JP5741097B2 - Composite oxide powder and method for producing the same - Google Patents

Description

  The present invention relates to a composite oxide powder and a method for producing the same, and more particularly to a fine and complex oxide powder having less impurities and a method for producing the same.

A composite oxide represented by the general formula ABO ₃ and having a perovskite crystal structure has excellent electrical characteristics and is widely used as a material constituting electronic parts. In particular, a composite oxide containing Zr at the B site of ABO ₃ is very important because the Curie point is lowered and the dielectric constant near room temperature can be increased.

  Such a composite oxide is generally manufactured by subjecting a raw material of an element constituting A and a raw material of an element constituting B to a solid phase reaction by heat treatment or the like (see, for example, Patent Document 1).

However, the case of producing a composite oxide contains Zr in the B site of the ABO _3, since it is difficult to solid solution Zr is the ABO _3, necessary to increase the temperature of the heat treatment, unreacted powder after reaction Zr raw material Problems such as remaining. On the other hand, when the heat treatment temperature is increased, ABO ₃ particles produced by the solid-phase reaction grow, so that there is a problem that a fine powder cannot be obtained and the electronic component cannot be reduced in size and performance.

  On the other hand, a method for producing a composite oxide using a reaction other than a solid phase reaction (for example, hydrothermal synthesis) is known (see, for example, Patent Document 2).

  However, when a composite oxide is produced by the method described in Patent Document 2, pores are generated inside the crystal particles due to the synthesis method, the equipment cost is high, and the content components are increased. There were also problems such as increasing.

JP 2005-8471 A JP-A-2005-75700

  The present invention has been made in view of such a situation, and an object of the present invention is to provide a fine complex oxide powder with less impurities and a method for producing the same.

In order to achieve the above object, a method for producing a composite oxide powder according to the present invention comprises:
A method for producing a composite oxide powder represented by the general formula A (BZr) O ₃ and having a perovskite crystal structure,
Preparing a raw material powder of Zr;
Preparing a raw material powder of the element constituting the A and a raw material powder of the element constituting the B;
A step of heat-treating the raw material powder of Zr, the raw material powder of the element constituting A, and the raw material powder of the element constituting B, at 800 to 1000 ° C.,
The Zr raw material powder contains an oxide of Zr having a monoclinic structure, and the half width of the monoclinic (111) peak observed by X-ray diffraction is 0.40 ° or more.

In the present invention, as the Zr raw material powder, a raw material containing a Zr oxide having a monoclinic structure and having a half width in the above range is used. By using such a raw material, the solid phase reaction for synthesizing A (BZr) O ₃ can be sufficiently advanced even if the heat treatment temperature is lowered. As a result, an A (BZr) O ₃ powder having almost no foreign phase (for example, unreacted Zr raw material) and high crystallinity is obtained in the powder after the reaction. Moreover, since the heat treatment temperature is low, A (BZr) grain growth of O ₃ particles can be suppressed, a small powder having an average particle size is obtained.

  Preferably, the Zr raw material powder further includes a Zr oxide having a tetragonal crystal structure, and the ratio of the Zr oxide having a tetragonal crystal structure to the whole Zr raw material powder is 10 to 60%. . By doing in this way, the effect of the present invention can be heightened.

Preferably, the Zr raw material powder has a specific surface area of 30 m ² / g or more by the BET method.

Preferably, the raw material powder of the element constituting A has a specific surface area of 20 m ² / g or more by the BET method.

Preferably, the raw material powder of the element constituting B has a specific surface area of 30 m ² / g or more by the BET method.

  The effect of this invention can be heightened by making the specific surface area of raw material powder into said range.

  Preferably, the A is Ba alone or at least one selected from Ba and Ca, Sr and Mg.

  Preferably, the B is Ti alone or at least one selected from Ti, Hf and Sn.

  By using the above elements as the elements constituting A and B, a composite oxide powder having excellent electrical characteristics can be obtained.

The composite oxide powder according to the present invention is
A composite oxide powder represented by a general formula A (BZr) O ₃ , which is a set of composite oxide particles having a perovskite crystal structure,
There are no pores in the composite oxide particles,
The composite oxide powder has an average particle size of 0.30 μm or less,
The amount of heterogeneous phase contained in the composite oxide powder is 1.0% or less.

