WO2014156201A1 - Phosphor, method for producing same and light emitting device using same - Google Patents

Phosphor, method for producing same and light emitting device using same Download PDF

Info

Publication number
WO2014156201A1
WO2014156201A1 PCT/JP2014/001860 JP2014001860W WO2014156201A1 WO 2014156201 A1 WO2014156201 A1 WO 2014156201A1 JP 2014001860 W JP2014001860 W JP 2014001860W WO 2014156201 A1 WO2014156201 A1 WO 2014156201A1
Authority
WO
WIPO (PCT)
Prior art keywords
phosphor
pyrophosphate
light
light emitting
manganese
Prior art date
Application number
PCT/JP2014/001860
Other languages
French (fr)
Japanese (ja)
Inventor
欣能 舩山
智治 戸村
Original Assignee
株式会社 東芝
東芝マテリアル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP2013-073073 priority Critical
Priority to JP2013073073 priority
Application filed by 株式会社 東芝, 東芝マテリアル株式会社 filed Critical 株式会社 東芝
Publication of WO2014156201A1 publication Critical patent/WO2014156201A1/en

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals comprising europium
    • C09K11/7734Aluminates; Silicates
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805Shape
    • H01L2224/4809Loop shape
    • H01L2224/48091Arched
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/85Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
    • H01L2224/85909Post-treatment of the connector or wire bonding area
    • H01L2224/8592Applying permanent coating, e.g. protective coating
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L33/00Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50Wavelength conversion elements
    • H01L33/501Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502Wavelength conversion materials

Abstract

Provided is a phosphor for a light emitting device, the phosphor having a high color rendering property and color reproducibility and, in particular, having excellent efficiency and weather resistance. The phosphor according to an embodiment comprises: europium and manganese activated alkaline earth magnesium silicate phosphor particles which are excited by ultra violet to blue light and emit green to yellow light; and a coating layer composed of at least one type of a calcium pyrophosphate, magnesium pyrophosphate, barium pyrophosphate and strontium pyrophosphate that evenly coats the surface of the phosphor particles.

Description

Phosphor, method for manufacturing the same, and light emitting device using the same

Embodiments of the present invention relate to a phosphor used in a light emitting device such as an LED lamp, particularly a phosphor emitting green light or yellow light, and a light emitting device using the same.

In recent years, technologies corresponding to environmental protection such as lead-free have expanded worldwide, and accordingly, a light source (lamp) for illumination is also a light emitting diode that emits white light from a fluorescent lamp containing Hg ( LED: Light Emitting Diode) lamp is moving. In general lighting applications, white LED lamps with high color rendering properties and long life are required, and white LED lamps that provide high efficiency and wide color reproducibility are used as backlights for liquid crystal display devices (LCD). It is requested.

In order to meet such a demand, instead of a white LED lamp combining a blue light emitting LED chip and a yellow phosphor (YAG phosphor), a blue light emitting LED chip and a silicate phosphor that emits green to yellow light. And white LED lamps that combine a nitride phosphor that emits red light.

However, this type of white LED lamp is superior in efficiency, color rendering, and color reproducibility compared to an LED lamp combining a blue light emitting LED chip and a yellow phosphor (YAG phosphor), but it has excellent heat resistance and There was a problem that weather resistance such as moisture resistance was poor. Among these, (Sr, Ba, Ca) 2 SiO 4 : Eu phosphors known as silicate phosphors emitting green to yellow light in combination with blue light emitting LEDs are not sufficient in terms of weather resistance, The appearance of a silicate phosphor that emits green to yellow light with better weather resistance has been desired.

International Publication No. 2008/096545

The present invention has been made to solve the technical problems as described above, and has an object to provide a phosphor for a light-emitting device that has high color rendering and color reproducibility, and is particularly excellent in efficiency and weather resistance. Yes. Another object of the present invention is to provide a light-emitting device such as a white LED lamp which is excellent in efficiency and weather resistance and has high color rendering properties and color reproducibility by using such a phosphor.

The phosphor according to the present embodiment includes europium (Eu) substantially represented by (Sr, Ba, Mg) 2 SiO 4 : Eu, Mn, strontium (Sr) activated by manganese (Mn), barium ( Ba), alkaline earth magnesium silicate phosphor particles, and calcium pyrophosphate (Ca 2 P 2 O 7 ), magnesium pyrophosphate (Mg 2 P 2 O 7 ), barium pyrophosphate (Ba 2 P 2 ) on the phosphor particle surface. O 7), a phosphor is uniformly coated with at least any one of pyrophosphate strontium (Sr 2 P 2 O 7) , fluorescence ultraviolet or by being excited by blue light emitting element emits green to yellow light It is a body.

