JP5371373B2 - Alumina sintered body, semiconductor manufacturing apparatus member, liquid crystal panel manufacturing apparatus member, and dielectric resonator member - Google Patents
Alumina sintered body, semiconductor manufacturing apparatus member, liquid crystal panel manufacturing apparatus member, and dielectric resonator member Download PDFInfo
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本発明は、アルミナ質焼結体ならびに半導体製造装置用部材、液晶パネル製造装置用部材および誘電体共振器用部材に関するもので、特に、半導体製造装置の内壁材（チャンバー）やマイクロ波導入窓、シャワーヘッド、フォーカスリング、シールドリングをはじめとする部材や、液晶パネル製造装置のステージ、ミラー、マスクホルダー、マスクステージ、チャック、レチクル等に用いる部材、およびマイクロ波やミリ波などの高周波領域において使用される種々の共振器用材料やＭＩＣ用誘電体基板材料、誘電体導波路用材料等に好適に用いることができる。 The present invention relates to an alumina sintered body, a member for a semiconductor manufacturing apparatus, a member for a liquid crystal panel manufacturing apparatus, and a member for a dielectric resonator, and in particular, an inner wall material (chamber), a microwave introduction window, a shower of a semiconductor manufacturing apparatus. Used in parts such as heads, focus rings, shield rings, liquid crystal panel manufacturing equipment stages, mirrors, mask holders, mask stages, chucks, reticles, and other high-frequency regions such as microwaves and millimeter waves. It can be suitably used for various resonator materials, MIC dielectric substrate materials, dielectric waveguide materials, and the like.
従来から、アルミナ質焼結体は耐熱性、耐薬品性、耐プラズマ性に優れ、さらに高周波領域での誘電正接（ｔａｎδ）が小さいことから、半導体、液晶用高周波プラズマ装置用部材、マイクロ波共振器などに用いられている。 Conventionally, sintered alumina has excellent heat resistance, chemical resistance, and plasma resistance, and also has a low dielectric loss tangent (tan δ) in the high frequency region. Used in containers.
半導体または液晶パネルの製造装置用部材はエッチング、クリーニング用として使用される反応性の高いハロゲン系腐食ガスやそれらのプラズマと接触するため、高い耐腐食性が要求され、一般的に９９．０質量％以上の高純度のアルミナ質焼結体が求められている。一方、高純度のアルミナ質焼結体となるにつれて焼結性の観点から誘電正接が大きくなり、これによりＭＨｚ帯での高周波の透過率が低下し、エネルギーロスの増加、発熱による部材の破損といった問題が発生することが知られている。 Semiconductor or liquid crystal panel manufacturing equipment members are in contact with highly reactive halogen-based corrosive gases used for etching and cleaning, and their plasmas, and therefore require high corrosion resistance, and generally 99.0 mass. % Or more high-purity alumina sintered body is required. On the other hand, the dielectric loss tangent increases from the viewpoint of sinterability as it becomes a high-purity alumina sintered body, which reduces the high-frequency transmittance in the MHz band, increases energy loss, and damages the member due to heat generation. Problems are known to occur.
アルミナ質焼結体の低損失化について、焼結助剤としてＳｉＯ２、ＣａＯ、ＭｇＯを含有させ、その含有量をコントロールし、ある範囲内とすることで、低温で焼成しつつ、高周波誘電特性を向上させたアルミナ質焼結体が知られている（例えば、特許文献１参照）。 For reducing the loss of the alumina sintered body, SiO 2 , CaO, and MgO are included as sintering aids, and the content is controlled to be within a certain range. There is known an alumina sintered body with improved sinter (see, for example, Patent Document 1).
この特許文献１には、アルミナ９９．８〜９９．９質量％と、残部が所定比率のＳｉＯ２、ＣａＯ、ＭｇＯからなる粒界相成分とから構成し、測定周波数８ＧＨｚにおけるＱ値が１００００以上（誘電正接が０．０００１以下）のマイクロ波共振器用等のアルミナ質焼結体が得られたことが記載されている。 This Patent Document 1 is composed of 99.8 to 99.9% by mass of alumina and a grain boundary phase component composed of SiO 2 , CaO, and MgO at a predetermined ratio, and the Q value at a measurement frequency of 8 GHz is 10,000 or more. It is described that an alumina sintered body for a microwave resonator having a dielectric loss tangent of 0.0001 or less was obtained.
また、少なくともＬａ、Ｃａ、Ｓｒ、Ｂａ、Ｓｍ、ＮｄおよびＴｉのうち一種を含みＡｌとの複合酸化物からなる異方性形状の第２相結晶粒子を含有させることで、アルミナ質焼結体の耐酸化性向上と機械的特性を向上させたアルミナ質焼結体が知られている（例えば、特許文献２参照）。 In addition, an alumina sintered body is obtained by containing anisotropic second-phase crystal particles made of a composite oxide with Al including at least one of La, Ca, Sr, Ba, Sm, Nd and Ti. An alumina sintered body with improved oxidation resistance and mechanical properties is known (see, for example, Patent Document 2).
この特許文献２には、アルミナ母相の平均結晶粒径が１０μｍ以下であり、かつ長径方向の長さが２０μｍ以上の第２相結晶粒子が、焼結体全量中１〜２０体積％存在することで、破壊靭性値４．７ＭＰａ・ｍ１／２と室温強度５８０ＭＰａ以上が得られたことが記載されている。
特許文献１のようにＳｉＯ２、ＣａＯ、ＭｇＯを含有したアルミナ質焼結体では、測定周波数８ＧＨｚにおける誘電正接が０．０００１以下のものが得られている。しかしながら、半導体製造装置用部材および液晶パネル製造装置用部材のような大型品にアルミナ質焼結体を用いた場合、アルミナ質焼結体中央部の密度が低く、このため、アルミナ質焼結体全体としてのＭＨｚ帯での誘電正接が大きく、例えば、ＭＨｚ帯の高周波が使用される半導体用高周波プラズマ装置用部材等に用いた場合には、ＭＨｚ帯の高周波の透過率が低下し、エネルギーロスの増加や、部材の破損といった問題が生じている。さらに近年ではＭＨｚ〜ＧＨｚ帯での広い周波数範囲での用途があり、そこでの低誘電正接化が求められていた。 As in Patent Document 1, an alumina sintered body containing SiO 2 , CaO, and MgO has a dielectric loss tangent of 0.0001 or less at a measurement frequency of 8 GHz. However, when an alumina sintered body is used for a large-sized product such as a member for a semiconductor manufacturing apparatus and a liquid crystal panel manufacturing apparatus, the density of the central part of the alumina sintered body is low. The dielectric loss tangent in the MHz band as a whole is large. For example, when used for a member for a high frequency plasma device for semiconductors in which a high frequency in the MHz band is used, the transmittance of the high frequency in the MHz band is reduced, resulting in energy loss. There are problems such as an increase in the number of members and breakage of members. Furthermore, in recent years, there are applications in a wide frequency range in the MHz to GHz band, and there has been a demand for a low dielectric loss tangent.
また、特許文献２では、第２相結晶粒子が焼結体全量中１〜２０体積％存在しており、破壊靭性や室温強度は高いものの、誘電正接が低く、ＭＨｚ帯の高周波が使用される半導体用高周波プラズマ装置用部材等に用いた場合には、ＭＨｚ帯の高周波の透過率が低下するという問題があった。 Moreover, in patent document 2, 1-20 volume% of 2nd phase crystal particles exist in the sintered compact whole quantity, and although fracture toughness and room temperature strength are high, a dielectric loss tangent is low and the high frequency of a MHz band is used. When used as a member for a high-frequency plasma device for semiconductors, etc., there has been a problem that the high-frequency transmittance in the MHz band is reduced.
本発明は、ＭＨｚ〜ＧＨｚ帯における誘電正接を小さくできるアルミナ質焼結体ならびに半導体製造装置用部材、液晶パネル製造装置用部材および誘電体共振器用部材を提供することを目的とする。 An object of the present invention is to provide an alumina sintered body, a member for a semiconductor manufacturing apparatus, a member for a liquid crystal panel manufacturing apparatus, and a member for a dielectric resonator that can reduce the dielectric loss tangent in the MHz to GHz band.
