JP5237557B2 - Sputtering target and manufacturing method thereof - Google Patents

Sputtering target and manufacturing method thereof Download PDF

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JP5237557B2
JP5237557B2 JP2007000417A JP2007000417A JP5237557B2 JP 5237557 B2 JP5237557 B2 JP 5237557B2 JP 2007000417 A JP2007000417 A JP 2007000417A JP 2007000417 A JP2007000417 A JP 2007000417A JP 5237557 B2 JP5237557 B2 JP 5237557B2
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sputtering target
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JP2008163441A (en
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一吉 井上
太 宇都野
公規 矢野
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出光興産株式会社
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  The present invention relates to a sputtering target and a manufacturing method thereof.

  An oxide semiconductor film made of a metal composite oxide has high mobility and visible light transmittance, such as a liquid crystal display device, a thin film electroluminescence display device, an electrophoretic display device, and a powder transfer display device. It is used for applications such as switching elements and drive circuit elements.

  Examples of the oxide semiconductor film made of a metal composite oxide include an oxide semiconductor film made of an oxide of In, Ga, and Zn (IGZO). An oxide semiconductor film formed using an IGZO sputtering target has an advantage of higher mobility than an amorphous silicon film, and has attracted attention (Patent Documents 1 to 10).

It is known that a compound represented by InGaO 3 (ZnO) m (m is an integer of 1 to 20) is a main component of the IGZO sputtering target. However, when sputtering (for example, DC sputtering) is performed using an IGZO sputtering target, the compound represented by InGaO 3 (ZnO) m grows abnormally and causes abnormal discharge, resulting in a defect in the resulting film. There was a point.

Further, the IGZO sputtering target is manufactured by mixing raw material powders to prepare a mixture, calcining, pulverizing, granulating and molding the mixture to produce a molded body, and sintering and reducing the molded body. However, since the number of processes is large, the productivity is lowered and the cost is increased.
In addition, the conductivity of the obtained sputtering target is about 90 S / cm (bulk specific resistance: 0.011 Ωcm), and it is difficult to obtain a target that has high resistance and does not generate cracks during sputtering.

Compounds represented by InGaO 3 (ZnO) 2 , InGaO 3 (ZnO) 3 , InGaO 3 (ZnO) 4 , InGaO 3 (ZnO) 5 and InGaO 3 (ZnO) 7 contained in the IGZO sputtering target, and a method for producing the same Is described in Patent Documents 11 to 15.

However, in Patent Documents 11 to 15, a spinel structure compound represented by ZnGa 2 O 4 and a homologous structure compound represented by InGaZnO 4 have not been obtained. Moreover, the particle size of the raw material powder used in patent documents 11-15 is 10 micrometers or less. Furthermore, although it describes that it can be used for a semiconductor element, there is no description about a specific resistance value, and it does not describe that it can be used for a sputtering target.
JP-A-8-295514 JP-A-8-330103 Japanese Patent Laid-Open No. 2000-044236 JP 2006-165527 A JP 2006-165528 A JP 2006-165529 A JP 2006-165530 A JP 20061655531 JP 2006-165532 A JP 2006-173580 A JP-A-63-239117 JP 63-210022 A JP 63-210023 A JP 63-210242 A JP-A 63-265818

An object of the present invention is to provide a sputtering target having a low bulk resistance, a high density, a more uniform and refined grain size, and a high bending strength while maintaining the characteristics of the IGZO sputtering target. It is.
Another object of the present invention is to provide a sputtering target that can suppress abnormal discharge that occurs when an oxide semiconductor film is formed using a sputtering method and can stably produce the oxide semiconductor film with high reproducibility. It is.

