CN107637167A - Light-emitting component - Google Patents

Abstract

The transparent (see-through) light-emitting element 100 of the present invention includes: a diffraction grating substrate 140, on which a textured layer 142 having a textured pattern 80 is formed on one side of a substrate 40; a first electrode 92; an organic layer 94; and a second electrode 98; wherein the first electrode 92, the organic layer 94, and the second electrode 98 are sequentially formed on the textured layer 142, and the average spacing of the textured pattern 80 is in the range of 150 to 650 nm. The transparent light-emitting element 100 can extract light with high efficiency.

Description

Light emitting element

technical field

The invention relates to a transparent (See-through) light-emitting element.

Background technique

As a light-emitting element expected as a next-generation display device or lighting device, there is an organic light-emitting diode called an organic EL element. One of the characteristics of the organic EL element is that the element itself is transparent (see-through). That is, a display device or a lighting device using an organic EL element can see through the organic EL element to the other side. For example, Patent Document 1 describes a transparent organic EL element.

Organic EL elements are expected to be used in various applications due to their transparency. For example, it is considered to be applied in the form of interior lighting such as lighting that integrates with the wall of the room when the lights are off to reduce the sense of presence or pressure, window lighting, or in the form of a light-emitting window, or It is applied in the form of vehicle lighting, making the sunroof of a car transparent, etc.

Regarding the organic EL element, the holes injected from the anode through the hole injection layer and the electrons injected from the cathode through the electron injection layer are respectively transported to the light-emitting layer, and these are recombined on organic molecules in the light-emitting layer. Excite organic molecules, thereby emitting light. Therefore, when an organic EL element is used as a display device or a lighting device, it is necessary to efficiently extract light from the light-emitting layer from the inside of the element. Therefore, it is known in Patent Document 2 that a concavo-convex structure for diffracting and/or scattering light is provided inside and outside the organic EL element.

[Prior Art Literature]

[Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-176674

[Patent Document 2] Japanese Patent Laid-Open No. 2006-236748

Contents of the invention

[Problems to be Solved by the Invention]

However, the organic EL element provided with the concavo-convex structure for extracting light as described above scatters the light passing through the element, so it is blurred and has low transparency.

Therefore, an object of the present invention is to provide a transparent light-emitting device capable of efficiently extracting light.

[Technical means to solve the problem]

According to an aspect of the present invention, a transparent light-emitting element is provided, which includes:

Diffraction grating substrate, which has a concavo-convex structure layer with concavo-convex patterns formed on one side of the substrate;

1st electrode;

an organic layer; and

2nd electrode, and

The first electrode, the organic layer, and the second electrode are sequentially formed on the concave-convex structure layer,

The average pitch of the concavities and convexes of the above-mentioned concavo-convex pattern is in the range of 150-650 nm.

In the above-mentioned transparent light-emitting device, the haze value of the above-mentioned diffraction grating substrate may be 2.0% or less.

In the above-mentioned transparent light-emitting element, the extension direction of the protrusions of the above-mentioned concave-convex pattern may be irregularly distributed in plan view, and

The outline of the convex portion included in the area per unit area of the concave-convex pattern in a plan view includes more linear sections than curved sections.

In the above-mentioned transparent light-emitting element, the width of the convex portion in a direction substantially perpendicular to the direction in which the convex portion extends may be constant in plan view.

In the above-mentioned transparent light-emitting element, the above-mentioned curve interval may be an interval in which multiple curves are formed by dividing the contour line of the above-mentioned convex portion in plan view by a length that is π (pi) times the average value of the width of the above-mentioned convex portion. In the case of a section, the ratio of the straight-line distance between the two end points of the section to the length of the above-mentioned contour line between the two end points is 0.75 or less, and

The linear section is a section other than the curved section among the plurality of sections.

In the above-mentioned transparent light-emitting element, the above-mentioned curve interval may be an interval in which multiple curves are formed by dividing the contour line of the above-mentioned convex portion in plan view by a length that is π (pi) times the average value of the width of the above-mentioned convex portion. In the case of two intervals, the angle between the line segment connecting one end of the interval and the midpoint of the interval and the line segment connecting the other end of the interval and the midpoint of the interval is 180° or less. Below 120°; and

The above-mentioned linear section is an interval that is not the above-mentioned curved section among the above-mentioned plurality of sections,

The ratio of the linear section among the plurality of sections is 70% or more.

In the above-mentioned transparent light-emitting device, the absolute value of the wavenumber can also be expressed by performing a two-dimensional high-speed Fourier transform on a concavo-convex analysis image obtained by analyzing the above-mentioned concavo-convex pattern with a scanning probe microscope. The origin of the value of 0 μm ⁻¹ is a circular or annular pattern approximately at the center, and the circular or annular pattern exists in a region where the absolute value of the wave number is in the range of 1.54 to 6.67 μm ⁻¹ .

[Effect of the invention]

The light-emitting element of the present invention is transparent and has high luminous efficiency. Therefore, the light-emitting device of the present invention is extremely effective for various light-emitting devices such as display devices and lighting devices.

Description of drawings

Fig. 1(a) and (b) are schematic cross-sectional views of a light emitting element according to an embodiment.

Fig. 2(a) is a schematic plan view of a concavo-convex pattern of the light emitting element according to the embodiment, and Fig. 2(b) is a cross-sectional image showing a cutting line in the schematic plan view of Fig. 2(a).

Fig. 3 is an example of a Fourier transform image showing a concavo-convex analysis image of a concavo-convex pattern.

Fig. 4 is a conceptual diagram showing an example of a case where a film mold is used to form a concave-convex pattern in the method of manufacturing a light emitting element according to the embodiment.

5 is a table showing the evaluation results of light-emitting elements of Examples 1 and 2 and Comparative Examples 1 to 3.

FIG. 6 is an example of a plan view analysis image (black and white image) of a concavo-convex pattern.

7( a ) and ( b ) are diagrams for explaining an example of a method of determining branching of convex portions in a plan view analysis image.

FIG. 8( a ) is a diagram for explaining a first definition method of a curve section, and FIG. 8( b ) is a diagram for explaining a second definition method of a curve section.

Reference number

40: Substrate

92: 1st electrode

94: organic layer

98: 2nd electrode

100: light emitting element

140: Diffraction grating substrate

142: Concave-convex structure layer

detailed description

Hereinafter, embodiments of the transparent light-emitting element of the present invention and a manufacturing method thereof will be described with reference to the drawings.

[Transparent light-emitting element]

A schematic cross-sectional view of the transparent light-emitting element of this embodiment is shown in FIG. 1( a ). The transparent light-emitting element 100 shown in FIG. 1(a) sequentially includes a concave-convex structure layer 142, a first electrode 92, an organic layer 94, and a second electrode 98 on a substrate 40, and further includes a sealing member 101 and a sealing adhesive layer. 103. Furthermore, in this application, the substrate 40 on which the concavo-convex structure layer 142 is formed is appropriately referred to as a diffraction grating substrate 140 .

＜Substrate＞

The substrate 40 is not particularly limited, and known substrates that transmit visible light can be suitably used. For example, substrates made of transparent inorganic materials such as glass; substrates made of polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, etc.) , Acrylic resin (polymethyl methacrylate, etc.), polycarbonate, polyvinyl chloride, styrene resin (ABS resin, etc.), cellulose resin (triacetyl cellulose, etc.), polyimide resin Substrates made of resins such as polyimide resins, polyimide amide resins, etc., cycloolefin polymers; SiN, SiO ₂ , SiC, SiO _X N are formed on the surface of these substrates made of resins A laminated substrate made of a gas barrier layer made of _Y , TiO ₂ , Al ₂ O ₃ and other inorganic substances and/or a gas barrier layer made of a resin material; A laminated substrate, etc., in which gas layers are alternately laminated. In terms of the application of the light-emitting element 100 , the base material 40 is preferably a base material having heat resistance and weather resistance to UV light and the like. In these respects, a substrate made of an inorganic material such as a glass or a quartz substrate is more preferable. Especially when the concave-convex structure layer 142 is formed of an inorganic material, if the base material 40 is formed of an inorganic material, the difference in refractive index between the base material 40 and the concave-convex structure layer 142 is small, and the light-emitting element 100 can be prevented. Unintentional refraction or reflection within, so better. Moreover, the base material 40 can also be a flexible film-like (sheet-like) base material. On the base material 40, in order to improve the adhesion, a surface treatment layer or an easy-to-adhesive layer can also be provided. To prevent the infiltration of gas, a gas barrier layer can also be provided. Moreover, a smoothing layer etc. may be provided in order to fill up the protrusion on the surface of a base material. The thickness of the base material 40 is preferably in the range of 1-20 mm.

＜Concave-convex structure layer＞

The concavo-convex structure layer 142 is a layer in which the fine concavo-convex pattern 80 is formed on the surface. In a light-emitting device, the concave-convex structure layer having a fine concave-convex pattern diffracts and/or scatters light, whereby light generated in the organic layer can be extracted to the outside of the device. However, when the concave-convex structure layer having the concave-convex pattern scatters light, the concave-convex structure layer not only scatters light originating from the organic layer, but also scatters light passing through the light-emitting element. Therefore, the light-emitting element with such a concave-convex structure layer cannot see through it to see the other side, or the image on the other side is blurred when seen through. The concave-convex structure layer 142 of the transparent light-emitting element 100 of this embodiment suppresses the scattering of light and extracts the light from the organic layer 94 to the outside of the light-emitting element 100 mainly by diffraction, thereby achieving both transparency and light-emitting element 100. Light extraction function.

FIG. 2(a) shows an example of a schematic plan view of the concavo-convex pattern 80 of the concavo-convex structure layer 142 of the present embodiment, and FIG. 2(b) shows a cross-sectional image on a cutting line in the schematic plan view of FIG. 2(a). . The cross-sectional shape of the concavo-convex structure layer 142 may be composed of a relatively gentle slope as shown in FIG. That is, the convex portion of the concave-convex pattern 80 may have a cross-sectional shape that narrows from the bottom toward the top on the substrate 40 side. The concave-convex pattern 80 of the concave-convex structure layer 142 has the following characteristics in plan view: as shown in FIG. ═) An elongated shape that extends, and its extension direction, bending direction (bending direction) and extension length are irregular. This kind of concave-convex pattern 80 is obviously different from stripes, wavy stripes, zigzag regularly aligned patterns or dot patterns, etc. In this aspect, it can be distinguished from circuit patterns such as regular or more straight lines. Concave-convex structure layer 142 having the above-mentioned features repeatedly presents concavo-convex cross-sections even when cut in any direction perpendicular to the surface of base material 40 . In addition, some or all of the plurality of protrusions and recesses of the concave-convex pattern 80 may branch in the middle in plan view (see FIG. 2( a )). In addition, in FIG. 2( a ), the pitches of the protrusions are uniform as a whole. Moreover, the concave part of the concave-convex pattern 80 may also be divided by the convex part, and may extend along the convex part.

The concave-convex pattern 80 can also be made into a dot structure, a corner column structure, a stripe structure composed of lines and gaps, a cylindrical shape, a conical shape, a truncated cone shape, a triangular column shape, and a triangular shape in addition to the above-mentioned irregular concave-convex pattern. Cone, triangular truncated pyramid, quadrangular column, quadrangular pyramid, quadrangular truncated pyramid, polygonal column, polygonal pyramid, polygonal truncated pyramid and other pillar structures, hole structure, microlens array structure, with the ability to diffract light Arbitrary patterns such as functional structures. In addition, irregular fine concave-convex patterns such as those formed by sandblasting can also be formed.

In the transparent light emitting element 100 , the average pitch of the concavities and convexes of the concavo-convex pattern 80 of the concavo-convex structure layer 142 is in the range of 150-650 nm. If the average pitch of the concavo-convex is less than the above lower limit, the pitch becomes too small for the wavelength of visible light to prevent diffraction of light by the concavo-convex, and a sufficient light extraction effect cannot be obtained. On the other hand, if the average pitch of the concavo-convex exceeds the above-mentioned upper limit, there is a tendency that the light scattering effect caused by the concavo-convex becomes large, and as shown in the following examples and comparative examples, the diffraction grating substrate 140 tends to be Since the haze value (haze) exceeds 2.0%, the transparency of the light-emitting element 100 is impaired and becomes opaque. The average pitch of the concavities and convexes of the concavo-convex pattern 80 is more preferably in the range of 150-300 nm. When the average pitch of the unevenness is in this range, the haze value becomes less than 0.20%, and the transparency of the light-emitting element 100 is higher. The average value of the depth distribution of the unevenness is preferably in the range of 20 to 200 nm. If the average value of the depth distribution of the unevenness does not reach the above-mentioned lower limit, there is a tendency that the depth is too small for the wavelength of visible light, so it becomes difficult to generate the desired diffraction. On the other hand, if the average value of the depth distribution of the unevenness When the value exceeds the upper limit, for example, the electric field distribution inside the organic layer 94 of the light-emitting element 100 becomes non-uniform and the electric field is concentrated at a specific position, so leakage current tends to occur easily, or the device life tends to be shortened. The average value of the depth distribution of the unevenness is more preferably in the range of 30 to 150 nm. The standard deviation of the depth of the unevenness is preferably in the range of 10 to 100 nm. If the standard deviation of the depth of the concavo-convex does not reach the above-mentioned lower limit, it tends to be as follows: relative to the wavelength of visible light, the depth is too small, so it becomes difficult to generate the required diffraction. On the other hand, if the standard deviation of the depth of the concavo-convex exceeds the If the upper limit is set, for example, the electric field distribution inside the organic layer 94 of the light-emitting element 100 becomes non-uniform and the electric field is concentrated at a specific position, which tends to cause leakage current or shorten the life of the element. The standard deviation of the depth of the unevenness is more preferably in the range of 15 to 75 nm.

