TW201333230A - Oxide sintered compact and sputtering target, and method for producing same - Google Patents

Oxide sintered compact and sputtering target, and method for producing same Download PDF

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TW201333230A
TW201333230A TW101140799A TW101140799A TW201333230A TW 201333230 A TW201333230 A TW 201333230A TW 101140799 A TW101140799 A TW 101140799A TW 101140799 A TW101140799 A TW 101140799A TW 201333230 A TW201333230 A TW 201333230A
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oxide
sintered body
zno
oxide sintered
sintering
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Hideo Hata
Yuki Tao
Moriyoshi Kanamaru
Akira Nambu
Yuki Iwasaki
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Kobelco Res Inst Inc
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Abstract

This oxide sintered compact is obtained by mixing and sintering zinc oxide, indium oxide, and an oxide of at least one metal selected from a group consisting of Ti, Mg, Al and Nb. When the oxide sintered compact is subjected to X-ray diffraction, ZnmIn2O3+m (where m is an integer from 5 to 7) phase is the main phase, and In2O3, and ZnO crystal phases are included, relative density is at least 85%, and specific resistance does not exceed 0.1Omegascm. According to this invention it is possible to obtain an oxide sintered compact having a low specific resistance and a high relative density.

Description

氧化物燒結體及濺鍍靶，以及其製造方法 Oxide sintered body and sputtering target, and manufacturing method thereof

本發明為關於在使用濺鍍法成膜成液晶顯示器或有機EL顯示器等顯示裝置中使用的薄膜電晶體(TFT)之氧化物半導體薄膜時所使用的氧化物燒結體及濺鍍靶，以及其製造方法。 The present invention relates to an oxide sintered body and a sputtering target used in forming an oxide semiconductor thin film of a thin film transistor (TFT) used in a display device such as a liquid crystal display or an organic EL display by a sputtering method, and Production method.

TFT中所使用的非晶質(amorphous)氧化物半導體，相較於汎用的非晶質矽(a-Si)為具有高的載體(carrier)移動度且光學能帶隙為大，可於低溫下成膜。因此，被期待著適用於要求大型．高解析度．高速驅動的新世代顯示器、或耐熱性為低的樹脂基板等。作為適合於此等用途的氧化物半導體之組成，已提案有例如含有In的非晶質氧化物半導體[In-Ga-Zn-O、In-Zn-O、In-Sn-O(ITO)等]。 An amorphous oxide semiconductor used in a TFT has a high carrier mobility and a large optical band gap compared to a general amorphous germanium (a-Si), and can be used at a low temperature. Film formation under the film. Therefore, it is expected to be applied to the requirements of large. High resolution. A new-generation display that is driven at a high speed or a resin substrate with low heat resistance. As a composition of an oxide semiconductor suitable for such applications, for example, an amorphous oxide semiconductor containing In [In-Ga-Zn-O, In-Zn-O, In-Sn-O (ITO), etc. has been proposed. ].

在形成上述氧化物半導體(膜)時，將與該膜為相同材料之濺鍍靶使用於濺鍍之濺鍍法為合適。濺鍍法時，為了製品之薄膜之特性安定化、製造之效率化，防止濺鍍中的異常放電、防止靶之破裂等為重要者，已提案有各式各樣之技術。 In the formation of the above oxide semiconductor (film), a sputtering target having the same material as the film is preferably used for a sputtering method of sputtering. In the sputtering method, various techniques have been proposed for the stability of the properties of the film of the product, the efficiency of the production, the prevention of abnormal discharge during sputtering, and the prevention of cracking of the target.

例如在專利文獻1中對於ITO靶提案著，藉由將晶粒之平均粒徑微細化來抑制異常放電之技術。 For example, Patent Document 1 proposes a technique for suppressing abnormal discharge by refining the average grain size of crystal grains for an ITO target.

又，在專利文獻2中對於ITO靶提案著，藉由提高燒 結密度之同時將粒徑予以微細化，來防止濺鍍中靶板之破裂之技術。 Moreover, in Patent Document 2, an ITO target is proposed, and the burning is improved. The technique of miniaturizing the particle size while preventing the cracking of the target in the sputtering.

更，在專利文獻3中提案著，藉由將In-Zn-O系的複合氧化物於燒結後在還原氣氛中進行退火處理，來提昇靶材料之導電率，並抑制濺鍍中的異常放電或靶之破裂之技術。 Further, Patent Document 3 proposes to improve the conductivity of the target material and suppress the abnormal discharge during sputtering by annealing the In-Zn-O-based composite oxide in a reducing atmosphere after sintering. Or the technique of rupture of the target.

近年，伴隨著顯示裝置之高性能化，要求著氧化物半導體薄膜之特性提昇或特性安定化，同時要求著顯示裝置生產之更進一步之效率化。因此，顯示裝置用氧化物半導體膜之製造中所使用的濺鍍靶及其素材之氧化物燒結體，希望為導電性優異、且具有高的相對密度。又，使用上述濺鍍靶所得到的氧化物半導體膜，希望為具有高的載體移動度。更，在考量生產性或製造成本等時，更進一步地抑制在濺鍍步驟之異常放電(電弧)亦為重要的，因而要求著成為靶材料及其素材的氧化物燒結體之改善。 In recent years, with the increase in the performance of display devices, improvements in characteristics and stability of oxide semiconductor thin films have been demanded, and further efficiency in the production of display devices has been demanded. Therefore, the sputtering target used for the production of the oxide semiconductor film for a display device and the oxide sintered body of the material thereof are desirably excellent in conductivity and high in relative density. Moreover, it is desirable that the oxide semiconductor film obtained by using the above-described sputtering target has a high carrier mobility. Further, in consideration of productivity, manufacturing cost, and the like, it is also important to further suppress abnormal discharge (arc) in the sputtering step, and thus an improvement in an oxide sintered body which is a target material and a material thereof is required.

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

[專利文獻1]日本國特開平7-243036號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 7-243036

[專利文獻2]日本國特開平5-311428號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 5-311428

[專利文獻3]日本國專利第3746094號公報 [Patent Document 3] Japanese Patent No. 3746094

本發明為有鑑於上述情事者，本發明之目的以提供一種適合於顯示裝置用氧化物半導體膜之製造中所使用的氧化物燒結體及濺鍍靶，其係兼具優異之導電性(低比電阻)之同時為高的相對密度，可使具有高載體移動度之氧化物半導體膜抑制異常放電之同時安定地進行成膜的氧化物燒結體及濺鍍靶，以及其製造方法。 In view of the above, an object of the present invention is to provide an oxide sintered body and a sputtering target which are suitable for use in the production of an oxide semiconductor film for a display device, which have excellent electrical conductivity (low In addition to the high relative density of the specific resistance, the oxide semiconductor film having a high carrier mobility can suppress the abnormal discharge while stably forming an oxide sintered body and a sputtering target, and a method for producing the same.

可解決上述課題之本發明之氧化物燒結體，其係將氧化鋅、氧化銦及至少1種選自於由Ti、Mg、Al及Nb所成之群之金屬氧化物混合及燒結而得到的氧化物燒結體，其要旨為將前述氧化物燒結體進行X射線繞射時，以ZnmIn2O3+m(m為5~7之整數)相作為主相並含有In2O3及ZnO之各結晶相，同時為相對密度85%以上、比電阻0.1 Ω．cm以下。 The oxide sintered body of the present invention which solves the above-mentioned problems, which is obtained by mixing and sintering zinc oxide, indium oxide and at least one metal oxide selected from the group consisting of Ti, Mg, Al and Nb. In the oxide sintered body, when the oxide sintered body is X-ray-diffracted, Zn m In 2 O 3+m (m is an integer of 5 to 7) phase as a main phase and contains In 2 O 3 and Each crystal phase of ZnO has a relative density of 85% or more and a specific resistance of 0.1 Ω. Below cm.

在本發明之較佳實施形態中，將前述氧化物燒結體中相對於全金屬元素之鋅、銦、Ti、Mg、Al、Nb之含有量(原子%)分別設定為[Zn]、[In]、[Ti]、[Mg]、[Al]、[Nb]時，相對於[Zn]之[In]之比、相對於[Zn]+[In]+[Ti]+[Mg]+[Al]+[Nb]之[Ti]+[Mg]+[Al]+[Nb]之比分別滿足下式，0.27≦[In]/[Zn]≦0.45 In a preferred embodiment of the present invention, the content (atomic %) of zinc, indium, Ti, Mg, Al, and Nb in the oxide sintered body with respect to the total metal element is set to [Zn], [In, respectively. ], [Ti], [Mg], [Al], [Nb], the ratio of [In] relative to [Zn], relative to [Zn]+[In]+[Ti]+[Mg]+[ The ratio of [Ti]+[Mg]+[Al]+[Nb] of Al]+[Nb] satisfies the following formula, respectively, 0.27≦[In]/[Zn]≦0.45

([Ti]+[Mg]+[Al]+[Nb])/([Zn]+[In]+[Ti]+[Mg]+[Al]+[Nb])≦0.1。 ([Ti]+[Mg]+[Al]+[Nb])/([Zn]+[In]+[Ti]+[Mg]+[Al]+[Nb])≦0.1.

