Laminate for light emitting device and process of preparing same

Abstract

Provided is a laminate for a light emitting device. The laminate for a light emitting device includes a glass substrate having potassium or a glass substrate coated with a mineral layer containing potassium, and an internal light extraction layer formed from a glass frit on the glass substrate. The internal light extraction layer includes an interface void layer at an interface with the glass substrate or the mineral layer. The laminate has an interface void layer inducing the scattering of light for effectively extracting light, which is lost at the interface between the substrate and the internal light extraction layer, to the outside. The laminate is suitable for the fields of optical devices such as organic light emitting diodes (OLEDs), backlights, lighting industry, etc.

Claims

1. A laminate for a light emitting device, comprising: a glass substrate comprising potassium or a glass substrate coated with a mineral layer comprising potassium; and an internal light extraction layer formed from a glass frit having a refractive index (RI) of 1.8 to 2.1 on said glass substrate, wherein the internal light extraction layer comprises an interface void layer at an interface with the glass substrate or the mineral layer.

2. The laminate of claim 1, wherein the glass substrate is a sodalime glass substrate.

3. The laminate according to claim 1, wherein a surface or the outermost region of the glass substrate is treated with potassium.

4. The laminate according to claim 1, wherein a surface of the glass substrate or the mineral layer comprises potassium at a concentration of 1 to 15% by weight.

5. The laminate according to claim 4, wherein the surface of the glass substrate or the mineral layer comprises potassium at a concentration of 5% by weight or less.

6. The laminate according to claim 1, wherein the interface void layer has a thickness of 1 to 5 ?m, and wherein the interface void layer has a void area ratio of 40 to 90%.

7. The laminate according to claim 1, wherein said glass frit comprises 55 to 84% by weight of Bi.sub.2O.sub.3, 0 to 20% by weight of BaO, 5 to 20% by weight of ZnO, 1 to 7% by weight of Al.sub.2O.sub.3, 5 to 15% by weight of SiO.sub.2, 5 to 20% by weight of B.sub.2O.sub.3, and 0.05 to 3% by weight of Na.sub.2O, based on the total weight of the glass frit.

8. The laminate according to claim 1, wherein the internal light extraction layer has a single layer of glass frit comprising said interface void layer at an interface with the glass substrate or the mineral layer.

9. The laminate according to claim 1, wherein the internal light extraction layer has a first glass frit layer comprising the interface void layer at an interface with the glass substrate or the mineral layer and a second glass frit layer covering and in contact with the first glass frit layer.

10. The laminate according to claim 1, wherein the internal light extraction layer comprises a single or double layer of glass frit and is devoid of any scattering elements at the outermost surface.

11. The laminate according to claim 10, wherein the internal light extraction layer is devoid of any scattering elements at the outermost region of at least 2 ?m from the outermost surface.

12. The laminate according to claim 1, wherein said internal light extraction layer has a total thickness of 6 to 30 ?m.

13. The laminate according to claim 1, wherein said internal light extraction layer has an outermost surface roughness (Ra) of less than 1 nm.

14. The laminate according to claim 1, wherein a concentration of potassium becomes smaller from the interface between said glass substrate and said internal light extraction layer to an outermost surface of said internal light extraction layer.

15. The laminate according to claim 1, wherein potassium has a concentration of less than 1% by weight on an outermost surface of said internal light extraction layer.

16. The laminate according to claim 1, further comprising a transparent electrode layer formed on the laminate for a light emitting device.

17. A process of preparing a laminate for a light emitting device, comprising: preparing a glass substrate comprising potassium; applying a glass frit paste onto said glass substrate to form a first glass frit layer; drying said first glass frit layer; and sintering said dried first glass frit layer to form an internal light extraction layer having a refractive index of 1.8 to 2.1, wherein the internal light extraction layer comprises an interface void layer at an interface with the glass substrate.

18. The process according to claim 17, further comprising: applying another glass frit paste onto the sintered first glass frit layer to form a second glass frit layer; drying the second glass frit layer; and sintering the dried second glass frit layer at a predetermined second temperature to form a double frit layer structure for an internal light extraction layer having a refractive index of 1.8 to 2.1.

19. The process according to claim 17, wherein the concentration of potassium is smaller from the interface between the glass substrate or the mineral layer and the internal light extraction layer to an outermost surface of the internal light extraction layer.

20. The process according to claim 17, wherein the interface void layer has a thickness of 1 to 5 ?m, and wherein the interface void layer has a void area ratio of 40 to 90%.

21. The process according to claim 17, wherein the outermost surface of the first or second glass frit layer comprises potassium at a concentration of less than 1% by weight.

22. The process according to claim 17, wherein the first glass frit layer is sintered at the first sintering temperature between 500? C. and 590? C.