The present invention has been made in view of the above problems, indium (In), the IGZO sputtering target containing an oxide of gallium (Ga) and zinc (Zn), a compound represented by ZnGa 2 O 4, InGaO 3 (ZnO) m (where m is an integer from 2 to 20) suppresses abnormal growth and can suppress abnormal discharge during sputtering, and the compound represented by InGaZnO 4 is InGaO 3. It was found that the abnormal growth of the compound represented by (ZnO) m (where m is an integer from 2 to 20) can be suppressed, and abnormal discharge during sputtering can be suppressed, and the present invention has been completed.
According to the present invention, the following sputtering target and the like are provided.
1. A sputtering target containing oxides of indium (In), gallium (Ga) and zinc (Zn),
A sputtering target including a homologous structural compound represented by InGaO 3 (ZnO) m (m is an integer of 1 to 20) and a spinel structural compound represented by ZnGa 2 O 4 .
2. 2. The sputtering target according to 1, comprising at least a homologous structure compound represented by InGaZnO 4 .
3. 3. The sputtering target according to 1 or 2, wherein an average particle size of the spinel structure compound represented by ZnGa 2 O 4 is 10 μm or less.
4). The sputtering target according to any one of 1 to 3, wherein the sintered body density is 6.0 g / cm 3 or more.
5. The sputtering target according to any one of 1 to 4, having a surface roughness (Ra) of 2 μm or less and an average bending strength of 50 MPa or more.
6). The sputtering target according to any one of 1 to 5, wherein the contents of Fe, Al, Si, Ni, and Cu are each 10 ppm (weight) or less.
7. Finely pulverize and mix granulate indium oxide, gallium oxide and zinc oxide to prepare a mixture,
Molding the mixture to produce a molded body,
The molded body is fired at 1250 ° C. or more and less than 1450 ° C. in an oxygen stream or in an oxygen pressure state.
The manufacturing method of the sputtering target in any one of 1-6.
8. An oxide semiconductor film obtained by sputtering the sputtering target according to any one of 1 to 6.

According to the present invention, there is provided a sputtering target having a low bending resistance, a high density, a more uniform and refined grain size, and a high bending strength while maintaining the characteristics of an IGZO sputtering target. Can do.
ADVANTAGE OF THE INVENTION According to this invention, the sputtering target which suppresses the abnormal discharge which generate | occur | produces when forming an oxide semiconductor film using sputtering method, and can manufacture an oxide semiconductor film stably with sufficient reproducibility can be provided. .

The sputtering target of the present invention (hereinafter sometimes referred to as the target of the present invention) contains oxides of indium (In), gallium (Ga), and zinc (Zn), and InGaO 3 (ZnO) m (m is 1). A spinel structure compound represented by ZnGa 2 O 4 and a homologous structure compound represented by

A homologous structural compound is a compound having a homologous phase.
The homologous phase (Homologous Series) is, for example, a Magneli phase represented by a composition formula of Ti n O 2n-1 where n is a natural number. In such a phase, a group of n continuously changing. There is a group of compounds.
Specific examples of the homologous structure compound include In 2 O 3. (ZnO) m (m is an integer of 2 to 20), InGaO 3 (ZnO) m (m is an integer of 2 to 20), and the like.

As disclosed in “Crystal Chemistry” (Kodansha, Mitsuko Nakahira, 1973) and the like, the spinel structure compound is usually referred to as the AB 2 X 4 type or the A 2 BX 4 type as a spinel structure. A compound having a crystal structure is referred to as a spinel structure compound.
In general, in the spinel structure, anions (usually oxygen) are close-packed in cubic, and cations are present in a part of the tetrahedral gap and octahedral gap.
In addition, a substituted solid solution in which atoms or ions in the crystal structure are partially substituted with other atoms, and an interstitial solid solution in which other atoms are added to interstitial positions are also included in the spinel structure compound.

  The crystal state of the compound in the target can be determined by observing a sample collected from the target (sintered body) by an X-ray diffraction method.

The spinel structure compound that is a constituent component of the target of the present invention is a compound represented by ZnGa 2 O 4 . That is, X-ray diffraction shows the peak pattern of 38-1240 in the JCPDS (Joint Committee on Powder Diffraction Standards) database or a similar (shifted) pattern.

By generating a compound represented by ZnGa 2 O 4 in the sputtering target, abnormal growth of the compound represented by InGaO 3 (ZnO) m (m is an integer of 2 to 20) can be suppressed, and the target Abnormal discharge during sputtering can be suppressed. Furthermore, it is possible to further suppress abnormal growth of the compound represented by InGaO 3 (ZnO) m (m is an integer of 2 to 20), preferably by generating a compound represented by InGaZnO 4 .
By suppressing the abnormal growth of the compound represented by InGaO 3 (ZnO) m (m is an integer of 2 to 20), the bending strength of the target can be increased, and the cracking of the target during sputtering can be suppressed. Can do.

Since the sputtering target of the present invention includes a plurality of crystal systems of a homologous structure compound represented by InGaO 3 (ZnO) m (m is an integer of 1 to 20) and a spinel structure compound represented by ZnGa 2 O 4 , Oxygen vacancies are generated due to crystal mismatch at these grain boundaries, and carriers are generated in the target. This carrier lowers the resistance of the target and suppresses abnormal discharge during sputtering.

