WO2018145288A1 - Luminescent material composition and light emitting device - Google Patents

Abstract

A luminescent material composition and a light emitting device. The luminescent material composition comprises a blue luminescent material, a green luminescent material, and a red luminescent material; the blue luminescent material is selected from any one or more of the following general formulae: Ca2-xLuHf2Al3O12:xCe, Ca3-yZr SiGa2O12:yCe, Ba1-rMgAl10O17:rEu, and Sr5 - m(PO4)3Cl:mEu; the green luminescent material is selected from any one or more of the following general formulae: Si6-zAl zOzN8-z:kEu, Ba 1-s-tMgAl10O17:sEu,tMn, and La3-vSi6N11:vTb; and the red luminescent material is formed of any one or more of 3.5Mg•O0.5MgF2•j(Ge1-nMnn)O2•iM3N4. The composition broadens display color gamut.

Description

Luminescent material composition and illuminating device Technical field

The present invention relates to the field of optical materials, and in particular to a luminescent material composition and a light-emitting device.

Background technique

In recent years, liquid crystal display (LCD) technology has been rapidly developed, and it has been widely used in mobile phones, notebook computers, and high-definition televisions. Since the liquid crystal material itself does not emit light, the backlight becomes an indispensable key component of the liquid crystal display device. At present, the backlights of LCDs mainly include cold cathode lamps (CCFLs) and white light diodes (LEDs). The white LED has many advantages such as good color reproduction, low power consumption and long life, so its market share in the field of liquid crystal display backlights is growing rapidly.

At present, the "LED chip + phosphor" method is still the mainstream way of white LED production due to high technology maturity and relatively low cost. For liquid crystal display LED backlights, white light is mainly produced by "blue LED chip + phosphor". The commonly used schemes are three kinds of Y ₃ Al ₅ O ₁₂ :Ce(YAG:Ce) scheme, β-SiAlON:Eu green phosphor (Low-end backlight uses silicate green powder) and nitride red phosphor combination scheme, β-SiAlON: Eu green phosphor and K ₂ SiF ₆ : Mn ⁴⁺ red phosphor. In the first scheme, the spectral peaks are relatively wide and the color purity is not good, and the display color gamut display range of the display is about 70% NTSC. The second technical solution shows that the gamut range can only be increased to 80% NTSC. In the third technical solution, since the purity of the fluoride red and pink is high, the display color gamut range can only be increased to above 85% NTSC.

However, the display color gamut range of the LED devices prepared in the prior art is still low.

Summary of the invention

A main object of the present invention is to provide a luminescent material composition and a light-emitting device to solve the problem of low display gamut range of LED devices in the prior art.

In order to achieve the above object, according to an aspect of the invention, there is provided a luminescent material composition comprising: a blue luminescent material selected from the group consisting of any one or more of the following formulas: Formula Ia _2-x LuHf ₂ Al ₃ O ₁₂ :xCe, General Formula IICa _3-y Zr ₂ SiGa ₂ O ₁₂ :yCe, Formula IIIBa _1-r MgAl ₁₀ O ₁₇ :rEu and Formula IVSr _5-m (PO ₄ ) ₃ Cl:mEu, wherein 0.002≤x≤0.2, 0.002≤y≤0.2, 0.002≤r≤0.2, 0.002≤m≤0.5, Ca in the formula I may be one of Ba, Sr, Mg or a plurality of substitutions, the Al element may be substituted by one or more of B, Ga, Si; Ca in the general formula II may be substituted by one or more of Ba, Sr, Mg, and the Al element may be B, Ga, One or more substitutions in Si, Si may be substituted by Al, Ce may be substituted by one or more moieties of Eu, Dy, Tb; Ba in Formula III may be substituted by Ca and/or Sr, and Eu may be Ce and / or Mn partial substitution; Sr in Formula IV may be substituted by one or more of Ba, Ca, Mg, Eu may be partially substituted by Ce and / or Mn; green luminescent material, green luminescent material is selected from The following formula represents Any one or more of a mixture formed: Formula _{ⅤSi 6-z Al z O z} N 8-z: kEu, Formula _{ⅥBa 1-st MgAl 10 O 17} : sEu, tMn general formula ⅦLa _3-v Si ₆ Any one of N ₁₁ :vTb, wherein 0.1≤z≤0.6, 0.0001≤k≤0.1, 0.001≤s≤0.2, 0.01 ≤t≤0.6, 0<v≤0.5, Eu in the general formula V may be Ce And/or Mn partial substitution; Ba in formula VI may be substituted by Ca and/or Sr, Eu may be substituted by Ce moiety; La in formula VII may be substituted by one or more of Y, Lu, Gd , Si may be substituted by one or more of C, Ge, Ti, N may be substituted by O moiety, Tb may be substituted by Ce and/or Eu, and Si _6-z Al _z O _z N _8-z : kEu Has the same crystal structure as Si ₅ AlON ₇ ; red luminescent material, red luminescent material is any one of general formula VIII3.5MgO·0.5MgF ₂ ·j(Ge _1-n Mn _n )O ₂ ·iM ₃ N ₄ Or a plurality of formed mixtures, wherein F may be substituted by one or more of Cl, Br, I, Ge may be substituted by Ti and/or Si, and Mg may be one or more of Ca, Sr, Ba Substituting, the M element is selected from the group consisting of Si and/or Ti, 0.77 ≤ j < 0.90, 0 ≤ i ≤ 0.067, and 0.015 ≤ n ≤ 0.03.