In the present application, the average pitch of concavo-convex means the pitch of concav-convex when measuring the pitch of concavo-convex on the surface formed with concavo-convex (the distance between adjacent convex parts or the distance between adjacent concave parts). average value. The average value of the pitch of such unevenness can be obtained by using a scanning probe microscope (for example, the product name "E-sweep" manufactured by Hitachi High-TechScience Co., Ltd., etc.), according to the following conditions:

Measuring method: cantilever intermittent contact method

Cantilever Material: Silicon

Cantilever rod width: 40 μm

The diameter of the tip of the cantilever: 10 nm

After measuring the unevenness of the surface to obtain the unevenness analysis image, the interval between any adjacent convex portions or adjacent concave portions in the unevenness analysis image is measured at a distance of 100 points or more, and the arithmetic mean thereof is calculated.

In addition, in the present application, the average value of the depth distribution of the unevenness and the standard deviation of the unevenness depth can be calculated as follows. Using a scanning probe microscope, under the above-mentioned conditions, the concave-convex shape of an arbitrary measurement area of 3 μm square (length 3 μm, width 3 μm) or 10 μm square (length 10 μm, width 10 μm) is measured to obtain a concave-convex analysis image. At this time, the data of the height of the concavities and convexities at the measurement points of 16384 or more points (128 points in length x 128 points in width) in the measurement area were obtained on a nanometer scale. In addition, the number of such measuring points varies depending on the type or setting of the measuring device used. For example, when using the aforementioned Hitachi High-Tech Science Co., Ltd. product name "E-sweep" as the measuring device In some cases, 65536 points (256 points in length x 256 points in width) can be measured in a 3 μm square measurement area (measurement at a resolution of 256×256 pixels). Then, regarding the unevenness height (unit: nm) measured as described above, first, the measurement point P having the highest height from the bottom surface of the substrate among all the measurement points is obtained. Then, with the plane parallel to the surface of the substrate including the measurement point P as a reference plane (horizontal plane), the depth value from the reference plane is obtained (subtracting the height value of each measurement point from the substrate from the measurement point P) The difference obtained from the height value of the distance from the base material) is used as the data of the concave-convex depth. Furthermore, this kind of concave-convex depth data can be obtained by automatic calculation using software in the measuring device, etc. The value obtained by this automatic calculation is used as the data of the depth of the concavo-convex. After obtaining the data of the depth of irregularities at each measurement point as described above, values that can be calculated by obtaining the arithmetic mean and standard deviation thereof are used as the average value of the distribution of irregularities and the standard deviation of the depth of irregularities, respectively. In this specification, the average pitch of the unevenness and the average value of the depth distribution of the unevenness can be obtained by the above-mentioned measuring method regardless of the material of the surface on which the unevenness is formed.

The concavo-convex pattern 80 may be an approximate periodic pattern: the Fourier transform image obtained by performing two-dimensional high-speed Fourier transform processing on the concavo-convex analysis image obtained by analyzing the concavo-convex shape shows a circular or annular pattern as shown in FIG. 3 , that is, the orientation of the bumps has no directivity but the pitch of the bumps has a distribution. A substrate having such an approximately periodic pattern is preferably used as a diffraction grating substrate used in a surface light-emitting element such as an organic EL element, as long as the distribution of the concave-convex pitch can diffract visible light.

Furthermore, as shown in FIG. 3, the Fourier transform image can show a circular or annular pattern with the origin having an absolute value of wave number 0 μm ^-1 as the approximate center. The circular or annular pattern can exist in The absolute value of the wave number is in the range of 1.54 to 6.67 μm ⁻¹ , more preferably in the range of 3.33 to 6.67 μm ⁻¹ . The circular pattern in the Fourier transform image is a pattern observed due to the aggregation of bright spots in the Fourier transform image. The term "round shape" here means that a pattern formed by a collection of bright spots looks like a roughly circular shape, and also includes the concept that a part of the shape looks like a convex shape or a concave shape. There is also a case where a pattern formed by a collection of bright spots looks roughly circular, and this is described as "circular". In addition, "annulus shape" is a concept that includes the shape of the outer circle or the inner circle of the ring that looks like a substantially circular shape, and also includes a part of the outer circle or the inner circle of the ring. Appears to be convex or concave. Also, "a circular or annular pattern exists in a region where the absolute value of the wave number is within the range of 1.54 to 6.67 μm ^-1 , more preferably within the range of 3.33 to 6.67 μm ^-1 " means the following : 30% or more (more preferably 50% or more, still more preferably 80% or more, and most preferably 90% or more) of the bright spots constituting the Fourier transform image exist within the range in which the absolute value of the wavenumber is 1.54 to 6.67, More preferably, it is in a region within a range of 3.33 to 6.67 μm ⁻¹ . Furthermore, the following is known about the relationship between the concavo-convex pattern and the Fourier transform image. When the pitch of the concave-convex pattern itself has no distribution or no directivity, the Fourier transform image also appears as an irregular pattern (no pattern), but when the concave-convex pattern is isotropic in the XY direction as a whole but the pitch is distributed, it appears Fourier transform image of a circle or donut. Also, when the concavities and convexities of the concavo-convex pattern have a single pitch, the rings appearing in the Fourier transform image tend to be sharp.

The above-mentioned two-dimensional fast Fourier transform processing of the concave-convex analysis image can be easily performed by electronic image processing using a computer equipped with two-dimensional high-speed Fourier transform processing software.

Furthermore, by processing the concave-convex analysis image so that the convex portions are represented in white and the concave portions are represented in black, a top view analytical image (black and white image) as shown in FIG. 6 can be obtained. FIG. 6 is a diagram showing an example of a planar analysis image of a measurement region in the concavo-convex structure layer 142 .

The width of the convex portion (white display portion) in the plan view analysis image is referred to as “the width of the convex portion”. Regarding the average value of the width of such a convex portion, it is possible to select any 100 or more convex portions from the convex portions of the plan view analysis image, and measure the extension direction of the convex portion for each of the above-mentioned 100 or more convex portions. The length from the boundary of the convex portion to the boundary on the opposite side in the substantially perpendicular direction was obtained by calculating the arithmetic mean thereof.

In addition, when calculating the average value of the width of a convex part, the value of the position randomly selected from the convex part of a top view analysis image is used as mentioned above, However, the value of the position of the branch of a convex part does not need to be used. In the convex portion, whether or not a certain region is a branched region can be determined, for example, based on whether or not the region extends over a certain length. More specifically, it can be determined based on whether or not the ratio of the extension length of the region to the width of the region is constant (for example, 1.5) or more.

Using FIGS. 7( a ) and 7 ( b ), for a region protruding in a direction approximately perpendicular to the extension axis of the convex portion at a midway position of a convex portion extending in a certain direction, a method of judging whether the region is branched As an example, here, the so-called extension axis of the convex portion is defined as the axis along the extending direction of the convex portion determined by the shape of the outer edge of the convex portion when the region to be determined whether to branch is excluded from the convex portion. imaginary axis. More specifically, the extension axis of the convex portion is a line drawn so as to pass through the substantially center point of the width of the convex portion, which is perpendicular to the extending direction of the convex portion. 7( a ) and FIG. 7( b ) are schematic diagrams for explaining only a part of the convex portion in the plan view analysis image, and the region S shows the convex portion. In FIG. 7( a ) and FIG. 7( b ), areas A1 and A2 protruding from the midway position of the convex portion are selected as areas to be determined whether or not to branch. In this case, when the regions A1 and A2 are excluded from the convex portion, the extension axes L1 and L2 are defined as a line passing through the substantially center point of the width of the convex portion perpendicular to the extending direction of the convex portion. Such an extension axis may be defined by image processing using a computer, may be defined by an operator performing analysis work, or may be defined by both image processing using a computer and manual work by an operator. In FIG. 7( a ), the region A1 protrudes in a direction perpendicular to the extension axis L1 at a midway position of the convex portion extending along the extension axis L1 . In FIG. 7( b ), the region A2 protrudes in a direction perpendicular to the extension axis L2 at a midway position of the convex portion extending along the extension axis L2 . Furthermore, regarding the regions protruding obliquely in the direction perpendicular to the extension axes L1, L2, it is sufficient to determine whether or not to branch using the same viewpoint as the region A1, A2 described below.

According to the above determination method, since the ratio of the extension length d2 of the area A1 to the width d1 of the area A1 is about 0.5 (less than 1.5), it is determined that the area A1 is not a branched area. In this case, the length d3 in the direction passing through the region A1 and perpendicular to the extension axis L1 is one of the measured values used to calculate the average value of the width of the convex portion. On the other hand, since the ratio of the extension length d5 of the area A2 to the width d4 of the area A2 is about 2 (1.5 or more), it is determined that the area A2 is a branched area. In this case, the length d6 in the direction passing through the region A2 and perpendicular to the extension axis L2 is not regarded as one of the measured values for calculating the average value of the width of the convex portion.

In the concave-convex pattern 80 of the concave-convex structure layer 142 , the width of the convex portion in the direction substantially perpendicular to the extending direction of the convex portion in plan view can be constant. Whether or not the width of the convex portion is constant can be determined based on the width of the convex portion of 100 points or more obtained by the above measurement. Specifically, the average value of the width of the protrusions and the standard deviation of the width of the protrusions were calculated from the widths of the protrusions at 100 or more points. Then, a value calculated by dividing the standard deviation of the width of the convex portion by the average value of the width of the convex portion (standard deviation of the width of the convex portion/average value of the width of the convex portion) was defined as the value of the width of the convex portion coefficient of variation. Regarding this coefficient of variation, the more constant the width of the convex portion is (the smaller the variation in width), the smaller the value of this coefficient of variation becomes. Therefore, whether or not the width of the convex portion is constant can be determined by whether or not the coefficient of variation is equal to or less than a specific value. For example, when the coefficient of variation is 0.25 or less, it can be defined that the width of the convex portion is constant.

Moreover, as shown in FIG. 6, the extending direction of the convex part (white part) contained in the uneven|corrugated pattern 80 is distributed irregularly in planar view. That is, the protrusions may not be in the shape of regularly arranged stripes or regularly arranged dots, but may have a shape extending in irregular directions. In addition, in the measurement area, that is, the specific area of the concave-convex pattern, the contour lines of the convex portions included in the area per unit area include more linear sections than curved sections in plan view.

"Containing more straight-line sections than curved sections" means that there is no concavo-convex pattern in which curved sections account for most of all sections on the contour line of a convex part. Whether or not the contour line of a convex portion in a plan view includes more straight-line sections than curved sections can be determined by, for example, using any one of the following two methods of defining curved sections.

<The first definition method of the curve section>

In the first definition method of the curved section, the curved section is defined as an interval formed by dividing the contour line of the convex portion in plan view by a length of π (pi) times the average value of the width of the convex portion. In the case of a section, the ratio of the straight-line distance between the two end points of the section to the length of the contour line between the two end points is 0.75 or less. In addition, the linear section is defined as a section other than the curved section among the above-mentioned plurality of sections, that is, a section in which the above-mentioned ratio is greater than 0.75. Hereinafter, with reference to FIG. 8( a ), an example of a program for determining whether or not the contour line of a convex portion in plan view includes more straight-line sections than curved sections using the above-mentioned first definition method will be described. FIG. 8( a ) is a diagram showing a part of a plan view analysis image of a concavo-convex pattern, and for convenience, the concave portions are shown in white. The region S1 represents a convex portion, and the region S2 represents a concave portion.

Procedure 1-1

One convex portion is selected from the plurality of convex portions in the measurement area. An arbitrary position on the contour line X of the convex portion is determined as a starting point. In FIG. 8( a ), as an example, point A is set as a starting point. On the contour line X of the convex portion, reference points are set at specific intervals from the starting point. Here, the specific interval is the length of π (pi)/2 times the average value of the width of the convex portion. In FIG. 8( a ), as an example, point B, point C, and point D are sequentially set.

Procedure 1-2

If the points A to D serving as reference points are set on the contour line X of the convex portion, the section to be judged is set. Here, the starting point and the ending point are used as reference points, and a section including the reference point serving as an intermediate point is set as a judgment object. In the example of FIG. 8( a ), when point A is selected as the start point of the section, point C set second from point A becomes the end point of the section. Regarding the distance from point A, here it is set to be the length of π/2 times the average value of the width of the convex portion, so point C is only π times the average value of the width of the convex portion from point A along the contour line X the length of those. Similarly, when point B is selected as the start point of the section, point D set second from point B becomes the end point of the section. In addition, here, the sections to be targeted are set in the order of setting, and the point A is assumed to be the first set point. That is, first, the section between point A and point C (section AC) is set as the section to be processed. Then, the length La of the contour line X of the convex portion connecting the points A and C shown in FIG. 8( a ) and the straight-line distance Lb between the points A and C were measured.

