WO2012173108A1

WO2012173108A1 - Electrically conductive oxide and method for producing same, and oxide semiconductor film

Info

Publication number: WO2012173108A1
Application number: PCT/JP2012/064986
Authority: WO
Inventors: 宮永　美紀; 浩一曽我部; 英章粟田; 岡田　浩; 吉村　雅司
Original assignee: 住友電気工業株式会社
Priority date: 2011-06-15
Filing date: 2012-06-12
Publication date: 2012-12-20
Also published as: KR20140036176A; KR102003077B1; CN103608310B; TWI532864B; JP6137382B2; CN103608310A; JPWO2012173108A1; TW201305371A; JP2016153370A; JP5929911B2

Abstract

An electrically conductive oxide comprises In, Al, at least one element M selected from the group consisting of Zn and Mg and O, and also comprises crystalline Al₂MO₄. A method for producing an electrically conductive oxide comprises: a step of preparing a first mixture comprising an Al₂O₃ powder and an MO powder, wherein M represents at least one element selected from the group consisting of Zn and Mg (S10); a step of pre-sintering the first mixture to produce a crystalline Al₂MO₄ powder (S20); a step of preparing a second mixture comprising the crystalline Al₂MO₄ powder and an In₂O₃ powder (S30); a step of molding the second mixture to produce a molding (S40); and a step of sintering the molding (S50). Thus, provided are: an electrically conductive oxide which is inexpensive, can be used suitably for a sputtering target, and enables the production of an oxide semiconductor film having high physical properties; a method for producing the electrically conductive oxide; and an oxide semiconductor film.

Description

Conductive oxide, method for producing the same, and oxide semiconductor film

The present invention relates to a conductive oxide, a manufacturing method thereof, and an oxide semiconductor film, and more particularly to a conductive oxide used as a target when forming an oxide semiconductor film by a sputtering method and a manufacturing method thereof.

In a liquid crystal display device, a thin film EL (electroluminescence) display device, an organic EL display device, and the like, an amorphous silicon film is mainly used for a channel layer of a conventional TFT (thin film transistor). In recent years, an oxide semiconductor film containing In—Ga—Zn-based composite oxide (IGZO) as a main component has attracted attention as a semiconductor film that can replace an amorphous silicon film.

For example, Japanese Patent Application Laid-Open No. 2008-199005 (Patent Document 1) discloses a technique for forming an amorphous oxide semiconductor film by a sputtering method using a target made of a sintered body of conductive oxide powder. It is disclosed. An oxide semiconductor film formed in this manner has an advantage of higher carrier mobility than an amorphous silicon film.

The sputtering method disclosed in Japanese Patent Application Laid-Open No. 2008-199005 (Patent Document 1) will be described in detail. First, a target and a substrate are placed facing each other in a sputtering apparatus. Then, a voltage is applied to the target to sputter rare gas ions on the target surface, and the constituent atoms of the target are ejected. The constituent atoms of the target are deposited on the substrate, whereby an IGZO (In—Ga—Zn—O-based composite oxide) film is formed.

As a target for suitably producing such an IGZO film by a sputtering method, Japanese Patent Application Laid-Open No. 2008-214697 (Patent Document 2) discloses a sputtering containing a compound represented by InGaZnO ₄ as a main component and containing a metal element having a positive tetravalence or higher. Disclose the target.

JP 2008-199005 A JP 2008-214697 A

However, since the IGZO sputtering target disclosed in Japanese Patent Application Laid-Open No. 2008-199005 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2008-214697 (Patent Document 2) contains expensive Ga, it is expensive. It is. For this reason, development of the conductive oxide which is cheap compared with IGZO and can be suitably used for a sputtering target to obtain an oxide semiconductor film having high physical properties is demanded.

An object of the present invention is to provide a conductive oxide that is inexpensive and can be suitably used as a sputtering target to obtain an oxide semiconductor film having high physical properties, a method for manufacturing the same, and an oxide semiconductor film.

According to one aspect, the present invention includes In, Al, M and O that are at least one element selected from the group consisting of Zn and Mg, and includes crystalline Al ₂ MO ₄ . It is a conductive oxide containing.

In the conductive oxide according to the present invention, crystalline Al ₂ ZnO ₄ can be included as crystalline Al ₂ MO ₄ . Here, the proportion of crystalline Al ₂ ZnO ₄ occupied in the cross-sectional area of the conductive oxide may be 60% or less than 10%. Here, crystalline In ₂ Al _{2 (1-m)} Zn _1-q O _7-p (0 ≦ m <1, 0 ≦ q <1, 0 ≦ p ≦ 3m + q) and crystalline In ₂ O ₃ It may further include at least one crystalline material selected from the group.

In the conductive oxide according to the present invention, crystalline Al ₂ MgO ₄ can be included as crystalline Al ₂ MO ₄ . Here, the ratio of crystalline Al ₂ MgO ₄ to the cross-sectional area of the conductive oxide can be set to 2% or more and 60% or less. Here, crystalline In ₂ Al _{2 (1-n)} Mg _1-t O _7-s (0 ≦ n <1, 0 ≦ t <1, 0 ≦ s ≦ 3n + t) and crystalline In ₂ O ₃ It may further include at least one crystalline material selected from the group.

In the conductive oxide according to the present invention, when the total atomic ratio of In, Al, and M is 100 atomic%, 10 to 50 atomic% In, 10 to 50 atomic% Al, and 15 to 40 atoms % M. can be included. Further, it may further contain at least one additive element selected from the group consisting of N, Al, Si, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, Sn, and Bi.

The conductive oxide according to the present invention can be used as a sputtering target.

According to another aspect, the present invention is an oxide semiconductor film formed using the conductive oxide described above.

According to still another aspect of the present invention, a first mixture containing Al ₂ O ₃ powder and MO powder is prepared, where M is at least one element selected from the group consisting of Zn and Mg. A step of preparing a crystalline Al ₂ MO ₄ powder by calcining the first mixture, and a second mixture comprising the crystalline Al ₂ MO ₄ powder and the In ₂ O ₃ powder. And a process for obtaining a molded body by molding the second mixture, and a process for sintering the molded body.

In the method for producing a conductive oxide according to the present invention, the MO powder is a ZnO powder, the crystalline Al ₂ MO ₄ powder is a crystalline Al ₂ ZnO ₄ powder, and a crystalline Al ₂ ZnO ₄ powder is produced. The calcining temperature of the mixture 1 may be 800 ° C. or more and less than 1200 ° C., and the sintering temperature of the molded body in the step of sintering the molded body may be 1280 ° C. or more and less than 1500 ° C.

