CN1934218A

CN1934218A - Phosphor and including the same, light emitting apparatus, illuminating apparatus and image display

Info

Publication number: CN1934218A
Application number: CN 200580008573
Authority: CN
Inventors: 瀬户孝俊; 木岛直人; 吉野正彦; 三上昌义; 茂岩统之; 伊村宏之
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Chemical Corp; Mitsubishi Kasei Corp
Priority date: 2004-01-16
Filing date: 2005-01-14
Publication date: 2007-03-21
Also published as: JP2005226067A; JP4617888B2

Abstract

A highly efficient red light emitting phosphor and white phosphor for use in displays and illuminating equipment capable of highly efficient light emission by joint use with a light source of near-ultraviolet to visible region light emission. There is provided a phosphor comprising a crystal phase with specified chemical composition.

Description

Light-emitting device and the means of illumination and the image display device of fluor and this fluor of use

Technical field

The present invention relates to by being combined in twinkler luminous near ultraviolet-visible-range and can absorbing these light and emission has the efficient light-emitting device that the fluor of long wavelength's visible light (phosphor) more obtains, and relate to described fluor itself.

Background technology

For showing and the indispensable white light that throws light on normally doses according to light that mixed principle obtains by combination blue light, green glow and red emission.In described indicating meter, on the tristimulus coordinates in wider range copy colors effectively, blue, green and red-emitting phosphors must have high as far as possible emissive porwer and good purity of color.In general illumination, depend on that some use, they must have high emission efficiency and shine target the color of color when looking like natural light irradiation, promptly so-called color rendering height.In luminescent lamp as representative illumination, main by the ultraviolet ray that mercury discharge causes as excitaton source with 254nm wavelength, and mix to use three kinds of fluor of the light of 450nm, 540nm that can launch human eye-level sensitivity and 610nm, thereby realized having the illumination of high color rendering.Yet, when in the scope that excites light wavelength at near-ultraviolet light-visible light, under As-Is, do not develop fluor with high emission efficiency.Especially, for the described exciting light in this wavelength region, compare with green-emitting phosphor with blue, the emission efficiency of red-emitting phosphors is very low, therefore there is demand already in the red-emitting phosphors with excellent properties.When any two or three light time that from a kind of fluor, obtains among above-mentioned 450nm, 540nm and the 610nm, compare with mixing three kinds of fluor, the method for mixing up is simple, but and expected performance stable.Yet this is not achieved.

In patent documentation 1 illustrated the multiple fluor of the emission blue light, green glow and the ruddiness that combine with luminous light source in near-ultraviolet light-visible region.The alkaline earth metal silicate fluor of emission blue light and ruddiness wherein, has been described.In addition, in patent documentation 2, Eu has been described ²⁺Excite (Ba, Ca, Sr, Mg)-the Si-O system can be under the situation of having only Ba and Ca at the 505nm place luminous and when adding Sr emission wavelength transfer to 580m.In non-patent literature 1, reported (Ba, Ca, Sr) ₃MgSi ₂O ₈: Eu, Mn.In addition, in non-patent literature 2, Ba has been described ₃MgSi ₂O ₈: Eu, Mn has emission peak at 442nm, 505nm and 620nm place, and its crystalline structure is merwinite (merwinite).

[patent documentation 1]

JP-T-2004-505470 (used here term JP-T means the open Japanese Translator of PCT patent application)

[patent documentation 2]

JP-T-2004-501512

[non-patent literature 1]

J.Electrochem.Soc.，Vol.115，No.7，733-738(1968)

[non-patent literature 2]

Appl.Phys.Lett.，Vol.84，No.15，2931-2933(2004)

Disclosure of the Invention

The objective of the invention is to research and develop and be used for combine with luminous light source in near-ultraviolet light-visible region efficient luminous demonstration or the high efficiency red light-emitting fluophor and the white light fluor of illumination.

In order to address the above problem, the inventor furthers investigate.As a result, find to have novel form and the alkaline-earth silicate fluor of specific crystal structure for the exciting light in near-ultraviolet light-visible region red-emitting or white light efficiently, so finished the present invention.

Especially, the inventor has found to be contained Ba and contained the M of Ca by what Eu and Mn excited ₂SiO ₄Therefore type silicate drawn the present invention.Especially, red-emitting phosphors of the present invention has the emission peak wavelength in the 590nm-620nm scope, therefore it is characterized in that launching the bright redness (reddish) of sensation.

That is to say, first main points of the present invention are the fluor that comprise the crystallization phases of have following formula [1], [2] or [3] chemical constitution, with second main points is to comprise first twinkler of emission 350nm-430nm light and by from the rayed of described first twinkler and the light-emitting device of second twinkler of visible emitting, and wherein above-mentioned second twinkler is the fluor of crystallization phases that comprises the chemical constitution of have following formula [1], [2] or [3]:

Eu _a0Mn _b0M ¹⁰ _c0M ²⁰ _d0M ³⁰O _e0Z ⁰ _f0 [1]

M wherein ¹⁰Be to comprise the dyad that is selected from least a element among Ba, Ca and the Sr that is equal to or greater than 85 moles of %, wherein Ca is 0.1-0.9 with the ratio (mol ratio) of the summation of Ba and Ca; M ²⁰Representative is selected from least a element in unit price, trivalent and the pentad; M ³⁰Represent one group to comprise the Si that is equal to or greater than 90 moles of % total amounts and the quadrivalent element of Ge; Z ⁰It is at least a element that is selected among negative monovalence and negative dyad, H and the N; With a0 be the number that satisfies 0.001≤a0≤0.6, b0 is the number that satisfies 0≤b0≤0.7, c0 and d0 are the numbers that satisfies 0≤d0/ (c0+d0)≤0.2, a0, b0, c0 and d0 satisfy 1.8≤(a0+b0+c0+d0)≤2.2 number, and e0 and f0 are the numbers that satisfies 0≤f0/ (e0+f0)≤0.035 and 3.6≤(e0+f0)≤4.4.

