# Patent

## Title
Fluorophor and method for production thereof and illuminator

## Abstract

A fluorophor comprising, as a main component, an α-type sialon crystal which contains at least an A element (wherein A represents one or more elements selected from among Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Er, Tm and Yb), an M element (wherein M represents one or more elements selected from among Li, Na, Mg, Ca, Y, La, Gd and Lu), Si, Al, oxygen and nitrogen, and is represented by the general formula: (Mx, Ay)(Si12−(m+n)Alm+n)(OnN16−n) (1) m=δM×x+δA×y (2) 0.2≦x≦2.4 (3) 0.001≦y≦0.4 (4) and 0.5×m<n≦4 (5). The fluorophor is reduced in the lowering of brightness, and is useful for a white color LED and the like.

## Background
TECHNICAL FIELD
The present invention relates to a phosphor comprising an inorganic compound as a main component and a manufacture thereof and an application thereof. More specifically, the application relates to a lighting apparatus and an emission apparatus of an image display device utilizing features of the phosphor, that is, properties to emit fluorescence of rather long wavelength from 530 nm to 585 nm.
BACKGROUND ART
A phosphor is utilized in a fluorescent display tube (VFD), a field emission display (EFD), a plasma display panel (PDP), a cathode-ray tube (CRT), a white color emission diode, and so on. In any of these applications, it is necessary to provide the phosphor with energy to excite the phosphor in order to render the emission and the phosphor is excited by the excitation source with high energy such as a vacuum ultraviolet ray, an ultraviolet ray, an electron beam, a blue light, and the like so as to emit a visible light. However, the phosphor deteriorates as a result of exposure to the above-mentioned excitation source such that there is an issue that the brightness of the phosphor decreases as it is used for a long period of time and the phosphor in which the brightness does not deteriorate is desired.
A white color LED has been used in a field of disaster light, beacon, and the like where reliability is required, a field of in-vehicle light, a back light of a mobile phone, and the like where reduction in size and weight is strongly desired, a field of direction board where visibility is required. The emission color of this white color LED, i.e., the white light may be obtained by mixing lights such that the white light is a mixture of a yellow light emitted by a phosphor and a blue light emitted by a blue color LED of wavelength from 430 to 480 nm as the emission source. The phosphor suitable for such white color LED is, by a small amount, arranged on the surface of the blue color LED chip as the emission source. Therefore, the phosphor which emits a yellow light upon irradiation of the blue color LED is desired for this application. Further, in view of reducing fluctuation of emission color caused by the temperature change of the application environment where the device is used, phosphor material emitting fluorescence with a small fluctuation in the emission intensity caused by the temperature change is also desired.
As the emission material to emit a yellow light upon irradiation of the blue color LED, garnet ((Y, Gd)3(Al, Ga)5O12:Ce. Hereinafter, referred to as “YAG:Ce”), which is an oxide, is known. This phosphor was formed by replacing Y sites partially with Gd and Al sites partially with Ga, and doping Ce3+ as the optically-activating ion at the same time (Non-patent reference 1). Although this phosphor is known as a highly efficient phosphor, the emission intensity is lowered as the temperature increases such that there is an issue that the emission color of the device varies depending on the temperature when it is used in the white color LED.
A phosphor comprising α-type sialon as a host crystal is proposed as a yellow color phosphor with a small temperature fluctuation of emission. The α-type sialon is a crystal to form an interstitial solid solution wherein Li, Ca, Mg, Y, or a lanthanide metal solid solves interstitially into the α-type Si3N4 crystal. The α-type Si3N4 crystal structure has two large spaces having diameters of about 0.1 nm interstitially in the unit cell. The structure is stabilized if metal atoms solid solve in such spaces. Therefore, the general formula of α-type sialon containing a metal element M is given by:

Mx(Si12−(m+n)Alm+n)(OnN16−n).

Here, x is the number of M atoms contained in the α-type Si3N4 unit cell. Further, m corresponds to the number of Al—N bonds substituting Si—N bonds in the α-type Si3N4 crystal structure and m=δ x (here, δ is the valence number of metal M). Here, n is the number of Al—O bonds substituting Si—N bonds. The electric neutrality is maintained by the above lattice substitution and interstitial solid solution. In the α-sialon, metal-nitrogen bonds are main bonds such that the α-sialon is a solid solution with a high percentage of nitrogen content.

It is publicly know before this patent application that α-type sialon becomes a phosphor if some of stabilizing metal atoms solid solving interstitially into the α-type sialon are substituted with optically activating metal ions (Non-patent references 2 to 4). Further, it is also publicly known that a phosphor material having Ca-α-sialon as a host crystal and being doped with Eu2+ becomes material to render a yellow color emission upon irradiation of a visible light of the violet-blue wavelength region (Patent references 1 and 2).
It is disclosed that this material emits a yellow light which is a complementary color of a blue color upon irradiation of the excitation light of the blue color LED, and that this material can be used as a phosphor for the white color LED by mixing lights of both colors (Patent reference 3). However, in these materials, there still is an issue that the emission intensity is not high enough because the amount of Eu2+solid solving into the α-type sialon lattice is small. Further, it was reported that Ca-α-sialon doped with Eu2+became a phosphor to emit a yellow light of 550 to 600 nm upon excitation by the blue light of 450 to 500 nm. However, in the composition having the best emission efficiency, the emission wavelength is from 585 to 600 nm such that a white color LED having the excitation source of the blue color LED emitting a light of 450 to 470 nm emits a white light with mixed colors which is a lamp color to have the correlated color temperature of 3000 K. Therefore, it was difficult to obtain the light emission of a daylight color, a day white color, and a white color of the correlated color temperature of 5000 K to 6500 K, which is usually used for an ordinary light.
The researches for adjusting solid solution metal and solid solution amount in the α-type sialon contained in the phosphor as the host crystal are conducted (Patent reference 4). Among such researches, it was reported that the emission peak wavelength varied in the range of 580 nm to 604 nm based on the composition control. However, there was an issue that the emission intensity was lowered when the peak wavelength was made less than 585 nm such that it was difficult to apply such phosphor to the practical use. That is, in the α-type sialon with an Eu luminescence center, a yellow-green color phosphor rendering the emission of shorter wavelength was desired.
In the conventional technology of the lighting apparatus, a white color emission diode of a combination of a blue color light-emitting diode device and a yellow color emitting phosphor to be excited by the blue color light is publicly known and is implemented in various kinds of lighting applications. As typical examples thereof, Japanese patent No. 2900928, “Light-emitting diode” (Patent reference 5); Japanese patent No. 2927279, “Light-emitting diode”(Patent reference 6); Japanese patent No. 3364229, “Wavelength conversion material and its manufacture and light-emitting device” (Patent reference 7); and so on are cited. In these light-emitting diodes, phosphors being used particularly often are phosphors in the Ce-activated yttrium-aluminum-garnet (YAG:Ce) system and expressed by the general formula:

(Y, Gd)3(Al, Ga)5O12:Ce3+.

However, the white color emission diode comprising: a blue color light-emitting diode device and a phosphor in the YAG:Ce system has the emission intensity which is lowered when the temperature increases such that there was an issue that the emission color fluctuated because of deteriorated balance between the blue and yellow lights when the devices were warmed up as the time goes by after turning on the switch.
In these backgrounds, a phosphor which emits a yellow-green color light of shorter wavelength than that of Ca-α-sialon doped with Eu2+ and shows the brightness of smaller temperature fluctuation than the phosphor in the YAG:Ce system was desired.
[Patent reference 1] Japanese patent application publication No. 2002-363554
[Patent reference 2] Japanese patent application publication No. 2003-336059
[Patent reference 3] Japanese patent application publication No. 2004-186278
[Patent reference 4] Japanese patent application publication No. 2004-67837
[Patent reference 5] Japanese patent No. 2900928
[Patent reference 6] Japanese patent No. 2927279
[Patent reference 7] Japanese patent No. 3364229
[Non-patent reference 1] Mukai, Nakamura, “White and UV LEDs,” Oyo Buturi, Vol. 68, 152-55 (1998).
[Non-patent reference 2] J. W. H. van Krevel, “On new rare-earth doped M-Si—Al—O—N materials luminescence properties and oxidation resistance,” Thesis, ISBN 90-386-2711-4, Eindhoven Technische Universiteit Eindhoven (2000).
[Non-patent reference 3] J. W. H. van Krevel et al. “Long wavelength Ca3+ emission in Y—Si—O—N materials”, J. Alloys and Compounds, 268, 272-277 (1998))
[Non-patent reference 4] J. W. H. van Krevel et al, “Luminescence properties of terbium-, cerium-, or europium-doped α-sialon materials,” J. Solid State Chem. 165, 19-24 (2002).
[Non-patent reference 5] R. J. Xie et al, “Preparation and Luminescence spectra of calcium-and rare-earth (R═Eu, Tb and Pr) codoped α-SiAlON ceramics”, J. Am. Ceram. Soc. 85, 1229-1234 (2002).
DESCRIPTION OF THE INVENTION
Problems to be Solved by the Invention
The present invention was conceived in response to such desire. And one of the objects is to provide an inorganic phosphor which emits a yellow-green color with a high intensity of shorter wavelength than that of a rare earth activated sialon phosphor such as a conventional Ca-α-sialon, has the emission intensity fluctuated only slightly by the temperature change, and is chemically stable. Another object of the present invention is to provide a lighting apparatus having a small temperature fluctuation and an endurable emission apparatus of an image display device by utilizing such phosphor.
Means for Solving Problems
The present inventors conducted detailed researches about the contents of oxygen and nitrogen in the phosphor having α-type sialon crystal as a host crystal under such situations and found a phosphor having α-type sialon crystal of a specific composition as a host crystal, which is activated by optically activating metal such as Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Er, Tm, or Yb, had the emission intensity with a small fluctuation due to the temperature change and emitted fluorescence with higher intensity than that of the conventionally-reported phosphor having nitride or oxynitride as a host crystal. Further, it was also found that a phosphor with a specific composition containing solid solution of a specific metal emitted a yellow-green color light of shorter wavelength.
That is, it was found that a crystal of a specific composition became a phosphor emitting fluorescence having a high intensity and a small temperature fluctuation as a result of intensive researches about an inorganic compound of α-type sialon as a major component comprising: an M element as a stabilizing element for α-sialon (here, M is one or more kinds of elements selected from Li, Na, Mg, ca, Y, La, Gd, and Lu) and an A element as an emission ion (here, A is one or more kinds of elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Er, Tm, and Yb). In particular, the inorganic compound activated by Eu was found to emit the yellow-green light of shorter wavelength than that of the conventionally-reported α-sialon phosphor and to become a phosphor emitting fluorescence of a high intensity.
Further, it was found to be possible to obtain a white color emission diode with a small temperature fluctuation and a high emission efficiency, and an image display device rendering bright coloring by utilizing such phosphor.
The phosphor of the present invention is a new phosphor containing a crystal as a host crystal having a totally different composition than that of sialon such as Ca1.47Eu0.03Si9Al3N16 or the like as disclosed in Chapter 11 of Non-patent reference 2.
In general, a phosphor of an inorganic compound activated with Mn or a rare earth element as a luminescence center element A renders an emission in which an emission color and an intensity thereof vary according to an electronic state around the A element. For example, it was reported that the phosphor having a luminescence center of divalent Eu emitted a blue color, a green color, a yellow color, and a red color by changing the host crystal. That is, the emission color and the intensity of the emission of the phosphor would be totally different if the constituent element or a liganding environment in the crystal structure taking in “A” or a host crystal structure thereof is changed although the phosphor has a similar composition such that such phosphor would be regarded as a totally different phosphor. In the present invention, the phosphor has a totally different composition as the host than that of any of sialon and nitride or oxynitride having been reported and the phosphor having such composition as the host so far has not been reported. Further, the phosphor having the composition of the present invention as the host emits fluorescence of higher intensity than a phosphor having a conventional crystal as the host. And the phosphor of a specific composition shows a yellow-green color emission.
The present inventors conducted intensive researches in consideration of the above-mentioned background so as to successfully provide a phosphor rendering emission with a high intensity of a specific wavelength region by implementing the configuration recited in any one from (1) to (10). Further, the method of manufacture recited in (11) was successfully provided. Further, the lighting apparatus and the image display device having excellent features were successfully provided by implementing the configuration recited in any one from (12) to (20). The following (1) to (20) describes the above more specifically.

