JP4372876B2 - Transparent conductive material, transparent conductive glass and transparent conductive film - Google Patents

Transparent conductive material, transparent conductive glass and transparent conductive film Download PDF

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Publication number
JP4372876B2
JP4372876B2 JP00504699A JP504699A JP4372876B2 JP 4372876 B2 JP4372876 B2 JP 4372876B2 JP 00504699 A JP00504699 A JP 00504699A JP 504699 A JP504699 A JP 504699A JP 4372876 B2 JP4372876 B2 JP 4372876B2
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transparent conductive
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sn
conductive material
oxide
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JP2000207935A (en
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一吉 井上
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出光興産株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a transparent conductive material highly useful as a material for a transparent conductive film for a display device, a sintered body thereof, a sputtering target for a transparent conductive film made of the sintered body, and a transparent film formed using the target. The present invention relates to a transparent conductive glass and a transparent conductive film having a conductive film.
[0002]
[Prior art]
In recent years, liquid crystal display devices, electroluminescence display devices, field emission displays, etc. that have lower power consumption and are thinner and lighter than conventional CRTs have been developed for control systems in office equipment and factories. ing.
[0003]
In such a flat light emission display, for example, an electroluminescence display device, development of an organic electroluminescence element using an organic compound has been progressing remarkably. As the structure of this organic electroluminescence device, a single layer structure in which a light emitting layer made of an organic compound layer is formed between an anode made of a transparent conductive film and a cathode, or a hole transport layer is made between an anode and a cathode. And a two-layer structure in which two layers of a light-emitting layer are formed, and a three-layer structure in which a hole transport layer, a light-emitting layer, and an electron transport layer are formed between an anode and a cathode. In such an organic electroluminescence device, in any of the device structures, the hole injected from the anode and the electron injected from the cathode are emitted through the hole transport layer or the electron transport layer. In this light emitting layer, these holes and electrons are recombined to emit light.
[0004]
Thus, when holes are injected into the light emitting layer from the anode of the organic electroluminescence element via the hole transport layer, it is desirable that the energy barrier be as small as possible between the anode and the hole transport layer. In order to reduce this energy barrier, it is necessary to reduce the difference between the work function of the anode material and the ionization potential of the organic compound used in the hole transport layer. Various organic compounds have been proposed as hole transport materials that can be used to form this hole transport layer. Among them, aromatic amine compounds, particularly triphenylamine derivatives, have excellent functions. It is known as having And in the triphenylamine which is this triphenylamine derivative, the ionization potential is 5.5-5.6 electron volts. On the other hand, as a transparent conductive film, indium oxide-tin oxide (hereinafter abbreviated as ITO) is well known as one having good transparency and low electrical resistance. And the work function of this ITO is 4.6 electron volts. Therefore, a large energy barrier exists between the anode made of such a general material and the hole transport layer.
[0005]
For this reason, for example, in Japanese Patent Application Laid-Open No. 9-63771, a metal oxide having a work function larger than that of ITO is used as an anode in an organic thin-film light emitting device in which an organic compound layer is provided between the anode and the cathode. It is proposed to use a thin film made of However, the anode made of this metal oxide thin film has a light transmittance of, for example, 10% in the case of ruthenium oxide and 20% in the case of vanadium oxide. In order to improve such a low light transmittance, it has been proposed to form a two-layer structure by laminating an ultra-thin film of 300 angstroms or less of the metal oxide on the ITO film. However, the light transmittance is about 40 to 60%, and the transparency of the display device is not sufficient.
[0006]
[Problems to be solved by the invention]
In view of such circumstances, the present invention provides a work function value with a small difference between high transparency that can be used as a transparent electrode for a display device such as an organic electroluminescence element and an ionization potential of a hole transport material. It aims at providing the transparent conductive material which has, the sintered compact, the target which consists of this sintered body, the transparent conductive glass manufactured using this target, and a transparent conductive film.
[0007]
[Means for Solving the Problems]
As a result of intensive studies for solving the above problems, the present inventor has found that one or more metal oxides selected from indium oxide, zinc oxide, and tin oxide are iridium oxide, rhenium oxide, and palladium oxide. According to the transparent conductive film formed by using a target composed of a sintered body of a composition containing one or more metal oxides selected from the above, it has been found that the above problems can be solved, The present invention has been completed based on these findings.
[0008]
That is, the gist of the present invention is as follows.
