WO2010041611A1 - 電子デバイス用基板、その製造方法、これを用いた電子デバイス、その製造方法及び有機led素子用基板 - Google Patents
電子デバイス用基板、その製造方法、これを用いた電子デバイス、その製造方法及び有機led素子用基板 Download PDFInfo
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- WO2010041611A1 WO2010041611A1 PCT/JP2009/067277 JP2009067277W WO2010041611A1 WO 2010041611 A1 WO2010041611 A1 WO 2010041611A1 JP 2009067277 W JP2009067277 W JP 2009067277W WO 2010041611 A1 WO2010041611 A1 WO 2010041611A1
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- H—ELECTRICITY
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- H10K50/85—Arrangements for extracting light from the devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
Definitions
- the present invention relates to an electronic device substrate, a manufacturing method thereof, an electronic device using the same, and a manufacturing method thereof, and more particularly to a substrate for an electronic device such as an organic LED (Organic Light Emitting Diode).
- an organic LED Organic Light Emitting Diode
- An organic LED element is a process in which an organic layer is sandwiched between electrodes, a voltage is applied between the electrodes, holes and electrons are injected, recombined in the organic layer, and a light emitting molecule moves from an excited state to a ground state. The generated light is extracted outside the device.
- light generated in the organic layer is transmitted to the electrode and reaches the interface with the glass substrate.
- the refractive index difference between the electrode and the glass substrate is large, a phenomenon occurs in which light transmitted through the electrode is reflected by the glass substrate and returns to the electrode / organic layer again. Therefore, the amount of light that can be extracted outside the organic LED element is currently less than 20% of the emitted light.
- Patent Document 1 proposes providing a light scattering layer on one side of a substrate to improve light extraction efficiency. Further, there is a document that proposes providing an electrode between a glass substrate and a glass layer (Patent Document 2).
- the present invention provides an electronic device substrate in which electrode wiring is formed on the first main surface side of a glass substrate having first and second main surfaces facing each other, wherein An auxiliary wiring pattern formed on one main surface, and a translucent glass layer formed on the glass substrate surface so as to cover the first main surface including the auxiliary wiring pattern.
- a through hole exposing the auxiliary wiring pattern is formed in a part of the glass layer on the auxiliary wiring pattern. According to this configuration, the entire auxiliary wiring pattern except for the connection region exposed from the through hole is enclosed by the glass layer, so there is no risk of deterioration of the auxiliary wiring pattern, and a stable and long-life auxiliary wiring pattern is formed. Can be provided.
- the surface of the glass layer obtained by applying and baking a glass material made of an oxide, a chalcogenide, a halide, or a mixture thereof is smooth, and includes electrode wiring formed on this upper layer.
- the thickness of the functional layer can be made stable and uniform.
- the glass refers to an amorphous inorganic material obtained by cooling a glass raw material melted or softened by heating.
- the present invention includes the above electronic device substrate, wherein the through hole is filled with a conductive member, and the surface of the glass layer and the surface of the conductive member constitute substantially the same surface. According to this configuration, since the surface including the through-hole region can be flattened, the functional layer formed in the upper layer can be made more uniform.
- the glass layer includes a base material having a first refractive index with respect to at least one wavelength of transmitted light, and the base material dispersed in the base material.
- a scattering glass layer made of glass having a scattering material having a second refractive index different from that of the material, formed on the scattering glass layer, and having the same or lower first refractive index as the first refractive index.
- a translucent electrode having a refractive index of 3.
- the scattering material in the scattering glass layer includes a distribution that decreases from the scattering glass layer toward the translucent electrode. . According to this configuration, it is possible to improve the light extraction efficiency.
- the density ⁇ 2 of the scattering material at a distance x (x ⁇ 0.2 ⁇ m) from the surface of the light-transmitting electrode side of the light-scattering glass layer is a glass layer.
- a material satisfying ⁇ 1 > ⁇ 2 is included with respect to the density ⁇ 1 of the scattering material in the central portion. According to this configuration, the surface is smooth while having scattering properties, and the reliability of elements formed on the substrate can be improved.
- the present invention includes the above electronic device substrate, wherein the glass layer surface has a surface roughness Ra of 30 nm or less.
- the present invention includes the electronic device substrate described above, wherein the content of the scattering material in the glass layer is at least 1 vol%.
- the present invention also includes the electronic device substrate, wherein the scattering material is a bubble.
- the present invention includes the electronic device substrate, wherein the scattering material is a material particle having a composition different from that of the base layer.
- the present invention includes the electronic device substrate, wherein the scattering material is a precipitated crystal of glass constituting the base layer.
- the present invention includes the electronic device substrate, wherein the number of the scattering material per 1 mm 2 of the glass layer is at least 1 ⁇ 10 4 .
- the present invention includes the electronic device substrate, wherein the scattering material having a maximum length of 5 ⁇ m or more among the scattering materials is 15 vol% or less.
- the present invention includes the electronic device substrate, wherein the glass layer is selectively formed on the glass substrate so as to form a desired pattern.
- the present invention includes the above electronic device substrate, wherein the first refractive index at at least one of wavelengths ⁇ (430 nm ⁇ ⁇ 650 nm) is 1.8 or more.
- the present invention provides the substrate for the electronic device, wherein the glass layer, the average thermal expansion coefficient at 400 ° C. from 100 ° C. is, 70 ⁇ 10 -7 (°C -1 ) from 95 ⁇ 10 -7 (°C -1 And a glass transition temperature of 450 ° C. to 550 ° C. is included.
- the present invention is the above electronic device substrate, wherein the glass layer has a P 2 O 5 content of 20 to 30 mol%, a B 2 O 3 content of 3 to 14 mol%, a Li 2 O, a Na 2 O, and a K 2 O.
- the total amount of Bi 2 O 3 is 10 to 20 mol%
- TiO 2 is 3 to 15 mol%
- Nb 2 O 5 is 10 to 20 mol%
- WO 3 is 5 to 15 mol%.
- the present invention includes the above electronic device substrate, wherein the auxiliary wiring pattern is a thick film wiring pattern.
- the present invention includes the above electronic device substrate, wherein the auxiliary wiring pattern is covered with a protective layer, and the glass layer is formed on the protective layer.
- the present invention includes the above electronic device substrate, wherein the auxiliary wiring pattern is a lattice pattern arranged vertically and horizontally.
- the present invention includes the electronic device substrate, wherein the auxiliary wiring pattern is a comb-like pattern.
- the present invention includes the electronic device substrate, wherein the through-hole includes a plurality of openings formed at equal intervals with respect to the lattice pattern.
- the present invention includes the above electronic device substrate, wherein the auxiliary wiring pattern is a light shielding pattern.
- the present invention includes the electronic device substrate, wherein the through hole has a tapered cross section whose diameter increases as the distance from the auxiliary wiring pattern increases.
- the through hole includes a cross section whose cross section is perpendicular to the first main surface.
- the present invention includes a step of forming an auxiliary wiring pattern on the first main surface of the glass substrate, and covers the first main surface including the entire surface excluding a part of the auxiliary wiring pattern. Forming a glass layer on the surface of the glass substrate, and manufacturing a substrate for an electronic device having a glass layer having a through hole in which a part of the auxiliary wiring pattern is exposed.
- the present invention provides the above-described method for manufacturing a substrate for an electronic device, comprising the step of filling the through hole with a conductive member so that the surface of the glass layer and the surface of the conductive member constitute substantially the same surface. Including what is included.
- the present invention includes the method for manufacturing a substrate for an electronic device described above, which includes a step of polishing a surface after the filling step.
- the electronic device of the present invention includes the first auxiliary wiring pattern except for a glass substrate, an auxiliary wiring pattern formed on the first main surface of the glass substrate, and a portion constituting a through hole.
- An electronic device substrate comprising a glass layer formed on the glass substrate surface so as to cover the main surface, and a functional element formed on the glass layer, the functional element,
- the conductive layer is conductively connected to the auxiliary wiring pattern through a through hole formed in a part of the glass layer.
- the through hole is filled with a conductive member, and is electrically connected to the functional element.
- the surface of the glass layer and the surface of the conductive member constitute substantially the same surface. including.
- the auxiliary wiring pattern includes a lattice pattern arranged vertically and horizontally.
- the auxiliary wiring pattern is a light shielding pattern and includes a black matrix.
- the present invention includes the electronic device, wherein the auxiliary wiring pattern is a comb-like pattern.
- the present invention includes the electronic device substrate, wherein the through holes are arranged at equal intervals along the auxiliary wiring pattern.
- the glass layer includes a base material having a first refractive index with respect to at least one wavelength of transmitted light, and the base material dispersed in the base material.
- a glass layer made of glass provided with a plurality of scattering materials having different second refractive indexes, and the functional element formed on the glass layer has a third or lower third refractive index.
- a translucent electrode having a refractive index of 5 mm, and the translucent electrode is conductively connected to a conductive member in the through hole. Furthermore, desirably, the distribution of the scattering material in the glass layer is reduced from the inside of the glass layer toward the translucent electrode.
- the functional element is a second layer formed on the translucent electrode so as to face the translucent electrode and a layer having a light emitting function composed of an organic layer.
- the second electrode is formed so as to avoid the through hole. That is, it is formed in a pattern that does not exist on the through hole. With this configuration, the second electrode is not formed on a non-planar surface, and the light emitting region is not formed. Therefore, it is possible to prevent a short circuit between the translucent electrode and the second electrode due to electric field concentration. it can.
- the present invention includes the above electronic device in which an external lead terminal is formed on the through hole.
- the auxiliary wiring pattern is formed in a stripe shape
- the translucent electrode is connected to the auxiliary wiring pattern, and is formed on the translucent electrode.
- a layer having a light emitting function, and a reflective electrode formed on the layer having the light emitting function and arranged in a direction orthogonal to the auxiliary wiring pattern.
- the present invention includes the above electronic device substrate including a light-shielding member formed in an upper layer or a lower layer of the auxiliary wiring pattern and wider than the auxiliary wiring pattern.
- the present invention includes the above electronic device substrate, wherein the light shielding member is a protective layer formed so as to cover the auxiliary wiring pattern.
- the present invention also includes a step of forming an auxiliary wiring pattern on the first main surface of the glass substrate, and the entire surface of the auxiliary wiring pattern excluding a part of the auxiliary wiring pattern for forming a through hole.
- the present invention includes a step of filling the through-hole with a conductive member constituting substantially the same surface as the glass layer surface in the method for manufacturing an electronic device, and the step of forming the functional element includes: Forming an electrode of the functional element so as to be in contact with the conductive member.
- the present invention it is possible to provide a substrate that has high light extraction efficiency and is compatible with a large area.
- substrate for electronic devices and organic LED element of Embodiment 3 of this invention (a) is a top view of the board
- FIG. 1A is a plan view showing an electronic device substrate according to an embodiment of the present invention
- FIG. 1B is an EE ′ showing an organic LED element formed on the electronic device substrate. It is sectional drawing in a surface.
- the substrate for an electronic device for forming the organic LED element of the present invention includes a glass substrate 101 and a lattice on the first main surface of the glass substrate 101 as shown in FIGS.
- An auxiliary wiring pattern (conductive wiring) 200 formed in a shape, and a translucent glass layer formed on the glass substrate surface so as to cover the first main surface including the auxiliary wiring pattern 200 102, and a through hole H exposing the auxiliary wiring pattern 200 is formed in a part of the glass layer 102.
- the three through holes H are provided at equal intervals on each of the vertical and horizontal sides constituting one lattice.
- Each through hole H is formed in a tapered shape in the glass layer 102, and an ITO layer as the translucent electrode 103 is integrally provided on the entire surface. Therefore, the light-transmitting electrode 103 is energized from the auxiliary wiring pattern 200 through this through hole, and constitutes a light emitting region 300 and takes out light to the glass substrate 101 side, and is a bottom emission type organic LED element. is there.
- the light emitting region 300 is an overlapping region of the translucent electrode 103, the layer 110 having a light emitting function made of an organic layer formed thereon, and the reflective electrode 120 formed on the upper layer. Since the entire region 300 is disposed within a certain distance from the through hole H, the voltage drop can be reduced.
- C and D each indicate a position.
- 2 (a) to 2 (d) are cross-sectional views showing an example of the first manufacturing method of the present invention for each process, and are cross sections corresponding to FIG. 1 (b).
- a glass substrate 101 is prepared, and surface polishing is performed as necessary.
- a silver paste for example, with a paste film thickness of 10 ⁇ m and a line width of 200 ⁇ m as shown in FIG.
- An auxiliary wiring pattern 200 mainly composed of 10 cm ⁇ 10 cm latticed silver is formed.
- This auxiliary wiring pattern may be set in a necessary range depending on the specific resistance of the wiring material, the film thickness, the wiring width, the current value required for the functional element connected thereto, the size of the electronic device, and the like.
- the film thickness of the auxiliary wiring is 0.5 to 30 ⁇ m
- the wiring width is 0.05 to 2 mm
- the distance between the auxiliary wirings is 2 to 50 cm.
- the thickness of the auxiliary wiring is set to 0.5 to 20 ⁇ m because it is difficult to form a step.
- the thickness of the auxiliary wiring is preferably thicker in order to reduce the specific resistance, and is desirably 0.5 ⁇ m or more. However, when it exceeds 30 ⁇ m, the step coverage is lowered, and there are many problems in practical use.
- the auxiliary wiring pattern is a grid pattern as shown in FIG. 1, but it is striped, comb-shaped, a shape in which branches extend in a direction perpendicular to the stripe straight line, or a symbol of resistance.
- Various shapes such as a shape connected by a broken line and a shape connected by arcs are possible.
- a glass paste is printed except for a portion where a through hole is formed by screen printing, and a glass layer 102 having a through hole H is formed. Then, baking is performed to form an electronic device substrate in which the auxiliary wiring pattern 200 is covered with a glass layer 102 with a through hole, as shown in FIG. Note that the glass layer 102 does not have to be formed at the end portion of the auxiliary wiring 200 taken out to the outside.
- the through hole is formed in a tapered shape in which the cross section of the plane parallel to the axis of the through hole (perpendicular direction to the substrate surface) is slanted. It may be a through hole. However, in the case where the electrode layer is formed directly on this as in this example, it is desirable that the through hole is formed in a tapered shape because the conductive connection between the electrode formed on the upper electrode and the auxiliary wiring is less likely to be broken. .
- the through hole may be provided as appropriate so as not to adversely affect the voltage drop.
- the auxiliary wiring has a grid shape, at least one through hole is provided on each side of the grid, and two or more are provided on each side. Is desirable. However, if the number is increased too much, surface irregularities may increase, so it is desirable that the length be about 2 to 5 on each side.
- the auxiliary wiring has a stripe shape, it is sufficient to provide about 1 to 5 pieces at the same interval as the stripe interval.
- the shape of the through hole in the plane can be a circle, ellipse, rectangle or the like, but an ellipse or rectangle having an opening larger in the longitudinal direction of the auxiliary wiring is desirable.
- an elliptical shape or a rectangular shape whose long axis or long side is 1.5 times or more as long as the short axis or short side is desirable. This is because a large amount of current substantially flows to the end of the through hole because the surface resistance of the auxiliary wiring ⁇ the surface resistance of the translucent electrode.
- the glass layer 102 may be any material that can form a translucent glass layer by firing, which will be described in detail later.
- the thickness of the glass layer may be about 1.1 to 10 times the thickness of the auxiliary wiring when the substrate is completed, and may be about 2 to 200 ⁇ m.
- an ITO film is formed on the entire surface as the translucent electrode 103 on the through-hole portion H and the glass layer 102, and as shown in FIG. 2C, an electrode-equipped electronic device substrate 100 is obtained. Then, as shown in FIG. 2D, a layer 110 having a light emitting function such as a hole injection layer, a light emitting layer, and an electron injection layer is formed by, for example, a vapor deposition method.
- a layer having a light emitting function that is, a hole injection layer, a light emitting layer, and an electron injection layer are usually sandwiched between a first electrode and a second electrode.
- the layer having a light emitting function is not limited to a dry process such as an evaporation method, but can be applied to a layer formed by a wet process such as a coating method.
- the present invention is not limited to this five-layer structure, and is not limited to an organic LED element, as long as it is a functional element having an electrode on at least the substrate side.
- the first electrode is a translucent electrode, but the second electrode may be a translucent electrode or a reflective electrode.
- the translucent electrode can be used with tin oxide or other materials in addition to the above-mentioned ITO.
- Various metallic electrodes can be used as the reflective electrode, but typical materials include aluminum, AgMg alloy, and Ca.
- the reflective electrode pattern may not be formed on the through hole. Desirable to prevent short circuit.