    (1) A phosphor comprising: α-type sialon crystal as a main component, wherein the α-type sialon crystal comprises: at least an A element (here, A is one or more kinds of elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Er, Tm, and Yb); an M element (here, M is one or more kinds of elements selected from Li, Na, Mg, Ca, Y, La, Gd, and Lu); Si; Al; oxygen; and nitrogen, wherein the α-sialon crystal is expressed by a general formula:

(Mx, Ay)(Si12−(m+n)Alm+n)(OnN16−n)  (1), and

m=δM×x+δA×y  (2),

wherein the α-sialon crystal (here, x is an amount of solid solution of M in a sialon unit cell, y is an amount of solid solution of A in the sialon unit cell, n is a content amount of oxygen in the sialon unit cell) is expressed by a composition formula having parameters x, y, and n, which are in a range expressed by:

0.2≦x≦2.4  (3),

0.001≦y≦0.4  (4), and

0.5×m<n≦4  (5).

    (2) The phosphor according to the above (1), wherein the parameter n is in a range expressed by:

0.6×m≦n≦2  (6)

    (3) The phosphor according to the above (1) or (2), wherein the M element is Ca, wherein the A element is Eu, and wherein the phosphor emits fluorescence having a peak in a wavelength range from 530 nm to 585 nm upon irradiation of an excitation source.
    (4) The phosphor according to any one of the above (1) to (3), wherein the M element is Ca, wherein the A element is Eu, wherein the parameters m and n are in a range expressed by:

0.6≦m≦1.4  (7), and

0.8≦n≦2  (8),

wherein the phosphor emits fluorescence having a peak in a wavelength range from 560 nm to 575 nm upon irradiation of an excitation source.

    (5) The phosphor according to any one of the above (1) to (4), wherein the excitation source is a violet light or a visible light having a wavelength which is 100 nm or more and 500 nm or shorter.
    (6) The phosphor according to any one of the above (1) to (5), wherein an emission color upon irradiation of the excitation source is represented by (x, y) values in the CIE Chromaticity coordinate and satisfies conditions:

0.3≦x≦0.5  (9), and

0.46≦y≦0.6  (10)

    (7) The phosphor according to any one of the above (1) to (6), comprises a primary particle of the sialon which is characterized by a diameter of 0.5 μm or more along a minor axis and an aspect ratio of 3 or more.
    (8) The phosphor according to the above (1), comprises: an amorphous phase or another crystalline phase than the α-type sialon, wherein a content amount of the α-type sialon crystal is 10 mass % or more.
    (9) The phosphor according to the above (8), wherein the content amount of the α-type sialon crystal is 50 mass % or more.
    (10) The phosphor according to the above (8) or (9), wherein the amorphous phase or the other crystalline phase is inorganic substance having electronic conductivity.
    (11) A method of manufacturing the phosphor recited in any one of the above (1) to (10) comprising: firing in a nitrogen atmosphere in a temperature range which is 1500 degree Celsius or higher and 2200 degree Celsius or lower a raw material mixture comprising: at least oxide of an M element (here, M is one or more kinds of elements selected from Li, Na, Mg, Ca, Y, La, Gd, and Lu); oxide of an A element (here, A is one or more kinds of elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Er, Tm, and Yb); silicon nitride; aluminum nitride; and silicon oxide or aluminum oxide.
    (12) A lighting apparatus comprising: an excitation source and a phosphor, wherein the phosphor comprises a phosphor recited in any one of the above (1) to (10).
    (13) The lighting apparatus according to the above (12), wherein the excitation source comprises: an inorganic EL device; an organic EL device; a laser diode (LD); or a light-emitting diode (LED) to emit a light of wavelength from 330 to 500 nm.
    (14) The lighting apparatus according to the above (12) or (13), wherein the excitation source is a LED or a LD which emits a light of wavelength from 330 to 420 nm, wherein the lighting apparatus comprises: the phosphor recited in any one of the above (1) to (10); a blue color phosphor having an emission peak in wavelength range of 450 nm to 500 nm by an excitation light of 330 nm to 420 nm; and a red color phosphor having an emission peak in wavelength range of 600 nm to 700 nm by an excitation light of 330 nm to 420 nm, and wherein the lighting apparatus emits a white light by mixing a blue light; a green light; and a red light.
    (15) The lighting apparatus according to the above (12) or (13), wherein the excitation source is a LED or a LD which emits a light of wavelength from 430 to 480 nm; and wherein the lighting apparatus emits a white light by mixing a blue light of the excitation source and a yellow light of the phosphor.
    (16) The lighting apparatus according to the above (12) or (13), wherein the excitation source is a LED or a LD which emits a light of wavelength from 430 to 480 nm, wherein the lighting apparatus comprises: the phosphor; and an orange or a red color phosphor (hereinafter, referred to as “second phosphor”) having an emission peak in wavelength range of 580 nm to 700 nm by an excitation light of 430 nm to 480 nm, and wherein the lighting apparatus emits a white light by mixing a yellow light of the phosphor and an orange or red light of the second phosphor.
    (17) The lighting apparatus according to the above (16), wherein the second phosphor is an Eu-activated CaAlSiN3.
    (18) The lighting apparatus according to the above (16), wherein the second phosphor is an Eu-activated Ca-α-sialon.
    (19) An image display device comprising: the phosphor recited in any one of the above (1) to (10); and an excitation source of the phosphor.
    (20) The image display device according to the above (19), wherein the excitation source is an electron beam, an electrical field, a vacuum ultraviolet ray, or an ultraviolet ray.
    (21) The image display device according to the above (19) or (20), comprising: any of a fluorescent display (VFD), a field emission display (FED), a plasma display panel (PDP), or a cathode-ray tube (CRT).


The phosphor of the present invention is characterized by a high intensity and a small temperature fluctuation of the brightness since an inorganic compound is contained as a main component wherein the A element (Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Er, Tm, Yb) solid solves into the inorganic compound which comprises α-type sialon crystal having a specific nitrogen/oxygen content composition as a host. Further, the phosphor of a specific composition to which Eu or the like is added renders an emission of shorter wavelength than the conventional orange or yellow sialon phosphor so as to be superior as the yellow-green phosphor. Further, since the phosphor is chemically stable, the brightness does not deteriorate in particular even if the phosphor is exposed to the excitation source. A useful phosphor to be utilized in VFD, FED, PDP, CRT, white color LED, and so on is provided.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a drawing showing values of m and n in examples.
FIG. 2 is a drawing showing emission intensities of phosphors (examples).
FIG. 3 is a drawing showing emission wavelengths of phosphors (examples).
FIG. 4 is a drawing showing a state of particles of a phosphor (Example 71).
FIG. 5 is a drawing showing a state of particles of a phosphor (Comparative example 1).
FIG. 6 is a drawing showing emission and excitation spectra of a phosphor (Example 29).
FIG. 7 is a drawing showing emission and excitation spectra of a phosphor (Comparative example 2).
FIG. 8 is a schematic drawing of a lighting apparatus (bullet-type LED lighting apparatus) according to the present invention.
FIG. 9 is a schematic drawing of a lighting apparatus (substrate-mounted LED lighting apparatus) according to the present invention.
FIG. 10 is a schematic drawing of an image display device (plasma display panel) according to the present invention.



DESCRIPTION OF REFERENCE NUMERALS
1 bullet-type light-emitting diode lamp
2, 3 lead wire
4 light emitting diode device
5 bonding wire
6, 8 resin
7 phosphor
21 tip-type white light-emitting diode lamp for mounting on a substrate
22, 23 lead wire
24 light emitting diode device
25 bonding wire
26, 28 resin
27 phosphor
29 alumina ceramics substrate
30 side surface member
31 red color phosphor
32 green color phosphor
33 blue color phosphor
34, 35, 36 ultraviolet ray emission cell
37, 38, 39, 40 electrode
41, 42 dielectric layer
43 protective layer
44, 45 glass substrate
BEST MODE TO CARRY OUT THE INVENTION
Hereafter, the present invention is described in detail. The phosphor of the present invention is a composition which includes at least an M element for stabilizing α-sialon, an activating A element, Si, Al, oxygen, and nitrogen, and includes an α-type sialon crystal as the main component. As a typical constituent element, A may be one or more kinds of elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Er, Tm, and Yb. As a typical element, M may be one or more kinds of elements selected from Li, Na, Mg, Ca, Y, La, Gd, and Lu. The A element functions as a luminescence center which emits fluorescence upon receiving the energy from an excitation source, and emission color differs depending on an added element. Therefore, an appropriate element for addition may be selected in order to obtain a desired color out of emission colors in a wavelength region extending from 400 to 700 nm according to the use. In particular, an Eu-doped phosphor shows a yellow-green emission having a peak in a wavelength region of from 530 to 580 nm, and hence is particularly appropriate for building a white color LED in combination with a blue color LED. The M element solves into the sialon lattice to form the solid solution and contributes to stabilization of the crystal structure. The M element may be selected from optically inert elements.
An α-type sialon crystal containing the A element and the M element is represented by a general formula:

(Mx, Ay)(Si12−(m+n)Alm+n)(OnN16−n).

