JP2006063286A - Fluorophor and light-emitting devic - Google Patents

Fluorophor and light-emitting devic Download PDF

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JP2006063286A
JP2006063286A JP2004250920A JP2004250920A JP2006063286A JP 2006063286 A JP2006063286 A JP 2006063286A JP 2004250920 A JP2004250920 A JP 2004250920A JP 2004250920 A JP2004250920 A JP 2004250920A JP 2006063286 A JP2006063286 A JP 2006063286A
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phosphor
element
light
emission
wavelength
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JP4729278B2 (en
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Akira Nagatomi
Katayuki Sakane
堅之 坂根
晶 永富
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Dowa Mining Co Ltd
同和鉱業株式会社
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Abstract

【Task】
Providing a phosphor capable of setting a peak wavelength of light emission in a range from yellow to red, and providing a light emitting device that combines the phosphor and the light emitting portion, has excellent color rendering properties and can emit various colors. .
[Solution]
Ba 3 N 2 , Zn 3 N 2 , AlN, Si 3 N 4 , Eu 2 O 3 are prepared as raw materials. For example, the molar ratio of each element is Ba: Zn: Al: Si: Eu = 0.493: 0.493: 1 : Each raw material is weighed, mixed, and fired so as to have a ratio of 0.015, and a phosphor with the composition formula (Ba 0.5 Zn 0.5 ) AlSiN 3 : Eu is obtained. By changing the ratio of Ba: Zn, The emission peak wavelength of the obtained phosphor can be set, and by combining the phosphor set with the emission peak wavelength and an appropriate light emitting part, it has excellent color rendering properties and various colors. A light emitting device can be manufactured.
[Selection] Figure 1

Description

  The present invention relates to fluorescent lamps used in display devices such as cathode ray tubes (CRT), plasma display panels (PDP), field emission displays (FED), and electroluminescence (EL), and lighting devices such as fluorescent display tubes and fluorescent lamps. The present invention relates to a light emitting diode (LED) that emits visible light or white light, particularly a phosphor suitable for a light emitting device and a lighting device, and a light emitting device using the phosphor. .

  Currently, discharge fluorescent lamps and glass tube incandescent bulbs used as lighting devices have various problems such as being hot when touched by hand, short life, and containing harmful substances such as mercury. Yes. However, in recent years, high-intensity LEDs that emit ultraviolet to green light have been developed one after another. Then, by combining ultraviolet to green light generated from the high-intensity LED and a phosphor having an excitation band in the ultraviolet to green wavelength range, the light is emitted in white and used as a next-generation lighting device. Research and development is underway to see if this is possible. This white LED lighting has less heat generation, it is composed of a semiconductor element and a phosphor, so it does not burn out like a light bulb, has a long life, and does not require harmful substances such as mercury It has advantages and is an ideal lighting device.

  Here, two methods are generally considered as a method of obtaining white light emission by combining the LED and the phosphor described above. One is a system in which a blue LED and a yellow phosphor are combined and a blue light emitted from the LED and a yellow light emitted from the yellow phosphor are mixed. The other is a combination of near-ultraviolet / ultraviolet LEDs and red (R), green (G), and blue (B) phosphors. This is a method for emitting green (G) and blue (B) phosphors.

As phosphors used for the LED, etc., red phosphors such as Y 2 O 2 S: Eu, La 2 O 2 S: Eu, 3.5 MgO · 0.5 MgF 2 · GeO 2 : Mn, (La, Mn, Sm ) 2 O 2 S · Ga 2 O 3 : Eu, ZnS: Cu, Al, SrAl 2 O 4 : Eu as green phosphor, BAM: Eu, Mn, Ba 2 SiO 4 : Eu, YAG: Ce as yellow phosphor BAM: Eu, Sr 5 (PO 4 ) 3 Cl: Eu, ZnS: Ag, (Sr, Ca, Ba, Mg) 10 (PO 4 ) 6 Cl 2 : Eu are known as blue phosphors. Then, by combining these phosphors with a light emitting unit such as an LED, it is possible to obtain light emitting devices and lighting devices having various colors such as white.

However, the white LED illumination by the combination of the blue LED and the yellow phosphor (for example, YAG: Ce) described above is insufficient for light emission on the long wavelength side in the visible light region. As a result, it is not possible to obtain white light emission that is slightly reddish like a light bulb.
On the other hand, white LED lighting using a combination of near-ultraviolet / ultraviolet LEDs and R / G / B phosphors emits various light in addition to white light depending on the combination of R / G / B phosphors and the mixing ratio. Color can be obtained, and the application range as a lighting device is wide.

However, as a further problem, when a YAG: Ce yellow phosphor is made to emit light using a blue LED as an excitation light source, the blue light is in an efficient excitation range and good yellow emission can be obtained. However, when the YAG: Ce yellow phosphor emits light with a near-ultraviolet / ultraviolet LED, the near-ultraviolet / ultraviolet light is out of the efficient excitation range of the YAG: Ce-based yellow phosphor, and the efficiency is high. There is a problem that light emission cannot be obtained.
Also, in white LED lighting using a combination of near-ultraviolet / ultraviolet LEDs and R / G / B phosphors, the red phosphor has a higher excitation efficiency on the longer wavelength side than the other phosphors. There is a problem that the luminous efficiency is low. For this reason, when blending R, G, and B phosphors, the mixing ratio of the red phosphors must be increased. As a result, the blending amount of the phosphors for improving the luminance is insufficient, and a high luminance white color is obtained. I can't. Further, since the emission spectrum of each of the R, G, and B phosphors is sharp, there is a problem that the color rendering property of the obtained white light emission is poor.