- Such a reflective electrode can form such a pattern using a mask, for example.
- the auxiliary wiring pattern is formed by screen printing of silver paste, but it can be formed by other printing methods, dipping methods, plating methods, vapor deposition methods, sputtering methods, etc.
- Metals such as Ag, Cu, Al, Cr, Mo, Pt, W, Ni, and Ru, metal compounds, metal pastes, and the like are applicable. What is necessary is just to select suitably as needed.
- auxiliary wiring in order to manufacture a large area thick auxiliary wiring with high productivity and low cost, it is suitable to manufacture by screen printing as described above, and at the same time the auxiliary wiring is formed by baking the glass layer.
- Use of a metal paste is advantageous in that it can be formed.
- FIG. 3A is a plan view of an electronic device substrate according to an embodiment of the present invention
- FIG. 3B is an FF ′ plane showing an organic LED element formed on the electronic device substrate. It is sectional drawing.
- the substrate for an electronic device for forming the organic LED element of the present invention includes a glass substrate 101 and the first main surface of the glass substrate 101 as shown in FIGS. 3 (a) and 3 (b). Including a first auxiliary wiring pattern 200a and a second auxiliary wiring pattern 200b formed in a comb-tooth shape, and the first and second auxiliary wiring patterns 200a and 200b.
- the through holes H a and H b are provided at equal intervals on each side constituting the comb teeth.
- Each through-hole H a for connecting to the first auxiliary wiring pattern 200a is formed in a tapered cross section, ITO layer as a first translucent electrode 103a thereon is opposing comb-like pattern Are integrally provided so as to avoid the top of the through hole Hb . Therefore, energization from the auxiliary wiring pattern 200a of the first light-transmitting electrode 103a is performed via the through-hole H a.
- each through hole Hb for connecting to the second auxiliary wiring pattern 103b is formed in a tapered shape in cross section, and an ITO layer as the second translucent electrode 103b is formed on the opposing comb teeth. avoid upper through-hole H a formed Jo pattern are integrally provided. Therefore, energization from the auxiliary wiring pattern 200b to the second translucent electrode 103b is performed through the through hole Hb .
- This organic LED element is a Bose emission type organic LED element that constitutes the light emitting region 300 and extracts light toward and above the glass substrate 101.
- the light emitting region 300 is a region where the first and second translucent electrodes 103a and 103b and the layer 110 having a light emitting function formed therebetween overlap with each other, but the entire light emitting region 300 has through holes H a , H Since it is disposed within a certain distance from b , the voltage drop can be reduced. Also with this configuration, it is possible to reduce the voltage drop and provide a highly efficient organic LED element. Even when the second electrode is a reflective electrode using a metal, if the light emission area becomes large, light emission unevenness due to a voltage drop can be considered in the same manner. Therefore, in this method, the second electrode is translucent. It is considered as effective as the case. In manufacturing, it is the same as the method shown in FIGS.
- FIG. 4A is a plan view of the electronic device substrate according to the embodiment of the present invention
- FIG. 4B is a cross-sectional view of the GG ′ plane showing the organic LED element formed on the electronic device substrate. It is sectional drawing.
- the substrate for an electronic device for forming the organic LED element of the present invention has a different shape of the through hole, and in the first embodiment, the cross section is tapered, but in the present embodiment, the through hole is perpendicular to the cross section. forming a H S, filling the conductive paste 201 thereto. The rest is the same as in the first embodiment.
- step Get a smooth surface without any.
- surface polishing is unnecessary, but when there is a step, it is more suitable for surface polishing to be an electronic device.
- a glass substrate 101 is prepared, and surface polishing is performed as necessary, and then, by screen printing, an auxiliary wiring mainly composed of silver having a paste film thickness of 80 ⁇ m and a line width of 200 ⁇ m, as in the first embodiment.
- a pattern 200 is formed.
- the thickness of the auxiliary wiring is preferably about 0.5 to 5 ⁇ m.
- a glass paste is printed on the entire surface of the glass substrate 101 by screen printing to form the glass layer 102.
- baking is performed to form an electronic device substrate in which the auxiliary wiring pattern is covered with a glass layer as shown in FIG.
- the auxiliary wiring 200 is covered with the glass layer 102. Note that the glass layer 102 does not have to be formed at the end portion of the auxiliary wiring 200 taken out to the outside.
- a silver paste was filled as a conductive paste 201 within the through hole H S, to obtain a polished smooth surface of the surface after firing.
- an ITO film is formed as a translucent electrode 103 on the entire surface of the upper layer to obtain an electrode-equipped electronic device substrate 100 as shown in FIG. 5 (d).
- a layer 110 having a light emitting function such as a hole injection layer, a light emitting layer, an electron injection layer, and a second electrode is formed by a coating method or the like.
- an aluminum layer on the through-hole H S is removed by photolithography, reflecting on the layer 110 having the light emitting function electrode 120
- An aluminum electrode is formed as follows. Further, the through-holes on the H S in such a mask sputtering may be sputtered as aluminum layer is not formed. Because who is not formed second electrode on the through-hole H S is less likely to occur a short circuit between the electrodes desirable.
- a through-hole formed by a laser is filled with a conductive member, and the surface is smoothed by surface polishing as necessary, and then a transparent electrode is formed on the surface of the smooth glass layer.
- the translucent electrode and the through hole can be electrically connected.
- the surface can be smoothed. Therefore, when forming an organic LED element, it is integrated with the entire smooth surface. In addition, highly reliable element formation can be performed.
- the through holes may be regularly formed on the auxiliary wiring on the surface at a predetermined interval, but the through holes are formed in accordance with the device formed on the through wiring.
- the conductive member may be formed in a part of the through hole.
- a glass substrate with auxiliary wiring in which through holes H are formed at predetermined intervals may be formed.
- the conductive element 201 is embedded at the location where the electrical connection is performed and the insulating member 202 is embedded at the location where the electrical connection is not performed, by the functional element formed thereon.
- surface smoothing can be performed to improve surface smoothness. Thereby, the characteristic of the electronic device formed in this upper layer can be improved and the life can be extended.
- FIG. 7A is a plan view of the electronic device substrate according to the embodiment of the present invention
- FIG. 7B is a cross-sectional view taken along the line II ′ showing the organic LED element formed on the electronic device substrate. It is.
- the electronic device substrate for forming the organic LED element of the present invention is formed in the same manner as the electronic device substrate described in the first embodiment, but the external connection terminal ( (Not shown) is also formed through the through hole Hout . Other portions are formed in the same manner as in the first embodiment. With this configuration, the external connection terminal portion formed in the vicinity of the edge of the glass substrate beyond the sealing portion from the element region is similarly formed in the same process as the internal through hole H. The rest is the same as in the first embodiment. As the external connection terminal, a plating layer may be formed so that bonding can be performed, or bumps can be formed.
- This configuration makes the external connection easy and reliable.
- the glass used for the glass layer includes B 2 O 3 —SiO 2 —ZnO, B 2 O 3 —SiO 2 —PbO, B 2 O 3 —P 2 O 5 —ZnO, and the like. Glass is mentioned.
- the refractive index of an organic layer used as a layer having a light emitting function is about 1.8 to 2.1 at 430 nm.
- the refractive index of the translucent electrode layer is generally about 1.9 to 2.1.
- the refractive index of the organic layer and the translucent electrode layer is close, and the emitted light reaches the interface between the translucent electrode layer and the translucent substrate without being totally reflected between the organic layer and the translucent electrode layer.
- a general glass substrate has a refractive index of about 1.5 to 1.6, which is lower than that of an organic layer or a translucent electrode layer.
- the light that has attempted to enter the glass substrate at a shallow angle is reflected in the direction of the organic layer by total reflection, is reflected again by the reflective electrode, and reaches the interface of the glass substrate again. At this time, since the incident angle to the glass substrate does not change, reflection cannot be taken out from the glass substrate by repeating reflection in the organic layer and the translucent electrode layer.
- the current amount of light that can be extracted outside the organic LED element is less than 20% of the emitted light.
- the light extraction efficiency can be improved by providing the glass layer of the present invention with light scattering properties. This is because the probability of changing the direction of light propagating inside the element by scattering and emitting it to the outside increases. Even when propagating through the element at an angle that cannot be extracted to the outside, the light is reflected by the reflective electrode and reaches the glass scattering layer again, so that light can be extracted to the outside as this is repeated.
- the refractive index of the glass scattering layer is preferably equal to or higher than the refractive index of the translucent electrode with which it is in contact.
- the emission wavelength having a refractive index of the glass of the glass scattering layer is 1.8 or more.
- a glass material in this case as a network former, for example, one or two or more kinds of components selected from P 2 O 5 , SiO 2 , B 2 O 3 , Ge 2 O, and TeO 2 are highly refracted.
- the rate component TiO 2 , Nb 2 O 5 , WO 3 , Bi 2 O 3 , La 2 O 3 , Gd 2 O 3 , Y 2 O 3 , ZrO 2 , ZnO, BaO, PbO, Sb 2 O 3 are selected.
- High refractive index glass containing one kind or two or more kinds of components can be used.
- the scattering material bubbles, crystal precipitates, and the like are conceivable.
- the reflection of the reflective electrode can be prevented by providing the glass surface with undulations.
- an element-forming thin film is usually formed by tracing the undulations of the base. Therefore, when the substrate is flat, if a reflective electrode is used, it becomes mirror-like and causes reflection. Therefore, by imparting undulation to the surface of the glass layer, the reflective electrode can be undulated and reflection can be suppressed.
- FIG. 8 is a cross-sectional explanatory view of an example in which undulations are provided on the surface of the glass layer.
- FIG. 8A is a cross-sectional explanatory view showing the undulation state of the glass substrate 101 and the glass layer 102 for explaining the relationship between the wavelength ⁇ and the surface roughness Ra, and the auxiliary wiring is shown for easy understanding. It has not been.
- FIG. 8B is a cross-sectional explanatory diagram in a state where an organic LED element is formed.
- a light emitting layer 113, an electron transport layer 114, an electron injection layer 115, a reflective electrode 120, and an auxiliary wiring pattern 200 are shown.
- the electrode-containing translucent substrate 100 is composed of a glass substrate 101, a glass layer 102 containing a scattering material 104, and an auxiliary wiring pattern 200, and the surface thereof has undulations.
- the organic layer 110 formed thereon has a light emitting function, and includes a hole transport layer 112, a light emitting layer 113, an electron transport layer 114, an electron injection layer 115, and a reflective electrode 120. And have a swell.
- the ratio Ra / R ⁇ a of the surface roughness Ra (JIS B0601-1994) of the surface of the glass scattering layer to the wavelength R ⁇ a of the surface waviness is 1.0 ⁇ 10 ⁇ 6 or more 3 It is desirable that it is 0.0 ⁇ 10 ⁇ 5 or less.
- the surface of the scattering layer is desirably smooth, and the surface roughness Ra of the surface constituting the undulation is desirably 30 nm or less, and particularly 10 nm or less. Is desirable.
- the organic LED element includes a light-transmitting substrate 100 with an auxiliary wiring and a light-transmitting electrode as an electronic device substrate, an organic layer 110, and a reflective electrode 120.
- the translucent substrate with electrode 100 includes a substrate 101 made of a translucent glass substrate, a glass layer 102, and a translucent electrode 103. By adopting this range, the film thickness of the translucent electrode 103 can be made uniform, and the distance between the electrodes can be made uniform. Therefore, electric field concentration can be suppressed, and the lifetime of the element can be extended.
- the light-transmitting substrate 100 with auxiliary wiring and light-transmitting electrode (as a substrate for an electronic device) used in the present invention is a light-transmitting glass substrate 101 and a glass having scattering characteristics formed on the glass substrate. It is desirable to include the layer 102 and the translucent electrode 103. That is, the glass layer includes a base material having a first refractive index with respect to one wavelength of transmitted light, and a plurality of second materials that are dispersed in the base material and have a second refractive index different from the base material.
- the scattering material 104 is preferably included and has a scattering property. In particular, it is desirable that the distribution of the scattering material in the glass layer decreases from the inside of the glass layer toward the translucent electrode.
- the translucent electrode 103 preferably has a third refractive index that is the same as or lower than the first refractive index.
- the emitted light can be efficiently guided to the glass substrate side, and the light extraction characteristics can be improved.
- the surface of the glass layer having scattering properties is smooth.
- the scattering material is not present within 0.2 ⁇ m from the surface of the glass layer.
- the density ⁇ 1 of the scattering material at half the thickness ( ⁇ / 2) of the glass layer 102 and the density ⁇ 2 of the scattering material in the portion close to the surface of the glass layer on the side in contact with the translucent electrode are: , ⁇ 1 > ⁇ 2 is desirable.
- the glass layer is formed directly on the glass substrate, it may be formed via a barrier layer, for example, after forming a silica thin film on the glass substrate by sputtering, and then forming a glass layer.
- a barrier layer for example, after forming a silica thin film on the glass substrate by sputtering, and then forming a glass layer.
- an extremely stable and flat surface can be obtained, and it is thermally stable by being composed of only inorganic substances. Thus, it becomes possible to form a long-life optical device.
- the glass powder may be applied onto the glass substrate by an appropriate method.
- it can be obtained by dispersing glass particles in a solvent or a mixture of a resin and a solvent and applying the dispersion to a desired thickness.
- glass particles having a maximum length of about 0.1 to 10 ⁇ m are used.
- the glass particles When the temperature is further raised, the glass particles start to be fused at a temperature 10 to 20 ° C. lower than the softening temperature of the glass. When the glass particles are fused, the gap formed between the glass particles is deformed by the softening of the glass, and a closed space is formed in the glass. In the uppermost layer of glass particles, the glass particles are fused together to form the surface of the glass layer. The gap that does not become a closed space on this surface remains as a dent.
- the softening and flow of the glass proceed, and the gaps inside the glass form spherical bubbles.
- the dent caused by the gap between the glass particles is smoothed.
- gas may be generated when the glass is softened to form bubbles.
- an organic substance adheres to the surface of the glass layer it may decompose to generate CO 2 and generate bubbles.
- a substance that decomposes by heat as described above may be introduced to actively generate bubbles. Such a state is usually obtained near the softening temperature.
- the viscosity of the glass is as high as 10 7.6 poise at the softening temperature, and if the bubble size is several ⁇ m or less, it is difficult to float on the surface. Therefore, by adjusting the material composition so as to generate small bubbles and adjusting the firing temperature to increase the holding time, it is possible to further smooth the surface while suppressing the rising of the bubbles. In this way, when the surface is cooled from a smooth state, the density of the scattering material is smaller on the surface than on the inside of the glass layer, and a glass layer having a scattering property with a smooth surface can be obtained.
- the material composition for forming the glass layer and the firing temperature it is possible to leave bubbles in the glass layer and to suppress the generation of bubbles and dents on the surface of the glass layer. Is possible.
- the firing temperature profile and adjusting the firing time so as to prevent the scattering material from rising and remain on the glass layer, it has excellent scattering characteristics, high surface smoothness, and electrodes. It becomes possible to provide a translucent substrate.
- the outermost surface of the glass layer can also form a curved surface having waviness.
- the waviness means that the wave length period ⁇ is 10 ⁇ m or more.
- the size of the swell is about 0.01 to 5 ⁇ m in Ra. Even when such undulation is present, micro smoothness is maintained.
- “moderate” means that the diameter of the opening of the recess ⁇ the diameter of the internal space.
- the firing temperature is desirably about 40 to 60 ° C. higher than the glass transition temperature. If the temperature is too low, sintering will be insufficient and the surface will not be smooth. Therefore, it is more desirable that the firing temperature be about 50 ° C. to 60 ° C. higher than the glass transition temperature.
- the glass layer can form a swell whose surface forms a curved surface, so that when the organic LED element formed on the upper layer is a reflective electrode, it is possible to suppress a decrease in aesthetic appearance due to reflection.
- reflection by the reflective electrode occurs at the time of non-light emission, and it has been a problem to impair the aesthetic appearance.
- the conditions are set when forming the glass layer. By optimizing, it is possible to increase the contact area between the electrode and the layer having a light emitting function without reducing the accuracy of the pattern formed on the upper layer or causing variation in the distance between the electrodes. Therefore, an effective element area can be increased, and a long-life and high-brightness organic LED element can be formed.
- the surface roughness is low. It is 30 nm or less, desirably 10 nm or less. If the surface roughness exceeds 30 nm, the coverage of the organic layer formed thereon may be deteriorated, and a short circuit occurs between the translucent electrode formed on the glass layer and the other electrode. There is a case.
- the element is not lit due to the short circuit between the electrodes, it may be possible to repair it by applying an overcurrent.