23. The process according to claim 17, wherein the glass substrate is a sodalime glass substrate.

24. The process according to claim 17, wherein a surface or the outermost region of the glass substrate is treated with potassium.

25. The process according to claim 17, wherein a surface of the glass substrate comprises potassium at a concentration of 1 to 15% by weight.

26. The process according to claim 17, wherein the first glass frit comprises 55 to 84% by weight of Bi.sub.2O.sub.3, 0 to 20% by weight of BaO, 5 to 20% by weight of ZnO, 1 to 7% by weight of Al.sub.2O.sub.3, 5 to 15% by weight of SiO.sub.2, 5 to 20% by weight of B.sub.2O.sub.3, and 0.05 to 3% by weight of Na.sub.2O, based on the total weight of the glass frit.

27. The process according to claim 17, wherein the internal light extraction layer has a total thickness of 6 to 30 ?m.

28. A process of preparing a laminate for a light emitting device, comprising: preparing a glass substrate; applying a glass frit paste comprising potassium on the glass substrate; drying and sintering the glass substrate coated with the glass frit paste to form a glass substrate coated with a mineral layer comprising glass frit comprising potassium; applying a glass frit paste onto the glass substrate coated with the mineral layer to form a first glass frit layer; drying the first glass frit layer; and sintering the dried first glass frit layer at a predeterminated first temperature to form an internal light extraction layer having a refractive index of 1.8 to 2.1, wherein the internal light extraction layer comprises an interface void layer at an interface with the mineral layer.

29. The process according to claim 28, further comprising: applying another glass frit paste onto the sintered first glass frit layer to form a second glass frit layer; drying the second glass frit layer; and sintering the dried second glass frit layer at a predetermined second temperature to form a double frit layer structure for an internal light extraction layer having a refractive index of 1.8 to 2.1.

30. The process according to claim 28, wherein the concentration of potassium is smaller from the interface between the glass substrate or the mineral layer and the internal light extraction layer to an outermost surface of the internal light extraction layer.

31. The process according to claim 28, wherein the interface void layer has a thickness of 1 to 5 ?m, and wherein the interface void layer has a void area ratio of 40 to 90%.

32. The process according to claim 28, wherein the outermost surface of the first or second glass frit layer comprises potassium at a concentration of less than 1% by weight.

33. The process according to claim 28, wherein the first glass frit layer is sintered at the first sintering temperature between 500? C. and 590? C.

34. The process according to claim 28, wherein the glass substrate is a sodalime glass substrate.

35. The process according to claim 28, wherein a surface or the outermost region of the glass substrate is treated with potassium.

36. The process according to claim 28, wherein a surface of the glass substrate comprises potassium at a concentration of 1 to 15% by weight.

37. The process according to claim 28, wherein the first glass frit comprises 55 to 84% by weight of Bi.sub.2O.sub.3, 0 to 20% by weight of BaO, 5 to 20% by weight of ZnO, 1 to 7% by weight of Al.sub.2O.sub.3, 5 to 15% by weight of SiO.sub.2, 5 to 20% by weight of B.sub.2O.sub.3, and 0.05 to 3% by weight of Na.sub.2O, based on the total weight of the glass fit.

38. The process according to claim 28, wherein the internal light extraction layer has a total thickness of 6 to 30 ?m.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic view showing a laminate for a light emitting device comprising an internal light extraction layer according to an embodiment of the present invention.

(2) FIG. 2 is a flowchart showing a process of preparing the laminate for a light emitting device comprising the internal light extraction layer according to an embodiment of the present invention.

(3) FIG. 3 are Scanning Electronic Microscope (SEM) photographs showing a cross-section of a glass frit layer sintered at a changed sintering temperature, when a sodalime glass substrate containing potassium and a sodalime glass substrate containing no potassium are used.

(4) FIG. 4 are SEM photographs respectively showing a cross-section and a bottom of an internal light extraction layer prepared as described in Example 1.

(5) FIG. 5 is an Atomic Force Microscopy (AFM) photograph showing a surface of an internal light extraction layer prepared as described in Example 1.

(6) FIG. 6 is a graph showing a haze ratio to total transmittance of the laminate for a light emitting device according to an embodiment of the present invention.

(7) FIG. 7 is a graph showing a haze ratio of the laminate for a light emitting device according to an embodiment of the present invention.

(8) FIG. 8 is a graph showing an absorbance of the laminate for a light emitting device according to an embodiment of the present invention.

(9) FIG. 9 is a graph showing an intensity distribution of light, externally emitted from the laminate for a light emitting device according to an embodiment of the present invention, with respect to a viewing angle.

