TW201348177A - Sintered object for forming low-refractive-index film and process for producing same - Google Patents

Sintered object for forming low-refractive-index film and process for producing same Download PDF

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TW201348177A
TW201348177A TW102110220A TW102110220A TW201348177A TW 201348177 A TW201348177 A TW 201348177A TW 102110220 A TW102110220 A TW 102110220A TW 102110220 A TW102110220 A TW 102110220A TW 201348177 A TW201348177 A TW 201348177A
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film
sintered body
less
oxide
mgf
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TW102110220A
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TWI564267B (en
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Atsushi Nara
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Jx Nippon Mining & Metals Corp
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Abstract

A sintered object which comprises zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F), characterized by containing the fluoride of magnesium (Mg) in an amount of 1.0-27 mol% in terms of Mg element amount. Provided, on the basis of this sintered object, is a sintered object which can be used in forming a thin film for use as an electrode for flexible displays, organic EL televisions, or touch panels, as an optical thin film for forming the protective layer, reflection layer, or semi-transparent layer of an optical information recording medium, or as the seed layer of a hard disk. With the sintered object, it is possible to provide a thin film which is optimal for such applications and which is amorphous, has such a satisfactory visible light transmittance that the extinction coefficient is 0.01 or lower (wavelength, 450 nm), and has a refractive index as low as 2.0 or less.

Description

低折射率膜形成用燒結體及其製造方法 Sintered body for forming low refractive index film and method of producing the same

本發明係關於一種非晶質且低折射率膜形成用燒結體及其製造方法。 The present invention relates to a sintered body for forming an amorphous and low refractive index film and a method for producing the same.

近年來，於如顯示器或太陽電池、觸控面板般處理光之領域中進行軟性化之研究。於在顯示器等中利用光之情形時，尤佳為於可見光區域之全域內為高透射率。又，若折射率較高則光損耗變大或者使顯示器之視野角依存性惡化，因此，期待有低折射率、或者用以提高膜之龜裂或蝕刻性能之非晶質膜。 In recent years, research on softening has been carried out in the field of processing light such as a display, a solar cell, or a touch panel. When light is used in a display or the like, it is particularly preferable to have high transmittance in the entire region of the visible light region. Further, when the refractive index is high, the optical loss is increased or the viewing angle dependence of the display is deteriorated. Therefore, an amorphous film having a low refractive index or a film cracking or etching property is expected.

非晶質膜之應力較小且與結晶膜相比難以發生龜裂，故而可認為，今後，面向軟性化而謀求有非晶質膜。 The amorphous film has a small stress and is less likely to be cracked than the crystal film. Therefore, it is considered that an amorphous film is required to be softened in the future.

例如，作為透明導電膜，氧化銦中添加錫而成之膜、即ITO(Indium-Tin-Oxide)膜透明且導電性優異，從而被用於各種顯示器等廣泛範圍之用途中。然而，該ITO必需結晶化以提高低電阻值或透射率，若為非晶質狀態則於短波長區域內具有吸收而不會成為透明膜，故而不適於軟性用途。 For example, as a transparent conductive film, a film obtained by adding tin to indium oxide, that is, an ITO (Indium-Tin-Oxide) film, is transparent and excellent in electrical conductivity, and is used in a wide range of applications such as various displays. However, the ITO must be crystallized to increase the low resistance value or the transmittance, and if it is in an amorphous state, it absorbs in a short-wavelength region and does not become a transparent film, so it is not suitable for soft use.

作為其他透明導電膜材料，已知有IZO(Indium-Zinc-Oxide)、AZO(Aluminium-Zinc-Oxide)、GZO(Gallium-Zinc-Oxide)等(專利文獻1~3)。然而，IZO雖可製成低電阻之非晶質膜，但有於短波長區域內具有吸收之問題。 IZO (Indium-Zinc-Oxide), AZO (Aluminium-Zinc-Oxide), GZO (Gallium-Zinc-Oxide), and the like are known as other transparent conductive film materials (Patent Documents 1 to 3). However, although IZO can be made into a low-resistance amorphous film, it has a problem of absorption in a short-wavelength region.

又，AZO、GZO成為ZnO之c軸配向結晶膜，故而有應力較大、膜剝離或膜破裂等問題，故而不適於軟性用途。進而，ITO、IZO、AZO、GZO之折射率均為2.0以上，故而要求有低折射率、高透射率且成為非晶質膜之材料。 Further, since AZO and GZO are c-axis alignment crystal films of ZnO, there are problems such as large stress, film peeling, or film breakage, and thus they are not suitable for soft use. Further, since the refractive indices of ITO, IZO, AZO, and GZO are both 2.0 or more, a material having a low refractive index and a high transmittance and being an amorphous film is required.

本發明之課題在於提供一種能夠獲得可維持良好之可見光透射率與折射率2.0以下之低折射率之薄膜、進而非晶質膜的燒結體。該薄膜之透射率較高、折射率較低且為非晶質膜，故而作為顯示器或太陽電池、觸控面板之透明導電膜或保護層而有用。 An object of the present invention is to provide a sintered body which can obtain a film having a low refractive index which can maintain a good visible light transmittance and a refractive index of 2.0 or less, and an amorphous film. Since the film has a high transmittance and a low refractive index and is an amorphous film, it is useful as a display, a solar cell, a transparent conductive film of a touch panel, or a protective layer.

又，於專利文獻4中，揭示有透光性導電性材料，其以ZnO與氟化鹼土金屬化合物作為主成分且實現廣泛之折射率。然而，此係結晶化膜，而無法獲得下述本發明般之非晶質膜之效果。又，於專利文獻5中，揭示有折射率較小且比電阻較小、進而非晶質之透明導電膜，但組成系統與本發明不同，從而有無法一起調整折射率與電阻值之問題。 Further, Patent Document 4 discloses a light-transmitting conductive material which has a wide refractive index by using ZnO and a fluorinated alkaline earth metal compound as main components. However, this is a crystallized film, and the effect of the amorphous film of the present invention described below cannot be obtained. Further, Patent Document 5 discloses a transparent conductive film having a small refractive index and a small specific resistance and further amorphous. However, the composition system is different from the present invention, and there is a problem that the refractive index and the resistance value cannot be adjusted together.

專利文獻1：日本特開2007-008780號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2007-008780

專利文獻2：日本特開2009-184876號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2009-184876

專利文獻3：日本特開2007-238375號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. 2007-238375

專利文獻4：日本特開2005-219982號公報 Patent Document 4: Japanese Patent Laid-Open Publication No. 2005-219982

專利文獻5：日本特開2007-035342號公報 Patent Document 5: Japanese Laid-Open Patent Publication No. 2007-035342

本發明之課題在於提供一種能夠獲得可維持良好之可見光透射率(消光係數0.01以下(波長450nm))與折射率2.0以下(波長550nm)之低折射率之薄膜、進而非晶質膜的燒結體。該薄膜之透射率較高、折射率較低且為非晶質膜，故而作為顯示器或太陽電池、觸控面板之透明導電膜或保護層而有用。 An object of the present invention is to provide a thin film which can maintain a good visible light transmittance (an extinction coefficient of 0.01 or less (wavelength: 450 nm)) and a refractive index of 2.0 or less (wavelength: 550 nm), and a sintered body of an amorphous film. . Since the film has a high transmittance and a low refractive index and is an amorphous film, it is useful as a display, a solar cell, a transparent conductive film of a touch panel, or a protective layer.

為解決上述課題，本發明人等進行了潛心研究，結果獲得如下見解：藉由製成以鋅(Zn)、鎂(Mg)、氧(O)、氟(F)作為主成分且鎂(Mg)含量以鎂之氟化物(MgF2)換算計含有1.0~27mol%的燒結體，而能夠形成如下薄膜，該薄膜可確保成膜後之薄膜之非晶質穩定性，且維持良好之可見光透射率(消光係數0.01以下(波長450nm))與折射率2.0以下(波長550nm)之低折射率。進而，獲得如下見解：實現未達10Ω．cm之低體電阻，可進行利用DC(直流)濺鍍之高速成膜，又，視需要可實施離子鍍、RF濺鍍。 In order to solve the above problems, the inventors of the present invention conducted intensive studies, and as a result, obtained the following findings: by using zinc (Zn), magnesium (Mg), oxygen (O), fluorine (F) as a main component and magnesium (Mg) The content contains 1.0 to 27 mol% of the sintered body in terms of magnesium fluoride (MgF 2 ), and can form a film which ensures the amorphous stability of the film after film formation and maintains good visible light transmission. The ratio (the extinction coefficient of 0.01 or less (wavelength: 450 nm)) and the refractive index of 2.0 or less (wavelength: 550 nm) have a low refractive index. Furthermore, the following insights are obtained: the implementation is less than 10Ω. The low bulk resistance of cm enables high-speed film formation by DC (direct current) sputtering, and ion plating and RF sputtering can be performed as needed.