- the roughness of the glass layer is desirably 10 nm or less, and more desirably 3 nm or less.
- the size of the scattering material is such that when there are bubbles in the glass layer, if the bubbles increase, the buoyancy increases in the glass layer formation process such as firing, and the bubbles easily rise. Can rupture and significantly reduce surface smoothness.
- the scattering property is lowered only in that portion. If such large bubbles are aggregated, they become uneven and can be visually recognized. For this reason, the ratio of bubbles having a diameter of 5 ⁇ m or more is desirably 15 vol% or less, more desirably 10 vol% or less, and further desirably 7 vol% or less.
- the ratio of the scattering material having the maximum length of 5 ⁇ m or more is desirably 15 vol% or less, desirably 10 vol% or less, and more desirably 7 vol% or less.
- the crystal size is 0.1 ⁇ m or more, it functions as a light scattering material.
- the firing temperature it is possible to precipitate crystals inside the glass layer while suppressing crystal precipitation on the surface of the glass layer. Specifically, it is desirable to increase the temperature from the glass transition temperature to about 60 ° C to 100 ° C. If the temperature rises to such a level, the viscosity of the glass is high and bubbles are unlikely to rise.
- the firing temperature is more desirably about 60 ° C. to 80 ° C. higher than the glass transition temperature, and most desirably 60 ° C. to 70 ° C.
- a light-transmitting substrate in which the density of the scattering material on the surface of the glass layer is smaller than the density of the scattering material inside the glass layer can be obtained. Further, a light-transmitting substrate is used in which the density ⁇ 1 of the scattering material at half the thickness of the glass layer and the density ⁇ 2 of the scattering material near the surface of the glass layer satisfy ⁇ 1 > ⁇ 2. This makes it possible to obtain a translucent substrate having sufficient scattering characteristics and a smooth surface.
- the scattering material may be a bubble, a material particle having a composition different from that of the base layer, or a precipitated crystal of the base layer. These may be a single substance or a mixture.
- the size, bubble distribution, and density of the bubbles can be adjusted by adjusting the baking conditions such as the baking temperature.
- the scattering material is a material particle having a composition different from that of the base layer
- the size, distribution, and density of the scattering material can be adjusted by adjusting the material composition and the firing conditions such as the firing temperature.
- the scattering material is a precipitated crystal of glass constituting the base layer
- the size, bubble distribution, and density of bubbles can be adjusted by adjusting the firing conditions such as the firing temperature.
- the first refractive index of the base layer at at least one wavelength among wavelengths ⁇ (430 nm ⁇ ⁇ 650 nm) is 1.8 or more.
- the refractive index can be easily adjusted by adjusting the material composition of the glass material.
- a glass substrate is used as the light-transmitting substrate used for forming the light-transmitting substrate.
- the material of the glass substrate include inorganic glass such as alkali glass, non-alkali glass, and quartz glass.
- the thickness of the glass substrate 101 is desirably 0.1 mm to 2.0 mm. However, if the thickness is too thin, the strength decreases, so that the thickness is particularly preferably 0.5 mm to 1.0 mm.
- the thermal expansion coefficient is 50 ⁇ 10 ⁇ 7 / ° C. or higher, preferably 70 ⁇ 10 ⁇ 7 / ° C. or higher, more preferably 80 ⁇ . 10 ⁇ 7 / ° C. or higher is desirable.
- the average thermal expansion coefficient of the glass layer from 100 ° C. to 400 ° C. is from 70 ⁇ 10 ⁇ 7 (° C. ⁇ 1 ) to 95 ⁇ 10 ⁇ 7 (° C. ⁇ 1 ), and the glass transition temperature is 450. It is desirable that the temperature is from 550C to 550C.
- ⁇ Glass layer> The undulation on the surface of the glass layer is as already described. Subsequently, the configuration of the glass layer, the production method, the characteristics, and the refractive index measurement method will be described in detail. In addition, although mentioned later for details, in order to implement
- glass layer 102 is formed by forming glass powder on a glass substrate by a method such as coating and baking at a desired temperature.
- the formed glass layer includes a base material 102 having a first refractive index, and a scattering material 104 having a second refractive index different from the base material and dispersed in the base material 102. .
- the distribution of the scattering material in the glass layer is reduced from the inside to the surface, and as described above, the glass layer has excellent scattering characteristics. Can maintain the smoothness of the surface. Accordingly, it is possible to realize light extraction with extremely high efficiency by being used on the light emitting surface side of a light emitting device or the like.
- a material (base material) having a coated main surface and high light transmittance is used.
- base material various kinds of glass and crystallized glass are used.
- a scattering material 104 for example, bubbles, precipitated crystals, material particles different from the base material, and phase-separated glass
- the particle refers to a small solid substance such as a filler or ceramic.
- Air bubbles refer to air or gas objects.
- phase-separated glass means the glass comprised by two or more types of glass phases.
- the scattering material is a bubble, the diameter of the scattering material refers to the length of the gap.
- the refractive index of the base material is equal to or higher than the refractive index of the translucent electrode material. This is because when the refractive index is low, a loss due to total reflection occurs at the interface between the base material and the translucent electrode material.
- the refractive index of the base material only needs to exceed at least a part of the emission spectrum range of the light emitting layer (for example, red, blue, green, etc.), but exceeds the entire emission spectrum range (430 nm to 650 nm). It is more desirable that it exceeds the entire visible light wavelength range (360 nm to 830 nm).
- the main surface of the glass layer is smooth in order to prevent a short circuit between the electrodes of the organic LED.
- the scattering material it is not desirable for the scattering material to protrude from the surface of the glass layer on the side in contact with the translucent electrode.
- the scattering material it is desirable that the scattering material is not present within 0.2 ⁇ m from the surface of the glass layer.
- the average roughness (Ra) of the surface of the glass layer is preferably 30 nm or less, more preferably 10 nm or less, and particularly preferably 1 nm or less.
- Both the scattering material and the base material may have a high refractive index, but the difference in refractive index ( ⁇ n) is preferably 0.2 or more at least in a part of the emission spectrum range of the light emitting layer. In order to obtain sufficient scattering characteristics, the difference in refractive index ( ⁇ n) is 0.2 or more over the entire emission spectrum range (430 nm to 650 nm) or the entire visible light wavelength range (360 nm to 830 nm). More desirable.
- the high light transmittance material has a high refractive index glass and the scattering material has a gaseous object, that is, a bubble.
- the base material since the refractive index of the base material is desirably as high as possible, it is desirable that the base material be glass having a high refractive index.
- a high refractive index component one or more components selected from P 2 O 5 , SiO 2 , B 2 O 3 , Ge 2 O, and TeO 2 are used as a high refractive index component as a network former.
- a high refractive index glass containing two or more kinds of components can be used.
- alkali oxides, alkaline earth oxides, fluorides, and the like may be used as long as the physical properties required for the refractive index are not impaired.
- Specific glass systems include B 2 O 3 —ZnO—La 2 O 3 system, P 2 O 5 —B 2 O 3 —R ′ 2 O—R ′′ O—TiO 2 —Nb 2 O 5 —WO 3 —.
- R ′ represents an alkali metal element
- R ′′ represents an alkaline earth metal element.
- the above is an example, and if it is the structure which satisfy
- the color of light emission can be changed.
- known ones such as transition metal oxides, rare earth metal oxides and metal colloids can be used alone or in combination.
- the glass layer is produced by coating and baking.
- the glass layer is made into a frit paste.
- the method to do is desirable.
- the glass softening point (Ts) of the glass layer is lower than the strain point (SP) of the glass substrate, and the difference in thermal expansion coefficient ⁇ . Is desirable to be small.
- the difference between the softening point and the strain point is preferably 30 ° C. or higher, and more preferably 50 ° C. or higher.
- the expansion rate difference between the glass layer and the glass substrate is desirably not more than ⁇ 10 ⁇ 10 -7 (1 / K), and more preferably not more than ⁇ 5 ⁇ 10 -7 (1 / K).
- the frit paste refers to a glass powder dispersed in a resin, a solvent, a filler or the like.
- the glass layer can be coated by patterning and baking the frit paste using a pattern forming technique such as screen printing. The technical outline is shown below.
- (Frit paste material) Glass powder
- the particle diameter of the glass powder is 1 ⁇ m to 10 ⁇ m.
- a filler may be added. Specifically, zircon, silica, alumina or the like is used as the filler, and the particle size is 0.1 ⁇ m to 20 ⁇ m.
- the glass material will be described below.
- P 2 O 5 is 20 to 30 mol%
- B 2 O 3 is 3 to 14 mol%
- the total amount of Li 2 O, Na 2 O, and K 2 O is 10 to 20 mol%.
- Bi 2 O 3 is 10 to 20 mol%
- TiO 2 is 3 to 15 mol%
- Nb 2 O 5 is 10 to 20 mol%
- WO 3 is 5 to 15 mol%
- the total amount of the above components is 90 mol% or more Use what is.
- the glass composition for forming the glass layer is not particularly limited as long as the desired scattering characteristics can be obtained and frit paste can be fired, but in order to maximize the extraction efficiency, for example, P 2 O 5 is used.
- a system containing one or more components of Nb 2 O 5 , Bi 2 O 3 , TiO 2 , WO 3 , B 2 O 3 , ZnO and La 2 O 3 as essential components A system containing one or more components of 2 O 5 , ZrO 2 , Ta 2 O 5 , WO 3 , a system containing SiO 2 as an essential component, and containing one or more components of Nb 2 O 5 , TiO 2 , Bi 2 O 3 as a main component, and a system containing SiO 2 , B 2 O 3 or the like as a network forming component.
- each component is as follows in terms of mol%.
- P 2 O 5 is an essential component that forms this glass-based skeleton and vitrifies it, but if the content is too small, the devitrification of the glass increases and it becomes impossible to obtain glass, so 15% or more Is desirable, and 18% or more is more desirable.
- the content is desirably 30% or less, and more desirably 28% or less.
- B 2 O 3 is an optional component that is a component that improves devitrification resistance and decreases the coefficient of thermal expansion by adding it to the glass. However, if the content is too large, the refractive index decreases. Therefore, 18% or less is desirable and 15% or less is more desirable.
- SiO 2 is an optional component that is a component that stabilizes the glass by adding a small amount and improves the devitrification resistance. However, if the content is too large, the refractive index decreases, so 15% The following is desirable, 10% or less is more desirable, and 8% or less is particularly desirable.
- Nb 2 O 5 is an essential component that simultaneously has the effects of improving the refractive index and enhancing weather resistance. Therefore, the content is desirably 5% or more, and more desirably 8% or more. On the other hand, if the content is too large, devitrification becomes strong and glass cannot be obtained. Therefore, the content is preferably 40% or less, and more preferably 35% or less.
- TiO 2 is an optional component that improves the refractive index.
- the content is desirably 15% or less, and more desirably 13% or less.
- WO 3 is an optional component that improves the refractive index, lowers the glass transition temperature, and lowers the firing temperature. However, when it is introduced excessively, the glass is colored, resulting in a decrease in light extraction efficiency. Is preferably 50% or less, more preferably 45% or less.
- Bi 2 O 3 is a component improving the refractive index, can be introduced in a relatively large amount in the glass while maintaining the stability of the glass. However, when it introduce
- Nb 2 O 5 , TiO 2 , WO 3 and Bi 2 O 3 must be included.
- the total amount of (Nb 2 O 5 + TiO 2 + WO 3 + Bi 2 O 3 ) is desirably 20% or more, and more desirably 25% or more.
- the amount is desirably 60% or less, and more desirably 55% or less.
- Ta 2 O 5 is an optional component that improves the refractive index. However, if the amount added is too large, devitrification resistance is lowered and the price is high, so the content is 10% or less. Desirably, 5% or less is more desirable.
- Alkali metal oxides (R 2 O) such as Li 2 O, Na 2 O, K 2 O have the effect of improving the meltability and lowering the glass transition temperature, and at the same time, increasing the affinity with the glass substrate. , Has the effect of increasing the adhesion. Therefore, it is desirable to contain one or more of these.
- the total amount of Li 2 O + Na 2 O + K 2 O is preferably 5% or more, and more preferably 10% or more. However, if it is contained excessively, the stability of the glass is impaired, and since both are components that lower the refractive index, the refractive index of the glass is lowered, and the desired light extraction efficiency is improved. I can't expect it. Therefore, the total content is desirably 40% or less, and more desirably 35% or less.
- Li 2 O is a component for decreasing the glass transition temperature and improving the solubility.
- the content is desirably 20% or less, and more desirably 15% or less.
- Both Na 2 O and K 2 O are optional components that improve the meltability, but if they are contained excessively, the refractive index is lowered, and the desired light extraction efficiency cannot be achieved. Therefore, the content is desirably 20% or less, and more desirably 15% or less.
- ZnO is a component that improves the refractive index and lowers the glass transition temperature.
- the content is desirably 20% or less, and more desirably 18% or less.
- BaO is a component for improving the refractive index and at the same time improving the solubility. However, if added excessively, the stability of the glass is impaired. Therefore, its content is desirably 20% or less, and 18% or less. More desirable. MgO, CaO, and SrO are optional components that improve the meltability, but at the same time, they are components that lower the refractive index. Therefore, any of them is desirably 10% or less, and more desirably 8% or less.
- the total amount of the above components is desirably 90% or more, more desirably 93% or more, and further desirably 95% or more.
- a small amount of a refining agent, a vitrification promoting component, a refractive index adjusting component, a wavelength converting component, or the like may be added within a range that does not impair the required glass properties.
- Sb 2 O 3 and SnO 2 are exemplified as the fining agent, GeO 2 , Ga 2 O 3 , In 2 O 3 as the vitrification promoting component, ZrO 2 as the refractive index adjusting component
- Examples of Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , Yb 2 O 3 , and wavelength conversion component include rare earth components such as CeO 2 , Eu 2 O 3 , and Er 2 O 3 .
- a glass layer containing B 2 O 3 , La 2 O 3 as an essential component, and containing one or more components of Nb 2 O 5 , ZrO 2 , Ta 2 O 5 , WO 3 is expressed in mol%, B 2 O 3 20-60%, SiO 2 0-20%, Li 2 O 0-20%, Na 2 O 0-10%, K 2 O 0-10%, ZnO 5-50%, La 2 O 3 5-25 %, Gd 2 O 3 0-25%, Y 2 O 3 0-20%, Yb 2 O 3 0-20%, but La 2 O 3 + Gd 2 O 3 + Y 2 O 3 + Yb 2 O 3 5%- 30%, ZrO 2 0-15%, Ta 2 O 5 0-20%, Nb 2 O 5 0-20%, WO 3 0-20%, Bi 2 O 3 0-20%, BaO 0-20% Glasses in the composition range are desirable.
- B 2 O 3 is a network forming oxide and is an essential component in this glass system. If the content is too small, glass formation will not occur or the glass will deteriorate in devitrification resistance. Therefore, the content is desirably 20% or more, and more desirably 25% or more. On the other hand, if the content is too large, the refractive index is lowered and the resistance is further lowered. Therefore, the content is limited to 60% or less, and more desirably 55% or less.
- SiO 2 is a component that improves the stability of the glass when added to this type of glass. However, if the amount introduced is too large, the refractive index decreases and the glass transition temperature increases. Therefore, the content is desirably 20% or less, and more desirably 18% or less. Li 2 O is a component that lowers the glass transition temperature. However, when the introduction amount is too large, the devitrification resistance of the glass is lowered. Therefore, the content is desirably 20% or less, and more desirably 18% or less.
- Na 2 O and K 2 O improve the solubility.
- each is preferably 10% or less, more preferably 8% or less.
- ZnO is an essential component that improves the refractive index of the glass and lowers the glass transition temperature. Therefore, the introduction amount is desirably 5% or more, and more desirably 7% or more.
- the amount is desirably 50% or less, and more desirably 45% or less.
- La 2 O 3 is an essential component that achieves a high refractive index and improves weather resistance when introduced into B 2 O 3 glass. Therefore, the content is desirably 5% or more, and more desirably 7% or more. On the other hand, when the introduction amount is too large, the glass transition temperature becomes high, or the devitrification resistance of the glass is lowered, so that a homogeneous glass cannot be obtained. Therefore, the content is desirably 25% or less, and more desirably 22% or less.
- Gd 2 O 3 is a component that achieves a high refractive index and improves weather resistance when introduced into B 2 O 3 glass, and improves the stability of the glass by coexisting with La 2 O 3 , If the amount introduced is too large, the stability of the glass will decrease, so its content is preferably 25% or less, more preferably 22% or less.