Eu _a1Mn _b1Mg _c1M ¹¹ _d1M ²¹O _e1Z ¹ _f1 [2]

M wherein ¹¹Representative is selected from least a element in monogen, the dyad except that Eu, Mn and Mg, trivalent element and the pentad, the ratio of wherein said dyad is equal to or greater than 80 moles of %, the ratio of the summation of Ba, Ca and Sr is equal to or greater than 40 moles of %, and the ratio (mol ratio) of Ca and the summation of Ba and Ca is 0.2-0.9; M ²¹Represent one group to comprise the Si that is equal to or greater than 90 moles of % total amounts and the quadrivalent element of Ge; Z ¹It is at least a element that is selected among negative monovalence and negative dyad, H and the N; With a1 be the number that satisfies 0.001≤a1≤0.8, b1 satisfies the number of 0＜b1≤0.8, c1 and d1 are the numbers that satisfies 0＜c1/ (c1+d1)≤0.2, a1, b1, c1 and d1 satisfy 1.8≤(a1+b1+c1+d1)≤2.2 number, and e1 and f1 are the numbers that satisfies 0≤f1/ (e1+f1)≤0.035 and 3.6≤(e1+f1)≤4.4.

Eu _a2Mn _b2Mg _c2M ¹² _d2M ²²O _e2Z ² _f2 [3]

M wherein ¹²Representative is selected from least a element in monogen, the dyad except that Eu, Mn and Mg, trivalent element and the pentad, the ratio of wherein said dyad is equal to or greater than 80 moles of %, the ratio of the summation of Ba, Ca and Sr is equal to or greater than 40 moles of %, and the ratio (mol ratio) of Ca and the summation of Ba and Ca is less than 0.2; M ²²Represent one group to comprise the Si that is equal to or greater than 90 moles of % total amounts and the quadrivalent element of Ge; Z ²It is at least a element that is selected among negative monovalence and negative dyad, H and the N; With a2 be the number that satisfies 0.01≤a2≤0.8, b2 is the number that satisfies 0＜b2≤0.8, c2 and d2 are the numbers that satisfies 0＜c2/ (c2+d2)≤0.2 or 0.3≤c2/ (c2+d2)≤0.8, a2, b2, c2 and d2 satisfy 1.8≤(a2+b2+c2+d2)≤2.2 number, and e2 and f2 are the numbers that satisfies 0≤f2/ (e2+f2)≤0.035 and 3.6≤(e2+f2)≤4.4.

According to the present invention, obtained having high brightness and be transferred to dark-toned redness or white phosphor, and the effectively light-emitting device with high color rendering of visible emitting can be provided from light colour.

The accompanying drawing summary

Fig. 1 is wherein membranaceous fluor contacted or formed an example of light-emitting device thereon with surface-emitting type GaN class diode demonstration figure.

Fig. 2 is the constructed profile that shows an example of the light-emitting device that comprises fluor of the present invention and first twinkler (350nm-430nm twinkler).

Fig. 3 is the constructed profile that shows an example of of the present invention litillumination devices.

Fig. 4 is the emmission spectrum of the fluor when embodiment A-3 when being used as the 400nm rayed of the predominant wavelength in the near-ultraviolet light zone of GaN class photodiode.

Fig. 5 is the emmission spectrum of the fluor when embodiment A-4 when being used as the 400nm rayed of the predominant wavelength in the near-ultraviolet light zone of GaN class photodiode.

Fig. 6 is the method demonstration figure that measures peak group's half breadth.

Fig. 7 shows the X-ray diffraction measuring result of the fluor of embodiment A-8.

Fig. 8 is the emmission spectrum demonstration figure of the fluor when embodiment A-8, embodiment A-9, embodiment A-10 and embodiment A-11 when being used as the 400nm rayed of the predominant wavelength in the near-ultraviolet light zone of GaN-class photodiode separately.

Fig. 9 is the emmission spectrum of the fluor when Embodiment B-2 when being used as the 400nm rayed of the predominant wavelength in the near-ultraviolet light zone of GaN class photodiode.

Figure 10 shows the X-ray diffraction measuring result of the fluor of Embodiment B-3.

Figure 11 is the emmission spectrum demonstration figure of the fluor of Embodiment B-3, Embodiment B-4, Embodiment B-5 and Embodiment B-6 when being used as the 400nm rayed of the predominant wavelength in the near-ultraviolet light zone of GaN class photodiode separately.

Figure 12 is the emmission spectrum of the fluor of Embodiment C-3 when being used as the 400nm rayed of the predominant wavelength in the UV-light zone of GaN class photodiode.

Figure 13 is the emmission spectrum of the fluor of Embodiment C-4 when being used as the 400nm rayed of the predominant wavelength in the UV-light zone of GaN class photodiode.

As the symbol among the figure, respectively, 1 expression second twinkler, 2 presentation surface light emitting-type GaN class LD, 3 expression substrates, 4 expression light-emitting devices, 5 expressions are installed wherein pack into face litillumination devices (lighting system), 12 expressions of luminous element of resin part, 9 expression conductor wires, 10 expression profiled members, 11 expressions that leads (lead), 6 expression inner leads (lead), 7 expression first twinklers (350nm-430nm twinkler), 8 expressions allow to comprise fluor of the present invention and are preserved casees, 13 expression light-emitting devices and 14 expression scatterer panels.

Embodiment

To describe embodiments of the present invention in detail below, but the present invention is not limited to following embodiment, and can in it wants point range, carries out multiple variation.

The present invention is the fluor that comprises the crystallization phases of the chemical constitution of have following formula [1], [2] or [3], with the described fluor of the crystallization phases of the chemical constitution that comprises have following formula [1], [2] or [3], and the light-emitting device that uses its luminous source of rayed of 350nm-430nm:

Eu _a0Mn _b0M ¹⁰ _c0M ²⁰ _d0M ³⁰O _e0Z ⁰ _f0 [1]

Eu _a1Mn _b1Mg _c1M ¹¹ _d1M ²¹O _e1Z ¹ _f1 [2]

Eu _a2Mn _b2Mg _c2M ¹² _d2M ²²O _e2Z ² _f2 [3]

At first, formula [1].