The parameter m is a value determined by x and y, and has a relation:

m=δM×x+δA×y.

Here, δM is the valence of the M element, and for example, 1 for Li, 2 for Mg or Ca, and 3 for Y or La.

According to the present invention, the parameters x and y in the formula have values in the range:

0.2≦x≦2.4,

0.001≦y≦0.4, and

0.5×m<n≦4.

The parameter x represents the number of M atoms which solid solve in the unit cell of sialon to form the solid solution. When x is smaller than 0.2, the α-sialon crystal is not stabilized so as to become β-sialon, thereby causing change of the emission color and reduction of the brightness. When x is larger than 2.4, crystalline phases other than the α-type sialon precipitate such that the reduction of the emission brightness may be caused. The parameter y represents the number of the A atoms as an activating element which solid solve in the unit cell of sialon to form the solid solution. When y is smaller than 0.001, the brightness is low because the number of optically active ions is too small, and when y is larger than 0.4, concentration quenching is caused by the interaction between the A atoms, thereby causing the reduction of the brightness.

The parameter n is a value related to the amount of the substitution-type solid solution of oxygen into the α-type Si3N4 structure and represents the number of oxygen atoms contained in a unit cell. Here, since the total number of oxygen atoms and nitrogen atoms which are contained in the unit cell is 16, the number of the nitrogen atoms contained in the unit cell is 16−n.
When the M element is monovalent and Li2O is used as a starting material, introduction of the number x of Li atoms into the crystal lattice results in introduction of the number 0.5×x of oxygen atoms. Thus, if an oxide is used as a starting material containing the M element, the number 0.5×δM×x of oxygen atoms are introduced. Here, δM is the valence of the M ion. That is, in the α-sialon which uses Si3N4, AlN and the oxide of M as the starting material, the following relation is given:

n=0.5×δM×x=0.5×m.

In the present invention, the inventors paid attention to the amount of n in the crystal lattice and found that the emission wavelength could be made shorter and the brightness could be enhanced by adopting a composition which contains a larger amount of oxygen than a composition of n=0.5×m which has been conventionally synthesized as the host crystal of a phosphor. That is, the inventors have found that the emission wavelength could be made shorter as well as the brightness could be made higher in a composition in which the value of n is in the range of:

0.5×m<n≦4.

When the value of n is equal to or smaller than 0.5×m, the amount of oxygen in the crystal lattice is small, and the emission wavelength tends to become longer. When the value of n is larger than 4, the proportion of crystalline phases other than α-sialon becomes larger such that the emission intensity may be lowered.

The reason why the emission wavelength is made shorter and the brightness is made higher by increasing the amount of oxygen in the sialon lattice is inferred as follows. In an Eu-activated sialon phosphor, fluorescence is emitted when an Eu2+ ion which has absorbed an excitation light renders a transition from the 5d orbital into the 4f orbital. Therefore, the color of the emission is determined by the energy levels of the Eu2+ ion. If the amount of oxygen in the sialon is increased, the energy difference by the transition increases because the proportion of oxygen and nitrogen atoms which surround the Eu2+ ion changes so as to lower the covalent nature, thereby causing the emission wavelength shorter. Moreover, the emission intensity may be made higher because of formation of large particles having excellent crystallinity since a large amount of liquid phase is generated during synthesis at a high temperature by increasing the oxygen amount so as to enhance reactivity.
In the present invention, a phosphor that contains sialon primary particles of a shape where a minor axis diameter thereof is 0.5 μm or larger and an aspect ratio thereof is 3 or larger shows a particularly high emission intensity. If the sialon primary particles are in the single crystal, the emission intensity is made even higher. Here, the aspect ratio means flatness and is defined as the ratio of the length of the major axis to that of the minor axis. Such a shape can be made by the reaction for a long period of time at the high temperature in a state where the large amount of liquid phase exists, that is, where the amount of n is large enough. The reaction time is preferably 24 hours or longer.
An especially high emission intensity may be achieved by a phosphor having a composition in which the above-mentioned value of n is in the range of:

0.6×m≦n≦2.

The value of n can be made larger by replacing part of the AlN constituent serving as an aluminum source of the starting material with Al2O3, or part of the Si3N4 constituent serving as a Si source with SiO2.
Since a phosphor of α-sialon containing Ca and being activated with Eu shows a high emission intensity, a phosphor which contains Ca as the M element and Eu as the A element may constitute a phosphor showing a high emission intensity. In particular, a phosphor in which the M element is Ca and the A element is Eu is more preferable for LED applications since such a phosphor emits fluorescence having a peak in the wavelength range from 530 nm to 585 nm.
In particular, a phosphor, in which the M element is Ca and the A element is Eu and the parameters m and n are in the range of:

0.6≦m≦1.4 and

0.8≦n≦2,

emits fluorescence which has a peak in the wavelength range from 560 nm to 575 nm upon irradiation of the excitation source. Hence, it is especially preferable to apply the phosphor to a white color LED employing a blue color LED as an excitation source thereof.

As an excitation source, a light (vacuum ultraviolet ray, ultraviolet ray, or visible light) having a wavelength region of 100 nm or longer and 500 nm or shorter, and a radiation ray such as an electron beam, an X-ray, and a neutron beam can be named. Further, the phosphor may also be utilized for excitation (inorganic EL device) in the electric field.
When the phosphor of the present invention is utilized in a powder state, it is preferable that a mean particle diameter is in the range of 0.1 μm or larger and 50 μm or smaller in view of the dispersibility into the resin and the fluidity of the powder. In particular, the phosphor with the mean particle diameter of 5 μm or larger and 10 μm or smaller is excellent in handleability. Further, the emission brightness is enhanced if the phosphor in the powder state comprises single crystal particles with the mean particle diameter of 5 μm or larger and 10 μm or smaller.
In order to obtain a phosphor having a high emission brightness, the amount of impurities contained in the α-type sialon crystals is preferably minimized as much as possible. In particular, it is desirable to select a raw material powder and control a synthesis process so that the total amount of impurity elements such as Fe, Co, and Ni is 500 ppm or less since the light emission is quenched if a large amount of impurity elements are contained.
In the present invention, it is desirable that the phosphor contains as much α-type sialon crystal of high purity as possible and it is even more desirable that the α-type sialon crystal comprises a single phase from the viewpoint of the fluorescence emission. However, it is possible for the phosphor to contain a mixture with another crystalline phase or an amorphous phase within a range where characteristics thereof are not lowered. In this case, it is desirable that the content of the α-type sialon crystals is 10 mass % or larger in order to obtain the high brightness thereof. More preferably, when the content is maintained at 50 mass % or higher, the brightness improves remarkably. In the present invention, as the range of the main component, the content of the α-type sialon crystal is at least 10 mass % or larger. The content of the α-type sialon crystal can be determined based on the multiphase analysis by the Rietveld method as the X-ray diffraction measurement is performed. In a simpler way, the content can be obtained from the ratios among the respective heights of the strongest lines of the α-type sialon crystal and the other crystals by utilizing the X-ray diffraction results.
It is possible to provide the electrical conductivity to the phosphor of the present invention by mixing inorganic substances having the electrical conductivity into the phosphor if the phosphor is applied to the field where the phosphor is excited by an electron beam. As the inorganic substance having the electrical conductivity, oxide, oxynitride, nitride, or a combination thereof of one or more kinds of elements selected from Zn, Al, Ga, In, and Sn may be named.
The phosphor of the present invention emits fluorescence of a specific color of the wavelength region of from 530 nm to 585 nm. If it is necessary to mix the specific color with other colors, it is possible to mix it with other inorganic phosphors which emit fluorescence of the other colors.
The phosphor of the present invention obtained as described above is characterized in that its excitation source ranges more widely from an electron beam, an X-ray, and an ultraviolet ray to a visible light as opposed to an ordinary oxide phosphor or the conventional sialon phosphor and that the phosphor of the present invention emits the fluorescence of the wavelength region of from 530 nm to 585 nm and, in particular, the fluorescence of a yellow-green color, if it has a specific composition, of the wavelength region of from 530 nm to 585 nm, which may be the yellow-green color expressed by (x, y) in the CIE Chromaticity coordinate with the relationship:

0.3≦x≦0.5, and

0.46≦y≦0.6.

By utilizing the aforementioned emission characteristics, the phosphor of the present invention is preferably applied to the lighting apparatus and the image display device. In addition, the phosphor of the present invention shows only a small fluctuation in the emission brightness as the temperature changes and demonstrates an excellent long-term stability in an oxidizing atmosphere and hydric environment.

