JP5606246B2 - Method for manufacturing phosphor - Google Patents

Description

  The present invention relates to a silicate phosphor used for a display, illumination and various light sources, and a light emitting device using the same.

  A light emitting diode (hereinafter referred to as an LED) in which a light emitting element as an excitation light source and a phosphor are combined is known, and various emission colors can be realized by the combination. Among them, in order to obtain a light emitting device that emits white light called a so-called white LED, a method of combining a light emitting element that emits blue light and a yellow phosphor, a light emitting element that emits near ultraviolet light, a blue phosphor, and yellow There is a method of combining a phosphor and a red phosphor. As a yellow phosphor used for white LEDs, YAG phosphors are well known, but are limited to LEDs using a blue light source because light emission is weak with light having a wavelength of 360 nm to 410 nm.

Silicate-based phosphors having a composition represented by M ₂ SiO ₄ : Eu are known as phosphors that emit yellow light with an emission spectrum when excited with light having a wavelength of 360 nm to 500 nm. For example, Non-Patent Document 1). For example, the crystal structure of Ba ₂ SiO ₄ : Eu ²⁺ is orthorhombic only, but the crystal structure of Sr ₂ SiO ₄ : Eu ²⁺ is monoclinic at 85 ° C. or lower, and is orthorhombic at higher temperatures. (For example, refer nonpatent literature 2).

The emission of orthorhombic Ba ₂ SiO ₄ : Eu ²⁺ and monoclinic Sr ₂ SiO ₄ : Eu ²⁺ becomes greenish yellow with a peak wavelength of about 520 to 540 nm. By replacing part of Sr in Sr ₂ SiO ₄ : Eu ²⁺ with Ba, an orthorhombic crystal can be obtained even at room temperature, and its emission becomes yellow with a peak wavelength of 570 nm and good color purity. Therefore, in order to obtain yellow light emission with good color purity in the silicate phosphor having a composition represented by M ₂ SiO ₄ : Eu, it is essential to contain Ba. Further, in order to obtain a band having a desirable wavelength between 520 and 600 nm, it was necessary to adjust by the Ba content.

G. Blasse, W.M. L. Wanmaher, J. et al. W. terVrugt, and A.A. Brill, Philips Res. Repts, 23, 189-200, (1968) S. H. M.M. Port, W. Janssen, G.M. Blasse, J. et al. Alloys and Compounds, 260, 93-97, (1997)

  However, the Ba compound is a toxic substance and is a substance regulated by the Deleterious Substances Control Law, which adversely affects the human body. Even for a phosphor that emits yellow light with high purity, it is desired to reduce the content of the Ba compound as much as possible.

Therefore, the present invention is capable of emitting green-yellow-orange light having a high color purity and having a single emission band at a wavelength of 520 nm to 600 nm when excited with light having a wavelength of 360 nm to 500 nm, and has reduced toxicity. Another object of the present invention is to provide a method for producing a silicate phosphor.

The method for producing a phosphor according to one aspect of the present invention is a method for producing a phosphor having a composition represented by the following general formula (2),
Sr raw material containing SrCO ₃ , Eu raw material containing Eu ₂ O ₃ , Si raw material containing SiO ₂ , at least one raw material powder of Ca and Ba selected from CaCO ₃ and BaCO ₃ , La ₂ O Mixing at least one raw material powder of La and Cs selected from ₃ and CsCl to obtain a mixture of raw material powders;
Firing the mixture in a reducing atmosphere composed of a mixed gas of N ₂ / H ₂ at a temperature of 1000 to 1600 ° C. for 3 to 10 hours and crushing to obtain a pulverized fired product,
Firing the pulverized fired product in a reducing atmosphere composed of a mixed gas of N ₂ / H ₂ at a temperature of 1000 to 1600 ° C. for 3 to 7 hours to obtain a first fired product,
Crushing the first calcined product and placing it in a furnace purged with nitrogen in a vacuum; and the first calcined product in the furnace is made of N _{2 /} H ₂ with a hydrogen concentration of 5% or more and 100% or less It comprises a step of baking at 1000-1600 ° C. for 2-6 hours in a reducing atmosphere.
_{(Sr 1-xyzw Ca x Ba} y A z Eu w) 2 Si v O 2 + 2v (2)
(In the general formula (2), A is at least one metal selected from La and Cs, and x, y, z, w, and v are numerical values that satisfy the following relationship.
0 ≦ x ≦ 0.8, 0 ≦ y ≦ 0.03, 0 <z ≦ 0.1, 0.001 ≦ w ≦ 0.2
0 <(1-xyzw) <1, 0.9 ≦ v ≦ 1.1)

