JPH0769635A - Fine semiconductor powder and production thereof - Google Patents

Abstract

PURPOSE:To produce a semiconductor ceramic capacitor of a laminate shape by a process similar to a process for producing a laminated ceramic capacitor by adding hydroxide of an alkaline earth metal to a titanium oxide hydrate slurry and carrying out heating, filtration and reduction. CONSTITUTION:Hydroxide of an alkaline earth metal is added to a titanium oxide hydrate slurry contg. 0.2-0.6wt.% SO3 basing on the amt. of TiO2 so that the concn. of the alkaline earth metal in the slurry is regulated to 0.1-0.8mol/l. The slurry is then heated to >=80 deg.C, held at the temp. for 0.5-5hr and filtered. The resultant powder is washed, dried and reduced at 1,100-1,400 deg.C to obtain the objective fine semiconductor powder having <=10mum particle diameter and <=500OMEGA.cm specific resistance. The surfaces of particles of this powder based on a TiO2-contg. perovskite type compd. as a reduced product of a TiO2- contg. perovskite type compd.

Description

Detailed Description of the Invention

[0001] INDUSTRIAL APPLICABILITY The present invention is useful Ti as a semiconductor ceramic raw material
The present invention relates to a semiconductor fine powder containing an O ₂ based perovskite type compound as a main component and a method for producing the same.

2. Description of the Related Art With the recent progress in size and weight reduction of electronic devices,
The electronic components used therein are also required to have a significantly small size and high reliability. T
The same applies to ferroelectric ceramics using an iO ₂ -based perovskite compound, and various studies have been conducted in terms of compounding technology, molding technology, sintering technology, etc. for the purpose of miniaturization and high performance. In addition, in order to improve the characteristics of the material itself, 1
A fine powder of a spherical TiO ₂ -based perovskite compound having a diameter of μm or less, preferably 0.5 μm or less, a narrow particle size distribution, has been developed. However, in reality, such a technique cannot satisfy the demand for downsizing in the market.

That is, although the conventional ceramics capacitor has excellent high frequency characteristics as compared with the tantalum capacitor and the film capacitor, the capacitance value obtained in the same size is small, so that the conventional product has a tantalum capacitor and a film capacitor. Could not be a substitute for. However, in the grain boundary insulation type semiconductor ceramic capacitor, since the boundary between particles in the ceramic is used as a dielectric layer or an insulating layer, the effective dielectric thickness is a fraction to several tens of minutes with respect to the thickness of the ceramic. It is 1 and can be made much smaller than conventional ceramic capacitors. Further, the surface-insulating semiconductor ceramics uses a glass-diffused layer formed at the interface between the semiconductor ceramics and the electrode as an insulating layer, and has a higher apparent dielectric constant than that of the grain boundary insulating type.

For the above reasons, various attempts have been made to use the semiconductor ceramic capacitor as a substitute for a tantalum capacitor or a film capacitor. In the current semiconductor ceramic capacitor, first, a semiconductor porcelain is manufactured and then electrodes are attached. It was manufactured by the above method, and there was a problem in the manufacturing technology that it was difficult to stack, which is an important point for downsizing and large capacity. For this reason, there is a limit to the use as a substitute for a tantalum capacitor or a film capacitor.

[0005] In order to manufacture a laminated semiconductor ceramic capacitor by a manufacturing process similar to that of a laminated ceramic capacitor, semiconductor fine powder is required, but in order to reduce a TiO ₂ -based perovskite compound, a high temperature of 1100 ° C or higher is required. However, the conventional TiO ₂ -based perovskite-type compound is sintered into a lump when subjected to the reduction treatment at such a high temperature, and a semiconductor fine powder having good characteristics cannot be obtained.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a semiconductor fine powder capable of producing a laminated semiconductor ceramic capacitor by a manufacturing process similar to that of a laminated ceramic capacitor, and a manufacturing method thereof.

Means for Solving the Problems The present invention has a particle size of 10 μm or less and a powder specific resistance of 500Ω.
TiO ₂ or less and the particle surface is a reduction product of a TiO ₂ -based perovskite-type compound
_The present invention provides a semiconductor fine powder whose main component is a _2- system perovskite type compound. In the semiconductor fine powder according to the present invention, it is preferable to further provide an insulating layer on the surface,
The MO / TiO ₂ molar ratio (M is an alkaline earth metal) is preferably 0.98 to 1.20, and 0.99 to
It is more preferably 1.10.

