CN103173217B - Heatproof nitride fluorescent material and the light-emitting device containing it - Google Patents

Abstract

The invention relates to a kind of heatproof nitride fluorescent material and the light-emitting device containing it, a kind of its heatproof nitride fluorescent material, there is the chemical formula of lower formula (I)：M¹ _yM² ₅O_zN_x:M³ _w(I) M of formula (I)¹、M²、M³, x, y, w and z be person as defined in description and claim.The present invention separately provides a kind of light-emitting device, comprise the light-emitting diodes material elements that can send a light source, and it is arranged at aforementioned heatproof nitride fluorescent material on this light-emitting diodes material elements, this heatproof nitride fluorescent material is lighted by absorbing this light source of at least a portion.The heatproof nitride fluorescent material of the present invention possesses good heat-resistant stability, and when being applied to light-emitting device, releasing photochromic naturally not dazzling.

Description

Heatproof nitride fluorescent material and the light-emitting device containing it

Technical field

The present invention relates to a kind of fluorescent material, more particularly to a kind of heatproof nitride fluorescent material.

Background technology

Day, sub- chemical industry started from 1996 to produce white light LEDs.United States Patent (USP) 5,998,925 discloses one kind and adopts wavelength The blue light-emitting diode of 450nm to 470nm as luminescence unit, with the yttrium-aluminium garnet fluorescence using cerium as active centre Material (Y₃Al₅O₁₂:Ce³⁺, also known as YAG:Ce³⁺) be combined, and obtain the luminescent system producing white light.Luminescence unit sends The relatively wide spectrum (spectral centroid is 580nm) that some blue light is absorbed by the phosphor and is converted into based on gold-tinted is released, due to big The gold-tinted radiation energy of amount stimulates HONGGUANG and green glow receptor in human eye, adds that original a small amount of blue ray radiation have stimulated blue light receptor, Appear as and create white light.

But blue-ray LED with the shortcoming being combined in inherently of YAG fluorescent powder is：Lead to color rendering because lacking HONGGUANG Not good, luminous efficiency can be reduced with being increased using temperature, and excites lower released light in high power light source, and its temperature is steady Qualitative not good.

For improving the shortcoming of YAG, many researchs are improved towards adding Si or S.Because silicon or silicate substrate have Higher heat stability and chemical stability, have stronger absorption in ultraviolet region, and highly purified silicon or earth silicon material Cheap and easy acquirement, therefore with Si⁴⁺Substitute Al³⁺Rare-earth ion activated siliceous luminescent material cause the attention of height.

US 2010/0142182 discloses a kind of illuminator, comprises a luminaire containing the first light-emitting component, and Second light-emitting component detached with luminaire.This first light-emitting component is provided with fluorescent material, can for example include Si and N with cerium As the yttrium-aluminium garnet fluorescent material of activator, this fluorescent material has following formula：

(Y_1-α-β-a-bLu_αGd_β)₃(Al_5-u-vGa_uSi_v)O_12-vN_v:Ce_a ³⁺

Wherein, 0≤α ＜ 1,0≤β ＜ 1,0 ＜ (alpha+beta+a+b)≤1,0≤u≤1,0 ＜ v ＜ 1,0 ＜ a≤0.2.

This fluorescent material is to be improved based on the structure of YAG, but the inherent defect containing Si fluorescent material is tolerable temperature Relatively low and more unstable, and release photochromic more gorgeous, easily overstimulation can be caused to human eye.If life-time service, easily cause People eyestrain.Though this fluorescent material adds the higher nitrogen of sintering temperature, its sintering temperature is 1500 DEG C, and tolerable temperature is still So relatively low and stability is not enough, it is similar to the YAG material not modified that it drills colour index (Ra value), all less than 80% and such It is more that fluorescent material is used for required deal during light-emitting device.

From the foregoing, a kind of research and development tolerable temperature height, color rendering and good thermal stability, and photochromic naturally not dazzling Fluorescent material is the current important topic of technique.

