TWI649293B - Sintered body, sputtering target and manufacturing method thereof - Google Patents
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
本發明提供一種燒結體、濺射靶及其製造方法，所述燒結體能夠在IZO靶中有效抑制燒結體表面和內部的體積電阻率的偏差。本發明的燒結體是由In、Zn、O所組成之氧化物的燒結體，從所述燒結體的表面沿厚度方向1mm的深度位置的體積電阻率Rs與從所述燒結體的表面沿厚度方向4mm的深度位置的體積電阻率Rd之差除以所述4mm的深度位置的體積電阻率Rd的比率，即(Rs-Rd)/Rd的絕對值以百分率表示為20%以下。 The present invention provides a sintered body, a sputtering target, and a method for manufacturing the same. The sintered body can effectively suppress deviations in volume resistivity between the surface and the inside of the sintered body in an IZO target. The sintered body of the present invention is a sintered body of an oxide composed of In, Zn, and O. The volume resistivity Rs at a depth position of 1 mm from the surface of the sintered body in the thickness direction and the thickness from the surface of the sintered body The ratio of the volume resistivity Rd at a depth position of 4 mm in the direction divided by the ratio of the volume resistivity Rd at the depth position of 4 mm, that is, the absolute value of (Rs-Rd) / Rd is expressed as a percentage of 20% or less.
Description
本發明涉及一種由In、Zn、O所組成的燒結體、包含所述燒結體被稱為所謂IZO靶之用於形成透明導電膜等的濺射靶及其製造方法，尤其提出一種能夠有助於濺射時形成穩定的IZO膜的技術。 The present invention relates to a sintered body composed of In, Zn, and O, a sputtering target for forming a transparent conductive film, and the like, which is called a so-called IZO target, and a method for manufacturing the same. A technique for forming a stable IZO film during sputtering.
例如，在製造搭載在個人電腦或文字處理器等上的液晶顯示器(LCD)、電致發光器(EL)及其他各種顯示裝置用電極、觸摸面板以及電子紙等的電極時，有時會採用濺射法在濺射靶的玻璃或塑膠等之成膜用基板上形成包含金屬複合氧化物的透明導電膜。 For example, when manufacturing electrodes for liquid crystal displays (LCDs), electroluminescence devices (ELs), and various other display devices, electrodes for touch panels, and electronic paper, which are mounted on personal computers or word processors, they are sometimes used. A sputtering method forms a transparent conductive film containing a metal composite oxide on a film-forming substrate such as glass or plastic of a sputtering target.
作為這種透明導電膜，目前光透過性及導電性優異的ITO(Indium Tin Oxide，銦錫氧化物)膜是主流，為了生成由In、Sn、O所組成的該ITO膜，廣泛使用ITO靶。 As such a transparent conductive film, an ITO (Indium Tin Oxide) film which is excellent in light transmittance and conductivity is currently the mainstream. In order to generate the ITO film composed of In, Sn, and O, an ITO target is widely used. .
但是，由於ITO膜的耐濕性較低，有因濕氣導致電阻值增大的缺點，因此作為上述透明導電膜，正在研究以由In、Zn、O所組成的IZO(Indium Zinc Oxide，銦鋅氧化物)膜來代替該ITO膜，以及使用IZO靶以生成IZO膜。 However, since the ITO film has low moisture resistance and has the disadvantage of increasing the resistance value due to moisture, studies on IZO (Indium Zinc Oxide, Indium, In Zinc oxide) film instead of the ITO film, and an IZO target is used to generate an IZO film.
然而，為了進行穩定的成膜，除了要求濺射靶高密度、低電阻以外，靶的密度和電阻在靶整體上是均勻的也很重要。 However, in order to perform stable film formation, in addition to requiring a sputtering target with high density and low resistance, it is also important that the density and resistance of the target be uniform throughout the target.
特別是電阻，若靶的厚度方向上的體積電阻率的偏差大，則在濺射中膜特性發生變化的同時，在由多個塊組合的濺射靶中也易於發生塊之間的體積電阻率的偏差，從而損害靶整體的品質穩定性。因此，在濺射靶中，需要確保厚度方向上的體積電阻率的均勻性。在以往的IZO靶中，由於厚度方向的體積電阻率的偏差大，因此存在不能形成穩定的IZO膜的問題。 Especially for resistance, if the variation in volume resistivity in the thickness direction of the target is large, the film characteristics change during sputtering, and the volume resistance between blocks is also prone to occur in a sputtering target composed of a plurality of blocks. The deviation of the rate deteriorates the overall quality stability of the target. Therefore, in the sputtering target, it is necessary to ensure the uniformity of the volume resistivity in the thickness direction. In the conventional IZO target, since the variation in the volume resistivity in the thickness direction is large, there is a problem that a stable IZO film cannot be formed.
另外，體積電阻率一般具有以下趨勢，與構成濺射靶的燒結體的內部相比，在燒結體的表面變高。但認為即使燒結體的體積電阻率在厚度方 向上不均勻，通過增加燒結體的表面的磨削量來製備濺射靶，也能夠在一定程度上確保體積電阻率的均勻性。但在這種情況下，由於需要根據磨削量的增大而增厚設定燒結體的厚度來製造，因此擔心在厚度方向的中央位置的密度的降低或因磨削量的增大而導致產品成品率的下降。 In addition, the volume resistivity generally has a tendency to be higher on the surface of the sintered body than the inside of the sintered body constituting the sputtering target. However, it is considered that even if the volume resistivity of the sintered body is on the thickness side, The unevenness in the upward direction can also ensure the uniformity of the volume resistivity to a certain extent by preparing a sputtering target by increasing the amount of grinding of the surface of the sintered body. However, in this case, since it is necessary to increase the thickness of the sintered body by increasing the thickness of the sintered body, there is a concern that the density in the center of the thickness direction may be reduced or the product may be caused by the increase in the amount of grinding. Decrease in yield.