M in the formula [1] ¹⁰Be to comprise the dyad that is selected from least a element among Ba, Ca and the Sr that is equal to or greater than 85 moles of %, wherein Ca is 0.1-0.9 with the ratio (mol ratio) of the summation of Ba and Ca.That is to say that it is most of or all by being selected from least a elementary composition among Ba, Ca and the Sr.Can in the scope of not damaging performance, comprise other dyads, and the example comprises V, Cr, Fe, Co, Ni, Cu, Zn, Mo, Ru, Pd, Ag, Cd, Sn, Sm, Tm, Yb, W, Re, Os, Ir, Pt, Hg, Pb etc.M ¹⁰Can amount to and be equal to or less than M ¹⁰The ratio of 15 moles of % comprise at least a element that is selected from these elements.Wherein, V, Zn, Mo, Sn, Sm, Tm, Yb, W, Pb etc. are difficult to influence described performance, and can amount to and be equal to or less than 15 moles of % and be included in M ¹⁰In.

M in formula [1] ¹⁰In, Ca is 0.1-0.9 with the ratio (mol ratio) of the summation of Ba and Ca.Yet, consider the emissive porwer of redness or white etc., the lower limit of the mol ratio of the summation of Ca and Ba and Ca preferably is equal to or greater than 0.2, and the upper limit preferably is equal to or less than 0.8.The summation of Ba and Ca is at M ¹⁰In ratio preferably be equal to or greater than 70 moles of %, more preferably be equal to or greater than 90 moles of % and further 100 moles of % more preferably.

M in the formula [1] ²⁰Representative is selected from least a element in unit price, trivalent and the pentad, and the example includes but not limited to Li, Na, K, Rb, Cs, B, Al, Ga, In, P, Sb, Bi, Ta, Nb, Rh, trivalent rare earth element such as Y and Sc etc.Passing through described M ¹⁰In dyad and activating element Eu ²⁺And Mn ²⁺Solid internal diffusion in firing and promote to introduce described unit price, trivalent or pentad on a small quantity as M on the meaning of crystallization of described silicate ¹⁰In element.Described M ²⁰Component comprises main replacement M ¹⁰The element of position, and M ²⁰Mole number and M ¹⁰And M ²⁰The ratio d0/ (c0+d0) of total moles be 0≤d0/ (c0+d0)≤0.2.Yet, consider the luminous intensity etc. of redness or white, it is preferably 0≤d0/ (c0+d0)≤0.1, and d0/ (c0+d0)=0 more preferably.

M in the formula [1] ³⁰Representative comprises the quadrivalent element group of the Si and the Ge of the total amount that is equal to or greater than 90 moles of %.Yet, consider the emissive porwer of redness or white etc., preferred M ³⁰The Si that comprises the amount that is equal to or greater than 80 moles of %, and more preferably M ³⁰Form by Si.Quadrivalent element except that Si and Ge comprises Zn, Ti, Hf etc.Consider the emissive porwer of redness or white etc., can in the scope of not damaging performance, comprise these elements.

Z in the formula [1] ⁰It is at least a element that is selected among negative monovalence and negative dyad, H and the N.It can be for example is negative univalent F, Cl, Br, I etc., and the same S, Se or Te for negative dyad with oxygen, and can comprise the OH base.The oxygen base can partly be transformed into ON base or N base.In addition, can comprise Z influencing under the few degree of fluorescence property ⁰, that is to say, with ratio based on the about 2 moles of % of being equal to or less than of all elements on impurity level.This is equivalent to Z ⁰/ (Z ⁰+ Sauerstoffatom) mol ratio is equal to or less than 0.035.Therefore, the scope of f0/ (e0+f0) is Z ⁰With (Z ⁰+ Sauerstoffatom) mol ratio is 0≤f0/ (e0+f0)≤0.035.Consider the performance of described fluor, it is preferably f0/ (e0+f0)≤0.01, and the preferred f0/ (e0+f0)=0 that uses usually.

For the Eu mol ratio a0 in the formula [1], a0 is the number that satisfies 0.001≤a0≤0.6.As luminescence center ion Eu ²⁺Described mol ratio a0 very hour, emissive porwer is tending towards reducing.On the other hand, even when it is very big, by being called the phenomenon of concentration quenching or temperature quenching, described emissive porwer also is tending towards reducing.Therefore, lower limit is preferably 0.005≤a0, and more preferably 0.02≤a0, and upper limit a0≤0.5 more preferably.

Mn mol ratio b0 in the formula [1] is that the selection to red emission or white light emission has material factor.When b0 is 0, does not obtain red peak and only provide blueness or blue-greenish colour peak.Yet, when b0 gets very little positive number, red peak in blue and green peak, occurs, thereby provide white light emission on the whole.When b0 got bigger positive number, blue and green peak almost disappeared, and mainly provides red peak.As red-emitting phosphors or white phosphor, the scope of b0 is 0＜b0≤0.7.It is contemplated that described fluor receives the irradiation of excitation light source to excite Eu ^{+ 2}, and the Eu that excites ^{+ 2}Energy transfer to Mn ^{+ 2}In, make Mn ^{+ 2}Red-emitting.Mainly according to M ¹⁰And M ²⁰Composition, the degree that energy shifts and slightly different, so the boundary value of b0 (being transformed into white phosphor at this value place red-emitting phosphors) is according to M ¹⁰And M ²⁰Composition and slightly different.Therefore, can not strictly judge the good scope of the b0 that is used for red emission and white light emission.Yet, as white phosphor, preferred 0＜b0≤0.2 and more preferably 0.02≤b0≤0.2, and as red-emitting phosphors, preferred 0.05≤b0≤0.7, and more preferably 0.1≤＜b0≤0.6.

