ORGANIC EL DEVICE SUBSTRATE, ORGANIC EL DEVICE, AND METHOD FOR MANUFACTURING ORGANIC EL DEVICE SUBSTRATE
20210104699 · 2021-04-08
Inventors
- Yasuo YAMAZAKI (Shiga, JP)
- Hironori Kaji (Kyoto, JP)
- Shosei KUBO (Kyoto, JP)
- Masashi TABE (Shiga, JP)
- Akihiko SAKAMOTO (Shiga, JP)
Cpc classification
H10K71/00
ELECTRICITY
H10K99/00
ELECTRICITY
International classification
Abstract
Provided is an organic EL device substrate (1) including, in order in a thickness direction: a light-transmitting plate; a high refractive index layer (4); and a transparent conductive layer (5), the organic EL device substrate (1) having a recessed groove portion (6) configured to divide the transparent conductive layer (5) at least into a first region (R1) and a second region (R2). When a thickness of the transparent conductive layer (5) is represented by t1 (μm), a minimum width of the recessed groove portion (6) is represented by w1 (μm), and a maximum depth of the recessed groove portion (6) with respect to a surface (5a) of the transparent conductive layer (5) on an opposite side of the high refractive layer (4) is represented by d1 (μm), the following relationships are established: t1≤d1; and d1/{(w1).sup.0.5}<0.1.
Claims
1. An organic EL device substrate, comprising, in order in a thickness direction: a light-transmitting plate; a high refractive index layer; and a transparent conductive layer, the organic EL device substrate having a recessed groove portion configured to divide the transparent conductive layer at least into a first region and a second region, wherein, when a thickness of the transparent conductive layer is represented by t1 (μm), a minimum width of the recessed groove portion is represented by w1 (μm), and a maximum depth of the recessed groove portion with respect to a surface of the transparent conductive layer on an opposite side of the high refractive layer is represented by d1 (μm), the following relationships are established:
t1≤d1; and
d1/{(w1).sup.0.5}<0.1.
2. The organic EL device substrate according to claim 1, wherein the recessed groove portion has a minimum width of 10 μm or more.
3. The organic EL device substrate according to claim 1, wherein an end portion of a side wall portion of the recessed groove portion on the surface side of the transparent conductive layer has a raised portion that is raised from the surface of the transparent conductive layer, and wherein, when a rectangular region having a dimension along a longitudinal direction of the recessed groove portion of 40 μm and a dimension along a width direction of the recessed groove portion of 10 μm is formed so as to comprise the end portion of the side wall portion, an area of a portion viewed in plan view in the rectangular region, in which a height of the raised portion with respect to the surface of the transparent conductive layer is 10 nm or more, is 10% or less of an area of the rectangular region.
4. An organic EL device, comprising: the organic EL device substrate of claim 1; and an organic EL element layer formed on the transparent conductive layer side of the organic EL device substrate.
5. A method of manufacturing an organic EL device substrate, the organic EL device substrate comprising, in order in a thickness direction: a light-transmitting plate; a high refractive index layer; and a transparent conductive layer, the method comprising a laser processing step of removing a part of the transparent conductive layer by laser processing to form a recessed groove portion configured to divide the transparent conductive layer at least into a first region and a second region, wherein the laser processing step comprises forming the recessed groove portion so that, when a thickness of the transparent conductive layer is represented by t1 (μm), a minimum width of the recessed groove portion is represented by w1 (μm), and a maximum depth of the recessed groove portion with respect to a surface of the transparent conductive layer on an opposite side of the high refractive layer is represented by d1 (μm), the following relationships are established:
t1≤d1; and
d1/{(w1).sup.0.5}<0.1.
6. The method of manufacturing an organic EL device substrate according to claim 5, wherein the laser processing step comprises forming the recessed groove portion so that the recessed groove portion has a minimum width of 10 μm or more.
7. The method of manufacturing an organic EL device substrate according to claim 5, further comprising a polishing step of polishing the surface of the transparent conductive layer after the laser processing step, wherein, after the polishing step, an end portion of a side wall portion of the recessed groove portion on the surface side of the transparent conductive layer has a raised portion that is raised from the surface of the transparent conductive layer, and wherein the surface of the transparent conductive layer is polished so that, when a rectangular region having a dimension along a longitudinal direction of the recessed groove portion of 40 μm and a dimension along a width direction of the recessed groove portion of 10 μm is formed so as to comprise the end portion of the side wall portion, an area of a portion viewed in plan view in the rectangular region, in which a height of the raised portion with respect to the surface of the transparent conductive layer is 10 nm or more, is 10% or less of an area of the rectangular region.