關於這種體積電阻率，在專利文獻1中記載了如下內容，在製造至少含有氧化銦和氧化鋅的濺射靶時，在燒成流程後，“對於得到的燒結體，為了將整體的體積電阻均勻化，雖然是任意流程，但較佳在還原流程中進行還原處理”。 Regarding such volume resistivity, Patent Document 1 describes that when a sputtering target containing at least indium oxide and zinc oxide is manufactured, after the firing process, "for the obtained sintered body, Although the resistance is uniform, although it is an arbitrary process, it is preferable to perform a reduction process in a reduction process. "
另外，在專利文獻2中記載了如下內容，高密度低電阻的In-Sn-Zn-Al系的濺射靶的體積電阻率較佳為10mΩcm以下，以及在製造所述靶時之燒結後的降溫時，為了防止裂紋的發生，並得到規定的晶型，將其降溫速度設為10℃/分以下，進一步設為5℃/分以下等。 In addition, Patent Document 2 describes that the volume resistivity of a high-density and low-resistance In-Sn-Zn-Al-based sputtering target is preferably 10 mΩcm or less, and that In order to prevent the occurrence of cracks and obtain a predetermined crystal form during temperature reduction, the temperature reduction rate is set to 10 ° C./min or less, and further set to 5 ° C./min or less.
另外，專利文獻3涉及ITO靶而不是IZO靶，其揭露了靶的厚度方向的體積電阻率的差異為20%以下的濺射靶。在該專利文獻3中記載了如下內容，為了減小靶的厚度方向的體積電阻率之差，主要通過將降溫時的環境設為大氣環境，平均冷卻速度設為0.1~3.0℃/分。而且顯示了燒結體中的體積電阻率之差與採用靶來成膜的薄膜的電阻之差之間存在較高的相關度。 In addition, Patent Document 3 relates to an ITO target instead of an IZO target, and discloses a sputtering target in which the difference in volume resistivity in the thickness direction of the target is 20% or less. This patent document 3 describes that in order to reduce the difference in volume resistivity in the thickness direction of the target, the environment at the time of temperature reduction is mainly an atmospheric environment, and the average cooling rate is set to 0.1 to 3.0 ° C./min. Furthermore, it was shown that there is a high correlation between the difference in volume resistivity in the sintered body and the difference in resistance of a thin film formed using a target.
[先前技術文獻] [Prior technical literature]
[專利文獻1]日本特開2011-68993號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2011-68993
[專利文獻2]日本特開2014-218706號公報 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-218706
[專利文獻3]國際公開第2014/156234號 [Patent Document 3] International Publication No. 2014/156234
在上述專利文獻1中，沒有記載任何關於降低厚度方向的體積電阻率的偏差的內容。另外，假設即使通過在燒結後作為其他流程進行還原處理，能夠實現體積電阻率的均勻化，由於這種其他流程的導入會導致成本的增大和工時的增加，因此從生產上的觀點來看是不希望的。 The above-mentioned Patent Document 1 does not describe anything about reducing the variation in the volume resistivity in the thickness direction. In addition, it is assumed that the volume resistivity can be made uniform by performing reduction treatment as another process after sintering. The introduction of such other processes will increase the cost and increase the man-hour, so from the production point of view It is undesired.
專利文獻2雖然提到了關於較佳體積電阻率低的內容，但是關於厚度方向的體積電阻率的偏差並未進行任何探討，關於降溫流程的記載也不是以體積電阻率的穩定化為目的的。 Although Patent Document 2 mentions that the volume resistivity is preferably low, the variation in the volume resistivity in the thickness direction is not discussed at all, and the description of the cooling process is not intended to stabilize the volume resistivity.
由於專利文獻3涉及ITO靶而不是IZO靶，其提出的技術不能直接應用於IZO靶。特別是IZO靶與ITO靶不同，由於燒結體表面存在表面變質層，表面變質層附近的體積電阻率會進一步增高，因此在IZO靶中，通過專利文獻3所記載的降溫流程的技術，不能充分地降低其體積電阻率的偏差。 Since Patent Document 3 relates to an ITO target instead of an IZO target, the technology proposed by it cannot be directly applied to an IZO target. In particular, the IZO target is different from the ITO target in that the surface resistive layer on the surface of the sintered body has a volume resistivity that is higher near the surface modified layer. Therefore, the technology of the cooling process described in Patent Document 3 in the IZO target is not sufficient. Ground to reduce the deviation of its volume resistivity.
本發明的問題在於，解決以往技術所存在的這種問題，目的在於提供一種燒結體、濺射靶及其製造方法，所述燒結體能夠在IZO靶中有效抑制燒結體表面和內部的體積電阻率的偏差。 The problem of the present invention is to solve such a problem existing in the prior art, and an object thereof is to provide a sintered body, a sputtering target, and a method for manufacturing the same. The sintered body can effectively suppress the volume resistance on the surface and inside of the sintered body in an IZO target. Rate deviation.