  In order to solve the above-mentioned problems, an oxynitride glass phosphor (see Patent Document 1) having a good excitation band on the long wavelength side and having a wide half-width emission peak compared to an oxide system or the like, sialon Have been reported (see Patent Documents 2 and 3). These nitrogen-containing phosphors have a higher proportion of covalent bonds than oxide-based phosphors and so on, and thus have a good excitation band even at 400 nm or more, and attract attention as phosphors for white LEDs. Collecting.

Japanese Patent Laid-Open No. 2001-214162 JP2003-336059 Japanese Patent Laid-Open No. 2003-124527

  A light emitting element that emits light from ultraviolet to green as described above, and an R, G, and B phosphor that has an excitation band in the ultraviolet to green wavelength range generated from the light emitting element and that can obtain a light emission peak with a wide half width. The color rendering properties of light emitting devices, including LEDs that emit white light and visible light, have been improved. However, according to the study by the present inventors, the color rendering performance has been improved by this method in the region where the correlated color temperature is high, and there is room for further improvement in the color rendering property in the region where the correlated color temperature is low. thing. And it became clear that the light emission of various colors is calculated | required in the area | region where the said correlated color temperature is low. However, even when trying to satisfy these requirements by using a mixture of current red phosphors and orange phosphors, phosphors having a desired emission peak are not found, and the excitation wavelengths of the phosphors differ. It was difficult to mix freely.

  The present invention has been made in order to solve the above-described problems. In addition to being able to set the emission peak wavelength in the range from yellow to red, the broad shape of the emission spectrum can be maintained regardless of the setting, and the excitation can be performed. An object of the present invention is to provide a phosphor whose wavelength range hardly changes. Another object of the present invention is to provide a light-emitting device in which the phosphor and the light-emitting portion are combined, which is excellent in color rendering even in a region having a low correlated color temperature and can emit light of various colors. And

  As a result of repeated studies by the present inventors in order to solve the above-described problems, the general formula MmAaBbNn: Z (where M element is an element having a valence of II and A element has a valence of III) Element B element is an element having an IV valence, N is nitrogen, and Z element is an activator.) In this phosphor, the emission peak wavelength can be set in the range from yellow to red in the phosphor, and the broad shape of the emission spectrum can be maintained regardless of the setting, and the excitation wavelength range is almost unchanged. The present invention has been completed with the idea that there is no such thing.

That is, the first configuration of the present invention is:
A phosphor represented by the general formula MmAaBbNn: Z,
In the phosphor, the M element is an element having a valence of II, the A element is an element having a valence of III, the B element is an element having a valence of IV, and N is nitrogen. Z element is an activator,
The M element is a phosphor composed of two or more elements, and m> 0, a> 0, b> 0, and n = 2 / 3m + a + 4 / 3b.

The second configuration is
The phosphor according to the first configuration, wherein the values of m, a, and b are m = a = b = 1.

The third configuration is
The M element is two or more elements selected from Mg, Ca, Sr, Ba, and Zn, the A element is one or more elements selected from B, Al, and Ga, and the B element is Si and The phosphor according to the first or second configuration, wherein the phosphor is / or Ge and the Z element is one or more elements selected from rare earth metals or transition metals.

The fourth configuration is
The phosphor according to the third configuration, wherein the A element is Al, the B element is Si, and the Z element is one or more elements selected from Eu, Mn, Sm, and Ce. is there.

The fifth configuration is
The phosphor according to any one of the first to fourth configurations, wherein the phosphor is in a powder form.

The sixth configuration is
The phosphor according to the fifth configuration, wherein the phosphor powder has an average particle size of 20 μm or less and 0.1 μm or more.

The seventh configuration is
The phosphor according to any one of the first to sixth configurations and a light emitting unit that emits light of a predetermined wavelength, the light of the predetermined wavelength as an excitation source, and the phosphor different from the predetermined wavelength A light-emitting device that emits light at a wavelength.

The eighth configuration is
The light emitting device according to a seventh configuration, wherein the predetermined wavelength is a wavelength of 250 nm to 550 nm.

The ninth configuration is
The light emitting device according to the seventh or eighth configuration, wherein the light emitting unit is a light emitting diode (LED).

  The phosphor according to any one of the first to fourth configurations can set the peak value of the emission wavelength in the range of 580 to 650 nm, and can maintain the broad shape of the emission spectrum regardless of the setting. It has an excitation wavelength for light in a wide wavelength range of ˜green (250 nm to 550 nm).

  In addition to the above-described effects, the phosphor according to the fifth or sixth configuration is a powder itself, so that it can be easily applied or filled into the application object.

  The light emitting device according to any one of the seventh to ninth configurations can emit light of various colors including white having high color rendering even in a region where the correlated color temperature is low.

  The phosphor according to the present invention is represented by the general formula MmAaBbNn: Z (where the M element is a II valent element, the A element is a III valent element, the B element is a IV valent element, N is nitrogen, and Z is attached). M element is a phosphor containing two or more kinds of elements.