Although the method of manufacturing the phosphor of the present invention is not prescribed, a phosphor having high brightness can be manufactured by the following method.
The phosphor of high-brightness is obtained by firing a raw material mixture containing at least oxide of M (wherein M is one or more kinds of elements selected from Li, Na, Mg, Ca, Y, La, Gd, and Lu), oxide of A (wherein A is one or more kinds of elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Er, Tm, and Yb), silicon nitride, aluminum nitride, and silicon oxide or aluminum oxide in a nitrogen atmosphere in the temperature range of 1500° C. or higher and 2200° C. or lower.
When the phosphor containing Ca, Eu, Si, Al, O, and N is synthesized, the starting material may be a mixture of silicon nitride, aluminum nitride, aluminum oxide or silicon oxide, a compound which becomes calcium oxide in the firing process (an addition amount of the compound is calculated by converting the equivalent amount of CaO), and europium oxide or a compound which becomes europium oxide in the firing process (an addition amount of the compound is calculated by converting the equivalent amount of EuO).
It is likely to obtain a stable α-type sialon and a phosphor of high brightness when the firing is conducted in a nitrogen atmosphere of a pressure range of 0.1 MPa or higher and 100 MPa or lower. It is likely that silicon nitride as a raw material is decomposed at a high firing temperature when the gas pressure is less than 0.1 MPa. And the gas pressure higher than 100 MPa leads high cost such that it is not preferable in view of the industrial productivity.
The above-mentioned mixed powder of metal compounds may be fired in a state where the packing fraction is kept at a bulk density of 40% or lower. The bulk density refers to the volume packing fraction of powder and is a value given by dividing the ratio of mass of the powder filled in a certain vessel to the volumetric capacity of the vessel by the theoretical density of the metal compounds. Since the reactivity of a boron nitride sintered compact with the metal compounds is low, the boron nitride sintered compact is suitable for the vessel.
The reason why the firing process is conducted as the bulk density is kept to be 40% or lower is that it is readily to synthesize crystals with a small amount of surface defects. That is, it is plausible that the crystals with the small amount of surface defects can be synthesized since contacts between crystals become less as the crystals grow with reaction products if the firing process is conducted in a state where more free space is provided around the raw material powder.
Next, the phosphor is synthesized by firing the thus-obtained mixture of the metal compounds in an inert atmosphere containing nitrogen in a temperature range of 1200° C. or higher and 2200° C. or lower. Since the firing temperature is high and the firing atmosphere is an inert atmosphere containing nitrogen, an electric furnace of a metal resistance heating type or a graphite resistance heating type, in which a high temperature member of the furnace made of carbon is used, is suitable. As the firing method, a sintering method such as a pressureless sintering method or a gas-pressure sintering method in which no mechanical pressure is applied from the outside is preferable since it is possible to conduct the firing as the bulk density is kept high in such a method.
When a powder aggregate obtained by the firing is firmly solidified, the powder aggregate is milled by a pulverizer usually used in the industry such as a ball mill and a jet mill. The milling is made until a mean particle diameter of 50 μm or smaller is attained. The mean particle diameter of from 0.1 μm to 5 μm is particularly preferable. If the mean particle diameter exceeds 50 μm, the fluidity of the powder and the dispersibility of the powder to resin tend to be inferior. Consequently, when a light emitting device is made by combining a light-emitting element, the emission intensity tends to become nonuniform depending on a portion of the element. If the mean particle diameter becomes smaller than 0.1 μm, the number of defects on the phosphor powder surface increases such that the emission intensity might be lowered depending on the composition of the phosphor.
If the phosphor powder after firing, the phosphor powder after milling treatment, or the phosphor powder after particle size adjustment is heat-treated in a temperature range of 1000° C. or higher and equal to or lower than the firing temperature, the defects introduced on the surface at the time of milling and the like decrease such that the brightness is improved.
By washing the product with water or a solvent constituted of an aqueous solution of an acid after the firing process, the content of a glass phase, a secondary phase, or an impurity phase contained in the product can be reduced, and the brightness is enhanced. In this case, the acid can be selected from one kind of substance or a mixture of sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, and organic acid. In particular, a mixture of hydrofluoric acid and sulfuric acid shows a pronounced effect on removing impurities.
As explained above, since the phosphor of the present invention shows higher brightness than the conventional sialon phosphor and smaller decline of the brightness of the phosphor when the phosphor is exposed to the excitation source, the phosphor is suitable for a VFD, an FED, a PDP, a CRT, a white color LED, and the like and, in particular, is suitable for the white color LED if it is combined with a blue color LED.
The lighting apparatus of the present invention comprises at least a light source and the phosphor of the present invention to be used therein. The lighting apparatus includes an LED lighting apparatus, an electroluminescence lighting apparatus, a fluorescent lamp, and the like. The LED lighting apparatus can be manufactured using the phosphor of the present invention by a publicly known method which is described in the Japanese Patent Laid-open Publication No. H05-152609, Japanese Patent Laid-open Publication No. H07-99345, Japanese Patent No. 2927279, and the like. In this case, the light source is preferably what emits a light of a wavelength region of from 330 to 500 nm. In particular, an LED light-emitting device emitting an ultraviolet (or violet) ray of a wavelength region of from 330 to 420 nm, or an LED light-emitting device emitting a blue light in a wavelength region of from 420 to 480 nm is especially preferred.
Such LED light-emitting devices include a nitride semiconductor such as GaN or InGaN, which can be a light source emitting a light of a predetermined wavelength by adjusting the composition.
In addition to the method of applying the phosphor of the present invention alone to the lighting apparatus, the lighting apparatus which emits a light of a desired color can be constructed by using another phosphor having other luminescence characteristics together with the phosphor of the present invention. As an example of the above-mentioned lighting apparatus, there is a lighting apparatus which emits a white light produced by mixing the blue light, the green light, and the red light by utilizing an ultraviolet LED light-emitting device emitting a light of 330 to 420 nm, a blue color phosphor which is excited by the light of this wavelength region so as to emit a light of the wavelength region which is 450 nm or longer and 500 nm or shorter, the yellow-green color phosphor of the present invention, and a red color phosphor which emits a light of the wavelength region of from 600 nm to 700 nm as it is excited by an excitation light of 330 to 420 nm. As such a blue color phosphor and a red color phosphor, BaMgAl10O17:Eu and Eu-activated CaAlSiN3 can be mentioned, respectively.
As another method, an LED light-emitting device which emits a blue light of a wavelength region of from 430 to 480 nm and the phosphor of the present invention may be combined. In this configuration, there is a lighting apparatus which emits a white light. When the blue light emitted by the LED is irradiated onto the phosphor, a yellow light is emitted such that this yellow light is mixed with the blue light of the LED itself so as to make the white light.
In another way, there is a lighting apparatus which emits a white light. An LED light-emitting device which emits a blue light of the wavelength region of from 430 to 480 nm, the phosphor of the present invention, and an orange or red color phosphor which shows a light emission peak in the wavelength region of from 580 nm to 700 nm by the excitation light of the wavelength region of from 430 to 480 nm are used such that the blue light of the excitation light source, the yellow light of the phosphor, and the orange or red light of the orange or red color phosphor are mixed so as to produce the white light. As the red color phosphor and the orange phosphor, Eu-activated CaAlSiN3 and Eu-activated Ca-α-sialon can be mentioned, respectively.
The image display device of the present invention comprises at least an excitation source and the phosphor of the present invention and includes a vacuum fluorescent display (VFD), a field emission display (FED or SED), a plasma display panel (PDP), a cathode-ray tube (CRT), and the like. It was confirmed that the phosphor of the present invention emits a light by the excitation light of a vacuum ultraviolet ray of wavelength of from 100 to 190 nm, an ultraviolet ray of wavelength of from 190 to 380 nm, an electron beam, or the like. The above-mentioned image display devices can be constructed by combining the excitation source and the phosphor of the present invention.
EXAMPLE
In the following, the present invention is described in more detail with reference to examples as described below. However, these examples are disclosed as a help for easy understanding of the present invention and the present invention is not limited to these examples.
Examples 1-70
In α-type sialon containing Ca and Eu, compositions having values of design parameters x, y, m, and n; and values of x, y, a, b, c, and d in a CaxEuySiaAlbOcNd material composition (Tables 1-1, 1-2, 2-1, and 2-2) were examined. The parameters of the design compositions of Examples 1 to 70 are shown in Table 1-1, Table 1-2, Table 2-1, and Table 2-2, respectively. The values of m and n of the compositions are shown in FIG. 1. Based on these designs, calcium carbonate powder, europium oxide powder, silicon nitride powder, aluminum nitride powder, and aluminum oxide powder were mixed according to the compositions as shown in Tables 4-1 and 4-2 in order to obtain the design compositions as shown in Table 3-1 and Table 3-2. Here, Tables 4-1 and 4-2 show the mixture compositions of Examples 1 to 70. Raw material powders used to obtain the mixture are: calcium carbonate powder (CaCO3; manufactured by Kojundo Chemical Laboratory Co., Ltd.); europium oxide (Eu2O3; purity 99.9%, manufactured by Shin-Etsu Chemical Co., Ltd.); silicon nitride powder having a particle size of a specific surface area of 11.2 m2/g, containing 1.29 wt % of oxygen, and containing 95% α-type silicon nitride (SN-E10 grade manufactured by Ube Industries, Ltd.); aluminum nitride powder having a particle size of a specific surface area of 3.3 m2/g, containing 0.85 wt % of oxygen (F grade manufactured by Tokuyama Corporation); and aluminum oxide powder of a particle size of a specific surface area of 13.6 m2/g (Taimicron grade manufactured by Taimei Chemicals Co., Ltd.). These kinds of powders were weighed so as to obtain each of the mixture compositions of Tables 4-1 and 4-2, and mixed in the air for 10 minutes by using an agate pestle and an agate mortar. Then, each of the thus-obtained mixtures was sifted through a sieve of 500 μm and allowed to fall naturally into a boron nitride crucible such that the powder was filled in the crucible. The bulk densities of the powders were about 25% to 30%.
The crucible containing the mixed powder was placed in an electric furnace of a graphite resistance heating type. In the operation of firing, first a firing atmosphere was made in a vacuum by a diffusion pump and the mixed powder contained in the crucible was heated from the room temperature to 800° C. at a rate of 500° C. per hour. Nitrogen gas having 99.999 volume % purity was introduced at 800° C. to raise the pressure of the atmosphere up to 0.5 MPa and then the temperature was further raised up to 1700° C. at a rate of 500° C. per hour. Then, the temperature was kept for 2 hours.
Subsequently, the synthesized compounds were ground by using an agate mortar, and a powder X-ray diffraction measurement was conducted using the Cu Kα ray. Then, no unreacted Si3N4, AlN, Al2O3, CaCO3, CaO, EuO, and Eu2O3 was detected such that it was confirmed that all examples contained 60% or more of α-type sialon.
After the firing process, the resultant fired product was ground by hand using a mortar and a crucible made of sintered silicon nitride after being crushed coarsely and then sifted through a 30 μm-mesh sieve. The mean particle diameter of each ground product ranged from 7 to 12 μm.
Here, in this specification, the mean particle diameter is defined as follows. In the measurement by the sedimentation method, the particle diameter is defined as a diameter of an equivalent sphere having the same sedimentation rate, and in the laser scattering method, it is defined as a diameter of an equivalent sphere having the same scattering characteristics. Further, the distribution of particle diameters is called a particle size (particle diameter) distribution. In the particle diameter distribution, a specified particle diameter is defined as a mean particle diameter D50 when the total mass of powder particles having diameters larger than the specified particle diameter is 50% of the total mass of the entire powder body. These definition and term are well known to the one skilled in the art and are described in various documents such as JIS Z 8901 “Powder Body for Test and Particle for Test” and the first chapter of “Basic Physical Properties of Powder” edited by The Society of Powder Technology, Japan (ISBN4-526-05544-1) In the present invention, a specimen was dispersed in water in which sodium hexamethaphosphate was added as a dispersing agent. Then, the volume-converted integrated frequency distribution of the particle diameters was measured by using a laser scattering-type measurement instrument. Here, the volume-converted distribution is identical to the weight-converted distribution. The particle diameter corresponding to that at 50% in the integrated (cumulative) frequency distribution was obtained and defined as the mean particle diameter D50. It should be noted that, in the following part of this specification, the mean particle diameter is based on the median value (D50) of the particle size distribution measured with a particle size distribution measurement means by the above-mentioned laser scattering method. As to a means for determining the mean particle diameter, various kinds of means have been developed and the development is still being performed such that the value measured by a newly developed means may differ slightly. However, it should be understood that the meaning and significance of the mean particle diameter itself is definite, and the means for measuring the mean particle diameter is not necessarily limited to the above-mentioned means.
As a result of irradiating a light of wavelength of 365 nm onto theses these powder samples using a lamp which emits the light, it was confirmed that these powder samples emit lights of yellow-green color to yellow color. Tables 5-1 and 5-2 and FIGS. 2 and 3 show results obtained by measuring emission spectra and excitation spectra of these powder samples by using a spectrophotofluorometer. The peak wavelengths and peak intensities of the excitation and emission spectra of Examples 1 to 70 are shown in Tables 5-1 and 5-2. In all examples, phosphors which were efficiently excited by an ultraviolet ray, a violet light, and a blue light of a wavelength region of from 300 nm to 450 nm and emitted yellow-green fluorescence having a peak in the wavelength region of from 530 nm to 585 nm. Here, since the counted values vary depending on the measuring instruments and conditions, the unit of the values is an arbitrary unit. That is, comparisons thereof can be made only within the present examples and comparative examples measured in the same conditions.
Example 71 and Comparative Example 1
A raw material powder mixture having the same composition as Example 29 (m=1, n=1.8) was prepared in the same processes as those of Example 29. The resultant mixture was heated from the room temperature to 800° C. at a rate of 500° C. per hour, and nitrogen gas having a purity of 99.999 volume % was introduced at 800° C. to adjust the pressure to 0.5 MPa. Then, the temperature was further raised to 1700° C. at a rate of 500° C. per hour and kept at 1700° C. for 24 hours to synthesize the compound. Next, the synthesized compound was ground by using an agate mortar and the compound was examined by a powder X-ray diffraction measurement using the Cu Kα ray such that it was confirmed that α-type sialon was produced.
The shape of the synthesized phosphor powder particles was observed with a scanning electron microscope (SEM). As shown in FIG. 4, it was confirmed that the phosphor particles were primary particles comprising single crystal particles having well-developed crystal faces and a length of about 3 μm. The actual phosphor was obtained in a state that these primary particles were aggregated. For comparison, the SEM picture of a specimen (Comparative example 1) having a sialon composition of ((Ca0.4625Eu0.0375)Si10.5Al1.5O0.5N15.5), in which m=1 and n=0.5, that was fired in the same firing conditions as Example 71 is shown in FIG. 5. It was confirmed that the amount of the liquid phase produced during the firing process was small since the value of n was small and hence particle growth was insufficient and the particles were small. The maximum intensity of the emission spectrum of this phosphor is 5,100 counts. That is, even in a composition where the value of m was small, the amount of generated liquid phase was increased by making the value of n larger such that the crystal growth was promoted and then the emission intensity of the phosphor was enhanced.
As a result of irradiating a light of a wavelength of 365 nm onto the ground powder with a lamp which emits the light, the yellow-green light emission was confirmed. FIG. 6 shows results obtained by measuring emission spectra and excitation spectra of this powder specimen with the spectrophotofluorometer. It turned out that the peak wavelength of the excitation spectrum was 445 nm. A phosphor emitting the yellow-green fluorescence having a peak in the wavelength region of 574 nm by this excitation was obtained. This phosphor can be excited by the excitation light of a broad region extending from 250 nm to 500 nm. In particular, it was found that the phosphor was characterized in that the excitation intensities of a violet color LED in the wavelength of 405 nm and a blue color LED in the wavelength of 450 nm were especially high. The color coordinates of the fluorescence were x=0.47 and y=0.52 and indicated a yellow-green color.
Comparative Example 2
In order to synthesize Eu-activated Ca-α-sialon of

