WO2008062693A1

WO2008062693A1 - Process for producing phosphor precursor

Info

Publication number: WO2008062693A1
Application number: PCT/JP2007/072003
Authority: WO
Inventors: Jun Takai; Hideharu Iwasaki
Original assignee: Kuraray Luminas Co., Ltd.
Priority date: 2006-11-21
Filing date: 2007-11-13
Publication date: 2008-05-29
Also published as: JP5300490B2; TW200835775A; JPWO2008062693A1

Abstract

A process for producing a precursor for a II-VI Group element phosphor, characterized by adding an amide compound containing a Group VI element to an aqueous liquid phase which contains an electrolyte compound comprising an inorganic acid salt or organic acid salt of a typical metal and contains a compound of a Group II element to thereby produce particles of a II-VI Group element compound semiconductor. By the process, a II-VI Group element compound semiconductor precursor for a phosphor can be produced as a monodisperse particulate reaction product having reduced unevenness in particle diameter. The particulate product is aggregates having an average particle diameter in terms of D50 of 8-30 µm and a standard deviation of 0.01-0.2.

Description

Specification

Method for producing phosphor precursor

Technical field

The present invention relates to a method for producing a π-νι group compound semiconductor particle useful for producing an inorganic phosphor. In particular, a method for producing phosphor precursor particles having a uniform particle size by controlling the particle size distribution of aggregates (secondary particles) composed of primary particles of a ιι-νι group compound semiconductor, and obtained by the same method The present invention relates to phosphor precursor particles.

Background art

[0002] II-VI group compound semiconductors, for example, compound semiconductors mainly composed of zinc sulfide or the like are doped with an activating element such as manganese, copper, silver, terbium, thulium, europium, or fluorine in the crystal structure. Thereafter, when further heat treatment or the like is performed, the light emission phenomenon is exhibited by irradiation with light, electrons or the like or application of voltage. Therefore, the above compound semiconductor is useful as a host material for phosphors, and in particular, compound semiconductor particles mainly composed of zinc sulfide or the like are used in plasma displays, electret luminescent displays, field emission displays, etc. It can be a precursor for producing a phosphor used in a display device.

[0003] Here, the term "precursor" means a compound semiconductor doped with an activator, which is in a stage before being subjected to heat treatment or the like. In other words, a compound semiconductor doped with an activator exhibits properties as a phosphor only after being subjected to heat treatment or the like. Therefore, the precursor in the previous stage to become a phosphor is strictly different from the phosphor itself. Indicates a distinction.

[0004] Methods for synthesizing phosphor precursors based on zinc sulfide include a method using a solid phase reaction and a method using a reaction in a liquid phase.

[0005] Regarding the former solid-phase synthesis method, the raw material zinc sulfide particles are grown together with inorganic salts called fluxes from 800 ° C to 1300 ° C at the very first temperature to grow into micron-sized particles. Followed by second calcination at 500 ° C. and 1000 ° C. to obtain phosphor particles (see Patent Documents !! to 3). In this method, since baking is performed at a high temperature, it is difficult to add a new component to the reaction system during the progress of the solid-phase reaction. It is difficult to dope the activator or coactivator inside the core so as to obtain a homogenized concentration distribution within the particles. Therefore, the solid phase synthesis method has a limit in obtaining a phosphor with higher brightness by doping the zinc sulfide matrix with an activator.

[0006] On the other hand, when the group II-VI phosphor precursor is synthesized by the latter liquid phase synthesis method, an activator or a coactivator is added while controlling the amount thereof during particle growth. Therefore, unlike the solid phase synthesis method, the concentration distribution of the activator or coactivator inside the obtained phosphor particles can be homogenized. Phosphor particles are formed through two processes, nucleation and particle growth. By controlling the degree of supersaturation during particle growth, monodisperse particles with a narrow particle size distribution are used. A product can be obtained.