  According to the present invention, when excited with light having a wavelength of 360 nm to 500 nm, it is possible to emit green-yellow-orange light having a single emission band at a wavelength of 520 nm to 600 nm and having good color purity and reducing toxicity. Provided are silicate-based phosphors and light-emitting devices using the same.

Schematic showing the structure of the light-emitting device concerning one Embodiment of this invention. The excitation spectrum of the fluorescent substance of Example 1 and Comparative Example 2. The emission spectrum of the phosphor of Example 1. 2 is an X-ray diffraction pattern of the phosphor of Example 1. FIG. X-ray diffraction pattern of conventional Sr ₂ SiO ₄ : Eu (monoclinic crystal). X-ray diffraction pattern of conventional (Sr, Ba) ₂ SiO ₄ : Eu (orthorhombic crystal). The emission spectrum of the phosphor of Reference Example 2. The emission spectrum of the phosphor of Reference Example 3. The emission spectrum of the phosphor of Example 4. The emission spectrum of white LED which combined the fluorescent substance of Example 1, and a 470 nm LED chip. The emission spectrum of the phosphor of Comparative Example 1. The emission spectrum of the phosphor of Comparative Example 2.

  Embodiments of the present invention will be described below.

As a result of intensive studies, the inventors of the present invention have changed the crystal structure from monoclinic to orthorhombic in the same manner as Ba in phosphors made of alkaline earth metal silicate compounds and activated with Eu ^2+. It has been found that there is an element having a function of causing At least one selected from La, Gd, Cs, and K, which has little toxicity and is harmless to the human body. The present invention has been made based on these findings.

A phosphor made of a Ba-containing alkaline earth metal silicate compound and activated with Eu ²⁺ can be represented, for example, by the following general formula (1).

(Sr, Ca, Ba, Eu) ₂ SiO ₄ (1)
The phosphor according to the embodiment of the present invention is represented by, for example, the following general formula (2).

_{(Sr 1-xyzw Ca x Ba} y A z Eu w) 2 Si v O 2 + 2v (2)
(In the general formula (2), A is at least one metal selected from La, Gd, Cs, and K, and x, y, z, w, and v are numerical values that satisfy the following relationship: .

0 ≦ x ≦ 0.8, 0 ≦ y ≦ 0.6, 0 <z ≦ 0.1, 0.001 ≦ w ≦ 0.2
0 <(1-xyzw) <1, 0.9 ≦ v ≦ 1.1)
If the Ca content is too high, the light emission efficiency decreases, but this can be avoided if x is 0.8 or less. In consideration of the influence on the human body, the Ba content is desired to be as small as possible, and y = 0 is most preferable. However, Ba may be contained in order to adjust the emission wavelength. In this case, if y is 0.6 or less, the influence of toxicity can be reduced.

  The element A other than the alkaline earth metal element is at least one selected from La, Gd, Cs, and K. These elements may be used alone or in combination of two or more. If the ratio of these elements is too large, a heterogeneous phase may appear and the luminous efficiency may decrease. This can be avoided if z is in the range of 0.1 or less.

As shown in the general formula (2), the phosphor according to the present invention is a silicate compound activated with Eu ²⁺ . The composition ratio w of Eu is preferably 0.001 or more and 0.2 or less. When w is less than 0.001, it is difficult to obtain sufficient light emission luminance. On the other hand, if w exceeds 0.2, the light emission luminance may decrease due to concentration quenching.