又，於使用離子鍍法形成低折射率膜之情形時，若離子鍍用之蒸發原料與膜之組成一致，則可直接使用該蒸發原料進行離子鍍，因此，存在可更簡便地進行操作之優點。然而，於作為副成分添加之氧化物之蒸氣壓與成為主要成分之氧化鋅(ZnO)大幅不同之情形時，若為離子鍍法則有未形成相同組成之薄膜之情形，因此，必需進行某種程度之調整。 Further, when a low refractive index film is formed by ion plating, if the evaporation raw material for ion plating is in accordance with the composition of the film, the evaporation raw material can be directly used for ion plating, so that it can be operated more easily. advantage. However, when the vapor pressure of the oxide added as the auxiliary component is significantly different from the zinc oxide (ZnO) which is the main component, if the film is formed by the ion plating method, the film having the same composition is not formed. Degree adjustment.

本發明係基於該見解，提供下述發明。 The present invention provides the following invention based on this finding.

1)一種燒結體，由鋅(Zn)、鎂(Mg)、氧(O)、氟(F)構成，其特徵在於：鎂(Mg)含量以鎂之氟化物(MgF2)換算計含有1.0~27mol%。 1) A sintered body comprising zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F), characterized in that magnesium (Mg) content is 1.0 in terms of magnesium fluoride (MgF 2 ) ~27mol%.

2)如上述1)之燒結體，其中X射線繞射中氟化鎂(MgF2)之峰強度相對於背景強度之比(氟化鎂峰強度/背景強度)為1.50以上。 2) The sintered body according to the above 1), wherein the ratio of the peak intensity of the magnesium fluoride (MgF 2 ) to the background intensity (magnesium fluoride peak intensity/background intensity) in the X-ray diffraction is 1.50 or more.

3)如上述1)或2)之燒結體，其進而含有以各元素之氧化物換算計0.2~10mol%之選自鎵(Ga)、硼(B)、鍺(Ge)、銦(In)、錫(Sn)之1種以上之元素。 (3) The sintered body according to the above 1) or 2) further comprising, in an amount of 0.2 to 10 mol%, in terms of an oxide of each element, selected from the group consisting of gallium (Ga), boron (B), germanium (Ge), and indium (In). One or more elements of tin (Sn).

4)如上述1)至3)中任一項之燒結體，其進而含有以氧化物重量換算計0.1~5wt%之形成熔點為1000℃以下之氧化物之金屬。 The sintered body according to any one of the above 1 to 3, further comprising 0.1 to 5 wt% of a metal having an oxide having a melting point of 1000 ° C or less in terms of oxide weight.

5)如上述4)之燒結體，其中上述熔點為1000℃以下之氧化物係選自B2O3、P2O5、K2O、V2O5、Sb2O3、TeO2、Ti2O3、PbO、Bi2O3、MoO3之群中之 一種以上之氧化物。 5) The sintered body according to the above 4), wherein the oxide having a melting point of 1000 ° C or less is selected from the group consisting of B 2 O 3 , P 2 O 5 , K 2 O, V 2 O 5 , Sb 2 O 3 , TeO 2 , An oxide of one or more of the group consisting of Ti 2 O 3 , PbO, Bi 2 O 3 , and MoO 3 .

6)如上述1)至5)中任一項之燒結體，其相對密度為90%以上。 6) The sintered body according to any one of the above 1) to 5), which has a relative density of 90% or more.

7)如上述1)至6)中任一項之燒結體，其體電阻未達10Ω．cm。 7) The sintered body according to any one of the above 1) to 6), which has a bulk resistance of less than 10 Ω. Cm.

8)如上述1)至7)中任一項之燒結體，其係濺鍍靶或離子鍍用材料。 8) The sintered body according to any one of the above 1) to 7) which is a sputtering target or a material for ion plating.

9)一種薄膜，由鋅(Zn)、鎂(Mg)、氧(O)、氟(F)構成，其特徵在於：鎂(Mg)含量以鎂之氟化物(MgF2)換算計含有1.0~27mol%。 9) A film comprising zinc (Zn), magnesium (Mg), oxygen (O), fluorine (F), characterized in that the content of magnesium (Mg) is 1.0% in terms of magnesium fluoride (MgF 2 ). 27 mol%.

10)如上述9)之薄膜，其進而含有以各元素之氧化物換算計0.2~10mol%之選自鎵(Ga)、硼(B)、鍺(Ge)、銦(In)、錫(Sn)之1種以上之元素。 10) The film according to the above 9), which further contains 0.2 to 10 mol% of gallium (Ga), boron (B), germanium (Ge), indium (In), and tin (Sn) in terms of oxide of each element. One or more elements.

11)如上述9)或10)之薄膜，其進而含有以氧化物重量換算計0.1~5wt%之形成熔點為1000℃以下之氧化物之金屬。 11) The film according to the above 9) or 10) further containing 0.1 to 5 wt% of a metal having an oxide having a melting point of 1000 ° C or less in terms of oxide weight.

12)如上述11)之薄膜，其中上述熔點為1000℃以下之氧化物係選自B2O3、P2O5、K2O、V2O5、Sb2O3、TeO2、Ti2O3、PbO、Bi2O3、MoO3之群中之一種以上之氧化物。 12) The film according to the above 11), wherein the oxide having a melting point of 1000 ° C or less is selected from the group consisting of B 2 O 3 , P 2 O 5 , K 2 O, V 2 O 5 , Sb 2 O 3 , TeO 2 , Ti An oxide of one or more of 2 O 3 , PbO, Bi 2 O 3 , and MoO 3 .

13)如上述9)至12)中任一項之薄膜，其係非晶質。 13) The film according to any one of the above 9) to 12) which is amorphous.

14)如上述9)至13)中任一項之薄膜，其折射率為2.0以下(波長550nm)。 14) The film according to any one of the above 9) to 13), which has a refractive index of 2.0 or less (wavelength: 550 nm).

15)如上述9)至14)中任一項之薄膜，其消光係數為0.01以下(波長450nm)。 15) The film according to any one of the above 9) to 14), which has an extinction coefficient of 0.01 or less (wavelength: 450 nm).

16)如上述9)至15)中任一項之薄膜，其中膜之電阻值為1×10-3~1×109Ω．cm。 The film according to any one of the above 9), wherein the film has a resistance value of from 1 × 10 -3 to 1 × 10 9 Ω. Cm.

17)如上述9)至16)中任一項之薄膜，其係藉由濺鍍或離子鍍而形成。 17) The film according to any one of the above 9) to 16) which is formed by sputtering or ion plating.

18)一種燒結體之製造方法，用於製造上述1)至5)中任一項之燒結體，其係於惰性環境下進行燒結。 18) A method for producing a sintered body for producing the sintered body according to any one of the above 1) to 5) which is sintered in an inert atmosphere.

19)一種離子鍍用材料之製造方法，其係將上述1)至5)中任一項之燒結體粉碎而製成粉末或粒狀。 (19) A method for producing a material for ion plating, which comprises pulverizing the sintered body according to any one of the above 1) to 5) to obtain a powder or a pellet.

根據上述，藉由形成以鋅(Zn)、鎂(Mg)、氧(O)、氟(F)作為主成分且鎂(Mg)含量以鎂之氟化物(MgF2)換算計含有1.0~27mol%的燒結體，而獲得如下優異之效果：可形成良好之可見光透射率(消光係數0.01以下(波長450nm))與折射率2.0以下(波長550nm)之低折射率之非晶質薄膜。進而，實現未達10Ω．cm之低體電阻，可進行利用DC(直流)濺鍍之高速成膜，又，視需要可實施離子鍍、RF濺鍍。 According to the above, zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F) are contained as main components, and magnesium (Mg) content is 1.0 to 27 mol in terms of magnesium fluoride (MgF 2 ). The sintered body of % has an excellent effect of forming a low refractive index amorphous film having a good visible light transmittance (having an extinction coefficient of 0.01 or less (wavelength: 450 nm)) and a refractive index of 2.0 or less (wavelength: 550 nm). Furthermore, the implementation is less than 10Ω. The low bulk resistance of cm enables high-speed film formation by DC (direct current) sputtering, and ion plating and RF sputtering can be performed as needed.

