JP2009256174A - Alumina sintered compact, member for semiconductor production apparatus, member for liquid-crystal-panel production apparatus, and member for dielectric resonator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alumina sintered compact lowering dielectric dissipation factor in 1 MHz to 8.5 GHz bands, to provide a member for a semiconductor production apparatus, and to provide a member for a liquid-crystal-panel production apparatus. <P>SOLUTION: The alumina sintered compact includes at least 99.3 mass% Al in terms of Al<SB>2</SB>O<SB>3</SB>, 0.05 to 0.3 mass% Si in terms of SiO<SB>2</SB>and 0.01 to 0.16 mass% Sr in terms of SrO, is constituted of alumina crystal grains 1 as main crystal grains, and has a crystal phase at triple points 2 constituted of the alumina crystal grains 1, the crystal phase containing the elements Si, Al, Sr, and O. Since the crystal phase containing the elements Si, Al, Sr, and O and having a low loss is present, and further, the average grain size of the alumina crystal grains 1 is ≥10 μm, the number of grain boundaries is reduced, thus dielectric dissipation factor in 1 MHz to 8.5 GHz can be lowered. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  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.

  Conventionally, alumina sintered bodies are excellent in heat resistance, chemical resistance, and plasma resistance, and have a low dielectric loss tangent (tan δ) in the high frequency region, so they have been used for semiconductors and high frequency plasma device members for liquid crystals. ing.

  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 decreases the high-frequency transmittance in the MHz band, increases energy loss, breaks the member due to heat generation, etc. Problems are known to occur.

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).

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 in 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.
JP-A-6-16469

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.

  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.

In the alumina sintered body of the present invention, Al is 99.3% by mass or more in terms of Al ₂ O ₃ , Si is 0.05 to 0.3% by mass in terms of SiO ₂ , and Sr is 0.01 to in terms of SrO. 0.16% by mass, alumina crystal particles as main crystal particles, a crystal phase containing elements of Si, Al, Sr and O is present at the triple point of the alumina crystal particles, and the alumina crystal particles The average particle size is 10 μm or more.

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 , the original excellent corrosion resistance, mechanical characteristics, and electrical characteristics of alumina can be maintained. , 0.05 to 0.3 wt% of Si in terms of SiO _2, containing 0.01 to 0.16 wt% of Sr in terms of SrO, a triple point made up of alumina crystal grains, conventional grain boundary phase Since there are many low-loss crystal phases containing Si, Al, Sr and O elements instead of glass composed of components, the dielectric loss tangent at a frequency of 1 MHz to 8.5 GHz can be reduced. Since the average particle size is 10 μm or more, the number of grain boundaries is reduced, the dielectric loss tangent can be further reduced, and the dielectric loss tangent at a frequency of 1 MHz to 8.5 GHz can be further reduced. That.

  Moreover, the alumina sintered body of the present invention is characterized by containing Mg in an amount of 0.01 to 0.1% by mass in terms of MgO and Ca in an amount of 0.01 to 0.16% by mass in terms of CaO. Such an alumina sintered body can suppress non-uniform abnormal grain growth of alumina crystal particles and suppress a decrease in strength. 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 a large sintered body with a large thickness is sufficiently sintered, and the characteristics such as the mechanical strength of the entire thick sintered body are improved. It can be improved.

The alumina sintered body of the present invention is characterized in that the crystal phase is a SrAl ₂ Si ₂ O ₈ type crystal phase. Since the SrAl ₂ Si ₂ O ₈ type crystal phase has a low loss in the MHz band, an alumina-based sintered body having a low loss in the MHz band can be obtained.

  Furthermore, in the alumina sintered body of the present invention, the crystal phase containing each element of Si, Al, Sr, and O exists at a triple point of 60% or more of the triple points composed of the alumina crystal particles. It is characterized by that. In such an alumina sintered body, there is a low-loss crystalline phase containing 60% or more of each element of Si, Al, Sr and O at the triple point in the sintered body. Since the abundance ratio of the amorphous phase that increases the tangent decreases or hardly exists, the dielectric loss tangent at a frequency of 1 MHz to 8.5 GHz can be reduced.

  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. In such a member for a semiconductor manufacturing device, a member for a liquid crystal panel manufacturing device, or a member for a dielectric resonator, the dielectric loss tangent is small in a frequency region between a measurement frequency of 1 MHz to 8.5 GHz. The transmittance can be improved, energy loss can be reduced, and damage to the member due to heat generation can be suppressed.