  Further, the composition ratio v of Si is preferably 0.9 or more and 1.1 or less. When v is less than 0.9, a second band near 500 nm appears and the emission spectrum may spread. On the other hand, if it exceeds 1.1, it is difficult to obtain sufficient light emission luminance. v is more preferably in the range of 0.95 to 1.05.

  The phosphor according to the embodiment of the present invention can be synthesized, for example, by the following method.

First, a predetermined amount of the constituent element oxide powder is weighed, an appropriate amount of ammonium chloride is added as a crystal growth agent, and mixed with a ball mill or the like. Instead of the oxide powder, various compounds that can be converted into oxides by thermal decomposition can also be used. For example, Eu ₂ O ₃ etc. as the Eu source, CaCO ₃ etc. as the Ca source, SrCO ₃ etc. as the Sr source, BaCO ₃ etc. as the Ba source, La ₂ O ₃ etc. as the La source, etc. Gd ₂ O _{3 and the} like, CsCl and the like as the Cs material, KCl and the like as the K material, and SiO _{2 and the} like as the Si material can be used. When such a raw material powder also acts as a crystal growth agent, a crystal growth agent such as ammonium chloride is not necessarily added separately.

  As the crystal growth agent, ammonium other than ammonium chloride, chloride of alkali metal or alkaline earth metal, fluoride, bromide, or iodide may be used. In order to prevent an increase in hygroscopicity, the amount of the crystal growth agent added is preferably about 0.5 wt% or more and 30 wt% or less with respect to the entire raw material powder.

Then, it is accommodated in a crucible and fired at a temperature of 1000 to 1600 ° C. for 3 to 10 hours in a reducing atmosphere composed of a mixed gas of N ₂ / H ₂ . The obtained fired product is pulverized using a mortar or the like and then fired again at a temperature of 1000 to 1600 ° C. for 3 to 7 hours in a reducing atmosphere composed of a mixed gas of N ₂ / H ₂ . The obtained first fired product is pulverized and accommodated in the container again. The degree of pulverization is not particularly limited, and the surface area may be increased by crushing a lump produced by firing using a mortar or the like.

  Place in the furnace again and purge with nitrogen under vacuum. The vacuum at this time is preferably 1000 Pa or less. If it is more than this, water attached to the material cannot be removed.

Next, the first fired product is fired at 1000 to 1600 ° C. for 2 to 6 hours in a reducing atmosphere of N _{2 /} H ₂ having a hydrogen concentration of 5% or more and 100% or less. The obtained fired product is pulverized using a mortar or the like and then passed through a sieve having an appropriate mesh width to obtain phosphor particles composed of the alkaline earth metal silicate compound represented by the general formula (2). Can be obtained.

On the surface of the phosphor particles according to the embodiment of the present invention, silicone resin, epoxy resin, fluororesin, tetraethoxysilane (TEOS), silica, zinc silicate, aluminum silicate, calcium polyphosphate, silicone oil, and A surface layer material made of at least one selected from silicone grease may be disposed. Thereby, a moisture-proof effect can be imparted. Zinc silicate and aluminum silicate are represented by, for example, ZnO.aSiO ₂ (1 ≦ a ≦ 4) and Al ₂ O ₃ .bSiO ₂ (1 ≦ b ≦ 10), respectively. It is not necessary for the surface of the phosphor particles to be completely covered with the surface layer material, and a part thereof may be exposed. If a surface layer material made of the above-described material is present on the surface of the phosphor particles, the effect can be obtained.

  The surface layer material can be disposed on the surface of the phosphor particles using the dispersion or solution. After the phosphor particles are immersed in the dispersion or solution for a predetermined time, the surface layer material is disposed by drying by heating or the like. In order to obtain the effect of the surface layer material without impairing the original function as the phosphor, the surface layer material is preferably present in a volume ratio of about 0.1 to 50% of the phosphor particles.

  FIG. 1 shows a cross section of a light emitting device according to an embodiment of the present invention.

  In the illustrated light emitting device, the resin stem 200 has a lead 201 and a lead 202 formed by molding a lead frame, and a resin portion 203 formed integrally therewith. The resin portion 203 has a concave portion 205 whose upper opening is wider than the bottom portion, and a reflective surface 204 is provided on the side surface of the concave portion.