(1) A transparent conductive material used for an organic electroluminescence device containing an organic compound having an ionization potential of 5.5 to 5.6 eV, and one or more metals selected from indium oxide, zinc oxide and tin oxide the oxide, the transparent conductive material comprising one or more metal oxide selected from oxide iridium beam Contact and palladium oxide, from composition containing% 0.5 to 20 atom relative to the total metal atoms .
(2) Indium oxide, zinc oxide and tin oxide are in their metal atomic ratio,
In / (In + Zn + Sn) = 0.00 to 1.00
Zn / (In + Zn + Sn) = 0.00-0.25
Sn / (In + Zn + Sn) = 0.00-1.00
The transparent conductive material according to (1), wherein
(3) Indium oxide, zinc oxide, and tin oxide are in their metal atomic ratio,
In / (In + Zn + Sn) = 0.50-1.00
Zn / (In + Zn + Sn) = 0.00 to 0.25
Sn / (In + Zn + Sn) = 0.00 to 0.50
The transparent conductive material according to (1), wherein
(4) Indium oxide, zinc oxide and tin oxide are in their metal atomic ratio,
In / (In + Zn + Sn) = 0.75-0.95
Zn / (In + Zn + Sn) = 0.05-0.20
Sn / (In + Zn + Sn) = 0.00-0.20
The transparent conductive material according to (1), wherein
(5) The transparent according to any one of (1) to (4) above, wherein an organic compound having an ionization potential of 5.5 to 5.6 eV forms a light emitting layer or a hole transport layer in the organic electroluminescence device. Conductive material.
(6) A sintered body obtained by sintering the transparent conductive material according to any one of (1) to (5) .
(7) A sputtering target comprising the sintered body according to (6) .
(8) A transparent conductive glass obtained by coating a glass surface with a transparent conductive film made of the transparent conductive material according to (1) .
(9) The transparent conductive glass according to (8), wherein the light transmittance is 70% or more and the work function of the transparent conductive film is 5.4 electron volts or more.
(10) A transparent conductive film formed by coating a transparent resin film surface with a transparent conductive film made of the transparent conductive material according to (1) .
(11) The transparent conductive film according to claim 10 , wherein the light transmittance is 70% or more and the work function of the transparent conductive film is 5.4 electron volts or more.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The transparent conductive material of the present invention is one or more metal oxides selected from indium oxide, zinc oxide and tin oxide, and one or more metal oxides selected from iridium oxide, rhenium oxide and palladium oxide. This is a transparent conductive material comprising a composition containing 0.5 to 20 atomic% of the metal oxide.
[0010]
And the transparent conductive material of the present invention that is more excellent in conductivity is indium oxide, zinc oxide, tin oxide in their metal atomic ratio,
In / (In + Zn + Sn) = 0.00 to 1.00
Zn / (In + Zn + Zn) = 0.00 to 0.25
Sn / (In + Zn + Sn) = 0.00-1.00
A composition containing 0.5 to 20 atomic% of one or more metal oxides selected from iridium oxide, rhenium oxide and palladium oxide in a metal oxide having a ratio of It is a transparent conductive material made of material.
[0011]
More preferable transparent conductive materials are indium oxide, zinc oxide, and tin oxide in their metal atomic ratio.
In / (In + Zn + Sn) = 0.50-1.00
Zn / (In + Zn + Sn) = 0.00 to 0.25
Sn / (In + Zn + Sn) = 0.00 to 0.50
A composition containing 0.5 to 20 atomic% of one or more metal oxides selected from iridium oxide, rhenium oxide and palladium oxide in a metal oxide having a ratio of It is a transparent conductive material made of material.
[0012]
And as a transparent conductive material with good conductivity, indium oxide, zinc oxide, tin oxide is in their metal atomic ratio,
In / (In + Zn + Sn) = 0.75-0.95
Zn / (In + Zn + Sn) = 0.05-0.20
Sn / (In + Zn + Sn) = 0.00-0.20
A composition containing 0.5 to 20 atomic% of one or more metal oxides selected from iridium oxide, rhenium oxide and palladium oxide in a metal oxide having a ratio of It is a transparent conductive material made of material.