本発明者等は、アルミナ質焼結体のＭＨｚ〜ＧＨｚ帯における誘電正接の低減を図るべく鋭意検討した結果、ＡｌをＡｌ２Ｏ３換算で９９．３質量％以上含有するとともに、アルミナ結晶粒子の３重点にＳｉ、Ａｌ、Ｍ（Ｍはアルカリ土類金属であって、少なくともＳｒまたはＢａを含む。）およびＯを含む結晶相または非晶質相を存在せしめ、Ｓｉ、Ａｌ、ＭおよびＯを含む結晶相を３重点のうちの１０％以上の３重点に存在せしめることにより、ＭＨｚ〜ＧＨｚ帯の広い周波数範囲で低誘電正接のアルミナ質焼結体を得ることができることを見出し、本発明に至った。
As a result of intensive investigations aimed at reducing the dielectric loss tangent in the MHz to GHz band of the alumina sintered body, the present inventors contained Al in an amount of 99.3% by mass in terms of Al 2 O 3 , and alumina crystal particles The crystal phase or amorphous phase containing Si, Al, M (M is an alkaline earth metal , and at least Sr or Ba ) and O are present at the three points of Si, Al, M, and O. It has been found that an alumina-based sintered body having a low dielectric loss tangent can be obtained in a wide frequency range of MHz to GHz band by allowing a crystal phase containing bismuth to exist at a triple point of 10% or more of the triple points. It came to.
すなわち、本発明のアルミナ質焼結体は、ＡｌをＡｌ２Ｏ３換算で９９．３質量％以上含有するとともに、元素としてＳｉ、ＡｌおよびＭ（Ｍはアルカリ土類金属であって、少なくともＳｒまたはＢａを含む。）を含有し、アルミナ結晶粒子を主結晶粒子とするアルミナ質焼結体であって、該アルミナ質焼結体の任意断面における前記アルミナ結晶粒子で構成される３重点に、元素としてＳｉ、Ａｌ、ＭおよびＯを含有する結晶相、または元素としてＳｉ、Ａｌ、ＭおよびＯを含有する非晶質相が存在するとともに、前記アルミナ結晶粒子で構成される３重点のうち１０％以上の３重点に、前記元素としてＳｉ、Ａｌ、ＭおよびＯを含有する前記結晶相が存在することを特徴とする。 That is, the alumina-based sintered body of the present invention contains 99.3% by mass or more of Al in terms of Al 2 O 3 , and includes Si, Al, and M (M is an alkaline earth metal , and at least Sr Or containing Ba. ), And an alumina sintered body having alumina crystal particles as main crystal particles, the triple point composed of the alumina crystal particles in an arbitrary cross section of the alumina sintered body, There is a crystal phase containing Si, Al, M and O as an element, or an amorphous phase containing Si, Al, M and O as an element, and 10 out of three points composed of the alumina crystal particles The crystal phase containing Si, Al, M, and O as the element exists at a triple point of at least%.
このようなアルミナ質焼結体では、ＡｌをＡｌ２Ｏ３換算で９９．３質量％以上含有し、アルミナ結晶粒子を主結晶粒子とするため、アルミナ本来の優れた耐腐食性と機械的特性、電気特性を維持することができるとともに、アルミナ結晶粒子で構成される３重点に、元素としてＳｉ、Ａｌ、ＭおよびＯを含有する結晶相または非晶質相が存在するため、３重点に元素としてＳｉ、Ａｌ、ＭおよびＯを含有する、例えばＳｒＡｌ２Ｓｉ２Ｏ８等の結晶相が存在する場合には低誘電正接化を促進でき、また、３重点に非晶質相が存在する場合には、焼結体が緻密化されているため、焼結体中の欠陥やボイドを低減し、これにより、低誘電正接化を達成できる。 In such an alumina sintered body, since Al is contained in an amount of 99.3% by mass or more in terms of Al 2 O 3 and the alumina crystal particles are the main crystal particles, the original excellent corrosion resistance and mechanical properties of alumina. In addition, the electrical characteristics can be maintained, and since the crystalline or amorphous phase containing Si, Al, M and O as elements exists at the triple point composed of alumina crystal particles, the element at the triple point When there is a crystalline phase such as SrAl 2 Si 2 O 8 containing Si, Al, M and O as a low-dielectric loss tangent can be promoted, and when an amorphous phase exists at the triple point Since the sintered body is densified, defects and voids in the sintered body can be reduced, thereby achieving a low dielectric loss tangent.
そして、元素としてＳｉ、Ａｌ、ＭおよびＯを含有する低誘電正接の結晶相が、アルミナ結晶粒子で構成される３重点のうち１０％以上の３重点に存在するため、アルミナ質焼結体の低誘電正接化をさらに図ることができ、測定周波数１ＭＨｚ〜８．５ＧＨｚにおける誘電正接を小さくすることができる。 And since the low dielectric loss tangent crystal phase containing Si, Al, M, and O as elements exists in three points of 10% or more of the three points composed of alumina crystal particles, The dielectric loss tangent can be further reduced, and the dielectric loss tangent at a measurement frequency of 1 MHz to 8.5 GHz can be reduced.
また、本発明のアルミナ質焼結体は、前記元素としてＳｉ、Ａｌ、ＭおよびＯを含有する結晶相が、ＭＡｌ２Ｓｉ２Ｏ８型結晶相からなることを特徴とする。ＭＡｌ２Ｓｉ２Ｏ８型結晶相は、１ＭＨｚ〜８．５ＧＨｚの領域において低誘電正接であるためアルミナ質焼結体の誘電正接を低下させるのに効果が高い。特に高周波領域の誘電正接低減に効果を発揮する。さらにアルカリ土類金属酸化物は焼結助剤として機能し、焼結性を向上することができ、大型の焼結体の中央部であってもボイドや欠陥を減らすことができるため特にＭＨｚ帯でより低損失のアルミナ質焼結体を得ることができる。さらに、焼結性が向上するため、例えば、肉厚の厚い大型の焼結体の厚さ方向中央部が十分に焼結し、肉厚の厚い大型の焼結体全体の機械的強度等の特性を向上できる。 Moreover, the alumina sintered body of the present invention is characterized in that the crystal phase containing Si, Al, M and O as the element comprises a MAl 2 Si 2 O 8 type crystal phase. Since the MAl 2 Si 2 O 8 type crystal phase has a low dielectric loss tangent in the region of 1 MHz to 8.5 GHz, it is highly effective in reducing the dielectric loss tangent of the alumina sintered body. In particular, it is effective in reducing dielectric loss tangent in the high frequency region. Furthermore, alkaline earth metal oxides function as a sintering aid, improve sinterability, and can reduce voids and defects even at the center of large sintered bodies, especially in the MHz band. Thus, a lower loss alumina sintered body can be obtained. Furthermore, since the sinterability is improved, for example, the central portion in the thickness direction of the thick sintered body having a large thickness is sufficiently sintered, and the mechanical strength of the entire large sintered body having a large thickness is The characteristics can be improved.
また、本発明のアルミナ質焼結体は、さらにＭｇＡｌ２Ｏ４およびＣａＡｌ１２Ｏ１９で表される化合物からなる結晶相のうち少なくとも一種を含有することを特徴とする。これらの結晶相を存在させることで、ＧＨｚ帯で誘電正接を高くする非晶質相を減少させることができ、１ＭＨｚ〜８．５ＧＨｚの領域において誘電正接を低下させることができる。特にＭｇＡｌ２Ｏ４、ＣａＡｌ１２Ｏ１９は、この結晶自体が低誘電正接であるため、ＧＨｚ帯の誘電正接低下に有効である。 In addition, the alumina sintered body of the present invention is characterized by further containing at least one of crystal phases composed of compounds represented by MgAl 2 O 4 and CaAl 12 O 19 . The presence of these crystal phases can reduce the amorphous phase that increases the dielectric loss tangent in the GHz band, and can lower the dielectric loss tangent in the region of 1 MHz to 8.5 GHz. In particular, MgAl 2 O 4 and CaAl 12 O 19 are effective for lowering the dielectric loss tangent in the GHz band because the crystal itself has a low dielectric loss tangent.
さらに、本発明のアルミナ質焼結体は、前記アルミナ結晶粒子の平均粒径が２５μｍ以上であることを特徴とする。このようなアルミナ質焼結体では、アルミナ結晶粒子の平均粒径を２５μｍ以上と大きくすることで粒界を減らすことができ、測定周波数１ＭＨｚ〜８．５ＧＨｚにおける誘電正接をさらに小さくすることができる。 Furthermore, the alumina sintered body of the present invention is characterized in that the average particle diameter of the alumina crystal particles is 25 μm or more. In such an alumina sintered body, the grain boundary can be reduced by increasing the average particle diameter of alumina crystal particles to 25 μm or more, and the dielectric loss tangent at a measurement frequency of 1 MHz to 8.5 GHz can be further reduced. .