Depending on the reducing conditions, such as temperature, time, type and amount of added metal, etc., the powder resistivity of the reduced powder is 10 ⁶
It is possible to control in the range of -10 ^-1 Ω · cm, but it is necessary for the raw material powder for semiconductor ceramic capacitors to have low powder resistance in order to reduce loss, and this powder resistance value is It is preferably 500 Ω · cm or less, and more preferably 300 Ω · cm or less.

The semiconductor fine powder according to the present invention is typically manufactured by the following method.

That is, a hydroxide of titanium oxide having an SO ₃ content of 0.2 to 0.6% by weight with respect to TiO ₂ is added to a hydroxide of an alkaline earth metal and a concentration of the alkaline earth metal is 0.2 to The TiO ₂ -based perovskite-type compound obtained by adding 0.8 mol / l and then heating the slurry to a temperature of 80 ° C. or higher and maintaining the temperature at the temperature for 0.5 to 10 hours is It has been found that even when reduced at a high temperature of 1100 to 1400 ° C. by a valence control system, a forced reduction system, or a combination thereof, it does not become a lump and is obtained as a semiconductor fine powder having a particle size of 10 μm or less. The invention has been completed.

A titanium oxide hydroxide slurry having an SO ₃ content of 0.2 to 0.6% by weight is washed with a hydrolysis product of an aqueous solution of titanyl sulfate, and then an alkali is further added to adsorb the titanium oxide hydroxide. It can also be obtained by removing the sulfuric acid radicals that are present, or by adding an appropriate amount of sulfuric acid to hydrous titanium oxide obtained by hydrolyzing an aqueous solution of titanium tetrachloride.

The hydrolysis product of the aqueous solution of titanyl sulfate forms large aggregates, but even if it is used as it is as a raw material for synthesizing a perovskite type compound, semiconductor fine powder having desired characteristics can be obtained.

However, it is desirable to use titania sol as a TiO ₂ raw material when obtaining semiconductor fine powder having a particularly small particle size of 1 μm or less. Such a titania sol has a pH of 2 or less by adding monobasic acid such as hydrochloric acid or nitric acid or trichloroacetic acid to a hydrous titanium oxide slurry having an SO ₃ content of 0.2 to 0.6% by weight. Obtained by adjusting. In order to use titania sol as a TiO ₂ raw material, it is necessary to remove chlorine ions or nitrate ions adsorbed on the titania sol particles. This is because the titania sol is added with an alkali such as NaOH, KOH or NH ₄ OH. It is made by blending and washing. The pH during neutralization is preferably 5-6. When the pH value is higher than this range, less SO ₃ is contained in the titania sol. In addition, NaO is used as an alkali during neutralization.
If H or KOH is used, adjust the pH of the slurry to 7
With the above adjustment, Na ⁺ and K ⁺ are adsorbed on the hydrous titanium oxide, and thus Na of the perovskite type compound synthesized is synthesized.
It is not preferable because the content of K and K increases.

Amorphous titanium oxide and X-containing titanium oxide can be used.
There are some which show an anatase type crystal structure as measured by line diffraction, but any hydrous titanium oxide can be used without any trouble.

The alkaline earth metal hydroxide used in the present invention is generally a white solid containing water of crystallization, but it may be used as it is, or may be used by dissolving it in water beforehand. Alkaline earth metal hydroxides easily react with carbon dioxide in the air to form carbonates, but since carbonates have lower solubility in water than hydroxides, they are different from the perovskite-type compound particles alone. Since it grows as particles of the above, it leads to non-uniform composition of the perovskite type compound particle powder, which is not preferable. Therefore, the alkaline earth metal hydroxide is not only sufficiently purified to remove the carbonate before being subjected to the reaction, but also the aqueous solution does not come into contact with carbon dioxide during the production reaction of the perovskite type compound and in the washing step after the reaction. You need to be careful. It is sufficient to purify the alkaline earth metal hydroxide by a known method, and the synthesis reaction and washing of the perovskite type compound may be carried out under a nitrogen atmosphere.