It is sectional drawing which shows the light-emitting device concerning this embodiment.

Hereinafter, this embodiment will be described in detail.
The phosphor according to the present embodiment uniformly coats the surface of the phosphor particles and europium and manganese-activated alkaline earth magnesium silicate phosphors that are excited by ultraviolet to blue light to emit green to yellow light. , Calcium pyrophosphate (Ca 2 P 2 O 7 ), magnesium pyrophosphate (Mg 2 P 2 O 7 ), barium pyrophosphate (Ba 2 P 2 O 7 ), strontium pyrophosphate (Sr 2 P 2 O 7 ), at least Or a coating layer made of one kind.

The phosphor according to the present embodiment is a phosphor mainly composed of alkaline earth magnesium silicate with europium (Eu) and manganese (Mn) as activators and coactivators, respectively. More specifically, it is composed mainly of europium having a composition substantially represented by the chemical formula: (Sr, Ba, Mg) 2 SiO 4 : Eu, Mn, manganese-activated alkaline earth magnesium silicate, A green to yellow phosphor that emits green or yellow light when excited by the emission of blue light.

In the phosphor of the present embodiment, the emission color of the phosphor can be changed in a wide range by changing the composition ratio of the alkaline earth metal and magnesium (Sr, Ba, Mg) as the base material. Specifically, in Eu-activated strontium silicate phosphor (Sr 2 SiO 4 : Eu), yellow is obtained by replacing a part of Sr with Ba in the range of 0.1 to 1.7 moles. The emission intensity of the blue region can be changed by substituting Mg in the range of 0.01 to 0.15 mol, and the red region can be changed by substituting Mn in the range of 0.001 to 0.01 mol. The emission spectrum of each wavelength region can be arbitrarily increased or decreased.

Here, the lower limit value of the addition amount of each element is a limit value where an effective emission spectrum change is not observed if it is less than that, and the upper limit value of the addition amount is that each element has a sufficient spectrum change effect. This is set in consideration of the density balance between the two. The molar ratio between Mg and Mn is preferably higher with Mg. When Mn is more than Mg, the resulting crystal powder is colored and the brightness is lowered.

Europium (Eu) is an activator (main activator) that forms a light emission center, and has a high transition probability, and therefore has high light emission efficiency. Eu as the main activator preferably replaces a part of the alkaline earth element in the range of 0.025 to 0.25 mol. If the Eu content is out of this range, the light emission luminance decreases. More preferably, it is in the range of 0.05 to 0.2 mol.

That is, the phosphor particles of the present embodiment has the formula: (Sr 2-x-y -z-u, Ba x, Mg y, Eu z, Mn u) SiO 4 (0.1 ≦ x ≦ 1.7, 0.01 ≦ y ≦ 0.15, 0.025 ≦ z ≦ 0.25, 0.001 ≦ u ≦ 0.01), and preferably activated europium and manganese-activated alkaline earth magnesium silicate.

The europium and manganese-activated alkaline earth magnesium silicate phosphor according to the present embodiment can be produced, for example, by the method shown below.
First, a phosphor raw material containing an element constituting a phosphor base material and an activator (main activator and coactivator) or a compound containing the element has a desired composition ((Sr, Ba, Mg) 2 SiO 4 : Eu · Mn), and if necessary, ammonium chloride or the like is added as a flux if necessary, and these are mixed in a dry method.

Specifically, a predetermined amount of strontium oxide, barium oxide, magnesium oxide, and silicon dioxide is mixed, and an appropriate amount of activator europium oxide and coactivator manganese oxide and flux are added to obtain a phosphor material. . Instead of strontium oxide, barium oxide, and magnesium oxide, carbonates such as strontium carbonate, barium carbonate, and magnesium carbonate may be used. As an activator, europium oxalate or europium carbonate can be used, and manganese carbonate, manganese oxalate, or the like can be used as a coactivator.

Next, such a phosphor material is filled in a heat-resistant container such as an alumina crucible together with activated carbon. After this mixed material is filled in a heat-resistant container, it is fired in a reducing gas atmosphere (for example, an atmosphere of 3 to 10% hydrogen-balance nitrogen). Firing conditions are important in controlling the crystal structure of the phosphor matrix ((Sr, Ba, Mg) 2 SiO 4 ). The firing temperature is preferably in the range of 1100 to 1400 ° C. Although the firing time depends on the set firing temperature, it is preferably 2 to 8 hours, and after firing, it is preferably cooled in the same atmosphere as firing. Thereafter, the obtained fired product is washed with ion-exchanged water through a pulverization step, dried, and then subjected to sieving to remove coarse particles as necessary, thereby activating europium and manganese-activated alkaline earth. A magnesium silicate phosphor can be obtained.