Procedure 1-3

Using the length La and the straight-line distance Lb measured in procedure 1-2, the ratio (Lb/La) of the straight-line distance Lb to the length La is calculated. When the ratio is equal to or less than 0.75, it is determined that the point B serving as the midpoint of the section AC of the contour line X of the convex portion exists in the curved section. On the other hand, when the above-mentioned ratio is greater than 0.75, it is determined that the point B exists in the straight line section. In addition, in the example shown in FIG.8(a), since the said ratio (Lb/La) becomes 0.75 or less, it is determined that the point B exists in the curve section.

Procedure 1-4

When each point set in the program 1-1 is selected as a starting point, the program 1-2 and the program 1-3 are executed.

Procedure 1-5

Procedures 1-1 to 1-4 are executed for all convex portions in the measurement area.

Procedure 1-6

When the ratio of the points determined to exist in the straight-line section among all the set points for all the convex parts in the measurement area is 50% or more of the whole, it is determined that the contour line of the convex part in plan view includes There are more linear intervals than curved intervals. On the other hand, for all the convex parts in the measurement area, if the ratio of the points determined to exist in the straight line section among all the set points is less than 50% of the whole, it is determined that the convex part is in the plan view. The lower contour line contains more curved intervals than straight intervals.

The processing of the above procedures 1-1 to 1-6 may be performed by a measurement function included in the measurement device, may be performed by an analysis software or the like different from the above measurement device, or may be performed manually.

Furthermore, regarding the process of setting points on the contour line of the convex part in the above-mentioned program 1-1, only when it is impossible to set more points than the above-mentioned points because the convex part circles around or exceeds the measurement area. Just finish processing. Also, since the above-mentioned ratio (Lb/La) cannot be calculated for the section outside the first set point and the last set point, it may be excluded from the above-mentioned determination. In addition, a convex portion whose length of the contour line is less than π times the average value of the width of the convex portion may be excluded from the above determination.

<Second definition method of curve interval>

In the second definition method of the curved section, the curved section is defined as an interval formed by dividing the contour line of the convex section in plan view by a length of π (circumference) times the average value of the width of the convex section. In the case of an interval, the line segment (line segment AB) connecting one end of the interval (point A) and the midpoint of the interval (point B) and the other end of the interval (point C) and the midpoint of the interval (point Of the two angles formed by the line segment (line segment CB) of B), the angle of the smaller one (the one that becomes 180° or less) is 120° or less. In addition, the linear section is defined as a section other than the curved section among the above-mentioned multiple sections, that is, a section in which the above-mentioned angle is larger than 120°. Hereinafter, with reference to FIG. 8( b ), an example of a program for determining whether or not the contour line of a convex portion in plan view includes more straight-line sections than curved sections using the above-mentioned second definition method will be described. FIG. 8( b ) is a diagram showing a part of a plan view analysis image of the same concavo-convex pattern as in FIG. 8( a ).

Procedure 2-1

One convex portion is selected from the plurality of convex portions in the measurement area. An arbitrary position on the contour line X of the convex portion is determined as a starting point. In FIG.8(b), point A is set as a start point as an example. On the contour line X of the convex portion, reference points are set at specific intervals from the starting point. Here, the specific interval is the length of π (pi)/2 times the average value of the width of the convex portion. In FIG. 8( b ), as an example, point B, point C, and point D are sequentially set.

Procedure 2-2

If the points A to D serving as reference points are set on the contour line X of the convex portion, the section to be judged is set. Here, the starting point and the ending point are used as reference points, and a section including the reference point serving as an intermediate point is set as a judgment object. In the example of FIG. 8( b ), when point A is selected as the start point of the section, point C set second from point A becomes the end point of the section. Regarding the distance from point A, here it is set to be the length of π/2 times the average value of the width of the convex portion, so point C is only π times the average value of the width of the convex portion from point A along the contour line X the length of those. Similarly, when point B is selected as the start point of the section, point D set second from point B becomes the end point of the section. In addition, here, the sections to be targeted are set in the order of setting, and the point A is assumed to be the first set point. That is, first, the section between point A and point C (section AC) is set as the section to be processed. Then, the angle θ of the smaller (180° or less) of the two angles formed by the line segment AB and the line segment CB is measured.

Procedure 2-3

When the angle θ is less than or equal to 120°, the determination point B is a point existing in the curved section, and on the other hand, when the angle θ is larger than 120°, the determination point B is a point existing in the straight line section. In addition, in the example shown in FIG.8(b), since angle (theta) becomes 120 degrees or less, it determines that point B exists in the curve section.

Procedure 2-4

Regarding the case where each point set in the program 2-1 is selected as the starting point, the program 2-2 and the program 2-3 are executed.

Procedure 2-5

Procedures 2-1 to 2-4 are executed for all convex portions in the measurement area.

Procedure 2-6

When the ratio of the points determined to exist in the straight-line section among all the set points for all the convex parts in the measurement area is 70% or more of the whole, it is determined that the contour line of the convex part in plan view includes There are more linear intervals than curved intervals. On the other hand, when the ratio of the points determined to exist in the straight-line section among all the set points for all the convex parts in the measurement area is less than 70% of the whole, it is judged that the convex part is in a plane view. The contour line of contains more curved intervals than straight intervals.

The processing of the above procedures 2-1 to 2-6 may be performed by a measurement function included in the measurement device, may be performed by executing analysis software or the like different from the measurement device, or may be performed manually.

Furthermore, regarding the processing of setting points on the contour line of the convex part in the above-mentioned program 2-1, only when more points than the above-mentioned points cannot be set because the convex part circles around or exceeds the measurement area Just finish processing. Also, since the above-mentioned angle θ cannot be calculated for the section outside the first set point and the last set point, it may be excluded from the above-mentioned determination. In addition, a convex portion whose length of the contour line is less than π times the average value of the width of the convex portion may be excluded from the above determination.

As described above, by using either of the first and second definition methods of the curved section, it can be determined whether or not the contour line X of the convex portion in plan view includes more straight section than the curved section for the measurement area. Furthermore, in the concavo-convex pattern 80 of a certain concavo-convex structure layer 142, "whether the contour line of the convex part included in the area per unit area contains more straight-line intervals than the curved intervals" can be based on the information from the concavo-convex structure layer 142 The concavo-convex pattern 80 is determined based on the determination result of one measurement area randomly selected. Alternatively, the judgment is made comprehensively based on the judgment results of a plurality of different measurement regions of the uneven pattern 80 of the uneven structure layer 142 . In this case, for example, the judgment result of the more judgment results for a plurality of different measurement areas may be used as "whether the contour line of the convex part included in the area per unit area contains more than the curve section in plan view?" The judgment result of the straight line interval".

Inorganic materials can be used as the material of the concave-convex structure layer 142, especially Si-based materials such as silicon dioxide, SiN, and SiON; Ti-based materials such as TiO ₂ ; ITO (indium tin oxide)-based materials; ZnO, ZnS, ZrO ₂ . , Al ₂ O ₃ , BaTiO ₃ , SrTiO ₂ and other inorganic materials. Among these, silicon dioxide or TiO ₂ is preferable in terms of film-forming properties and the relationship of the refractive index. These inorganic materials may be materials formed by a sol-gel method or the like (sol-gel materials). In addition, _SiOx , _SiNx , _SiOxNY , etc. formed using polysilazane solution as a raw material may also be used as the material of the concavo _- convex structure layer 142. Furthermore, curable resin may also be used as the material of the concavo-convex structure layer 142 . As the curable resin, resins such as photocurable and thermally curable, moisture curable, chemically curable (two-liquid mixture) and the like can be used, for example. Specifically, epoxy-based, acrylic-based, methacrylic-based, vinyl ether-based, oxetane-based, urethane-based, melamine-based, urea-based, polyester-based, and polyolefin-based , phenolic, cross-linked liquid crystal, fluorine, polysiloxane, polyamide and other monomers, oligomers, polymers and other resins.

The material of the concavo-convex structure layer 142 may be one containing an ultraviolet absorbing material in the above-mentioned inorganic material or curable resin. The ultraviolet absorbing material has a function of suppressing deterioration of the film by absorbing ultraviolet rays to convert light energy into a harmless form such as heat. As the ultraviolet absorber, conventionally known ones can be used, for example, benzotriazole-based absorbers, triazine-based absorbers, salicylic acid derivative-based absorbers, benzophenone-based absorbers, and the like can be used.

The thickness of the concavo-convex structure layer 142 is preferably 100 nm˜10 μm. If the thickness of the concavo-convex structure layer 142 is less than 100 nm, it becomes difficult to transfer the concavo-convex shape by imprinting described below. When the thickness of the concavo-convex structure layer 142 exceeds 10 μm, structural defects such as cracks are likely to occur. Here, the thickness of the concave-convex structure layer 142 means the average value of the distance from the bottom surface of the concave-convex structure layer 142 to the surface on which the concave-convex pattern 80 is formed.

When the adhesion between the base material 40 and the uneven structure layer 142 is weak, an adhesive layer may be provided between the base material 40 and the uneven structure layer 142 . The following layer may be a silane coupling agent or the like. As the silane coupling agent, one having an acryloyl group or a methacryloyl group can be used, for example, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be used.

＜1st electrode＞

The first electrode 92 may be a transmissive transparent electrode for transmitting light from the organic layer 94 formed thereon to the substrate 40 side. Furthermore, the first electrode 92 is preferably laminated so that the uneven pattern 80 formed on the surface of the uneven structure layer 142 is maintained on the surface of the first electrode 92 .

As a material of the first electrode 92, for example, indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO), gold, platinum, silver, and copper that are composites thereof can be used. Among these, ITO is preferable from the viewpoint of transparency and conductivity. The thickness of the first electrode 92 is preferably in the range of 20 to 500 nm. In addition, a structure in which substantially uninterrupted continuous conductive nanowires are randomly networked (meshed) or the like may be used as the first electrode 92 . In addition, any electrode material applicable to a transparent light-emitting element can also be used.

＜Organic layer＞

The organic layer 94 is formed on the first electrode 92 . The surface of the organic layer 94 can also maintain the concave-convex pattern 80 formed on the surface of the concave-convex structure layer 142 . Alternatively, the surface of the organic layer 94 may be flat without maintaining the concave-convex pattern 80 formed on the surface of the concave-convex structure layer 142 . When the surface of the organic layer 94 maintains the concave-convex pattern 80 formed on the surface of the concave-convex structure layer 142 , plasmon absorption by the second electrode 98 described below is reduced, and the light extraction efficiency is improved.

The organic layer 94 is not particularly limited as long as it is an organic layer that can be used in an organic EL element, and known organic layers can be appropriately used. The organic layer 94 may be a laminate of various organic thin films, for example, a laminate composed of a hole transport layer, a light emitting layer, and an electron transport layer. Here, examples of materials for the hole transport layer include phthalocyanine derivatives, naphtholcyanine derivatives, porphyrin derivatives, N,N'-bis(3-methylphenyl)-(1,1' -biphenyl)-4,4'-diamine (TPD) or 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl (α-NPD) and other aromatic diphenyl Amine compounds, oxazole, oxadiazole, triazole, imidazole, imidazolone, stilbene derivatives, pyrazoline derivatives, tetrahydroimidazole, polyaryl alkanes, butadiene, 4,4',4"-tri (N-(3-methylphenyl)N-phenylamino)triphenylamine (m-MTDATA), but not limited thereto. In order for the light-emitting layer to make holes injected from the first electrode 92 and holes injected from the first electrode 92 2 Electrons injected into the electrode 98 are recombined to emit light. As materials that can be used for the light-emitting layer, anthracene, naphthalene, pyrene, pyrene, corone, perylene, phthaloperylene, naphthalene, diphenylbutadiene, Tetraphenylbutadiene, coumarin, oxadiazole, bisbenzoxazoline, bistyryl, cyclopentadiene, aluminum hydroxyquinoline complex (Alq3) and other organometallic complexes, three -(p-triphenyl-4-yl)amine, 1-aryl-2,5-bis(2-thienyl)pyrrole derivatives, pyran, quinacridone, rubrene, stilbene derivatives , distyrylarene derivatives, distyrylamine derivatives and various fluorescent pigments, etc. Also, it is also preferable to use a suitable mixture of light-emitting materials selected from these compounds. Also, it is also preferable A material system that exhibits luminescence derived from a spin multiple state, such as a phosphorescent luminescent material that produces phosphorescent luminescence, and a compound having a site composed of these in a part of the molecule. Furthermore, the above-mentioned phosphorescent luminescent material is preferably In order to contain heavy metals such as iridium, the above-mentioned luminescent material can also be doped into the host material with high carrier mobility as a guest material, and the dipole-dipole interaction (Forster mechanism) and electron exchange interaction (Dexter mechanism) can be used. and emit light. Again, as the material of the electron transport layer, can enumerate: heterocyclic tetracarboxylic anhydrides such as nitro-substituted stilbene derivatives, diphenylbenzoquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, carbon di Imides, fenylene methane derivatives, anthraquinone dimethane and anthrone derivatives, oxadiazole derivatives, aluminum oxyquinoline complexes (Alq3) and other organometallic complexes, etc. It can also be used in Among the above-mentioned oxadiazole derivatives, thiadiazole derivatives in which the oxygen atom of the oxadiazole ring is replaced by a sulfur atom, and quinoxaline derivatives having a quinoxaline ring known as an electron-withdrawing group are used as electron transport materials. It is also possible to use polymer materials that incorporate these materials into polymer chains, or use these materials as the main chain of polymers. Furthermore, the hole transport layer or electron transport layer can also function as a light emitting layer.