Further, the blue light-emitting material is any one of Ba _1-r MgAl ₁₀ O ₁₇ :rEu and Sr _5-m (PO ₄ ) ₃ Cl:mEu, and the green light-emitting material is La _3-v Si ₆ N ₁₁ : Any one of vTb and Ba _1-st MgAl ₁₀ O ₁₇ : sEu, tMn.

Further, in the above formula VIII, 0.05 ≤ i ≤ 0.067.

Further, the green light-emitting material is any one of Si _6-z Al _z O _z N _8-z :kEu and Ba _1-st MgAl ₁₀ O ₁₇ :sEu, tMn.

Further, in the above formula VIII, 0.05 ≤ i ≤ 0.067.

According to another aspect of the present invention, a light emitting device includes an LED chip and a light conversion portion, and the light conversion portion absorbs primary light emitted from the LED chip and converts it into a higher wavelength secondary light, and the light conversion portion The luminescent material is contained, and the luminescent material is a luminescent material of any of the above.

Further, the LED chip emits a peak wavelength range of 355 to 375 nm, and the blue light-emitting material of the luminescent material is any one of Ba _1-r MgAl ₁₀ O ₁₇ :rEu and Sr _5-m (PO ₄ ) ₃ Cl:mEu. The green luminescent material is any one of La _3-v Si ₆ N ₁₁ :vTb and Ba _1-st MgAl ₁₀ O ₁₇ :sEu, tMn.

Further, the red luminescent material in the luminescent material is a mixture of any one or more of 3.5MgO·0.5MgF ₂ ·j(Ge _1-n Mn _n )O ₂ ·iM ₃ N ₄ , wherein 0.05≤ i ≤ 0.067.

Further, the LED chip emits a peak wavelength in the range of 360 to 370 nm, preferably 362 to 367 nm.

Further, the LED chip emits a peak wavelength range of 380 to 420 nm, and the green light-emitting material in the luminescent material is Si _6-z Al _z O _z N _8-z : kEu and Ba _1-st MgAl ₁₀ O ₁₇ : sEu, tMn Any one.

Further, the red luminescent material in the luminescent material is a mixture of any one or more of 3.5MgO·0.5MgF ₂ ·j(Ge _1-n Mn _n )O ₂ ·iM ₃ N ₄ , wherein 0.05≤ i ≤ 0.067.

Further, the LED chip emits a peak wavelength in the range of 390 to 410 nm, preferably 400 to 407 nm.

According to the technical solution of the present invention, the luminescent material composition comprises a blue luminescent material having a stable structure, a green luminescent material having a relatively high radiant energy, and a red luminescent material having a longer wavelength, which can be expanded when applied to a white light LED light source. The spectral range of the white light emitted by the wide white LED further broadens the display color gamut range when the white LED is used for the backlight of the display device, and improves the display effect of the liquid crystal display device.

