as an evaporation method.
In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used in order to improve the film formability and prevent the generation of pinholes in the film.

  When forming a smooth layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent, the solvent to be used includes alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, Terpenes such as α- or β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, toluene, xylene, tetramethylbenzene, etc. Aromatic hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropiate Glycol ethers such as lenglycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Acetic esters such as ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, diethylene glycol Dialkyl ether, dipropylene glycol Alkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. When the thickness is smaller than 10 nm, the coating property may be impaired when the coating means comes into contact with the surface of the smooth layer in the step of applying a silicon compound described later by a coating method such as a wire bar or a wireless bar. Moreover, when larger than 30 nm, it may become difficult to smooth the unevenness | corrugation after apply | coating a silicon compound.
The surface roughness is a roughness related to the amplitude of fine irregularities measured using an AFM (atomic force microscope). This surface roughness is calculated from the cross-sectional curve of the unevenness measured continuously by measuring a number of times within several tens of μm with a detector having a stylus having a minimum tip radius of AFM.

(Additive to smooth layer)
The smooth layer may contain an additive. The additive contained in the smooth layer is preferably reactive silica particles in which a photosensitive group having photopolymerization reactivity is introduced on the surface of the photosensitive resin (hereinafter also simply referred to as “reactive silica particles”).

  Here, examples of the photopolymerizable photosensitive group include a polymerizable unsaturated group represented by a (meth) acryloyloxy group. The photosensitive resin preferably contains a compound capable of undergoing a photopolymerization reaction with the photosensitive group introduced on the surface of the reactive silica particles, for example, an unsaturated organic compound having a polymerizable unsaturated group. The photosensitive resin may have a solid content adjusted by mixing a general-purpose diluent solvent with reactive silica particles or an unsaturated organic compound having a polymerizable unsaturated group.

Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By using the average particle size in the above range, when used in combination with a matting agent composed of inorganic particles having an average particle size of 1 to 10 μm described later, a smooth layer having both optical properties such as light distribution and hard coat properties. It becomes easy to form.
In order to make it easier to obtain the above effect, the average particle diameter is preferably in the range of 0.001 to 0.01 μm. The smooth layer preferably contains the above inorganic particles in a mass ratio of 20% to 60%. By adding 20% or more, the adhesion between the substrate 11 and the barrier layer 12 is improved. On the other hand, if it exceeds 60%, the film may be bent or cracks may occur when heat treatment is performed, and optical properties such as transparency and refractive index of the barrier layer 12 may be affected.

In this example, as the reactive silica particles, a hydrolyzable silyl group is hydrolyzed to form a silyloxy group between the silica particles and chemically bonded to the polymerizable unsaturated group modified hydrolyzable. Silane can be used.
Examples of the hydrolyzable silyl group include a carboxylylated silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oximesilyl group, and a hydridosilyl group.
Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.

  The thickness of the smooth layer is preferably 1 to 10 μm, more preferably 2 to 7 μm. By setting it to 1 μm or more, the smoothness of the base material 11 having a smooth layer becomes sufficient. Moreover, by making it 10 μm or less, it becomes easy to adjust the balance of optical characteristics, and it is possible to easily suppress curling when a smooth layer is provided only on one surface of the substrate 11.

The smooth layer may contain a matting agent as another additive. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable.
As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 18 parts per 100 parts by mass of the solid content of the smooth layer. It is preferable that they are mixed in a proportion of not more than part by mass, more preferably not more than 16 parts by mass.

(Bleed-out prevention layer)
The barrier layer 12 can be provided with a bleed-out prevention layer. The bleed-out prevention layer suppresses the phenomenon that when the film-like substrate 11 having a smooth layer is heated, unreacted oligomers and the like move from the substrate 11 to the surface and contaminate the surface of the substrate 11. In order to do so, it is provided on the opposite surface of the substrate having a smooth layer. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  As the bleed-out preventing layer, an unsaturated organic compound having a polymerizable unsaturated group can be used. Examples of the unsaturated organic compound include a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or a unit price unsaturated organic compound having one polymerizable unsaturated group in the molecule. Is preferably used.

  Here, as the polyunsaturated organic compound, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meta ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolprop Tetra (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Examples of unit unsaturated organic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and lauryl. (Meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-eth Ciethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- Examples include methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. .

The bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like.
Examples of this thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof, and the like. Acetal resins such as vinyl resins, polyvinyl formal, polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonate resins, etc. Is mentioned.

  Moreover, as a thermosetting resin, the thermosetting urethane resin which consists of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, a silicon resin etc. are mentioned.

  In addition, ionizing radiation curable resins are cured by irradiating ionizing radiation (ultraviolet rays or electron beams) to ionizing radiation curable paints in which one or more of photopolymerizable prepolymers or photopolymerizable monomers are mixed. Can be made. Here, the photopolymerizable prepolymer is particularly preferably an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing. As the acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. As the photopolymerizable monomer, the above polyunsaturated organic compounds can be used.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl). ) -1-propane, α-acyloxime ester, thioxanthone and the like.

  The bleed-out prevention layer is prepared by blending a matting agent and other necessary components, and then preparing a coating solution with a diluting solvent as necessary, and applying the coating solution to the substrate surface by a conventionally known coating method. It can be formed by irradiating the liquid with ionizing radiation and curing it. In addition, as ionizing radiation, ultraviolet rays having a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like are irradiated. Alternatively, an electron beam having a wavelength region of 100 nm or less emitted from a scanning type or curtain type electron beam accelerator is irradiated.

  The thickness of the bleed-out prevention layer is preferably 1 to 10 μm, and particularly preferably 2 to 7 μm. Heat resistance can be sufficiently achieved by setting the thickness to 1 μm or more. Moreover, by setting it as 10 micrometers or less, while becoming easy to adjust the balance of an optical characteristic, the curling at the time of providing the smooth layer in one surface of the base material 11 can be suppressed.

[Planarization layer]
The planarization layer 13 is a layer provided to smooth the unevenness on the surface of the barrier layer 12 and is a light-transmitting layer formed on the barrier layer 12. As the planarizing layer 13, a polysilazane modified layer is preferably used. Preferably, the surface of the planarizing layer 13 is a polysilazane modified layer. The polysilazane modified layer is a layer formed by subjecting a coating film of a polysilazane-containing liquid to a modification treatment. This modified layer is mainly formed from a silicon oxide or a silicon oxynitride compound.

  As a method for forming a polysilazane modified layer, a layer containing a silicon oxide or silicon oxynitride compound is formed by applying a coating solution containing at least one polysilazane compound on a substrate and then performing a modification treatment. The method of doing is mentioned.

  The silicon oxide or silicon oxynitride compound for forming the polysilazane modified layer of silicon oxide or silicon oxynitride compound is supplied as a gas as in CVD (Chemical Vapor Deposition). Rather than being supplied, a more uniform and smooth layer can be formed by applying to the substrate surface. In the case of the CVD method or the like, it is known that foreign substances called unnecessary particles are generated in the gas phase simultaneously with the step of depositing the source material having increased reactivity in the gas phase on the surface of the substrate. As these generated particles accumulate, the smoothness of the surface decreases. In the coating method, it is possible to suppress the generation of these particles by preventing the raw material from being present in the gas phase reaction space. For this reason, a smooth surface can be formed by using a coating method.

(Coating film of polysilazane-containing liquid)
The coating film of the polysilazane-containing liquid is formed by applying a coating liquid containing a polysilazane compound in at least one layer on the substrate.

  Any appropriate method can be adopted as a coating method. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method. The coating thickness can be appropriately set according to the purpose. For example, the coating thickness can be set so that the thickness after drying is preferably about 1 nm to 100 μm, more preferably about 10 nm to 10 μm, and most preferably about 10 nm to 1 μm.

“Polysilazane” is a polymer having a silicon-nitrogen bond, and is a ceramic precursor inorganic polymer such as SiO ₂ , Si ₃ N ₄ composed of Si—N, Si—H, N—H, etc., and both intermediate solid solutions SiOxNy. is there. Polysilazane is represented by the following general formula (I).

  In order to apply the film base material without damaging the film base material, it is preferable that the film base material is converted to silica at a relatively low temperature as described in JP-A-8-112879.

  In the formula, each of R1, R2, and R3 independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, an alkoxy group, or the like.

  Perhydropolysilazane in which all of R 1, R 2, and R 3 are hydrogen atoms is particularly preferable from the viewpoint of the denseness as the obtained barrier film.

  On the other hand, 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 the base substrate is improved and the polysilazane is hard and brittle. The ceramic film can be provided with toughness, and there is an advantage that generation of cracks can be suppressed even when the (average) film thickness is increased. These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), is a liquid or solid substance, and varies depending on the molecular weight. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.

