JP4790365B2 - High frequency dielectric composition - Google Patents
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- JP4790365B2 JP4790365B2 JP2005297772A JP2005297772A JP4790365B2 JP 4790365 B2 JP4790365 B2 JP 4790365B2 JP 2005297772 A JP2005297772 A JP 2005297772A JP 2005297772 A JP2005297772 A JP 2005297772A JP 4790365 B2 JP4790365 B2 JP 4790365B2
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- 239000000203 mixture Substances 0.000 title claims description 43
- 239000006104 solid solution Substances 0.000 claims description 34
- 229910052839 forsterite Inorganic materials 0.000 claims description 30
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 30
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 15
- 238000010304 firing Methods 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 21
- 239000012298 atmosphere Substances 0.000 description 15
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 238000003826 uniaxial pressing Methods 0.000 description 1
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Description
本発明は、高周波用誘電体組成物に関する。 The present invention relates to a high frequency dielectric composition.
高周波用誘電体材料は、近年の情報通信技術の発展により、通信回路の特性を決定する重要な材料となりつつある。このような誘電体に要求される特性としては、一般に、(i)マイクロ波帯における比誘電率（εｒ）が高いこと、(ii)誘電損失が小さいこと、すなわち品質係数（Ｑ・ｆ；但しＱは誘電正接ｔａｎδの逆数、ｆは共振周波数）が高いこと、(iii)共振周波数の温度係数（τｆ）の絶対値が小さいこと、が挙げられる。特に、誘電損失は誘電体に交流電場を加えた時に熱として失われるエネルギーの量を表し、高周波においてはその値が小さいことが重要となる。 High-frequency dielectric materials are becoming important materials for determining the characteristics of communication circuits due to the recent development of information communication technology. The characteristics required for such a dielectric generally include (i) a high dielectric constant (ε r ) in the microwave band, and (ii) a low dielectric loss, that is, a quality factor (Q · f; However, Q is the reciprocal of the dielectric loss tangent tan δ, f is the resonance frequency), and (iii) the absolute value of the temperature coefficient (τ f ) of the resonance frequency is small. In particular, dielectric loss represents the amount of energy lost as heat when an alternating electric field is applied to a dielectric, and it is important that the value be small at high frequencies.
このような高周波用誘電体セラミックスの一つとして、フォルステライトが知られている。このものは、ＭｇＯとＳｉＯ２の反応生成物（Ｍｇ２ＳｉＯ４）よりなり、比較的優れた高周波特性を有している。 Forsterite is known as one of such high-frequency dielectric ceramics. This product is made of a reaction product of MgO and SiO 2 (Mg 2 SiO 4 ) and has relatively excellent high frequency characteristics.
本発明者らは、これまでにフォルステライトの製造工程において、混入する不純物および粉末の粒度を制御することにより、マイクロ波領域での誘電損失の小さいフォルステライト誘電体を開発している（特許文献１、非特許文献１参照）。
しかしながら、フォルステライトからなる高周波用誘電体組成物を作製する場合、原料のＭｇＯやＳｉＯ２に混入している不純物や種々の目的で添加される元素によって、最終的な生成物である誘電体焼結体中にフォルステライト以外の相が形成され、誘電特性に影響を与えることがある。このため、誘電特性の良いフォルステライトを得るためには、製造プロセスの繊細な管理が必要となる。 However, when producing a dielectric composition for high frequency made of forsterite, the final product, the dielectric firing, depends on impurities mixed in the raw material MgO and SiO 2 and elements added for various purposes. Phases other than forsterite are formed in the aggregate, which may affect the dielectric properties. For this reason, in order to obtain forsterite with good dielectric properties, delicate management of the manufacturing process is required.
また、フォルステライトを得るための焼結温度は一般に１４５０℃程度である。しかし、例えば誘電体組成物を、基板の焼成と同時に電極の形成を行う同時焼成によって製造される電子デバイス等に応用する場合などにおいては、焼結温度があまり高くないことが望まれる。 The sintering temperature for obtaining forsterite is generally about 1450 ° C. However, for example, when the dielectric composition is applied to an electronic device or the like manufactured by simultaneous firing in which electrodes are formed simultaneously with firing of the substrate, it is desired that the sintering temperature is not so high.
本発明は、上記した事情に鑑みてなされたものであり、その目的は、良好な誘電特性を実現でき、比較的低温で焼成できる新規な高周波用誘電体組成物を提供することにある。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel high-frequency dielectric composition that can realize good dielectric properties and can be fired at a relatively low temperature.