Crystallization phases Eu in above-mentioned formula [1] _A0Mn _B0M ¹⁰ _C0M ²⁰ _D0M ³⁰O _E0Z ⁰ _F0In, Eu ²⁺And Mn ²⁺The M of involved dyad ¹⁰Replace M ³⁰Mainly occupied by Si, described negatively charged ion mainly is an oxygen, M ²⁰Comprise except that divalence and the unit price the quadrivalent element, trivalent or pentad as principal element, and (M ¹⁰+ M ²⁰), M ³⁰Be respectively 2,1 and 4 with total mol ratio of Sauerstoffatom in its essentially consist.Even when sometimes positively charged ion deficiency or negatively charged ion deficiency taking place, also have no significant effect required fluorescence property.Therefore, as the M that will mainly be occupied by Si ³⁰Total mol ratio in described chemical formula, be fixed as (M at 1 o'clock ¹⁰+ M ²⁰) mol ratio (a0+b0+c0+d0) in 1.8≤(a0+b0+c0+d0)≤2.2 scope, and wherein preferred (a0+b0+c0+d0)=2.In addition, in total mol ratio (e0+f0) in the site of negatively charged ion side usually in the scope 3.6≤(e0+f0)≤4.4, and wherein preferred e0=4 and f0=0.

Can be by following (A) or hybrid system (B), preparation is as being shown in the M in the above-mentioned formula [1] ¹⁰Source, M ²⁰Source and M ³⁰The source with as the Eu of activating element and the mixture of Mn element source, and fire described mixture by thermal treatment and prepare and be used for described fluor of the present invention.

(A) made up the porphyrization of use drying and crushing machine such as hummer runner milling (hummer mill), roller mill, ball mill or micronizer mill (jet mill), or the porphyrization of use mortar and pestle, with the mixing of using mixing tank such as ribbon blender, V-type mixing tank or Henschel (Henschel) mixing tank, or the blended dry blending method of use mortar and pestle.

(B) use pulverizer or mortar and pestle to add entry etc. to form slurry condition or solution state, mix by pulverizer, mortar and pestle, furnace pot and stirring rod etc., and legal by the wet mixing of dry described mixtures such as spraying drying, heat drying, seasoning.

In these methods, being used for the element source compound of described activating element, preferably use liquid medium especially, because it must whole uniform mixing and disperses a spot of compound.In addition, also because obtain being used for the overall uniform mixture of other element source compound, the latter's wet method is preferred.And, by thermally resistant container as use with as described in fluor the crucible or the pallet of the material of low reactivity are arranged, be generally 750 ℃-1400 ℃, under preferred 900 ℃-1300 ℃ temperature, under the single or hybird environment of gas, heat as carbon monoxide, carbonic acid gas, nitrogen, hydrogen and argon gas heated in 10 minutes to 24 hours implement as described in facture.If desired, after described thermal treatment, wash, drying, stage treatment etc.

As above-mentioned heating environment, select to be used to obtain wherein said activating element and help the required environment of luminous ionic state (valency).In the situation of divalence Eu of the present invention and Mn etc., preferably heat heating under the neutrality of carbon monoxide, nitrogen, hydrogen, argon gas etc. or the reducing atmosphere and more preferably comprising under the reducing atmosphere of carbon monoxide or hydrogen.Further more preferably in described environment, there is carbon.Especially, by heating with the carbon heater smelting furnace, can being achieved using under the reducing atmosphere that container heats as the crucible of being made by carbon, heats etc. under the coexistence on carbon pearl etc. under the reducing atmosphere.

Described M ¹⁰Source, described M ²⁰Source, described M ³⁰The element source compound of source and described activating element comprises M respectively ¹⁰, M ²⁰, M ³⁰With the various oxide compounds of activating element, oxyhydroxide, carbonate, nitrate, vitriol, oxalate, carboxylate salt, halogenide etc., among these, consider to have reactivity, and when firing, do not produce NO with composite oxides _x, SO _xDeng selecting.

For as M ¹⁰And above-mentioned Ba, the Ca and the Sr that enumerate, if specifically enumerate described M ¹⁰Source compound, Ba source compound comprise BaO, Ba (OH) ₂8H ₂O, BaCO ₃, Ba (NO ₃) ₂, BaSO ₄, Ba (OCO) ₂2H ₂O, Ba (OCOCH ₃) ₂, BaCl ₂Deng, the Ca source compound comprises CaO, Ca (OH) ₂, CaCO ₃, Ca (NO ₃) ₂4H ₂O, CaSO ₄2H ₂O, Ca (OCO) ₂H ₂O, Ca (OCOCH ₃) ₂H ₂O, CaCl ₂Deng and the Sr source compound comprise SrO, Sr (OH) ₂8H ₂O, SrCO ₃, Sr (NO ₃) ₂, SrSO ₄, Sr (OCO) ₂H ₂O, Sr (OCOCH ₃) ₂0.5H ₂O, SrCl ₂Deng.

For as M ³⁰And the above-mentioned Si and the Ge that enumerate, if specifically enumerate described M ³⁰Source compound, the Si source compound comprises SiO ₂, H ₄SiO ₄, Si (OCOCH ₃) ₄Deng and the Ge source compound comprise GeO ₂, Ge (OH) ₄, Ge (OCOCH ₃) ₄, GeCl ₄Deng.

In addition, for the above-mentioned Eu and the Mn that enumerate as described activating element, if specifically enumerate described element source compound, they comprise Eu ₂O ₃, Eu ₂(SO ₄) ₃, Eu ₂(OCO) ₆, EuCl ₂, EuCl ₃, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O, MnO ₂, Mn ₂O ₃, Mn ₃O ₄, MnO, Mn (OH) ₂, MnCO ₃, Mn (OCOCH ₃) ₂2H ₂O, Mn (OCOCH ₃) ₃NH ₂O, MnCl ₂4H ₂O etc.

Then, following formula [2] will be described.

