TWI842834B - Oxide sintered body, sputtering target and method for manufacturing sputtering target - Google Patents
Oxide sintered body, sputtering target and method for manufacturing sputtering target Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 238000004544 sputter deposition Methods 0.000 title description 20
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
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Abstract
本發明係一種氧化物燒結體(1)，氧化物燒結體(1)之表面之維氏硬度之平均值超過500 Hv且未達900 Hv。The present invention is an oxide sintered body (1), the average value of the Vickers hardness of the surface of the oxide sintered body (1) exceeds 500 Hv and does not reach 900 Hv.
Description
本發明係關於一種氧化物燒結體、濺鍍靶材及濺鍍靶材之製造方法。 The present invention relates to an oxide sintered body, a sputtering target and a method for manufacturing the sputtering target.
先前，於利用薄膜電晶體(以下稱為「TFT(Thin Film Transistor)」)驅動之方式之液晶顯示器或有機EL(Electroluminescence，電致發光)顯示器等顯示裝置中，TFT之通道層主要採用非晶質矽膜或結晶質矽膜。 Previously, in display devices such as liquid crystal displays or organic EL (Electroluminescence) displays that use thin film transistors (hereinafter referred to as "TFT") drive, the channel layer of TFT mainly uses amorphous silicon film or crystalline silicon film.
另一方面，近年來，隨著顯示器之高精細化之要求，氧化物半導體作為TFT之通道層中所使用之材料受到注目。 On the other hand, in recent years, with the demand for higher-precision displays, oxide semiconductors have attracted attention as materials used in the channel layer of TFTs.
氧化物半導體之中，尤其，包括銦、鎵、鋅及氧之非晶形氧化物半導體(In-Ga-Zn-O，以下簡記為「IGZO」)由於具有較高之載子移動率，故而被較佳地使用。然而，IGZO具有由於使用In及Ga作為原料故而原料成本較高之缺點。 Among oxide semiconductors, amorphous oxide semiconductors including indium, gallium, zinc and oxygen (In-Ga-Zn-O, hereinafter referred to as "IGZO") are preferably used because of their high carrier mobility. However, IGZO has the disadvantage of high raw material cost because it uses In and Ga as raw materials.
自降低原料成本之觀點而言，提出有Zn-Sn-O(以下簡記為「ZTO」)、或代替IGZO之Ga而添加有Sn之In-Sn-Zn-O(以下簡記為「ITZO」)。 From the perspective of reducing raw material costs, Zn-Sn-O (hereinafter referred to as "ZTO") or In-Sn-Zn-O (hereinafter referred to as "ITZO") in which Sn is added instead of Ga in IGZO has been proposed.
ITZO由於與IGZO相比顯示非常高之移動率，故而作為對TFT之小型化及面板之窄邊緣化有利之下一代氧化物半導體材料備受期待。 Since ITZO has a much higher mobility than IGZO, it is expected to be the next generation oxide semiconductor material that will be beneficial to the miniaturization of TFTs and the narrowing of panel edges.
然而，ITZO由於熱膨脹係數較大、且熱導率較低，故而有於向Cu或Ti等之背襯板之接合時及濺鍍時因熱應力容易產生龜裂之問題。 However, due to its large thermal expansion coefficient and low thermal conductivity, ITZO is prone to cracking due to thermal stress during bonding to a backing plate such as Cu or Ti or during sputter plating.
於最近之研究中，報告稱氧化物半導體材料之最大問題即可靠性可藉由使膜緻密化而改善。 In recent studies, it is reported that the biggest problem of oxide semiconductor materials, reliability, can be improved by making the film denser.
為了使膜緻密化而有效的是高功率製膜。然而，於大型量產裝置中電漿集中之靶材之端部之斷裂成為問題，尤其ITZO系材料之靶材有容易斷裂之傾向。 High-power film formation is effective for making the film dense. However, in large-scale mass production equipment, the breakage of the end of the target material where the plasma is concentrated becomes a problem, especially the target material of ITZO series materials tends to break easily.
例如，於非專利文獻1(Journal of the Ceramic Society of Japan,104,[7],654-658(1996))中記載有，於陶瓷中，維氏硬度與拉伸強度存在比例關係。 For example, it is stated in non-patent document 1 (Journal of the Ceramic Society of Japan, 104, [7], 654-658 (1996)) that in ceramics, Vickers hardness and tensile strength are proportional.
於文獻1(日本專利特開2012-180247號公報)中記載有一種氧化物燒結體，其係將氧化鋅、氧化錫、及選自由Al、Hf、Ni、Si、Ga、In及Ta所組成之群中之至少1種金屬(M金屬)之氧化物混合及燒結而獲得的氧化物燒結體，且維氏硬度為400Hv以上。於文獻1中記載有，即便使用此種氧化物燒結體利用直流濺鍍法進行成膜亦不易產生結核，能夠長時間穩定地放電。 Document 1 (Japanese Patent Publication No. 2012-180247) describes an oxide sintered body obtained by mixing and sintering zinc oxide, tin oxide, and oxides of at least one metal (M metal) selected from the group consisting of Al, Hf, Ni, Si, Ga, In, and Ta, and having a Vickers hardness of 400 Hv or more. Document 1 describes that even if this oxide sintered body is used for film formation by direct current sputtering, nodules are not easily generated, and discharge can be stable for a long time.
於文獻1中記載有，將包含氧化物燒結體之濺鍍靶材之維氏硬度規定為特定範圍內，但文獻1中之維氏硬度係測定將氧化物燒結體以t/2(t：厚度)切斷之切斷面之表面之位置的值。因此，於文獻1中，關於氧化物燒結體之表面中之維氏硬度並未記載。 Document 1 states that the Vickers hardness of a sputtering target material including an oxide sintered body is specified within a specific range, but the Vickers hardness in Document 1 is a value measured at the position of the surface of a cut surface of the oxide sintered body cut at t/2 (t: thickness). Therefore, Document 1 does not state the Vickers hardness of the surface of the oxide sintered body.
近年來，要求提高濺鍍時之龜裂耐性之靶材，於文獻1中記載有，藉由氧化物燒結體之硬度控制而抑制結核之產生之推測，但關於 提高龜裂耐性之方法並未記載。又，於文獻1中，雖然有為了控制氧化物燒結體之硬度而適當地控制燒結條件及其後之熱處理條件之記載，但是於文獻1中所記載之該條件下，難以提高龜裂耐性。 In recent years, there has been a demand for targets with improved crack resistance during sputtering. Reference 1 describes the speculation that the generation of nodules can be suppressed by controlling the hardness of the oxide sintered body, but there is no description of the method for improving crack resistance. In addition, although reference 1 describes that the sintering conditions and the subsequent heat treatment conditions are appropriately controlled in order to control the hardness of the oxide sintered body, it is difficult to improve crack resistance under the conditions described in reference 1.
本發明之目的在於提供一種提高龜裂耐性之氧化物燒結體及濺鍍靶材、以及提供一種該濺鍍靶材之製造方法。 The purpose of the present invention is to provide an oxide sintered body and a sputtering target material with improved crack resistance, and to provide a method for manufacturing the sputtering target material.
[1A].一種氧化物燒結體，上述氧化物燒結體之表面之維氏硬度之平均值超過500Hv且未達900Hv。 [1A]. An oxide sintered body, wherein the average Vickers hardness of the surface of the oxide sintered body exceeds 500 Hv and does not reach 900 Hv.
[2A].一種濺鍍靶材，其包含如[1A]之氧化物燒結體。 [2A]. A sputtering target comprising an oxide sintered body as described in [1A].
[1].一種濺鍍靶材，其係包含氧化物燒結體之濺鍍靶材，且上述氧化物燒結體之表面之維氏硬度之平均值超過500Hv且未達900Hv。 [1]. A sputtering target, which is a sputtering target comprising an oxide sintered body, and the average Vickers hardness of the surface of the oxide sintered body exceeds 500 Hv and does not reach 900 Hv.
[2].如[1]或[2A]之濺鍍靶材，其中上述氧化物燒結體包含銦元素、錫元素及鋅元素。 [2]. A sputtering target as described in [1] or [2A], wherein the oxide sintered body contains indium, tin and zinc.
[3].如[2]之濺鍍靶材，其中上述氧化物燒結體進而包含X元素，X元素係選自由鍺元素、矽元素、釔元素、鋯元素、鋁元素、鎂元素、鐿元素及鎵元素所組成之群中之至少1種以上之元素。 [3]. A sputtering target as described in [2], wherein the oxide sintered body further comprises an X element, and the X element is at least one element selected from the group consisting of germanium, silicon, yttrium, zirconium, aluminum, magnesium, vanadium and gallium.
[4].如[2]或[3]之濺鍍靶材，其中上述氧化物燒結體滿足由下述式(1)、(2)及(3)表示之原子組成比之範圍。 [4]. A sputtering target as described in [2] or [3], wherein the oxide sintered body satisfies the atomic composition ratio range represented by the following formulas (1), (2) and (3).
0.40≦Zn/(In+Sn+Zn)≦0.80 (1) 0.40≦Zn/(In+Sn+Zn)≦0.80 (1)
0.15≦Sn/(Sn+Zn)≦0.40 (2) 0.15≦Sn/(Sn+Zn)≦0.40 (2)
0.10≦In/(In+Sn+Zn)≦0.35 (3) 0.10≦In/(In+Sn+Zn)≦0.35 (3)
[5].如[2]至[4]中任一項之濺鍍靶材，其中 上述氧化物燒結體包含由In2O3(ZnO)m[m=2~7]表示之六方晶層狀化合物及由Zn2SnO4表示之尖晶石結構化合物。 [5] The sputtering target according to any one of [2] to [4], wherein the oxide sintered body comprises a hexagonal layered compound represented by In 2 O 3 (ZnO) m [m=2-7] and a spinel structure compound represented by Zn 2 SnO 4 .
[5A].如[2]至[4]中任一項之濺鍍靶材，其中上述氧化物燒結體包含由In2O3(ZnO)m[m=2~7]表示之六方晶層狀化合物及由Zn2-xSn1-yInx+yO4[0≦x<2，0≦y<1]表示之尖晶石結構化合物。 [5A]. The sputtering target of any one of [2] to [4], wherein the oxide sintered body comprises a hexagonal layered compound represented by In2O3 (ZnO)m[m=2~7] and a spinel structure compound represented by Zn2 - xSn1-yInx + yO4 [0≦x<2, 0≦y<1].
[6].一種濺鍍靶材之製造方法，其係用以製造如[1]至[5]、[2A]及[5A]中任一項之濺鍍靶材者，且包含如下步驟：將上述氧化物燒結體之原料造粒，獲得粒徑為25μm以上150μm以下之原料造粒粉；將上述原料造粒粉填充至模具內，將填充於上述模具內之上述原料造粒粉成形而獲得成形體；以及將上述成形體以1310℃以上1440℃以下進行燒結。 [6]. A method for manufacturing a sputtering target, which is used to manufacture a sputtering target as described in any one of [1] to [5], [2A] and [5A], and comprises the following steps: granulating the raw material of the oxide sintered body to obtain a raw material granulated powder having a particle size of 25 μm to 150 μm; filling the raw material granulated powder into a mold, and forming the raw material granulated powder filled in the mold to obtain a molded body; and sintering the molded body at a temperature of 1310°C to 1440°C.
[7].如[6]之濺鍍靶材之製造方法，其中上述原料造粒粉之粒徑為25μm以上75μm以下。 [7]. A method for manufacturing a sputtering target material as described in [6], wherein the particle size of the raw material granulated powder is greater than 25 μm and less than 75 μm.
根據本發明之一態樣，可提供提高龜裂耐性之氧化物燒結體及濺鍍靶材。 According to one aspect of the present invention, an oxide sintered body and a sputtering target with improved crack resistance can be provided.
根據本發明之一態樣，可提供本發明之一態樣之濺鍍靶材之製造方法。 According to one aspect of the present invention, a method for manufacturing a sputtering target material according to one aspect of the present invention can be provided.