[0013]
And as the most preferable transparent conductive material, indium oxide, zinc oxide, and tin oxide are in their metal atomic ratio,
In / (In + Zn + Sn) = 0.85-0.95
Zn / (In + Zn + Sn) = 0.07-0.20
Sn / (In + Zn + Sn) = 0.00-0.15
A composition containing 0.5 to 20 atomic% of one or more metal oxides selected from iridium oxide, rhenium oxide and palladium oxide in a metal oxide having a ratio of It is a transparent conductive material made of material.
[0014]
In the transparent conductive material of the present invention, the basic component is indium oxide, zinc oxide, tin oxide, or a mixture of these metal oxides, as described above, each of indium oxide, zinc oxide or tin oxide alone. Alternatively, a mixture of indium oxide and zinc oxide, a mixture of indium oxide and tin oxide, or a mixture of indium oxide, zinc oxide, and tin oxide may be used.
[0015]
And, regarding the content ratio of each component in this basic constituent component, indium oxide may not be necessary, but in order to obtain a low surface resistance when used as a transparent conductive film, its atomic ratio It is good to use the composition whose is 0.5 or more. In addition, although zinc oxide may not be necessary, a small amount of a composition containing, for example, 0.05 or more in atomic ratio is used in order to improve the etching property of the film when the transparent conductive film is formed. Good. When the etching property of the transparent conductive film is not sufficient, the etching property can be improved by adding a small amount of water or hydrogen during sputtering film formation. And about this zinc oxide, when the content rate exceeds 0.25, durability of a transparent conductive film may fall. Furthermore, tin oxide may not be required, but when it is necessary to maintain the conductivity of the target, it is preferable to use a target containing this, but the surface thereof as a transparent conductive film When a material with low resistance is required, it is preferable that the content ratio of this material is 0.5 or less in terms of atomic ratio.
[0016]
Next, iridium oxide, rhenium oxide and palladium oxide to be contained in the above basic constituent components may be used alone or in a mixture at an arbitrary mixing ratio. And these content rates are 0.5-20 atomic% with respect to all the metal atoms of the transparent conductive material obtained by mix | blending these metal oxides. This can be expressed in terms of metal atomic ratio.
Ir / (In + Zn + Sn + Ir) = 0.005 to 0.20
Re / (In + Zn + Sn + Re) = 0.005 to 0.20
Pd / (In + Zn + Sn + Pd) = 0.005 to 0.20
And preferably
Ir / (In + Zn + Sn + Ir) = 0.01-0.10
Re / (In + Zn + Sn + Re) = 0.01-0.10
Pd / (In + Zn + Sn + Pd) = 0.01-0.10
More preferably Ir / (In + Zn + Sn + Ir) = 0.03 to 0.08
Re / (In + Zn + Sn + Re) = 0.03 to 0.08
Pd / (In + Zn + Sn + Pd) = 0.03 to 0.08
It is. When the content of these iridium oxide, rhenium oxide and palladium oxide is less than 0.5 atomic%, the work function of the obtained transparent conductive film cannot be sufficiently increased, and this content exceeds 20 atomic%. This is because the transparency is lowered.
[0017]
A metal oxide composition obtained by adding 0.5 to 20 atom% of these iridium oxide, rhenium oxide and palladium oxide with respect to the above basic constituent components is As a sputtering target, a transparent conductive film formed by using this is made to have a light transmittance of 70% or more and a work function of 5.4 electron volts or more. The value of the work function of the transparent conductive film is almost the same level as 5.5 to 5.6 electron volts, which is an average value of the ionization potential of an organic compound used as a light emitting material or a hole transport material in an organic electroluminescence device. It is. Therefore, when this transparent conductive film is used as the anode of an organic electroluminescence device, the energy barrier when holes are injected from the anode into the hole transport layer or the light emitting layer is reduced, and high hole injection efficiency is obtained. As a result, the driving voltage of the organic electroluminescence element can be lowered, and the heat generated due to the presence of the energy barrier is suppressed, and stable light emission for a long period of time becomes possible.
[0018]
Next, with respect to the method for producing the transparent conductive material of the present invention, the above metal oxide powders are mixed in a predetermined ratio and mixed uniformly by a mixing and grinding machine such as a wet ball mill, a bead mill, or an ultrasonic wave. -Obtained by grinding. The mixing and pulverization of the raw material powder is preferably as finely pulverized as described above. However, it is usually desirable to perform the mixing and pulverizing treatment so that the average particle diameter is 1 μm or less.