The firing of the phosphor material can be performed using a rotary heating furnace as shown below. That is, the above-described phosphor raw material is put into a rotating tubular heating furnace that is arranged to be inclined with respect to the horizontal direction, and is continuously passed. Then, the phosphor material is rapidly heated to a predetermined firing temperature in the heating furnace, and the furnace is moved from the upper side to the lower side while rolling according to the rotation of the heating furnace. In this way, the phosphor material is heated and fired for a necessary and sufficient time. Thereafter, the fired product is continuously discharged from the heating furnace, and the discharged fired product is rapidly cooled. In such a firing step, the inside of the tubular heating furnace and the cooling part of the fired product discharged from the heating furnace are preferably maintained in an oxygen-free state from which oxygen has been removed. It is desirable to maintain in an inert gas atmosphere such as argon or nitrogen or a reducing gas atmosphere containing hydrogen.

According to such a firing method, since the phosphor material is rapidly heated while rolling in the process of moving in the heating furnace, uniform thermal energy can be applied to the phosphor material in an oxygen-free state. As a result, the firing can be completed in a shorter time compared to the conventional firing method using a crucible, and efficient phosphor particles can be obtained without causing a decrease in luminance due to thermal history. In addition, since the aggregation of the phosphor particles can be suppressed by this firing method, it is not necessary to perform pulverization after firing, and deterioration of the phosphor due to repeated pulverization steps can be suppressed. Furthermore, since the phosphor raw material is heated and fired while rolling in the heating furnace, phosphor particles having a uniform particle diameter in a shape close to a sphere can be obtained.

The surface of the phosphor particles obtained by the above method is coated with calcium pyrophosphate (Ca 2 P 2 O 7 ), magnesium pyrophosphate (Mg 2 P 2 O 7 ), barium pyrophosphate (Ba 2 P 2 ) using a coating agent. Surface treatment for uniformly coating at least one metal pyrophosphate salt of O 7 ) and strontium pyrophosphate (Sr 2 P 2 O 7 ) is performed. Thus, by forming a film (coating layer) of the above-described metal pyrophosphate on the surface of the phosphor particles, the weather resistance of the phosphor under high temperature and high humidity is improved, and the luminance decreases with time from green to yellow emission. And the luminance maintenance rate is high.

Since the above film (coating layer) is a non-luminescent component, an excessive amount of coating causes a significant decrease in luminance of the obtained phosphor. On the other hand, if the coating on the phosphor is insufficient, it is difficult to obtain the weather resistance effect. From such a viewpoint, the film (coating layer) is preferably in the range of 0.05 to 5.0% by weight with respect to the phosphor particles.

Specifically, the surface treatment with the coating agent is carried out as follows. That is, phosphor particles prepared as described above are dispersed in water or a mixture of water and ethyl alcohol (C 2 H 5 OH), and as a coating agent, pyrophosphoric acid such as sodium pyrophosphate or potassium pyrophosphate is used. Using salt and at least one of calcium, magnesium, barium, and strontium chloride, weigh and inject so that the reaction coating is in the range of 0.05 to 5.0% by weight with respect to the phosphor particles. . The temperature of the phosphor dispersion liquid in the surface treatment is preferably 25 ° C. to 40 ° C.

After adding the coating agent, the mixture is stirred for 30 to 120 minutes, and the resulting phosphor is washed, filtered, dried, and sieved so that the phosphor particle surface is uniformly coated with pyrophosphate. Is obtained. The europium and manganese-activated alkaline earth magnesium silicate phosphors thus obtained have excellent weather resistance.

The average particle size of the europium and manganese-activated alkaline earth magnesium silicate phosphor of the present embodiment is not particularly limited, but is preferably in the range of 10 μm to 20 μm. The average and particle size means the D 50 showing a particle size of 50% by weight integrated value.

Further, the obtained europium and manganese-activated alkaline earth magnesium silicate phosphor is a phosphor that emits green to yellow light when excited by the radiation of an ultraviolet or blue light emitting element, and also has good luminous efficiency. High luminance can be obtained. Therefore, by using this phosphor as a green to yellow light emitting phosphor, it is possible to realize a light emitting device such as an LED lamp with high emission luminance.