In the method for producing a conductive oxide according to the present invention, the MO powder is an MgO powder, the crystalline Al ₂ MO ₄ powder is a crystalline Al ₂ MgO ₄ powder, and a crystalline Al ₂ MgO ₄ powder is produced. The calcining temperature of the mixture No. 1 can be 800 ° C. or higher and lower than 1200 ° C., and the sintering temperature of the molded body in the step of sintering the molded body can be 1300 ° C. or higher and 1500 ° C. or lower.

According to the present invention, there are provided a conductive oxide, a method for producing the same, and an oxide semiconductor film which are inexpensive and can be suitably used as a sputtering target to obtain an oxide semiconductor film having high physical properties.

It is a flowchart which shows the manufacturing method of an electroconductive oxide.

[Conductive oxide]
The conductive oxide according to an embodiment of the present invention includes In, Al, M and O that are at least one element selected from the group consisting of Zn and Mg, and is crystalline Al. ₂ Including MO ₄ Since the conductive oxide of the present embodiment includes In, Al, M, which is at least one element selected from the group consisting of Zn and Mg, and O, expensive Ga contained in IGZO is contained. Since it is not included, it is cheaper than IGZO. In addition, since the conductive oxide of this embodiment includes crystalline Al ₂ MO ₄ , the characteristics of the oxide semiconductor film obtained by sputtering using the conductive oxide as a target are stabilized. In crystalline Al ₂ MO ₄ , Zn and Mg corresponding to M both have a valence of +2 and their ionic radii are very close, so crystalline Al ₂ ZnO ₄ and crystalline Al ₂ MgO ₄ All have a spinel crystal structure.

In the conductive oxide of this embodiment, it is preferable that crystalline Al ₂ ZnO ₄ is included as crystalline Al ₂ MO ₄ . By including crystalline Al ₂ ZnO ₄ , the characteristics of the oxide semiconductor film obtained by sputtering using a conductive oxide as a target can be stabilized and the etching rate can be increased. Therefore, a conductive oxide containing crystalline Al ₂ ZnO ₄ is preferably used as a target for forming an oxide semiconductor film by a sputtering method.

Here, (meaning the area of the cross section when cut at any one side of the conductive oxide, the same. Or less) the cross-sectional area of the conductive oxide containing crystalline Al ₂ ZnO ₄ crystalline Al ₂ occupying the The ratio of ZnO ₄ is preferably 10% or more and 60% or less, and more preferably 14% or more and 50% or less. If the proportion of crystalline Al ₂ ZnO _{4 in} the cross-sectional area of the conductive oxide is lower than 10%, the characteristics of the oxide semiconductor film obtained by sputtering using the conductive oxide as a target become unstable, and the etching rate Becomes lower. When the ratio of crystalline Al ₂ ZnO _{4 in} the cross-sectional area of the conductive oxide is higher than 60%, the surface roughness Ra of the oxide semiconductor film obtained by sputtering using the conductive oxide as a target becomes rough.

The proportion of crystalline Al ₂ ZnO ₄ occupied in the cross-sectional area of the conductive oxide containing crystalline Al ₂ ZnO ₄ can be obtained by EDX (Energy Dispersive X-ray spectrometry). More specifically, the electrons (reflected electron image) reflected from the cross section resulting from the incident electron beam irradiated onto the cross section of the conductive oxide sample are observed. Then, by performing fluorescent X-ray analysis of regions having different contrasts and specifying the crystalline Al ₂ ZnO ₄ region, the ratio of the area of the crystalline Al ₂ ZnO ₄ region to the cross-sectional area can be measured. . The surface roughness Ra refers to the arithmetic average roughness Ra defined by JIS B0601: 2001, and can be measured by an AFM (atomic force microscope) or the like.

The conductive oxide containing crystalline Al ₂ ZnO ₄ is crystalline In ₂ Al _{2 (1-m)} Zn _1-q O _7-p (0 ≦ m <1, 0 ≦ q <1, 0 ≦ It is preferable to further include at least one crystalline material selected from the group consisting of p ≦ 3m + q) and crystalline In ₂ O ₃ . By including crystalline In ₂ Al _{2 (1-m)} Zn _1-q O _7-p , the surface roughness Ra of the oxide semiconductor film obtained by sputtering using a conductive oxide as a target can be reduced. it can. By including crystalline In ₂ O ₃ , the thermal conductivity of the conductive oxide is increased, so that the discharge is stabilized when direct current sputtering is performed using the conductive oxide as a target. In addition, the field-effect mobility of the oxide semiconductor film obtained by sputtering using a conductive oxide as a target can be increased.

In conductive oxide containing a crystalline Al ₂ ZnO _4, crystalline Al ₂ ZnO _4, the presence of crystalline _{_{In 2 Al 2 (1-m}} ) Zn 1-q O 7-p and crystalline In ₂ O ₃ is , Confirmed by the chemical composition determined by ICP (inductively coupled plasma) emission analysis and the crystal phase identified by X-ray diffraction. For example, the presence of crystalline _{_{In 2 Al 2 (1-m}} ) Zn 1-q O 7-p is, X-rays diffraction peaks of crystalline _{_{In 2 Al 2 (1-m}} ) Zn 1-q O 7-p is This is confirmed by shifting to a higher angle side than the X-ray diffraction peak of crystalline In ₂ Al ₂ Zn ₁ O ₇ . Note that crystalline Al ₂ ZnO ₄ has a spinel crystal structure, crystalline In ₂ Al _{2 (1-m)} Zn _1-q O _7-p has a hexagonal crystal structure, In ₂ O ₃ has a cubic crystal structure.

In the conductive oxide of this embodiment, it is preferable that crystalline Al ₂ MgO ₄ is included as crystalline Al ₂ MO ₄ . By including crystalline Al ₂ MgO ₄ , the characteristics of the oxide semiconductor film obtained by sputtering using a conductive oxide as a target can be stabilized, and the field-effect mobility of the oxide semiconductor film can be increased. Therefore, a conductive oxide containing crystalline Al ₂ MgO ₄ is preferably used as a target for forming an oxide semiconductor film by a sputtering method.

Here, a crystalline ratio of Al ₂ MgO ₄ occupied in the cross-sectional area of the conductive oxide containing crystalline Al ₂ MgO ₄ is preferably 2% to 60%, more preferably at most 20% more than 5%. By using a conductive oxide containing crystalline MgAl ₂ O ₄ at such an area ratio as a sputtering target, an oxide semiconductor film with high field-effect mobility can be manufactured. Further, when a conductive oxide containing crystalline Al ₂ MgO ₄ further comprising a crystalline In ₂ O _3, the proportion of crystalline In ₂ O ₃ occupying the sectional area of the conductive oxide, 40% 98% The following is preferable, and 40% or more and 60% or less are more preferable. Using the conductive oxide containing crystalline In ₂ O ₃ at such an area ratio as a sputtering target, an oxide semiconductor film with high field-effect mobility is manufactured by forming an oxide semiconductor film Can do.