本発明の半導体製造装置用部材、液晶パネル製造装置用部材および誘電体共振器用部材は、上記のアルミナ質焼結体からなることを特徴とする。アルミナ質焼結体が測定周波数１ＭＨｚ〜８．５ＧＨｚの間の周波数領域において誘電正接が５×１０−４以下であるため、ＭＨｚ〜ＧＨｚ帯での高周波の透過率を向上でき、エネルギーロスを低減し、発熱による部材の破損を抑制することができる。 The member for a semiconductor manufacturing apparatus, the member for a liquid crystal panel manufacturing apparatus, and the member for a dielectric resonator according to the present invention are made of the above-mentioned alumina sintered body. Since the alumina sintered body has a dielectric loss tangent of 5 × 10 −4 or less in the frequency range between 1 MHz and 8.5 GHz, the high frequency transmittance in the MHz to GHz band can be improved and energy loss is reduced. In addition, damage to the member due to heat generation can be suppressed.
本発明のアルミナ質焼結体では、ＡｌをＡｌ２Ｏ３換算で９９．３質量％以上含有し、アルミナ結晶粒子を主結晶粒子とするため、アルミナ本来の優れた耐腐食性と機械的特性、電気特性を維持することができるとともに、アルミナ結晶粒子で構成される３重点に、元素としてＳｉ、Ａｌ、ＭおよびＯを含有する結晶相または非晶質相が存在するため、例えばＳｒＡｌ２Ｓｉ２Ｏ８等の結晶相が存在する場合には低誘電正接化を促進でき、また、３重点に非晶質相が存在する場合には、焼結体が緻密化されているため、焼結体中の欠陥やボイドを低減し、これにより、低誘電正接化を達成でき、さらには、低誘電正接の結晶相が３重点のうち１０％以上の３重点に存在するため、アルミナ質焼結体の低誘電正接化をさらに図ることができ、測定周波数１ＭＨｚ〜８．５ＧＨｚにおける誘電正接をさらに小さくすることができ、測定周波数１ＭＨｚにおける誘電正接が５×１０−４以下、かつ測定周波数８．５ＧＨｚにおける誘電正接が５×１０−４以下を達成できる。 In the alumina sintered body of the present invention, since Al is contained in an amount of 99.3% by mass or more in terms of Al 2 O 3 and the alumina crystal particles are the main crystal particles, the original excellent corrosion resistance and mechanical properties of alumina. In addition, the electrical characteristics can be maintained, and the crystalline or amorphous phase containing Si, Al, M and O as elements exists at the triple point composed of the alumina crystal particles. For example, SrAl 2 Si When a crystal phase such as 2 O 8 is present, low dielectric loss tangent can be promoted, and when an amorphous phase is present at the triple point, the sintered body is densified, By reducing defects and voids in the body, this can achieve low dielectric loss tangent, and furthermore, the crystalline phase of low dielectric loss tangent exists at the triple point of 10% or more of the triple points, so alumina-based sintering Can further reduce the body's dielectric loss tangent. You can further reduce the dielectric loss tangent at a measuring frequency 1MHz～8.5GHz, dielectric loss tangent 5 × 10 -4 or less at a measuring frequency 1 MHz, and a dielectric loss tangent 5 × 10 -4 or less at a measuring frequency 8.5GHz Can be achieved.
従って、半導体製造装置用部材、液晶パネル製造装置用部材および誘電体共振器用部材として用いられる部材に、本発明のアルミナ質焼結体を用いることにより、反応性の高いハロゲン系腐食ガスやそれらのプラズマに対して、高い耐腐食性を有するとともに、アルミナ質焼結体がＭＨｚ〜ＧＨｚ帯で低損失であるため、ＭＨｚ〜ＧＨｚ帯での高周波の透過率を向上でき、エネルギーロスを低減し、装置全体の低誘電正接化を促すことができる。 Therefore, by using the alumina sintered body of the present invention as a member for a semiconductor manufacturing apparatus member, a liquid crystal panel manufacturing apparatus member and a dielectric resonator member, highly reactive halogen-based corrosive gases and their Since it has high corrosion resistance to plasma and the alumina sintered body has low loss in the MHz to GHz band, it can improve the high frequency transmittance in the MHz to GHz band, reduce energy loss, It is possible to promote low dielectric loss tangent of the entire device.
本発明のアルミナ質焼結体は、ＡｌをＡｌ２Ｏ３換算で９９．３質量％以上、その他の副成分を０．７質量％以下含有する。アルミナを９９．３質量％以上含有し、アルミナ結晶粒子を主結晶粒子とすることにより、焼結性の改善と同時にアルミナの優れた耐腐食性と機械的特性、電気特性を維持することが可能となる。副成分の量が０．７質量％以上となると、機械的・電気的特性の低下、耐食性の低下へと繋がる。よってＡｌをＡｌ２Ｏ３換算で９９．３質量％以上、副成分は０．７質量％以下とするのが好ましい。 The alumina sintered body of the present invention contains Al in an amount of 99.3% by mass or more in terms of Al 2 O 3 and 0.7% by mass or less of other subcomponents. By containing 99.3% by mass of alumina and using alumina crystal particles as the main crystal particles, it is possible to improve the sinterability and maintain the excellent corrosion resistance, mechanical properties, and electrical properties of alumina. It becomes. When the amount of the auxiliary component is 0.7% by mass or more, it leads to a decrease in mechanical / electrical characteristics and a decrease in corrosion resistance. Therefore, it is preferable that Al is 99.3% by mass or more in terms of Al 2 O 3 and the subcomponent is 0.7% by mass or less.
さらに半導体や液晶パネルの製造装置用部材として応用するためには、ハロゲン系ガス下でのプラズマに対する耐食性に優れる必要があるため、ＡｌをＡｌ２Ｏ３換算で９９．５質量％以上、副成分は０．５質量％以下とするのが好ましい。なお、ハロゲン系ガスとしては、例えばＳＦ６、ＣＦ４、ＣＨＦ３、ＣｌＦ３、ＮＦ３、Ｃ４Ｆ８、ＨＦ等のフッ素系ガス、Ｃｌ２、ＨＣｌ、ＢＣｌ３、ＣＣｌ４等の塩素系ガス、或いはＢｒ２、ＨＢｒ、ＢＢｒ３等の臭素系ガスなどがある。また、半導体、液晶パネルなどのエッチング効果を高めるために上記ハロゲン系ガスとともにＡｒ等の不活性ガスを導入してプラズマを発生させることもある。 Furthermore, in order to apply as a member for a semiconductor or liquid crystal panel manufacturing apparatus, it is necessary to have excellent corrosion resistance against plasma under a halogen-based gas. Therefore, Al is 99.5% by mass or more in terms of Al 2 O 3 , and a subsidiary component Is preferably 0.5% by mass or less. Examples of the halogen-based gas include fluorine-based gases such as SF 6 , CF 4 , CHF 3 , ClF 3 , NF 3 , C 4 F 8 , and HF, and chlorine-based gases such as Cl 2 , HCl, BCl 3 , and CCl 4. There is a gas or a bromine-based gas such as Br 2 , HBr, or BBr 3 . In order to enhance the etching effect of semiconductors, liquid crystal panels, etc., plasma may be generated by introducing an inert gas such as Ar together with the halogen-based gas.
アルミナは、焼結性という観点から、９９．９質量％以下であることが望ましい。さらにアルミナ結晶粒子で構成される３重点に、元素としてＳｉ、Ａｌ、Ｍ（Ｍはアルカリ土類金属）およびＯを含有する化合物からなる結晶相、または元素としてＳｉ、Ａｌ、ＭおよびＯを含有する非晶質相が存在する。図１に、アルミナ質焼結体の概略断面図を示す。符号１はアルミナ結晶粒子であり、符号２は、３重点（粒界）である。 Alumina is desirably 99.9% by mass or less from the viewpoint of sinterability. Furthermore, the triple point composed of alumina crystal particles contains a crystal phase composed of a compound containing Si, Al, M (M is an alkaline earth metal) and O as elements, or Si, Al, M and O as elements. An amorphous phase exists. FIG. 1 shows a schematic cross-sectional view of an alumina sintered body. Reference numeral 1 is alumina crystal particles, and reference numeral 2 is a triple point (grain boundary).