  The two or more elements contained in the M element are both elements having a valence of II in the phosphor. The M element is preferably an element selected from Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, etc., and more preferably an element selected from Mg, Ca, Sr, Ba, Zn. It is preferable.

  The element A is one or more elements having a valence of III in the phosphor. The element A is preferably an element selected from B (boron), Al, Ga, In, Tl, Y, Sc, P, As, Sb, Bi, and the like, and further selected from B, Al, and Ga. The element is preferably Al, and most preferably Al. This is because AlN, which is a nitride, is used as a general heat transfer material and structural material, is easily available, is inexpensive, and has a low environmental impact.

The B element is one or more elements having an IV valence in the phosphor. The B element is preferably an element selected from C, Si, Ge, Sn, Ti, Hf, Mo, W, Cr, Pb, Zr, and the like, and further, an element selected from Si and Ge. Preferably it is Si, and most preferably Si. This is because Si 3 N 4 , which is a nitride, is used as a general heat transfer material and structural material, is easily available, is inexpensive, and has a low environmental impact.

  The Z element is one or more elements selected from rare earth metal elements or transition metal elements. Here, in order to improve a good color rendering property in a light emitting device or a lighting device using the phosphor, it is preferable that light emission of the phosphor has a spectrum with a wide half-value width. From this point of view, the Z element is preferably selected from Eu, Mn, Sm, and Ce, but is most preferably Eu. This is because when Eu is used, the phosphor exhibits strong light emission from yellow to red, so that the luminous efficiency and color rendering are high, and it is optimal as an activator for the phosphor used in the light-emitting device and the lighting device. In addition, the fluorescent substance which has light emission of a different wavelength can be obtained with the kind of Z element which substituted a part of M element of a fluorescent substance composition.

Here, it will be described that the peak wavelength of the emission wavelength of the phosphor according to the present invention can be set in the range of 580 to 650 nm by using M element as two or more elements.
However, by using one kind of element as the M element and substituting the one kind of element with another kind of element, light emission having a different peak wavelength can be obtained depending on the substituted element. By changing the amount of the agent Z, light emission having different peak wavelengths can be obtained. However, with this method, the peak wavelength cannot be changed in a wide range. In addition, when the M element is replaced with another kind of element, there is also a problem that the emission intensity is weakened depending on the substituted element.

  However, the peak value of the emission wavelength can be set in the range of 580 to 650 nm by substituting the M element with two or more elements and controlling the combination of the two or more elements and the composition ratio. In addition, the broad shape of the emission spectrum can be maintained regardless of the setting, and it is possible to have an excitation wavelength for light in a wide wavelength range from ultraviolet to green (250 nm to 550 nm). In addition, even if an element that shows the disadvantage that the emission intensity decreases when the M element is completely replaced with one kind of element, it is emitted by combining two or more elements in combination with other elements. It has been found that the intensity and brightness are greatly improved. (However, if the peak wavelength of the emission spectrum is changed to the longer wavelength side, it will move away from the peak wavelength (555 nm) where the luminance is highest, so even if the emission intensity is improved, the luminance may be reduced. is there.)

  As an example of M element having two or more elements, various combinations selected from elements having a valence of II are possible, but among elements having a valence of II, Mg, Ca, More preferably selected from Sr, Ba, Zn, Mg-Ca, Mg-Sr, Mg-Ba, Mg-Zn, Ca-Sr, Ca-Ba, Ca-Zn, Sr-Ba, Sr-Zn, Most preferred is any combination of Ba-Zn. In this way, light having different peak wavelengths can be obtained by combining two or more M elements. Furthermore, the emission wavelength can also be changed by changing the composition ratio of the two or more M elements, and a finer peak wavelength can be set.

Next, the relationship between the host structure of the phosphor according to the present invention and the light emission characteristics will be described.
When the matrix structure of the phosphor according to the present invention has a chemically stable structure, an impurity phase that does not contribute to light emission is less likely to occur in the phosphor. Therefore, in order to make the host structure of the phosphor have a chemically stable structure, when the host body of the phosphor is expressed as a composition formula MmAaBbNn, m> 0, a> 0, b> 0, n = 2 / 3m + a + 4 / 3b is preferred. This is because the M element is a + II valence, the A element is a + III valence, the B element is a + IV valence, and the N is a -III valence, so the values of m, a, b, and n are n = 2 / If the composition satisfies 3m + a + 4 / 3b, the sum of the valences of the elements becomes zero, and the charge neutrality is maintained. Further, when the values of m, a, and b are m = a = b = 1, the phosphor is particularly excellent in emission characteristics and excitation band characteristics. However, it is conceivable that a slight composition shift occurs. In the phosphor according to the present invention, the luminous efficiency decreases as the oxygen concentration in the phosphor increases. Therefore, it is considered that the smaller the amount of oxygen contained in the matrix structure, the higher the luminous efficiency.

  In addition, the phosphor according to the present invention has the general formula MmAaBbNn: Zz (where m> 0, a> 0, b> 0, n = 2 / 3m + a + 4 / 3b, z> 0). When expressed, the molar ratio z / (m + z) between the M element and the activator Z element is preferably in the range of 0.0001 or more and 0.5 or less. When the molar ratio z / (m + z) between the M element and the activator Z element is in the range, it is possible to avoid a decrease in light emission efficiency due to concentration quenching due to excessive activator content, It is also possible to avoid a decrease in light emission efficiency due to a lack of light emission contributing atoms due to an insufficient activator content. As for the amount of activation, the optimum value of z / (m + z) varies slightly depending on the type of activator element Z and the type of M element, but more preferably in the range of 0.005 or more and 0.1 or less. If there is, good light emission can be obtained. Furthermore, the emission wavelength can be slightly shifted from the longer wavelength side to the shorter wavelength side depending on the amount of the activator, which is beneficial when controlling the slight emission wavelength shift.

