JP5000230B2 - Lanthanum oxide containing oxide target - Google Patents

Description

  The present invention relates to an oxide target used when forming a conductive film. More specifically, the present invention relates to an oxide target made of an oxide sintered body containing lanthanum.

In a transparent conductive film containing indium oxide as a main component, indium oxide (ITO) doped with tin is generally used. This is because a transparent conductive film excellent in conductivity can be obtained by improving the carrier concentration by doping with tin.
However, the ITO film needs to use a strong acid (for example, aqua regia) for the etching process, and when used for an electrode for a TFT liquid crystal, there is a problem that the underlying metal wiring may be corroded. is doing. Furthermore, since the ITO target used when producing the ITO film by sputtering is likely to be blackened by reduction, a change in its characteristics with time is a problem.

  A transparent conductive film having excellent etching and light transmittance as compared with the ITO film and a sputtering target suitable for obtaining the transparent conductive film, which is superior to the ITO film, and a transparent conductive film made of indium oxide and zinc oxide. It has been proposed (Patent Documents 1 and 2). These transparent conductive films made of indium oxide and zinc oxide are known to have a high etching rate with a weak acid. However, when the metal thin film formed on the transparent conductive film is etched, the transparent conductive film made of indium oxide and zinc oxide may be etched at the same time, and only the metal thin film on the transparent conductive film is selectively etched. In some cases it was inappropriate.

In addition, it has been reported that a transparent conductive film containing indium oxide and a lanthanoid element is useful as an organic EL electrode or a transflective / semi-reflective LCD electrode (Patent Documents 3-11). However, oxides of lanthanoid elements are not conductive, and when targets are prepared by mixing these oxides with indium oxide, only targets with low conductivity may be obtained. For this reason, abnormal discharge may occur during sputtering, or the target surface may become black, which may cause inconveniences such as a reduction in sputtering speed.
JP-A-6-234565 JP 7-235219 A JP 2004-68054 A JP 2004-119272 A JP 2004-139780 A JP 2004-146136 A JP 2004-158315 A JP 2004-240091 A JP 2004-294630 A JP 2004-333882 A JP 2005-314734 A

  The present invention has been made in view of the above-described problems, and an object thereof is to provide an oxide target that has high conductivity and does not cause abnormal discharge or surface blackening of the target.

According to the present invention, the following oxide target (hereinafter simply referred to as target) is provided.
1. An oxide target containing indium (In) and lanthanum (La), which contains an oxide represented by LaInO ₃ .
2. 2. The oxide target according to 1, wherein a ratio [La / (La + In): atomic ratio] of La to the total content of In and La is 0.001 to 0.5.
3. An oxide target containing tin (Sn) and lanthanum (La), wherein the oxide target contains an oxide represented by La ₂ Sn ₂ O ₇ .
4). 4. The oxide target according to 3, wherein the ratio [La / (La + Sn): atomic ratio] of La to the total content of Sn and La is 0.001 to 0.5.
5. An oxide target containing indium (In), tin (Sn) and lanthanum (La), characterized by containing an oxide represented by La ₂ Sn ₂ O ₇ and / or LaInO ₃ Oxide target.
6). 6. The oxide target according to 5, wherein a ratio [La / (La + Sn + In): atomic ratio] of La to the total content of In, Sn, and La is 0.001 to 0.5.
7). The oxide target according to any one of 1 to 6, wherein the sintered density is 6.5 g / cm ³ or more.
8). Bulk resistance is 1 ohm-cm or less, The oxide target in any one of 1-7 characterized by the above-mentioned.

  Since the oxide target of the present invention includes an oxide having a predetermined structure containing a lanthanum element and has excellent conductivity, it becomes an oxide target without abnormal discharge. These oxide targets are used as sputtering targets, electron beam targets, or ion plating targets, and serve as raw materials for thin film formation.