[0019]
Moreover, in order to obtain a sintered body using this transparent conductive material, after granulating this, it may be shaped into a desired shape by press molding and sintered by firing. The firing condition in this case is usually 1,200 to 1,500 ° C., preferably 1,250 to 1,480 ° C., for 10 to 72 hours, preferably 24 to 48 hours. Moreover, the temperature increase rate in this case should just be 1-50 degrees C / min.
[0020]
And as a transparent base material used when forming a film using the target obtained by shaping and sintering in this way, a conventionally used glass substrate or a synthetic resin having high transparency is used. Made films and sheets are used. As this synthetic resin, polycarbonate resin, polymethyl methacrylate resin, polyester resin, polyethersulfone resin, polyarylate resin and the like are suitable.
[0021]
Next, in forming a transparent conductive film on a transparent substrate by sputtering using the above target, a magnetron sputtering apparatus is preferably used. And as conditions at the time of film-forming by sputtering using this apparatus, although the output of plasma fluctuates with the surface area of a target or the film thickness of a transparent conductive film, this plasma output is usually used per 1 cm 2 of surface area of a target. A transparent conductive film having a desired film thickness can be obtained by adjusting the film formation time to 5 to 120 minutes in the range of 0.3 to 4 W. The film thickness of the transparent conductive film varies depending on the type of display device, but is usually 200 to 6,000 angstroms, preferably 600 to 2,000 angstroms.
[0022]
The target made of the sintered body can also be used when a film is formed by an electron beam apparatus or an ion plating apparatus. Also when forming a film using these apparatuses, the transparent conductive film can be formed under the same film forming conditions as in the above sputtering apparatus.
The transparent conductive glass and transparent conductive film of the present invention thus obtained have a transparent conductive film made of a metal oxide composition having the same composition as the sintered body used for film formation, and the transparent conductive film With regard to the transparency, the light transmittance of light having a wavelength of 500 nm exceeds 70%. In addition, as for the conductivity of the transparent conductive film, many have a specific resistance of 5 mΩ · cm or less. As described above, the work function of the transparent conductive film is higher than that of the conventionally used ITO film, and the ionization potential value of the organic compound forming the light emitting layer and the hole transport layer of the organic electroluminescence element It has a value of 5.4 electron volts or more, which is almost the same level.
[0023]
Therefore, the transparent conductive glass and the transparent conductive film of the present invention can be suitably used as transparent electrodes for various display devices including organic electroluminescence elements.
[0024]
【Example】
Hereinafter, the present invention will be described in more detail by way of examples of the present invention.
[Example 1]
(1) As a raw material for producing a transparent conductive material, an indium oxide powder, a tin oxide powder, and an iridium oxide powder have an atomic ratio of these metals,
In / (In + Zn + Sn) = 0.90
Zn / (In + Zn + Sn) = 0.00
Sn / (In + Zn + Sn) = 0.10
And
Ir / (In + Zn + Sn + Ir) = 0.04
Then, the mixture was fed to a wet ball mill and mixed and ground for 72 hours to obtain a transparent conductive material powder.
The metal atomic ratio of the obtained transparent conductive material is shown in Table 1.
[0025]
(2) Manufacture of sintered body After granulating the powder of the transparent conductive material obtained in the above (1), it is press-shaped into a size of 4 inches in diameter and 5 mm in thickness, and this is charged into a firing furnace. The baking was performed at 36 ° C. for 36 hours.
[0026]
The sintered body thus obtained had a density of 6.8 g / cm 3 and a bulk electric resistance of 0.98 mΩ · cm.
The measurement results of the physical properties of the obtained sintered body are shown in Table 1.
(3) Production of transparent conductive glass A sputtering target having a diameter of 4 inches and a thickness of 5 mm was prepared from the sintered body obtained in the above (1), and this was mounted on a DC magnetron sputtering apparatus, and glass was obtained at room temperature. A film was formed on the substrate.
[0027]
As sputtering conditions here, an atmosphere is used by mixing an appropriate amount of oxygen gas with argon gas, sputtering pressure 3 × 10 −1 Pa, ultimate pressure 5 × 10 −4 Pa, substrate temperature 25 ° C., input power 80 W, The film formation time was 14 minutes.