The phosphor according to the present invention is powdered in consideration of the ease of application or filling in the production of a light emitting device or the like according to a post-process, but the average particle size of the phosphor powder is 20 μm or less. The thickness is preferably 0.1 μm or more. More preferably, it is 10 μm or less and 1.0 μm or more. This is because, in the phosphor powder, light emission is considered to occur mainly on the particle surface, so if the average particle size is 20 μm or less, the surface area per unit weight of the powder can be secured and the decrease in luminance can be avoided. It is. In addition, if the average particle size is 20 μm or less, the phosphor powder can be pasted and applied to a phosphor element or the like to increase the coating density of the phosphor powder. Also from this viewpoint, it is possible to avoid a decrease in luminance. Further, when applied to a display as the light emitting device according to the present invention, the average particle size of the phosphor powder is preferably 20 μm or less from the viewpoint of increasing the definition of the display.
On the other hand, according to the study by the present inventors, although the detailed reason is unknown, it is preferable that the average particle diameter of the phosphor powder is preferably larger than 0.1 μm from the viewpoint of the luminous efficiency of the phosphor powder. found. From the above, it is preferable that the average particle size of the phosphor powder according to the present invention is 20 μm or less and 0.1 μm or more.

  The phosphor obtained by the above-described manufacturing method has an emission peak wavelength set in any of the range of 580 to 650 nm by adjusting the type and composition of two or more elements contained in the M element. However, the broad shape of the emission spectrum could be maintained, and the range of excitation wavelengths remained almost unchanged. Furthermore, regardless of the setting of the peak wavelength of the light emission, all had a good excitation band in a wide range of the wavelength range of 250 to 550 nm.

(Phosphor production method)
The phosphor production method according to the present invention will be described by taking (Sr, Mg) AlSiN 3 : Eu (provided that z / (m + z) = 0.015) as an example.
First, nitride raw materials for two types of M element, A element, and B element are prepared. Each nitride may be a commercially available raw material, but preferably has a higher purity, preferably 2N or higher, more preferably 3N or higher. For the raw material particle size, fine particles are preferable for promoting the reaction. However, since the size and shape of the obtained phosphor change depending on the particle size and shape of the raw material, use a nitride material suitable for the purpose. That's fine. Furthermore, the raw material is not limited to the nitride raw material, and a target composition may be obtained by preparing a raw material in which metal fine particles of each element are mixed and nitriding the mixed raw material.

  From the viewpoint of lowering the oxygen concentration contained in the matrix constituent element as well as the raw material of the element Z, it is preferable that it is a nitride or metal Eu, but the activator has a small activation amount, and the oxygen contained in the phosphor. Since the absolute amount of is small, a commercially available oxide may be used. A higher purity is preferable, and a material having a purity of 2N or more, more preferably 3N or more is prepared.

In the production of (Sr, Mg) AlSiN 3 : Eu (where z / (m + z) = 0.015), for example, nitrides of two types of M element, A element, and B element, Sr 3 N 2 (2N), Mg 3 N 2 (2N), AlN (3N), and Si 3 N 4 (3N) may be prepared. Eu 2 O 3 (3N) may be prepared as the Z element.
When Sr is M 1 m 1 and Mg is M 2 m 2 , M = M 1 m 1 + M 2 m 2 , and these raw materials have a molar ratio of each element (m 1 + m 2 ): a : Each raw material is weighed and mixed so that b: z = 0.985: 1: 1: 1.015. Of course, the values of 0.985 for the M element and 0.015 for the Z element match the set value of z / (m + z) = 0.015, and vary depending on the set value. As for the weighing / mixing, if it is handled in the air, the oxygen concentration contained in the matrix constituent element becomes high due to oxidation or decomposition, resulting in a problem that the emission characteristics are deteriorated and the aimed phosphor cannot be produced. Therefore, operation in the glove box under an inert atmosphere is convenient. Further, since nitride is easily affected by moisture, it is preferable to use an inert gas from which moisture has been sufficiently removed. In the case of wet mixing used in oxide phosphors, etc., dry mixing is preferable because the nitride raw material is decomposed by moisture and ammonia is generated. The mixing may be performed by a normal mixing method using a ball mill or a mortar.

Place the raw material after mixing in a crucible and fire it in an inert atmosphere such as nitrogen at 1000 ° C or higher, preferably 1400 ° C or higher, more preferably 1500-1600 ° C for 30 minutes or longer, more preferably 3 hours or longer. To do. The holding time can be shortened because the sintering proceeds more rapidly as the sintering temperature is higher. On the other hand, even when the sintering temperature is low, the desired light emission characteristics can be obtained by maintaining the temperature for a long time. However, the longer the sintering time is, the more the particle growth proceeds and the larger the particle size. Therefore, the sintering time may be set according to the target particle size. In addition, it is preferable to use a crucible made of BN (boron nitride) as the crucible because it can avoid mixing impurities from the crucible. After firing is completed, the fired product is taken out of the crucible, and ground using a mortar, ball mill, or other pulverizing means so as to have a predetermined average particle size, and the composition formula (Sr, Mg) AlSiN 3 : Eu (however, The phosphor represented by z / (m + z) = 0.015) can be manufactured.