A first aspect of the oxide target of the present invention is a target consisting of a sintered body of an oxide containing indium (In) and lanthanum (La), which contains an oxide represented by Laino ₃ (Hereinafter, this target is referred to as target I).
When this target I is used, the conductivity of the target is higher and the target surface is less blackened and stable without abnormal discharge during sputtering compared to the case of a target composed of In ₂ O ₃ and La ₂ O _3. The sputtered state is maintained. Thereby, the transparent conductive film which has the light transmittance equivalent to an ITO film | membrane is obtained stably.

The target I includes an oxide having a form represented by LaInO ₃ , and preferable examples of the oxide constituting the target include the following.
(A) LaInO ₃
(B) A mixture of LaInO ₃ and In ₂ O ₃
(C) Mixture of LaInO ₃ and La ₂ O ₃ Of these, the sintered body of (b) is preferred. Note that the structure of the oxide in the target is identified from a chart obtained by X-ray diffraction measurement. The same applies to targets II and III described later.

In this target, the ratio of La to the total of La and In (atomic ratio: La / (La + In)) is preferably 0.001 to 0.5, more preferably 0.01 to 0.2, and particularly preferably. Is 0.01 to 0.15. If it is less than 0.001, the effect of adding La atoms may not be obtained. If it exceeds 0.5, La ₂ O ₃ will be present alone, and the resistance of the target will become too large, resulting in sputtering. Sometimes, problems such as abnormal discharge may occur. Moreover, there exists a problem which the intensity | strength of target itself falls and it cracks or deform | transforms in the sintering process in a target manufacturing process.

The atomic ratio of La and In in the target can be controlled by adjusting the mixing ratio of the indium compound and lanthanum compound that are raw materials before sintering. Depending on the mixing ratio before sintering, a lanthanum / indium compound such as LaInO ₃ composed of an indium compound and a lanthanum compound corresponding to the stoichiometric ratio is generated, and the remaining indium compound exists as a crystalline substance or an amorphous substance. Estimated.

Examples of the method for producing the target I include a method of sintering a mixture of these using a compound containing an indium atom and a compound containing a lanthanum atom as a raw material.
Examples of the compound containing indium atoms include indium oxide and indium hydroxide. Indium oxide is preferable.
Examples of the compound containing a lanthanum atom include lanthanum oxide and lanthanum hydroxide. Preferably, it is lanthanum oxide.

The above starting materials are preferably pulverized and mixed with a bead mill or the like. Thereby, a raw material can be mixed uniformly and the particle size of a raw material can be made small.
The average particle size of the raw material is at most 3 μm, preferably 1 μm or less, more preferably 0.8 μm or less. When it exceeds 3 μm, for example, La ₂ O ₃ is present as insulating particles in the target as it is, which may cause abnormal discharge. The formation of LaInO ₃ can be confirmed by X-ray diffraction.
A material powder formed into a predetermined shape is fired. Baking conditions are 1000-1600 degreeC. Preferably, it is 1200-1500 degreeC, More preferably, it is 1250-1450 degreeC. Is less than 1000 ° C., less reactive of _La 2 _{O 3,} may not produce the Laino _3. If it exceeds 1600 ° C., In ₂ O ₃ may be sublimated or thermally decomposed to change the composition, or the produced LaInO ₃ may be decomposed.
In the present invention, the sintered body contains LaInO ₃ , but the oxide in this form can be formed by the above-described sintering. The particle size of the LaInO ₃ produced can be measured by EPMA mapping. The particle size of LaInO ₃ is 10 μm or less, preferably 5 μm or less. When LaInO ₃ particles exceeding 10 μm are present, abnormal discharge may occur due to the difference in conductivity around the particles. When the thickness is 10 μm or less, these abnormal discharges are suppressed and stable sputtering can be performed.

A second aspect of the oxide target of the present invention is a target consisting of a sintered body of an oxide containing tin (Sn) and lanthanum (La), oxide represented by La ₂ Sn ₂ O ₇ (Hereinafter, this target is referred to as “target II”).
When this target II is used, a stable sputtering state is maintained without blackening of the target surface and abnormal discharge during sputtering, as compared with a target made of simply SnO ₂ and La ₂ O ₃ .