Furthermore, from the viewpoint of facilitating electron injection from the second electrode 98, a metal fluoride such as lithium fluoride (LiF) or Li ₂ O ₃ may be provided between the organic layer 94 and the second electrode 98 or A layer composed of metal oxides, Ca, Ba, Cs and other highly active alkaline earth metals, organic insulating materials, etc. is used as the electron injection layer. Also, from the viewpoint of facilitating hole injection from the first electrode 92, a triazole derivative, an oxadiazole derivative, an imidazole derivative, Polyaryl alkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styryl anthracene derivatives Thinone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, or conductive polymer oligomers, especially thiophene oligomers, etc. as hole injection Floor.

Also, when the organic layer 94 is a laminated body composed of a hole transport layer, a light-emitting layer, and an electron transport layer, the thicknesses of the hole transport layer, the light-emitting layer, and the electron transport layer are preferably 1 The range of ˜200 nm, the range of 5-100 nm, and the range of 5-200 nm.

＜Second electrode＞

The second electrode 98 is formed on the organic layer 94 . A material having a relatively small work function can be appropriately used as the second electrode 98 without particular limitation. For example, it can be a metal electrode such as LiF, Al, Ag, MgAg, MgIn, AlLi or an electrode obtained by laminating them. In addition, the thickness of the second electrode 98 is preferably in the range of 5 to 25 nm. If the thickness of the second electrode 98 is less than the aforementioned lower limit, the resistance of the second electrode 98 tends to increase. When the thickness of the second electrode 98 exceeds the upper limit, the transparency of the light emitting element 100 tends to be impaired due to the low transmittance of the second electrode 98 . In addition, the surface of the second electrode 98 may maintain the concave-convex pattern 80 formed on the surface of the concave-convex structure layer 142 .

＜Sealing member＞

The sealing member 101 is provided facing the base material 40 , and a space (sealed space) 105 is formed between the sealing member 101 and the base material 40 . The first electrode 92 , the organic layer 94 , and the second electrode 98 are located in the sealed space 105 . The sealing member 101 can be fixed so as to face the base material 40 by the sealing adhesive layer 103 . The sealing adhesive layer 103 is located between the base material 40 and the sealing member 101 in the Z direction (the normal direction of the base material 40) of FIG. It may be provided so as to surround the organic layer 94 . Water or oxygen is prevented from penetrating into the sealed space 105 by the sealing member 101 and the sealing adhesive layer 103 . Thereby, deterioration of the organic layer 94 etc. is suppressed, and the lifetime of the light emitting element 100 is improved. In addition, in order to efficiently extract light emitted from the organic layer 94 , it is preferable that the sealing adhesive layer 103 is not in contact with the organic layer 94 and that the sealing adhesive layer 103 is formed with a predetermined distance from the organic layer 94 . The above-mentioned specific interval is preferably, for example, 1 μm or more.

The material of the sealing member 101 may be a material with high gas barrier properties. For example, a known gas barrier film used in packaging materials, such as a plastic film deposited with silicon oxide or aluminum oxide, a ceramic layer, and an impact film can be used. Relaxed polymer layer laminates, metal foils laminated with polymer films, glass or metal airtight cans, etched glass, etc.

As the material of the sealing adhesive layer 103, any adhesive that is usually used for glass, plastic substrates, etc. can be used without limitation, for example, polyvinyl acetate adhesives, acrylic oligomers, methyl Light-curing and thermosetting acrylic adhesives with reactive vinyl groups such as acrylic oligomers, epoxy resin adhesives, moisture-curing adhesives such as 2-cyanoacrylate, etc., vinyl copolymers adhesives, polyester adhesives, polyimide adhesives, amino resin adhesives made of urea resin or melamine resin, phenol resin adhesives, polyurethane adhesives, reactive (methanol) base) acrylic adhesives, rubber adhesives, etc.

The sealed space 105 may also be filled with an inert gas or the like. As an inert gas, in addition to nitrogen (N ₂ ), rare gases such as helium (He) and argon (Ar) can be preferably used, and rare gases mixed with helium and argon are also preferred. The ratio of the active gas to the gas is preferably 90-100% by volume. In addition, the sealed space 105 may be filled with fillers such as solid or liquid resin, glass, fluorine-based inert oil, or gel material. These fillers are preferably transparent or cloudy. Furthermore, a water-absorbing substance may also be disposed in the sealed space 105 . For example, barium oxide or the like can be used as the water-absorbing substance. Specifically, for example, a high-purity barium oxide powder manufactured by Aldrich can be attached to the sealing member 101 by using a fluororesin-based semi-permeable membrane (Microtex S-NTF8031Q manufactured by Nitto Denko) with an adhesive agent. in the sealed space 105. In addition, a water-absorbent material commercially available from Japan Gore-Tex Co., Ltd., Futaba Electronics Co., Ltd., etc. can also be preferably used.

The light-emitting element 100 of this embodiment includes the concavo-convex structure layer 142 functioning as a diffraction grating, so the light extraction efficiency is high, so the luminous efficiency is high. Furthermore, since the uneven pattern 80 of the uneven structure layer 142 has an average pitch of the unevenness in the range of 150 to 650 nm, the haze value of the diffraction grating substrate 140 composed of the uneven structure layer 142 and the substrate 40 is 2.0% or less. Since the light-emitting element 100 uses the diffraction grating substrate 140 with such a small haze value, it has high transparency and is transparent. That is, the light emitting element 100 of this embodiment is a transparent light emitting element and has high luminous efficiency.

Furthermore, like the light-emitting element 100a shown in FIG. ) to set the optical function layer 142a. The optical function layer 142a may be a layer having a fine concave-convex pattern 80a formed on the surface. In this case, similar to the concave-convex pattern 80 of the above-mentioned concave-convex structure layer 142, the concave-convex pattern 80a of the optical function layer 142a may have a structure having the function of diffracting light, and the average pitch of the concave-convex is preferably in the range of 150 to 650 nm. . In addition, the optical functional layer 142a that can be used to extract the light of the light-emitting element without damaging the penetrability of the light-emitting element 100a can be used without any particular limitation. Any optical member with a structure that extracts light to the outside of the element by reflection or the like. As such members, for example, various lens members such as convex lenses, concave lenses, Fresnel lenses, prism lenses, cylindrical lenses, lenticular lenses, microlenses composed of fine concavo-convex layers, etc. Radiation gratings, components with anti-reflection functions, etc. Among these, a lens member is preferable at the point that light can be extracted more efficiently. Moreover, a plurality of lens members may be used as such a lens member, and in this case, a so-called microlens (array) may be formed by arranging fine lens members. A commercially available item can also be used as the optical function layer 142a. By disposing the optical function layer 142a, the total reflection of the light passing through the substrate 40 at the interface between the substrate 40 (including the optical function layer) and the air can be suppressed, thereby improving the light extraction efficiency.

The configuration of the first electrode 92, the organic layer 94, and the second electrode 98 is not limited to the configuration described above, and may be any configuration that can be used for a transparent light-emitting element. Also, the first electrode 92, the organic layer 94, and the second electrode 98 may be sealed by covering them with a sealant instead of sealing the first electrode 92, the organic layer 94, and the second electrode 98 by forming the sealed space 105 with the sealing member 101 and the sealing adhesive 103 as described above. The first electrode 92, the organic layer 94, and the second electrode 98 are sealed. Also, any sealing method can be used without any particular limitation as long as it is a sealing method that does not impair the penetrating properties of the light emitting elements 100 and 100a.

[Manufacturing method of light-emitting element]

Next, a method of manufacturing the light-emitting elements 100 and 100a described above will be described with reference to FIGS. 1( a ) and ( b ). The manufacturing method of the light-emitting element 100 shown in Fig. 1 (a) roughly comprises the following steps: the step of forming the concavo-convex structure layer 142 on the substrate 40; the step of forming the first electrode 92; the step of forming the organic layer 94; the step of electrode 98; and the step of sealing organic layer 94. The manufacturing method of the light-emitting element 100a shown in FIG. 1( b ) further includes the step of disposing the optical function layer 142a on the substrate 40 in addition to each step of the manufacturing method of the light-emitting element 100 . Hereinafter, each step will be described in order. Furthermore, in the following description, the case where the concavo-convex structure layer 142 is formed by a sol-gel method is taken as an example for description.

＜Formation of concavo-convex structure layer＞

First, the concave-convex structure layer 142 is formed on the substrate 40 . The concavo-convex structure layer 142 can be formed, for example, by a method as described below.

In the case of forming the concave-convex structure layer 142 made of an inorganic material, a solution of a precursor of the inorganic material is prepared. When the sol-gel method is used to form the concave-convex structure layer 142 made of an inorganic material, a metal alkoxide is prepared as a precursor. For example, when forming the concavo-convex structure layer 142 made of silicon dioxide, as the precursor of silicon dioxide, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetraisopropoxy Tetraalkane represented by tetraalkoxysilane such as tetra-n-propoxysilane, tetra-n-propoxysilane, tetra-isobutoxysilane, tetra-n-butoxysilane, tetra-second butoxysilane, tetra-tert-butoxysilane, etc. Oxide monomer, or methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane ( MTES), Ethyltriethoxysilane, Propyltriethoxysilane, Isopropyltriethoxysilane, Phenyltriethoxysilane, Methyltriethoxysilane, Ethyltripropoxysilane Silane, Propyltripropoxysilane, Isopropyltripropoxysilane, Phenyltripropoxysilane, Methyltriisopropoxysilane, Ethyltriisopropoxysilane, Propyltriisopropyl Trialkoxysilane, isopropyltriisopropoxysilane, phenyltriisopropoxysilane, tolyltriethoxysilane and other trialkoxysilane monomers represented by trialkoxysilane; dimethyl Dimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldi- Isobutoxysilane, Dimethyldi-Second-Butoxysilane, Dimethyldi-Tertibutoxysilane, Diethyldimethoxysilane, Diethyldiethoxysilane, Diethyl dipropoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldi-isobutoxysilane, diethyldi-second-butoxysilane , Diethyldi-tertiary butoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipropoxysilane, dipropyldiisopropoxysilane, Dipropyl bis-n-butoxysilane, dipropyl bis-isobutoxysilane, dipropyl bis-second butoxysilane, dipropyl bis-tertiary butoxysilane, diisopropyl Dimethoxysilane, diisopropyldiethoxysilane, diisopropyldipropoxysilane, diisopropyldiisopropoxysilane, diisopropyldi-n-butoxysilane, Isopropyl bis-isobutoxysilane, diisopropyl bis-second butoxysilane, diisopropyl bis-tertiary butoxysilane, diphenyl dimethoxysilane, diphenyl bis Ethoxysilane, diphenyldipropoxysilane, diphenyldiisopropoxysilane, diphenylbis-n-butoxysilane, diphenylbis-isobutoxysilane, diphenylbis - Dialkoxysilane monomers such as 2-butoxysilane, diphenylbis-3-butoxysilane and other dialkoxysilanes. Furthermore, an alkyltrialkoxysilane or a dialkyldialkoxysilane whose carbon number of an alkyl group is C4-C18 can also be used. Vinyltrimethoxysilane, vinyltriethoxysilane and other vinyl monomers can also be used; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxy 3-Glycidoxypropylmethyldimethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropylmethyldiethoxysilane, 3-Glycidoxypropyltriethyl Monomers with epoxy groups such as oxysilane; monomers with styryl groups such as p-styryltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methyl Acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. have methacrylic Acrylic monomers; 3-acryloyloxypropyltrimethoxysilane and other acryloyl monomers; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxy Monomers with amino groups such as silyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, etc.; 3-ureidopropyl 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and other monomers with mercapto groups; bis(triethoxysilane 3-isocyanatopropyltriethoxysilane and other monomers with isocyanate groups; polymers obtained by polymerizing a small amount of these monomers; Metal alkoxides such as functional groups introduced into part of the above-mentioned materials or composite materials of polymers. Moreover, some or all of the alkyl groups or phenyl groups of these compounds may be substituted with fluorine. Furthermore, examples thereof include metal acetylacetonate, metal carboxylate, oxychloride, chloride, or a mixture thereof, but are not limited thereto. Examples of the metal species include Ti, Sn, Al, Zn, Zr, In, etc., or mixtures thereof other than Si, but are not limited thereto. It is also possible to use those obtained by appropriately mixing the precursors of the aforementioned metal oxides. Furthermore, as a precursor of silica, a silane coupling agent having an affinity with silica, a reactive hydrolyzing group, and a water-repellent organic functional group in the molecule can be used. Examples include: silane monomers such as n-octyltriethoxysilane, methyltriethoxysilane, and methyltrimethoxysilane; vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, Vinyl silanes such as (2-methoxyethoxy)silane, vinylmethyldimethoxysilane; 3-methacryloxypropyltriethoxysilane, 3-methacryloxy Propyltrimethoxysilane and other methacryloylsilanes; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidol Oxypropyl triethoxysilane and other epoxy silanes; Sulfur silane such as oxysilane; 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxy Silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane and other aminosilanes; make the Polymers such as monomers polymerized. In addition, a mesoporous concave-convex structure layer can also be formed by adding a surfactant to these materials.

When using a mixture of TEOS and MTES as the precursor of the inorganic material, the mixing ratio can be set to 1:1 in terms of molar ratio. The precursor generates amorphous silicon dioxide through hydrolysis and polycondensation reactions. In order to adjust the pH of the solution as a synthesis condition, an acid such as hydrochloric acid or a base such as ammonia is added. The pH value is preferably 4 or less or 10 or more. Moreover, water may be added for hydrolysis. The amount of water to be added may be 1.5 times or more in molar ratio with respect to the metal alkoxide species.