在製造IZO靶時，將形成為規定形狀的成型體進行加熱燒結時，為了提高燒結體的密度以及實現優異的膜特性，在升溫過程中，較佳導入有氧氣的氧氣燒結或大氣燒結。但發明人經過深入研究的結果是得到了如下見解，若在降溫過程中也是導入有氧氣的環境，則作為燒結體的表面附近的氧氣損失減少的結果，濺射靶的厚度方向上的體積電阻率之差的差異很大。 In the case of manufacturing an IZO target, when a molded body formed into a predetermined shape is heated and sintered, in order to increase the density of the sintered body and achieve excellent film characteristics, oxygen sintering or atmospheric sintering with oxygen is preferably introduced during the temperature rise process. However, as a result of intensive research, the inventors have obtained the following insight. If the environment where oxygen is introduced during the temperature reduction process, as a result of the decrease in oxygen loss near the surface of the sintered body, the volume resistance in the thickness direction of the sputtering target is reduced. The difference in rates varies widely.
因此發現，成型體的加熱燒結後的降溫時的環境與升溫時不同，通過設置為氮氣環境或氬氣環境，能夠抑制燒結體的表面附近的氧氣損失的減少，抑制厚度方向上的體積電阻率的偏差，製造具有更加均勻的體積特性的濺射靶。 Therefore, it has been found that the environment at the time of temperature reduction after heating and sintering of the molded body is different from that at the time of temperature increase. By setting the environment to a nitrogen atmosphere or an argon atmosphere, it is possible to suppress the reduction of oxygen loss near the surface of the sintered body and suppress the volume resistivity in the thickness direction Deviation, to produce a sputtering target with more uniform volume characteristics.
在該見解的基礎上，本發明的燒結體是由In、Zn、O所組成之氧化物的燒結體，從所述燒結體的表面沿厚度方向為1mm的深度位置的體積電阻率Rs與從所述燒結體的表面沿厚度方向為4mm的深度位置的體積電阻率Rd之差除以該4mm的深度位置的體積電阻率Rd的比率，即(Rs-Rd)/Rd的絕對值以百分率表示為20%以下。 Based on this knowledge, the sintered body of the present invention is a sintered body of an oxide composed of In, Zn, and O. The volume resistivity Rs from the surface of the sintered body at a depth position of 1 mm in the thickness direction and from The ratio of the volume resistivity Rd at the depth position of the sintered body at a depth position of 4 mm divided by the volume resistivity Rd at the depth position of 4 mm, that is, the absolute value of (Rs-Rd) / Rd is expressed as a percentage It is less than 20%.
在此，所述比率(Rs-Rd)/Rd的絕對值以百分率表示較佳為15%以下，進一步地，更佳為10%以下。 Here, the absolute value of the ratio (Rs-Rd) / Rd expressed as a percentage is preferably 15% or less, and more preferably 10% or less.
上述燒結體能夠是含有7at%~20at%，較佳10at%~17at%的Zn/(In+Zn)的燒結體。 The sintered body can be a sintered body containing 7 at% to 20 at%, preferably 10 at% to 17 at% of Zn / (In + Zn).
另外，本發明的濺射靶是由In、Zn、O所組成的氧化物的濺射靶，從所述濺射靶的表面沿厚度方向為0mm的深度位置的體積電阻率Rf與從所述濺射靶的表面沿厚度方向為3mm的深度位置的體積電阻率Ra之差除以該3mm的深度位置的體積電阻率Ra的比率，即(Rf-Ra)/Ra的絕對值以百分率表示為20%以下。 In addition, the sputtering target of the present invention is a sputtering target of an oxide composed of In, Zn, and O, and the volume resistivity Rf at a depth position of 0 mm from the surface of the sputtering target in the thickness direction is from the above-mentioned. The ratio of the volume resistivity Ra at the depth position of the sputtering target surface at a depth of 3 mm divided by the volume resistivity Ra at the depth position of 3 mm, that is, the absolute value of (Rf-Ra) / Ra is expressed as a percentage 20% or less.
在此，上述比率(Rf-Ra)/Ra的絕對值以百分率表示較佳為15%以下，進一步地，更佳為10%以下。 Here, the absolute value of the ratio (Rf-Ra) / Ra expressed as a percentage is preferably 15% or less, and more preferably 10% or less.
上述濺射靶能夠是含有7at%~20at%，較佳10at%~17at%的Zn/(In+Zn)的濺射靶。 The sputtering target can be a sputtering target containing Zn / (In + Zn) of 7 at% to 20 at%, preferably 10 at% to 17 at%.
本發明的濺射靶的製造方法包括：將含有氧化銦粉末及氧化鋅粉末的粉末原料進行混合並成型；將由此得到的成型體進行加熱燒結，將成型體進行加熱燒結後的降溫在氮氣環境或氬氣環境下進行。 The method for manufacturing a sputtering target of the present invention includes: mixing and molding powder raw materials containing indium oxide powder and zinc oxide powder; heating and sintering the obtained molded body; and reducing the temperature of the molded body after heating and sintering in a nitrogen atmosphere Or under argon atmosphere.
在該製造方法中，較佳將所述降溫時的降溫速度設為超過1℃/分，更佳設為3℃/分。 In this manufacturing method, it is preferable to set the temperature reduction rate at the time of said temperature reduction to more than 1 degree-C / min, and it is more preferable to set it to 3 degree-C / min.