本出願において、アルミナ結晶粒子１で構成される３重点２とは、３個以上のアルミナ結晶粒子１で形成される粒界で、２つのアルミナ結晶粒子１で構成される２面間粒界５とは異なる。３重点２は焼結体の任意断面において多数見られるが、多数の３重点２には、元素としてＳｉ、ＡｌおよびＭ（Ｍはアルカリ土類金属）を含有する化合物からなる結晶相、または非晶質相が存在している。また、３重点２には、これらの結晶相または非晶質相が存在しておらず、他の結晶相が存在する場合がある。 In the present application, the triple point 2 constituted by the alumina crystal particles 1 is a grain boundary formed by three or more alumina crystal particles 1, and a two-plane grain boundary 5 constituted by two alumina crystal particles 1. Is different. Many triple points 2 are observed in an arbitrary cross section of the sintered body, but many triple points 2 have a crystal phase composed of a compound containing Si, Al and M (M is an alkaline earth metal) as elements, or non- A crystalline phase is present. Further, in the triple point 2, there is a case where these crystal phases or amorphous phases are not present and other crystal phases are present.
アルミナ結晶粒子１で構成される３重点２に、元素としてＳｉ、Ａｌ、ＭおよびＯを含有する化合物からなる結晶相、例えばＳｒＡｌ２Ｓｉ２Ｏ８等の低誘電正接の結晶相が存在する場合には、結晶相の存在により直接的にＭＨｚ〜ＧＨｚでの低誘電正接化を促進でき、また、３重点に非晶質相が存在する場合には、焼結体が緻密化されているため、焼結体中の欠陥やボイドを低減し、これにより、ＭＨｚでの低誘電正接化を達成できる。 When a crystal phase composed of a compound containing Si, Al, M and O as an element, for example, a low dielectric loss tangent crystal phase such as SrAl 2 Si 2 O 8, is present at the triple point 2 composed of the alumina crystal particles 1 In this case, the low dielectric loss tangent at MHz to GHz can be directly promoted by the presence of the crystalline phase, and when the amorphous phase is present at the triple point, the sintered body is densified. , Defects and voids in the sintered body can be reduced, thereby achieving a low dielectric loss tangent at MHz.
そして、本発明では、焼結体の任意断面において、アルミナ結晶粒子１で構成される３重点２のうち１０％以上の３重点２に、元素としてＳｉ、Ａｌ、ＭおよびＯを含有する化合物からなる結晶相が存在していることが特徴である。アルミナ結晶粒子１で構成される３重点２のうち１０％以上の３重点２に結晶相が存在するとは、任意断面の所定面積において、アルミナ結晶粒子１で構成される多数の３重点２のうちの少なくとも１０％に、Ｓｉ、Ａｌ、ＭおよびＯを含有する化合物からなる結晶相が存在していることを意味する。 And in this invention, in the arbitrary cross section of a sintered compact, it is from the compound containing Si, Al, M, and O as an element in the triple point 2 of 10% or more among the triple points 2 comprised by the alumina crystal particle 1. This is characterized by the presence of a crystalline phase. The crystal phase is present at the triple point 2 of 10% or more of the triple points 2 composed of the alumina crystal particles 1. Of the numerous triple points 2 composed of the alumina crystal particles 1 in a predetermined area of an arbitrary cross section. This means that a crystal phase composed of a compound containing Si, Al, M and O exists in at least 10% of the above.
本発明では、多数の３重点２のうちの少なくとも１０％に、Ｓｉ、Ａｌ、ＭおよびＯを含有する化合物からなる結晶相を存在せしめるために、後述するように、結晶相を構成する原料粉末を混合粉砕し、この混合粉末をアルミナ粉末に添加している。従来のように、アルミナ粉末に、Ｓｉ、ＡｌおよびＭの原料粉末をそれぞれ個別に添加したものでは、アルミナ結晶粒子１の３重点２に、Ｓｉ、ＡｌおよびＭが偏って存在し、非晶質相、あるいは誘電正接の高い結晶相として存在し、Ｓｉ、Ａｌ、ＭおよびＯを含有する化合物からなる結晶相を少しは生成できる可能性はあるものの、本発明のように、多数の３重点２のうちの少なくとも１０％に、Ｓｉ、Ａｌ、ＭおよびＯを含有する結晶相を存在させることができず、アルミナ質焼結体全体の誘電正接を増大させる傾向があった。 In the present invention, since at least 10% of the many triple points 2 has a crystal phase composed of a compound containing Si, Al, M and O, as described later, the raw material powder constituting the crystal phase The mixed powder is added to the alumina powder. In the case where the raw material powders of Si, Al, and M are individually added to the alumina powder as in the prior art, Si, Al, and M are present in a biased manner at the triple point 2 of the alumina crystal particles 1 and are amorphous. Although there is a possibility that a crystal phase composed of a compound containing Si, Al, M and O exists slightly as a phase or a crystal phase having a high dielectric loss tangent, as in the present invention, a large number of triple points 2 At least 10% of them could not have a crystal phase containing Si, Al, M and O, and there was a tendency to increase the dielectric loss tangent of the entire alumina sintered body.
このように、低誘電正接の結晶相が３重点２のうち１０％以上の３重点２に存在するため、アルミナ質焼結体の低誘電正接化を図ることができる。１ＭＨｚ〜８．５ＧＨｚの間の周波数領域において誘電正接を低下させるためには、低誘電正接のＳｉ、Ａｌ、ＭおよびＯを含有する結晶相が存在する粒界３重点２の比率は２０％以上が好ましい。また、低誘電正接の結晶相が存在する粒界３重点２の比率は６０％未満とされている。 Thus, since the low dielectric loss tangent crystal phase is present at the triple point 2 of 10% or more of the triple points 2, the alumina sintered body can be made to have a low dielectric loss tangent. In order to lower the dielectric loss tangent in the frequency region between 1 MHz and 8.5 GHz, the ratio of the grain boundary triple point 2 where the crystal phase containing Si, Al, M and O of low dielectric loss tangent is 20% or more. Is preferred. Further, the ratio of the grain boundary triple point 2 where the crystal phase of low dielectric loss tangent exists is less than 60%.
また、本発明では、アルミナ結晶粒子１で構成される３重点２で、上記結晶相が存在していない３重点２には、元素としてＳｉ、Ａｌ、ＭおよびＯを含有する非晶質相が存在している場合がある。この非晶質相が存在する３重点２は、任意断面の所定面積において９０％以下、特には８０％以下であることが望ましい。上記したように、非晶質相の存在により焼結体の緻密性を向上できるが、非晶質相自体は誘電正接を高くするため、少ない方が望ましい。 In the present invention, the triple point 2 composed of the alumina crystal particles 1 and the triple point 2 where the crystal phase does not exist has an amorphous phase containing Si, Al, M and O as elements. May exist. The triple point 2 where the amorphous phase exists is desirably 90% or less, particularly 80% or less in a predetermined area of an arbitrary cross section. As described above, the denseness of the sintered body can be improved by the presence of the amorphous phase, but the amorphous phase itself increases the dielectric loss tangent.
Ｓｉ、Ａｌ、Ｍ（Ｍはアルカリ土類金属）およびＯ元素を含有する化合物からなる低損失の結晶相は、電気的特性の観点より、ＭＡｌ２Ｓｉ２Ｏ８型結晶（Ｍはアルカリ土類金属）であることが好ましく、この結晶の生成により誘電正接を低減できる。Ｓｉ、Ａｌ、Ｍ（Ｍはアルカリ土類金属）およびＯ元素を含有する化合物からなる低損失の結晶相としては、他に、ＭＡｌ２Ｓｉ２Ｏ８の定比組成ではなく、化学量論組成から少しずれたものであっても良い。 From the viewpoint of electrical characteristics, a low-loss crystal phase composed of a compound containing Si, Al, M (M is an alkaline earth metal) and an O element is an MAl 2 Si 2 O 8 type crystal (M is an alkaline earth). Metal), and the generation of this crystal can reduce the dielectric loss tangent. As a low-loss crystal phase composed of a compound containing Si, Al, M (M is an alkaline earth metal) and an O element, other than the stoichiometric composition of MAl 2 Si 2 O 8 , stoichiometric composition It may be a little off.
アルカリ土類金属としては、Ｍｇ、Ｃａ、Ｓｒ、Ｂａなどがあるが、誘電特性、焼結性の観点からＭｇ、Ｃａ、Ｓｒが好ましい。中でも、とりわけ低誘電正接の観点から、Ｓｒが好ましい。 Examples of the alkaline earth metal include Mg, Ca, Sr, and Ba, and Mg, Ca, and Sr are preferable from the viewpoints of dielectric properties and sinterability. Among these, Sr is particularly preferable from the viewpoint of low dielectric loss tangent.