- Y 2 O 3 and Yb 2 O 3 achieve a high refractive index, improve the weather resistance when introduced into B 2 O 3 glass, and improve the stability of the glass by coexisting with La 2 O 3 Although it is a component, if the amount introduced is too large, the stability of the glass will decrease, so the content is desirably 20% or less, and desirably 18% or less.
- Rare earth oxides such as La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 are essential components for achieving a high refractive index and improving the weather resistance of glass.
- the total amount of these components, La 2 O 3 + Gd 2 O 3 + Y 2 O 3 + Yb 2 O 3, is preferably 5% or more, and more preferably 8% or more.
- the amount is desirably 30% or less, and more desirably 25% or less.
- ZrO 2 is a component for improving the refractive index, but if the content is too large, the devitrification resistance is lowered or the liquidus temperature is excessively improved, so the content is 15% or less. It is desirable that it is 10% or less.
- Ta 2 O 5 is a component for improving the refractive index.
- the content is 20% or less. Desirably, it is more desirable that it is 15% or less.
- Nb 2 O 5 is a component for improving the refractive index, but if the content is too large, the devitrification resistance is lowered or the liquidus temperature is excessively improved, so the content is 20% or less. Desirably, it is more desirable that it is 15% or less.
- WO 3 is a component for improving the refractive index, but if the content is too large, the devitrification resistance is lowered or the liquidus temperature is excessively improved, so the content is 20% or less. It is desirable that it is 15% or less.
- Bi 2 O 3 is a component for improving the refractive index.
- the content is desirably 20% or less, and more desirably 15% or less.
- BaO is a component that improves the refractive index, but if the content is too large, the devitrification resistance is lowered, so that it is preferably 20% or less, and more preferably 15% or less.
- the total amount of the components described above is desirably 90% or more, and more desirably 95% or more. Even components other than those described above may be added within the range not impairing the effects of the present invention for the purpose of clarifying and improving solubility. Examples of such components include Sb 2 O 3 , SnO 2 , MgO, CaO, SrO, GeO 2 , Ga 2 O 3 , In 2 O 3 , and fluorine.
- a glass layer containing SiO 2 as an essential component and containing one or more components of Nb 2 O 5 , TiO 2 , and Bi 2 O 3 is expressed in terms of mol%, SiO 2 20 to 50%, B 2 O 3 0 to 20%, Nb 2 O 5 1-20%, TiO 2 1-20%, Bi 2 O 3 0-15%, ZrO 2 0-15%, Nb 2 O 5 + TiO 2 + Bi 2 O 3 + ZrO 2 5-40 %, Li 2 O 0-40%, Na 2 O 0-30%, K 2 O 0-30%, Li 2 O + Na 2 O + K 2 O 1-40%, MgO 0-20%, CaO 0-20%, A glass having a composition range of SrO 0 to 20%, BaO 0 to 20%, ZnO 0 to 20% is desirable.
- SiO 2 is an essential component that works as a network former for forming glass. If its content is too small, glass will not be formed, so 20% or more is desirable, and 22% or more is more desirable. desirable.
- B 2 O 3 helps to form glass by adding a relatively small amount with SiO 2 to reduce devitrification. However, if the content is too large, the refractive index is lowered, so the content is 20% or less. Desirably, it is more desirable that it is 18% or less.
- Nb 2 O 5 is an essential component for improving the refractive index, and its content is preferably 1% or more, and more preferably 3% or more. However, since excessive addition reduces the devitrification resistance of the glass and makes it impossible to obtain a homogeneous glass, its content is preferably 20% or less, more preferably 18% or less. desirable.
- TiO 2 is an essential component for improving the refractive index, and its content is preferably 1% or more, and more preferably 3% or more.
- the content is desirably 20% or less, and more desirably 18% or less.
- Bi 2 O 3 is a component for improving the refractive index, but when added excessively, the devitrification resistance of the glass is lowered, it becomes impossible to obtain a homogeneous glass, and further coloration is caused. Increases the loss due to absorption when light propagates through. Therefore, the content is desirably 15% or less, and more desirably 12% or less.
- ZrO 2 is a component that improves the refractive index without deteriorating the coloring degree.
- the content is desirably 15% or less, and more desirably 10% or less.
- Nb 2 O 5 + TiO 2 + Bi 2 O 3 + ZrO 2 is desirably 5% or more, and more desirably 8% or more.
- the total amount is too large, the devitrification resistance of the glass is lowered or coloring occurs, so that it is preferably 40% or less, more preferably 38% or less.
- Li 2 O, Na 2 O, and K 2 O are components that improve the solubility and lower the glass transition temperature, and further increase the affinity with the glass substrate. Therefore, the total amount Li 2 O + Na 2 O + K 2 O of these components is preferably 1% or more, and more preferably 3% or more.
- the content of the alkali oxide component is desirably 40% or less, and 35% or less. Is more desirable.
- BaO is a component that improves the refractive index and at the same time improves the solubility. However, when it is excessively contained, the stability of the glass is impaired, and a homogeneous glass cannot be obtained, so its content is 20% or less. Is desirable, and 15% or less is more desirable.
- MgO, CaO, SrO, and ZnO are components that improve the solubility of the glass. If added appropriately, the devitrification resistance of the glass can be reduced, but if it is excessively contained, the devitrification becomes high and homogeneous. Therefore, the content is preferably 20% or less and more preferably 15% or less.
- the total amount of the components described above is desirably 90% or more.
- components other than those described above may be added within the range not impairing the effects of the present invention for the purpose of clarifying and improving solubility. Examples of such components include Sb 2 O 3 , SnO 2 , GeO 2 , Ga 2 O 3 , In 2 O 3 , WO 3 , Ta 2 O 5 , La 2 O 3 , Gd 2 O 3 , Y 2 O. 3 and Yb 2 O 3 .
- a glass layer containing Bi 2 O 3 as a main component and containing SiO 2 , B 2 O 3 or the like as a glass forming aid is expressed in terms of mol%, Bi 2 O 3 10 to 50%, B 2 O 3 1 -40%, SiO 2 0-30%, but B 2 O 3 + SiO 2 10-40%, P 2 O 5 0-20%, Li 2 O 0-15%, Na 2 O 0-15%, K 2 O 0-15%, TiO 2 0-20%, Nb 2 O 5 0-20%, TeO 2 0-20%, MgO 0-10%, CaO 0-10%, SrO 0-10%, BaO 0
- a glass having a composition range of ⁇ 10%, GeO 2 0-10%, and Ga 2 O 3 0-10% is desirable.
- Bi 2 O 3 is an essential component that achieves a high refractive index and stably forms glass even when introduced in a large amount. Therefore, the content is desirably 10% or more, and more desirably 15% or more. On the other hand, if added in excess, the glass will be colored, absorbing the light that should be transmitted, and lowering the extraction efficiency. In addition, the devitrification is increased and a homogeneous glass can be obtained. It will disappear. Therefore, the content is desirably 50% or less, and more desirably 45% or less.
- B 2 O 3 is an essential component that works as a network former and assists glass formation in a glass containing a large amount of Bi 2 O 3 , and its content is preferably 1% or more, and more preferably 3% or more. However, when the addition amount is too large, the refractive index of the glass is lowered.
- SiO 2 is a component that helps to form glass by using Bi 2 O 3 as a network former. However, if the content is too large, it causes a decrease in refractive index, so 30% or less is desirable, and 25% or less is more desirable.
- the total amount is preferably 5% or more, and more preferably 10% or more.
- the refractive index is lowered, so that it is preferably 40% or less, and more preferably 38%.
- P 2 O 5 is a component that assists in glass formation and suppresses deterioration of the degree of coloration. However, if the content is too large, it causes a decrease in refractive index, so 20% or less is desirable, and 18% or less is more. desirable.
- Li 2 O, Na 2 O, and K 2 O are components for improving the glass solubility and further lowering the glass transition temperature.
- the devitrification resistance of the glass is lowered and is homogeneous. It becomes impossible to obtain glass. For this reason, 15% or less is desirable respectively, and 13% or less is more desirable.
- the total amount of the above alkali oxide components, Li 2 O + Na 2 O + K 2 O is too large, the refractive index is lowered, and the devitrification resistance of the glass is further lowered. The following is more desirable.
- TiO 2 is a component that improves the refractive index. However, when the content is too large, coloring occurs or the devitrification resistance is lowered, so that a homogeneous glass cannot be obtained. Therefore, the content is desirably 20% or less, and more desirably 18% or less.
- Nb 2 O 5 is a component that improves the refractive index.
- the content is desirably 20% or less, and more desirably 18% or less.
- TeO 2 is a component that improves the refractive index without deteriorating the degree of coloring. However, excessive introduction reduces the devitrification resistance and causes coloring when fired after frit formation.
- the content is desirably 20% or less, and more desirably 15% or less.
- GeO 2 is a component that improves the stability of the glass while maintaining a relatively high refractive index. However, since it is extremely expensive, the content is desirably 10% or less, and more desirably 8% or less. It is further desirable not to include.
- Ga 2 O 3 is a component that improves the stability of the glass while maintaining a relatively high refractive index. However, since it is extremely expensive, the content is desirably 10% or less, and 8% or less. More desirably, it is even more desirable not to include.
- the total amount of the components described above is desirably 90% or more, and more desirably 95% or more. Even components other than those described above may be added within the range not impairing the effects of the present invention for purposes such as clarifying, improving solubility, and adjusting the refractive index. Examples of such components include Sb 2 O 3 , SnO 2 , In 2 O 3 , ZrO 2 , Ta 2 O 5 , WO 3 , La 2 O 3 , Gd 2 O 3 , Y 2 O 3 , Yb 2 O. 3 and Al 2 O 3 .
- Resin Resin supports glass powder and filler in the coating after screen printing.
- Specific examples include ethyl cellulose, nitrocellulose, acrylic resin, vinyl acetate, butyral resin, melamine resin, alkyd resin, and rosin resin.
- Solvent dissolves the resin and adjusts the viscosity required for printing. Also, it is desirable not to dry during printing, but to dry quickly in the drying process. A boiling point of 200 ° C to 230 ° C is desirable. Blend to adjust viscosity, solid content ratio, drying speed. Specific examples include ether solvents (butyl carbitol (BC), butyl carbitol acetate (BCA), diethylene glycol di-n-butyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether due to the dry compatibility of the paste during screen printing.
- ether solvents butyl carbitol (BC), butyl carbitol acetate (BCA), diethylene glycol di-n-butyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether due to the dry compatibility of the paste during screen printing.
- a surfactant may be used for viscosity adjustment and glass powder dispersion promotion.
- a silane coupling agent may be used to modify the surface of the glass powder.
- the vehicle refers to a mixture of resin, solvent, and surfactant. Specifically, a resin, a surfactant, or the like is put into a solvent heated to 50 ° C. to 80 ° C., and then allowed to stand for about 4 to 12 hours, followed by filtration. Next, the glass powder and the vehicle are mixed with a planetary mixer and then uniformly dispersed with three rolls. Thereafter, the mixture is kneaded with a kneader to adjust the viscosity. Usually, the vehicle is 20 to 30 wt% with respect to 70 to 80 wt% of the glass powder.
- the glass paste produced in (1) is printed using a screen printer. It is possible to control the film thickness of the glass paste film formed by screen mesh mesh roughness, emulsion thickness, pressing pressure during printing, squeegee pressing amount, and the like. Dry after printing.
- the firing includes a binder removal process for decomposing and disappearing the resin in the glass paste and a firing process for sintering and softening the glass powder.
- the binder removal temperature is 350 ° C. to 400 ° C. for ethyl cellulose and 200 ° C. to 300 ° C. for nitrocellulose, and heating is performed in an air atmosphere for 30 minutes to 1 hour. Thereafter, the temperature is raised to sinter and soften the glass.
- the firing temperature is usually 20 ° C. higher than the softening temperature from the softening temperature.
- the shape and size of the bubbles remaining inside vary depending on the firing temperature. Then, it cools and a glass layer is formed on a board
- the thickness of the obtained film is usually 5 to 30 ⁇ m when a general screen printer is used, but a thicker glass layer can be formed by laminating at the time of printing.
- a glass sheet film is formed on a PET film or the like by using a doctor blade printing method, a die coating printing method, or the like, and then dried to obtain a green sheet.
- the green sheet can be thermocompression bonded onto the substrate, and a glass layer can be obtained through the same firing process.
- the glass layer obtained by this method has a thickness of 50 ⁇ m to 400 ⁇ m. However, a thicker glass layer can be formed by stacking green sheets.
- the calculation software used is a software “SPEOS” (trade name) manufactured by OPTIS. While this software is a ray tracing software, it is possible to apply the Mie scattering theoretical formula to the glass layer.
- the glass scattering layer had a thickness of 30 ⁇ m and a refractive index of 2.0.
- the thickness of the organic layer used as a layer having a light emitting function such as a charge injection / transport layer and a light emitting layer is actually about 0.1 ⁇ m to 0.3 ⁇ m in total.
- the angle of light changes the thickness.
- the minimum thickness allowed by software is set to 1 ⁇ m.
- the total thickness of the glass substrate and the glass layer was set to 100 ⁇ m.
- the organic layer and the light-transmitting electrode were divided into three parts: an electron injection layer and a light-emitting layer, a hole injection / transport layer, and a light-transmitting electrode. In the calculation, these refractive indexes are the same. However, the refractive index of the organic layer and the translucent electrode are approximately the same value, and the calculation result is not greatly changed. In any case, the refractive index is 1.9. It was.
- the organic layer is thin, a waveguide mode due to interference stands when considered strictly, but even if handled geometrically, the result does not change greatly, so it is enough to estimate the effect of the present invention by calculation It is.
- emitted light is emitted from a total of six surfaces without directivity.
- the cathode reflectance was set to 100%. The calculation was performed with the total luminous flux amount being 1000 lm and the number of light beams being 100,000 or 1 million. The light emitted from the translucent substrate was captured by the light receiving surface installed on the upper 10 ⁇ m of the translucent substrate, and the extraction efficiency was calculated from the illuminance.
- the content rate of the scattering material in a glass layer As for the content rate of the scattering material in a glass layer, 1 vol% or more is desirable. Although the behavior varies depending on the size of the scattering material, if the content of the scattering material in the glass layer is 1 vol%, the light extraction efficiency can be 40% or more. Moreover, if the content rate of the scattering material in a glass layer is 5 vol% or more, since light extraction efficiency can be made 65% or more, it is more desirable. Moreover, if the content rate of the scattering material in a glass layer is 10 vol% or more, since a light extraction efficiency can be improved to 70% or more, it is further desirable.
- the content rate of the scattering material in a glass layer is 15 vol% vicinity, since a light extraction efficiency can be improved to 80% or more, it is especially desirable. In consideration of mass production of the glass layer, 10 vol% to 15 vol% which is not easily affected by manufacturing variations is desirable.
- the light extraction efficiency can be made 70% or more even when the content of the scattering material is in the range of 1 vol% to 20 vol%. In particular, the content of the scattering material is 2 vol%. In the range of ⁇ 15 vol%, the light extraction efficiency can be increased to 80% or more. If the diameter of the scattering material is 2 ⁇ m, the light extraction efficiency can be made 65% or more even when the scattering material content is in the range of 1 vol% to 20 vol%. In particular, the scattering material content is 5 vol%. If it is above, light extraction efficiency can be 80% or more.
- the light extraction efficiency can be 60% or more even when the content of the scattering material is in the range of 1 vol% to 20 vol%. In particular, the content of the scattering material is 5 vol%. If it is above, light extraction efficiency can be 80% or more. In addition, when the diameter of the scattering material is 5 ⁇ m, the light extraction efficiency can be 50% or more even when the content of the scattering material is in the range of 1 vol% to 20 vol%. In particular, the content of the scattering material is 10 vol%. If it is above, light extraction efficiency can be 80% or more.
- the light extraction efficiency can be 45% or more even when the scattering material content is in the range of 1 vol% to 20 vol%. In particular, the scattering material content is 10 vol%. If it is above, light extraction efficiency can be 80% or more. In addition, if the diameter of the scattering material is 10 ⁇ m, the light extraction efficiency can be made 40% or more even when the content of the scattering material is in the range of 1 vol% to 20 vol%. In particular, the content of the scattering material is 15 vol%. If it is above, light extraction efficiency can be 80% or more. From the above, it can be seen that when the diameter of the scattering material is large, the light extraction efficiency improves as the content increases. On the other hand, when the diameter of the scattering material is small, the light extraction efficiency is improved even if the content is small.
- the relationship between the light extraction efficiency (%) and the refractive index of the scattering material was obtained by calculation.
- the calculation was performed by dividing the organic layer and the translucent electrode into three parts: an electron injection / transport layer and a light emitting layer, a hole injection / transport layer, and a translucent electrode.