SO of hydrous titanium oxide used in the present invention
_The content of ₃ is preferably 0.2 to 0.6% by weight. If the SO ₃ content deviates from this range, it becomes difficult to obtain the reduced product in powder form. Conventionally, SO ₃ in a perovskite type compound forms a sulfate, and since this compound is a paraelectric substance, mixing of the compound into the perovskite type compound powder lowers the relative dielectric constant of the ceramics obtained from the powder. It was said to be unfavorable because it leads to.

However, the present invention succeeds in obtaining a reduced product as a powder by adjusting the amount of SO ₃ within an appropriate range, and a novel material based on a new idea different from the conventional idea. Is provided.

The mixing ratio of the hydrous titanium oxide and the alkaline earth metal hydroxide is preferably 1.0 to 1.5 in terms of MO / TiO ₂ molar ratio. That is, when the molar ratio is less than 1.0, the reaction rate is slow, which is not preferable, and when it is more than 1.5, the reaction rate is not particularly high and is meaningless.

The concentration of alkaline earth metal hydroxide is 0.1
The preferred range is 0.8 mol / l. That is, when the concentration is less than 0.1 mol / l, not only the reaction requires a long time, but also the composition of the obtained reaction product varies greatly from lot to lot, which is not preferable. If the alkaline earth metal concentration is low, MO / TiO ₂
It is preferable to increase the molar ratio.

There is no particular problem if the reaction temperature for synthesizing the perovskite type compound is 80 ° C. or higher. However, if the reaction temperature becomes higher, a reaction vessel having a higher pressure is required, which is not preferable, and it is practically 100 to 130 ° C. Is appropriate.

MO in the generated perovskite type compound
The / TiO ₂ molar ratio is preferably in the range of 0.98 to 1.20, more preferably in the range of 0.99 to 1.10.

SO ₃ contained in hydrous titanium oxide
Almost all of the above is included in the synthesized perovskite type compound.

The TiO ₂ type perovskite type compound of the present invention includes barium titanate and strontium titanate. Dielectric constant, dielectric loss of semiconductor capacitor,
For the purpose of controlling the electrical characteristics such as the rate of change in the dielectric constant with temperature and the resistance, Ba of barium titanate can be partially replaced by one or more elements selected from Ca, Sr and Mg. Similarly, for strontium titanate, a part of Sr is Ba, Ca and Mg.
It may be partially replaced by one or more elements more selected. The amount of substitution at this time varies depending on the required properties, but usually a substitution amount up to about 30 mol% will sufficiently improve the properties. It is also possible to partially replace Ti with Zr.

The reduction is a known method, that is, a forced reduction method,
It can be carried out by a valence control method, a combination method thereof, or the like, and the temperature is suitably in the range of 1100 to 1400 ° C. That is, if it is lower than this range, the reduction does not proceed, and if it is higher than this range, the particles sinter to form a lump. When reducing by a valence control method, an oxide of an element, which is considered to be effective in manufacturing semiconductor porcelain, such as Nd
₂ O ₃ , La ₂ O ₃ , Dy ₂ O ₃ , Sm ₂ O ₃ , Pr ₂ O ₃ , Gd
_At least one metal oxide selected from the group consisting of trivalent metal oxides of ₂ O ₃ and Ho ₂ O ₃ , or Nb ₂ O ₅ ,
Addition of at least one metal oxide selected from the group consisting of pentavalent metal oxides of Ta ₂ O ₅ is effective, and at least one metal oxide selected from the group consisting of ZnO, SiO _{2 and the} like is effective. It is also effective to add the metal oxide together with the trivalent or pentavalent metal oxide.

The insulating layer is formed on the surface of the semiconductor fine powder of the present invention by MnO ₂ , CuO, Bi ₂ O ₃ , PbO, Tl ₂ O.
_At least one oxide selected from the group consisting of ₃ , Sb ₂ O ₃ , Fe ₂ O _{3 and the} like is added together with the oxide of the trivalent or pentavalent element to reduce it, and then heat treatment is performed. Alternatively, the reducing powder may be added with the above-mentioned additive for forming the insulating layer and fired. Furthermore, after the reduction is completed, the insulating layer can be formed by reoxidizing in an oxidizing atmosphere and forming an oxide film on the surface.