又，若為離子鍍，則可避免作為副成分添加之氧化物之蒸發速度與成為主要成分之氧化鋅(ZnO)大幅不同之問題，因此，其結果為，具有如下效果：可形成與離子鍍用原料大致相同組成之薄膜，且能夠高速成膜。 Further, in the case of ion plating, it is possible to avoid the problem that the evaporation rate of the oxide added as the subcomponent is significantly different from the zinc oxide (ZnO) which is a main component. Therefore, as a result, it is possible to form and ion plating. A film having substantially the same composition as the raw material is used, and the film can be formed at a high speed.

圖1係表示MgF2之峰強度相對於背景強度之比(MgF2峰強度/背景強度)的測定結果之圖。 Fig. 1 is a graph showing the results of measurement of the ratio of the peak intensity of MgF 2 to the background intensity (MgF 2 peak intensity/background intensity).

圖2係表示與ZnO對比之各氧化物及氟化物之蒸氣壓曲線之圖。 Fig. 2 is a graph showing vapor pressure curves of respective oxides and fluorides in comparison with ZnO.

圖3係表示與ZnO對比之Al2O3、MgO、SiO2之氧化物之蒸氣壓曲線之圖。 Fig. 3 is a graph showing vapor pressure curves of oxides of Al 2 O 3 , MgO, and SiO 2 in comparison with ZnO.

本發明之燒結體由鋅(Zn)、鎂(Mg)、氧(O)、氟(F)構成，其特徵在於：鎂(Mg)含量以鎂之氟化物(MgF2)換算計含有1.0~27mol%。 The sintered body of the present invention is composed of zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F), and is characterized in that the content of magnesium (Mg) is 1.0% in terms of magnesium fluoride (MgF 2 ). 27 mol%.

又，本發明之燒結體之特徵之一在於：X射線繞射中氟化鎂(MgF2) 之峰強度相對於背景強度之比(氟化鎂峰強度/背景強度)為1.50以上。 Further, one of the characteristics of the sintered body of the present invention is that the ratio of the peak intensity of the magnesium fluoride (MgF 2 ) to the background intensity (magnesium fluoride peak intensity/background intensity) in the X-ray diffraction is 1.50 or more.

進而，本發明之燒結體可含有以各元素之氧化物換算計0.2~10mol%之選自鎵(Ga)、硼(B)、鍺(Ge)、銦(In)、錫(Sn)之1種以上之元素。 Further, the sintered body of the present invention may contain, in an amount of 0.2 to 10 mol%, in terms of an oxide of each element, selected from the group consisting of gallium (Ga), boron (B), germanium (Ge), indium (In), and tin (Sn). Kind of above elements.

又，本發明之燒結體可含有以氧化物重量換算計0.1~5wt%之形成熔點為1000℃以下之氧化物之金屬。作為該熔點為1000℃以下之氧化物，使用選自B2O3、P2O5、K2O、V2O5、Sb2O3、TeO2、Ti2O3、PbO、Bi2O3、MoO3之群中之一種以上之氧化物即可。 Further, the sintered body of the present invention may contain 0.1 to 5 wt% of a metal having an oxide having a melting point of 1000 ° C or less in terms of oxide weight. The oxide having a melting point of 1000 ° C or less is selected from the group consisting of B 2 O 3 , P 2 O 5 , K 2 O, V 2 O 5 , Sb 2 O 3 , TeO 2 , Ti 2 O 3 , PbO, and Bi 2 . One or more oxides of the group of O 3 and MoO 3 may be used.

以上添加元素(氧化物)可任意選擇，且可提高依據各自之添加元素之特性。該等燒結體係作為濺鍍靶、進而作為離子鍍材料而有用。以下，對應用本發明之燒結體之情形進行詳細說明。 The above added elements (oxides) can be arbitrarily selected, and the characteristics depending on the respective added elements can be improved. These sintered systems are useful as a sputtering target and further as an ion plating material. Hereinafter, the case where the sintered body of the present invention is applied will be described in detail.

本發明之燒結體由鋅(Zn)、鎂(Mg)、氧(O)、氟(F)構成，且鎂(Mg)含量以鎂之氟化物(MgF2)換算計含有1.0~27mol%。 The sintered body of the present invention is composed of zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F), and the magnesium (Mg) content is 1.0 to 27 mol% in terms of magnesium fluoride (MgF 2 ).

於調整原料時，將各氧化物及氟化物之比率以其合計成為100mol%之組成之方式進行調整，雖將剩餘部分設為ZnO，但Zn含量可根據該剩餘部分之ZnO換算而求出。藉由設為此種組成，而可製作良好之可見光之透射率與低折射率之非晶質膜，從而可獲得本發明之上述效果。 In the case of adjusting the raw material, the ratio of each oxide and fluoride is adjusted so as to have a total composition of 100 mol%, and the remaining portion is ZnO, but the Zn content can be obtained from the remaining portion of ZnO. By adopting such a composition, an amorphous film having a good transmittance of visible light and a low refractive index can be produced, whereby the above effects of the present invention can be obtained.

再者，於本發明中，雖以氧化物換算或氟化物換算計規定燒結體中之各金屬含量，但燒結體中之各金屬之一部分係以複合氧化物之形式存在。又，於通常使用之燒結體之成分分析中，並非氧化物或氟化物而是以金屬之形式，測定各自之含量。因此，藉由根據燒結體中之各金屬之分析值換算成各氧化物、氟化物量而求出各組成範圍。 In the present invention, the content of each metal in the sintered body is determined in terms of oxide conversion or fluoride conversion, but one part of each metal in the sintered body exists as a composite oxide. Moreover, in the component analysis of the sintered body which is generally used, the content of each is measured not in the form of a metal but not an oxide or a fluoride. Therefore, each composition range is obtained by converting the analysis value of each metal in the sintered body into the amount of each oxide and fluoride.

該氟化鎂對膜之非晶質化及低折射率化有效。若未達1.0mol%則無添加之效果，若超過27mol%，則產生膜之高電阻率化之問題，故而設為上述數值範圍。 The magnesium fluoride is effective for amorphization and low refractive index of the film. If it is less than 1.0 mol%, there is no effect of addition, and if it exceeds 27 mol%, the problem of high resistivity of the film occurs, so the above numerical range is set.

該燒結體中之氟化鎂(MgF2)之存在可利用X射線繞射進行確認。即，將X射線繞射中氟化鎂(MgF2)之峰強度相對於背景強度之比(氟化鎂峰強度/背景強度)設為1.50以上。 The presence of magnesium fluoride (MgF 2 ) in the sintered body can be confirmed by X-ray diffraction. That is, the ratio of the peak intensity of the magnesium fluoride (MgF 2 ) to the background intensity (magnesium fluoride peak intensity/background intensity) in the X-ray diffraction is set to 1.50 or more.

於MgF2之峰強度之測定中，利用將製造而成之濺鍍靶切斷者或將濺鍍靶粉碎之粉末並藉由X射線繞射法進行測定。即，測定MgF2之(110)面之峰出現之2θ：27.3°附近之強度並且測定背景強度(28.0~29.0°之強度之平均值)。 In the measurement of the peak intensity of MgF 2 , the produced sputtering target or the powder which pulverized the sputtering target was measured by an X-ray diffraction method. Namely, the intensity in the vicinity of 2θ: 27.3° at which the peak of the (110) plane of MgF 2 appeared was measured, and the background intensity (the average of the intensities of 28.0 to 29.0 °) was measured.

藉此，求出MgF2之峰強度相對於背景強度之比(MgF2峰強度/背景強度)。為此，可使用Rigaku公司製造之UltimalV作為測定裝置。 Thereby, the ratio of the peak intensity of MgF 2 to the background intensity (MgF 2 peak intensity/background intensity) was determined. For this purpose, Ultimal V manufactured by Rigaku Corporation can be used as the measuring device.

如上所述，作為進而添加之元素，有選自鎵(Ga)、硼(B)、鍺(Ge)、銦(In)、錫(Sn)之1種以上之元素，且可含有0.2~10at%之該等元素。藉由添加以元素量換算計0.2~10mol%之該等元素之氧化物，而可賦予導電性。 As described above, as an element to be further added, one or more elements selected from the group consisting of gallium (Ga), boron (B), germanium (Ge), indium (In), and tin (Sn) may be contained in an amount of 0.2 to 10 at. % of these elements. Conductivity can be imparted by adding an oxide of 0.2 to 10 mol% of these elements in terms of element amount.

該等元素之氧化物之添加量若以元素量換算計未達0.2mol%，則其效果較少，於超過10mol%之情形時，效果飽和，故而最理想為設為上述範圍。 When the amount of the oxide of the element is less than 0.2 mol% in terms of the amount of the element, the effect is small, and when it exceeds 10 mol%, the effect is saturated. Therefore, it is most preferable to set it as the above range.