- an electron injection / transport layer (thickness: 1 ⁇ m, refractive index: 1.9), a light emitting layer (thickness: 1 ⁇ m, refractive index: 1.9), a hole injection / transport layer (thickness: 1 ⁇ m, Refractive index: 1.9), glass layer (thickness: 30 ⁇ m, base material refractive index: 2.0, scattering material diameter: 2 ⁇ m, number of scattering materials: about 36 million, scattering material content: 15 vol. %), A glass substrate (thickness: 100 ⁇ m, refractive index: 1.54), and a luminous flux of 1000 lm divided into 100,000 (wavelength 550 nm).
- the light extraction efficiency is 80% or more. Is particularly desirable. Even if the difference between the refractive index of the base material and the refractive index of the scattering material is 0.1 (the refractive index of the scattering material is 1.9), the light extraction efficiency can be 65% or more.
- ⁇ n of the glass layer was set to 1.0.
- the content of the scattering material in the glass layer is 1 vol% or more, it is desirable because the light extraction efficiency can be 55% or more even if the thickness of the glass layer is about 15 ⁇ m.
- the content of the scattering material in the glass layer is 5 vol% to 15 vol%, the light extraction efficiency can be 80% or more even if the thickness of the glass layer is 15 ⁇ m or less or 60 ⁇ m or more. Particularly desirable.
- ⁇ n of the glass layer was set to 1.0.
- the number of scattering substances per 1 mm 2 of the glass layer is 1 ⁇ 10 4 or more, the light extraction efficiency can be 55% or more, which is desirable.
- the number of scattering materials per 1 mm 2 of the glass layer is 2.5 ⁇ 10 5 or more, the light extraction efficiency can be 75% or more, which is more desirable.
- the number of scattering materials per 1 mm 2 of the glass layer is 5 ⁇ 10 5 to 2 ⁇ 10 6 , the light extraction efficiency can be increased to 80% or more, which is particularly desirable.
- the refractive index of the translucent electrode is larger than the refractive index of the glass layer, total reflection occurs on the surface of the glass layer, and the amount of light entering the glass layer is reduced. Therefore, the light extraction efficiency is reduced. Therefore, the refractive index of the glass layer of the present invention is desirably equal to or higher than the refractive index of the translucent electrode.
- the glass layer has a surface on which a translucent electrode is provided.
- the glass layer of the present invention may contain a scattering material.
- the diameter of the scattering material is larger, the light extraction efficiency can be improved even if the content is small.
- the larger the diameter the larger the arithmetic average roughness (Ra) of the main surface of the glass layer when protruding from the main surface of the glass layer.
- the translucent electrode is provided on the main surface of the glass layer. Therefore, the larger the arithmetic average roughness (Ra) of the main surface of the glass layer, the more easily a short circuit occurs and the problem that the organic LED element does not emit light tends to occur.
- the translucent electrode (anode) 103 desirably has a translucency of 80% or more in order to extract light generated in the organic layer 110 to the outside.
- a high work function is required to inject many holes.
- ITO, SnO 2 , ZnO, IZO (Indium Zinc Oxide), AZO (ZnO—Al 2 O 3 : zinc oxide doped with aluminum), GZO (ZnO—Ga 2 O 3 : doped with gallium) Zb oxide), Nb-doped TiO 2 , Ta-doped TiO 2 and the like are used.
- the thickness of the translucent electrode 103 is desirably 100 nm or more.
- the refractive index of the translucent electrode 103 is 1.9 to 2.2.
- ITO indium gallium gallium
- SnO 2 has a standard of 10 wt%. From this, the refractive index of ITO can be lowered by increasing the Sn concentration.
- the translucent electrode may be a cathode.
- the organic layer 110 is a layer having a light emitting function, and includes a hole injection layer 111, a hole transport layer 112, a light emitting layer 113, an electron transport layer 114, and an electron injection layer 115.
- the refractive index of the organic layer 110 is 1.7 to 1.8.
- These hole injection layer, hole transport layer, light emitting layer, electron transport layer, and electron injection layer may be made of materials and structures used in ordinary organic LEDs. Also, various known applications such as not providing some layers, making some layers two layers, and adding other layers may be used.
- the reflective electrode (cathode) 120 is made of a metal having a small work function or an alloy thereof.
- the cathode 120 include alkali metals, alkaline earth metals, and metals belonging to Group 3 of the periodic table. Of these, aluminum (Al), magnesium (Mg), or alloys thereof are preferably used because they are inexpensive and have good chemical stability.
- a laminated electrode or the like obtained by depositing Al on a co-deposited film of Al or MgAg, a thin film deposited film of LiF or Li20, or the like is used. In the polymer system, a laminate of calcium (Ca) or barium (Ba) and aluminum (Al) is used.
- the reflective electrode may be used as the anode.
- both the anode and the cathode can be translucent electrodes.
- a glass substrate different from the element substrate is prepared as the counter substrate.
- the glass substrate is processed as necessary to form a water catching material storage for storing the water catching material.
- the water catching material storage part applies a resist to the glass substrate and exposes a part of the substrate by exposure and development.
- the exposed part is formed by etching to form a water catching material storage part.
- the substrate on which the organic LED element is formed and the opposing substrate are overlapped and bonded.
- a sealing material is applied to the surface of the counter substrate on which the water catching material storage portion is provided using a dispenser.
- an epoxy-based ultraviolet curable resin can be used as the sealing material.
- a sealing material is apply
- the sealing material and the pair of substrates separate the substrate where the organic LED element exists from the outside of the substrate.
- the water catching material it is possible to prevent the organic LED element from being deteriorated due to moisture remaining or entering the sealed space.
- both the anode and the cathode are translucent electrodes, both translucent electrodes are connected to the drive circuit.
- the translucent substrate with translucent electrode of the present invention is not limited to an organic LED element, but is an optical device such as an inorganic LED element, various light emitting devices such as liquid crystal, or a light receiving device such as a light amount sensor or a solar cell. It is effective for improving the efficiency of
- Example 1 As the glass substrate 101, a glass substrate “PD200” (trade name) manufactured by Asahi Glass Co., Ltd. was used. This glass has a strain point of 570 ° C. and a thermal expansion coefficient of 83 ⁇ 10 ⁇ 7 (1 / ° C.). As shown in FIG. 1, a glass substrate 101 is screen-printed using a silver paste, and as shown in FIG. 2A, for example, a paste film thickness of 10 ⁇ m, a line width of 200 ⁇ m, and a 10 cm ⁇ 10 cm grid shape An auxiliary wiring pattern 200 mainly composed of silver is formed.
- a paste film thickness of 10 ⁇ m for example, a paste film thickness of 10 ⁇ m, a line width of 200 ⁇ m, and a 10 cm ⁇ 10 cm grid shape
- An auxiliary wiring pattern 200 mainly composed of silver is formed.
- the glass layer 102 is a layer obtained by baking a high refractive index glass frit paste.
- glass having the composition shown in Table 1 is used as the glass layer 102.
- This glass has a glass transition temperature of 483 ° C., a yield point of 528 ° C., and a thermal expansion coefficient of 83 ⁇ 10 ⁇ 7 (1 / ° C.).
- the refractive index nF of this glass at the F-line (486.13 nm) is 2.03558
- the refractive index nd at the d-line (587.56 nm) is 1.99810
- the refractive index nC at the C-line (656.27 nm) is 1.98344.
- the refractive index was measured with a refractometer (trade name: KRP-2, manufactured by Kalnew Optical Industry Co., Ltd.).
- the glass transition point (Tg) and the bending point (At) were measured by a thermal analysis method (trade name: TD5000SA, manufactured by Bruker) at a temperature rising rate of 5 ° C./min.
- the glass layer 102 was formed by the following procedure.
- the powder raw material was prepared so that it might become a composition shown by the ratio of Table 1.
- the prepared powder raw material was dry pulverized with an alumina ball mill for 12 hours to produce a glass powder having an average particle size (d50, particle size of 50% integrated value, unit ⁇ m) of 1 to 3 ⁇ m.
- 75 g of the obtained glass powder was kneaded with 25 g of an organic vehicle (about 10% by mass of ethyl cellulose dissolved in ⁇ -terpineol or the like) to prepare a paste ink (glass paste).
- This glass paste is uniformly printed on the glass substrate 101 so that the film thickness after firing becomes 15 ⁇ m, 30 ⁇ m, 60 ⁇ m, and 120 ⁇ m, except for the portion where the through hole H is formed.
- the shape of the through hole is an ellipse, and is provided at an interval of 5 cm so that the major axis (100 ⁇ m) is in the longitudinal direction of the auxiliary wiring and the minor axis (50 ⁇ m) is in the direction perpendicular to the auxiliary wiring. Further, the side surface of the through hole has a shape that widens upward.
- the temperature was once returned to room temperature, raised to 450 ° C. in 45 minutes, held at 450 ° C.
- the angle of the slope of the glass layer due to the undulation of the surface excluding the vicinity of the through hole H of the glass layer can be about 27 ° at the maximum, and this angle is the edge portion of the opening insulating film used in the passive organic LED panel It is considered that there is no problem in the coverage of organic films, metal films and the like.
- the glass particles are not classified when the frit is produced, and large particles are contained.
- This swell is considered to be due to the fact that large particles remain as swells during firing. Therefore, when other conditions are the same, the swell can be reduced by making the particle size small and uniform, and can be adjusted to increase the swell by increasing the particle size. I think that the.
- the local roughness was measured for a glass substrate on which no auxiliary wiring pattern was formed.
- the arithmetic average roughness Ra of the surface of the glass layer is 31.0 nm.
- the arithmetic average roughness Ra of the surface was 23.5 nm.
- the scatterers in the glass layer are bubbles, and the bubbles do not exist on the surface.
- the scattering material may be exposed on the surface. It is necessary to prevent a short circuit of the organic LED element.
- the polished surface has a smooth surface.
- the total light transmittance and haze value of each glass substrate for electronic devices were measured.
- Suga Test Instruments Haze Meter HGM-2 was used as a measuring device.
- the base plate of the glass substrate “PD200” described above was measured. Table 2 shows the measurement results.
- an organic LED element as shown in FIG. 1 is manufactured using the glass substrate for electronic devices formed above with a 30-micrometer-thick thing.
- the firing temperature of the glass layer is not only 550 ° C. but also about 570 ° C. and 580 ° C. Also conducted experiments.
- an ITO film as the light-transmitting electrode 103 is formed by sputtering so as to have a film thickness of 150 nm on the scattering glass layer 102 and the glass substrate 101 on which the scattering glass layer 102 is not formed.
- Sputtering is performed at room temperature, Ar 99.5 SCCM, O 2 0.5 SCCM, pressure 0.47 Pa, input power 2.35 W / cm 2 .
- mask film formation is performed using a metal mask.
- ultrasonic cleaning using pure water was performed, and then the surface was cleaned by irradiating ultraviolet rays with an excimer UV generator.
- ⁇ -NPD N, N′-diphenyl-N, N′-bis (l-naphthyl) as an organic film having a light emitting function is formed on the ITO film as the translucent electrode 103 by using a vacuum deposition apparatus.
- ⁇ -NPD and Alq 3 form a circular pattern having a diameter of 12 mm using a mask, and LiF and Al form a pattern using a mask having a 2 mm square region on the ITO pattern through the organic film. Then, the organic LED element is completed.
- a concave portion is formed on the PD 200 as a counter substrate by sandblasting, and a photosensitive epoxy resin is applied to the bank around the concave portion for peripheral sealing.
- a photosensitive epoxy resin is applied to the bank around the concave portion for peripheral sealing.
- put the element substrate and the counter substrate in the glove box paste the water catching material containing CaO in the counter substrate recess, then bond the element substrate and the counter substrate together, irradiate with ultraviolet rays, and seal the periphery
- the resin was cured.
- an organic LED element was formed using a glass substrate for electronic devices on which no auxiliary wiring pattern was formed. Table 3 shows the state of occurrence of a short circuit between the electrodes in each element.
- self-repair refers to causing an overcurrent of 10 mA to flow through the element and causing the short-circuited portion to self-repair with its Joule heat.
- FIG. 9 shows current-voltage characteristics of an element with and without a glass layer. Thus, almost the same characteristics are obtained, and it can be seen that there is no large leakage current even in the element formed on the glass layer.
- current luminance characteristics are shown in FIG. Thus, regardless of the presence or absence of the scattering glass layer, the amount of light flux was proportional to the current, and when the scattering glass layer was present, the amount of light flux increased by 15% compared to the case without it.
- the refractive index of the glass layer is higher than the refractive index of ITO, which is a translucent electrode, at the emission wavelength of Alq3 (450 nm to 700 nm), so that the EL emission light of Alq3 is the interface between the ITO and the scattering glass layer. It is shown that it is possible to efficiently extract light into the atmosphere by suppressing total reflection.
- the angle dependence of color was evaluated.
- a multi-channel spectrometer (trade name: C10027) manufactured by Hamamatsu Photonics Co., Ltd. is used, and the angle dependence of the emission luminance and emission color is measured by rotating the element with respect to the spectrometer. went.
- an angle formed between the normal direction of the element and the direction from the element toward the spectroscope was defined as a measurement angle ⁇ [°]. That is, the state where the spectroscope is installed in front of the element is 0 °.
- FIG. 11 shows the measurement results of an organic LED element without a scattering glass layer
- FIG. 12 is a graph obtained by standardizing the luminance at a wavelength showing the maximum luminance at each measurement angle as 1.
- FIG. 12 It can be seen from FIG. 12 that the spectrum is shifted depending on the measurement angle.
- FIG. 13 shows a measurement result of an element having a scattering glass layer
- FIG. 14 is a graph obtained by normalizing the luminance at a wavelength indicating the maximum luminance at each measurement angle as 1.
- FIG. 14 It can be seen from FIG. 14 that even if the measurement angle changes, the spectrum is hardly shifted. Furthermore, the result of converting the spectrum into chromaticity coordinates is shown in Table 4 and FIG.
- the cross-section of those fired at 570 ° C. and 580 ° C. was polished, and an SEM photograph was taken at a magnification of 10,000 times. From the photograph, the number of bubbles and the glass layer of the bubbles The relationship between the distance from the surface was investigated.
- the length in the transverse direction of the SEM photograph was 12.5 ⁇ m.
- a line was drawn from the surface of the glass layer to the SEM photograph in increments of 0.25 ⁇ m, and the number of bubbles that could be confirmed in this 0.25 ⁇ m ⁇ 12.5 ⁇ m frame was counted.
- bubbles present across a plurality of frames were counted as being in the lower frame. The result is shown in FIG.
- the X axis indicates the distance from the surface of the glass layer.
- the point of 0.5 ⁇ m is the number of bubbles confirmed in a frame of 0.25 ⁇ m to 0.5 ⁇ m measured from the surface of the glass layer.
- the firing temperature is 570 ° C.
- the curve a in the case of 0.5 ⁇ m to 580 ° C. from the surface, as shown by the curve b, the bubbles become closer to the surface from 1.25 ⁇ m to the surface. It can be confirmed that the number is decreasing. In addition, no dent was observed on the surface in any case.
- the point that satisfies is also clear.
- FIG. 16 shows the case where the firing temperatures are 570 ° C. and 580 ° C., but similar results could be obtained even if the firing temperature was slightly changed.
- the cause cannot be determined. There are the following two possibilities. (1) In the case of the 580 ° C. fired product, the bubbles are expanded by the higher temperature, making it easier to count. (2) The decomposition of the organic residue adhered to the glass powder was more advanced at 580 ° C., and the number of bubbles increased.
- bubbles and crystals are generated by different mechanisms, it is possible to generate only bubbles or crystals only by controlling the glass material, powder particle size, surface condition, firing conditions (atmosphere, pressure), etc. is there. For example, by increasing the number of glass network formers or increasing the number of alkali oxide components that suppress crystal precipitation, crystal precipitation is suppressed, and if fired under reduced pressure, bubble generation is suppressed.
- the particle size distribution of bubbles in the glass layer produced this time was measured. If the thickness of the glass layer is 15 ⁇ m, all bubbles in the glass layer can be identified under a microscope. Bubbles in a 90.5 ⁇ m ⁇ 68.1 ⁇ m visual field were identified and counted by image processing. Table 6 shows the measurement results at arbitrary three locations on the glass layer.
- the bubble diameter distribution in many cases had a bubble diameter of 2 ⁇ m or less, and the average diameter was 1.3 to 1.4 ⁇ m.
- the number of bubbles per 1 mm 2 of the glass layer was 1.1 ⁇ 10 5 to 2.2 ⁇ 10 5 .