  As another example of polysilazane which is ceramicized at a low temperature, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with the polysilazane represented by the above general formula (I) (Japanese Patent Laid-Open No. 5-238827), glycidol is reacted. Glycidol-added polysilazane (Japanese Patent Laid-Open No. 6-122852) obtained by reaction, alcohol-added polysilazane obtained by reacting alcohol (Japanese Patent Laid-Open No. 6-240208), metal carboxylate obtained by reacting metal carboxylate Addition polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane (JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, metal obtained by adding metal fine particles Polysilazane containing fine particles JP-A-7-196986 publication), and the like.

  Specific examples of the organic solvent for preparing a liquid containing polysilazane include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, and fats. Ethers such as cyclic ethers can be used. Specific examples include 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. These solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of solvents may be mixed. Note that alcohol-based or water-containing solvents are not preferable because they easily react with polysilazane.

  The polysilazane concentration in the polysilazane-containing coating solution is about 0.2 to 35% by mass, although it varies depending on the target silica film thickness and the pot life of the coating solution.

  The organic polysilazane may be a derivative in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like. By having an alkyl group, especially a methyl group having the smallest molecular weight, the adhesion to the base material can be improved, and the hard and brittle silica film can be toughened, and even if the film thickness is increased, cracks are not generated. Occurrence is suppressed.

  In order to promote the conversion to a silicon oxide compound, an amine or metal catalyst may be added. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials.

(Polysilazane-containing layer forming step)
The coating film of the polysilazane-containing liquid preferably has moisture removed before or during the modification treatment. Therefore, it is preferable to divide into the 1st process for the purpose of removing the solvent in a polysilazane content layer, and the 2nd process for the purpose of removing the water | moisture content in a polysilazane content layer after that.

  In the first step, drying conditions for mainly removing the solvent can be appropriately determined by a method such as heat treatment, but the conditions may be such that moisture is removed at this time. The heat treatment temperature is preferably high from the viewpoint of rapid treatment, but the temperature and treatment time are determined in consideration of thermal damage to the resin substrate. For example, when a PET substrate having a glass transition temperature (Tg) of 70 ° C. is used as the resin substrate, the heat treatment temperature can be set to 200 ° C. or less. The treatment time is preferably set to a short time so that the solvent is removed and the thermal damage to the substrate is reduced. If the heat treatment temperature is 200 ° C. or less, the treatment time can be set within 30 minutes.

  The second step is a step for removing moisture in the polysilazane-containing layer, and the method for removing moisture is preferably in a form maintained in a low humidity environment. Since the humidity in the low humidity environment varies depending on the temperature, a preferable form of the relationship between the temperature and the humidity is indicated by the definition of the dew point temperature. A preferable dew point temperature is 4 degrees or less (temperature 25 degrees / humidity 25%), a more preferable dew point temperature is -8 degrees (temperature 25 degrees / humidity 10%) or less, and a more preferable dew point temperature is (temperature 25 degrees / humidity 1%). ) −31 degrees or less, and the maintained time varies depending on the thickness of the polysilazane-containing layer. Under the condition that the thickness of the polysilazane-containing layer is 1 μm or less, the preferable dew point temperature is −8 ° C. or less, and the maintained time is 5 minutes or more. Moreover, you may dry under reduced pressure in order to make it easy to remove a water | moisture content. The pressure in the vacuum drying can be selected from normal pressure to 0.1 MPa.

  As a preferable condition of the second step with respect to the condition of the first step, for example, when the solvent is removed at a temperature of 60 to 150 ° C. and a processing time of 1 to 30 minutes in the first step, the dew point of the second step is 4 degrees or less. The treatment time can be selected from 5 minutes to 120 minutes under conditions for removing moisture. The first process and the second process can be distinguished by changing the dew point, and can be classified by changing the dew point of the process environment by 10 degrees or more.

  The polysilazane-containing layer is preferably subjected to a modification treatment while maintaining its state even after moisture is removed in the second step.

(Water content of polysilazane-containing layer)
The water content of the polysilazane-containing layer can be detected by the following analysis method.

Headspace-gas chromatograph / mass spectrometry apparatus: HP6890GC / HP5973MSD
Oven: 40 ° C. (2 min), then heated to 150 ° C. at a rate of 10 ° C./min Column: DB-624 (0.25 mm × 30 m)
Inlet: 230 ° C
Detector: SIM m / z = 18
HS condition: 190 ° C, 30min

The water content in the polysilazane-containing layer is defined as a value obtained by dividing the water content obtained by the above analysis method by the volume of the polysilazane-containing layer, and preferably 0.1% in a state where moisture is removed by the second step. It is as follows. A more preferable moisture content is 0.01% or less (below the detection limit).
This is a preferred mode for promoting the dehydration reaction of polysilazane converted to silanol by removing water before or during the modification treatment.

(Modification process)
For the modification treatment, a known method based on the conversion reaction of polysilazane can be selected. Production of a silicon oxide film or a silicon oxynitride film by a substitution reaction of a silazane compound requires a high temperature of 450 ° C. or more, and is difficult to adapt to a flexible substrate such as plastic. For adaptation to plastic substrates, a conversion reaction using plasma, ozone, or ultraviolet light that can be converted at a lower temperature is preferable.

(Plasma treatment)
A known method can be used for the plasma treatment as the modification treatment, but atmospheric pressure plasma treatment is preferable. In the case of atmospheric pressure plasma treatment, nitrogen gas and / or Group 18 atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. are used as the discharge gas. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  As an example of plasma processing, atmospheric pressure plasma processing will be described. Specifically, as described in International Publication No. 2007-026545, the atmospheric pressure plasma is formed by forming two or more electric fields having different frequencies in the discharge space, and the first high-frequency electric field and the second high-frequency electric field. It is preferable to form an electric field superimposed with the electric field.

In the atmospheric pressure plasma treatment, the frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, the strength V1 of the first high-frequency electric field, the strength V2 of the second high-frequency electric field, The relationship with the intensity IV of the discharge start electric field is
V1 ≧ IV> V2 or V1> IV ≧ V2
And the output density of the second high-frequency electric field is 1 W / cm ² or more.

  By adopting such discharge conditions, for example, a discharge gas having a high discharge start electric field strength such as nitrogen gas can start discharge, maintain a high density and stable plasma state, and perform high-performance thin film formation. Can do.

  When the discharge gas is nitrogen gas by the above measurement, the discharge start electric field strength IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first applied electric field strength is , By applying V1 ≧ 3.7 kV / mm, the nitrogen gas can be excited into a plasma state.

  Here, as the frequency of the first power supply, 200 kHz or less can be preferably used. The electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 1 kHz.

  On the other hand, as the frequency of the second power source, 800 kHz or more can be preferably used. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  The formation of a high-frequency electric field from such two power sources is necessary for initiating discharge of a discharge gas having a high discharge start electric field strength by the first high-frequency electric field, and the second high-frequency electric field is high. A dense and good quality thin film can be formed by increasing the plasma density by the frequency and the high power density.

(UV irradiation treatment)
As a modification treatment method, treatment by ultraviolet irradiation is also preferable. Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidation ability, and it is possible to produce silicon oxide films or silicon oxynitride films that have high density and insulation at low temperatures. It is.

By this ultraviolet irradiation, the substrate is heated, and O ₂ and H ₂ O contributing to ceramicization (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated. The conversion to ceramics is promoted, and the resulting ceramic film becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

  In the method according to the present embodiment, any commonly used ultraviolet ray generator can be used.

  In this example, “ultraviolet rays” generally refers to electromagnetic waves having a wavelength of 10 to 400 nm, but in the case of ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, preferably 210 to 210. An ultraviolet ray of 350 nm is used.

  In the irradiation with ultraviolet rays, the irradiation intensity and the irradiation time are set within a range where the substrate carrying the irradiated coating film is not damaged.

For example, when a plastic film is used as the substrate, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the substrate surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm ^2. The distance between the base material and the lamp is set so that the irradiation becomes 0.1 seconds to 10 minutes.

  Generally, when the substrate temperature during the ultraviolet irradiation treatment is 150 ° C. or higher, the substrate is damaged in the case of a plastic film or the like, such as deformation of the substrate or deterioration of strength. However, in the case of a highly heat-resistant film such as polyimide or a base material such as metal, processing at a higher temperature is possible. Therefore, there is no general upper limit to the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

  Examples of such ultraviolet ray generation methods include metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. )), UV light laser, and the like. Also, when irradiating the polysilazane coating film with the generated UV light, the UV light from the source is reflected on the reflector and then applied to the coating film in order to achieve uniform irradiation to improve efficiency. Is desirable.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be coated. For example, in the case of batch processing, a substrate (eg, silicon wafer) having a polysilazane coating film on the surface can be processed in an ultraviolet baking furnace equipped with the above-described ultraviolet light source. The ultraviolet baking furnace itself is generally known, and for example, it is possible to use those manufactured by I-Graphics Co., Ltd. In addition, when the substrate having a polysilazane coating film on the surface is a long film, the ceramic is obtained by continuously irradiating ultraviolet rays in a drying zone having the ultraviolet ray generation source as described above while being conveyed. Can be The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate to be applied and the coating composition.