The transparent conductive film on the transparent conductive glass thus obtained had a thickness of 1,200 angstroms and was amorphous. And it was 81% as a result of measuring the light transmittance of this transparent conductive film about the light ray with a wavelength of 500 nm with the spectrophotometer. Moreover, the specific resistance of the transparent conductive film measured by the four-probe method was 1.2 mΩ · cm, and the conductivity was high. Further, the work function was measured by ultraviolet photoelectron spectroscopy and found to be 5.46 electron volts.
The evaluation results of these transparent conductive films are shown in Table 2.
[0028]
[Example 2]
(1) Production of transparent conductive glass The same sputtering target as in Example 1 was used, and the substrate temperature was changed to 215 ° C. among the sputtering conditions. Glass was produced.
Table 2 shows the evaluation results of the transparent conductive film on the obtained transparent conductive glass.
[0029]
Example 3
(1) As a raw material for producing a transparent conductive material, an indium oxide powder, a tin oxide powder, and an iridium oxide powder have an atomic ratio of these metals,
In / (In + Zn + Sn) = 0.70
Zn / (In + Zn + Sn) = 0.00
Sn / (In + Zn + Sn) = 0.30
And
Ir / (In + Zn + Sn + Ir) = 0.08
Then, the mixture was fed to a wet ball mill and mixed and ground for 72 hours to obtain a transparent conductive material powder.
The metal atomic ratio of the obtained transparent conductive material is shown in Table 1.
[0030]
(2) Production of sintered body Using the transparent conductive material powder obtained in (1) above, a sintered body was obtained in the same manner as in (2) of Example 1.
The measurement results of the physical properties of the obtained sintered body are shown in Table 1.
(3) Production of transparent conductive glass A transparent conductive glass was produced in the same manner as (3) of Example 1 except that the sintered body obtained in (2) above was used. Table 2 shows the evaluation results of the physical properties of the transparent conductive film on the obtained transparent conductive glass.
[0031]
Example 4
(1) As a raw material for producing a transparent conductive material, an indium oxide powder, a tin oxide powder, and an iridium oxide powder have an atomic ratio of these metals,
In / (In + Zn + Sn) = 0.25
Zn / (In + Zn + Sn) = 0.00
Sn / (In + Zn + Sn) = 0.75
And
Ir / (In + Zn + Sn + Ir) = 0.05
Then, the mixture was fed to a wet ball mill and mixed and ground for 72 hours to obtain a transparent conductive material powder.
The metal atomic ratio of the obtained transparent conductive material is shown in Table 1.
[0032]
(2) Production of sintered body Using the transparent conductive material powder obtained in (1) above, a sintered body was obtained in the same manner as in (2) of Example 1.
The measurement results of the physical properties of the obtained sintered body are shown in Table 1.
(3) Production of transparent conductive glass A transparent conductive glass was produced in the same manner as (3) of Example 1 except that the sintered body obtained in (2) above was used. Table 2 shows the evaluation results of the physical properties of the transparent conductive film on the obtained transparent conductive glass.
[0033]
Example 5
(1) As a raw material for producing a transparent conductive material, an indium oxide powder and an iridium oxide powder have an atomic ratio of these metals,
In / (In + Zn + Sn) = 1.00
Zn / (In + Zn + Sn) = 0.00
Sn / (In + Zn + Sn) = 0.00
And
Ir / (In + Zn + Sn + Ir) = 0.04
Then, the mixture was fed to a wet ball mill and mixed and ground for 72 hours to obtain a transparent conductive material powder.
The metal atomic ratio of the obtained transparent conductive material is shown in Table 1.
[0034]
(2) Production of sintered body Using the transparent conductive material powder obtained in (1) above, a sintered body was obtained in the same manner as in (2) of Example 1.
The measurement results of the physical properties of the obtained sintered body are shown in Table 1.
(3) Production of transparent conductive glass A transparent conductive glass was produced in the same manner as (3) of Example 1 except that the sintered body obtained in (2) above was used. Table 2 shows the evaluation results of the physical properties of the transparent conductive film on the obtained transparent conductive glass.
[0035]
Example 6
(1) As a raw material for producing a transparent conductive material, zinc oxide powder, tin oxide powder, and iridium oxide powder, the atomic ratio of these metals is
In / (In + Zn + Sn) = 0.00
Zn / (In + Zn + Sn) = 0.20
Sn / (In + Zn + Sn) = 0.80
And
Ir / (In + Zn + Sn + Ir) = 0.05
Then, the mixture was fed to a wet ball mill and mixed and ground for 72 hours to obtain a transparent conductive material powder.