DRAWINGS

The accompanying drawings, which are incorporated in the claims of the claims In the drawing:

1 is a schematic cross-sectional structural view of a light-emitting device provided by the present invention;

2 is a luminescence spectrum of the blue light-emitting material Sr _4.8 (PO ₄ ) ₃ Cl:0.2Eu provided by the present invention;

Figure 3 is a luminescence spectrum of the green luminescent material Ba _0.85 MgAl ₁₀ O ₁₇ : 0.05Eu, 0.1 Mn provided by the present invention;

_{4 is} a luminescence spectrum of a red luminescent material 3.5MgO· _{0.5MgF 2} ·0.85(Ge _0.9821 Mn _0.0179 )O ₂ ·0.15/3Si ₃ N ₄ provided by the present invention.

Wherein, the above figures include the following reference numerals:

2, LED chip; 3, light conversion department.

detailed description

It should be noted that the embodiments in the present application and the features in the embodiments may be combined with each other without conflict. The invention will be described in detail below with reference to the drawings in conjunction with the embodiments.

The inventors of the present invention analyzed the factors influencing the display color gamut of the LED device one by one, and found that the conventional green phosphor has lower luminescence energy, and the fluoride series red powder has a shorter emission peak, which leads to the display gamut range of the LED device. Lower, for this reason, the present application has performed various performance tests on the prior art green light-emitting materials and red light-emitting materials, and proposed a new combination of light-emitting materials and a light-emitting device using the same.

In an exemplary embodiment of the present application, a luminescent material composition is provided, including a blue luminescent material, a green luminescent material, and a red luminescent material, and the blue luminescent material is represented by any one or more of the following formulas. A mixture formed: general formula ICa _2-x LuHf ₂ Al ₃ O ₁₂ :xCe, general formula IICa _3-y Zr ₂ SiGa ₂ O ₁₂ :yCe, general formula IIIBa _1-r MgAl ₁₀ O ₁₇ :rEu and general formula IVSr _5-m (PO ₄ ) ₃ Cl:mEu, wherein 0.002≤x≤0.2, 0.002≤y≤0.2, 0.002≤r≤0.2, 0.002≤m≤0.5, Ca in the formula I can be Ba, Sr, One or more substitutions in Mg, Al may be substituted by one or more of B, Ga, Si; Ca in Formula II may be substituted by one or more of Ba, Sr, Mg, and Al may be Substituted by one or more of B, Ga, Si, Si may be substituted by Al, and Ce may be substituted by one or more moieties of Eu, Dy, Tb; Ba in the general formula III may be Ca and / Or Sr substituted, Eu may be partially substituted by Ce and / or Mn; Sr in the general formula IV may be substituted by one or more of Ba, Ca, Mg, Eu may be partially substituted by Ce and / or Mn; Green luminescent material, the green Forming a mixture of any one or more luminescent material is selected from the following general formula: Formula _{ⅤSi 6-z Al z O z} N 8-z: kEu, Formula _{ⅥBa 1-st MgAl 10 O 17} : sEu, tMn And any one of the formula VIILa _3-v Si ₆ N ₁₁ :vTb, wherein 0.1≤z≤0.6, 0.0001≤k≤0.1, 0.001≤s≤0.2, 0.01≤t≤0.6, 0<v≤0.5, The Eu in the general formula V may be partially substituted by Ce and/or Mn; the Ba in the general formula VI may be substituted by Ca and/or Sr, and the Eu may be substituted by a Ce moiety; It may be substituted by one or more of Y, Lu, Gd, Si may be substituted by one or more of C, Ge, Ti, N may be substituted by O moiety, and Tb may be substituted by Ce and/or Eu. And Si _6-z Al _z O _z N _8-z :kEu has the same crystal structure as Si ₅ AlON ₇ ; red luminescent material, the red luminescent material is of the formula VIII3.5MgO·0.5MgF ₂ ·j (Ge ₁ a mixture of any one or more of _-n Mn _n )O ₂ ·iM ₃ N ₄ wherein F may be substituted by one or more of Cl, Br, I, and Ge may be Ti and/or Substituting Si, Mg may be substituted by one or more of Ca, Sr, Ba, M element is selected from Si and/or Ti, 0.77≤j<0.9 0, 0 ≤ i ≤ 0.067, 0.015 ≤ n ≤ 0.03.