(10) FIG. 10 are graphs showing the changes in a potassium ion concentration distribution and SEM photographs of a glass substrate after the glass substrate is potassium ion-treated by an ion exchanging method and the internal light extraction layer is formed on the glass substrate according to a process of the present invention.

(11) FIG. 11 is an SEM photograph showing a laminate for a light emitting device prepared by a method that forms a low-refractive index glass frit containing a large amount of potassium on a glass substrate.

DETAILED DESCRIPTION

Terms

(12) Hereinafter, the terms used in the specification will be described.

(13) When the term about is used together with a numerical value, about is construed to imply all values including an error range within a significant figure of a corresponding numerical value.

(14) The term laminate denotes a structure in which two or more layers are stacked, and may be separately used in an electronic device, or used in a state where another layer (for example, transparent electrode, or the like) is additionally stacked on the laminate.

(15) The term glass frit is a raw material for forming an internal light extraction layer, and may denote a glass powder, or a paste state in which a solvent, a binder, etc., are mixed with the glass powder. It should be understood that the term frit used in the specification denotes the glass frit.

(16) The term glass frit layer denotes a layer in which a paste comprising the glass frit is applied on a substrate.

(17) The term internal light extraction layer denotes a layer which is formed after the glass frit layer is sintered (glass frit being melted). When the internal light extraction layer is used for an optical device such as an OLED, the internal light extraction layer is formed between the substrate and the transparent electrode, prevents light emitted from a light emission layer (organic layer) from being lost due to a refractive index difference among the substrate, a transparent electrode layer and the organic layer, and effectively extracts light, which is isolated in the inside due to a refractive index difference between the substrate and air, to the outside the substrate. Another material, such as an additive, in addition to the glass fit, may be additionally contained in the internal light extraction layer including even (small content of) scattering particles.

(18) The term interface void layer is a layer full of voids (open porosities) in contact with the glass substrate or the coated glass substrate with a mineral layer. However, the interface void layer is not easily separated from the glass substrate or the coated glass substrate by an external impact, heat, and a physical external force, and induces the scattering of light. FIG. 1 is a schematic view illustrating a laminate for a light emitting device comprising an internal light extraction layer according to an embodiment of the present invention. ILE indicates Internal Light Extraction Layer, whose reflective index is from 1.8 to 2.1, G indicates Glass Substrate, and V indicates Void whose reflective index is about 1.

(19) The term laminate for a light emitting device denotes a structure in which the internal light extraction layer is stacked on the substrate.

(20) <Substrate>

(21) The substrate used in the present invention comprises potassium or is coated with a mineral layer comprising potassium. The substrate may preferably be a glass substrate, which acts as a support for the light emitting device, having a thickness of 150 ?m to several millimeters. The thickness of the glass substrate is preferably 0.3 to 2.0 mm or even 0.5 to 1 mm. The glass substrate (or the coated glass substrate) in the present invention could be sodalime, borosilicate, etc., or a glass-ceramic type substrate regardless of the haze ratio of the glass substrate.

(22) The transmittance of visible light of the glass substrate is preferably at least about 70%.

(23) Any substrate that can endure a high-temperature sintering process may be used in the present invention.

(24) A sodalime glass substrate may be used as the glass substrate, and potassium may be injected into or coated on the glass substrate devoid of potassium or containing an insufficient amount of potassium (e.g., potassium is present only as an impurity). Any known treatment methods may be used, including but not limited to spin-coating, dipping, self-assembled monolayer (SAM) treatment, ion exchanging method, sol-gel coating, or the like.

(25) <Glass Frit>

(26) The glass frit of the present invention is a raw material suitable for forming an internal light extraction layer, and may be a powder or a paste. Due to the ease at which a high refractive index is achieved, a glass frit is a very useful raw material in forming the internal light extraction layer. Therefore, the glass frit described in the specification may be applied to all internal light extraction layers containing a glass material. When forming the internal light extraction layer by sintering the glass frit, a composition of a glass material is the same as that of a glass material contained in the internal light extraction layer. Thus, the following features of the glass frit composition correspond to the features of a composition of the glass material contained in the internal light extraction layer.

(27) The glass fit for the internal light extraction layer has a refractive index of 1.8 to 2.1, preferably 1.85 to 2.0. The range of the refractive index is the value corresponding to a refractive index of each of the light transmissive electrode layers and the organic layer of a general optical device, particularly an OLED device, and is for minimizing an influence of a refractive index difference on light extraction efficiency.

(28) The thermal expansion coefficient could be 70 to 90?10.sup.?7/? C. The thermal expansion coefficient is set as a range for preventing the glass substrate (which is a light transmissive substrate that is the basis of formation of the internal light extraction layer) from being deformed or deteriorated in a process of sintering the fit.