[0007] Regarding the synthesis of II-VI group phosphor precursors in the liquid phase, a method of synthesizing particles under hydrothermal conditions (see, for example, Patent Document 4) and a method of controlling particle size distribution ( For example, see Patent Document 5).

[0008] On the other hand, the phosphor base material and each raw material component solution containing the constituent elements of the activator or coactivator are mixed to coprecipitate the phosphor base crystal, activator or coactivator. A method for producing a phosphor by precipitation is disclosed (see Patent Document 6). Further, as a method for producing a II-VI compound semiconductor, a method of reacting a Group 11 element-containing compound with a Group VI element-containing amide compound such as thioacetamide under hydrothermal conditions is also disclosed (Patent Document 7 and Non-Patent Document 7). (See Patent Literature 1).

Patent Document 1: JP-A-8-183954

Patent Document 2: JP-A-7-62342

Patent Document 3: JP-A-6-330035

Patent Document 4: Japanese Patent Laid-Open No. 2005-306713

Patent Document 5: JP-A-2005-139372

Patent Document 6: Japanese Unexamined Patent Application Publication No. 2005-132947

Patent Literature 7: Special Table 2004-520260

Non-Patent Document 1: J. Chem. Soc. Faraday Trans., 1 (80) 563—570 (1984) Disclosure of the Invention

Problems to be solved by the invention [0009] The phosphor particles obtained by the methods disclosed in Patent Documents 4 to 7 and the like are fine primary particles having an average particle diameter of about several nanometers. These primary particles can aggregate with each other to form secondary particles having a particle size of several hundreds of micrometers, while there may be particles that remain as small particles having a particle size of several nanometers to several tens of nanometers. This gives a particle product with a broad particle size distribution. Particle products with large variations in particle size have irregular particle shapes and a large difference in sedimentation speed, which requires complicated processes such as particle recovery and washing, or a very long time. There is a problem in that it is inconvenient to handle. Therefore, it has been desired to develop a method for preparing monodispersed phosphor precursor particles having a narrow particle size distribution.

Means for solving the problem

[0010] As a result of diligent research, the present inventors made a reaction between a group II element and a raw material compound containing a group VI element in an aqueous liquid phase to which an electrolyte compound composed of a specific metal salt was added. It was found that when primary particles of a Group VI compound semiconductor were produced, the primary particles were further aggregated to form secondary particles having a uniform particle size, and the present invention was completed.

That is, the present invention adds a group VI element-containing amide compound to an aqueous liquid phase containing an electrolyte compound composed of an inorganic acid salt or an organic acid salt of a typical metal and a group II element-containing compound, and π-νι Provided is a method for producing a group II-VI phosphor precursor, characterized in that particles of a group III compound semiconductor are produced.

[0012] The II-VI group compound semiconductor particles obtained by the present invention are not limited to the primary particles generated by the reaction with the Group II element-containing compound immediately after the addition of the Group VI element-containing amide compound. Secondary particles (aggregates) formed by aggregation in the liquid phase are also included. Therefore, another embodiment of the present invention is an aggregate of II-VI compound semiconductors represented by D.

The aggregate is characterized by an average particle size of 8-30 m and a standard deviation of 0.0;! -0.2.

The invention's effect

[0013] According to the method of the present invention, II-VI compound semiconductor particles whose particle size distribution is controlled to be monodispersed can be obtained. Therefore, if the phosphor precursor particles obtained by the present invention are used, the efficiency of the steps such as the washing and recovery operation of the particles is remarkably improved, and The efficiency of the entire manufacturing process of the light body can be improved.