As can be seen here, above-mentioned existing fluorescent material method, product structure and use on it is clear that still suffered from inconvenience with Defect, and be urgently further improved.In order to solve above-mentioned problem, relevant manufactures there's no one who doesn't or isn't painstakingly to be sought to solve Jue Zhi road, but have no that applicable design is developed completing for a long time always, and conventional method and product do not have appropriate side Method and structure can solve the problem that the problems referred to above, and this is clearly the problem that related dealer suddenly to be solved.Therefore how to found a kind of new Heatproof nitride fluorescent material and the light-emitting device containing it, real belong to currently one of important research and development problem, also become current industry Boundary pole needs improved target.

Content of the invention

It is an object of the invention to, overcome the defect that existing fluorescent material exists, and provide a kind of new heatproof to nitrogenize Thing fluorescent material, technical problem to be solved is that the method for in the past improvement YAG mainly replaces Al with Si, and the present inventor is in view of contain The fluorescent material of Si is more unstable and photochromic more gorgeous dazzling under high temperature, therefore develops one kind to replace portion to add N Divide 0, and do not contain the fluorescent material of Si.Therefore, the first object of the present invention, that is, providing a kind of Heat-resistant stable degree high and photochromic Naturally heatproof nitride fluorescent material, is very suitable for practicality.

Another object of the present invention is to, a kind of light-emitting device is provided, comprises a light-emitting diodes material that can send a light source Material element, and it is arranged at the aforementioned heatproof nitride fluorescent material on this light-emitting diodes material elements；This heatproof nitride fluorescent Material is lighted by absorbing this light source of at least a portion, thus more suitable for practicality.

The object of the invention to solve the technical problems employs the following technical solutions to realize.Propose according to the present invention Its there is the chemical formula of lower formula (I)：

M¹ _yM² ₅O_zN_x:M³ _w(I)

M¹It is selected from Sc³⁺、Y³⁺、La³⁺、Sm³⁺、Gd³⁺、Pm³⁺、Er³⁺、Lu³⁺, or an aforesaid combination；M²Selected from Al^{3 +}、In³⁺、Ga³⁺, or an aforesaid combination；M³It is selected from Tm³⁺、Bi³⁺、Tb³⁺、Ce³⁺、Eu³⁺、Mn³⁺、Er³⁺、Yb³⁺、Ho³⁺、Gd^{3 +}、Pr³⁺、Dy³⁺、Nd³⁺, or an aforesaid combination；And x is the integer of 3-8,2.7≤y≤3,0 ＜ w≤0.3, and 0≤z≤7.5.

The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.

Aforesaid heatproof nitride fluorescent material, wherein said in 0.01≤w≤0.06.

Aforesaid heatproof nitride fluorescent material, this wherein said heatproof nitride fluorescent material is to be selected from Y_2.98Al₅O_7.5N₃:Tm_0.02、

Y_2.95Al₅O₆N₄:Bi_0.05、

Y_2.94Al₅O₆N₄:Tb_0.06、

Y_2.95Al₅O_7.5N₃:Ce_0.05、

Y_2.95Al₅O₆N₄:Ce_0.05、

Y_2.95Al₅O_4.5N₅:Ce_0.05、

Y_2.95Al₅O₆N₄:Mn_0.05、

Y_2.75GaAl₄O₆N₄:Mn_0.25、

Y_2.94Al₅N₈:Bi_0.06、

Y_2.94Al₅N₈:Tm_0.06、

Y_2.95Al₅N₈:Ce_0.05、

Y_2.95Al₅N₈:Mn_0.05、

Y_2.95Ga₅N₈:Mn_0.05、

Y_2.94Al₅O₆N₄:Bi_0.06、

Y_2.94Al₅O₆N₄:Mn_0.06、

Y_2.94Al₅O₆N₄:Ce_0.06、

Lu_1.72Gd_1.2Al₅O₆N₄:Ce_0.05Pr_0.03、

Lu_1.72Er₁Ga₅O_4.5N₅:Mn_0.25Dy_0.03、

Lu_1.92Sc₁Al₅O₆N₄:Ce_0.05Yb_0.03、

Sm_1.92La₁Al₅O₆N₄:Ce_0.05Ho_0.03、

Y_2.32Gd_0.6In₁Al₄O₆N₄:Ce_0.05Nd_0.03,

Or Lu_1.95Pm₁Al₅O₆N₄:Ce_0.05.