(Ca1.3875, Eu0.1125)(Si9Al3)(O0N15),

in which the parameters m=3 and n=0, from the same raw material powders as the examples, a Ca3N2 powder (99% purity manufactured by Cerac, Inc.), an EuN powder (laboratory-synthesized) having been prepared by nitriding metallic Eu at 600° C. in an ammonia gaseous stream, a Si3N4 powder identical to that used for the examples, and an AlN powder identical to that used for the examples were mixed as the mixed raw material powders at the following mixed compositions:

Ca3N2:EuN:Si3N4:AlN=7.03:1.71:45.63:45.63 (mol %); and
Ca3N2:EuN:Si3N4:AlN=10.87:2.96:66.69:19.49 (mass %) in an ambient atmosphere containing equal to or less than 1 ppm of oxygen and moisture in the glove box and the mixed raw material powders were treated in the same processes as described for the examples so as to synthesize the phosphor. According to the X-ray diffraction measurement, α-type sialon was detected in the synthesized compound, but no other crystalline phases were detected. FIG. 7 shows emission and excitation spectra of the powder sample measured with the spectrophotofluorometer. The emission wavelength of the phosphor was 604 nm and emission intensity was 6209. The composition of the comparative example was out of the composition range of the present invention, and hence was unsuitable. Consequently, the emission wavelength of the obtained phosphor was longer than that of the present invention. The color coordinates of the fluorescence were x=0.55 and y=0.45, and indicated an orange color.










TABLE 1-1









Parameter
Designed Composition (# of atoms in unit cell)















Example
m
n
Ca(x)
Eu(y)
Si
Al
O
N


















1
0.5
0.5
0.2313
0.0188
11.00
1.00
0.50
15.50


2
0.5
0.6
0.2313
0.0188
10.90
1.10
0.60
15.40


3
0.5
0.7
0.2313
0.0188
10.80
1.20
0.70
15.30


4
0.5
0.8
0.2313
0.0188
10.70
1.30
0.80
15.20


5
0.5
1
0.2313
0.0188
10.50
1.50
1.00
15.00


6
0.5
1.2
0.2313
0.0188
10.30
1.70
1.20
14.80


7
0.5
1.4
0.2313
0.0188
10.10
1.90
1.40
14.60


8
0.5
1.5
0.2313
0.0188
10.00
2.00
1.50
14.50


9
0.5
1.6
0.2313
0.0188
9.90
2.10
1.60
14.40


10
0.5
1.8
0.2313
0.0188
9.70
2.30
1.80
14.20


11
0.75
0.5
0.3469
0.0281
10.75
1.25
0.50
15.50


12
0.75
0.6
0.3469
0.0281
10.65
1.35
0.60
15.40


13
0.75
0.7
0.3469
0.0281
10.55
1.45
0.70
15.30


14
0.75
0.8
0.3469
0.0281
10.45
1.55
0.80
15.20


15
0.75
1
0.3469
0.0281
10.25
1.75
1.00
15.00


16
0.75
1.2
0.3469
0.0281
10.05
1.95
1.20
14.80


17
0.75
1.4
0.3469
0.0281
9.85
2.15
1.40
14.60


18
0.75
1.5
0.3469
0.0281
9.75
2.25
1.50
14.50


19
0.75
1.6
0.3469
0.0281
9.65
2.35
1.60
14.40


20
0.75
1.8
0.3469
0.0281
9.45
2.55
1.80
14.20


21
1
0.6
0.4625
0.0375
10.40
1.60
0.60
15.40


22
1
0.7
0.4625
0.0375
10.30
1.70
0.70
15.30


23
1
0.8
0.4625
0.0375
10.20
1.80
0.80
15.20


24
1
1
0.4625
0.0375
10.00
2.00
1.00
15.00


25
1
1.2
0.4625
0.0375
9.80
2.20
1.20
14.80


26
1
1.4
0.4625
0.0375
9.60
2.40
1.40
14.60


27
1
1.5
0.4625
0.0375
9.50
2.50
1.50
14.50


28
1
1.6
0.4625
0.0375
9.40
2.60
1.60
14.40


29
1
1.8
0.4625
0.0375
9.20
2.80
1.80
14.20


30
1.5
0.8
0.6938
0.0563
9.70
2.30
0.80
15.20


31
1.5
1
0.6938
0.0563
9.50
2.50
1.00
15.00


32
1.5
1.2
0.6938
0.0563
9.30
2.70
1.20
14.80


33
1.5
1.4
0.6938
0.0563
9.10
2.90
1.40
14.60


34
1.5
1.5
0.6938
0.0563
9.00
3.00
1.50
14.50


35
1.5
1.6
0.6938
0.0563
8.90
3.10
1.60
14.40


36
1.5
1.8
0.6938
0.0563
8.70
3.30
1.80
14.20


37
2
1.2
0.9250
0.0750
8.80
3.20
1.20
14.80


38
2
1.4
0.9250
0.0750
8.60
3.40
1.40
14.60



















TABLE 1-2









Parameter
Designed Composition















Example
m
n
Ca (x)
Eu (y)
Si
Al
O
N


















39
2
1.5
0.9250
0.0750
8.50
3.50
1.50
14.50


40
2
1.6
0.9250
0.0750
8.40
3.60
1.60
14.40


41
2
1.8
0.9250
0.0750
8.20
3.80
1.80
14.20


42
0.5
1
0.2313
0.0188
10.50
1.50
1.00
15.00


43
0.75
1
0.3469
0.0281
10.25
1.75
1.00
15.00


44
1
1
0.4625
0.0375
10.00
2.00
1.00
15.00


45
1.2
1
0.5550
0.0450
9.80
2.20
1.00
15.00


46
1.4
1
0.6475
0.0525
9.60
2.40
1.00
15.00


47
1.6
1
0.7400
0.0600
9.40
2.60
1.00
15.00


48
1.8
1
0.8325
0.0675
9.20
2.80
1.00
15.00


49
0.5
1.5
0.2313
0.0188
10.00
2.00
1.50
14.50


50
0.75
1.5
0.3469
0.0281
9.75
2.25
1.50
14.50


51
1
1.5
0.4625
0.0375
9.50
2.50
1.50
14.50


52
1.2
1.5
0.5550
0.0450
9.30
2.70
1.50
14.50


53
1.4
1.5
0.6475
0.0525
9.10
2.90
1.50
14.50


54
1.6
1.5
0.7400
0.0600
8.90
3.10
1.50
14.50


55
1.8
1.5
0.8325
0.0675
8.70
3.30
1.50
14.50


56
2
1.5
0.9250
0.0750
8.50
3.50
1.50
14.50


57
2.2
1.5
1.0175
0.0825
8.30
3.70
1.50
14.50


58
2.4
1.5
1.1100
0.0900
8.10
3.90
1.50
14.50


59
2.6
1.5
1.2025
0.0975
7.90
4.10
1.50
14.50


60
2.8
1.5
1.2950
0.1050
7.70
4.30
1.50
14.50


61
0.5
1.7
0.2313
0.0188
9.80
2.20
1.70
14.30


62
0.75
1.7
0.3469
0.0281
9.55
2.45
1.70
14.30


63
1
1.7
0.4625
0.0375
9.30
2.70
1.70
14.30


64
1.2
1.7
0.5550
0.0450
9.10
2.90
1.70
14.30


65
1.4
1.7
0.6475
0.0525
8.90
3.10
1.70
14.30


66
1.6
1.7
0.7400
0.0600
8.70
3.30
1.70
14.30


67
1.8
1.7
0.8325
0.0675
8.50
3.50
1.70
14.30


68
2
1.7
0.9250
0.0750
8.30
3.70
1.70
14.30


69
2.2
1.7
1.0175
0.0825
8.10
3.90
1.70
14.30


70
2.4
1.7
1.1100
0.0900
7.90
4.10
1.70
14.30


















TABLE 2-1









Designed Composition (atom %)