  Although it does not specifically limit as a use of the complex oxide powder concerning this invention, It is suitable as a material which comprises an electronic component.

FIGS. 1A and 1B are Zr mapping images in the composite oxide powder according to the example of the present invention, and FIGS. 1C and 1D are comparative examples of the present invention. It is a mapping image of Zr in the complex oxide powder concerning.

  Hereinafter, the present invention will be described based on embodiments shown in the drawings.

<Composite oxide powder>
The composite oxide powder according to the present embodiment is an aggregate of particles represented by the general formula A (BZr) O ₃ and having a perovskite crystal structure. The element constituting A in the above formula occupies a specific position called A site in the perovskite crystal structure, and the element constituting B occupies a specific position called B site.

Zr replaces the element constituting B and exists at the B site. That is, Zr is dissolved in the B site of the composite oxide represented by ABO ₃ . The substitution ratio (solid solution ratio) of Zr at the B site is preferably more than 0% and 20% or less, assuming that the total number of atoms occupying the B site is 100%.

  In the present embodiment, the element constituting A is preferably Ba alone or at least one selected from Ba and Ca, Sr and Mg. The element constituting B is preferably Ti alone or at least one selected from Ti, Hf and Sn. By selecting the above elements as the elements constituting A and B, a composite oxide powder particularly suitable for producing a dielectric layer of an electronic component can be obtained.

  The composite oxide powder according to this embodiment has an average particle size of 0.30 μm or less, preferably 0.20 μm or less, and the amount of heterogeneous phase contained in the composite oxide powder is preferably 1.0% or less. Preferably it is 0.5% or less.

In the present embodiment, the amount of heterophase indicates a ratio in which a phase other than the compound represented by the general formula A (BZr) O ₃ is included. As a method of measuring the amount of the different phase, in this embodiment, it is measured by Rietveld analysis.

Specifically, the produced composite oxide powder is subjected to X-ray diffraction, and the obtained diffraction intensity is analyzed by Rietveld, whereby the peak intensities of the main component (A (BZr) O ₃ ) and the heterogeneous component are obtained. And the peak intensity ratio is obtained to calculate the amount of heterogeneous phase.

  The method for measuring the particle diameter is not particularly limited, but in this embodiment, the powder is observed using an electron microscope such as SEM or TEM, the area of the particle is calculated from the particle outline, and the equivalent circle diameter is calculated. The value obtained by calculating the diameter is defined as the particle diameter of the particle. Then, the particle diameter of 500 or more raw material powder particles may be measured, and the particle diameter at which the cumulative number becomes 50% may be set as the average particle diameter.

  From the above, the composite oxide powder according to the present embodiment is a fine powder with few impurities. And since this complex oxide powder is manufactured by the method mentioned later, the defect (hole) of the nanometer size (several nanometer-several tens nanometer) resulting from a manufacturing method does not arise in particle | grains. Therefore, an electronic component manufactured using the composite oxide powder has a high temperature load life and the like.

  For example, when a composite oxide powder is manufactured using a hydrothermal synthesis method, defects of nanometer size (about several tens of nanometers) derived from OH groups contained in the raw material seed crystal are likely to occur.

  Therefore, such a composite oxide powder can be suitably used as a raw material for a material constituting an electronic component.

<Method for producing composite oxide powder>
Next, the method for producing the composite oxide powder according to this embodiment will be specifically described below.

  First, a raw material powder of Zr, a raw material powder of an element constituting A, and a raw material powder of an element constituting B are prepared.

The Zr raw material powder may contain carbonate, oxalate, nitrate, hydroxide, organometallic compound, etc., but in this embodiment, the Zr oxide having a monoclinic structure (m powder -ZrO ₂₎ it is contained at least.

In the present embodiment, in the Zr raw material powder, the half width of the monoclinic (111) plane peak is 0.40 ° or more, preferably 0.50 ° or more. By setting the full width at half maximum in the above range, even when the heat treatment temperature is set to 1000 ° C. or lower in the heat treatment step described later, the solid phase reaction can sufficiently proceed. As a result, there is an advantage that unreacted ZrO ₂ hardly remains.