又，鍺氧化物、硼氧化物亦為玻璃形成氧化物，而對膜之非晶質化及低折射率化有效。若以元素量換算計未達0.2mol%則無添加之效果，若超過10mol%，則產生膜高電阻率化之問題，故而設為上述數值範圍。 Further, niobium oxide and boride oxide are also oxides formed on glass, and are effective for amorphization and low refractive index of the film. When it is less than 0.2 mol% in terms of element amount, there is no effect of addition, and if it exceeds 10 mol%, there arises a problem that the film has high resistivity, and thus it is set to the above numerical range.

進而有效的是，本發明之燒結體含有形成熔點為1000℃以下之氧化物(低熔點氧化物)之金屬。氧化鋅(ZnO)較易還原、蒸發，故而會有無法那樣程度地提昇燒結溫度且難以提高燒結體之密度的情況。然而，藉由添加此種低熔點氧化物，而具有不那樣程度地提昇燒結溫度便可達成高密度化之效果。 Further, it is effective that the sintered body of the present invention contains a metal which forms an oxide (low melting point oxide) having a melting point of 1000 ° C or less. Zinc oxide (ZnO) is more easily reduced and evaporated, so that the sintering temperature may not be increased to such an extent that it is difficult to increase the density of the sintered body. However, by adding such a low-melting-point oxide, the effect of increasing the density can be achieved by increasing the sintering temperature to such an extent.

作為上述低熔點氧化物，例如可列舉：B2O3、P2O5、K2O、V2O5、Sb2O3、TeO2、Ti2O3、PbO、Bi2O3、MoO3。該等氧化物可各自單獨添加及複合添加， 且可達成本案發明之目的。 Examples of the low melting point oxide include B 2 O 3 , P 2 O 5 , K 2 O, V 2 O 5 , Sb 2 O 3 , TeO 2 , Ti 2 O 3 , PbO, and Bi 2 O 3 . MoO 3 . The oxides may be separately added and compounded separately, and may achieve the object of the invention.

形成上述低熔點氧化物之金屬較佳為含有以氧化物重量換算計0.1~5wt%。若未達0.1wt%，則無法充分發揮其效果，又，若超過5wt%，則有特性根據組成發生變動之虞，故而欠佳。 The metal forming the above-mentioned low melting point oxide preferably contains 0.1 to 5 wt% in terms of weight of the oxide. If it is less than 0.1% by weight, the effect cannot be sufficiently exerted, and if it exceeds 5 wt%, the characteristics may vary depending on the composition, which is not preferable.

於將本發明之燒結體用作濺鍍靶之情形時，相對密度較佳為設為90%以上。較理想為設為相對密度92%以上、進而設為相對密度99%以上。本案發明可獲得此種高密度之靶。 When the sintered body of the present invention is used as a sputtering target, the relative density is preferably set to 90% or more. Preferably, the relative density is 92% or more, and the relative density is 99% or more. The present invention achieves such a high density target.

密度之提高具有如下效果：提高濺鍍膜之均勻性，又，可抑制濺鍍時之微粒之產生。 The increase in density has an effect of improving the uniformity of the sputtering film and suppressing the generation of particles at the time of sputtering.

該燒結體係用以工業性地製造尤其良好之可見光之透射率(消光係數0.01以下(波長450nm))與折射率2.0(波長550nm)以下之低折射率的薄膜。進而，可使上述消光係數達成<0.005(波長450nm)。此種良好之可見光之透射率與低折射率之薄膜係尤其作為軟性顯示器用、有機EL電視用、觸控面板用電極用、光資訊記錄媒體之保護層之薄膜而有用。 This sintering system is used to industrially produce a film having a particularly good transmittance of visible light (having an extinction coefficient of 0.01 or less (wavelength: 450 nm)) and a refractive index of 2.0 (wavelength of 550 nm) or less. Further, the above extinction coefficient can be made to be <0.005 (wavelength: 450 nm). Such a good transmittance of visible light and a film having a low refractive index are particularly useful as a film for a protective display, an organic EL television, an electrode for a touch panel, and a protective layer for an optical information recording medium.

本發明中，如此使用以鋅(Zn)、鎂(Mg)、氧(O)、氟(F)作為主成分且鎂(Mg)含量以鎂之氟化物(MgF2)換算計含有1.0~27mol%之燒結體而形成之薄膜係確保薄膜之非晶質穩定性，進而可形成如下薄膜：可維持良好之可見光之透射率(消光係數0.01以下(波長450nm))與折射率2.0以下(波長550nm)之低折射率。 In the present invention, zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F) are used as main components, and magnesium (Mg) content is 1.0 to 27 mol in terms of magnesium fluoride (MgF 2 ). The film formed of the sintered body of % ensures the amorphous stability of the film, and further forms a film capable of maintaining good transmittance of visible light (extinction coefficient of 0.01 or less (wavelength: 450 nm)) and refractive index of 2.0 or less (wavelength of 550 nm). ) low refractive index.

本發明之燒結體可藉由在惰性環境下，對平均粒徑為5μm以下之各構成元素之粉末進行常壓燒結或高溫加壓燒結而製造。 The sintered body of the present invention can be produced by subjecting a powder of each constituent element having an average particle diameter of 5 μm or less to atmospheric pressure sintering or high-temperature pressure sintering in an inert atmosphere.

進而，藉由使用本發明之燒結體，而具有如下顯著之效果：可獲得生產性得到提高、品質優異之材料，且能夠以低成本且穩定地製造良好之可見光之透射率(消光係數0.01以下(波長450nm)與折射率2.0以下(波長550nm)之低折射率薄膜。 Further, by using the sintered body of the present invention, it is possible to obtain a material having improved productivity and excellent quality, and it is possible to stably produce a good transmittance of visible light at a low cost (with an extinction coefficient of 0.01 or less). A low refractive index film (wavelength: 450 nm) and a refractive index of 2.0 or less (wavelength: 550 nm).

進而，該燒結體實現未達10Ω．cm之低體電阻，且可進行利用DC(直流)濺鍍之高速成膜。又，DC濺鍍裝置具有如下優點：價格便宜，容易控制，電力之消耗量亦不多便可。再者，於本發明中，根據製造條件及材料之選擇，亦存在必需進行離子鍍、RF濺鍍之情形，但即便於該情形時亦有成膜速度之提高。 Further, the sintered body is achieved to be less than 10 Ω. Low body resistance of cm, and high-speed film formation by DC (direct current) sputtering. Moreover, the DC sputtering apparatus has the advantages of being inexpensive, easy to control, and having a small amount of power consumption. Further, in the present invention, depending on the production conditions and material selection, it is necessary to perform ion plating or RF sputtering, but even in this case, the film formation speed is improved.

繼而，對將本案發明之燒結體用於離子鍍之情形進行說明。於本發明之低折射率膜形成用離子鍍用材料中，選自鎵(Ga)、硼(B)、鍺(Ge)、銦(In)、錫(Sn)之1種以上之元素之氧化物(Ga2O3、B2O3、GeO2、In2O3、SnO2)及氟化鎂(MgF2)具有與氧化鋅類似之蒸氣壓，故而可無問題地用作離子鍍用材料。將與ZnO對比之各氧化物及氟化物之蒸氣壓曲線示於圖1。 Next, a case where the sintered body of the present invention is used for ion plating will be described. In the material for ion plating for forming a low refractive index film of the present invention, oxidation of one or more elements selected from the group consisting of gallium (Ga), boron (B), germanium (Ge), indium (In), and tin (Sn) The materials (Ga 2 O 3 , B 2 O 3 , GeO 2 , In 2 O 3 , SnO 2 ) and magnesium fluoride (MgF 2 ) have a vapor pressure similar to that of zinc oxide, so that they can be used for ion plating without problems. material. The vapor pressure curves of the respective oxides and fluorides in comparison with ZnO are shown in Fig. 1.

為進行對比，而將與ZnO對比之Al2O3、MgO、SiO2之氧化物之蒸氣壓曲線示於圖3。由圖2與圖3明確可確認，圖3所示之氧化物係與ZnO相比，於蒸氣壓上存在較大之差異。 For comparison, the vapor pressure curves of the oxides of Al 2 O 3 , MgO, and SiO 2 in comparison with ZnO are shown in FIG. As is clear from Fig. 2 and Fig. 3, the oxide system shown in Fig. 3 has a large difference in vapor pressure as compared with ZnO.

