TW201615596A - And semiconductor device - Google Patents

Abstract

To provide an oxide sintered compact contains indium, tungsten, and at least one of zinc and tin and contains, as a crystal phase, a double oxide crystal phase containing tungsten and at least one of zinc and tin. A semiconductor device 10 includes an oxide semiconductor film 14 formed by a sputtering method using the oxide sintered compact as a target.

Description

氧化物燒結體及半導體裝置 Oxide sintered body and semiconductor device

本發明係關於一種可較佳地用作用以利用濺鍍法形成氧化物半導體膜之靶的氧化物燒結體及包含使用該氧化物燒結體而形成之氧化物半導體膜的半導體裝置。 The present invention relates to an oxide sintered body which can be preferably used as a target for forming an oxide semiconductor film by a sputtering method, and a semiconductor device including an oxide semiconductor film formed using the oxide sintered body.

作為於液晶顯示裝置、薄膜EL(電致發光)顯示裝置、有機EL顯示裝置等中作為半導體裝置即TFT(薄膜電晶體)之通道層而發揮功能的半導體膜，先前主要使用非晶矽膜。 An amorphous germanium film is mainly used as a semiconductor film that functions as a channel layer of a TFT (thin film transistor) which is a semiconductor device in a liquid crystal display device, a thin film EL (electroluminescence) display device, or an organic EL display device.

然而，近年來，作為此種半導體膜，以In-Ga-Zn系複合氧化物(以下，亦稱為IGZO)為主成分之氧化物半導體膜由於與非晶矽膜相比載子之移動率較大之優點而被矚目。 However, in recent years, as a semiconductor film, an oxide semiconductor film containing In-Ga-Zn composite oxide (hereinafter also referred to as IGZO) as a main component has a carrier mobility as compared with an amorphous germanium film. The advantage of the larger is highlighted.

例如，日本專利特開2008-199005號公報(專利文獻1)揭示：該以IGZO為主成分之氧化物半導體膜係藉由使用靶之濺鍍法而形成。 For example, Japanese Laid-Open Patent Publication No. 2008-199005 (Patent Document 1) discloses that the oxide semiconductor film containing IGZO as a main component is formed by a sputtering method using a target.

又，日本專利特開2004-091265號公報(專利文獻2)中，作為於利用濺鍍法等形成氧化物半導體膜時可較佳地使用之材料，揭示主要包含銦且包含鎢之氧化物燒結體。 In the case of forming an oxide semiconductor film by a sputtering method or the like, a material which can be preferably used in the case of forming an oxide semiconductor film is disclosed in Japanese Laid-Open Patent Publication No. 2004-091265. body.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開2008-199005號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-199005

[專利文獻2]日本專利特開2004-091265號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-091265

日本專利特開2008-199005號公報(專利文獻1)所揭示之包含以IGZO為主成分之氧化物半導體膜作為通道層之半導體裝置即TFT(薄膜電晶體)中，由於使用以市場價格較高之金屬鎵為原料之氧化鎵作為原料，因此，存在製造成本較高之問題。 In a TFT (thin film transistor) which is a semiconductor device including an oxide semiconductor film containing IGZO as a channel layer, which is disclosed in Japanese Laid-Open Patent Publication No. 2008-199005 (Patent Document 1), it is used at a high market price due to its use. Since gallium oxide is a raw material of gallium oxide as a raw material, there is a problem that manufacturing cost is high.

又，日本專利特開2004-091265號公報(專利文獻2)所揭示之包含使用主要包含銦且包含鎢之氧化物燒結體而製作之氧化物半導體膜作為通道層之半導體裝置即TFT中，存在如下問題：OFF電流較高而為1×10^-11A左右，若不使驅動電壓高至70V左右，則無法使ON電流相對於OFF電流之比充分地變大。 In the TFT which is a semiconductor device which uses an oxide semiconductor film which is mainly composed of an indium and contains an oxide sintered body of tungsten as a channel layer, is present in the TFT disclosed in Japanese Laid-Open Patent Publication No. 2004-091265 (Patent Document 2). a problem: OFF current is high and is approximately 1 × 10 ^-11 A, if the driving voltage is high to about 70V, the ON current is not so large relative to the OFF current ratio becomes sufficiently.

本發明之目的在於解決上述問題，提供一種可較佳地用於形成特性較高之半導體裝置之氧化物半導體膜的氧化物燒結體、包含使用該氧化物燒結體而形成之氧化物半導體膜之半導體裝置。 An object of the present invention is to provide an oxide sintered body which can be preferably used for forming an oxide semiconductor film of a semiconductor device having high characteristics, and an oxide semiconductor film formed using the oxide sintered body. Semiconductor device.

根據一態樣，本發明係一種氧化物燒結體，其係包含銦、鎢、與鋅及錫之至少1種者，且作為結晶相，包括包含鎢、與鋅及錫之至少1種之多氧化物結晶相。 According to one aspect, the present invention is an oxide sintered body comprising at least one of indium, tungsten, and zinc and tin, and as a crystalline phase, including at least one of tungsten, zinc, and tin. Oxide crystalline phase.

又，根據另一態樣，本發明係一種半導體裝置，其包含使用根據上述態樣之氧化物燒結體作為靶利用濺鍍法所形成之氧化物半導體膜。 Moreover, according to another aspect, the present invention provides a semiconductor device comprising an oxide semiconductor film formed by a sputtering method using an oxide sintered body according to the above aspect as a target.

根據上述內容，可提供一種可較佳地用於形成特性較高之半導體裝置之氧化物半導體膜的氧化物燒結體、包含使用該氧化物燒結體而形成之氧化物半導體膜之半導體裝置。 According to the above, an oxide sintered body which can be preferably used for forming an oxide semiconductor film of a semiconductor device having high characteristics, and a semiconductor device including an oxide semiconductor film formed using the oxide sintered body can be provided.

10‧‧‧半導體裝置 10‧‧‧Semiconductor device

11‧‧‧基板 11‧‧‧Substrate

12‧‧‧閘極電極 12‧‧‧ gate electrode

13‧‧‧閘極絕緣膜 13‧‧‧Gate insulation film

14‧‧‧氧化物半導體膜 14‧‧‧Oxide semiconductor film

14c‧‧‧通道部 14c‧‧‧Channel Department

14d‧‧‧汲極電極形成用部 14d‧‧‧Bare electrode forming part

14s‧‧‧源極電極形成用部 14s‧‧‧Source electrode forming part

15‧‧‧源極電極 15‧‧‧Source electrode

16‧‧‧汲極電極 16‧‧‧汲electrode

C_W‧‧‧通道寬度 C _W ‧‧‧ channel width

C_L‧‧‧通道長度 C _L ‧‧‧ channel length

圖1係表示本發明之半導體裝置之一例之概略圖，(A)表示概略俯 視圖，(B)表示(A)所示之IB-IB線之概略剖視圖。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an example of a semiconductor device of the present invention, and (A) is a schematic view showing a schematic view. View, (B) shows a schematic cross-sectional view of the IB-IB line shown in (A).

圖2(A)~(D)係表示本發明之半導體裝置之製造方法之一例的概略剖視圖。 2(A) to 2(D) are schematic cross-sectional views showing an example of a method of manufacturing a semiconductor device of the present invention.

<本發明之實施形態之說明> <Description of Embodiments of the Present Invention>

本發明之一實施形態即氧化物燒結體係包含銦、鎢、與鋅及錫之至少1種者，且作為結晶相，包括包含鎢、與鋅及錫之至少1種之多氧化物結晶相。本實施形態之氧化物燒結體由於包括包含鎢、與鋅及錫之至少1種之多氧化物結晶相作為結晶相，因此，於包含使用該氧化物燒結體而形成之氧化物半導體膜作為通道層之半導體裝置即TFT(薄膜電晶體)中，可使其OFF電流降低，並且可以較低之驅動電壓提高ON電流相對於OFF電流之比。又，可提高氧化物燒結體之導熱率。 In one embodiment of the present invention, the oxide sintering system includes at least one of indium, tungsten, and zinc and tin, and the crystalline phase includes a polycrystalline oxide phase containing at least one of tungsten and zinc and tin. The oxide sintered body of the present embodiment includes a tungsten oxide film and a polycrystalline oxide crystal phase of at least one of zinc and tin as a crystal phase. Therefore, the oxide semiconductor film formed using the oxide sintered body is used as a channel. In a semiconductor device of a layer, that is, a TFT (Thin Film Transistor), the OFF current can be lowered, and the ratio of the ON current to the OFF current can be increased with a lower driving voltage. Further, the thermal conductivity of the oxide sintered body can be increased.

本實施形態之氧化物燒結體可進而包括方鐵錳礦型相作為結晶相。藉此，於包含使用該氧化物燒結體而形成之氧化物半導體膜作為通道層之半導體裝置即TFT中，可使其OFF電流降低，並且可以較低之驅動電壓提高ON電流相對於OFF電流之比。又，可提高氧化物燒結體之導熱率。 The oxide sintered body of the present embodiment may further include a bixbyite type phase as a crystal phase. Thereby, in the TFT which is a semiconductor device including the oxide semiconductor film formed using the oxide sintered body as the channel layer, the OFF current can be lowered, and the lower driving voltage can be used to increase the ON current with respect to the OFF current. ratio. Further, the thermal conductivity of the oxide sintered body can be increased.

於本實施形態之氧化物燒結體包括包含鎢、與鋅及錫之至少1種之多氧化物結晶相及方鐵錳礦型相作為結晶相之情形時，可使氧化物燒結體之一剖面中多氧化物結晶相及方鐵錳礦型相之合計面積相對於該剖面之面積的佔有率即雙相佔有率為95%以上且100%以下。藉此，於包含使用該氧化物燒結體而形成之氧化物半導體膜作為通道層之半導體裝置即TFT中，可使其OFF電流降低，且以較低之驅動電壓提高ON電流相對於OFF電流之比，並且可減少其特性之主面內之不均。又，可提高氧化物燒結體之導熱率。 When the oxide sintered body of the present embodiment includes tungsten, a polycrystalline oxide phase of at least one of zinc and tin, and a bixbyite phase as a crystal phase, the oxide sintered body can be partially cross-sectioned. The ratio of the total area of the polycrystalline crystalline phase and the bixbyite type phase to the area of the cross section, that is, the two-phase occupancy rate is 95% or more and 100% or less. Thereby, in the TFT which is a semiconductor device including the oxide semiconductor film formed using the oxide sintered body as the channel layer, the OFF current can be lowered, and the ON current can be increased with respect to the OFF current with a lower driving voltage. Ratio, and can reduce the unevenness in the main face of its characteristics. Further, the thermal conductivity of the oxide sintered body can be increased.

於本實施形態之氧化物燒結體中，可使氧化物燒結體之一剖面中 包含鎢、與鋅及錫之至少1種之多氧化物結晶相之面積相對於該剖面之面積的佔有率即多氧化物結晶相佔有率為大於0%且為50%以下。藉此，於包含使用該氧化物燒結體而形成之氧化物半導體膜作為通道層之半導體裝置即TFT中，可使其OFF電流降低，且以較低之驅動電壓提高ON電流相對於OFF電流之比，並且可減少其特性之主面內之不均。又，可提高氧化物燒結體之導熱率。 In the oxide sintered body of the present embodiment, one of the oxide sintered bodies can be formed in a cross section. The occupation ratio of the area of the polycrystalline oxide crystal phase containing at least one of tungsten, zinc, and tin to the area of the cross section is more than 0% and 50% or less. Thereby, in the TFT which is a semiconductor device including the oxide semiconductor film formed using the oxide sintered body as the channel layer, the OFF current can be lowered, and the ON current can be increased with respect to the OFF current with a lower driving voltage. Ratio, and can reduce the unevenness in the main face of its characteristics. Further, the thermal conductivity of the oxide sintered body can be increased.

於本實施形態之氧化物燒結體中，多氧化物結晶相可包含選自由ZnWO₄型相、Zn₂W₃O₈型相、WSnO₄型相、WSn₂O₅型相、及WSn₃O₆型相所組成之群中之至少1種結晶相。藉此，於包含使用該氧化物燒結體而形成之氧化物半導體膜作為通道層之半導體裝置即TFT中，可使其OFF電流降低，並且可以較低之驅動電壓提高ON電流相對於OFF電流之比。又，可提高氧化物燒結體之導熱率。 In the oxide sintered body of the present embodiment, the polycrystalline oxide phase may include a selected from the group consisting of a ZnWO ₄ type phase, a Zn ₂ W ₃ O ₈ type phase, a WSnO ₄ type phase, a WSn ₂ O ₅ type phase, and WSn ₃ O. crystal phase of at least one of the group consisting of _6-phase type. Thereby, in the TFT which is a semiconductor device including the oxide semiconductor film formed using the oxide sintered body as the channel layer, the OFF current can be lowered, and the lower driving voltage can be used to increase the ON current with respect to the OFF current. ratio. Further, the thermal conductivity of the oxide sintered body can be increased.

於本實施形態之氧化物燒結體中，可使鎢相對於氧化物燒結體中所含之全部金屬元素及矽之含有率為0.5原子%以上且20原子%以下。藉此，於包含使用該氧化物燒結體而形成之氧化物半導體膜作為通道層之半導體裝置即TFT中，可以較低之驅動電壓提高ON電流相對於OFF電流之比。又，可提高氧化物半導體膜之成膜速度。 In the oxide sintered body of the present embodiment, the content of all the metal elements and antimony contained in the tungsten relative to the oxide sintered body is 0.5 atom% or more and 20 atom% or less. Thereby, in the TFT which is a semiconductor device including the oxide semiconductor film formed using the oxide sintered body as the channel layer, the ratio of the ON current to the OFF current can be increased with a lower driving voltage. Further, the film formation rate of the oxide semiconductor film can be increased.

於本實施形態之氧化物燒結體中，可使選自由鋁、鈦、鉻、鎵、鉿、鋯、矽、鉬、釩、鈮、鉭、及鉍所組成之群中之至少1種元素相對於氧化物燒結體中所含之全部金屬元素及矽的含有率為0.1原子%以上且10原子%以下。藉此，於包含使用該氧化物燒結體而形成之氧化物半導體膜作為通道層之半導體裝置即TFT中，可使其OFF電流降低，並且可以較低之驅動電壓提高ON電流相對於OFF電流之比。 In the oxide sintered body of the present embodiment, at least one element selected from the group consisting of aluminum, titanium, chromium, gallium, lanthanum, zirconium, hafnium, molybdenum, vanadium, niobium, tantalum, and niobium may be relatively The content of all the metal elements and cerium contained in the oxide sintered body is 0.1 atom% or more and 10 atom% or less. Thereby, in the TFT which is a semiconductor device including the oxide semiconductor film formed using the oxide sintered body as the channel layer, the OFF current can be lowered, and the lower driving voltage can be used to increase the ON current with respect to the OFF current. ratio.

本發明之另一實施形態即半導體裝置係包含使用上述實施形態之氧化物燒結體作為靶利用濺鍍法所形成之氧化物半導體膜的半導體裝置。本實施形態之半導體裝置由於包含使用上述實施形態之氧化物 燒結體作為靶利用濺鍍法所形成的氧化物半導體膜，故而具有較高之特性。 A semiconductor device according to another embodiment of the present invention includes a semiconductor device using the oxide sintered body of the above-described embodiment as an oxide semiconductor film formed by sputtering. The semiconductor device of the present embodiment includes the oxide of the above embodiment. Since the sintered body is used as a target by an oxide semiconductor film formed by a sputtering method, it has high characteristics.