Brief Description of Drawings

[0014] [FIG. 1] Particle size distribution of phosphor precursor particles obtained in Example 1 (A)

[FIG. 2] SEM photograph of phosphor precursor particles obtained in Example 1 (A) (upper photo: sukeno-reno 10 ^ 111, magnification 3000 times, lower photo: scale bar 60 ^ 111, magnification 60 times) )

[Fig. 3] Particle size distribution of phosphor precursor particles obtained in Example 2

FIG. 4 Particle size distribution of phosphor precursor particles obtained in Example 3

FIG. 5: Particle size distribution of phosphor precursor particles obtained in Example 4

FIG. 6: Particle size distribution of phosphor precursor particles obtained in Example 6

FIG. 7: Particle size distribution of phosphor precursor particles obtained in Example 7

FIG. 8: Particle size distribution of phosphor precursor particles obtained in Example 8

FIG. 9: Particle size distribution of phosphor precursor particles obtained in Comparative Example 1

[FIG. 10] SEM photograph of phosphor precursor particles obtained in Comparative Example 1 (scale bar 6 am, magnification 5000 times)

FIG. 11: Particle size distribution of phosphor precursor particles obtained in Comparative Example 2

BEST MODE FOR CARRYING OUT THE INVENTION

The term “II group VI compound semiconductor” used in the present application is composed of group II elements (Be, Mg, Zn, Cd, Hg) and group VI elements (O, S, Se, Te). It is a general term for binary compound semiconductors and mixed crystal semiconductors. Examples of II-VI group compound semiconductors used in the present invention include zinc sulfide, zinc selenide, cadmium sulfide, cadmium selenide, and the like. · It may be partially replaced by non-metal ions (activator or coactivator).

[0016] Group II element-containing compounds used in the present invention are not particularly limited, but include inorganic acid salts such as zinc chloride, zinc nitrate, zinc sulfate, cadmium chloride, cadmium nitrate, cadmium sulfate, and zinc acetate. Organic acid salts such as zinc propionate, zinc oxalate, cadmium acetate, cadmium propionate, and cadmium oxalate can be used. These compounds may be used alone or in combination. This compound can be used at any concentration, but if the concentration is too high, II-VI compound semiconductors are produced. While the rate of growth increases and other ions such as activators are not introduced homogeneously, if the concentration is too low, the growth rate of the particles is slow, so the volumetric efficiency is reduced and the effect of the electrolyte is dilute. This is not preferable because it is difficult to control the particle size distribution. In view of these points, in the present invention, the group II element-containing compound is used at a concentration of 0.01 mol / liter to 5 mol / liter, preferably 0.1 mol / liter to 2 mol / liter. The

As the group VI element-containing amide compound used in the present invention, thioamides such as thioformamide, thioacetamide, and thiopropionamide can be used. These may be used singly or as a mixture of a plurality of types, but thioacetamide is preferably used from the viewpoints of economy and availability. Regarding the use amount of thioamides, considering reaction efficiency and volumetric efficiency, 1.0 to 100 times, preferably 1.7 to 30 times, more preferably, relative to the number of moles of the group X element-containing compound 1. Use in an amount that gives 9 to 5 times the number of moles.

[0018] The liquid phase medium used in the present invention is typically water. Unless the solubility of the additive (electrolyte) described later is significantly reduced, a polar organic compound (for example, methanol, ethanol, etc.) In addition to alcohol!

[0019] In the present invention, a mother substance produced by adding a compound containing an activator or a coactivator element capable of becoming a luminescence center in an aqueous liquid phase together with a group II element-containing compound and a group VI element-containing amide. The element crystal can be doped with ions of the element. Elements that can be used as the emission center include transition metals such as manganese, copper, silver, gold, and iridium, halogens such as chlorine, iodine, and bromine, cerium, iridium, praseodymium, neodymium, samarium, europium, gadolinium, tenolebium, Rare earths such as dysprosium, honorium, enorebium, sillium, ytterbium. If necessary, examples include aluminum, gallium, indium, and halogens such as fluorine, chlorine, bromine and iodine which act as donors for the transition metals and rare earths that are acceptors. These elements can be introduced by using halides such as chloride, bromide and iodide, organic acid salts such as formic acid, acetic acid and propionic acid, complex salts such as acetylylacetonate and the like. These compounds may be used alone or as a mixture of a plurality of types. Furthermore, a coordinating compound such as pyridine and phosphine can be present together. Of the above compounds The amount used is usually a force ranging from 0.0001 parts by weight to 20 parts by weight as ions to be introduced with respect to 100 parts by weight of the π-νι group compound semiconductor to be produced. In consideration of economy, the range is from 0.0002 to 10 parts by weight.