1:板狀之氧化物燒結體 1: Plate-shaped oxide sintered body
1A:圓筒狀之氧化物燒結體 1A: Cylindrical oxide sintered body
1B:圓形之氧化物燒結體 1B: Round oxide sintered body
1C:分割成複數個之氧化物燒結體 1C: Sintered oxide bodies divided into multiple pieces
3:背襯板 3: Backing board
圖1係表示本發明之一實施形態之靶材之形狀的立體圖。 Figure 1 is a three-dimensional diagram showing the shape of a target material in one embodiment of the present invention.
圖2係表示本發明之一實施形態之靶材之形狀的立體圖。 FIG2 is a three-dimensional diagram showing the shape of the target material of one embodiment of the present invention.
圖3係表示本發明之一實施形態之靶材之形狀的立體圖。 FIG3 is a three-dimensional diagram showing the shape of the target material of one embodiment of the present invention.
圖4係表示本發明之一實施形態之靶材之形狀的立體圖。 FIG4 is a three-dimensional diagram showing the shape of the target material of one embodiment of the present invention.
圖5係於實施例中製備之原料造粒粉之SEM(scanning electron microscope，掃描式電子顯微鏡)觀察圖像。 Figure 5 is a SEM (scanning electron microscope) observation image of the raw material granulated powder prepared in the embodiment.
圖6係實施例之氧化物燒結體之XRD(X ray diffraction，X射線繞射測定)圖。 Figure 6 is an XRD (X ray diffraction) diagram of the oxide sintered body of the embodiment.
濺鍍靶材之龜裂以靶材中之強度較弱之部分為起點而產生。 The cracks of the sputtering target material start from the weaker part of the target material.
因此，本發明者考慮降低濺鍍靶材面內之強度之不均，尤其提高最低強度，作為用以提高龜裂耐性之對策。 Therefore, the inventors of the present invention considered reducing the strength unevenness within the surface of the sputtering target, especially increasing the minimum strength, as a measure to improve the crack resistance.
本發明者對濺鍍靶材之製造條件進行銳意研究，結果獲得以下知識見解：藉由使原料造粒粉之粒徑及燒結溫度最佳化，而氧化物燒結體之濺鍍面中之維氏硬度之最小值提高，平均值提高。 The inventor of the present invention has conducted intensive research on the manufacturing conditions of sputtering targets, and obtained the following knowledge and insights: By optimizing the particle size and sintering temperature of the raw material granulated powder, the minimum value of the Vickers hardness of the sputtering surface of the oxide sintered body is increased, and the average value is increased.
又，亦獲得如下知識見解：氧化物燒結體中之維氏硬度之平均值有最佳範圍，若維氏硬度過高則於靶材之研削加工步驟中產生微龜裂，龜裂耐性降低。 In addition, the following knowledge and insights were obtained: the average value of the Vickers hardness in the oxide sintered body has an optimal range. If the Vickers hardness is too high, micro cracks will be generated during the grinding process of the target material, and the crack resistance will be reduced.
本發明者基於該等知識見解發明了本發明。 The inventor invented the present invention based on such knowledge and insights.
以下，一面參照圖式等一面對實施形態進行說明。但是，只要為業者則容易地理解實施形態能夠以較多之不同態樣加以實施，且可於不脫離主旨及其範圍之情況下對其形態及詳細情況進行各種變更。因此，本發明並不限定於以下之實施形態之記載內容而解釋。 The following describes the implementation forms with reference to the drawings, etc. However, it is easy for practitioners to understand that the implementation forms can be implemented in many different forms, and various changes can be made to the forms and details without departing from the main purpose and scope. Therefore, the present invention is not limited to the following description of the implementation forms.
於圖式中，存在大小、層之厚度及區域為了明瞭化而誇張 表示之情形。因此，未必限定為該尺度。再者，圖式係模式性地表示理想例之圖，本發明並不限定於圖式所示之形狀及值等。 In the diagram, the size, thickness of the layer, and the area are exaggerated for the sake of clarity. Therefore, it is not necessarily limited to this scale. Furthermore, the diagram is a diagram schematically showing an ideal example, and the present invention is not limited to the shapes and values shown in the diagram.
於本說明書中所使用之「第1」、「第2」、「第3」之序數詞係為了避免構成要素之混同而標註者，並不依數字規律進行限定。 The ordinal numbers "1st", "2nd", and "3rd" used in this manual are used to avoid confusion between constituent elements and are not limited according to numerical rules.
於本說明書等中，「膜」或「薄膜」之用語與「層」之用語根據情況能夠相互替換。 In this specification, the term "membrane" or "film" and the term "layer" can be used interchangeably as appropriate.
於本說明書等之燒結體及氧化物半導體薄膜中，「化合物」之用語與「結晶相」之用語根據情況能夠相互替換。 In the sintered bodies and oxide semiconductor thin films in this specification, the term "compound" and the term "crystalline phase" can be used interchangeably depending on the situation.
於本說明書中，存在將「氧化物燒結體」簡稱為「燒結體」之情形。 In this manual, "oxide sintered body" is sometimes referred to as "sintered body".
於本說明書中，存在將「濺鍍靶材」簡稱為「靶材」之情形。 In this manual, "sputtering target" is sometimes referred to as "target".
本發明之一實施形態之濺鍍靶材(以下，有時簡稱為本實施形態之濺鍍靶材)包含氧化物燒結體。 A sputtering target material of one embodiment of the present invention (hereinafter sometimes referred to as the sputtering target material of the present embodiment) includes an oxide sintered body.
本實施形態之濺鍍靶材例如係將氧化物燒結體之塊體切削及研磨成適合作為濺鍍靶材之形狀而獲得。 The sputtering target of this embodiment is obtained by, for example, cutting and grinding a block of an oxide sintered body into a shape suitable for a sputtering target.
又，本實施形態之濺鍍靶材亦可藉由將對氧化物燒結體之塊體進行研削及研磨所獲得之濺鍍靶材素材接合於背襯板而獲得。 In addition, the sputtering target of the present embodiment can also be obtained by bonding the sputtering target material obtained by grinding and polishing a block of an oxide sintered body to a backing plate.
又，作為另一態樣之本實施形態之濺鍍靶材，亦可列舉僅由氧化物燒結體構成之靶材。 Furthermore, as another aspect of the sputtering target of this embodiment, a target consisting only of an oxide sintered body can also be cited.
氧化物燒結體之形狀並不特別限定。 The shape of the oxide sintered body is not particularly limited.
亦可為如圖1之符號1所示之板狀之氧化物燒結體。 It can also be a plate-shaped oxide sintered body as shown by symbol 1 in Figure 1.
亦可為如圖2之符號1A所示之圓筒狀之氧化物燒結體。 It can also be a cylindrical oxide sintered body as shown by symbol 1A in Figure 2.
於氧化物燒結體為板狀之情形時，該氧化物燒結體之平面形狀既可為如圖1之符號1所示之矩形，亦可為如圖3之符號1B所示之圓形。 When the oxide sintered body is in the form of a plate, the plane shape of the oxide sintered body can be either a rectangle as shown by symbol 1 in FIG. 1 or a circle as shown by symbol 1B in FIG. 3 .
氧化物燒結體既可為一體成型物，亦可如圖4所示被分割成複數個。亦可將分割成複數個之氧化物燒結體(符號1C)之各者固定於背襯板3。如此，存在將使複數個氧化物燒結體1C接合於1個背襯板3所得之濺鍍靶材稱為多分割式濺鍍靶材之情形。背襯板3係氧化物燒結體之保持及冷卻用之構件。背襯板3之材料並不特別限定。作為背襯板3之材料，例如，使用選自由Cu、Ti及SUS等所組成之群中之至少一種之材料。 The oxide sintered body can be a one-piece molded body or divided into a plurality of parts as shown in FIG4. Each of the oxide sintered bodies (symbol 1C) divided into a plurality of parts can also be fixed to the backing plate 3. In this way, there is a case where the sputtering target obtained by joining a plurality of oxide sintered bodies 1C to a backing plate 3 is called a multi-split sputtering target. The backing plate 3 is a component for holding and cooling the oxide sintered body. The material of the backing plate 3 is not particularly limited. As the material of the backing plate 3, for example, at least one material selected from the group consisting of Cu, Ti and SUS is used.
於本實施形態之靶材中，氧化物燒結體之表面之維氏硬度之平均值(Hav)超過500Hv且未達900Hv。於本說明書中，維氏硬度之測定係使用硬度計(Hardness Tester)(AKASHI MVK-E3)，依據JIS Z 2244：2009實施。測定點係採取沿著氧化物燒結體(142×305mm尺寸)之中央之線距單側之端每30mm之資料，將所採取之資料之平均值設為氧化物燒結體之表面之維氏硬度之平均值(Hav)。 In the target material of this embodiment, the average value ( Hav ) of the Vickers hardness of the surface of the oxide sintered body exceeds 500Hv and does not reach 900Hv. In this specification, the Vickers hardness is measured using a hardness tester (AKASHI MVK-E3) in accordance with JIS Z 2244: 2009. The measurement point is to take data every 30mm from the end of one side along the line of the center of the oxide sintered body (142×305mm size), and the average value of the taken data is set as the average value ( Hav ) of the Vickers hardness of the surface of the oxide sintered body.
藉由氧化物燒結體之表面之維氏硬度之平均值(Hav)超過500Hv，而靶材之濺鍍面中之強度較弱之部分較少。因此，本實施形態之濺鍍靶材之龜裂耐性提高。 Since the average Vickers hardness ( Hav ) of the surface of the oxide sintered body exceeds 500Hv, the number of weak parts in the sputtering surface of the target is small. Therefore, the crack resistance of the sputtering target of this embodiment is improved.
若維氏硬度過高則有於研削加工步驟中產生微龜裂之情 況。然而，於本實施形態中，由於氧化物燒結體之表面之維氏硬度之平均值(Hav)未達900Hv，故而可抑制於靶材之研削加工步驟中產生微龜裂。其結果，亦可抑制起因於微龜裂之龜裂耐性之降低。 If the Vickers hardness is too high, micro-cracks may occur during the grinding process. However, in this embodiment, since the average value ( Hav ) of the Vickers hardness of the surface of the oxide sintered body is less than 900Hv, the micro-cracks can be suppressed during the grinding process of the target. As a result, the reduction of the crack resistance caused by the micro-cracks can be suppressed.
氧化物燒結體之表面之維氏硬度之平均值(Hav)較佳為520Hv以上850Hv以下，更佳為600Hv以上750Hv以下。 The average value (H av ) of the Vickers hardness of the surface of the oxide sintered body is preferably 520 Hv to 850 Hv, more preferably 600 Hv to 750 Hv.
氧化物燒結體之表面之維氏硬度之最小值(Hmin)較佳為超過500Hv，更佳為600Hv以上。若維氏硬度之最小值(Hmin)超過500Hv，則靶材之濺鍍面中之強度較弱之部分更少，龜裂耐性進而提高。再者，於本說明書中，維氏硬度之最小值(Hmin)係測定氧化物燒結體之表面之10個部位之維氏硬度，該10個部位之維氏硬度之值中最低之值。 The minimum value (H min ) of the Vickers hardness of the surface of the oxide sintered body is preferably more than 500 Hv, more preferably more than 600 Hv. If the minimum value (H min ) of the Vickers hardness exceeds 500 Hv, the number of weaker parts in the sputtered surface of the target material is reduced, and the crack resistance is further improved. In addition, in this specification, the minimum value (H min ) of the Vickers hardness is measured at 10 locations on the surface of the oxide sintered body, and the lowest value among the values of the Vickers hardness of the 10 locations.