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 , the original excellent corrosion resistance, mechanical properties, and electrical properties of alumina can be maintained. , Si containing 0.05 to 0.3 mass% in terms of SiO ₂ , Sr in an amount of 0.01 to 0.16 mass% in terms of SrO, and the triple point composed of alumina crystal particles, Si, Al, Sr Since there is a low-loss crystal phase containing each element of O and O, the dielectric loss tangent at a frequency of 1 MHz to 8.5 GHz can be reduced, and further, the average grain size of the alumina crystal particles is 10 μm or more. , The dielectric loss tangent can be further reduced, and the dielectric loss tangent at a frequency of 1 MHz to 8.5 GHz can be further reduced.

  Therefore, by using the alumina sintered body of the present invention for the semiconductor manufacturing apparatus member, the liquid crystal panel manufacturing apparatus member, and the dielectric resonator member, it is possible to prevent highly reactive halogen-based corrosive gases and their plasmas. In addition to having high corrosion resistance, the alumina sintered body has a low loss in the MHz to GHz band, so that it can improve the high frequency transmittance in the MHz to GHz band, reduce energy loss, Damage can be suppressed.

In the alumina sintered body of the present invention, Al is 99.3% by mass or more in terms of Al ₂ O ₃ , Si is 0.05 to 0.3% by mass in terms of SiO ₂ , and Sr is 0.01 to in terms of SrO. Contains 0.16% by mass. By containing Al in an amount of 99.3% by mass or more in terms of Al ₂ O ₃ , it becomes possible to improve the sinterability and maintain the excellent corrosion resistance, mechanical properties, and electrical properties of alumina. On the other hand, when Al is less than 99.3% by mass in terms of Al ₂ O ₃ , the corrosion resistance deteriorates and cannot be applied to the corrosion resistant member.

In particular, in order to be applied 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, so Al is 99.5% by mass or more in terms of Al ₂ O _3. Is preferred. From the viewpoint of sinterability, it is desirable that Al is 99.9% by mass or less in terms of Al ₂ O ₃ . 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.

Further, these elements contained Si in an amount of 0.05 to 0.3% by mass in terms of SiO ₂ and Sr in an amount of 0.01 to 0.16% by mass in terms of SrO. This is because a crystal phase containing each element of O and O is precipitated.

On the other hand, when Si is less than 0.05 in terms of SiO ₂ , it is difficult to form a low-loss crystal phase, and when it exceeds 0.3% by mass, sintering is difficult. In particular, from the viewpoint of dielectric loss tangent and sinterability, Si is preferably 0.1 to 0.2% by mass in terms of SiO ₂ .

  When Sr is less than 0.01 in terms of SrO, it is difficult to form a low-loss crystal phase, and when it is more than 0.16% by mass, it is difficult to sinter. In particular, from the viewpoints of dielectric loss tangent and sinterability, Sr is preferably 0.03 to 0.13 mass% in terms of SrO.

  Furthermore, in the alumina sintered body of the present invention, it is desirable to contain 0.01 to 0.1% by mass of Mg in terms of MgO and 0.01 to 0.16% by mass of Ca in terms of CaO. Thereby, the non-uniform | heterogenous abnormal grain growth of an alumina crystal particle can be suppressed, and a strength fall can be suppressed. Furthermore, alkaline earth metal oxides function as a sintering aid, can improve sinterability, and can reduce voids and defects. A low-loss alumina sintered body can be obtained. Furthermore, since the sinterability is improved, for example, the central part in the thickness direction of a large sintered body with a large thickness is sufficiently sintered, and the characteristics such as the mechanical strength of the entire thick sintered body are improved. Can be improved.

  From the viewpoint of dielectric loss tangent and sinterability, Mg is preferably contained in an amount of 0.02 to 0.08% by mass in terms of MgO. Similarly, from the viewpoint of dielectric loss tangent and sinterability, Ca is preferably 0.02 to 0.1% by mass in terms of CaO.

  The alumina sintered body of the present invention has alumina crystal particles as main crystal particles, and a low-loss crystal phase composed of a compound containing Si, Al, Sr and O elements exists at the grain boundaries of the alumina crystal particles. . 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.

  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.