[0020] In the present invention, particles of a π-νι group phosphor are generated by the reaction of the group II or group VI element-containing compound. The primary particles of the phosphor particles are fine particles having a particle size of several nm to 30 nm, but further aggregate in the aqueous liquid phase in which the electrolyte compound is dissolved to form secondary particles of an appropriate size. . The particle size distribution of the secondary particles obtained by the present invention shows narrow monodispersity. The average particle size of the agglomerates usually obtained is usually less than 30, im and the standard deviation is less than 0.2. Preferably, the average particle size of the agglomerates is 8-30 m and the standard deviation is 0.0;! -0.2.

[0021] The term "particle size" used herein means an average particle size obtained by determining the center particle size D50 from the particle size distribution curve unless otherwise specified.

[0022] In the present invention, the additive (flocculating agent) that can further agglomerate the primary particles generated in the aqueous liquid phase is not particularly limited as long as it is an electrolyte compound that can be dissolved in the aqueous liquid phase. It is preferable not to be mixed in the II-VI phosphor precursor. This is because if the ions generated when the electrolyte is dissolved in the liquid phase are mixed into the phosphor precursor, the performance as a phosphor deteriorates and the brightness decreases. From such a viewpoint, examples of the additive preferably used in the present invention include inorganic acids or organic acid salts of typical metals, and more preferable are inorganic acid salts or organic acid salts of alkaline earth metals. Examples of the typical metal include metal elements such as magnesium, calcium, and sodium, and particularly preferable metals are magnesium and calcium. As additive compounds containing these metals, the ability to use halides such as hydroxides, sulfates, nitrates, chlorides and bromides, and organic acid salts such as formic acid, acetic acid and propionic acid, especially water The use of oxides and sulfates is preferred. The present invention can be carried out by adding the above compound in an arbitrary amount together with the Group II element-containing compound to the liquid phase in advance, and further adding a Group VI element-containing amide compound. The addition amount of the additive compound is usually in the range of 0.0001 to 20 parts by weight with respect to 100 parts by weight of the IHV group compound semiconductor to be produced, but is preferable from the viewpoint of the agglomeration effect and economy. Is in the range of 0.0002 to 10 parts by weight. Also generate From the standpoint of controlling the particle size distribution of the aggregates to avoid mixing into the product, the preferred addition amount is 0.5 to 40 mol% based on the molar amount of the Group II-containing compound used. a range, particularly preferably in the range of 0.8 to 30 mole ^_0/0.

In the present invention, the II-VI group phosphor precursor can be produced by a batch method or a continuous method. The temperature of the liquid phase is not particularly limited as long as the progress of the reaction and the agglomeration effect of the particles are not impaired, but varies depending on the type and amount (concentration) of components contained in the liquid phase. obtain. Usually, the temperature of the liquid phase is adjusted to be in the range of 20 ° C to 120 ° C. Liquid phase temperature control can be performed from outside the reaction vessel using a conventional temperature-controllable heating device, even if a temperature-controllable heating device is installed in the liquid phase. Good. However, when the reaction temperature is low, the reaction in which the particle growth is slow takes a long time, so the productivity per hour is lowered, which is not desirable from the viewpoint of economy. Also, from the viewpoint of operability, if the temperature is too low, the viscosity of the entire liquid phase becomes high, and it becomes difficult to diffuse the reaction liquid at a constant flow rate. The irritating effect of the gas becomes stronger and the operability deteriorates. In view of these points, the method of the present invention is preferably carried out in the range of 60 ° C to 100 ° C, more preferably 65 ° C to 90 ° C.

[0024] In the method of the present invention, a part from the start to the end, that is, from the time immediately before each component is added to the liquid phase to the time immediately before collecting the phosphor precursor particle product. Or, it is possible to perform stirring continuously or intermittently at any stirring speed during the entire period.