<本發明之實施形態之詳細內容> <Details of Embodiment of the Present Invention>

[實施形態1：氧化物燒結體] [Embodiment 1: Oxide sintered body]

本發明之一實施形態即氧化物燒結體係包含銦、鎢、與鋅及錫之至少1種者，且作為結晶相，包括包含鎢、與鋅及錫之至少1種之多氧化物結晶相。本實施形態之氧化物燒結體由於包括包含鎢、與鋅及錫之至少1種之多氧化物結晶相作為結晶相，因此，於包含使用該氧化物燒結體而形成之氧化物半導體膜作為通道層之半導體裝置即TFT(薄膜電晶體)中，可使其OFF電流降低，並且可以較低之驅動電壓提高ON電流相對於OFF電流之比。又，可提高氧化物燒結體之導熱率。 In one embodiment of the present invention, the oxide sintering system includes at least one of indium, tungsten, and zinc and tin, and the crystalline phase includes a polycrystalline oxide phase containing at least one of tungsten and zinc and tin. The oxide sintered body of the present embodiment includes a tungsten oxide film and a polycrystalline oxide crystal phase of at least one of zinc and tin as a crystal phase. Therefore, the oxide semiconductor film formed using the oxide sintered body is used as a channel. In a semiconductor device of a layer, that is, a TFT (Thin Film Transistor), the OFF current can be lowered, and the ratio of the ON current to the OFF current can be increased with a lower driving voltage. Further, the thermal conductivity of the oxide sintered body can be increased.

(含有In、W、與Zn及Sn之至少1種) (containing at least one of In, W, and Zn, and Sn)

本實施形態之氧化物燒結體就於包含使用其而形成之氧化物半導體膜作為通道層之半導體裝置即TFT(薄膜電晶體)中使OFF電流降低，且以較低之驅動電壓提高ON電流相對於OFF電流之比，並且提高氧化物燒結體之導熱率之觀點而言，較佳為包含In(銦)、W(鎢)、與Zn(鋅)及Sn(錫)之至少1種，且以In為主成分。此處，所謂主成分，係指相對於本實施形態之氧化物燒結體中所含之金屬元素及Si(矽)，In之含有率為50原子%以上。 The oxide sintered body of the present embodiment lowers the OFF current in a TFT (Thin Film Transistor) which is a semiconductor device including the oxide semiconductor film formed using the oxide semiconductor film as a channel layer, and increases the ON current with a lower driving voltage. From the viewpoint of the ratio of the OFF current and the thermal conductivity of the oxide sintered body, it is preferable to contain at least one of In (indium), W (tungsten), Zn (zinc), and Sn (tin), and In is the main component. Here, the main component is a metal element and Si (yttrium) contained in the oxide sintered body of the present embodiment, and the content of In is 50 atom% or more.

(多氧化物結晶相) (multi-oxide crystalline phase)

本實施形態之氧化物燒結體就於包含使用其而形成之氧化物半導體膜作為通道層之半導體裝置即TFT(薄膜電晶體)中使OFF電流降低，且以較低之驅動電壓提高ON電流相對於OFF電流之比，並且提高氧化物燒結體之導熱率之觀點而言，包括包含W、與Zn及Sn之至少1種之多氧化物結晶相作為結晶相。 The oxide sintered body of the present embodiment lowers the OFF current in a TFT (Thin Film Transistor) which is a semiconductor device including the oxide semiconductor film formed using the oxide semiconductor film as a channel layer, and increases the ON current with a lower driving voltage. From the viewpoint of the ratio of the OFF current and the improvement of the thermal conductivity of the oxide sintered body, a polycrystalline oxide crystal phase containing at least one of W and Zn and Sn is included as a crystal phase.

多氧化物結晶相就於包含使用包含其之氧化物燒結體而形成之 氧化物半導體膜作為通道層之半導體裝置即TFT(薄膜電晶體)中使OFF電流降低，且以較低之驅動電壓提高ON電流相對於OFF電流之比，並且提高氧化物燒結體之導熱率之觀點而言，較佳為包含選自由ZnWO₄型相、Zn₂W₃O₈型相、WSnO₄型相、WSn₂O₅型相、及WSn₃O₆型相所組成之群中之至少1種結晶相。該多氧化物結晶相係藉由X射線繞射測定進行鑑定。 The polycrystalline oxide phase lowers the OFF current in a TFT (Thin Film Transistor) which is a semiconductor device including a oxide semiconductor film formed using the oxide sintered body containing the oxide sintered body, and is improved at a lower driving voltage. From the viewpoint of the ratio of the ON current to the OFF current and the thermal conductivity of the oxide sintered body, it is preferable to include a layer selected from the group consisting of a ZnWO ₄ type phase, a Zn ₂ W ₃ O ₈ type phase, a WSnO ₄ type phase, and WSn _{2 .} At least one crystal phase of the group consisting of the O ₅ type phase and the WSn ₃ O ₆ type phase. The polycrystalline crystalline phase was identified by X-ray diffraction measurements.

ZnWO₄型相係指ZnWO₄相、於ZnWO₄相之一部分包含In、W及Zn以外之金屬元素及Si之至少1種之相、及於該等相中氧缺失一部分或過剩之相，為具有與ZnWO₄相同樣之晶體結構之相之總稱。Zn₂W₃O₈型相係指Zn₂W₃O₈相、於Zn₂W₃O₈相之一部分包含In、W及Zn以外之金屬元素及Si之至少1種之相、及於該等相中氧缺失一部分或過剩之相，為具有與Zn₂W₃O₈相同樣之晶體結構之相之總稱。WSnO₄型相係指WSnO₄相、於WSnO₄相之一部分包含In、W及Sn以外之金屬元素及Si之至少1種之相、及於該等相中氧缺失一部分或過剩之相，為具有與WSnO₄相同樣之晶體結構之相之總稱。WSn₂O₅型相係指WSn₂O₅相、於WSn₂O₅相之一部分包含In、W及Sn以外之金屬元素及Si之至少1種之相、及於該等相中氧缺失一部分或過剩之相，為具有與WSn₂O₅相同樣之晶體結構之相之總稱。WSn₃O₆型相係指WSn₃O₆相、於WSn₃O₆相之一部分包含In、W及Sn以外之金屬元素及Si之至少1種之相、及於該等相中氧缺失一部分或過剩之相，為具有與WSn₃O₆相同樣之晶體結構之相之總稱。該等多氧化物結晶相既可存在一者，亦可存在複數者。 ZnWO ₄ means ZnWO ₄ phase-phase, phase portion in ZnWO ₄ containing a metal element other than the In, W, and Zn, and at least one kind of phase of Si, and oxygen to such phase or deletion of a portion of excess phase, as A general term for phases having the same crystal structure as the ZnWO ₄ phase. The Zn ₂ W ₃ O ₈ phase means a Zn ₂ W ₃ O ₈ phase, and a phase containing at least one of a metal element other than In, W, and Zn and at least one of Si in a part of the Zn ₂ W ₃ O ₈ phase, and A part of the oxygen phase in which the oxygen is missing or a surplus phase is a general term for the phase having the same crystal structure as the Zn ₂ W ₃ O ₈ phase. The WSnO ₄ type phase refers to a WSnO ₄ phase, a phase containing at least one of a metal element other than In, W, and Sn and Si in one of the WSnO ₄ phases, and a phase in which a part of the oxygen is missing or excess in the phase. A general term for phases having the same crystal structure as WSnO ₄ . The WSn ₂ O ₅ type phase refers to a WSn ₂ O ₅ phase, a metal element other than In, W, and Sn and a phase of at least one of Si in a part of the WSn ₂ O ₅ phase, and a part of oxygen in the phase Or the excess phase is a general term for the phase having the same crystal structure as the WSn ₂ O ₅ phase. The WSn ₃ O ₆ type phase refers to a WSn ₃ O ₆ phase, a metal element other than In, W, and Sn and a phase of at least one of Si in a part of the WSn ₃ O ₆ phase, and a part of oxygen in the phase or excess of the phase, having the generic name WSn ₃ O ₆ phase of a crystal structure of the same phase. The plurality of oxide crystal phases may exist in one or plural.

此處，ZnWO₄相具有以空間群P12/c1(13)表示之晶體結構，為具有JCPDS Card之01-088-0251所規定之晶體結構之鎢酸鋅化合物結晶相。Zn₂W₃O₈相具有以空間群P63mc(186)表示之晶體結構，為C.R.Seances Acad.Sci.(Ser.C),1970,pp271-136所揭示之鎢酸鋅化合物結晶相。WSnO₄結晶相具有以空間群Pnna(52)表示之晶體結構，為具有 JCPDS Card之01-070-1049所規定之晶體結構之鎢酸錫化合物結晶相。WSn₂O₅相具有以空間群P121/c1(14)表示之晶體結構，為Inorg.Chem.,(2007),46,pp7005-7011所揭示之鎢酸錫化合物結晶相。WSn₃O₆相具有以空間群C12/c1(15)表示之晶體結構，為Inorg.Chem.,(2007),46,pp7005-7011所揭示之鎢酸錫化合物結晶相。 Here, the ZnWO ₄ phase has a crystal structure represented by a space group P12/c1 (13), and is a crystal phase of a zinc tungstate compound having a crystal structure defined by 01-088-0251 of JCPDS Card. The Zn ₂ W ₃ O ₈ phase has a crystal structure represented by a space group P63mc (186) and is a crystal phase of a zinc tungstate compound disclosed in CR Seances Acad. Sci. (Ser. C), 1970, pp 271-136. The WSnO ₄ crystal phase has a crystal structure represented by a space group Pnna (52) and is a crystal phase of a tin tungstate compound having a crystal structure as defined by J-07DS Card 01-070-1049. The WSn ₂ O ₅ phase has a crystal structure represented by a space group P121/c1 (14), which is a crystal phase of a tin tungstate compound disclosed by Inorg. Chem., (2007), 46, pp 7005-7011. The WSn ₃ O ₆ phase has a crystal structure represented by a space group C12/c1 (15), and is a crystal phase of a tin tungstate compound disclosed by Inorg. Chem., (2007), 46, pp 7005-7011.

又，所謂於ZnWO₄相、Zn₂W₃O₈相、WSnO₄相、WSn₂O₅相、及WSn₃O₆相中之任一相之一部分包含構成該等多氧化物結晶相以外之金屬元素及Si之至少1種的相，亦可為於ZnWO₄相、Zn₂W₃O₈相、WSnO₄相、WSn₂O₅相、及WSn₃O₆相中之任一相之一部分固溶有構成該等多氧化物結晶相以外之金屬元素及Si之至少1種的晶體結構，例如，構成上述多氧化物結晶相以外之金屬元素及Si之至少1種既可固溶置換於ZnWO₄相、Zn₂W₃O₈相、WSnO₄相、WSn₂O₅相、及WSn₃O₆相中之任一相之W部位、及/或Zn部位或Sn部位之一部分，亦可***至ZnWO₄相、Zn₂W₃O₈相、WSnO₄相、WSn₂O₅相、及WSn₃O₆相中之任一相之晶格間。 Further, one of the ZnWO ₄ phase, the Zn ₂ W ₃ O ₈ phase, the WSnO ₄ phase, the WSn ₂ O ₅ phase, and the WSn ₃ O ₆ phase includes a portion other than the polycrystalline oxide phase. At least one of a metal element and Si may be a part of any one of a ZnWO ₄ phase, a Zn ₂ W ₃ O ₈ phase, a WSnO ₄ phase, a WSn ₂ O ₅ phase, and a WSn ₃ O ₆ phase. A crystal structure constituting at least one of a metal element other than the polycrystalline oxide phase and Si is solid-solved, and for example, at least one of a metal element other than the polycrystalline oxide phase and Si may be solid-dissolved and replaced. The W portion of the ZnWO ₄ phase, the Zn ₂ W ₃ O ₈ phase, the WSnO ₄ phase, the WSn ₂ O ₅ phase, and the WSn ₃ O ₆ phase, and/or one of the Zn site or the Sn site may also be Inserted between the crystal lattices of any of the ZnWO ₄ phase, the Zn ₂ W ₃ O ₈ phase, the WSnO ₄ phase, the WSn ₂ O ₅ phase, and the WSn ₃ O ₆ phase.

(方鐵錳礦型相) (square iron manganese type phase)

於本實施形態之氧化物燒結體中，就於包含使用其而形成之氧化物半導體膜作為通道層之半導體裝置即TFT中使OFF電流降低，且以較低之驅動電壓提高ON電流相對於OFF電流之比，並且提高氧化物燒結體之導熱率之觀點而言，較佳為進而包含方鐵錳礦型相作為結晶相。 In the oxide sintered body of the present embodiment, the OFF current is lowered in the TFT which is a semiconductor device including the oxide semiconductor film formed using the oxide semiconductor film as the channel layer, and the ON current is increased with respect to the lower driving voltage. From the viewpoint of the ratio of the current and the increase in the thermal conductivity of the oxide sintered body, it is preferred to further contain a bixbyite type phase as a crystal phase.

方鐵錳礦型相係指方鐵錳礦相、以及於方鐵錳礦相之一部分包含In及W以外之金屬元素及Si之至少1種之相，為具有與方鐵錳礦相同樣之晶體結構者之總稱。方鐵錳礦型相係藉由X射線繞射測定進行鑑定。此處，方鐵錳礦相係氧化銦(In₂O₃)之結晶相之1種，係指JCPDS Card之6-0416所規定之晶體結構，亦稱為稀土類氧化物C型相(或C-稀土結構相)。又，於方鐵錳礦相之一部分包含In及W以外之金屬元素及Si之至少1種之相亦可為於方鐵錳礦相之一部分固溶有In及W以外之金屬 元素及Si之至少1種之晶體結構。 The bixbyite type phase system refers to a bixbyite phase, and a phase containing at least one of a metal element other than In and W and a part of Si in the side of the bixbyite phase, and is a crystal structure having the same crystal structure as the bixbyite phase. General name. The bixbyite type phase was identified by X-ray diffraction measurement. Here, the crystal phase of the indium oxide (In ₂ O ₃ ) phase of the bixbyite phase refers to the crystal structure specified in J04DS Card 6-0416, also known as the rare earth oxide C type phase (or C). - rare earth structural phase). Further, at least one of the metal elements other than In and W and the phase of Si may be one of the metal elements other than In and W and at least one of Si in one part of the side of the ferromanganese ore phase. The crystal structure of the species.

(多氧化物結晶相佔有率) (multi-oxide crystal phase occupancy rate)

於本實施形態之氧化物燒結體中，就於包含使用其而形成之氧化物半導體膜作為通道層之半導體裝置即TFT(薄膜電晶體)中使OFF電流降低，且以較低之驅動電壓提高ON電流相對於OFF電流之比，並且提高氧化物燒結體之導熱率之觀點而言，氧化物燒結體之一剖面中包含鎢、與鋅及錫之至少1種之多氧化物結晶相之面積相對於該剖面之面積的佔有率即多氧化物結晶相佔有率較佳為大於0%且為50%以下，更佳為0.5%以上且30%以下，進而較佳為0.5%以上且15%以下。 In the oxide sintered body of the present embodiment, the OFF current is lowered in the TFT (thin film transistor) which is a semiconductor device including the oxide semiconductor film formed using the oxide semiconductor film as the channel layer, and the driving voltage is lowered with a lower driving voltage. From the viewpoint of the ratio of the ON current to the OFF current and the thermal conductivity of the oxide sintered body, the cross section of the oxide sintered body includes an area of tungsten, a polycrystalline oxide phase of at least one of zinc and tin. The occupancy ratio of the area of the cross section, that is, the polycrystalline oxide crystal phase occupancy ratio is preferably more than 0% and not more than 50%, more preferably 0.5% or more and 30% or less, further preferably 0.5% or more and 15%. the following.