The SO contained in the powder in the reduction treatment step
_Since most of ₃ is volatilized, the SO ₃ content of the semiconductor fine powder after reduction is 10% or less of the SO ₃ content before reduction.

The semiconductor fine powder of the present invention has a particle size of 10 μm or less and a resistance of 500 Ω · cm or less, and is suitable for any semiconductor ceramic capacitor such as grain boundary insulation type, reoxidation type and surface insulation type. Can also be used effectively. In particular, it is effectively used when manufacturing a high-capacity multilayer semiconductor ceramic capacitor by a manufacturing process similar to that of a multilayer capacitor.

Hereinafter, the present invention will be described in more detail with reference to examples. The following examples are given for illustrative purposes only and the scope of the invention is not limited thereby. Example 1 The hydrous titanium oxide obtained by hydrolyzing an aqueous solution of titanyl sulfate was washed with pure water until the electric conductivity of the supernatant liquid reached 1500 μS / cm, and then water was added until the pH of the slurry reached 8.5. Aqueous sodium oxide solution was added. Hydrochloric acid was added dropwise to the slurry to adjust the pH of the slurry to 7, and then the supernatant of the slurry had an electric conductivity of 200 μS /
It was washed with pure water until it became cm. A part of the hydrous titanium oxide was dried, and the SO ₃ content determined by chemical analysis was 0.41% by weight.

4600 g of hydrous titanium oxide having a water content of 95% thus obtained was transferred to a SUS reaction container,
After flowing nitrogen gas into the reaction vessel for 20 minutes, Ba (O 2
After adding 1358 g of (H) ₂ .8H ₂ O, pure water was further added to adjust the slurry to BaO 0.21 mol / l. The slurry was heated to 110 ° C. and kept at that temperature for 3 hours. The slurry was cooled to a temperature of 40 ° C., washed with pure water by decantation in a nitrogen gas atmosphere, and then filtered. The obtained cake was dried at 110 ° C. in the atmosphere.

The dried product was treated with N ₂ (90% by volume) + H ₂ (1
(0 vol%) Reduction was carried out at 1350 ° C. for 8 hours in a gas stream to obtain a black reduced powder containing barium titanate as a crystal phase. The reduced powder was compression-molded at 280 kg / cm ² and the DC resistance of the molded body was measured using a universal bridge manufactured by Yokogawa Hewlett-Packard Co., and the powder resistance value was calculated by the following formula.・ It was cm.

Powder resistance value (Ω · cm) = DC resistance (Ω)
x (cross-sectional area (cm ² ) / thickness (cm)) When the powder was observed with an electron microscope, the particle size was 0.2 to 3 μm, and the specific surface area measured by the BET method was 1.8 m ² / g. Met. The BaO / TiO ₂ molar ratio determined by chemical analysis was 1.005, and the SO ₃ content was 0.013% by weight.

Example 2 Hydrous titanium oxide obtained by hydrolyzing an aqueous solution of titanyl sulfate was washed with pure water until the electric conductivity of the supernatant became 2100 μS / cm, and then the pH of the slurry was adjusted to 8.0. Aqueous sodium hydroxide solution was added until. Hydrochloric acid was added dropwise to the slurry to adjust the pH of the slurry to 7, and then the supernatant of the slurry had an electric conductivity of 150 μS /
It was washed with pure water until it became cm. After that, hydrochloric acid was added to the slurry again to adjust the pH of the slurry to 1.0 to obtain a titania sol dispersion liquid. An aqueous sodium hydroxide solution was added dropwise to the titania sol dispersion liquid to adjust the pH of the dispersion liquid to 6, and then the electric conductivity of the supernatant liquid was 130 μS /
It was washed with pure water up to cm. A part of the hydrous titanium oxide was dried, and the SO ₃ content determined by chemical analysis was 0.
It was 32% by weight.

3200 g of hydrous titanium oxide having a water content of 92% thus obtained was transferred to a SUS reaction container,
After flowing nitrogen gas into the reaction vessel for 20 minutes, Sr (O
H) ₂ · 8H ₂ O After adding 1100g was further adjusted to a slurry of SrO0.3 mol / l by the addition of pure water. The slurry was heated to the boiling point and kept at that temperature for 5 hours. After cooling the slurry to a temperature of 40 ° C. and decanting with pure water in a nitrogen gas atmosphere,
Nb ₂ O ₅ powder 1 having an average particle size of 0.6 μm was added to the slurry.
3 g and SiO ₂ powder 4 having an average particle size of 0.01 μm 4
g was added and mixed, and then filtered. The obtained cake was dried at 110 ° C. in the atmosphere.

