Glass ceramic composition and glass ceramic substrate
Provided is a glass ceramic composition which can be fired at a temperature of 1000° C. or lower, and a sintered body of which has a low relative permittivity and a high Q value, stable temperature characteristic and high reliability, and is excellent in plating solution resistance. The glass ceramic composition provides a low dielectric constant layer for inclusion in a laminate glass ceramic substrate in a ceramic multilayer module. It includes a first ceramic having forsterite as the main constituent, a second ceramic having at least one of SrTiO 3 and TiO 2 as the main constituent, a third ceramic having BaZrO 3 as the main constituent, a fourth ceramic having at least one of ZrO 2 and MnO as the main constituent, and 3 weight % or more of a borosilicate glass containing Li 2 O, MgO, B 2 O 3 , SiO 2 and ZnO, which further contains an additive constituent including at least one of CaO and SrO.
1. A glass ceramic composition comprising:
at least 55 weight % of a first ceramic comprising forsterite as the main constituent,
a second ceramic comprising at least one of strontium titanate and titanium oxide as the main constituent,
a third ceramic comprising barium zirconate as the main constituent,
a fourth ceramic comprising zirconium oxide or manganese oxide as the main constituent, and
a borosilicate glass, wherein
the first ceramic is the main constituent of the composition,
the content of said second ceramic is 3 weight % to 13 weight % when the second ceramic has strontium titanate as the main constituent, and is 0.3 weight % to 10 weight % when the second ceramic has titanium oxide as the main constituent,
the content of said third ceramic is 4 weight % to 8 weight %,
the content of said fourth ceramic is 5 weight % to 20 weight % when the fourth ceramic has zirconium oxide as the main constituent, and is 1 weight % to 9 weight % when the fourth ceramic has manganese oxide as the main constituent,
the content of said borosilicate glass is 3 weight % to 15 weight %, and
wherein said borosilicate glass contains lithium in an amount of 4 to 10 weight % on a Li 2 O equivalent basis, magnesium in an amount of 30 to 45 weight % on a MgO equivalent basis, boron in an amount of 15 to 25 weight % on a B 2 O 3 equivalent basis, silicon in an amount of 15 to 30 weight % on a SiO 2 equivalent basis and zinc in an amount of 6 to 20 weight % on a ZnO equivalent basis, up to 15 weight % Al on an Al 2 O 3 equivalent basis, and further contains at least 2 weight percent on a CaO equivalent basis plus SrO equivalent basis of an additive constituent comprising at least one of calcium oxide and strontium oxide, wherein the upper limit of the content of said additive constituent is 15 weight % on a CaO equivalent basis in the case of calcium oxide and is 25 weight % on a SrO equivalent basis in the case of strontium oxide based on the total weight of the borosilicate glass.
2. A glass ceramic composition according to claim 1 in which the second ceramic comprising strontium titanate as the main constituent, the strontium titanate has a molar ratio of SrO/TiO 2 of 0.92 to 1.05, and has a specific surface area of 1.5 to 7.5 m 2 /g.
3. A glass ceramic composition according to claim 2 in which the first ceramic has median grain diameter of 1 μm or less, and the forsterite has a MgO/SiO 2 molar ratio of 1.92 to 2.04.
4. A glass ceramic composition according to claim 1 in which the content of the second ceramic is 6.3 weight % to 13 weight % of which 6 weight % to 10 weight % is SrTiO 3 and 0.3 weight % to 3 weight % is TiO 2 .
5. A glass ceramic composition according to claim 1 in which the content of silicon in the borosilicate glass is 20 to 26.5 weight percent.
6. A glass according to claim 1 in which the fourth ceramic has manganese oxide as the main constituent.
7. A fired glass ceramic substrate comprising a fired glass ceramic composition according to claim 6 .
8. A glass ceramic substrate laminate comprising a low dielectric constant layer and a high dielectric constant layer,
wherein said low dielectric constant layer is a glass ceramic substrate according to claim 7 , and said high dielectric constant layer is a fired second glass ceramic composition which comprises a ceramic having strontium zirconate as the main constituent, a ceramic having strontium titanate as the main constituent, a ceramic having forsterite as the main constituent and 1 weight % to 12 weight % of a second borosilicate glass,
wherein said second borosilicate glass contains lithium in an amount of 3 to 15 weight % on a Li 2 O equivalent basis, magnesium in an amount of 20 to 50 weight % on a MgO equivalent basis, boron in an amount of 15 to 30 weight % on a B 2 O 3 equivalent basis, silicon in an amount of 10 to 35 weight % on a SiO 2 equivalent basis and zinc in an amount of 6 to 20 weight % on a ZnO equivalent basis, and further contains a second additive constituent comprising at least one of calcium oxide and strontium oxide, wherein the upper limit of the content of said second additive constituent is 15 weight % on a CaO equivalent basis in the case of calcium oxide and is 25 weight % on a SrO equivalent basis in the case of strontium oxide based on the total weight of the second borosilicate glass.