多氧化物結晶相佔有率係以如下方式算出。首先，使用附帶能量分散型螢光X射線分析儀之掃描型二次電子顯微鏡(SEM-EDX)，利用SEM觀察經鏡面拋光加工之氧化物燒結體之剖面，利用EDX分析各相之組成。利用X射線繞射測定之θ-2θ法鑑定各相之晶體結構。藉由X射線繞射測定所鑑定之各相係金屬元素之組成比率不同。氧化物燒結體之相間之金屬元素之組成比率之差異與利用上述EDX所分析之相間之組成比率之差異的傾向一致。例如，於在X射線繞射測定中鑑定到In₂O₃相、WSn₂O₅相、及WSn₃O₆相之情形時，利用EDX之分析中，In₂O₃相中In比率(例如In/(In+W+Sn))變高，WSn₂O₅相及WSn₃O₆相中，W比率(例如W/(In+W+Sn))及/或Sn之比率(例如Sn/(In+W+Sn))變高。可利用SEM-EDX求出各燒結粉末之金屬比率，將In比率較高之區域判斷為In₂O₃相，將W比率及/或Sn比率變高之區域判斷為WSn₂O₅相及WSn₃O₆相。 The polycrystalline crystalline phase occupancy ratio was calculated as follows. First, a cross section of the mirror-polished oxide sintered body was observed by SEM using a scanning secondary electron microscope (SEM-EDX) equipped with an energy dispersive fluorescent X-ray analyzer, and the composition of each phase was analyzed by EDX. The crystal structure of each phase was identified by the θ-2θ method of X-ray diffraction measurement. The composition ratio of each phase metal element identified by X-ray diffraction measurement is different. The difference in the composition ratio of the metal elements between the phases of the oxide sintered body is consistent with the tendency of the difference in the composition ratio between the phases analyzed by the above EDX. For example, in the case where the In ₂ O ₃ phase, the WSn ₂ O ₅ phase, and the WSn ₃ O ₆ phase are identified in the X-ray diffraction measurement, the In ratio in the In ₂ O ₃ phase in the analysis by EDX (for example) In/(In+W+Sn)) becomes high, in the WSn ₂ O ₅ phase and the WSn ₃ O ₆ phase, the ratio of the W ratio (for example, W/(In+W+Sn)) and/or Sn (for example, Sn/ (In+W+Sn)) becomes high. Can be determined by using SEM-EDX ratio of each sintered powder metal, the higher the In ratio of the region is determined relative to In ₂ O _3, and the ratio W / Sn ratio is high or the region is determined relative to WSn ₂ O ₅ and WSn ₃ O ₆ phase.

(多氧化物結晶相及方鐵錳礦型相之雙相佔有率) (Double-phase occupancy of polycrystalline oxide phase and bixbyite type phase)

於本實施形態之氧化物燒結體包含多氧化物結晶相及方鐵錳礦型相作為結晶相之情形時，就於包含使用氧化物燒結體而形成之氧化物半導體膜作為通道層之半導體裝置即TFT中使OFF電流降低，且以較 低之驅動電壓提高ON電流相對於OFF電流之比，減少其特性之主面內之不均，並且提高氧化物燒結體之導熱率之觀點而言，氧化物燒結體之一剖面中多氧化物結晶相及方鐵錳礦型相之合計面積相對於該剖面之面積的佔有率即雙相佔有率較佳為95%以上且100%以下，更佳為98%以上且100%以下。 In the case where the oxide sintered body of the present embodiment includes a polycrystalline oxide phase and a bixbyite phase as a crystal phase, the semiconductor device including the oxide semiconductor film formed using the oxide sintered body as a channel layer is a semiconductor device. The OFF current is lowered in the TFT, and The low driving voltage increases the ratio of the ON current to the OFF current, reduces the unevenness in the main surface of the characteristic, and increases the thermal conductivity of the oxide sintered body. The occupancy ratio of the total area of the crystal phase and the bixbyite type phase to the area of the cross section, that is, the two-phase occupancy rate is preferably 95% or more and 100% or less, more preferably 98% or more and 100% or less.

此處，由於氧化物燒結體之方鐵錳礦型相之面積之佔有率係以與多氧化物結晶相之面積相對於氧化物燒結體之剖面之面積的佔有率即多氧化物結晶相佔有率同樣之方法算出，因此，多氧化物結晶相及方鐵錳礦型相之合計面積相對於剖面面積的佔有率即雙相佔有率係以與多氧化物結晶相之面積相對於氧化物燒結體之剖面面積之佔有率即多氧化物結晶相佔有率同樣之方法算出。 Here, the occupancy ratio of the area of the bixbyite type phase of the oxide sintered body is the occupancy ratio of the area of the polycrystalline oxide crystal phase to the area of the cross section of the oxide sintered body, that is, the polycrystalline oxide crystal phase occupation ratio. In the same manner, the ratio of the total area of the polycrystalline oxide phase and the bixbyite phase to the cross-sectional area, that is, the two-phase occupancy, is based on the area of the polycrystalline oxide phase with respect to the oxide sintered body. The occupation ratio of the cross-sectional area, that is, the occupancy rate of the polycrystalline oxide phase is calculated in the same manner.

(鎢含有率) (tungsten content)

於本實施形態之氧化物燒結體中，就於包含使用其而形成之氧化物半導體膜作為通道層之半導體裝置即TFT中，以較低之驅動電壓提高ON電流相對於OFF電流之比，並且提高氧化物半導體膜之成膜速度之觀點而言，鎢相對於氧化物燒結體中所含之全部金屬元素及Si之含有率較佳為0.5原子%以上且20原子%以下，更佳為0.5原子%以上且10原子%以下，進而較佳為7原子%以上且10原子%以下。 In the oxide sintered body of the present embodiment, in the TFT which is a semiconductor device including the oxide semiconductor film formed using the oxide semiconductor film as the channel layer, the ratio of the ON current to the OFF current is increased with a lower driving voltage, and From the viewpoint of increasing the film formation rate of the oxide semiconductor film, the content of all metal elements and Si contained in the oxide sintered body is preferably 0.5 atom% or more and 20 atom% or less, more preferably 0.5. The atomic % or more and 10 atomic % or less are further preferably 7 atomic % or more and 10 atomic % or less.

此處，氧化物燒結體中之W等金屬元素或Si之含量係藉由ICP(電感耦合電漿)質量分析進行測定。鎢含有率係W之含量相對於氧化物燒結體中之全部金屬元素及Si之合計含量之百分率。 Here, the content of a metal element such as W or Si in the oxide sintered body is measured by mass spectrometry of ICP (inductively coupled plasma). The percentage of the tungsten content rate W to the total content of all the metal elements and Si in the oxide sintered body.

(金屬元素及Si之含有率) (Metal element and Si content rate)

就於包含使用本實施形態之氧化物燒結體而形成之氧化物半導體膜作為通道層之半導體裝置即TFT中使OFF電流降低，並且以較低之驅動電壓提高ON電流相對於OFF電流之比之觀點而言，選自由Al(鋁)、Ti(鈦)、Cr(鉻)、Ga(鎵)、Hf(鉿)、Zr(鋯)、Si(矽)、Mo(鉬)、 V(釩)、Nb(鈮)、Ta(鉭)、及Bi(鉍)所組成之群中之至少1種元素相對於氧化物燒結體中所含之全部金屬元素及Si(矽)之含有率較佳為0.1原子%以上且10原子%以下，更佳為0.1原子%以上且5原子%以下，進而較佳為0.1原子%以上且1原子%以下。 In the TFT which is a semiconductor device including the oxide semiconductor film formed using the oxide sintered body of the present embodiment as a channel layer, the OFF current is lowered, and the ratio of the ON current to the OFF current is increased with a lower driving voltage. From the viewpoint, it is selected from the group consisting of Al (aluminum), Ti (titanium), Cr (chromium), Ga (gallium), Hf (yttrium), Zr (zirconium), Si (germanium), Mo (molybdenum), The inclusion of at least one element of the group consisting of V (vanadium), Nb (铌), Ta (钽), and Bi (铋) with respect to all metal elements and Si (矽) contained in the oxide sintered body The rate is preferably 0.1 atom% or more and 10 atom% or less, more preferably 0.1 atom% or more and 5 atom% or less, still more preferably 0.1 atom% or more and 1 atom% or less.

此處，於Al、Ti、Cr、Ga、Hf、Si、V、及Nb之至少1種元素之含有率為0.1原子%以上時，有包含使用該氧化物燒結體而獲得之氧化物半導體的半導體裝置之OFF電流變低之效果，但若該元素之含有率大於10原子%，則有半導體裝置之ON電流變低之傾向。 When the content ratio of at least one element of Al, Ti, Cr, Ga, Hf, Si, V, and Nb is 0.1 atom% or more, the oxide semiconductor obtained by using the oxide sintered body is included. The effect of the OFF current of the semiconductor device is low. However, if the content of the element is more than 10 atom%, the ON current of the semiconductor device tends to be low.

又，於Zr、Mo、Ta、及Bi之至少1種元素之含有率為0.1原子%以上時，有包含使用該氧化物燒結體而獲得之氧化物半導體的半導體裝置之ON電流變高之效果，但若該元素之含有率大於10原子%，則有半導體裝置之OFF電流變高之傾向。 In addition, when the content of at least one element of Zr, Mo, Ta, and Bi is 0.1 atom% or more, the ON current of the semiconductor device including the oxide semiconductor obtained by using the oxide sintered body is increased. However, if the content of the element is more than 10 atom%, the OFF current of the semiconductor device tends to increase.

使用本實施形態之氧化物燒結體而形成之氧化物半導體膜由於用作半導體裝置之半導體層，因此較理想為電阻率高於作為透明導電膜所期待之電阻率。具體而言，使用本實施形態之氧化物燒結體而形成之氧化物半導體膜較佳為電阻率為1×10^-4Ωcm以上。為此，氧化物燒結體中可含之Si之含有率以Si/In原子數比計較佳為小於0.007，又，氧化物燒結體中可含之Ti之含有率以Ti/In原子數比計較佳為小於0.004。 Since the oxide semiconductor film formed using the oxide sintered body of the present embodiment is used as a semiconductor layer of a semiconductor device, it is preferable that the specific resistance is higher than that expected as a transparent conductive film. Specifically, the oxide semiconductor film formed by using the oxide sintered body of the present embodiment preferably has a specific resistance of 1 × 10 ^-4 Ωcm or more. For this reason, the content of Si which may be contained in the oxide sintered body is preferably less than 0.007 in terms of the atomic ratio of Si/In, and the content of Ti contained in the oxide sintered body is calculated by the ratio of Ti/In atomic ratio. Good is less than 0.004.

氧化物半導體膜之電阻率係藉由四端子法進行測定。利用濺鍍法形成Mo電極作為電極材，一面對外側之電極彼此掃描-40V~+40V之電壓而使電流流過，一面測定內側之電極間之電壓，算出電阻值。 The resistivity of the oxide semiconductor film was measured by a four-terminal method. A Mo electrode was formed as an electrode material by a sputtering method, and a voltage of -40 V to +40 V was applied to the electrodes facing the outside to cause a current to flow, and the voltage between the electrodes on the inner side was measured to calculate a resistance value.

(氧化物燒結體之製造方法) (Manufacturing method of oxide sintered body)

本實施形態之氧化物燒結體之製造方法並無特別限制，但就高效率地進行製造之觀點而言，包括：製備原料粉末之混合物之步驟、對混合物進行煅燒之步驟、使煅燒粉末成形之步驟、及對成形體進行燒 結之步驟。 The method for producing the oxide sintered body of the present embodiment is not particularly limited. However, from the viewpoint of efficient production, the method includes the steps of: preparing a mixture of raw material powders, calcining the mixture, and forming the calcined powder. Step and burning the shaped body The steps to conclude.

1.準備原料粉末之步驟 1. Steps of preparing raw material powder

作為氧化物燒結體之原料粉末，準備氧化銦粉末(例如In₂O₃粉末)、氧化鎢粉末(例如WO₃粉末)、氧化鋅粉末(例如ZnO粉末)、氧化錫粉末(例如SnO₂粉末)等構成氧化物燒結體之金屬元素及Si之氧化物粉末。再者，作為氧化鎢粉末，使用如WO_2.72粉末、WO_2.0粉末所表示之具有與WO₃粉末相比缺失氧之化學組成之粉末作為原料就獲得較高之導熱率方面而言，更為理想。就防止非刻意之金屬元素及Si向氧化物燒結體之混入而獲得穩定物性之觀點而言，原料粉末之純度較佳為99.9質量%以上之高純度。 As a raw material powder of the oxide sintered body, an indium oxide powder (for example, In ₂ O ₃ powder), a tungsten oxide powder (for example, WO ₃ powder), a zinc oxide powder (for example, ZnO powder), or a tin oxide powder (for example, SnO ₂ powder) are prepared. The metal element constituting the oxide sintered body and the oxide powder of Si. Note that, as tungsten oxide powder, a powder used as WO _2.72, WO _2.0 represents the powder having a WO ₃ powder absence of oxygen compared to the chemical composition of the powder as a raw material of high thermal conductivity is obtained in terms of rates, more preferably . The purity of the raw material powder is preferably 99.9% by mass or more, from the viewpoint of preventing the incorporation of unintentional metal elements and Si into the oxide sintered body to obtain stable physical properties.

2.製備原料粉末之一次混合物之步驟 2. Step of preparing a primary mixture of raw material powders

首先，將上述原料粉末中之WO_2.72粉末或WO_2.0粉末、ZnO粉末、SnO₂粉末等氧化物粉末即原料粉末粉碎混合。此時，作為氧化物燒結體之結晶相，於欲獲得ZnWO₄型相之情形時，將WO_2.72粉末或WO_2.0粉末與ZnO粉末以按莫耳比計1：1之比率混合作為原料粉末，於欲獲得Zn₂W₃O₈型相之情形時，將WO_2.72粉末或WO_2.0粉末與ZnO粉末以按莫耳比計3：2之比率混合作為原料粉末，於欲獲得WSnO₄型相之情形時，將WO_2.72粉末或WO_2.0粉末與SnO₂粉末以按莫耳比計1：1之比率混合作為原料粉末，於欲獲得WSn₂O₅型相之情形時，將WO_2.72粉末或WO_2.0粉末與SnO₂粉末以按莫耳比計1：2之比率混合作為原料粉末，於欲獲得WSn₃O₆型相之情形時，將WO_2.72粉末或WO_2.0粉末與SnO₂粉末以按莫耳比計1：3之比率混合作為原料粉末。對於將原料粉末粉碎混合之方法，並無特別限制，可為乾式及濕式中之任一種方式，具體而言，利用球磨機、行星式球磨機、珠磨機等將原料粉末粉碎混合。以此方式，獲得原料粉末之一次混合物。此處，利用濕式之粉碎混合方式而獲得之混合物之乾燥可較佳地利用自然乾燥或噴霧乾燥器等乾燥 方法。 First, the WO _2.72 powder or the oxide powder such as WO _2.0 powder, ZnO powder or SnO ₂ powder, which is the raw material powder, is pulverized and mixed. At this time, as a crystal phase of the oxide sintered body, when a ZnWO ₄ type phase is to be obtained, WO _2.72 powder or WO _2.0 powder and ZnO powder are mixed as a raw material powder at a ratio of 1:1 in molar ratio. In the case where a Zn ₂ W ₃ O ₈ type phase is to be obtained, WO _2.72 powder or WO _2.0 powder and ZnO powder are mixed as a raw material powder in a ratio of 3:2 in molar ratio, in order to obtain a WSnO ₄ type phase. In the case, WO _2.72 powder or WO _2.0 powder and SnO ₂ powder are mixed as a raw material powder in a ratio of 1:1 by mole ratio, and in the case where a WSn ₂ O ₅ type phase is to be obtained, WO _2.72 powder or WO is used. _2.0 powder and SnO ₂ powder are mixed as a raw material powder at a ratio of 1:2 in molar ratio, and in the case where a WSn ₃ O ₆ type phase is to be obtained, WO _2.72 powder or WO _2.0 powder and SnO ₂ powder are pressed The ratio of the ear ratios of 1:3 was mixed as a raw material powder. The method of pulverizing and mixing the raw material powder is not particularly limited, and may be any of a dry type and a wet type. Specifically, the raw material powder is pulverized and mixed by a ball mill, a planetary ball mill, a bead mill or the like. In this way, a primary mixture of the raw material powders is obtained. Here, the drying of the mixture obtained by the wet pulverization mixing method can preferably be carried out by a drying method such as a natural drying or a spray dryer.