The target II contains an oxide having a form represented by La ₂ Sn ₂ O ₇ , and preferable examples of the oxide constituting the target include the following.
(A) La ₂ Sn ₂ O ₇
(B) A mixture of La ₂ Sn ₂ O ₇ and SnO ₂
(C) Mixture of La ₂ Sn ₂ O ₇ and La ₂ O ₃ Among the above, the sintered body of (b) is preferable.

In this target, the ratio of La to the total of La and Sn (atomic ratio: La / (La + Sn)) is preferably 0.001 to 0.5, more preferably 0.01 to 0.2, particularly Preferably, it is 0.01-0.15. If it is less than 0.001, the effect of adding La may not be obtained. If it exceeds 0.5, La ₂ O ₃ will be present alone, and insulating particles will be present in the target. Thus, problems such as abnormal discharge may occur during sputtering.

The atomic ratio of La and Sn can be controlled by adjusting the mixing ratio of the tin compound and the lanthanum compound before sintering. La ₂ Sn ₂ O ₇ oxide consisting of tin compound and lanthanum compound corresponding to the stoichiometric ratio is generated by mixing ratio before sintering, and the remaining tin compound exists as crystalline or amorphous substance Presumed to be.

Examples of the method for producing the target II include a method of sintering a mixture of these using a compound containing a tin atom and a compound containing a lanthanum atom as raw materials.
Examples of the compound containing a tin atom include tin oxide (stannous oxide, stannic oxide), metastannic acid, and the like. Preferably, it is tin oxide (stannic oxide).
The above starting materials are preferably pulverized and mixed with a bead mill or the like. Thereby, a raw material can be mixed uniformly and the particle size of a raw material can be made small.
The average particle size of the raw material is at most 3 μm, preferably 1 μm or less, more preferably 0.8 μm or less. When it exceeds 3 μm, for example, La ₂ O ₃ is present as insulating particles in the target as it is, which may cause abnormal discharge. The production of La ₂ Sn ₂ O ₇ can be confirmed by X-ray diffraction.

A material powder formed into a predetermined shape is fired. Baking conditions are 1000-1600 degreeC. Preferably, it is 1200-1500 degreeC, More preferably, it is 1250-1450 degreeC. Is less than 1000 ° C., the reaction of _La 2 _{O 3} is _low, there may not be found the generation of La 2 _Sn 2 _{O 7.} If it exceeds 1600 ° C., La ₂ O ₃ may be sublimated or thermally decomposed to change the composition, or the produced La ₂ Sn ₂ O ₇ may be decomposed.
In the present invention, the sintered body contains La ₂ Sn ₂ O _7, oxide of this embodiment may be formed by sintering the above. The particle size of La ₂ Sn ₂ O ₇ produced can be measured by EPMA mapping. The particle size of La ₂ Sn ₂ O ₇ is 10 μm or less, preferably 5 μm or less. When La ₂ Sn ₂ O ₇ particles exceeding 10 μm are present, abnormal discharge may occur due to the difference in conductivity around the particles. When the thickness is 10 μm or less, these abnormal discharges are suppressed and stable sputtering can be performed.

A third aspect of the oxide target of the present invention is a target composed of an oxide sintered body containing indium (In), tin (Sn), and lanthanum (La), and includes La ₂ Sn ₂ O ₇ and And / or an oxide represented by LaInO ₃ (hereinafter, this target is referred to as target III).
When this target III is used, compared with a target made of simply In ₂ O ₃ , SnO ₂ and La ₂ O ₃ , the target has higher conductivity, and there is no blackening of the target surface, and abnormal discharge during sputtering. And a stable sputtering state is maintained.

The target III includes an oxide having a form represented by La ₂ Sn ₂ O ₇ and / or LaInO ₃ , and preferable examples of the oxide constituting the target include the following.
(A) A mixture of La ₂ Sn ₂ O ₇ and In ₂ O ₃
(B) A mixture of La ₂ Sn ₂ O ₇ , In ₂ O ₃ and SnO ₂
(C) A mixture of La ₂ Sn ₂ O ₇ , LaInO ₃ and In ₂ O ₃
(D) La ₂ Sn ₂ O ₇ , LaInO ₃ and SnO ₂ mixture Among the above, a sintered body made of (a), (b) or (c) is preferable.