圖2所示之Al2O3、MgO、SiO2之氧化物係添加於ZnO中作為濺鍍靶材者，但於蒸氣壓上存在較大之不同，因此，可認為稍微不適合作為離子鍍用材料。關於此種材料，製作濺鍍用靶並使用即可。 The Al shown in FIG. 2 2 O 3, MgO, SiO 2 oxide added to the ZnO as a target by sputtering, but there is a big different on the vapor pressure, therefore, may be considered somewhat unsuitable as ion plating with material. For such a material, a target for sputtering can be produced and used.

於製作離子鍍用材料時，於成為主成分之氧化鋅(ZnO)中添加氟化鎂(MgF2)之原料粉末，或者於成為主成分之氧化鋅(ZnO)中添加選自鎵(Ga)、硼(B)、鍺(Ge)、銦(In)、錫(Sn)之1種以上之元素之氧化物(Ga2O3、B2O3、GeO2、In2O3、SnO2)之原料粉末，並將該等預先混合、燒結而一體化，製成燒結體，又，將其進而粉碎而製成粉末或粒狀，從而可用於離子鍍之材料。 When a material for ion plating is produced, a raw material powder of magnesium fluoride (MgF 2 ) is added to zinc oxide (ZnO) which is a main component, or zinc oxide (ZnO) which is a main component is added to gallium (Ga). An oxide of one or more elements of boron (B), germanium (Ge), indium (In), and tin (Sn) (Ga 2 O 3 , B 2 O 3 , GeO 2 , In 2 O 3 , SnO 2 The raw material powder is preliminarily mixed, sintered, and integrated to form a sintered body, which is further pulverized to obtain a powder or a granule, thereby being used for a material for ion plating.

離子鍍之材料之成分組成可根據成膜之目的而任意進行調節。例如，可用於軟性顯示器、有機EL電視、觸控面板用電極、形成光資 訊記錄媒體之保護層。如上所述，由於在蒸氣壓中無較大之變化，故而可使離子鍍用材料之成分組成反映為低折射率膜之成分組成。因此，能夠高速成膜，可具有穩定之非晶質性、且透射率較高之優異之特性。 The composition of the material of the ion plating can be arbitrarily adjusted according to the purpose of film formation. For example, it can be used for flexible displays, organic EL televisions, electrodes for touch panels, and formation of light resources. The protective layer of the recording medium. As described above, since there is no large change in the vapor pressure, the composition of the ion plating material can be reflected as the composition of the low refractive index film. Therefore, it is possible to form a film at a high speed, and it is possible to have stable amorphous properties and excellent transmittance.

實施例 Example

以下，基於實施例及比較例進行說明。再者，本實施例僅為一例，並不受該例任何限制。即，本發明係僅由申請專利範圍所限制者，且包含本發明中所包含之實施例以外之各種變形。 Hereinafter, description will be made based on examples and comparative examples. Furthermore, this embodiment is only an example and is not limited by this example. That is, the present invention is limited only by the scope of the patent application, and includes various modifications other than the embodiments included in the invention.

(實施例1) (Example 1)

準備3N當量且平均粒徑5μm以下之ZnO粉、3N當量且平均粒徑5μm以下之MgF2粉、及3N當量且平均粒徑5μm以下之GeO2粉。繼而，將ZnO粉、MgF2粉及GeO2粉調和成ZnO：MgF2：GeO2=85.0：13.6：1.4mol%之摻合比，並將其混合後，於900℃、Ar環境中、250kgf/cm2之壓力下對粉末材料進行熱壓燒結。利用機械加工，將該燒結體最後加工成靶形狀。 3N equivalents of ZnO powder having an average particle diameter of 5 μm or less, 3N equivalents of MgF 2 powder having an average particle diameter of 5 μm or less, and 3N equivalents of GeO 2 powder having an average particle diameter of 5 μm or less were prepared. Then, the ZnO powder, the MgF 2 powder and the GeO 2 powder are blended into a blend ratio of ZnO:MgF 2 :GeO 2 =85.0:13.6:1.4 mol%, and after mixing, at 900 ° C, Ar environment, 250 kgf The powder material was subjected to hot press sintering under a pressure of /cm 2 . The sintered body is finally processed into a target shape by mechanical processing.

以上之結果為，實施例1之濺鍍靶之相對密度成為92.0%，又，體電阻值成為1.2Ω．cm，且可進行穩定之DC濺鍍。成膜速度為2.6Å/sec，成膜速度良好。折射率成為1.90(波長633nm)，顯示非晶質性。又，比電阻值成為1×106Ω．cm，消光係數(γ=450nm)成為<0.005。 As a result of the above, the relative density of the sputtering target of Example 1 was 92.0%, and the bulk resistance value was 1.2 Ω. Cm, and stable DC sputtering can be performed. The film formation rate was 2.6 Å/sec, and the film formation speed was good. The refractive index was 1.90 (wavelength: 633 nm) and showed amorphous properties. Moreover, the specific resistance value becomes 1 × 10 6 Ω. Cm, the extinction coefficient (γ = 450 nm) becomes <0.005.

將該結果示於表1與表2。 The results are shown in Tables 1 and 2.

MgF2之XRD峰強度係將所獲得之濺鍍靶粉碎，並藉由粉末X射線繞射法進行測定。即，於2θ：27.3°附近出現之峰強度成為553，又，測定背景強度(28.0~29.0°之強度之平均值)。 The XRD peak intensity of MgF 2 was obtained by pulverizing the obtained sputtering target and measuring by powder X-ray diffraction. That is, the peak intensity appearing in the vicinity of 2θ: 27.3° was 553, and the background intensity (the average of the intensities of 28.0 to 29.0°) was measured.

MgF2之峰強度相對於背景強度之比(MgF2峰強度/背景強度)成為19.5。將該結果示於圖1。 The ratio of the peak intensity of MgF 2 to the background intensity (MgF 2 peak intensity/background intensity) was 19.5. This result is shown in FIG.

再者，使用Rigaku公司製造之UltimalV作為測定裝置，測定條件係設為管電壓40kv、管電流30mA、掃描速度8°/min、步距角0.02°。 Further, Ulmital V manufactured by Rigaku Co., Ltd. was used as a measuring device, and the measurement conditions were a tube voltage of 40 kV, a tube current of 30 mA, a scanning speed of 8°/min, and a step angle of 0.02°.

(實施例2) (Example 2)

準備3N當量且平均粒徑5μm以下之ZnO粉、3N當量且平均粒徑5μm以下之MgF2粉、及3N當量且平均粒徑5μm以下之GeO2粉。繼而，將ZnO粉、MgF2粉及GeO2粉調合成ZnO：MgF2：GeO2=82.0：9.8：8.2mol%之摻合比，並將其混合後，於800℃、大氣中對粉末材料進行熱壓燒結。將該燒結體粉碎並製成粒徑1~6mm尺寸之粒狀體而製成離子鍍材料。 3N equivalents of ZnO powder having an average particle diameter of 5 μm or less, 3N equivalents of MgF 2 powder having an average particle diameter of 5 μm or less, and 3N equivalents of GeO 2 powder having an average particle diameter of 5 μm or less were prepared. Then, ZnO powder, MgF 2 powder and GeO 2 powder were blended into a blend ratio of ZnO:MgF 2 :GeO 2 =82.0:9.8:8.2 mol%, and after mixing, the powder material was taken at 800 ° C in the atmosphere. Hot press sintering is performed. The sintered body was pulverized and formed into a granular body having a particle diameter of 1 to 6 mm to prepare an ion plating material.

繼而，使用該離子鍍材料實施離子鍍，結果可確認，如下述比較例1般，於坩堝內未確認到未蒸發殘留物，幾乎無因離子鍍時之ZnO與MgF2、GeO2之蒸氣壓差所致之差異。實施例2之離子鍍材料可進行穩定之離子鍍，製作而成之膜之透射率達到86.6%(405nm)，折射率成為1.92， 顯示非晶質性。又，比電阻值成為1×105Ω．cm，消光係數(λ=450nm)成為<0.005。將該結果示於表1與表2。 Then, ion plating was carried out using the ion plating material. As a result, it was confirmed that, as in the following Comparative Example 1, no evaporation residue was observed in the crucible, and there was almost no vapor pressure difference between ZnO and MgF 2 and GeO 2 during ion plating. The difference caused. The ion plating material of Example 2 was subjected to stable ion plating, and the transmittance of the film produced was 86.6% (405 nm), and the refractive index was 1.92, showing amorphousness. Moreover, the specific resistance value becomes 1 × 10 5 Ω. Cm, the extinction coefficient (λ = 450 nm) becomes <0.005. The results are shown in Tables 1 and 2.