3.對一次混合物進行煅燒之步驟 3. The step of calcining a mixture

繼而，對所獲得之一次混合物進行煅燒。一次混合物之煅燒溫度並無特別限制，為了不使煅燒物之粒徑變得過大而燒結密度降低，較理想為未達1200℃，為了獲得作為結晶相之ZnWO₄型相、Zn₂W₃O₈型相、WSnO₄型相、WSn₂O₅型相、及/或WSn₃O₆型相作為煅燒物，較理想為500℃以上。為此，較佳為500℃以上且未達1000℃，更佳為550℃以上且900℃以下。以此方式，獲得包含作為結晶相之ZnWO₄型相、Zn₂W₃O₈型相、WSnO₄型相、WSn₂O₅型相、及/或WSn₃O₆型相之煅燒物。煅燒環境較佳為大氣環境、或含有25體積%以上氧氣之氧氣-氮氣混合環境。 Then, the obtained primary mixture is calcined. The calcination temperature of the primary mixture is not particularly limited, and the sintered density is lowered so as not to increase the particle diameter of the calcined product, preferably less than 1200 ° C, in order to obtain a ZnWO ₄ type phase as a crystal phase, Zn ₂ W ₃ O _The type ₈ phase, the WSnO ₄ type phase, the WSn ₂ O ₅ type phase, and/or the WSn ₃ O ₆ type phase are preferably used as a calcined product, and are preferably 500 ° C or higher. For this reason, it is preferably 500 ° C or more and less than 1000 ° C, more preferably 550 ° C or more and 900 ° C or less. In this manner, a calcined product containing a ZnWO ₄ type phase, a Zn ₂ W ₃ O ₈ type phase, a WSnO ₄ type phase, a WSn ₂ O ₅ type phase, and/or a WSn ₃ O ₆ type phase as a crystal phase is obtained. The calcination environment is preferably an atmospheric environment or an oxygen-nitrogen mixed environment containing 25% by volume or more of oxygen.

4.製備原料粉末之二次混合物之步驟 4. Step of preparing a secondary mixture of raw material powders

繼而，藉由與上述相同之粉碎混合之方法，將所獲得之煅燒物與上述原料粉末中之In₂O₃粉末粉碎混合。以此方式，獲得原料粉末之二次混合物。 Then, the obtained calcined product was pulverized and mixed with the In ₂ O ₃ powder in the above raw material powder by the same method of pulverization and mixing as described above. In this way, a secondary mixture of the raw material powders is obtained.

5.使二次混合物成形之步驟 5. Steps for shaping the secondary mixture

繼而，使所獲得之二次混合物成形。使二次混合物成形之方法並無特別限制，就提高燒結密度方面而言，較佳為單軸壓製法、CIP(冷均壓處理)法、流延法等。以此方式，獲得成形體。 Then, the obtained secondary mixture is shaped. The method of forming the secondary mixture is not particularly limited, and in terms of increasing the sintered density, a uniaxial pressing method, a CIP (cold equalizing treatment) method, a casting method, and the like are preferable. In this way, a shaped body is obtained.

6.對成形體進行燒結之步驟 6. Steps of sintering the shaped body

繼而，對所獲得之成形體進行燒結。成形體之燒結溫度並無特別限制，但就使燒結密度(指實際之燒結密度相對於理論密度之百分率)為90%以上而提高導熱率方面而言，較佳為1000℃以上且1500℃以下，更佳為1050℃以上且1200℃以下。又，燒結環境並無特別限制，但就防止氧化物燒結體之構成結晶之粒徑變大而防止龜裂產生方面、及導熱率提高方面而言，較佳為大氣壓-大氣環境、氧氣環境、氮氣- 氧氣混合環境等，特佳為大氣壓-大氣環境。以此方式，獲得本實施形態之氧化物燒結體。 Then, the obtained shaped body is sintered. The sintering temperature of the molded body is not particularly limited, but the sintered density (which is a percentage of the actual sintered density to the theoretical density) is 90% or more, and the thermal conductivity is preferably 1000 ° C or more and 1500 ° C or less. More preferably, it is 1050 ° C or more and 1200 ° C or less. In addition, the sintering environment is not particularly limited, but it is preferably an atmospheric pressure-atmosphere environment or an oxygen atmosphere in terms of preventing the particle size of the constituent crystal of the oxide sintered body from increasing, preventing the occurrence of cracks, and improving the thermal conductivity. Nitrogen - Oxygen mixed environment, etc., especially for atmospheric pressure - atmospheric environment. In this manner, the oxide sintered body of the present embodiment is obtained.

[實施形態2：半導體裝置] [Embodiment 2: Semiconductor device]

參照圖1，本發明之另一實施形態即半導體裝置10包含使用實施形態1之氧化物燒結體作為靶利用濺鍍法所形成的氧化物半導體膜14。本實施形態之半導體裝置由於包含使用上述實施形態之氧化物燒結體作為靶利用濺鍍法所形成的氧化物半導體膜，故而具有較高之特性。 Referring to Fig. 1, a semiconductor device 10 according to another embodiment of the present invention includes an oxide semiconductor film 14 formed by a sputtering method using the oxide sintered body of the first embodiment as a target. Since the semiconductor device of the present embodiment includes the oxide semiconductor film formed by the sputtering method using the oxide sintered body of the above-described embodiment as a target, it has high characteristics.

本實施形態之半導體裝置10並無特別限定，例如為包含使用實施形態1之氧化物燒結體作為靶利用濺鍍法所形成之氧化物半導體膜14作為通道層的半導體裝置即TFT(薄膜電晶體)。本實施形態之半導體裝置10之一例即TFT由於包含使用上述實施形態之氧化物燒結體作為靶利用濺鍍法所形成的氧化物半導體膜14作為通道層，因此，其OFF電流變低，並且於較低之驅動電壓下ON電流相對於OFF電流之比變高。 The semiconductor device 10 of the present embodiment is not particularly limited, and is, for example, a TFT (thin film transistor) which is a semiconductor device including the oxide semiconductor film 14 formed by sputtering using the oxide sintered body of the first embodiment as a channel layer. ). The TFT which is an example of the semiconductor device 10 of the present embodiment includes the oxide semiconductor film 14 formed by the sputtering method using the oxide sintered body of the above-described embodiment as a channel layer. Therefore, the OFF current is lowered, and The ratio of the ON current to the OFF current becomes higher at the lower driving voltage.

更具體而言，本實施形態之半導體裝置10即TFT如圖1所示，包括：基板11、配置於基板11上之閘極電極12、作為絕緣層而配置於閘極電極12上之閘極絕緣膜13、作為通道層而配置於閘極絕緣膜13上之氧化物半導體膜14、及以互不接觸之方式配置於氧化物半導體膜14上之源極電極15及汲極電極16。 More specifically, as shown in FIG. 1, the TFT of the semiconductor device 10 of the present embodiment includes a substrate 11, a gate electrode 12 disposed on the substrate 11, and a gate disposed on the gate electrode 12 as an insulating layer. The insulating film 13, the oxide semiconductor film 14 disposed on the gate insulating film 13 as a channel layer, and the source electrode 15 and the drain electrode 16 which are disposed on the oxide semiconductor film 14 without contacting each other.

(半導體裝置之製造方法) (Method of Manufacturing Semiconductor Device)

參照圖2，本實施形態之半導體裝置10之製造方法並無特別限制，但就高效率地製造高特性之半導體裝置之觀點而言，較佳為包括：於基板11上形成閘極電極12之步驟(圖2(A))、於閘極電極12上形成閘極絕緣膜13作為絕緣層之步驟(圖2(B))、於閘極絕緣膜13上形成氧化物半導體膜14作為通道層之步驟(圖2(C))、及於氧化物半導體膜14上以互不接觸之方式形成源極電極15及汲極電極16之步驟(圖2(D))。 2, the method of manufacturing the semiconductor device 10 of the present embodiment is not particularly limited. However, from the viewpoint of efficiently manufacturing a semiconductor device having high characteristics, it is preferable to form the gate electrode 12 on the substrate 11. Step (Fig. 2(A)), a step of forming a gate insulating film 13 as an insulating layer on the gate electrode 12 (Fig. 2(B)), and forming an oxide semiconductor film 14 as a channel layer on the gate insulating film 13. The step (Fig. 2(C)) and the step of forming the source electrode 15 and the drain electrode 16 on the oxide semiconductor film 14 without contacting each other (Fig. 2(D)).

1.形成閘極電極之步驟 1. Steps of forming a gate electrode

參照圖2(A)，於基板11上形成閘極電極12。基板11並無特別限制，但就提高透明性、價格穩定性、及表面平滑性方面而言，較佳為石英玻璃基板、無鹼玻璃基板、鹼玻璃基板等。閘極電極12並無特別限制，但就抗氧化性較高且電阻較低方面而言，較佳為Mo電極、Ti電極、W電極、Al電極、Cu電極等。閘極電極12之形成方法並無特別限制，但就可於基板之主面上大面積且均勻地形成方面而言，較佳為真空蒸鍍法、濺鍍法等。 Referring to FIG. 2(A), a gate electrode 12 is formed on the substrate 11. The substrate 11 is not particularly limited, but a quartz glass substrate, an alkali-free glass substrate, an alkali glass substrate, or the like is preferable in terms of improving transparency, price stability, and surface smoothness. The gate electrode 12 is not particularly limited, but a Mo electrode, a Ti electrode, a W electrode, an Al electrode, a Cu electrode, or the like is preferable in terms of high oxidation resistance and low electrical resistance. The method of forming the gate electrode 12 is not particularly limited, but a vacuum deposition method, a sputtering method, or the like is preferable in terms of large-area and uniform formation on the main surface of the substrate.

2.形成閘極絕緣膜之步驟 2. Step of forming a gate insulating film

參照圖2(B)，於閘極電極12上形成閘極絕緣膜13作為絕緣層。閘極絕緣膜13並無特別限制，但就絕緣性較高方面而言，較佳為SiO_x膜、SiN_x膜等。閘極絕緣膜13之形成方法並無特別限制，但就可於形成有閘極電極之基板之主面上大面積且均勻地形成方面及確保絕緣性方面而言，較佳為電漿CVD(化學氣相沈積)法等。 Referring to Fig. 2(B), a gate insulating film 13 is formed as an insulating layer on the gate electrode 12. The gate insulating film 13 is not particularly limited, but a SiO _x film, a SiN _x film, or the like is preferable in terms of high insulation. The method of forming the gate insulating film 13 is not particularly limited, but is preferably plasma CVD in terms of large-area and uniform formation on the main surface of the substrate on which the gate electrode is formed and in ensuring insulation. Chemical vapor deposition).

3.形成氧化物半導體膜之步驟 3. Step of forming an oxide semiconductor film

參照圖2(C)，於閘極絕緣膜13上形成氧化物半導體膜14作為通道層。就製造特性較高之半導體裝置10之觀點而言，氧化物半導體膜14係使用實施形態1之氧化物燒結體作為靶利用濺鍍法形成。此處，所謂濺鍍法，係指如下方法：於成膜室內使靶與基板對向而配置，對靶施加電壓，並以稀有氣體離子對靶之表面進行濺鍍，藉此，使構成靶之原子自靶釋出而堆積於基板(亦包括形成有上述閘極電極及閘極絕緣膜之基板)上，藉此形成由構成靶之原子構成之膜。 Referring to FIG. 2(C), an oxide semiconductor film 14 is formed as a channel layer on the gate insulating film 13. The oxide semiconductor film 14 is formed by a sputtering method using the oxide sintered body of the first embodiment as a target from the viewpoint of the semiconductor device 10 having high manufacturing characteristics. Here, the sputtering method refers to a method in which a target is placed opposite to a substrate in a deposition chamber, a voltage is applied to the target, and a surface of the target is sputtered with rare gas ions, thereby constituting the target. The atoms are released from the target and deposited on the substrate (including the substrate on which the gate electrode and the gate insulating film are formed), thereby forming a film composed of atoms constituting the target.

4.形成源極電極及汲極電極之步驟 4. Steps of forming a source electrode and a drain electrode

參照圖2(D)，於氧化物半導體膜14上以互不接觸之方式形成源極電極15及汲極電極16。源極電極15及汲極電極16並無特別限制，但就抗氧化性較高、電阻較低、且與氧化物半導體膜之接觸電阻較低方面 而言，較佳為Mo電極、Ti電極、W電極、Al電極、Cu電極等。形成源極電極15及汲極電極16之方法並無特別限制，但就可於形成有氧化物半導體膜之基板之主面上大面積且均勻地形成方面而言，較佳為真空蒸鍍法、濺鍍法等。以互不接觸之方式形成源極電極15及汲極電極16之方法並無特別限制，但就可於形成有氧化物半導體膜之基板之主面上形成大面積且均勻之源極電極及汲極電極之圖案方面而言，較佳為藉由使用光阻劑之蝕刻法而形成。 Referring to FIG. 2(D), the source electrode 15 and the drain electrode 16 are formed on the oxide semiconductor film 14 so as not to contact each other. The source electrode 15 and the drain electrode 16 are not particularly limited, but have high oxidation resistance, low electrical resistance, and low contact resistance with an oxide semiconductor film. In particular, a Mo electrode, a Ti electrode, a W electrode, an Al electrode, a Cu electrode, or the like is preferable. The method of forming the source electrode 15 and the drain electrode 16 is not particularly limited. However, in terms of large-area and uniform formation on the main surface of the substrate on which the oxide semiconductor film is formed, vacuum evaporation is preferred. , sputtering method, etc. The method of forming the source electrode 15 and the drain electrode 16 in a non-contact manner is not particularly limited, but a large-area and uniform source electrode and a crucible can be formed on the main surface of the substrate on which the oxide semiconductor film is formed. In terms of the pattern of the electrode, it is preferably formed by an etching method using a photoresist.

[實施例] [Examples]

(實施例1~實施例5) (Examples 1 to 5)

1.粉末原料之準備 1. Preparation of powder raw materials

準備粒度為0.5μm~1.2μm且純度為99.9質量%之WO_2.72粉末、平均粒徑為1.0μm且純度為99.99質量%之ZnO粉末、及平均粒徑為1.0μm且純度為99.99質量%之In₂O₃粉末。 WO _2.72 powder having a particle size of 0.5 μm to 1.2 μm and a purity of 99.9% by mass, ZnO powder having an average particle diameter of 1.0 μm and a purity of 99.99% by mass, and In having an average particle diameter of 1.0 μm and a purity of 99.99% by mass were prepared. ₂ O ₃ powder.

2.原料粉末之一次混合物之製備 2. Preparation of primary mixture of raw material powder

首先，藉由將所準備之原料粉末中之WO_2.72粉末與ZnO粉末加入球磨機中並粉碎混合18小時，而製備原料粉末之一次混合物。將WO_2.72粉末與ZnO粉末之莫耳混合比設為WO_2.7：ZnO=1：1。作為上述粉碎混合時之分散介質，使用乙醇。使所獲得之原料粉末之一次混合物於大氣中乾燥。 First, the raw material powder prepared by the powder in the WO _2.72 ZnO powder with a ball mill and pulverized and mixed added 18 hours, a mixture of the raw material powder was prepared. The molar mixing ratio of WO _2.72 powder and ZnO powder was set to WO _2.7 : ZnO = 1:1. As the dispersion medium at the time of the above pulverization and mixing, ethanol is used. The primary mixture of the obtained raw material powder was dried in the atmosphere.