9. A glass ceramic composition according to claim 8 in which the low dielectric constant layer glass ceramic composition fired has a content of said borosilicate glass of 3 weight % to 15 weight % and which said borosilicate glass contains lithium in an amount of 4 to 10 weight % on a Li 2 O equivalent basis, magnesium in an amount of 30 to 40 weight % on a MgO equivalent basis, boron in an amount of 15 to 25 weight % on a B 2 O 3 equivalent basis, silicon in an amount of 15 to 30 weight % on a SiO 2 equivalent basis, up to 15 weight % Al on a Al 2 O 3 equivalent basis, and the additive constituent is at least 2 weight percent on a CaO equivalent basis plus SrO equivalent basis.
10. A laminate glass ceramic substrate according to claim 8 , wherein said high dielectric constant layer glass ceramic composition contains zirconium oxide in an amount of 5 weight % to 20 weight % or manganese oxide in an amount of 1 weight % to 9 weight %, or both.
11. A glass ceramic composition according to claim 10 in which the low dielectric constant layer glass ceramic composition has a content of said borosilicate glass of 3 weight % to 15 weight % and which said borosilicate glass contains lithium in an amount of 4 to 10 weight % on a Li 2 O equivalent basis, magnesium in an amount of 30 to 45 weight % on a MgO equivalent basis, boron in an amount of 15 to 25 weight % on a B 2 O 3 equivalent basis, silicon in an amount of 15 to 30 weight % on a SiO 2 equivalent basis, up to 15 weight % Al on a Al 2 O 3 equivalent basis, and the additive constituent is at least 2 weight percent on a CaO equivalent basis plus SrO equivalent basis.
12. A glass ceramic substrate comprising a fired glass ceramic composition according to claim 1 .
13. A glass ceramic substrate laminate comprising a low dielectric constant layer and a high dielectric constant layer, wherein
said low dielectric constant layer is a fired glass ceramic composition according to claim 12 , and
said high dielectric constant layer is a fired second glass ceramic composition which comprises a ceramic having strontium zirconate as the main constituent, a ceramic having strontium titanate as the main constituent, a ceramic having forsterite as the main constituent and 1 weight % to 12 weight % of a second borosilicate glass,
wherein said second borosilicate glass contains lithium in an amount of 3 to 15 weight % on a Li 2 O equivalent basis, magnesium in an amount of 20 to 50 weight % on a MgO equivalent basis, boron in an amount of 15 to 30 weight % on a B 2 O 3 equivalent basis, silicon in an amount of 10 to 35 weight % on a SiO 2 equivalent basis and zinc in an amount of 6 to 20 weight % on a ZnO equivalent basis, and further contains a second additive constituent comprising at least one of calcium oxide and strontium oxide, wherein the upper limit of the content of said second additive constituent is 15 weight % on a CaO equivalent basis in the case of calcium oxide and is 25 weight % on a SrO equivalent basis in the case of strontium oxide based on the total weight of the second borosilicate glass.
14. A glass ceramic composition according to claim 13 in which the low dielectric constant layer glass ceramic composition has a content of said borosilicate glass of 3 weight % to 15 weight % and which said borosilicate glass contains lithium in an amount of 4 to 10 weight % on a Li 2 O equivalent basis, magnesium in an amount of 30 to 45 weight % on a MgO equivalent basis, boron in an amount of 15 to 25 weight % on a B 2 O 3 equivalent basis, silicon in an amount of 15 to 30 weight % on a SiO 2 equivalent basis, up to 15 weight % Al on a Al 2 O 3 equivalent basis, and the additive constituent is at least 2 weight percent on a CaO equivalent basis plus SrO equivalent basis.
15. A laminate glass ceramic substrate according to claim 13 , wherein said high dielectric constant layer glass ceramic composition contains zirconium oxide in an amount of 5 weight % to 20 weight % or manganese oxide in an amount of 1 weight % to 9 weight %, or both.
16. A glass ceramic composition according to claim 15 in which the low dielectric constant layer glass ceramic composition has a content of said borosilicate glass of 3 weight % to 15 weight % and which said borosilicate glass contains lithium in an amount of 4 to 10 weight % on a Li 2 O equivalent basis, magnesium in an amount of 30 to 45 weight % on a MgO equivalent basis, boron in an amount of 15 to 25 weight % on a B 2 O 3 equivalent basis, silicon in an amount of 15 to 30 weight % on a SiO 2 equivalent basis, up to 15 weight % Al on a Al 2 O 3 equivalent basis, and the additive constituent is at least 2 weight percent on a CaO equivalent basis plus SrO equivalent basis.