(Vacuum ultraviolet irradiation treatment; excimer irradiation treatment)
In the present embodiment, a more preferable method for the modification treatment is treatment by irradiation with vacuum ultraviolet rays. The treatment with vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the silazane compound, and bonds of atoms are only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by the action of.
As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.

(Excimer emission)
Since noble gas atoms such as Xe, Kr, Ar, Ne and the like are chemically bonded to form no molecule, they are called inert gases. However, a rare gas atom (excited atom) that has gained energy by discharge or the like can combine with other atoms to form a molecule. When the rare gas is xenon,
e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ^{2 *} + Xe
Then, when the excited excimer molecule Xe ^{2 *} transitions to the ground state, excimer light of 172 nm is emitted. A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high.

  Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge is a lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. This is a very thin discharge called micro discharge. When the micro discharge streamer reaches the tube wall (dielectric), the electric charge accumulates on the dielectric surface, and the micro discharge disappears.
As described above, the electric barrier discharge is a discharge in which micro discharge spreads over the entire tube wall and is repeatedly generated and extinguished. For this reason, flickering of light that can be seen with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.

  As a method for efficiently obtaining excimer light emission, electrodeless field discharge can be used in addition to dielectric barrier discharge. Electrodeless electric field discharge by capacitive coupling, also called RF discharge. The lamp and electrodes and their arrangement may be basically the same as for dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.

  In the case of dielectric barrier discharge, micro discharge occurs only between the electrodes, so the outer electrode covers the entire outer surface and allows light to pass through to extract the light to the outside in order to discharge in the entire discharge space. Must. For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere.

  In order to prevent this, it is necessary to provide an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

  Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are arranged in close contact, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

  When electrodeless field discharge is used, it is not necessary to make the external electrodes mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the outer surface of the lamp. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

  The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside. Therefore, a very inexpensive light source can be provided.

  Since the double cylindrical lamp is processed by connecting both ends of the inner and outer tubes, it is more likely to be damaged during handling and transportation than a thin tube lamp. Further, the outer diameter of the tube of the thin tube lamp is about 6 to 12 mm, and if it is too thick, a high voltage is required for starting.

  As for the form of discharge, either dielectric barrier discharge or electrodeless field discharge can be used. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed, and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.

  The Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light having a short wavelength of 172 nm at a single wavelength. Since this light has a large oxygen absorption coefficient, radical oxygen atomic species and ozone can be generated at a high concentration with a small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane-containing layer can be modified in a short time. Therefore, compared with low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. .

  Since the excimer lamp has high light generation efficiency, it can be lit with low power. In addition, light having a long wavelength that causes a temperature rise due to light is not emitted, and energy is irradiated at a single wavelength in the ultraviolet region, so that the rise in the surface temperature of the object to be fired is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

(Smoothness: surface roughness Ra)
The surface roughness (Ra) of the surface of the planarizing layer 13 is preferably 2 nm or less, and more preferably 1 nm or less. When the surface roughness is in the above range, when used as a resin substrate for an organic electroluminescence device, the light transmission efficiency is improved by a smooth film surface with less unevenness, and energy conversion is achieved by reducing the leakage current between electrodes. It is preferable because efficiency is improved.
The surface roughness (Ra) of the surface of the flattening layer 13 is, for example, when a smooth layer is formed by coating, after applying a coating solution that constitutes the smooth layer, drying under conditions that uniformly remove the solvent and moisture. Therefore, it can be set to 2 nm or less. Furthermore, the surface roughness (Ra) of the planarizing layer 13 can be reduced to 2 nm or less by optimizing the concentration and viscosity of the coating liquid, the coating speed, and selecting the leveling agent.
The surface roughness (Ra) of the planarizing layer 13 can be measured by the following method.

(Surface roughness measurement method; AFM measurement)
The surface roughness is calculated from an uneven sectional curve continuously measured with an AFM (Atomic Force Microscope), for example, DI3100 manufactured by Digital Instruments, with a detector having a stylus with a minimum tip radius. This is a roughness related to the amplitude of fine irregularities measured by a stylus many times in a section whose measurement direction is several tens of μm.

[First electrode (anode side), second electrode (cathode)]
(First electrode)
In the organic EL element 10, the first electrode 14 is a substantial anode. The organic EL element 10 is a bottom emission type element that passes through the first electrode 14 and extracts light from the substrate 11 side. For this reason, the 1st electrode 14 needs to be formed with a translucent conductive layer.

  The first electrode 14 is, for example, a layer composed mainly of silver and is composed of silver or an alloy composed mainly of silver. Examples of the method for forming the first electrode 14 include a method using a wet process such as a coating method, an ink jet method, a coating method, a dipping method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, and the like. And a method using the dry process. Of these, the vapor deposition method is preferably applied.

  As an example, the alloy mainly composed of silver (Ag) constituting the first electrode 14 is silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), silver indium (AgIn). ) And the like.

  The first electrode 14 as described above may have a configuration in which silver or an alloy layer mainly composed of silver is divided into a plurality of layers as necessary.

  Furthermore, the first electrode 14 preferably has a thickness in the range of 4 to 12 nm. A thickness of 12 nm or less is preferable because the absorption component and reflection component of the layer are kept low and the light transmittance of the first electrode 14 is maintained. Further, when the thickness is 4 nm or more, the conductivity of the layer is also ensured.

The first electrode 14 as described above may be covered with a protective film at the top, or may be laminated with another conductive layer. In this case, it is preferable that the protective film and the conductive layer have light transmittance so that the light transmittance of the organic EL element 10 is not impaired.
Moreover, it is good also as a structure which provided the layer according to the necessity under the 1st electrode 14, ie, between the planarization layer 13 and the 1st electrode 14. FIG. For example, an improvement in the characteristics of the first electrode 14 or a base layer for facilitating the formation may be formed.
Further, the first electrode 14 may have a configuration other than the main component of silver. For example, various transparent conductive material thin films such as other metals and alloys, ITO, zinc oxide, tin oxide and the like may be used.

(Second electrode)
The second electrode 16 is an electrode layer that functions as a cathode for supplying electrons to the organic functional layer 15, and a metal, an alloy, an organic or inorganic conductive compound, and a mixture thereof are used. Specifically, gold, aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO, ZnO, TiO ₂ and oxide semiconductors such as SnO ₂ .

  The second electrode 16 can be formed of these conductive materials by a method such as vapor deposition or sputtering. The sheet resistance as the second electrode 16 is several hundred Ω / sq. The following is preferable, and the thickness is usually selected in the range of 5 nm to 5 μm, preferably 5 nm to 200 nm.

  If the organic EL element 10 is a double-sided light emitting type that also takes out the emitted light h from the second electrode 16 side, a conductive material having good light transmittance is selected from the above-described conductive materials, and the second The electrode 16 is configured.

[Organic functional layer]
The organic functional layer 15 has a configuration in which [hole injection layer 15a / hole transport layer 15b / light emitting layer 15c / electron transport layer 15d / electron injection layer 15e] is laminated in this order on the first electrode 14 serving as an anode. As an example, it is necessary to have at least the light emitting layer 15c composed of an organic material. The hole injection layer 15a and the hole transport layer 15b may be provided as a hole transport / injection layer having a hole transport property and a hole injection property. The electron transport layer 15d and the electron injection layer 15e may be provided as a single layer having electron transport properties and electron injection properties. Of these organic functional layers 15, for example, the electron injection layer 15e may be composed of an inorganic material.

  In addition to these layers, the organic functional layer 15 may have a hole blocking layer, an electron blocking layer, and the like laminated as necessary. Furthermore, the light emitting layer 15c has each color light emitting layer that generates light emitted in each wavelength region, and each of these color light emitting layers is laminated via a non-light emitting intermediate layer to form a light emitting layer unit. Also good. The intermediate layer may function as a hole blocking layer and an electron blocking layer.

[Light emitting layer]
The light emitting layer 15c contains, for example, a phosphorescent light emitting compound as a light emitting material.
The light emitting layer 15c is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer 15d and holes injected from the hole transport layer 15b, and the light emitting portion of the light emitting layer 15c. Even within the layer, it may be an interface with an adjacent layer in the light emitting layer 15c.

  Such a light emitting layer 15c is not particularly limited in its configuration as long as the contained light emitting material 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 (not shown) between the light emitting layers 15c.

  The total thickness of the light emitting layer 15c is preferably in the range of 1 to 100 nm, and more preferably 1 to 30 nm because it can be driven at a lower voltage. In addition, the sum total of the thickness of the light emitting layer 15c is a thickness also including the said intermediate | middle layer, when a nonluminous intermediate | middle layer exists between the light emitting layers 15c.

  In the case of the light emitting layer 15c having a configuration in which a plurality of layers are laminated, the thickness of each light emitting layer is preferably adjusted to a range of 1 to 50 nm, and more preferably adjusted to a range of 1 to 20 nm. When 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 15c as described above can be formed of a light emitting material or a host compound, which will be described later, by a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method.

  The light emitting layer 15c may be a mixture of a plurality of light emitting materials, or 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 in the same light emitting layer 15c.