3.一次混合物之煅燒 3. Calcination of a mixture

繼而，將所獲得之原料粉末之一次混合物加入氧化鋁製坩堝中，於大氣環境中以800℃之溫度煅燒8小時。關於煅燒溫度，若為形成結晶相之溫度，則就可使煅燒粉之粒徑儘可能小方面而言，以低為佳。以此方式獲得包含ZnWO₄型相作為結晶相之煅燒物。 Then, the primary mixture of the obtained raw material powders was placed in a crucible made of alumina, and calcined at a temperature of 800 ° C for 8 hours in an atmospheric environment. Regarding the calcination temperature, if the temperature at which the crystal phase is formed, the particle size of the calcined powder can be made as small as possible, and it is preferably as low as possible. In this way, a calcined product containing a ZnWO ₄ type phase as a crystal phase is obtained.

4.原料粉末之二次混合物之製備 4. Preparation of secondary mixture of raw material powder

繼而，將所獲得之煅燒物與所準備之作為原料粉末之In₂O₃粉末一 併投入坩堝(pot)，進而放入粉碎混合球磨機12小時而粉碎混合12小時，藉此製備原料粉末之二次混合物。關於煅燒物與In₂O₃粉末之混合比率，使WO_2.72粉末、ZnO粉末、及In₂O₃粉末之莫耳混合比成為如表1之實施例1~實施例5所示之比。作為上述粉碎混合時之分散介質，使用乙醇。所獲得之混合粉末係以噴霧乾燥進行乾燥。 Then, the obtained calcined product was put into a pot together with the prepared In ₂ O ₃ powder as a raw material powder, and further placed in a pulverized mixing ball mill for 12 hours, and pulverized and mixed for 12 hours, thereby preparing a raw material powder. Secondary mixture. Regarding the mixing ratio of the calcined product and the In ₂ O ₃ powder, the molar mixing ratio of the WO _2.72 powder, the ZnO powder, and the In ₂ O ₃ powder was set to the ratios shown in Examples 1 to 5 of Table 1. As the dispersion medium at the time of the above pulverization and mixing, ethanol is used. The obtained mixed powder was dried by spray drying.

5.二次混合物之成形 5. Formation of secondary mixture

繼而，藉由壓製而使所獲得之二次混合物成形，進而，藉由CIP於室溫(5℃~30℃)之靜水中以190MPa之壓力進行加壓成形，獲得直徑100mm且厚度約9mm之圓板狀成形體。 Then, the obtained secondary mixture is formed by pressing, and further, by CIP, at a pressure of 190 MPa in still water at room temperature (5 ° C to 30 ° C), a diameter of 100 mm and a thickness of about 9 mm are obtained. A disk-shaped formed body.

6.成形體之燒結 6. Sintering of the shaped body

繼而，將所獲得之成形體於大氣環境中以表1之實施例1~實施例5所示之燒結溫度燒結8小時，藉此獲得氧化物燒結體。 Then, the obtained molded body was sintered in an atmosphere at a sintering temperature shown in Examples 1 to 5 of Table 1 for 8 hours, whereby an oxide sintered body was obtained.

7.氧化物燒結體之物性評價 7. Physical property evaluation of oxide sintered body

所獲得之氧化物燒結體之結晶相之鑑定係自氧化物燒結體之一部分採取樣品，藉由利用粉末X射線繞射法之結晶分析而進行。作為X射線，使用Cu之Kα射線，進行結晶相之鑑定。將氧化物燒結體中存在之結晶相彙總於表1。 The identification of the crystal phase of the obtained oxide sintered body was carried out from a part of the oxide sintered body by crystallization analysis by powder X-ray diffraction. As the X-ray, the crystal phase was identified using Kα ray of Cu. The crystal phases present in the oxide sintered body are summarized in Table 1.

所獲得之氧化物燒結體之上述剖面中之多氧化物結晶相及作為方鐵錳礦型相之In₂O₃型相係以如下方式進行鑑定。 The polycrystalline oxide phase in the above cross section of the obtained oxide sintered body and the In ₂ O ₃ type phase which is a bixbyite type phase were identified as follows.

自氧化物燒結體之一部分採取樣品，研磨樣品之表面而使其變得平滑。繼而，使用SEM-EDX，利用SEM觀察樣品之表面，利用EDX分析各晶粒之金屬元素之組成比。根據該等晶粒之金屬元素之組成比之傾向對晶粒進行分組，結果，可分為Zn含有率及W含有率較高之晶粒組與Zn含有率及W含有率非常低而In含有率較高之晶粒組。結論為：Zn含有率及W含有率較高之晶粒組為作為多氧化物結晶相之ZnWO₄型相，Zn含有率及W含有率非常低而In含有率較高之晶粒組為作為方鐵 錳礦型相之In₂O₃型相。 A sample is taken from one part of the oxide sintered body, and the surface of the sample is ground to make it smooth. Then, using SEM-EDX, the surface of the sample was observed by SEM, and the composition ratio of the metal elements of each crystal grain was analyzed by EDX. The crystal grains are grouped according to the tendency of the composition ratio of the metal elements of the crystal grains, and as a result, the crystal group having a high Zn content and the W content ratio, the Zn content and the W content are extremely low, and the In content is included. A higher rate of grain groups. It is concluded that the crystal group having a high Zn content and a high W content is a ZnWO ₄ type phase which is a polycrystalline oxide phase, and a crystal group having a very low Zn content and a W content and a high In content is used as a crystal group. The In ₂ O ₃ phase of the bixbyite type phase.

將氧化物燒結體之上述剖面中多氧化物結晶相之面積相對於該剖面面積的佔有率即多氧化物結晶相佔有率、以及氧化物燒結體之上述剖面中多氧化物結晶相及作為方鐵錳礦型相之In₂O₃型相之合計面積相對於該剖面面積的佔有率即雙相佔有率(以下，亦稱為多氧化物結晶相及作為方鐵錳礦型相之In₂O₃型相之雙相佔有率)彙總於表1。 The occupation ratio of the area of the polycrystalline oxide phase in the cross section of the oxide sintered body to the cross-sectional area, that is, the polycrystalline oxide crystal phase occupation ratio, and the polycrystalline oxide crystal phase in the cross section of the oxide sintered body and the square The occupation ratio of the total area of the In ₂ O ₃ type phase of the ferromanganese type phase to the cross-sectional area, that is, the two-phase occupancy ratio (hereinafter, also referred to as a polycrystalline oxide phase and In ₂ O ₃ as a bixbyite type phase) The two-phase occupancy of the type phase is summarized in Table 1.

所獲得之氧化物燒結體中之金屬元素及Si之含量係藉由ICP質量分析法進行測定。基於該等之含量，算出W相對於氧化物燒結體中所含之金屬元素及Si之含有率。將結果彙總於表1。再者，於表1中，「添加元素」意指選自Al(鋁)、Ti(鈦)、Cr(鉻)、Ga(鎵)、Hf(鉿)、Zr(鋯)、Si(矽)、Mo(鉬)、V(釩)、Nb(鈮)、Ta(鉭)、及Bi(鉍)之元素M，但實施例1~實施例5中，未使用添加元素。 The content of the metal element and Si in the obtained oxide sintered body was measured by ICP mass spectrometry. Based on the content, the content ratio of W to the metal element and Si contained in the oxide sintered body was calculated. The results are summarized in Table 1. Further, in Table 1, "additional element" means selected from the group consisting of Al (aluminum), Ti (titanium), Cr (chromium), Ga (gallium), Hf (yttrium), Zr (zirconium), and Si (lanthanum). Element M of Mo (molybdenum), V (vanadium), Nb (铌), Ta (钽), and Bi (铋), but in Examples 1 to 5, no additive element was used.

所獲得之氧化物燒結體之導熱率係藉由雷射閃光法進行測定。自氧化物燒結體之一部分採取樣品，加工成直徑20mm×厚度1mm之圓板狀。為了使熱之吸收及輻射率變佳，於樣品表面塗佈碳噴霧後，對樣品表面照射脈衝雷射光。雷射光係波長為1.06μm，脈衝寬度為0.4ms。將於將實施例1之導熱率設為1時各實施例之相對導熱率彙總於表1。 The thermal conductivity of the obtained oxide sintered body was measured by a laser flash method. A sample was taken from one portion of the oxide sintered body and processed into a disk shape having a diameter of 20 mm and a thickness of 1 mm. In order to improve the absorption of heat and the radiance, after the carbon spray is applied to the surface of the sample, the surface of the sample is irradiated with pulsed laser light. The laser light has a wavelength of 1.06 μm and a pulse width of 0.4 ms. The relative thermal conductivity of each of the examples will be summarized in Table 1 when the thermal conductivity of Example 1 is set to 1.

8.靶之製作 8. Target production

將所獲得之氧化物燒結體加工成直徑3英吋(76.2mm)且厚度5.0mm之靶。 The obtained oxide sintered body was processed into a target having a diameter of 3 inches (76.2 mm) and a thickness of 5.0 mm.

9.半導體裝置之製作 9. Production of semiconductor devices

(1)閘極電極之形成 (1) Formation of gate electrode

參照圖2(A)，首先，作為基板11而準備50mm×50mm×厚度0.6mm之合成石英玻璃基板，於該基板11上利用濺鍍法形成厚度100nm之Mo電極作為閘極電極12。 Referring to Fig. 2(A), first, a synthetic quartz glass substrate of 50 mm × 50 mm × 0.6 mm in thickness is prepared as the substrate 11, and a Mo electrode having a thickness of 100 nm is formed as a gate electrode 12 on the substrate 11 by sputtering.

(2)閘極絕緣膜之形成 (2) Formation of gate insulating film

參照圖2(B)，繼而，於閘極電極12上利用電漿CVD法形成厚度200nm之非晶質SiO_x膜作為閘極絕緣膜13。 Referring to Fig. 2(B), an amorphous SiO _x film having a thickness of 200 nm is formed as a gate insulating film 13 by a plasma CVD method on the gate electrode 12.

(3)氧化物半導體膜之形成 (3) Formation of an oxide semiconductor film

參照圖2(C)，繼而，於閘極絕緣膜13上，藉由使用由實施例1~實施例5各者之氧化物燒結體加工而成之靶的RF(交流)磁控濺鍍法，而形成厚度35nm之氧化物半導體膜14。此處，靶之直徑3英吋(76.2mm)之平面為濺鍍面。 Referring to FIG. 2(C), an RF (alternating current) magnetron sputtering method using a target processed from the oxide sintered bodies of each of the first to fifth embodiments is applied to the gate insulating film 13. On the other hand, an oxide semiconductor film 14 having a thickness of 35 nm is formed. Here, the plane of the target having a diameter of 3 inches (76.2 mm) is a sputtered surface.

具體而言，於濺鍍裝置(未圖示)之成膜室內之進行水冷之基板保持器上，以露出閘極絕緣膜13之方式配置形成有上述閘極電極12及閘極絕緣膜13之基板11。以與閘極絕緣膜13對向之方式以90mm之距離配置上述靶。將成膜室內設為6×10^-5Pa左右之真空度，以如下方式對靶進行濺鍍。 Specifically, the gate electrode 12 and the gate insulating film 13 are disposed on the substrate holder that is water-cooled in the deposition chamber of the sputtering apparatus (not shown) so that the gate insulating film 13 is exposed. Substrate 11. The target was placed at a distance of 90 mm so as to face the gate insulating film 13. The target was cast to a vacuum of about 6 × 10 ^-5 Pa, and the target was sputtered as follows.

首先，於在閘極絕緣膜13與靶之間放入擋板之狀態下，向成膜室內導入Ar(氬)氣與O₂(氧)氣體之混合氣體直至成為0.5Pa之壓力。混合氣體中之O₂氣體含有率為1體積%。對靶施加120W之RF電力而引起濺鍍放電，藉此進行10分鐘靶表面之清潔(預濺鍍)。 First, in a state where a baffle is placed between the gate insulating film 13 and the target, a mixed gas of Ar (argon) gas and O ₂ (oxygen) gas is introduced into the film forming chamber to a pressure of 0.5 Pa. The O ₂ gas content in the mixed gas was 1% by volume. 120 W of RF power was applied to the target to cause a sputter discharge, whereby the target surface was cleaned (presputtered) for 10 minutes.

繼而，對同一靶施加120W之濺鍍RF電力，於將成膜室內之環境維持為原狀之狀態下，卸除上述擋板，藉此於閘極絕緣膜13上使氧化物半導體膜14成膜。再者，對於基板保持器，不特別施加偏壓電壓，僅進行水冷。此時，以氧化物半導體膜14之厚度成為35nm之方式設定成膜時間。以此方式，藉由使用由氧化物燒結體加工而成之靶的RF(交流)磁控濺鍍法，而形成氧化物半導體膜14。該氧化物半導體膜14於半導體裝置10即TFT(薄膜電晶體)中作為通道層發揮功能。將各實施例中之氧化物半導體膜14之成膜速度彙總於表2。由表2可知，若W之含有率過高，則成膜速度降低。 Then, 120 W of sputtering RF power is applied to the same target, and the barrier is removed while the environment in the film formation chamber is maintained as it is, thereby forming the oxide semiconductor film 14 on the gate insulating film 13. . Further, with respect to the substrate holder, no bias voltage was applied, and only water cooling was performed. At this time, the film formation time was set so that the thickness of the oxide semiconductor film 14 became 35 nm. In this manner, the oxide semiconductor film 14 is formed by RF (alternating current) magnetron sputtering using a target processed from an oxide sintered body. This oxide semiconductor film 14 functions as a channel layer in a TFT (thin film transistor) which is a semiconductor device 10 . The film formation rates of the oxide semiconductor films 14 in the respective examples are summarized in Table 2. As is clear from Table 2, if the content ratio of W is too high, the film formation rate is lowered.

繼而，藉由對所形成之氧化物半導體膜14之一部分進行蝕刻，而 形成源極電極形成用部14s、汲極電極形成用部14d、及通道部14c。此處，將源極電極形成用部14s及汲極電極形成用部14d之主面之大小設為100μm×100μm，通道長度C_L(參照圖1(A)及(B)以及圖2，所謂通道長度C_L，係指源極電極15與汲極電極16之間之通道部14c之距離)係設為40μm，通道寬度C_W(參照圖1(A)及(B)以及圖2，所謂通道寬度C_W，係指通道部14c之寬度)係設為50μm。此時，圖1及圖2中所記載之通道部係以半導體裝置即薄膜電晶體(TFT)於75mm×75mm之基板主面內以3mm間隔配置縱25個×橫25個之方式，於75mm×75mm之基板主面內以3mm間隔配置有縱25個×橫25個。 Then, a part of the formed oxide semiconductor film 14 is etched to form a source electrode forming portion 14s, a gate electrode forming portion 14d, and a channel portion 14c. Here, the size of the main surface of the source electrode forming portion 14s and the gate electrode forming portion 14d is set to 100 μm × 100 μm, and the channel length C _L (see FIGS. 1(A) and (B) and FIG. The channel length C _{L is} the distance between the source electrode 15 and the channel portion 14c between the drain electrodes 16 and is 40 μm, and the channel width C _W (refer to FIGS. 1(A) and (B) and FIG. 2, the so-called The channel width C _W means that the width of the channel portion 14c is 50 μm. In this case, the channel portions described in FIG. 1 and FIG. 2 are arranged in a horizontal direction of 25 mm × 25 in a main surface of a substrate of 75 mm × 75 mm by a thin film transistor (TFT) of a semiconductor device, at a distance of 75 mm. In the main surface of the substrate of ×75 mm, 25 vertical × 25 horizontal are arranged at intervals of 3 mm.

具體而言，上述氧化物半導體膜14之一部分蝕刻係藉由如下方式進行：製備以體積比計為草酸：水=1：10之蝕刻水溶液，並將依次形成有閘極電極12、閘極絕緣膜13及氧化物半導體膜14之基板11浸漬於該蝕刻水溶液中。此時，使蝕刻水溶液於熱浴內升溫至40℃。 Specifically, a part of the etching of the oxide semiconductor film 14 is performed by preparing an etching aqueous solution having a volume ratio of oxalic acid:water=1:10, and sequentially forming the gate electrode 12 and insulating the gate. The substrate 11 of the film 13 and the oxide semiconductor film 14 is immersed in the etching solution. At this time, the etching aqueous solution was heated to 40 ° C in a heat bath.