(29) The glass fit of the present invention comprises 55 to 84% by weight Bi.sub.2O.sub.3, 0 to 20% by weight BaO, and preferably 5 to 20% by weight ZnO, 1 to 7% by weight Al.sub.2O.sub.3, 5 to 15% by weight SiO.sub.2, 5 to 20% by weight B.sub.2O.sub.3, and 0.05 to 3% by weight Na.sub.2O, based on the total weight of the glass frit.

(30) Bi.sub.2O.sub.3 is an essential component for lowering a densification temperature of the glass frit and increasing a refractive index, and BaO is an assistant component that may be combined with Bi.sub.2O.sub.3 for increasing a refractive index. The Bi.sub.2O.sub.3 content in the glass frit may be preferably 60 to 80% by weight, more preferably 62 to 78% by weight, and most preferably 65 to 75% by weight. The BaO content may be preferably 0 to 10% by weight, more preferably 0 to 5% by weight, and most preferably 0 to 2% by weight. In some embodiments, the BaO content may be zero (0). When the Bi.sub.2O.sub.3 content is less than the lowest limit of the ranges above, it is difficult to achieve a refractive index range of 1.8 to 2.1 due to a lowered refractive index, and moreover, an increase in sintering temperature, which is not preferable. When the Bi.sub.2O.sub.3 content is greater than the upper most limit of the ranges above, absorption of blue-range light by the glass fit become stronger, and the thermal stability in the sintering decreases, causing a deterioration of the surface of the internal light extraction layer. Since BaO is weak in lowering a densification temperature of the glass frit, BaO may replace a part of the Bi.sub.2O.sub.3. However, when the content of BaO is greater than the upper most limit of the ranges above, a sintering temperature exceeds the suitable range.

(31) ZnO is a component for lowering a densification temperature of the glass fit. The ZnO content in the glass fit may be 5 to 20% by weight, preferably 5 to 15% by weight, and more preferably 5 to 13% by weight. When the content of ZnO is greater than the upper most limit of the ranges above, it is not preferable because a phase of the glass frit becomes unstable, acid tolerance is weakened, and the absorption of green-range light by the glass fit becomes stronger.

(32) Al.sub.2O.sub.3 is a component for stabilizing the phase of the glass frit. The Al.sub.2O.sub.3 content in the glass frit may be 1 to 7% by weight, preferably 1.5 to 5% by weight, and more preferably 2 to 4% by weight. When the Al.sub.2O.sub.3 content is less than the lowest limit in the above ranges, it is not preferable because the phase of the glass frit becomes unstable and the chemical resistance is weakened. When the Al.sub.2O.sub.3 content is greater than the upper most limit of the above ranges, it is not preferable because the refractive index of the glass fit is lowered and the sintering temperature increases.

(33) SiO.sub.2 is a component for stabilizing the phase of the glass fit. The SiO.sub.2 content in the glass fit may be 5 to 15% by weight, preferably 6 to 14% by weight, and more preferably 7 to 12% by weight. When the SiO.sub.2 content is less than the lowest limit of the above ranges, it is not preferable because the phase of the glass frit becomes unstable. When the SiO.sub.2 content is greater than the upper most limit of the above ranges, it is not preferable because the refractive index of the glass fit is lowered and the sintering temperature increases.

(34) B.sub.2O.sub.3 is a component for lowering the thermal expansion coefficient, stabilizing the phase of the glass fit, and lowering the densification temperature. The B.sub.2O.sub.3 content in the glass frit may be 5 to 20% by weight, preferably 6 to 15% by weight, and more preferably 7 to 12% by weight. When the B.sub.2O.sub.3 content is less than the lowest limit of the above ranges, it is not preferable because the phase of the glass frit becomes unstable. When the B.sub.2O.sub.3 content is greater than the upper most limit of the above ranges, it is not preferable because the water resistance of the internal light extraction layer is weakened.

(35) Na.sub.2O is a component added for lowering the densification temperature of the glass frit. The Na.sub.2O content in the glass frit may be 0.05 to 3% by weight, preferably 0.1 to 2% by weight, and more preferably 0.5 to 1.5% by weight. When the Na.sub.2O content is less than the lowest limit of the above ranges, it is not preferable because the sintering temperature of the glass fit increases. When the Na.sub.2O content is greater than the upper most limit of the above ranges, it is not preferable because a chemical resistance is weakened.

(36) The glass frit may contain an unavoidable small amount of TiO.sub.2 or ZrO.sub.2 (e.g., 0.05% by weight or less), but not more.

(37) Furthermore, the glass frit may not contain any one of Nb, P, Pb, Ta, Y, Sn, Gd, La, V, and Mo.