  The light-emitting layer 15c 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 or a guest material) to emit light from the light-emitting material.

(Host compound)
As the host compound contained in the light emitting layer 15c, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. Furthermore, the compound whose phosphorescence quantum yield is less than 0.01 is preferable. The host compound preferably has a volume ratio in the layer of 50% or more among the compounds contained in the light emitting layer 15c.

  As a host compound, a well-known host compound may be used independently, or multiple types may be used. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element 10 can be made highly efficient. In addition, by using 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 may be a conventionally known low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). .

  As the known host compound, a compound having a hole transporting ability and an electron transporting ability, preventing an increase in emission wavelength, and having a high Tg (glass transition temperature) compound is preferable. Glass transition point (Tg) here is a value calculated | required by the method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry: Differential scanning calorimetry).

  Specific examples of the host compound applicable to the organic electroluminescence element include compounds H1 to H79 described in paragraphs [0163] to [0178] of JP2013-4245A. The compounds H1 to H79 described in paragraphs [0163] to [0178] of JP2013-4245 are incorporated in the present specification.

  In addition, as specific examples of other known host compounds, compounds described in the following documents may be used. For example, Japanese Patent Application Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860 Gazette, 2002-334787 gazette, 2002-15871 gazette, 2002-334788 gazette, 2002-43056 gazette, 2002-334789 gazette, 2002-75645 gazette, 2002-338579 gazette. No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No. 2002-203683, No. 2002-363227, No. 2002-231453. No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060. 2002-302516, 2002-305083, 2002-305084, 2002-308837, and the like.

(Luminescent material)
Examples of the light-emitting material that can be used for the organic electroluminescence element of the present embodiment include phosphorescent compounds (also referred to as phosphorescent compounds and phosphorescent materials).

  A phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, a phosphorescent compound emits phosphorescence at room temperature (25 ° C.), and a phosphorescence quantum yield of 0.01 at 25 ° C. Although defined as the above compounds, the preferred phosphorescence quantum yield is 0.1 or more.

  The phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 version, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, when the phosphorescent compound is used in this example, the phosphorescence quantum yield (0.01 or more) is achieved in any solvent. It only has to be done.

  There are two types of light emission principles of the phosphorescent compound. One is that recombination of carriers occurs on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent compound to obtain light emission from the phosphorescent compound. The other is a carrier trap type in which the phosphorescent compound becomes a carrier trap, and carriers are recombined on the phosphorescent compound to emit light from the phosphorescent compound. In either case, it is a condition that the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of a general organic electroluminescence device, but preferably contains a group 8-10 metal in the periodic table of elements. It is a complex compound. More preferred are iridium compounds, osmium compounds, platinum compounds (platinum complex compounds), and rare earth complexes, and most preferred are iridium compounds.

  In the organic electroluminescence device of this embodiment, at least one light emitting layer 15c may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compounds in the light emitting layer 15c is the same as that of the light emitting layer 15c. It may change in the thickness direction.

  The phosphorescent compound is preferably 0.1% by volume or more and less than 30% by volume with respect to the total amount of the light emitting layer 15c.

  As the phosphorescent compound applicable to the organic electroluminescence device, the general formula (4), the general formula (5), and the general formula (6) described in paragraphs [0185] to [0235] of JP2013-4245A can be used. Preferred examples include the compounds represented and exemplary compounds. Moreover, Ir-46, Ir-47, and Ir-48 are shown below as other exemplary compounds. Compounds represented by general formula (4), general formula (5) and general formula (6) described in paragraphs [0185] to [0235] of JP2013-4245A and exemplified compounds (Pt-1 to Pt) -3, Os-1, Ir-1 to Ir-45) are incorporated herein.

  The above phosphorescent compound (also referred to as phosphorescent metal complex) is, for example, Organic Letters vol.3 No.16, pages 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, pages 1685-1687. (1991), J. 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., Vol. 26, 1171 (2002), European Journal of Organic Chemistry, Vol. 4, pages 695-709 (2004), and further described in these documents Can be synthesized by applying a method such as the reference.

(Fluorescent material)
Fluorescent materials include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes Examples thereof include dyes, polythiophene dyes, and rare earth complex phosphors.

[Injection layer: hole injection layer, electron injection layer]
The injection layer is a layer provided between the electrode and the light emitting layer 15c in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and its forefront of industrialization (November 30, 1998, NT. 2) Chapter 2 “Electrode Materials” (pages 123 to 166) of the 2nd volume of “S. Co., Ltd.”, which includes a hole injection layer 15a and an electron injection layer 15e.

  The injection layer can be provided as necessary. The hole injection layer 15a is disposed between the anode and the light emitting layer 15c or the hole transport layer 15b, and the electron injection layer 15e is disposed between the cathode and the light emitting layer 15c or the electron transport layer 15d.

  The details of the hole injection layer 15a are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, and the like. Specific examples thereof include phthalocyanine represented by copper phthalocyanine. Examples thereof include a layer, an oxide layer typified by vanadium oxide, an amorphous carbon layer, and a polymer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  Details of the electron injection layer 15e are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, and specifically, strontium, aluminum, and the like are representative. Examples thereof include a metal layer, an alkali metal halide layer typified by potassium fluoride, an alkaline earth metal compound layer typified by magnesium fluoride, and an oxide layer typified by molybdenum oxide. The electron injection layer 15e is desirably a very thin layer, and the thickness is preferably in the range of 1 nm to 10 μm, although it depends on the material.

[Hole transport layer]
The hole transport layer 15b is made of a hole transport material having a function of transporting holes, and in a broad sense, the hole injection layer 15a and the electron blocking layer are also included in the hole transport layer 15b. The hole transport layer 15b can be provided as a single layer or a plurality of layers.

  The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  Although the above-mentioned thing can be used as a positive hole transport material, It is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styryl amine compound, especially an aromatic tertiary amine compound.

  Representative examples of 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 (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-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbenzene; N-phenylcarbazole, as well as two of those described in US Pat. No. 5,061,569 Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  Also, a so-called p-type hole transport material as described in JP-A-11-251067, J. Huang et.al., Applied Physics Letters, 80 (2002), p. 139 can be used. . These materials are preferably used because a highly efficient light-emitting element can be obtained.

  The hole transport layer 15b is formed by thinning the hole transport 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, or an LB method. be able to. Although there is no restriction | limiting in particular about the thickness of the positive hole transport layer 15b, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The hole transport layer 15b may have a single layer structure composed of one or more of the above materials.

  Further, the material of the hole transport layer 15b can be doped with impurities to increase the p property. Examples thereof include those described in JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Appl. Phys., 95, 5773 (2004), and the like. .

  Thus, it is preferable to increase the p property of the hole transport layer 15b because an element with lower power consumption can be manufactured.

[Electron transport layer]
The electron transport layer 15d is made of a material having a function of transporting electrons. In a broad sense, the electron transport layer 15e and a hole blocking layer (not shown) are also included in the electron transport layer 15d. The electron transport layer 15d can be provided as a single layer structure or a stacked structure of a plurality of layers.

  As an electron transport material (also serving as a hole blocking material) constituting the layer portion adjacent to the light emitting layer 15c in the electron transport layer 15d having a single layer structure and the electron transport layer 15d having a multilayer structure, electrons injected from the cathode are used. What is necessary is just to have the function to transmit to the light emitting layer 15c. Such a material can be arbitrarily selected from conventionally known compounds. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives. Further, in the above oxadiazole derivative, 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 are also used as the material for the electron transport layer 15d. Can do. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq3), 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 (Znq), and the like, and the central metals of these metal complexes are In, Mg, A metal complex replaced with Cu, Ca, Sn, Ga, or Pb can also be used as the material of the electron transport layer 15d.

  In addition, even if it is metal-free or metal phthalocyanine, or the terminal thereof is substituted with an alkyl group or a sulfonic acid group, it can be preferably used as the material for the electron transport layer 15d. Further, a distyrylpyrazine derivative exemplified also as a material of the light emitting layer 15c can be used as a material of the electron transport layer 15d, and n-type Si and n-type similarly to the hole injection layer 15a and the hole transport layer 15b. An inorganic semiconductor such as -SiC can also be used as the material of the electron transport layer 15d.

  The electron transport layer 15d 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, or an LB method. Although there is no restriction | limiting in particular about the thickness of 15 d of electron carrying layers, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer 15d may have a single layer structure composed of one or more of the above materials.

  Further, the electron transport layer 15d can be doped with impurities to increase the n property. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J. Appl. Phys., 95, 5773 (2004), etc. What has been described. Further, the electron transport layer 15d preferably contains potassium, a potassium compound, or the like. As the potassium compound, for example, potassium fluoride can be used. Thus, when the n property of the electron transport layer 15d is increased, an element with lower power consumption can be manufactured.