In the target of the present invention, the average particle size of the spinel structure compound represented by ZnGa 2 O 4 is preferably 10 μm or less, more preferably 5 μm or less.
By setting the average particle diameter of the spinel structure compound represented by ZnGa 2 O 4 to 10 μm or less, the grain growth of the compound represented by InGaO 3 (ZnO) m (m is an integer of 2 to 20) is more reliably performed. It is possible to suppress the cracking of the target during sputtering by increasing the bending strength of the target.

The average particle diameter of the spinel structure compound represented by ZnGa 2 O 4 can be evaluated by observing a secondary electron image of a scanning electron microscope (SEM), for example.

The sintered body density of the target of the present invention is preferably 6.0 g / cm 3 or more.
By setting the sintered compact density of the target to 6.0 g / cm 3 or more, the bending strength of the target can be increased and cracking of the target during sputtering can be suppressed. On the other hand, when the sintered compact density of the target is less than 6.0 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 of the sintered body, it is preferable to form with a cold isostatic pressure (CIP) or the like or to sinter with a hot isostatic pressure (HIP) or the like in the target manufacturing method described later.

The bulk resistance of the target of the present invention is preferably less than 5 mΩcm.
When the bulk resistance is 5 mΩcm or more, abnormal discharge may be induced during sputtering or foreign matter (nodules) may be generated.
The bulk resistance of the target of the present invention can be measured by the four probe method.

  The target of the present invention preferably has a surface roughness (Ra) of 2 μm or less and an average bending strength of 50 MPa or more, more preferably a surface roughness (Ra) of 0.5 μm or less and an average bending strength. It is 55 MPa or more.

By setting the surface roughness (Ra) of the target to 2 μm or less, the average bending strength of the target can be maintained at 50 MPa or more, and cracking of the target during sputtering can be suppressed.
The surface roughness (Ra) can be measured by the AFM method, and the average bending strength can be measured according to JIS R 1601.

In the target of the present invention, the contents of Fe, Al, Si, Ni and Cu are each preferably 10 ppm (weight) or less.
Fe, Al, Si, Ni, and Cu are impurities in the target of the present invention, and by setting the content to 10 ppm (weight) or less, the threshold value of the oxide semiconductor film obtained by forming this target Stable operating condition can be obtained by suppressing voltage fluctuation.
The content of the impurity element can be measured by inductively coupled plasma (ICP) emission spectrometry.

The sputtering target of the present invention contains, for example, a positive tetravalent metal element in addition to the oxides of indium (In), gallium (Ga), and zinc (Zn) as long as the effects of the present invention are not impaired. May be.
The oxide semiconductor film obtained using the sputtering target of the present invention is amorphous, and even if a positive tetravalent metal element is contained, there is no carrier generation effect (doping effect) and stable semiconductor characteristics are exhibited. .

The sputtering target of the present invention is
Finely pulverize and mix granulate indium oxide, gallium oxide and zinc oxide to prepare a mixture,
Molding the mixture to produce a molded body,
The molded body can be produced by heat treatment at 1250 ° C. or more and less than 1450 ° C. in an oxygen stream or in an oxygen-pressed state.

Material of the sputtering target of the present invention are indium oxide, gallium oxide and zinc oxide, gallium oxide is preferably indium oxide powder having a specific surface area of 6~10m 2 / g, a specific surface area of 5 to 10 m 2 / g Zinc oxide powder having a powder and specific surface area of 2 to 4 m 2 / g, or indium oxide powder having a median diameter of 1 to 2 μm, gallium oxide powder having a median diameter of 1 to 2 μm, and median diameter of 0.8 to 1 Zinc oxide powder which is .6 μm.

  The purity of each raw material is usually 2N (99% by mass) or more, preferably 3N (99.9% by mass) or more, more preferably 4N (99.99% by mass) or more. When the purity is lower than 2N, impurities such as Fe, Al, Si, Ni, and Cu may be contained. If these impurities are contained, the operation of the oxide semiconductor film manufactured using this target is stable. There is a risk of not doing so.

  For the fine pulverization of the raw material, an ordinary mixing and pulverizing machine can be used. For example, the raw material can be uniformly mixed and pulverized using a wet medium stirring mill, a bead mill, or an ultrasonic device.