8. The organic EL device substrate according to claim 2, wherein an end portion of a side wall portion of the recessed groove portion on the surface side of the transparent conductive layer has a raised portion that is raised from the surface of the transparent conductive layer, and wherein, when a rectangular region having a dimension along a longitudinal direction of the recessed groove portion of 40 μm and a dimension along a width direction of the recessed groove portion of 10 μm is formed so as to comprise the end portion of the side wall portion, an area of a portion viewed in plan view in the rectangular region, in which a height of the raised portion with respect to the surface of the transparent conductive layer is 10 nm or more, is 10% or less of an area of the rectangular region.
9. The method of manufacturing an organic EL device substrate according to claim 6, further comprising a polishing step of polishing the surface of the transparent conductive layer after the laser processing step, wherein, after the polishing step, an end portion of a side wall portion of the recessed groove portion on the surface side of the transparent conductive layer has a raised portion that is raised from the surface of the transparent conductive layer, and wherein the surface of the transparent conductive layer is polished so that, when a rectangular region having a dimension along a longitudinal direction of the recessed groove portion of 40 μm and a dimension along a width direction of the recessed groove portion of 10 μm is formed so as to comprise the end portion of the side wall portion, an area of a portion viewed in plan view in the rectangular region, in which a height of the raised portion with respect to the surface of the transparent conductive layer is 10 nm or more, is 10% or less of an area of the rectangular region.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0018]
[0019]
[0020]
[0021]
[0022]
[0023]
[0024]
DESCRIPTION OF EMBODIMENT
[0025] Now, an embodiment of the present invention is described with reference to the accompanying drawings.
[0026] As illustrated in
[0027] The light-transmitting plate 2 is formed of a glass, a resin, or the like. Examples of the glass for forming the light-transmitting plate 2 include soda lime glass, borosilicate glass, alkali-free glass, and quartz glass. Examples of the resin for forming the light-transmitting plate 2 include an acrylic resin, a silicone resin, an epoxy resin, a polyester resin, and a polycarbonate resin.
[0028] The irregular layer 3 is formed of a sintered glass layer having an irregular shape. It is preferred that a refractive index nd of the irregular layer 3 be substantially the same as a refractive index nd of the light-transmitting plate 2. In this case, it is preferred that the refractive index nd of the irregular layer 3 fall within a range of ±0.1 with respect to the refractive index nd of the light-transmitting plate 2. Here, the refractive index nd represents a refractive index at a wavelength of 588 nm. The surface of the light-transmitting plate 2 may be formed of an irregular surface instead of the irregular layer 3. As a method of forming the irregular surface, there are given mechanical treatment methods, such as a sandblasting method, a press forming method, and a roll forming method, and chemical treatment methods, such as a sol-gel spray method, an etching method, and an atmospheric-pressure plasma treatment method. In addition, a substance having a refractive index different from that of a base material for the high refractive index layer 4 may be dispersed in the base material for the high refractive index layer 4 instead of the irregular shape such as the irregular layer 3 or the irregular surface or in combination therewith. It is preferred that the dispersed substance be a substance having a refractive index smaller than the refractive index of the base material for the high refractive index layer 4. Examples of the dispersion substance include: gases (air bubbles), such as air, oxygen, nitrogen, and carbon dioxide; ceramics particles, such as titania, zirconia, and silica; and inorganic particles, such as glass (amorphous glass or crystallized glass) particles.