(38) Here, a composition of the glass frit according to an embodiment of the present invention does not contain any transition metals such as Fe, V, Cr, Mn, Ni, Co, Cu, Pd, Ag, Au, Pt, Cd, but may optionally contain a small amount of Ce. Transition metals suppress a high-temperature reduction of Bi.sub.2O.sub.3 or the like to thereby prevent the yellowing of a film during the sintering process. Thus, a transition element is generally added into the glass frit with Bi.sub.2O.sub.3. However, all transition metals show a strong absorbing characteristic within a specific light wavelength range, and particularly, when a light path increases due to scattering in the internal light extraction layer, light absorption by a transition element can cause a fatal loss of light. In this regard, it is crucial to avoid adding a transition element into a composition of the glass frit. However, since an oxide of Ce, which is a lanthanoid, is limited to a dark blue range in light absorbing characteristics, a Ce oxide has weak optical influence on an OLED lighting device having a phosphor blue light source. Further, a Ce oxide aids complete burning in a burn-out process of an organic component in preparing the internal light extraction layer. Therefore, CeO.sub.2 may be added in an amount of 0.3% by weight or less, and preferably 0.1% by weight. On the other hand, in a specific embodiment of the present invention, CeO.sub.2 may not be added.

(39) <Preparation of Laminate for a Light Emitting Device>

(40) FIG. 2 is a flowchart illustrating a process for preparing the laminate for a light emitting device according to an embodiment of the present invention. The meaning of ILE, V and G are the same as those disclosed in FIG. 1. F indicates glass frit before sintering, and EC indicates ethyl cellulose.

(41) First, a substrate which contains potassium or has been surface-treated with potassium, or a substrate coated with a mineral layer containing potassium is prepared (step (a)). Basic physical properties, such as refractive index, necessary for the substrate are as described above. A paste including the glass frit (preferably, without scattering particles) is applied on said substrate (step (b)), and then dried (step (c)). A composition of the glass frit included in the paste is as described above, and the paste includes the glass frit in an amount of 70 to 80% by weight and the remaining composition of the paste includes a binder, a solvent, and the like. Any coating method generally known in the art may be used to apply the paste, including but not limited to screen printing, slit die coating, bar coating, roll coating, or the like.

(42) The dried glass frit is sintered at a temperature of 500 to 590? C. (step (d)). Potassium comprised in the substrate is diffused into the glass frit layer during the sintering process.

(43) Even an injection of only a small amount of potassium can change the thermal characteristic of the glass frit, such that an interface void layer can be produced (step (e)). Further, since potassium has a slow diffusion rate, a thickness and void area ratio of the interface void layer can be controlled effectively.

(44) FIG. 3 shows whether the interface void layer is formed according to whether a sodalime substrate contains potassium, and also shows the changes in the cross-section of the internal light extraction layer. When a glass substrate containing no potassium is used (Column A), the interface void layer is not formed within an entire temperature range, and the interface light extraction layer is formed at 545? C. On the other hand, when a substrate containing potassium is used (Column B), an internal light extraction layer comprising the interface void layer is formed at 545? C., and then, as sintering is slowly performed at the interface of the glass fit, an internal light extraction layer comprising no interface void layer is formed at 595? C. Accordingly, it can be seen that the internal light extraction layer comprising the interface void layer may be prepared by controlling a sintering temperature of the glass fit layer coated on the glass substrate comprising potassium, and moreover, it is possible to adjust a thickness and void area density of the interface void layer.

(45) A small amount of voids may be formed inside the internal light extraction layer during the sintering process irrespective of whether the substrate comprises potassium. This is inevitable in the glass fit layer sintering process, and thus, the voids may be preferably formed so as not to affect a total transmittance, absorbance, and haze ratio of the laminate for a light emitting device.

(46) The concentration of potassium at the surface of the glass substrate or the mineral layer may preferably be 1 to 15% by weight. When the concentration of potassium is greater than the upper limit of 15% by weight, transmittance can be severely reduced. Also, the thickness of the interface void layer may preferably be within a range of 1 to 5 ?m. When the thickness of the interface void layer is less than the lower limit, a scattering effect is minimal, and when the thickness of the interface void layer is greater than the upper limit, multi scattering occurs which decreases transmittance, thereby causing a loss of light. A void area ratio of the interface void layer may be adjusted by controlling the sintering time and temperature, and may preferably be 40 to 95%, preferably from 70 to 95% so as to enable light to be efficiently extracted to the outside.