When elements other than Sr, Mg, Al, Si, Eu are used as M element (M 1 , M 2 element), A element, B element, Z element, the mixing ratio of M 1 and M 2 When changing the activation amount of the activator, even if it is changed, by adjusting the blending amount at the time of charging each raw material to a predetermined composition ratio, by the same manufacturing method as described above, the predetermined composition formula Can be produced.

(Manufacture of lighting devices to be light emitting devices)
By combining the phosphor according to the present invention in a powder form with a light emitting unit that emits light in a wavelength range of 250 nm to 550 nm, preferably in a wavelength range of 300 nm to 420 nm, A light emitting device such as a display device can be manufactured.
As the light emitting section, for example, an LED light emitting element that emits light in a range from ultraviolet to blue, a discharge lamp that generates ultraviolet light, and the like can be used. Then, when a mixture of the phosphor according to the present invention and another phosphor is combined with the LED light emitting element, various light emitting devices such as lighting devices and display devices can be manufactured. When a mixture of the phosphor according to the above and other phosphors is combined with the discharge lamp, various fluorescent lamps, light emitting devices such as lighting devices and display devices can be manufactured.
A method of combining the phosphor according to the present invention with the LED light emitting element and the discharge lamp may be performed by a known method. For example, a method of directly applying the phosphor to the light emitting part, a silicon etc. After the dispersion in the resin, a method of applying the dispersion to the light emitting part, a method of applying the phosphor to a transparent substrate formed of resin or the like, and arranging the substrate on the light emitting part is adopted. be able to.
In the above-described light emitting device, when the LED light emitting element, the discharge lamp, and the like emit light, these light emitting portions emit light of a predetermined wavelength, and part or all of the light of the predetermined wavelength serves as an excitation source, and the phosphor However, it is possible to obtain a light emitting device such as white light that emits light at a wavelength different from the predetermined wavelength and has excellent color rendering properties.

Hereinafter, based on an Example, this invention is demonstrated more concretely.
Example 1
Commercially available Ba 3 N 2 (2N), Zn 3 N 2 (2N), AlN (3N), Si 3 N 4 (3N), Eu 2 O 3 (3N) are prepared, and M element is Ba: Zn = 0.5 : 0.5, each raw material is weighed so that the molar ratio of each element is Ba: Zn: Al: Si: Eu = 0.493: 0.493: 1: 1: 0.015, and a mortar is used in a glove box under a nitrogen atmosphere And mixed. The mixed raw materials are put in a BN crucible, heated at a rate of 15 ° C / min to 1600 ° C in a nitrogen atmosphere, held and fired at 1600 ° C for 3 hours, and then cooled from 1600 ° C to 200 ° C in 1 hour. After the firing, crushing was performed to obtain a phosphor having a composition formula (Ba 0.5 Zn 0.5 ) AlSiN 3 : Eu (where z / (m + z) = 0.015).

  The obtained phosphor was excited with monochromatic excitation light having a wavelength of 460 nm, and an emission spectrum was measured. The emission spectrum is shown by a solid line in FIG. Here, FIG. 1 is a graph in which the horizontal axis represents the wavelength of light and the vertical axis represents the relative light emission intensity of the phosphor. The relative emission intensity on the vertical axis is a value when the emission intensity at the peak wavelength in the emission spectrum of Comparative Example 1 described later is normalized as 100%. Further, although not shown in FIG. 1, similarly, the luminance in the emission spectrum of Comparative Example 1 was normalized as 100%.

  Further, the excitation spectrum was measured, and the result is shown in FIG. Here, FIG. 3 is a graph in which the vertical axis represents the emission intensity of the phosphor and the horizontal axis represents the wavelength of light. Excitation spectrum uses monochromatic light of various wavelengths to excite the phosphor to be measured, measures the emission intensity of a given wavelength emitted by the phosphor, and measures the excitation wavelength dependence of the emission intensity of the given wavelength It is a thing. In this measurement, monochromatic light with a wavelength of 250 nm to 600 nm was irradiated to the phosphor according to Example 1, and the excitation dependence of the emission intensity of light with a wavelength of 609.0 nm emitted from the phosphor was measured. is there.

As is apparent from FIG. 1, the phosphor had a broad peak in a wide wavelength range from 500 nm to 800 nm, showed the highest emission at a wavelength of 609.0 nm, and the relative emission intensity was 138.9%.
On the other hand, the relative luminance in light emission of the phosphor was 199.9%, and the chromaticity (x, y) of light emission was x = 0.578 and y = 0.420. In addition, the orange emission color was confirmed visually. The measurement results are shown in Table 1.

(Example 2)
Commercially available Sr 3 N 2 (2N), Mg 3 N 2 (2N), AlN (3N), Si 3 N 4 (3N), Eu 2 O 3 (3N) are prepared, and M element is Sr: Mg = 0.5 : 0.5, and the same treatment as in Example 1 was performed except that each raw material was weighed so that the molar ratio of each element was Sr: Mg: Al: Si: Eu = 0.493: 0.493: 1: 1: 0.015. Thus, a phosphor having the composition (Sr 0.5 Mg 0.5 ) AlSiN 3 : Eu (where z / (m + z) = 0.015) was obtained. As in Example 1, the emission spectrum measurement results are shown in FIG. Further, the excitation spectrum was measured, and the result is shown in FIG.