本発明者らは、良好な誘電特性を実現でき、比較的低温で焼成できる新規な高周波用誘電体組成物を開発すべく鋭意研究してきたところ、フォルステライトにテフォライト（Ｍｎ２ＳｉＯ４）を固溶させることにより、１４００℃程度と、一般的にフォルステライトの焼成に好ましいとされる１４５０℃よりも低温で焼成可能であり、特にマイクロ波領域でのＱ・ｆ値が大きい高周波用誘電体組成物を得られることを見出した。また、テフォライト単体でも同様に低温焼成が可能で誘電特性の良い高周波用誘電体組成物を得られることを見出し、本発明を完成するに至った。 The present inventors have conducted intensive research to develop a novel high-frequency dielectric composition that can realize good dielectric properties and can be fired at a relatively low temperature. As a result, tefolite (Mn 2 SiO 4 ) is fixed to forsterite. When dissolved, it can be fired at a temperature of about 1400 ° C., which is lower than 1450 ° C., which is generally preferred for firing forsterite, and has a high Q · f value particularly in the microwave region. I found out I could get something. Further, the present inventors have found that a high-frequency dielectric composition having a good dielectric property and capable of being fired at a low temperature can be obtained by using tefolite alone.
すなわち、本発明はテフォライト単体またはテフォライトとフォルステライトの固溶体からなる、一般式Ｍｇ２−ｘＭｎｘＳｉＯ４（但し０＜ｘ≦２．０）で示される高周波用誘電体組成物である。 That is, the present invention is a high-frequency dielectric composition represented by the general formula Mg 2−x Mn x SiO 4 (where 0 <x ≦ 2.0), comprising a single tefolite or a solid solution of tefolite and forsterite.
本発明によれば、特にマイクロ波領域において高純度フォルステライトに匹敵する優れた誘電特性をもつとともに、比較的低温で焼成可能な高周波用誘電体組成物を得ることができる。 According to the present invention, it is possible to obtain a high-frequency dielectric composition that has excellent dielectric properties comparable to high-purity forsterite, particularly in the microwave region, and can be fired at a relatively low temperature.
本発明の高周波用誘電体組成物は、テフォライト単体またはテフォライトとフォルステライトの固溶体からなる、一般式Ｍｇ２−ｘＭｎｘＳｉＯ４（但し０＜ｘ≦２．０）で示されるものである。Ｍｎの組成比、すなわち上記一般式中のｘの値の範囲については、０より大きく２．０以下であれば特に制限はないが、ｘが０．０５以上０．１５以下の範囲で特に高いＱ・ｆ値をもつ高周波用誘電体組成物を得ることができる。 The high-frequency dielectric composition of the present invention is represented by the general formula Mg 2-x Mn x SiO 4 (where 0 <x ≦ 2.0), which is composed of tefolite alone or a solid solution of tefolite and forsterite. The composition ratio of Mn, that is, the range of the value x in the above general formula is not particularly limited as long as it is larger than 0 and 2.0 or less, but is particularly high when x is in the range of 0.05 to 0.15. A high frequency dielectric composition having a Q · f value can be obtained.
このような高周波用誘電体組成物は、原料であるＭｇＯ、ＭｎＯ、ＳｉＯ２を混合して焼成することにより得ることができる。本発明の高周波用誘電体組成物の製造プロセスの一例を示す工程図を図１に示す。 Such a high-frequency dielectric composition can be obtained by mixing and firing raw materials MgO, MnO, and SiO 2 . FIG. 1 is a process diagram showing an example of a process for producing a high frequency dielectric composition of the present invention.
まず、原料であるＭｇＯ、ＭｎＯ、ＳｉＯ２（テフォライト単体を目的の組成物とする場合はＭｎＯ、ＳｉＯ２）を、目的とする高周波用誘電体組成物中の原子数の比に基づいて秤量し、混合、粉砕する。ＭｇＯ、ＭｎＯ、ＳｉＯ２としては、それぞれ高純度のものを使用することが好ましく、具体的には純度９９．９％以上のものを使用することが好ましい。また、粒度はできるだけ小さいことが好ましいが、仮焼成において充分反応する程度であればよい。粉砕は、例えばボールミル等を用いた一般的な方法で行うことができる。 First, MgO as a raw material, MnO, SiO 2 (if the Teforaito alone for the purpose of the composition MnO, SiO 2), and weighed on the basis of the atomic ratio of high frequency dielectric composition of interest , Mix and grind. As MgO, MnO, and SiO 2 , it is preferable to use those having high purity, and specifically, it is preferable to use those having a purity of 99.9% or more. Further, the particle size is preferably as small as possible, but it is sufficient that the particle size is sufficiently reacted in the pre-baking. The pulverization can be performed by a general method using, for example, a ball mill.