Eu _a1Mn _b1Mg _c1M ¹¹ _d1M ²¹O _e1Z ¹ _f1 [2]

M in the formula [2] ¹¹Representative is selected from monogen, removes Eu, at least a element in dyad, trivalent element and the pentad outside Mn and the Mg, and the summation ratio that the ratio that satisfies described dyad is equal to or greater than 80 moles of %, Ba, Ca and Sr is equal to or greater than 40 moles of %, and the ratio (mol ratio) of Ca and the summation of Ba and Ca is the condition of 0.2-0.9.Element except that Ba, Ca and Sr is described especially, described monogen comprises Li, Na, K, Rb, Cs etc., described dyad comprises V, Cr, Fe, Co, Ni, Cu, Zn, Mo, Ru, Pd, Ag, Cd, Sn, Sm, Tm, Yb, W, Re, Os, Ir, Pt, Hg, Pb etc., described trivalent element comprises B, Al, Ga, In etc., with rare earth element such as Y or Sc, and described pentad comprises P, Sb and Bi.Yet they are not limited thereto.In superincumbent all dyads, V, Zn, Mo, Sn, Sm, Tm, Yb, W and Pb are difficult for the described performance of influence.

Passing through M ¹¹In described dyad and activating element Eu ²⁺And Mn ²⁺Solid internal diffusion in firing and promote to introduce the described unit price, trivalent or the pentad that are equal to or less than 20 moles of % total amounts on the meaning of crystallization of described silicate.Consider the emissive porwer of redness or white etc., Ca is preferably 0.2-0.8 with the ratio (mol ratio) of the summation of Ba and Ca.Consider the emissive porwer of redness or white etc., the summation ratio of Ba, Ca and Sr preferably is equal to or greater than 80 moles of %, more preferably the summation ratio of Ba and Ca be equal to or greater than 80 moles of % and further more preferably the summation ratio of Ba, Ca and Sr be 100 moles of %.

M in the formula [2] ²¹Represent one group to comprise the Si that is equal to or greater than 90 moles of % total amounts and the quadrivalent element of Ge.Yet, consider the emissive porwer of redness or white etc., preferred M ²¹Comprise the Si that is equal to or greater than 80 moles of % amount and more preferably M ²¹Form by Si.Described quadrivalent element except that Si and Ge also comprises Zn, Ti, Hf etc.Consider the emissive porwer of redness or white etc., can in the scope of not damaging performance, comprise these elements.

Z in the formula [2] ¹It is at least a element that is selected among negative monovalence and negative dyad, H and the N.It can be for example is negative univalent F, Cl, Br, I etc., and the same S, Se or Te for negative dyad with oxygen, and can comprise the OH base.The oxygen base can partly be transformed into ON base or N base.In addition, can influence the few degree of fluorescence property and comprise Z ¹, that is to say, with ratio based on the about 2 moles of % of being equal to or less than of all elements on impurity level.This is equivalent to Z ¹/ (Z ¹+ Sauerstoffatom) mol ratio is equal to or less than 0.035.Therefore, the scope of f1/ (e1+f1) is Z ¹With (Z ¹+ Sauerstoffatom) mol ratio is 0≤f1/ (e1+f1)≤0.035.Consider the performance of described fluor, be preferably f1/ (e1+f1)≤0.01 and preferred f1/ (e1+f1)=0.

For the Eu mol ratio a1 in the formula [2], a1 is the number that satisfies 0.001≤a1≤0.8.As luminescence center ion Eu ²⁺Described mol ratio a1 very hour, emissive porwer is tending towards reducing.On the other hand, even when it is very big, by being called the phenomenon of concentration quenching or temperature quenching, described emissive porwer also is tending towards reducing.Therefore, lower limit is preferably 0.005≤a1 and 0.02≤a1 more preferably, and upper limit a1≤0.5 more preferably.

Mn mol ratio b1 in the formula [2] is that the selection to red emission or white light emission has material factor.When b1 is 0, does not obtain red peak and only produce blueness or blue-greenish colour peak.Yet, when b1 gets very little positive number, red peak in blue and green peak, occurs, thereby produce white light emission on the whole.When b1 got bigger positive number, blue and green peak almost disappeared, and mainly produces red peak.As red-emitting phosphors or white phosphor, the scope of b1 is 0＜b1≤0.8.It is contemplated that described fluor receives the irradiation of excitation light source to excite Eu ^{+ 2}And the Eu that excites ^{+ 2}Energy transfer to Mn ^{+ 2}In, make Mn ^{+ 2}Red-emitting.The degree that energy shifts is mainly according to M ¹¹And M ²¹Composition and slightly different, so the boundary value of b1 (being transformed into white phosphor at this value place red-emitting phosphors) is according to M ¹¹And M ²¹Composition and slightly different.Therefore, can not strictly judge the good scope of the b1 that is used for red emission and white light emission.Yet, as white phosphor, preferred 0＜b1≤0.15, and more preferably 0.01≤b1≤0.15, and as red-emitting phosphors, preferred 0.03≤b1≤0.8, and more preferably 0.06≤b1≤0.4.

Mg in the formula [2] is mainly comprised the M of dyad ¹¹Replace and the mole number of Mg and Mg and M ¹¹The ratio c1/ (c1+d1) of total mole number be 0＜c1/ (c1+d1)≤0.2.Yet, consider the emissive porwer of redness or white etc., be preferably 0＜c1/ (c1+d1)≤0.7.

Crystallization phases Eu in above-mentioned formula [2] _A1Mn _B1Mg _C1M ¹¹ _D1M ²¹O _E1Z ¹ _F1In, Eu ²⁺, Mn ²⁺And Mg ^{+ 2}The M that is mainly comprised dyad ¹¹Replace M ²¹Mainly occupied by Si and Ge, described negatively charged ion mainly is an oxygen, and M ¹¹, M ²¹Be respectively 2,1 and 4 with total mol ratio of Sauerstoffatom in its essentially consist.Even when sometimes positively charged ion deficiency or negatively charged ion deficiency taking place, also have no significant effect required fluorescence property.Therefore, as the M that will be mainly occupied by Si and Ge ²¹Total mol ratio in described chemical formula, be fixed as (M at 1 o'clock ¹¹+ Eu+Mn+Mg) mol ratio (a1+b1+c1+d1) is preferably 1.9-2.1 in 1.8≤(a1+b1+c1+d1)≤2.2 scope, and more preferably (a1+b1+c1+d1)=2.In addition, in the scope of total mol ratio (e1+f1) 3.6≤(e1+f1)≤4.4 in the site of negatively charged ion side, be preferably 3.8-4.2 and more preferably e1=4 and f1=0.