  A light emitting chip 206 is mounted with Ag paste or the like at the center of the substantially circular bottom surface of the recess 205. As the light-emitting chip 206, a chip that emits ultraviolet light or a chip that emits light in the visible region can be used. For example, it is possible to use a GaAs-based or GaN-based semiconductor light emitting element. The electrodes (not shown) of the light emitting chip 206 are connected to the leads 201 and 202 by bonding wires 207 and 208 made of Au or the like, respectively. The arrangement of the leads 201 and 202 can be changed as appropriate.

  A fluorescent layer 209 is disposed in the recess 205 of the resin portion 203. The phosphor layer 209 can be formed by dispersing the phosphor 210 according to the embodiment of the present invention in a resin layer 211 made of, for example, a silicone resin at a ratio of 5 wt% to 50 wt%.

  As the light emitting chip 206, a flip chip type having an n-type electrode and a p-type electrode on the same surface can be used. In this case, problems caused by the wire such as wire breakage and peeling and light absorption by the wire are solved, and a highly reliable and high-luminance semiconductor light-emitting device can be obtained. In addition, an n-type substrate may be used for the light emitting chip 206 to have the following configuration. Specifically, an n-type electrode is formed on the back surface of the n-type substrate, a p-type electrode is formed on the upper surface of the semiconductor layer on the substrate, and the n-type electrode or the p-type electrode is mounted on a lead. The p-type electrode or the n-type electrode can be connected to the other lead by a wire.

  The size of the light emitting chip 206 and the size and shape of the recess 205 can be changed as appropriate. The phosphor according to the embodiment of the present invention exhibits a green-yellow-orange emission color of 520 nm to 600 nm when excited with light having a wavelength of 360 nm to 500 nm. Specifically, the emission spectrum of the phosphor according to the embodiment of the present invention has a single emission band between 520 nm and 600 nm. Note that having a single emission band means having a band shape having a single emission peak and no shoulder-like undulations. When the phosphor according to the embodiment of the present invention is used in combination with a blue light-emitting phosphor and a red light-emitting phosphor, white light can be obtained.

Since the phosphor according to the embodiment of the present invention has an orthorhombic structure, a light emitting device that emits light with good color purity can be obtained by providing a phosphor layer containing the phosphor.
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further in detail, this invention is not limited only to an Example.

Example 1
First, a phosphor having a composition represented by (Sr _0.915 La _0.06 Eu _0.025 ) ₂ SiO ₄ was prepared. As raw material powders, SrCO ₃ powder, La ₂ O ₃ powder, Eu ₂ O ₃ powder and SiO ₂ powder were prepared and weighed in predetermined amounts. NH ₄ Cl as a crystal growth agent was added at a ratio of 1.5% by weight with respect to the total amount of the raw material powder, and uniformly mixed by a ball mill.

The obtained mixed raw material was filled in an alumina crucible with a lid, and calcined in the atmosphere at 600 ° C. for 1 hour to decompose NH ₄ Cl. Next, it was fired at a temperature of 1000 to 1600 ° C. for 3 to 7 hours in a reducing atmosphere composed of a mixed gas of N ₂ / H ₂ to obtain a first fired product. This was pulverized and again stored in a crucible, placed in a furnace, and the inside of the furnace was purged with nitrogen under vacuum. Furthermore, it was fired at a temperature of 1000 to 1600 ° C. for 2 to 6 hours in a reducing atmosphere of N _{2 /} H ₂ with a hydrogen concentration of 5% or more and 100% or less to obtain a second fired product. The fired product was pulverized in a mortar and passed through a sieve having an opening of 75 μm to obtain the phosphor of Example 1.

  The excitation spectrum of this phosphor is shown as curve a in FIG. In FIG. 2, a curve b is an excitation spectrum of a phosphor of Comparative Example 2 described later. It can be seen from the curve a that the phosphor of this example can be excited in a wide wavelength range from UV to yellow similar to the phosphor of Comparative Example 2.