(4)源極電極及汲極電極之形成 (4) Formation of source electrode and drain electrode

參照圖2(D)，繼而於氧化物半導體膜14上相互分離地形成源極電極15及汲極電極16。 Referring to FIG. 2(D), the source electrode 15 and the drain electrode 16 are formed separately on the oxide semiconductor film 14 from each other.

具體而言，以僅氧化物半導體膜14之源極電極形成用部14s及汲極電極形成用部14d之主面露出之方式，於氧化物半導體膜14上塗佈光阻劑(未圖示)，並進行曝光及顯影。於氧化物半導體膜14之源極電極形成用部14s及汲極電極形成用部14d各者之主面上，利用濺鍍法相互分離地形成作為源極電極15之厚度為100nm之Mo電極、與作為汲極電極16之厚度為100nm之Mo電極。其後，將氧化物半導體膜14上之光阻劑剝離。作為此種源極電極、汲極電極之Mo電極係以半導體裝置即薄膜電晶體(TFT)於75mm×75mm之基板主面內以3mm間隔配置縱25個×橫25個之方式，對應於一個通道部各配置1個源極電極、汲極電極。藉此，作為半導體裝置10，製造具備氧化物半導體膜14作為通道層之 TFT。 Specifically, a photoresist is applied onto the oxide semiconductor film 14 so that only the main surface of the source electrode forming portion 14s and the gate electrode forming portion 14d of the oxide semiconductor film 14 are exposed (not shown). ), and exposure and development. On the main surface of each of the source electrode forming portion 14s and the gate electrode forming portion 14d of the oxide semiconductor film 14, a Mo electrode having a thickness of 100 nm as the source electrode 15 is formed separately from each other by sputtering. And a Mo electrode having a thickness of 100 nm as the drain electrode 16. Thereafter, the photoresist on the oxide semiconductor film 14 is peeled off. The Mo electrode as the source electrode and the drain electrode is arranged in a vertical direction of 25 mm × 25 in a main surface of a substrate of 75 mm × 75 mm by a semiconductor device, that is, a thin film transistor (TFT), corresponding to one. One source electrode and one drain electrode are disposed in each of the channel portions. Thereby, as the semiconductor device 10, the oxide semiconductor film 14 is provided as a channel layer. TFT.

繼而，將所獲得之半導體裝置10即TFT於氮氣環境中以300℃進行1小時熱處理。 Then, the obtained semiconductor device 10, that is, the TFT, was heat-treated at 300 ° C for 1 hour in a nitrogen atmosphere.

10.半導體裝置之特性評價 10. Characteristics evaluation of semiconductor devices

以如下方式評價半導體裝置即TFT之特性。首先，使閘極電極、源極電極及汲極電極接觸測定針。對源極電極與汲極電極之間施加7V之源極-汲極間電壓V_ds，並使施加於源極電極與閘極電極之間之源極-閘極間電壓V_gs自-10V變化至15V，測定彼時之源極-汲極間電流I_ds。將源極-閘極間電壓V_gs為-5V時之源極-汲極間電流I_ds定義為OFF電流。將各實施例中之OFF電流之值彙總於表2。將源極-閘極間電壓V_gs為15V時之源極-汲極間電流I_ds定義為ON電流，將ON電流之值相對於OFF電流之值之比彙總於表2。 The characteristics of the semiconductor device, that is, the TFT, were evaluated in the following manner. First, the gate electrode, the source electrode, and the drain electrode are brought into contact with the measuring needle. A source-drain voltage V _{ds of} 7 V is applied between the source electrode and the drain electrode, and a source-gate voltage V _gs applied between the source electrode and the gate electrode is varied from -10 V. To 15V, the source-drain current I _{ds at} that time is measured. The source-drain current I _ds when the source-gate voltage V _gs is -5 V is defined as an OFF current. The values of the OFF currents in the respective examples are summarized in Table 2. The source-drain current I _ds when the source-gate voltage V _gs is 15 V is defined as an ON current, and the ratio of the value of the ON current to the value of the OFF current is summarized in Table 2.

繼而，對於75mm×75mm之基板主面內以3mm間隔配置有縱25個×橫25個之半導體裝置即TFT之全部，求出源極-汲極間電流I_ds為1×10^-5A時之源極-閘極間電壓V_gs，將源極-閘極間電壓V_gs之不均作為△V_gs彙總於表2。此處，不均△V_gs越小，意味著主面內之半導體裝置即TFT特性之不均越小。 Then, in the main surface of the substrate of 75 mm × 75 mm, all of the TFTs of 25 semiconductor devices of 25 vertical and 25 horizontal are arranged at intervals of 3 mm, and the source-drain current I _ds is determined to be 1 × 10 ^-5 A. the source - the voltage V _gs between the gate, the source - gate voltage V _gs between the variation △ V _gs as summarized in table 2. Here, the smaller the unevenness ΔV _{gs is, the} smaller the variation in TFT characteristics of the semiconductor device in the main surface is.

(實施例6~實施例8) (Examples 6 to 8)

1.粉末原料之準備 1. Preparation of powder raw materials

準備粒度為0.5μm~1.2μm且純度為99.9質量%之WO_2.0粉末代替粒度為0.5μm~1.2μm且純度為99.9質量%之WO_2.72粉末，除此以外，以與實施例1~實施例5之情形相同之方式，準備WO_2.0粉末、ZnO粉末、及In₂O₃粉末。 WO _2.0 powder having a particle size of 0.5 μm to 1.2 μm and a purity of 99.9% by mass was prepared in place of WO _2.72 powder having a particle size of 0.5 μm to 1.2 μm and a purity of 99.9% by mass, and in addition to Examples 1 to 5 In the same manner, WO _2.0 powder, ZnO powder, and In ₂ O ₃ powder were prepared.

2.原料粉末之一次混合物之製備 2. Preparation of primary mixture of raw material powder

首先，向球磨機加入所準備之原料粉末中之WO_2.0粉末與ZnO粉末，進行18小時粉碎混合，藉此製備原料粉末之一次混合物。將WO_2.0粉末與ZnO粉末之莫耳混合比設為WO_2.0：ZnO=3：2。作為上述粉碎混合時之分散介質，使用乙醇。使所獲得之原料粉末之一次混合物於 大氣中乾燥。 First, the WO _2.0 powder and the ZnO powder in the prepared raw material powder were added to a ball mill, and pulverized and mixed for 18 hours, thereby preparing a primary mixture of the raw material powder. The molar mixing ratio of the WO _2.0 powder and the ZnO powder was set to WO _2.0 : ZnO = 3:2. As the dispersion medium at the time of the above pulverization and mixing, ethanol is used. The primary mixture of the obtained raw material powder was dried in the atmosphere.

3.一次混合物之煅燒 3. Calcination of a mixture

繼而，將所獲得之原料粉末之一次混合物加入氧化鋁製坩堝中，於大氣環境中以950℃之溫度煅燒5小時。關於煅燒溫度，若為形成結晶相之溫度，則就可使煅燒粉之粒徑儘可能小方面而言，以低為佳。以此方式，獲得包含Zn₂W₃O₈型相作為結晶相之煅燒物。 Then, the primary mixture of the obtained raw material powders was placed in a crucible made of alumina, and calcined at a temperature of 950 ° C for 5 hours in an atmospheric environment. Regarding the calcination temperature, if the temperature at which the crystal phase is formed, the particle size of the calcined powder can be made as small as possible, and it is preferably as low as possible. In this way, a calcined product containing a Zn ₂ W ₃ O ₈ type phase as a crystal phase was obtained.

4.原料粉末之二次混合物之製備 4. Preparation of secondary mixture of raw material powder

繼而，將所獲得之煅燒物與所準備之作為原料粉末之In₂O₃粉末一併投入坩堝，進而放入粉碎混合球磨機12小時，粉碎混合12小時，藉此製備原料粉末之二次混合物。關於煅燒物與In₂O₃粉末之混合比率，使WO_2.0粉末、ZnO粉末、及In₂O₃粉末之莫耳混合比成為如表1之實施例6~實施例8所示般之比。作為上述粉碎混合時之分散介質，使用乙醇。所獲得之混合粉末係以噴霧乾燥進行乾燥。 Then, the obtained calcined product was put into a crucible together with the prepared In ₂ O ₃ powder as a raw material powder, and further placed in a pulverizing mixing ball mill for 12 hours, and pulverized and mixed for 12 hours, thereby preparing a secondary mixture of the raw material powder. Regarding the mixing ratio of the calcined product and the In ₂ O ₃ powder, the molar mixing ratio of the WO _2.0 powder, the ZnO powder, and the In ₂ O ₃ powder was as shown in Examples 6 to 8 of Table 1. As the dispersion medium at the time of the above pulverization and mixing, ethanol is used. The obtained mixed powder was dried by spray drying.

5.二次混合物之成形 5. Formation of secondary mixture

繼而，使用所獲得之二次混合物，除此以外，以與實施例1~實施例5之情形相同之方式，獲得直徑100mm且厚度約9mm之圓板狀成形體。 Then, a disk-shaped molded body having a diameter of 100 mm and a thickness of about 9 mm was obtained in the same manner as in the case of Example 1 to Example 5 except that the obtained secondary mixture was used.

6.成形體之燒結 6. Sintering of the shaped body

繼而，將所獲得之成形體於大氣環境中以表1之實施例6~實施例8所示之燒結溫度燒結8小時，藉此獲得氧化物燒結體。 Then, the obtained molded body was sintered in an atmosphere at a sintering temperature shown in Examples 6 to 8 of Table 1 for 8 hours, whereby an oxide sintered body was obtained.

7.氧化物燒結體之物性評價 7. Physical property evaluation of oxide sintered body

藉由利用粉末X射線繞射法之結晶分析進行。作為X射線，使用Cu之Kα射線，進行結晶相之鑑定，確認到作為方鐵錳礦型相之In₂O₃型相與作為多氧化物結晶相之Zn₂W₃O₈型相之存在。繼而，將利用SEM-EDX分組之Zn含有率及W含有率較高之晶粒組總結為作為多氧化物結晶相之Zn₂W₃O₈型相，除此以外，以與實施例1~實施例5之情 形相同之方式進行多氧化物結晶相佔有率之算出、多氧化物結晶相及作為方鐵錳礦型相之In₂O₃型相之雙相佔有率之算出、W含有率之算出及相對導熱率之算出。將結果彙總於表1。再者，於實施例6~實施例8中，未使用添加元素。 It was carried out by crystallization analysis using a powder X-ray diffraction method. As the X-ray, the crystal phase was identified by using Kα ray of Cu, and it was confirmed that the In ₂ O ₃ type phase which is a bixbyite type phase and the Zn ₂ W ₃ O ₈ type phase which is a polycrystalline crystal phase exist. Then, the crystal grain group having a higher Zn content and W content in the SEM-EDX group is summarized as a Zn ₂ W ₃ O ₈ phase as a polycrystalline crystal phase, and otherwise, in the same manner as in Example 1 In the same manner as in the case of Example 5, the calculation of the occupancy rate of the polycrystalline oxide crystal phase, the calculation of the two-phase occupancy ratio of the polycrystalline oxide phase and the In ₂ O ₃ type phase as the bixbyite type phase, and the W content ratio were calculated. Calculate and calculate the relative thermal conductivity. The results are summarized in Table 1. Further, in Examples 6 to 8, no additive element was used.

8.靶之製作 8. Target production

以與實施例1~實施例5之情形相同之方式，將所獲得之氧化物燒結體加工成直徑3英吋(76.2mm)且厚度5.0mm之靶。 The obtained oxide sintered body was processed into a target having a diameter of 3 inches (76.2 mm) and a thickness of 5.0 mm in the same manner as in the case of Examples 1 to 5.

9.半導體裝置之製作 9. Production of semiconductor devices

以與實施例1~實施例5之情形相同之方式製作半導體裝置即TFT。將各實施例中之氧化物半導體膜14之成膜速度彙總於表2。 A TFT which is a semiconductor device was produced in the same manner as in the case of the first to fifth embodiments. The film formation rates of the oxide semiconductor films 14 in the respective examples are summarized in Table 2.

10.半導體裝置之特性評價 10. Characteristics evaluation of semiconductor devices

以與實施例1~實施例5之情形相同之方式，作為半導體裝置即TFT之特性，測定源極-閘極間電壓V_gs為-5V時之源極-汲極間電流I_ds作為OFF電流之值、源極-閘極間電壓V_gs為15V時之源極-汲極間電流I_ds即ON電流之值相對於該OFF電流之值的比、源極-閘極間電壓V_gs之不均△V_gs。將結果彙總於表2。 In the same manner as in the first to fifth embodiments, the source-drain current I _ds when the source-gate voltage V _gs is -5 V is _measured as the OFF current as a characteristic of the TFT which is a semiconductor device. The source-drain current I _ds when the source-gate voltage V _gs is 15V is the ratio of the value of the ON current to the value of the OFF current, and the source-gate voltage V _gs Uneven ΔV _gs . The results are summarized in Table 2.

(實施例9~實施例13) (Examples 9 to 13)

1.粉末原料之準備 1. Preparation of powder raw materials

準備平均粒徑為1.0μm且純度為99.99質量%之SnO₂粉末代替平均粒徑為1.0μm且純度為99.99質量%之ZnO粉末，除此以外，以與實施例1~實施例5之情形相同之方式，準備WO_2.72粉末、SnO₂粉末、及In₂O₃粉末。 The SnO ₂ powder having an average particle diameter of 1.0 μm and a purity of 99.99% by mass was prepared in place of the ZnO powder having an average particle diameter of 1.0 μm and a purity of 99.99% by mass, except for the cases of Examples 1 to 5. In this manner, WO _2.72 powder, SnO ₂ powder, and In ₂ O ₃ powder were prepared.

2.原料粉末之一次混合物之製備 2. Preparation of primary mixture of raw material powder

首先，將所準備之原料粉末中之WO_2.72粉末與SnO₂粉末加入球磨機中，並粉碎混合18小時，藉此製備原料粉末之一次混合物。將WO_2.72粉末與SnO₂粉末之莫耳混合比設為WO_2.72：SnO₂=1：1。作為上述粉 碎混合時之分散介質，使用乙醇。使所獲得之原料粉末之一次混合物於大氣中乾燥。 First, the WO _2.72 powder and the SnO ₂ powder in the prepared raw material powder were placed in a ball mill and pulverized and mixed for 18 hours, thereby preparing a primary mixture of the raw material powder. The molar mixing ratio of WO _2.72 powder and SnO ₂ powder was set to WO _2.72 : SnO ₂ = 1:1. As the dispersion medium at the time of the above pulverization and mixing, ethanol is used. The primary mixture of the obtained raw material powder was dried in the atmosphere.

3.一次混合物之煅燒 3. Calcination of a mixture

繼而，將所獲得之原料粉末之一次混合物加入氧化鋁製坩堝中，於大氣環境中以650℃之溫度煅燒5小時。關於煅燒溫度，若為形成結晶相之溫度，則就可使煅燒粉之粒徑儘可能小方面而言，以低為佳。以此方式，獲得包含WSnO₄型相作為結晶相之煅燒物。 Then, the primary mixture of the obtained raw material powders was placed in a crucible made of alumina, and calcined at a temperature of 650 ° C for 5 hours in an atmospheric environment. Regarding the calcination temperature, if the temperature at which the crystal phase is formed, the particle size of the calcined powder can be made as small as possible, and it is preferably as low as possible. In this way, a calcined product containing a WSnO ₄ type phase as a crystalline phase was obtained.