氧化物燒結體之表面之維氏硬度之最大值(Hmax)較佳為未達900Hv，更佳為850Hv以下。若維氏硬度之最大值(Hmax)未達900Hv，則進而抑制靶材之研削加工步驟中之微龜裂之產生，其結果，龜裂耐性進而提高。再者，於本說明書中，維氏硬度之最大值(Hmax)係測定氧化物燒結體之表面之10個部位中之維氏硬度，該10個部位之維氏硬度之值中最大之值。 The maximum value (H max ) of the Vickers hardness of the surface of the oxide sintered body is preferably less than 900 Hv, and more preferably less than 850 Hv. If the maximum value (H max ) of the Vickers hardness is less than 900 Hv, the generation of micro cracks in the grinding process of the target material is further suppressed, and as a result, the crack resistance is further improved. In addition, in this specification, the maximum value (H max ) of the Vickers hardness is the maximum value among the values of the Vickers hardness of 10 locations measured on the surface of the oxide sintered body.
本實施形態之氧化物燒結體較佳為包含銦元素(In)、錫元素(Sn)及鋅元素(Zn)。 The oxide sintered body of this embodiment preferably contains indium element (In), tin element (Sn) and zinc element (Zn).
本實施形態之氧化物燒結體亦可於不損及本發明之效果之範圍中含有In、Sn及Zn以外之其他金屬元素，亦可實質上僅含有In、Sn及Zn，或者亦可僅由In、Sn及Zn構成。此處，所謂「實質上」，係指氧化 物燒結體之金屬元素之95質量%以上100質量%以下(較佳為98質量%以上100質量%以下)為銦元素(In)、錫元素(Sn)及鋅元素(Zn)。本實施形態之氧化物燒結體亦可於不損及本發明之效果之範圍中除了In、Sn、Zn及氧元素(O)以外還包含不可避免之雜質。此處所言之不可避免之雜質，係指並非刻意添加之元素，係於原料或製造步驟中混入之元素。 The oxide sintered body of the present embodiment may contain other metal elements other than In, Sn and Zn within the scope that does not impair the effect of the present invention, may contain only In, Sn and Zn substantially, or may be composed of only In, Sn and Zn. Here, "substantially" means that 95% by mass or more and 100% by mass or less (preferably 98% by mass or more and 100% by mass or less) of the metal elements of the oxide sintered body are indium element (In), tin element (Sn) and zinc element (Zn). The oxide sintered body of the present embodiment may contain inevitable impurities in addition to In, Sn, Zn and oxygen element (O) within the scope that does not impair the effect of the present invention. The unavoidable impurities mentioned here refer to elements that are not intentionally added, but are mixed in during the raw materials or manufacturing steps.
本實施形態之氧化物燒結體亦較佳為包含銦元素(In)、錫元素(Sn)、鋅元素(Zn)及X元素。 The oxide sintered body of this embodiment also preferably contains indium element (In), tin element (Sn), zinc element (Zn) and X element.
本實施形態之氧化物燒結體亦可於不損及本發明之效果之範圍中含有In、Sn、Zn及X元素以外之其他金屬元素，亦可實質上僅含有In、Sn、Zn及X元素，或者亦可僅由In、Sn、Zn及X元素構成。此處，所謂「實質上」，係指氧化物燒結體之金屬元素之95質量%以上100質量%以下(較佳為98質量%以上100質量%以下)為In、Sn、Zn及X元素。本實施形態之氧化物燒結體亦可於不損及本發明之效果之範圍中除了In、Sn、Zn、X元素及氧元素(O)以外還包含不可避免之雜質。此處所言之不可避免之雜質，係指並非刻意添加之元素，係於原料或製造步驟中混入之元素。 The oxide sintered body of the present embodiment may contain other metal elements other than In, Sn, Zn and X elements within a range that does not impair the effects of the present invention, may substantially contain only In, Sn, Zn and X elements, or may consist of only In, Sn, Zn and X elements. Here, the term "substantially" means that 95% by mass to 100% by mass (preferably 98% by mass to 100% by mass) of the metal elements of the oxide sintered body are In, Sn, Zn and X elements. The oxide sintered body of the present embodiment may contain inevitable impurities in addition to In, Sn, Zn, X elements and oxygen (O) within a range that does not impair the effects of the present invention. The unavoidable impurities mentioned here refer to elements that are not intentionally added, but are mixed in during the raw materials or manufacturing steps.
X元素係選自由鍺元素(Ge)、矽元素(Si)、釔元素(Y)、鋯元素(Zr)、鋁元素(Al)、鎂元素(Mg)、鐿元素(Yb)及鎵元素(Ga)所組成之群中之至少1種以上之元素。 The X element is at least one element selected from the group consisting of germanium (Ge), silicon (Si), yttrium (Y), zirconium (Zr), aluminum (Al), magnesium (Mg), ytterbium (Yb) and gallium (Ga).
作為不可避免之雜質之例，有鹼金屬(Li、Na、K、Rb等)、鹼土類金屬(Ca、Sr、Ba等)、氫(H)元素、硼(B)元素、碳(C)元素、氮(N)元素、氟(F)元素及氯(Cl)元素。 Examples of unavoidable impurities include alkali metals (Li, Na, K, Rb, etc.), alkaline earth metals (Ca, Sr, Ba, etc.), hydrogen (H), boron (B), carbon (C), nitrogen (N), fluorine (F), and chlorine (Cl).
雜質濃度可藉由ICP(Inductively Coupled Plasma，感應耦 合電漿)或SIMS(secondary ion mass spectrometry，二次離子質譜儀)測定。 Impurity concentration can be measured by ICP (Inductively Coupled Plasma) or SIMS (secondary ion mass spectrometry).
所獲得之燒結體中之雜質濃度(H、C、N、F、Si、Cl)可藉由使用扇區型動態二次離子質譜儀(IMS 7f-Auto，AMETEK CAMECA公司製造)之SIMS分析而定量評價。 The impurity concentration (H, C, N, F, Si, Cl) in the obtained sintered body can be quantitatively evaluated by SIMS analysis using a sector-type dynamic secondary ion mass spectrometer (IMS 7f-Auto, manufactured by AMETEK CAMECA).
具體而言，首先使用一次離子Cs+，以14.5kV之加速電壓進行濺鍍直至距測定對象之燒結體表面20μm之深度為止。然後，針對光柵100μm見方(100μm×100μm之尺寸)、測定區域30μm見方(30μm×30μm之尺寸)、深度1μm，一面利用一次離子進行濺鍍一面對雜質(H、C、N、F、Si、Cl)之質譜強度進行積分。 Specifically, we first sputtered the primary ions Cs + at an accelerating voltage of 14.5 kV until the depth of 20 μm from the surface of the sintered body to be measured. Then, we sputtered the primary ions while integrating the mass spectrum intensity of impurities (H, C, N, F, Si, Cl) for a grating of 100 μm square (100 μm × 100 μm size), a measurement area of 30 μm square (30 μm × 30 μm size), and a depth of 1 μm.
進而，根據質譜算出雜質濃度之絕對值，將各雜質藉由離子注入控制摻雜量並注入至燒結體而製作雜質濃度已知之標準試樣。關於標準試樣藉由SIMS分析獲得雜質(H、C、N、F、Si、Cl)之質譜強度，將雜質濃度之絕對值與質譜強度之關係式製成校準曲線。 Furthermore, the absolute value of the impurity concentration is calculated based on the mass spectrum, and each impurity is controlled by ion implantation and injected into the sintered body to produce a standard sample with a known impurity concentration. The mass spectrum intensity of the impurities (H, C, N, F, Si, Cl) of the standard sample is obtained by SIMS analysis, and the relationship between the absolute value of the impurity concentration and the mass spectrum intensity is made into a calibration curve.
最後，使用測定對象之燒結體之質譜強度與校準曲線，算出測定對象之雜質濃度，將其設為雜質濃度之絕對值(atom‧cm-3)。 Finally, the impurity concentration of the object to be measured is calculated using the mass spectrum intensity of the sintered body of the object to be measured and the calibration curve, and is set as the absolute value of the impurity concentration (atom‧cm -3 ).
關於所獲得之燒結體之雜質濃度(B、Na)，亦可藉由使用扇區型動態二次離子質譜儀(IMS 7f-Auto，AMETEK CAMECA公司製造)之SIMS分析定量評價。將一次離子設為O2 +，將一次離子之加速電壓設為5.5kV進 行各雜質之質譜之測定，除此以外，可藉由與H、C、N、F、Si、Cl之測定相同之評價獲得測定對象之雜質濃度之絕對值(atom‧cm-3)。 The impurity concentration (B, Na) of the obtained sintered body can also be quantitatively evaluated by SIMS analysis using a sector-type dynamic secondary ion mass spectrometer (IMS 7f-Auto, manufactured by AMETEK CAMECA). The mass spectrum of each impurity is measured by setting the primary ion to O 2 + and the primary ion acceleration voltage to 5.5 kV. In addition, the absolute value of the impurity concentration of the measured object (atom‧cm -3 ) can be obtained by the same evaluation as the measurement of H, C, N, F, Si, and Cl.
於本實施形態之氧化物燒結體中，更佳為，各元素之原子組成比滿足以下之式(1)~(3)之至少1個。 In the oxide sintered body of this embodiment, it is more preferable that the atomic composition ratio of each element satisfies at least one of the following formulas (1) to (3).
0.40≦Zn/(In+Sn+Zn)≦0.80 (1) 0.40≦Zn/(In+Sn+Zn)≦0.80 (1)
0.15≦Sn/(Sn+Zn)≦0.40 (2) 0.15≦Sn/(Sn+Zn)≦0.40 (2)
0.10≦In/(In+Sn+Zn)≦0.35 (3) 0.10≦In/(In+Sn+Zn)≦0.35 (3)
於式(1)~(3)中，In、Zn及Sn分別表示氧化物燒結體中之銦元素、鋅元素及錫元素之含量。 In formulas (1) to (3), In, Zn, and Sn represent the contents of indium, zinc, and tin in the oxide sintered body, respectively.
若Zn/(In+Sn+Zn)為0.40以上，則於氧化物燒結體中容易產生尖晶石相，容易獲得半導體特性。 If Zn/(In+Sn+Zn) is greater than 0.40, a spinel phase is easily generated in the oxide sintered body, and semiconductor properties are easily obtained.
若Zn/(In+Sn+Zn)為0.80以下，則於氧化物燒結體中可抑制因尖晶石相之異常晶粒生長所致之強度之降低。又，若Zn/(In+Sn+Zn)為0.80以下，則可抑制氧化物半導體薄膜之移動率之降低。 If Zn/(In+Sn+Zn) is less than 0.80, the decrease in strength due to abnormal grain growth of the spinel phase in the oxide sintered body can be suppressed. Also, if Zn/(In+Sn+Zn) is less than 0.80, the decrease in mobility of the oxide semiconductor thin film can be suppressed.
Zn/(In+Sn+Zn)更佳為0.50以上、0.70以下。 Zn/(In+Sn+Zn) is preferably greater than 0.50 and less than 0.70.
若Sn/(Sn+Zn)為0.15以上，則於氧化物燒結體中可抑制因尖晶石相之異常晶粒生長所致之強度之降低。 If Sn/(Sn+Zn) is 0.15 or more, the decrease in strength due to abnormal grain growth of the spinel phase in the oxide sintered body can be suppressed.
若Sn/(Sn+Zn)為0.40以下，則於氧化物燒結體中，可抑制導致濺鍍時之異常放電之氧化錫之凝聚。又，若Sn/(Sn+Zn)為0.40以下，則使用濺鍍靶材成膜之氧化物半導體薄膜可容易地進行利用草酸等弱酸之蝕刻加工。若Sn/(Sn+Zn)為0.15以上，則可抑制蝕刻速度變得過快而蝕刻之控制變得容易。 If Sn/(Sn+Zn) is less than 0.40, the aggregation of tin oxide that causes abnormal discharge during sputtering can be suppressed in the oxide sintered body. Also, if Sn/(Sn+Zn) is less than 0.40, the oxide semiconductor thin film formed using a sputtering target can be easily etched using weak acids such as oxalic acid. If Sn/(Sn+Zn) is greater than 0.15, the etching speed can be suppressed from becoming too fast and the etching control becomes easy.