Here, the ratios of crystalline Al ₂ MgO ₄ and crystalline In ₂ O ₃ in the cross-sectional area of the conductive oxide are calculated as follows. First, the peaks of crystalline Al ₂ MgO ₄ and crystalline In ₂ O ₃ are confirmed by X-ray diffraction. Next, the conductive oxide is cut at an arbitrary surface. The cut surface of the conductive oxide is irradiated with an incident electron beam using an analytical scanning electron microscope to observe electrons reflected from the cross section (reflected electron image). In such a backscattered electron image, by performing fluorescent X-ray analysis on regions with different contrasts, the region where Al and Mg are mainly observed is identified as crystalline Al ₂ MgO ₄ , and only the In peak is observed. The region to be formed is identified as crystalline In ₂ O ₃ . In this way, the ratio of the area of crystalline MgAl ₂ O ₄ and crystalline In ₂ O ₃ occupying the cross section is calculated.

The conductive oxide containing crystalline Al ₂ MgO ₄ is crystalline In ₂ Al _{2 (1-n)} Mg _1-t O _7-s (0 ≦ n <1, 0 ≦ t <1, 0 ≦ s ≦ 3n + t) and at least one crystalline material selected from the group consisting of crystalline In ₂ O ₃ is preferable.

By including crystalline In ₂ Al _{2 (1-n)} Mg _1-t O _7-s , the field-effect mobility of an oxide semiconductor film obtained by sputtering using a conductive oxide as a target can be increased. . Such crystalline In ₂ Al _{2 (1-n)} Mg _1-t O _7-s is prepared by mixing crystalline powders of crystalline In ₂ Al ₂ MgO ₇ and crystalline Al ₂ MgO ₄ under predetermined conditions. It is formed by modification and deficiency of Al and Mg in crystalline In ₂ Al ₂ MgO ₇ . When Al and Mg are deficient in this way (that is, when n and t are both n> 0 and t> 0), the oxygen stoichiometric ratio is smaller than “7” corresponding to the stoichiometric ratio of this deficiency. It may take a value (ie, s> 0). By producing an oxide semiconductor film using such a conductive oxide containing crystalline In ₂ Al _{2 (1-n)} Mg _1-t O _7-s as a sputtering target, high field-effect mobility can be obtained. This oxide semiconductor film can be manufactured.

Although it is difficult to directly calculate the values of n and t in the crystalline In ₂ Al _{2 (1-n)} Mg _1-t O _7-s , the crystalline In ₂ Al _{2 (1-n )} The presence or absence of Mg _1-t O _7-s can be confirmed. The presence or absence of crystalline In ₂ Al _{2 (1-n)} Mg _1-t O _7-s is determined by determining the composition of the conductive oxide by ICP emission analysis and identifying the crystalline phase by X-ray diffraction. To do. For example, in spite of the fact that ICP emission analysis specifies that the atomic concentration ratio of In: Al: Mg in the conductive oxide is 2: 2: 1, When the presence of In ₂ Al ₂ MgO ₇ is confirmed, in the conductive oxide, crystalline In ₂ Al _{2 (1-n)} Mg _1-t O _7-s (as well as crystalline Al ₂ MgO ₄ ( 0 <n <1, 0 <t <1, 0 ≦ s ≦ 3n + t). In addition, when the presence of crystalline In ₂ O ₃ , In ₂ Al ₂ MgO ₇ , and Al ₂ MgO ₄ is confirmed by X-ray diffraction, the composition by ICP emission analysis and the analytical electron microscope are also used. In contrast to the composition considered from the area ratio of In ₂ O ₃ , In ₂ Al ₂ MgO ₇ , and Al ₂ MgO ₄ , In ₂ Al _{2 (1-n)} Mg _{1 -t} O _7-s is considered to exist.

By including crystalline In ₂ O ₃ , the thermal conductivity of the conductive oxide is increased, so that the discharge is stabilized when direct current sputtering is performed using the conductive oxide as a target. In addition, the field-effect mobility of the oxide semiconductor film obtained by sputtering using a conductive oxide as a target can be increased.

In conductive oxide containing a crystalline Al ₂ MgO _4, crystalline Al ₂ MgO _4, the presence of crystalline _{_{In 2 Al 2 (1-n}} ) Mg 1-t O 7-s and crystalline In ₂ O ₃ is , Confirmed by the chemical composition determined by ICP emission analysis and the crystal phase identified by X-ray diffraction. For example, the presence of crystalline _{_{In 2 Al 2 (1-n}} ) Mg 1-t O 7-s is, X-rays diffraction peaks of crystalline _{_{In 2 Al 2 (1-n}} ) Mg 1-t O 7-s is This is confirmed by shifting to a higher angle side than the X-ray diffraction peak of crystalline In ₂ Al ₂ Mg ₁ O ₇ . Note that crystalline Al ₂ MgO ₄ has a spinel crystal structure, crystalline In ₂ Al _{2 (1-n)} Mg _1-t O _7-s has a hexagonal crystal structure, In ₂ O ₃ has a cubic crystal structure.

In the conductive oxide of this embodiment, when the total atomic ratio of In, Al, and M is 100 atomic%, 10 to 50 atomic% In, 10 to 50 atomic% Al, and 15 to 40 atoms % M is preferable. A conductive oxide having such an atomic ratio is inexpensive and can be suitably used as a sputtering target to obtain an oxide semiconductor film having high physical properties (for example, high etching rate, high field effect mobility, etc.). .

The conductive oxide of this embodiment is at least one additive element selected from the group consisting of N, Al, Si, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, Sn, and Bi. Further, it is preferable that these additional elements are contained in an amount of 0.1 × 10 ²² atm / cc to 5.0 × 10 ²² atm / cc. That is, the total concentration of the additive elements contained in the conductive oxide of this embodiment is preferably 0.1 × 10 ²² atm / cc or more and 5.0 × 10 ²² atm / cc or less. Here, the additive element and atomic concentration contained in the conductive oxide can be measured by SIMS (secondary ion mass spectrometry).

The conductive oxide of this embodiment is suitably used for a sputtering target. Here, the “target for sputtering method” means a material obtained by forming a film by sputtering method into a plate shape, or the plate-like material on a backing plate (back plate for attaching a target material). The backing plate is a generic term for affixed materials and the like, and the backing plate can be manufactured using materials such as oxygen-free copper, steel, stainless steel, aluminum, aluminum alloy, molybdenum, and titanium. The shape of the target described above is not particularly limited, and may be a round shape or a square shape. The target may have a disk shape (flat plate shape) with a diameter of 1 cm, or a square shape (flat plate with a diameter exceeding 2 m, such as a sputtering target for a large LCD (liquid crystal display device). (Rectangular).