4.原料粉末之二次混合物之製備 4. Preparation of secondary mixture of raw material powder

繼而，將所獲得之煅燒物與所準備之作為原料粉末之In₂O₃粉末一併投入坩堝，進而放入粉碎混合球磨機12小時，粉碎混合12小時，藉此製備原料粉末之二次混合物。關於煅燒物與In₂O₃粉末之混合比率，使WO_2.72粉末、SnO₂粉末、及In₂O₃粉末之莫耳混合比成為如表1之實施例9~實施例13所示之比。作為上述粉碎混合時之分散介質，使用乙醇。所獲得之混合粉末係以噴霧乾燥進行乾燥。 Then, the obtained calcined product was put into a crucible together with the prepared In ₂ O ₃ powder as a raw material powder, and further placed in a pulverizing mixing ball mill for 12 hours, and pulverized and mixed for 12 hours, thereby preparing a secondary mixture of the raw material powder. Regarding the mixing ratio of the calcined product and the In ₂ O ₃ powder, the molar mixing ratio of the WO _2.72 powder, the SnO ₂ powder, and the In ₂ O ₃ powder was changed as shown in Examples 9 to 13 of Table 1. As the dispersion medium at the time of the above pulverization and mixing, ethanol is used. The obtained mixed powder was dried by spray drying.

5.二次混合物之成形 5. Formation of secondary mixture

繼而，使用所獲得之二次混合物，除此以外，以與實施例1~實施例5之情形相同之方式獲得直徑100mm且厚度約9mm之圓板狀成形體。 Then, a disk-shaped molded body having a diameter of 100 mm and a thickness of about 9 mm was obtained in the same manner as in the case of Example 1 to Example 5 except that the obtained secondary mixture was used.

6.成形體之燒結 6. Sintering of the shaped body

繼而，將所獲得之成形體於大氣環境中以表1之實施例9~實施例13所示之燒結溫度燒結8小時，藉此獲得氧化物燒結體。 Then, the obtained molded body was sintered in an atmosphere at a sintering temperature shown in Examples 9 to 13 of Table 1 for 8 hours, whereby an oxide sintered body was obtained.

7.氧化物燒結體之物性評價 7. Physical property evaluation of oxide sintered body

藉由利用粉末X射線繞射法之結晶分析進行。作為X射線，使用Cu之Kα射線，進行結晶相之鑑定，確認到作為方鐵錳礦型相之In₂O₃型相與作為多氧化物結晶相之WSnO₄型相之存在。繼而，使用SEM-EDX，分為Sn含有率及W含有率較高之晶粒組與Sn含有率及W含 有率非常低而In含有率較高之晶粒組，結論為：Sn含有率及W含有率較高之晶粒組為作為多氧化物結晶相之WSnO₄型相，Sn含有率及W含有率非常低而In含有率較高之晶粒組為作為方鐵錳礦型相之In₂O₃型相，除此以外，以與實施例1~實施例5之情形相同之方式進行多氧化物結晶相佔有率之算出、多氧化物結晶相及作為方鐵錳礦型相之In₂O₃型相之雙相佔有率之算出、W含有率之算出及相對導熱率之算出。將結果彙總於表1。再者，於實施例9~實施例13中未使用添加元素。 It was carried out by crystallization analysis using a powder X-ray diffraction method. As the X-ray, the K phase of Cu was used to identify the crystal phase, and it was confirmed that the In ₂ O ₃ type phase which is a bixbyite type phase and the WSnO ₄ type phase which is a polycrystalline crystal phase exist. Then, using SEM-EDX, it is divided into a crystal group having a high Sn content and a W content, a crystal grain group having a very low Sn content and a W content, and a high In content, and the conclusion is: Sn content and The crystal group having a higher W content is a WSnO ₄ type phase which is a polycrystalline oxide crystal phase, and a crystal group having a very low Sn content and a W content and a high In content is a tetraammine type phase. The calculation of the occupancy rate of the polycrystalline oxide phase, the polycrystalline oxide phase, and the In ₂ as a bixbyite type phase were carried out in the same manner as in the case of Examples 1 to 5 except for the ₂ O ₃ type phase. The calculation of the two-phase occupancy of the O ₃ phase, the calculation of the W content, and the calculation of the relative thermal conductivity. The results are summarized in Table 1. Further, in Examples 9 to 13, no additive element was used.

8.靶之製作 8. Target production

以與實施例1~實施例5之情形相同之方式，將所獲得之氧化物燒結體加工成直徑3英吋(76.2mm)且厚度5.0mm之靶。 The obtained oxide sintered body was processed into a target having a diameter of 3 inches (76.2 mm) and a thickness of 5.0 mm in the same manner as in the case of Examples 1 to 5.

9.半導體裝置之製作 9. Production of semiconductor devices

以與實施例1~實施例5之情形相同之方式製作半導體裝置即TFT。將各實施例中之氧化物半導體膜14之成膜速度彙總於表2。 A TFT which is a semiconductor device was produced in the same manner as in the case of the first to fifth embodiments. The film formation rates of the oxide semiconductor films 14 in the respective examples are summarized in Table 2.

10.半導體裝置之特性評價 10. Characteristics evaluation of semiconductor devices

以與實施例1~實施例5之情形相同之方式，作為半導體裝置即TFT之特性，測定源極-閘極間電壓V_gs為-5V時之源極-汲極間電流I_ds作為OFF電流之值、源極-閘極間電壓V_gs為15V時之源極-汲極間電流I_ds即ON電流之值相對於該OFF電流之值的比、源極-閘極間電壓V_gs之不均△V_gs。將結果彙總於表2。 In the same manner as in the first to fifth embodiments, the source-drain current I _ds when the source-gate voltage V _gs is -5 V is _measured as the OFF current as a characteristic of the TFT which is a semiconductor device. The source-drain current I _ds when the source-gate voltage V _gs is 15V is the ratio of the value of the ON current to the value of the OFF current, and the source-gate voltage V _gs Uneven ΔV _gs . The results are summarized in Table 2.

(實施例14~實施例16) (Examples 14 to 16)

1.粉末原料之準備 1. Preparation of powder raw materials

以與實施例9~實施例13之情形相同之方式，準備WO_2.72粉末、SnO₂粉末、及In₂O₃粉末。 WO _2.72 powder, SnO ₂ powder, and In ₂ O ₃ powder were prepared in the same manner as in the case of Example 9 to Example 13.

2.原料粉末之一次混合物之製備 2. Preparation of primary mixture of raw material powder

首先，將所準備之原料粉末中之WO_2.72粉末與SnO₂粉末加入球磨機中，並粉碎混合18小時，藉此製備原料粉末之一次混合物。將WO_2.72 粉末與SnO₂粉末之莫耳混合比設為WO_2.72：SnO₂=1：2。作為上述粉碎混合時之分散介質，使用乙醇。使所獲得之原料粉末之一次混合物於大氣中乾燥。 First, the WO _2.72 powder and the SnO ₂ powder in the prepared raw material powder were placed in a ball mill and pulverized and mixed for 18 hours, thereby preparing a primary mixture of the raw material powder. The molar mixing ratio of WO _2.72 powder and SnO ₂ powder was set to WO _2.72 : SnO ₂ = 1:2. As the dispersion medium at the time of the above pulverization and mixing, ethanol is used. The primary mixture of the obtained raw material powder was dried in the atmosphere.

3.一次混合物之煅燒 3. Calcination of a mixture

繼而，將所獲得之原料粉末之一次混合物加入氧化鋁製坩堝中，於大氣環境中以800℃之溫度煅燒5小時。關於煅燒溫度，若為形成結晶相之溫度，則就可使煅燒粉之粒徑儘可能小方面而言，以低為佳。以此方式，獲得包含WSn₂O₅型相作為結晶相之煅燒物。 Then, the primary mixture of the obtained raw material powders was placed in a crucible made of alumina, and calcined at 800 ° C for 5 hours in an atmospheric environment. Regarding the calcination temperature, if the temperature at which the crystal phase is formed, the particle size of the calcined powder can be made as small as possible, and it is preferably as low as possible. In this way, a calcined product containing a WSn ₂ O ₅ type phase as a crystalline phase was obtained.

4.原料粉末之二次混合物之製備 4. Preparation of secondary mixture of raw material powder

繼而，將所獲得之煅燒物與所準備之作為原料粉末之In₂O₃粉末一併投入坩堝，進而放入粉碎混合球磨機12小時，粉碎混合12小時，藉此製備原料粉末之二次混合物。關於煅燒物與In₂O₃粉末之混合比率，使WO_2.72粉末、SnO₂粉末、及In₂O₃粉末之莫耳混合比成為如表1之實施例14~實施例16所示之比。作為上述粉碎混合時之分散介質，使用乙醇。所獲得之混合粉末係以噴霧乾燥進行乾燥。 Then, the obtained calcined product was put into a crucible together with the prepared In ₂ O ₃ powder as a raw material powder, and further placed in a pulverizing mixing ball mill for 12 hours, and pulverized and mixed for 12 hours, thereby preparing a secondary mixture of the raw material powder. Regarding the mixing ratio of the calcined product and the In ₂ O ₃ powder, the molar mixing ratio of the WO _2.72 powder, the SnO ₂ powder, and the In ₂ O ₃ powder was as shown in Examples 14 to 16 of Table 1. As the dispersion medium at the time of the above pulverization and mixing, ethanol is used. The obtained mixed powder was dried by spray drying.

5.二次混合物之成形 5. Formation of secondary mixture

繼而，使用所獲得之二次混合物，除此以外，以與實施例1~實施例5之情形相同之方式獲得直徑100mm且厚度約9mm之圓板狀成形體。 Then, a disk-shaped molded body having a diameter of 100 mm and a thickness of about 9 mm was obtained in the same manner as in the case of Example 1 to Example 5 except that the obtained secondary mixture was used.

6.成形體之燒結 6. Sintering of the shaped body

繼而，將所獲得之成形體於大氣環境中以表1之實施例14~實施例16所示之燒結溫度燒結8小時，藉此獲得氧化物燒結體。 Then, the obtained molded body was sintered in an atmosphere at a sintering temperature shown in Examples 14 to 16 of Table 1 for 8 hours, whereby an oxide sintered body was obtained.

7.氧化物燒結體之物性評價 7. Physical property evaluation of oxide sintered body

藉由利用粉末X射線繞射法之結晶分析進行。作為X射線，使用Cu之Kα射線，進行結晶相之鑑定，確認到作為方鐵錳礦型相之In₂O₃型相與作為多氧化物結晶相之WSn₂O₅型相之存在。繼而，將利用 SEM-EDX分組之Sn含有率及W含有率較高之晶粒組總結為作為多氧化物結晶相之WSn₂O₅型相，除此以外，以與實施例9~實施例13之情形相同之方式，進行多氧化物結晶相佔有率之算出、多氧化物結晶相及作為方鐵錳礦型相之In₂O₃型相之雙相佔有率之算出、W含有率之算出及相對導熱率之算出。將結果彙總於表1。再者，於實施例14~實施例16中未使用添加元素。 It was carried out by crystallization analysis using a powder X-ray diffraction method. As the X-ray, the crystal phase was identified by using Kα ray of Cu, and it was confirmed that the In ₂ O ₃ type phase which is a bixbyite type phase and the WSn ₂ O ₅ type phase which is a polycrystalline crystal phase exist. Then, by using the packet of Sn SEM-EDX, and W contains a higher content ratio of the crystal grains of the oxide as a multiple group summarized as WSn crystalline phase of type phase ₂ O _5, except that in Example 9 to Example In the same manner as in the case of 13, the calculation of the occupancy rate of the polycrystalline oxide crystal phase, the calculation of the two-phase occupancy ratio of the polycrystalline oxide phase and the In ₂ O ₃ type phase as the bixbyite type phase, and the calculation of the W content ratio were performed. And the calculation of the relative thermal conductivity. The results are summarized in Table 1. Further, in Examples 14 to 16, no additive element was used.

8.靶之製作 8. Target production

以與實施例1~實施例5之情形相同之方式，將所獲得之氧化物燒結體加工成直徑3英吋(76.2mm)且厚度5.0mm之靶。 The obtained oxide sintered body was processed into a target having a diameter of 3 inches (76.2 mm) and a thickness of 5.0 mm in the same manner as in the case of Examples 1 to 5.

9.半導體裝置之製作 9. Production of semiconductor devices

以與實施例1~實施例5之情形相同之方式製作半導體裝置即TFT。將各實施例中之氧化物半導體膜14之成膜速度彙總於表2。 A TFT which is a semiconductor device was produced in the same manner as in the case of the first to fifth embodiments. The film formation rates of the oxide semiconductor films 14 in the respective examples are summarized in Table 2.

10.半導體裝置之特性評價 10. Characteristics evaluation of semiconductor devices

以與實施例1~實施例5之情形相同之方式，作為半導體裝置即TFT之特性，測定源極-閘極間電壓V_gs為-5V時之源極-汲極間電流I_ds作為OFF電流之值、源極-閘極間電壓V_gs為15V時之源極-汲極間電流I_ds即ON電流之值相對於該OFF電流之值的比、源極-閘極間電壓V_gs之不均△V_gs。將結果彙總於表2。 In the same manner as in the first to fifth embodiments, the source-drain current I _ds when the source-gate voltage V _gs is -5 V is _measured as the OFF current as a characteristic of the TFT which is a semiconductor device. The source-drain current I _ds when the source-gate voltage V _gs is 15V is the ratio of the value of the ON current to the value of the OFF current, and the source-gate voltage V _gs Uneven ΔV _gs . The results are summarized in Table 2.

(實施例17~實施例19) (Examples 17 to 19)

1.粉末原料之準備 1. Preparation of powder raw materials

準備粒度為0.5μm~1.2μm且純度為99.9質量%之WO_2.0粉末代替粒度為0.5μm~1.2μm且純度為99.9質量%之WO_2.72粉末，除此以外，以與實施例9~實施例13之情形相同之方式，準備WO_2.0粉末、SnO₂粉末、及In₂O₃粉末。 WO _2.0 powder having a particle size of 0.5 μm to 1.2 μm and a purity of 99.9% by mass was prepared in place of WO _2.72 powder having a particle size of 0.5 μm to 1.2 μm and a purity of 99.9% by mass, and in addition to Examples 9 to 13 In the same manner, WO _2.0 powder, SnO ₂ powder, and In ₂ O ₃ powder were prepared.

2.原料粉末之一次混合物之製備 2. Preparation of primary mixture of raw material powder

首先，將所準備之原料粉末中之WO_2.0粉末與SnO₂粉末加入球磨 機中，並粉碎混合18小時，藉此製備原料粉末之一次混合物。將WO_2.0粉末與SnO₂粉末之莫耳混合比設為WO_2.0：SnO₂=1：3。作為上述粉碎混合時之分散介質，使用乙醇。使所獲得之原料粉末之一次混合物於大氣中乾燥。 First, the WO _2.0 powder and the SnO ₂ powder in the prepared raw material powder were placed in a ball mill and pulverized and mixed for 18 hours, thereby preparing a primary mixture of the raw material powders. The molar mixing ratio of the WO _2.0 powder and the SnO ₂ powder was set to WO _2.0 :SnO ₂ = 1:3. As the dispersion medium at the time of the above pulverization and mixing, ethanol is used. The primary mixture of the obtained raw material powder was dried in the atmosphere.

3.一次混合物之煅燒 3. Calcination of a mixture

繼而，將所獲得之原料粉末之一次混合物加入氧化鋁製坩堝中，於大氣環境中以950℃之溫度煅燒5小時。關於煅燒溫度，若為形成結晶相之溫度，則就可使煅燒粉之粒徑儘可能小方面而言，以低為佳。以此方式，獲得包含WSn₃O₆型相作為結晶相之煅燒物。 Then, the primary mixture of the obtained raw material powders was placed in a crucible made of alumina, and calcined at a temperature of 950 ° C for 5 hours in an atmospheric environment. Regarding the calcination temperature, if the temperature at which the crystal phase is formed, the particle size of the calcined powder can be made as small as possible, and it is preferably as low as possible. In this way, a calcined product containing a WSn ₃ O ₆ type phase as a crystal phase was obtained.