又，在本發明之較佳實施形態中，相對於前述氧化物燒結體中所含有的前述ZnmIn2O3+m、前述In2O3及前述ZnO之合計，各結晶相之體積比為滿足下式者，ZnmIn2O3+m/(ZnmIn2O3+m+In2O3+ZnO)≧0.75 Further, in a preferred embodiment of the present invention, the volume ratio of each crystal phase is the total of the Zn m In 2 O 3+m , the In 2 O 3 and the ZnO contained in the oxide sintered body. To satisfy the following formula, Zn m In 2 O 3+m /(Zn m In 2 O 3+m +In 2 O 3 +ZnO)≧0.75

0.005≦In2O3/(ZnmIn2O3+m+In2O3+ZnO)≦0.15 0.005≦In 2 O 3 /(Zn m In 2 O 3+m +In 2 O 3 +ZnO)≦0.15

0.005≦ZnO/(ZnmIn2O3+m+In2O3+ZnO)≦0.20(其中，ZnmIn2O3+m為Zn5In2O8、Zn6In2O9、Zn7In2O10之合計)。 0.005 ≦ ZnO / (Zn m In 2 O 3 + m + In 2 O 3 + ZnO) ≦ 0.20 (where Zn m In 2 O 3+m is Zn 5 In 2 O 8 , Zn 6 In 2 O 9 , Zn 7 In 2 O 10 total).

又，可解決上述課題之本發明之濺鍍靶，其係使用上述任何一項之氧化物燒結體而得到的濺鍍靶。 Moreover, the sputtering target of the present invention which solves the above-mentioned problems is a sputtering target obtained by using the oxide sintered body of any of the above.

又，可解決上述課題之本發明相關的前述氧化物燒結體之較佳製造方法，其要旨為將氧化鋅、氧化銦及至少1種選自於由Ti、Mg、Al及Nb所成之群之金屬氧化物混合並於黑鉛模中設置後，包含下述第一燒結步驟與第二燒結步驟，同時以加壓壓力100~500kgf/cm2來進行前述第一燒結步驟與前述第二燒結步驟；第一燒結步驟：藉由燒結溫度950~1050℃、於該溫度域之保持時間0.1~5小時來進行燒結；第二燒結步驟：前述第一燒結步驟後，藉由燒結溫度1100~1200℃、於該溫度域之保持時間0.1~5小時來進行燒結。 Moreover, the preferred method for producing the oxide sintered body according to the present invention, which is to solve the above problems, is characterized in that zinc oxide, indium oxide, and at least one selected from the group consisting of Ti, Mg, Al, and Nb are used. After the metal oxide is mixed and disposed in the black lead mold, the first sintering step and the second sintering step are performed, and the first sintering step and the second sintering are performed at a pressing pressure of 100 to 500 kgf/cm 2 . a first sintering step: sintering is performed by a sintering temperature of 950 to 1050 ° C and a holding time in the temperature range of 0.1 to 5 hours; and a second sintering step: after the first sintering step, by a sintering temperature of 1100 to 1200 The sintering is carried out at a temperature in the temperature range of 0.1 to 5 hours.

藉由本發明可得到具有低比電阻、高相對密度的氧化物燒結體及濺鍍靶。又，只要使用本發明之濺鍍靶，由於 可使高載體移動度之氧化物半導體膜抑制異常放電等並安定地進行成膜，故生產性會提昇。 According to the present invention, an oxide sintered body having a low specific resistance and a high relative density and a sputtering target can be obtained. Also, as long as the sputtering target of the present invention is used, The oxide semiconductor film having a high carrier mobility can be stably formed by suppressing abnormal discharge or the like, and productivity can be improved.

又，藉由本發明之製造方法，可製造具有上述特性之氧化物燒結體。 Moreover, the oxide sintered body having the above characteristics can be produced by the production method of the present invention.

[實施發明之的最佳形態] [Best Mode for Carrying Out the Invention]

本發明團隊對於含有氧化鋅與氧化銦之氧化物燒結體，以提供就抑制濺鍍中之異常放電，並可進行長時間之安定成膜，且適合於成膜成為高載體移動度之氧化物半導體膜之濺鍍靶用氧化物燒結體而進行不斷重複之檢討。 The inventors of the present invention provide an oxide containing zinc oxide and indium oxide to provide an oxide which inhibits abnormal discharge during sputtering and can be stably formed for a long period of time, and is suitable for film formation to form a high carrier mobility. The oxide sintered body for a sputtering target of a semiconductor film is continuously reviewed.

其結果發現，當設定如下述之構成時，可達成所期望之目的：其係將氧化鋅、氧化銦及至少1種選自於由Ti、Mg、Al及Nb所成之群之金屬(以下稱為M金屬)氧化物之各粉末混合及燒結而得到的氧化物燒結體，將上述氧化物燒結體進行X射線繞射時，以ZnmIn2O3+m(m為5~7之整數)相作為主相並含有In2O3及ZnO之各結晶相。 As a result, it has been found that a desired object can be achieved by setting zinc oxide, indium oxide, and at least one metal selected from the group consisting of Ti, Mg, Al, and Nb (hereinafter, An oxide sintered body obtained by mixing and sintering each of the powders of the M metal oxide is Zn m In 2 O 3+m (m is 5 to 7) when the oxide sintered body is X-ray-diffracted. The integer) phase serves as a main phase and contains each crystal phase of In 2 O 3 and ZnO.

詳細為在對於將上述氧化物燒結體進行X射線繞射時之相構成研究時發現：(i)Zn與In在作為此等結合的ZnmIn2O3+m(m為5~7之整數)相(主相)及In2O3、ZnO存在，並成為如此般之相構成時，可大幅抑制濺鍍時之異常放電，(ii)M金屬對於載體移動度之提昇發揮有用之效果，(iii)藉由控制相對密度與比電阻可更進一步地提昇在濺鍍中抑制異常放電之產生之效果。然後發現(iv)為了得到具有如此般相構成之氧化物燒結體，只要藉由使 用指定的燒結條件來進行燒結即可，遂而完成本發明。 Specifically, in the study of the phase composition for X-ray diffraction of the above oxide sintered body, it was found that: (i) Zn and In are combined as Zn m In 2 O 3+m (m is 5 to 7) When the integer phase (main phase), In 2 O 3 , and ZnO are present, and the composition is such a phase, the abnormal discharge during sputtering can be greatly suppressed, and (ii) the M metal exerts a useful effect on the carrier mobility. (iii) The effect of suppressing the occurrence of abnormal discharge in sputtering can be further improved by controlling the relative density and the specific resistance. Then, it was found that (iv) in order to obtain an oxide sintered body having such a phase, it is only necessary to carry out sintering by using specified sintering conditions, and the present invention has been completed.

首先，對於本發明相關的氧化物燒結體之構成進行詳細說明。如同上述般，本發明之氧化物燒結體在將上述氧化物燒結體進行X射線繞射時，其特徵為含有以ZnmIn2O3+m(m為5~7之整數)作為主相及In2O3、ZnO之各結晶相之氧化物燒結體。 First, the configuration of the oxide sintered body according to the present invention will be described in detail. As described above, in the oxide sintered body of the present invention, when the oxide sintered body is X-ray-diffracted, it is characterized in that Zn m In 2 O 3+m (m is an integer of 5 to 7) as a main phase And an oxide sintered body of each crystal phase of In 2 O 3 and ZnO.

本發明之X射線繞射條件如同下述。 The X-ray diffraction conditions of the present invention are as follows.