- the number of bubbles when the glass layer thickness is 30 ⁇ m is 2.2 ⁇ .
- the number of bubbles is 4.4 ⁇ 10 5 to 8.8 ⁇ 10 5 .
- Example 2 (Measurement of wiring resistance) 87.2 g of Ag powder having an average particle diameter of 1 ⁇ m, 2.7 g of Bi—Zn—B glass frit, and 10 g of an organic vehicle (a solution of 10 wt% ethyl cellulose in ⁇ -terpineol) were kneaded to obtain an Ag paste. Created.
- a wiring pattern as shown in FIG. 17 was formed on a 5 cm square soda lime glass substrate surface-coated with a silica film by a screen printing method.
- X is a line width
- the mask dimensions are 100 ⁇ m, 200 ⁇ m, and 500 ⁇ m.
- the unit of the number in a figure is mm.
- the resistance of the formed wiring pattern was measured. The measurement was performed by a two-terminal method using a SANWA tester CD-782C. The contact resistance between the probe and the wiring was corrected by subtracting from the actual measurement value using the value when the probe was brought close to the contact resistance. Table 7 shows the wiring dimensions and resistance measurement results.
- Example 3 Measurement of contact resistance of wiring and ITO
- a TEG Test Element Group
- the pad shown in FIG. 18 was formed using the Ag paste and Au paste obtained by the above method.
- the unit of the numbers in the figure is mm.
- the film thicknesses of the Ag and Au patterns were 11.5 ⁇ m and 5.0 ⁇ m, respectively.
- a glass layer was formed by the following procedure.
- the bulk glass was put in an electric furnace at 500 ° C., and the strain was removed by lowering the temperature to room temperature at a rate of 100 ° C. per hour.
- the produced flakes were dry-ground with an alumina ball mill for 1 hour to obtain glass powder.
- the mass average particle diameter of the obtained glass powder was 3 ⁇ m.
- the refractive index (n d ), glass transition point (T g ), average linear expansion coefficient ( ⁇ 50-300 ) at 50 ° C. to 300 ° C., and glass softening point (T s ) of the obtained glass were as follows. It was measured. The results are shown in Table 8.
- Refractive index (n d ) After the glass was polished, it was measured at 25 ° C. at a measurement wavelength of 587.6 nm by a V-block method using a precision refractometer KPR-2000 manufactured by Kalnew.
- T g Glass transition point
- Average linear expansion coefficient at 50 ° C to 300 ° C ( ⁇ 50-300 )
- the glass was processed into a round bar shape having a diameter of 5 mm and a length of 200 mm, and then measured with a thermal thermal expansion meter TD5000SA manufactured by Bruker AXS Co., Ltd. at a heating rate of 5 ° C./min.
- Glass softening point (T s ) After pulverizing the glass in an agate mortar, the glass powder having a particle size of 74 ⁇ m to 106 ⁇ m is sieved, 120 mg of this is put into a platinum pan, and the heating rate is increased by 10 ° C. The temperature at the inflection point of the DTA curve accompanying the softening flow appearing on the higher temperature side than the glass transition point (T g ) was defined as the glass softening point (T s ).
- FIG. 19 shows a state in which the wiring pattern and the glass layer pattern are overlaid.
- the unit of the number in a figure is mm.
- the film thickness of the glass layer formed on the Ag wiring pattern is 20 ⁇ m
- the film thickness of the glass layer formed on the Au wiring pattern is 17 ⁇ m.
- ITO was deposited by mask sputtering as shown in FIG.
- the unit of the number in a figure is mm.
- Sputtering is performed at room temperature, Ar: 99.5 SCCM, O 2 : 0.5 SCCM, pressure: 0.47 Pa, input power: 2.35 W / cm 2 , and film thickness is 150 nm.
- annealing was performed in an air atmosphere at 200 ° C. for 1 hour in order to improve the transmittance of ITO and reduce the resistance.
- the sheet resistance of the ITO after annealing was 33 ⁇ / ⁇ .
- a TEG having six ITO and wiring metal contacts was formed through the glass layer opening.
- the resistance at both ends of this contact TEG was measured, and the contact resistance was calculated by subtracting the ITO resistance from the measured value.
- the resistance of ITO was calculated from the sheet resistance (33 ⁇ / ⁇ ), the distance between contacts, and the ITO pattern width of 3 mm. Since the contact hole diameter is smaller than the ITO width (3 mm), the resistance of ITO is expected to be larger than the above value, and the error becomes larger as the contact diameter is smaller. Therefore, when the contact diameter is small, the actual contact resistance is expected to be smaller than the calculated value. The results are shown in Table 9.
- the contact resistance decreases as the contact diameter increases, but it was found that the values are almost equal between 500 ⁇ m and 1000 ⁇ m.
- Example 4 (Resistance measurement of ITO with grid-like auxiliary wiring)
- a test pattern for connecting ITO through the opening of the glass layer was formed on the lattice-like auxiliary wiring pattern, and it was examined whether the resistance of ITO was lowered by electrical connection with the auxiliary wiring.
- a grid-like wiring pattern shown in FIG. 22 was formed using the glass substrate, Ag paste, and Au paste described above.
- the film thickness of the Ag wiring pattern is 13.5 ⁇ m
- the film thickness of the Au wiring pattern is 7 ⁇ m.
- the unit of the number in a figure is mm.
- a glass layer having an opening of 500 ⁇ m ⁇ was formed on the grid-like wiring pattern shown in FIG. 23 using the glass paste described above.
- the film thickness of the glass layer formed on the Ag wiring pattern is 20 ⁇ m
- the film thickness of the glass layer formed on the Au wiring pattern is 15 ⁇ m.
- the substrate with a glass layer thus prepared had a total light transmittance of 85.0 and a haze value of 71.0.
- a haze computer (trade name: HZ-2) manufactured by Suga Test Instruments Co., Ltd. was used, and measurement was performed using a base plate of a glass substrate PD200 as a reference.
- FIG. 24 shows the positional relationship between the wiring and the opening. In addition, the unit of the number in a figure is mm. Next, ITO is mask-sputtered.
- the formed ITO pattern is a square with a side length of 31 mm so as to cover the opening of the glass layer. Thereafter, the same heat treatment as described above was performed to reduce the resistance and increase the transmittance of ITO. Thereby, ITO electrically assisted by the grid-like Ag wiring and Au wiring was formed.
- the Cerasolzer manufactured by Senju Metal Co., Ltd. was heated and adhered to the ITO at positions 1 to 5 in FIG. 25 to reduce the contact resistance with the tester. Above, the resistance between each point and the lower left terminal was measured.
- the unit of the numbers in the figure is mm.
- the points 1 to 4 are located at the center of each lattice.
- a Cerasolzer was attached to an ITO pattern that had been annealed with a side of 31 mm as shown in FIG. 26, and each resistance between points 0 and 1 to 5 was measured. The results are shown in Table 10.
- the resistance value increases as the distance from point 0 increases, which is not preferable.
- the one provided with the auxiliary wiring of Ag or Au has a substantially constant resistance value even when the distance from the point 0 is increased, and has a lower resistance than the reference. Since the sheet resistance is 50 m ⁇ / ⁇ to 100 m ⁇ / ⁇ in the Al-based and Ag-based auxiliary wirings usually formed by sputtering, it can be seen that a low resistance auxiliary wiring of 1/10 or more is realized. Since the level difference of the wiring is flattened by the glass layer formed thereon, there is no problem such as disconnection of ITO in the wiring part.
- the contact resistance with a mask size of 500 ⁇ m ⁇ is 32 ⁇ in the case of Ag wiring and 17 ⁇ in the case of Au wiring.
- 16 openings of 500 ⁇ m ⁇ are arranged in one auxiliary wiring grid, so that the contact resistance with the auxiliary wiring is 2.0 ⁇ in the case of Ag and 1 in the case of Au. .1 ⁇ , which is sufficiently smaller than the sheet resistance of ITO.
- the surface of the opening auxiliary wiring is rough, which may cause a short circuit.
- short-circuiting of the element in the opening can be prevented by using a method such as not forming a cathode in the opening or filling a resin to smooth and insulate the opening. Is possible.
- the present invention is effective for increasing the area of the OLED element as shown below.
- the apparent sheet resistance is 0.6 ⁇ / ⁇ . If 5 cm uniform light emission is obtained at 10 ⁇ / ⁇ , it is estimated that uniform light emission of 83 cm (5 cm ⁇ 10 / 0.6 ⁇ 83 cm) on one side is possible using this auxiliary wiring. Although there is a loss of 1% in the aperture ratio, if the glass layer is a high refractive index glass scattering layer, the light extraction is greatly improved, so there is no problem. Moreover, if it is a wiring line of this grade, it will not be visually recognized if it does not care about an external appearance, or if a scattering film is stuck on the panel outer surface.
- the auxiliary wiring line width is further increased, the size can be further increased.
- the sheet resistance is about 0.1 ⁇ / ⁇ .
- the line width necessary for setting the sheet resistance to 1 ⁇ when arranged on the grid is 2.5 mm (FIG. 29), and the aperture ratio is reduced by about 20% (FIG. 29). 30).
- the organic LED element has been described.