[0029] The high refractive index layer 4 has a refractive index larger than the refractive index of the light-transmitting plate 2. The refractive index nd of the high refractive index layer is not particularly limited, and is, for example, from 1.8 to 2.1. The high refractive index layer 4 is made of glass (amorphous glass or crystallized glass), a resin, ceramics, or the like. It is preferred that the high refractive index layer 4 be formed of a sintered glass layer. Examples of the glass for forming the sintered glass layer include inorganic glasses, such as soda lime glass, borosilicate glass, aluminosilicate glass, phosphate glass, bismuth-based glass, lead-based glass, and lanthanum-based glass. Of those, bismuth-based glass is particularly preferred because bismuth-based glass is lead-free glass having a high refractive index and can be sintered at a low temperature. However, bismuth-based glass has a high specific dielectric constant, and hence the charge density in a surface layer portion of the high refractive index layer 4 is liable to be increased, with the result that a leakage current from a recessed groove portion 6 described later is liable to be increased. Thus, in the organic EL element substrate comprising the high refractive index layer 4 containing bismuth-based glass, the usefulness of the present invention capable of reducing the generation of a leakage current is particularly outstanding. The specific dielectric constant of the high refractive index layer 4 is preferably from 9 to 23, more preferably from 10 to 22.
[0030] Examples of the transparent conductive layer 5 include indium tin oxide (ITO), aluminum zinc oxide (AZO), and indium zinc oxide (IZO).
[0031] As glass powder to be used for forming the irregular layer 3, for example, glass powder containing, in terms of mass %, 30% of SiO.sub.2, 40% of B.sub.2O.sub.3, 10% of ZnO, 5% of Al.sub.2O.sub.3, and 15% of K.sub.2O can be used. In addition, the irregular shape of the irregular layer 3 also depends on the particle diameter of the glass powder in addition to the heat treatment condition for sintering a frit paste. The powder grain size (D.sub.50) of the glass powder is within a range of preferably from 0.3 μm to 15 μm, more preferably from 1.0 μm to 10 μm, still more preferably from 1.5 μm to 8 μm.
[0032] As the glass powder to be used for forming the high refractive index layer 4, for example, bismuth-based glass powder containing, in terms of mass %, 70% of Bi.sub.2O.sub.3, 5% of SiO.sub.2, 10% of ZnO, 10% of B.sub.2O.sub.3, and 5% of Al.sub.2O.sub.3 and having a specific dielectric constant of 17 can be used. When light-transmitting electrodes or the like are to be formed on the surface of the high refractive index layer 4, it is preferred that the surface of the high refractive index layer 4 be smooth. In order to obtain the smooth surface, it is preferred that the grain size of the glass powder be appropriately set in addition to the heat treatment condition for sintering the frit paste. The powder grain size (D.sub.50) of the glass powder is preferably from 0.1 μm to 20 μm, more preferably from 0.2 μm to 15 μm, still more preferably from 0.3 μm to 10 μm.
[0033] The recessed groove portion 6 configured to divide the transparent conductive layer 5 at least into a first region R1 and a second region R2 is formed in the transparent conductive layer 5. The recessed groove portion 6 has the following feature. Specifically, as illustrated in
t1≤d1 (1)
d1/{(w1).sup.0.5}<0.1 (2)
In the expression (2), values converted in terms of μm are used for d1 and w1.
[0034] According to the expression (1), the first region R1 and the second region R2 are completely separated from each other, and hence the first region R1 and the second region R2 are not brought into direct conduction with each other through the transparent conductive layer 5. In the expression (1), it is preferred that t1<d1 be established. In this case, as illustrated in
[0035] In addition, according to the expression (2), the maximum depth d1 of the recessed groove portion 6 becomes appropriate with respect to the minimum width w1 thereof. Thus, when an organic EL device is manufactured through use of the organic EL device substrate 1 having such dimensional relationship, an insulation layer such as an organic EL element layer can be formed on the entire surface of the recessed groove portion 6. Therefore, the generation of a leakage current can be reduced to a problem-free level. In the expression (2), d1/{(w1).sup.0.5} is preferably 0.08 or less, more preferably 0.06 or less, still more preferably 0.04 or less.
[0036] The maximum depth d1 of the recessed groove portion 6 is preferably 1 μm or less, more preferably 0.8 μm or less, still more preferably 0.5 μm or less.
[0037] The minimum width w1 of the recessed groove portion 6 is preferably 10 μm or more, more preferably 15 μm or more, still more preferably 20 μm or more. Here, it is preferred that the minimum width w1 of the recessed groove portion 6 be a width at a position corresponding to the bottom wall portion 6a. In addition, it is preferred that a pair of side wall portions 6b of the recessed groove portion 6, which are opposed to each other in a groove width direction, be inclined outward so that the groove width of the recessed groove portion 6 is enlarged from the bottom wall portion 6a to the surface 5a side of the transparent conductive layer 5.