Next, a light emitting device having a light emitting part containing the green or yellow phosphor will be described. The white lamp will be described. FIG. 1 is a cross-sectional view schematically showing a configuration of a white lamp used in the light emitting device according to the present embodiment.

As shown in FIG. 1, a light emitting device (LED device) 1 includes an insulating substrate 3 having electrodes 2A and 2B formed on the surface, an LED element 4 as a light emitting element mounted on the insulating substrate 3, and an LED element 4. A reflector base 5 for forming a recess to be housed, a reflector 6 affixed to the reflector base 5 and reflecting material 5a that reflects light emitted from the LED element 4 in the front direction, and a transparent resin 7 It comprises a transparent resin sealing layer 9 in which phosphor particles 8 are dispersed, and a bonding wire 10 for energizing the LED element 4 from the electrode 2B. In the white lamp of this embodiment, the transparent resin sealing layer (phosphor-containing layer) 9 that is a light-emitting portion contains a red phosphor that emits red light together with the green to yellow light-emitting phosphor of this embodiment. Thus, a white LED lamp can be obtained.

Here, the red phosphor that emits red light is a phosphor that emits red light when excited by a blue light emitting LED chip. Specifically, for example, Eu-activated Sr, Ca nitride fluorescence. Body, Eu-activated Ca nitride phosphor, Eu-activated Sr, Ca sulfide phosphor, Eu-activated Ca sulfide phosphor, Eu, Ce-activated Ca sulfide phosphor, Eu, Sm-activated La oxysulfide At least one phosphor selected from the product phosphors is used. In such an LED lamp, high-luminance white light with high color rendering is obtained by color mixing of green light to yellow light emitted from green to yellow phosphors and red light emission emitted from red phosphors.
In FIG. 1, an LED element is used as the light-emitting element, but other light-emitting elements such as an EL element can also be used.

Hereinafter, specific examples of the present invention will be described. However, the present invention is not limited to these examples, and the present invention can be arbitrarily modified and implemented without departing from the gist of the present invention.
<Fabrication of phosphor>
Examples 1 to 10
The raw material containing the phosphor matrix and the element constituting the activator or the compound containing the element, the Mg and Mn amounts are constant, and the Sr, Ba and Eu amounts are changed to change from the green region to the yellow region. In addition, it was weighed with the composition shown in Table 1 below.

Figure JPOXMLDOC01-appb-T000001

Sample No. shown in Table 1 Ammonium chloride was added as a flux to each of the phosphor materials 1 to 10 and mixed well.
Appropriate amount of activated carbon is added to each phosphor material obtained and filled into an alumina crucible and fired at 1200 ° C. for 5 hours in a reducing gas atmosphere (3 to 10% hydrogen-balance nitrogen atmosphere). It was. The obtained fired products were pulverized and sieved, and further fired at 1250 ° C. for 5 hours in a reducing gas atmosphere. Thereafter, each fired product obtained was pulverized and sieved, washed with water and dried, and further sieved to obtain sample Nos. Shown in Table 1. Europium and manganese-activated alkaline earth magnesium silicate phosphors having a composition of 1 to 10 ((Sr, Ba, Mg) 2 SiO 4 : Eu, Mn) were obtained.

The obtained sample No. 1 to 10 were dispersed in a mixed solution of water and ethyl alcohol (C 2 H 5 OH). After preparing each phosphor dispersion of 1 to 10, sample No. 1 was prepared using calcium chloride, magnesium chloride, barium chloride, strontium chloride together with sodium pyrophosphate or potassium pyrophosphate. Each phosphor of 1 to 10 was weighed and charged so as to be reactively coated with pyrophosphate shown in Table 2 in the range of 0.05 to 5.0% by weight. At this time, the temperature of the phosphor dispersion liquid was set to 30 ° C., and after stirring for 90 minutes, filtration, drying and sieving were carried out, and the phosphor surface shown in Table 2 below was uniformly coated on the phosphor surface. The phosphors of Examples 1 to 10 were obtained.

Figure JPOXMLDOC01-appb-T000002

Comparative Examples 1-10
Sample No. The phosphors of Comparative Examples 1 to 10 were obtained in the same manner as in Examples 1 to 10, except that 1 to 10 was not coated with a coating agent (surface treatment agent).