The dried product was treated with N ₂ (90% by volume) + H ₂ (1
(0 vol%) Reduction was carried out in a gas stream at 1200 ° C. for 1 hour to obtain a black reduced powder containing strontium titanate as a crystal phase. The powder resistance value of the reduced powder measured in the same manner as in Example 1 was 250 Ω · cm.

Observation with an electron microscope revealed that the particle size was 0.3 to 1 μm and the specific surface area measured by the BET method was 2.5 m ² / g. The SrO / TiO ₂ molar ratio determined by chemical analysis was 1.022, and the SO ₃ content was 0.011% by weight.

Example 3 Hydrous titanium oxide 46 used in Example 2 and having a water content of 93%
After transferring 00 g to a reaction container made of SUS and flowing nitrogen gas into the reaction container for 20 minutes, 1 (1) of Ba (OH) ₂ .8H ₂ O was added.
After adding 340 g and 120 g of Sr (OH) ₂ .8H ₂ O, pure water was further added to BaO + SrO 0.3 mol / l
Was adjusted to a slurry of. The slurry was heated to 110 ° C. and kept at that temperature for 3 hours. Slurry temperature is 40 ℃
And then washed by decantation with pure water in a nitrogen gas atmosphere. Then, 18 g of La ₂ O ₃ powder having an average particle diameter of 0.6 μm was added to and mixed with the slurry,
After this time, it was filtered. The obtained cake was dried at 110 ° C. in the atmosphere.

The dried product was treated with N ₂ (90% by volume) + H ₂ (1
(0% by volume) In a gas stream, reduction was performed at 1200 ° C. for 1 hour to obtain a black reduced powder containing barium titanate in which strontium was solid-dissolved as a crystal phase. The powder resistance value of the reduced powder measured in the same manner as in Example 1 was 140 Ω · cm.

Observation with an electron microscope revealed that the particle size was 0.5 to ² μm and the specific surface area measured by the BET method was 1.3 m ² / g. The (BaO + SrO) / TiO ₂ molar ratio determined by chemical analysis was 1.007.

Example 4 Hydrous titanium oxide 48 having a water content of 92% used in Example 2
00 g was transferred to a SUS reaction vessel, nitrogen gas was allowed to flow in the reaction vessel for 20 minutes, and then Sr (OH) ₂ .8H ₂ O was added to 1 g.
After adding 480 g and 70 g of Ca (OH) ₂ , pure water was further added to adjust the slurry to SrO + CaO 0.3 mol / l. The slurry was heated to the boiling point and kept at that temperature for 2 hours. The slurry was cooled to a temperature of 40 ° C., washed with pure water by decantation in a nitrogen gas atmosphere, and then the slurry had an average particle size of 0.6.
18 g of La ₂ O ₃ powder of 0.5 μm and average particle size of 0.5 μm
4 g of ZnO powder (1) was added and mixed, and then filtered. The obtained cake was dried at 110 ° C. in the atmosphere.

The dried product was treated with N ₂ (90% by volume) + H ₂ (1
(0% by volume) In a gas stream, reduction was performed at 1140 ° C. for 1 hour to obtain a black reduced powder containing strontium titanate in which calcium was dissolved as a crystal phase. The powder resistance value of the reduced powder measured in the same manner as in Example 1 was 330 Ω · cm.

Observation with an electron microscope revealed that the particle size was 0.4 to 1.5 μm, and the (SrO + CaO) / TiO ₂ molar ratio determined by chemical analysis was 1.001.