[0038] End portions 6b1 of the side wall portions 6b of the recessed groove portion 6 on the surface 5a side of the transparent conductive layer 5 have raised portions 7 that are raised from the surface 5a of the transparent conductive layer 5, respectively. It is preferred that the raised portions 7 have the following feature. Specifically, as shown in
[0039] The organic EL device substrate 1 may satisfy the following relational expression.
d1/t1<4 (3)
[0040] As illustrated in
[0041] It is preferred that, when the thickness of the organic EL element layer 12 in a non-formation region of the recessed groove portion 6 of the transparent conductive layer 5 is represented by t2, the following relationship is established between the thickness t2 and the maximum depth d1 of the recessed groove portion 6.
d1/t2≤3 (4)
[0042] The maximum depth d1 of the recessed groove portion 6 is more preferably 2.5 times or less, still more preferably 2 times or less the thickness t2 of the organic EL element layer 12.
[0043] Light emitted from the organic EL element layer 12 passes through the transparent conductive layer 5 and the light-transmitting plate 2 to be extracted outside from the light-transmitting plate 2 side. In this case, light reflected from the cathodes 13 is also extracted outside from the light-transmitting plate 2 side.
[0044] In the organic EL device 11 configured as described above, the light extraction efficiency is high, and a leakage current that may adversely affect the light-emitting characteristics is extremely small. Therefore, the organic EL device 11 can be suitably used for, for example, illumination.
[0045] Next, a method of manufacturing the organic EL device configured as described above is described. A method of manufacturing an organic EL device substrate is also described in the method of manufacturing an organic EL device.
[0046] The method of manufacturing an organic EL device comprises: an irregular layer forming step of forming the irregular layer 3 on the light-transmitting plate 2; a high refractive index layer forming step of forming the high refractive index layer 4 on the irregular layer 3; a transparent conductive layer forming step of forming the transparent conductive layer 5 on the high refractive index layer 4; an organic EL element layer forming step of forming the organic EL element layer 12 on the transparent conductive layer 5; and a cathode forming step of forming the cathodes 13 on the organic EL element layer 12. Of those, the steps of from the irregular layer forming step to the transparent conductive layer forming step are those related to the method of manufacturing an organic EL device substrate. The manufacturing process of the organic EL device substrate is performed, for example, by a glass manufacturer, and the remaining steps comprised in the manufacturing process of the organic EL device are performed, for example, by an organic EL device manufacturer.
[0047] In the irregular layer forming step, after a frit paste containing glass powder is applied or printed on the surface of the light-transmitting plate 2, the frit paste is sintered (first heat treatment). With this, the irregular layer 3 formed of a sintered glass layer is formed on the light-transmitting plate 2. In this case, the heat treatment temperature in the first heat treatment is required to be set to be lower than the heat-resistant temperature of the light-transmitting plate 2, and is preferably lower than the softening point (for example, 730° C.) of the light-transmitting plate 2, more preferably lower by from about 50° C. to about 200° C. than the softening point of the light-transmitting plate 2.
[0048] In the high refractive index layer forming step, after a frit paste containing glass powder is applied or printed on the irregular layer 3 (or the irregular layer 3 and the light-transmitting plate 2), the frit paste is sintered (second heat treatment). With this, the high refractive index layer 4 formed of a sintered glass layer is formed on the irregular layer 3. In this case, it is preferred that the heat treatment temperature in the second heat treatment be lower than the heat treatment temperature in the first heat treatment. With this, the irregular layer 3 formed by the first heat treatment maintains the form thereof also in the second heat treatment.
[0049] In the transparent conductive layer forming step, first, the transparent conductive layer 5 is formed on the high refractive index layer 4 by a known procedure such as sputtering, vapor deposition, or CVD. After that, a part of the transparent conductive layer 5 is removed by laser processing in accordance with a predetermined patterning shape (laser processing step). With this, the recessed groove portion 6 is formed in the transparent conductive layer 5, to thereby divide the transparent conductive layer 5 at least into the first region R1 and the second region R2. For example, a pulse laser is used for laser processing.