As is clear from FIG. 1, the phosphor according to Example 2 had a broad peak, showed the highest emission at a wavelength of 632.8 nm, and the relative emission intensity was 178.1%.
On the other hand, the relative luminance in light emission of the phosphor was 159.0%, and the chromaticity (x, y) of light emission was x = 0.629 and y = 0.370. Note that a dark orange luminescent color could be confirmed visually. The measurement results are shown in Table 1.

(Example 3)
Commercially available Ca 3 N 2 (2N), Sr 3 N 2 (2N), AlN (3N), Si 3 N 4 (3N), Eu 2 O 3 (3N) are prepared, and M element is Ca: Sr = 0.5 : 0.5, and the same treatment as in Example 1 was performed except that each raw material was weighed so that the molar ratio of each element was Ca: Sr: Al: Si: Eu = 0.493: 0.493: 1: 1: 0.015. A phosphor having a composition (Ca 0.5 Sr 0.5 ) AlSiN 3 : Eu (where z / (m + z) = 0.015) was obtained. As in Example 1, the emission spectrum measurement results are shown in FIG. 1 using a two-dot chain line. Further, the excitation spectrum was measured, and the result is shown in FIG.

As is clear from FIG. 1, the phosphor according to Example 3 had a broad peak, showed the highest emission at a wavelength of 648.9 nm, and the relative emission intensity was 217.3%.
On the other hand, the relative luminance in light emission of the phosphor was 117.1%, and the chromaticity (x, y) of light emission was x = 0.659 and y = 0.340. In addition, the red luminescent color was confirmed visually. The measurement results are shown in Table 1.

(Comparative Example 1)
Commercially available Sr 3 N 2 (2N), AlN (3N), Si 3 N 4 (3N), Eu 2 O 3 (3N) are prepared, M element is Sr alone, and the molar ratio of each element is Sr: Al : SrAlSiN 3 : Eu (provided that z / (m + z) =), except that each raw material was weighed so that Si: Eu = 0.985: 1: 1: 0.015. 0.015) phosphor was obtained. As in Example 1, the measurement results of the emission spectrum are shown in FIG. Further, the excitation spectrum was measured, and the result is shown in FIG.

  As is clear from FIG. 1, the phosphor according to Comparative Example 1 had a broad peak and exhibited the highest light emission at a wavelength of 631.2 nm. As described above, the emission intensity and luminance at this time were set to 100%. The chromaticity (x, y) of the light emission was x = 0.617, y = 0.382. Note that a dark orange luminescent color could be confirmed visually. The measurement results are shown in Table 1.

Study on (Examples 1 to 3) and (Comparative Example 1)
By using, for example, a combination of two elements selected from Mg, Ca, Sr, Ba, and Zn as the M element, it is possible to obtain phosphors having different emission wavelengths. Furthermore, these phosphors can set the peak value of the emission wavelength in the range of 609 to 650 nm by selecting and combining M elements, and broad emission from yellow to red (wavelength of 500 nm to 800 nm) Had a spectrum. Furthermore, these phosphors had a broad, flat and highly efficient excitation band on the long wavelength side from near ultraviolet / ultraviolet to green (wavelength 250 nm to 550 nm).

Further, when the M element is replaced with two kinds of elements selected from, for example, Mg, Ca, Sr, Ba, and Zn, the emission intensity and luminance are higher than in the case of using Sr alone as the M element as in Comparative Example 1. It has also been found that it is possible to obtain excellent phosphors. For example, when Example 2 and Comparative Example 1 are compared with each other, the emission wavelength is almost the same, but Example 2 is improved by 50% or more in both emission intensity and luminance as compared with Comparative Example 1.
From the above, it became clear that phosphors with various emission wavelengths can be produced by combining M elements, and brightness and emission intensity can be greatly improved by using two or more elements instead of single elements as M elements. There was found.

  As apparent from FIGS. 3 to 5, the excitation spectrum of the phosphor is flat over a wide range from a wavelength of about 250 nm to 600 nm. In other words, it was found that the phosphor exhibits high-efficiency emission with a wide range of excitation light from a wavelength of about 250 nm to 600 nm. From this result, it is clear that the phosphor is high in light when either blue LED (excitation wavelength near 460) or near ultraviolet / ultraviolet LED (excitation wavelength near 380 to 410 nm) is used as excitation light. It has been found that the phosphor can emit light efficiently.

  Further, from the above results, the phosphors according to Examples 1 to 3 were used alone or in combination, and when one was combined with a blue LED, the other was further green (G) / blue ( B) Even when phosphors are mixed and combined with near-ultraviolet / ultraviolet LEDs, it has been found that it is possible to produce illuminations such as white LEDs having excellent color rendering properties.