The metal atomic ratio of the obtained transparent conductive material is shown in Table 1.
[0036]
(2) Production of sintered body Using the transparent conductive material powder obtained in (1) above, a sintered body was obtained in the same manner as in (2) of Example 1.
The measurement results of the physical properties of the obtained sintered body are shown in Table 1.
(3) Production of transparent conductive glass A transparent conductive glass was produced in the same manner as (3) of Example 1 except that the sintered body obtained in (2) above was used. Table 2 shows the evaluation results of the physical properties of the transparent conductive film on the obtained transparent conductive glass.
[0037]
Example 7
(1) As a raw material for producing a transparent conductive material, an indium oxide powder, a zinc oxide powder, a tin oxide powder, and an iridium oxide powder have an atomic ratio of these metals,
In / (In + Zn + Sn) = 0.80
Zn / (In + Zn + Sn) = 0.10
Sn / (In + Zn + Sn) = 0.10
And
Ir / (In + Zn + Sn + Ir) = 0.06
Then, the mixture was fed to a wet ball mill and mixed and ground for 72 hours to obtain a transparent conductive material powder.
The metal atomic ratio of the obtained transparent conductive material is shown in Table 1.
[0038]
(2) Production of sintered body Using the transparent conductive material powder obtained in (1) above, a sintered body was obtained in the same manner as in (2) of Example 1.
The measurement results of the physical properties of the obtained sintered body are shown in Table 1.
(3) Production of transparent conductive glass A transparent conductive glass was produced in the same manner as (3) of Example 1 except that the sintered body obtained in (2) above was used. Table 2 shows the evaluation results of the physical properties of the transparent conductive film on the obtained transparent conductive glass.
[0039]
Example 8
(1) As a raw material for producing a transparent conductive material, an indium oxide powder, a zinc oxide powder, a tin oxide powder, and an iridium oxide powder have an atomic ratio of these metals,
In / (In + Zn + Sn) = 0.05
Zn / (In + Zn + Sn) = 0.90
Sn / (In + Zn + Sn) = 0.05
And
Ir / (In + Zn + Sn + Ir) = 0.06
Then, the mixture was fed to a wet ball mill and mixed and ground for 72 hours to obtain a transparent conductive material powder.
The metal atomic ratio of the obtained transparent conductive material is shown in Table 1.
[0040]
(2) Production of sintered body Using the transparent conductive material powder obtained in (1) above, a sintered body was obtained in the same manner as in (2) of Example 1.
The measurement results of the physical properties of the obtained sintered body are shown in Table 1.
(3) Production of transparent conductive glass A transparent conductive glass was produced in the same manner as (3) of Example 1 except that the sintered body obtained in (2) above was used. Table 2 shows the evaluation results of the physical properties of the transparent conductive film on the obtained transparent conductive glass.
[0041]
Example 9
(1) As a raw material for producing a transparent conductive material, an indium oxide powder, a zinc oxide powder, and an iridium oxide powder have an atomic ratio of these metals,
In / (In + Zn + Sn) = 0.85
Zn / (In + Zn + Sn) = 0.15
Sn / (In + Zn + Sn) = 0.00
And
Ir / (In + Zn + Sn + Ir) = 0.06
Then, the mixture was fed to a wet ball mill and mixed and ground for 72 hours to obtain a transparent conductive material powder.
The metal atomic ratio of the obtained transparent conductive material is shown in Table 1.
[0042]
(2) Production of sintered body Using the transparent conductive material powder obtained in (1) above, a sintered body was obtained in the same manner as in (2) of Example 1.
The measurement results of the physical properties of the obtained sintered body are shown in Table 1.
(3) Production of transparent conductive glass A transparent conductive glass was produced in the same manner as (3) of Example 1 except that the sintered body obtained in (2) above was used. Table 2 shows the evaluation results of the physical properties of the transparent conductive film on the obtained transparent conductive glass.
[0043]
Example 10
(1) Production of transparent conductive glass A transparent conductive glass was prepared in the same manner as (3) of Example 1 except that the sputtering target obtained in Example 9 was used and the substrate temperature was 215 ° C among the sputtering conditions. Made glass.
Table 2 shows the evaluation results of the physical properties of the transparent conductive film on the obtained transparent conductive glass.