従来、Ｍｇ、Ｃａ等のアルカリ土類金属が焼結助剤として知られていたが、アルカリ土類金属のうち、Ｓｒ、Ｂａについてはイオン半径が大きいため、焼結助剤として用いられておらず、特に、Ｓｒについては、積極的に使用した例は存在しない。本発明では、特にＳｒについては、焼結助剤として用いるのではなく、低誘電正接の結晶相であるＳｒＡｌ２Ｓｉ２Ｏ８の結晶相を析出させるために用い、その低誘電正接の結晶相の存在により直接的にアルミナ質焼結体の誘電正接を低くできる。 Conventionally, alkaline earth metals such as Mg and Ca have been known as sintering aids, but among alkaline earth metals, Sr and Ba are not used as sintering aids because of their large ionic radii. In particular, there is no example of positive use of Sr. In the present invention, in particular, Sr is not used as a sintering aid, but is used for precipitating a crystal phase of SrAl 2 Si 2 O 8 , which is a low dielectric loss tangent crystal phase. Therefore, the dielectric loss tangent of the alumina sintered body can be lowered directly.
尚、本発明において、ＭＡｌ２Ｓｉ２Ｏ８型結晶で表される化合物とは、Ｍの構成元素の一部が他の元素で置換されたものであっても良い。 In the present invention, the compound represented by the MAl 2 Si 2 O 8 type crystal may be one in which a part of the constituent element of M is substituted with another element.
本発明のアルミナ質焼結体では、測定周波数１ＭＨｚの誘電正接を５×１０−４以下で、測定周波数８．５ＧＨｚの誘電正接を５×１０−４以下とすることにより、測定周波数１ＭＨｚ〜８．５ＧＨｚの間の周波数領域においても誘電正接が５×１０−４以下を見込むことができる。上記周波数範囲において、より低誘電正接の２×１０−４以下を見込むという観点から、測定周波数１ＭＨｚの誘電正接を２×１０−４以下で、８．５ＧＨｚの誘電正接を２×１０−４以下とすることが好ましい。 In the alumina sintered body of the present invention, the measurement frequency is 1 MHz to 8 by setting the dielectric loss tangent at a measurement frequency of 1 MHz to 5 × 10 −4 or less and the dielectric loss tangent at a measurement frequency of 8.5 GHz to 5 × 10 −4 or less. Even in the frequency region between 5 GHz, the dielectric loss tangent can be expected to be 5 × 10 −4 or less. From the viewpoint of expecting a lower dielectric loss tangent of 2 × 10 −4 or lower in the above frequency range, the dielectric loss tangent of the measurement frequency 1 MHz is 2 × 10 −4 or lower and the dielectric loss tangent of 8.5 GHz is 2 × 10 −4 or lower. It is preferable that
すなわち、アルミナ質焼結体の誘電正接を１ＭＨｚの周波数で測定し、５×１０−４以下を確認することにより空間電荷分極、界面分極、双極子分極による誘電正接の増大が殆ど無いことを確認できる。しかもこれらの要因による誘電正接の増大によるピークは１ＭＨｚより低い周波数帯か、または近傍の数ＭＨｚの周波数にあるため、１ＭＨｚで５×１０−４以下を確認することにより１ＧＨｚ付近まではこれらの要因による誘電正接の増大は殆ど無いことを見込める。 That is, the dielectric loss tangent of the alumina sintered body is measured at a frequency of 1 MHz, and it is confirmed that there is almost no increase in the dielectric loss tangent due to space charge polarization, interface polarization, and dipole polarization by confirming that it is 5 × 10 −4 or less. it can. Moreover, since the peak due to the increase in the dielectric loss tangent due to these factors is in a frequency band lower than 1 MHz or in the vicinity of several MHz, these factors are observed up to around 1 GHz by confirming 5 × 10 −4 or less at 1 MHz. It is expected that there is almost no increase in the dielectric loss tangent due to.
また、８．５ＧＨｚで誘電正接が５×１０−４以下を確認することによりイオン分極による誘電正接の増大が無いことを確認できる。しかも、イオン分極による誘電正接の増大によるピークは８．５ＧＨｚより高い周波数帯または、近傍の数ＧＨｚの周波数で起こっており、８．５ＧＨｚで５×１０−４以下を確認することにより１ＧＨｚ付近まではイオン分極の要因による誘電正接の増大は無いことを見込める。 Further, by confirming that the dielectric loss tangent is 8.5 × 10 −4 or less at 8.5 GHz, it can be confirmed that there is no increase in dielectric loss tangent due to ion polarization. Moreover, the peak due to the increase of the dielectric loss tangent due to ion polarization occurs in a frequency band higher than 8.5 GHz or a frequency of several GHz nearby, and by confirming a frequency of 5 × 10 −4 or less at 8.5 GHz, it reaches about 1 GHz. Can be expected not to increase the dielectric loss tangent due to the factor of ion polarization.
よって、１ＭＨｚで５×１０−４以下、８．５ＧＨｚで５×１０−４以下を確認することによって、１ＭＨｚ〜８．５ＧＨｚの間、特には、１０ＭＨｚ〜１ＧＨｚの間の周波数領域においても誘電正接が５×１０−４以下を見込むことができる。 Therefore, by confirming 5 × 10 −4 or less at 1 MHz and 5 × 10 −4 or less at 8.5 GHz, the dielectric loss tangent is also in the frequency region between 1 MHz and 8.5 GHz, particularly between 10 MHz and 1 GHz. Can be expected to be 5 × 10 −4 or less.
また、本発明のアルミナ質焼結体は、さらにＭｇＡｌ２Ｏ４およびＣａＡｌ１２Ｏ１９で表される化合物からなる結晶相のうち少なくとも一種を含有することが望ましい。これら結晶相を生成させることで、誘電正接を高くする非晶質相を減少させることができ、１ＭＨｚ〜８．５ＧＨｚの領域において誘電正接を低下させることができる。特にＭｇＡｌ２Ｏ４、ＣａＡｌ１２Ｏ１９は、ＧＨｚ帯での誘電正接が低いため、アルミナ質焼結体のＧＨｚ帯の誘電正接低下に有効である。 Moreover, it is desirable that the alumina sintered body of the present invention further contains at least one of crystal phases composed of compounds represented by MgAl 2 O 4 and CaAl 12 O 19 . By generating these crystal phases, the amorphous phase that increases the dielectric loss tangent can be reduced, and the dielectric loss tangent can be lowered in the region of 1 MHz to 8.5 GHz. In particular, MgAl 2 O 4 and CaAl 12 O 19 have a low dielectric loss tangent in the GHz band, and are therefore effective in reducing the dielectric loss tangent in the GHz band of an alumina sintered body.
さらに本発明のアルミナ質焼結体はアルミナ結晶粒子の平均粒径Ｄ５０が２５μｍ以上であることが望ましい。これにより、誘電正接を安定して低減できる。低誘電正接をより安定させるという観点から、アルミナ結晶粒子の平均粒径Ｄ５０は４０μｍ以上が好ましい。アルミナ結晶粒子の平均粒径Ｄ５０は、機械的特性という観点から、７０μｍ以下であることが望ましい。尚、平均粒径Ｄ５０とは、累積粒度分布の微粒側から累積５０％の粒径をいう。 Further alumina sintered body of the present invention is preferably an average particle diameter D 50 of the alumina crystal particles is 25μm or more. Thereby, the dielectric loss tangent can be stably reduced. From the viewpoint of more stable low dielectric loss tangent, the average particle diameter D 50 of the alumina crystal particles is preferably at least 40 [mu] m. The average particle diameter D 50 of the alumina crystal particles, from the viewpoint of mechanical properties, is desirably 70μm or less. Incidentally, the average particle diameter D 50, refers to the particle size of cumulative 50% fine particle side of the cumulative particle size distribution.
本発明のアルミナ質焼結体は、産業機械用部品として用いられ、とりわけ半導体製造装置や液晶製造装置に用いられる大型で、厚みのある部材として好適に用いることができる。本発明における半導体製造装置用部材とは、半導体製造装置の内壁材（チャンバー）やマイクロ波導入窓、シャワーヘッド、フォーカスリング、シールドリング等をいう。液晶パネル製造装置用部材とは、ステージ、ミラー、マスクホルダー、マスクステージ、チャック、レチクル等をいう。 The alumina-based sintered body of the present invention is used as a part for industrial machinery, and can be suitably used as a large and thick member used particularly for a semiconductor manufacturing apparatus or a liquid crystal manufacturing apparatus. The member for a semiconductor manufacturing apparatus in the present invention means an inner wall material (chamber), a microwave introduction window, a shower head, a focus ring, a shield ring, or the like of the semiconductor manufacturing apparatus. A member for a liquid crystal panel manufacturing apparatus refers to a stage, a mirror, a mask holder, a mask stage, a chuck, a reticle, and the like.