[0050] In the laser processing step, the recessed groove portion 6 is formed so that the relationships of the above-mentioned expressions (1) and (2) are established. In this case, the minimum width w1 and/or the maximum depth d1 of the recessed groove portion 6 are/is adjusted, for example, through adjustment of a laser power and an irradiation spot diameter.
[0051] After the laser processing step, the raised portions 7 that are raised from the surface 5a of the transparent conductive layer 5 may be formed in the end portions 6b1 of the side wall portions 6b of the recessed groove portion 6 on the surface 5a side of the transparent conductive layer 5 due to the influence of heat during the laser processing. Therefore, in the transparent conductive layer forming step in this embodiment, the surface 5a of the transparent conductive layer 5 is polished after the laser processing step. The polishing step is performed, for example, by buffing. With this, the raised portion area is set to be 10% or less of the area of the rectangular region S. The raised portions 7 are not limited to those formed by the laser processing.
[0052] In the organic EL element layer forming step, the organic EL element layer 12 is formed on the transparent conductive layer 5 by vapor deposition. The organic EL element layer 12 is formed also in the recessed groove portion 6, to thereby serve to keep insulation between the first region R1 and the second region R2. In this case, it is preferred that the organic EL element layer 12 be formed so that the relationship of the above-mentioned expression (3) is established.
[0053] In the cathode forming step, the cathodes 13 are formed on the organic EL element layer 12 by a known procedure such as sputtering, vapor deposition, or CVD.
EXAMPLES
[0054] First, the manufacturing conditions of each of organic EL devices according to Examples of the present invention are described.
[0055] As a light-transmitting plate, a soda lime glass substrate having a thickness of 0.7 mm was prepared. A frit paste for forming an irregular layer was applied on the surface of the glass substrate so as to have a thickness of about 25 μm through use of a screen printing machine. After the frit paste for forming an irregular layer was dried at 130° C., first heat treatment was performed at 600° C. through use of an electric furnace. Through the first heat treatment, glass particles of glass powder in the frit paste for forming an irregular layer were fused to each other to form an irregular layer on the surface of the glass substrate.
[0056] A frit paste for forming a high refractive index layer was applied on each of the glass substrate and the irregular layer so as to have a thickness of about 80 μm through use of a die coater. After the frit paste for forming a high refractive index layer was dried at 130° C., second heat treatment was performed at 580° C. through use of the electric furnace. The heat treatment temperature in the second heat treatment is lower than the heat treatment temperature in the first heat treatment, and hence the irregular layer formed by the first heat treatment maintains the form thereof also in the second heat treatment. Through the second heat treatment, glass particles of glass powder in the frit paste for forming a high refractive index layer are fused to each other and flow in a planar direction, with the result that a high refractive index layer having a flat and smooth surface is formed.
[0057] A transparent conductive layer formed of an ITO film having a thickness of 120 nm was formed on the high refractive index layer by a sputtering device. After that, the transparent conductive layer was subjected to laser processing by a pulse laser device (R-100 manufactured by Raydiance Inc.) having a wavelength of 1,550 nm, to thereby form a recessed groove portion in the transparent conductive layer. In this case, the depth and width of the recessed groove portion were controlled through adjustment of a laser power and an irradiation spot diameter.
[0058] After the above-mentioned laser processing, the surface of the transparent conductive film was polished by buffing to manufacture an organic EL device substrate.
[0059] Further, an organic layer having a thickness of 150 nm comprising a hole injection layer, a light-emitting layer, an electron transport layer, and an electron injection layer, and aluminum electrodes (cathodes) each having a thickness of 80 nm were formed on the above-mentioned organic EL device substrate by vacuum vapor deposition, to thereby manufacture an organic EL device.
[0060] Meanwhile, each of organic EL devices according to Comparative Examples was manufactured by changing the depth and width of the recessed groove portion under a laser irradiation condition different from that in Examples in the manufacturing process of each of the organic EL devices according to Examples described above. The manufacturing conditions other than the laser irradiation condition are the same as those in Examples.
[0061] A leakage current was evaluated in each of Examples 1 to 9 and Comparative Examples 1 to 4. A leakage current was evaluated by manufacturing organic EL devices each having a light-emitting area of 2 mm×2 mm and measuring current-voltage characteristics of each of the manufactured organic EL devices by a 2400-series source meter manufactured by Keithley Instruments in each of Examples 1 to 9 and Comparative Examples 1 to 4. In this case, a current value at a time when a voltage was 2 V was defined as a leakage current (mA/cm.sup.2). The results are shown in Table 1.