  In a general alumina sintered body, subcomponents added as a sintering aid exist between the alumina crystal particles 1 as glass or crystals having a high dielectric loss tangent, and increase the dielectric loss tangent of the entire alumina sintered body. There was a trend. However, when a low-loss crystal phase composed of a compound containing each element of Si, Al, Sr and O is deposited on the triple point 2 composed of alumina crystal particles 1 as in the present invention, this crystal phase Since the dielectric loss tangent of itself is low, the dielectric loss tangent in the MHz band of the entire alumina sintered body can be lowered.

In addition, as described above, alkaline earth metals such as Mg and Ca have been conventionally known as sintering aids, but among alkaline earth metals, Sr and Ba have a large ionic radius, so sintering. It is not used as an auxiliary agent, and in particular, there is no example of actively using Sr. In the present invention, in particular, Sr is not used as a sintering aid, but is used to precipitate SrAl ₂ Si ₂ O ₈ type crystal, which is a low dielectric loss tangent crystal phase. The presence can directly lower the dielectric loss tangent of the alumina sintered body.

The low dielectric loss tangent crystal phase comprising a compound containing Si, Al, Sr and O elements is preferably a SrAl ₂ Si ₂ O ₈ type crystal from the viewpoint of electrical characteristics as described above. The dielectric loss tangent can be reduced by the generation. Another low dielectric loss tangent crystal phase comprising a compound containing Si, Al, Sr and O elements is not a stoichiometric composition of SrAl ₂ Si ₂ O ₈ but a little deviated from the stoichiometric composition. May be. In the present invention, the SrAl ₂ Si ₂ O ₈ type crystal is a concept including one in which a part of the constituent elements is replaced with another element.

  In the present invention, it is desirable that a crystal phase composed of a compound containing Si, Al, and M as elements is present at the triple point 2 of 60% or more of the triple points 2 composed of the alumina crystal particles 1. The crystal phase is present in the triple point 2 of 60% or more of the triple point 2 constituted by the alumina crystal particles 1 is that a large number of the alumina crystal particles 1 are formed in a predetermined area of an arbitrary cross section of the alumina sintered body. This means that a crystal phase composed of a compound containing Si, Al and Sr exists in at least 60% of the triple point 2 of the above.

  In the present invention, in order to make a crystal phase composed of a compound containing Si, Al and M present in at least 60% of the many triple points 2, as described later, the raw material powder constituting the crystal phase is mixed. The mixed powder is pulverized and calcined, a crystal phase composed of a compound containing Si, Al and Sr is synthesized and added to the alumina powder.

  Thus, since the low dielectric loss tangent crystal phase is present in the triple point 2 of 60% or more of the triple points 2, the alumina sintered body can be further reduced in the dielectric loss tangent. In order to reduce the dielectric loss tangent even in the frequency region between 1 MHz and 8.5 GHz, the ratio of the grain boundary triple point 2 where the crystal phase of the low dielectric loss tangent exists is preferably 90% or more.

  In the present invention, the triple point 2 composed of the alumina crystal particles 1 and the triple point 2 where the above crystal phase does not exist has an amorphous phase containing Si, Al and Sr as elements. Or a crystal phase to be described later exists. The triple point where the amorphous phase exists is substantially absent or 10% or less in a predetermined area of an arbitrary cross section.

  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 is different from the inter-plane grain boundary 5 constituted by two alumina crystal particles 1.

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 . These crystals are present at the triple point 2 constituted by the alumina crystal particles 1. 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.

Further, the alumina sintered body of the present invention has an average particle diameter D ₅₀ is equal to or greater than 10 [mu] m. Since the average particle diameter is thus large, the number of grain boundaries is reduced, the dielectric loss tangent can be further reduced, and the dielectric loss tangent at a frequency of 1 MHz to 8.5 GHz can be further reduced. From the viewpoint of further stabilizing the low dielectric loss tangent, the average particle diameter D ₅₀ of the alumina crystal particles 1 is preferably 15 μm or more. The average particle diameter D ₅₀ of the alumina crystal particles 1 is desirably 70 μm or less from the viewpoint of mechanical properties. Incidentally, the average particle diameter D _50, refers to the particle size of cumulative 50% fine particle side of the cumulative particle size distribution.

  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.

  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 dielectric resonator member such as a support for various dielectric resonators.