4.原料粉末之二次混合物之製備 4. Preparation of secondary mixture of raw material powder

繼而，將所獲得之煅燒物與所準備之作為原料粉末之In₂O₃粉末一併投入坩堝，進而放入粉碎混合球磨機12小時，粉碎混合12小時，藉此製備原料粉末之二次混合物。關於煅燒物與In₂O₃粉末之混合比率，使WO_2.0粉末、SnO₂粉末、及In₂O₃粉末之莫耳混合比成為如表1之實施例17~實施例19所示之比。作為上述粉碎混合時之分散介質，使用乙醇。所獲得之混合粉末係以噴霧乾燥進行乾燥。 Then, the obtained calcined product was put into a crucible together with the prepared In ₂ O ₃ powder as a raw material powder, and further placed in a pulverizing mixing ball mill for 12 hours, and pulverized and mixed for 12 hours, thereby preparing a secondary mixture of the raw material powder. Regarding the mixing ratio of the calcined product and the In ₂ O ₃ powder, the molar mixing ratio of the WO _2.0 powder, the SnO ₂ powder, and the In ₂ O ₃ powder was as shown in Examples 17 to 19 of Table 1. As the dispersion medium at the time of the above pulverization and mixing, ethanol is used. The obtained mixed powder was dried by spray drying.

5.二次混合物之成形 5. Formation of secondary mixture

繼而，使用所獲得之二次混合物，除此以外，以與實施例1~實施例5之情形相同之方式獲得直徑100mm且厚度約9mm之圓板狀成形體。 Then, a disk-shaped molded body having a diameter of 100 mm and a thickness of about 9 mm was obtained in the same manner as in the case of Example 1 to Example 5 except that the obtained secondary mixture was used.

6.成形體之燒結 6. Sintering of the shaped body

繼而，將所獲得之成形體於大氣環境中以表1之實施例17~實施例19所示之燒結溫度燒結8小時，藉此獲得氧化物燒結體。 Then, the obtained molded body was sintered in an atmosphere at a sintering temperature shown in Examples 17 to 19 of Table 1 for 8 hours, whereby an oxide sintered body was obtained.

7.氧化物燒結體之物性評價 7. Physical property evaluation of oxide sintered body

藉由利用粉末X射線繞射法之結晶分析進行。作為X射線，使用Cu之Kα射線，進行結晶相之鑑定，確認到作為方鐵錳礦型相之In₂O₃ 型相與作為多氧化物結晶相之WSn₃O₆型相之存在。繼而，將利用SEM-EDX分組之Sn含有率及W含有率較高之晶粒組總結為作為多氧化物結晶相之WSn₃O₆型相，除此以外，以與實施例9~實施例13之情形相同之方式，進行多氧化物結晶相佔有率之算出、多氧化物結晶相及作為方鐵錳礦型相之In₂O₃型相之雙相佔有率之算出、W含有率之算出及相對導熱率之算出。將結果彙總於表1。再者，於實施例17~實施例19中未使用添加元素。 It was carried out by crystallization analysis using a powder X-ray diffraction method. As the X-ray, the crystal phase was identified by using Kα ray of Cu, and it was confirmed that the In ₂ O ₃ type phase which is a bixbyite type phase and the WSn ₃ O ₆ type phase which is a polycrystalline crystal phase exist. Then, a group of crystal grains having a high Sn content and a W content of the SEM-EDX group is summarized as a WSn ₃ O ₆ type phase as a polycrystalline crystal phase, and in addition to the examples 9 to 10 In the same manner as in the case of 13, the calculation of the occupancy rate of the polycrystalline oxide crystal phase, the calculation of the two-phase occupancy ratio of the polycrystalline oxide phase and the In ₂ O ₃ type phase as the bixbyite type phase, and the calculation of the W content ratio were performed. And the calculation of the relative thermal conductivity. The results are summarized in Table 1. Further, in Examples 17 to 19, the additive element was not used.

8.靶之製作 8. Target production

以與實施例1~實施例5之情形相同之方式，將所獲得之氧化物燒結體加工成直徑3英吋(76.2mm)且厚度5.0mm之靶。 The obtained oxide sintered body was processed into a target having a diameter of 3 inches (76.2 mm) and a thickness of 5.0 mm in the same manner as in the case of Examples 1 to 5.

9.半導體裝置之製作 9. Production of semiconductor devices

以與實施例1~實施例5之情形相同之方式製作半導體裝置即TFT。將各實施例中之氧化物半導體膜14之成膜速度彙總於表2。 A TFT which is a semiconductor device was produced in the same manner as in the case of the first to fifth embodiments. The film formation rates of the oxide semiconductor films 14 in the respective examples are summarized in Table 2.

10.半導體裝置之特性評價 10. Characteristics evaluation of semiconductor devices

以與實施例1~實施例5之情形相同之方式，作為半導體裝置即TFT之特性，測定源極-閘極間電壓V_gs為-5V時之源極-汲極間電流I_ds作為OFF電流之值、源極-閘極間電壓V_gs為15V時之源極-汲極間電流I_ds即ON電流之值相對於該OFF電流之值的比、源極-閘極間電壓V_gs之不均△V_gs。將結果彙總於表2。 In the same manner as in the first to fifth embodiments, the source-drain current I _ds when the source-gate voltage V _gs is -5 V is _measured as the OFF current as a characteristic of the TFT which is a semiconductor device. The source-drain current I _ds when the source-gate voltage V _gs is 15V is the ratio of the value of the ON current to the value of the OFF current, and the source-gate voltage V _gs Uneven ΔV _gs . The results are summarized in Table 2.

(實施例20~實施例36) (Example 20 to Example 36)

於製備原料粉末之二次混合物時，作為原料粉末，除煅燒物及In₂O₃粉末以外，如表3之實施例20~實施例36所示般添加包含添加元素之氧化物粉末(Al₂O₃、TiO₂、Cr₂O₃、Ga₂O₃、HfO₂、SiO₂、V₂O₅、Nb₂O₃、ZrO₂、MoO₂、Ta₂O₃、Bi₂O₃)，除此以外，以與實施例1~實施例19之情形相同之方式，製作氧化物燒結體。將包含添加元素之氧化物粉末之莫耳混合比率示於表3。將所獲得之氧化物燒結體加工成靶， 製作包含藉由使用該靶之RF磁控濺鍍法而形成之氧化物半導體膜的半導體裝置即TFT。 In the preparation of the secondary mixture of the raw material powder, as the raw material powder, an oxide powder containing an additive element (Al _{2 ) was} added as shown in Example 20 to Example 36 of Table 3 except for the calcined product and the In ₂ O ₃ powder. O ₃ , TiO ₂ , Cr ₂ O ₃ , Ga ₂ O ₃ , HfO ₂ , SiO ₂ , V ₂ O ₅ , Nb ₂ O ₃ , ZrO ₂ , MoO ₂ , Ta ₂ O ₃ , Bi ₂ O ₃ ), Otherwise, an oxide sintered body was produced in the same manner as in the case of Example 1 to Example 19. The molar mixing ratio of the oxide powder containing the added element is shown in Table 3. The obtained oxide sintered body is processed into a target, and a TFT which is a semiconductor device including an oxide semiconductor film formed by RF magnetron sputtering using the target is produced.

將所獲得之氧化物燒結體之物性彙總於表3，將所獲得之半導體裝置即TFT之特性彙總於表4。物性及特性之測定方法與實施例1~實施例19相同。 The physical properties of the obtained oxide sintered body are summarized in Table 3, and the characteristics of the obtained semiconductor device, that is, TFT, are summarized in Table 4. The measurement methods of physical properties and characteristics were the same as those of Examples 1 to 19.

(比較例1~比較例2) (Comparative Example 1 to Comparative Example 2)

製作氧化物燒結體時，於製備原料粉末之混合物後，不進行煅燒而使原料粉末之混合物成形並進行燒結，除此以外，以與實施例1~實施例8或實施例9~實施例19之情形相同之方式，製作氧化物燒結體而加工成靶，製作包含藉由使用該靶之RF磁控濺鍍法而形成之氧化物半導體膜的半導體裝置即TFT。確認，藉由不進行煅燒而使原料粉末之混合物成形並進行燒結，而未生成多氧化物結晶相。比較例1~比較例2之間，WO_2.72粉末或WO_2.0粉末、ZnO粉末或SnO₂粉末、及In₂O₃粉末之莫耳混合比率不同。將氧化物燒結體之物性彙總於表3，將半導體裝置即TFT之特性彙總於表4。物性及特性之測定方法與實施例相同。 In the case of producing an oxide sintered body, after the mixture of the raw material powders is prepared, the mixture of the raw material powders is molded without being calcined, and sintering is carried out, except for Examples 1 to 8 or Examples 9 to 19 In the same manner, an oxide sintered body was produced and processed into a target, and a TFT which is a semiconductor device including an oxide semiconductor film formed by RF magnetron sputtering using the target was produced. It was confirmed that the mixture of the raw material powders was molded and sintered without being calcined, and no polycrystalline oxide phase was formed. Between Comparative Example 1 and Comparative Example 2, the molar mixing ratio of WO _2.72 powder or WO _2.0 powder, ZnO powder or SnO ₂ powder, and In ₂ O ₃ powder was different. The physical properties of the oxide sintered body are summarized in Table 3, and the characteristics of the TFT which is a semiconductor device are summarized in Table 4. The measurement methods of physical properties and characteristics are the same as in the examples.

參照表1~表4，包含使用包含銦、鎢、與鋅及錫之至少1種、且 包括包含鎢、與鋅及錫之至少1種之多氧化物結晶相作為結晶相之氧化物燒結體而形成之氧化物半導體膜作為通道層的半導體裝置即TFT(薄膜電晶體)中，可使OFF電流降低至未達1×10^-11A，並且以較低之驅動電壓將ON電流相對於OFF電流之比提高為數量級8(所謂數量級8，意指1×10⁸以上且未達1×10⁹，以下相同)。又，可提高氧化物燒結體之導熱率。再者，於表2及表4中之ON電流相對於OFF電流之比之欄中，所謂數量級9，意指1×10⁹以上且未達1×10¹⁰，所謂數量級5，意指1×10⁵以上且未達1×10⁶。 Referring to Tables 1 to 4, an oxide sintered body containing at least one of indium, tungsten, zinc, and tin and including a polycrystalline phase containing at least one of tungsten, zinc, and tin as a crystal phase is used. formation of the oxide semiconductor film that is TFT (thin film transistor) as the channel layer of a semiconductor device, the OFF current can be reduced to less than 1 × 10 ^-11 a, and the lower the driving voltage with respect to current ON OFF The ratio of the currents is increased to the order of 8 (the so-called order of 8, meaning 1 × 10 ⁸ or more and less than 1 × 10 ⁹ , the same below). Further, the thermal conductivity of the oxide sintered body can be increased. Furthermore, in the column of the ratio of the ON current to the OFF current in Tables 2 and 4, the order of magnitude 9 means 1 × 10 ⁹ or more and less than 1 × 10 ¹⁰ , so-called order of 5, meaning 1 × 10 ⁵ or more and less than 1 × 10 ⁶ .

應認為，此次所揭示之實施形態及實施例於所有方面均為例示，而並非限制性者。本發明之範圍由申請專利範圍所示而非上述之說明，意圖包括與申請專利範圍均等之意思及範圍內之全部變更。 The embodiments and examples disclosed herein are to be considered in all respects as illustrative and not restrictive. The scope of the present invention is defined by the scope of the claims and not the description of the claims.

10‧‧‧半導體裝置 10‧‧‧Semiconductor device

11‧‧‧基板 11‧‧‧Substrate

12‧‧‧閘極電極 12‧‧‧ gate electrode

13‧‧‧閘極絕緣膜 13‧‧‧Gate insulation film

14‧‧‧氧化物半導體膜 14‧‧‧Oxide semiconductor film

14c‧‧‧通道部 14c‧‧‧Channel Department

14d‧‧‧汲極電極形成用部 14d‧‧‧Bare electrode forming part

14s‧‧‧源極電極形成用部 14s‧‧‧Source electrode forming part

15‧‧‧源極電極 15‧‧‧Source electrode

16‧‧‧汲極電極 16‧‧‧汲electrode

C_W‧‧‧通道寬度 C _W ‧‧‧ channel width

C_L‧‧‧通道長度 C _L ‧‧‧ channel length

Claims (8)

一種氧化物燒結體，其係包含銦、鎢、與鋅及錫之至少1種者；且作為結晶相，包括包含鎢、與鋅及錫之至少1種之多氧化物結晶相。 An oxide sintered body comprising at least one of indium, tungsten, and zinc and tin; and the crystalline phase includes a polycrystalline oxide crystal phase containing at least one of tungsten, zinc, and tin. 如請求項1之氧化物燒結體，其中作為結晶相，進而包括方鐵錳礦型相。 The oxide sintered body of claim 1, wherein the crystal phase further comprises a bixbyite type phase. 如請求項2之氧化物燒結體，其中氧化物燒結體之一剖面中上述多氧化物結晶相及上述方鐵錳礦型相之合計面積相對於上述剖面面積之佔有率即雙相佔有率為95%以上且100%以下。 The oxide sintered body of claim 2, wherein the total area of the polycrystalline oxide phase and the bixbyite phase in the cross section of the oxide sintered body is equal to the occupied area of the cross-sectional area, that is, the two-phase occupancy rate is 95. More than % and less than 100%. 如請求項1之氧化物燒結體，其中氧化物燒結體之一剖面中上述多氧化物結晶相之面積相對於上述剖面面積之佔有率即多氧化物結晶相佔有率為大於0%且為50%以下。 The oxide sintered body according to claim 1, wherein a ratio of an area of the polycrystalline oxide crystal phase in the cross section of the oxide sintered body to the cross-sectional area, that is, a polycrystalline oxide crystal phase occupation ratio of more than 0% and 50% %the following. 如請求項1之氧化物燒結體，其中上述多氧化物結晶相包含選自由ZnWO₄型相、Zn₂W₃O₈型相、WSnO₄型相、WSn₂O₅型相、及WSn₃O₆型相所組成之群中之至少1種結晶相。 The oxide sintered body of claim 1, wherein the polycrystalline oxide phase comprises a layer selected from the group consisting of a ZnWO ₄ type phase, a Zn ₂ W ₃ O ₈ type phase, a WSnO ₄ type phase, a WSn ₂ O ₅ type phase, and WSn ₃ O At least one crystal phase of the group consisting of the type ₆ phases. 如請求項1之氧化物燒結體，其中鎢相對於氧化物燒結體中所含之全部金屬元素及矽之含有率為0.5原子%以上且20原子%以下。 The oxide sintered body of claim 1, wherein the content of tungsten relative to all metal elements and cerium contained in the oxide sintered body is 0.5 atom% or more and 20 atom% or less. 如請求項1至6中任一項之氧化物燒結體，其中選自由鋁、鈦、鉻、鎵、鉿、鋯、矽、鉬、釩、鈮、鉭、及鉍所組成之群中之至少1種元素相對於氧化物燒結體中所含之全部金屬元素及矽之含有率為0.1原子%以上且10原子%以下。 The oxide sintered body according to any one of claims 1 to 6, wherein at least one selected from the group consisting of aluminum, titanium, chromium, gallium, cerium, zirconium, hafnium, molybdenum, vanadium, niobium, tantalum, and niobium The content of all the metal elements and cerium contained in the oxide sintered body is 0.1 atom% or more and 10 atom% or less. 一種半導體裝置，其包含使用如請求項1之氧化物燒結體作為靶利用濺鍍法所形成之氧化物半導體膜。 A semiconductor device comprising an oxide semiconductor film formed by sputtering using the oxide sintered body of claim 1 as a target.