  Moreover, as a material (electron transporting compound) of the electron transport layer 15d, for example, General Formula (1), General Formula (2), and Paragraphs [0057] to [0148] described in JP2013-4245A and It is preferable to use the compound represented by General formula (3), and the exemplary compounds 1-111 can be used. In addition, as other exemplary compounds, compounds 112 to 134 are shown below. The compounds represented by general formula (1), general formula (2), and general formula (3) described in paragraphs [0057] to [0148] of JP2013-4245 are incorporated in the present specification.

[Blocking layer: hole blocking layer, electron blocking layer]
As described above, the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  In a broad sense, the hole blocking layer has the function of the electron transport layer 15d. 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. Moreover, the structure of the electron carrying layer 15d mentioned later can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer 15c.

  On the other hand, the electron blocking layer has the function of the hole transport layer 15b in a broad sense. The electron blocking layer is made of a material that has a function of transporting holes but has a very small ability to transport electrons, and improves the probability of recombination of electrons and holes by blocking electrons while transporting holes. be able to. Moreover, the structure of the positive hole transport layer 15b mentioned later can be used as an electron blocking layer as needed. The thickness of the blocking layer is preferably 3 to 100 nm, and more preferably 5 to 30 nm.

[Sealing member]
The sealing member 18 covers the organic EL element 10, and the plate-like (film-like) sealing member 18 is fixed to the base material 11 side by the sealing resin layer 17. The sealing member 18 is provided so as to cover at least the organic functional layer 15, and is provided so as to expose the terminal portions (not shown) of the organic EL element 10 and the second electrode 16. In addition, an electrode may be provided on the sealing member 18 so that the organic EL element 10 of the organic EL element 10 and the terminal portions of the second electrode 16 are electrically connected to this electrode.

  Specific examples of the plate-like (film-like) sealing member 18 include a glass substrate and a polymer substrate, and these substrate materials may be used in the form of a thin film. Examples of the glass substrate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

  Especially, since the element can be thinned, a polymer substrate in the form of a thin film can be preferably used as the sealing member 18.

Furthermore, the polymer substrate in the form of a film has an oxygen permeability measured by a method according to JIS-K-7126-1987 of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less, JIS-K. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method based on −7129-1992 is 1 × 10 ⁻³ g / (m ² · 24 h) or less. It is preferable that

  Further, the above substrate material may be processed into a concave plate shape and used as the sealing member 18. In this case, the above-described substrate member is subjected to processing such as sand blasting or chemical etching to form a concave shape.

  Moreover, not only this but a metal material may be used. Examples of the metal material include 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. By using such a metal material as a sealing member 18 in the form of a thin film, the entire light emitting panel provided with the organic EL element 10 can be thinned.

[Sealing resin layer]
The sealing resin layer 17 for fixing the sealing member 18 to the base material 11 side is used for sealing the organic EL element 10 sandwiched between the sealing member 18 and the base material 11. Such a structure in which the organic EL element formed on the substrate 11 is covered with a sealing material is exemplified as a solid-sealed structure. The sealing resin layer 17 is, for example, a photocurable or thermosetting adhesive having a reactive vinyl group of an acrylic acid-based oligomer or a methacrylic acid-based oligomer, or an epoxy-based thermosetting or chemical curing property. Examples thereof include (two-component mixed) adhesives, hot-melt type polyamides, polyesters, polyolefins, and cationic curing type ultraviolet curable epoxy resins.

  From the viewpoint of simplicity of the manufacturing process, it is preferable to form the sealing resin layer 17 with a thermosetting adhesive. Moreover, as a form of the sealing resin layer 17, it is preferable to use the thermosetting adhesive processed into the sheet form. When a sheet-like thermosetting adhesive is used, the adhesive exhibits non-fluidity at room temperature (about 25 ° C.) and exhibits fluidity at a temperature in the range of 50 to 130 ° C. when heated. (Sealant) is used.

As the thermosetting adhesive, any adhesive can be used. From the viewpoint of improving the adhesion between the sealing member 18 adjacent to the sealing resin layer 17 and the base material 11, a suitable thermosetting adhesive is appropriately selected. For example, as the thermosetting adhesive, it is possible to use a resin mainly composed of a compound having an ethylenic double bond at the molecular end or side chain and a thermal polymerization initiator. More specifically, a thermosetting adhesive made of an epoxy resin, an acrylic resin, or the like can be used. Moreover, according to the bonding apparatus and hardening processing apparatus which are used by the manufacturing process of the organic EL element 10, you may use a fusion type thermosetting adhesive.
Moreover, what mixed 2 or more types of above-mentioned adhesives may be used as an adhesive agent, and the adhesive agent provided with both thermosetting and ultraviolet-curing property may be used.

[Effect of organic electroluminescence device]
The organic EL element 10 described above includes silicon, oxygen, and carbon formed by the above-described plasma CVD method, and includes a barrier layer in which the distribution curve of each element satisfies the above conditions (i) to (iii). Thereby, the adhesiveness of a base material and a sealing member can be improved.
The barrier layer is formed from an inorganic film containing silicon, oxygen, and carbon, and has a characteristic of excellent thermal diffusivity. In particular, the inclusion of carbon is considered to improve the thermal conductivity as compared with an inorganic film made only of silicon and oxygen. Since it has a distribution of carbon content in the thickness direction, it can be estimated that it has similar characteristics to a configuration in which a plurality of layers having different compositions are stacked in the thickness direction. That is, a layer having excellent thermal diffusivity due to the inclusion of carbon is interposed in the laminated inorganic film, so that the thermal diffusivity in the surface direction by this layer is improved. For this reason, it is considered that the barrier layer has excellent thermal diffusivity.
Therefore, damage to a flexible substrate such as a resin film can be suppressed when processing is performed to cure the sealing resin layer during solid sealing. In particular, even when a thermosetting resin is used for the sealing resin layer and a high-temperature treatment is performed for a long time as a curing treatment, the barrier layer dissipates heat applied to the organic EL element, so that the flexible substrate Can alleviate heat damage.

  By providing the planarizing layer on the base material, it is possible to proceed with the curing process of the sealing resin layer even in an organic EL element that has been conventionally poor in adhesion between the sealing resin layer and the base material. Adhesiveness between the stopping resin layer and the substrate can be increased. That is, the unevenness on the surface of the base material and the barrier layer is alleviated, a flattening layer is formed in order to prevent a defect due to a short circuit of the electrode, and the organic EL element is prevented from being peeled even in a configuration in which the surface on which the electrode is formed is smoothed. be able to.

  As a result, in the organic EL element, it is possible to prevent the electrode from being short-circuited or peeled off. Therefore, with the above configuration, the reliability of the organic EL element can be improved.

<2. Organic Electroluminescence Element (Second Embodiment: Reverse Stacking Configuration)>
[Configuration of organic electroluminescence element]
Next, a second embodiment of the present invention will be described. In FIG. 6, schematic structure of the organic electroluminescent element of 2nd Embodiment is shown. The configuration of the organic electroluminescence element will be described below based on this figure.

  The organic EL element 20 of the second example shown in FIG. 6 includes a base material 11, a barrier layer 12, a planarization layer 13, a first electrode 14, an organic functional layer 15, a second electrode 16, a sealing resin layer 17, and A sealing member 18 is provided. Further, only the organic functional layer 15 is stacked in the reverse order, which is different from the organic EL element 10 of the first embodiment described with reference to FIG. Hereinafter, the detailed description which overlaps about the component similar to the organic EL element 10 of 1st Embodiment is abbreviate | omitted, and the characteristic structure of the organic EL element 20 of 2nd Embodiment is demonstrated.

  In the organic EL element 20 shown in FIG. 6, an organic functional layer 15 and a second electrode 16 serving as an anode are laminated in this order on a first electrode 14 serving as a cathode, and further a sealing resin layer 17 and a sealing member. 18 is solid-sealed. In such a configuration, only a portion where the organic functional layer 15 is sandwiched between the first electrode 14 and the second electrode 16 becomes a light emitting region in the organic EL element 20. The organic EL element 20 is configured as a bottom emission type in which generated light (hereinafter referred to as emitted light h) is extracted from at least the substrate 11 side.

  Such an organic EL element 20 is not limited to an overall layer structure like the organic electroluminescence element of the first embodiment, and may have a general layer structure. In the organic EL element 20 of the second embodiment, an electron injection layer 15e / electron transport layer 15d / light emitting layer 15c / hole transport layer 15b / hole injection layer 15a are arranged in this order on the first electrode 14 serving as a cathode. The second electrode 16 serving as an anode is laminated on the upper portion.

  As described in the first embodiment, the organic functional layer 15 may have various configurations as necessary, and may be provided with a hole blocking layer or an electron blocking layer that is not shown here. Good. In the configuration as described above, only the portion sandwiched between the first electrode 14 and the second electrode 16 becomes a light emitting region in the organic EL element 20 as in the first embodiment.

  Moreover, also in the organic EL element 20 having the above-described configuration, by providing the barrier layer 12 as in the first embodiment, thermal damage to the flexible base material is alleviated even if the sealing resin is cured. be able to. For this reason, the adhesiveness of sealing resin and a base material can be made high, and peeling of an element etc. can be prevented. Furthermore, the provision of a planarizing layer on the substrate can prevent defects due to short circuits and the like. Therefore, the reliability of the organic EL element can be improved.