次いで、得られた原料の混合粉末を乾燥後、仮焼成する。仮焼成は例えば焼成温度１１５０℃程度、焼成時間３時間程度で行えばよい。これにより、フォルステライトとテフォライトとの良好な固溶相を合成することができる。得られた固溶体は再び粉砕、乾燥して粉末とされる。粉砕は、例えばボールミル等を用いた一般的な方法で行うことができる。 Next, the obtained mixed powder of raw materials is dried and then calcined. The temporary baking may be performed, for example, at a baking temperature of about 1150 ° C. and a baking time of about 3 hours. Thereby, a good solid solution phase of forsterite and tefolite can be synthesized. The obtained solid solution is again pulverized and dried to form a powder. The pulverization can be performed by a general method using, for example, a ball mill.
次に、乾燥後の固溶体粉末にバインダを加えて造粒する。バインダとしてはポリビニルアルコール、メチルセルロースなどの有機質の糊料を好ましく使用できる。造粒後、得られた固溶体の粉粒体を成形する。成形は、例えば一軸プレスにより成形後、冷間等方圧プレス（ＣＩＰ）により再成形することにより行うことができる。 Next, a binder is added to the dried solid solution powder and granulated. As the binder, organic pastes such as polyvinyl alcohol and methyl cellulose can be preferably used. After granulation, the obtained solid solution powder is formed. The molding can be performed, for example, by molding with a uniaxial press and then reforming with a cold isostatic press (CIP).
次いで、得られた成形体を脱脂後、本焼成する。脱脂処理は成形物に含まれるバインダ等の有機物を徐々に焼失させる条件で行えばよく、例えば３００〜５００℃で４〜８時間程度行えば良い。また、本焼成は焼成温度１４００℃、焼成時間２時間程度で行うことができる。なお、本明細書において焼成温度とは加熱炉内に熱電対を設置して測定した温度をいう。但し、加熱炉の中心位置では±２〜３℃、炉内全体では測定位置により±３０℃程度の誤差が生じる。 Next, the obtained molded body is degreased and then fired. The degreasing treatment may be performed under the condition that organic substances such as a binder contained in the molded product are gradually burned off, and may be performed, for example, at 300 to 500 ° C. for about 4 to 8 hours. Further, the main baking can be performed at a baking temperature of 1400 ° C. and a baking time of about 2 hours. In the present specification, the firing temperature refers to a temperature measured by installing a thermocouple in a heating furnace. However, an error of about ± 2 to 3 ° C. occurs at the center position of the heating furnace and about ± 30 ° C. depending on the measurement position in the entire furnace.
以下、実施例を挙げて本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
＜実施例１−１＞
（１）焼結体の作成
純度９９．９％以上、平均粒径０．８ｍｍ、比表面積１．７８ｍ２／ｇのＳｉＯ２粉末、純度９９．９％以上、平均粒径０．８２μｍ、比較面積１．７８ｍ２ ／ｇのＭｇＯ粉末、及び純度９９．９％以上のＭｎＯ粉末を、目的とする固溶体Ｍｇ１．９７Ｍｎ０．０３ＳｉＯ４（ｘ＝０．０３）中の各元素の組成比に基づいて秤量した後、蒸留水を加えて、ジルコニアボールを用いてボールミルで２４時間混合した。混合後の原料粉末を、約１００℃で２４時間乾燥した後、空気中で１１５０℃で３時間仮焼成した。得られた仮焼成物をジルコニアボールを用いたボールミルにて蒸留水中で２４時間粉砕した後、１００℃で２４時間乾燥して固溶体粉末を得た。
得られた固溶体粉末にバインダとしてポリビニルアルコールを１％添加し、造粒した。得られた造粒物を、直径１２ｍｍの金型を用いて８ＭＰａ、２分間の一軸加圧により成形した後、２００ＭＰａ、２分間の冷間等方圧プレス（ＣＩＰ）で再成形して、ペレット状の成形物を得た。
次いで、成形物を加熱炉に入れ、４００℃で６時間加熱して脱脂した後、昇温し、１４００℃で２時間の本焼成を行って焼結体を得た。なお、焼成における昇温・降温速度は５℃／ｍｉｎとした。
<Example 1-1>
(1) Creation of sintered body SiO 2 powder having a purity of 99.9% or more, an average particle diameter of 0.8 mm, a specific surface area of 1.78 m 2 / g, a purity of 99.9% or more, an average particle diameter of 0.82 μm, comparison An MgO powder having an area of 1.78 m 2 / g and an MnO powder having a purity of 99.9% or more are composed of each element in the target solid solution Mg 1.97 Mn 0.03 SiO 4 (x = 0.03). After weighing based on the ratio, distilled water was added and mixed with a zirconia ball in a ball mill for 24 hours. The mixed raw material powder was dried at about 100 ° C. for 24 hours and then calcined in air at 1150 ° C. for 3 hours. The obtained calcined product was pulverized in distilled water for 24 hours with a ball mill using zirconia balls and then dried at 100 ° C. for 24 hours to obtain a solid solution powder.