  3 and 4 show the emission spectrum of the phosphor of this example when excited at 395 nm and the X-ray diffraction pattern of the phosphor, respectively. The emission spectrum used here is obtained by measuring the emission spectrum of a phosphor excited by a light emitting diode having peak wavelengths of 395 nm and 470 nm using an IMUC-7000G type instantaneous multi-photometry system manufactured by Otsuka Electronics. As shown in the emission spectrum of FIG. 3, it has a single emission peak and does not show shoulder-like undulations. From this, it can be seen that the phosphor of this example has a single peak in the emission spectrum when excited with light having a wavelength of 360 nm to 500 nm. Further, the X-ray diffraction pattern is consistent with a JCPDS (Joint Committee on Powder Diffraction Standards) card 39-1256. The JCPDS card relates to a powder X-ray diffraction database, and refers to a card edited and published by JCPDS. Since there is no peak at 2θ = 34.2 °, it can be seen from the X-ray diffraction diagram of FIG. 4 that the phosphor of this example has an orthorhombic crystal structure.

For reference, an X-ray diffraction diagram of a conventional Sr ₂ SiO ₄ : Eu phosphor is shown in FIG. This diffraction pattern coincides with the JCPDS card 76-1630 and has a monoclinic crystal structure because a peak exists at 2θ = 34.2 °. FIG. 6 shows an X-ray diffraction pattern of a conventional (Sr, Ba) ₂ SiO ₄ : Eu phosphor. As shown in the X-ray diffraction diagram of FIG. 6, it matches the JCPDS card 39-1256 and has no peak at 2θ = 34.2 °, so that the conventional (Sr, Ba) ₂ SiO ₄ : Eu phosphor Has an orthorhombic crystal structure. Compared with the X-ray diffraction pattern shown in FIG. 4, it is clear that the phosphor according to the embodiment of the present invention has an orthorhombic crystal structure, similar to a phosphor containing conventional Ba.

( Reference Example 2)
First, a phosphor having a composition represented by (Sr _0.915 Gd _0.060 Eu _0.025 ) ₂ SiO ₄ was prepared. As raw material powders, SrCO ₃ powder, Gd ₂ O ₃ powder, Eu ₂ O ₃ powder and SiO ₂ powder were prepared and weighed in predetermined amounts. NH ₄ Cl as a crystal growth agent was added at a ratio of 1.5% by weight with respect to the total amount of the raw material powder, and uniformly mixed by a ball mill.

Thereafter, the phosphor of Reference Example 2 was obtained by the same production method as in Example 1. FIG. 7 shows an emission spectrum of the phosphor when excited with a wavelength of 395 nm. As shown in the emission spectrum of FIG. 7, it can be seen that the phosphor of this example has a single band between wavelengths of 520 nm and 600 nm when excited with light having a wavelength of 360 nm to 500 nm. .

( Reference Example 3)
First, a phosphor having a composition represented by (Sr _0.920 K _0.055 Eu _0.025 ) ₂ SiO ₄ was prepared. As raw material powders, SrCO ₃ powder, KCl powder, Eu ₂ O ₃ powder and SiO ₂ powder were prepared, weighed in a predetermined amount, and uniformly mixed by a ball mill. In this case, NH ₄ Cl was not added because KCl as the K raw material plays a role as a crystal growth agent.

Thereafter, the phosphor of Reference Example 3 was obtained by the same production method as in Example 1. FIG. 8 shows an emission spectrum of the phosphor when excited with a wavelength of 395 nm. As shown in the emission spectrum of FIG. 8, it can be seen that the phosphor of this example has a single band between the wavelengths of 520 nm and 600 nm when excited with light having a wavelength of 360 nm to 500 nm. .

Example 4
First, a phosphor having a composition represented by (Sr _0.915 Cs _0.03 La _0.03 Eu _0.025 ) ₂ SiO ₄ was prepared. As raw material powders, SrCO ₃ powder, CsCl powder, La ₂ O ₃ powder, Eu ₂ O ₃ powder and SiO ₂ powder were prepared, weighed in predetermined amounts, and uniformly mixed by a ball mill. Here, CsCl as a Cs raw material plays a role as a crystal growth agent, but NH ₄ Cl was also added at the same time for adjusting the Cl ratio.