[Oxide semiconductor film]
An oxide semiconductor film according to another embodiment of the present invention is formed using the conductive oxide of the above embodiment, and preferably using the conductive oxide of the above embodiment as a target. It is formed by a sputtering method. Since the oxide semiconductor film of this embodiment is formed using the conductive oxide of the above embodiment, the characteristics are stabilized, the etching rate is increased, and / or the field effect transfer is performed. The degree becomes higher. In the sputtering method, a target and a substrate are placed facing each other in a sputtering apparatus, a voltage is applied to the target to sputter rare gas ions on the surface of the target, and target atoms are ejected. Is formed on the substrate to form an oxide semiconductor film.

[Method for producing conductive oxide]
Referring to FIG. 1, the manufacturing method further conductive oxide which is another embodiment of the present invention, when at least one element selected from the group consisting of Zn and Mg and M, Al ₂ O ₃ A step of preparing a first mixture containing the powder and the MO powder (S10), a step of producing a crystalline Al ₂ MO ₄ powder by calcining the first mixture (S20), and a crystalline Al ₂ A step of preparing a second mixture containing MO ₄ powder and In ₂ O ₃ powder (S30), a step of obtaining a molded body by molding the second mixture (S40), and sintering the molded body A step (S50) of producing a conductive oxide.

According to the method for producing a conductive oxide of the present embodiment, an inexpensive conductive oxide that is preferably used for forming a semiconductor oxide by including the above-described steps, more specifically, oxidized by a sputtering method. An inexpensive conductive oxide that is suitably used as a target for forming a physical semiconductor film can be efficiently produced.

(Preparation process of the first mixture)
When at least one element selected from the group consisting of Zn and Mg is M, the step (S10) of preparing the first mixture containing the Al ₂ O ₃ powder and the MO powder includes Al ₂ O as a raw material powder. _This is performed by mixing ₃ powder and MO powder (that is, ZnO powder and / or MgO powder). Here, the purity of the Al ₂ O ₃ powder and the MO powder is not particularly limited, but is preferably 99.9% by mass or more and 99.99% by mass or more from the viewpoint of improving the quality of the conductive oxide to be produced. Is preferred. The mixing ratio of the Al ₂ O ₃ powder and the MO powder is not particularly limited, but from the viewpoint of increasing the yield of the crystalline Al ₂ MO ₄ powder, the molar ratio is Al ₂ O ₃ : MO = 1: 0.95 to 1.05 is preferable.

The mixing method of the Al ₂ O ₃ powder and the MO powder is not particularly limited, and may be a dry mixing method or a wet mixing method. As such a mixing method, a method such as mixing by a normal ball mill, mixing by a planetary ball mill, mixing by a bead mill, stirring mixing by ultrasonic waves, or the like is preferably used. The drying method when the wet mixing method is used may be natural drying or forced drying using a spray dryer or the like.

(Production process of crystalline Al ₂ MO ₄ powder)
The step (S20) of producing the crystalline Al ₂ MO ₄ powder is performed by calcining the first mixture. The calcining temperature of the first mixture is preferably 800 ° C. or higher and lower than 1200 ° C. When the calcination temperature is less than 800 ° C., unreacted raw material powder remains and it becomes difficult to produce a crystalline Al ₂ MO ₄ powder having sufficient crystallinity. When the calcining temperature is 1200 ° C. or higher, the grain size of the crystalline Al ₂ MO ₄ powder obtained by calcining becomes large, and it becomes difficult to obtain a dense sintered body in the subsequent sintering step. It takes time to pulverize the crystalline Al ₂ MO ₄ powder before the sintering step. The calcining atmosphere is not particularly limited, but is preferably an air atmosphere from the viewpoint of suppressing desorption of oxygen from the powder and being simple.

Formation of crystalline Al ₂ MO ₄ powder by calcination is confirmed by the chemical composition determined by ICP emission analysis and the crystal phase identified by X-ray diffraction.

The crystalline Al ₂ MO ₄ powder thus obtained preferably has an average particle size of 0.1 μm to 1.5 μm. Here, the value calculated by the light scattering method shall be employ | adopted for the average particle diameter of powder.

(Preparation process of the second mixture)
Crystalline Al ₂ MO ₄ powder and In ₂ O ₃ preparing a second mixture comprising a powder (S30) is carried out by mixing the crystalline Al ₂ MO ₄ powder and In ₂ O ₃ powder . Here, the purity of the In ₂ O ₃ powder is not particularly limited, but is preferably 99.9% by mass or more and more preferably 99.99% by mass or more from the viewpoint of increasing the quality of the conductive oxide to be produced. Further, the mixing ratio of the crystalline Al ₂ MO ₄ powder and the I ₂ O ₃ powder is not particularly limited, but from the viewpoint of enhancing the conductivity of the conductive oxide, the crystalline Al ₂ MO ₄ : I ₂ O ₃ = 1: 0.95 to 1 is preferable.

The mixing method of the crystalline Al ₂ MO ₄ powder and the I ₂ O ₃ powder is not particularly limited, and may be a dry mixing method or a wet mixing method. As such a mixing method, a method such as mixing by a normal ball mill, mixing by a planetary ball mill, mixing by a bead mill, stirring mixing by ultrasonic waves, or the like is preferably used. The drying method when the wet mixing method is used may be natural drying or forced drying using a spray dryer or the like.

In the case of producing a conductive oxide containing an additive element, N, Al, Si, Ti, V, Cr, Zr, Nb, Mo, Hf, together with crystalline Al ₂ MO ₄ powder and In ₂ O ₃ powder. , Ta, W, Sn, and Bi. The raw material powder containing at least one additive element selected from the group consisting of Bi is mixed. Such additive element raw material powder is not particularly limited, but from the viewpoint of suppressing mixing of impurity elements other than constituent elements and additive elements and oxygen desorption, AlN powder, Al ₂ O ₃ powder, SiO ₂ powder, TiO ₂ powder V ₂ O ₅ powder, Cr ₂ O ₃ powder, ZrO ₂ powder, Nb ₂ O ₃ powder, MoO ₂ powder, HfO ₂ powder, Ta ₂ O ₃ powder, WO ₃ powder, SnO ₂ powder, and Bi ₂ O ₃ Powder is preferably used. By adding such additive element raw material powder, the conductive oxide was selected from N, Al, Si, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, Sn, and Bi. A conductive oxide that includes at least one kind of additive element and can manufacture an oxide semiconductor film with high field-effect mobility can be manufactured.
(Molding process)
In the step of obtaining a molded body by molding the second mixture (S40), the method of molding the second mixture is not particularly limited, but from the viewpoint of high productivity, press molding, CIP (cold etc.) A method such as (pressure-pressing) molding or cast molding is preferably used. Further, from the viewpoint of efficiently forming in stages, it is preferable to perform CIP molding after press molding.