Can be by following (A) or hybrid system (B), preparation is as being shown in the M in the above-mentioned formula [2] ¹¹Source, M ²¹Source and Mg source and mixture as the element source compound of the Eu of activating element and Mn, and fire described mixture by thermal treatment and prepare and be used for described fluor of the present invention.

(A) combine the porphyrization that uses drying and crushing machine such as hummer runner milling (hummer mill), roller mill, ball mill or micronizer mill, or the porphyrization of use mortar and pestle, with the mixing of using mixing tank such as ribbon blender, V-type mixing tank or Henschel mixing tank, or the blended dry blending method of use mortar and pestle.

In these hybrid systems, being used for the element source compound of described activating element, preferably use liquid medium especially, because it must whole uniform mixing and disperses a spot of compound.In addition, also because obtain being used for the overall uniform mixture of other element source compound, the latter's wet method is preferred.And, by thermally resistant container as use with as described in fluor the crucible or the pallet of the material of low reactivity are arranged, be generally 750 ℃-1400 ℃, under preferred 900 ℃-1300 ℃ temperature, under the single or hybird environment of gas, heat as carbon monoxide, carbonic acid gas, nitrogen, hydrogen and argon gas heated in 10 minutes to 24 hours implement as described in heat treating process.If desired, after described thermal treatment, wash, drying, stage treatment etc.

Described M ¹¹Source, described M ²¹The element source compound of source, described Mg source and described activating element comprises M respectively ¹¹, M ²¹, Mg and activating element various oxide compounds, oxyhydroxide, carbonate, nitrate, vitriol, oxalate, carboxylate salt, halogenide etc., among these, consider to have reactivity, and when firing, do not produce NO with composite oxides _x, SO _xDeng selecting.

For as M ¹¹And above-mentioned Ba, the Ca and the Sr that enumerate, if specifically enumerate described M ¹¹Source compound, Ba source compound comprise BaO, Ba (OH) ₂8H ₂O, BaCO ₃, Ba (NO ₃) ₂, BaSO ₄, Ba (OCO) ₂2H ₂O, Ba (OCOCH ₃) ₂, BaCl ₂Deng, the Ca source compound comprises CaO, Ca (OH) ₂, CaCO ₃, Ca (NO ₃) ₂4H ₂O, CaSO ₄2H ₂O, Ca (OCO) ₂H ₂O, Ca (OCOCH ₃) ₂H ₂O, CaCl ₂Deng and the Sr source compound comprise SrO, Sr (OH) ₂8H ₂O, SrCO ₃, Sr (NO ₃) ₂, SrSO ₄, Sr (OCO) ₂H ₂O, Sr (OCOCH ₃) ₂0.5H ₂O, SrCl ₂Deng.

For as M ²¹And the above-mentioned Si and the Ge that enumerate, if specifically enumerate described M ²¹Source compound, the Si source compound comprises SiO ₂, H ₄SiO ₄, Si (OCOCH ₃) ₄Deng and the Ge source compound comprise GeO ₂, Ge (OH) ₄, Ge (OCOCH ₃) ₄, GeCl ₄Deng.

For Mg, if specifically enumerate described Mg source compound, they comprise MgO, Mg (OH) ₂, MgCO ₃, Mg (OH) ₂3MgCO ₃3H ₂O, Mg (NO ₃) ₂6H ₂O, MgSO ₄, Mg (OCO) ₂2H ₂O, Mg (OCOCH ₃) ₂4H ₂O, MgCl ₂Deng.

Then, following formula [3] will be described.

Eu _a2Mn _b2Mg _c2M ¹² _d2M ²²O _e2Z ² _f2 [3]

M in the formula [3] ¹²Representative is selected from least a element in monogen, the dyad except that Eu, Mn and Mg, trivalent element and the pentad, and the ratio that satisfies described dyad is equal to or greater than 80 moles of %, the summation ratio of Ba, Ca and Sr is equal to or greater than 40 moles of %, and the ratio (mol ratio) of the summation of Ca and Ba and Ca is less than 0.2 condition.

Element except that Ba, Ca and Sr is described especially, described monogen comprises Li, Na, K, Rb, Cs etc., described dyad comprises V, Cr, Fe, Co, Ni, Cu, Zn, Mo, Ru, Pd, Ag, Cd, Sn, Sm, Tm, Yb, W, Re, Os, Ir, Pt, Hg, Pb etc., described trivalent element comprises B, Al, Ga, In etc., with rare earth element as Y or Sc and as described in pentad comprise P, Sb and Bi etc.Yet they are not limited thereto.In superincumbent all dyads, V, Zn, Mo, Sn, Sm, Tm, Yb, W and Pb are difficult for the described performance of influence.

Passing through M ¹²In described dyad and activating element Eu ²⁺And Mn ²⁺Solid internal diffusion in firing and promote to introduce described unit price, trivalent or the pentad of the total amount that is equal to or less than 20 moles of % on the meaning of crystallization of described silicate.

Consider scarlet component etc., the ratio (mol ratio) of Ca and the summation of Ba and Ca is preferably less than 0.1, and more preferably 0.Consider the emissive porwer of redness or white etc., the summation ratio of Ba, Ca and Sr preferably is equal to or greater than 80 moles of %, more preferably the summation ratio of Ba and Ca be equal to or greater than 80 moles of % and further more preferably the summation ratio of Ba, Ca and Sr be 100 moles of %.

M in the formula [3] ²²Represent one group to comprise the Si that is equal to or greater than 90 moles of % total amounts and the quadrivalent element of Ge.Yet, consider the emissive porwer of red and white etc., preferred M ²²Comprise the Si that is equal to or greater than 80 moles of % amount and more preferably M ²²Form by Si.Described quadrivalent element except that Si and Ge also comprises Zn, Ti, Hf etc.Consider the emissive porwer of redness or white etc., can in the scope of not damaging performance, comprise these elements.