分析裝置：理學電機製「X射線繞射裝置RINT-1500」 Analytical device: Neo-mechanical mechanism "X-ray diffraction device RINT-1500"

分析條件：靶：Cu Analysis conditions: target: Cu

單色化：使用單色器(K α) Monochromatization: using a monochromator (K α)

靶出力：40kV-200mA Target output: 40kV-200mA

(連續測定)θ/2 θ掃描 (continuous measurement) θ/2 θ scan

光柵：發散1/2°、散射1/2°、受光0.15mm Grating: divergence 1/2°, scattering 1/2°, light receiving 0.15 mm

單色器受光光柵：0.6mm Monochromator light receiving grating: 0.6mm

掃描速度：2°/min Scanning speed: 2°/min

採樣寬度：0.02° Sample width: 0.02°

測定角度(2 θ)：5~90° Measuring angle (2 θ): 5~90°

對於使用此測定所得到的繞射波峰，界定為具有以ICDD(International Center for Diffraction Data)卡之20-1440、20-1441、06-0416、36-1451所記載的結晶構造之結晶相(分別為對應於Zn5In2O8、Zn7In2O10、In2O3、ZnO)。又，Zn6In2O9為界定為具有下述參考文獻(1)、 (2)中所記載之結晶構造之結晶相。 The diffraction peak obtained by using this measurement is defined as a crystal phase having a crystal structure described in 20-1440, 20-1441, 06-0416, and 36-1451 of the ICDD (International Center for Diffraction Data) card (respectively Corresponding to Zn 5 In 2 O 8 , Zn 7 In 2 O 10 , In 2 O 3 , ZnO). Further, Zn 6 In 2 O 9 is a crystal phase defined as having the crystal structure described in the following references (1) and (2).

參考文獻(1) M. Nakamura, N. Kimizuka and T. Mohri: J. Solid State Chem. 86 (1990) 16-40； 參考文獻(2) M. Nakamura, N. Kimizuka, T. Mohri and M. Isobe: J. Solid State Chem. 105 (1993) 535-549。 References (1) M. Nakamura, N. Kimizuka and T. Mohri: J. Solid State Chem. 86 (1990) 16-40; References (2) M. Nakamura, N. Kimizuka, T. Mohri and M. Isobe: J. Solid State Chem. 105 (1993) 535-549.

接著，對於藉由上述X射線繞射之檢測而界定的本發明之化合物進行詳細說明。 Next, the compound of the present invention defined by the above-described detection of X-ray diffraction will be described in detail.

(關於ZnmIn2O3+m化合物) (About Zn m In 2 O 3+m compound)

ZnmIn2O3+m化合物(相)為構成本發明之氧化物燒結體之氧化鋅與氧化銦結合所形成者。此化合物之結晶構造為六方晶，對於氧化物燒結體之載體移動度之提昇具大貢獻。 The Zn m In 2 O 3+m compound (phase) is formed by combining zinc oxide and indium oxide which constitute the oxide sintered body of the present invention. The crystal structure of this compound is hexagonal crystal, which contributes greatly to the improvement of carrier mobility of the oxide sintered body.

ZnmIn2O3+m化合物之m為5(Zn5In2O8)、6(Zn6In2O9)、7(Zn7In2O10)中之至少任意一個。當m為4以下、或8以上之整數時，氧化物半導體膜之半導體特性會劣化，由於載體移動度會下降，故不宜。尚，由於此等為與Zn、In及M金屬之複合氧化物之結晶，故m會成為整數。 m of the Zn m In 2 O 3+m compound is at least one of 5 (Zn 5 In 2 O 8 ), 6 (Zn 6 In 2 O 9 ), and 7 (Zn 7 In 2 O 10 ). When m is 4 or less, or an integer of 8 or more, the semiconductor characteristics of the oxide semiconductor film are deteriorated, and the carrier mobility is lowered, which is not preferable. Further, since these are crystals of a composite oxide with Zn, In, and M metals, m becomes an integer.

在本發明為含有上述ZnmIn2O3+m化合物作為主相。在此，所謂的「主相」，意味著在藉由上述X射線繞射所檢測出的全化合物中，ZnmIn2O3+m(Zn5In2O8(m=5)、Zn6In2O9(m=6)、Zn7In2O10(m=7)之合計)為比率最多之化合物。 In the present invention, the above-mentioned Zn m In 2 O 3+m compound is contained as a main phase. Here, the term "main phase" means Zn m In 2 O 3+m (Zn 5 In 2 O 8 (m=5), Zn in the total compound detected by the X-ray diffraction described above. 6 In 2 O 9 (m=6), Zn 7 In 2 O 10 (m=7) in total) is the compound with the highest ratio.

又，本發明之氧化物燒結體為必須含有In2O3及ZnO之各結晶相(化合物)。藉由使In2O3及ZnO含有於氧化物燒結體中可抑制異常放電。雖然該詳細之機制尚不明確，但藉由含有不僅是複合氧化物(ZnmIn2O3+m)，亦含有單獨金屬元素之氧化物(In2O3、及ZnO)，局部之導電率或熱傳導率會提昇，推察因而抑制了異常放電。 Further, the oxide sintered body of the present invention is required to contain each crystal phase (compound) of In 2 O 3 and ZnO. Abnormal discharge can be suppressed by including In 2 O 3 and ZnO in the oxide sintered body. Although the detailed mechanism is not clear, it is partially conductive by containing not only a composite oxide (Zn m In 2 O 3+m ) but also an oxide of a single metal element (In 2 O 3 , and ZnO). The rate or thermal conductivity is increased, and the investigation suppresses the abnormal discharge.

本發明之上述各結晶相中亦包含後述之M金屬為固溶之情形。更，In2O3及ZnO中亦包含除了M金屬以外，Zn或In為固溶之情形。 The above-mentioned respective crystal phases of the present invention also include a case where the M metal described later is solid-solved. Further, in 2 O 3 and ZnO, Zn or In is a solid solution in addition to the M metal.

本發明中所使用的M金屬，對於藉由濺鍍而形成之膜之載體移動度提昇為有用之元素。M金屬為至少1種選自於由Ti、Mg、Al及Nb所成之群。在本發明可單獨使用上述M金屬，或亦可併用2種以上。當中，就半導體特性之觀點而言，較佳的M金屬為Ti、Mg、Al。 The M metal used in the present invention is a useful element for improving the carrier mobility of a film formed by sputtering. The M metal is at least one selected from the group consisting of Ti, Mg, Al, and Nb. In the present invention, the above M metals may be used singly or in combination of two or more kinds. Among them, preferred M metals are Ti, Mg, and Al from the viewpoint of semiconductor characteristics.

M金屬係以作為對於僅由氧化鋅與氧化銦所成的氧化物燒結體之載體移動度提昇為貢獻大之元素而被選出之元素。相較於未含有M金屬之情形，藉由較佳為使用以後述指定之比率含有本發明所限定的M金屬之氧化物燒結體，載體移動度為提昇。 The M metal is an element selected as an element that contributes to the increase in carrier mobility of the oxide sintered body formed only of zinc oxide and indium oxide. In the case where the M metal is not contained, the carrier mobility is improved by preferably containing the oxide sintered body of the M metal defined in the present invention at a ratio specified later.

尚，為了使展現出載體移動度提昇之效果，宜為M金屬之至少一部份(較佳為其大部分)為固溶於上述結晶相中。惟，並不限定於此，只要是不會阻礙本發明之載體移動度提昇之效果，M金屬之一部份可作為氧化物存在(例如，5體積%以下)。 Further, in order to exhibit the effect of enhancing the mobility of the carrier, it is preferred that at least a portion (preferably a majority of) of the M metal is dissolved in the crystalline phase. However, the present invention is not limited thereto, and any part of the M metal may exist as an oxide (for example, 5% by volume or less) as long as it does not impede the effect of the carrier mobility improvement of the present invention.

接著，對於在本發明之氧化物燒結體中，相對於氧以外之全金屬元素之各金屬元素之含有量(原子%)進行說明。將氧化物燒結體中相對於全金屬元素之鋅、銦、Ti、Mg、Al、Nb之含有量(原子%)分別設定為[Zn]、[In]、[Ti]、[Mg]、[Al]、[Nb]時，使相對於[Zn]之[In]之比、相對於[Zn]+[In]+[Ti]+[Mg]+[Al]+[Nb]之[Ti]+[Mg]+[Al]+[Nb]之比設定如下述界定之範圍內，就可得到上述所希望之效果之觀點而言，故宜。在此，[Ti]、[Mg]、[Al]、[Nb]為M金屬之一種，例如在各燒結體中不含Ti時，以作為[Ti]=0而算出。 Next, the content (atomic %) of each metal element of the all-metal element other than oxygen in the oxide sintered body of the present invention will be described. The content (atomic %) of zinc, indium, Ti, Mg, Al, and Nb in the oxide sintered body relative to the total metal element is set to [Zn], [In], [Ti], [Mg], [ [Al], [Nb], the ratio of [In] relative to [Zn], relative to [Zn]+[In]+[Ti]+[Mg]+[Al]+[Nb][Ti] The ratio of +[Mg]+[Al]+[Nb] is set within the range defined below, and it is preferable to obtain the above-described desired effect. Here, [Ti], [Mg], [Al], and [Nb] are one type of M metal. For example, when Ti is not contained in each sintered body, it is calculated as [Ti]=0.