(Sintering process)
An electroconductive oxide is obtained by the process (S50) of sintering a molded object. The sintering temperature of the molded body depends on the type of crystalline Al ₂ MO ₄ powder containing the molded body (here, M is at least one element selected from the group consisting of Zn and Mg).

If the shaped body contains a crystalline Al ₂ ZnO ₄ powder as crystalline Al ₂ MO ₄ powder, the sintering temperature of the molded body, preferably less than 1280 ° C. or higher 1500 ° C.. When the sintering temperature is less than 1280 ° C., the crystalline Al ₂ ZnO ₄ powder and In ₂ O ₃ powder are not sufficiently sintered, and it is difficult to produce a dense sintered body necessary as a sputtering target. It is. When the sintering temperature is 1500 ° C. or higher, crystalline Al ₂ ZnO ₄ is not formed but only crystalline In ₂ Al _{2 (1-m)} Zn _1-q O _7-p is formed. An oxide semiconductor film obtained by sputtering using a target becomes unstable in characteristics, and its surface roughness Ra increases and its etching rate decreases. Here, when the sintering temperature of the compact is 1280 ° C. or higher and lower than 1300 ° C., crystalline Al ₂ ZnO ₄ and crystalline In ₂ O ₃ are formed in the crystalline phase. When the sintering temperature of the formed body is 1300 ° C. or higher and lower than 1500 ° C., crystalline Al ₂ ZnO ₄ and crystalline In ₂ Al _{2 (1-m)} Zn _1-q O _7-p are formed in the crystalline phase. The

If the shaped body contains a crystalline Al ₂ MgO ₄ powder as crystalline Al ₂ MO ₄ powder, the sintering temperature of the molded body is preferably 1300 ° C. or higher 1500 ° C. or less. When the sintering temperature is less than 1300 ° C., the crystalline Al ₂ MgO ₄ powder and In ₂ O ₃ powder are not sufficiently sintered, and it is difficult to produce a dense sintered body necessary as a sputtering target. It is. When the sintering temperature is higher than 1500 ° C., Mg is desorbed, resulting in a variation in the composition of the sintered body and inhomogeneity. Here, when the sintering temperature of the compact is 1300 ° C. or higher and lower than 1390 ° C., crystalline Al ₂ MgO ₄ and crystalline In ₂ O ₃ are formed in the crystalline phase. When the sintering temperature of the formed body is 1390 ° C. or higher and lower than 1500 ° C., crystalline Al ₂ ZnO ₄ and crystalline In ₂ Al _{2 (1-n)} Zn _1-t O _7-s are formed in the crystalline phase. The

[Example A]
1. Preparation of first mixture Al ₂ O ₃ powder (purity: 99.99% by mass, BET (Brunauer, Emmett, Teller) specific surface area: 10 m ² / g) and ZnO powder (purity: 99.99% by mass, BET Specific surface area: 4 m ² / g) at a molar mixing ratio of Al ₂ O ₃ : ZnO = 1: 1 by pulverization and mixing for 3 hours using a ball mill apparatus, to obtain Al ₂ O ₃ − as the first mixture. A ZnO mixture was prepared. Water was used as a dispersion medium during pulverization and mixing. This mixture was dried with a spray dryer to obtain a first mixture.

2. A first mixture prepared resulting crystalline Al ₂ ZnO ₄ powder was placed in an aluminum oxide crucible and calcined for 5 hours at a temperature of 900 ° C. in an air atmosphere. Thus, a crystalline Al ₂ ZnO ₄ powder that is a calcined powder formed of crystalline Al ₂ ZnO ₄ was obtained. The presence of crystalline Al ₂ ZnO ₄ was confirmed by the chemical composition determined by ICP emission analysis and the crystal phase identified by X-ray diffraction.

3. Preparation of Second Mixture The obtained crystalline Al ₂ ZnO ₄ powder (calcined powder) and In ₂ O ₃ powder (purity: 99.99 mass%, BET specific surface area: 5 m ² / g) were crystallized. The mixture is pulverized and mixed for 6 hours using a ball mill apparatus at a molar mixing ratio of fine Al ₂ ZnO ₄ : In ₂ O ₃ = 1: 0.95, whereby In ₂ O ₃ -crystalline Al ₂ ZnO is used as the second mixture. _Four mixtures were prepared. Water was used as a dispersion medium during pulverization and mixing. This mixture was dried with a spray dryer to obtain a second mixture.

4). Molding The obtained second mixture was press-molded under the condition of a surface pressure of 1.0 ton f / cm ² , and CIP-molded under the condition of each surface pressure of 2.0 ton f / cm ² . A disk-shaped molded body having a diameter of 100 mm and a thickness of about 9 mm was obtained.

5. Sintering The eight molded bodies obtained were 1250 ° C (Example A1), 1280 ° C (Example A2), 1300 ° C (Example A3), 1350 ° C (Example A4), 1375 ° C (Example A5), 1400 ° C ( Eight sintered bodies having different crystalline composition ratios as conductive oxides (Example A6), 1450 ° C. (Example A7), and 1500 ° C. (Example AR1), respectively, for 5 hours. A1 to A7 and Example AR1) were obtained.

The relative density of the obtained sintered body (conductive oxide) was calculated by the following method. First, the bulk density of the obtained sintered body was measured by the Archimedes method. Next, the sintered body was pulverized and the true density of the powder was measured by a pycnometer method. Next, the relative density of the sintered body was calculated by dividing the bulk density by the true density.

Further, the proportion of crystalline Al ₂ ZnO ₄ , crystalline In ₂ Al _{2 (1-m)} Zn _1-q O _7-p and crystalline In ₂ O ₃ in the cross-sectional area of these conductive oxides, The main surfaces of these conductive oxides were polished and calculated by EDX (energy dispersive X-ray analysis) of the main surface after polishing. The results are summarized in Table 1.

6). Production and Evaluation of Oxide Semiconductor Films by Sputtering Eight oxide semiconductor films were produced by DC (direct current) magnetron sputtering using the obtained eight conductive oxides as targets. Specifically, a synthetic quartz glass substrate having a size of 25 mm × 25 mm × thickness 0.6 mm was disposed as a film formation substrate on a water-cooled substrate holder in the film formation chamber of the sputtering apparatus. The conductive oxide was disposed at a distance of 40 mm so that the main surface thereof was opposed to the main surface of the synthetic quartz glass substrate. Here, a part of the main surface of the synthetic quartz glass substrate was covered with a metal mask.