As the solvent of the precursor solution used in the sol-gel method, for example, alcohols such as methanol, ethanol, isopropyl alcohol (IPA), butanol; hexane, heptane, octane, decane, cyclo Aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ethers such as diethyl ether, tetrahydrofuran, and dioxane; acetone, methyl ethyl ketone, and isophorone , cyclohexanone and other ketones; butoxyethyl ether, hexyloxyethyl alcohol, methoxy-2-propanol, benzyloxyethanol and other ether alcohols; ethylene glycol, propylene glycol and other glycols, ethylene glycol Glycol ethers such as alcohol dimethyl ether, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether acetate; esters such as ethyl acetate, ethyl lactate, and γ-butyrolactone; phenols such as phenol and chlorophenol ; Amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone; Chloroform, dichloromethane, tetrachloroethane, monochlorobenzene, dichlorobenzene Halogen-based solvents such as carbon disulfide; heteroatom-containing compounds such as carbon disulfide; water; and mixed solvents of these. In particular, ethanol and isopropanol are preferable, and those mixed with water are also preferable.

As an additive to the precursor solution used in the sol-gel method, polyethylene glycol, polyethylene oxide, hydroxypropyl cellulose, polyvinyl alcohol for adjusting viscosity, or polyvinyl alcohol as a solution stabilizer can be used. Alkanolamines such as triethanolamine, β-diketones such as acetylacetone, β-ketoesters, formamide, dimethylformamide, dioxane, etc. Also, as an additive to the precursor solution, a material that generates an acid or a base by irradiating light such as energy rays typified by ultraviolet light such as excimer UV light can be used. By adding such a material, it becomes possible to gel (harden) the precursor solution by irradiating light to form an inorganic material.

Moreover, polysilazane can also be used as a precursor of an inorganic material. Polysilazane is oxidized by heating or irradiating energy rays such as excimers to perform ceramization (silicon dioxide modification) to form silicon dioxide, SiN, or SiON. Furthermore, the so-called "polysilazane" is a polymer having a silicon-nitrogen bond, and is composed of SiO ₂ , Si ₃ N ₄ and intermediates composed of Si-N, Si-H, N-H, etc. Solid solution SiO _{X NY} and other ceramic precursor inorganic polymers. More preferably, it is a compound described in JP-A-8-112879 that is represented by the following general formula (1) and is modified into silica or the like by ceramization at a relatively low temperature.

General formula (1):

－Si(R1)(R2)－N(R3)－

In the formula, R1, R2, and R3 respectively represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.

Among the compounds represented by the above general formula (1), perhydropolysilazane (also referred to as PHPS) in which all of R1, R2, and R3 are hydrogen atoms, or a part of the hydrogen moiety bonded to Si is particularly preferred. An organopolysilazane substituted with an alkyl group or the like.

As other examples of polysilazanes that are ceramicized at low temperatures, silicon alkoxide-added polysilazanes obtained by reacting polysilazanes with silicon alkoxides (for example, JP-A 5- 238827), polysilazane obtained by reacting polysilazane with dehydrated glycerin (for example, Japanese Patent Application Laid-Open No. 6-122852), polysilazane and alcohol The alcohol-added polysilazane obtained (for example, Japanese Patent Application Laid-Open No. 6-240208), the metal carboxylate-added polysilazane obtained by reacting polysilazane with a metal carboxylate (for example, , Japanese Patent Laid-Open Publication No. 6-299118), acetylacetonate complex-added polysilazane obtained by reacting polysilazane with metal-containing acetylacetonate complex (for example, JP KOKAI Publication No. 6-306329), metal microparticle-added polysilazane obtained by adding metal microparticles to polysilazane (for example, JP-A-7-196986), and the like.

As a solvent for the polysilazane solution, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, ethers such as aliphatic ethers, and alicyclic ethers can be used. In order to promote modification to a silicon oxide compound, an amine or metal catalyst may be added.

In the case of using polysilazane as the precursor of the inorganic material, the precursor solution can be hardened by heating or irradiation of energy rays such as excimers to form the inorganic material.

The precursor solution of the inorganic material prepared as above is coated on the substrate. In order to improve adhesion, for example, a surface treatment layer or an easy-adhesive layer can be provided on the substrate, and in order to prevent the infiltration of moisture or oxygen, for example, a gas barrier layer can also be provided on the substrate. As the coating method of the precursor solution, any coating method such as a bar coating method, a spin coating method, a spray coating method, a dip coating method, a die coating method, and an inkjet method can be used. In terms of uniformly coating the precursor solution on a large-area substrate and quickly completing the coating before the precursor solution hardens, bar coating, die coating and spin coating are preferred. Law.

After coating the precursor solution, the substrate may be kept in the atmosphere or under reduced pressure in order to evaporate the solvent in the coating film (precursor film). If the holding time is short, the viscosity of the coating film becomes too low, and the concave-convex pattern cannot be transferred to the coating film. If the holding time is too long, the polymerization reaction of the precursor proceeds, and the viscosity of the coating film becomes too high. High, it becomes impossible to transfer the concave-convex pattern to the coating film. In addition, after coating the precursor solution, the hardening of the coating film progresses with the evaporation of the solvent, and the physical properties such as the viscosity of the coating film also change in a short time. From the viewpoint of the stability of the concave-convex pattern formation, it is desirable that the drying time range in which the pattern transfer can be carried out well is sufficiently wide, which can be determined according to the drying temperature (holding temperature), drying pressure, the material type of the precursor, and the type of the precursor. The mixing ratio of the types of materials, the amount of solvent used in the preparation of the precursor solution (concentration of the precursor) and the like are adjusted. Furthermore, as long as the substrate is directly held, the solvent in the coating film (precursor film) evaporates, so it is not necessarily necessary to perform active drying operations such as heating or blowing air, as long as the substrate on which the coating film is formed is left for a specific period of time, Alternatively, it may be carried out within a specific time period in order to carry out subsequent steps.

Next, a concave-convex pattern was formed on the coating film using a mold for transferring the concave-convex pattern.

A film mold (sheet mold) or metal mold as described below can be used as the mold for transferring the concave-convex pattern, and it is preferable to use a flexible or flexible film mold.

The size, especially the length, of the film mold can be appropriately set according to the size of the light-emitting element to be manufactured or the number of light-emitting elements to be continuously manufactured in one manufacturing process (number of batches). For example, a long mold having a length of 10 m or more may be produced, and the film mold wound on a roll may be continuously transferred to a plurality of substrates while being continuously unwound from the roll. The film mold can have a width of 50 to 3000 mm and a thickness of 1 to 500 μm. Between the base material and the unevenness forming material, surface treatment or easy-adhesion treatment may be given in order to improve the adhesiveness. In addition, if necessary, a mold release process may be performed on the uneven pattern surface. The concavo-convex pattern can be formed into any shape by any method. The concave-convex pattern of the film mold can be made into: lens structure or structure with functions of light diffusion or diffraction; stripe structure composed of points or lines and gaps; cylindrical, conical, truncated conical, triangular columnar, triangular Cone, triangular truncated pyramid, quadrangular columnar, quadrangular pyramidal, quadrangular truncated pyramidal, polygonal columnar, polygonal pyramidal, polygonal truncated pyramid and other pillar structures; or any pattern such as hole structure. Among them, an irregular concave-convex pattern in which the pitch of the concave-convex is not uniform and the orientation of the concave-convex is non-directional is ideal. The average pitch of the unevenness is preferably in the range of 150 to 650 nm, more preferably in the range of 150 to 300 nm. The average value of the depth distribution of unevenness is preferably in the range of 20 to 200 nm, more preferably in the range of 30 to 150 nm. The standard deviation of the unevenness depth is preferably in the range of 10 to 100 nm, more preferably in the range of 15 to 75 nm. The light diffracted from such a concavo-convex pattern is not a single or narrow-band wavelength light, but has a relatively wide wavelength band, and the diffracted light has no directivity and is oriented in all directions.

When using a film-shaped mold as a mold for transferring a concavo-convex pattern, the mold may be pressed against the precursor film using a pressure roller. Compared with the pressurized type, in the roll manufacturing process using the pressure roller, it has the following advantages: because the contact time between the mold and the coating film is shorter, it can prevent the mold or the substrate and the platform for setting the substrate, etc. The pattern deformation caused by the difference in the thermal expansion coefficient of the precursor film can prevent bubbles or residual gas marks in the pattern due to the bumping of the solvent in the precursor film; due to the line contact with the substrate (coating film), the transfer can be made The printing pressure and peeling force are reduced, and it is easy to deal with large areas; no air bubbles will be trapped during pressing. In addition, the substrate may be heated while being pressed against the mold. As an example of pressing the mold against the coating film (precursor film) using a pressure roller, as shown in FIG. , whereby the concavo-convex pattern of the film mold 50 can be transferred to the coating film 42 on the substrate 40 . That is, when the film mold 50 is pressed against the coating film 42 by the pressing roller 122, the film mold 50 and the substrate 40 are conveyed synchronously, and the surface of the coating film 42 on the substrate 40 is covered with the film mold 50. . At this time, the pressing roller 122 is pressed against the back surface of the film mold 50 (the surface opposite to the surface on which the concave-convex pattern is formed) and rotated, whereby the film mold 50 and the substrate 40 are brought into close contact with each other while advancing. Furthermore, when feeding the elongated film mold 50 toward the pressing roller 122 , it is more advantageous to directly unwind the film mold 50 from the film take-up roller on which the elongated film mold 50 is wound.

The precursor film may also be pre-fired after the precursor film is pressed against the mold. By performing pre-firing, the precursor is converted into an inorganic material to harden the coating film, thereby curing the concave-convex pattern, and the pattern becomes difficult to deform when peeled off. When performing calcination, it is preferable to heat at the temperature of room temperature - 300 degreeC in air|atmosphere. Furthermore, pre-firing does not necessarily have to be performed. In addition, when a material that generates an acid or a base by irradiation of light such as ultraviolet rays is added to the precursor solution, energy rays such as ultraviolet rays such as excimer UV light may be irradiated instead of pre-conditioning the precursor film. Baking hardens the coating film.

After pressing the mold or pre-firing the precursor film, the mold is peeled off from the coating film (precursor film or inorganic material film formed by converting the precursor film). A known peeling method can be used as the peeling method of the mold. The mold can also be peeled off while heating the coating film, thereby preventing the gas generated from the coating film from escaping and generating air bubbles in the film. In the case of using a roll process, the peeling force can be reduced compared to a press-type plate-shaped mold, and the mold can be easily peeled off from the coating film without remaining a coating film on the mold. In particular, since the pressing is carried out while heating the coating film, the reaction proceeds easily, and the mold is easily peeled off from the coating film immediately after pressing. Furthermore, in order to improve the releasability of a mold, you may use a peeling roll. As shown in FIG. 4 , the peeling roller 123 is arranged on the downstream side of the pressing roller 122, and the film-shaped mold 50 is rotated and supported by the peeling roller 123 while applying force to the coating film 42, whereby the coating film 42 can be removed. The state where the film mold 50 is adhered is maintained only for the distance between the pressing roller 122 and the peeling roller 123 (for a certain period of time). Then, on the downstream side of the peeling roller 123, the film-shaped mold 50 is pulled up to the upper side of the peeling roller 123. The route of the film-shaped mold 50 is changed, whereby the film-shaped mold 50 is formed from the coating film ( Concave-convex structure layer) 142 is peeled off. In addition, the above-mentioned pre-firing or heating of the coating film 42 may be performed while the film mold 50 is attached to the coating film 42 . Furthermore, when using the peeling roller 123, peeling of the mold 50 can be made easier by peeling, for example, heating from room temperature to 300 degreeC.

The uneven structure layer 142 may be fully cured after the mold 50 is peeled off from the uneven coating film (uneven structure layer) 142 . In this manufacturing method, the concavo-convex structure layer 142 can be formally hardened by main firing. In the case of using a precursor converted into silica by a sol-gel method, the hydroxyl group contained in the silica (amorphous silica) constituting the concave-convex structure layer is detached by main firing, thereby The concavo-convex structure layer 142 becomes stronger. The main firing can be carried out at a temperature of 200-1200° C. for about 5 minutes to 6 hours. At this time, when the concavo-convex structure layer 142 is made of silicon dioxide, it becomes amorphous or crystalline, or a mixed state of amorphous and crystalline depending on the firing temperature and firing time. Furthermore, formal hardening does not necessarily have to take place. In addition, when a material that generates acid or alkali by irradiation of ultraviolet light or other light is added to the precursor solution, the concave-convex structure layer 142 can be fired instead of being fired by irradiating energy rays such as excimer UV light such as ultraviolet light. , so that the concavo-convex structure layer 142 is formally hardened.