<Powder evaluation>
5 g of each of the phosphor powders of Examples 1 to 10 and Comparative Examples 1 to 10 prepared as described above were weighed into a 50 ml beaker and heated at a high temperature and high humidity in a high temperature and high humidity atmosphere (temperature 85 ° C., humidity 85%). A forced weather resistance test was conducted by putting in a wet tank for 72 hours, and the emission luminance of the phosphor after the test was measured.
In addition, the light emission luminance (initial value before the test) of each example is the reference value 100% of the light emission luminance (initial value before the test) of the phosphor powder of each comparative example that was not subjected to the surface treatment. Obtained as a relative value.
In addition, for the forced weather resistance test of the phosphor powder, the luminance maintenance rate when the emission luminance before being put into a high-temperature and high-humidity tank (temperature 85 ° C./humidity 85%) is taken as 100% is calculated by the following calculation method [1]. Measured according to the formula.
Powder luminance maintenance ratio (%) = Luminance luminance after forced weathering test ÷ Luminance luminance before forced weathering test × 100 [1]
Moreover, the body color change of each phosphor after the forced weather resistance test was confirmed visually.
Table 3 shows the measurement results of the light emission luminance and the luminance maintenance ratio and the evaluation results of the body color change.

Figure JPOXMLDOC01-appb-T000003

As is apparent from the results shown in Table 3, the phosphor powders of Examples 1 to 10 of the present embodiment are compared with the phosphor powders of Comparative Examples 1 to 10 in terms of emission luminance (initial value before weather resistance test). ) Shows a slight difference in brightness due to surface treatment, but no decrease in brightness was observed in the brightness maintenance rate of the forced weather resistance test under a high-temperature and high-humidity atmosphere (temperature 85 ° C, humidity 85%). It was confirmed that the luminance was maintained. Further, in the evaluation of the body color change, the surface treatment did not show a change in the body color, but the comparative example without any surface treatment showed a phenomenon that the body color turned white. As a result of analyzing them with an X-ray diffractometer (XRD), a peak of strontium carbonate was confirmed in all of them. This is thought to be caused by the reaction between the moisture in the high-temperature and high-humidity tank and Sr (strontium) of the phosphor matrix, and the degree of whitening increases as the Sr (strontium) ratio increases. The maintenance rate also worsened.

That is, as defined in the present invention, europium, manganese-activated alkaline earth silicate phosphors are converted to calcium pyrophosphate (Ca 2 P 2 O 7 ), magnesium pyrophosphate (Mg 2 P 2 O 7 ), barium pyrophosphate ( In each example of the phosphor coated with reaction coating of Ba 2 P 2 O 7 ) and strontium pyrophosphate (Sr 2 P 2 O 7 ), the phosphor powder was placed in a high-temperature and high-humidity atmosphere (temperature 85 ° C./humidity 85%). From the above results, it was proved that the weather resistance and the luminance maintenance ratio in the weather resistance test were significantly improved as compared with the comparative examples which were not coated.

<Green LED lamp single color evaluation / yellow LED lamp single color evaluation>
Using the phosphor powders of Examples 1 to 10 and Comparative Examples 1 to 10, LED lamps shown in FIG. 1 were produced as follows.
That is, each of the phosphors of Examples 1 to 10 and Comparative Examples 1 to 10 is used as a green and yellow phosphor, and mixed with a mixed liquid of an epoxy resin and an acid anhydride curing agent to produce a blue light emitting LED. After dropping on a chip (0.4 mm square) 4 using a dispenser and curing the epoxy resin, a hemispherical transparent epoxy resin cap is coated thereon, and each example and each comparative example are applied. A light emitting device was manufactured, and an LED lamp was lit for 1000 hours in a high temperature and high humidity atmosphere (temperature 85 ° C., humidity 85%).

The light emission luminance (initial value before the weather resistance test) of each example is the reference value 100 based on the light emission luminance (each initial value before the weather resistance test) of the LED lamp using the phosphor powder without surface treatment of each comparative example. % And calculated as a relative value.
In addition, the LED lamp is lit for 1000 hours in a high-temperature, high-humidity atmosphere (temperature: 85 ° C., humidity: 85%), and brightness deterioration (weather resistance) is measured from the start of lighting to the end of lighting (after 1000 hours). ) A test was conducted, and the luminance maintenance rate was measured according to the following calculation method [2].
LED luminance maintenance ratio (%) = emission luminance after luminance degradation test / emission luminance before luminance degradation test × 100 ... [2]
Table 4 shows the measurement results of the light emission luminance and the luminance maintenance rate.