In this target, the atomic ratio of La (La / (La + In + Sn)) is preferably 0.001 to 0.5, more preferably 0.01 to 0.3, and particularly preferably 0.01 to 0.25. It is. If it is less than 0.001, the effect of adding La may not be obtained, and if it exceeds 0.5, La ₂ O ₃ will be present alone, the strength of the target will be too small, and sputtering will not be possible. Cracks may occur due to heat stress. In addition, the strength of the target itself may decrease, and problems such as cracking may occur during the target manufacturing process.

Moreover, it is preferable that ratio (atomic ratio) of content of La and Sn in a target satisfy | fills the relationship of a following formula.
La / (La + In + Sn) <Sn / (La + In + Sn)
This is because La ₂ Sn ₂ O ₇ is easily generated because La and Sn easily react. That is, when La is present in excess of Sn, almost all of Sn is consumed by La, so LaInO ₃ is mainly generated. As a result, the amount of Sn doping into In ₂ O ₃ decreases, which may increase the bulk resistance of the target.
On the other hand, when the content of La is made smaller than the content of Sn so as to satisfy the above formula, La is consumed by Sn, but excess Sn is doped into In ₂ O ₃ . Thereby, the resistance value of the target is reduced, and a stable sputtering state can be maintained.

  The Sn content [atomic ratio: Sn / (La + In + Sn)] satisfies the above-described relationship and is preferably in the range of 0.03 to 0.45, particularly preferably in the range of 0.05 to 0.3. .

The atomic ratio of La, In, and Sn is obtained by adjusting the mixing ratio of the indium compound, tin compound, and lanthanum compound before sintering. Prior to sintering, a La ₂ Sn ₂ O ₇ compound composed of a tin compound and a lanthanum compound corresponding to the stoichiometric ratio is generated by mixing ratio, and a LaInO ₃ compound composed of an indium compound and a lanthanum compound is generated, and the remaining indium compound It is presumed that tin compounds exist as crystalline substances or amorphous substances.

Examples of the method for producing target III include a method of sintering a mixture of these using a compound containing indium atoms, a compound containing tin atoms, and a compound containing lanthanum atoms as a raw material.
Specific examples of the compound containing an indium atom, the compound containing a tin atom, and the compound containing a lanthanum atom are the same as those of the target I or II described above.

A material powder formed into a predetermined shape is fired. Baking conditions are 1000-1600 degreeC. Preferably it is 1200-1500 degreeC, More preferably, it is 1250-1450 degreeC. Is less than 1000 ° C., less reactive of _La 2 _{O 3,} may not seen La 2 _Sn 2 _{O 7} product formation and Laino ₃ of. If it exceeds 1600 ° C., In ₂ O ₃ may be sublimated or thermally decomposed to change the composition, or the produced La ₂ Sn ₂ O ₇ or LaInO ₃ may be decomposed.
In the present invention, the sintered body contains La ₂ Sn ₂ O ₇ and / or LaInO ₃ , but the oxide in this form can be formed by a sintering reaction (thermal reaction).

In target I~III of the present invention, the density of the sintered body constituting the target is preferably 6.5 g / cm ³ or more, more preferably 6.6~7.2g / cm ^3. If the density of the sintered body is less than 6.5 g / cm ³ , the target surface may be blackened and abnormal discharge may occur.
In order to obtain a sintered body having a high density, it is preferable to form by a cold isostatic pressure (CIP) or the like in a forming step before firing, or to sinter by a hot isostatic pressure (HIP) or the like.

  The sintered body constituting the target of the present invention has little blackening during sputtering and high conductivity. Specifically, the bulk resistance of the sintered body can be 1 Ωcm or less. Furthermore, 0.1 Ωcm or less is also possible. In the present invention, in particular, the bulk resistance can be reduced by setting the composition of La / (La + Sn + In) <Sn / (La + Sn + In).