Aforesaid heatproof nitride fluorescent material, the radiation wave-length coverage of wherein said this heatproof nitride fluorescent material For 380-700nm.

Aforesaid heatproof nitride fluorescent material, the excitation wavelength range of wherein said this heatproof nitride fluorescent material For 250-500nm.

The object of the invention to solve the technical problems also employs the following technical solutions to realize.According to proposed by the present invention A kind of light-emitting device, it comprises：One light-emitting diodes material elements, can send a light source；And one by claim the 1-5 item appoint Heatproof nitride fluorescent material described in one, is disposed on this light-emitting diodes material elements；This heatproof nitride fluorescent material Material is lighted by absorbing this light source of at least a portion.

The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.

Aforesaid light-emitting device, the radiation wave-length coverage of this wherein said heatproof nitride fluorescent material is 380- 700nm.

By technique scheme, heatproof nitride fluorescent material of the present invention and under at least having containing its light-emitting device Row advantage and beneficial effect：This heatproof nitride fluorescent material, via various difference elements of arranging in pairs or groups, makes this heatproof nitride fluorescent Required coloured light released by material；Compare with the material that the past is improved based on YAG, the present invention does not contain S or Si, and It is that part or all of O, the covalent bond structure being had by N are replaced with N, make this nitride fluorescent material improved thermo stability, Tolerable temperature is higher；When this heatproof nitride fluorescent material is applied to light-emitting device, after light source activation, that is released is photochromic More naturally not dazzling, and color rendering is preferable.

In sum, heatproof nitride fluorescent material of the present invention and the light-emitting device containing it, a kind of its heatproof nitride Fluorescent material, has the chemical formula of lower formula (I)：

M¹ _yM² ₅O_zN_x:M³ _w(I)

The M of formula (I)¹、M²、M³, x, y, w and z be person as defined in description and claim.The present invention separately carries For a kind of light-emitting device, comprise the light-emitting diodes material elements that can send a light source, and be arranged at this light-emitting diodes material unit Aforementioned heatproof nitride fluorescent material on part, this heatproof nitride fluorescent material is sent out by absorbing this light source of at least a portion Light.The heatproof nitride fluorescent material of the present invention possesses good heat-resistant stability, and when being applied to light-emitting device, releasing photochromic Naturally not dazzling.The present invention is a significant progress in technology, and has obvious good effect, really novel, progressive, real for one New design.

Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention, And can be practiced according to the content of description, and in order to allow the above and other objects of the present invention, feature and advantage can Become apparent, below especially exemplified by preferred embodiment, and coordinate accompanying drawing, describe in detail as follows.

Brief description

Fig. 1 is a relative spectral power distributions figure, and the relative spectral power of embodiment 13 and comparative example 2 is described；A () is real Applying the analysis result of example 13 and (b) is the analysis result of comparative example 2；

Fig. 2 is a radiating light spectrogram；

Fig. 3 is a radiating light spectrogram；

Fig. 4 is a CIE chromaticity coordinate figure；

Fig. 5 is a CIE chromaticity coordinate figure；And

Fig. 6 is a light decay curve chart, and the light decay curve of embodiment 5 and comparative example 1 is described；A () is the analysis knot of embodiment 5 Fruit and (b) are the analysis result of comparative example 1.

Specific embodiment

For further illustrating that the present invention is to reach technological means and effect that predetermined goal of the invention is taken, below in conjunction with Accompanying drawing and preferred embodiment, to according to heatproof nitride fluorescent material proposed by the present invention and it is concrete containing its light-emitting device Embodiment, method, step, structure, feature and its effect, after describing in detail such as.

Heatproof nitride fluorescent material of the present invention, has the chemical formula of lower formula (I)：

M¹ _yM² ₅O_zN_x:M³ _w(I)

M¹For active centre metallic element, it is trivalent rare earth element.M¹It is selected from Sc³⁺、Y³⁺、La³⁺、Sm³⁺、Gd³⁺、 Pm³⁺、Er³⁺、Lu³⁺, or an aforesaid combination.