Figure JPOXMLDOC01-appb-T000004

As is apparent from the results shown in Table 4, the emission luminance (initial value before the weather resistance test) of the green and yellow LED lamps using the phosphor powders of Examples 1 to 10 is the fluorescence of Comparative Examples 1 to 10. Compared with green and yellow LED lamps using body powder, there was almost no difference due to the presence or absence of surface treatment, but luminance degradation (weather resistance) in a high-temperature, high-humidity atmosphere (temperature 85 ° C, humidity 85%) In the test, the improvement in the luminance maintenance rate was confirmed in all cases as compared with the comparative example.

That is, as defined in the present invention, europium, manganese-activated alkaline earth magnesium silicate phosphor, calcium pyrophosphate (Ca 2 P 2 O 7 ), magnesium pyrophosphate (Mg 2 P 2 O 7 ), barium pyrophosphate ( In each example of a monochromatic LED lamp using a phosphor coated with reactive coating of Ba 2 P 2 O 7 ) and strontium pyrophosphate (Sr 2 P 2 O 7 ), a high-temperature and high-humidity atmosphere (temperature 85 ° C./humidity 85 From the above results, it was proved that the luminance maintenance rate of the luminance deterioration (weather resistance) test of%) was significantly improved as compared with the comparative examples of the single color LED lamps using the phosphors that were not coated. .

<Evaluation of white LED lamp>
In order to evaluate as a white LED lamp, the LED lamp shown in FIG. 1 was produced as follows.
Example 11
Sample No. Europium, a manganese-activated alkaline earth silicate phosphor, which is a green light emitting phosphor of Example 1, in which calcium pyrophosphate (Ca 2 P 2 O 7 ) is surface-treated with respect to the phosphor of Sample 1, The yellow light-emitting phosphor of Example 2 in which magnesium pyrophosphate (Mg 2 P 2 O 7 ) was surface-treated with respect to the phosphor of No. 2 , and the manganese-activated alkaline earth magnesium silicate phosphor were used. A red light-emitting phosphor nitride-based red light-emitting phosphor (CaAlSiN 3 : Eu) was mixed so that the white light emission was white. This phosphor for GYR white LED is mixed with a mixed liquid of an epoxy resin and an acid anhydride curing agent, and the liquid is dropped onto a blue light emitting LED chip (0.4 mm square) 4 using a dispenser. After the epoxy resin was cured, a hemispherical transparent epoxy resin cap was coated thereon to produce a white LED lamp according to Example 11.

Example 12
Sample No. The green phosphor of Example 3 in which strontium pyrophosphate (Sr 2 P 2 O 7 ) was surface-treated with respect to the phosphor of No. 3, europium and manganese-activated alkaline earth magnesium silicate phosphor of Sample 3, Using the yellow-emitting phosphor europium and manganese-activated alkaline earth magnesium silicate phosphor of Example 4 in which barium pyrophosphate (Ba 2 P 2 O 7 ) was surface-treated on the phosphor of No. 4 from the lamp A red light-emitting phosphor nitride-based red light-emitting phosphor (CaAlSiN 3 : Eu) was mixed so that the white light emission was white. This phosphor for GYR white LED is mixed with a mixed liquid of an epoxy resin and an acid anhydride curing agent, and the liquid is dropped onto a blue light emitting LED chip (0.4 mm square) using a dispenser to form an epoxy. After the resin was cured, a hemispherical transparent epoxy resin cap was coated thereon to produce a white LED lamp according to Example 12.

Comparative Example 11
Except for using the green-emitting phosphor europium and manganese activated alkaline earth silicate phosphor of Comparative Example 1 and the yellow-emitting phosphor europium and manganese activated alkaline earth magnesium silicate phosphor of Comparative Example 2 Treated as in Example 11. That is, calcium pyrophosphate (Ca 2 P 2 O 7 ) and sample No. A white LED lamp according to Comparative Example 11 in which the phosphor 2 was not coated with magnesium pyrophosphate (Mg 2 P 2 O 7 ) was produced.

Comparative Example 12
Except for using the green-emitting phosphor of Comparative Example 3 europium and manganese-activated alkaline earth magnesium silicate phosphor and the yellow-emitting phosphor of Comparative Example 4 europium and manganese-activated alkaline earth magnesium silicate phosphor. Treated as in Example 12. That is, sample no. 3 phosphors of strontium pyrophosphate (Sr 2 P 2 O 7 ) and sample no. A white LED lamp according to Comparative Example 12 in which the phosphor 4 was not coated with barium pyrophosphate (Ba 2 P 2 O 7 ) was produced.