另外，在該製造方法中，較佳在大氣或氧氣環境下進行成型體的加熱燒結。 Moreover, in this manufacturing method, it is preferable to heat-sinter a molded body in the atmosphere or an oxygen environment.
根據本發明，由於能夠縮小濺射靶的表面和內部的體積電阻率之差，因此濺射時的膜特性的變化減少，能夠實現形成穩定的薄膜。另外，由於製造穩定品質的濺射靶所需要的燒結體表面的磨削量變少，因此能夠改善材料的成品率。 According to the present invention, since the difference in volume resistivity between the surface and the inside of the sputtering target can be reduced, changes in film characteristics during sputtering are reduced, and stable thin films can be formed. In addition, since the amount of grinding of the surface of the sintered body required to produce a sputtering target of stable quality is reduced, the yield of the material can be improved.
以下對本發明的實施方式進行詳細說明。 Hereinafter, embodiments of the present invention will be described in detail.
本發明的一個實施方式的燒結體是由銦、鋅以及氧所組成的燒結體，從所述燒結體的表面沿厚度方向為1mm的深度位置的體積電阻率Rs與從所述燒結體的表面沿厚度方向為4mm的深度位置的體積電阻率Rd之差除以該4mm的深度位置的體積電阻率Rd的比率，即(Rs-Rd)/Rd的絕對值以百分率表示為20%以下。 A sintered body according to an embodiment of the present invention is a sintered body composed of indium, zinc, and oxygen, and the volume resistivity Rs at a depth position of 1 mm from the surface of the sintered body in the thickness direction and from the surface of the sintered body The ratio of the volume resistivity Rd at a depth position of 4 mm in the thickness direction divided by the volume resistivity Rd at the depth position of 4 mm, that is, the absolute value of (Rs-Rd) / Rd is expressed as a percentage of 20% or less.
另外，本發明的一個實施方式的濺射靶是由燒結體所組成的濺射靶，所述燒結體由銦、鋅以及氧所組成。從所述濺射靶的表面沿厚度方向為0mm的深度位置(即，濺射靶的表面位置)的體積電阻率Rf與從所述濺射靶的表面沿厚度方向為3mm的深度位置的體積電阻率Ra之差除以該3mm的深度位置的體積電阻率Ra的比率，即(Rf-Ra)/Ra的絕對值以百分率表示為20%以下。 A sputtering target according to an embodiment of the present invention is a sputtering target composed of a sintered body composed of indium, zinc, and oxygen. The volume resistivity Rf at a depth position of 0 mm from the surface of the sputtering target in the thickness direction (that is, the surface position of the sputtering target) and the volume at a depth position of 3 mm in the thickness direction from the surface of the sputtering target. The ratio of the difference in resistivity Ra divided by the volume resistivity Ra at the depth position of 3 mm, that is, the absolute value of (Rf-Ra) / Ra is expressed as a percentage of 20% or less.
(組成) (composition)
構成濺射靶的燒結體由In、Zn以及O所組成，例如包含以通式In2O3(ZnO)m表示的非晶質氧化物。在此，通式中的m是整數，該m值能夠取3~20的範圍內的值。 The sintered body constituting the sputtering target is composed of In, Zn, and O, and includes, for example, an amorphous oxide represented by the general formula In 2 O 3 (ZnO) m. Here, m in the general formula is an integer, and the value of m can take a value in a range of 3 to 20.
鋅以鋅的原子比Zn/(In+Zn)表示有時含有7at%~20at%，典型地有時含有10at%~17at%。鋅的量能夠根據目標膜的導電性適當更改。 Zinc is represented by the zinc atomic ratio Zn / (In + Zn), and sometimes contains 7 at% to 20 at%, and typically contains 10 at% to 17 at%. The amount of zinc can be appropriately changed according to the conductivity of the target film.
In、Zn等的成分的含量能夠通過X射線螢光分析(XRF)進行測量。 The content of components such as In and Zn can be measured by X-ray fluorescence analysis (XRF).
上述燒結體除了In和Zn以外，在不損害本發明的特性的範圍內也可以含有其他的元素。例如，在含有Fe、Al、Si、Cu以及Pb中的至少一種元素的情況下，這些各元素的含量能夠設定為100wtppm以下。另外，在含有Sn和Zr中的至少一種元素的情況下，這些各元素的含量能夠設定為1000wtppm以下。 The sintered body may contain other elements in addition to In and Zn within a range that does not impair the characteristics of the present invention. For example, when at least one element of Fe, Al, Si, Cu, and Pb is contained, the content of each of these elements can be set to 100 wtppm or less. When at least one of Sn and Zr is contained, the content of each of these elements can be set to 1000 wtppm or less.
(體積電阻率) (Volume resistivity)
在燒結體的實施方式中，如下文所述，從加熱燒結並降溫後得到的燒結體的表面沿厚度方向磨削1mm而露出的面(1mm的深度位置)的體積電阻率Rs與從所述燒結體的表面沿厚度方向磨削4mm而露出的面(4mm的 深度位置)的體積電阻率Rd之差除以該4mm的深度位置的靶面的體積電阻率Rd的比率，即(Rs-Rd)/Rd的絕對值以百分率表示為20%以下。 In an embodiment of the sintered body, the volume resistivity Rs of the surface (depth position of 1 mm) exposed by grinding the surface of the sintered body in the thickness direction by 1 mm in the thickness direction as described below, and The surface of the sintered body is ground by grinding 4 mm in the thickness direction to expose the surface (4 mm The difference between the volume resistivity Rd of the depth position) divided by the volume resistivity Rd of the target surface at the depth position of 4 mm, that is, the absolute value of (Rs-Rd) / Rd is expressed as a percentage of 20% or less.