A conductive film can be formed using the target of the present invention. As a film forming method, an RF magnetron sputtering method, a DC magnetron sputtering method, an electron beam evaporation method, an ion plating method, or the like can be used. Of these, the RF magnetron sputtering method is preferably used. Even when the target bulk resistance exceeds 1 Ωcm, if the RF magnetron sputtering method is employed, a stable sputtering state can be maintained without abnormal discharge. In the case of a low resistance where the bulk resistance of the target is 1 Ωcm or less, an industrially advantageous DC magnetron sputtering method may be employed.
Thereby, a stable sputtering state is maintained without abnormal discharge, and industrially stable film formation becomes possible.

A method for measuring the characteristics of the targets prepared in Examples and Comparative Examples is shown below.
(1) Density The density was calculated from the weight and outer dimensions of the target cut into a certain size.
(2) Atomic ratio of each element in the target The abundance of each element was measured by ICP (Inductively Coupled Plasma) measurement.
(3) Bulk resistance of target The resistivity was measured by a four-probe method using a resistivity meter (Mitsubishi Yuka, Loresta).
(4) Structure of oxide present in target The structure of the oxide was identified by analyzing the chart obtained by X-ray diffraction.

Example 1
700 g of indium oxide having a purity of 99.99% or more and 300 g of lanthanum oxide having a purity of 99.99% or more were mixed, and pulverized and mixed in a dry bead mill for about 5 hours.
Subsequently, the powder obtained above was inserted into a 10 mmφ mold, and preformed at a pressure of 100 kg / cm ^{2 with} a mold press molding machine. Next, the compact was compacted at a pressure of 4 t / cm ² using a cold isostatic press molding machine and then fired at 1350 ° C. for 10 hours to obtain a sintered body. This sintered body was processed into a target (grinding, polishing, attaching to a backing plate).

As a result of performing X-ray diffraction measurement on the obtained target, it was confirmed that the target was composed of an oxide containing LaInO ₃ and In ₂ O ₃ as main components.
FIG. 1 shows an X-ray chart of the target.
As a result of ICP analysis, the atomic ratio [La / (La + In)] was 0.27.
The dispersion state of In and La was confirmed by in-plane element distribution measurement of the sintered body by EPMA (Electron Probe Micro Analyzer). As a result, the composition was substantially uniform.
Moreover, the density of the target was 6.78 g / cm ³ and the bulk resistance was 260 Ωcm.

Example 2
900 g of tin oxide and 100 g of lanthanum oxide were mixed and pulverized and mixed in a dry bead mill for about 5 hours.
Next, the obtained powder was inserted into a 10 mmφ mold, and preformed with a mold press molding machine at a pressure of 100 kg / cm ² . Next, after being consolidated by a cold isostatic press molding machine at a pressure of 4 t / cm ² , it was fired at 1350 ° C. for 10 hours to form a sintered body and processed into a target.

As a result of X-ray diffraction measurement, it was confirmed that the target thus obtained was composed of an oxide mainly composed of La ₂ Sn ₂ O ₇ and SnO ₂ .
FIG. 2 shows an X-ray chart of the target.
As a result of ICP analysis, the atomic ratio [La / (La + Sn)] was 0.09.
The dispersion state of Sn and La was confirmed by measuring the element distribution in the plane of the sintered body by EPMA, but the composition was substantially uniform. Moreover, the density of the target was 6.64 g / cm ³ and the bulk resistance was 950 Ωcm.

Examples 3-12
Each powder of indium oxide, tin oxide and lanthanum oxide was mixed so as to have the composition shown in Table 1, and pulverized and mixed in a dry bead mill for about 5 hours.
Next, the obtained powder was inserted into a 10 mmφ mold, and preformed with a mold press molding machine at a pressure of 100 kg / cm ² . Next, after being consolidated by a cold isostatic press molding machine at a pressure of 4 t / cm ² , it was fired at 1350 ° C. for 10 hours to form a sintered body and processed into a target.