The luminescent material composition includes a blue luminescent material having a stable structure, a green luminescent material having a relatively high radiant energy, and a red luminescent material having a longer wavelength, which can broaden the white light emitted by the white LED when applied to the white LED light source. The spectral range further broadens the display color gamut range when the white LED is used for the backlight of the display device, and improves the display effect of the liquid crystal display device.

In a preferred embodiment of the present application, the blue light-emitting material is any one of Ba _1-r MgAl ₁₀ O ₁₇ :rEu and Sr _5-m (PO ₄ ) ₃ Cl:mEu, and the green light-emitting material is La. _3-v Si ₆ N ₁₁ :vTb and Ba _1-st MgAl ₁₀ O ₁₇ : sEu, tMn. The luminescent material composition formed by the above blue luminescent material, green luminescent material and red luminescent material emits a wider spectrum of white light under the excitation of an LED chip emitting a peak wavelength range of 355 to 375 nm, and displays the LED display device. The expansion effect of the color gamut is more obvious.

In order to further broaden the display color gamut by utilizing the change in the wavelength of the red luminescent material, it is preferable that 0.05 ≤ i ≤ 0.067 in the above 3.5 MgO·0.5 MgF ₂ ·j(Ge _1-n Mn _n )O ₂ ·iM ₃ N ₄ .

In another preferred embodiment of the present application, preferably, the green luminescent material is any one of Si _6-z Al _z O _z N _8-z : kEu and Ba _1-st MgAl ₁₀ O ₁₇ : sEu, tMn . The luminescent material composition formed by the above blue luminescent material, green luminescent material and red luminescent material emits a wider spectrum of white light under the excitation of an LED chip emitting a peak wavelength range of 380 to 420 nm, and displays the LED display device. The expansion effect of the color gamut is more obvious.

In order to further broaden the display color gamut by utilizing the change in the wavelength of the red luminescent material, it is preferable that 0.05 ≤ i ≤ 0.067 in the above 3.5 MgO·0.5 MgF ₂ ·j(Ge _1-n Mn _n )O ₂ ·iM ₃ N ₄ .

In another exemplary embodiment of the present application, a light-emitting device is provided. As shown in FIG. 1 , the light-emitting device includes an LED chip 2 and a light conversion portion 3, and the light conversion portion 3 absorbs the primary light emitted by the LED chip 2, And converted into secondary light of a higher wavelength, the light conversion part contains a light-emitting material, and the light-emitting material is any one of the above-mentioned light-emitting materials.

The luminescent material composition includes a blue luminescent material having a stable structure, a green luminescent material having a relatively high luminescent energy, and a red luminescent material having a longer wavelength, which can broaden the spectral range of the emitted white light when applied to the illuminating device. Further, when the white LED is used for the backlight of the display device, the color gamut range is displayed, and the display effect of the liquid crystal display device is improved.

In another preferred embodiment of the present application, the LED chip 2 emits a peak wavelength range of 355-375 nm, and the blue luminescent material in the luminescent material is Ba _1-r MgAl ₁₀ O ₁₇ :rEu and Sr _5-m (PO ₄ Any one of ₃ Cl:mEu, the green luminescent material is any one of La _3-v Si ₆ N ₁₁ :vTb and Ba _1-st MgAl ₁₀ O ₁₇ :sEu, tMn. Under the excitation of the LED chip, the luminescent material composition formed by the blue luminescent material, the green luminescent material and the red luminescent material emits a wider spectrum of white light, and the effect of expanding the display gamut of the LED display device is more obvious.

In order to further broaden the display color gamut by utilizing the change in the wavelength of the red luminescent material, it is preferable that the red luminescent material in the luminescent material is any of 3.5MgO·0.5MgF ₂ ·j(Ge _1-n Mn _n )O ₂ ·iM ₃ N ₄ . One or more formed mixtures, wherein 0.05 ≤ i ≤ 0.067. In order to increase the blue light excitation energy to expand the display color gamut, it is further preferred that the LED chip 2 emits a peak wavelength range of 360 to 370 nm, more preferably 362 to 367 nm.