Sn/(Sn+Zn)更佳為0.15以上0.35以下。 Sn/(Sn+Zn) is preferably greater than 0.15 and less than 0.35.
若In/(In+Sn+Zn)為0.10以上，則可降低所獲得之濺鍍靶材之體電阻。又，若In/(In+Sn+Zn)為0.10以上，則可抑制氧化物半導體薄膜之移動率變得極低。 If In/(In+Sn+Zn) is greater than 0.10, the bulk resistance of the sputtering target can be reduced. Also, if In/(In+Sn+Zn) is greater than 0.10, the mobility of the oxide semiconductor film can be suppressed from becoming extremely low.
若In/(In+Sn+Zn)為0.35以下，則於濺鍍成膜時，可抑制膜成為導電體，容易獲得作為半導體之特性。 If In/(In+Sn+Zn) is less than 0.35, the film can be prevented from becoming a conductor during sputtering, making it easier to obtain semiconductor properties.
In/(In+Sn+Zn)較佳為0.10以上0.30以下。 In/(In+Sn+Zn) is preferably greater than 0.10 and less than 0.30.
於本實施形態之氧化物燒結體包含X元素之情形時，較佳為，各元素之原子比滿足下述式(1X)。 When the oxide sintered body of the present embodiment contains the element X, it is preferred that the atomic ratio of each element satisfies the following formula (1X).
0.001≦X/(In+Sn+Zn+X)≦0.05 (1X) 0.001≦X/(In+Sn+Zn+X)≦0.05 (1X)
(式(1X)中，In、Zn、Sn及X分別表示氧化物燒結體中之銦元素、鋅元素、錫元素及X元素之含量。) (In formula (1X), In, Zn, Sn and X represent the contents of indium, zinc, tin and X in the oxide sintered body respectively.)
若為上述式(1X)之範圍內，則可使本實施形態之氧化物燒結體之龜裂耐性充分高。 If it is within the range of the above formula (1X), the crack resistance of the oxide sintered body of this embodiment can be sufficiently high.
X元素較佳為選自由矽元素(Si)、鋁元素(Al)、鎂元素(Mg)、鐿元素(Yb)及鎵元素(Ga)所組成之群中之至少一種。 The X element is preferably at least one selected from the group consisting of silicon (Si), aluminum (Al), magnesium (Mg), ytterbium (Yb) and gallium (Ga).
X元素更佳為選自由矽元素(Si)、鋁元素(Al)及鎵元素(Ga)所組成之群中之至少一種。 The X element is preferably at least one selected from the group consisting of silicon (Si), aluminum (Al) and gallium (Ga).
鋁元素(Al)及鎵元素(Ga)由於作為原料之氧化物之組成穩定，且龜裂耐性之提高效果較高，故而更佳。 Aluminum (Al) and gallium (Ga) are preferred because the composition of the oxides used as raw materials is stable and the effect of improving the crack resistance is higher.
若X/(In+Sn+Zn+X)為0.001以上，則可抑制濺鍍靶材之強度降低。若X/(In+Sn+Zn+X)為0.05以下，則使用包含該氧化物燒結體之濺鍍靶材成膜之氧化物半導體薄膜容易進行利用草酸等弱酸之蝕刻加工。進而，若X/(In+Sn+Zn+X)為0.05以下，則可抑制TFT特性尤其是 移動率之降低。 If X/(In+Sn+Zn+X) is 0.001 or more, the strength reduction of the sputtering target can be suppressed. If X/(In+Sn+Zn+X) is 0.05 or less, the oxide semiconductor film formed by the sputtering target containing the oxide sintered body can be easily etched using weak acids such as oxalic acid. Furthermore, if X/(In+Sn+Zn+X) is 0.05 or less, the reduction of TFT characteristics, especially mobility, can be suppressed.
X/(In+Sn+Zn+X)較佳為0.001以上0.05以下，更佳為0.003以上0.03以下，進而較佳為0.005以上0.01以下，更進一步較佳為0.005以上且未達0.01。 X/(In+Sn+Zn+X) is preferably 0.001 or more and 0.05 or less, more preferably 0.003 or more and 0.03 or less, further preferably 0.005 or more and 0.01 or less, and further preferably 0.005 or more and less than 0.01.
於本實施形態之氧化物燒結體含有X元素之情形時，X元素既可僅為1種，亦可為2種以上。於包含2種以上之X元素時，式(1X)中之X設為X元素之原子比之合計。 When the oxide sintered body of the present embodiment contains an X element, the X element may be only one or two or more. When two or more X elements are contained, X in formula (1X) is the total atomic ratio of the X elements.
氧化物燒結體中之X元素之存在形態並不特別規定。作為氧化物燒結體中之X元素之存在形態，例如，可列舉作為氧化物存在之形態、固溶之形態及於晶界偏析之形態。 The existing form of the X element in the oxide sintered body is not particularly specified. As the existing form of the X element in the oxide sintered body, for example, the form of the X element existing as an oxide, the form of the X element existing as a solid solution, and the form of the X element segregating at the grain boundary can be listed.
氧化物燒結體之各金屬元素之原子比可藉由原料之調配量而控制。又，各元素之原子比可藉由感應耦合電漿發射光譜分析裝置(ICP-AES)對含有元素進行定量分析而求出。 The atomic ratio of each metal element in the oxide sintered body can be controlled by adjusting the amount of raw materials. In addition, the atomic ratio of each element can be obtained by quantitatively analyzing the contained elements using an inductively coupled plasma emission spectrometer (ICP-AES).
本實施形態之氧化物燒結體較佳為含有由Zn2-xSn1-yInx+yO4[0≦x<2，0≦y<1]表示之尖晶石結構化合物。於本說明書中，存在將尖晶石結構化合物稱為尖晶石化合物之情形。於Zn2-xSn1-yInx+yO4中，x為0，y為0之情形時，由Zn2SnO4表示。 The oxide sintered body of the present embodiment preferably contains a spinel structure compound represented by Zn2 - xSn1 -yInx + yO4 [0≦x<2, 0≦y<1]. In this specification, the spinel structure compound is sometimes referred to as a spinel compound. In Zn2 - xSn1-yInx +yO4 , when x is 0 and y is 0, it is represented by Zn2SnO4 .
本實施形態之氧化物燒結體較佳為含有由In2O3(ZnO)m表示之六方晶層狀化合物。於本實施形態中，於由In2O3(ZnO)m表示之式中，m為2~7之整數，較佳為3~5之整數。若m為2以上，則化合物採用六方晶層狀結構。若m為7以下，則氧化物燒結體之體電阻變低。 The oxide sintered body of the present embodiment preferably contains a hexagonal layered compound represented by In 2 O 3 (ZnO) m . In the present embodiment, in the formula represented by In 2 O 3 (ZnO) m , m is an integer of 2 to 7, preferably an integer of 3 to 5. If m is 2 or more, the compound adopts a hexagonal layered structure. If m is 7 or less, the bulk resistance of the oxide sintered body becomes low.
本實施形態之氧化物燒結體更佳為含有由In2O3(ZnO)m[m=2~7]表示之六方晶層狀化合物及由Zn2-xSn1-yInx+yO4[0≦x<2，0≦y<1] 表示之尖晶石結構化合物。 The oxide sintered body of the present embodiment more preferably contains a hexagonal layered compound represented by In2O3 (ZnO) m [m=2-7] and a spinel structure compound represented by Zn2 - xSn1-yInx + yO4 [0≦x<2, 0≦y<1].
包括氧化銦與氧化鋅之六方晶層狀化合物係於利用X射線繞射法之測定中表示歸屬於六方晶層狀化合物之X射線繞射圖案之化合物。氧化物燒結體中含有之六方晶層狀化合物係由In2O3(ZnO)m表示之化合物。 The hexagonal layered compound including indium oxide and zinc oxide is a compound that shows an X-ray diffraction pattern belonging to a hexagonal layered compound in measurement using an X-ray diffraction method. The hexagonal layered compound contained in the oxide sintered body is a compound represented by In 2 O 3 (ZnO) m .
本實施形態之氧化物燒結體亦可含有由Zn2-xSn1-yInx+yO4[0≦x<2，0≦y<1]表示之尖晶石結構化合物及由In2O3表示之方鐵錳礦結構化合物。 The oxide sintered body of this embodiment may also contain a spinel structure compound represented by Zn 2-x Sn 1-y In x+y O 4 [0≦x<2, 0≦y<1] and a ferromanganite structure compound represented by In 2 O 3 .
於本實施形態之氧化物燒結體含有X元素之情形時，若X元素之含有比率為上述式(1X)之範圍內，則亦可使濺鍍靶材之體電阻充分低。 When the oxide sintered body of this embodiment contains the X element, if the content ratio of the X element is within the range of the above formula (1X), the bulk resistance of the sputtering target can be sufficiently low.
本實施形態之濺鍍靶材之體電阻較佳為50mΩcm以下，更佳為25mΩcm以下，進而較佳為10mΩcm以下，更進一步較佳為5mΩcm以下，特佳為3mΩcm以下。若體電阻為50mΩcm以下，則可利用直流濺鍍進行穩定之成膜。 The bulk resistance of the sputtering target of this embodiment is preferably 50mΩcm or less, more preferably 25mΩcm or less, further preferably 10mΩcm or less, further preferably 5mΩcm or less, and particularly preferably 3mΩcm or less. If the bulk resistance is 50mΩcm or less, DC sputtering can be used for stable film formation.
體電阻值可使用公知之電阻率計基於四探針法(JIS R 1637：1998)測定。較佳為，測定部位係9個部位左右，將所測定出之9個部位之值之平均值設為體電阻值。 The bulk resistance value can be measured using a known resistivity meter based on the four-probe method (JIS R 1637:1998). Preferably, the measurement locations are about 9 locations, and the average value of the values measured at the 9 locations is set as the bulk resistance value.
測定部位於氧化物燒結體之平面形狀為四邊形之情形時，較佳為將面分割成3×3之9個部分，設為各四邊形之中心點9個部位。 When the plane shape of the oxide sintered body is a quadrilateral, it is better to divide the surface into 9 parts of 3×3 and set the 9 parts as the center points of each quadrilateral.
再者，於氧化物燒結體之平面形狀為圓形之情形時，較佳為將與圓內切之正方形分割成3×3之9個部分，設為各正方形之中心點9個 部位。 Furthermore, when the planar shape of the oxide sintered body is a circle, it is better to divide the square inscribed in the circle into 9 parts of 3×3, and set the 9 positions as the center points of each square.
自防止異常放電及製造容易性之觀點而言，本實施形態之氧化物燒結體之平均結晶粒徑較佳為10μm以下，更佳為8μm以下。 From the perspective of preventing abnormal discharge and facilitating manufacturing, the average crystal grain size of the oxide sintered body of this embodiment is preferably less than 10 μm, and more preferably less than 8 μm.
若平均結晶粒徑為10μm以下，則可防止起因於晶界之異常放電。氧化物燒結體之平均結晶粒徑之下限並不特別規定，但自製造容易性之觀點而言較佳為1μm以上。 If the average crystal grain size is less than 10μm, abnormal discharge caused by grain boundaries can be prevented. The lower limit of the average crystal grain size of the oxide sintered body is not specifically specified, but it is preferably greater than 1μm from the perspective of ease of manufacturing.
平均結晶粒徑可藉由原料之選擇及製造條件之變更調整。具體而言，較佳為使用平均粒徑較小之原料，更佳為使用平均粒徑為1μm以下之原料。進而，於燒結時，存在燒結溫度越高，或燒結時間越長，則平均結晶粒徑越大之傾向。 The average crystal grain size can be adjusted by selecting raw materials and changing manufacturing conditions. Specifically, it is better to use raw materials with a smaller average grain size, and it is more preferable to use raw materials with an average grain size of less than 1μm. Furthermore, during sintering, the higher the sintering temperature or the longer the sintering time, the larger the average crystal grain size tends to be.