MgF2之峰強度係將所獲得之離子鍍材料粉碎，並藉由粉末X射線繞射法進行測定。即，於2θ：27.3°附近出現之峰強度成為553，又，測定背景強度(28.0~29.0°之強度之平均值)。 The peak intensity of MgF 2 was obtained by pulverizing the obtained ion plating material by a powder X-ray diffraction method. That is, the peak intensity appearing in the vicinity of 2θ: 27.3° was 553, and the background intensity (the average of the intensities of 28.0 to 29.0°) was measured.

MgF2之峰強度相對於背景強度之比(MgF2峰強度/背景強度)成為16.3。將該結果示於圖3。 The ratio of the peak intensity of MgF 2 to the background intensity (MgF 2 peak intensity/background intensity) was 16.3. This result is shown in FIG.

再者，使用Rigaku公司製造之UltimalV作為測定裝置，測定條件係設為管電壓40kv、管電流30mA、掃描速度8°/min、步距角0.02°。 Further, Ulmital V manufactured by Rigaku Co., Ltd. was used as a measuring device, and the measurement conditions were a tube voltage of 40 kV, a tube current of 30 mA, a scanning speed of 8°/min, and a step angle of 0.02°.

(實施例3) (Example 3)

準備3N當量且平均粒徑5μm以下之ZnO粉、3N當量且平均粒徑5μm以下之MgF2粉、3N當量且平均粒徑5μm以下之GeO2粉、3N當量且平均粒徑5μm以下之Ga2O3粉。繼而，將ZnO粉、MgF2粉、Ga2O3粉及GeO2粉調合成ZnO：MgF2：Ga2O3：GeO2=73.5：16.8：4.1：5.6mol%之摻合比，並將其混合後，於1100℃、Ar環境中、250kgf/cm2之壓力下對粉末材料進行熱壓燒結。利用機械加工，將該燒結體最後加工成靶形狀。 3N equivalents of ZnO powder having an average particle diameter of 5 μm or less, 3N equivalents of MgF 2 powder having an average particle diameter of 5 μm or less, 3N equivalents of GeO 2 powder having an average particle diameter of 5 μm or less, and 3 N equivalents of Ga 2 having an average particle diameter of 5 μm or less. O 3 powder. Then, ZnO powder, MgF 2 powder, Ga 2 O 3 powder and GeO 2 powder are conditioned to a blend ratio of ZnO:MgF 2 :Ga 2 O 3 :GeO 2 =73.5:16.8:4.1:5.6 mol%, and After the mixing, the powder material was subjected to hot press sintering at a pressure of 250 kgf/cm 2 at 1,100 ° C in an Ar environment. The sintered body is finally processed into a target shape by mechanical processing.

以上之結果為，實施例3之濺鍍靶之相對密度成為99.6%，又，體電阻值成為4×10-3Ω．cm，且可進行穩定之DC濺鍍。折射率成為1.84(波長633nm)，顯示非晶質性。又，比電阻值成為1×10-1Ω．cm，消光係數(λ=450nm)成為<0.005。將該結果示於表1與表2。 As a result of the above, the relative density of the sputtering target of Example 3 was 99.6%, and the bulk resistance value was 4 × 10 -3 Ω. Cm, and stable DC sputtering can be performed. The refractive index was 1.84 (wavelength: 633 nm) and showed amorphous properties. Moreover, the specific resistance value becomes 1 × 10 -1 Ω. Cm, the extinction coefficient (λ = 450 nm) becomes <0.005. The results are shown in Tables 1 and 2.

MgF2之XRD峰強度係將所獲得之濺鍍靶粉碎，並藉由粉末X射線繞射法進行測定。即，於2θ：27.3°附近出現之峰強度成為553，又，測定背景強度(28.0~29.0°之強度之平均值)。 The XRD peak intensity of MgF 2 was obtained by pulverizing the obtained sputtering target and measuring by powder X-ray diffraction. That is, the peak intensity appearing in the vicinity of 2θ: 27.3° was 553, and the background intensity (the average of the intensities of 28.0 to 29.0°) was measured.

MgF2之峰強度相對於背景強度之比(MgF2峰強度/背景強度)成為24.1。 The ratio of the peak intensity of MgF 2 to the background intensity (MgF 2 peak intensity/background intensity) was 24.1.

再者，使用Rigaku公司製造之UltimalV作為測定裝置，測定條件係設為管電壓40kv、管電流30mA、掃描速度8°/min、步距角0.02°。 Further, Ulmital V manufactured by Rigaku Co., Ltd. was used as a measuring device, and the measurement conditions were a tube voltage of 40 kV, a tube current of 30 mA, a scanning speed of 8°/min, and a step angle of 0.02°.

(實施例4) (Example 4)

準備3N當量且平均粒徑5μm以下之ZnO粉、3N當量且平均粒徑5μm以下之MgF2粉、及3N當量且平均粒徑5μm以下之SnO2粉。繼而，將ZnO粉、MgF2粉及SnO2粉調合成ZnO：MgF2：SnO2粉=83.5：8.1：4.1：8.4mol%之摻合比，並將其混合後，於1050℃、Ar環境中、250kgf/cm2之壓力下對粉末材料進行熱壓燒結。利用機械加工，將該燒結體最後加工成靶形狀。 3N equivalents of ZnO powder having an average particle diameter of 5 μm or less, 3N equivalents of MgF 2 powder having an average particle diameter of 5 μm or less, and 3N equivalents of SnO 2 powder having an average particle diameter of 5 μm or less were prepared. Then, the ZnO powder, the MgF 2 powder and the SnO 2 powder are adjusted into a blend ratio of ZnO:MgF 2 :SnO 2 powder=83.5:8.1:4.1:8.4 mol%, and after mixing, at 1050 ° C, Ar environment The powder material was subjected to hot press sintering at a pressure of 250 kgf/cm 2 . The sintered body is finally processed into a target shape by mechanical processing.

以上之結果為，實施例4之濺鍍靶之相對密度成為99.2%，又，體電阻值成為6×10-3Ω．cm，且可進行穩定之DC濺鍍。折射率成為1.96(波長633nm)，顯示非晶質性。又，比電阻值成為1×10-2Ω．cm，消光係數(λ=450nm)成為0.008。將該結果示於表1與表2。 As a result of the above, the relative density of the sputtering target of Example 4 was 99.2%, and the bulk resistance value was 6 × 10 -3 Ω. Cm, and stable DC sputtering can be performed. The refractive index was 1.96 (wavelength: 633 nm) and showed amorphous properties. Moreover, the specific resistance value becomes 1 × 10 -2 Ω. Cm, the extinction coefficient (λ = 450 nm) becomes 0.008. The results are shown in Tables 1 and 2.

MgF2之XRD峰強度係將所獲得之濺鍍靶粉碎，並藉由粉末X射線繞射法進行測定。即，於2θ：27.3°附近出現之峰強度成為553，又，測定背景強度(28.0~29.0°之強度之平均值)。 The XRD peak intensity of MgF 2 was obtained by pulverizing the obtained sputtering target and measuring by powder X-ray diffraction. That is, the peak intensity appearing in the vicinity of 2θ: 27.3° was 553, and the background intensity (the average of the intensities of 28.0 to 29.0°) was measured.

MgF2之峰強度相對於背景強度之比(MgF2峰強度/背景強度)成為14.2。 The ratio of the peak intensity of MgF 2 to the background intensity (MgF 2 peak intensity/background intensity) was 14.2.

再者，使用Rigaku公司製造之UltimalV作為測定裝置，測定條件係設為管電壓40kv、管電流30mA、掃描速度8°/min、步距角0.02°。 Further, Ulmital V manufactured by Rigaku Co., Ltd. was used as a measuring device, and the measurement conditions were a tube voltage of 40 kV, a tube current of 30 mA, a scanning speed of 8°/min, and a step angle of 0.02°.

(實施例5) (Example 5)

準備3N當量且平均粒徑5μm以下之ZnO粉、3N當量且平均粒徑5μm以下之MgF2粉、3N當量且平均粒徑5μm以下之In2O3粉、及3N當量且平均粒徑5μm以下之GeO2粉。繼而，將ZnO粉、MgF2粉、In2O3粉及GeO2粉調合成ZnO：MgF2：In2O3：GeO2=83.9：6.1：2.77：7.2mol%之摻合 比，並將其混合後，於1050℃、Ar環境中、250kgf/cm2之壓力下對粉末材料進行熱壓燒結。利用機械加工，將該燒結體最後加工成靶形狀。 3N equivalents of ZnO powder having an average particle diameter of 5 μm or less, 3N equivalents of MgF 2 powder having an average particle diameter of 5 μm or less, 3 N equivalents of In 2 O 3 powder having an average particle diameter of 5 μm or less, and 3 N equivalents and an average particle diameter of 5 μm or less. GeO 2 powder. Then, ZnO powder, MgF 2 powder, In 2 O 3 powder and GeO 2 powder are conditioned to a blend ratio of ZnO:MgF 2 :In 2 O 3 :GeO 2 =83.9:6.1:2.77:7.2 mol%, and After mixing, the powder material was subjected to hot press sintering at a pressure of 250 kgf/cm 2 at 1050 ° C in an Ar environment. The sintered body is finally processed into a target shape by mechanical processing.