(47) Moreover, since a void is formed at only an interface between the substrate or the mineral layer and the internal light extraction layer, the surface of the internal light extraction layer has minimal air bubbles, unlike the internal light extraction layer which uses air bubbles as a scattering factor. Therefore, the surface roughness of the internal light extraction layer may be preferably formed to be less than 1 nm. Also, the surface roughness of the glass frit layer needs to have a sufficient thickness so as not to be affected by a structure of the interface void layer, for which a multi glass frit layer may be formed. Regardless of the glass fit layer being formed as a single layer or two or more multi-layers, a total thickness of the internal light extraction layer is in the range from 6 to 30 ?m, preferably from 10 to 20 ?m. When the thickness of the internal light extraction layer is less than 6 ?m, a surface roughness of the internal light extraction layer can become 1 nm or more, or increases the risk of air bubbles being generated at the surface. When the thickness of the internal light extraction layer is greater than 30 ?m, light extraction efficiency can be reduced.

(48) The laminate for a light emitting device of the present invention can effectively extract light (which is lost at the interface) to the outside, maintain optical characteristics, such as absorbance, etc., at a level equal to or better than conventional scattering type laminates for a light emitting device that uses air bubbles as a scattering factor, have much better total light transmittance and light transmittance in a vertical direction than conventional scattering type laminates for a light emitting device that have the same diffusive performance, and have a far more uniform haze ratio than conventional scattering type laminates within the visible light wavelength range. The laminate for a light emitting device of the present invention may be used in a state where a transparent electrode layer is additionally stacked on the internal light extraction layer, as applied to an optical device such as an OLED. As the transparent electrode layer, indium tin oxide (ITO), transparent conductive oxide (TOC), graphene, or the like can be used. A conventional deposition method of the transparent electrode layer, such as sputtering, may be used.

(49) Of course we can add a barrier layer between the internal light extraction layer and the electrode wherein the barrier layer consists of silicon oxide (SiO.sub.2), silicon nitride (Si.sub.3N.sub.4), titanium oxide (TiO.sub.2), tin oxide (SnO.sub.2), silicon oxynitride (SiON) and the like and preferably has an RI of more than 1.8 and a thickness of less than 100 nm. Meanwhile, it is possible to protect the internal light extraction layer during the chemical etching process and increase the light extraction effect by adding the step of depositing a barrier layer whose thickness is 5 to 50 nm on the internal light extraction layer. The barrier layer can be formed as a monolayer or as a multilayer, for example, where SiO.sub.2 and Si.sub.3N.sub.4 layers are alternatively stacked.

EXAMPLES

(50) Detailed examples are as described below. However, the examples only serve the purpose of providing a better understanding of the present invention, and should not be construed as limiting the scope of the present invention in any way.

Example 1: Preparation of a Laminate for a Light Emitting Device with Potassium-Containing Glass Substrate

(51) A glass substrate, which has a thickness of 0.7 mm and comprises 5 wt % Na.sub.2O and 6 wt % K.sub.2O, is prepared as described in Embodiment 10 of U.S. Pat. No. 6,905,991. A paste comprising 75 wt % of a glass frit, which comprises 70 wt % of Bi.sub.2O.sub.3, 3 wt % of Al.sub.2O.sub.3, 10 wt % of ZnO, 7 wt % of SiO.sub.2, 9 wt % of B.sub.2O.sub.3, and 1 wt % of Na.sub.2O based on the total weight of the glass frit, 3 wt % of ethyl cellulose as a binder, and 22 wt % of solvent based on the total amount of the paste is prepared. The refractive index is 1.91 at 550 nm.

(52) The glass substrate is cleaned, and then the paste comprising the glass frit is applied on the glass substrate by the screen printing method. A solvent is evaporated by drying the coated paste in an oven at a temperature of 130? C. for about 20 minutes. Thereafter, ethyl cellulose contained in the dried paste is removed by leaving the dried paste under a temperature of 430? C. for about 20 minutes.

(53) The prepared glass frit layer is sintered at a temperature of 540? C. for about 10 minutes. Heating to remove ethyl cellulose and sintering of the glass frit layer may be performed by a successive process using a roll hearth furnace (RHF), or may be performed by using separate ovens.

(54) FIG. 4 are SEM photographs showing an internal light extraction layer prepared as described in Example 1. The left photograph (FIG. 4(a)) shows a captured cross section of the internal light extraction layer, and the right photograph (FIG. 4(b)) shows an interface void layer captured in a downward direction. It can be seen that grains of the glass frit remain without being sintered, thereby forming voids between the grains. The size of these grains is about 1 ?m to 5 ?m.

(55) FIG. 5 is an AFM photograph showing the surface of the internal light extraction layer prepared as described in Example 1. It can be seen that an average value of surface roughness (Ra) is 0.25 nm, which is less than 1 nm.

Example 2: Preparation of a Laminate for a Light Emitting Device with Potassium-Containing Glass Substrate

(56) A laminate for a light emitting device comprising an interface void layer is prepared in the same process as Example 1, except that a sintering temperature is set to 550? C.