  The full width at half maximum is a measure of crystallinity in general. The larger the full width at half maximum, the poorer the crystallinity, but in this embodiment, the full width at half maximum is preferably within the above range. The upper limit of the full width at half maximum is not particularly limited.

In the present embodiment, it is preferable that the Zr raw material powder further includes a Zr oxide (t-ZrO ₂ ) powder having a tetragonal crystal structure. By including m-ZrO ₂ and t-ZrO ₂ powder in the Zr raw material powder, the above advantages can be further enhanced. More preferably, the raw material powder of Zr is a mixed powder of m-ZrO ₂ powder and t-ZrO ₂ powder.

The content ratio of t-ZrO ₂ in the Zr raw material powder (tetragonal crystallization ratio of ZrO ₂ ) is preferably 10 to 60%, more preferably 30 to 60%. When the raw material powder of Zr contains only m-ZrO ₂ powder, the heat treatment temperature can be lowered and the solid-phase reaction proceeds sufficiently, but problems such as the occurrence of a different phase such as BaZrO ₃ may occur. Therefore, in the present embodiment, t-ZrO ₂ powder is included in the Zr raw material powder, and the tetragonalization rate of ZrO ₂ is within the above range. By doing in this way, said advantage can further be heightened.

It should be noted that even if the tetragonal crystallization ratio of ZrO ₂ exceeds 60%, it is considered that the reactivity of the element constituting B with the raw material powder is high and good characteristics can be obtained, but in this embodiment, ZrO ₂ The upper limit of the tetragonal crystallization rate is 60%.

Note that the tetragonal crystallization rate of ZrO ₂ is obtained from the tetragonal crystallographic 101-plane peak intensity It ₁₀₁ and the monoclinic 111-plane peak intensity Im ₁₁₁ obtained by X-ray diffraction. %) = 100 × It ₁₀₁ / (It ₁₀₁ + Im ₁₁₁ ).

The specific surface area of the Zr raw material powder by the BET method is preferably 30 m ² / g or more, more preferably 50 m ² / g or more. By making a specific surface area into said range, the reactivity of raw material powder can be improved more.

  The raw material powder of the element constituting A may be an oxide, or various compounds that become oxides by heat treatment, such as carbonates, oxalates, nitrates, hydroxides, organometallic compounds, etc. They can be selected and mixed for use.

Specifically, when A is an alkaline earth element such as Ba, Ca, or Sr, it may be an oxide (such as BaO) or a carbonate (such as BaCO ₃ ).

The specific surface area by the BET method of the raw material powder of the element constituting A is preferably 20 m ² / g or more, more preferably 30 m ² / g or more. By making a specific surface area into said range, the reactivity of raw material powder can be improved more.

  The raw material powder for the element constituting B may be an oxide or various compounds that become oxides by heat treatment, such as carbonates, oxalates, nitrates, hydroxides, organometallic compounds, etc. They can be selected and mixed for use.

Specifically, when B is Ti, it may be an oxide (such as TiO ₂ ), a chloride (such as TiCl ₄ ), or a hydroxide (such as Ti (OH) ₄ ). Also good.

The specific surface area by the BET method of the raw material powder of the element constituting B is preferably 30 m ² / g or more, more preferably 50 m ² / g or more. By making a specific surface area into said range, the reactivity of raw material powder can be improved more.

  Next, the raw materials prepared above are weighed and mixed so as to have a predetermined composition ratio, and pulverized as necessary to obtain a raw material mixture. As a method for mixing and pulverizing, for example, a wet method in which a raw material together with a solvent such as water is put into a known pulverization container such as a ball mill and mixed and pulverized can be mentioned. Moreover, you may mix and grind | pulverize by the dry method performed using a dry mixer. At this time, it is preferable to add a dispersant in order to improve the dispersibility of the charged raw materials. A well-known thing should just be used as a dispersing agent.

  Subsequently, the obtained raw material mixture is dried as necessary, and then heat-treated. The temperature rising rate in the heat treatment is preferably 200 to 400 ° C./hour. Moreover, the holding temperature in heat processing is 800-1000 degreeC, Preferably it is 900-1000 degreeC. Further, the holding time may be appropriately determined according to the reaction state, but is preferably 2 to 8 hours. The atmosphere in the heat treatment is preferably in air or in a reduced pressure atmosphere.