- the organic LED element is effective for either the top emission structure or the back emission structure, and the inorganic LED element is not limited to the above structure.
- application to electronic devices such as DRAM is also effective.
- the substrate for electronic devices of the present invention covers the auxiliary wiring with a glass layer and has a smooth surface, so that it is possible to provide a long-life and highly reliable electronic device. It is. Moreover, the visibility of a reflective electrode can be suppressed by having a wave
Abstract
Description
一般的に、有機層で生成された光が電極へと伝わりガラス基板との界面に到達する。しかし、電極とガラス基板との屈折率差が大きいため、電極を伝わった光がガラス基板で反射され、再び電極・有機層へ戻るという現象が生じる。そのため、有機LED素子の外部に取り出せる光の量は、発光光の20%足らずになっているのが現状である。
そこで、基板の片面に光散乱層を設け、光取り出し効率を向上させることを提案している文献がある(特許文献1)。
また、ガラス基板とガラス層との間に、電極を設けることを提案している文献がある(特許文献2)。
本発明は、光取り出し効率が高く、かつ、大面積化に対応した基板を提供することを目的とする。
この構成によれば、スルーホールから露呈する接続用領域を除く、補助配線パターン全体をガラス層で封じ込めているため、補助配線パターンの劣化のおそれがなく、安定でかつ長寿命の補助配線パターンを提供することができる。また、酸化物、カルコゲン物、ハロゲン化物あるいはこれらの混合物などからなるガラス原料を塗布し焼成することによって得られたガラス層の表面は平滑であり、この上層に形成される電極配線をはじめとする機能層の膜厚を安定して均一なものとすることができる。ここでガラスとは、ガラス原料を加熱により溶融または軟化させたものを冷却して得られる非晶質無機物をいうものとする。
この構成によれば、スルーホールの領域も含めて表面の平坦化を図ることができるため、上層に形成される機能層のさらなる均一化をはかることが可能となる。
さらに、望ましくは、上記構成/に加えて、前記散乱物質の前記散乱性のガラス層内分布が、前記散乱性のガラス層内部から前記透光性電極にむかって、小さくなっているものを含む。
この構成によれば、光の取り出し効率の向上を図ることができる。
この構成によれば、散乱性を有しながらも表面が平滑で、この基板上に形成される素子の信頼性の向上を図ることができる。
さらに、望ましくは、前記散乱物質の前記ガラス層内分布が、前記ガラス層内部から前記透光性電極にむかって、小さくなっているものを含む。
この構成により、平坦でない表面には、第2の電極が形成されておらず、発光領域を形成しないため、電界集中による透光性電極および第2の電極間の短絡を生じるのを防ぐことができる。
以下、図面を用いて、本発明の実施の形態1の電子デバイス用基板およびこれを用いた有機LED素子について説明する。図1(a)は、本発明の実施の形態の電子デバイス用基板を示す平面図であり、図1(b)はこの電子デバイス用基板上に形成された有機LED素子を示すE-E’面での断面図である。
まず、ガラス基板101を用意し、必要に応じて表面研磨を行ったのち、銀ペーストを用いてスクリーン印刷により、図2(a)に示すように、たとえば、ペースト膜厚10μm、ライン幅200μmで、10cm×10cmの格子状の銀を主成分とする補助配線パターン200を形成する。
そして、焼成を行い、図2(b)に示すように、補助配線パターン200をスルーホール付きのガラス層102で被覆した電子デバイス用基板を形成する。なお、外部に取り出される補助配線200の端部の部分にはガラス層102が形成されていなくてもよい。
そして、図2(d)に示すように、正孔注入層、発光層、電子注入層などの発光機能を有する層110をたとえば蒸着法で形成する。
透光性電極は、前記したITOの他に酸化錫や他の材料でも使用できる。反射性電極は、各種金属性の電極が使用できるが、代表的な材料としては、アルミニウム、AgMg合金、Caなどが考えられる。
次に、本発明の実施の形態2の電子デバイス用基板およびこれを用いた有機LED素子について説明する。図3(a)は、本発明の実施の形態の電子デバイス用基板の平面図であり、図3(b)はこの電子デバイス用基板に形成された有機LED素子を示すF-F’面の断面図である。
この構成によっても、電圧降下を低減し、高効率の有機LED素子を提供することができる。また第2の電極が金属を用いた反射性電極の場合でも、発光面積が大きくなった場合は同様に電圧降下による発光ムラが考えられる為、本手法は第2の電極が透光性である場合と同様に有効と考えられる。
製造に際しては、図2(a)乃至(d)に示した方法と同様である。
次に、本発明の実施の形態3の電子デバイス用基板およびこれを備えた有機LED素子について説明する。図4(a)は、本発明の実施の形態の電子デバイス用基板の平面図であり、図4(b)はこの電子デバイス用基板に形成された有機LED素子を示すG-G’面の断面図である。
そしてこれを出発材料として表面に電極を形成し電子デバイスを形成する。
まず、ガラス基板101を用意し、必要に応じて表面研磨を行ったのち、スクリーン印刷により、前記実施の形態1と同様に、ペースト膜厚80μm、ライン幅200μmの銀を主成分とする補助配線パターン200を形成する。
この例では後でガラス層101の表面を研磨するため、補助配線の膜厚は0.5~5μm程度が望ましい。
そして、焼成を行い、図5(a)に示すように、補助配線パターンをガラス層で被覆した電子デバイス用基板を形成する。この時点では、補助配線200はガラス層102により覆われている。なお、外部に取り出される補助配線200の端部の部分にはガラス層102が形成されていなくてもよい。
そして最後に、スパッタリング法により第2の電極としてアルミニウム層を形成した後、必要に応じてフォトリソグラフィによりスルーホールHS上のアルミニウム層を除去し、発光機能を有する層110上に反射性電極120としてアルミニウム電極を形成する。
また、マスクスパッタなどでスルーホールHS上にはアルミニウム層が形成されないようにスパッタしてもよい。スルーホールHS上には第2の電極が形成されていない方が電極間の短絡を生じにくいので望ましい。
この構成によれば、スルーホールの微細化により発光面積の増大をはかることができるだけでなく、表面をより平滑化することができるため、有機LED素子を形成するとき、平滑な表面全体に一体的に信頼性の高い素子形成を行うことが可能となる。
次に、本発明の実施の形態4として、電子デバイス用基板を備えた有機LED素子について説明する。図7(a)は、本発明の実施の形態の電子デバイス用基板の平面図であり、図7(b)はこの電子デバイス用基板に形成された有機LED素子を示すI-I’断面図である。
他部については前記実施の形態1と同様に形成される。
この構成により、素子領域から封止部を超えてガラス基板の端縁近傍に形成された外部接続端子部が、内部のスルーホールHと同一工程で同様に形成されている。
他は前記実施の形態1と同様である。なお外部接続端子としてはめっき層を形成し、ボンディング可能となるようにしてもよいし、バンプを形成することも可能である。
この場合のガラス材料として望ましくは、ネットワークフォーマとしては、例えば、P2O5、SiO2、B2O3、Ge2O、TeO2から選ばれる一種類または二種類以上の成分を、高屈折率成分として、TiO2、Nb2O5、WO3、Bi2O3、La2O3、Gd2O3、Y2O3、ZrO2、ZnO、BaO、PbO、Sb2O3から選ばれる一種類または二種類以上の成分を含有する高屈折率ガラスを使用することが出来る。
この範囲に採ることで、透光性電極103の膜厚を均一にすることができ、電極間距離を均一にすることができる。したがって、電界集中を抑制することができ、素子の長寿命化をはかることができる。
ガラス層をガラス粉末を焼成して形成する場合、ガラス粉末を適切な方法で、ガラス基板上に塗布すればよい。例えば、溶剤あるいは樹脂と溶剤を混合したものにガラス粒子を分散させ、所望の厚さに塗布することで得られる。例えば、ガラス粒子の大きさは最大長さで0.1から10μm程度のものを用いる。樹脂と溶剤を混合した場合には、ガラス粒子が分散した樹脂膜を加熱し、樹脂を分解すると、ガラス粒子の間には、隙間が空いている状態となる。
材料系によって最適な焼成条件は異なるが、散乱物質の種類や大きさをコントロールすることで、散乱物質が最表面に存在するのを抑制し、表面平滑性に優れたガラス層を得ることができる。
このため、直径が5μm以上の気泡の割合が15vol%以下であるのが望ましく、さらに望ましくは、10vol%以下であり、さらに望ましくは7vol%以下である。また、散乱物質が気泡以外の場合でも、相対的にその部分の散乱物質の数が少なくなるため、その部分のみ散乱性が低下することになる。従って散乱物質の最大長さが5μm以上のものの割合が15vol%以下であるのが望ましく、望ましくは10vol%以下であり、さらに望ましくは7vol%以下である。
また、ガラス層の半分の厚さにおける散乱物質の密度ρ1と、ガラス層の表面に近い部分の散乱物質の密度ρ2とが、ρ1>ρ2を満たすような透光性基板を用いることで、十分な散乱特性を有しかつ平滑な表面を持つ透光性基板を得ることが可能となる。
散乱物質が気泡である場合には、焼成温度などの焼成条件を調整することで、気泡の大きさや気泡分布や密度を調整可能である。
散乱物質がベース層とは異なる組成をもつ材料粒子である場合には、材料組成物の調整、焼成温度などの焼成条件を調整することで、散乱物質の大きさや分布や密度を調整可能である。
前記散乱物質が前記ベース層を構成するガラスの析出結晶である場合には、焼成温度などの焼成条件を調整することで、気泡の大きさや気泡分布や密度を調整可能である。
<基板>
透光性基板の形成に用いられる透光性の基板としては、ガラス基板が用いられる。ガラス基板の材料としては、アルカリガラス、無アルカリガラスまたは石英ガラスなどの無機ガラスがある。ガラス基板101の厚さは、0.1mm~2.0mmが望ましい。但し、あまり薄いと強度が低下するので、0.5mm~1.0mmであることが特に望ましい。
ガラス層表面のうねりについてはすでに説明したとおりである。また続いて、ガラス層の構成、作製方法、特性および屈折率の測定方法について、詳細に説明する。なお、詳細は後述するが、有機LED素子の主眼である光取り出し効率の向上を実現するためには、ガラス層の屈折率は、透光性電極材料の屈折率よりも同等若しくは高くすることが望ましい。
本実施の形態では、ガラス層102は、前述したように、塗布などの方法でガラス基板上にガラス粉末を形成し、所望の温度で焼成することで形成される。形成されたガラス層は、第1の屈折率を有するベース材102と、前記ベース材102中に分散された、前記ベース材と異なる第2の屈折率を有する散乱物質104とを具備している。このガラス層では、内部から表面にむかって、前記ガラス層中の前記散乱物質の層内分布が、小さくなっており、ガラス層を用いることで前述したように、優れた散乱特性を有しつつも表面の平滑性を維持することがでる。これにより、発光デバイスなどの光出射面側に用いることで極めて高効率の光取り出しを実現することができる。
また、ガラス層としては、コーティングされた主表面を有する光透過率の高い材料(ベース材)が用いられる。ベース材としては、各種ガラス、結晶化ガラスが用いられる。なお、ベース材の内部には、散乱性物質104(例えば、気泡、析出結晶、ベース材とは異なる材料粒子、分相ガラスがある。)が形成されている。ここで、粒子とは固体の小さな物質をいい、例えば、フィラーやセラミックスがある。また、気泡とは、空気若しくはガスの物体をいう。また、分相ガラスとは、2種類以上のガラス相により構成されるガラスをいう。なお、散乱物質が気泡の場合、散乱物質の径とは空隙の長さをいう。
ガラス層の作製方法は、塗布および焼成により行うが、特に、10~100μmの厚膜を大面積にうねりを形成するように、均一かつ迅速に形成するという観点から、ガラスをフリットペースト化して作製する方法が望ましい。フリットペースト法を活用するために、ガラス基板の熱変形を抑制するために、ガラス層のガラスの軟化点(Ts)がガラス基板の歪点(SP)よりも低く、かつ熱膨張係数αの差が小さいことが望ましい。軟化点と歪点の差は30℃以上であることが望ましく、50℃以上であることがより望ましい。また、ガラス層とガラス基板の膨張率差は、±10×10-7(1/K)以下であることが望ましく、±5×10-7(1/K)以下であることがより望ましい。ここで、フリットペーストとは、ガラス粉末が樹脂、溶剤、フィラーなどに分散したものを指す。フリットペーストをスクリーン印刷などのパターン形成技術を用いてパターニング、焼成することで、ガラス層被覆が可能となる。以下技術概要を示す。
1.ガラス粉末
ガラス粉末粒径は1μm~10μmである。焼成された膜の熱膨張を制御するため、フィラーを入れることがある。フィラーは、具体的には、ジルコン、シリカ、アルミナなどが用いられ、粒径は0.1μm~20μmである。
本発明では、前記ガラス層として、たとえば、P2O5が20~30mol%、B2O3が、3~14mol%、Li2OとNa2OとK2Oの合量が10~20mol%、Bi2O3が10~20mol%、TiO2が3~15mol%、Nb2O5が10~20mol%、WO3が5~15mol%を含み、以上成分の合量が、90mol%以上であるものを用いる。
P2O5は、このガラス系の骨格を形成しガラス化させる必須成分であるが、含有量が小さすぎる場合、ガラスの失透性が大きくなりガラスを得ることができなくなるため、15%以上が望ましく、18%以上がより望ましい。一方、含有量が大きすぎると屈折率が低下するため、発明の目的を達成することができなくなる。従って、含有量は30%以下が望ましく、28%以下がより望ましい。
MgO、CaO、SrOは、溶融性を向上させる任意成分であるが、同時に屈折率を低下させる成分であるため、いずれも10%以下であることが望ましく、8%以下であることがより望ましい。
B2O3は、ネットワーク形成酸化物であり、このガラス系における必須成分である。
含有量が少なすぎる場合、ガラス形成しなくなるか、ガラスの耐失透性の低下をもたらすため、20%以上含有することが望ましく、25%以上であることがより望ましい。一方、含有量が多すぎると、屈折率が低下し、さらに対抗性の低下を招くため、含有量は60%以下に制限され、より望ましくは55%以下である。
Li2Oは、ガラス転移温度を低下させる成分である。しかしながら、導入量が大きすぎる場合、ガラスの耐失透性が低下してしまう。そのため、含有量は20%以下が望ましく、18%以下がより望ましい。
ZnOは、ガラスの屈折率を向上させるとともに、ガラス転移温度を低下させる必須成分である。そのため、導入量は5%以上が望ましく、7%以上がより望ましい。一方、添加量が大きすぎる場合、耐失透性が低下してしまい均質なガラスが得られなくなってしまうため、50%以下であることが望ましく、45%以下であることがより望ましい。
Y2O3およびYb2O3は高屈折率を達成し、かつB2O3系ガラスに導入すると耐侯性を向上させ、La2O3と共存させることにより、ガラスの安定性を向上させる成分であるが、導入量が大きすぎる場合、ガラスの安定性が低下してしまうため、含有量はそれぞれ20%以下であることが望ましく、18%以下であることが望ましい。
高屈折率のガラスを得るためには、Nb2O5+TiO2+Bi2O3+ZrO2が5%以上であることが望ましく、8%以上であることがより望ましい。一方、この合量が大きすぎると、ガラスの耐失透性が低下したり、着色を生じたりするため、40%以下が望ましく、38%以下がより望ましい。
Bi2O3は、高屈折率を達成し、かつ多量に導入しても安定にガラスを形成する必須成分である。そのため、その含有量は、10%以上が望ましく、15%以上がより望ましい。一方、過剰に添加すると、ガラスに着色が生じ、本来透過すべき光を吸収してしまい、取り出し効率が低下してしまうことに加え、失透性が高くなり、均質なガラスを得ることができなくなってしまう。そのため、含有量は50%以下が望ましく、45%以下がより望ましい。
B2O3は、Bi2O3を多量に含むガラスにおいて、ネットワークフォーマとして働き、ガラス形成を助ける必須成分であり、その含有量は、1%以上が望ましく、3%以上がより望ましい。しかしながら、添加量が大きすぎる場合、ガラスの屈折率が低下してしまうため、40%以下が望ましく、38%以下がより望ましい。
樹脂は、スクリーン印刷後、塗膜中のガラス粉末、フィラーを支持する。具体例としては、エチルセルロース、ニトロセルロース、アクリル樹脂、酢酸ビニル、ブチラール樹脂、メラミン樹脂、アルキッド樹脂、ロジン樹脂などが用いられる。
溶剤は、樹脂を溶解しかつ印刷に必要な粘度を調整する。また印刷中には乾燥せず、乾燥工程では、すばやく乾燥することが望ましい。沸点200℃から230℃のものが望ましい。粘度、固形分比、乾燥速度調整のためブレンドして用いる。具体例としては、スクリーン印刷時のペーストの乾燥適合性からエーテル系溶剤(ブチルカルビトール(BC)、ブチルカルビトールアセテート(BCA)、ジエチレングリコールジ-n-ブチルエーテル、ジプロピレングリコールブチルエーテル、トリプロピレングリコールブチルエーテル、酢酸ブチルセロソルブ)、アルコール系溶剤(α-テルピネオール、パインオイル、ダワノール)、エステル系溶剤(2,2,4-トリメチル-1,3-ペンタンジオールモノイソブチレート)、フタル酸エステル系溶剤(DBP(ジブチルフタレート)、DMP(ジメチルフタレート)、DOP(ジオクチルフタレート))がある。主に用いられているのは、α-テルピネオールや2,2,4-トリメチル-1,3-ペンタンジオールモノイソブチレート)である。
粘度調整、ガラス粉末分散促進の為、界面活性剤を使用しても良い。ガラス粉末表面改質の為、シランカップリング剤を使用しても良い。
(1)ガラスペースト
ガラス粉末とビヒクルを準備する。ここで、ビヒクルとは、樹脂、溶剤、界面活性剤を混合したものをいう。具体的には、50℃~80℃に加熱した溶剤中に樹脂、界面活性剤などを投入し、その後4時間から12時間程度静置したのち、ろ過し、得られる。
次に、ガラス粉末とビヒクルとを、プラネタリーミキサーで混合した後、3本ロールで均一分散させる。その後粘度調整のため、混練機で混練する。通常ガラス粉末70~80wt%に対してビヒクル20~30wt%とする。
(1)で作製したガラスペーストをスクリーン印刷機を用いて印刷する。スクリーン版のメッッシュ荒さ、乳剤の厚み、印刷時の押し圧、スキージ押し込み量などで形成されるガラスペースト膜の膜厚を制御できる。印刷後乾燥させる。
焼成は、ガラスペースト中の樹脂を分解・消失させる脱バインダ処理とガラス粉末を焼結、軟化させる焼成処理からなる。脱バインダ温度は、エチルセルロースで350℃~400℃、ニトロセルロースで200℃~300℃であり、30分から1時間大気雰囲気で加熱する。その後温度を上げて、ガラスを焼結、軟化させる。焼成温度は軟化温度から軟化温度より20℃高い温度が普通である。焼成温度により内部に残存する気泡の形状、大きさが異なる。その後、冷却して基板上にガラス層が形成される。得られる膜の厚さは、一般的なスクリーン印刷機を使用する場合には通常、5μm~30μmであるが、印刷時に積層することでさらに厚いガラス層が形成可能である。
また計算を簡単にする為、有機層および透光性電極を電子注入層および発光層、正孔注入・輸送層、および透光性電極の3つに分けて計算した。計算ではこれらの屈折率を同じとしているが、有機層と透光性電極の屈折率は同程度の値であり、計算結果を大きく変えるものではない為、いずれの場合も屈折率は1.9とした。
また有機層が薄いことから、厳密に考えると干渉による導波路モードが立つが、幾何光学的に扱っても、大きく結果を変えることはないので、今回の発明の効果を計算で見積もるには十分である。有機層では、合計6面から指向性を持たずに発光光が出射するものとする。また簡単の為に陰極の反射率は100%とした。全光束量を1000lmとし、光線本数を10万本あるいは100万本として計算した。透光性基板から出射した光は、透光性基板の上部10μmに設置した受光面で捕らえ、その照度から取り出し効率を算出した。
ガラス層中における散乱物質の含有率は、1vol%以上が望ましい。散乱物質の大きさで挙動が異なるが、ガラス層中における散乱物質の含有率が1vol%あれば、光取り出し効率を40%以上にすることができる。また、ガラス層中における散乱物質の含有率が5vol%以上であれば、光取り出し効率を65%以上にすることができるので、より望ましい。また、ガラス層中における散乱物質の含有率が10vol%以上であれば、光取り出し効率を70%以上に向上することができるので、さらに望ましい。また、ガラス層中における散乱物質の含有率が15vol%近傍であれば、光取り出し効率を80%以上に向上することができるので、特に望ましい。なお、ガラス層の量産を考えると、製造ばらつきの影響を受けにくい10vol%~15vol%が望ましい。