相對於[Zn]之[In]之比([In]/[Zn]；以下稱為比率(1))，較佳為0.27以上、更佳為0.28以上；較佳為0.45以下、更佳為0.40以下。當比率(1)變小時，變得會生成[ZnmIn2O3+m]為m≦4之複合氧化物(Zn4In2O7等)，比電阻率會變高而載體移動度會下降。另一方面，當比率(1)變大時，變得會生成[ZnmIn2O3+m]為m≧8之複合氧化物(Zn8In2O11等)，載體移動度會下降。 The ratio of [In]/[Zn] with respect to [Zn] (hereinafter referred to as ratio (1)) is preferably 0.27 or more, more preferably 0.28 or more; preferably 0.45 or less, more preferably Below 0.40. When the ratio (1) becomes small, a composite oxide (Zn 4 In 2 O 7 or the like) in which [Zn m In 2 O 3+m ] is m≦4 is formed, and the specific resistivity becomes high and the carrier mobility is increased. Will fall. On the other hand, when the ratio (1) becomes large, a composite oxide (Zn 8 In 2 O 11 or the like) in which [Zn m In 2 O 3+m ] is m≧8 is formed, and the carrier mobility is lowered. .

又，相對於[Zn]+[In]+[Ti]+[Mg]+[Al]+[Nb]之[Ti]+[Mg]+[Al]+[Nb]之比(([Ti]+[Mg]+[Al]+[Nb])/([Zn]+[In]+[Ti]+[Mg]+[Al]+[Nb])；以下稱為比率(2))，較佳為0.1以下、更佳為0.05以下。當比率(2)變大時，M金屬會與In或Zn生成複合氧化物而薄膜之半導體特性會劣化，並由於載體移動度會下降之故。尚，關於比率(2)之下限雖未特別限定，但就薄膜半導體特性之安定化觀點 而言，較佳為0.001以上、更佳為0.005以上。 Also, relative to [Zn]+[In]+[Ti]+[Mg]+[Al]+[Nb][Ti]+[Mg]+[Al]+[Nb] ratio (([Ti] +[Mg]+[Al]+[Nb])/([Zn]+[In]+[Ti]+[Mg]+[Al]+[Nb]); hereinafter referred to as ratio (2)), It is preferably 0.1 or less, more preferably 0.05 or less. When the ratio (2) becomes large, the M metal forms a composite oxide with In or Zn, and the semiconductor characteristics of the film are deteriorated, and the carrier mobility is lowered. Further, although the lower limit of the ratio (2) is not particularly limited, the viewpoint of the stability of the thin film semiconductor is considered. Preferably, it is 0.001 or more, More preferably, it is 0.005 or more.

接下來，對於相對於氧化物燒結體中所含有的ZnmIn2O3+m(其中，[ZnmIn2O3+m]為[Zn5In2O8]、[Zn6In2O9]、[Zn7In2O10]之合計，以下亦同)、In2O3及ZnO之合計之各結晶相之體積比進行說明。以下將相對於[ZnmIn2O3+m]+[In2O3]+[ZnO]之合計之ZnmIn2O3+m之比、In2O3比、ZnO比，分別稱為[ZnmIn2O3+m]比、[In2O3]比、[ZnO]比。藉由適當控制此等比率可更進一步地抑制濺鍍時之異常放電。 Next, with respect to Zn m In 2 O 3+m contained in the oxide sintered body (where [Zn m In 2 O 3+m ] is [Zn 5 In 2 O 8 ], [Zn 6 In 2 ] The volume ratio of each crystal phase in which the total of O 9 ], [Zn 7 In 2 O 10 ], and the total amount of In 2 O 3 and ZnO are combined will be described. Hereinafter, the ratio of Zn m In 2 O 3+m, the ratio of In 2 O 3 , and the ratio of ZnO of [Zn m In 2 O 3+m ]+[In 2 O 3 ]+[ZnO] are respectively referred to as It is a ratio of [Zn m In 2 O 3+m ], a ratio of [In 2 O 3 ], and a ratio of [ZnO]. Abnormal discharge at the time of sputtering can be further suppressed by appropriately controlling these ratios.

首先，[ZnmIn2O3+m]比較佳設定為0.75以上。藉由將[ZnmIn2O3+m]比設定為0.75以上，可更進一步地抑制異常放電。更佳的下限為0.8以上、又更佳為0.85以上。[ZnmIn2O3+m]比之上限未特別限定，只要是在含有後述In2O3與ZnO之範圍內決定即可。 First, [Zn m In 2 O 3+m ] is preferably set to 0.75 or more. By setting the [Zn m In 2 O 3+m ] ratio to 0.75 or more, abnormal discharge can be further suppressed. A more preferable lower limit is 0.8 or more, and more preferably 0.85 or more. The upper limit of [Zn m In 2 O 3+m ] is not particularly limited, and may be determined within a range containing In 2 O 3 and ZnO to be described later.

[In2O3]比較佳為0.005~0.15。當[In2O3]比未達0.005時，有無法充分得到抑制異常放電效果之情形。另一方面，當[In2O3]比超過0.15時，由於異常放電之產生次數會變多，故不宜。[In2O3]比更佳為0.01以上、又更佳為0.03以上；更佳為0.13以下、又更佳為0.1以下。 [In 2 O 3 ] is preferably 0.005 to 0.15. When the ratio of [In 2 O 3 ] is less than 0.005, the effect of suppressing the abnormal discharge cannot be sufficiently obtained. On the other hand, when the ratio of [In 2 O 3 ] exceeds 0.15, the number of occurrences of abnormal discharge increases, which is not preferable. The ratio of [In 2 O 3 ] is more preferably 0.01 or more, still more preferably 0.03 or more; more preferably 0.13 or less, still more preferably 0.1 or less.

又，[ZnO]比較佳為0.005~0.20。當[ZnO]比未達0.005時，有無法充分得到抑制異常放電效果之情形。另一方面，當[ZnO]比超過0.20時，由於異常放電之產生次數會變多，故不宜。[ZnO]比更佳為0.01以上、又更佳為0.03以上；更佳為0.15以下、又更佳為0.13以下。 Further, [ZnO] is preferably 0.005 to 0.20. When the ratio of [ZnO] is less than 0.005, the effect of suppressing the abnormal discharge cannot be sufficiently obtained. On the other hand, when the ratio of [ZnO] exceeds 0.20, the number of occurrences of abnormal discharge increases, which is not preferable. The ratio of [ZnO] is more preferably 0.01 or more, still more preferably 0.03 or more; more preferably 0.15 or less, still more preferably 0.13 or less.

本發明之氧化物燒結體之結晶相，實質上希望為以ZnmIn2O3+m、In2O3及ZnO所構成。在本發明中，作為其他可能含有之結晶相，舉例如在製造上不可避免而生成的Zn2TiO4、InNbO4等，能以5體積%左右之比例來含有此等結晶相。尚，不可避免而生成的結晶相之比例，可藉由XRD來進行測定。 The crystal phase of the oxide sintered body of the present invention is substantially composed of Zn m In 2 O 3+m , In 2 O 3 and ZnO. In the present invention, as another crystal phase which may be contained, for example, Zn 2 TiO 4 or InNbO 4 which is unavoidably produced in the production, such a crystal phase can be contained in a ratio of about 5% by volume. Further, the ratio of the crystal phase which is inevitably formed can be measured by XRD.

本發明之氧化物燒結體，進而以使用該氧化物燒結體而得到的濺鍍靶，其特徵為相對密度85%以上、比電阻0.1 Ω．cm以下。 The oxide sintered body of the present invention further has a sputtering target obtained by using the oxide sintered body, and has a relative density of 85% or more and a specific resistance of 0.1 Ω. Below cm.

(相對密度85%以上) (relative density is 85% or more)

本發明之氧化物燒結體之相對密度為非常高，較佳為85%以上、更佳為95%以上。高相對密度不僅能防止在濺鍍中之鍍瘤(nodule)之產生，亦能帶來直到靶壽命(target life)為止維持持續安定之放電等優點。 The relative density of the oxide sintered body of the present invention is very high, preferably 85% or more, more preferably 95% or more. The high relative density not only prevents the occurrence of nodules during sputtering, but also provides the advantage of maintaining a stable discharge up to the target life.

(比電阻0.1 Ω．cm以下) (specific resistance is less than 0.1 Ω.cm)

本發明之氧化物燒結體之比電阻為小的0.1 Ω．cm以下，較佳為0.01 Ω．cm以下。藉此，可成為在濺鍍中為進一步抑制異常放電之成膜，可將使用濺鍍靶之物理蒸鍍(濺鍍法)有效率地運用於顯示裝置之生產線。 The specific resistance of the oxide sintered body of the present invention is 0.1 Ω which is small. Below cm, preferably 0.01 Ω. Below cm. Thereby, it is possible to form a film for further suppressing abnormal discharge during sputtering, and it is possible to efficiently apply physical vapor deposition (sputtering method) using a sputtering target to a production line of a display device.