  In addition, if it is in the range of said holding temperature and holding time, it does not need to be constant temperature, and temperature may change in steps, even if temperature changes so that it may become high gradually or it may become low. Good.

In the present embodiment, since the above-described powder is used as the Zr raw material powder, even when the heat treatment temperature is in the above range, the reaction in which Zr is solid-solved sufficiently at the B site of the perovskite crystal structure proceeds sufficiently. . As a result, a composite oxide powder containing almost no phase (impurities) other than A (BZr) O ₃ , such as unreacted ZrO ₂ , can be obtained. Moreover, since the heat treatment temperature is low, the growth of the produced A (BZr) O ₃ particles is suppressed, and a (fine) powder having a small particle diameter can be obtained.

  For example, an electronic component having a dielectric layer and an electrode layer can be manufactured using the composite oxide powder thus obtained. A known method can be applied to the production of the electronic component. For example, a dielectric layer paste containing the composite oxide powder can be prepared, and a green laminate can be produced using the dielectric layer paste. And a green laminated body can be baked and an electronic component can be obtained.

  As mentioned above, although embodiment of this invention has been described, this invention is not limited to the embodiment mentioned above at all, and can be variously modified within the range which does not deviate from the summary of this invention.

  Hereinafter, although this invention is demonstrated based on a more detailed Example, this invention is not limited to these Examples.

<Experimental example 1>
First, as a raw material powder of Zr, we were prepared ZrO ₂ powder containing a _ZrO 2 (t-ZrO ₂₎ having _ZrO 2 and (m-ZrO ₂₎ tetragonal structure with a monoclinic structure. The specific surface area of this ZrO ₂ powder was the value shown in Table 1, and the tetragonalization rate and the half width of the peak on the (111) plane of monoclinic crystal (ΔH (111)) were the values shown in Table 1.

The tetragonalization rate was calculated using the tetragonal (101) peak intensity (It ₍₁₀₁₎ ) and the monoclinic (111) peak intensity (Im ₍₁₁₁₎ ). Moreover, the measurement conditions of the X-ray diffraction in a tetragonalization rate and a half value width ((DELTA) H (111)) were made into the same measurement conditions as the X-ray diffraction performed in the measurement of the amount of different phases mentioned later.

Then, as the raw material powder of elements constituting the A, BaCO ₃ (specific surface area: ^20m 2 / g) was prepared as a raw material powder of elements constituting the B, TiO ₂ (specific surface area: 48.5m ² / g ) Was prepared.

These raw materials were weighed so as to satisfy the general formula Ba (Ti _0.90 Zr _0.10 ) O ₃ and mixed with water and a dispersant by a ball mill. The obtained mixed powder was processed under the following heat treatment conditions to produce a composite oxide powder.

  The heat treatment conditions were temperature rising rate: 400 ° C./hour, holding temperature: temperature shown in Table 1, temperature holding time: 4 hours, cooling rate: 400 ° C./hour, atmosphere: in air.

With respect to the obtained composite oxide powder (BaTi _0.90 Zr _0.10 O ₃ ), the amount of different phases and the average particle size were measured by the following method.

<Amount of heterogeneous phase>
In order to obtain the amount of different phases, X-ray diffraction was first performed. A Cu—Kα ray was used as the X-ray source. The measurement conditions were a voltage of 45 kV and a current of 40 mA, a range of 2θ = 20 ° to 120 °, and a scanning speed of 2 deg / min.

  Rietveld analysis was performed from the X-ray diffraction intensity obtained by the measurement, and each peak intensity was refined to evaluate the amount of different phases. The results are shown in Table 1.

<Average particle size>
SEM observation was performed about the primary particle which comprises the obtained powder, 500 particles were observed, the particle | grain outline was discriminate | determined, the area | region of particle | grains was calculated | required, and the equivalent circle diameter of the area was made into the particle diameter. The particle diameter at which the cumulative number was 50% was taken as the average particle diameter. The results are shown in Table 1.