Example 3: Preparation of a Laminate for a Light Emitting Device with Potassium-Containing Glass Substrate

(57) A laminate for a light emitting device comprising an interface void layer is prepared in the same process as Example 1, except that a sintering temperature is set to 560? C.

Example 4: Preparation of a Laminate for a Light Emitting Device with Potassium-Treated Glass Substrate

(58) A solution containing a potassium ion is coated on a surface of a float plate glass or a general sodalime glass substrate having a thickness of 0.7 mm using a wetting method. The coated glass substrate is heat-treated at a high temperature of 400? C. or more to induce ion exchange between sodium and potassium ions. After the ion exchange, a surface residual stress of the substrate is 450 MPa, and a stress depth is 15 ?m. The remaining processes are performed in the same process as Example 1, thereby preparing a laminate for a light emitting device comprising an interface void layer.

Example 5: Preparation of a Laminate for a Light Emitting Device with a Glass Substrate Coated with a Mineral Layer Comprising Potassium

(59) A low-refractive index (n=1.54 at 550 nm) glass fit paste (PA-FD4115C?, provided by Phoenix Materials) containing potassium is coated on a surface of a float plate glass or a general sodalime glass substrate having a thickness of 0.7 mm, which do not comprise potassium or comprise potassium as an amount of impurities, using the screen printing method. After drying and sintering the low-refractive index glass frit paste, a mineral layer having a thickness of about 6 to 12 ?m is formed. After forming a glass fit layer in the same composition and process conditions as Example 1, the remaining process is performed as Example 1, thereby preparing a laminate for a light emitting device containing an interface void layer.

Example 6: Preparation of a Laminate for a Light Emitting Device with Potassium-Containing Glass Substrate

(60) A laminate for a light emitting device comprising an interface void layer is prepared in the same process as Example 1, except the concentration of Na.sub.2O and K.sub.2O contained in the glass substrate. The concentration of Na.sub.2O is 5 wt % and that of K.sub.2O is 6 wt %. The glass substrate is prepared as described in an embodiment of U.S. Pat. No. 6,905,991 (see Composition 10 in ANNEX, columns 11 and 12).

Example 7: Preparation of a Laminate for a Light Emitting Device Comprising a Double Layered Internal Light Extraction Layer

(61) After forming the glass layer containing interface void layer with the same composition and process conditions as described in Example 1 (the first glass frit layer), the second glass frit layer having a thickness of about 1 to 5 ?m is formed on the first glass frit layer to secure the flatness of the outermost surface of the internal light extraction layer and prevent the flatness of the outermost surface being degraded by the interface void layer. The composition of the second glass frit paste is the same as that of the glass frit paste described in Example 1 (the first glass frit paste). The second glass frit layer is formed by coating the second glass frit paste on the first glass frit layer using screen printing, and performing the remaining processes in the same processes as Example 1. Total thickness of the first glass frit layer and the second glass frit layer is 25 ?m and the flatness of the outermost surface of the internal light extraction layer (the first glass frit layer+the second glass frit layer) satisfies the condition of ?Ra<1 nm.

Comparative Example 1: Preparation of a Laminate for a Light Emitting Device

(62) A laminate for a light emitting device is prepared in the same process as Example 4, except that a surface is not treated with a potassium ion.

Comparative Example 2: Preparation of a Laminate for a Light Emitting Device

(63) A laminate for a light emitting device, which comprises a scattering type internal light extraction layer comprising 1.1 wt % of TiO.sub.2 particles having a diameter of 400 nm and air bubbles which are generated by oxygen dissociated from oxides contained in a glass frit, as scattering elements, is prepared using the glass frit having the same composition as in the Examples. The scattering type internal light extraction layer has a thickness of 10 ?m. On the scattering type internal light extraction layer, a second glass frit layer is stacked using the glass frit having the same composition as in the Examples without TiO.sub.2, and then, sintered at a temperature of 545? C.

Comparative Example 3: Preparation of a Laminate for a Light Emitting Device

(64) A laminate for a light emitting device is prepared in the same process as Comparative Example 2, but the concentration of TiO.sub.2 particles is increased to 2.0 wt %.

Comparative Example 4: Preparation of a Laminate for a Light Emitting Device

(65) A laminate for a light emitting device is prepared in the same process as Comparative Example 2, but the concentration of TiO.sub.2 particles is decreased to 0.9 wt %.

(66) Evaluating the Optical Characteristics of the Laminates for a Light Emitting Device

(67) Table 1 shows the transmittance and haze ratio of the laminates for a light emitting device prepared according to Examples 1 to 4 and Comparative Examples 1 to 4. Compared to the laminate of Comparative Example 1 in which an internal void layer is not formed, the total transmittance decreases, and the haze ratio increases considerably. Compared to the laminates of Comparative Examples 2 to 4 which comprise scattering elements, the haze ratios are superior. The total thickness of the light extraction layer is about 20 to 25 ?m in all cases.