接著，對於製造本發明之氧化物燒結體之方法進行說明。 Next, a method of producing the oxide sintered body of the present invention will be described.

本發明之氧化物燒結體為將氧化鋅、氧化銦及M金屬 氧化物之各粉末混合及燒結而得到者。又，濺鍍靶可藉由將氧化物燒結體進行加工而製造。圖1中為表示，將氧化物之粉末以進行(a)混合．粉碎→(b)乾燥．造粒→(c)預備成形→(d)脫脂→(e)熱壓製而得到氧化物燒結體，再將該氧化物燒結體以進行(f)加工→(g)黏合而得到濺鍍靶為止之基本步驟。上述步驟之中，本發明之特徵為適當地控制如下述所詳述般之燒結條件((e)熱壓製)，而其以外之步驟並未特別限定，可適當地選擇通常所使用之步驟。以下為對於各步驟進行說明，惟本發明並不限定於此等內容。 The oxide sintered body of the present invention is zinc oxide, indium oxide and M metal The powder of each oxide is mixed and sintered to obtain. Further, the sputtering target can be produced by processing an oxide sintered body. Figure 1 shows that the oxide powder is used for (a) mixing. Crush → (b) dry. Granulation → (c) preliminary forming → (d) degreasing → (e) hot pressing to obtain an oxide sintered body, and then the oxide sintered body is subjected to (f) processing → (g) bonding to obtain a sputtering target The basic steps. Among the above steps, the present invention is characterized in that the sintering conditions ((e) hot pressing) as described in detail below are appropriately controlled, and the other steps are not particularly limited, and the usual steps can be appropriately selected. Hereinafter, each step will be described, but the present invention is not limited to these contents.

首先，將氧化鋅粉末、氧化銦粉末及M金屬氧化物之粉末摻合成為指定之比例，並進行混合．粉碎。所使用的各原料粉末之純度，分別較佳約為99.99%以上。當存在有微量的雜質元素時，係因而有損及氧化物半導體膜之半導體特性之虞。各原料粉末之摻合比例，較佳為使相對於[Zn]之[In]之比、相對於[Zn]+[In]+[Ti]+[Mg]+[Al]+[Nb]之[Ti]+[Mg]+[Al]+[Nb]比以成為如上述範圍內之方式來進行控制。 First, a powder of zinc oxide powder, indium oxide powder and M metal oxide is blended into a specified ratio and mixed. Smash. The purity of each raw material powder used is preferably about 99.99% or more. When a trace amount of an impurity element is present, the semiconductor characteristics of the oxide semiconductor film are impaired. The blending ratio of each raw material powder is preferably such that the ratio of [In] to [Zn] is relative to [Zn]+[In]+[Ti]+[Mg]+[Al]+[Nb] The [Ti]+[Mg]+[Al]+[Nb] ratio is controlled so as to be within the above range.

(a)混合．粉碎較佳為使用球磨機，並將原料粉未與水一併投入來進行。此等步驟中所使用的球或珠粒，較佳為使用例如尼龍、氧化鋁、氧化鋯等材質者。此時，以均勻進行混合為目的，可混合分散劑或用來確保之後成形步驟之容易性之黏合劑(binder)。 (a) Mixing. The pulverization is preferably carried out by using a ball mill and putting the raw material powder together with water. The balls or beads used in these steps are preferably those using materials such as nylon, alumina, and zirconia. At this time, for the purpose of uniformly mixing, a dispersant or a binder for ensuring the ease of the subsequent forming step can be mixed.

接著，對於以上述步驟所得到的混合粉末，較佳為使 用例如噴霧乾燥機(spray dryer)等來進行(b)乾燥．造粒。 Next, it is preferred to use the mixed powder obtained in the above step. Drying (b) by, for example, a spray dryer or the like. Granulation.

乾燥．造粒後為進行(c)預備成形。在成形之際，將乾燥．造粒後之粉末充填於指定尺寸之模具中，使用模具壓製來預備成形。此預備成形係以提昇在熱壓製步驟中設置於指定模之際之操作性為目的而進行者，故只要施加0.5~1.0tonf/cm2左右之加壓力使成為成形體即可。 dry. After granulation, (c) preliminary forming is performed. At the time of forming, it will dry. The granulated powder is filled in a mold of a specified size and pressed to prepare for molding. This preliminary molding is performed for the purpose of improving the workability at the time of setting in the hot stamping step, and it is sufficient to apply a pressing force of about 0.5 to 1.0 tonf/cm 2 to form a molded body.

尚，當添加分散劑或黏合劑於混合粉末時，為了將分散劑或黏合劑除去，宜為將預備成形後之成形體予以加熱來進行(d)脫脂。加熱條件只要是能達成脫脂目的未特別限定，例如，可在大氣中，以大約500℃左右來保持5小時左右即可。 When a dispersant or a binder is added to the mixed powder, in order to remove the dispersant or the binder, it is preferred to heat (d) degrease the molded body after preliminary molding. The heating condition is not particularly limited as long as it can achieve degreasing, and for example, it can be maintained in the air at about 500 ° C for about 5 hours.

脫脂後，將成形體設置於所希望形狀的黑鉛模中並藉由(e)熱壓製來進行燒結。黑鉛模為還原性材料，由於可使設置後的成形體在還原性氣氛中燒結，故可效率良好地進行還原而降低比電阻。 After degreasing, the formed body is placed in a black lead mold of a desired shape and sintered by (e) hot pressing. Since the black lead mold is a reducing material, since the formed body after the sintering can be sintered in a reducing atmosphere, the reduction can be efficiently performed to lower the specific resistance.

在本發明為藉由將燒結區分成2階段之加熱步驟來進行(圖2)，可使成為所希望的結晶相構成，並提高相對密度。雖然詳細的機構尚不明確，惟認為於第一燒結步驟會進行燒結體之緻密化及還原，並於第二燒結步驟進而進行還原之同時，原料氧化物會進行固溶反應而生成所希望的複合氧化物(ZnmIn2O3+m(m=5、6、7))。又，藉由使燒結區分成2階段之步驟來進行，由於可實施燒結體之緻密化及複合氧化物之生成為分別最合適之條件，故推測 能以高相對密度得到具有所希望之結晶相之氧化物燒結體。 In the present invention, by performing the heating step of dividing the sintering into two stages (Fig. 2), it is possible to form a desired crystal phase and increase the relative density. Although the detailed mechanism is not clear, it is considered that the densification and reduction of the sintered body are performed in the first sintering step, and further reduction is performed in the second sintering step, and the raw material oxide undergoes a solid solution reaction to form a desired one. Composite oxide (Zn m In 2 O 3+m (m=5, 6, 7)). Further, by performing the step of dividing the sintering into two stages, since the densification of the sintered body and the formation of the composite oxide can be performed as the most suitable conditions, it is presumed that a desired crystal phase can be obtained at a high relative density. An oxide sintered body.

第一燒結步驟之條件為燒結溫度：950~1050℃，並以於該溫度之保持時間：0.1~5小時來進行燒結。當燒結溫度未達950℃或超過1050℃時，無法達成所希望的相對密度。較佳燒結溫度為975℃以上、1040℃以下。又，當燒結時間過短時，無法充分緻密化，無法達成所希望的相對密度。因此，燒結時間以0.1小時以上、較佳為0.5小時以上、更佳為1.0小時以上。尚，當燒結時間越長時，雖相對密度亦會變高，由於生產性會惡化，故以5小時以下、較佳為4小時以下、更佳為3小時以下。 The conditions of the first sintering step are sintering temperature: 950 to 1050 ° C, and sintering is performed at a temperature retention time of 0.1 to 5 hours. When the sintering temperature is less than 950 ° C or exceeds 1050 ° C, the desired relative density cannot be achieved. The sintering temperature is preferably 975 ° C or higher and 1040 ° C or lower. Further, when the sintering time is too short, sufficient densification cannot be achieved, and a desired relative density cannot be achieved. Therefore, the sintering time is 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1.0 hour or longer. Further, when the sintering time is longer, the relative density is also increased, and the productivity is deteriorated, so that it is 5 hours or shorter, preferably 4 hours or shorter, more preferably 3 hours or shorter.