若該比率(Rs-Rd)/Rd超過20%，則由於將燒結體用於濺射靶時之濺射中的膜特性變化而不能進行穩定的成膜，因此為了用於濺射靶，需要對燒結體表面進行大量的磨削。其結果是，為了製造規定厚度的濺射靶，必須預先預測該磨削量，製備厚度厚的燒結體，在這種情況下，擔心厚度方向的中央位置的密度的降低，另外，因磨削量的增大而導致成品率的下降。 If the ratio (Rs-Rd) / Rd exceeds 20%, stable film formation cannot be performed due to the change in film characteristics during sputtering when a sintered body is used for a sputtering target. Therefore, it is necessary to use it for a sputtering target. A large amount of grinding is performed on the surface of the sintered body. As a result, in order to manufacture a sputtering target having a predetermined thickness, it is necessary to predict the grinding amount in advance and prepare a thick sintered body. In this case, there is a concern that the density at the center position in the thickness direction is lowered. The increase of the amount leads to the decrease of the yield.
因此，從該觀點出發，(Rs-Rd)/Rd的比率較佳為15%以下，尤其更佳為10%以下。 Therefore, from this viewpoint, the ratio (Rs-Rd) / Rd is preferably 15% or less, and particularly preferably 10% or less.
另外，在濺射靶的實施方式中，較佳地，對燒結體進行研磨而得到的濺射靶的表面(0mm的深度位置)的體積電阻率Rf與從所述濺射靶的表面沿厚度方向磨削3mm而露出的面(3mm的深度位置)的體積電阻率Ra之差除以在該3mm的深度位置的體積電阻率Ra的比率，即(Rf-Ra)/Ra的絕對值以百分率表示為20%以下。 In addition, in the embodiment of the sputtering target, it is preferable that the volume resistivity Rf of the surface (the depth position of 0 mm) of the sputtering target obtained by grinding the sintered body and the thickness along the surface of the sputtering target. The ratio of the volume resistivity Ra of the surface exposed at a depth of 3mm (3mm depth position) divided by the volume resistivity Ra at the depth position of 3mm, that is, the absolute value of (Rf-Ra) / Ra in percentage Expressed as 20% or less.
由此，能夠在濺射時實現穩定的成膜。換言之，若該比率超過20%，則在濺射時，隨著厚度的減少，膜特性也發生變化，因此成膜不穩定。 This enables stable film formation during sputtering. In other words, if the ratio exceeds 20%, the film characteristics change as the thickness decreases during sputtering, and thus film formation is unstable.
比率(Rf-Ra)/Ra較佳為15%以下，更佳為10%以下。 The ratio (Rf-Ra) / Ra is preferably 15% or less, and more preferably 10% or less.
燒結體或濺射靶的上述體積電阻率的測量能夠針對以下的面進行。由JIS R6001(1998)中規定之#400之細微性研磨用微粉的磨削部件以0.2mm的磨削厚度進行精加工後的面。 The above-mentioned volume resistivity measurement of a sintered body or a sputtering target can be performed for the following surfaces. The surface after finishing is finely ground with a grinding thickness of 0.2 mm from # 400 fine powder for fine grinding specified in JIS R6001 (1998).
上述體積電阻率能夠根據JIS 1637中記載的四探針法進行測量。更具體而言，在將燒結體或濺射靶的測量面沿縱向和橫向以3×3進行九等分後的四個角落的區域和中央區域共5個地方進行測量。能夠將該5個地方的測量值的平均值作為本發明的體積電阻率。測量點例如能夠作為各個區域的中心。 The volume resistivity can be measured according to the four-probe method described in JIS 1637. More specifically, the measurement was performed at five places in the four corner areas and the central area after the measurement surface of the sintered body or the sputtering target was divided into nine equal parts at 3 × 3 in the longitudinal and transverse directions. The average value of the measured values at these five places can be used as the volume resistivity of the present invention. The measurement point can be, for example, the center of each region.
(結晶粒徑) (Crystal size)
通過設定上文所述的厚度方向的電阻差，從而能夠將自表面磨削1mm的面的組織的結晶粒的大小Ds與自表面磨削4mm的面(例如厚度方向 的中心位置的面)的結晶粒的大小Dd的差異設定為20%以下。結晶粒的大小從靶表面的中心的5mm的角中選擇任意4處進行觀察。之後，利用編碼法從300倍SEM圖像的照片中求出結晶粒大小的平均值。上述結晶粒的差異是將自表面磨削1mm的面和自表面磨削4mm的面(例如厚度中心位置的面)進行比較，將各自大小的相對差(Ds-Dd)/Dd的絕對值作為結晶粒徑的差異。 By setting the resistance difference in the thickness direction described above, the size Ds of the crystal grains in the structure of the surface whose surface is ground by 1 mm and the surface whose surface is ground by 4 mm (for example, in the thickness direction) can be achieved. The difference in the size Dd of the crystal grains in the surface of the center position is set to 20% or less. The size of the crystal grains was observed by selecting any four positions from an angle of 5 mm at the center of the target surface. Then, the average value of the crystal grain size was calculated from the photograph of the 300-times SEM image by the encoding method. The difference between the above crystal grains is to compare the surface ground from 1 mm from the surface ground and the surface ground from 4 mm (for example, the surface at the center of the thickness), and use the absolute value of the relative difference (Ds-Dd) / Dd of each size as Difference in crystal size.