1% of polyvinyl alcohol was added to the obtained solid solution powder as a binder and granulated. The resulting granulated product was molded by uniaxial pressing at 8 MPa for 2 minutes using a mold with a diameter of 12 mm, and then remolded by cold isostatic pressing (CIP) at 200 MPa for 2 minutes to produce pellets. A shaped molding was obtained.
Next, the molded product was put into a heating furnace, heated at 400 ° C. for 6 hours for degreasing, then heated, and subjected to main firing at 1400 ° C. for 2 hours to obtain a sintered body. The temperature increase / decrease rate in firing was 5 ° C./min.
（２）試験
(i)相対密度
相対密度は、アルキメデス法で見かけ密度を求め、その値を理論密度で除することにより求めた。
(2) Test
(i) Relative density Relative density was determined by calculating the apparent density by the Archimedes method and dividing the value by the theoretical density.
(ii)誘電特性
上記（１）で得られた焼結体の両端面を研磨した後、Ｈａｋｋｉ ａｎｄ Ｃｏｌｅｍａｎ（ハッキ アンド コールマン）法を改良した両端短絡形誘電体共振器法（ＪＩＳ Ｒ １６２７）により比誘電率εｒ、品質係数Ｑ・ｆ値及び温度係数τｆを測定した。なお、測定周波数は１４〜１８ＧＨｚで行った。温度係数τｆは＋２０〜＋８０℃の温度範囲で共振周波数の変化から求めた。
(ii) Dielectric properties After polishing both end faces of the sintered body obtained in the above (1), the both ends short-circuited dielectric resonator method (JIS R 1627) improved from the Hakki and Coleman method. The relative dielectric constant ε r , the quality factor Q · f value, and the temperature coefficient τ f were measured. The measurement frequency was 14 to 18 GHz. The temperature coefficient τ f was obtained from the change in resonance frequency in the temperature range of +20 to + 80 ° C.
(iii)粉末Ｘ線回折（ＸＲＤ）法による解析
得られた焼結体について、粉末Ｘ線回折法による解析（線源：ＣｕＫα）を行った。
(iii) Analysis by powder X-ray diffraction (XRD) method The obtained sintered body was analyzed by a powder X-ray diffraction method (radiation source: CuKα).
(iv)ＷＰＰＤ法による格子定数の精密化
(iii)で得られた粉末Ｘ線解析のデータをＷＰＰＤ（Whole-Powder-Pattern Decomposition；全粉末パターン分解）法を用いて解析し、格子定数を精密化した。
(iv) Refinement of lattice constant by WPPD method
The powder X-ray analysis data obtained in (iii) was analyzed using a WPPD (Whole-Powder-Pattern Decomposition) method to refine the lattice constant.
＜実施例１−２＞
原料粉末を、目的とする固溶体Ｍｇ１．９５Ｍｎ０．０５ＳｉＯ４（ｘ＝０．０５）中の各元素の組成比に基づいて秤量した。その他は、実施例１と同様にして焼結体を作成し、試験を行った。
<Example 1-2>
The raw material powder was weighed based on the composition ratio of each element in the target solid solution Mg 1.95 Mn 0.05 SiO 4 (x = 0.05). Other than that, a sintered body was prepared and tested in the same manner as in Example 1.