(68) TABLE-US-00001 TABLE 1 Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 1 Example 2 Example 3 Example 4 Thickness of 3 2.5 2.5 2 interface void layer (?m) Thickness of 10 10 10 scattering layer containing TiO.sub.2 particles (?m) Total 58.9 60.4 64.6 70.7 80.5 59.5 56.7 63.3 transmittance (%) Haze ratio (%) 90.6 88.3 87.8 70.2 9.6 79.4 85.4 67.4

(69) FIG. 6 is a graph comparing the changes in the total transmittance in the range of visible light (X-axis) with respect to the haze ratio of the laminates (Y-axis) prepared in Examples 1 to 4 (marked as ?) and Comparative Examples 2 to 4 (marked as ?). The total transmittance of the laminate for a light emitting device of the present invention is about 2% to 7% higher than that of a laminate for a light emitting device of the Comparative Examples having the same diffusive performance.

(70) FIGS. 7 to 9 are graphs comparing optical characteristics of the laminate for a light emitting device (illustrated as a solid line) prepared in Example 1 and those of the laminate for a light emitting device (illustrated as a dotted line) prepared in Comparative Example 2.

(71) FIG. 7 is a graph showing the haze ratio. The X-axis shows the wavelength (?) and the Y-axis shows the haze ratio (HR, %). The haze ratio of the laminate for a light emitting device according to the present invention (marked as solid line) is consistently uniform within an entire wavelength range of visible light. In the laminate for a light emitting device of Comparative Example 2 (marked as dotted line), however, the longer the wavelength, the lower the haze ratio. Thus, there is a 30% or more difference in the haze ratio between the maximum value and the minimum value.

(72) FIG. 8 is a graph showing absorbance. The X-axis shows the wavelength (?) and the Y-axis shows the absorbance (Ab, %). Absorbance of the laminate for a light emitting device according to the present invention (marked as solid line) is almost equal to that of the laminate for a light emitting device of Comparative Example 2 (marked as dotted line), within an entire wavelength range of visible light.

(73) FIG. 9 is a graph showing an intensity distribution of externally emitted light with respect to a viewing angle. The X-axis shows the angle viewed from the front (?) and the Y-axis shows the intensity (A.U.). The laminate for a light emitting device according to the present invention (marked as solid line) has a light diffusing performance almost equal to the laminate for a light emitting device of Comparative Example 2 (marked as dotted line), over a viewing angle of ?80? to 80?. However, the laminate for a light emitting device according to the present invention has a light concentration (light transmittance) far superior than the laminate for a light emitting device of Comparative Example 2, within a viewing angle of ?20? to 20?.

(74) FIG. 10 shows distributions of potassium concentration of the substrate, which is treated with potassium by the ion exchanging method described in Example 4 (before sintering, left drawing, FIG. 10(a)), and the laminate for a light emitting device which a glass fit layer is applied on said substrate treated with potassium, and then, an internal light extraction layer is formed by sintering (after sintering, right drawing, FIG. 10(b)). Potassium ion concentration of the substrate treated with potassium becomes higher towards the surface. However, after the internal light extraction layer is formed by applying the glass frit layer on said substrate and sintering, potassium ions are diffused and move from the surface of the glass substrate to the internal light extraction layer.

(75) FIG. 11 is an SEM photograph showing a cross section of the laminate for a light emitting device prepared in Example 5. The photograph shows the formation of the interface void layer between the low-refractive index glass frit layer and the internal light extraction layer. Therefore, the laminate for a light emitting device may be prepared by a method of coating the low-refractive index glass fit layer containing a potassium ion on a general glass substrate.

(76) In summary, the laminate for a light emitting device of the present invention comprising the interface void layer can maintain optical characteristics, such as absorbance, etc., at a level equal to or more superior than the existing scattering type laminate for a light emitting device which uses an air bubble as a scattering factor, have a much superior total transmittance in the range of visible light and light transmittance in a vertical direction than conventional scattering type laminates for a light emitting device having the same diffusive performance, and have a far more uniform haze ratio than conventional scattering type laminates within an entire wavelength range of visible light.

INDUSTRIAL APPLICABILITY

(77) A laminate for a light emitting device of the present invention can be widely used for light emitting devices requiring the effective extraction of light, and is particularly suitable for the fields of optical devices, such as organic light emitting diodes (OLEDs), backlights, lighting industry, etc., since it has superior optical characteristics.

SYMBOLS

(78) ILE: Internal Light Extraction Layer (RI: 1.8?2.1)

(79) G: Glass Substrate

(80) V: Void (RI?1)

(81) F: Glass Frit

(82) EC: Ethyl Cellulose

(83) A: Air