[0025] The time required for carrying out the method of the present invention is appropriately determined by those skilled in the art by observing the progress of the reaction and the degree of formation of aggregated particles according to the conditions such as the scale of the implementation. Forces that can be selected Usually;! To 20 hours, preferably 3 to; the reaction can be carried out in 10 hours

Yes

Example

[0026] The present invention will be described in more detail with reference to the following examples. The present invention is not limited to these examples, and the examples are described without departing from the scope of the technical idea of the present invention. Needless to say, it can be implemented with appropriate modifications and changes.

[0027] In the following examples, the particle size distribution of the particle product is SALD— The distribution was evaluated by measuring with a laser diffraction scattering method using the 2100, and determining the median diameter D using the SALD-2100 analytical software attached to the instrument.

[0028] In addition, SEM observation was performed using Hitachi S4000 under the condition of an acceleration voltage of 5 kV.

[0029] Example 1: Production of zinc sulfide particles

(A) When magnesium sulfate is used as the electrolyte

In a 500 ml three-necked flask equipped with a stirrer, thermometer and condenser, dissolve zinc nitrate hexahydrate 37.2 g (125 mm monole) in 250 ml of water and add 0.5 g of isotonic acid. The pH was adjusted to 2. Thereto was added 0 · 752 g of magnesium sulfate (6.25 mmol, corresponding to 5 mol% of the molar amount of zinc nitrate), and the temperature was raised to 70 ° C. with stirring. After the temperature of the solution was raised to 70 ° C., 11.8 g (250 mmol) of thioacetamide was added. After stirring for 2 hours, nitrogen was introduced into the flask at 200 ml / min to remove dissolved hydrogen sulfide. From the resulting slurry, the particle product was separated by centrifugation and washed with water to obtain 11.8 g of zinc sulfide (yield 97%). The average particle size was 18.8 m. Figure 1 shows the particle size distribution curve obtained for the particle product, and Figure 2 shows the SEM observation photograph.

(B) When calcium sulfate is used as the electrolyte

In the above (A), except for adding magnesium sulfate 0 · 85 g (6.25 mmol) in place of magnesium sulfate, the same procedure as in (A) above was followed, and 11.8 g of zinc sulfide (yield 97%) Got. The average particle size was 18.0 Hm.

[0030] Example 2

In Example 1 (A), the same procedure as in Example 1 (A) was followed except that the amount of magnesium sulfate used was 3. Og (25 mmol, corresponding to 20 mol% of the molar amount of zinc nitrate). 19.9 g of zinc sulfide was obtained (yield 98%). The average particle size was 24.3 m.

[0031] Example 3

In Example 1 (A), the same procedure as in Example 1 (A), except that the amount of magnesium sulfate used was 0.3 g (2.5 mmol, corresponding to 2 mol% relative to zinc nitrate). According to the above, 11.3 g of zinc sulfide was obtained (yield 93%). The average particle size was 8.2 m. [0032] Example 4

In Example 1 (A), except that magnesium sulfate was changed to magnesium chloride hexahydrate 2.54 g (12.5 mmol, corresponding to 10 mol% of the molar amount of zinc nitrate), Example 1 (A) and In the same manner, 10.9 g of zinc sulfide was obtained (yield 89%). The average particle size was 18. 8 111.

Example 5: Production of manganese-doped zinc sulfide particles

In a 500 ml three-necked flask equipped with a stirrer, thermometer and condenser, dissolve zinc nitrate hexahydrate 37.2 g (125 mm monole) in 250 ml of water and add 0.5 g of isotonic acid. The pH was adjusted to 2. In this zinc nitrate aqueous solution, add manganese sulfate 0.012g (0.125mmol) and acid magnesium 0 · 752g (6.25mm monole, stone mackerel monole !: 5 monole ⁰ / ο ί こ卞目) The mixture was added and heated to 70 ° C while stirring. After confirming that the temperature of the solution was raised to 70 ° C., 18.8 g (250 mmol) of thioacetamide was added at a time. After stirring for 2 hours, nitrogen was introduced into the flask at 200 ml / min to remove dissolved hydrogen sulfide. From the obtained slurry, the particle product was separated by centrifugation and washed with water to obtain 11 · 7 g of manganese-doped zinc sulfide (yield 96%). The average particle size was 17.6 m.