In still another preferred embodiment of the present application, the LED chip 2 emits a peak wavelength range of 380 to 420 nm, and the green light-emitting material of the luminescent material is Si _6-z Al _z O _z N _8-z : kEu and Ba _1-st MgAl ₁₀ O ₁₇ : sEu, tMn. Under the excitation of the LED chip, the luminescent material composition formed by the blue luminescent material, the green luminescent material and the red luminescent material emits a wider spectrum of white light, and the effect of expanding the display gamut of the LED display device is more obvious.

In order to further broaden the display color gamut by utilizing the change in the wavelength of the red luminescent material, it is preferable that the red luminescent material in the luminescent material is any of 3.5MgO·0.5MgF ₂ ·j(Ge _1-n Mn _n )O ₂ ·iM ₃ N ₄ . One or more formed mixtures, wherein 0.05 ≤ i ≤ 0.067.

As described above, the present application includes a luminescent material composition of a blue luminescent material, a green luminescent material, and a red luminescent material, which can broaden the spectral range of white light emitted by the white LED when applied to a white LED light source, thereby widening When the white LED is used for a backlight of a display device, the color gamut range is displayed, and the display effect of the liquid crystal display device is improved. The amount of each of the above-mentioned luminescent materials has no essential influence on the realization of the above effects. In order to adjust the light intensity, color temperature and the like of the emitted white light to a conventional preferred range, it is preferable that the weight ratio of the blue luminescent material, the green luminescent material and the red luminescent material is (1 to 3): (2 to 6): (2 to 4).

In order to increase the blue light excitation energy to expand the display color gamut, it is further preferred that the LED chip 2 emits a peak wavelength in the range of 390 to 410 nm, more preferably 400 to 407 nm.

The light-emitting device of the present application is not particularly limited as long as it has the above characteristics. As the sealant, silica gel, epoxy resin, silicone resin, urea resin or the like can be used, but it is not limited thereto. Further, the light conversion unit may contain an additive such as SiO ₂ , TiO ₂ , ZrO ₂ or Al ₂ O _{3 in} addition to the phosphor and the sealant.

Incidentally, the blue light-emitting material, the green light-emitting material, and the red light-emitting material used in the light-emitting device of the present invention may be produced by a known appropriate method or may be directly obtained.

Advantageous effects of the present application will be further described below in conjunction with the examples and comparative examples.

Comparative example 1

An LED light-emitting device was prepared in the manner as shown in FIG. The LED chip 2 is a peak wavelength chip at 450 nm, the green light-emitting material in the light conversion portion 3 is Si _5.70 Al _0.30 O _0.30 N _7.70 : 0.05Eu ²⁺ , and the red luminescent material is K ₂ SiF ₆ : 0.01 Mn ⁴⁺ . The green light-emitting material and the red light-emitting material were mixed and dispersed in a silica gel at a weight ratio of 25:75 to prepare a light conversion portion. The light conversion portion is further assembled into an LED light emitting device.

Comparative example 2

An LED light-emitting device was prepared in the manner as shown in FIG. The LED chip 2 is a peak wavelength chip at 365 nm, the blue light-emitting material in the light conversion portion 3 is Ba _0.85 MgAl ₁₀ O ₁₇ :0.15Eu, and the green light-emitting material is Lu _2.94 Al ₅ Si ₁₂ :0.06Ce, red light-emitting material. Ca _0.99 AlSiN ₃ : 0.01 Eu was used. The blue light-emitting material, the green light-emitting material and the red light-emitting material were mixed and dispersed in a silica gel at a weight ratio of 25:40:35 (the weight ratio of the silica gel to the phosphor was 88:12) to prepare a light conversion portion. The light conversion portion is further assembled into an LED light emitting device.

Example 1

The white LED light-emitting device of the present invention was prepared in the manner as shown in FIG. Wherein, the LED chip 2 is a peak wavelength chip at 365 nm, the blue light in the light conversion portion 3 is Ba _0.85 MgAl ₁₀ O ₁₇ : 0.15Eu, and the green light emitting material is La _2.84 Si ₆ N ₁₁ : 0.16 Tb, red light emitting material. _{3.5 MgO} · _{0.5 MgF 2} ·0.85 (Ge _0.9821 Mn _0.0179 )O ₂ ·0.15/3Si ₃ N _{4 was used} . The blue light-emitting material, the green light-emitting material and the red light-emitting material were mixed and dispersed in a silica gel at a weight ratio of 30:40:30 (the weight ratio of the silica gel to the phosphor was 90:10) to prepare a light conversion portion. The light conversion portion is further assembled into an LED light emitting device.