第二燒結步驟之條件為燒結溫度：1100~1200℃，並以於該溫度之保持時間：0.1~5小時來進行燒結。當燒結溫度低時，無法生成所希望的複合氧化物或生成量會變少。因此，燒結溫度設定為1100℃以上、較佳為1125℃以上。另一方面，當燒結溫度過高時，對於複合氧化物之固溶反應會過度地進行，而變得無法確保所希望的氧化鋅、氧化銦量。因此，燒結溫度設定為1200℃以下、較佳為1150℃以下。又，當燒結時間過短時，會變得無法確保充足量的複合氧化物。因此，燒結時間設定為0.1小時以上、較佳為0.5小時以上、更佳為1.0小時以上。另一方面，當燒結時間過長時，由於上述固溶反應之過度進行，而變得無法確保氧化鋅量等。因此，燒結時間設定為5小時以下、較佳為4小時以下、更佳為3小時以下。 在上述2階段之燒結步驟中，熱壓製時之加壓條件為第一燒結步驟、第二燒結步驟均為施加100~500kgf/cm2左右之壓力。當壓力過低時，有緻密化無法充分進行之情形。另一方面，當壓力過高時，有黑鉛模破損之虞，又，促進緻密化效果會飽和，同時需要壓製設備之大型化。較佳的加壓條件為150kgf/cm2以上、400kgf/cm2以下。尚，加壓條件可第一燒結步驟與第二燒結步驟為相同或相異，惟就生產性觀點而言，宜為在相對之壓力下來進行。 The conditions of the second sintering step are sintering temperature: 1100 to 1200 ° C, and sintering is performed at a temperature retention time of 0.1 to 5 hours. When the sintering temperature is low, the desired composite oxide cannot be formed or the amount of formation becomes small. Therefore, the sintering temperature is set to 1100 ° C or higher, preferably 1125 ° C or higher. On the other hand, when the sintering temperature is too high, the solid solution reaction with respect to the composite oxide proceeds excessively, and the desired amount of zinc oxide or indium oxide cannot be secured. Therefore, the sintering temperature is set to 1200 ° C or lower, preferably 1150 ° C or lower. Further, when the sintering time is too short, it becomes impossible to secure a sufficient amount of the composite oxide. Therefore, the sintering time is set to 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1.0 hour or longer. On the other hand, when the sintering time is too long, the amount of zinc oxide or the like cannot be ensured because the solid solution reaction proceeds excessively. Therefore, the sintering time is set to 5 hours or shorter, preferably 4 hours or shorter, more preferably 3 hours or shorter. In the above-described two-stage sintering step, the pressing conditions at the time of hot pressing are such that the first sintering step and the second sintering step are both applied with a pressure of about 100 to 500 kgf/cm 2 . When the pressure is too low, there is a case where densification cannot be sufficiently performed. On the other hand, when the pressure is too high, there is a flaw in the black lead mold, and the densification effect is saturated, and the size of the pressing equipment is required. The preferred pressurization conditions are 150 kgf/cm 2 or more and 400 kgf/cm 2 or less. Further, the pressurization condition may be the same or different from the first sintering step and the second sintering step, but it is preferably carried out under a relative pressure from the viewpoint of productivity.

昇溫速度未特別限定，例如，可為至第一燒結步驟之溫度域為止之昇溫速度為10~20℃/分左右，而第一燒結步驟後，至第二燒結步驟之溫度域為止之昇溫速度為2~10℃/分左右。 The temperature increase rate is not particularly limited. For example, the temperature increase rate to the temperature range of the first sintering step may be about 10 to 20 ° C / min, and the temperature increase rate after the first sintering step and the temperature range to the second sintering step. It is about 2~10 °C / min.

在燒結步驟宜為藉由H2、甲烷、CO等之還原性氣體、Ar、N2等之惰性氣體氣氛來進行。特別是在使用黑鉛模之本發明，為了抑制黑鉛之氧化、消失，較佳為使燒結氣氛成為惰性氣體氣氛。控制氣氛之方法未特別限定，例如，可藉由將Ar氣體或N2氣體導入至爐內來調整氣氛。又，氣氛氣體之壓力，為了抑制蒸氣壓為高的氧化鋅之蒸發，宜使成為大氣壓。 The sintering step is preferably carried out by a reducing gas such as H 2 , methane or CO, or an inert gas atmosphere such as Ar or N 2 . In particular, in the present invention using a black lead mold, in order to suppress oxidation and disappearance of black lead, it is preferred to make the sintering atmosphere an inert gas atmosphere. The method of controlling the atmosphere is not particularly limited. For example, the atmosphere can be adjusted by introducing Ar gas or N 2 gas into the furnace. Further, in order to suppress the evaporation of zinc oxide having a high vapor pressure, the pressure of the atmosphere gas is preferably atmospheric.

如上述般操作而得到氧化物燒結體後，藉由常法來進行(f)加工→(g)黏合時，可得到本發明之濺鍍靶。如此般操作而得到的濺鍍靶之相對密度及比電阻亦與氧化物燒結體為相同地，為非常良好者，較佳的相對密度大約為85%以上，較佳的比電阻大約為0.1 Ω．cm以下。 After the oxide sintered body is obtained as described above, the sputtering target of the present invention can be obtained by (f) processing → (g) bonding by a usual method. The relative density and specific resistance of the sputtering target obtained in such a manner are also very good as in the case of the oxide sintered body, and the preferred relative density is about 85% or more, and the preferred specific resistance is about 0.1 Ω. . Below cm.

本專利申請案係基於2011年11月4日提出申請的日本國專利申請案特願2011-242891號來主張優先権。參考2011年11月4日所提出日本國專利申請案特願2011-242891號之全說明書內容，並予以援用於本專利申請案。 This patent application claims priority based on Japanese Patent Application No. 2011-242891 filed on Nov. 4, 2011. The contents of the full specification of Japanese Patent Application No. 2011-242891, filed on November 4, 2011, are hereby incorporated by reference.

[實施例] [Examples]

以下，例舉實施例來將本發明更具體地進行說明，惟本發明並不限定於下述實施例，在可適合本發明之宗旨之範圍內予以適當地加以變更為可能的，此等均包含於本發明之技術範圍。 In the following, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples, and may be appropriately changed within the scope of the gist of the present invention. It is included in the technical scope of the present invention.

將氧化鋅粉末(純度99.99%)、氧化銦粉末(純度99.99%)、及氧化鈦、氧化鎂、氧化鋁、氧化鈮之各粉末(各純度99.99%)以如表2中所示之比率予以摻合，並加入水及分散劑(聚羧酸銨)以尼龍球磨機混合20小時。接著，對於以上述步驟所得到的混合粉末進行乾燥、造粒。 Zinc oxide powder (purity: 99.99%), indium oxide powder (purity: 99.99%), and each of titanium oxide, magnesium oxide, aluminum oxide, and cerium oxide (each purity: 99.99%) were given at a ratio as shown in Table 2. Blend and add water and a dispersing agent (ammonium polycarboxylate) for 20 hours in a nylon ball mill. Next, the mixed powder obtained in the above step is dried and granulated.

將如此般所得到的粉末以模具壓製予以預備成形後(成形壓力：1.0tonf/cm2、成形體尺寸： 110×t13mm、t為厚度)，在大氣氣氛下昇溫(昇溫速度1℃/min)至500℃，並以該溫度保持5小時來脫脂。將所得到的成形體設置於黑鉛模中，以如表3所示之條件(A~F)來進行熱壓製。壓製壓力為使第一燒結步驟、第二燒結步驟皆設定為一定。此時，將N2氣體導入於熱壓製爐內，在N2氣 氛下進行燒結。將所得到的燒結體進行機械加工精飾成為 100×t5mm，並與Cu製墊板黏合而製成濺鍍靶。 The powder thus obtained was preliminarily molded by pressing with a mold (forming pressure: 1.0 tonf/cm 2 , and the size of the molded body: 110 × t13 mm, t is the thickness), the temperature was raised in an air atmosphere (temperature rising rate 1 ° C / min) to 500 ° C, and the temperature was maintained for 5 hours to degrease. The obtained molded body was placed in a black lead mold, and hot pressed was carried out under the conditions (A to F) shown in Table 3. The pressing pressure is such that both the first sintering step and the second sintering step are set to be constant. At this time, N 2 gas was introduced into a hot press furnace, and sintering was performed under a N 2 atmosphere. The obtained sintered body is machined and finished 100 x t5 mm, and bonded to a Cu backing plate to form a sputtering target.

將如此般所得到的濺鍍靶安裝於濺鍍裝置來進行DC(直流)磁控管濺鍍。濺鍍條件設定為DC濺鍍功率150W、Ar/0.1體積%O2氣氛、壓力0.8mTorr。更，使用以此條件而成膜的薄膜來製作通道長10μm、通道寬100μm的薄膜電晶體。 The sputtering target thus obtained was mounted on a sputtering apparatus to perform DC (Direct Current) magnetron sputtering. The sputtering conditions were set to a DC sputtering power of 150 W, an Ar/0.1 vol% O 2 atmosphere, and a pressure of 0.8 mTorr. Further, a thin film transistor having a channel length of 10 μm and a channel width of 100 μm was produced using a film formed by this condition.