The mixing ratio of each raw material is, for example, In: Ga: Zn = 45: 30: 25 (Molar ratio: In: Ga: Zn = 1: 1: 1) or In 2 O 3 : Ga 2 O 3 : Weigh so that ZnO = 51: 34: 15 (In 2 O 3 : Ga 2 O 3 : ZnO = 1: 1: 1 in molar ratio).

In the sputtering target of the present invention, the mixing ratio of each raw material is an atomic ratio represented by In / (In + Ga + Zn), an atomic ratio represented by Ga / (In + Ga + Zn), and an atomic ratio represented by Zn / (In + Ga + Zn). For example, it mixes so that the following formula may be satisfy | filled.
0.2 <In / (In + Ga + Zn) <0.77
0.2 <Ga / (In + Ga + Zn) <0.50
0.03 <Zn / (In + Ga + Zn) <0.50

  When In / (In + Ga + Zn) is 0.77 or more, the conductivity of the oxide semiconductor film obtained by film formation is increased, which may make it difficult to use the semiconductor as a semiconductor. On the other hand, when In / (In + Ga + Zn) is 0.2 or less, the carrier mobility when used as a semiconductor of an oxide semiconductor film obtained by film formation may be reduced.

  When Ga / (In + Ga + Zn) is 0.5 or more, the carrier mobility when used as a semiconductor of an oxide semiconductor film obtained by film formation may be reduced. On the other hand, when Ga / (In + Ga + Zn) is 0.2 or less, the conductivity of the oxide semiconductor film obtained by film formation is increased, which may make it difficult to use as a semiconductor. In addition, the semiconductor characteristics may change due to disturbances such as heating, and the threshold voltage (Vth) shift may increase.

  When Zn / (In + Ga + Zn) is 0.03 or less, the oxide semiconductor film may be crystallized. On the other hand, when Zn / (In + Ga + Zn) is 0.5 or more, there may be a problem in the stability of the oxide semiconductor film itself, which may increase the Vth shift.

  The atomic ratio of each element in the target can be obtained by measuring the abundance of each element by ICP (Inductively Coupled Plasma) measurement.

Each raw material after pulverization and mixed granulation, for example, increase the specific surface area of each raw material after mixed granulation by 1.0 to 2.5 m 2 / g from the specific surface area of each raw material before mixed granulation, Or a mixture is prepared so that the average median diameter of each raw material may be set to 0.6-1.0 micrometer.
If the increase in the specific surface area of each raw material is less than 1.0 m 2 / g, or the average median diameter of each raw material is less than 0.6 μm, the amount of impurities mixed from the pulverizing equipment during fine pulverization and mixed granulation May increase.

In the above fine pulverization and mixed granulation, if the specific surface area of indium oxide and gallium oxide before the fine pulverization and mixed granulation is almost the same, fine pulverization and mixed granulation can be performed more efficiently. And the difference in specific surface area between indium oxide and gallium oxide before mixed granulation is preferably 3 m 2 / g or less. When the difference in specific surface area is not within the above range, efficient fine pulverization and mixed granulation cannot be performed, and gallium oxide particles may remain in the obtained sintered body.

  In addition, if the median diameters of indium oxide and gallium oxide before pulverization and mixed granulation are approximately the same, fine pulverization and mixed granulation can be performed more efficiently. The difference in median diameter between indium and gallium oxide is preferably 1 μm or less. If the difference in median diameter is not within this range, gallium oxide particles may remain in the obtained sintered body.

Examples of the molding process for molding the mixture include mold molding, cast molding, injection molding, and the like, but in order to obtain a sintered body having a high density of the sintered body, it is preferable to mold with CIP (cold isostatic pressure) or the like. .
In the molding process, molding aids such as polyvinyl alcohol, methyl cellulose, polywax, and oleic acid may be used.

The sintered compact for sputtering targets of the present invention can be produced by firing the compact obtained by the above method.
The firing temperature is 1250 ° C. or higher and lower than 1450 ° C., preferably 1300 ° C. or higher and lower than 1450 ° C. Moreover, baking time is 2-100 hours normally, Preferably it is 4-40 hours.
If the firing temperature is lower than 1250 ° C., the sintered body density of the obtained sintered body may not be improved. On the other hand, when the firing temperature is 1450 ° C. or higher, zinc may evaporate and the composition of the sintered body may change and / or voids (voids) may be generated in the target.