[0044]
Example 11
(1) Production of transparent conductive film The same as (3) of Example 1, except that the sputtering target used in Example 10 was used and a transparent resin film made of polycarbonate resin was used as the substrate instead of the glass substrate. Thus, a transparent conductive film was produced.
Table 2 shows the evaluation results of the properties of the transparent conductive film on the transparent conductive film obtained here.
[0052]
[Example 12 ]
(1) As a raw material for producing a transparent conductive material, an indium oxide powder, a zinc oxide powder and a palladium oxide powder have an atomic ratio of these metals,
In / (In + Zn + Sn) = 0.80
Zn / (In + Zn + Sn) = 0.20
Sn / (In + Zn + Sn) = 0.00
And
Pd / (In + Zn + Sn + Pd) = 0.05
Then, the mixture was fed to a wet ball mill and mixed and ground for 72 hours to obtain a transparent conductive material powder. The metal atomic ratio of the obtained transparent conductive material is shown in Table 1.
[0053]
(2) Production of sintered body Using the transparent conductive material powder obtained in (1) above, a sintered body was obtained in the same manner as in (2) of Example 1.
The measurement results of the physical properties of the obtained sintered body are shown in Table 1.
(3) Production of transparent conductive glass A transparent conductive glass was produced in the same manner as (3) of Example 1 except that the sintered body obtained in (2) above was used. Table 2 shows the evaluation results of the physical properties of the transparent conductive film on the obtained transparent conductive glass.
[0054]
[Comparative Example 1]
(1) As a raw material for producing a transparent conductive material, an indium oxide powder and a tin oxide powder in these metal atomic ratios,
In / (In + Zn) = 0.85
Zn / (In + Zn) = 0.15
Then, the mixture was fed to a wet ball mill and mixed and ground for 72 hours to obtain a transparent conductive material powder.
(2) Production of sintered body Using the transparent conductive material obtained in the above (1), a sintered body was obtained in the same manner as in (2) of Example 1.
(3) Production of transparent conductive glass A transparent conductive glass was produced in the same manner as (3) of Example 1 except that the sintered body obtained in (2) above was used. The results of evaluating the transparent conductive film formed on the obtained transparent conductive glass are shown in Table 2.
[0055]
[Comparative Example 2]
(1) As a raw material for producing a transparent conductive material, an indium oxide powder and a tin oxide powder in these metal atomic ratios,
In / (In + Sn) = 0.90
Sn / (In + Sn) = 0.10
Then, the mixture was fed to a wet ball mill and mixed and ground for 72 hours to obtain a transparent conductive material powder.
(2) Manufacture of sintered body Manufacture of transparent conductive glass in the same manner as (3) of Example 1 except that the sintered body obtained in (2) above was used and the substrate temperature was 215 ° C. Did. The results of evaluating the transparent conductive film formed on the obtained transparent conductive glass are shown in Table 2.
[0056]
[Table 1]
[0058]
[Table 2]
[0060]
【The invention's effect】
According to the transparent conductive material of the present invention, a transparent conductive film having high transparency and a high work function can be formed. Moreover, the transparent conductive glass or transparent conductive film having this transparent conductive film has a high hole injection efficiency when used for an electrode of a display device such as an organic electroluminescence element, and maintains a stable light emitting state for a long period of time. Can do.

Claims (11)

  1. A transparent conductive material used for an organic electroluminescence device containing an organic compound having an ionization potential of 5.5 to 5.6 eV, wherein one or more metal oxides selected from indium oxide, zinc oxide and tin oxide are used. , one or more metal oxides, transparent conductive material comprising a composition containing% 0.5 to 20 atom relative to the total metal atoms selected from oxidized iridium beam Contact and palladium oxide.
  2. Indium oxide, zinc oxide, and tin oxide are in their metal atomic ratio.
    In / (In + Zn + Sn) = 0.00 to 1.00
    Zn / (In + Zn + Sn) = 0.00-0.25
    Sn / (In + Zn + Sn) = 0.00-1.00
    The transparent conductive material according to claim 1, wherein
  3. Indium oxide, zinc oxide, and tin oxide are in their metal atomic ratio.
    In / (In + Zn + Sn) = 0.50-1.00
    Zn / (In + Zn + Sn) = 0.00 to 0.25
    Sn / (In + Zn + Sn) = 0.00 to 0.50
    The transparent conductive material according to claim 1, wherein
  4. Indium oxide, zinc oxide, and tin oxide are in their metal atomic ratio.
    In / (In + Zn + Sn) = 0.75-0.95
    Zn / (In + Zn + Sn) = 0.05-0.20
    Sn / (In + Zn + Sn) = 0.00-0.20
    The transparent conductive material according to claim 1, wherein
  5. The transparent conductive material according to claim 1, wherein an organic compound having an ionization potential of 5.5 to 5.6 eV forms a light emitting layer or a hole transport layer in the organic electroluminescence device.