Example
Ca
Eu
Si
Al
O
N
















1
0.8186
0.0664
38.9381
3.5398
1.7699
54.8673


2
0.8186
0.0664
38.5841
3.8938
2.1239
54.5133


3
0.8186
0.0664
38.2301
4.2478
2.4779
54.1593


4
0.8186
0.0664
37.8761
4.6018
2.8319
53.8053


5
0.8186
0.0664
37.1681
5.3097
3.5398
53.0973


6
0.8186
0.0664
36.4602
6.0177
4.2478
52.3894


7
0.8186
0.0664
35.7522
6.7257
4.9558
51.6814


8
0.8186
0.0664
35.3982
7.0796
5.3097
51.3274


9
0.8186
0.0664
35.0442
7.4336
5.6637
50.9735


10
0.8186
0.0664
34.3363
8.1416
6.3717
50.2655


11
1.2225
0.0991
37.8855
4.4053
1.7621
54.6256


12
1.2225
0.0991
37.5330
4.7577
2.1145
54.2731


13
1.2225
0.0991
37.1806
5.1101
2.4670
53.9207


14
1.2225
0.0991
36.8282
5.4626
2.8194
53.5683


15
1.2225
0.0991
36.1233
6.1674
3.5242
52.8634


16
1.2225
0.0991
35.4185
6.8722
4.2291
52.1586


17
1.2225
0.0991
34.7137
7.5771
4.9339
51.4537


18
1.2225
0.0991
34.3612
7.9295
5.2863
51.1013


19
1.2225
0.0991
34.0088
8.2819
5.6388
50.7489


20
1.2225
0.0991
33.3040
8.9868
6.3436
50.0441


21
1.6228
0.1316
36.4912
5.6140
2.1053
54.0351


22
1.6228
0.1316
36.1404
5.9649
2.4561
53.6842


23
1.6228
0.1316
35.7895
6.3158
2.8070
53.3333


24
1.6228
0.1316
35.0877
7.0175
3.5088
52.6316


25
1.6228
0.1316
34.3860
7.7193
4.2105
51.9298


26
1.6228
0.1316
33.6842
8.4211
4.9123
51.2281


27
1.6228
0.1316
33.3333
8.7719
5.2632
50.8772


28
1.6228
0.1316
32.9825
9.1228
5.6140
50.5263


29
1.6228
0.1316
32.2807
9.8246
6.3158
49.8246


30
2.4130
0.1957
33.7391
8.0000
2.7826
52.8696


31
2.4130
0.1957
33.0435
8.6957
3.4783
52.1739


32
2.4130
0.1957
32.3478
9.3913
4.1739
51.4783


33
2.4130
0.1957
31.6522
10.0870
4.8696
50.7826


34
2.4130
0.1957
31.3043
10.4348
5.2174
50.4348


35
2.4130
0.1957
30.9565
10.7826
5.5652
50.0870


36
2.4130
0.1957
30.2609
11.4783
6.2609
49.3913


37
3.1897
0.2586
30.3448
11.0345
4.1379
51.0345


38
3.1897
0.2586
29.6552
11.7241
4.8276
50.3448


















TABLE 2-2









Designed Composition (atom %)













Example
Ca
Eu
Si
Al
O
N
















39
3.1897
0.2586
29.3103
12.0690
5.1724
50.0000


40
3.1897
0.2586
28.9655
12.4138
5.5172
49.6552


41
3.1897
0.2586
28.2759
13.1034
6.2069
48.9655


42
0.8186
0.0664
37.1681
5.3097
3.5398
53.0973


43
1.2225
0.0991
36.1233
6.1674
3.5242
52.8634


44
1.6228
0.1316
35.0877
7.0175
3.5088
52.6316


45
1.9406
0.1573
34.2657
7.6923
3.4965
52.4476


46
2.2561
0.1829
33.4495
8.3624
3.4843
52.2648


47
2.5694
0.2083
32.6389
9.0278
3.4722
52.0833


48
2.8806
0.2336
31.8339
9.6886
3.4602
51.9031


49
0.8186
0.0664
35.3982
7.0796
5.3097
51.3274


50
1.2225
0.0991
34.3612
7.9295
5.2863
51.1013


51
1.6228
0.1316
33.3333
8.7719
5.2632
50.8772


52
1.9406
0.1573
32.5175
9.4406
5.2448
50.6993


53
2.2561
0.1829
31.7073
10.1045
5.2265
50.5226


54
2.5694
0.2083
30.9028
10.7639
5.2083
50.3472


55
2.8806
0.2336
30.1038
11.4187
5.1903
50.1730


56
3.1897
0.2586
29.3103
12.0690
5.1724
50.0000


57
3.4966
0.2835
28.5223
12.7148
5.1546
49.8282


58
3.8014
0.3082
27.7397
13.3562
5.1370
49.6575


59
4.1041
0.3328
26.9625
13.9932
5.1195
49.4881


60
4.4048
0.3571
26.1905
14.6259
5.1020
49.3197


61
0.8186
0.0664
34.6903
7.7876
6.0177
50.6195


62
1.2225
0.0991
33.6564
8.6344
5.9912
50.3965


63
1.6228
0.1316
32.6316
9.4737
5.9649
50.1754


64
1.9406
0.1573
31.8182
10.1399
5.9441
50.0000


65
2.2561
0.1829
31.0105
10.8014
5.9233
49.8258


66
2.5694
0.2083
30.2083
11.4583
5.9028
49.6528


67
2.8806
0.2336
29.4118
12.1107
5.8824
49.4810


68
3.1897
0.2586
28.6207
12.7586
5.8621
49.3103


69
3.4966
0.2835
27.8351
13.4021
5.8419
49.1409


70
3.8014
0.3082
27.0548
14.0411
5.8219
48.9726


















TABLE 3-1









Designed Composition (mol %)












Example
CaO
EuO
Si3N4
AlN
Al2O3















1
4.7845
0.3879
75.8621
17.2414
1.7241


2
4.7517
0.3853
74.6575
17.8082
2.3973


3
4.7194
0.3827
73.4694
18.3673
3.0612


4
4.6875
0.3801
72.2973
18.9189
3.7162


5
4.6250
0.3750
70.0000
20.0000
5.0000


6
4.5641
0.3701
67.7632
21.0526
6.2500


7
4.5049
0.3653
65.5844
22.0779
7.4675


8
4.4758
0.3629
64.5161
22.5806
8.0645


9
4.4471
0.3606
63.4615
23.0769
8.6538


10
4.3908
0.3560
61.3924
24.0506
9.8101


11
6.7137
0.5444
69.3548
22.5806
0.8065


12
6.6707
0.5409
68.2692
23.0769
1.4423


13
6.6282
0.5374
67.1975
23.5669
2.0701


14
6.5862
0.5340
66.1392
24.0506
2.6899


15
6.5039
0.5273
64.0625
25.0000
3.9063


16
6.4236
0.5208
62.0370
25.9259
5.0926


17
6.3453
0.5145
60.0610
26.8293
6.2500


18
6.3068
0.5114
59.0909
27.2727
6.8182


19
6.2688
0.5083
58.1325
27.7108
7.3795


20
6.1942
0.5022
56.2500
28.5714
8.4821


21
8.3584
0.6777
62.6506
27.7108
0.6024


22
8.3084
0.6737
61.6766
28.1437
1.1976


23
8.2589
0.6696
60.7143
28.5714
1.7857


24
8.1618
0.6618
58.8235
29.4118
2.9412


25
8.0669
0.6541
56.9767
30.2326
4.0698


26
7.9741
0.6466
55.1724
31.0345
5.1724


27
7.9286
0.6429
54.2857
31.4286
5.7143


28
7.8835
0.6392
53.4091
31.8182
6.2500


29
7.7949
0.6320
51.6854
32.5843
7.3034


30
11.0705
0.8976
51.5957
36.1702
0.2660


31
10.9539
0.8882
50.0000
36.8421
1.3158


32
10.8398
0.8789
48.4375
37.5000
2.3438


33
10.7281
0.8698
46.9072
38.1443
3.3505


34
10.6731
0.8654
46.1538
38.4615
3.8462


35
10.6186
0.8610
45.4082
38.7755
4.3367


36
10.5114
0.8523
43.9394
39.3939
5.3030


37
13.0896
1.0613
41.5094
43.3962
0.9434


38
12.9673
1.0514
40.1869
43.9252
1.8692


















TABLE 3-2









Designed Composition (mol %)