Next, the pressure ^inside the film forming chamber was reduced to 1 × 10 ⁻⁴ Pa. Next, in a state where a shutter is put between the synthetic quartz glass substrate and the conductive oxide (target), Ar gas is introduced into the film forming chamber up to a pressure of 1 Pa, and direct current power of 30 W is applied to cause sputtering discharge. Thus, the surface of the conductive oxide (target) was cleaned (pre-sputtering) for 10 minutes. Next, Ar gas was introduced into the film formation chamber to a pressure of 20 Pa, 50 W direct current power was applied to cause sputtering discharge, and the oxide semiconductor film was formed for 1 hour by removing the shutter. Note that no bias voltage was applied to the substrate holder, and the substrate holder was only water-cooled. When the synthetic quartz glass substrate was taken out of the deposition chamber after the oxide semiconductor film was formed, only the region on the synthetic quartz glass substrate that was not covered with the metal mask was In—Al—Zn-based composite oxide (IAZO). The oxide semiconductor film was formed. The obtained oxide semiconductor film was amorphous when its crystallinity was evaluated by X-ray diffraction (SmartLab manufactured by Rigaku Corporation).

(1) Evaluation of surface roughness Ra The surface roughness Ra of the obtained oxide semiconductor film was measured in the range of 10 μm × 10 μm square by AFM (atomic force microscope). The results are summarized in Table 1.

(2) Evaluation of etching rate On a synthetic quartz glass substrate, a step between a region where an oxide semiconductor film is formed and a region covered with a metal mask and where an oxide semiconductor film is not formed is a stylus type surface. The thickness of the formed oxide semiconductor film was determined by measuring with a roughness meter.

Thereafter, an etching aqueous solution of phosphoric acid: acetic acid: water = 4: 1: 100 was prepared at a molar ratio, and the synthetic quartz glass substrate on which the oxide semiconductor film was formed was immersed in the etching solution. At this time, the etching solution was heated to 50 ° C. in the hot bath. The immersion time was set to 2 minutes, and the thickness of the oxide semiconductor film remaining without being etched during that time was measured with a stylus type surface roughness meter. The etching rate was calculated by dividing the difference in thickness of the oxide semiconductor film before and after etching by the etching time. The results are summarized in Table 1.

As is clear from Table 1, as shown in Examples A1 to A7, the conductive oxide containing In, Al, Zn, and O and containing crystalline Al ₂ ZnO ₄ is By sputtering as a target, an oxide semiconductor film having stable characteristics and a high etching rate was able to be manufactured. Furthermore, as shown in Examples A3 to A7, a conductive oxide having a ratio of crystalline Al ₂ ZnO ₄ to a cross-sectional area of 10% or more and 60% or less has a surface roughness Ra by sputtering using the conductive oxide as a target. A fine oxide semiconductor film could be produced.

[Example B]
(Examples B1 to B6)
In Examples B1 to B6 of Example B, conductive oxidation comprising crystalline Al ₂ MgO ₄ and crystalline In ₂ Al _{2 (1-n)} Mg _1-n O _7-4n (0 ≦ n <1) A product was made.

1. Prepare first mixture Al ₂ O ₃ powder (purity: 99.99 mass%, BET specific surface area: 5 m ² / g) and MgO powder (purity: 99.99 mass%, BET specific surface area: 6 m ² / g) Was placed in a ball mill apparatus so that the molar mixing ratio was Al ₂ O ₃ : MgO = 1: 1. These powders were pulverized and mixed for 30 minutes using water as a dispersion solvent. Thereafter, water was volatilized by a spray dryer to obtain a first mixture made of an Al ₂ O ₃ —MgO mixture.

2. Preparation of crystalline Al ₂ MgO ₄ powder Next, the first mixture of the above placed in an aluminum oxide crucible, by performing calcination for 5 hours in the air atmosphere at 900 ° C., crystalline Al ₂ MgO ₄ A powder was obtained. The presence of crystalline Al ₂ MgO ₄ was confirmed by the chemical composition determined by ICP emission analysis and the crystal phase identified by X-ray diffraction.

3. Preparation of Second Mixture The above crystalline Al ₂ MgO ₄ powder and In ₂ O ₃ powder (purity: 99.99 mass%, BET specific surface area: 8 m ² / g) were mixed at a molar mixing ratio of Al ₂ MgO _4. : In ₂ O ₃ = 1: 1. These particles were pulverized and mixed for 6 hours using water as a dispersion solvent. Thereafter, water was volatilized by a spray dryer to obtain a _second mixture of In ₂ O ₃ -crystalline Al ₂ MgO ₄ .

4). Molding The second mixture obtained above is press-molded under the condition of a surface pressure of 1.0 ton f / cm ² , and CIP-molded at each surface pressure of 2.0 ton f / cm ^2. A disk-shaped molded body having a thickness of about 9 mm was produced.

5. Sintering The compact thus obtained was fired for 5 hours in the atmosphere at the temperature shown in the column of “Sintering temperature” in Table 2 below to produce a conductive oxide. By setting the sintering temperature to 1390 ° C. or higher and 1500 ° C. or _lower , a conductive oxide containing crystalline Al ₂ MgO ₄ and crystalline In ₂ Al _{2 (1-n)} Mg _1-n O _7-4n can be obtained. Obtained.

(Example B7)
The conductive oxide of Example B7 was produced by the same production method as in Example B1, except that the preparation method of the second mixture and the sintering temperature of the compact were different from Example B1. That is, in Example B7, in the step of preparing the second mixture, in addition to crystalline Al ₂ MgO ₄ powder and In ₂ O ₃ powder, AlN powder (purity: 99.99 mass%, BET specific surface area: 5 m ² / By adding g), a _second mixture of In ₂ O ₃ —AlN—crystalline Al ₂ MgO ₄ mixed powder was obtained. By using this second mixture, sintering was carried out at a sintering temperature of 1390 ° C. in an atmospheric pressure and nitrogen atmosphere for 5 hours to prepare a disk-shaped molded body having a diameter of 100 mm and a thickness of about 9 mm.

(Examples B8 to B20)
In Examples B8 to B20, the conductivity of Examples B8 to B20 is the same as that of Example B7 except that the method for preparing the second mixture and the sintering temperature and sintering atmosphere of the molded body are different. An oxide was produced. That is, in Examples B8 to B20, the AlN powder of Example B7 was replaced with an oxide powder containing additive elements (Al ₂ O ₃ powder, SiO ₂ powder, TiO ₂ powder, V ₂ O ₅ powder, Cr ₂ O ₃ powder, ZrO ₂ powder, Nb ₂ O ₃ powder, MoO ₂ powder, HfO ₂ powder, Ta ₂ O ₃ powder, WO ₃ powder, SnO ₂ powder, Bi ₂ O ₃ powder) Sintering was performed therein to produce conductive oxides of Examples B8 to B20.