An example of a method of manufacturing a mold for transferring a concavo-convex pattern will be described. First, a master pattern for forming the concavo-convex pattern of the mold is produced. For example, the concavo-convex pattern of the master mold is preferably the method of using the self-assembly (microphase separation) of block copolymers (hereinafter, appropriately referred to as "BCP (BlockCopolymer)) described in WO2012/096368 of the applicant. Thermal annealing method"), or the self-assembly method of block copolymers in a solvent environment described in WO2013/161454 (hereinafter, appropriately referred to as "BCP solvent annealing method"), or the method disclosed in WO2011/007878A1 by It is formed by a method of heating and cooling a vapor-deposited film on a polymer film to form unevenness from wrinkles on the polymer surface (hereinafter, appropriately referred to as "BKL (Buckling) method"). The concave-convex pattern can also be formed by using the photolithography method instead of the BCP thermal annealing method, the BKL method and the BCP solvent annealing method. In addition, for example, microfabrication methods such as cutting processing, electron beam direct mapping, particle beam processing, and manipulation probe processing, microfabrication using self-assembly of fine particles, or sandblasting can also be used. and so on to make the concave-convex pattern of the master mold. When using the BCP thermal annealing method and the BCP solvent annealing method to form a pattern, the material for forming the pattern can use any material, but it is preferably selected from styrene-based polymers such as polystyrene, such as polymethacrylic acid. A block composed of a combination of two types from the group consisting of polyalkylmethacrylate of methyl ester, polyethylene oxide, polybutadiene, polyisoprene, polyvinylpyridine, and polylactic acid copolymer. In addition, the uneven pattern obtained by solvent annealing can also be etched by irradiating energy rays represented by ultraviolet rays such as excimer UV light, or by dry etching such as RIE (reactive ion etching) or ICP etching. Etching is carried out by the type etching method. Moreover, you may heat-process the above-mentioned etched uneven|corrugated pattern.

After the patterned master is formed by the BCP thermal annealing method, the BKL method, or the BCP solvent annealing method, a mold on which the concave-convex pattern of the master mold is transferred can be formed by electroforming or the like in the following manner. Firstly, a seed layer for electroforming to be a conductive layer can be formed on a master mold with a concave-convex pattern by electroless plating, sputtering or evaporation. The seed layer is preferably 10 nm or more in order to make the current density uniform in the subsequent electroforming step and to make the thickness of the metal layer deposited by the subsequent electroforming step constant. As the material of the seed layer, nickel, copper, gold, silver, platinum, titanium, cobalt, tin, zinc, chromium, gold-cobalt alloy, gold-nickel alloy, boron-nickel alloy, solder, copper-nickel alloy, etc. can be used, for example. - Chromium alloys, tin-nickel alloys, nickel-palladium alloys, nickel-cobalt-phosphorus alloys, or alloys thereof, etc. Next, a metal layer is deposited on the seed layer by electroforming (electrolytic plating). The thickness of the metal layer can be set to a thickness of 10 to 30000 μm in the whole including the thickness of the seed layer, for example. As the material of the metal layer deposited by electroforming, any one of the above-mentioned kinds of metals that can be used as the seed layer can be used. The formed metal layer preferably has appropriate hardness and thickness in terms of ease of handling such as pressing, peeling, and cleaning of the resin layer formed by the subsequent mold.

The metal layer including the seed layer obtained as described above was peeled off from the master mold having a concave-convex pattern to obtain a metal substrate. As for the peeling method, physical peeling may be used, and peeling may be performed by dissolving and removing the material for forming the concave-convex pattern of the master mold using an organic solvent, acid, alkali, or the like. When peeling the metal substrate from the master mold, remaining material components can be removed by washing. As a cleaning method, wet cleaning using a surfactant or the like, or dry cleaning using ultraviolet rays or plasma can be used. In addition, for example, an adhesive or an adhesive may be used to attach and remove remaining material components. The metal substrate (metal mold) on which the pattern has been transferred from the master mold obtained in the above manner can be used as a mold for transferring a concave-convex pattern.

Furthermore, by using the obtained metal substrate, the concavo-convex structure (pattern) of the metal substrate is transferred to a film-form support substrate, whereby a flexible mold like a film-form mold can be produced. For example, after applying a curable resin to a support substrate, the uneven structure of the metal substrate is pressed against the resin layer to harden the resin layer. As the supporting substrate, for example, substrates made of inorganic materials such as glass, quartz, and silicon; , polycarbonate (PC), cycloolefin polymer (COP), polymethyl methacrylate (PMMA), polystyrene (PS), polyimide (PI), polyarylate and other organic materials material, nickel, copper, aluminum and other metal materials. In addition, the thickness of the supporting substrate can be set in the range of 1 to 500 μm.

As the curable resin, resins such as photocurable and thermally curable, moisture curable, chemically curable (two-liquid mixture) and the like can be used, for example. Specifically, for example, epoxy-based, acrylic-based, methacrylic-based, vinyl ether-based, oxetane-based, urethane-based, melamine-based, urea-based, polyester-based, polyolefin-based, phenol-based Various resins such as monomers, oligomers, polymers, etc. The thickness of the curable resin is preferably within a range of 0.5 to 500 μm. If the thickness is less than the above-mentioned lower limit, the height of the unevenness formed on the surface of the cured resin layer is likely to become insufficient, and if the thickness exceeds the above-mentioned upper limit, there is a possibility that the influence of the volume change of the resin that occurs during curing may be reduced. If it is too large, it becomes impossible to form the concave-convex shape well.

As the method of coating the curable resin, for example, spin coating method, spray coating method, dip coating method, drop method, gravure printing method, screen printing method, letterpress printing method, die coating method, curtain coating method, etc. Various coating methods such as coating method, inkjet method, sputtering method, etc. Furthermore, the conditions for curing the curable resin vary depending on the type of resin used, for example, the curing temperature is preferably in the range of room temperature to 250° C., and the curing time is in the range of 0.5 minutes to 3 hours. Also, a method of curing the curable resin by irradiating energy rays such as ultraviolet rays or electron beams may be used. In this case, the irradiation dose is preferably in the range of 20 mJ/cm ² to 10 J/cm ² .

Next, the metal substrate is detached from the cured cured resin layer. The method for detaching the metal substrate is not limited to the mechanical peeling method, and known methods can be used. The film-shaped resin mold having a cured resin layer formed with concavities and convexities on a support substrate obtained in the above manner can be used as a mold for transferring concavo-convex patterns.

In addition, a rubber-based resin material is applied to the concave-convex structure (pattern) of the metal substrate obtained by the above method, and the applied resin material is cured and peeled off from the metal substrate, whereby a transferred metal substrate can be produced. rubber mold with embossed pattern. The obtained rubber mold can be used as a mold for transferring a concavo-convex pattern. Natural rubber and synthetic rubber can be used as the rubber-based resin material, especially silicone rubber, or a mixture or copolymer of silicone rubber and other materials. As the silicone rubber, for example, polyorganosiloxane, cross-linked polyorganosiloxane, polyorganosiloxane/polycarbonate copolymer, polyorganosiloxane/polyphenylene copolymer, polyorganosiloxane Oxane/polystyrene copolymer, polytrimethylsilylpropyne, polytetramethylpentene, etc. Compared with other resin materials, silicone rubber is inexpensive, has excellent heat resistance, high thermal conductivity, is elastic, and is difficult to deform even under high temperature conditions. better. Furthermore, since silicone rubber-based materials have high gas or water vapor permeability, they can easily pass through the transfer material's solvent or water vapor. Therefore, when a rubber mold is used to transfer a concave-convex pattern to a film of a resin material or a precursor solution of an inorganic material, a silicone rubber-based material is preferable. In addition, the surface free energy of the rubber-based material is preferably 25 mN/m or less. Thereby, when transferring the uneven|corrugated pattern of a rubber mold to the coating film on a base material, the releasability becomes favorable, and transfer failure can be prevented. The rubber mold can be, for example, a length of 50 to 1000 mm, a width of 50 to 3000 mm, and a thickness of 1 to 50 mm. In addition, if necessary, a release treatment may be performed on the uneven pattern surface of the rubber mold.

<Formation of the first electrode>

After the concave-convex structure layer 142 is formed on the base material 40 as described above, in order to remove foreign matter etc. adhering to the base material 40 and the concave-convex structure layer 142, it is cleaned with a brush, followed by alkaline cleaning using an aqueous solvent. Agents and organic solvents to remove organic matter, etc. Then, as shown in FIG. laminated. In this manner, the first electrode 92 having a concavo-convex pattern is formed. As a method of laminating the first electrode 92 , known methods such as vapor deposition, sputtering, and spin coating can be suitably used. Among these methods, the sputtering method is preferable from the viewpoint of improving the adhesion. Furthermore, there are cases where the substrate 40 and the uneven structure layer 142 are placed at a high temperature of about 300° C. during sputtering. Apply a photoresist on the formed first electrode, expose it with a mask pattern for the first electrode, develop it with a developer, and then etch the first electrode with an etchant to obtain a specific pattern The first electrode 92. It is preferable to clean the obtained first electrode 92 with a brush, remove organic substances and the like with an alkaline detergent using an aqueous solvent and an organic solvent, and then perform UV ozone treatment.

＜Formation of organic layer＞

Next, an organic layer 94 is laminated on the first electrode 92 . As a method for laminating the organic layer 94 , known methods such as vapor deposition, sputtering, spin coating, and die coating can be suitably used. The patterning of the organic layer 94 can be performed using a known patterning method such as forming a film by disposing a mask of a specific shape on a base material.

<Formation of the second electrode>

Next, a second electrode (metal electrode) 98 is laminated on the organic layer 94 . The metal electrode 98 can be laminated by known methods such as vapor deposition and sputtering. The patterning of the metal electrode 98 can be performed using a known patterning method such as forming a film by disposing a mask of a specific shape on a base material.

＜Sealing＞

Furthermore, as shown in FIG.1(a), (b), the sealing member 101 is attached, and the organic layer 94 is sealed. When producing such a sealing structure, first, the adhesive layer 103 is formed on the surface of the substrate 40 on which the uneven structure layer 142 is disposed so as to surround the organic layer 94 . The adhesive layer 103 can be formed at a desired position by applying the adhesive using a scannable dispenser and/or a movable stage. In addition, the adhesive layer 103 can be formed with a desired line width by controlling the scanning speed and discharge amount of the dispenser. Next, the sealing member 101 is disposed on the concave-convex structure layer 142, the first electrode 92, the organic layer 94, and the metal electrode 98 so as to face the substrate 40, and is bonded to the substrate 40 through the adhesive layer 103, thereby The space 105 between the base material 40 and the sealing member 101 is sealed. When the adhesive layer 103 is formed of a material cured by energy ray irradiation, the adhesive layer 103 is irradiated with energy rays after sealing to harden the adhesive layer 103 . For example, in the case of a photocurable adhesive, the visible region of light is irradiated from the sealing member 101 side or the substrate 40 side from the ultraviolet region obtained by a high-pressure mercury lamp or a halogen lamp, thereby making the adhesive layer 103 Hardened. Moreover, when the adhesive agent layer 103 is thermosetting, it can harden by heating the adhesive agent layer 103 in the range of 50-150 degreeC, for example. Thereby, the base material 40 and the sealing member 101 are integrated, and the organic layer 94 is disposed in the sealed space 105 .

Furthermore, after the organic layer 94 is formed, it is preferable not to expose it to the atmosphere, but to seal it under, for example, a nitrogen atmosphere (for example, use a glove box replaced with high-purity nitrogen with a purity of 99.999% or higher). In addition, in the sealing step, although in the above description, the sealing member 101 is provided after the adhesive layer 103 is formed on the base material 40, it may be placed between the base material 40 and the base material 40 so as to face the base material 40. After the sealing member 101 is provided in the space, an adhesive is injected into the space to form the adhesive layer 103 .

The light-emitting element 100 shown in FIG. 1( a ) is produced by the above-mentioned production method.

＜Arrangement of Optical Functional Layer＞

Furthermore, as shown in FIG. 1( b ), an optical function layer may be disposed on the surface of the substrate 40 opposite to the surface on which the concave-convex structure layer 142 is formed (the surface that becomes the light extraction surface after the formation of the light-emitting element). 142a.

The optical function layer 142a can be directly formed on the substrate 40 by the same method as the concave-convex structure layer 142 . Alternatively, the optical function layer 142a can also be formed on a base material different from the base material 40 by the same method as the concave-convex structure layer 142, and installed on the base material 40 through an adhesive layer and/or an adhesive layer.

As the material of the adhesive layer and/or the adhesive layer, well-known materials capable of bonding the optical function layer 142a on the substrate 40 can be suitably applied, for example, acrylic adhesives, ethylene-vinyl acetate copolymers, natural Rubber-based adhesives, polyisobutylene, butyl rubber, styrene-butylene-styrene copolymer, styrene-isobutylene-styrene block copolymer, etc. synthetic rubber-based adhesives, polyurethane-based adhesives, polyester-based adhesives As an alternative, commercially available products (UV curable optical adhesives NOA60, NOA61, NOA71, NOA72, NOA81 manufactured by Norland Corporation, UV-3400 manufactured by Toagosei) can also be used. Among them, from the viewpoint that the adhesive layer and/or the adhesive layer do not affect the optical path of light emitted from the base material 40, it is preferable to use a material having a refractive index equal to that of the base material 40. Adhesives or adhesives. The method of applying such an adhesive and adhesive is not particularly limited, and known methods can be appropriately used. Furthermore, the adhesive and the bonding agent can also be coated on any one of the base material 40 and the optical function layer 142a.

Furthermore, the disposition of the optical function layer 142a can be implemented before the formation of the concave-convex structure layer 142, or after the formation of the concave-convex structure layer 142, or after the sealing step, and the order of these steps is not particularly limited.

By the above method, the light emitting element 100a including the optical function layer 142a as shown in FIG. 1( b ) is formed.