Example
CaO
EuO
Si3N4
AlN
Al2O3















39
12.9070
1.0465
39.5349
44.1860
2.3256


40
12.8472
1.0417
38.8889
44.4444
2.7778


41
12.7294
1.0321
37.6147
44.9541
3.6697


42
4.6250
0.3750
70.0000
20.0000
5.0000


43
6.5039
0.5273
64.0625
25.0000
3.9063


44
8.1618
0.6618
58.8235
29.4118
2.9412


45
9.3539
0.7584
55.0562
32.5843
2.2472


46
10.4435
0.8468
51.6129
35.4839
1.6129


47
11.4433
0.9278
48.4536
38.1443
1.0309


48
12.3639
1.0025
45.5446
40.5941
0.4950


49
4.4758
0.3629
64.5161
22.5806
8.0645


50
6.3068
0.5114
59.0909
27.2727
6.8182


51
7.9286
0.6429
54.2857
31.4286
5.7143


52
9.0984
0.7377
50.8197
34.4262
4.9180


53
10.1702
0.8246
47.6440
37.1728
4.1885


54
11.1558
0.9045
44.7236
39.6985
3.5176


55
12.0652
0.9783
42.0290
42.0290
2.8986


56
12.9070
1.0465
39.5349
44.1860
2.3256


57
13.6883
1.1099
37.2197
46.1883
1.7937


58
14.4156
1.1688
35.0649
48.0519
1.2987


59
15.0941
1.2238
33.0544
49.7908
0.8368


60
15.7287
1.2753
31.1741
51.4170
0.4049


61
4.4188
0.3583
62.4204
23.5669
9.2357


62
6.2313
0.5052
57.1856
28.1437
7.9341


63
7.8390
0.6356
52.5424
32.2034
6.7797


64
9.0000
0.7297
49.1892
35.1351
5.9459


65
10.0648
0.8161
46.1140
37.8238
5.1813


66
11.0448
0.8955
43.2836
40.2985
4.4776


67
11.9498
0.9689
40.6699
42.5837
3.8278


68
12.7880
1.0369
38.2488
44.7005
3.2258


69
13.5667
1.1000
36.0000
46.6667
2.6667


70
14.2918
1.1588
33.9056
48.4979
2.1459


















TABLE 4-1









Mixed Composition (wt %)












Example
CaCO3
Eu2O3
Si3N4
AlN
Al2O3















1
3.9700
0.5700
88.1550
5.8540
1.4600


2
3.9700
0.5600
87.3410
6.0880
2.0400


3
3.9700
0.5600
86.5270
6.3210
2.6200


4
3.9700
0.5600
85.7130
6.5540
3.2000


5
3.9600
0.5600
84.0850
7.0210
4.3700


6
3.9600
0.5600
82.4580
7.4860
5.5300


7
3.9600
0.5600
80.8300
7.9520
6.6900


8
3.9600
0.5600
80.0190
8.1840
7.2700


9
3.9600
0.5600
79.2070
8.4170
7.8500


10
3.9600
0.5600
77.5840
8.8810
9.0100


11
5.8400
0.8300
84.5660
8.0460
0.7100


12
5.8400
0.8300
83.7660
8.2750
1.2900


13
5.8400
0.8300
82.9680
8.5030
1.8600


14
5.8400
0.8300
82.1680
8.7310
2.4300


15
5.8400
0.8300
80.5710
9.1880
3.5700


16
5.8400
0.8300
78.9760
9.6440
4.7100


17
5.8300
0.8300
77.3800
10.1010
5.8500


18
5.8300
0.8300
76.5840
10.3290
6.4200


19
5.8300
0.8300
75.7860
10.5570
6.9900


20
5.8300
0.8300
74.1940
11.0130
8.1300


21
7.6500
1.0900
80.3210
10.3810
0.5600


22
7.6500
1.0900
79.5370
10.6050
1.1200


23
7.6400
1.0900
78.7530
10.8300
1.6800


24
7.6400
1.0900
77.1860
11.2780
2.8000


25
7.6400
1.0900
75.6210
11.7250
3.9300


26
7.6400
1.0900
74.0550
12.1730
5.0500


27
7.6400
1.0900
73.2730
12.3960
5.6100


28
7.6400
1.0900
72.4900
12.6200
6.1700


29
7.6300
1.0900
70.9280
13.0660
7.2900


30
11.0700
1.5800
72.2790
14.8070
0.2700


31
11.0600
1.5800
70.7690
15.2380
1.3500


32
11.0600
1.5800
69.2600
15.6690
2.4400


33
11.0600
1.5800
67.7510
16.1000
3.5200


34
11.0500
1.5800
66.9970
16.3150
4.0600


35
11.0500
1.5800
66.2420
16.5290
4.6000


36
11.0500
1.5800
64.7350
16.9590
5.6800


37
14.2500
2.0300
63.3270
19.3460
1.0500


38
14.2400
2.0300
61.8710
19.7620
2.0900


















TABLE 4-2









Mixed Composition (wt %)












Example
CaCO3
Eu2O3
Si3N4
AlN
Al2O3















39
14.2400
2.0300
61.1430
19.9590
2.6100


40
14.2400
2.0300
60.4150
20.1760
3.1400


41
14.2400
2.0300
58.9610
20.5910
4.1800


42
3.9600
0.5600
84.0850
7.0210
4.3700


43
5.8400
0.8300
80.5710
9.1880
3.5700


44
7.6400
1.0900
77.1860
11.2780
2.8000


45
9.0400
1.2900
74.5640
12.8950
2.2100


46
10.4000
1.4800
72.0170
14.4680
1.6400


47
11.7200
1.6700
69.5390
15.9970
1.0800


48
13.0000
1.8500
67.1290
17.4840
0.5300


49
3.9600
0.5600
80.0190
8.1840
7.2700


50
5.8300
0.8300
76.5840
10.3290
6.4200


51
7.6400
1.0900
73.2730
12.3960
5.6100


52
9.0300
1.2900
70.7080
13.9970
4.9700


53
10.3900
1.4800
68.2170
15.5530
4.3600


54
11.7100
1.6700
65.7930
17.0650
3.7600


55
12.9900
1.8500
63.4360
18.5370
3.1800


56
14.2400
2.0300
61.1430
19.9690
2.6100


57
15.4600
2.2000
58.9100
21.3620
2.0600


58
16.6400
2.3700
56.7370
22.7200
1.5300


59
17.8000
2.5400
54.6190
24.0420
1.0100


60
18.9200
2.7000
52.5550
25.3300
0.5000


61
3.9600
0.5600
78.3950
8.6490
8.4300


62
5.8300
0.8300
74.9900
10.7850
7.5600


63
7.6300
1.0900
71.7090
12.8430
6.7300


64
9.0300
1.2900
69.1680
14.4370
6.0800


65
10.3900
1.4800
66.6980
15.9860
5.4500


66
11.7100
1.6700
64.2960
17.4930
4.8300


67
12.9900
1.8500
61.9610
18.9580
4.2400


68
14.2400
2.0300
59.6870
20.3840
3.6600


69
15.4600
2.2000
57.4750
21.7710
3.0900


70
16.6400
2.3700
55.3200
23.1230
2.5400





















TABLE 5-1










Excitation
Emission
Emission



Parameter
Wavelength
Wavelength
Intensity












Example
m
n
(nm)
(nm)
(arbitrary unit)















1
0.5
0.5
411
571
2469


2
0.5
0.6
410
572
2816


3
0.5
0.7
409
572
2824


4
0.5
0.8
412
569
3164


5
0.5
1
412
569
3329


6
0.5
1.2
410
568
3528


7
0.5
1.4
412
568
3673


8
0.5
1.5
412
568
4053


9
0.5
1.6
413
567
4133


10
0.5
1.8
418
568
4566


11
0.75
0.5
409
574
3522


12
0.75
0.6
412
573
3653


13
0.75
0.7
409
573
3569


14
0.75
0.8
410
573
3777


15
0.75
1
417
568
4661


16
0.75
1.2
412
568
4952


17
0.75
1.4
412
568
4811


18
0.75
1.5
419
568
5916


19
0.75
1.6
419
568
5831


20
0.75
1.8
418
568
5421


21
1
0.6
410
575
4622


22
1
0.7
412
573
4868


23
1
0.8
412
574
4708


24
1
1
412
572
5547


25
1
1.2
412
573
5819


26
1
1.4
412
573
6379


27
1
1.5
418
572
6259


28
1
1.6
420
573
6567


29
1
1.8
419
569
6211


30
1.5
0.8
412
580
6286


31
1.5
1
418
579
6530


32
1.5
1.2
418
578
6766


33
1.5
1.4
438
578
7140


34
1.5
1.5
438
577
6529


35
1.5
1.6
439
575
7549


36
1.5
1.8
444
575
4572


37
2
1.2
437
583
6537


38
2
1.4
442
581
6578





















TABLE 5-2










Excitation
Emission
Emission



Parameter
Wavelength
Wavelength
Intensity












Example
m
n
(nm)
(nm)
(arbitrary unit)