  Thereafter, the phosphor of Example 4 was obtained by the same production method as in Example 1. FIG. 9 shows the emission spectrum of this phosphor when excited with a wavelength of 395 nm. As shown in the emission spectrum of FIG. 9, it can be seen that the phosphor of this example has a single band between the wavelengths of 520 nm and 600 nm when excited with light having a wavelength of 360 nm to 500 nm. .

(Example 5)
First, a phosphor having a composition represented by (Sr _0.915 Ba _0.03 La _0.03 Eu _0.025 ) ₂ SiO ₄ was prepared. As raw material powders, SrCO ₃ powder, BaCO ₃ powder, La ₂ O ₃ powder, Eu ₂ O ₃ powder and SiO ₂ powder were prepared, weighed in predetermined amounts, and uniformly mixed by a ball mill. NH ₄ Cl as a crystal growth agent was added at a ratio of 1.5% by weight with respect to the total amount of the raw material powder, and uniformly mixed by a ball mill.

  Thereafter, the phosphor of Example 5 was obtained by the same production method as in Example 1. The emission spectrum of this phosphor when excited with a wavelength of 395 nm was a peak wavelength of 575 nm, and the emission spectrum when excited with a wavelength of 470 nm was a peak wavelength of 580 nm. Similar to the phosphors of Examples 1 to 4, the phosphor of this example has a single emission band between 520 nm and 600 nm in the emission spectrum when excited with light having a wavelength of 360 nm to 500 nm. there were.

From the results of X-ray diffraction, it was confirmed that each of the phosphors of Reference Examples 2 and 3 and Examples 4 and 5 had an orthorhombic crystal structure as in Example 1.

(Example 6) (LED)
The resin mixture was prepared by dispersing the phosphor of Example 1, the blue phosphor, and the red phosphor in an epoxy resin. In addition, as the blue phosphor, a europium activated alkaline earth chlorophosphate phosphor was used, and as the red phosphor, a europium activated lanthanum oxysulfide phosphor was used. This resin mixture was applied to an LED package on which an LED chip having an emission peak wavelength of 395 nm was mounted, and a light emitting device as shown in FIG. 1 was produced.

  It was confirmed that white light with good color rendering properties was emitted from the obtained light emitting device.

(Example 7) (LED)
The phosphor of Example 1 was dispersed in an epoxy resin to prepare a resin mixture. This resin mixture was applied to an LED package on which an LED chip having an emission peak wavelength of 470 nm was mounted to produce a white LED.

  The emission spectrum of the obtained white LED is shown in FIG. In this case, the luminescent color was chromaticity value x = 0.337, y = 0.303, and the color temperature was 5247K. In this way, a white LED that emits white light with good color rendering can be produced.

(Comparative Example 1)
First, a phosphor having a composition represented by (Sr _0.285 Ba _0.665 Eu _0.05 ) ₂ SiO ₄ was prepared. As raw material powders, SrCO ₃ powder, BaCO ₃ powder, Eu ₂ O ₃ powder and SiO ₂ powder were prepared and weighed in predetermined amounts. NH ₄ Cl as a crystal growth agent was added at a ratio of 1.5% by weight with respect to the total amount of the raw material powder, and uniformly mixed by a ball mill.

  Thereafter, the phosphor of Comparative Example 1 was obtained in the same manner as in Example 1. FIG. 11 shows an emission spectrum of the phosphor when excited with a wavelength of 395 nm. From the emission spectrum of FIG. 11, it can be seen that the emission is green with a single band at 525 nm. However, since the phosphor of this comparative example contains more than 0.6 Ba, the problem of toxicity is It cannot be avoided.