以上之結果為，實施例5之濺鍍靶之相對密度成為99.3%，又，體電阻值成為3×10-3Ω．cm，且可進行穩定之DC濺鍍。折射率成為1.93(波長633nm)，顯示非晶質性。又，比電阻值成為1×10-1Ω．cm，消光係數(λ=450nm)成為<0.005。將該結果示於表1與表2。 As a result of the above, the relative density of the sputtering target of Example 5 was 99.3%, and the bulk resistance value was 3 × 10 -3 Ω. Cm, and stable DC sputtering can be performed. The refractive index was 1.93 (wavelength: 633 nm) and showed amorphous properties. Moreover, the specific resistance value becomes 1 × 10 -1 Ω. Cm, the extinction coefficient (λ = 450 nm) becomes <0.005. The results are shown in Tables 1 and 2.

MgF2之XRD峰強度係將所獲得之濺鍍靶粉碎，並藉由粉末X射線繞射法進行測定。即，於2θ：27.3°附近出現之峰強度成為553，又，測定背景強度(28.0~29.0°之強度之平均值)。 The XRD peak intensity of MgF 2 was obtained by pulverizing the obtained sputtering target and measuring by powder X-ray diffraction. That is, the peak intensity appearing in the vicinity of 2θ: 27.3° was 553, and the background intensity (the average of the intensities of 28.0 to 29.0°) was measured.

MgF2之峰強度相對於背景強度之比(MgF2峰強度/背景強度)成為9.8。 The ratio of the peak intensity of MgF 2 to the background intensity (MgF 2 peak intensity/background intensity) was 9.8.

再者，使用Rigaku公司製造之UltimalV作為測定裝置，測定條件係設為管電壓40kv、管電流30mA、掃描速度8°/min、步距角0.02°。 Further, Ulmital V manufactured by Rigaku Co., Ltd. was used as a measuring device, and the measurement conditions were a tube voltage of 40 kV, a tube current of 30 mA, a scanning speed of 8°/min, and a step angle of 0.02°.

(比較例1) (Comparative Example 1)

準備3N當量且平均粒徑5μm以下之ZnO粉、及3N當量且平均粒徑5μm以下之MgF2粉。繼而，將ZnO粉與MgF2粉調合成ZnO：MgF2=99.2：0.8mol%之摻合比，並將其混合後，於1100℃、Ar環境中、250kgf/cm2之壓力下對粉末材料進行熱壓燒結。利用機械加工，將該燒結體最後加工成靶形狀。MgF2量未達到設為本案發明之目標之量。 3N equivalents of ZnO powder having an average particle diameter of 5 μm or less and 3N equivalents of MgF 2 powder having an average particle diameter of 5 μm or less were prepared. Then, the ZnO powder and the MgF 2 powder are blended into a blend ratio of ZnO:MgF 2 =99.2:0.8 mol%, and after mixing, the powder material is pressed at 1100 ° C, Ar environment, under a pressure of 250 kgf / cm 2 Hot press sintering is performed. The sintered body is finally processed into a target shape by mechanical processing. The amount of MgF 2 did not reach the amount set as the object of the present invention.

以上之結果為，比較例1之濺鍍靶之相對密度成為98.0%，又，體電阻值成為2×10-3Ω．cm，且可進行穩定之DC濺鍍。折射率為2.01(波長633nm)而不充分，未顯示非晶質性。又，比電阻值成為1×10-2Ω．cm，消光係數(λ=450nm)成為<0.005。將該結果示於表1與表2。 As a result of the above, the relative density of the sputtering target of Comparative Example 1 was 98.0%, and the bulk resistance value was 2 × 10 -3 Ω. Cm, and stable DC sputtering can be performed. The refractive index of 2.01 (wavelength 633 nm) was insufficient, and no amorphous property was shown. Moreover, the specific resistance value becomes 1 × 10 -2 Ω. Cm, the extinction coefficient (λ = 450 nm) becomes <0.005. The results are shown in Tables 1 and 2.

MgF2之XRD峰強度係將所獲得之濺鍍靶粉碎，並藉由粉末X射線繞射法進行測定。即，於2θ：27.3°附近出現之峰強度成為553，又，測定背景強度(28.0~29.0°之強度之平均值)。 The XRD peak intensity of MgF 2 was obtained by pulverizing the obtained sputtering target and measuring by powder X-ray diffraction. That is, the peak intensity appearing in the vicinity of 2θ: 27.3° was 553, and the background intensity (the average of the intensities of 28.0 to 29.0°) was measured.

MgF2之峰強度相對於背景強度之比(MgF2峰強度/背景強度)成為1.7。 The ratio of the peak intensity of MgF 2 to the background intensity (MgF 2 peak intensity/background intensity) was 1.7.

再者，使用Rigaku公司製造之UltimalV作為測定裝置，測定條件係設為管電壓40kv、管電流30mA、掃描速度8°/min、步距角0.02°。 Further, Ulmital V manufactured by Rigaku Co., Ltd. was used as a measuring device, and the measurement conditions were a tube voltage of 40 kV, a tube current of 30 mA, a scanning speed of 8°/min, and a step angle of 0.02°.

(比較例2) (Comparative Example 2)

準備3N當量且平均粒徑5μm以下之ZnO粉、3N當量且平均粒徑5μm以下之MgF2粉、及3N當量且平均粒徑5μm以下之Ga2O3粉。繼而，將ZnO粉、MgF2粉及Ga2O3粉調合成ZnO：MgF2：Ga2O3=69.2：29.0：1.8mol%之摻合比，並將其混合後，於1050℃、Ar環境中、250kgf/cm2之壓力下對粉末材料進行熱壓燒結。利用機械加工，將該燒結體最後加工成靶形狀。 3N equivalents of ZnO powder having an average particle diameter of 5 μm or less, 3N equivalents of MgF 2 powder having an average particle diameter of 5 μm or less, and 3 N equivalents of Ga 2 O 3 powder having an average particle diameter of 5 μm or less were prepared. Then, the ZnO powder, the MgF 2 powder and the Ga 2 O 3 powder are conditioned to a blend ratio of ZnO:MgF 2 :Ga 2 O 3 =69.2:29.0:1.8 mol%, and after mixing, at 1050 ° C, Ar The powder material is subjected to hot press sintering in an environment at a pressure of 250 kgf/cm 2 . The sintered body is finally processed into a target shape by mechanical processing.

以上之結果為，比較例2之濺鍍靶之相對密度成為97.6%，又，體電阻值成為>10Ω．cm，且無法進行穩定之DC濺鍍。折射率成為1.78(波長633nm)，顯示非晶質性。又，比電阻值成為>1×109Ω．cm，消光係數(λ=450nm)成為<0.005。將該結果示於表1與表2。 As a result of the above, the relative density of the sputtering target of Comparative Example 2 was 97.6%, and the bulk resistance value was >10 Ω. Cm, and stable DC sputtering is not possible. The refractive index was 1.78 (wavelength: 633 nm) and showed amorphous properties. Moreover, the specific resistance value becomes >1 × 10 9 Ω. Cm, the extinction coefficient (λ = 450 nm) becomes <0.005. The results are shown in Tables 1 and 2.

MgF2之XRD峰強度係將所獲得之濺鍍靶粉碎，並藉由粉末X射線繞射法進行測定。即，於2θ：27.3°附近出現之峰強度成為553，又，測定背景強度(28.0~29.0°之強度之平均值)。 The XRD peak intensity of MgF 2 was obtained by pulverizing the obtained sputtering target and measuring by powder X-ray diffraction. That is, the peak intensity appearing in the vicinity of 2θ: 27.3° was 553, and the background intensity (the average of the intensities of 28.0 to 29.0°) was measured.

MgF2之峰強度相對於背景強度之比(MgF2峰強度/背景強度)成為36.4。將該結果示於圖1。 The ratio of the peak intensity of MgF 2 to the background intensity (MgF 2 peak intensity/background intensity) was 36.4. This result is shown in FIG.

