GLASS SUBSTRATE, ORGANIC EL ILLUMINATOR, AND METHOD FOR PRODUCING GLASS SUBSTRATE
20170125741 ยท 2017-05-04
Assignee
Inventors
Cpc classification
C03C3/078
CHEMISTRY; METALLURGY
International classification
Abstract
A glass substrate for an organic EL element, which can improve the light-extraction efficiency of the organic EL element, can be produced with a high productivity. The glass substrate serves as a light-extraction side transparent substrate of an organic EL element. The refractive index d of the glass substrate is 1.60 or more, and Na.sub.2O+K.sub.2O are contained at 10 mol % to 20 mol % as glass components. A light-extraction side surface has a relief structure obtained by die molding.
Claims
1. A glass substrate serving as a light-extraction side transparent substrate of an organic EL element, wherein a refractive index d is 1.60 or more, and Na.sub.2O+K.sub.2O are contained at 10 mol % to 20 mol % as glass components, and a light-extraction side surface has a relief structure.
2. The glass substrate according to claim 1, wherein the substrate contains TiO.sub.2 at 12 mol % to 24 mol % and BaO at 5 mol % to 15 mol % as glass components.
3. The glass substrate according to, claim 1, wherein a component content rate of Na.sub.2O is larger than a component content rate of K.sub.2O.
4. The glass substrate according to claim 1, wherein K.sub.2O is contained at 1 mol % to 10 mol % as a glass component.
5. The glass substrate according to claim 1, wherein a rear face of the light-extraction side surface in said glass substrate has a relief structure.
6. The glass substrate according to claim 5, wherein the relief structure of the light-extraction side surface and the relief structure of said rear face in said glass substrate are formed to be reversely symmetrical.
7. The glass substrate according to claim 5, wherein the relief structure of the light-extraction side surface and the relief structure of said rear face in said glass substrate are formed to be reversely asymmetrical.
8. The glass substrate according to claim 5, wherein said relief structure is a lens array.
9. The glass substrate according to claim 7, wherein one of said relief structures on the front face and the rear face is a lens array and the other relief structure is a prism array.
10. An organic EL illuminator comprising the glass substrate according to claim 1.
11. An organic EL illuminator comprising the glass substrate according to claim 5, wherein a high refractive layer having a refractive index higher than the refractive index of the glass substrate is formed on said rear face, and a transparent conductive layer of an organic EL element is formed on an upper side of the high refractive layer.
12. A method for producing a glass substrate serving as a light-extraction side transparent substrate of an organic EL element, the method comprising: a step of molding melting glass containing TiO.sub.2 at 10 mol % to 24 mol %, BaO at 5 mol % to 15 mol %, and Na.sub.2O+K.sub.2O at 10 mol % to 20 mol % as glass components into a thin-plate shape by rolling or extending; and a step of performing die pressing for forming a relief structure on a surface of a glass substrate simultaneously with said molding step or thereafter.
13. The method for producing a glass substrate according to claim 12, wherein a die which is used in said step of performing die pressing has a die inner surface which is not in contact with a surface of a curved convex part formed on the glass substrate.
14. The method for producing a glass substrate according to claim 12, wherein said step of performing die pressing is performed simultaneously on a front face and a rear face of said glass substrate.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0016]
[0017]
[0018]
[0019]
[0020]
[0021]
[0022]
[0023]
DESCRIPTION OF EMBODIMENTS
[0024] In the glass substrate according to an embodiment of the present invention, the refractive index d is 1.60 or more. As a result of the refractive index d of the glass substrate being 1.60 or more, the difference in refractive index between the glass substrate and a transparent conductive layer (ITO or the like) or an organic layer can be reduced, and the ratio of light confined in the organic EL element due to total reflection occurring on the interface of the glass substrate and the transparent conductive layer, or the like, in the light emitted in the organic layer can be reduced. It is preferred that the refractive index d of the glass substrate is 1.70 or less.
[0025] As a result, the difference in refractive index between the glass substrate and the air layer outside thereof can be made comparatively small, and the ratio of light confined in the organic EL element due to total reflection occurring on the interface of the glass substrate and the air layer in the light emitted in the organic layer can be reduced.
[0026] The refractive index herein is a refractive index of a d-ray (588 nm) measured with a commercial refractive index meter. It is measured, for example, by using a precision refractive index meter (KPR-30V) manufactured by Kalnew Optical Industrial Co., Ltd.