  The method for producing an alumina sintered body according to the present invention includes, for example, mixing an aluminum oxide powder with a raw material powder obtained by mixing and heat-treating a Si source and an alkaline earth metal source, and forming the mixed powder, and then 1650- Bake at 1800 ° C.

The raw material powder obtained by mixing and heat-treating an alkaline earth metal source containing Sr and an Si source is a predetermined powder so as to produce an alkaline earth metal source containing Si source and Sr, for example, SrAl ₂ Si ₂ O ₈ . It is a powder obtained by mixing at a ratio and calcining at 500 ° C to 1400 ° C. The Si source and the alkaline earth metal source containing Sr may be any of metals, oxides, hydroxides, carbonates, nitrates, and other salts. By using the alkaline earth metal raw material powder containing Si and Sr, the distribution of the alkaline earth metal containing Si and Sr in the alumina sintered body is made uniform, and the non-uniform sintered structure is eliminated. It becomes possible.

  In addition, it is possible to preferentially cause a reaction between Si and an alkaline earth metal, and to generate a crystal having a low dielectric loss tangent composed of Si, Sr, Al, and O elements between alumina crystal particles. If the distribution of the alkaline earth metal containing Si and Sr is not uniform, an amorphous phase (glass) or a crystalline phase with a high dielectric loss tangent is generated, and this increases the dielectric loss tangent of the entire alumina sintered body. Become.

  In some cases, the raw material powder obtained by mixing and baking the alkaline earth metal source containing Sr and the Si source and the raw material powder containing the Mg source are mixed with the aluminum oxide powder 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.

  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 1650 to 1800 ° C. As a result, a sintered body having a high density and a crystal phase made of a compound containing Si, Sr, Al, and O elements between alumina crystal particles is produced.

  A method for measuring the dielectric loss tangent of the alumina sintered body of the present invention will be described.

The sintered body dissipation factor was 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, measurement frequency 1MHz Even in the frequency region between ˜8.5 GHz, the dielectric loss tangent can be expected to be 5 × 10 ⁻⁴ or less. By this method, 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. It is possible to design a low dielectric loss tangent material in the 8.5 GHz band.

  When measuring with a network analyzer using a sample having a dimension when measuring the dielectric loss tangent with a capacitance meter based on JIS C2141, the measurement frequency may slightly deviate from 8.5 GHz. This deviation comes from the accuracy of the sample outer dimensions and the dielectric constant variation of the material. In the case of an alumina sintered body sufficiently sintered with a purity of 99.3% or more, 8.5 ± 0.3 GHz is expected.

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.

Therefore, the dielectric loss tangent at the measurement frequency of 1 MHz and 8.5 GHz is 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 frequency at 1 MHz and 8.5 GHz is measured. When the dielectric loss tangent is in the range of 5 × 10 ⁻⁴ or less, the dielectric loss tangent can be recognized as 5 × 10 ⁻⁴ or less even in the frequency range between 1 MHz to 8.5 GHz, particularly 10 to 100 MHz, The dielectric loss tangent at a measurement frequency of 1 MHz to 8.5 GHz can be measured easily and accurately.

First, SiO ₂ and SrCO ₃ , CaCO ₃ , and BaCO ₃ powders were weighed and mixed to obtain a mixed powder. This powder was heat-treated at 1000 ° C. to 1300 ° C. and pulverized in an alumina ball mill for 48 to 72 hours to produce a raw material powder.

Purity to 99.95% of _Al 2 _{O 3} powder, and the raw material powders described above, and the addition of the Mg _{(OH) 2} powder, which in mixed 48 hours alumina balls mill adding a predetermined amount of water slurry did. 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 cylindrical molded body (diameter 60 mm × height 30 mm). Was fired at a temperature of 1680 ° C. to obtain an alumina sintered body having a diameter of 50 mm and a height of 25 mm.

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 . By X-ray diffraction measurement, it was confirmed that all the samples in Table 1 had alumina crystal particles as main crystal particles. Furthermore, the presence / absence of a crystal phase composed of a compound represented by MgAl ₂ O ₄ or CaAl ₁₂ O ₁₉ was confirmed by X-ray diffraction measurement, and listed in Table 1 as the presence / absence of spinel.

  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.

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. Was done. 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 2 as <5.

  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.

  First, using a network analyzer, a sample having a diameter of 50 mm × thickness 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 1 mm is cured. The electrode was 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. .