This M²For anion lattice, it is selected from Al³⁺、In³⁺、Ga³⁺, or an aforesaid combination.

This M³For active centre metallic element, or for the element that adds lustre to, there is fine setting effect, contribute to lifting the nitridation of this heatproof The brightness of thing fluorescent material.M³It is selected from Tm³⁺、Bi³⁺、Tb³⁺、Ce³⁺、Eu³⁺、Mn³⁺、Er³⁺、Yb³⁺、Ho³⁺、Gd³⁺、Pr³⁺、Dy^{3 +}、Nd³⁺, or an aforesaid combination.

In formula (I), 3≤x≤8,2.7≤y≤3,0 ＜ w≤0.3, and 0≤z≤7.5.

The present invention, via various difference elements of arranging in pairs or groups, makes this heatproof nitride fluorescent material release required coloured light；And The present invention replaces part or all of 0 with N, and because N has covalent bond structure, this heatproof nitride fluorescent material is bonded strength enhancing Not easy fracture, tolerable temperature improves, and sintering temperature is at 1800 DEG C, and good thermal stability.

Separately, as active centre metallic element M³Including Tm³⁺Or Bi³⁺When, this heatproof fluorescent material is released after being subject to light source activation Blue light, as active centre metallic element M³Including Tb³⁺Or Ce³⁺When, this heatproof fluorescent material releases green-yellow light after being subject to light source activation, As active centre metallic element M³Including Eu³⁺Or Mn³⁺When, this heatproof fluorescent material releases HONGGUANG after being subject to light source activation.This activation Central metal element (or the element that claims to add lustre to) is in addition to related to radiation optical wavelength, it helps lift this heatproof nitride fluorescent material The intensity of giving out light of material.

It is preferred that 0.01≤w≤0.06.When w is less than 0.01, the luminance shortage of this heatproof nitride fluorescent material；When When this w is more than 0.06, the radiation wavelength of this heatproof nitride fluorescent material can increase, and leads to brightness to decline.It is more preferably 0.01≤w≤0.03.

It is preferred that this heatproof nitride fluorescent material is to be selected from

Y_2.98Al₅O_7.5N₃:Tm_0.02、

Y_2.95Al₅O₆N₄:Bi_0.05、

Y_2.94Al₅O₆N₄:Tb_0.06、

Y_2.95Al₅O_7.5N₃:Ce_0.05、

Y_2.95Al₅O₆N₄:Ce_0.05、

Y_2.95Al₅O_4.5N₅:Ce_0.05、

Y_2.95Al₅O₆N₄:Mn_0.05、

Y_2.75GaAl₄O₆N₄:Mn_0.25、

Y_2.94Al₅N₈:Bi_0.06、

Y_2.94Al₅N₈:Tm_0.06、

Y_2.95Al₅N₈:Ce_0.05、

Y_2.95Al₅N₈:Mn_0.05、

Y_2.95Ga₅N₈:Mn_0.05、

Y_2.94Al₅O₆N₄:Bi_0.06、

Y_2.94Al₅O₆N₄:Mn_0.06、

Y_2.94Al₅O₆N₄:Ce_0.06、

Lu_1.72Gd_1.2Al₅O₆N₄:Ce_0.05Pr_0.03、

Lu_1.72Er₁Ga₅O_4.5N₅:Mn_0.25Dy_0.03、

Lu_1.92Sc₁Al₅O₆N₄:Ce_0.05Yb_0.03、

Sm_1.92La₁Al₅O₆N₄:Ce_0.05Ho_0.03、

Y_2.32Gd_0.6In₁Al₄O₆N₄:Ce_0.05Nd_0.03,

Or Lu_1.95Pm₁Al₅O₆N₄:Ce_0.05.