Example 5 Hydrous titanium oxide 48 having a water content of 92% used in Example 2
After transferring 00 g to a reaction container made of SUS and flowing nitrogen gas into the reaction container for 20 minutes, 1 (1) of Ba (OH) ₂ .8H ₂ O was added.
After 480 g and 70 g of Mg (OH) ₂ were added, pure water was further added to adjust the slurry to BaO + MgO 0.3 mol / l. The slurry was heated to the boiling point and kept at that temperature for 2 hours. The slurry was cooled to a temperature of 40 ° C., washed with pure water by decantation in a nitrogen gas atmosphere, and then the slurry had an average particle size of 0.6.
18 g of ₂ μm Ta ₂ O ₅ powder and 0.5 μm average particle size
4 g of ZnO powder (1) was added and mixed, and then filtered. The obtained cake was dried at 110 ° C. in the atmosphere.

The dried product was treated with N ₂ (90% by volume) + H ₂ (1
(0 vol%) Reduction was carried out in a gas stream at 1180 ° C. for 2 hours to obtain a black reduced powder containing barium titanate in which magnesium was solid-dissolved as a crystal phase. The powder resistance value of the reduced powder measured in the same manner as in Example 1 was 45 Ω · cm.

Observation with an electron microscope revealed that the particle size was 0.4 to 1.5 μm, and the (BaO + MgO) / TiO ₂ molar ratio determined by chemical analysis was 1.001.

Example 6 After 100 g of the reduced powder obtained in Example 1 was slurried with toluene, 6 g of PbO powder was added and mixed. After the slurry was dried, it was heated in air at 800 ° C. for 30 minutes to obtain a powder in which an insulating layer was formed on the particle surface. The powder resistance value calculated by the same method as in Example 1 was 0.7.
It was x10 ⁴ Ω · cm.

Comparative Example 1 Barium titanate powder synthesized in the same manner as in Example 1 using hydrous titanium oxide having an SO ₃ content of 0.1% by weight was N ₂ (90% by volume) + H ₂ (10% by volume) When reduced in a gas stream at 1350 ° C. for 8 hours,
The reduced product became a lump and could not be obtained as a powder.

Comparative Example 2 In Comparative Example 1, the reduction temperature was changed to 1200 ° C. for reduction, but the obtained product was lumpy as in Comparative Example 1 and could not be obtained as a powder.

Comparative Example 3 Barium titanate powder synthesized in the same manner as in Example 1 using hydrous titanium oxide having an SO ₃ content of 0.8% by weight was mixed with N ₂ (90% by volume) + H ₂ (10% by volume) When reduced in a gas stream at 1350 ° C. for 8 hours,
The reduced product became a lump and could not be obtained as a powder.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Chisato Kariyama 25 Titan Kogyo Co., Ltd., 1978, Kogushi, Ube City, Yamaguchi Prefecture

Claims (6)

[Claims] 1. A particle diameter of 10 μm or less and a powder specific resistance of 50.
T is characterized in that it is 0 Ω · cm or less, and the particle surface is a reduction product of a TiO ₂ -based perovskite-type compound.
The semiconductor fine powder based on iO ₂ based perovskite. 2. A coated semiconductor fine powder, further comprising an insulating layer on the surface of the semiconductor fine powder according to claim 1. 3. The semiconductor fine particles according to claim 1 or 2, wherein the MO / TiO ₂ molar ratio (M is an alkaline earth metal) is 0.98 to 1.20. 4. A MO / TiO ₂ molar ratio of 0.99 to 1.10.
4. The semiconductor fine particles according to claim 3, wherein 5. The content of SO _{3 with} respect to TiO ₂ is 0.2 to.
The concentration of the hydrous titanium oxide slurry is 0.6% by weight, and the concentration of the alkaline earth metal in the slurry is 0.1 to 0.8 mol /
Alkaline earth metal hydroxide was added so as to be 1 liter, and then the slurry was heated to 80 ° C. or higher and kept at the temperature for 0.5 to 5 hours, filtered, washed and dried,
The method for producing a semiconductor fine powder according to claim 1, wherein the reduction is performed at 1100 ° C to 1400 ° C. 6. When reducing, Nd ₂ O ₃ , La ₂ O ₃ ,
Dy ₂ O ₃ , Sm ₂ O ₃ , Pr ₂ O ₃ , Gd ₂ O ₃ , and Ho
_At least one metal oxide selected from the group consisting of trivalent metal oxides of ₂ O ₃ , or Nb ₂ O ₅ and Ta ₂ O ₅
The method for producing a semiconductor fine powder according to claim 5, wherein at least one metal oxide selected from the group consisting of pentavalent metal oxides is added and mixed.