＜実施例１−３＞
原料粉末を、目的とする固溶体Ｍｇ１．９Ｍｎ０．１ＳｉＯ４（ｘ＝０．１）中の各元素の組成比に基づいて秤量した。その他は、実施例１と同様にして固溶体および焼結体を作成し、試験を行った。
<Example 1-3>
The raw material powder was weighed based on the composition ratio of each element in the target solid solution Mg 1.9 Mn 0.1 SiO 4 (x = 0.1). Otherwise, a solid solution and a sintered body were prepared and tested in the same manner as in Example 1.
＜実施例１−４＞
原料粉末を、目的とする固溶体Ｍｇ１．８５Ｍｎ０．１５ＳｉＯ４（ｘ＝０．１５）中の各元素の組成比に基づいて秤量した。その他は、実施例１と同様にして固溶体および焼結体を作成し、試験を行った。
<Example 1-4>
The raw material powder was weighed based on the composition ratio of each element in the target solid solution Mg 1.85 Mn 0.15 SiO 4 (x = 0.15). Otherwise, a solid solution and a sintered body were prepared and tested in the same manner as in Example 1.
＜実施例１−５＞
原料粉末を、目的とする固溶体Ｍｇ１．５Ｍｎ０．５ＳｉＯ４（ｘ＝０．５）中の各元素の組成比に基づいて秤量した。その他は、実施例１と同様にして固溶体および焼結体を作成し、試験を行った。
<Example 1-5>
The raw material powder was weighed based on the composition ratio of each element in the target solid solution Mg 1.5 Mn 0.5 SiO 4 (x = 0.5). Otherwise, a solid solution and a sintered body were prepared and tested in the same manner as in Example 1.
＜実施例１−６＞
原料粉末を、目的とする固溶体ＭｇＭｎＳｉＯ４（ｘ＝１）中の各元素の組成比に基づいて秤量した。その他は、実施例１と同様にして固溶体および焼結体を作成し、試験を行った。
<Example 1-6>
The raw material powder was weighed based on the composition ratio of each element in the target solid solution MgMnSiO 4 (x = 1). Otherwise, a solid solution and a sintered body were prepared and tested in the same manner as in Example 1.
＜実施例１−７＞
原料粉末を、目的とするテフォライト単体Ｍｎ２ＳｉＯ４（ｘ＝２）中の各元素の組成比に基づいて秤量した。その他は、実施例１と同様にして固溶体および焼結体を作成し、試験を行った。
<Example 1-7>
The raw material powder was weighed based on the composition ratio of each element in the target tephrite simple substance Mn 2 SiO 4 (x = 2). Otherwise, a solid solution and a sintered body were prepared and tested in the same manner as in Example 1.
＜実施例２−１＞
原料粉末を、目的とする固溶体Ｍｇ１．９５Ｍｎ０．０５ＳｉＯ４（ｘ＝０．０５）中の各元素の組成比に基づいて秤量した。また、仮焼成および本焼成を窒素雰囲気下（還元雰囲気下）で行った。その他は、実施例１と同様にして固溶体および焼結体を作成し、試験を行った。
<Example 2-1>
The raw material powder was weighed based on the composition ratio of each element in the target solid solution Mg 1.95 Mn 0.05 SiO 4 (x = 0.05). Moreover, temporary baking and main baking were performed in nitrogen atmosphere (reducing atmosphere). Otherwise, a solid solution and a sintered body were prepared and tested in the same manner as in Example 1.
＜実施例２−２＞
原料粉末を、目的とする固溶体Ｍｇ１．９Ｍｎ０．１ＳｉＯ４（ｘ＝０．１）中の各元素の組成比に基づいて秤量した。また、仮焼成および本焼成を窒素雰囲気下（還元雰囲気下）で行った。その他は、実施例１と同様にして固溶体および焼結体を作成し、試験を行った。
<Example 2-2>
The raw material powder was weighed based on the composition ratio of each element in the target solid solution Mg 1.9 Mn 0.1 SiO 4 (x = 0.1). Moreover, temporary baking and main baking were performed in nitrogen atmosphere (reducing atmosphere). Otherwise, a solid solution and a sintered body were prepared and tested in the same manner as in Example 1.