It is preferred that the radiation wave-length coverage of this heatproof nitride fluorescent material is 380-700nm.Work as M³Including the element that adds lustre to Tb³⁺、Er³⁺、Yb³⁺Or Ho³⁺, the radiation wave-length coverage of this heatproof nitride fluorescent material is 380-530nm；Work as M³Including adding lustre to Element Gd³⁺、Pr³⁺、Dy³⁺Or Nd³⁺, the radiation wave-length coverage of this heatproof nitride fluorescent material is in 530-700nm.

It is preferred that the excitation wavelength range of this heatproof nitride fluorescent material is 250-500nm.

It is preferred that between the particle size range of this heatproof Nitride phosphor is 50nm-10 μm.

The preparation method of this heatproof Nitride phosphor can be coagulated for solid state process (solid-state method), citrate Glue method, and coprecipitation, are not limited to single kind of method preparation.

It is preferred that this heatproof Nitride phosphor is by prepared by solid state process.The advantage of solid state process is that preparation method is simple, Be conducive to producing in a large number, therefore have industry using value.More preferably, the sintering temperature of solid state process is 1800 DEG C, reduction temperature Spend for 1500 DEG C.

Light-emitting device of the present invention, comprises：One light-emitting diodes material elements, can send a light source；And an aforementioned heatproof nitridation Thing fluorescent material, this heatproof nitride fluorescent material is arranged on this light-emitting diodes material elements；This heatproof nitride fluorescent material Material is lighted by absorbing this light source of at least a portion.

It is preferred that this light-emitting diodes material elements can such as but not limited to contain aluminum, gallium, nitrogen, phosphorus, or an aforesaid combination Chip.More preferably, this light-emitting diodes material elements is the LED chip selected from blue light, blue light or green glow.

It is preferred that the main peak ranges of the luminescent spectrum of this light source are 350-500nm.

It is preferred that this heatproof nitride fluorescent material is to be arranged at this light-emitting diodes material unit by evaporation or vapour deposition On part.More preferably, this heatproof nitride fluorescent material passes through evaporation or vapour deposition is formed on this light-emitting diodes material elements One thin film, this thin film has smooth high-quality surface as minute surface.

The present invention will be described further with regard to following examples, however, it should be noted that this embodiment only illustrates With, and it is not necessarily to be construed as the restriction of present invention enforcement.

<Chemical sources>

Bismuth oxide (Bi₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Barium fluoride (BaF₂)：Purchased from ACROS company, purity 99.9%, reagent level.

Dithulium trioxide (Tm₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Cerium oxide (CeO₂)：Purchased from ACROS company, purity 99.9%, reagent level.

Ammonium hydrogen carbonate (NH₄HCO₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Manganese oxide (MnO₂)：Purchased from ACROS company, purity 99.9%, reagent level.

Yittrium oxide (Y₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Aluminium oxide (Al₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Bismuth dioxide (BiO₂)：Purchased from ACROS company, purity 99.9%, reagent level.

Terbia. Diterbium trioxide (Tb₄O₇)：Purchased from ACROS company, purity 99.9%, reagent level.

Gallium oxide (Ga₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Gadolinia. (Gd₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Luteium oxide (Lu₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Erbia (Er₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Dysprosia (Dy₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Praseodymium oxide (Pr₆O₁₁)：Purchased from ACROS company, purity 99.9%, reagent level.

Scia (Sc₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Ytterbium oxide (Yb₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Disamarium trioxide (Sm₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Holmia (Ho₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Dineodymium trioxide (Nd₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Promethium oxide (Pm₂O₃)：Purchased from ACROS company, purity 99.9%, reagent level.

Barium magnesium aluminate (Barium magnesium aluminate, BaMgAl₁₀O₁₇, abbreviation BAM)：Purchased from day origin This chemical company.

Cerium：Yttrium-aluminium garnet (abbreviation YAG:Ce)：Purchased from basic chemical company of Japan.

Erbium：Yttrium-aluminium garnet (abbreviation YAG:Er)：Purchased from basic chemical company of Japan.

YN：By YCl₃And Li₃N synthesizes under 1800 DEG C of nitrogen environments.

AlN：By AlCl₃And Li₃N synthesizes under 1800 DEG C of nitrogen environments.