平均結晶粒徑可利用以下方式測定。 The average crystal grain size can be measured in the following way.
於對氧化物燒結體之表面進行研磨且平面形狀為四邊形之情形時，將面等面積地分割成16個部分，於各四邊形之中心點16個部位中，測定於倍率1000倍(80μm×125μm)之框內所觀察之粒徑，分別求出16個部位之框內之粒子粒徑之平均值，最後將16處測定值之平均值設為平均結晶粒徑。 When the surface of the oxide sintered body is polished and the plane shape is a quadrilateral, the surface is divided into 16 parts with equal area. The grain size observed in the frame with a magnification of 1000 times (80μm×125μm) is measured at the 16 locations at the center of each quadrilateral. The average value of the grain size in the frame of the 16 locations is calculated respectively. Finally, the average value of the measured values at the 16 locations is set as the average crystal grain size.
於對氧化物燒結體之表面進行研磨且平面形狀為圓形之情形時，將與圓內切之正方形等面積地分割成16個部分，於各正方形之中心點16個部位中，測定於倍率1000倍(80μm×125μm)之框內所觀察之粒子之粒徑，求出16個部位之框內之粒子粒徑之平均值。 When the surface of the oxide sintered body is polished and the plane shape is a circle, the square inscribed in the circle is divided into 16 parts with equal area. The particle size of the particles observed in the frame with a magnification of 1000 times (80μm×125μm) is measured at the 16 locations at the center of each square, and the average particle size of the particles in the frame of the 16 locations is calculated.
關於粒徑，係針對縱橫比未達2之粒子，基於JIS R 1670： 2006，測定結晶粒之粒徑作為圓當量徑。作為圓當量徑之測定順序，具體而言，用圓規量微結構照片之測定對象晶粒而讀取相當於對象晶粒之面積之直徑。關於縱橫比為2以上之粒子，將最長徑與最短徑之平均值設為該粒子之粒徑。結晶粒可藉由掃描式電子顯微鏡(SEM)觀察。六方晶層狀化合物、尖晶石化合物及方鐵錳礦結構化合物可藉由下述實施例中所記載之方法確認。 Regarding the particle size, for particles with an aspect ratio of less than 2, the particle size of the crystal grains is measured as the equivalent circular diameter based on JIS R 1670: 2006. Specifically, the measurement procedure of the equivalent circular diameter is to measure the target crystal grains in the microstructure photograph with a compass and read the diameter equivalent to the area of the target crystal grain. For particles with an aspect ratio of more than 2, the average value of the longest diameter and the shortest diameter is set as the particle size of the particle. The crystal grains can be observed by a scanning electron microscope (SEM). Hexagonal layered compounds, spinel compounds and ferromanganese structure compounds can be confirmed by the methods described in the following examples.
於本實施形態之氧化物燒結體包含六方晶層狀化合物與尖晶石化合物之情形時，六方晶層狀化合物之平均結晶粒徑與尖晶石化合物之平均結晶粒徑之差較佳為1μm以下。藉由將平均結晶粒徑設為該範圍，可提高氧化物燒結體之強度。 When the oxide sintered body of the present embodiment includes a hexagonal layered compound and a spinel compound, the difference between the average crystal grain size of the hexagonal layered compound and the average crystal grain size of the spinel compound is preferably less than 1 μm. By setting the average crystal grain size to this range, the strength of the oxide sintered body can be improved.
更佳為，本實施形態之氧化物燒結體之平均結晶粒徑為10μm以下，且六方晶層狀化合物之平均結晶粒徑與尖晶石化合物之平均結晶粒徑之差為1μm以下。 More preferably, the average crystal grain size of the oxide sintered body of the present embodiment is less than 10 μm, and the difference between the average crystal grain size of the hexagonal layered compound and the average crystal grain size of the spinel compound is less than 1 μm.
又，於本實施形態之氧化物燒結體包含方鐵錳礦結構化合物與尖晶石化合物之情形時，較佳為，方鐵錳礦結構化合物之平均結晶粒徑與尖晶石化合物之平均結晶粒徑之差為1μm以下。藉由將平均結晶粒徑設為該範圍，可提高氧化物燒結體之強度。 Furthermore, when the oxide sintered body of the present embodiment includes a ferromanganese structure compound and a spinel compound, it is preferred that the difference between the average crystal grain size of the ferromanganese structure compound and the average crystal grain size of the spinel compound is less than 1 μm. By setting the average crystal grain size to this range, the strength of the oxide sintered body can be improved.
更佳為，本實施形態之氧化物燒結體之平均結晶粒徑為10μm以下，且方鐵錳礦結構化合物之平均結晶粒徑與尖晶石化合物之平均結晶粒徑之差為1μm以下。 More preferably, the average crystal grain size of the oxide sintered body of the present embodiment is less than 10 μm, and the difference between the average crystal grain size of the ferromanganese structure compound and the average crystal grain size of the spinel compound is less than 1 μm.
本實施形態之氧化物燒結體之相對密度較佳為95%以上，更佳為96% 以上。 The relative density of the oxide sintered body of this embodiment is preferably above 95%, and more preferably above 96%.
若本實施形態之氧化物燒結體之相對密度為95%以上，則本實施形態之濺鍍靶材之機械強度較高，且導電性優異。因此，可進而提高將本實施形態之濺鍍靶材裝設於RF(radio frequency，射頻)磁控濺鍍裝置或DC(direct current，直流)磁控濺鍍裝置進行濺鍍時之電漿放電之穩定性。氧化物燒結體之相對密度係將根據燒結體中之氧化物各自之固有之密度及該等組成比算出的相對於理論密度之氧化物燒結體之實際測定出之密度以百分率表示者。氧化物燒結體之相對密度例如係將根據氧化銦、氧化鋅及氧化錫、以及根據需要含有之X元素之氧化物各自之固有之密度及該等組成比算出的相對於理論密度之氧化物燒結體之實際測定出之密度以百分率表示者。 If the relative density of the oxide sintered body of the present embodiment is 95% or more, the mechanical strength of the sputtering target of the present embodiment is high and the electrical conductivity is excellent. Therefore, the stability of plasma discharge when the sputtering target of the present embodiment is installed in an RF (radio frequency) magnetron sputtering device or a DC (direct current) magnetron sputtering device for sputtering can be further improved. The relative density of the oxide sintered body is the density of the oxide sintered body actually measured relative to the theoretical density calculated based on the inherent density of each oxide in the sintered body and the composition ratio, expressed as a percentage. The relative density of the oxide sintered body is, for example, the density of the oxide sintered body actually measured relative to the theoretical density calculated based on the intrinsic density of the oxides of indium oxide, zinc oxide, tin oxide, and the X element contained as required, and the composition ratio thereof, expressed as a percentage.
氧化物燒結體之相對密度可基於阿基米德法測定。相對密度(單位：%)具體而言係用氧化物燒結體之空中重量除以體積(=燒結體之水中重量/計測溫度下之水比重)，設為基於下述式(數5)之相對於理論密度ρ(g/cm3)之百分率之值。 The relative density of oxide sintered bodies can be measured based on the Archimedean method. Specifically, the relative density (unit: %) is the value obtained by dividing the weight of the oxide sintered body in air by the volume (=weight of the sintered body in water/specific gravity of water at the measuring temperature) and setting it as a percentage of the theoretical density ρ (g/cm 3 ) based on the following formula (Equation 5).
相對密度={(氧化物燒結體之空中重量/體積)/理論密度ρ}×100 Relative density = {(weight of oxide sintered body in air/volume)/theoretical density ρ}×100
ρ=(C1/100/ρ1+C2/100/ρ2…+Cn/100/ρn)-1 (數5) ρ=(C 1 /100/ρ 1 +C 2 /100/ρ 2… +C n /100/ρ n ) -1 (number 5)
再者，於式(數5)中，C1~Cn分別表示氧化物燒結體或氧化物燒結體之構成物質之含量(質量%)，ρ1~ρn表示與C1~Cn對應之各構成物質之密度(g/cm3)。 Furthermore, in formula (5), C 1 to C n represent the contents (mass %) of the oxide sintered body or the constituents of the oxide sintered body, respectively, and ρ 1 to ρ n represent the densities (g/cm 3 ) of the constituents corresponding to C 1 to C n .
再者，由於密度與比重大致同等，故而各構成物質之密度可使用化學手冊 基礎編I 日本化學會編 修訂2版(丸善股份有限公司)中所記載之氧化物之比重之值。 Furthermore, since density and specific gravity are roughly the same, the density of each constituent substance can be determined by using the specific gravity of the oxides listed in the Chemical Handbook Basic Edition I, edited by the Chemical Society of Japan, Revised 2nd Edition (Maruzen Co., Ltd.).
本實施形態之氧化物燒結體之製造方法包含混合、粉碎步驟、造粒步驟、成形步驟及燒結步驟。氧化物燒結體之製造方法亦可包含其他步驟。作為其他步驟，可列舉退火步驟。 The method for manufacturing the oxide sintered body of this embodiment includes mixing, pulverizing, granulating, forming and sintering. The method for manufacturing the oxide sintered body may also include other steps. As other steps, an annealing step may be listed.
以下，列舉製造ITZO系氧化物燒結體之情形為例，對各步驟具體地進行說明。 Below, we take the production of ITZO-based oxide sintered bodies as an example to explain each step in detail.
本實施形態之氧化物燒結體可經由將銦原料、鋅原料、錫原料及X元素原料混合及粉碎之混合、粉碎步驟、將原料混合物造粒之造粒步驟、成形之成形步驟、將成形物燒結之燒結步驟、及根據需要對燒結體進行退火之退火步驟而製造。 The oxide sintered body of this embodiment can be manufactured by mixing and pulverizing indium raw material, zinc raw material, tin raw material and X element raw material, a pulverizing step, a granulating step of granulating the raw material mixture, a forming step of forming, a sintering step of sintering the formed product, and an annealing step of annealing the sintered body as needed.
混合、粉碎步驟係將氧化物燒結體之原料混合及粉碎而獲得原料混合物之步驟。原料混合物例如較佳為粉末狀。 The mixing and pulverizing step is a step of mixing and pulverizing the raw materials of the oxide sintered body to obtain a raw material mixture. The raw material mixture is preferably in a powder form, for example.
於混合、粉碎步驟中，首先，準備氧化物燒結體之原料。 In the mixing and pulverizing step, first, prepare the raw materials for the oxide sintering.
製造包含In、Zn及Sn之氧化物燒結體之情形時之原料如下。 The raw materials for manufacturing a sintered body of oxides containing In, Zn, and Sn are as follows.
銦原料(In原料)只要為包含In之化合物或金屬，則並不特別限定。 The indium raw material (In raw material) is not particularly limited as long as it is a compound or metal containing In.
鋅原料(Zn原料)只要為包含Zn之化合物或金屬，則並不特別限定。 The zinc raw material (Zn raw material) is not particularly limited as long as it is a compound or metal containing Zn.
錫原料(Sn原料)只要為包含Sn之化合物或金屬，則並不特 別限定。 The tin raw material (Sn raw material) is not particularly limited as long as it is a compound or metal containing Sn.
製造包含X元素之氧化物燒結體之情形時之原料如下。 The raw materials for manufacturing a sintered body of oxide containing element X are as follows.
X元素之原料亦只要為包含X元素之化合物或金屬，則並不特別限定。 The raw material of element X is not particularly limited as long as it is a compound or metal containing element X.
In原料、Zn原料、Sn原料及X元素之原料較佳為氧化物。 The raw materials of In, Zn, Sn and X elements are preferably oxides.