TABLE-US-00001 TABLE 1 Example Example Example Example Example Example Example 1 2 3 4 5 6 7 Thickness t1 (nm) of 120 120 120 120 120 120 120 transparent conductive layer Thickness t2 (nm) of 150 150 150 150 150 150 150 organic EL element layer Maximum depth d1 (nm) 200 200 200 800 800 200 450 of recessed groove portion Minimum width w1 200 25 10 200 100 25 25 (μm) of recessed groove portion d1/[(w1).sup.0.5] 0.01 0.04 0.06 0.06 0.08 0.04 0.09 *d1 and w1 are obtained by conversion in terms of μm Raised portion area (%) 0.50 0.50 0.50 0.50 0.50 2.60 0.50 Leakage current 3 × 10.sup.−6 5 × 10.sup.−6 1 × 10.sup.−5 1 × 10.sup.−5 5 × 10.sup.−5 3 × 10.sup.−5 7 × 10.sup.−5 (mA/cm.sup.2) Comparative Comparative Comparative Comparative Example Example Example Example Example Example 8 9 1 2 3 4 Thickness t1 (nm) of 120 120 120 120 120 120 transparent conductive layer Thickness t2 (nm) of 150 150 150 150 150 150 organic EL element layer Maximum depth d1 (nm) 200 200 550 800 250 550 of recessed groove portion Minimum width w1 200 200 25 50 5 25 (μm) of recessed groove portion d1/[(w1).sup.0.5] 0.01 0.01 0.11 0.11 0.11 0.11 *d1 and w1 are obtained by conversion in terms of μm Raised portion area (%) 5.00 10.00 0.50 0.50 0.50 15.00 Leakage current 1 × 10.sup.−5 7 × 10.sup.−5 1 × 10.sup.−4 5 × 10.sup.−4 1 × 10.sup.−3 3 × 10.sup.−3 (mA/cm.sup.2)
[0062] It can be confirmed in Table 1 that, in each of Examples 1 to 9 in which d1/{(w1).sup.0.5} became less than 0.1, a leakage current is 7×10.sup.−5 mA/cm.sup.2 or less, and hence a value suitable as the organic EL device is obtained. Here, the state of the recessed groove portion in the organic EL device substrate used in the organic EL device of Example 2 was observed with a scanning electron microscope. As a result, as shown in
[0063] In contrast, in each of Comparative Examples 1 to 4 in which d1/{(w1).sup.0.5} became 0.1 or more, a leakage current was 1×10.sup.−4 mA/cm.sup.2 or more, and hence a leakage current became much larger than as in the case of Examples 1 to 9.
[0064] Here, in each of Examples 1 to 9 and Comparative Examples 1 to 3, the ratio of the raised portion area with respect to the area of the rectangular region was 10% or less. Therefore, even in Comparative Examples 1 to 3, a leakage current was smaller than that in Comparative Example 4 in which the ratio of the raised portion area with respect to the area of the rectangular region was more than 10%.
[0065] The present invention is not limited to the configurations of the above-mentioned embodiment and Examples. In addition, the action and effect of the present invention are not limited to those described above. The present invention may be modified in various forms within the range not departing from the spirit of the present invention.
[0066] In the above-mentioned embodiment, there is illustrated the case in which the organic EL element layer 12 is formed in the recessed groove portion 6, and the recessed groove portion 6 is insulated. However, as illustrated in
REFERENCE SIGNS LIST
[0067] 1 organic EL device substrate [0068] 2 light-transmitting plate [0069] 3 irregular layer [0070] 4 high refractive index layer [0071] 5 transparent conductive layer [0072] 5a surface [0073] 6 recessed groove portion [0074] 6a bottom wall portion [0075] 6b side wall portion [0076] 7 raised portion [0077] 11 organic EL device [0078] 12 organic EL element layer [0079] 13 cathode [0080] 21 insulating resin [0081] R1 first region [0082] R2 second region [0083] S rectangular region [0084] d1 maximum depth of recessed groove portion [0085] w1 minimum width of recessed groove portion