CeN：By CeCl₃And Li₃N synthesizes under 1800 DEG C of nitrogen environments.

GaN：By GaCl₃And Li₃N synthesizes under 1800 DEG C of nitrogen environments.

<Embodiment 1-25>

[embodiment 1]

Preparation heatproof nitride fluorescent material

According to chemical dosage ratio, weigh 33.65g Y₂O₃、0.39g Tm₂O₃、20.39g Al₂O₃, 4.10g AlN, will be aforementioned Raw material and 2.9g flux BaF₂It is uniformly mixed to form a mixture.Chemical kind needed for preparation embodiment 1 is recorded in detail In table 1.

This mixture is inserted in crucible, and is warming up to 1650 DEG C with the heating rate of 5 DEG C/min in nitrogen and forged Burn 24 hours, then room temperature is cooled to the speed of 5 DEG C/min, obtain the powder through calcination.

Grind this powder through calcination, then after cleaning and drying, sieved with 400 mesh mesh screens.

Again this ground powder is placed in N₂/H₂For, in 85%/15% reducing atmosphere, at 1500 DEG C, reduction 12 is little When, the heatproof Nitride phosphor of prepared embodiment 1.

Luminous test

Will be purple light excited with 400nm for embodiment 1 heatproof Nitride phosphor sample, by electroluminescent (PhotoLuminesecence, abbreviation PL) phenomenon measures the blue light of a length of 460nm of radioactive wave of this embodiment 1 sample.Implement The luminous test result of example 1 is recorded in table 2.

[embodiment 2-25]

The preparation process of heatproof nitride fluorescent material of embodiment 2-25, preparation condition and method of testing and embodiment 1 Identical, different places are species and the consumption of feed chemicals, and the raw material type used by embodiment 2-25 is recorded in table 1 in detail.

The heatproof nitride fluorescent material sample of embodiment 2-25 is carried out luminous test, excitation wavelength and measured putting Ejected wave length and radiation light color are recorded in table 2.

<Comparative example 1-4>

The fluorescent material of comparative example 1-3 is commercially available material, respectively YAG:Ce、YAG:Er and BAM.

Comparative example 4 is Y₃Al₂O_7.5:Ce, is according to chemical dosage ratio, weighs raw material Y₂O₃、Al₂O₃, and CeO₂, will be aforementioned former Material and flux BaF₂It is uniformly mixed to form a mixture.Prepare the chemical kind needed for comparative example 4 and be recorded in table 1 in detail.

The fluorescent material sample of comparative example 1-4 is carried out luminous test, excitation wavelength and measured radiation optical wavelength It is recorded in table 2 with radiation light color.

Table 2

As shown in Table 2, the YAG of comparative example 1:Ce material is excited by blue light, and radiating light is the sodium yellow of wavelength 530nm；Than It is YAG compared with example 2:Er, the purple light excited rear red light releasing wavelength 620nm.It follows that active centre is different, excitation wavelength And radiation wavelength is also different.

The heatproof nitride fluorescent material of embodiment 1-23 does not contain Si or S, replaces part or all of 0 with N, and by taking Join different components and active centre, it is the assorted heatproof nitride fluorescent material of 450-675nm that radiation wave-length coverage is obtained Material.

Excitation wavelength and radiation optical wavelength, the rising of N content and the relative reduction of oxygen content from embodiment 4-6 Radiation optical wavelength can't be impacted.The radiation wavelength of each embodiment is mainly and active centre metallic element M³Species Relevant：M³Including Tm³⁺Or Bi³⁺When, this heatproof nitride fluorescent material releases blue light, when active centre metal after being subject to light source activation Element M³Including Tb³⁺Or Ce³⁺When, this heatproof nitride fluorescent material releases yellow-green light after being subject to light source activation, works as active centre Metallic element M³Including Eu³⁺Or Mn³⁺When, this heatproof nitride fluorescent material releases HONGGUANG after being subject to light source activation.Work as M³Including increasing Photoelement Tb³⁺、Er³⁺、Yb³⁺Or Ho³⁺, the radiation wave-length coverage of this heatproof nitride fluorescent material is 380-530nm；Work as M³Bag Include the element Gd that adds lustre to³⁺、Pr³⁺、Dy³⁺Or Nd³⁺.