[0034] rnmrne: Same gallium dope sulphur

A 2 liter three-necked flask equipped with a stirrer, thermometer, condenser, hexahydrosulfuric acid broth 223.2 g (750 mm monolith), stone) ¾ magnesium 4 · 5 g (37.5 mm monole, stone mason (Corresponds to 5 mol% with respect to zinc acid), copper nitrate trihydrate 1.39 g (5.75 mmol), gallium nitrate hexahydrate 670 mg (l.84 millimonole), and 750 ml of water The sample was held and added with 1-5 g of isotonic acid, and the temperature was raised to 90 ° C. while stirring. After raising the temperature, 84.5 g (1125 mmol) of thioacetamide was added and stirred for 2 hours. After cooling to room temperature, nitrogen was introduced at 200 ml / min to remove dissolved hydrogen sulfide. Particles were separated from the resulting slurry by a centrifugal separator and washed with water to obtain 70.9 g (yield 97%) of copper-gallium-doped zinc sulfide. The average particle size was 10. 6 11 m.

Example 7: Production of copper gallium-doped zinc sulfide particles

A 500 ml three-necked flask equipped with a stirrer, thermometer and condenser, zinc nitrate hexahydrate 77.4 g (250 mm monolith, stone) ¾ magnesium 1 · 5 g (37.5 mm monole, stone choic acid) It corresponds to 5 mole ^_0/0 of the molar amount of zinc), copper nitrate trihydrate 462 mg (l. 91 mmol), nitrate gully 226 mg (0.61 millimonoles) of humum hexahydrate and 250 ml of water were added and held, and 0.3 g of stone forcing acid was added, and the mixture was further heated to 90 ° C. with stirring. After raising the temperature, 28.5 g (375 mmol) of thiourea was added and stirred for 2 hours. After cooling to room temperature, nitrogen was introduced at 200 ml / min, and dissolved hydrogen sulfide was removed. Particles were separated from the resulting slurry by a centrifuge and washed with water to obtain 23.9 g of copper-gallium doped zinc sulfide (yield 98%). The average particle size was 12.3 ^ 111.

Example 8: Production of silver gallium-doped zinc sulfide particles

In a 3-liter flask with a capacity of 2 liters equipped with a stirrer, thermometer and condenser, 298 g of zinc nitrate hexahydrate (l monore), 6 mg of magnesium sulfate (50 millimonore, 5 mol% of the molar amount of zinc nitrate) ), Silver nitrate 92mg (0.54mmol), gallium nitrate hexahydrate 55mg (0.15mmol), water 1000ml and stirring, nitric acid 2g was added and the temperature was raised to 90 ° C with stirring. I let you. After the temperature increase, 113 g (l.5 mol) of thioacetamide was added and stirred for 2 hours. After cooling to room temperature, nitrogen was introduced at 200 ml / min to remove dissolved hydrogen sulfide. Particles were separated from the resulting slurry by a centrifuge and washed with water to obtain 94 lg of silver gallium-doped zinc sulfide (yield 97%). The average particle size was 9.6 m.

[0037] Comparative Example 1

Example 1 (A) was carried out in the same manner as in Example 1 (A) except that magnesium sulfate was not used, to obtain 11.8 g (yield 97%) of zinc sulfide. The average particle size was 39.7 111. Figure 9 shows the particle size distribution curve obtained for the particle product, and Figure 10 shows the SEM observation photograph.