另外，構成濺射靶的燒結體的平均結晶粒徑例如能夠為1.0μm~5.0μm，較佳為2.0μm~3.0μm。結晶粒徑能夠在將燒結體的一部分切斷並對切斷面進行鏡面研磨後，通過對SEM圖像進行觀察而測量。 The average crystal grain size of the sintered body constituting the sputtering target can be, for example, 1.0 μm to 5.0 μm, and preferably 2.0 μm to 3.0 μm. The crystal grain size can be measured by cutting a part of the sintered body, mirror-polishing the cut surface, and then observing the SEM image.
(密度) (density)
燒結體、濺射靶的相對密度能夠為95%以上，較佳為98%以上。 The relative density of the sintered body and the sputtering target can be 95% or more, and preferably 98% or more.
特別是在本發明中，由於通過降低厚度方向的體積電阻率的偏差，能夠減少由燒結體製備濺射靶時的研磨量，因此也能夠提高在厚度方向的中心位置的密度。換言之，若厚度方向的體積電阻率的偏差大，則預計製備濺射靶時的研磨量會變多，需要預先製備厚度厚的燒結體。但在這種情況下，由於厚度厚，在加熱燒結時熱難以傳導到厚度方向的中心附近，從而導致得到的燒結體或濺射靶的厚度方向的中心位置的密度低下。 In particular, in the present invention, since the variation in the volume resistivity in the thickness direction is reduced, the polishing amount when a sputtering target is prepared from a sintered body can be reduced, and thus the density at the center position in the thickness direction can also be increased. In other words, if the variation in the volume resistivity in the thickness direction is large, the polishing amount at the time of preparing the sputtering target is expected to increase, and it is necessary to prepare a thick sintered body in advance. However, in this case, since the thickness is thick, it is difficult to conduct heat to the vicinity of the center in the thickness direction during heating and sintering, resulting in a low density in the center position in the thickness direction of the obtained sintered body or sputtering target.
相對密度能夠由根據原料粉的密度計算的理論密度和利用阿基米德法測量的燒結體的密度通過以下公式算出：相對密度=(利用阿基米德法測量的密度)÷(理論密度)×100(%)。另外，IZO 10.7%的理論密度為7.00g/cm3。 The relative density can be calculated from the theoretical density calculated from the density of the raw material powder and the density of the sintered body measured by the Archimedes method with the following formula: Relative density = (Density measured by the Archimedes method) ÷ (Theoretical density) × 100 (%). The theoretical density of IZO 10.7% was 7.00 g / cm 3 .
(製造方法) (Production method)
以上所述的燒結體、濺射靶，例如能夠通過以下所述的方法製造。 The sintered body and the sputtering target described above can be produced, for example, by the method described below.
首先，例如將至少含有氧化銦粉末和氧化鋅粉末的原料粉末根據需要與成型黏合劑混合。 First, for example, a raw material powder containing at least an indium oxide powder and a zinc oxide powder is mixed with a molding adhesive as needed.
接著，將混合的粉末原料填充到模具中加壓成型，並製備規定形狀的成型體。在此，例如可以使400~1000kgf/cm2的壓力作用1分鐘~3分鐘。 Next, the mixed powder raw material is filled into a mold and pressure-molded to prepare a molded body having a predetermined shape. Here, for example, a pressure of 400 to 1000 kgf / cm 2 can be applied for 1 minute to 3 minutes.
之後將該成型體在燒結爐內，例如加熱到1350℃~1500℃的溫度並進行燒結。該加熱溫度的保持時間能夠為1小時~100小時，較佳為5小時~30 小時。在能夠得到密度高、膜特性優異的濺射靶的方面，該加熱燒結較佳在大氣或氧氣環境等的氧化環境下進行。 Thereafter, the molded body is sintered in a sintering furnace, for example, heated to a temperature of 1350 ° C to 1500 ° C. The holding time of the heating temperature can be from 1 hour to 100 hours, preferably from 5 hours to 30 hours. hour. In order to obtain a sputtering target with high density and excellent film characteristics, the thermal sintering is preferably performed in an oxidation environment such as the atmosphere or an oxygen environment.
上述加熱燒結後的降溫重要的是，不在大氣或氧氣環境下而在氮氣環境或氬氣環境下進行冷卻。通過在氮氣環境下進行冷卻，抑制了燒結體的表面附近的氧氣損失的減少，能夠將燒結體的厚度方向的體積電阻率的偏差抑制到上述的程度。換言之，在大氣環境或氧氣環境下進行該降溫的情況下，表面附近的氧氣損失減少，由此導致厚度方向的體積電阻率變動大而變得不均勻。 It is important that the temperature reduction after the heating and sintering is performed in a nitrogen atmosphere or an argon atmosphere without cooling in an atmosphere or an oxygen environment. By cooling in a nitrogen atmosphere, reduction in the loss of oxygen in the vicinity of the surface of the sintered body is suppressed, and the variation in the volume resistivity in the thickness direction of the sintered body can be suppressed to the above-mentioned level. In other words, when the temperature reduction is performed in an atmospheric environment or an oxygen environment, the loss of oxygen in the vicinity of the surface is reduced, which causes a large variation in volume resistivity in the thickness direction and becomes non-uniform.