(Example BR1)
In Example BR1, a conductive oxide was produced by a process different from the method for producing the conductive oxide of Examples B1 to B20. That is, in the method for producing the conductive oxide of Example BR1, first, Al ₂ O ₃ powder (purity: 99.99 mass%, BET specific surface area: 11 m ² / g) and MgO powder (purity: 99.99 mass%). , BET specific surface area: 4 m ² / g) and In ₂ O ₃ powder (purity: 99.99 mass%, BET specific surface area: 5 m ² / g), the molar mixing ratio is In ₂ O ₃ : Al ₂ O ₃ : MgO = 1: 1: 1 was charged into the bead mill apparatus. These mixed powders were pulverized and mixed for 30 minutes using water as a dispersion solvent. Thereafter, water was volatilized by a spray dryer to obtain an In ₂ O ₃ —Al ₂ O ₃ —MgO mixture.

Next, the obtained mixture was put in an aluminum oxide crucible and calcined in an air atmosphere at 1200 ° C. for 5 hours to obtain crystalline In ₂ Al ₂ MgO ₇ powder.

The crystalline In ₂ Al ₂ MgO ₇ powder obtained above was molded by uniaxial pressure molding to produce a disk-shaped molded body having a diameter of 100 mm and a thickness of 9 mm. The molded body was fired at 1500 ° C. for 5 hours in an air atmosphere to produce a conductive oxide of Example BR1. Due to the powder mixing method and the sintering temperature of 1500 ° C. or higher, only crystalline In ₂ Al ₂ MgO ₇ is formed, and crystalline MgAl ₂ O ₄ and crystalline In ₂ Al _{2 (1-n)} _mg _1-n O 7-4n was not formed.

(Example BR2)
In Example BR2, a conductive oxide was produced by a process different from the method for producing the conductive oxide of Examples B1 to B20. That is, first, In ₂ O ₃ powder (purity: 99.99 mass%, BET specific surface area: 5 m ² / g) was charged into a bead mill apparatus. The In ₂ O ₃ powder was pulverized and mixed for 30 minutes using water as a dispersion solvent. Thereafter, by evaporating the water by spray drying, to form a granulated powder comprising only an In ₂ O _3.

Next, the granulated powder obtained above was molded by uniaxial pressure molding to produce a compact on a disc having a diameter of 100 mm and a thickness of 9 mm. The molded body thus produced was sintered at 1500 ° C. for 5 hours in an air atmosphere to produce a conductive oxide of Example BR2.

(Example B21 to B26)
The conductivity of Examples B21 to B26 is the same as Example B1 except that the mixing ratio of the raw material powders in the first mixture and the second mixture is different from Example B1 and the sintering temperature is less than 1390 ° C. An oxide was produced. That is, in Examples B21 to B26, the mixing ratio of the Al ₂ O ₃ powder, the MgO powder, and the In ₂ O ₃ particles was adjusted so that the atomic ratio shown in the column “Atom concentration ratio” in Table 3 was obtained. . Note that, by setting the sintering temperature to less than 1390 ° C., the conductive oxide did not contain crystalline In ₂ Al _{2 (1-n)} Mg _1-n O _7-4n .

(Example B27)
A conductive oxide of Example B27 was produced in the same manner as in Example B7 except that the sintering temperature was different from that of Example B7. Note that, by setting the sintering temperature to less than 1390 ° C., the conductive oxide did not contain crystalline In ₂ Al _{2 (1-n)} Mg _1-n O _7-4n .

(Example B28-B40)
The conductive oxides of Examples B28 to B40 were prepared in the same manner as in Examples B8 to B20, except that the sintering temperature was different from that of Examples B8 to B20. Note that, by setting the sintering temperature to less than 1390 ° C., the conductive oxide did not contain crystalline In ₂ Al _{2 (1-n)} Mg _1-n O _7-4n .

For the conductive oxides of Examples B1 to B40 and Examples BR1 to BR2, the atomic ratio (unit: atomic%) of In, Al, and Mg was measured using ICP emission analysis. The results are shown in the column “Atom concentration ratio” in Tables 2 and 3. In addition, the conductive oxides produced in Examples B1 to B40 and Examples BR1 to BR2 were cut on an arbitrary surface, and the cut surfaces were subjected to fluorescent X-ray analysis using an analytical scanning electron microscope, whereby conductive oxides were obtained. The ratio of crystalline Al ₂ MgO _{4 and} the ratio of crystalline In ₂ O ₃ occupying the cross-sectional area was calculated. The results are shown in the columns of “Al ₂ MgO ₄ ratio in cross-sectional area” and “In ₂ O ₃ ratio in cross-sectional area” in Tables 2 and 3. In addition, the crystalline In ₂ O ₃ region could not be confirmed by the cross sections of the conductive oxides of Examples B1 to B20 and evaluation by X-ray diffraction.

The conductive oxides prepared in Examples B1 to B40 were subjected to crystal analysis by powder X-ray diffraction. Specifically, the diffraction angle 2θ was measured by irradiating Cu Kα rays as X-rays, and it was confirmed by the diffraction peaks that both In ₂ O ₃ and Al ₂ MgO ₄ were crystalline. On the other hand, in the conductive oxide produced in Example BR1, the presence of Al ₂ MgO ₄ was not confirmed even by evaluation using an analytical scanning electron microscope and X-ray diffraction, and In ₂ Al ₂ MgO was detected by X-ray diffraction. A diffraction peak of ₇ was confirmed.

Further, the composition of the additive element and the number of atoms per 1 cm ³ (atom / cm ³ ) of the conductive oxides prepared in Examples B1 to B40 and Examples BR1 to BR2 were calculated by SIMS. The results are shown in the “added elements” and “concentration” columns of Tables 2 and 3.

(Evaluation: Field effect mobility)
An oxide semiconductor film was formed by DC (direct current) magnetron sputtering using the conductive oxides obtained in Examples B1 to B40 and Examples BR1 and BR2 as targets. A TFT including the oxide semiconductor film as a channel layer was manufactured, and the field-effect mobility of each TFT was calculated to evaluate the performance of the conductive oxides of Examples B1 to B40 and Examples BR1 to BR2.

The above-mentioned field effect mobility was specifically calculated as follows. First, the conductive oxides obtained in Examples B1 to B40 and Examples BR1 to BR2 were processed into targets having a diameter of 3 inches (76.2 mm) and a thickness of 5.0 mm. And the target was arrange | positioned in a sputtering device so that a 3 inch diameter surface might become a sputtering surface. On the other hand, a film formation substrate made of a conductive Si wafer of 25 mm × 25 mm × 0.5 mm (<0.02 Ωcm) is placed on a water-cooled substrate holder of a sputtering apparatus, and a part of the surface of the film formation substrate is placed. Was covered with a metal mask. At this time, the distance between the target and the deposition substrate was 40 mm.