(Comparative Example 2)
A phosphor having a composition represented by (Sr _0.915 Ba _0.06 Eu _0.025 ) ₂ SiO ₄ was prepared. As raw material powders, SrCO ₃ powder, BaCO ₃ powder, Eu ₂ O ₃ powder and SiO ₂ powder were prepared and weighed in predetermined amounts. NH ₄ Cl as a crystal growth agent was added at a ratio of 1.5% by weight with respect to the total amount of the raw material powder, and uniformly mixed by a ball mill. Thereafter, the phosphor of Comparative Example 2 was obtained by the same production method as in Example 1.

  FIG. 12 shows an emission spectrum of the phosphor when excited with a wavelength of 395 nm. Since it contains Ba, the phosphor of Comparative Example 2 has a single emission spectrum between wavelengths of 520 nm and 600 nm when excited with light of a wavelength of 360 nm to 500 nm, as shown in the emission spectrum of FIG. Has one band.

On the other hand, Examples 1 and 4 show bands having the same emission wavelength even without containing Ba. Example 5 shows an emission band equivalent to that of Comparative Example 2, but the amount of Ba is halved compared to Comparative Example 2.

Table 1 below summarizes the compositions, emission peaks, and crystal forms of the phosphors of the examples and comparative examples described above.

  As shown in Table 1, the phosphor according to the embodiment of the present invention in which at least a part of Ba is substituted with at least one selected from La, Gd, Cs, and K is an orthorhombic crystal. It has a structure. As a result, when excited at 395 nm or 475 nm, a single band appears between wavelengths 520 nm and 600 nm, and emission with high purity is emitted.

  It is clearly shown that this is comparable to the case of the conventional Ba-containing phosphor of Comparative Example 2.

200 ... Resin stem; 201 ... Lead; 202 ... Lead; 203 ... Resin part 204 ... Reflecting surface; 205 ... Recessed part; 206 ... Light emitting chip 207 ... Bonding wire; 208 ... Bonding wire 209 ... Fluorescent layer; ... resin layer.

Claims (5)

A method for producing a phosphor having a composition represented by the following general formula (2):
Sr raw material containing SrCO ₃ , Eu raw material containing Eu ₂ O ₃ , Si raw material containing SiO ₂ , at least one raw material powder of Ca and Ba selected from CaCO ₃ and BaCO ₃ , La ₂ O Mixing at least one raw material powder of La and Cs selected from ₃ and CsCl to obtain a mixture of raw material powders;
Firing the mixture in a reducing atmosphere composed of a mixed gas of N ₂ / H ₂ at a temperature of 1000 to 1600 ° C. for 3 to 10 hours and crushing to obtain a pulverized fired product,
Firing the pulverized fired product in a reducing atmosphere composed of a mixed gas of N ₂ / H ₂ at a temperature of 1000 to 1600 ° C. for 3 to 7 hours to obtain a first fired product,
Crushing the first calcined product and placing it in a furnace purged with nitrogen in a vacuum; and the first calcined product in the furnace is made of N _{2 /} H ₂ with a hydrogen concentration of 5% or more and 100% or less A method for producing a phosphor, comprising a step of baking at 1000 to 1600 ° C. for 2 to 6 hours in a reducing atmosphere.
_{(Sr 1-xyzw Ca x Ba} y A z Eu w) 2 Si v O 2 + 2v (2)
(In the general formula (2), A is at least one metal selected from La and Cs, and x, y, z, w, and v are numerical values that satisfy the following relationship.
0 ≦ x ≦ 0.8, 0 ≦ y ≦ 0.03, 0 <z ≦ 0.1, 0.001 ≦ w ≦ 0.2
0 <(1-xyzw) <1, 0.9 ≦ v ≦ 1.1) The method for producing a phosphor according to claim 1, comprising further the step of adding a crystal growth agent to the mixture of the raw material powder. The said vacuum is 1000 Pa or less, The manufacturing method of the fluorescent substance of Claim 1 or 2 characterized by the above-mentioned. The phosphor by pulverizing method for manufacturing the phosphor according to any one of claims 1 to 3 further comprising the step of obtaining the phosphor particles. The manufacturing method of the fluorescent substance of Claim 4 which further comprises the process of arrange | positioning surface material on the surface of the said granular fluorescent substance.