As a result of X-ray diffraction measurement, it was confirmed that the target thus obtained was composed of an oxide containing In ₂ O _3, La ₂ Sn ₂ O ₇ , and LaInO ₃ as main components. The X-ray chart of the target produced in Example 3-12 is shown to FIGS. 3-12, respectively.
Table 2 shows the results of ICP analysis of the target, in-plane element distribution measurement results by EPMA, density and bulk resistance.

Comparative Example 1
400 g of indium oxide and 600 g of lanthanum oxide were mixed, and pulverized and mixed in a dry bead mill for about 5 hours.
Subsequently, the powder obtained above was inserted into a 10 mmφ mold, and preformed at a pressure of 100 kg / cm ^{2 with} a mold press molding machine. Next, it was consolidated at a pressure of 4 t / cm ² using a cold isostatic press molding machine, and then fired at 1350 ° C. for 10 hours.

In the sintered body taken out from the furnace, many cracks were generated and cracks were observed, and the target (grinding, polishing, pasting to backing plate) processing could not be performed.
As a result of X-ray diffraction measurement, this sintered body was confirmed to be a sintered body made of an oxide mainly composed of LaInO ₃ and La ₂ O ₃ .
FIG. 13 shows an X-ray chart of this sintered body.
As a result of ICP analysis, the atomic ratio [La / (La + In)] was 0.56.
As a result of confirming the dispersion state of In and La by measuring the element distribution in the plane of the sintered body by EPMA, the composition was substantially non-uniform. Further, the bulk resistance was 2 MΩcm or more, which was almost an insulating material.

  The target of the present invention is a transparent conductive film for various uses such as a transparent conductive film for liquid crystal display devices (LCD), a transparent conductive film for electroluminescence (EL) display elements, and a transparent conductive film for solar cells. It is suitable as a target for obtaining by vapor deposition or ion plating. For example, an electrode of an organic EL element and a transparent conductive film for a semi-transmissive / semi-reflective LCD can be obtained.

2 is an X-ray chart of a target manufactured in Example 1. FIG. 3 is an X-ray chart of a target produced in Example 2. 6 is an X-ray chart of a target produced in Example 3. 6 is an X-ray chart of a target produced in Example 4. 6 is an X-ray chart of a target produced in Example 5. FIG. 10 is an X-ray chart of a target produced in Example 6. 10 is an X-ray chart of a target produced in Example 7. 10 is an X-ray chart of a target produced in Example 8. 10 is an X-ray chart of a target produced in Example 9. 10 is an X-ray chart of a target produced in Example 10. 10 is an X-ray chart of a target manufactured in Example 11. 10 is an X-ray chart of a target manufactured in Example 12. 3 is an X-ray chart of a sintered body produced in Comparative Example 1.

Claims (5)

A sputtering target substantially consisting of an oxide of indium (In) and lanthanum (La), comprising an oxide represented by LaInO ₃ ,
The oxide sputtering target, wherein a ratio [La / (La + In): atomic ratio] of La to the total content of In and La is 0.001 to 0.27 . A sputtering target substantially composed of an oxide of tin (Sn) and lanthanum (La), comprising an oxide represented by La ₂ Sn ₂ O ₇ ;
The oxide sputtering target characterized in that the ratio [La / (La + Sn): atomic ratio] of La to the total content of Sn and La is 0.001 to 0.5. A sputtering target substantially made of an oxide of indium (In), tin (Sn), and lanthanum (La), containing an oxide represented by La ₂ Sn ₂ O ₇ and / or LaInO ₃ ,
An oxide sputtering target, wherein a ratio [La / (La + Sn + In): atomic ratio] of La to the total content of In, Sn, and La is 0.001 to 0.39. The oxide target according to claim 1, wherein the sintered density is 6.5 g / cm ³ or more. Bulk resistance is 1 ohm-cm or less, The oxide target in any one of Claims 1-4 characterized by the above-mentioned.

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