Example 4
In Example 4, commercially available Ba 3 N 2 (2N), Mg 3 N 2 (2N), AlN (3N), Si 3 N 4 (3N), Eu 2 O 3 (3N) were prepared, and M element was added. Example 1 except that each raw material was weighed so that Ba: Mg = 0.75: 0.25 and the molar ratio of each element was Ba: Mg: Al: Si: Eu = 0.739: 0.246: 1: 1: 0.015. The same treatment was performed to obtain a phosphor having a composition (Ba 0.739 Mg 0.246 ) AlSiN 3 : Eu (where z / (m + z) = 0.015). As in Example 1, the measurement results of the emission spectrum are shown in FIG. The relative emission intensity on the vertical axis is a value when the emission intensity at the peak wavelength in the emission spectrum of Comparative Example 2 described later is normalized as 100%. Further, although not shown in FIG. 2, similarly, the luminance in the emission spectrum of Comparative Example 2 was normalized as 100%.
Further, the excitation spectrum was measured, and the result is shown in FIG.

As is clear from FIG. 2, the phosphor according to Example 4 had a broad peak, showed the highest emission at a wavelength of 598.6 nm, and the relative emission intensity was 100.7%.
On the other hand, the relative luminance in the light emission of the phosphor was 105.1%, and the chromaticity (x, y) of the light emission was x = 0.556 and y = 0.441. In addition, visually, yellow-orange luminescent color was confirmed. The measurement results are shown in Table 1.

(Example 5)
In Example 5, commercially available Ba 3 N 2 (2N), Mg 3 N 2 (2N), AlN (3N), Si 3 N 4 (3N), Eu 2 O 3 (3N) are prepared, and M element is prepared. Example 1 except that each raw material was weighed so that Ba: Mg = 0.5: 0.5 and the molar ratio of each element was Ba: Mg: Al: Si: Eu = 0.493: 0.493: 1: 1: 0.015. The same treatment was performed to obtain a phosphor having the composition (Ba 0.493 Mg 0.493 ) AlSiN 3 : Eu (where z / (m + z) = 0.015). As in Example 1, the measurement result of the emission spectrum is shown in FIG. Further, the excitation spectrum was measured, and the result is shown in FIG.

As is clear from FIG. 2, the phosphor according to Example 5 had a broad peak, showed the highest emission at a wavelength of 604.6 nm, and the relative emission intensity was 142.4%.
On the other hand, the relative luminance in light emission of the phosphor was 135.0%, and the chromaticity (x, y) of light emission was x = 0.573 and y = 0.425. In addition, visually, yellow-orange luminescent color was confirmed. The measurement results are shown in Table 2.

(Example 6)
In Example 6, commercially available Ba 3 N 2 (2N), Mg 3 N 2 (2N), AlN (3N), Si 3 N 4 (3N), Eu 2 O 3 (3N) were prepared, and M element was added. Example 1 except that Ba: Mg = 0.25: 0.75 and each raw material was weighed so that the molar ratio of each element was Ba: Mg: Al: Si: Eu = 0.246: 0.739: 1: 1: 0.015. The same treatment was performed to obtain a phosphor having the composition (Ba 0.246 Mg 0.739 ) AlSiN 3 : Eu (where z / (m + z) = 0.015). Similarly to Example 1, the measurement result of the emission spectrum is shown in FIG. 2 using a two-dot chain line. Further, the excitation spectrum was measured, and the result is shown in FIG.

As is clear from FIG. 2, the phosphor according to Example 6 had a broad peak, showed the highest emission at a wavelength of 645.8 nm, and the relative emission intensity was 110.9%.
On the other hand, the relative luminance in light emission of the phosphor was 59.7%, and the chromaticity (x, y) of light emission was x = 0.629 and y = 0.369. In addition, the red luminescent color was confirmed visually. The measurement results are shown in Table 2. However, in Example 6, although the relative light emission intensity was improved, the relative luminance was as low as 59.7% because the peak of the light emission wavelength was large and changed to the long wavelength side, so that the luminance was the highest. This is because it has moved away from the higher peak wavelength (555 nm).

(Comparative Example 2)
Commercially available Ba 3 N 2 (2N), AlN (3N), Si 3 N 4 (3N), Eu 2 O 3 (3N) are prepared, M element is Ba alone, and the molar ratio of each element is Ba: Al : Si: Eu = 0.985: 1: 1: The same treatment as in Example 1 was performed except that each raw material was weighed so as to be 0.015, and the composition BaAlSiN 3 : Eu (where z / (m + z) = 0.015) phosphor was obtained. As in Example 1, the measurement results of the emission spectrum are shown in FIG. Further, the excitation spectrum was measured, and the result is shown in FIG.

As is clear from FIG. 2, the phosphor according to Comparative Example 2 had a broad peak and showed the highest light emission at a wavelength of 604.6 nm. As described above, the emission intensity and luminance at this time were set to 100%.
On the other hand, the chromaticity (x, y) of light emission was x = 0.666 and y = 0.431. Note that a dark orange luminescent color could be confirmed visually. The measurement results are shown in Table 2.

Study on (Examples 4 to 6) and (Comparative Example 2)
For example, when two elements of Ba and Mg are selected as the M element and the ratio of Ba and Mg is changed, when Ba: Mg = 0.5: 0.5 shown in Example 5, both the emission intensity and the luminance are comparative examples. It was found that it was improved by 30% or more compared to 2. Further, when Ba: Mg = 0.25: 0.75 shown in Example 6, the emission wavelength was significantly shifted to the longer wavelength side compared with 604.6 nm of Comparative Example 2, and red emission with a wavelength of 645.8 nm was exhibited.