さらに本発明のアルミナ質焼結体は、マイクロ波やミリ波等の高周波領域において、誘電体共振器、ＭＩＣ用誘電体基板や導波路等としても用いられる。特に種々の誘電体共振器の支持体として好適に使用できる。 Furthermore, the alumina sintered body of the present invention is also used as a dielectric resonator, a dielectric substrate for MIC, a waveguide or the like in a high frequency region such as a microwave or a millimeter wave. In particular, it can be suitably used as a support for various dielectric resonators.
本発明のアルミナ質焼結体の製法は、例えば、Ｓｉ源とアルカリ土類金属源とをあらかじめＭＡｌ２Ｓｉ２Ｏ８型結晶を生成する組成比で秤量し混合した原料粉末を作製し、この原料粉末をアルミナ粉末に添加し、成形したのち、１５００〜１８００℃で焼成する。 The method for producing an alumina sintered body of the present invention is, for example, by preparing a raw material powder in which a Si source and an alkaline earth metal source are weighed and mixed in advance at a composition ratio for generating MAl 2 Si 2 O 8 type crystals, The raw material powder is added to the alumina powder, molded, and then fired at 1500 to 1800 ° C.
アルカリ土類金属源とＳｉ源とを混合した原料粉末とは、Ｓｉ源とアルカリ土類金属源をＭＡｌ２Ｓｉ２Ｏ８型結晶を生成する所定の比率で秤量し、例えば専用の容器で乾式混合して得られる粉末である。ここでいうＳｉ源、アルカリ土類金属源としては、金属、酸化物、水酸化物、炭酸塩、硝酸塩等の塩類のいずれであっても良い。Ｓｉとアルカリ土類金属の混合した混合粉末を用いることで、アルミナ質焼結体中でのＳｉとアルカリ土類金属の分布を均一なものとし、ＭＡｌ２Ｓｉ２Ｏ８型結晶の生成を促進し、不均一な焼結組織を抑制することが可能となる。 The raw material powder obtained by mixing the alkaline earth metal source and the Si source is obtained by weighing the Si source and the alkaline earth metal source at a predetermined ratio for generating MAl 2 Si 2 O 8 type crystals, It is a powder obtained by mixing. The Si source and alkaline earth metal source here may be any of salts such as metals, oxides, hydroxides, carbonates, nitrates and the like. By using a mixed powder of Si and alkaline earth metal mixed, the distribution of Si and alkaline earth metal in the alumina sintered body is made uniform, and the generation of MAl 2 Si 2 O 8 type crystals is promoted. In addition, a non-uniform sintered structure can be suppressed.
ＭＡｌ２Ｓｉ２Ｏ８型結晶を生成する組成比で混合したＳｉ源とアルカリ土類金属源との混合粉末を用いることにより、Ｓｉとアルカリ土類金属との反応を優先的に起こし、アルミナ結晶粒子間にＳｉとアルカリ土類金属、Ａｌ、Ｏ元素からなる誘電正接の低い結晶、例えばＭＡｌ２Ｓｉ２Ｏ８型結晶を、アルミナ結晶粒子で構成される３重点のうち１０％以上の３重点に存在させることが可能となる。Ｓｉとアルカリ土類金属の分布が不均一であると、非晶質相が多く生成したり、あるいは高誘電正接の結晶相が生成し、アルミナ質焼結体全体の誘電正接が増大する原因となる。また、ＭＡｌ２Ｓｉ２Ｏ８型結晶を生成する組成比で混合したＳｉ源とアルカリ土類金属源との混合粉末を仮焼する場合よりも、工程数を削減でき、低コスト化を図ることができる。 By using a mixed powder of a Si source and an alkaline earth metal source mixed at a composition ratio that generates MAl 2 Si 2 O 8 type crystals, a reaction between Si and the alkaline earth metal is preferentially caused to produce alumina crystals. A crystal having a low dielectric loss tangent composed of Si, an alkaline earth metal, Al, and an O element, for example, MAl 2 Si 2 O 8 type crystal, between the particles, a triple point of 10% or more of the three points composed of alumina crystal particles It is possible to exist in If the distribution of Si and alkaline earth metal is not uniform, a large amount of amorphous phase is formed, or a crystalline phase with a high dielectric loss tangent is generated, which increases the dielectric loss tangent of the entire alumina sintered body. Become. In addition, the number of processes can be reduced and the cost can be reduced as compared with the case of calcining a mixed powder of an Si source and an alkaline earth metal source mixed at a composition ratio that generates MAl 2 Si 2 O 8 type crystals. Can do.
アルミナ粉末に、上記アルカリ土類金属源とＳｉ源とを混合した混合粉末と、Ｍｇ源を含む原料粉末とを混合し、焼成する場合もある。Ｍｇ源としては、金属、金属酸化物、金属水酸化物、金属炭酸塩などの塩類等を粉末あるいは水溶液等として使用することが可能である。さらに、アルカリ土類金属源とＳｉ源とＭｇ源とを含む混合粉末を作製し、この混合粉末をアルミナ粉末に添加し、成形し、焼成しても良い。 A mixed powder obtained by mixing the alkaline earth metal source and the Si source with the alumina powder and a raw material powder containing the Mg source may be mixed and fired. As the Mg source, it is possible to use salts such as metals, metal oxides, metal hydroxides, and metal carbonates as powders or aqueous solutions. Furthermore, a mixed powder containing an alkaline earth metal source, a Si source, and a Mg source may be produced, and this mixed powder may be added to an alumina powder, molded, and fired.
成形には、プレス成形、鋳込み、冷間静水圧成形、或いは冷間静水圧処理などの成形法が使用可能である。次に、得られた成形体を１５００〜１８００℃の温度範囲で焼成する。これにより高密度で、アルミナ結晶粒子の粒界にＳｉとアルカリ土類金属、Ａｌ、Ｏ元素を含有する化合物からなる結晶相が生成した焼結体を作製する。 For molding, a molding method such as press molding, casting, cold isostatic pressing, or cold isostatic pressing can be used. Next, the obtained molded body is fired in a temperature range of 1500 to 1800 ° C. As a result, a sintered body having a high density and a crystal phase made of a compound containing Si, an alkaline earth metal, Al, and an O element is produced at the grain boundaries of the alumina crystal particles.
次に、焼結体を測定周波数１ＭＨｚと８．５ＧＨｚで誘電正接を測定し、１ＭＨｚで５×１０−４以下、８．５ＧＨｚで５×１０−４以下とするものを良品として使うことにより、測定周波数１ＭＨｚ〜８．５ＧＨｚの間の周波数領域においても誘電正接が５×１０−４以下を見込むことができる。これにより、誘電正接に関して高精度なキャパシタンスメータ（ヒューレットパッカード社製：ＨＰ−４２７８Ａ）とネットワークアナライザ（アジレント・テクノロジー社製：８７２２ＥＳ）を使用することができ、従来のインピーダンスアナライザでは保障できない１ＭＨｚ〜８．５ＧＨｚ帯における低誘電正接材料の設計が可能となる。ネットワークアナライザによる測定周波数は８．５ＧＨｚから多少ずれることがある。 Next, the sintered body a dielectric loss tangent were measured at a measuring frequency of 1MHz and 8.5 GHz, 1MHz at 5 × 10 -4 or less, by using non-defective ones to be 5 × 10 -4 or less at 8.5 GHz, The dielectric loss tangent can be expected to be 5 × 10 −4 or less even in the frequency region between the measurement frequencies of 1 MHz to 8.5 GHz. As a result, it is possible to use a highly accurate capacitance meter (Hewlett Packard: HP-4278A) and network analyzer (Agilent Technology: 8722ES) with respect to the dielectric loss tangent, and 1 MHz to 8 which cannot be guaranteed by a conventional impedance analyzer. It is possible to design a low dielectric loss tangent material in the 5 GHz band. The frequency measured by the network analyzer may deviate somewhat from 8.5 GHz.