為了進一步得到抑制氧氣損失的減少的效果，加熱燒結後的降溫速度較佳為超過1℃/分的速度，更佳為超過3℃/分的速度，尤其特佳為超過5℃/分的速度。由此，進一步抑制了燒結體的厚度方向上的體積電阻率的偏差，從而能夠製造具有更加均勻的體積電阻率的燒結體。 In order to further obtain the effect of suppressing the reduction of oxygen loss, the temperature reduction rate after heating and sintering is preferably a rate exceeding 1 ° C / min, more preferably a rate exceeding 3 ° C / min, and particularly preferably a rate exceeding 5 ° C / min. . This further suppresses variations in the volume resistivity in the thickness direction of the sintered body, so that a sintered body having a more uniform volume resistivity can be manufactured.
降溫例如可以通過向燒結爐內導入調整溫度後的冷氣較佳氮氣、氬氣來進行。 The temperature can be lowered, for example, by introducing into the sintering furnace the temperature-adjusted cold air, preferably nitrogen or argon.
上述的環境、降溫速度較佳至少在1400℃~1000℃的範圍內進行，不足1000℃也能夠進行自然降溫。這是由於在IZO靶中，特別是高溫區域的降溫速度、降溫環境會對其體積特性產生很大影響。 The above-mentioned environment and cooling rate are preferably performed at least in a range of 1400 ° C to 1000 ° C, and natural cooling can be performed below 1000 ° C. This is because in the IZO target, the cooling rate and the cooling environment in a high-temperature region have a great influence on its volume characteristics.
將降溫後得到的燒結體的單側表面，沿燒結體的厚度方向，通過機械磨削或化學磨削等的公知的方法對其厚度例如磨削1%~20%，較佳1%~10%。具體而言，該磨削量，在燒結體的厚度方向上例如能夠為0.1mm~2.0mm，較佳為0.1mm~1.0mm。但是，製造濺射靶時的磨削量並不限於這個範圍，能夠為任意的量。該磨削能夠使用JIS R6001(1998)中規定之#80之細微性研磨用微粉的磨削部件進行。 The single-sided surface of the sintered body obtained after the temperature reduction is ground along a thickness direction of the sintered body by a known method such as mechanical grinding or chemical grinding, for example, by 1 to 20%, preferably 1 to 10%. %. Specifically, the grinding amount can be, for example, 0.1 mm to 2.0 mm, and preferably 0.1 mm to 1.0 mm in the thickness direction of the sintered body. However, the amount of grinding at the time of manufacturing a sputtering target is not limited to this range, and it can be an arbitrary amount. This grinding can be performed using a finely ground fine powder grinding member of # 80 specified in JIS R6001 (1998).
在該實施方式中，如上文所述在厚度方向上的體積電阻率的偏差小，因此需要的磨削量變少。由此，能夠改善材料的成品率。 In this embodiment, since the variation in the volume resistivity in the thickness direction is small as described above, the amount of grinding required is reduced. This can improve the yield of the material.
(實施例) (Example)
接著，根據本發明試製濺射靶，並確認了其性能，因此下面進行說明。但是，此處的說明的目的僅是示例，並不限於此。 Next, a sputtering target was trial-produced according to the present invention, and its performance was confirmed. Therefore, it will be described below. However, the purpose of the description herein is merely an example, and is not limited thereto.
以如表1所示的各組成將氧化銦粉末和氧化鋅粉末進行混合並粉碎，將其投入到模具中，使800kgf/cm2的壓力作用1分鐘而得到成型體。將該成型體在電爐內加熱到1400℃，將其保持10小時並燒結後進行降溫。 In each composition shown in Table 1 as the indium oxide powder and zinc oxide powder were mixed and pulverized, and was poured into a mold, so that pressure of 800kgf / cm 2 for one minute to obtain a molded body. This molded body was heated to 1400 ° C. in an electric furnace, held for 10 hours and sintered, and then cooled.
在此，加熱燒結後的降溫在實施例1~7中是在氮氣環境下進行，而在對比例1~5中是在大氣環境下進行。另外，在實施例1~7及對比例1~5中，如表1所示，使加熱燒結時的升溫、保持環境、以及降溫速度發生變化。表1所示的降溫速度是位於1400℃~1000℃之間時的速度，溫度降低到不足1000℃後為自然降溫。 Here, the temperature reduction after heating and sintering was performed in a nitrogen environment in Examples 1 to 7, and performed in an atmospheric environment in Comparative Examples 1 to 5. In addition, in Examples 1 to 7 and Comparative Examples 1 to 5, as shown in Table 1, the temperature rise during heating and sintering, the maintenance of the environment, and the rate of temperature decrease were changed. The cooling rate shown in Table 1 is the speed between 1400 ° C and 1000 ° C. When the temperature drops below 1000 ° C, the temperature will fall naturally.