Furthermore, as precursors of inorganic materials for forming the uneven structure layer 142, precursors such as TiO ₂ , ZnO, ZnS, ZrO ₂ , Al ₂ O ₃ , BaTiO ₃ , SrTiO ₂ , and ITO may be used instead of the above two. Precursor of silicon oxide.

In addition to the sol-gel method, the concave-convex structure layer 142 may be formed using a method using a dispersion liquid of fine particles of an inorganic material, a liquid phase deposition method (LPD: Liquid Phase Deposition), or the like.

In the case of forming the concave-convex structure layer 142 using curable resin, for example, after coating the curable resin on the substrate, a mold having a concave-convex pattern is pressed against the coated curable resin layer to form the coating film. By performing curing, the concavo-convex pattern of the mold can be transferred to the curable resin layer. The curable resin can also be applied after being diluted with an organic solvent. As an organic solvent used in this case, what dissolves the resin before hardening can be selected and used. For example, alcohol-based solvents such as methanol, ethanol, and isopropanol (IPA); and ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK) can be selected from known ones. As the method of coating the curable resin, for example, spin coating method, spray coating method, dip coating method, drop method, gravure printing method, screen printing method, letterpress printing method, die coating method, curtain coating method, etc. Various coating methods such as coating method, inkjet method, sputtering method, etc. As the mold having a concavo-convex pattern, for example, a desired mold such as a film mold or a metal mold can be used. Furthermore, although the conditions for curing the curable resin vary depending on the type of resin used, for example, the curing temperature is preferably in the range of room temperature to 250° C., and the curing time is in the range of 0.5 minutes to 3 hours. Also, a method of curing by irradiating energy rays such as ultraviolet rays or electron beams may be used, and in this case, the irradiation dose is preferably in the range of 20 mJ/cm ² to 10 J/cm ² .

In addition, in the above-mentioned manufacturing method, the concave-convex structure layer 142 is manufactured by forming a coating film (precursor film) on the base material 40 and pressing the mold against the coating film, but instead of the above method, by using a mold A precursor film is formed on the concave-convex pattern, the precursor film is attached to the substrate 40 and the mold is peeled off to form the concave-convex structure layer 142 on the substrate 40 . In this case, as a method of forming the precursor film on the mold, in addition to the above-mentioned coating method as a method of coating the precursor solution on the substrate 40, physical vapor deposition such as vapor deposition and sputtering may also be used. A method using a known dry process such as a deposition (PVD) method and a chemical vapor deposition (CVD) method. In this case, metals, metal oxides, metal nitrides, metal oxynitrides, metal sulfides, metal carbides, metal halides, and mixtures thereof (metal oxynitrides, metal oxyhalides) can be formed. , metal carbonitride, etc.) and the concave-convex structure layer 142 composed of.

The concave-convex structure layer formed on the mold by dry process can be bonded to the substrate 40 by the following method, for example. First, an adhesive is coated on the substrate 40 . The base material 40 and the mold are superimposed so that the adhesive layer on the base material 40 adheres to the concave-convex structure layer on the mold, and the adhesive is hardened. Thereby, the base material 40 and the concavo-convex structure layer are bonded via the adhesive. Next, the mold was peeled off from the concavo-convex structure layer. In this way, the diffraction grating substrate 140 in which the concavo-convex structure layer 142 is formed on the base material 40 can be formed.

Furthermore, a coating layer (not shown) may also be formed on the surface of the concavo-convex structure layer 142 . The coating layer preferably has a film thickness within a range of 25 to 150% of the standard deviation of the unevenness depth of the unevenness structure layer 142 . Thereby, when there are foreign substances or defects on the surface of the concave-convex structure layer 142, they can be covered, so the leakage current of the light-emitting elements 100, 100a can be effectively suppressed, and the light-emitting elements 100, 100a have good light extraction efficiency.

As the material of the coating layer (coating material), _SiOx , TiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , ZnS, and BaTiO exemplified above as materials that can be used as the material of the uneven structure layer 142 can be used. _3. SrTiO ₂ , ITO, etc. contain known fine particles, fillers, ultraviolet absorbing materials, and the like. In particular, it is preferable to form the covering layer using the same material as that used for the uneven structure layer 142 . Since the covering material is the same material as that of the uneven structure layer 142 , reflection of light at the interface between the covering layer and the uneven structure layer 142 can be suppressed. In the case of forming the coating layer by the sol-gel method, as for the precursor solution of the inorganic material used for forming the coating layer, it is preferable to use a precursor solution for forming the concave-convex structure layer 142 and further dilute it with a solvent. become one. This makes it easier to form the covering layer with a desired film thickness thinner than the concavo-convex structure layer 142 .

In addition to the sol-gel method, a method using a dispersion of fine particles of an inorganic material, a liquid phase deposition method (LPD: Liquid Phase Deposition), a method using polysilazane, etc. can also be used to form the coating layer.

Moreover, a coating layer can also be formed using a silane coupling agent as a coating material. Thereby, the adhesion between the coating layer and layers such as electrodes formed thereon can be improved, and the resistance in the cleaning step or high-temperature treatment step in the manufacturing steps of the light-emitting elements 100 and 100a can be improved. The type of silane coupling agent used in the coating layer is not particularly limited. For example, RSiX ₃ (R is at least 1 group selected from vinyl, glycidyloxy, acryloyl, methacryloyl, amine and mercapto) can be used. organic functional group, X is an organic compound represented by a halogen element or an alkoxyl group).

In addition, as the material of the coating layer, curable resin materials may be used in addition to the above-mentioned inorganic materials. As the curable resin material, the curable resin materials exemplified above as materials that can be used as the material of the concavo-convex structure layer 142 can be used. When a curable resin is used to form the covering layer, for example, the covering layer can be formed by applying the curable resin on the uneven structure layer 142 and then curing it.

Furthermore, the surface of the concavo-convex structure layer 142 (the surface of the coating layer when the coating layer is formed) may also be subjected to a hydrophobization treatment. The method of hydrophobization treatment can be used as long as known methods are used. For example, if it is a silica surface, hydrophobization treatment can also be carried out by using dimethyldichlorosilane, trimethylalkoxysilane, etc., or using A method of hydrophobizing a trimethylsilylating agent such as hexamethyldisilazane and silicone oil, or a surface treatment method of metal oxide powder using supercritical carbon dioxide can also be used. If the surface of the uneven structure layer 142 is hydrophobic, moisture can be easily removed from the surface of the uneven structure layer 142 in the manufacturing steps of the light-emitting elements 100, 100a, so defects such as dark spots in the light-emitting elements 100, 100a can be prevented. generation, or deterioration of the device.

In addition, a gas barrier layer may be provided on the surface of the concavo-convex structure layer 142 (the surface of the coating layer when the coating layer is formed) in order to prevent the penetration of moisture, oxygen, and other gases.

[Example]

Hereinafter, the light-emitting device of the present invention will be specifically described using examples and comparative examples, but the present invention is not limited to these examples. In the following Examples 1 and 2 and Comparative Examples 1 to 3, light-emitting elements were produced using different diffraction grating substrates or substrates without concavo-convex patterns, and the transparency and luminous efficiency (power efficiency) of the light-emitting elements were evaluated. Evaluation.

Example 1

＜Production of film mold＞

First, in order to produce a diffraction grating substrate, a film mold having an uneven surface was fabricated using the BCP solvent annealing method. A block copolymer manufactured by Polymer Source Co., Ltd. composed of polystyrene (hereinafter, abbreviated as "PS" as appropriate) and polymethyl methacrylate (hereinafter, abbreviated as "PMMA" as appropriate) as described below was prepared.

Mn of PS fragment = 510,000,

Mn=500,000 of the PMMA fragment,

Mn of block copolymer=1,010,000,

The volume ratio of PS fragments to PMMA fragments (PS:PMMA)=54:46,

Molecular weight distribution (Mw/Mn) = 1.18, Tg of PS fragment = 107°C,

Tg of PMMA fragment = 134°C

The volume ratio of the PS segment and the PMMA segment in the block copolymer (PS segment: PMMA segment) is based on the density of polystyrene being 1.05g/cm ³ and the density of polymethyl methacrylate being 1.19g/cm ³ form calculated. The number average molecular weight (Mn) and weight average molecular weight (Mw) of polymer fragments or polymers were obtained using gel permeation chromatography (manufactured by Tosoh Co., Ltd., model "GPC-8020", TSK-GEL SuperH1000, SuperH2000 , SuperH3000 and SuperH4000 connected in series) and measured. The glass transition point (Tg) of the polymer segment was measured using a differential scanning calorimeter (manufactured by Perkin-Elmer, product name "DSC7"), while the temperature was raised at a rate of 20°C/min in the temperature range of 0 to 200°C. To measure. The solubility parameters of polystyrene and polymethyl methacrylate are 9.0 and 9.3, respectively (refer to the 2nd edition of the Handbook of Chemistry).

Toluene was added to 230 mg of this block copolymer and 57.5 mg of polyethylene oxide, polyethylene glycol 2050 (average Mn=2050) manufactured by Aldrich, and dissolved so that the total amount became 15 g, and a block was prepared. Copolymer solution.

The block copolymer solution was obtained by filtering the block copolymer solution with a membrane filter having a pore size of 0.5 μm. Spin-coat a mixed solution of 1 g of KBM-5103 manufactured by Shin-Etsu Silicones, 1 g of ion-exchanged water, 0.1 ml of acetic acid, and 19 g of isopropanol on a glass substrate (after 10 seconds at a rotation speed of 500 rpm, and then at 800 rpm for 45 seconds). The treatment was performed at 130° C. for 15 minutes to obtain a silane-coupling-treated glass. The obtained block copolymer solution was applied to a film thickness of 140 to 160 nm on silane coupling-treated glass as a base material by spin coating. Spin coating was performed at a rotation speed of 200 rpm for 10 seconds, and then at 300 rpm for 30 seconds.

Next, a solvent annealing treatment was performed by allowing the substrate on which the thin film was formed to stand at room temperature for 24 hours in a desiccator previously filled with chloroform vapor. A screw bottle filled with 100 g of chloroform was installed in a desiccator (capacity 5 L), and the atmosphere in the desiccator was filled with chloroform of saturated vapor pressure. Asperities were observed on the surface of the thin film after the solvent annealing treatment, and it was found that microlayer separation occurred in the block copolymer constituting the thin film. The cross-section of the thin film was observed with a transmission electron microscope (TEM) (H-7100FA manufactured by Hitachi Corporation). They are arranged in two stages in the direction (height direction) perpendicular to the substrate surface, and when examined together with the analytical image of the atomic force microscope, the PS part is phase-separated from the PMMA part into a horizontal cylindrical structure. The PS part becomes the core (island), and the PMMA part is in a (sea) state surrounding the PS part.

On the surface of the thin film waved by the above-mentioned solvent annealing treatment, a thin nickel layer of about 20 nm is formed as a current seed layer by sputtering. Next, this base material with thin film was placed in a nickel sulfamate bath, and electroforming (maximum current density: 0.05 A/cm ² ) was performed at a temperature of 50° C. to deposit nickel until the thickness reached 250 μm. The substrate with thin film was mechanically peeled off from the nickel electroform obtained in the above manner. Next, the nickel electroformed body was immersed in a tetrahydrofuran solvent for 2 hours, and then an acrylic UV-curable resin was applied, cured, and peeled off. This operation was repeated 3 times, whereby a part of the electroformed body was attached to the surface of the electroformed body. Surface polymer components are removed. Thereafter, it was immersed in Chemisol 2303 manufactured by The Japan Cee-Bee Chemical, and washed while stirring at 50° C. for 2 hours. Thereafter, UV ozone treatment was performed on the nickel electroformed body for 10 minutes.

Next, the nickel electroformed body was immersed in HD-2101TH manufactured by Daikin Chemical Sales Co., Ltd. for about 1 minute, dried, and left to stand overnight. On the next day, the nickel electroformed body was dipped in HDTH manufactured by Daikin Chemical Sales Co., Ltd., and cleaned by ultrasonic treatment for about 1 minute. In this way, a demolded nickel mold was obtained.

Next, a fluorine-based UV-curable resin was coated on a PET substrate (manufactured by Toyobo Co., Ltd., COSMOSHINE A-4100), and the fluorine-based UV-curable resin was cured by irradiating ultraviolet light at 600 mJ/cm ² while pressing against a nickel mold. After the resin has hardened, the nickel mold is peeled off from the hardened resin. In this way, a film-shaped mold composed of a PET substrate with a resin film on which the surface shape of the nickel mold was transferred was obtained.

＜Formation of concavo-convex structure layer＞

In order to form a concavo-convex structure layer by a sol-gel method, a solution of a precursor of an inorganic material (sol-gel material solution) was prepared as follows. Add 0.75 mol of tetraethoxysilane (TEOS) and 0.25 mol of dimethyldiethoxysilane (DMDES) dropwise to a solution obtained by mixing 22 mol of ethanol, 5 mol of water, 0.004 mol of concentrated hydrochloric acid and 4 mol of acetylacetone, and then add Surfactant S-386 (manufactured by Seimi Chemical) 0.5 wt% as an additive was stirred at 23° C. and a humidity of 45% for 2 hours to obtain a SiO ₂ precursor solution. The precursor solution is bar-coated on the substrate to form a coating film of the precursor solution. As a substrate, an alkali-free glass substrate (manufactured by Nippon Electric Glass Co., Ltd., OA10GF) having a refractive index of 1.517 (λ=589 nm) of 100 mm×100 mm×0.7 mm (thickness) was used. A doctor blade (manufactured by YOSHIMITSU SEIKI CORPORATION) was used as a bar coater. The doctor blade was designed so that the film thickness of the coating film was 5 μm, but it was adjusted so that the film thickness of the coating film was 40 μm by affixing an imide tape with a thickness of 35 μm to the doctor blade.