氧化銦、氧化鋅、氧化錫及X元素氧化物等原料較佳為高純度。氧化物燒結體之原料之純度較佳為99質量%以上，更佳為99.9質量%以上，進而較佳為99.99質量%以上。若使用高純度之原料則獲得緻密之組織之燒結體，包括該燒結體之濺鍍靶材之體積電阻率變低。 The raw materials such as indium oxide, zinc oxide, tin oxide and X element oxide are preferably of high purity. The purity of the raw materials of the oxide sintered body is preferably 99 mass% or more, more preferably 99.9 mass% or more, and further preferably 99.99 mass% or more. If high-purity raw materials are used, a sintered body with a dense structure is obtained, including the volume resistivity of the sputtering target of the sintered body becomes lower.
作為原料之金屬氧化物之1次粒子之平均粒徑較佳為0.01μm以上10μm以下，更佳為0.05μm以上5μm以下，進而較佳為0.1μm以上5μm以下。 The average particle size of the primary particles of the metal oxide used as the raw material is preferably 0.01 μm to 10 μm, more preferably 0.05 μm to 5 μm, and further preferably 0.1 μm to 5 μm.
若作為原料之金屬氧化物之1次粒子之平均粒徑為0.01μm以上則不易凝聚，若平均粒徑為10μm以下則混合性充分，獲得緻密之組織之燒結體。平均粒徑採用中值粒徑D50，利用雷射繞射式粒度分佈測定裝置SALD-300V(島津製作所股份有限公司製造)測定。 If the average particle size of the primary particles of the metal oxide used as the raw material is 0.01μm or more, it is not easy to aggregate. If the average particle size is 10μm or less, the mixing property is sufficient, and a sintered body with a dense structure is obtained. The average particle size adopts the median particle size D50 and is measured using the laser diffraction particle size distribution measuring device SALD-300V (manufactured by Shimadzu Corporation).
對氧化物燒結體之原料添加用以解除凝聚之分散劑與用以調整為適合於利用噴霧乾燥器之造粒之黏度之增黏劑，利用珠磨機等混合粉碎。作為分散劑，例如，可列舉丙烯酸甲基丙烯酸共聚物氨中和物等，作為增黏劑，例如，可列舉聚乙烯醇等。 A dispersant for deagglomeration and a thickener for adjusting the viscosity suitable for granulation using a spray dryer are added to the raw materials of the oxide sintered body, and the mixture is mixed and crushed using a bead mill or the like. Examples of the dispersant include ammonia neutralized products of acrylic acid and methacrylic acid copolymers, and examples of the thickener include polyvinyl alcohol, etc.
混合、粉碎步驟中所獲得之原料混合物可直接造粒，但亦可於造粒 前實施煅燒處理。煅燒處理通常以700℃以上900℃以下將原料混合物燒成1小時以上5小時以下。 The raw material mixture obtained in the mixing and pulverizing step can be directly granulated, but it can also be calcined before granulation. The calcination treatment is usually carried out by calcining the raw material mixture at a temperature of 700°C to 900°C for 1 hour to 5 hours.
未實施煅燒處理之原料混合物、或實施有煅燒處理之原料混合物藉由造粒處理，可改善下述(4)之成形步驟中之流動性及填充性。 The raw material mixture that has not been calcined or the raw material mixture that has been calcined can be granulated to improve the fluidity and filling properties in the forming step (4) below.
於本說明書中，有時將對氧化物燒結體之原料進行造粒而獲得原料造粒粉之步驟稱為造粒步驟。 In this specification, the step of granulating the raw material of the oxide sintered body to obtain the raw material granulated powder is sometimes referred to as the granulation step.
造粒處理可使用噴霧乾燥器等進行。造粒步驟中所獲得之造粒粉為了於成形步驟中均勻地填充於模具，較理想為真球狀。 Granulation can be carried out using a spray dryer or the like. The granulated powder obtained in the granulation step is ideally in a true spherical shape in order to be evenly filled into the mold in the forming step.
造粒條件係調整所導入之原料漿料濃度、噴霧乾燥器之轉數及熱風溫度等而適當選定。 Granulation conditions are appropriately selected by adjusting the concentration of the raw material slurry introduced, the speed of the spray dryer, and the hot air temperature.
關於漿料溶液之製備，於使用未實施煅燒處理之原料混合物之情形時，直接使用混合、粉碎步驟中所獲得之漿料溶液，於使用實施有煅燒處理之原料混合物之情形時，再次經過混合、粉碎步驟，製備成漿料溶液後使用。 Regarding the preparation of the slurry solution, when using a raw material mixture that has not been calcined, the slurry solution obtained in the mixing and crushing steps is directly used. When using a raw material mixture that has been calcined, it is mixed and crushed again to prepare a slurry solution before use.
於本實施形態之氧化物燒結體之製造方法中，將藉由造粒處理而形成之原料造粒粉之粒徑控制為25μm以上150μm以下之範圍內。 In the method for manufacturing the oxide sintered body of this embodiment, the particle size of the raw material granulated powder formed by the granulation treatment is controlled to be within the range of 25μm to 150μm.
若原料造粒粉之粒徑為25μm以上，則原料造粒粉相對於在下述(4)之成形步驟中所使用之模具之表面的滑動性提高，可將原料造粒粉充分地填充於模具內。 If the particle size of the raw material granulated powder is 25 μm or more, the slipperiness of the raw material granulated powder relative to the surface of the mold used in the molding step (4) below is improved, and the raw material granulated powder can be fully filled into the mold.
若原料造粒粉之粒徑為150μm以下，則可抑制粒徑過大而模具內之填充率變低。 If the particle size of the raw material granulated powder is less than 150μm, the particle size can be prevented from being too large and the filling rate in the mold becoming low.
原料造粒粉之粒徑較佳為25μm以上75μm以下。 The particle size of the raw material granulated powder is preferably greater than 25μm and less than 75μm.
獲得粒徑為特定範圍內之原料造粒粉之方法並不特別限定。例如，可列舉如下方法：將實施過造粒處理之原料混合物(原料造粒粉)放入篩網，篩選屬於所期望之粒徑範圍之原料造粒粉。用於該方法之篩網較佳為具有可供所期望之粒徑之原料造粒粉通過之尺寸之開口部的篩網。較佳為使用第1篩網及第2篩網，該第1篩網用於以粒徑範圍之下限值為基準篩選原料造粒粉，該第2篩網用於以粒徑範圍之上限值為基準篩選原料造粒粉。例如，於將原料造粒粉之粒徑控制為25μm以上150μm以下之範圍內之情形時，首先，使用具有未達25μm之原料造粒粉能夠通過但不使25μm以上之原料造粒粉通過之尺寸之開口部的篩網(第1篩網)，篩選具有25μm以上之粒徑之原料造粒粉。其次，對該篩選後之原料造粒粉，使用具有150μm以下之原料造粒粉能夠通過但不使超過150μm之原料造粒粉通過之尺寸之開口部的篩網(第2篩網)，篩選25μm以上150μm以下之範圍內之原料造粒粉。亦可為先使用第2篩網，其次使用第1篩網之順序。 The method for obtaining raw material granulated powder having a particle size within a specific range is not particularly limited. For example, the following method can be cited: a raw material mixture (raw material granulated powder) that has been subjected to a granulation treatment is placed in a sieve to screen the raw material granulated powder belonging to the desired particle size range. The sieve used in this method is preferably a sieve having an opening of a size that allows the raw material granulated powder of the desired particle size to pass through. It is preferred to use a first sieve and a second sieve, the first sieve being used to screen the raw material granulated powder based on the lower limit value of the particle size range, and the second sieve being used to screen the raw material granulated powder based on the upper limit value of the particle size range. For example, when the particle size of the raw material granulated powder is controlled to be within the range of 25 μm to 150 μm, first, a sieve (first sieve) having an opening of a size that allows raw material granulated powder less than 25 μm to pass through but does not allow raw material granulated powder of more than 25 μm to pass through is used to screen the raw material granulated powder having a particle size of more than 25 μm. Next, a sieve (second sieve) having an opening of a size that allows raw material granulated powder of less than 150 μm to pass through but does not allow raw material granulated powder of more than 150 μm to pass through is used to screen the raw material granulated powder within the range of 25 μm to 150 μm. The order may also be to use the second sieve first and then the first sieve.
控制原料造粒粉之粒徑範圍之方法並不限定於上述使用篩網之方法，只要供於下述(4)之成形步驟之原料造粒粉為25μm以上、150μm以下之範圍內即可。 The method for controlling the particle size range of the raw material granulated powder is not limited to the above-mentioned method of using a screen, as long as the raw material granulated powder provided for the forming step (4) below is within the range of 25μm or more and 150μm or less.
再者，於實施過煅燒處理之原料混合物中，由於粒子彼此結合，故而於進行造粒處理之情形時，較佳為，於造粒處理前進行粉碎處理。 Furthermore, in the raw material mixture that has been subjected to calcination, since the particles are bound together, it is preferred to perform a pulverization process before granulation when granulation is performed.
於本說明書中，有時稱將造粒步驟中所獲得之原料造粒粉填充至模具內，並將填充於模具內之上述原料造粒粉成形而獲得成形體之步驟為成形步驟。 In this specification, the step of filling the raw material granulated powder obtained in the granulation step into a mold and forming the raw material granulated powder filled in the mold to obtain a molded body is sometimes referred to as the forming step.
作為成形步驟中之成形方法，例如，可列舉模具加壓成形。 As a forming method in the forming step, for example, die pressure forming can be cited.
作為濺鍍靶材，於獲得燒結密度較高之燒結體之情形時，較佳為，於成形步驟中藉由模具加壓成形等而預成形之後，藉由冷均壓(CIP；Cold Isostatic Pressing)成形等進而壓密化。 When obtaining a sintered body with a higher sintering density as a sputtering target, it is preferable to perform pre-forming by die pressure forming in the forming step and then further densify by cold isostatic pressing (CIP) forming.
原料造粒粉之粒徑較佳為25μm以上150μm以下，若為25μm以上75μm以下則更佳。 The particle size of the raw material granulated powder is preferably greater than 25μm and less than 150μm, and it is even better if it is greater than 25μm and less than 75μm.
若原料造粒粉之粒徑為25μm以上150μm以下，則可將原料造粒粉充分地填充至成形步驟中所使用之模具內，故而亦可降低成形體中之密度之不均。 If the particle size of the raw material granulated powder is greater than 25μm and less than 150μm, the raw material granulated powder can be fully filled into the mold used in the molding step, thereby reducing the density unevenness in the molded body.
於本說明書中，有時稱將成形步驟中所獲得之成形體於特定之溫度範圍內燒結之步驟為燒結步驟。 In this specification, the step of sintering the formed body obtained in the forming step within a specific temperature range is sometimes referred to as the sintering step.
於燒結步驟中，可使用常壓燒結、熱壓燒結、或熱均壓(HIP；Hot Isostatic Pressing)燒結等通常進行之燒結方法。 In the sintering step, commonly used sintering methods such as atmospheric pressure sintering, hot pressure sintering, or hot isostatic pressing (HIP) sintering can be used.
燒結溫度較佳為1310℃以上1440℃以下，更佳為1320℃以上1430℃以下。 The sintering temperature is preferably above 1310°C and below 1440°C, and more preferably above 1320°C and below 1430°C.
若燒結溫度為1310℃以上1440℃以下，則容易將氧化物燒結體之表面之維氏硬度之平均值(Hav)控制為上述範圍內。即，藉由使用 造粒步驟中所得之具有特定範圍內之粒徑之原料造粒粉製作成形體，並將該成形體以特定溫度燒結，可降低氧化物燒結體中之強度之不均，亦可防止維氏硬度過大。 If the sintering temperature is 1310°C or higher and 1440°C or lower, it is easy to control the average value ( Hav ) of the Vickers hardness of the surface of the oxide sintered body within the above range. That is, by using the raw material granulated powder having a particle size within a specific range obtained in the granulation step to produce a compact, and sintering the compact at a specific temperature, the strength variation in the oxide sintered body can be reduced, and the Vickers hardness can be prevented from being too high.
若燒結溫度為1310℃以上，則獲得充分之燒結密度，濺鍍靶材之體電阻亦可變低。 If the sintering temperature is above 1310℃, sufficient sintering density can be obtained and the bulk resistance of the sputtering target can also be reduced.