With respect to the white LED lamps according to Examples 11 and 12 and Comparative Examples 11 and 12, light emission luminance was measured.
In addition, each light-emitting luminance was calculated | required as a relative value with respect to the light-emitting luminance of the white LED lamp of the comparative example 11 as the reference value of 100%.
In addition, a white LED lamp is lit for 1000 hours in a high-temperature and high-humidity atmosphere (temperature: 85 ° C., humidity: 85%), and brightness deterioration (weather resistance) is measured from the start of lighting to the end of lighting (after 1000 hours). The brightness maintenance rate was measured according to the following calculation method [3].
Luminance maintenance rate (%) = Luminance after luminance degradation test (%) ÷ Luminance (%) x 100
... [3]
Table 5 shows the measurement results of the light emission luminance and the luminance maintenance rate.

Figure JPOXMLDOC01-appb-T000005

As is clear from the results shown in Table 5, sample No. 1 and no. The white LED lamp according to Example 11 in which Ca 2 P 2 O 7 and Mg 2 P 2 O 7 were surface-treated with respect to 2 was compared with the white LED lamp according to Comparative Example 11 that was not surface-treated, Although there is almost no difference in the luminance of white light emission, it can be seen that the luminance is greatly improved after a luminance deterioration test under a high temperature and high humidity atmosphere (temperature 85 ° C., humidity 85%). Sample No. 3 and no. The white LED lamp according to Example 12 in which Sr 2 P 2 O 7 and Ba 2 P 2 O 7 were surface-treated with respect to 4 was compared with the white LED lamp according to Comparative Example 12 that was not surface-treated, Although there is almost no difference in the luminance of white light emission, it can be seen that the luminance is significantly improved after the light emission luminance deterioration test in a high temperature and high humidity atmosphere (temperature 85 ° C., humidity 85%).

That is, as defined in the present invention, europium, manganese-activated alkaline earth magnesium silicate phosphor, calcium pyrophosphate (Ca 2 P 2 O 7 ), magnesium pyrophosphate (Mg 2 P 2 O 7 ), barium pyrophosphate ( By using a phosphor coated with at least one of Ba 2 P 2 O 7 ) and strontium pyrophosphate (Sr 2 P 2 O 7 ), a white LED lamp can be used in a high temperature and high humidity atmosphere (temperature 85). From the above results, it was proved that the luminance maintenance rate in the luminance deterioration (weather resistance) test at a temperature of 85 ° C./humidity was greatly improved.

According to the phosphor according to the present invention, green to yellow light is emitted by excitation of the blue LED. Furthermore, calcium pyrophosphate (Ca 2 P 2 O 7 ), magnesium pyrophosphate (Mg 2 P 2 O 7 ), barium pyrophosphate (Ba 2 P 2 O 7 ), strontium pyrophosphate (Sr 2 P) By coating with at least one of 2 O 7 ), it becomes possible to realize a light emitting device such as a white LED lamp having excellent weather resistance such as heat resistance and moisture resistance.

Claims (7)

  1. Europium and manganese activated alkaline earth magnesium silicate phosphor particles excited by ultraviolet to blue light and emitting green to yellow light,
    A phosphor comprising: a coating layer made of at least one of calcium pyrophosphate, magnesium pyrophosphate, barium pyrophosphate, and strontium pyrophosphate that uniformly coats the surface of the phosphor particles.
  2. 2. The phosphor according to claim 1, wherein the coating layer is 0.05 to 5% by weight with respect to the phosphor particles.
  3. The phosphor particles are coated with at least one of the calcium pyrophosphate, magnesium pyrophosphate, barium pyrophosphate and strontium pyrophosphate on the surface thereof in water or an alcohol aqueous solution, and then washed, filtered, dried, and dried. The phosphor according to claim 1 or 2, wherein the phosphor is subjected to a sieving step.
  4. Said phosphor particles, the chemical formula: (Sr 2-x-y -z-u, Ba x, Mg y, Eu z, Mn u) SiO 4 (0.1 ≦ x ≦ 1.7,0.01 ≦ y ≦ 0.15, 0.025 ≦ z ≦ 0.25, 0.001 ≦ u ≦ 0.01), and is activated alkaline earth magnesium silicate activated by manganese and manganese. The phosphor according to claim 3.
  5. A light emitting device comprising: the phosphor according to any one of claims 1 to 4; and a light emitting element that emits ultraviolet or blue light that excites the phosphor to emit light.
  6. The light emitting device according to claim 5, wherein the light emitting element is an LED.
  7. Calcium pyrophosphate, magnesium pyrophosphate, barium pyrophosphate and pyrophosphoric acid in water or alcohol aqueous solution on the surface of europium and manganese activated alkaline earth magnesium silicate phosphor particles excited by ultraviolet to blue light to emit green to yellow light A method for producing a phosphor, comprising a step of reactively coating at least one of strontium.
PCT/JP2014/001860 2013-03-29 2014-03-28 Phosphor, method for producing same and light emitting device using same WO2014156201A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2013-073073 2013-03-29
JP2013073073 2013-03-29