After the coating film of the precursor solution was left at 25° C. for 1 minute, the film-shaped mold fabricated in the above manner was superimposed on the coating film. At this time, the film mold was pressed against the coating film by rotationally moving a pressure roller heated to 80° C. on the film mold. Thereafter, the film-form mold was peeled off, followed by heating at 300° C. for 60 minutes using an oven, and the coating film was mainly fired. In this way, the concavo-convex structure layer in which the concavo-convex pattern of the film-form mold was transferred was formed on the glass substrate. In addition, the pressure roller has a heater inside, and the outer periphery is coated with heat-resistant silicone with a thickness of 4 mm, and the roll diameter φ is 50 mm and the length in the axial direction is 350 mm.

<Measurement of average pitch of unevenness>

The concave-convex shape of the surface of the concave-convex structure layer was measured using an atomic force microscope (scanning probe microscope "NanonaviIII Station/E-sweep" with an environmental control unit manufactured by Hitachi-hightech Co., Ltd.) to obtain a concave-convex analysis image. The measurement is performed on an arbitrary measurement area of 10 μm square (10 μm in length and 10 μm in width). The analysis conditions of the atomic force microscope are as follows.

Measurement mode: Dynamic Force Mode

Cantilever: SI-DF40 (material: Si, rod width: 40μm, tip diameter: 10nm)

Measurement environment: in the atmosphere

Measuring temperature: 25°C

In the obtained concavo-convex analysis image, the interval between arbitrary adjacent convex portions or adjacent concavity portions was measured at 100 or more points, and the average value thereof was calculated to be the average pitch of concavo-convex. According to the analysis image obtained in this example, the average pitch of the concavities and convexes of the concavo-convex pattern of the concavo-convex structure layer was 270 nm as shown in the table of FIG. 5 .

＜Evaluation of haze value＞

The haze value (haze) of the substrate on which the concavo-convex structure layer was formed was measured using Haze-gard plus (manufactured by BYK-Gardner GmbH). The haze value was 0.1% as shown in the table of FIG. 5 .

＜Formation of light emitting part＞

Then, ITO was formed into a film with a thickness of 120nm by sputtering on the concave-convex structure layer, and then, the hole transport layer (4, 4', 4" tris(9-carbazole ) triphenylamine, thickness: 35nm), light-emitting layer (4,4',4"tris(9-carbazole) triphenylamine doped with tris(2-phenylpyridine)iridium(III) complex, thickness 15nm; 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene doped with tris(2-phenylpyridine)iridium(III) complex, thickness 15nm), electron transport layer (1, 3,5-tris(N-phenylbenzimidazol-2-yl)benzene, thickness: 65 nm). Furthermore, a lithium fluoride layer (thickness: 1 nm), an aluminum layer (thickness: 50 nm), and a silver layer (thickness: 15 nm) were evaporated.

Example 2

A light-emitting element was produced in the same manner as in Example 1 except that a film-shaped mold was produced using a block copolymer made of Polymer Source, which is composed of PS and PMMA as described below.

Mn of PS fragment=800,000,

Mn=750,000 of the PMMA fragment,

Mn of block copolymer=1,550,000,

The volume ratio of PS fragments to PMMA fragments (PS:PMMA)=55:45,

Molecular weight distribution (Mw/Mn) = 1.28, Tg of PS fragment = 107°C,

Tg of PMMA fragment = 134°C

As shown in the table of FIG. 5 , the average pitch of the concavities and convexes of the concavo-convex pattern of the concavo-convex structure layer was 590 nm. In addition, the haze value of the base material on which the concavo-convex structure layer was formed was 1.5%.

Comparative example 1

A light-emitting element was fabricated in the same manner as in Example 1, except that a transparent electrode was directly formed on the substrate without forming a concavo-convex structure layer. As shown in the table of FIG. 5 , the haze value of the base material on which no concavo-convex structure layer was formed was 0.0%.

Comparative example 2

A light-emitting element was produced in the same manner as in Example 1 except that a film-shaped mold was produced using a block copolymer made of Polymer Source, which is composed of PS and PMMA as described below.

Mn of PS fragment=900,000,

Mn=800,000 of the PMMA fragment,

Mn of block copolymer=1,700,000,

The volume ratio of PS fragments to PMMA fragments (PS:PMMA)=55:45,

Molecular weight distribution (Mw/Mn) = 1.26, Tg of PS fragment = 107°C,

Tg of PMMA fragment = 134°C

As shown in the table of FIG. 5 , the average pitch of the concavities and convexes of the concavo-convex pattern of the concavo-convex structure layer was 770 nm. Also, the haze value of the base material on which the uneven structure layer was formed was 7.9%.

Comparative example 3

A light-emitting element was produced in the same manner as in Example 1 except that a transparent electrode was formed on a green glass substrate with a scattering film (manufactured by KIMOTO Co., Ltd.) in which fine particles with a diameter of several μm to 20 μm were optionally embedded.

As shown in the table of FIG. 5 , the average pitch of the asperities of the green glass substrate with the scattering film was 8000 nm. Also, the haze value of the green glass substrate with the scattering film was 90.5%.

＜Evaluation of Luminous Efficiency＞

The luminous efficiencies (power efficiencies) of the light-emitting elements of Examples 1 and 2 and Comparative Examples 1 to 3 were measured by the following method. A voltage was applied to the light-emitting element, and the applied voltage V and the current I flowing through the light-emitting element were measured with an application measuring device (manufactured by ADC Co., Ltd., R6244). The luminous flux L is measured. Calculate the luminance value L' based on the measured values of the applied voltage V, current I and total luminous flux L obtained in the above manner, using the following calculation formula (F1):

Power efficiency=(L'/I/V)×S (F1)

And calculate the power efficiency of the light emitting element. In the above formula, S is the light emitting area of the device. Furthermore, regarding the value of the luminance L', assuming that the light distribution characteristic of the light-emitting element complies with Lambert's law, the following calculation formula (F2) is used:

L'＝L/π/S (F2)

Do the conversion.

The calculated results of the power efficiency are shown in the table of FIG. 5 . The power efficiency of the light-emitting elements of Examples 1 and 2 and Comparative Examples 2 and 3 was higher than that of the light-emitting element of Comparative Example 1 which did not include a concavo-convex structure layer. The reason for this is considered to be that in the light-emitting elements of Examples 1 and 2 and Comparative Examples 2 and 3, the light generated in the light-emitting layer is diffracted and/or scattered by the concave-convex structure layer or the scattering film, and is emitted from the inside of the element. is extracted.

＜Visual evaluation＞

The transparency of the light-emitting elements of Examples 1 and 2 and Comparative Examples 1 to 3 was evaluated in the following manner. Paper on which letters were printed in "Arial" at a font size of 10 points was prepared, and the produced light-emitting element was placed between the observer and the paper. The distance between the observer and the light emitting element was set to 1 m. While changing the distance between the light-emitting element and the paper, the observer penetrates the light-emitting element to focus on the paper and take a photo with a digital camera, and visually observe the text of the photo. The results are shown in the table of FIG. 5 . In the table of Fig. 5, the characters that can be clearly read even if the distance between the light emitting element and the paper is 5 m or more are described as ◎; even if the distance between the light emitting element and the paper is 5 m or more, the characters If the text is clear but the contrast is low, it will be marked as ○; when the distance between the light-emitting element and the paper is less than 5m, the text can be read clearly, but when the distance between the light-emitting element and the paper is more than 5m , those who could not read the characters were recorded as Δ; those who could not read the characters at all even if the distance between the light-emitting element and the paper was less than 5 m were recorded as ×.

In the light-emitting elements of Example 1 and Comparative Example 1, the area where the concave-convex structure layer was formed, including the area where the metal electrode was formed, was completely transparent, and even if the distance between the light-emitting element and the paper was 5 m or more, it was clear understand the text clearly. The light-emitting element of Comparative Example 1 is considered to be transparent and have high character readability because it does not have the concavo-convex structure layer and does not scatter the light passing through the light-emitting element. Regarding the light-emitting element of Example 1, since the average pitch of the concavities and convexities of the concavo-convex pattern of the concavo-convex structure layer is in the range of 150 to 650 nm, especially in the range of 250 to 300 nm, the scattering of light passing through the light emitting element is suppressed, so It is considered transparent and the text is more readable. Penetration is believed to be maintained.

In the light-emitting element of Example 2, the area where the concave-convex structure layer is formed, including the area where the metal electrode is formed, is completely transparent, and characters can be clearly read even if the distance between the light-emitting element and the paper is 5 m or more. . Regarding the light-emitting element of Example 2, since the average pitch of the concavities and convexities of the concavo-convex pattern of the concavo-convex structure layer is in the range of 150 to 650 nm, and the scattering of light penetrating the light-emitting element is suppressed, it is considered to be transparent and readable. higher. However, the contrast of the characters visually observed through this light-emitting element was slightly lower than that observed through the light-emitting elements of Example 1 and Comparative Example 1.

In the light-emitting device of Comparative Example 2, the area where the concave-convex structure layer was formed, including the area where the metal electrode was formed, was completely transparent. If the distance between the light-emitting device and the paper was less than 5 m, characters could be read clearly. However, when the distance between the light-emitting element and the paper was 5 m or more, characters could not be read clearly. In the light-emitting element of Comparative Example 2, since the average pitch of the concavo-convex patterns of the concavo-convex structure layer exceeds 650 nm, light passing through the light-emitting element is considered to be largely scattered and have insufficient transparency.

In the light-emitting element of Comparative Example 3, the area where the concave-convex structure layer was formed, including the area where the metal electrode was formed, was completely opaque. Can't understand text. Since the rough glass substrate with a scattering film used in the light-emitting element of Comparative Example 3 has an average pitch of concavities and convexities much larger than 650 nm, light passing through the light-emitting element is considered to be scattered greatly, and the light-emitting element appears opaque.

From the above results, it can be seen that the haze value of the base material of the concave-convex structure layer formed with the concave-convex structure layer with the average pitch of the concave-convex structure being 150-650 nm is 2.0% or less, and the light-emitting element produced using this substrate is transparent and has high power efficiency. high.

Although the present invention has been described above with examples and comparative examples, the light-emitting element of the present invention is not limited to the above examples, and can be appropriately modified within the scope of the technical ideas described in the claims.

[industrial availability]

The light-emitting element of the present invention is transparent and has high luminous efficiency. Such a light-emitting device can be used in various applications such as window materials and lighting devices for buildings, vehicle-mounted lighting devices, and transparent displays.

Claims (7)

1. A transparent (See-through) light-emitting element, which has: Diffraction grating substrate, which has a concavo-convex structure layer with concavo-convex patterns formed on one side of the substrate; 1st electrode; an organic layer; and the second electrode; and The first electrode, the organic layer, and the second electrode are sequentially formed on the concave-convex structure layer, The average pitch of the concavities and convexes of the above-mentioned concavo-convex pattern is in the range of 150-650 nm. 2. The transparent light-emitting device according to claim 1, wherein the haze value of the diffraction grating substrate is 2.0% or less. 3. The transparent light-emitting element according to claim 1 or 2, wherein the extension direction of the protrusions of the concave-convex pattern is irregularly distributed in plan view, and The outline of the convex portion included in the area per unit area of the concave-convex pattern in a plan view includes more linear sections than curved sections. 4. The transparent light-emitting element according to claim 3, wherein the width of the protrusion is constant in a direction substantially perpendicular to the direction in which the protrusion extends in plan view. 5. The transparent light-emitting element according to claim 3 or 4, wherein the above-mentioned curve interval is an interval in which the above-mentioned convex portion is divided by a length that is π (pi) times the average value of the width of the above-mentioned convex portion in plan view. When a plurality of sections are formed by the outline of the section, the ratio of the straight-line distance between the two ends of the section to the length of the above-mentioned outline between the two ends is 0.75 or less; The linear section is a section other than the curved section among the plurality of sections. 6. The transparent light-emitting element according to claim 3 or 4, wherein the above-mentioned curve interval is an interval in which the above-mentioned convex portion is divided by a length that is π (circumference ratio) times the average value of the width of the above-mentioned convex portion in plan view When multiple sections are formed by the outline of the section, the angle between the line segment connecting one end of the section and the midpoint of the section and the line segment connecting the other end of the section and the midpoint of the section is 180 If the angle is less than 120°, the angle is less than 120°; The above-mentioned linear section is an interval that is not the above-mentioned curved section among the above-mentioned plurality of sections, The ratio of the linear section among the plurality of sections is 70% or more. 7. The transparent light-emitting element according to any one of claims 1 to 6, wherein the Fourier transform obtained by performing two-dimensional high-speed Fourier transform processing on the concave-convex analysis image obtained by analyzing the concave-convex pattern with a scanning probe microscope The converted image shows a circular or annular pattern approximately centered on the origin with an absolute value of wave number 0 μm ^-1 , and the circular or annular pattern exists when the absolute value of wave number is 1.54 to 6.67 μm ^{- 1} within the area within the range.