[0027] The refractive index d in a glass substrate can be adjusted, as appropriate, by a glass composition. Glass components for increasing the refractive index d include refractive index adjusting components such as TiO.sub.2, BaO, and ZnO which are contained in appropriate amounts with respect to SiO.sub.2 which is the principal component. In order to obtain the refractive index d of the glass substrate which is 1.60 or more, TiO.sub.2 is contained at 12 mol % to 24 mol %, preferably 12 mol % to 20 mol %, and BaO is contained at 5 mol % to 15 mol %, preferably 10 mol % to 15 mol %. Further, ZnO can be contained, as necessary, at 0 mol % to 14 mol %. By increasing the content rate of TiO.sub.2, BaO, and ZnO, it is possible to increase the refractive index d, but where the content rate of TiO.sub.2 is too high, coloration or crystallization of the glass substrate tends to occur. Where the content rate of BaO is too high, the glass substrate is difficult to mold into a plate, and where the content rate of ZnO is too high, crystallization tends to occur.
[0028] In addition to TiO.sub.2, BaO, and ZnO, such components as Al.sub.2O.sub.3, Bi.sub.2O.sub.3, La.sub.2O.sub.8, Nb.sub.2O.sub.5, and Y.sub.2O.sub.3 can be selectively contained as the refractive index adjusting components among the glass components. It is preferred that one or a plurality of components selected from among these components be contained at 5 mol % or less.
[0029] The glass substrate according to the embodiment of the present invention has a relief structure formed by die molding on the light-extraction side surface of an organic EL element. The feature of providing a relief structure on the light-extraction side surface of a glass substrate is well known, as disclosed in the abovementioned related art, and it is also well known that such a relief structure can suppress the phenomenon of the light emitted from the organic layer being confined inside the organic EL element due to total reflection at the interface of the glass substrate and the air layer. However, where the relief structure is to be formed by processing such as roughening or etching of the glass substrate surface, as in the related art, complex processing steps are added and a step of subsequent chemical treatment and removal of the chemical reagent by drying after the chemical treatment is also added, the time required for the entire process of producing the glass substrate is increased and a high productivity cannot be obtained.
[0030] By contrast, in the glass substrate of the embodiment of the present invention, a relief structure is formed on the light-extraction side surface of the glass substrate by die molding. As a result, a step of die molding can be simply implemented with respect to the melting glass heated in the step of rolling or extending the melting glass which has been performed in the usual production of glass substrates, and it is not necessary to provide a step of chemical treatment and drying and removal of the chemical reagent. Therefore, a relief structure can be formed on the light-extraction side surface of a glass substrate, without extending significantly the time required for the entire process of producing the glass substrate. A glass substrate that can improve the light-extraction efficiency of the organic EL element can thus be obtained with a high productivity.
[0031] A moldability improving component is contained in an appropriate amount, in addition to the above-described refractive index adjusting component(s), as a glass component of the glass substrate according to the embodiment of the present invention. The moldability improving component is necessary for obtaining a viscosity suitable for molding the melting glass heated to 1000 C. or less. Problems associated with the glass containing no such component are that heating at a temperature significantly higher than 1000 C. is needed in order to obtain the viscosity necessary for molding, excessive heat resistance is required for a die (metal die) necessary for performing the die molding, and limitations are placed on the dimensions and shape of the relief structure which is to be molded. In the glass substrate according to the embodiment of the present invention, since the moldability improving component is contained at the appropriate amount, it is possible to obtain a suitable viscosity needed for die molding at a comparatively low temperature of, for example, 6000 C. to 1000 C.
[0032] The glass substrate according to the embodiment of the present invention contains the appropriate amount of an alkali component as the moldability improving component. Na.sub.2O and K2O are contained in appropriate amounts as the alkali components. In order to obtain the satisfactory die moldability, it is preferred that Na.sub.2O+K.sub.2O be contained at 10 mol % to 20 mol % as the glass components. Since Na.sub.2O is a component that can increase the refractive index of the glass substrate by replacing SiO.sub.2 which is the main component of the glass substrate, in order to increase the refractive index, it is preferred that the component content rate of N.sub.2O Na.sub.2O+K.sub.2O be greater than the component content rate of K.sub.2O. Further, since K.sub.2O acts to suppress the crystallization of TiO.sub.2, it is preferred that K.sub.2O be contained at 1 mol % to 10 mol % in Na.sub.2O+K.sub.2O.
[0033]
[0034] With the slit-down molding depicted in
[0035] FIG., 2 illustrates an exemplary embodiment of a die provided to a second molding roller 3 it depicted in
[0036] The dies depicted in
[0037] Although the die is formed on the surface of the molding roller in the examples depicted in the figures, a similar relief structure can be also formed on the surface of the glass substrate G by pressing a press plate, rather than the roller, on which a die of the above-described shape was formed.
[0038] In as glass substrate according to another embodiment of the present invention, not only the light-extraction side surface has the relief structure molded by the die, as described hereinabove, but also a rear face of the light-extraction side surface in the glass substrate has a relief structure molded by a die.