The firing is preferably performed in an oxygen stream or under oxygen pressure. By firing in an oxygen atmosphere, transpiration of zinc can be suppressed, and a sintered body free from voids (voids) can be produced. In this sintered body, a homologous structural compound represented by InGaZnO 4 and a spinel structural compound represented by ZnGa 2 O 4 are generated, which can be confirmed by an X-ray diffraction method.

The sputtering target of the present invention can be produced by, for example, polishing the sintered body after firing to a desired surface roughness.
For example, the above sintered body is ground with a surface grinder so that the average surface roughness (Ra) is 2 μm or less, and the sputter surface is further mirror-finished so that the average surface roughness (Ra) is 1000 angstroms or less. Can do.

  Mirror surface processing (polishing) is not particularly limited, and known polishing techniques such as mechanical polishing, chemical polishing, and mechanochemical polishing (a combination of mechanical polishing and chemical polishing) can be used. For example, polishing to # 2000 or more with a fixed abrasive polisher (polishing liquid: water) or lapping with loose abrasive lapping (abrasive: SiC paste, etc.), and then lapping by changing the abrasive to diamond paste Is mentioned.

In the manufacturing method of the sputtering target of this invention, it is preferable when the obtained sputtering target is wash-processed.
Examples of the cleaning treatment include air blow and running water cleaning. For example, when performing a cleaning process (removal of foreign matter) by air blow, it can be more effectively removed by suctioning with a dust collector from the opposite side of the nozzle.

  It is preferable to perform ultrasonic cleaning after the cleaning treatment such as air blow and running water cleaning. This ultrasonic cleaning is effective by performing multiple oscillations at a frequency of 25 to 300 KHz. For example, ultrasonic cleaning may be performed by oscillating 12 types of frequencies at 25 KHz increments between 25 to 300 KHz.

  The method for producing a sputtering target of the present invention does not require a calcination step at all, and a high-density sintered body for a sputtering target can be obtained. In addition, a sintered body having a low bulk resistance can be obtained without requiring any reduction process. Moreover, since the said calcination process and a reduction | restoration process can be skipped, the sputtering target of this invention is a sputtering target with high productivity.

An oxide semiconductor 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. When the bulk resistance of the target exceeds 1 Ωcm, if a RF magnetron sputtering method is employed, a stable sputtering state can be maintained without abnormal discharge. In addition, when the bulk resistance of the target is 10 mΩcm or less, an industrially advantageous DC magnetron sputtering method can be employed.
Thereby, a stable sputtering state is maintained without abnormal discharge, and industrially stable film formation becomes possible.

  An oxide semiconductor film formed using the sputtering target of the present invention has an advantage that the generation of nodules and particles is small and the film characteristics are excellent because the sputtering target has a high density.

  The present invention will be described with reference to comparative examples by way of examples. In addition, a present Example shows only a suitable example, This example does not restrict | limit this invention. Accordingly, the present invention includes modifications based on the technical idea or other embodiments.

The measuring method of the characteristic of the sputtering target produced by the Example and the comparative example is shown below.
(1) Density Calculated from the weight and outer dimensions of the target cut out to a certain size.
(2) Bulk resistance of target The resistivity was measured by a four-probe method using a resistivity meter (Mitsubishi Yuka, Loresta).
(3) Structure of oxide present in target The structure of the oxide was identified by analyzing the chart obtained by X-ray diffraction.
(4) Specific surface area of raw material powder It measured by BET method.
(5) Median diameter of raw material powder It measured using the particle size distribution measuring apparatus.
(6) Average bending strength Determined by a three-point bending test.
(6) Weibull coefficient of sputtering target A cumulative failure probability with respect to bending strength and a Weibull plot in a single mode were determined by a median rank method, and a Weibull coefficient (m value) indicating variation in the failure probability was determined. In addition, m value was obtained for the Weibull coefficient by obtaining a linear regression line.

Example 1
The ratio of 99.99% purity indium oxide powder surface area of 6 m 2 / g, purity gallium oxide powder and the specific surface area of 99.99%, which is a specific surface area of 6 m 2 / g is 3m 2 / g 99. 99% of the zinc oxide powder was weighed so that the weight ratio was In 2 O 3 : Ga 2 O 3 : ZnO = 45: 30: 25, and mixed and ground using a wet medium stirring mill. In addition, 1 mmφ zirconia beads were used as the medium of the wet medium stirring mill.