  In the above-described embodiment, the substrate, the barrier layer, and the planarization layer are provided, and an element including the first electrode, the organic functional layer, and the second electrode is provided thereon, and the element is solid-sealed. A bottom emission type organic electroluminescence device is described. The organic electroluminescence device in which the device is provided on such a base material, the barrier layer, and the planarization layer is not limited to the bottom emission type, for example, a top emission type configuration in which light is extracted from the second electrode side, or both sides It is good also as a double-sided emission type | mold structure which takes out light from. If the organic electroluminescence element is a top emission type, a transparent material may be used for the second electrode, and the emitted light h may be extracted from the second electrode side. Further, if the organic electroluminescence element is a double-sided light emitting type, a transparent material may be used for the second electrode, and the emitted light h may be extracted from both sides.

[Uses of organic electroluminescence elements]
Since the organic electroluminescent elements having the above-described configurations are surface light emitters as described above, they can be used as various light emission sources. For example, lighting devices such as home lighting and interior lighting, backlights for clocks and liquid crystals, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, Examples include a light source of an optical sensor. Moreover, it is not limited to these light emission light sources, It can use also as another light source.
In particular, it can be effectively used as a backlight of a liquid crystal display device combined with a color filter and an illumination light source.

  In addition, the organic electroluminescence element of each embodiment may be used as a kind of lamp for illumination or an exposure light source, a projection device that projects an image, and a still image or a moving image is directly visually recognized. It may be used as a type of display device (display). In this case, with the recent increase in the size of lighting devices and displays, the light emitting surface may be enlarged by so-called tiling, in which light emitting panels provided with organic electroluminescence elements are joined together in a plane.

  The driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. A color or full-color display device can be manufactured by using two or more kinds of organic electroluminescence elements having different emission colors.

<3. Method for Manufacturing Organic Electroluminescent Element (Third Embodiment)>
[Method of manufacturing organic electroluminescence element]
As an example of a method for manufacturing the organic electroluminescence element, a method for manufacturing the organic electroluminescence element 10 shown in FIG. 1 will be described.

  First, the barrier layer 12 is formed on the substrate 11 to a thickness of about 5 nm to 3 μm. The barrier layer 12 is preferably formed by plasma CVD using the manufacturing apparatus shown in FIG. By this method, the barrier layer 12 containing silicon, oxygen, and carbon and each element having a predetermined element distribution curve can be formed.

  Next, the planarization layer 13 is formed on the barrier layer 12 with a thickness of about 1 nm to 100 μm. For example, a polysilazane-containing liquid is applied on the barrier layer 12 to a predetermined thickness. And the planarization layer 13 which consists of a polysilazane modified layer is formed in this coating film by performing an excimer process.

  Next, the first electrode 14 is formed on the planarization layer 13. The first electrode 14 is formed from a transparent conductive material. For example, an electrode having a thickness of about 3 nm to 15 nm mainly composed of silver or a transparent conductive material such as ITO of about 100 nm is formed. The formation of the first electrode 14 includes a spin coating method, a casting method, an ink jet method, a vapor deposition method, a sputtering method, a printing method, etc., but it is easy to obtain a homogeneous layer and it is difficult to generate pinholes. The vacuum deposition method is particularly preferable. Further, before and after the formation of the first electrode 14, an auxiliary electrode pattern is formed as necessary.

Next, a hole injection layer 15a, a hole transport layer 15b, a light emitting layer 15c, an electron transport layer 15d, and an electron injection layer 15e are formed thereon in this order to form the organic functional layer 15. The formation of each of these layers includes a spin coating method, a casting method, an ink jet method, a vapor deposition method, a sputtering method, a printing method, etc., but it is easy to obtain a homogeneous layer, and pinholes are difficult to generate. Vacuum deposition or spin coating is particularly preferred. Further, different formation methods may be applied for each layer. The case of employing an evaporation method for formation of these layers, the depositing conditions thereof are varied according to kinds of materials used, generally collection was boat heating temperature of 50 ° C. to 450 ° C. The compound, vacuum 10 ^-6 Pa to 10 ^- It is desirable to select each condition as appropriate within a range of ² Pa, a deposition rate of 0.01 nm / second to 50 nm / second, a substrate temperature of −50 ° C. to 300 ° C., and a thickness of 0.1 μm to 5 μm.

  Next, the second electrode 16 serving as a cathode is formed by an appropriate forming method such as vapor deposition or sputtering. At this time, the organic functional layer 15 is formed in a pattern in which a terminal portion is drawn from the upper side of the organic functional layer 15 to the periphery of the base material 11 while maintaining an insulating state with respect to the first electrode 14.

  Next, solid sealing of the 1st electrode 14, the organic functional layer 15, and the 2nd electrode 16 which were provided on the base material 11 is performed. A sealing resin layer 17 is formed on one surface of the sealing member 18. Then, the sealing resin layer 17 forming surface of the sealing member 18 is placed on the first electrode 14, so that the end portions of the lead electrodes of the first electrode 14 and the second electrode 16 come out of the sealing resin layer 17. The organic functional layer 15 and the second electrode 16 are overlapped on the base material 11. After the base material 11 and the sealing member 18 are overlapped, the base material 11 and the sealing member 18 are pressed. Furthermore, in order to cure the sealing resin layer 17, the sealing resin layer 17 is heated to a curing temperature or higher. At this time, the sealing resin layer 17 is sufficiently cured so that there is no problem in the adhesion between the planarization layer 13 and the sealing resin layer 17.

  As described above, a solid-sealed organic EL element 10 including the barrier layer 12 and the planarization layer 13 on the substrate 11 is obtained. In the production of such an organic EL element 10, it is preferable to produce from the first electrode 14 to the second electrode 16 consistently by a single evacuation, but a different formation method is applied by taking out from the vacuum atmosphere in the middle. It doesn't matter. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to a following example.

[Production of bottom emission type organic electroluminescence device]
Each organic EL element of Samples 101 to 117 was fabricated such that the area of the light emitting region was 5 cm × 5 cm. Table 1 below shows the configuration of each layer in each of the organic EL elements of Samples 101 to 117.

[Procedure for manufacturing organic electroluminescence element of sample 101]
In preparation of the sample 101, first, a barrier layer (Si, O, C) is formed on a transparent biaxially stretched polyethylene naphthalate film substrate, and a planarizing layer comprising a polysilazane modified layer is formed on the barrier layer. The following compound No. A base layer made of 10 and a conductive layer made of silver were formed to produce a translucent electrode. Further, a light emitting functional layer and a counter electrode were formed on the translucent electrode, and then solid sealed with a sealing member, whereby an organic EL element of Sample 101 was produced.

[Formation of barrier layer (Si, O, C)]
The base material was mounted on the barrier layer manufacturing apparatus shown in FIG. 5 described above, and the barrier layer was formed to a thickness of 300 nm on the base material under the following film forming conditions (plasma CVD conditions).
Source gas (HMDSO) supply: 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 1.2 kW
Frequency of power source for plasma generation: 80 kHz
Film transport speed: 0.5 m / min

[Formation of planarization layer]
First, as a polysilazane-containing liquid, a 10% by mass dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) was prepared.
Next, a polysilazane-containing liquid is applied onto the substrate with a wireless bar so that the average film thickness after drying is 300 nm, and is treated for 1 minute in an atmosphere of temperature 85 ° C. and humidity 55% RH. Dried. Further, the polysilazane layer was formed by holding for 10 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.) to perform dehumidification.

Next, the base material on which the polysilazane layer is formed is fixed on the operation stage, and the following ultraviolet ray apparatus is used to perform the reforming treatment under the following reforming treatment conditions, thereby flattening the base material comprising the polysilazane modified layer. A layer was formed.
Ultraviolet irradiation device: excimer irradiation device manufactured by M.D.COM MODEL: MECL-M-1-200
Irradiation wavelength: 172 nm
Lamp filled gas: Xe
Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1.0%
Excimer lamp irradiation time: 5 seconds

[Formation of underlayer and first electrode]
Next, the base material on which the planarizing layer was formed was fixed to a base material holder of a commercially available vacuum deposition apparatus. 10 was put in a resistance heating boat made of tungsten, and the base material holder and the heating boat were mounted in the first vacuum chamber of the vacuum evaporation apparatus. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.

Next, after depressurizing the first vacuum chamber of the vacuum evaporation apparatus to 4 × 10 ⁻⁴ Pa, The heating boat containing 10 was energized and heated, and the base layer of the first electrode was provided with a thickness of 10 nm at a deposition rate of 0.1 nm / second to 0.2 nm / second.
Next, the base material formed up to the underlayer was transferred to the second vacuum chamber while being vacuumed, and the second vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then the heating boat containing silver was energized and heated. Thus, a first electrode made of silver having a thickness of 8 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second.