[0039]
[0040] Even when the relief structure is formed on both the front face and the rear face of the glass substrate G, as depicted in
[0041] Examples of glass components of the glass substrate according to the embodiment of the present invention are described hereinbelow. Tables 1, 2, and 3 represent examples of the present invention and comparative examples. Samples No. 1 to No. 9 in Tables 1 and 2 represent examples of the present invention, and samples No. 10 to No. 12 in Table 3 represent comparative examples. Units of the numerical values of the compounding ratios of glass components in Tables 1 to 3 are mol %.
TABLE-US-00001 TABLE 1 Component\Sample No. 1 No. 2 No. 3 No. 4 SiO.sub.2 63.49 60.0 60.0 65.0 Na.sub.2O 8.39 10.0 5.0 5.0 K.sub.2O 5.52 5.0 10.0 5.0 TiO.sub.2 12.16 15.0 15.0 15.0 BaO 3.62 5.0 5.0 5.0 ZnO 6.82 5.0 5.0 5.0 Refractive index 1.606 1.633 1.622 1.624 Die moldability Good Good Good Good Note
TABLE-US-00002 TABLE 2 Component\Sample No. 5 No. 6 No. 7 No. 8 No. 9 SiO.sub.2 65.0 55.0 60.0 60.0 50.0 Na.sub.2O 5.0 5.0 5.0 5.0 5.0 K.sub.2O 10.0 10.0 15.0 10.0 10.0 TiO.sub.2 15.0 15.0 15.0 20.0 15.0 BaO 5.0 5.0 10.0 5.0 15.0 ZnO 0.0 10.0 0.0 0.0 5.0 Refractive index 1.606 1.638 1.627 1.644 1.659 Die moldability Good Good Good Good Good Note
TABLE-US-00003 TABLE 3 Component\Sample No. 10 No. 11 No. 12 SiO.sub.2 65.0 65.0 50.0 Na.sub.2O 5.0 5.0 5.0 K.sub.2O 10.0 0.0 10.0 TiO.sub.2 10.0 20.0 25.0 BaO 5.0 5.0 5.0 ZnO 5.0 5.0 5.0 Refractive index 1.585 Die moldability Good Poor Note Large coloration
[0042] Blocks of samples for measuring the refractive index in Tables 1 to were produced b placing 250 g of glass raw materials compounded such as to obtain the glass compositions described in the tables in a glass melting furnace (platinum crucible) and melting at 1400 C. to 1500 C. The temperature was then lowered, the components were stirred for 15 min with a platinum stirrer, and the melt was cast into an iron die (707020mm). Each block was placed into an electric furnace and gradually cooled by lowering the temperature to obtain glass. A sample was obtained by cutting out a small piece (about 10105mm) from the glass. A refractive index of a d-ray (588 mm) was measured using a precision refractive index meter (KPR-30V) manufactured by Kainew Optical Industrial Co., Ltd.
[0043] In the evaluation of die moldability in Tables 1 to 3, glass raw materials compounded such as to obtain the glass compositions described in the tables were melted at 1400 C. to 1500 C. and then molded into a thin-plate shape. The temperature was then lowered to 600 C. to 1000 C., and in this state, a circular flat die with a diameter of 100 m to 800 m was pressed against the plate and separated therefrom. The plate was then gradually cooled, and it was evaluated, whether or not the molding was performed with a relief difference of 10 m to20 m or more. Where the relief difference of 10 m to 20 m or more was formed, the evaluation was Good, and where such relief difference was not formed, the evaluation was Poor.
[0044] As shown by the samples in Tables 1 and 2, for samples No. 1 to No. 9 which contained 10 mol % to 20 mol % of Na.sub.2O+K.sub.2O, which are alkali components, in the glass compositions with a refractive index d of 1.60 or more, the die moldability was Good and a relief structure effective for improving the light-extraction efficiency could be formed by die pressing in a state in which the temperature was adjusted to a range of 600 C. to 1000 C. By contrast, as shown by sample No. 11 in Table 3, when the alkali components were contained, at less than 10 mol % (only Na.sub.2O was at 5 mol %), a predetermined relief difference could not be obtained after lowering the temperature to 600 C. to 1000 C.
[0045] When the content rate of BaO, which is a glass component for increasing the refractive index, is made about 5 mol % to 15 mol % in the glass composition containing 10 mol % to 20 mol % of Na.sub.2O+K.sub.2O, which are alkali components, a content of TiO.sup.2 of 12 mol % to 24 mol % is effective for increasing the refractive index d of the glass substrate to 1.60 or more. Where a large amount of BaO is compounded, a plate is difficult to mold. Therefore, it is preferred that the content. rate thereof be suppressed to a predetermined range. Further, where the content rate of TiO.sub.2 is 25 mol % or more as in sample No. 12, in such glass composition, coloration of the glass substrate increases and good transparency cannot be ensured.