And after making the specific surface area after mixing and grinding | pulverizing of each raw material 2 m < 2 > / g from the specific surface area before grinding | pulverization, it was made to dry with a spray dryer. The obtained mixed powder was filled in a mold and pressure-molded with a cold press to produce a molded body.
The obtained molded body was sintered for 4 hours at a high temperature of 1400 ° C. in an oxygen atmosphere while circulating oxygen. As a result, a sintered body for IGZO sputtering target (sputtering target) having a sintered body density of 6.06 g / cm 3 was obtained without performing a calcination step. It was confirmed by X-ray diffraction that crystals of ZnGa 2 O 4 and InGaZnO 4 were present in the sintered body. The X-ray diffraction chart is shown in FIG.
Further, the bulk resistance of this sintered body was 4.2 mΩcm.
When this sintered body was measured for impurities by ICP analysis, the contents of Fe, Al, Si, Ni and Cu were each less than 10 ppm.

Example 2
An indium oxide powder having a median diameter of 1.5 μm, a gallium oxide powder having a median diameter of 2.0 μm, and a zinc oxide powder having a median diameter of 1.0 μm are approximately In 2 O 3 : Ga 2 O 3 by weight ratio: It weighed so that it might become ZnO = 55: 25: 20, and mixed and ground using the wet medium stirring mill. In addition, 1 mmφ zirconia beads were used as the medium of the wet medium stirring mill.

And after making the average median diameter of each raw material after mixing and pulverizing 0.8 μm, it was dried with a spray dryer. The obtained mixed powder was filled in a mold and pressure-molded with a cold press to produce a molded body.
The obtained molded body was sintered for 4 hours at a high temperature of 1400 ° C. in an oxygen atmosphere while circulating oxygen. As a result, a sintered body for an IGZO sputtering target having a sintered body density of 6.14 g / cm 3 was obtained without performing a calcination step. X-ray diffraction confirmed that crystals of ZnGa 2 O 4 , InGaZnO 4 , and In 2 O 3 (ZnO) 4 were present in the sintered body. An X-ray diffraction chart is shown in FIG.
The bulk resistance of this sintered body was 3.8 mΩcm.

Example 3
An indium oxide powder having a median diameter of 1.5 μm, a gallium oxide powder having a median diameter of 2.0 μm, and a zinc oxide powder having a median diameter of 1.0 μm are approximately In 2 O 3 : Ga 2 O 3 by weight ratio: It weighed so that it might become ZnO = 35: 25: 40, and it mixed and ground using the wet-medium stirring mill. In addition, 1 mmφ zirconia beads were used as the medium of the wet medium stirring mill.

And after making the average median diameter of each raw material after mixing and pulverizing 0.8 μm, it was dried with a spray dryer. The obtained mixed powder was filled in a mold and pressure-molded with a cold press to produce a molded body.
The obtained molded body was sintered for 4 hours at a high temperature of 1400 ° C. in an oxygen atmosphere while circulating oxygen. As a result, a sintered body for an IGZO sputtering target having a sintered body density of 6.02 g / cm 3 was obtained without performing a calcination step. It was confirmed by X-ray diffraction that crystals of ZnGa 2 O 4 and InGaZnO 4 were present in the sintered body. The X-ray diffraction chart is shown in FIG.
Further, the bulk resistance of this sintered body was 4.9 mΩcm.

Comparative Example 1
An indium oxide powder having a median diameter of 1.5 μm, a gallium oxide powder having a median diameter of 2.0 μm, and a zinc oxide powder having a median diameter of 1.0 μm are approximately In 2 O 3 : Ga 2 O 3 by weight ratio: They were weighed so that ZnO = 34: 46: 20, and mixed and ground using a wet medium stirring mill. In addition, 1 mmφ zirconia beads were used as the medium of the wet medium stirring mill.

And after making the average median diameter of each raw material after mixing and pulverizing 0.8 μm, it was dried with a spray dryer. The obtained mixed powder was filled in a mold and pressure-molded with a cold press to produce a molded body.
The obtained molded body was sintered for 4 hours at a temperature of 1200 ° C. in an oxygen atmosphere while circulating oxygen. As a result, a sintered body for an IGZO sputtering target having a sintered body density of 5.85 g / cm 3 was obtained. It was confirmed by X-ray diffraction that ZnGa 2 O 4 crystals exist in the sintered body, but InGaO 3 (ZnO) m was not generated. The X-ray diffraction chart is shown in FIG. The bulk resistance of this sintered body was 450 mΩcm.