  As described above, from Examples 1 to 6, it was found that both the luminance and the emission intensity can be significantly improved by using two or more elements as the M element instead of a single element. It has also been found that when two or more elements are used, the emission wavelength can be shifted by changing the composition ratio of the two or more elements.

(Example 7)
A commercially available ultraviolet LED (emission wavelength: 386.2 nm) having a nitride semiconductor as a light emitting part is prepared, and the phosphor obtained in Example 2 and a commercially available blue phosphor (BAM: Eu) are provided on the LED. And a commercially available green phosphor (ZnS: Cu, Al) were applied by a known method to produce a white LED. At this time, the emission spectrum in the case of mixing the phosphor according to the example, BAM: Eu, ZnS: Cu, Al was simulated, and a blend capable of obtaining white light was obtained from the simulation result. In Example 7, the formulation was determined so that a light bulb color corresponding to a color temperature of 3000K was obtained. FIG. 11 shows an emission spectrum of the white LED when the ultraviolet LED emits light. FIG. 11 is a graph in which the horizontal axis represents the wavelength of light (nm) and the vertical axis represents the emission intensity. As is clear from the results of FIG. 11, each phosphor in the white LED was excited by light from the ultraviolet LED to emit light, and white light corresponding to a color temperature of 2875 K could be obtained. The average color rendering index (Ra) was 94, which was excellent in color rendering. Furthermore, by changing the composition of the phosphor according to the example, it was possible to obtain white LEDs with different correlated color temperatures and excellent color rendering.

(Example 8)
A blue light LED (light emission wavelength: 460.0 nm) having a nitride semiconductor as a light emitting portion was prepared, and the phosphor obtained in Example 2 and a commercially available yellow phosphor (YAG: Ce) were placed on the LED. Then, a white LED was produced by coating by a known method, and the blue LED was emitted. At this time, the mixture of the emission spectrum of the blue LED and the emission spectrum of the phosphor according to the example was simulated, and a blend capable of obtaining white light was obtained from the simulation result. In Example 8, the formulation was determined so that a light bulb color corresponding to a color temperature of 3000K was obtained. FIG. 12 shows an emission spectrum when the blue LED is caused to emit light. FIG. 12 is a graph in which the horizontal axis represents the wavelength of light (nm) and the vertical axis represents the emission intensity, as in FIG. As is clear from the results of FIG. 12, each phosphor in the white LED was excited by light from the blue LED and emitted light, and white light corresponding to a color temperature of 3016K could be obtained. The average color rendering index (Ra) was 86, which was sufficiently excellent in color rendering. Furthermore, white LEDs having different correlated color temperatures could be obtained by changing the composition of the phosphor according to the example.

6 is a graph showing emission spectra of phosphors according to Examples 1 to 3 and Comparative Example 1. It is a graph which shows the emission spectrum of the fluorescent substance which concerns on Examples 4-6 and the comparative example 2. FIG. 3 is a graph showing an excitation spectrum of the phosphor according to Example 1. 6 is a graph showing an excitation spectrum of a phosphor according to Example 2. 6 is a graph showing an excitation spectrum of a phosphor according to Example 3. 6 is a graph showing an excitation spectrum of a phosphor according to Comparative Example 1. 6 is a graph showing an excitation spectrum of a phosphor according to Example 4. 6 is a graph showing an excitation spectrum of a phosphor according to Example 5. 10 is a graph showing an excitation spectrum of a phosphor according to Example 6. 6 is a graph showing an excitation spectrum of a phosphor according to Comparative Example 2. 10 is a graph showing an emission spectrum of a white LED according to Example 7. 10 is a graph showing an emission spectrum of a white LED according to Example 8.

Claims (9)

  1. A phosphor represented by the general formula MmAaBbNn: Z,
    In the phosphor, the M element is an element having a valence of II, the A element is an element having a valence of III, the B element is an element having a valence of IV, and N is nitrogen. Z element is an activator,
    The phosphor is characterized in that the M element is composed of two or more elements, and m> 0, a> 0, b> 0, and n = 2 / 3m + a + 4 / 3b.
  2.   2. The phosphor according to claim 1, wherein the values of m, a, and b are m = a = b = 1.
  3.   The M element is two or more elements selected from Mg, Ca, Sr, Ba, and Zn, the A element is one or more elements selected from B, Al, and Ga, and the B element is Si and 3. The phosphor according to claim 1, wherein the phosphor is one or more elements selected from rare earth metals and transition metals.
  4.   The phosphor according to claim 3, wherein the A element is Al, the B element is Si, and the Z element is one or more elements selected from Eu, Mn, Sm, and Ce.
  5.   The phosphor according to any one of claims 1 to 4, wherein the phosphor is in a powder form.
  6.   The phosphor according to claim 5, wherein the phosphor powder has an average particle size of 20 μm or less and 0.1 μm or more.
  7.   7. The phosphor according to claim 1, and a light emitting unit that emits light of a predetermined wavelength, the light of the predetermined wavelength as an excitation source, and the phosphor at a wavelength different from the predetermined wavelength. A light-emitting device that emits light.
  8.   The light-emitting device according to claim 7, wherein the predetermined wavelength is a wavelength of 250 nm to 550 nm.
  9.   9. The light emitting device according to claim 7, wherein the light emitting unit is a light emitting diode (LED).
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