すなわち、従来、測定周波数１ＭＨｚにおける誘電正接は、キャパシタンス・メータ（ＨＰ−４２７８Ａ）、測定周波数８．５ＧＨｚにおける誘電正接は、空洞共振器法（ネットワーク・アナライザ ８７２２ＥＳ）を用いて測定を行ない、測定誤差がそれぞれ±２×１０−４以下、±０．１×１０−４以下の精度の良い誘電正接が得られることが知られているが、半導体、液晶パネル製造装置用部材に要求される１ＭＨｚ〜８．５ＧＨｚ、特に１０ＭＨｚ〜１ＧＨｚにおける周波数領域では、インピーダンスアナライザ（ヒューレットパッカード社製：ＨＰ−４２９１Ａ）による測定しかなく、その測定誤差は小さくても±３０×１０−４程度であり、５×１０−４以下の誘電正接については測定精度が極めて低い。 That is, conventionally, the dielectric loss tangent at a measurement frequency of 1 MHz is measured using a capacitance meter (HP-4278A), and the dielectric loss tangent at a measurement frequency of 8.5 GHz is measured using a cavity resonator method (network analyzer 8722ES). Are known to obtain accurate dielectric loss tangents of ± 2 × 10 −4 or less and ± 0.1 × 10 −4 or less, respectively, but from 1 MHz required for semiconductor and liquid crystal panel manufacturing apparatus members In the frequency region of 8.5 GHz, particularly 10 MHz to 1 GHz, there is only measurement using an impedance analyzer (HP-4291A, manufactured by Hewlett-Packard Company), and the measurement error is about ± 30 × 10 −4 even if it is small, 5 × 10 Measurement accuracy is very low for dielectric loss tangent of -4 or less.
そこで、１ＭＨｚ〜８．５ＧＨｚにおける周波数領域の誘電損失を、測定精度の低いインピーダンスアナライザで直接測定することなく、測定周波数１ＭＨｚと８．５ＧＨｚにおける誘電正接を間接的に測定し、測定周波数１ＭＨｚと８．５ＧＨｚにおける誘電正接が５×１０−４以下の範囲にある場合には、測定周波数１ＭＨｚ〜８．５ＧＨｚ、特には１０〜１００ＭＨｚの間の周波数領域においても誘電正接を５×１０−４以下と推定でき、測定周波数１ＭＨｚ〜８．５ＧＨｚにおける誘電正接を容易にかつ正確に推定できる。 Therefore, the dielectric loss tangent at the measurement frequency of 1 MHz and 8.5 GHz is indirectly measured without directly measuring the dielectric loss in the frequency domain from 1 MHz to 8.5 GHz with an impedance analyzer with low measurement accuracy, and the measurement frequencies of 1 MHz and 8 are measured. If the dielectric loss tangent at .5GHz is in the range of 5 × 10 -4 or less, measurement frequency 1MHz～8.5GHz, particularly a 5 × 10 -4 or less dielectric loss tangent in the frequency region between 10~100MHz The dielectric loss tangent at the measurement frequency of 1 MHz to 8.5 GHz can be estimated easily and accurately.
まず、ＳｉＯ２とＳｒＣＯ３、ＣａＣＯ３、ＢａＣＯ３との粉末を、ＭＡｌ２Ｓｉ２Ｏ８型結晶を生成するように秤量し、乾式混合して原料粉末を得た。 First, powders of SiO 2 , SrCO 3 , CaCO 3 , and BaCO 3 were weighed so as to produce MAl 2 Si 2 O 8 type crystals, and dry-mixed to obtain a raw material powder.
純度が９９．９５％のＡｌ２Ｏ３粉末に、前記原料粉末と、Ｍｇ（ＯＨ）２粉末とを添加し、これに所定量の水を加えアルミナボールミルにて４８時間混合してスラリーとした。このスラリーにバインダーを加えて乾燥したのち、造粒し、これを１ｔ／ｃｍ２の圧力で金型成形して円柱状成形体（直径６０ｍｍ×高さ３０ｍｍ）を作製し、大気中において１６７０℃の温度で焼成を行ない、直径５０ｍｍ×高さ２５ｍｍのアルミナ質焼結体を得た。 The raw material powder and Mg (OH) 2 powder are added to 99.95% pure Al 2 O 3 powder, and a predetermined amount of water is added thereto and mixed in an alumina ball mill for 48 hours to form a slurry. . The slurry was added to the slurry, dried, granulated, and molded with a pressure of 1 t / cm 2 to produce a cylindrical molded body (diameter 60 mm × height 30 mm), and 1670 ° C. in the atmosphere. The alumina sintered body having a diameter of 50 mm and a height of 25 mm was obtained.
尚、試料Ｎｏ．１は、純度が９９．９５％のＡｌ２Ｏ３粉末に、ＳｉＯ２粉末、ＳｒＣＯ３粉末、ＣａＣＯ３粉末、Ｍｇ（ＯＨ）２粉末をそれぞれ別個に添加し、これに所定量の水を加えボールミルにて４８時間混合してスラリーとした。このスラリーにバインダーを加えて乾燥したのち、造粒し、これを１ｔ／ｃｍ２の圧力で金型成形して成形体（直径６０ｍｍ×高さ３０ｍｍ）を作製し、大気中にて１６７０℃の温度で焼成を行なった。 Sample No. In No. 1, SiO 2 powder, SrCO 3 powder, CaCO 3 powder, and Mg (OH) 2 powder are separately added to 99.95% pure Al 2 O 3 powder, and a predetermined amount of water is added thereto. The mixture was mixed with a ball mill for 48 hours to form a slurry. The slurry was added to the slurry, dried, granulated, and molded with a pressure of 1 t / cm 2 to produce a molded body (diameter 60 mm × height 30 mm). Firing was performed at temperature.
また、試料Ｎｏ．１４は、純度が９９．９５％のＡｌ２Ｏ３粉末に、ＳｉＯ２粉末、ＣａＣＯ３粉末、Ｍｇ（ＯＨ）２粉末をそれぞれ別個に添加し、これに所定量の水を加えボールミルにて４８時間混合してスラリーとした。このスラリーにバインダーを加えて乾燥したのち、造粒し、この混合粉末を１ｔ／ｃｍ２の圧力で金型成形して成形体（直径６０ｍｍ×高さ３０ｍｍ）を作製し、大気中において１６７０℃の温度で焼成を行なった。 Sample No. In No. 14, SiO 2 powder, CaCO 3 powder, and Mg (OH) 2 powder were separately added to 99.95% pure Al 2 O 3 powder, and a predetermined amount of water was added thereto, and then 48 Mix for a time to make a slurry. The slurry is added to the slurry, dried, granulated, and the mixed powder is molded at a pressure of 1 t / cm 2 to produce a molded body (diameter 60 mm × height 30 mm). Firing was performed at a temperature of.
このアルミナ質焼結体の元素の定量分析を、ＩＣＰ発光分光分析にて行い、表１に、ＡｌをＡｌ２Ｏ３換算、ＳｉをＳｉＯ２換算で、ＳｒをＳｒＯ換算、ＭｇをＭｇＯ換算で、ＣａをＣａＯ換算で、ＢａをＢａＯ換算で記載した。尚、Ａｌ、Ｓｉ、Ｓｒ、Ｍｇ、Ｃａ、Ｂａ以外の元素を残部とし、その量も記載した。残部は、主にＮａ２Ｏと、Ｆｅ２Ｏ３であった。また、Ｘ線回折測定により全試料はアルミナ結晶粒子を主成分とすることを確認した。さらに、ＭｇＡｌ２Ｏ４、ＣａＡｌ１２Ｏ１９で表される化合物からなる結晶相の有無について、Ｘ線回折測定により確認し、表１に記載した。 Quantitative analysis of the elements of this alumina sintered body is performed by ICP emission spectroscopic analysis. In Table 1, Al is converted to Al 2 O 3 , Si is converted to SiO 2 , Sr is converted to SrO, and Mg is converted to MgO. , Ca is described in terms of CaO, and Ba is described in terms of BaO. In addition, elements other than Al, Si, Sr, Mg, Ca, and Ba are used as the balance, and their amounts are also described. The balance was mainly Na 2 O and Fe 2 O 3 . Further, it was confirmed by X-ray diffraction measurement that all the samples were mainly composed of alumina crystal particles. Further, the presence or absence of a crystal phase composed of compounds represented by MgAl 2 O 4 and CaAl 12 O 19 was confirmed by X-ray diffraction measurement and listed in Table 1.
得られた焼結体の高さ方向中央部から厚み１ｍｍの試料を切り出して、密度、誘電正接を測定し、表２に記載した。密度はアルキメデス法にて測定した。 A sample having a thickness of 1 mm was cut out from the center in the height direction of the obtained sintered body, and the density and dielectric loss tangent were measured. The density was measured by the Archimedes method.