(Organic functional layer-second electrode)
Subsequently, the pressure was reduced to 1 × 10 ⁻⁴ Pa using a commercially available vacuum deposition apparatus, and then the compound HT-1 was deposited at a deposition rate of 0.1 nm / second while moving the base material. A transport layer (HTL) was provided.
Next, compound A-3 (blue light emitting dopant), compound A-1 (green light emitting dopant), compound A-2 (red light emitting dopant) and compound H-1 (host compound), compound A-3 having a film thickness In contrast, the vapor deposition rate was changed depending on the location so that it was linearly 35 wt% to 5 wt%, and the compound A-1 and the compound A-2 each had a concentration of 0.2 wt% without depending on the film thickness. Thus, at a deposition rate of 0.0002 nm / sec, the compound H-1 was co-deposited to a thickness of 70 nm by changing the deposition rate from 64.6 wt% to 94.6 wt% depending on the location. A light emitting layer was formed.
Thereafter, Compound ET-1 was deposited to a thickness of 30 nm to form an electron transport layer, and potassium fluoride (KF) was further formed to a thickness of 2 nm. Furthermore, aluminum 110nm was vapor-deposited and the 2nd electrode was formed.
In addition, said compound No. 10, Compound HT-1, Compound A-1 to Compound 3, Compound H-1, and Compound ET-1 are compounds shown below.

[Solid sealing]
Next, an aluminum foil with a thickness of 25 μm is used as a sealing member, and a thermosetting sheet adhesive (epoxy resin) is bonded as a sealing resin layer on one surface of the aluminum foil with a thickness of 20 μm. The stopper member was used to superimpose the sample up to the second electrode. At this time, the adhesive forming surface of the sealing member and the organic functional layer surface of the element were continuously overlapped so that the end portions of the extraction electrodes of the first electrode and the second electrode were exposed.

  Next, the sample was placed in a decompression device, and the laminated base material and the sealing member were pressed and held for 5 minutes under a decompression condition of 0.1 MPa at 90 ° C. Subsequently, the sample was returned to an atmospheric pressure environment and further heated at 120 ° C. for 30 minutes to cure the adhesive.

The sealing step is performed under atmospheric pressure and in a nitrogen atmosphere with a moisture content of 1 ppm or less, in accordance with JIS B 9920, with a measured cleanliness of class 100, a dew point temperature of −80 ° C. or less, and an oxygen concentration of 0.8 ppm or less. At atmospheric pressure. In addition, the description regarding formation of the lead-out wiring from an anode and a cathode is abbreviate | omitted.
Through the above steps, an organic EL element of Sample 101 was produced.

[Procedure for manufacturing organic electroluminescent element of sample 102]
The organic EL of sample 102 was the same as sample 101 described above except that the substrate was changed to a 12 μm thick biaxially stretched polyethylene terephthalate (PET) film (manufactured by Teijin Ltd., trade name: NSC, single-sided corona treatment). An element was produced.

[Procedure for Manufacturing Organic Electroluminescence Element of Sample 103]
In the step of forming the planarization layer, the organic EL element of Sample 103 was produced in the same procedure as Sample 101 except that the modification treatment was not performed and a planarization layer made of an unmodified polysilazane layer was formed. .

[Procedure for manufacturing organic electroluminescent element of sample 104]
An organic EL element of Sample 104 was fabricated in the same procedure as Sample 101 except that the planarization layer was not formed.

[Procedure for Producing Organic Electroluminescent Element of Sample 105]
An organic EL element of Sample 105 was produced in the same procedure as Sample 101 except that the solid sealing curing temperature was changed to 100 ° C.

[Procedure for manufacturing organic electroluminescence element of sample 106]
An organic EL element of Sample 106 was produced in the same procedure as Sample 101 except that the barrier layer was not formed.

[Procedure for Manufacturing Organic Electroluminescence Element of Sample 107]
Sample 101 except that the base material was changed to a 12 μm thick biaxially stretched polyethylene terephthalate (PET) film (manufactured by Teijin Ltd., trade name: NSC, single-sided corona treatment), and no barrier layer was formed. The organic EL element of Sample 107 was fabricated in the same procedure as described above.

[Procedure for Manufacturing Organic Electroluminescence Element of Sample 108]
The organic EL element of Sample 108 was prepared in the same procedure as Sample 101, except that a planarizing layer made of an unmodified polysilazane layer was formed without forming a barrier layer and without performing a modification treatment. did.

[Procedure for Producing Organic Electroluminescent Element of Sample 109]
An organic EL element of Sample 109 was produced in the same procedure as Sample 101, except that the barrier layer was not formed and the solid sealing curing temperature was changed to 100 ° C.

[Procedure for manufacturing organic electroluminescence element of sample 110]
In the procedure of Sample 101 described above, an organic EL element of Sample 110 was produced by the same procedure as Sample 101, except that the barrier layer was changed to a barrier layer using an organic / inorganic hybrid polymer (organic / inorganic HBP).

[Formation of barrier layer (organic / inorganic HBP)]
First, an organic / inorganic HBP coating solution was prepared.
27.7 g (30 mol%) of polymethoxysiloxane (MS-51 manufactured by Mitsubishi Chemical Corporation), 12.7 g (45 mol%) of 3-glycidoxypropyltremethoxysilane, 22.1 g (5 Mol%) 3-aminopropyltriethoxysilane and 49.2 g (10 mol%) aluminum sec-butoxide were stirred in a flask for 5 minutes while cooling with ice.
To this mixture, 7.6 g of distilled water was slowly added dropwise and the mixture was stirred for 5 minutes. Further, 65.5 g (10 mol%) of zirconium propoxide was added and stirred for 5 minutes, then 15.3 g of distilled water was added to the mixture and stirring was continued for 15 minutes. Finally, 122.5 g of distilled water was added to the mixture and stirred at room temperature for 2 hours to obtain a transparent and uniform coating solution.

Next, the adjusted coating solution was applied to the substrate by a bar coating method and thermally cured at 130 ° C. The film thickness after drying was 300 nm.
Through the above steps, a barrier layer made of an organic / inorganic hybrid polymer (organic / inorganic HBP) was formed on the substrate.

  Thereafter, the second electrode was formed from the planarization layer on the barrier layer by the same procedure as that of the sample 101, solid-sealed, and the organic EL element of the sample 110 was manufactured.

[Procedure for manufacturing organic electroluminescent element of sample 111]
In the step of forming the planarization layer, the organic EL element of Sample 110 was fabricated in the same procedure as Sample 110, except that the modification treatment was not performed and the planarization layer made of the unmodified polysilazane layer was formed. .

[Procedure for manufacturing organic electroluminescence element of sample 112]
An organic EL element of Sample 112 was fabricated in the same procedure as Sample 110 except that the planarization layer was not formed.

[Procedure for manufacturing organic electroluminescent element of sample 113]
The organic EL of sample 113 is the same as sample 110 except that the base material is changed to a 12 μm thick biaxially stretched polyethylene terephthalate (PET) film (trade name: NSC, single-sided corona treatment manufactured by Teijin Limited). An element was produced.

[Procedure for Manufacturing Organic Electroluminescence Element of Sample 114]
An organic EL element of Sample 114 was fabricated in the same procedure as Sample 110 except that the solid sealing curing temperature was changed to 100 ° C.

[Procedure for manufacturing organic electroluminescent element of sample 115]
An organic EL element of Sample 115 was produced in the same procedure as Sample 112 except that the solid sealing curing temperature was changed to 100 ° C.

[Procedure for Manufacturing Organic Electroluminescence Element of Sample 116]
The organic EL of the sample 116 is subjected to the same procedure as the sample 101 except that the supply amount of the oxygen gas (O ₂ ) is changed to 1000 sccm under the film forming conditions of the barrier layer (Si, O, C) of the sample 101. An element was produced.

[Procedure for Producing Organic Electroluminescent Element of Sample 117]
The above sample except that the applied power from the plasma generating power source was changed to 0.8 kW and the film conveyance speed was changed to 0.5 m / min under the film forming conditions of the barrier layer (Si, O, C) of the sample 101. An organic EL element of Sample 117 was produced in the same procedure as in 101.

[Evaluation of organic electroluminescence device]
(Surface roughness: surface smoothness)
In Samples 101 to 103 and Samples 105 to 117, the surface roughness Ra (nm) was measured for the surface of the planarization layer. In sample 104, the surface roughness Ra (nm) of the surface of the barrier layer was measured.
The surface roughness Ra is calculated from an uneven sectional curve continuously measured with a detector having a stylus having a minimum tip radius using an atomic force microscope (AFM) DI3100 manufactured by Digital Instruments, and has a minimum tip radius. Was measured many times in the section having a measurement direction of 30 μm with the stylus of No. 1 and obtained from the average roughness with respect to the amplitude of fine irregularities.