Example 2

The white LED light-emitting device of the present invention was prepared in the manner as shown in FIG. The LED chip 2 is a peak wavelength chip at 405 nm, the blue light-emitting material in the light conversion portion 3 is Sr _4.8 (PO ₄ ) ₃ Cl: 0.2Eu, and the green light-emitting material is Ba _0.5 MgAl ₁₀ O ₁₇ : 0.07Eu, 0.43. Mn, red luminescent material is 3.5MgO·0.5MgF ₂ ·0.8(Ge _0.981 Mn _0.019 )O ₂ ·0.2/3Si ₃ N ₄ . The blue light-emitting material, the green light-emitting material and the red light-emitting material are mixed and dispersed in an epoxy resin at a weight ratio of 25:45:30 (the weight ratio of the epoxy resin to the phosphor is 92:8) to prepare a light conversion portion. . The light conversion portion is further assembled into an LED light emitting device.

The preparation process of the embodiment 3-12 is basically the same as that of the embodiment 2, and different LED chips and luminescent materials are used, as shown in Table 1.

Table 1

The light effect and color coordinates were detected by HAAS-2000 high-precision fast spectrum analyzer. The color gamut was calculated by color coordinate and color gamut calculation formula. The test results are shown in Table 2.

Table 2

	Display color gamut (%NTSC)	Light efficiency (lm/W)
Comparative example 1	90	95
Comparative example 2	91	90
Example 1	98	98
Example 2	95	96
Example 3	96	95
Example 4	95	97
Example 5	96	96
Example 6	94	98
Example 7	97	94
Example 8	94	97
Example 9	93	98
Example 10	94	96
Example 11	93	96
Example 12	93	98

As can be seen from the data in Table 2, when the light converting portion is a mixture formed of the luminescent material of the present application, the display color gamut of the illuminating device is remarkably improved while maintaining high luminous efficiency. In addition, according to the comparison of Examples 1 and 2, it can be found that when the luminescent material composition is combined with the LED chip having an appropriate emission peak wavelength, the display color gamut can be further broadened, and the light effect can be improved.

From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:

The luminescent material composition includes a blue luminescent material having a stable structure, a green luminescent material having a relatively high radiant energy, and a red luminescent material having a longer wavelength, which can broaden the white light emitted by the white LED when applied to the white LED light source. The spectral range further broadens the display color gamut range when the white LED is used for the backlight of the display device, and improves the display effect of the liquid crystal display device.

The above description is only the preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes can be made to the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims (12)

1. A luminescent material composition, comprising:

   a blue luminescent material selected from the group consisting of any one or more of the following formulas: Formula ICa _2-x LuHf ₂ Al ₃ O ₁₂ :xCe, Formula IICa _3-y Zr ₂ SiGa ₂ O ₁₂ :yCe, the general formula IIIBa _1-r MgAl ₁₀ O ₁₇ :rEu and the general formula IVSr _5-m (PO ₄ ) ₃ Cl:mEu, wherein 0.002≤x≤0.2, 0.002≤y≤0.2, 0.002≤r≤0.2, 0.002≤m≤0.5, Ca in the general formula I may be substituted by one or more of Ba, Sr, Mg, and the Al element may be one or more of B, Ga, Si Substituting; Ca in the general formula II may be substituted by one or more of Ba, Sr, Mg, Al may be substituted by one or more of B, Ga, Si, Si may be substituted by Al, Ce may Substituted by one or more moieties of Eu, Dy, Tb; Ba in the general formula III may be substituted by Ca and/or Sr, and Eu may be partially substituted by Ce and/or Mn; Sr may be substituted by one or more of Ba, Ca, Mg, and Eu may be partially substituted by Ce and/or Mn;