若燒結溫度為1440℃以下，則可抑制燒結時之氧化鋅昇華。 If the sintering temperature is below 1440℃, the sublimation of zinc oxide during sintering can be suppressed.
於燒結步驟中，較佳為，將自室溫到達至燒結溫度為止之升溫速度設為0.1℃/分鐘以上3℃/分鐘以下。 In the sintering step, it is preferred to set the heating rate from room temperature to the sintering temperature to be greater than 0.1°C/minute and less than 3°C/minute.
又，亦可於升溫之過程中，將溫度以700℃以上800℃以下保持1小時以上10小時以下，並以特定溫度保持特定時間之後，升溫至燒結溫度為止。 In addition, during the heating process, the temperature can be maintained at 700°C to 800°C for 1 hour to 10 hours, and after maintaining the specific temperature for a specific time, the temperature can be raised to the sintering temperature.
燒結時間根據燒結溫度而不同，但較佳為1小時以上、50小時以下，更佳為2小時以上30小時以下，進而較佳為3小時以上20小時以下。 The sintering time varies depending on the sintering temperature, but is preferably more than 1 hour and less than 50 hours, more preferably more than 2 hours and less than 30 hours, and even more preferably more than 3 hours and less than 20 hours.
作為燒結時之環境，例如，可列舉空氣或氧氣之環境、包含空氣或氧氣與還原性氣體之環境、或包含空氣或氧氣與惰性氣體之環境。作為還原性氣體，例如，可列舉氫氣、甲烷氣體及一氧化碳氣體等。作為惰性氣體，例如，可列舉氬氣及氮氣等。 Examples of the sintering environment include an air or oxygen environment, an environment containing air or oxygen and a reducing gas, or an environment containing air or oxygen and an inert gas. Examples of the reducing gas include hydrogen, methane, and carbon monoxide. Examples of the inert gas include argon and nitrogen.
於本實施形態之氧化物燒結體之製造方法中，退火步驟並非必需。於實施退火步驟之情形時，通常，將溫度以700℃以上1100℃以下保持1 小時以上5小時以下。 In the method for manufacturing the oxide sintered body of this embodiment, the annealing step is not necessary. When the annealing step is performed, the temperature is usually maintained at 700°C to 1100°C for 1 hour to 5 hours.
退火步驟可將燒結體暫時冷卻之後，再次升溫並退火，亦可於自燒結溫度降溫時進行退火。 The annealing step can be performed by temporarily cooling the sintered body and then heating it again for annealing, or by cooling it down from the sintering temperature.
作為退火時之環境，例如，可列舉空氣或氧氣之環境、包含空氣或氧氣與還原性氣體之環境、或包含空氣或氧氣與惰性氣體之環境。作為還原性氣體，例如，可列舉氫氣、甲烷氣體及一氧化碳氣體等。作為惰性氣體，例如，可列舉氬氣及氮氣等。 As the environment during annealing, for example, there can be listed an environment of air or oxygen, an environment containing air or oxygen and a reducing gas, or an environment containing air or oxygen and an inert gas. As the reducing gas, for example, there can be listed hydrogen gas, methane gas, and carbon monoxide gas. As the inert gas, for example, there can be listed argon gas and nitrogen gas.
再者，於製造與ITZO系不同之系統之氧化物燒結體之情形時，亦可藉由與上述相同之步驟製造。 Furthermore, when manufacturing an oxide sintered body of a system different from the ITZO system, it can also be manufactured by the same steps as above.
藉由將利用上述製造方法所獲得之氧化物燒結體切削加工為適當之形狀，並根據需要對氧化物燒結體之表面進行研磨，可製造濺鍍靶材。 By cutting the oxide sintered body obtained by the above-mentioned manufacturing method into a suitable shape and polishing the surface of the oxide sintered body as needed, a sputtering target can be manufactured.
具體而言，藉由將氧化物燒結體切削加工為適合裝設於濺鍍裝置之形狀，而獲得濺鍍靶材素材(有時亦稱為靶材素材)。藉由將該靶材素材接著於背襯板，而獲得濺鍍靶材。 Specifically, a sputtering target material (sometimes also referred to as a target material) is obtained by cutting an oxide sintered body into a shape suitable for installation in a sputtering device. A sputtering target is obtained by attaching the target material to a backing plate.
於將氧化物燒結體用作靶材素材之情形時，燒結體之表面粗糙度Ra較佳為0.5μm以下。作為調整燒結體之表面粗糙度Ra之方法，例如，可列舉利用平面研削盤研削燒結體之方法。 When an oxide sintered body is used as a target material, the surface roughness Ra of the sintered body is preferably less than 0.5 μm. As a method for adjusting the surface roughness Ra of the sintered body, for example, a method of grinding the sintered body using a flat grinding disk can be cited.
濺鍍靶材素材之表面較佳為藉由100號~1,000號之金剛石磨石，進行精加工，特佳為藉由400號~800號之金剛石磨石進行精加工。藉由使用100號以上或1,000號以下之金剛石磨石，可防止濺鍍靶材素材之斷裂。 The surface of the sputtering target material is preferably finished with a diamond grindstone of No. 100 to No. 1,000, and is particularly preferably finished with a diamond grindstone of No. 400 to No. 800. By using a diamond grindstone of No. 100 or above or No. 1,000 or below, the sputtering target material can be prevented from breaking.
較佳為，濺鍍靶材素材之表面粗糙度Ra為0.5μm以下，且具備無方向性之研削面。若濺鍍靶材素材之表面粗糙度Ra為0.5μm以下且具備無方向性之研削面，則可防止異常放電及顆粒之產生。 Preferably, the surface roughness Ra of the sputtering target material is less than 0.5μm and has a non-directional grinding surface. If the surface roughness Ra of the sputtering target material is less than 0.5μm and has a non-directional grinding surface, abnormal discharge and particle generation can be prevented.
最後，對所獲得之濺鍍靶材素材進行清潔處理。作為清潔處理之方法，例如，可列舉鼓風器及流水洗淨等任一個方法。於利用鼓風器將異物去除時，藉由自鼓風器之噴嘴所朝向之側利用集塵機吸氣，可更有效地去除異物。 Finally, the obtained sputtering target material is cleaned. As a method of cleaning, for example, any method such as a blower and running water cleaning can be listed. When using a blower to remove foreign matter, the foreign matter can be removed more effectively by using a dust collector to suck air from the side where the blower nozzle is facing.
再者，除了以上之鼓風器或流水洗淨之清潔處理以外，亦可進而實施超音波洗淨等。作為超音波洗淨，於頻率25kHz以上300kHz以下之間多重振動地進行之方法較為有效。例如，較佳為如下方法：於頻率25kHz以上300kHz以下之間，每25kHz地使12種頻率多重振動而進行超音波洗淨。 Furthermore, in addition to the above-mentioned cleaning treatments of blowers or running water cleaning, ultrasonic cleaning can also be further implemented. As ultrasonic cleaning, a method of multiple vibrations between a frequency of 25kHz or more and 300kHz or less is more effective. For example, the following method is preferred: between a frequency of 25kHz or more and 300kHz or less, 12 frequencies are multiple-vibrated every 25kHz to perform ultrasonic cleaning.
濺鍍靶材素材之厚度通常為2mm以上20mm以下，較佳為3mm以上12mm以下，更佳為4mm以上9mm以下，進而較佳為4mm以上6mm以下。 The thickness of the sputtering target material is usually between 2mm and 20mm, preferably between 3mm and 12mm, more preferably between 4mm and 9mm, and even more preferably between 4mm and 6mm.
藉由將經過上述步驟及處理所獲得之濺鍍靶材素材接合於背襯板，可製造濺鍍靶材。又，亦可將複數個濺鍍靶材素材安裝於1個背襯板，實質上製造1個濺鍍靶材(多分割式濺鍍靶材)。 By joining the sputtering target material obtained through the above steps and treatments to a backing plate, a sputtering target can be manufactured. In addition, multiple sputtering target materials can be mounted on one backing plate to essentially manufacture one sputtering target (multi-split sputtering target).
本實施形態之濺鍍靶材包含氧化物燒結體，且該氧化物燒結體之表面之維氏硬度之平均值(Hav)超過500Hv且未達900Hv，故而係龜裂耐性提高之濺鍍靶材。 The sputtering target of this embodiment includes an oxide sintered body, and the average value ( Hav ) of the Vickers hardness of the surface of the oxide sintered body exceeds 500 Hv and is less than 900 Hv, so it is a sputtering target with improved crack resistance.
若使用本實施形態之濺鍍靶材進行濺鍍成膜，則龜裂耐性提高，故而可穩定地製造氧化物半導體薄膜。 If the sputtering target of this embodiment is used for sputtering film formation, the crack resistance is improved, so the oxide semiconductor thin film can be stably manufactured.
以下，基於實施例對本發明具體地進行說明。本發明並不限定於實施例。 The present invention is described in detail below based on the embodiments. The present invention is not limited to the embodiments.
製作包括ITZO系氧化物燒結體之濺鍍靶材。 Manufacture of sputtering targets including ITZO oxide sintered bodies.
首先，作為原料，以成為原子比(In：25原子%、Sn：15原子%、Zn：60原子%)之方式稱量以下之粉末。 First, as raw materials, weigh the following powders in such a way that the atomic ratio (In: 25 atomic%, Sn: 15 atomic%, Zn: 60 atomic%) is obtained.
‧In原料：純度99.99質量%之氧化銦粉末 ‧In raw materials: Indium oxide powder with a purity of 99.99% by mass
(平均粒徑：0.3μm) (Average particle size: 0.3μm)
‧Sn原料：純度99.99質量%之氧化錫粉末 ‧Sn raw material: Tin oxide powder with a purity of 99.99% by mass
(平均粒徑：1.0μm) (Average particle size: 1.0μm)
‧Zn原料：純度99.99質量%之氧化鋅粉末 ‧Zn raw material: Zinc oxide powder with a purity of 99.99% by mass
(平均粒徑：3.0μm) (Average particle size: 3.0μm)
作為用作原料之上述氧化物之粉末之平均粒徑採用中值粒徑D50，該平均粒徑利用雷射繞射式粒度分佈測定裝置SALD-300V(島津製作所股份有限公司製造)測定。 The average particle size of the above-mentioned oxide powder used as a raw material adopts the median particle size D50, and the average particle size is measured using a laser diffraction particle size distribution measuring device SALD-300V (manufactured by Shimadzu Corporation).
其次，對該等原料添加作為分散劑之丙烯酸甲基丙烯酸共聚物氨中和物(三明化成股份有限公司製造，Bangster X754B)、作為增黏劑之聚乙烯醇、及水，利用珠磨機混合粉碎2小時，獲得固形物成分濃度70質量%之造粒用漿料溶液。將所獲得之漿料溶液供給至噴霧乾燥器，以轉數12,000旋轉，以熱風溫度150℃之條件進行造粒而獲得原料造粒粉。 Next, the raw materials were added with ammonia neutralized acrylic acid-methacrylic acid copolymer (Bangster X754B manufactured by Sanming Chemical Co., Ltd.) as a dispersant, polyvinyl alcohol as a thickener, and water, and mixed and pulverized for 2 hours using a bead mill to obtain a granulation slurry solution with a solid content concentration of 70 mass%. The obtained slurry solution was supplied to a spray dryer, which was rotated at 12,000 revolutions and granulated at a hot air temperature of 150°C to obtain a raw material granulation powder.
藉由使原料造粒粉通過200網目之篩網而將超過75μm之粒 徑之造粒粉去除，其次藉由通過500網目之篩網而將未達25μm之造粒粉去除，將原料造粒粉之粒徑調整為25μm以上75μm以下之範圍內。 The raw material granulated powder is passed through a 200 mesh screen to remove the granulated powder with a particle size of more than 75μm, and then passed through a 500 mesh screen to remove the granulated powder with a particle size less than 25μm, so that the particle size of the raw material granulated powder is adjusted to a range of more than 25μm and less than 75μm.