  6. The sintered compact formed by sintering the transparent conductive material in any one of Claims 1-5 .
  7. A sputtering target comprising the sintered body according to claim 6 .
  8. A transparent conductive glass obtained by coating a glass surface with a transparent conductive film made of the transparent conductive material according to claim 1 .
  9. The transparent conductive glass according to claim 8 , wherein the light transmittance is 70% or more and the work function of the transparent conductive film is 5.4 electron volts or more.
  10. A transparent conductive film formed by coating the transparent resin film surface with the transparent conductive film made of the transparent conductive material according to claim 1 .
  11. The transparent conductive film according to claim 10 , wherein the light transmittance is 70% or more and the work function of the transparent conductive film is 5.4 electron volts or more.
JP00504699A 1999-01-12 1999-01-12 Transparent conductive material, transparent conductive glass and transparent conductive film Expired - Fee Related JP4372876B2 (en)

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Application Number Priority Date Filing Date Title
JP00504699A JP4372876B2 (en) 1999-01-12 1999-01-12 Transparent conductive material, transparent conductive glass and transparent conductive film

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
JP00504699A JP4372876B2 (en) 1999-01-12 1999-01-12 Transparent conductive material, transparent conductive glass and transparent conductive film
EP13161290.5A EP2610229A3 (en) 1998-08-31 1999-08-19 Transparent electroconductive glass coated with transparent electroconductive film containing IZTO
US09/529,416 US6534183B1 (en) 1998-08-31 1999-08-19 Target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass, and transparent electroconductive film
EP13161293.9A EP2610230A2 (en) 1998-08-31 1999-08-19 Target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass, and transparent electroconductive film
EP99938524A EP1033355A4 (en) 1998-08-31 1999-08-19 Target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass and transparent electroconductive film
CNB998019828A CN1281544C (en) 1998-08-31 1999-08-19 Target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass and transparent electroconductive film
EP13161296.2A EP2610231A2 (en) 1998-08-31 1999-08-19 Target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass, and transparent electroconductive film
PCT/JP1999/004453 WO2000012445A1 (en) 1998-08-31 1999-08-19 Target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass and transparent electroconductive film
KR1020007004590A KR100622168B1 (en) 1998-08-31 1999-08-19 Target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass and transparent electroconductive film
TW088114565A TW514622B (en) 1998-08-31 1999-08-25 Target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass and transparent EL
US10/302,928 US6689477B2 (en) 1998-08-31 2002-11-25 Target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass and transparent electroconductive film

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Publication number Priority date Publication date Assignee Title
JP2002110365A (en) * 2000-10-04 2002-04-12 Idemitsu Kosan Co Ltd Transparent electrode substrate for organic electroluminescent display element and organic electroluminescent display element
JP4234006B2 (en) * 2001-07-17 2009-03-04 出光興産株式会社 Sputtering target and transparent conductive film
US7897067B2 (en) 2003-05-20 2011-03-01 Idemitsu Kosan Co., Ltd. Amorphous transparent conductive film, sputtering target as its raw material, amorphous transparent electrode substrate, process for producing the same and color filter for liquid crystal display
JP2005064273A (en) * 2003-08-13 2005-03-10 Idemitsu Kosan Co Ltd Electrode for photoelectromotive force element and photoelectromotive force element employing the same
CN100558930C (en) * 2004-02-17 2009-11-11 日矿金属株式会社 Sputtering target, optical information recording medium and process for producing the same
JP4552950B2 (en) 2006-03-15 2010-09-29 住友金属鉱山株式会社 Oxide sintered body for target, manufacturing method thereof, manufacturing method of transparent conductive film using the same, and transparent conductive film obtained
JP4994068B2 (en) * 2006-08-09 2012-08-08 出光興産株式会社 Oxide conductive material and manufacturing method thereof
KR100863910B1 (en) 2007-07-03 2008-10-17 삼성에스디아이 주식회사 Organic light emitting device

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