＜実施例２−３＞
原料粉末を、目的とするテフォライト単体Ｍｎ２ＳｉＯ４（ｘ＝２）中の各元素の組成比に基づいて秤量した。また、仮焼成および本焼成を窒素雰囲気下（還元雰囲気下）で行った。その他は、実施例１と同様にして固溶体および焼結体を作成し、試験を行った。
<Example 2-3>
The raw material powder was weighed based on the composition ratio of each element in the target tephrite simple substance Mn 2 SiO 4 (x = 2). Moreover, temporary baking and main baking were performed in nitrogen atmosphere (reducing atmosphere). Otherwise, a solid solution and a sintered body were prepared and tested in the same manner as in Example 1.
＜比較例＞
原料粉末を、目的とするフォルステライト単体Ｍｇ２ＳｉＯ４（ｘ＝０）中の各元素の組成比に基づいて秤量した。その他は、実施例１と同様にして固溶体および焼結体を作成し、試験を行った。
<Comparative example>
The raw material powder was weighed based on the composition ratio of each element in the target forsterite simple substance Mg 2 SiO 4 (x = 0). Otherwise, a solid solution and a sintered body were prepared and tested in the same manner as in Example 1.
［結果と考察］
表１には、各実施例および比較例における焼結体の比誘電率εｒ、品質係数Ｑ・ｆ、温度係数τｆ、相対密度、格子定数を示した。また、図２には、各実施例および比較例における焼結体のＸ線回折チャートを、図３にはｘの値と比誘電率εｒとの関係、図４にはｘの値と品質係数Ｑ・ｆとの関係を、図５にはｘの値と温度係数τｆとの関係を、それぞれ示した。
[Results and discussion]
Table 1 shows the relative dielectric constant ε r , the quality factor Q · f, the temperature coefficient τ f , the relative density, and the lattice constant of the sintered bodies in the examples and comparative examples. Further, in FIG. 2, the X-ray diffraction chart of a sintered body in each example and comparative example, the relationship between the value and the relative dielectric constant epsilon r of x in FIG. 3, FIG. 4 and the value of x Quality FIG. 5 shows the relationship between the coefficient Q · f, and FIG. 5 shows the relationship between the value of x and the temperature coefficient τ f .
表１より、Ｍｎ元素の組成比（ｘの値）の増加に伴い、格子定数が大きくなっていることから、固溶体が形成されていることが分かる。また、実施例の焼結体はいずれも相対密度が約９３％〜９９％であり、焼成温度１４００℃で充分に高密度の焼結体が得られていることが分かった。 From Table 1, it can be seen that a solid solution is formed because the lattice constant increases as the composition ratio (value of x) of the Mn element increases. In addition, it was found that the sintered bodies of the examples had a relative density of about 93% to 99%, and a sufficiently high density sintered body was obtained at a firing temperature of 1400 ° C.
表１および図３より、テフォライトとフォルステライトとの固溶体（実施例１−１〜１−６、および実施例２−１〜２−２）およびテフォライト単体（実施例１−７、実施例２−３）からなる焼結体は、フォルステライト単体（比較例）からなる焼結体と比較して比誘電率εｒが高くなっていた。また、比誘電率εｒとｘの値との間には直線的な相関関係が見出された。このことから、Ｍｎ元素の組成比を調整することにより比誘電率を所望の値にコントロール可能である。 From Table 1 and FIG. 3, solid solutions of tefolite and forsterite (Examples 1-1 to 1-6 and Examples 2-1 to 2-2) and tephrite alone (Examples 1-7 and Example 2-) The sintered body made of 3) had a higher relative dielectric constant ε r than the sintered body made of forsterite alone (comparative example). A linear correlation was found between the relative dielectric constant ε r and the value of x. From this, the relative dielectric constant can be controlled to a desired value by adjusting the composition ratio of the Mn element.
また、表１および図４より、テフォライトとフォルステライトとの固溶体およびテフォライト単体からなる焼結体は、フォルステライト単体からなる焼結体にほぼ匹敵する品質係数Ｑ・ｆを示した。特に０．０５≦ｘ≦０．１５の範囲内で、フォルステライト単体と比較して品質係数Ｑ・ｆの大きな改善が見られ、ｘ＝０．０５でＱ・ｆ＝１８０３３３ＧＨｚを達成することができた。 Further, from Table 1 and FIG. 4, the sintered body composed of a solid solution of tefolite and forsterite and the single unit of tefolite exhibited a quality factor Q · f almost comparable to the sintered body composed of the single unit of forsterite. In particular, within the range of 0.05 ≦ x ≦ 0.15, a significant improvement in the quality factor Q · f is seen compared to the forsterite alone, and it is possible to achieve Q · f = 180333 GHz at x = 0.05. did it.