(相對密度之測定) (Measurement of relative density)

相對密度為濺鍍後，將靶自墊板取下後予以鏡面研磨，測定以反射電子顯微鏡(SEM)所觀察的氣孔率而求得。具體為進行SEM觀察(1000倍)並拍攝照片，測定50μm方形領域中氣孔佔有面積率而設定為氣孔率。觀察任意相異的20個視野，並將該平均值設定為該試樣之平均氣孔率。將以100%減去氣孔率之值設定為燒結體之相對密度(%)。將相對密度為85%以上者評價為合格。 After the relative density was after sputtering, the target was removed from the backing plate, mirror-polished, and the porosity was measured by a reflection electron microscope (SEM). Specifically, SEM observation (1000 times) was carried out, and photographs were taken, and the area occupied by the pores in the 50 μm square area was measured and set to the porosity. 20 fields of view which are arbitrarily different were observed, and the average value was set as the average porosity of the sample. The value of the porosity of 100% minus the porosity was set as the relative density (%) of the sintered body. Those having a relative density of 85% or more were evaluated as qualified.

(比電阻之測定) (measurement of specific resistance)

燒結體之比電阻為對於上述製作的濺鍍靶藉由四接頭法來測定。將比電阻為0.1 Ω．cm以下者評價為合格。 The specific resistance of the sintered body was measured by the four-joint method for the sputtering target produced above. The specific resistance is 0.1 Ω. Those who are below cm are evaluated as qualified.

(結晶相之比率) (ratio of crystalline phase)

各結晶相之比率為濺鍍後，將靶自墊板取下後裁切出10mm方形之試片，測定使用X射線繞射之繞射線強度而 求得。 After the ratio of each crystal phase is after sputtering, the target is removed from the backing plate, and a test piece of 10 mm square is cut out, and the intensity of the X-ray diffraction is measured. Seek.

分析裝置：理學電機製「X射線繞射裝置RINT-1500」 Analytical device: Neo-mechanical mechanism "X-ray diffraction device RINT-1500"

分析條件：靶：Cu Analysis conditions: target: Cu

單色化：使用單色器(K α) Monochromatization: using a monochromator (K α)

靶出力：40kV-200mA Target output: 40kV-200mA

(連續測定)θ/2 θ掃描 (continuous measurement) θ/2 θ scan

光柵：發散1/2°、散射1/2°、受光0.15mm Grating: divergence 1/2°, scattering 1/2°, light receiving 0.15 mm

單色器受光光柵：0.6mm Monochromator light receiving grating: 0.6mm

掃描速度：2°/min Scanning speed: 2°/min

採樣寬度：0.02° Sample width: 0.02°

測定角度(2 θ)：5~90° Measuring angle (2 θ): 5~90°

對於藉由此測定所得到的繞射波峰，依據ICDD(International Center for Diffraction Data)卡鑑定為如表1中所示各結晶相之波峰，並測定繞射波峰之高度。尚，對於Zn6In2O9，由於ICDD卡中未有記載，故基於上述參考文獻(1)、(2)中所示結晶構造，並藉由結晶構造因子計算來求得理論繞射強度，來決定進行測定之波峰。此等波峰為選擇以該結晶相之繞射強度為充分高、且與其他結晶相之波峰之重複為盡可能少之波峰。於各結晶相之指定波峰之波峰高度，係使其測定值分別設定為I(ZnmIn2O3+m)、I(In2O3)、I(ZnO)(「I」為表示測定值之意思)，並藉由下式來求得[ZnmIn2O3+m](表4中 的「P1」)、[In2O3](表4中的「P2」)、[ZnO](表4中的「P3」)之體積比率。 The diffraction peaks obtained by this measurement were identified as peaks of respective crystal phases as shown in Table 1 in accordance with ICDD (International Center for Diffraction Data) card, and the height of the diffraction peaks was measured. Further, for Zn 6 In 2 O 9 , since it is not described in the ICDD card, the theoretical diffraction intensity is obtained by calculation of the crystal structure factor based on the crystal structure shown in the above references (1) and (2). To determine the peak of the measurement. These peaks are selected such that the diffraction intensity of the crystal phase is sufficiently high, and the repetition of the peaks with the other crystal phases is as small as possible. The peak height of the designated peak of each crystal phase is set to I(Zn m In 2 O 3+m ), I(In 2 O 3 ), and I(ZnO), respectively ("I" means measurement The meaning of the value), and [Zn m In 2 O 3+m ] ("P1" in Table 4), [In 2 O 3 ] ("P2" in Table 4), [ The volume ratio of ZnO] ("P3" in Table 4).

[ZnmIn2O3+m]=I(ZnmIn2O3+m)/(I(ZnmIn2O3+m)+I(In2O3)+I(ZnO)) [Zn m In 2 O 3+m ]=I(Zn m In 2 O 3+m )/(I(Zn m In 2 O 3+m )+I(In 2 O 3 )+I(ZnO))

[In2O3]=I(In2O3)/(I(ZnmIn2O3+m)+I(In2O3)+I(ZnO)) [In 2 O 3 ]=I(In 2 O 3 )/(I(Zn m In 2 O 3+m )+I(In 2 O 3 )+I(ZnO))

[ZnO]=I(ZnO)/(I(ZnmIn2O3+m)+I(In2O3)+I(ZnO)) [ZnO]=I(ZnO)/(I(Zn m In 2 O 3+m )+I(In 2 O 3 )+I(ZnO))

結晶相之比率為將[ZnmIn2O3+m]為0.75以上、[In2O3]為0.005~0.15、[ZnO]為0.005~0.20者評價為合格。 The ratio of the crystal phase was evaluated as [Zn m In 2 O 3+m ] of 0.75 or more, [In 2 O 3 ] of 0.005 to 0.15, and [ZnO] of 0.005 to 0.20.

(異常放電) (abnormal discharge)

異常放電為測定濺鍍中之異常放電之次數來進行評價。具體為重複1分鐘之濺鍍100次，以目視觀察濺鍍後取出之靶，並計算異常放電之痕跡之個數而求得。異常放電為將異常放電次數為2次以下者評價為合格。 The abnormal discharge was evaluated by measuring the number of abnormal discharges in the sputtering. Specifically, the sputtering was repeated 100 times for 1 minute, and the target taken out after the sputtering was visually observed, and the number of traces of the abnormal discharge was calculated. The abnormal discharge was evaluated as being acceptable if the number of abnormal discharges was 2 or less.

(載體移動度) (carrier mobility)

載體移動度為使用以上述的濺鍍條件所成膜的薄膜，來製作通道長10μm、通道寬100μm的薄膜電晶體，並測定該薄膜電晶體之移動度。載體移動度為將15cm2/Vs以上者評價為合格。 The carrier mobility was a film formed by using the above-described sputtering conditions, and a film transistor having a channel length of 10 μm and a channel width of 100 μm was produced, and the mobility of the film transistor was measured. The carrier mobility was evaluated as being acceptable by 15 cm 2 /Vs or more.

結果如表4所示。 The results are shown in Table 4.

滿足本發明之較佳組成、製造條件之No.1~5、9~11，抑制了異常放電之同時，展現出高載體移動度。即，在進行濺鍍時異常放電之產生為2次以下，並確認到安定進行放電。又，如此般操作所得到的濺鍍靶之相對密度及比電阻亦得到良好的結果。上述薄膜之載體移動度亦得到15cm2/Vs以上之高載體移動度。 No. 1 to 5 and 9 to 11 which satisfy the preferred composition and manufacturing conditions of the present invention suppress the abnormal discharge and exhibit high carrier mobility. In other words, the occurrence of abnormal discharge during sputtering was two or less, and it was confirmed that the discharge was stable. Moreover, the relative density and specific resistance of the sputtering target obtained in such a manner were also good. The carrier mobility of the above film also achieved a high carrier mobility of 15 cm 2 /Vs or more.

另一方面，關於未滿足本發明之較佳組成之No.6~8，以及未滿足本發明之較佳製造條件之No.12~14，產生多的異常放電，又，載體移動度為低等，無法得到所希望之效果。 On the other hand, regarding No. 6 to 8 which does not satisfy the preferred composition of the present invention, and No. 12 to 14 which do not satisfy the preferred manufacturing conditions of the present invention, a large amount of abnormal discharge is generated, and the carrier mobility is low. Wait, you can't get the desired effect.