Z in the formula [3] ²It is at least a element that is selected among negative monovalence and negative dyad, H and the N.It can be for example is negative univalent F, Cl, Br, I etc., and the same S, Se or Te for negative dyad with oxygen, and can comprise the OH base.The oxygen base can partly be transformed into ON base or N base.In addition, can influence the few degree of fluorescence property and comprise Z ², that is to say, with ratio based on the about 2 moles of % of being equal to or less than of all elements on impurity level.This is equivalent to Z ²/ (Z ²+ Sauerstoffatom) mol ratio is equal to or less than 0.035.Therefore, Z ²With (Z ²+ Sauerstoffatom) scope of mol ratio f2/ (e2+f2) is 0≤f2/ (e2+f2)≤0.035.Consider the performance of described fluor, it is preferably f2/ (e2+f2)≤0.01 and preferred f2/ (e2+f2)=0.

For the Eu mol ratio a2 in the formula [3], a2 is the number that satisfies 0.01＜a2≤0.8.As luminescence center ion Eu ²⁺Described mol ratio a2 very hour, emissive porwer is tending towards reducing, and preferably is equal to or greater than 0.001, more preferably is equal to or greater than 0.01.On the other hand, even when it is very big, by being called the phenomenon of concentration quenching or temperature quenching, described emissive porwer also is tending towards reducing.The upper limit is a2≤0.5 more preferably.

Mn mol ratio b2 in the formula [3] is that the selection to red emission or white light emission has material factor.When b2 is 0, does not obtain red peak and only produced blueness or blue-greenish colour peak.Yet, when b2 gets very little positive number, red peak in blue and green peak, occurs, thereby produce white light emission on the whole.When b2 got bigger positive number, blue and green peak almost disappeared, and mainly produces red peak.As red-emitting phosphors or white phosphor, the scope of b2 is 0＜b2≤0.8.It is contemplated that described fluor receives the irradiation of excitation light source to excite Eu ^{+ 2}, and the Eu that excites ^{+ 2}Energy transfer to Mn ^{+ 2}In, make Mn ^{+ 2}Red-emitting.The degree that energy shifts is mainly according to M ¹²And M ²²Composition and slightly different, so the boundary value of b2 (being transformed into white phosphor at this value place red-emitting phosphors) is according to M ¹²And M ²²Composition and slightly different.Therefore, can not strictly judge the good scope of the b2 that is used for red emission and white light emission.Yet, consider the intensity of the glow color that comprises described ruddiness and described white light etc., more preferably 0.002≤b2≤0.6 and further more preferably 0.005≤b2≤0.4.In the present invention, term " white " should broadly make an explanation, and means the two or more maximum value that are present in the emmission spectrum, and each is the broad band emission peak.

Mg in the formula [3] is mainly comprised the M of dyad ¹²Replace and the mole number of Mg and Mg and M ¹²The ratio c2/ (c2+d2) of total mole number be 0＜c2/ (c2+d2)≤0.2 or 0.3≤c2/ (c2+d2)≤0.8.Yet, consider the emissive porwer of redness or white etc., be preferably 0＜c2/ (c2+d2)≤0.7.

Crystallization phases Eu in above-mentioned formula [3] _A2Mn _B2Mg _C2M ¹² _D2M ²²O _E2Z ² _F2In, Eu ²⁺, Mn ²⁺And Mg ^{+ 2}The M that is mainly comprised dyad ¹²Replace M ²²Mainly occupied by Si and Ge, described negatively charged ion mainly is an oxygen, and M ¹², M ²²Be respectively 2,1 and 4 with total mol ratio of Sauerstoffatom in its essentially consist.Even when sometimes positively charged ion deficiency or negatively charged ion deficiency taking place, also have no significant effect required fluorescence property.Therefore, as the M that will be mainly occupied by Si and Ge ²²Total mol ratio in described chemical formula, be fixed as (M at 1 o'clock ¹²+ Eu+Mn+Mg) mol ratio (a2+b2+c2+d2) is preferably 1.9-2.1 in 1.8≤(a2+b2+c2+d2)≤2.2 scope, and more preferably (a2+b2+c2+d2)=2.In addition, in the scope of total mol ratio (e2+f2) 3.6≤(e2+f2)≤4.4 in the site of negatively charged ion side, and more preferably e2=4 and f2=0.

Can be by following (A) or hybrid system (B), preparation is as being shown in the M in the above-mentioned formula [3] ¹²Source, M ²²Source and Mg source and mixture as the element source compound of the Eu of activating element and Mn, and fire described mixture by thermal treatment and prepare and be used for described fluor of the present invention.

(A) combine the porphyrization that uses drying and crushing machine such as hummer runner milling (hummer mill), roller mill, ball mill or micronizer mill (jet mill), or the porphyrization of use mortar and pestle, with the mixing of using mixing tank such as ribbon blender, V-type mixing tank or Henschel mixing tank, or the blended dry blending method of use mortar and pestle.

Described M ¹²Source, described M ²²The element source compound of source, described Mg source and described activating element comprises M respectively ¹², M ²², Mg and activating element various oxide compounds, oxyhydroxide, carbonate, nitrate, vitriol, oxalate, carboxylate salt, halogenide etc., among these, consider to have reactivity, and when firing, do not produce NO with composite oxides _x, SO _xDeng selecting.

For as M ¹²And above-mentioned Ba, the Ca and the Sr that enumerate, if specifically enumerate described M ¹²Source compound, Ba source compound comprise BaO, Ba (OH) ₂8H ₂O, BaCO ₃, Ba (NO ₃) ₂, BaSO ₄, Ba (OCO) ₂2H ₂O, Ba (OCOCH ₃) ₂, BaCl ₂Deng, the Ca source compound comprises CaO, Ca (OH) ₂, CaCO ₃, Ca (NO ₃) ₂4H ₂O, CaSO ₄2H ₂O, Ca (OCO) ₂H ₂O, Ca (OCOCH ₃) ₂H ₂O, CaCl ₂Deng and the Sr source compound comprise SrO, Sr (OH) ₂8H ₂O, SrCO ₃, Sr (NO ₃) ₂, SrSO ₄, Sr (OCO) ₂H ₂O, Sr (OCOCH ₃) ₂0.5H ₂O, SrCl ₂Deng.