また、誘電正接ｔａｎδは、１ＭＨｚ、１２ＭＨｚ、８．５ＧＨｚにて行ない、それぞれキャパシタンス・メータ（ＨＰ−４２７８Ａ）、インピーダンスアナライザ（ＨＰ−４２９１Ａ）、空洞共振器法（ネットワークアナライザ ８７２２ＥＳ）を用いて測定を行なった。キャパシタンス・メータの測定誤差は±２×１０−４以下であり、空洞共振器法の測定誤差は±０．１×１０−４以下であるものの、インピーダンスアナライザの測定誤差は±３０×１０−４であるため、インピーダンスアナライザによる１２ＭＨｚの誘電正接が５×１０−４未満の場合には、＜５と表１に記載した。 The dielectric loss tangent tan δ is measured at 1 MHz, 12 MHz, and 8.5 GHz, and measured using a capacitance meter (HP-4278A), impedance analyzer (HP-4291A), and cavity resonator method (network analyzer 8722ES), respectively. I did it. Although the measurement error of the capacitance meter is ± 2 × 10 −4 or less and the measurement error of the cavity resonator method is ± 0.1 × 10 −4 or less, the measurement error of the impedance analyzer is ± 30 × 10 −4. Therefore, when the 12 MHz dielectric loss tangent by the impedance analyzer is less than 5 × 10 −4 , it is described in Table 1 as <5.
尚、インピーダンスアナライザにより、１ＭＨｚ〜１ＧＨｚにおける誘電正接の周波数依存性も確認した。その結果、今回のサンプルにおいて装置の精度上１ＭＨｚ〜１ＧＨｚにおける誘電正接は、１〜１０ＭＨｚと１００ＭＨｚ〜１ＧＨｚにおける誘電正接が高く、その間の周波数帯で低いという傾向があり、特に１０〜１００ＭＨｚにおける誘電正接が低いという傾向があった。また、１０〜１００ＭＨｚの周波数帯で誘電正接にピークはみられず、フラットな形状であった。 In addition, the frequency dependence of the dielectric loss tangent at 1 MHz to 1 GHz was also confirmed by an impedance analyzer. As a result, the dielectric loss tangent at 1 MHz to 1 GHz in this sample tends to be high at 1 to 10 MHz and 100 MHz to 1 GHz and low in the frequency band between them, particularly at 10 to 100 MHz. Tended to be low. Moreover, no peak was observed in the dielectric loss tangent in the frequency band of 10 to 100 MHz, and the shape was flat.
先ず、ネットワークアナライザを用い、直径５０ｍｍ×厚み１ｍｍの試料を治具にて挟持し、８．５ＧＨｚにおける誘電正接を求め、次に、インピーダンスアナライザを用い、上記直径５０ｍｍ×厚み１ｍｍの試料を治具にて挟持し、１２ＭＨｚにおける誘電正接を求め、この後、ＪＩＳ Ｃ２１４１に基づき、上記直径５０ｍｍ×厚み１ｍｍの試料の上下面に電極を形成し、キャパシタンス・メータにて１ＭＨｚにおける誘電正接を求めた。 First, using a network analyzer, a sample having a diameter of 50 mm × thickness of 1 mm is sandwiched by a jig to obtain a dielectric loss tangent at 8.5 GHz. Next, using an impedance analyzer, the sample having a diameter of 50 mm × thickness of 1 mm is fixed to the jig. Then, the dielectric loss tangent at 12 MHz was obtained. After that, electrodes were formed on the upper and lower surfaces of the sample having a diameter of 50 mm and a thickness of 1 mm based on JIS C2141, and the dielectric loss tangent at 1 MHz was obtained with a capacitance meter.
また、各焼結体中の結晶相の分析は、透過型電子顕微鏡（ＴＥＭ）を用いて、エネルギー分散型Ｘ線分光分析（ＥＤＳ）と制限視野電子線回折により行ない、Ｓｉ、Ａｌ、Ｍ（Ｍ＝Ｃａ、Ｓｒ、Ｂａ）、Ｏ元素を含む化合物からなる低損失の結晶相である、ＭＡｌ２Ｓｉ２Ｏ８の有無について粒界３重点を１試料について３０箇所確認し、ＭＡｌ２Ｓｉ２Ｏ８型結晶相の発生割合と、非晶質相の発生割合を表２に記載した。尚、制限視野電子線回折により非晶質相か否かを確認した。図２に、試料Ｎｏ．１２の電子回折像を示した。 Moreover, the analysis of the crystal phase in each sintered body is performed by energy dispersive X-ray spectroscopy (EDS) and limited-field electron diffraction using a transmission electron microscope (TEM), and Si, Al, M ( M = Ca, Sr, Ba), a low-loss crystal phase composed of a compound containing an O element, and the presence or absence of MAl 2 Si 2 O 8 , 30 grain boundaries were confirmed at 30 points per sample, and MAl 2 Si 2 Table 2 shows the generation ratio of the O 8 type crystal phase and the generation ratio of the amorphous phase. In addition, it was confirmed by the limited visual field electron diffraction whether it was an amorphous phase. In FIG. 12 electron diffraction images were shown.
さらに、アルミナ結晶粒子の平均粒径Ｄ５０は、上記試料の走査型電子顕微鏡写真（５００倍）について、０．０４３２ｍｍ２の範囲で、画像解析装置にて各結晶粒子の直径を求め、平均粒径Ｄ５０を算出し、表２に記載した。 Further, the average particle diameter D 50 of the alumina crystal particles, the scanning electron micrograph of the sample (500 fold) in the range of 0.0432Mm 2, determine the diameter of each crystal grain in an image analyzer, the average particle calculating the diameter D 50, as described in Table 2.
表１、２より、アルミナ結晶粒子で構成される３重点に、Ｓｉ、Ａｌ、Ｍ、Ｏ元素を含む化合物からなる結晶相または非晶質相が生成し、アルミナ結晶粒子で構成される３重点のうち１０％以上の３重点に、元素としてＳｉ、Ａｌ、ＭおよびＯを含有する結晶相が存在する本発明の試料では、誘電正接が８．５ＧＨｚにおいて２．３×１０−４以下であるとともに、１ＭＨｚにおいて２×１０−４以下の場合には、１２ＭＨｚにおいても５×１０−４以下の低損失であることがわかる。 From Tables 1 and 2, the triple point composed of alumina crystal particles is produced by the formation of a crystal phase or an amorphous phase composed of a compound containing Si, Al, M, and O elements. In the sample of the present invention in which a crystal phase containing Si, Al, M and O as elements is present at the triple point of 10% or more, the dielectric loss tangent is 2.3 × 10 −4 or less at 8.5 GHz. In addition, in the case of 2 × 10 −4 or less at 1 MHz, it is found that the loss is 5 × 10 −4 or less even at 12 MHz.
一方、ＳｉＯ２粉末、ＳｒＣＯ３粉末、ＣａＣＯ３粉末、Ｍｇ（ＯＨ）２粉末をそれぞれ別個にアルミナ粉末に添加した試料Ｎｏ．１では、Ｓｉ、Ａｌ、ＭおよびＯを含有する結晶相が存在する３重点の割合が３％と少なく、８．５ＧＨｚおよび１ＭＨｚにおける誘電正接が大きいことがわかる。 On the other hand, Sample No. 2 was prepared by separately adding SiO 2 powder, SrCO 3 powder, CaCO 3 powder, and Mg (OH) 2 powder to the alumina powder. 1 shows that the ratio of the triple point where the crystal phase containing Si, Al, M and O exists is as small as 3%, and the dielectric loss tangent at 8.5 GHz and 1 MHz is large.
また、ＳｉＯ２粉末、ＣａＣＯ３粉末、Ｍｇ（ＯＨ）２粉末をそれぞれ別個にアルミナ粉末に添加した試料Ｎｏ．１４では、酸化アルミニウム結晶粒子の３重点にＳｉとＣａ、Ａｌ、Ｏ元素からなる結晶相が存在するものの、該結晶相が存在する３重点は３％と少なく、８．５ＧＨｚでは１．４×１０−４以下と低損失であったが、１ＭＨｚにおいて４０×１０−４、１２ＭＨｚにおいて７×１０−４と高く、ＭＨｚ帯において誘電損失が高かった。 In addition, sample No. 1 in which SiO 2 powder, CaCO 3 powder, and Mg (OH) 2 powder were separately added to the alumina powder. 14, although the crystal phase composed of Si, Ca, Al, and O element exists at the triple point of the aluminum oxide crystal particles, the triple point where the crystal phase exists is as low as 3%, and 1.4 × at 8.5 GHz. Although the loss was as low as 10 −4 or less, it was as high as 40 × 10 −4 at 1 MHz and 7 × 10 −4 at 12 MHz, and the dielectric loss was high in the MHz band.
１・・・アルミナ結晶粒子
２・・・３重点
1 ... Alumina crystal particles 2 ... 3 points
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