光取り出し効率(%)と散乱物質の屈折率との関係を計算により求めた。ここでも計算を簡略にするため、有機層および透光性電極を電子注入・輸送層および発光層、正孔注入・輸送層、および透光性電極の3つに分けて計算した。ここで、電子注入・輸送層(厚さ:1μm、屈折率:1.9)、発光層(厚さ:1μm、屈折率:1.9)、正孔注入・輸送層(厚さ:1μm、屈折率:1.9)、ガラス層(厚さ:30μm、ベース材の屈折率:2.0、散乱物質の径:2μm、散乱物質の数:約3600万個、散乱物質の含有量:15vol%)、ガラス基板(厚さ:100μm、屈折率:1.54)、光束1000lmを10万本に分割して計算した(波長550nm)。この結果、ベース材の屈折率(2.0)と散乱物質の屈折率との差が0.2以上(散乱物質の屈折率が1.8以下)であれば、光取り出し効率を80%以上にすることができるので、特に望ましい。なお、ベース材の屈折率と散乱物質の屈折率との差が0.1であっても(散乱物質の屈折率が1.9)、光取り出し効率を65%以上にすることができる。
上記と同じ構成で、ガラス層のΔnを1.0とした。この場合、ガラス層中における散乱物質の含有率が1vol%以上であれば、ガラス層の厚さが約15μmであっても、光取り出し効率を55%以上にすることができるので、望ましい。また、ガラス層中における散乱物質の含有率が5vol%~15vol%あれば、ガラス層の厚さが15μm以下や60μm以上であっても、光取り出し効率を80%以上にすることができるので、特に望ましい。
上記と同じ構成で、ガラス層のΔnを1.0とした。この場合、ガラス層1mm2当たりの散乱物質の数が1×104個以上あれば、光取り出し効率を55%以上にすることができるので、望ましい。また、ガラス層1mm2当たりの散乱物質の数が2.5×105個以上あれば、光取り出し効率を75%以上にすることができるので、より望ましい。また、ガラス層1mm2当たりの散乱物質の数が5×105~2×106個あれば、光取り出し効率を80%以上にすることができるので、特に望ましい。
ガラス層の屈折率を測定するには、下記の2つの方法がある。
一つは、ガラス層の組成を分析し、その後、同一組成のガラスを作製し、プリズム法にて屈折率を評価する。他の一つは、ガラス層を1~2μmまで薄く研磨し、泡のない10μmΦ程度の領域で、エリプソ測定し、屈折率を評価する。なお、本発明では、プリズム法にて屈折率を評価することを前提としている。
ガラス層は、透光性電極が設けられる表面を有している。上述したように、本発明のガラス層は、散乱物質を含有していることもある。上述したように、散乱物質の径としては、大きければ大きいほど含有量が少なくても光取り出し効率の向上が図れる。しかし、発明者の実験によれば、径が大きければ大きいほど、ガラス層の主表面から突出した場合にガラス層の主表面の算術平均粗さ(Ra)が大きくなる傾向にある。上述したように、ガラス層の主表面には透光性電極が設けられる。そのため、ガラス層の主表面の算術平均粗さ(Ra)が大きいほど、短絡が発生しやすくなり、有機LED素子が発光しないという問題が生じやすい。
透光性電極(陽極)103は、有機層110で発生した光を外部に取り出すために、80%以上の透光性があることが望ましい。また、多くの正孔を注入するため、仕事関数が高いものが要求される。具体的には、ITO、SnO2、ZnO、IZO(Indium Zinc Oxide)、AZO(ZnO-Al2O3:アルミニウムがドーピングされた亜鉛酸化物)、GZO(ZnO-Ga2O3:ガリウムがドーピングされた亜鉛酸化物)、NbドープTiO2、TaドープTiO2などの材料が用いられる。透光性電極103の厚さは、100nm以上が望ましい。なお、透光性電極103の屈折率は、1.9~2.2である。ここで、ITOを例にとり説明すると、キャリア濃度を増加させると、ITOの屈折率を低下させることができる。市販されているITOは、SnO2が10wt%が標準となっているが、これより、Sn濃度を増やすことで、ITOの屈折率を下げることができる。但し、Sn濃度増加により、キャリア濃度は増加するが、移動度および透過率の低下があるため、これらのバランスをとって、Sn量を決める必要がある。
なお、透光性電極を陰極としても良いことは言うまでもない。
有機層110は、発光機能を有する層であり、正孔注入層111と、正孔輸送層112と、発光層113と、電子輸送層114と、電子注入層115とにより構成される。有機層110の屈折率は、1.7~1.8である。これら正孔注入層、正孔輸送層、発光層、電子輸送層および電子注入層は、通常の有機LEDに使用される材料や構成が使用されればよい。また、一部の層を設けない、一部の層を2層にする、他の層を付加するなど、種々の公知の応用をしてもよい。
反射性電極(陰極)120は、仕事関数の小さな金属またはその合金が用いられる。陰極120は、具体的には、アルカリ金属、アルカリ土類金属および周期表第3属の金属などが挙げられる。このうち、安価で化学的安定性の良い材料であることから、アルミニウム(Al)、マグネシウム(Mg)またはこれらの合金などが望ましく用いられる。また、Al、MgAgの共蒸着膜、LiFまたはLi20の薄膜蒸着膜の上にAlを蒸着した積層電極等が用いられる。また、高分子系では、カルシウム(Ca)またはバリウム(Ba)とアルミニウム(Al)の積層等が用いられる。
なお、反射性電極を陽極としても良いことは言うまでもない。また、陽極と陰極の両方とも透光性電極とすることもできる。
また本発明の透光性電極付き透光性基板は、有機LED素子に限定されることなく、無機LED素子、液晶など、種々の発光デバイス、あるいは光量センサ、太陽電池などの受光デバイスなど光デバイスの高効率化に有効である。
ガラス基板101は、旭硝子株式会社製ガラス基板「PD200」(商品名)を用いた。このガラスは歪点570℃、熱膨張係数83×10-7(1/℃)である。図1に示すように、ガラス基板101に、銀ペーストを用いてスクリーン印刷により、図2(a)に示すように、たとえば、ペースト膜厚10μm、ライン幅200μmで、10cm×10cmの格子状の銀を主成分とする補助配線パターン200を形成する。
このガラスのF線(486.13nm)での屈折率nFは2.03558、d線(587.56nm)での屈折率ndは1.99810、C線(656.27nm)での屈折率nCは1.98344である。屈折率は、屈折率計(カルニュー光学工業社製、商品名:KRP-2)で測定した。ガラス転移点(Tg)および屈服点(At)は、熱分析装置(Bruker社製、商品名:TD5000SA)で熱膨張法により、昇温速度5℃/分で測定した。
各電子デバイス用ガラス基板(ガラス層付き基板)の全光透過率とヘイズ値を測定した。測定装置として、スガ試験機ヘーズメータHGM-2を用いた。リファレンスとして、上述したガラス基板「PD200」の素板を測定した。測定した結果を表2に示す。
(1)580℃焼成品の方が、温度が高い分だけ泡が膨張しており、カウントし易くなっている、
(2)ガラス粉末に付着した有機系の残渣物の分解が580℃でより進んでいて、泡数が多くなった。
(配線抵抗の測定)
平均粒径1μmのAg粉末87.2gと、Bi-Zn―B系ガラスフリット2.7g、有機ビヒクル(α-テルピネオールにエチルセルロースを10重量%溶解した溶液)10gとを混練して、Agペーストを作成した。
シリカ膜で表面コートされた大きさ5cm角、厚さ0.55mmのソーダライムガラス基板上に、図17に示されるような配線パターンを、スクリーン印刷法により形成した。ここで、Xは線幅であり、マスク寸法で100μm、200μm、500μmとした。なお、図中における数字の単位は、mmである。
(配線・ITOのコンタクト抵抗測定)
次に、透光性電極と補助配線のコンタクト特性を評価するTEG(Test Element Group)を作製した。上述の方法で得られたAgペースト及びAuペーストを用いて、図18に示すパッドを形成した。ここで、図中の数字の単位は、mmである。Ag及びAuパターンの膜厚は、それぞれ11.5μmと5.0μmであった。次に、以下の手順で、ガラス層を形成した。表8のモル%で示される組成となるように、P2O5、B2O3、Li2O、Bi2O3、Nb2O5、WO3、ZnOの各粉末原料を合計で200gとなるよう秤取し、混合した。その後、混合した粉末原料を、白金坩堝を用いて1050℃で1時間溶解し、続けて950℃で1時間溶解して融液を得た。この融液の半量をカーボン鋳型に流し出し、バルク状のガラスを得た。次に、残りの融液を双ロールの隙間に流し出して急冷し、フレーク状のガラスを得た。また、バルク状ガラスは500℃の電気炉に入れ、1時間あたり100℃の速度で室温まで温度を下げることにより、歪みを取り除いた。作製したフレークをアルミナ製のボールミルで1時間乾式粉砕して、ガラスの粉末を得た。得られたガラスの粉末の質量平均粒径は、いずれも、3μmであった。
ガラスを研磨した後、カルニュー社製精密屈折計KPR-2000によって、Vブロック法で、測定波長587.6nmで25℃で測定した。
ガラスを直径5mm長さ200mmの丸棒状に加工した後、ブルッカー・エイエックスエス社製熱膨張計TD5000SAによって、昇温速度を5℃/minにして測定した。
ガラスを直径5mm長さ200mmの丸棒状に加工した後、ブルッカー・エイエックスエス社製熱熱膨張計TD5000SAによって、昇温速度を5℃/minにして測定した。50℃におけるガラス棒の長さをL50とし、300℃におけるガラス棒の長さをL300としたとき、50℃~300℃における平均線膨張係数(α50-300)は、α50-300={(L300/L50)―1}/(300-50)によって求めた。
ガラスをめのう乳鉢で粉砕した後、粒径74μmから106μmまでのガラス粉末を篩い分け、この120mgを白金パンに入れ、エスアイアイ・ナノテクノロジー社製熱TG/DTA EXSTAR6000によって昇温速度を10℃/minにして測定し、ガラス転移点(Tg)よりも高温側に現れる軟化流動に伴うDTA曲線の屈曲点における温度をガラス軟化点(Ts)とした。
(格子状補助配線付きITOの抵抗測定)
次に格子状の補助配線パターン上にガラス層の開口部を介してITOを接続するテストパターンを形成して、ITOが補助配線との電気的接続により低抵抗化しているか調べた。上述のガラス基板、Agペースト及びAuペーストを用いて図22に示す格子状の配線パターンを形成した。ここで、Ag配線パターンの膜厚は13.5μmであり、Au配線パターンの膜厚は7μmである。なお、図中の数字の単位は、mmである。ついで上述のガラスペーストを用いて、図23に示す格子状配線パターン上に500μm□の開口部を有するガラス層を形成した。ここで、Ag配線パターン上に形成したガラス層の膜厚は20μmであり、Au配線パターン上に形成したガラス層の膜厚は15μmである。こうして作製されたガラス層付き基板の全光透過率は85.0、ヘイズ値は71.0であった。測定装置はスガ試験機社製ヘーズコンピュータ(商品名:HZ-2)を用い、リファレンスとしてガラス基板PD200の素板を用いて測定した。図24に配線と開口部の位置関係を示す。なお、図中の数字の単位は、mmである。ついでITOをマスクスパッタする。形成されたITOのパターンは、一辺の長さが31mmの正方形でガラス層の開口部を被覆するように形成する。その後上述と同じ熱処理を施して、ITOの低抵抗化、高透過率化を行った。これにより、格子状のAg配線およびAu配線で電気的に補助されたITOが形成された。ITOの低抵抗化の度合いを調査するために、図25の点1から点5の位置のITOに千住金属社製セラソルザを半田ごてで加熱、付着させ、テスタとのコンタクト抵抗を低下させた上で各点と左下端子部との間の抵抗を測定した。
また、光散乱性が良好でありかつ安定で信頼性の高い散乱性のガラス層を用いることで、光の取り出し効率あるいは取り込み効率を増大することができ、発光デバイス、受光デバイスなどをはじめ電子デバイス全般に適用可能である。
Claims (11)
- 相対向する第1および第2の主面を具備したガラス基板の前記第1の主面側に電極配線が形成される電子デバイス用基板であって、
前記ガラス基板の前記第1の主面上に形成された補助配線パターンと、
前記補助配線パターンを含み前記第1の主面上を覆うように、前記ガラス基板表面に形成された透光性のガラス層とを具備し、
前記補助配線パターン上の前記ガラス層の一部に前記補助配線パターンを露呈するスルーホールが形成されたことを特徴とする電子デバイス用基板。 - ガラス基板と、
前記ガラス基板上に設けられる導電性配線と、
ガラスからなり、第1面と前記第1面に対向する第2面とを貫通する複数の貫通孔を有し、前記第2面が前記ガラス基板及び前記導電性配線に対面するように前記ガラス基板及び前記導電性配線上に形成される散乱層と、
前記散乱層の前記第1面上に形成される電極とを備えたことを特徴とする電子デバイス用基板。 - 請求項1または2に記載の電子デバイス用基板であって、
前記ガラス層表面の表面粗さRaが30nm以下である電子デバイス用基板。 - 請求項1乃至3のいずれかに記載の電子デバイス用基板であって、
前記補助配線パターンが、縦横に配列された格子状パターンである電子デバイス用基板。 - 請求項1乃至4のいずれかに記載の電子デバイス用基板であって、
前記ガラス基板の第1の主面上に形成された補助配線パターンが、ライン幅が0.05~2mm、膜厚が0.5~30μmの導体層によって形成されている電子デバイス用基板。 - 請求項5に記載の電子デバイス用基板であって、
前記補助配線パターンが銀導体で構成されている電子デバイス用基板。 - ガラス基板の第1の主面上に補助配線パターンを形成する工程と、
前記補助配線パターンを含み前記第1の主面上を覆うように、前記ガラス基板表面にガラス層を形成する工程と、
前記補助配線パターン上の一部のガラス層を除去して前記補助配線パターンを露呈してスルーホールを形成する工程とを含み、
前記補助配線パターンの一部が露呈したスルーホールを有するガラス層を有する電子デバイス用基板を製造することを特徴とする電子デバイス用基板の製造方法。 - ガラス基板と、
前記ガラス基板の第1の主面上に形成された補助配線パターンと、
スルーホールを構成する部分を除き前記補助配線パターンを含み前記第1の主面上を覆うように形成された透光性のガラス層とを具備してなる電子デバイス用基板と、
前記ガラス層上に形成された機能素子とを具備し、
前記機能素子が、前記ガラス層の一部に形成されたスルーホールを介して前記補助配線パターンに導電接続されたことを特徴とする電子デバイス。 - ガラス基板と、
前記ガラス基板上に設けられる導電性配線と、
ガラスからなり、第1面と前記第1面に対向する第2面とを貫通する複数の貫通孔を有し、前記第2面が前記ガラス基板及び前記導電性配線に対面するように前記ガラス基板及び前記導電性配線上に形成される散乱層と、
前記散乱層の前記第1面上に形成される電極とを備えたことを特徴とする有機LED用基板。 - 前記散乱層は、P2O5を必須成分として含有しNb2O5、Bi2O3、TiO2、WO3、の一成分以上を含有するガラス、B2O3、ZnOおよびLa2O3を必須成分として含有しNb2O5、ZrO2、Ta2O5、WO3の一成分以上を含有するガラス、SiO2を必須成分として含有しNb2O5、TiO2の一成分以上を含有するガラス及びBi2O3を主成分として含有しネットワーク形成成分としてSiO2及びB2O3を含有するガラスからなるグループのうちいずれか一つであることを特徴とする請求項9に記載の有機LED用基板。
- ガラス基板の第1の主面上に補助配線パターンを形成する工程と、
前記補助配線パターンを含み前記第1の主面上を覆うように、前記ガラス基板表面にガラス層を形成する工程と、
前記補助配線パターン上の一部のガラス層を除去して前記補助配線パターンを露呈してスルーホールを形成する工程と、
前記ガラス層上に機能素子を形成する工程と、
前記機能素子と前記補助配線パターンとを電気的に接続する工程とを備えたことを特徴とする電子デバイスの製造方法。
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- 2009-10-02 KR KR1020117007935A patent/KR20110081968A/ko not_active Application Discontinuation
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Cited By (15)
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JPWO2012014812A1 (ja) * | 2010-07-26 | 2013-09-12 | 旭硝子株式会社 | 有機led素子の散乱層用ガラス及び有機led素子 |
JP2012025634A (ja) * | 2010-07-26 | 2012-02-09 | Asahi Glass Co Ltd | ガラス組成物および基板上にそれを具備する部材 |
WO2012014812A1 (ja) * | 2010-07-26 | 2012-02-02 | 旭硝子株式会社 | 有機led素子の散乱層用ガラス及び有機led素子 |
JP2012069920A (ja) * | 2010-08-09 | 2012-04-05 | Mitsubishi Chemicals Corp | 有機電界発光素子、有機elモジュール、有機el表示装置、及び有機el照明 |
WO2012102268A1 (ja) * | 2011-01-25 | 2012-08-02 | 出光興産株式会社 | 有機エレクトロルミネッセンス素子、及び照明装置 |
US9099672B2 (en) | 2011-01-25 | 2015-08-04 | Idemitsu Kosan Co., Ltd. | Organic electroluminescent element and illumination device |
CN102569603A (zh) * | 2012-01-13 | 2012-07-11 | 张家港市金港镇东南电子厂 | 一种led陶瓷基板及其制作方法 |
US8963414B2 (en) | 2012-01-17 | 2015-02-24 | Kabushiki Kaisha Toshiba | Organic electroluminescent device, lighting apparatus, and method for manufacturing the organic electroluminescent device |
JP2013149376A (ja) * | 2012-01-17 | 2013-08-01 | Toshiba Corp | 有機電界発光素子、照明装置及び有機電界発光素子の製造方法 |
JP2015505639A (ja) * | 2012-02-03 | 2015-02-23 | コーニンクレッカ フィリップス エヌ ヴェ | Oled素子及びその製造 |
JP2015095438A (ja) * | 2013-11-14 | 2015-05-18 | 凸版印刷株式会社 | 透明電極、透明電極の製造方法、透明電極を備えた有機エレクトロルミネッセンス素子 |
JP2020529097A (ja) * | 2017-08-02 | 2020-10-01 | 京東方科技集團股▲ふん▼有限公司Boe Technology Group Co.,Ltd. | 配線構造及びその製造方法、oledアレイ基板及び表示装置 |
JP7156952B2 (ja) | 2017-08-02 | 2022-10-19 | 京東方科技集團股▲ふん▼有限公司 | 配線構造及びその製造方法、oledアレイ基板及び表示装置 |
JP2019102444A (ja) * | 2017-11-28 | 2019-06-24 | エルジー ディスプレイ カンパニー リミテッド | Oled照明装置 |
US11133484B2 (en) | 2017-11-28 | 2021-09-28 | Lg Display Co., Ltd. | OLED lighting apparatus |
Also Published As
Publication number | Publication date |
---|---|
KR20110081968A (ko) | 2011-07-15 |
TW201024245A (en) | 2010-07-01 |
EP2352360A1 (en) | 2011-08-03 |
JP5655567B2 (ja) | 2015-01-21 |
JPWO2010041611A1 (ja) | 2012-03-08 |
US8530748B2 (en) | 2013-09-10 |
EP2352360B1 (en) | 2021-09-15 |
EP2352360A4 (en) | 2014-07-16 |
CN102172101A (zh) | 2011-08-31 |
CN102172101B (zh) | 2015-07-08 |
JP2015008159A (ja) | 2015-01-15 |
JP5862736B2 (ja) | 2016-02-16 |
US20110180308A1 (en) | 2011-07-28 |
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