39
2
1.5
442
581
6256


40
2
1.6
449
578
6439


41
2
1.8
449
578
6381


42
0.5
1
401
568
2297


43
0.75
1
412
571
4660


44
1
1
412
571
5193


45
1.2
1
410
574
5601


46
1.4
1
412
577
6506


47
1.6
1
412
580
6300


48
1.8
1
413
582
5450


49
0.5
1.5
412
569
3228


50
0.75
1.5
412
569
5121


51
1
1.5
412
571
5770


52
1.2
1.5
419
574
6020


53
1.4
1.5
438
574
5849


54
1.6
1.5
437
577
6126


55
1.8
1.5
437
579
6383


56
2
1.5
449
582
6084


57
2.2
1.5
449
583
6370


58
2.4
1.5
449
583
6330


59
2.6
1.5
449
583
6428


60
2.8
1.5
449
587
6213


61
0.5
1.7
419
568
4130


62
0.75
1.7
418
568
6664


63
1
1.7
436
568
6911


64
1.2
1.7
438
570
7472


65
1.4
1.7
438
573
6791


66
1.6
1.7
448
575
7817


67
1.8
1.7
449
577
7385


68
2
1.7
449
580
7151


69
2.2
1.7
449
580
6817


70
2.4
1.7
449
581
7110









Next, a lighting apparatus using the phosphor which comprises the nitride of the present invention is explained.
Example 72
A so-called bullet-type white light-emitting diode lamp (1) shown in FIG. 8 was produced. There are two lead wires (2, 3), one of which (2) has a recess, in which a blue light-emitting diode device (4) is placed. The lower electrode of the blue light-emitting diode device (4) and the bottom surface of the recess are electrically connected with conductive paste, and the upper electrode and the other lead wire (3) are electrically connected to a gold filament (5). The phosphor used in the present example is a phosphor produced as Example 71. The phosphor (7) is dispersed in resin and mounted in the vicinity of the light emitting diode device (4). The first resin (6) in which this phosphor is dispersed is transparent, and covers the entire blue light-emitting diode device (4). The tip portion of the lead wire including the recess, the blue light-emitting diode device, and the first resin in which the phosphor is dispersed are sealed with transparent second resin (8). The entire part of the transparent second resin (8) is roughly cylindrical, the tip portion of which is formed as a lens-like curved surface. Thus, the diode lamp is commonly called a bullet-type diode lamp.
In the present example, the phosphor powder of Example 71 was mixed into epoxy resin in a concentration of 37 wt %, and a proper amount of the resultant mixture was dropped using a dispenser to form the first resin (6) in which the phosphor (7) was dispersed. The resultant color coordinates were x=0.34 and y=0.34, which represent a white color.
Example 73
A tip-type white light-emitting diode lamp (21) for mounting on a substrate was produced. The structure is shown in FIG. 9. Two lead wires (22, 23) are fixed to a white alumina ceramic substrate (29) having high visible light reflectivity. One end of each of these wires is located nearly at the central part of the substrate, and the other end of each extends to the outside to serve as an electrode to be soldered when the lamp is mounted on an electric substrate. A blue light-emitting diode device (24) is placed and fixed to the one end of one (22) of the lead wires so that the diode is located at the central part of the substrate. The lower electrode of the blue light-emitting diode device (24) and the lead wire below are electrically connected with conductive paste, and the upper electrode and the other lead wire (23) are electrically connected to a gold filament (25).
A mixture of first resin (26) and a phosphor (27) is mounted in the vicinity of the light emitting diode device. The first resin in which this phosphor is dispersed is transparent, and covers the entire blue light-emitting diode device (24). Moreover, on the ceramic substrate, a wall surface member (30) having a hole opened at the central part is fixed. The central part of the wall surface member (30) is formed into a hole in which the first resin (26) which contains the blue light-emitting diode device (24) and the phosphor (27) dispersed therein is to be accommodated, and the portion which faces the central part forms a slope. This slope is a reflective surface for taking out a light forward, and the shape of the curved surface of that slope is determined in consideration of the direction of light reflection. Moreover, at least the surface which constitutes the reflective surface forms a surface having high visible light reflectivity with white or metallic luster. In the present example, the wall surface member is constituted of white silicone resin (30). The hole at the central part of the wall surface member forms a recess as the final shape of the tip-type light emitting diode lamp, and is filled up with second transparent resin (28) to seal all of the blue light-emitting diode device (24) and the first resin (26) in which the phosphor (27) is dispersed. In the present example, the same epoxy resin is used for both the first resin (26) and second resin (28). The ratio of phosphor addition, the attained chromaticity, and the like are approximately identical to those in the foregoing example.
Next, an example of design of an image display device using the phosphor of the present invention is described.
Example 74
FIG. 10 is a schematic diagram of a principle of a plasma display panel as an image display device. A red color phosphor (CaAlSiN3:Eu2+) (31), a green color phosphor (32) of Example 71 of the present invention, and a blue color phosphor (BaMgAl10O17:Eu) (33) are applied on the internal surface of respective cells (34, 35, 36). The cells (34, 35, 36) are located on a glass substrate (44) to which a dielectric layer (41) and electrodes (37, 38, 39) are provided. If electric power is supplied to the electrodes (37, 38, 39, 40), a vacuum ultraviolet ray is generated by Xe discharge in the cells. The phosphors are excited by the vacuum ultraviolet ray to emit red, yellow-green, and blue visible lights. The emitted lights are observed from the outside through a protective layer (43), a dielectric layer (42), and a glass substrate (45) to function as an image display.
INDUSTRIAL APPLICABILITY
The nitride phosphor of the present invention shows a light emission at a wavelength shorter than the conventional sialon or oxynitride phosphor does. And it is superior as a yellow-green color phosphor and shows only a small decrease of phosphor brightness when exposed to the excitation source. Thus, the nitride phosphor of the present invention can be suitably used for VFD, FED, PDP, CRT, white color LED, and the like. It is expected that the phosphor of the present invention will be much applied to various kinds of display devices in the material design so as to contribute to the development of the industry.

## Claims

1. A phosphor comprising: α-type sialon crystal as a main component, wherein the α-type sialon crystal comprises:
at least an A element, which is Eu;
an M element, which is Ca;
Si;
Al;
oxygen; and
nitrogen,
wherein the α-type sialon crystal is expressed by a general formula:


(Mx,Ay)(Si12−(m+n)Alm+n)(OnN16−n)  (1), and



m=δM×x+δA×y  (2),


wherein the α-type sialon crystal is expressed by a composition formula having parameters x, y, m, and n, which are in a range expressed by:


0.2≦x≦2.4  (3),



0.001≦y≦0.4  (4),



0.5×m<n≦4  (5),



0.6≦m≦1.4  (7), and



0.8≦n≦2  (8);


wherein x is an amount of solid solution of M in a sialon unit cell, y is an amount of solid solution of A in the sialon unit cell, and n is a content amount of oxygen in the sialon unit cell; and
wherein the phosphor emits fluorescence having a peak in a wavelength range from 560 nm to 575 nm upon irradiation of an excitation source.

2. The phosphor according to claim 1, wherein the excitation source is a violet light or a visible light having a wavelength which is 100 nm or more and 500 nm or shorter.

3. The phosphor according to claim 1, wherein an emission color upon irradiation of the excitation source is represented by (x, y) values in the CIE Chromaticity coordinate and satisfies conditions:


0.3≦x≦0.5  (9)



0.46≦y≦0.6  (10).

4. The phosphor according to claim 1, comprises a primary particle of the α-type sialon crystal which is characterized by a diameter of 0.5 μm or more along a minor axis and an aspect ratio of 3 or more.

5. The phosphor according to claim 1, comprises: an amorphous phase or another crystalline phase than the α-type sialon crystal, wherein a content amount of the α-type sialon crystal is 10 mass % or more.

6. The phosphor according to claim 5, wherein the content amount of the α-type sialon crystal is 50 mass % or more.

7. The phosphor according to claim 5, wherein the amorphous phase or the other crystalline phase is inorganic substance having electronic conductivity.

8. A lighting apparatus comprising: an excitation source and a phosphor, wherein the phosphor comprises at least the phosphor comprising: α-type sialon crystal as a main component,
wherein the α-type sialon crystal comprises:
at least an A element, which is Eu;
an M element, which is Ca;
Si;
Al;
oxygen; and
nitrogen,

wherein the α-type sialon crystal is expressed by a general formula:


(Mx,Ay) (Si12−(m+n)Alm+n)(OnN16−n)  (1), and



m=δM×x+δA×y  (2),


wherein the α-type sialon crystal is expressed by a composition formula having parameters x, y, m, and n, which are in a range expressed by:


0.2≦x≦2.4  (3),



0.001≦y≦0.4  (4),



0.5×m<n≦4  (5),



0.6≦m≦1.4  (7), and



0.8≦n≦2  (8);


wherein x is an amount of solid solution of M in a sialon unit cell, y is an amount of solid solution of A in the sialon unit cell, and n is a content amount of oxygen in the sialon unit cell; and
wherein the phosphor emits fluorescence having a peak in a wavelength range from 560 nm to 575 nm upon irradiation of an excitation source.

9. The lighting apparatus according to claim 8, wherein the excitation source comprises: an inorganic EL device; an organic EL device; a laser diode (LD); or a light-emitting diode (LED) to emit a light of wavelength from 330 to 500 nm.

10. The lighting apparatus according to claim 8,
wherein the excitation source is a LED or a LD which emits a light of wavelength from 330 to 420 nm,
wherein the phosphor further comprises:
a blue color phosphor having an emission peak in wavelength range of 450 nm to 500 nm by an excitation light of 330 nm to 420 nm; and
a red color phosphor having an emission peak in wavelength range of 600 nm to 700 nm by an excitation light of 330 nm to 420 nm, and

wherein the lighting apparatus emits a white light by mixing a blue light; a color of a light emitted by the phosphor other than the blue color and red color phosphors; and a red color.

11. The lighting apparatus according to claim 8, wherein the excitation source is a LED or a LD which emits a light of wavelength from 430 to 480 nm; and wherein the lighting apparatus emits a white light by mixing a blue light of the excitation source and a light emitted by the phosphor.

12. The lighting apparatus according to claim 8,
wherein the excitation source is a LED or a LD which emits a light of wavelength from 430 to 480 nm;
wherein the phosphor further comprises:
an orange or a red color phosphor (hereinafter, referred to as “second phosphor”) having an emission peak in wavelength range of 580 nm to 700 nm by an excitation light of 430 nm to 480 nm, and

wherein the lighting apparatus emits a white light by mixing a light emitted by the phosphor and an orange or red light of the second phosphor.

13. The lighting apparatus according to claim 12, wherein the second phosphor is an Eu-activated CaAlSiN3.

14. The lighting apparatus according to claim 12, wherein the second phosphor is an Eu-activated Ca-α-sialon.

15. An image display device comprising:
at least the phosphor recited in claim 1; and an excitation source of the phosphor.

16. The image display device according to claim 15, wherein the excitation source is an electron beam, an electrical field, a vacuum ultraviolet ray, or an ultraviolet ray.

17. The image display device according to claim 15, wherein the image display device is a fluorescent display (VFD), a field emission display (FED), a plasma display panel (PDP), or a cathode-ray tube (CRT).

18. A method of manufacturing a phosphor,
wherein the phosphor comprises: α-type sialon crystal as a main component,
wherein the α-type sialon crystal comprises: at least an A element, which is Eu; an M element, which is Ca; Si; Al; oxygen; and nitrogen,
wherein the α-sialon crystal is expressed by a general formula:


(Mx,Ay)(Si12−(m+n)Alm+n)(OnN16−n)  (1); and



m=δM×x+δA×y  (2),


wherein the α-type sialon crystal is expressed by a composition formula having parameters x, y, and n, which are in a range expressed by:


0.2≦x≦2.4  (3); and



0.001≦y≦0.4  (4),


wherein a relation between m and n is expressed by:


0.5×m<n≦4  (5), and


wherein x is an amount of solid solution of Ca in a sialon unit cell, y is an amount of solid solution of Eu in the sialon unit cell, and n is a content amount of oxygen in the sialon unit cell; and
wherein the phosphor emits fluorescence having a peak in a wavelength range from 530 nm to 585 nm.

19. The method according to claim 18, wherein the parameters m and n are in a range expressed by:


0.6×m≦n≦2  (6).

20. The method of manufacturing the phosphor according to claim 18, comprising: firing in a nitrogen atmosphere in a temperature range which is 1500 degree Celsius or higher and 2200 degree Celsius or lower a raw material mixture comprising: at least oxide of Ca; oxide of Eu; silicon nitride; aluminum nitride; and silicon oxide or aluminum oxide.