圖5表示於實施例1中製備之原料造粒粉之SEM觀察圖像。 Figure 5 shows the SEM observation image of the raw material granulated powder prepared in Example 1.
其次，將該原料造粒粉均勻地填充至內徑300mm×600mm×9mm之模具，利用冷壓機進行加壓成形。加壓成形後，利用冷均壓加壓裝置(CIP裝置)以294MPa之壓力進行成形，獲得成形體。 Next, the raw material granulated powder is evenly filled into a mold with an inner diameter of 300mm×600mm×9mm and press-formed using a cold press. After press-forming, a cold isostatic press device (CIP device) is used to form the molded body at a pressure of 294MPa.
將3片如此獲得之成形體利用燒結爐於氧環境下升溫至780℃之後，以780℃保持5小時，進而升溫至1325℃，以該燒結溫度(1325℃)保持20小時，然後，進行爐內冷卻而獲得氧化物燒結體。再者，於2℃/分鐘之升溫速度下進行。 The three formed bodies thus obtained were heated to 780°C in an oxygen environment using a sintering furnace, then kept at 780°C for 5 hours, and then heated to 1325°C, and kept at the sintering temperature (1325°C) for 20 hours, and then cooled in the furnace to obtain an oxide sintered body. Furthermore, the heating rate was 2°C/min.
將3片所獲得之氧化物燒結體分別切斷，進行平面研削，獲得3片142mm×305mm×5mmt之氧化物燒結體板。將其中1片用於特性評價，將2片用於G1靶材[142mm×610mm(分割成2個部分)×5mmt]。 The three obtained oxide sintered bodies were cut separately and plane-ground to obtain three 142mm×305mm×5mmt oxide sintered body plates. One of them was used for characteristic evaluation, and two were used for G1 target materials [142mm×610mm (divided into two parts)×5mmt].
平面研削係使用平面研削裝置，首先使用#100之金剛石磨石對氧化物燒結體板進行平面研削，然後利用#200→#400→#800較細之粒度號數之金剛石磨石，依次進行研削加工。 Surface grinding uses a surface grinding device. First, a #100 diamond grindstone is used to grind the oxide sintered plate. Then, diamond grindstones with finer grit numbers of #200 → #400 → #800 are used to grind in sequence.
利用光學顯微鏡觀察研削加工後之氧化物燒結體板，結果未特別觀察到微龜裂等。 The oxide sintered plate after grinding was observed under an optical microscope, and no micro cracks were observed.
使用所獲得之氧化物燒結體板3片中1片，首先，測定維氏硬度之後，適當切出為特定尺寸，進行各種測定。 Using one of the three oxide sintered plates obtained, first measure the Vickers hardness, then cut it into a specific size and perform various measurements.
維氏硬度之測定係使用硬度計(Hardness Tester)(AKASHI MVK- E3)，依據JIS Z 2244：2009實施。測定點係採取氧化物燒結體(142×305mm尺寸)之中央之線上距單側之端每30mm之資料10點，利用平均值進行評價。 The Vickers hardness is measured using a hardness tester (AKASHI MVK- E3) in accordance with JIS Z 2244: 2009. The measurement points are 10 points on the center line of the oxide sintered body (142×305mm size) at every 30mm from the end of one side, and the average value is used for evaluation.
將已完成維氏硬度測定之氧化物燒結體板切出用於X射線繞射測定，使用X射線繞射測定裝置(XRD)，藉由以下之條件調查結晶結構。其結果，於實施例1之氧化物燒結體中，確認存在由In2O3(ZnO)m(式中，m=2~7之整數)表示之六方晶層狀化合物及由Zn2-xSn1-yInx+yO4[0≦x<2，0≦y<1]表示之尖晶石化合物。圖6表示實施例1之氧化物燒結體之XRD圖。 The oxide sintered body plate after the Vickers hardness test was cut out for X-ray diffraction test, and the crystal structure was investigated under the following conditions using an X-ray diffraction tester (XRD). As a result, in the oxide sintered body of Example 1, a hexagonal layered compound represented by In 2 O 3 (ZnO) m (where m=an integer from 2 to 7) and a spinel compound represented by Zn 2-x Sn 1-y In x+y O 4 [0≦x<2, 0≦y<1] were confirmed to exist. FIG6 shows the XRD pattern of the oxide sintered body of Example 1.
‧裝置：RIGAKU(股)製造Smartlab ‧Equipment: Smartlab manufactured by RIGAKU Co., Ltd.
‧X射線：Cu-Kα射線(波長1.5418×10-10m) ‧X-ray: Cu-Kα ray (wavelength 1.5418×10 -10 m)
‧平行光束，2θ-θ反射法，連續掃描(2.0°/分鐘) ‧Parallel beam, 2θ-θ reflection method, continuous scanning (2.0°/min)
‧取樣間隔：0.02° ‧Sampling interval: 0.02°
‧發散狹縫(Divergence Slit，DS)：1.0mm ‧Divergence Slit (DS): 1.0mm
‧散射狹縫(Scattering Slit，SS)：1.0mm ‧Scattering Slit (SS): 1.0mm
‧受光狹縫(Receiving Slit，RS)：1.0mm ‧Receiving Slit (RS): 1.0mm
同樣地使用剩餘之氧化物燒結體板，利用感應耦合電漿發射光譜分析裝置(ICP-AES，島津製作所股份有限公司製造)分析氧化物燒結體之原子比。結果如下。 Similarly, the remaining oxide sintered body plate was used to analyze the atomic ratio of the oxide sintered body using an inductively coupled plasma emission spectrometer (ICP-AES, manufactured by Shimadzu Corporation). The results are as follows.
Zn/(In+Sn+Zn)=0.60 Zn/(In+Sn+Zn)=0.60
Sn/(Sn+Zn)=0.20 Sn/(Sn+Zn)=0.20
In/(In+Sn+Zn)=0.25 In/(In+Sn+Zn)=0.25
實施例2~5之氧化物燒結體除了將實施例1中之燒結溫度分別變更為表1中所記載之燒結溫度以外，與實施例1同樣地製造。 The oxide sintered bodies of Examples 2 to 5 are manufactured in the same manner as Example 1 except that the sintering temperatures in Example 1 are changed to the sintering temperatures listed in Table 1.
比較例1~2之氧化物燒結體除了將實施例1中之燒結溫度分別變更為表1中所記載之燒結溫度以外，與實施例1同樣地製造。 The oxide sintered bodies of Comparative Examples 1 and 2 are manufactured in the same manner as Example 1, except that the sintering temperatures in Example 1 are changed to the sintering temperatures listed in Table 1.
比較例2之氧化物燒結體於研削加工後，利用光學顯微鏡進行觀察，結果確認到微龜裂。 The oxide sintered body of Comparative Example 2 was observed under an optical microscope after grinding, and micro cracks were confirmed.
比較例3~4之氧化物燒結體除了不實施實施例1中之原料之造粒而藉由模具而成形，以及將燒結溫度分別變更為表1中所記載之燒結溫度以外，與實施例1同樣地製造。 The oxide sintered bodies of Comparative Examples 3 and 4 were manufactured in the same manner as Example 1, except that the granulation of the raw materials in Example 1 was not performed but the sintering was performed by a mold, and the sintering temperature was changed to the sintering temperature listed in Table 1.
比較例5~6之氧化物燒結體除了將實施例1中之燒結溫度分別變更為表1中所記載之燒結溫度以外，與實施例1同樣地製造。 The oxide sintered bodies of Comparative Examples 5 and 6 were manufactured in the same manner as Example 1 except that the sintering temperatures in Example 1 were changed to the sintering temperatures listed in Table 1.
其次，藉由使用實施例1~5以及比較例1~6之氧化物燒結體板2片並接合於背襯板，而製造G1尺寸：142mm×610mm(分割成2個部分)×5mmt之濺鍍靶材。 Next, by using two oxide sintered plates of Examples 1 to 5 and Comparative Examples 1 to 6 and bonding them to a backing plate, a sputtering target with a G1 size of 142 mm × 610 mm (divided into 2 parts) × 5 mmt was manufactured.
於所有靶材中，接合率為98%以上。於將氧化物燒結體接合於背襯板時，氧化物燒結體未產生龜裂，可良好地製造濺鍍靶材。接合率(bonding rate)藉由X射線CT而確認。 The bonding rate of all targets is over 98%. When the oxide sintered body is bonded to the backing plate, the oxide sintered body does not crack, and the sputtering target can be manufactured well. The bonding rate is confirmed by X-ray CT.
使用已製作出之濺鍍靶材，利用G1濺鍍裝置，以環境氣體為100%Ar、濺鍍電力為1kW之條件進行預濺鍍1小時。此處，所謂G1濺鍍裝置，係指基板尺寸為300mm×400mm左右之第1代量產用濺鍍裝置。於預濺鍍之後，以表2所示之成膜條件改變各功率實施連續放電2小時，於放電結束後打開腔室，目視確認龜裂之有無，提高功率，再次重複放電測試，藉此評價龜裂耐性。 Using the prepared sputtering target, pre-sputtering was performed for 1 hour using a G1 sputtering device with an ambient gas of 100% Ar and a sputtering power of 1 kW. Here, the so-called G1 sputtering device refers to the first-generation mass production sputtering device with a substrate size of about 300mm×400mm. After pre-sputtering, continuous discharge was performed for 2 hours with the power changed under the film forming conditions shown in Table 2. After the discharge was completed, the chamber was opened to visually check for the presence of cracks, and the power was increased and the discharge test was repeated again to evaluate the crack resistance.
龜裂耐性係濺鍍靶材不產生斷裂之最大限度之濺鍍電力。將龜裂耐性為1.80kW以上之情形設為合格。將各濺鍍靶材之龜裂耐性之評價結果示於表1。 The crack resistance is the maximum sputtering power at which the sputtering target does not break. The crack resistance of 1.80kW or more is considered acceptable. The evaluation results of the crack resistance of each sputtering target are shown in Table 1.
根據使用實施例1~5之氧化物燒結體之濺鍍靶材，可知龜裂耐性優異。認為其原因在於氧化物燒結體之表面之維氏硬度較高。 The sputtering target material using the oxide sintered bodies of Examples 1 to 5 shows excellent resistance to cracking. This is believed to be due to the higher Vickers hardness of the surface of the oxide sintered bodies.
可知使用比較例1、3及4之氧化物燒結體之濺鍍靶材未產生研削研磨時之微龜裂，但濺鍍時之龜裂耐性較實施例1~5差。認為原因在於比較例1、3及4之氧化物燒結體之表面之維氏硬度較低。 It can be seen that the sputtering target material using the oxide sintered bodies of Comparative Examples 1, 3 and 4 did not produce micro cracks during grinding and polishing, but the crack resistance during sputtering was worse than that of Examples 1 to 5. It is believed that the reason is that the Vickers hardness of the surface of the oxide sintered bodies of Comparative Examples 1, 3 and 4 is lower.
可知使用比較例5之氧化物燒結體之濺鍍靶材未產生研削研磨時之微龜裂，但濺鍍時之龜裂耐性較實施例1~5差。認為原因在於比較例5之氧化物燒結體之表面之維氏硬度較低。 It can be seen that the sputtering target material of the oxide sintered body of Comparative Example 5 did not produce micro cracks during grinding and polishing, but the crack resistance during sputtering was worse than that of Examples 1 to 5. It is believed that the reason is that the Vickers hardness of the surface of the oxide sintered body of Comparative Example 5 is lower.
關於比較例6之氧化物燒結體，利用光學顯微鏡觀察研削加工後之氧化物燒結體，結果確認到微龜裂。 Regarding the oxide sintered body of Comparative Example 6, the oxide sintered body after grinding was observed using an optical microscope, and micro cracks were confirmed.
1:板狀之氧化物燒結體 1: Plate-shaped oxide sintered body
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