Examples 4 and 5
Next, the sintered body for the IGZO sputtering target produced in Example 1 was precision polished (Example 4: precision polishing by polishing, Example 5: surface grinding in the longitudinal direction) to produce a sputtering target. The target surface was analyzed by observing the secondary electron image of the manufactured sputtering target with a scanning electron microscope (SEM). As a result, the average particle diameter of the ZnGa 2 O 4 crystals in the targets of Example 4 and Example 5 was 4.4 μm. Moreover, when the surface roughness was measured with a surface roughness meter, the surface roughness Ra of the target of Example 4 was 0.5 μm, and the surface roughness Ra of the target of Example 5 was 1.8 μm. there were.

Comparative Example 2
The sintered body for IGZO sputtering target produced in Comparative Example 1 was precisely polished (surface grinding in the longitudinal direction) to produce a sputtering target. The target surface was analyzed by observing the secondary electron image of the manufactured sputtering target with a scanning electron microscope (SEM). As a result, the average particle diameter of the ZnGa 2 O 4 crystal in the target was 14 μm. Moreover, when the surface roughness of the target was measured with a surface roughness meter, the surface roughness Ra was 3.5 μm.

  Next, the Weibull coefficient and the average bending strength were evaluated for the sputtering targets of Examples 4 and 5 and Comparative Example 2, respectively. The results are shown in Table 1.

  The Weibull coefficient means that the larger the value, the more the non-destructive stress becomes less variable. From Table 1, it was confirmed that the sputtering target of the present invention was a stable material with little variation.

The surface roughness after surface grinding usually corresponds to the crystal grain size. If the particle size is not uniform, Ra becomes larger and the bending strength decreases accordingly.
From Table 1, it was confirmed that the crystal grain size of the sputtering target of the present invention is fine and the surface roughness is small, so that it has excellent quality.

Example 6
The target (4 inch φ, thickness 5 mm) of Example 4 was bonded to a backing plate and mounted on a DC sputtering film forming apparatus. In an Ar atmosphere of 0.3 Pa, continuous sputtering was performed at 100 W for 100 hours, and nodules generated on the surface were measured. As a result, no nodules were observed on the surface.

Comparative Example 3
The target of Comparative Example 2 (4 inches φ, thickness 5 mm) was bonded to a backing plate and mounted on a DC sputtering film forming apparatus. In an Ar atmosphere of 0.3 Pa, continuous sputtering was performed at 100 W for 100 hours, and nodules generated on the surface were measured. As a result, nodules were found on almost half of the target surface.

  The target of the present invention is a transparent conductive film for various uses, such as a transparent conductive film for a liquid crystal display (LCD), a transparent conductive film for an electroluminescence (EL) display element, a transparent conductive film for a solar cell, and an oxide semiconductor film. It is suitable as a target for obtaining by a sputtering method. For example, an electrode of an organic EL element, a transparent conductive film for a semi-transmissive / semi-reflective LCD, an oxide semiconductor film for driving a liquid crystal, and an oxide semiconductor film for driving an organic EL element 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 Comparative Example 1.

Claims (7)

  1. A sputtering target comprising a sintered body containing oxides of indium (In), gallium (Ga) and zinc (Zn),
    A sputtering target including a homologous structural compound represented by InGaO 3 (ZnO) m (m is an integer of 1 to 20) and a spinel structural compound represented by ZnGa 2 O 4 .
  2. The sputtering target according to claim 1, comprising at least a homologous structure compound represented by InGaZnO 4 .
  3. The sputtering target according to claim 1 or 2, wherein an average particle size of the spinel structure compound represented by ZnGa 2 O 4 is 10 µm or less.
  4. The sputtering target according to claim 1, wherein the sintered body density is 6.0 g / cm 3 or more.
  5.   The sputtering target according to claim 1, wherein the surface roughness (Ra) is 2 μm or less and the average bending strength is 50 MPa or more.
  6.   The sputtering target according to any one of claims 1 to 5, wherein the contents of Fe, Al, Si, Ni, and Cu are each 10 ppm (weight) or less.
  7. Finely pulverize and mix granulate indium oxide, gallium oxide and zinc oxide to prepare a mixture,
    Molding the mixture to produce a molded body,
    The molded body is fired at 1250 ° C. or more and less than 1450 ° C. in an oxygen stream or in an oxygen pressure state.
    The manufacturing method of the sputtering target in any one of Claims 1-6.
JP2007000417A 2007-01-05 2007-01-05 Sputtering target and manufacturing method thereof Active JP5237557B2 (en)