さらに、空気中（酸化雰囲気下）で焼成を行った実施例１−１〜１−７と、窒素雰囲下気（還元雰囲気下）で焼成を行った実施例２−１〜２−３とを比較して、比誘電率εｒ、品質係数Ｑ・ｆおよび温度係数τｆの値には大きな違いはなかった。このことから、テフォライト単体またはテフォライトとフォルステライトの固溶体からなる高周波用誘電体組成物は、酸化雰囲気下または還元雰囲気下のいずれで焼成しても良好な誘電特性をもつことが分かった。 Furthermore, Examples 1-1 to 1-7 fired in air (under an oxidizing atmosphere), and Examples 2-1 to 2-3 fired in a nitrogen atmosphere (under a reducing atmosphere) The relative dielectric constant ε r , quality factor Q · f, and temperature coefficient τ f were not significantly different. From this, it was found that the dielectric composition for high frequency composed of tefolite alone or a solid solution of tefolite and forsterite has good dielectric properties even when fired in either an oxidizing atmosphere or a reducing atmosphere.
以上のように本発明によれば、特にマイクロ波領域において高純度フォルステライトに匹敵する優れた誘電特性をもつとともに、比較的低温で焼成可能な高周波用誘電体組成物を得ることができる。
また、一般的な誘電体組成物では還元雰囲気下で焼成すると誘電特性が低下してしまうため好ましくない。これに対し、本発明の高周波用誘電体組成物は酸化雰囲気下でも、Ｎ２雰囲気等の還元雰囲気下でも焼成可能であり、特に還元的雰囲気下で焼成する方がやや良好な誘電特性を示す傾向にある。この理由は必ずしも明らかではないが、酸化的雰囲気では含まれるＭｎ（II）がＭｎ（III）やＭｎ（IV）に変化するためではないかと推定される。
このことから、本発明の高周波用誘電体組成物は、例えば酸化しやすい金属材料を用いた電極との同時焼成を行う場合には還元的雰囲気で焼成を行うなど、目的に応じて酸化、還元のうちいずれの雰囲気下で焼成するかを自由に選択することができ、特に一般的な誘電体組成物では好ましくないとされる還元雰囲気下の焼成でも良好な誘電特性を達成することができるから、応用範囲が広いという利点がある。
As described above, according to the present invention, it is possible to obtain a high-frequency dielectric composition that has excellent dielectric properties comparable to high-purity forsterite, particularly in the microwave region, and can be fired at a relatively low temperature.
In addition, when a general dielectric composition is baked in a reducing atmosphere, the dielectric characteristics deteriorate, which is not preferable. In contrast, the high-frequency dielectric composition of the present invention can be fired in an oxidizing atmosphere or a reducing atmosphere such as an N 2 atmosphere, and exhibits slightly better dielectric properties, especially when fired in a reducing atmosphere. There is a tendency. The reason for this is not necessarily clear, but it is presumed that Mn (II) contained in the oxidizing atmosphere is changed to Mn (III) or Mn (IV).
Therefore, the high-frequency dielectric composition of the present invention can be oxidized or reduced according to the purpose, for example, in a reducing atmosphere when co-firing with an electrode using a metal material that is easily oxidized. It is possible to freely select which atmosphere to fire, and it is possible to achieve good dielectric characteristics even when firing in a reducing atmosphere, which is not preferable for general dielectric compositions. There is an advantage that the application range is wide.
Claims (1)
純度９９．９％以上のＭｇＯ、ＭｎＯ、ＳｉＯ２を、目的とする高周波用誘電体組成物中の原子数の比に基づいて秤量し、混合する工程と、得られた混合物を焼成する工程とを経ることにより製造される高周波用誘電体組成物。 A high-frequency dielectric composition represented by the general formula Mg 2-x Mn x SiO 4 (where 0.05 ≦ x ≦ 0.15 ), comprising a single tefolite or a solid solution of tefolite and forsterite,
A step of weighing and mixing MgO, MnO, and SiO 2 having a purity of 99.9% or more based on the ratio of the number of atoms in the intended high-frequency dielectric composition, and a step of firing the obtained mixture The dielectric composition for high frequency manufactured by going through.
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