具體為No.6~8之組成皆超出本發明所限定的In與Zn之比率([In]/[Zn])。氧化物燒結體中檢測出Zn4In2O7(m=4)、Zn8In2O11(m=8)。No.6~8之載體移動度為低。尚，No.6之Zn4In2O7之體積比為0.85。No.7之Zn8In2O11之體積比為0.82。No.8之Zn4In2O7之體積比為0.84。 Specifically, the composition of Nos. 6 to 8 exceeds the ratio of In to Zn ([In]/[Zn]) defined by the present invention. Zn 4 In 2 O 7 (m=4) and Zn 8 In 2 O 11 (m=8) were detected in the oxide sintered body. The carrier mobility of No. 6~8 is low. Further, the volume ratio of Zn 4 In 2 O 7 of No. 6 was 0.85. The volume ratio of No. 7 to Zn 8 In 2 O 11 was 0.82. The volume ratio of No. 8 to Zn 4 In 2 O 7 was 0.84.

No.12、13皆為第一燒結步驟之溫度為超出本發明所限定範圍之例，燒結體之相對密度為低，異常放電之次數為多。No.14為第二燒結步驟之溫度為超出本發明所限定範圍之例，結晶相為不含In2O3，而幾乎只有Zn7In2O10之例，異常放電之次數為多。 Both Nos. 12 and 13 are examples in which the temperature of the first sintering step is outside the range defined by the present invention, the relative density of the sintered body is low, and the number of abnormal discharges is large. No. 14 is an example in which the temperature of the second sintering step is outside the range defined by the present invention, and the crystal phase is an example containing no In 2 O 3 and almost only Zn 7 In 2 O 10 , and the number of abnormal discharges is large.

[圖1]圖1之圖為表示用來製造本發明之氧化物燒結體及濺鍍靶之基本步驟。 Fig. 1 is a view showing the basic steps for producing the oxide sintered body and the sputtering target of the present invention.

[圖2]圖2之曲線為表示本發明之製造方法中所使用的燒結步驟(第一燒結步驟與第二燒結步驟)之一例。 2] Fig. 2 is a view showing an example of a sintering step (first sintering step and second sintering step) used in the production method of the present invention.

Claims (6)

一種氧化物燒結體，其係將氧化鋅、氧化銦及至少1種選自於由Ti、Mg、Al及Nb所成之群之金屬氧化物混合及燒結而得到的氧化物燒結體，其特徵為將前述氧化物燒結體進行X射線繞射時，以ZnmIn2O3+m(m為5~7之整數)相作為主相並含有In2O3及ZnO之各結晶相，同時為相對密度85%以上、比電阻0.1 Ω．cm以下。 An oxide sintered body obtained by mixing and sintering zinc oxide, indium oxide, and at least one metal oxide selected from the group consisting of Ti, Mg, Al, and Nb, and is characterized by When X-ray diffraction is performed on the oxide sintered body, a phase of Zn m In 2 O 3+m (m is an integer of 5 to 7) is used as a main phase, and each crystal phase of In 2 O 3 and ZnO is contained, and It has a relative density of 85% or more and a specific resistance of 0.1 Ω. Below cm. 如申請專利範圍第1項之氧化物燒結體，其係在前述氧化物燒結體中，將相對於全金屬元素之鋅、銦、Ti、Mg、Al、Nb之含有量(原子%)分別設定為[Zn]、[In]、[Ti]、[Mg]、[Al]及[Nb]時，相對於[Zn]之[In]之比、相對於[Zn]+[In]+[Ti]+[Mg]+[Al]+[Nb]之[Ti]+[Mg]+[Al]+[Nb]之比分別滿足下式，0.27≦[In]/[Zn]≦0.45([Ti]+[Mg]+[Al]+[Nb])/([Zn]+[In]+[Ti]+[Mg]+[Al]+[Nb])≦0.1。 The oxide sintered body of the first aspect of the invention is characterized in that the content of the zinc, indium, Ti, Mg, Al, and Nb (atomic %) of the all-metal element is set in the oxide sintered body. For [Zn], [In], [Ti], [Mg], [Al], and [Nb], the ratio of [In] relative to [Zn], relative to [Zn]+[In]+[Ti The ratio of [Ti]+[Mg]+[Al]+[Nb] of +[Mg]+[Al]+[Nb] satisfies the following formula, respectively, 0.27≦[In]/[Zn]≦0.45([Ti ]+[Mg]+[Al]+[Nb])/([Zn]+[In]+[Ti]+[Mg]+[Al]+[Nb])≦0.1. 如申請專利範圍第1項之氧化物燒結體，其中，相對於前述氧化物燒結體中所含有的前述ZnmIn2O3+m、前述In2O3及前述ZnO之合計，各結晶相之體積比為滿足下式者，ZnmIn2O3+m/(ZnmIn2O3+m+In2O3+ZnO)≧0.75 0.005≦In2O3/(ZnmIn2O3+m+In2O3+ZnO)≦0.15 0.005≦ZnO/(ZnmIn2O3+m+In2O3+ZnO)≦0.20 (其中，ZnmIn2O3+m為Zn5In2O8、Zn6In2O9、Zn7In2O10之合計)。 The oxide sintered body according to the first aspect of the invention, wherein each of the Zn m In 2 O 3+m , the In 2 O 3 and the ZnO are contained in the oxide sintered body The volume ratio is such that Zn m In 2 O 3+m /(Zn m In 2 O 3+m +In 2 O 3 +ZnO)≧0.75 0.005≦In 2 O 3 /(Zn m In 2 O 3+m +In 2 O 3 +ZnO)≦0.15 0.005≦ZnO/(Zn m In 2 O 3+m +In 2 O 3 +ZnO)≦0.20 (wherein Zn m In 2 O 3+m is Zn 5 Total of In 2 O 8 , Zn 6 In 2 O 9 , and Zn 7 In 2 O 10 ). 如申請專利範圍第2項之氧化物燒結體，其中，相對於前述氧化物燒結體中所含有的前述ZnmIn2O3+m、前述In2O3及前述ZnO之合計，各結晶相之體積比為滿足下式者，ZnmIn2O3+m/(ZnmIn2O3+m+In2O3+ZnO)≧0.75 0.005≦In2O3/(ZnmIn2O3+m+In2O3+ZnO)≦0.15 0.005≦ZnO/(ZnmIn2O3+m+In2O3+ZnO)≦0.20(其中，ZnmIn2O3+m為Zn5In2O8、Zn6In2O9、Zn7In2O10之合計)。 The oxide sintered body according to the second aspect of the invention, wherein the crystal phase is the total of the Zn m In 2 O 3+m , the In 2 O 3 and the ZnO contained in the oxide sintered body. The volume ratio is such that Zn m In 2 O 3+m /(Zn m In 2 O 3+m +In 2 O 3 +ZnO)≧0.75 0.005≦In 2 O 3 /(Zn m In 2 O 3+m +In 2 O 3 +ZnO)≦0.15 0.005≦ZnO/(Zn m In 2 O 3+m +In 2 O 3 +ZnO)≦0.20 (wherein Zn m In 2 O 3+m is Zn 5 Total of In 2 O 8 , Zn 6 In 2 O 9 , and Zn 7 In 2 O 10 ). 一種使用申請專利範圍第1項之氧化物燒結體而得到的濺鍍靶。 A sputtering target obtained by using the oxide sintered body of the first application of the patent scope. 一種氧化物燒結體之製造方法，其係申請專利範圍第1項之氧化物燒結體之製造方法，其特徵為將氧化鋅、氧化銦及至少1種選自於由Ti、Mg、Al及Nb所成之群之金屬氧化物混合並設置於黑鉛模後，包含下述第一燒結步驟與第二燒結步驟，並以加壓壓力100~500kgf/cm2來進行前述第一燒結步驟與前述第二燒結步驟；第一燒結步驟：藉由燒結溫度950~1050℃、於該溫度域之保持時間0.1~5小時來進行燒結；第二燒結步驟：前述第一燒結步驟後，藉由燒結溫度1100~1200℃、於該溫度域之保持時間0.1~5小時來進行燒結。 A method for producing an oxide sintered body, which is the method for producing an oxide sintered body according to the first aspect of the invention, characterized in that zinc oxide, indium oxide and at least one selected from the group consisting of Ti, Mg, Al and Nb After the formed metal oxide is mixed and disposed in the black lead mold, the first sintering step and the second sintering step are performed, and the first sintering step and the foregoing are performed at a pressure of 100 to 500 kgf/cm 2 . a second sintering step; a first sintering step: sintering is performed by a sintering temperature of 950 to 1050 ° C and a holding time in the temperature range of 0.1 to 5 hours; and a second sintering step: after the first sintering step, by a sintering temperature Sintering is carried out at a temperature of 1 to 1200 ° C for 0.1 to 5 hours.
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