Refer to Fig. 1, from the relative spectral power distribution figure of (a) embodiment 13 and (b) comparative example 2, when comparative example 2 (YAG:Er) sample and embodiment 13 (Y_2.95Al₅N₈:Mn_0.05) sample when being similarly subjected to 460nm blue light and exciting, embodiment 13 There is preferably luminous intensity.

Refer to Fig. 2 and Fig. 3.Fig. 2 is the fluorescence spectra of comparative example 3 (BAM), is 400nm when comparative example 3 is subject to wavelength Purple light excited, release wavelength be 450nm blue light, spectrum frequency average be 446.9.Fig. 3 is embodiment 15 (Y_2.94Al₅O₆N₄: Bi_0.06) be subject to wavelength to be the purple light excited of below 400nm, release the spectrogram that wavelength is 450nm blue light, spectrum frequency average is 701.1, the luminous efficacy of display embodiment 15 is better than comparative example 3.

Refer to Fig. 4 and Fig. 5.Specifically, comparative example 4 (Y₃Al₂O_7.5:Ce outward appearance) is white powder, In structure and yttrium-aluminium garnet (structure be Y₃Al_3-5O_9-12) different.As shown in Figure 4, when attempting the indigo plant with wavelength as 450nm When light excites comparative example 4, its CIE (chromaticity coordinates) chromaticity coordinate is shown in region of blue light, display Comparative example 4 is not excited by blue-light source, does not have fluorescence to release, does not have fluorescence phenomenon.

Embodiment 4 is Y_2.95Al₅O_7.5N₃:Ce_0.05, it is (AlN) with the difference of comparative example 4 in structure₃；Can by Fig. 5 Know, when the blue light with wavelength as 450nm excites embodiment 4, its CIE chromaticity coordinate is located at white portion, and display embodiment 4 is subject to Blue light excites and radiates yellow fluorescence, and yellow fluorescence and part are not affected by the blue light absorbing and form white light.The present invention It has been in structure many (AlN) with the difference of existing fluorescent material_m, 3≤m≤8, and fluorescence phenomenon can be produced.

Refer to Fig. 6, by (a) comparative example 1 (YAG) and (b) embodiment 5 (Y_2.95Al₅O₆N₄:Ce_0.05) light decay curve can Know, in destructive testing, when the temperature increases, the intensity of giving out light of fluorescent material has the situation generation of decay.Embodiment 5 The anti-light performance that declines is better than comparative example 1 thus it is speculated that being because that embodiment 5 has the covalent bond structure of N, makes this heatproof nitride fluorescent material Material is more stable in high temperature environments, and the degree of the strength retrogression that gives out light is little, has good heat stability.

In terms of color rendering, the color rendering (Ra value) of general YAG material is 80%.Past replaces Al with Si or S and is changed The fluorescent material of matter YAG, due to the structure substantially without departing from yttrium-aluminium garnet (YAG), therefore color rendering does not have substantially Change, Ra value is also 80% about；And heatproof nitride fluorescent material of the present invention has the color rendering better than current material, Ra value Up to more than 85%.

In sum, heatproof nitride fluorescent material of the present invention is via various difference elements of arranging in pairs or groups, and so that this heatproof is nitrogenized Required coloured light released by thing fluorescent material；By replacing part or all of 0 with N, make heatproof nitride fluorescent material of the present invention There is covalent bond structure, be bonded strength enhancing not easy fracture, at 1800 DEG C, tolerable temperature improves sintering temperature, and heat stability Well.When heatproof nitride fluorescent material of the present invention is applied to light-emitting device, luminous intensity and luminous efficacy are good, tolerable temperature Height, and there is good color rendering, releasing photochromic naturally not dazzling.

The above, only presently preferred embodiments of the present invention, when the scope that the present invention is implemented being limited with this, that is, Generally the simple equivalence changes made according to scope of the present invention patent and invention description content and modification, all still belong to the present invention In the range of patent covers.