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2014525209A JP5989775B2 (en) 2013-03-29 2014-03-28 Phosphor, method for manufacturing the same, and light emitting device using the same

Publications (1)

Publication Number Publication Date
WO2014156201A1 true WO2014156201A1 (en) 2014-10-02

Family

ID=51623211

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/001860 WO2014156201A1 (en) 2013-03-29 2014-03-28 Phosphor, method for producing same and light emitting device using same

Country Status (2)

Country Link
JP (1) JP5989775B2 (en)
WO (1) WO2014156201A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04270783A (en) * 1991-02-27 1992-09-28 Toshiba Corp Blue luminescent stimulable phosphor and fluorescent lamp
JP2006269938A (en) * 2005-03-25 2006-10-05 Nichia Chem Ind Ltd Light emitting device, phosphor for light emitting element and its manufacturing method
JP2008063446A (en) * 2006-09-07 2008-03-21 Sharp Corp Coated phosphor, method for producing the same and light-emitting device comprising the coated phosphor
WO2008096545A1 (en) * 2007-02-09 2008-08-14 Kabushiki Kaisha Toshiba White light-emitting lamp and illuminating device using the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009141982A1 (en) * 2008-05-19 2009-11-26 株式会社 東芝 Linear white light source, and backlight and liquid crystal display device using linear white light source

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04270783A (en) * 1991-02-27 1992-09-28 Toshiba Corp Blue luminescent stimulable phosphor and fluorescent lamp
JP2006269938A (en) * 2005-03-25 2006-10-05 Nichia Chem Ind Ltd Light emitting device, phosphor for light emitting element and its manufacturing method
JP2008063446A (en) * 2006-09-07 2008-03-21 Sharp Corp Coated phosphor, method for producing the same and light-emitting device comprising the coated phosphor
WO2008096545A1 (en) * 2007-02-09 2008-08-14 Kabushiki Kaisha Toshiba White light-emitting lamp and illuminating device using the same

Also Published As

Publication number Publication date
JPWO2014156201A1 (en) 2017-02-16
JP5989775B2 (en) 2016-09-07

Similar Documents

Publication Publication Date Title
KR101331392B1 (en) Fluorescent substance, process for producing the same, and light emitting device using said fluorescent substance
US7026755B2 (en) Deep red phosphor for general illumination applications
KR101168173B1 (en) Phosphor and method for producing the same
US7038370B2 (en) Phosphor converted light emitting device
JP5143549B2 (en) Phosphors for use in LEDs and mixtures thereof
TWI391472B (en) Phosphor, production method thereof, and light-emitting apparatus using phosphor
JP5715327B2 (en) Red line emitting phosphors for use in light emitting diode applications
JP5503871B2 (en) Charge compensated nitride phosphors for use in lighting applications
KR101168178B1 (en) Phospher and method for production thereof, and luminous utensil
US7274045B2 (en) Borate phosphor materials for use in lighting applications
JP4892193B2 (en) Phosphor mixture and light emitting device
US7768189B2 (en) White LEDs with tunable CRI
US7329371B2 (en) Red phosphor for LED based lighting
US7938983B2 (en) Illumination system comprising a radiation source and a fluorescent material
JP4511885B2 (en) Phosphor, LED and light source
KR101147560B1 (en) Fluorescent substance and light-emitting equipment
JP4524468B2 (en) Phosphor, method for producing the same, light source using the phosphor, and LED
EP1753840B1 (en) Illumination system comprising a radiation source and a fluorescent material
DE60312733T2 (en) Lighting device with radiation source and fluorescent material
EP1566426A2 (en) Phosphor converted light emitting device
JP2005264160A (en) Phosphor, method for producing the same and light emitting device
TWI375710B (en)
US8771547B2 (en) Oxycarbonitride phosphors and light emitting devices using the same
US8350465B2 (en) Doped garnet fluorescent substance having red shift for pc LEDs
JP2004115633A (en) Silicate phosphor and light-emitting unit therewith

Legal Events

Date Code Title Description
ENP Entry into the national phase in:

Ref document number: 2014525209

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14774586

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase in:

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14774586

Country of ref document: EP

Kind code of ref document: A1