Then, the inside of the sputtering apparatus is evacuated to about 1 × 10 ⁻⁴ Pa, and with the shutter placed between the substrate and the target, Ar gas is introduced into the film forming chamber to set the pressure in the film forming chamber to 1 Pa. Further, the surface of the target was cleaned (pre-sputtering) for 10 minutes by applying 120 W DC power to the target and performing sputtering discharge.

Thereafter, Ar gas containing 15% by volume of oxygen gas at a flow rate ratio is introduced into the film forming chamber so that the pressure in the film forming chamber is 0.8 Pa, and further, a sputtering direct current power of 120 W is applied to the target, whereby a glass substrate is obtained. An oxide semiconductor film with a thickness of 70 nm was formed thereon. The substrate holder was only cooled with water and no bias voltage was applied.

In order to process the oxide semiconductor film thus fabricated into a predetermined channel width and channel length, a resist having a predetermined shape was applied, exposed, and developed on the oxide semiconductor film. Then, the glass substrate with the oxide semiconductor film is immersed in an aqueous etching solution adjusted to a molar ratio of phosphoric acid: acetic acid: water = 4: 1: 100 so that a predetermined channel width and channel length are obtained. The oxide semiconductor film was etched.

Next, a resist was applied on the oxide semiconductor film, exposed, and developed so that only portions of the oxide semiconductor film where the source electrode and the drain electrode were formed were exposed. By forming a metal layer made of Ti, a metal layer made of Al, and a metal layer made of Mo in this order on the portion where the resist is not formed (electrode forming portion) by sputtering, Ti / A source electrode and a drain electrode having a three-layer structure of Al / Mo and a film thickness of 100 nm were formed. After that, the resist over the oxide semiconductor film was peeled off, whereby a TFT including an oxide semiconductor film made of In—Al—Mg—O as a channel layer was manufactured.

The field effect mobility (μ _fe ) was calculated as follows for the TFT fabricated as described above. First, a voltage of 5V is applied between the source electrode and the drain electrode of the TFT, the source electrode, the voltage to be applied to (V _gs) is changed to 20V from -10V between the gate electrode made of Si wafer, The g _m value at V _gs = 10V was calculated by substituting the drain current (I _ds ) at that time into the equation (1). Next, the field effect mobility (μ _fe ) was calculated by substituting the g _m value calculated above into Equation (2) and further substituting W = 20 μm and L = 15 μm. The results are shown in the “field effect mobility” column of Tables 2 and 3. In addition, it shows that the characteristic of TFT is so favorable that the value of field effect mobility is high.

g _m = dI _ds / dV _gs (1)
μ _fe = g _m · L / (W · C _i · V _ds ) (2)
(Evaluation results and discussion)
From the results shown in Tables 2 and 3, the oxide semiconductor films manufactured using the conductive oxides of Examples B1 to B40 are in comparison with the oxide semiconductor films manufactured using the conductive oxides of Examples BR1 to BR2. Thus, the field effect mobility of the TFT is high. This is presumably because the conductive oxides of Examples B1 to B40 contain In, Al, Mg, O, and contain crystalline Al ₂ MgO ₄ as the crystalline material.

It should be considered that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

The conductive oxide according to the present invention can be preferably used as a target for sputtering film formation.

S10 Step of preparing the first mixture, S20 Step of preparing crystalline Al ₂ MO ₄ powder, S30 Step of preparing the second mixture, Step of obtaining S40 molded body, S50 Step of sintering the molded body.

Claims

A conductive oxide containing In, Al, and at least one element selected from the group consisting of Zn and Mg, and O, and containing crystalline Al 2 MO 4 .
Conductive oxide according to claim 1 comprising a crystalline Al 2 ZnO 4 as the crystalline Al 2 MO 4.
The conductive oxide according to claim 2, wherein a ratio of the crystalline Al 2 ZnO 4 occupying in a cross-sectional area of the conductive oxide is 10% or more and 60% or less.
Selected from the group consisting of crystalline In 2 Al 2 (1-m ) Zn 1-q O 7-p (0 ≦ m <1,0 ≦ q <1,0 ≦ p ≦ 3m + q) and crystalline In 2 O 3 The conductive oxide according to claim 2, further comprising at least one crystalline material.
Conductive oxide according to claim 1 comprising a crystalline Al 2 MgO 4 as the crystalline Al 2 MO 4.
The conductive oxide according to claim 5, wherein a ratio of the crystalline Al 2 MgO 4 to a cross-sectional area of the conductive oxide is 2% or more and 60% or less.
Selected from the group consisting of crystalline In 2 Al 2 (1-n) Mg 1-t O 7-s (0 ≦ n <1, 0 ≦ t <1, 0 ≦ s ≦ 3n + t) and crystalline In 2 O 3 The conductive oxide according to claim 5, further comprising at least one crystalline material.
2. The atomic ratio of the total of In, Al, and M includes 10 to 50 atomic% In, 10 to 50 atomic% Al, and 15 to 40 atomic% M, assuming that the total atomic ratio of In, Al and M is 100 atomic%. 8. The conductive oxide according to any one of 1 to 7.
The element according to claim 1 further comprising at least one additive element selected from the group consisting of N, Al, Si, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, Sn, and Bi. The conductive oxide in any one.
The conductive oxide according to claim 1, which is used for a sputtering target.
An oxide semiconductor film formed using the conductive oxide according to any one of claims 1 to 10.
A step (S10) of preparing a first mixture containing Al 2 O 3 powder and MO powder, where M is at least one element selected from the group consisting of Zn and Mg;
Producing a crystalline Al 2 MO 4 powder by calcining the first mixture (S20);
Preparing a second mixture containing the crystalline Al 2 MO 4 powder and In 2 O 3 powder (S30);
A step of obtaining a molded body by molding the second mixture (S40);
A method of producing a conductive oxide, comprising: sintering the molded body (S50).
The MO powder is a ZnO powder, the crystalline Al 2 MO 4 powder is a crystalline Al 2 ZnO 4 powder, and the first mixture in the step of preparing the crystalline Al 2 ZnO 4 powder (S20). The calcination temperature is 800 ° C or higher and lower than 1200 ° C, and the sintering temperature of the molded body in the step of sintering the molded body (S50) is 1280 ° C or higher and lower than 1500 ° C. Production method of oxide.
The MO powder is an MgO powder, the crystalline Al 2 MO 4 powder is a crystalline Al 2 MgO 4 powder, and the first mixture in the step of preparing the crystalline Al 2 MgO 4 powder (S20). The calcination temperature is 800 ° C or higher and lower than 1200 ° C, and the sintering temperature of the molded body in the step of sintering the molded body (S50) is 1300 ° C or higher and 1500 ° C or lower. Production method of oxide.