The above, be only presently preferred embodiments of the present invention, not the present invention is made with any pro forma restriction, though So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any is familiar with this professional technology people Member, in the range of without departing from technical solution of the present invention, when the technology contents of available the disclosure above make a little change or modification For the Equivalent embodiments of equivalent variations, as long as being without departing from technical solution of the present invention content, according to the technical spirit pair of the present invention Any simple modification, equivalent variations and modification that above example is made, all still fall within the range of technical solution of the present invention.

Claims (7)

1. a kind of heatproof nitride fluorescent material is it is characterised in that it has the chemical formula of lower formula (I)：

M¹ _yM² ₅O_zN_x：M³ _w(I)

M¹It is selected from Sc³⁺、Y³⁺、La³⁺、Sm³⁺、Gd³⁺、Pm³⁺、Er³⁺、Lu³⁺, or an aforesaid combination；

M²Selected from Al³⁺、In³⁺、Ga³⁺, or an aforesaid combination；

M³It is selected from Tm³⁺、Bi³⁺、Tb³⁺、Ce³⁺、Mn³⁺、Yb³⁺、Ho³⁺、Pr³⁺、Dy³⁺、Nd³⁺, or an aforesaid combination；And

X is the integer of 3-8,2.7≤y≤3,0 ＜ w≤0.3, and 0≤z≤7.5.

2. heatproof nitride fluorescent material as claimed in claim 1 is it is characterised in that 0.01≤w≤0.06.

3. heatproof nitride fluorescent material as claimed in claim 1 is it is characterised in that this heatproof nitride fluorescent material is choosing From in

Y_2.98Al₅O_7.5N₃：Tm_0.02、

Y_2.95Al₅O₆N₄：Bi_0.05、

Y_2.94Al₅O₆N₄：Tb_0.06、

Y_2.95Al₅O_7.5N₃：Ce_0.05、

Y_2.95Al₅O₆N₄：Ce_0.05、

Y_2.95Al₅O_4.5N₅：Ce_0.05、

Y_2.95Al₅O₆N₄：Mn_0.05、

Y_2.75GaAl₄O₆N₄：Mn_0.25、

Y_2.94Al₅N₈：Bi_0.06、

Y_2.94Al₅N₈：Tm_0.06、

Y_2.95Al₅N₈：Ce_0.05、

Y_2.95Al₅N₈：Mn_0.05、

Y_2.95Ga₅N₈：Mn_0.05、

Y_2.94Al₅O₆N₄：Bi_0.06、

Y_2.94Al₅O₆N₄：Mn_0.06、

Y_2.94Al₅O₆N₄：Ce_0.06、

Lu_1.72Gd_1.2Al₅O₆N₄：Ce_0.05Pr_0.03、

Lu_1.72Er₁Ga₅O_4.5N₅：Mn_0.25Dy_0.03、

Lu_1.92Sc₁Al₅O₆N₄：Ce_0.05Yb_0.03、

Sm_1.92La₁Al₅O₆N₄：Ce_0.05Ho_0.03、

Y_2.32Gd_0.6In₁Al₄O₆N₄：Ce_0.05Nd_0.03,

Or Lu_1.95Pm₁Al₅O₆N₄：Ce_0.05.

4. heatproof nitride fluorescent material as claimed in claim 1 is it is characterised in that the putting of this heatproof nitride fluorescent material Penetrating wave-length coverage is 380-700nm.

5. heatproof nitride fluorescent material as claimed in claim 1 it is characterised in that this heatproof nitride fluorescent material swash Sending out wave-length coverage is 250-500nm.

6. a kind of light-emitting device is it is characterised in that it comprises：

One light-emitting diodes material elements, can send a light source；And

The one heatproof nitride fluorescent material any one of claim the 1-5 item, is disposed on this light-emitting diodes material On material element；

This heatproof nitride fluorescent material is lighted by absorbing this light source of at least a portion.

7. light-emitting device as claimed in claim 6 is it is characterised in that the radiation wave-length coverage of this heatproof nitride fluorescent material For 380-700nm.