[0038] Comparative Example 2

A 500 ml three-necked flask equipped with a stirrer, thermometer and condenser, zinc nitrate hexahydrate 37.2 g (125 millimonoles), stone) ¾ magnesium 0 · 08 g (0. 125 millimonoles, stone choic acid) equivalent to 0.1 Monore ^_0/0 of the molar amount of zinc), water 250ml was Karoe stirring, a nitric acid 0. 5 g were added Caro, further stirring, the temperature was raised to 90 ° C. After the temperature rise, 18.8 g (250 mol) of thioacetamide was added and stirred for 2 hours. After cooling to room temperature, nitrogen was introduced at 200 ml / min to remove dissolved hydrogen sulfide. Particles were separated from the resulting slurry by a centrifugal separator and washed with water to obtain 11.6 g (yield 94%) of zinc sulfide. The average particle size was 5.7 m. [0039] The results of Examples and Comparative Examples are summarized in Table 1.

[0040] [Table 1] Table 1

The particle size distribution and standard deviation in Table 1 were determined based on the particle size distribution curves obtained in Examples and Comparative Examples. There is no significant difference in product yield between the examples and comparative examples, but the particle size distribution and standard deviation between the examples (1-8) and the comparative examples (1, 2). There are significant differences. The average particle size of the particles obtained in the examples falls within the range of 8 to 30 111, which is not much larger than the extremely large value or extremely small value as obtained in the comparative example. In the examples, the standard deviation is less than 0.2, and it can be seen that there is little variation in the particle size of the generated particles. This difference in particle size distribution becomes more apparent from the shape of the particle size distribution curves in FIGS. In particular, from FIGS. 1 and 3 to 8, which correspond to the results of the examples of the present invention, the force S is used to confirm the monodispersity of the particle diameters of the particles obtained in the examples of the present invention.

[0041] Further, according to the SEM photograph of the particle product obtained from Example 1 (A) (Fig. 2), the particle product is a combination of fine particles aggregated with each other! One larger particle is formed, the particle size is apparently uniform, and it can be seen that there is no significant difference in the external shape of each particle. On the other hand, the SEM photograph of the particle product obtained from Comparative Example 1 (Fig. 10) According to the above, there are irregular shapes having irregular shapes, and the formation of apparently uniform particles as in Example 1 (A) has occurred! /, N! /, Force S confirmation it can.

Industrial applicability

The present invention provides a method for producing a monodispersed particle product having a narrow particle size distribution for II-VI group compound semiconductors, which are precursor compounds of inorganic phosphors. According to the production method of the present invention, it is possible to efficiently produce inorganic phosphor precursor particles that are easy to handle / in industrial processes. Furthermore, since the method of the present invention is a production method based on a liquid phase synthesis method, it is possible to uniformly introduce an activator or a coactivator element that can be a luminescence center into a base material compound. Useful for the production of phosphors with high brightness

Claims

The scope of the claims

[1] A group VI element-containing amide compound is added to an aqueous liquid phase containing a typical metal inorganic acid salt or organic acid salt electrolyte compound and a group π element-containing compound to form a π-νι group compound semiconductor. A method for producing a group II-VI phosphor precursor, characterized in that:

[2] The production method according to claim 1, wherein the aqueous liquid phase further contains a compound containing an activator or a coactivator element.

[3] The method according to claim 1, wherein the electrolyte compound comprises at least one of an alkaline earth metal hydroxide, sulfate, nitrate, halide, and organic acid salt.

[4] Group II-VI compound semiconductor by adding Group VI element-containing amide compound to aqueous liquid phase containing electrolyte compound and Group II element-containing compound of inorganic or organic acid salt of typical metal In which the electrolyte compound is added in an amount of 0.5 to 40 mol% based on the molar amount of the group X element-containing compound, and the aggregate D

The average particle size represented by 5 is 8-30 m, and the standard deviation is 0.0;

0

Said method.

[5] Aggregates of II-VI group compound semiconductors, wherein the average particle size represented by D is 8-30 111

50

An aggregate characterized by having a standard deviation of 0.01 to 0.2.