(Storability)
The organic EL elements of the above samples, which are installed in a curved shape on a cylindrical member having a diameter of 400 mm, are held in their shape for 80 minutes at 85 ° C. and 85% RH, and then the temperature is lowered to −40 ° C. over 90 minutes. (Humidity state), held at −40 ° C. for 80 minutes, and then the temperature was raised to 85 ° C. (humidity 85% RH) over 90 minutes, and the cycle of holding for 80 minutes was repeated 10 cycles. Thereafter, this element was held for 500 hours in an environment of 60 ° C. and 90% RH, and then turned on using a constant voltage power source, and the occurrence ratio (occurrence rate, initial DS occurrence rate) of the dark spot (non-light emitting portion) area was examined. .
The dark spot occurrence rate was obtained by photographing the light emitting surface of the organic EL element and applying predetermined image processing to the image data.
The measured dark spot generation rate was discriminated on the basis of 5 to 5 criteria (5 is good), and the light emitting performance of the organic EL device was evaluated.
5 Evaluation: Dark spot generation rate is 0% (no dark spots are generated)
4 Evaluation: Dark spot occurrence rate is greater than 0% and less than 5% 3 Evaluation: Dark spot occurrence rate is 5% or more and less than 10% 2 Evaluation: Dark spot occurrence rate is 10% or more and less than 20% 1 Evaluation: Dark spot occurrence rate 20% or more

(XPS data)
XPS data was measured for Samples 101 to 105, Sample 116, and Sample 117 in which barrier layers (Si, O, C) were formed by plasma CVD. The XPS data was obtained by XPS depth profile measurement under the following conditions to obtain silicon atomic ratio, oxygen atomic ratio, and carbon atomic ratio in the distance from the surface of the thin film layer in the film thickness direction. . An oxygen carbon atom was also obtained.
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 name “VG Theta Probe” manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval

  Table 1 shows the evaluation results of the organic electroluminescence elements of Samples 101 to 117.

  As a result of the XPS depth profiling measurement, each of the element distribution curves of carbon, oxygen, and silicon is obtained for the sample 101 and the samples 102 to 105 in which the barrier layer (Si, O, C) is formed under the same conditions as the sample 101. In the region of 90% or more of the film thickness, the relationship of (atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) is satisfied, and the carbon distribution curve has a plurality of distinct extreme values. It was. The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve was 6 at%.

  In addition, in the sample 117 in which the applied power from the plasma generating power source is changed to 0.8 kW and the film conveyance speed is changed to 0.5 m / min, each element distribution curve of carbon, oxygen, and silicon has 90% or more of the film thickness. In this region, the relationship of (atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) was satisfied, and the carbon distribution curve had a plurality of distinct extreme values. The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve was 9 at%.

  On the other hand, in the sample 116 in which the oxygen gas supply amount is 1000 scc, which is twice that of the sample 101, the distribution curve of each element is (atomic ratio of oxygen)> (silicon atoms) in a region of 90% or more of the film thickness. Ratio)> (atomic ratio of carbon), and the carbon distribution curve had a plurality of distinct extreme values. However, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve was 3 at%.

  As shown in Table 1, each element distribution curve satisfies the relationship of (atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) in the region of 90% or more of the film thickness, A barrier layer containing Si, O, and C having a plurality of distinct extreme values and an absolute value of a difference between a maximum value and a minimum value of the atomic ratio of carbon in the carbon distribution curve being 5 at% or more; Samples 101 to 103, sample 105, and sample 117 provided with the chemical layer on the substrate had good results in both smoothness and storage stability.

  However, each element distribution curve satisfies the relationship of (atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) in a region where the film thickness is 90% or more of the film thickness. A barrier layer containing Si, O, and C having an absolute value of 3 at% in absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve, and a planarizing layer. The sample 116 provided on the base material had good smoothness, but the storage stability was lower than those of the samples 101 to 103, the sample 105, and the sample 117. From this result, the barrier layer satisfies the relationship (atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon), has a plurality of distinct extreme values in the carbon distribution curve, and has a carbon distribution. By not satisfying the condition that the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the curve is 5 at% or more, it is considered that the performance of the barrier layer is lowered and the storability of the organic EL device is lowered.

  Furthermore, the sample 104 satisfies the relationship of (atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) in the region where each element distribution curve is 90% or more of the film thickness. And having a barrier layer containing Si, O, C in which the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more, Since the planarization layer is not provided, the smoothness is low due to the influence of the barrier layer having a large Ra, and the surface roughness Ra exceeds 2 nm. For this reason, it is thought that the short circuit of the element occurred in the pressurization / heating process of solid sealing. Therefore, the organic EL element preferably includes a planarization layer having a surface roughness Ra of 2 nm or less.

  Sample 101 and sample 102 differed in the type of substrate used, but similar results were obtained. From this result, by providing the barrier layer containing Si, O, and C and the planarizing layer, an organic EL element having good characteristics can be configured without depending on the material of the base material.

  In the sample 103 in which the polysilazane unmodified layer is formed as the planarization layer, the storage stability is deteriorated as compared with the sample 101. From this result, an organic EL element with high storage stability can be produced by using the polysilazane modified layer as the planarizing layer.

  The sample 105 has worse storage stability than the sample 101. This is probably because Sample 105 has a lower curing temperature than Sample 101 and the curing condition of the sealing resin layer is low, and thus the adhesion to the substrate is low and peeling or the like has occurred. From this result, it can be seen that the sample 101 is excellent in storage characteristics by increasing the curing temperature (curing conditions), thereby improving the adhesion between the base material and the sealing resin layer.

  Samples 106 to 109 have extremely poor storage stability. This is probably because the samples 106 to 109 did not have a barrier layer, and thus the thermal damage to the base material could not be alleviated in the heat treatment for curing the sealing resin layer, and the base material was damaged. .

Samples 110 to 115 in which the barrier layer was formed of an organic / inorganic hybrid polymer (organic / inorganic HBP) yielded the same results as samples 106 to 109 in which the barrier layer was not formed. From this result, when the barrier layer is formed of an organic / inorganic hybrid polymer, the thermal conductivity is lower and the heat dissipation is inferior than when the barrier layer is formed of an inorganic film containing Si, O, and C. For this reason, it is considered that the heat damage to the base material could not be alleviated and the base material was damaged.
Furthermore, in the samples 114 and 115 having a solid sealing temperature of 100 ° C., the curing condition of the sealing resin layer is low, so that the adhesion to the substrate is low, and it is considered that peeling or the like occurred.

  The present invention is not limited to the configuration described in the above-described embodiment, and various modifications and changes can be made without departing from the configuration of the present invention.

  DESCRIPTION OF SYMBOLS 10,20 ... Organic EL element, 11 ... Base material, 12 ... Barrier layer, 13 ... Planarization layer, 14 ... 1st electrode, 15 ... Organic functional layer, 15a. .. Hole injection layer, 15b... Hole transport layer, 15c... Light emitting layer, 15d... Electron transport layer, 15e. Sealing resin layer, 18 ... sealing member, 30 ... manufacturing apparatus, 31 ... delivery roll, 32, 33, 34, 35 ... transport roll, 36, 37 ... film forming roll 38 ... Gas supply pipe, 39 ... Power source for plasma generation, 40 ... Film, 41, 42 ... Magnetic field generator, 43 ... Winding roll

Claims (6)

A flexible substrate;
Provided on the flexible substrate, which has at least silicon atoms, oxygen atoms, and carbon atoms, the distance from the surface of the layer in the thickness direction, and the total amount of silicon atoms, oxygen atoms, and carbon atoms Silicon distribution curve and oxygen distribution showing the relationship between the ratio of the amount of silicon atoms (the atomic ratio of silicon), the ratio of the amount of oxygen atoms (the atomic ratio of oxygen), and the ratio of the amount of carbon atoms (the atomic ratio of carbon), respectively In the curve and the carbon distribution curve, the following conditions (i) to (iii):
(I) In a region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the layer, the following formula (1):
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (1)
Or in the region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the layer, the following formula (2):
(Atomic ratio of carbon)> (Atomic ratio of silicon)> (Atomic ratio of oxygen) (2)
Satisfying the condition represented by
(Ii) the carbon distribution curve has at least one extreme value;
(Iii) a barrier layer satisfying that the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more;
A planarization layer provided on the barrier layer;
A pair of electrodes;
An organic functional layer having at least one light emitting layer between the electrodes,
An organic electroluminescence element that is solid-sealed by a sealing resin layer and a sealing member.   The organic electroluminescence device according to claim 1, wherein the planarizing layer is made of polysilazane.   The organic electroluminescence device according to claim 2, wherein the planarizing layer is a polysilazane modified film.   The organic electroluminescence device according to claim 1, wherein the planarization layer has a surface roughness (Ra) of 2 nm or less.   The organic electroluminescence element according to claim 1, wherein the sealing resin layer is a photocurable or thermosetting adhesive. Forming a barrier layer on the flexible substrate by a plasma CVD method;
Forming a planarization layer on the barrier layer;
Forming a pair of electrodes and an organic functional layer having at least one light emitting layer between the electrodes on the planarizing layer;
Applying a sealing resin layer, and solid-sealing with a sealing member. A method for producing an organic electroluminescent element.

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