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, Sr, Regarding the presence or absence of the crystal phase containing the O element, 30 grain boundary triple points were confirmed, and the generation ratio of the crystal phase and the generation ratio of the amorphous phase are shown in Table 2. Whether the grain boundary triple point is an amorphous phase was confirmed by limited-field electron diffraction. The amorphous phase contained Si, Al, Sr, and O elements. The crystal phase containing Si, Al, Sr, and O elements was an MAl ₂ Si ₂ O ₈ type crystal phase, and M was at least one of Sr, Ca, and Ba as shown in Table 1. In FIG. 9 electron diffraction photographs are shown.

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.

From Tables 1 and 2, Al is 99.3% by mass or more in terms of Al ₂ O ₃ , Si is 0.05 to 0.3% by mass in terms of SiO ₂ , and Sr is 0.01 to 0.16 in terms of SrO. In the sample of the present invention containing SrAl ₂ Si ₂ O ₈ type crystal phase at the grain boundary of alumina crystal particles and having an average particle size of 10 μm or more, the dielectric loss tangent is 8.5 × 10 × 10 at 2.2 GHz. ^-4 or less When the frequency is 4 × 10 ⁻⁴ or less at 1 MHz, it is found that the loss is less than 5 × 10 ^{−4 at} 12 MHz.

In contrast, by heat-treating the powder of SiO ₂ and SrCO _3, CaCO _3, but was prepared by adding the _Al 2 _{O 3} powder, a sample amount of SiO ₂ is less and 0.02 wt% No. 1, the dielectric loss was high at 29 × 10 ^{−4 at} 1 MHz and 6.2 × 10 ^{−4 at} 8.5 GHz.

In addition, sample No. 14 was produced as follows. Add SiO ₂ powder, CaCO ₃ powder and Mg (OH) ₂ powder separately to Al ₂ O ₃ powder with purity of 99.95% by mass, add predetermined amount of water to this, and mix for 48 hours by ball mill To give a slurry. The slurry is added with a binder, 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) and fired at 1600 ° C. Was done.

The center part (thickness 1 mm) in the height direction of the obtained sintered body was cut out, and the density and dielectric properties were measured by the same method as in the examples. As a result of the analysis, a few crystals composed of Si and Ca, Al, and O elements are formed between the aluminum oxide crystal particles, and the rest are MgAl ₂ O ₄ , and most of them contain Si, Al, Sr, and O elements. It was a crystalline phase. The value of dielectric loss tangent was as low as 1.4 × 10 ⁻⁴ or less at 8.5 GHz, but it was as high as 40 × 10 ^{−4 at} 1 MHz and 7 × 10 ^{−4 at} 12 MHz, and the dielectric loss was in the MHz band. it was high.

It is a schematic sectional drawing which shows the structure of the alumina sintered compact of this invention. Sample Nos. 9 is an electron diffraction photograph of 9;

Explanation of symbols

1 ... Alumina crystal particles 2 ... 3 points

Claims (7)

It contains 99.3% by mass or more of Al in terms of Al ₂ O ₃ , 0.05 to 0.3% by mass of Si in terms of SiO ₂ , 0.01 to 0.16% by mass of Sr in terms of SrO, and alumina. Crystal grains are main crystal grains, a crystal phase containing each element of Si, Al, Sr and O is present at a triple point composed of the alumina crystal grains, and the average grain diameter of the alumina crystal grains is 10 μm or more. An alumina sintered body characterized in that   The alumina sintered body according to claim 1, further comprising 0.01 to 0.1% by mass of Mg in terms of MgO and 0.01 to 0.16% by mass of Ca in terms of CaO. The alumina-based sintered body according to claim 1 or 2, wherein the crystal phase is a SrAl ₂ Si ₂ O ₈ type crystal phase.   The crystal phase containing each element of said Si, Al, Sr, and O exists in 60% or more of 3 points | pieces among the 3 points | pieces comprised with the said alumina crystal particle, The Claim 1 thru | or 3 characterized by the above-mentioned. The alumina sintered body according to any one of the above.   A member for a semiconductor manufacturing apparatus, comprising the alumina sintered body according to any one of claims 1 to 4.   A member for a liquid crystal panel manufacturing apparatus, comprising the alumina sintered body according to any one of claims 1 to 4.   A dielectric resonator member comprising the alumina sintered body according to any one of claims 1 to 4.