From Table 1, even when the heat treatment temperature is lowered by using a powder containing m-ZrO ₂ and having a half width of 0.40 ° or more as the raw material powder of Zr, the average particle diameter Was 0.30 μm or less, and it was confirmed that a complex oxide powder with few impurities was obtained.

Further, Example 2 and Reference Example 9 and Comparative Examples 11 and 16 were observed with a scanning transmission electron microscope (STEM), and measured using an attached energy dispersive X-ray spectrometer (EDS). The characteristic X-rays of the obtained Zr were quantitatively analyzed to obtain a mapping image for Zr. The results are shown in FIGS.

1A is a mapping image of Example 2, and FIG. 1B is a mapping image of Reference Example 9 . 1C is a mapping image of Comparative Example 11, and FIG. 1D is a mapping image of Comparative Example 16.

1A to 1D clearly show that the distribution of Zr is more uniform in FIGS. 1A and 1B than in FIGS. 1C and 1D. . That is, in FIGS. 1C and 1D, there are a region where Zr is low and a region where Zr is high. The region with a small amount of Zr is in a state where Zr is dissolved in the BaTiO ₃ particles, and the region with a large amount of Zr is considered to be caused by an unreacted Zr raw material. In contrast, in FIGS. 1 (A) and (B), since the solid-phase reaction has proceeded sufficiently, Zr is solid-solved in BaTiO ₃ particles, and Ba (Ti _0.90 Zr _0.10 ) O _3. It was confirmed that there were almost no impurities (such as unreacted Zr raw material). In addition, no nanometer-sized defects (holes) due to the production method were observed in the particles.

<Experimental example 2>
As raw material powders of Zr, m-ZrO ₂ is included, and with a half-value width of the ZrO ₂ powder is a value shown in Table 2, as the raw material powder of elements constituting the A, BaCO ₃ (specific surface area: 20 m ² / G) and CaCO ₃ (specific surface area: 30 m ² / g) in the same manner as in Experimental Example 1, the general formula (Ba _0.99 Ca _0.01 ) (Ti _0.90 Zr _0.10 ) A composite oxide powder satisfying O ₃ was prepared, and the characteristics were evaluated in the same manner as in Experimental Example 1. The results are shown in Table 2.

From Table 2, even when a composite oxide powder represented by (Ba, Ca) (Ti, Zr) O ₃ was produced as A (BZr) O ₃ , the same results as in Experimental Example 1 were obtained. It was.

  From the above, according to the present invention, it was confirmed that a fine powder with few impurities could be obtained.

Claims (6)

A method for producing a composite oxide powder represented by a general formula A (BZr) O3, which is a set of composite oxide particles having a perovskite crystal structure,
Preparing a raw material powder of Zr;
Preparing a raw material powder of the element constituting the A and a raw material powder of the element constituting the B;
Mixing the raw material powder of the Zr, the raw material powder of the element constituting the A, and the raw material powder of the element constituting the B ;
Heat-treating the mixed powder at 800 to 1000 ° C.,
Raw material powder of the Zr is monoclinic comprises an oxide of Zr having the structure of monoclinic observed by X-ray diffraction (111) Ri der half width 0.40 ° or more peaks,
A method for producing a composite oxide powder , wherein the Zr raw material powder has a proportion of Zr oxide having a tetragonal structure of 30 to 60% with respect to the entire Zr raw material powder . The method for producing a composite oxide powder according to claim 1 , wherein the Zr raw material powder has a specific surface area of 30 m 2 / g or more by a BET method. 3. The method for producing a composite oxide powder according to claim 1, wherein the raw material powder of the element constituting A has a specific surface area of 20 m 2 / g or more by BET method. The method for producing a composite oxide powder according to any one of claims 1 to 3 , wherein the raw material powder of the element constituting B has a specific surface area of 30 m2 / g or more by the BET method. Wherein A is, Ba alone or, Ba and Ca, a manufacturing method of a composite oxide powder according to at least one of any one of claims 1-4 is selected from Sr and Mg. Wherein B is, Ti alone or method of producing a composite oxide powder according to any one of claims 1 to 5, which is at least one selected from Ti and Hf and Sn.

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