再者，使用Rigaku公司製造之UltimalV作為測定裝置，測定條件係設為管電壓40kv、管電流30mA、掃描速度8°/min、步距角0.02°。 Further, Ulmital V manufactured by Rigaku Co., Ltd. was used as a measuring device, and the measurement conditions were a tube voltage of 40 kV, a tube current of 30 mA, a scanning speed of 8°/min, and a step angle of 0.02°.

[產業上之可利用性] [Industrial availability]

使用本發明之燒結體而形成之薄膜可提供如下燒結體，該燒結體能夠獲得可維持消光係數0.01以下(波長450nm)之良好之可見光之透射率與折射率2.0以下之低折射率的薄膜、進而非晶質膜。該薄膜之透射率較高、折射率較低且為非晶質膜，故而作為顯示器或太陽電池、觸控面 板之透明導電膜或保護層而有用。例如，可用於軟性顯示器、有機EL電視、觸控面板用電極、形成光資訊記錄媒體之保護層。 The film formed by using the sintered body of the present invention can provide a sintered body capable of obtaining a film having a low refractive index of a visible light having a good extinction coefficient of 0.01 or less (wavelength: 450 nm) and a refractive index of 2.0 or less. Further, an amorphous film. The film has a high transmittance, a low refractive index, and is an amorphous film, so as a display or a solar cell, a touch surface Useful for a transparent conductive film or a protective layer of a board. For example, it can be used for a flexible display, an organic EL television, an electrode for a touch panel, and a protective layer for forming an optical information recording medium.

進而，本發明之較大之特徵為：減少靶體電阻值，賦予導電性，根據材料可進行穩定之DC濺鍍。而且，具有作為該DC濺鍍之特徵的可使濺鍍之控制性容易並提高成膜速度且提高濺鍍效率之明顯之效果。雖視需要實施離子鍍、RF濺鍍，但於該情形時亦可看到成膜速度之提高。 Further, the present invention is characterized in that the target resistance value is reduced, the conductivity is imparted, and stable DC sputtering can be performed depending on the material. Further, it has a remarkable effect of making the controllability of sputtering easy to improve the film formation speed and improving the sputtering efficiency as a feature of the DC sputtering. Although ion plating or RF sputtering is performed as needed, in this case, an increase in film formation speed can also be seen.

如此，具有如下明顯之效果：能夠以低成本且穩定地製造可維持良好之可見光之透射率與折射率2.0以下之低折射率的薄膜。 As described above, it is possible to produce a film having a low refractive index which can maintain a good transmittance of visible light and a refractive index of 2.0 or less at a low cost and stably.

Claims (19)

一種燒結體，由鋅(Zn)、鎂(Mg)、氧(O)、氟(F)構成，其特徵在於：鎂(Mg)含量以鎂之氟化物(MgF2)換算計含有1.0~27mol%。 A sintered body composed of zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F), characterized in that magnesium (Mg) content is 1.0 to 27 mol in terms of magnesium fluoride (MgF 2 ) %. 如申請專利範圍第1項之燒結體，其中，X射線繞射中氟化鎂(MgF2)之峰強度相對於背景強度之比(氟化鎂峰強度/背景強度)為1.50以上。 The sintered body of the first aspect of the invention, wherein the ratio of the peak intensity of the magnesium fluoride (MgF 2 ) to the background intensity (magnesium fluoride peak intensity/background intensity) in the X-ray diffraction is 1.50 or more. 如申請專利範圍第1或2項之燒結體，其進一步含有以各元素之氧化物換算計0.2~10mol%之選自鎵(Ga)、硼(B)、鍺(Ge)、銦(In)、錫(Sn)之1種以上的元素。 The sintered body according to claim 1 or 2, which further contains 0.2 to 10 mol% of gallium (Ga), boron (B), germanium (Ge), indium (In) in terms of oxide of each element. One or more elements of tin (Sn). 如申請專利範圍第1至3項中任一項之燒結體，其進一步含有以氧化物重量換算計0.1~5wt%之形成熔點為1000℃以下之氧化物的金屬。 The sintered body according to any one of claims 1 to 3, further comprising 0.1 to 5 wt% of a metal having an oxide having a melting point of 1000 ° C or less in terms of oxide weight. 如申請專利範圍第4項之燒結體，其中，該熔點為1000℃以下之氧化物係選自B2O3、P2O5、K2O、V2O5、Sb2O3、TeO2、Ti2O3、PbO、Bi2O3、MoO3之群中之一種以上的氧化物。 The sintered body of claim 4, wherein the oxide having a melting point of 1000 ° C or less is selected from the group consisting of B 2 O 3 , P 2 O 5 , K 2 O, V 2 O 5 , Sb 2 O 3 , TeO. 2 , one or more oxides of the group of Ti 2 O 3 , PbO, Bi 2 O 3 , and MoO 3 . 如申請專利範圍第1至5項中任一項之燒結體，其相對密度為90%以上。 The sintered body according to any one of claims 1 to 5, which has a relative density of 90% or more. 如申請專利範圍第1至6項中任一項之燒結體，其體電阻未達10Ω．cm。 The sintered body of any one of the claims 1 to 6 has a bulk resistance of less than 10 Ω. Cm. 如申請專利範圍第1至7項中任一項之燒結體，其係濺鍍靶或離子鍍用材料。 The sintered body according to any one of claims 1 to 7, which is a sputtering target or a material for ion plating. 一種薄膜，由鋅(Zn)、鎂(Mg)、氧(O)、氟(F)構成，其特徵在於：鎂(Mg)含量以鎂之氟化物(MgF2)換算計含有1.0~27mol%。 A film composed of zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F), characterized in that magnesium (Mg) content is 1.0 to 27 mol% in terms of magnesium fluoride (MgF 2 ) . 如申請專利範圍第9項之薄膜，其進一步含有以各元素之氧化物換算計0.2~10mol%之選自鎵(Ga)、硼(B)、鍺(Ge)、銦(In)、錫(Sn)之1種以上的元素。 The film of claim 9 which further contains 0.2 to 10 mol% of gallium (Ga), boron (B), germanium (Ge), indium (In), and tin (in terms of oxide of each element). One or more elements of Sn). 如申請專利範圍第9或10項之薄膜，其進一步含有以氧化物重量換算計0.1~5wt%之形成熔點為1000℃以下之氧化物的金屬。 The film of claim 9 or 10, further comprising 0.1 to 5 wt% of a metal having an oxide having a melting point of 1000 ° C or less in terms of oxide weight. 如申請專利範圍第11項之薄膜，其中，該熔點為1000℃以下之氧化物係選自B2O3、P2O5、K2O、V2O5、Sb2O3、TeO2、Ti2O3、PbO、Bi2O3、MoO3之群中之一種以上的氧化物。 The film of claim 11, wherein the oxide having a melting point of 1000 ° C or less is selected from the group consisting of B 2 O 3 , P 2 O 5 , K 2 O, V 2 O 5 , Sb 2 O 3 , TeO 2 One or more oxides of the group of Ti 2 O 3 , PbO, Bi 2 O 3 , and MoO 3 . 如申請專利範圍第9至12項中任一項之薄膜，其係非晶質膜。 A film according to any one of claims 9 to 12 which is an amorphous film. 如申請專利範圍第9至13項中任一項之薄膜，其折射率為2.0以下(波長550nm)。 The film of any one of claims 9 to 13 has a refractive index of 2.0 or less (wavelength 550 nm). 如申請專利範圍第9至14項中任一項之薄膜，其消光係數為0.01以下(波長450nm)。 The film of any one of claims 9 to 14 has an extinction coefficient of 0.01 or less (wavelength: 450 nm). 如申請專利範圍第9至15項中任一項之薄膜，其中，膜之電阻值為1×10-3~1×109Ω．cm。 The film of any one of claims 9 to 15, wherein the film has a resistance value of from 1 × 10 -3 to 1 × 10 9 Ω. Cm. 如申請專利範圍第9至16項中任一項之薄膜，其係藉由濺鍍或離子鍍而形成之膜。 The film of any one of claims 9 to 16, which is a film formed by sputtering or ion plating. 一種燒結體之製造方法，用於製造申請專利範圍第1至5項中任一項之燒結體，其係於惰性環境下進行燒結。 A method of producing a sintered body for producing a sintered body according to any one of claims 1 to 5, which is sintered in an inert environment. 一種離子鍍用材料之製造方法，其係將申請專利範圍第1至5項中任一項之燒結體粉碎而製成粉末或粒狀。 A method for producing a material for ion plating, which is obtained by pulverizing a sintered body according to any one of claims 1 to 5 to obtain a powder or a pellet.
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