[0046] Discussed hereinbelow is a light-extraction efficiency improvement effect obtained when a relief structure is formed by die molding on a glass substrate. Here, a convex lens array shape was considered as an example of the relief structure that can be formed by die molding, and the light-extraction efficiency under predetermined conditions were simulation calculated by a light ray tracing method. In the light ray tracing method, a total of 20,000 light rays which were randomly emitted from the light-emitting face of a complete diffusion surface were traced and emitted to the outside from the glass substrate having a convex lens array on the surface, and the ratio of light rays that reached the sensor surface was taken as the light-extraction efficiency.
[0047] The calculation conditions are described below. Light-emitting surface area 10 mm10 mm. Two-layer structure with a thickness of light-emitting portion d1=0.2+0.2 mm, where the light-emitting surface is the uppermost surface. The refractive index of the light-emitting portion: 1.591. The thickness of the transparent conductive layer (ITO) d2=0.0001 mm. The refractive index of the transparent conductive layer: 2.095. The thickness of the glass substrate d3=0.3 mm. The sensor surface is assumed to detect. light rays in a virtual sensor disposed above the glass substrate at a distance of 0.05 mm (d4) therefrom.
[0048]
[0049] In
[0050] FIG.7(b) illustrates the relationship between the light-extraction efficiency (%) and the lens diameter d (m) in the case with constant lens height h=20 m and lens surface ratio=80.6%. The figure clearly shows that the light-extraction efficiency can be increased by decreasing the lens diameter and increasing the refractive index of the glass substrate. In particular, the light-extraction efficiency can be effectively increased by setting the refractive index of the glass substrate to 1.60 or more with the lens diameter being within a range of 100 m to 430 m.
[0051]
[0052]
[0053] The results of simulation of the light-extraction efficiency improvement effect in the model configuration of the organic EL element depicted in
[0054] Here, the model in which the high refractive layer 100 is provided between the glass substrate G and the transparent conductive layer 101, as depicted in
<First Model>
[0055] Light emission surface area 10 mm10 mm.
[0056] The thickness of the high refractive layer 100 is da=0.02 mm, and the refractive index thereof is 1.9.
[0057] The relief structure on the light-extraction side surface of the glass substrate G is a lens array (honeycomb arrangement of convex lenses on the upper side, lens diameter d=0.08 mm, lens height h=0.025 mm, lens pitch p=0.085 mm (see
[0058] The relief structure on the rear face side (transparent conductive layer side) of the glass substrate G is a prism array (prism height Lh=0.025 mm, prism bottom side Lb=0.05 mm (see
[0059] The simulation results are shown in Table 4.
TABLE-US-00004 TABLE 4 Light-extraction Relief structure of glass substrate (yes/no) efficiency Front face side Rear face side (%) None (flat) None (flat) 26.9 Lens array None (flat) 45.7 None (flat) Prism array 32.0 Lens array Prism array 51.2
<Second Model>
[0060] Light emission surface area: 2 mm2 mm.
[0061] The relief structure on the light-extraction side surface of the glass substrate G is a lens array (honeycomb arrangement of convex lenses on the upper side, lens diameter d=0.08 mm, lens height h=0.025 mm, lens pitch p=0.085 mm (see
[0062] The relief structure on the rear face side (transparent conductive layer code) of the glass substrate G is a lens array (same as hereinabove).
[0063] The simulation results are shown on Table 5.
TABLE-US-00005 TABLE 5 Light-extraction Relief structure of glass substrate (yes/no) efficiency Front face side Rear face side (%) None (flat) None (flat) 25.2 Lens array None (flat) 38.0 None (flat) Lens array 38.3 Lens array Lens array 39.5
[0064] These simulation results clearly indicate that the light-extraction efficiency can be improved more effectively by forming a relief structure on both the light-extraction side surface and the rear face of the glass substrate G.
[0065] As mentioned hereinabove, in the organic EL element using the glass substrate according to the embodiment of the present invention as a light-extracting side transparent substrate, the light-extraction efficiency can be effectively increased. The organic EL element using the glass substrate can be used as a light-emitting element for organic EL devices for various applications, and where it is used in an organic EL illuminator in which a high brightness needs to be obtained at a low power consumption, the increase in the illuminator performance is particularly high.s particularly high.
REFERENCE SIGNS LIST
[0066] 1: orifice, 2: first molding roller, 3: second molding roller, [0067] 10: slit orifice, 11: molding roller [0068] Gm: melting glass, Ga: thin-plate shape glass [0069] Gc: curtain-like glass, G(G1, G2, G3), (Gb, Gd: glass substrates [0070] M, M1, M2: curved convex part, P: conical or pyramidal convex part, [0071] 100: high refractive layer, 101: transparent conductive layer, 102: [0072] light-emitting portion, 103: reflective electrode layer