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JP2007000417A JP5237557B2 (en) 2007-01-05 2007-01-05 Sputtering target and manufacturing method thereof
CN201110128377.1A CN102212787B (en) 2006-12-13 2007-11-30 The sputtering target and the oxide semiconductor film
CN2013101763782A CN103320755A (en) 2006-12-13 2007-11-30 Sputtering target and oxide semiconductor film
EP20070832831 EP2096188B1 (en) 2006-12-13 2007-11-30 Sputtering target
EP13181009.5A EP2669402A1 (en) 2006-12-13 2007-11-30 Sputtering target and oxide semiconductor film
US12/518,988 US8784700B2 (en) 2006-12-13 2007-11-30 Sputtering target and oxide semiconductor film
EP12161406.9A EP2471972B1 (en) 2006-12-13 2007-11-30 Sputtering target
KR1020137025207A KR101420992B1 (en) 2006-12-13 2007-11-30 Sputtering target
PCT/JP2007/073134 WO2008072486A1 (en) 2006-12-13 2007-11-30 Sputtering target and oxide semiconductor film
CN 200780045870 CN101558184B (en) 2006-12-13 2007-11-30 The sputtering target and the oxide semiconductor film
KR1020097012157A KR101699968B1 (en) 2006-12-13 2007-11-30 Sputtering target and oxide semiconductor film
TW102137473A TWI465595B (en) 2006-12-13 2007-12-11 Sputtering target and oxide semiconductor film
TW96147237A TWI427165B (en) 2006-12-13 2007-12-11 Sputtering target and oxide semiconductor film
US14/018,606 US20140001040A1 (en) 2006-12-13 2013-09-05 Sputtering target and oxide semiconductor film
US14/333,589 US20140339073A1 (en) 2006-12-13 2014-07-17 Sputtering Target and Oxide Semiconductor Film

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KR101658256B1 (en) * 2008-12-15 2016-09-20 이데미쓰 고산 가부시키가이샤 Sintered complex oxide and sputtering target comprising same
KR101056948B1 (en) * 2008-12-31 2011-08-16 주식회사 나노신소재 Metal oxide target for amorphous oxide film containing aluminum and its manufacturing method
WO2010140548A1 (en) * 2009-06-05 2010-12-09 Jx日鉱日石金属株式会社 Oxide sintered body, method for producing same, and starting material powder for producing oxide sintered body
JP4843083B2 (en) 2009-11-19 2011-12-21 出光興産株式会社 In-Ga-Zn-based oxide sputtering target
JP5407969B2 (en) * 2010-03-23 2014-02-05 住友電気工業株式会社 Conductive oxide and method for producing the same
JP5526904B2 (en) * 2010-03-23 2014-06-18 住友電気工業株式会社 Conductive oxide sintered body and manufacturing method thereof
JP2012144410A (en) * 2011-01-14 2012-08-02 Kobelco Kaken:Kk Oxide sintered compact, and sputtering target
CN103124805B (en) * 2011-06-08 2017-02-15 株式会社半导体能源研究所 Sputtering target, a sputtering target and a method for producing a thin film forming method
CN104379800B (en) * 2012-05-31 2019-06-07 出光兴产株式会社 Sputtering target
SG11201505097QA (en) * 2012-06-29 2015-08-28 Semiconductor Energy Lab Method for using sputtering target and method for manufacturing oxide film
JP5965338B2 (en) * 2012-07-17 2016-08-03 出光興産株式会社 Sputtering target, oxide semiconductor thin film, and manufacturing method thereof
JP6284710B2 (en) * 2012-10-18 2018-02-28 出光興産株式会社 Sputtering target, oxide semiconductor thin film, and manufacturing method thereof
JP6341198B2 (en) * 2013-04-12 2018-06-13 日立金属株式会社 Oxide semiconductor target, oxide semiconductor film, manufacturing method thereof, and thin film transistor
CN105873881A (en) 2013-12-27 2016-08-17 出光兴产株式会社 Oxide sintered body, method for producing same and sputtering target
TW201544458A (en) * 2014-02-21 2015-12-01 Semiconductor Energy Lab Semiconductor film, transistor, semiconductor device, display device, and electronic appliance
WO2016136611A1 (en) * 2015-02-27 2016-09-01 Jx金属株式会社 Oxide sintered body and sputtering target comprising oxide sintered body
JP6285076B2 (en) * 2015-03-23 2018-02-28 Jx金属株式会社 Oxide sintered body and sputtering target comprising the oxide sintered body

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