   a green luminescent material selected from the group consisting of any one or more of the following formulas: a formula VSi _6-z Al _z O _z N _8-z : kEu, a formula VIBa _1-st MgAl ₁₀ O ₁₇ : sEu, tMn and any one of the formula VIILa _3-v Si ₆ N ₁₁ :vTb, wherein 0.1≤z≤0.6, 0.0001≤k≤0.1, 0.001≤s≤0.2, 0.01≤t≤0.6 , 0 < v ≤ 0.5, Eu in the general formula V may be partially substituted by Ce and / or Mn; Ba in the general formula VI may be substituted by Ca and / or Sr, Eu may be partially substituted by Ce; La in the general formula VII may be substituted by one or more of Y, Lu, Gd, Si may be substituted by one or more of C, Ge, Ti, N may be substituted by O moiety, and Tb may be Ce and/or Eu substituted, and Si _6-z Al _z O _z N _8-z :kEu has the same crystal structure as Si ₅ AlON ₇ ;

   a red luminescent material, the red luminescent material being a mixture of any one or more of the formula VIII3.5MgO·0.5MgF ₂ ·j(Ge _1-n Mn _n )O ₂ ·iM ₃ N ₄ , wherein F may be substituted by one or more of Cl, Br, I, Ge may be substituted by Ti and/or Si, Mg may be substituted by one or more of Ca, Sr, Ba, and M element is selected from Si and / or Ti, 0.77 ≤ j < 0.90, 0 ≤ i ≤ 0.067, 0.015 ≤ n ≤ 0.03.
2. The luminescent material composition according to claim 1, wherein the blue luminescent material is any one of Ba _1-r MgAl ₁₀ O ₁₇ :rEu and Sr _5-m (PO ₄ ) ₃ Cl:mEu The green luminescent material is any one of La _3-v Si ₆ N ₁₁ :vTb and Ba _1-st MgAl ₁₀ O ₁₇ :sEu, tMn.
3. The luminescent material composition according to claim 1 or 2, wherein 0.05 ≤ i ≤ 0.067 in the formula VIII.
4. The luminescent material composition according to claim 1, wherein the green luminescent material is Si _6-z Al _z O _z N _8-z : kEu and Ba _1-st MgAl ₁₀ O ₁₇ : sEu, tMn Any of them.
5. The luminescent material composition according to claim 1 or 4, wherein 0.05 ≤ i ≤ 0.067 in the formula VIII.
6. A light-emitting device, characterized in that the light-emitting device comprises an LED chip (2) and a light conversion portion (3), and the light conversion portion (3) absorbs the primary light emitted by the LED chip (2) and converts it into The higher wavelength secondary light, the light conversion portion containing a light-emitting material, the light-emitting material being the light-emitting material according to any one of claims 1 to 5.
7. The illuminating device according to claim 6, wherein the LED chip (2) emits a peak wavelength range of 355 to 375 nm, and the blue luminescent material of the luminescent material is Ba _1-r MgAl ₁₀ O ₁₇ :rEu and Any one of Sr _5-m (PO ₄ ) ₃ Cl:mEu, the green light-emitting material is any one of La _3-v Si ₆ N ₁₁ :vTb and Ba _1-st MgAl ₁₀ O ₁₇ :sEu, tMn.
8. The illuminating device according to claim 6 or 7, wherein the red luminescent material in the luminescent material is 3.5MgO·0.5MgF ₂ ·j(Ge _1-n Mn _n )O ₂ ·iM ₃ N ₄ Any one or more of the resulting mixtures, wherein 0.05 ≤ i ≤ 0.067.
9. Light-emitting device according to claim 8, characterized in that the LED chip (2) emits a peak wavelength in the range of 360 to 370 nm, preferably 362 to 367 nm.
10. The illuminating device according to claim 6, wherein the LED chip (2) emits a peak wavelength range of 380 to 420 nm, and the green luminescent material of the luminescent material is Si _6-z Al _z O _z N _8-z : kEu and Ba _1-st MgAl ₁₀ O ₁₇ : sEu, tMn.
11. The illuminating device according to claim 6 or 10, wherein the red luminescent material in the luminescent material is 3.5MgO·0.5MgF ₂ ·j(Ge _1-n Mn _n )O ₂ ·iM ₃ N ₄ Any one or more of the resulting mixtures, wherein 0.05 ≤ i ≤ 0.067.
12. Light-emitting device according to claim 11, characterized in that the LED chip (2) emits a peak wavelength in the range from 390 to 410 nm, preferably from 400 to 407 nm.

Images