對於如此得到的燒結體，使用#80的研磨用微粉的砂紙，從燒結體的表面沿厚度方向手動磨削1mm而製備濺射靶。進一步地，通過同樣的磨削方法，最終將燒結體的表面磨削到5mm左右，在其中途的各深度位置，使用NPS株式會社製造的電阻率測量器(型號：Σ-5+)測量體積電阻率，分別測量了距離燒結體的表面1mm的深度位置的體積電阻率Rs、距離燒結體的表面4mm的深度位置的體積電阻率Rd、以及燒結體的表面的體積電阻率Rb。在測量各體積電阻率之前，使用#400的研磨用微粉的砂紙，將測量面手動磨削精加工0.2mm的厚度。另外，利用這些資料，分別計算出Rs和Rd之差的比率(Rs-Rd)/Rd×100、Rb和Rd之差的比率(Rb-Rd)/Rd×100。將其結果表示在表1中。 The thus-obtained sintered body was manually ground in a thickness direction of 1 mm from the surface of the sintered body by using # 80 fine grinding sandpaper to prepare a sputtering target. Further, by the same grinding method, the surface of the sintered body was finally ground to about 5 mm, and the volume was measured at various depth positions in the middle using a resistivity measuring device (model: Σ-5 +) manufactured by NPS Corporation. The resistivity was measured for volume resistivity Rs at a depth position of 1 mm from the surface of the sintered body, volume resistivity Rd at a depth position of 4 mm from the surface of the sintered body, and volume resistivity Rb of the surface of the sintered body. Before measuring the volume resistivity, the measuring surface was manually ground to a thickness of 0.2 mm using # 400 fine powdered abrasive paper. In addition, using these data, the ratio (Rs-Rd) / Rd × 100 of the difference between Rs and Rd and the ratio (Rb-Rd) / Rd × 100 of the difference between Rb and Rd were calculated. The results are shown in Table 1.
另外，在該實施例中，距離燒結體的表面1mm的深度位置的體積電阻率Rs與距離濺射靶的表面0mm的深度位置的體積電阻率Rf相等。另外，距離燒結體的表面4mm的深度位置的體積電阻率Rd與距離濺射靶的表面的3mm的深度位置的體積電阻率Ra相等。 In this embodiment, the volume resistivity Rs at a depth position of 1 mm from the surface of the sintered body is equal to the volume resistivity Rf at a depth position of 0 mm from the surface of the sputtering target. The volume resistivity Rd at a depth position of 4 mm from the surface of the sintered body is equal to the volume resistivity Ra at a depth position of 3 mm from the surface of the sputtering target.
表1中，“差值比率的最大值(%)”是計算在到達5mm左右的深度位置之前的各深度位置處所測量的體積電阻的最大和最小之差的比率。另外，“確認到20%時的磨削量(mm)”，是指以磨削量4mm的深度位置的體積電阻率作為基準的體積電阻比率，隨著從表面向深處，變為20%時的磨削量。 In Table 1, the "maximum value (%) of the difference ratio" is a ratio for calculating the difference between the maximum and minimum of the volume resistance measured at each depth position before reaching a depth position of about 5 mm. In addition, "the grinding amount (mm) when 20% is confirmed" refers to the volume resistivity ratio based on the volume resistivity at a depth position of 4mm as the reference, and becomes 20% as it goes from the surface to the depth. The amount of grinding at the time.
另外，對實施例1中的結晶粒進行了測量，距離燒結體表面1mm的磨削面是2.45μm，4mm的磨削面是2.59μm，相對差(Ds-Dd)/Dd的絕對值是5.4%。 In addition, the crystal grains in Example 1 were measured. The ground surface at a distance of 1 mm from the surface of the sintered body was 2.45 μm, the ground surface at 4 mm was 2.59 μm, and the absolute value of the relative difference (Ds-Dd) / Dd was 5.4. %.
如表1中所示，在使降溫環境為氮氣的實施例1~7中，無論升溫、保持環境為氧氣還是大氣，而且無論其組成，燒結體的1mm深度位置的體積電阻率Rs和燒結體的4mm深度位置的體積電阻率Rd之差的比率均為20%以下，實現了體積電阻率的降低以及偏差的抑制。 As shown in Table 1, in Examples 1 to 7 in which the temperature-reducing environment was nitrogen, the volume resistivity Rs and the sintered body at a depth of 1 mm in the sintered body were irrespective of the temperature rise, the environment was oxygen, or the atmosphere, regardless of the composition. The ratios of the differences in the volume resistivity Rd at the 4 mm depth position are all 20% or less, and the volume resistivity is reduced and the deviation is suppressed.
特別是，在利用超過5℃/分的高速進行降溫的實施例3和6中，實現了進一步的體積電阻率的降低以及偏差的抑制。 In particular, in Examples 3 and 6 where temperature reduction was performed at a high speed exceeding 5 ° C / min, further reduction in volume resistivity and suppression of deviation were achieved.
與之相對，在對比例1~5中，在將成型體進行加熱燒結後，因在大氣環境下進行降溫，燒結體的1mm深度位置的體積電阻率Rs和燒結體的4mm深度位置的體積電阻率Rd之差的比率超過20%，變得相當大，成為體積電阻率的偏差較大的燒結體。 In contrast, in Comparative Examples 1 to 5, after the molded body was heated and sintered, the volume resistivity Rs at the 1 mm depth position of the sintered body and the volume resistance at the 4 mm depth position of the sintered body were lowered in the atmospheric environment due to temperature reduction. The ratio of the difference in the ratios Rd exceeds 20%, which becomes quite large, and becomes a sintered body with large variation in volume resistivity.
通過以上所述可知，通過本發明，能夠有效抑制燒結體表面和內部的體積電阻率的偏差。 From the above, it can be understood that, according to the present invention, it is possible to effectively suppress variations in volume resistivity between the surface and the inside of the sintered body.
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