For as M ²²And the above-mentioned Si and the Ge that enumerate, if specifically enumerate described M ²²Source compound, the Si source compound comprises SiO ₂, H ₄SiO ₄, Si (OCOCH ₃) ₄Deng and the Ge source compound comprise GeO ₂, Ge (OH) ₄, Ge (OCOCH ₃) ₄, GeCl ₄Deng.

The present inventor finds that the fluor with the specific crystal structure except that above-mentioned compositing range demonstrates extra high emissive porwer, thereby has finished the present invention.Usually use crystallographic system, spacer to wait and define described crystalline structure.Yet, in described crystallization phases of the present invention,, therefore can not carry out organization definition without exception because the change of described crystallographic system or described spacer has taken place in the distortion (small structural modification) of the crystalline structure relevant with forming change.Then, disclose to define and helped the required X-ray diffraction pattern of luminous described crystallization phases.Usually, in order to determine the identity of two kinds of compound crystal structures by described X-ray diffraction pattern, comprise that identical on angle (2 θ) of about 6 diffraction peaks based on the maximum diffraction peak of its crystalline structure is sufficient.Yet when the component ratio was different from compound of the present invention, even crystalline structure is identical, the angle of described diffraction peak also was offset.Therefore, the specific angle of described diffraction peak can not be defined as numerical value.Therefore, the inventor is paid close attention at interval to the face of the diffraction peak that the use Bragg equation calculates, and has determined the angular region of described diffraction peak by following characterizing method.

Bragg equation

D=λ/{ 2 * sin (θ) } (equation 1)

θ=arcsin{ λ/(2 * d) } (equation 2)

D: face is (dust) at interval

θ: the Braag angle (°)

λ: the X-beam wavelength of CuK α=1.54184 dusts

In addition, (equation 2) is the equation that changes in (equation 1).When described face interval with reference to diffraction peak was defined as 4.17 dusts-3.95 dust, the scope of diffraction angle described in (equation 2) (2 θ) became 21.3 °～22.5 °.

From the angle (θ 0) of measured reference diffraction peak, described face interval (d0) with reference to diffraction peak becomes by (equation 1) and becomes following (equation 3).

D0=λ/{ 2 * sin (θ 0) } (equation 3)

From Small angle one side will except that described with reference to five peaks the diffraction peak as P1, P2, P3, P4 and P5, the described angular range that each peak occurs is successively as R1, R2, R3, R4 and R5.

The following angular range R1 that determines wherein to occur P1.When diffraction plane have for be derived from described face with reference to diffraction peak at interval (d0) 0.720 times face at interval, and the face spacing bias relevant with described structural distortion got do at 1.5% o'clock, the start angle of described angular range R1 (R1s) and termination point (R1e) derive from following (equation 1):

R1s：2×arcsin{λ/(2×d0×0.720×1.015)}

R1e：2×arcsin{λ/(2×d0×0.720×0.985)}

Below substitution (equation 3) respectively:

R1s：2×arcsin{sin(θ0)/(0.720×1.015)}

R1e：2×arcsin{sin(θ0)/(0.720×0.985)}

When being defined as respectively, the following angular range that will wherein occur P2, P3, P4 and P5 in the same manner is derived from interval 0.698 times, 0.592 times, 0.572 times and 0.500 times of described face with reference to diffraction peak, do at 1.5% o'clock with the face spacing bias relevant with described structural distortion got without exception, each angular region is as follows:

R2s：2×arcsin{sin(θ0)/(0.698×1.015)}

R2e：2×arcsin{sin(θ0)/(0.698×0.985)}

R3s：2×arcsin{sin(θ0)/(0.592×1.015)}

R3e：2×arcsin{sin(θ0)/(0.592×0.985)}

R4s：2×arcsin{sin(θ0)/(0.572×1.015)}

R4e：2×arcsin{sin(θ0)/(0.572×0.985)}

R5s：2×arcsin{sin(θ0)/(0.500×1.015)}

R5e：2×arcsin{sin(θ0)/(0.500×0.985)}

That is to say that for the X-ray diffraction measuring result that so obtains, by the existence at the peak separately among the reference peak P0-P5 that confirms to occur in the above-mentioned angular region, susceptible of proof is as the existence of specific crystal structure as described in defining among the present invention.This crystallization phases is to be different from the merwinite of describing in non-patent literature 1 and the non-patent literature 2.Above-mentioned angular range R1-R5 is more preferably as follows, wherein the deviation at described the interval relevant with described structural distortion is got without exception and does 1.0%.

R1:2 * arcsin{sin (θ 0)/(0.720 * 1.010) } to 2 * arcsin{sin (θ 0)/(0.720 * 0.990) }

R2:2 * arcsin{sin (θ 0)/(0.698 * 1.010) } to 2 * arcsin{sin (θ 0)/(0.698 * 0.990) }

R3:2 * arcsin{sin (θ 0)/(0.592 * 1.010) } to 2 * arcsin{sin (θ 0)/(0.592 * 0.990) }

R4:2 * arcsin{sin (θ 0)/(0.572 * 1.010) } to 2 * arcsin{sin (θ 0)/(0.572 * 0.990) }

R5:2 * arcsin{sin (θ 0)/(0.500 * 1.010) } to 2 * arcsin{sin (θ 0)/(0.500 * 0.990) }

Although the method that is used for preparation characterization above-mentioned crystallization phases of the present invention without limits, the raw material that for example can have the particle size that is equal to or less than 10 μ m by use, the water-free raw material of silica wherein particularly, make to fire not exist before and form uneven localized agglomeration thing, and in using the crucible of making by carbon, under reducing atmosphere, fire, and obtain desirable crystallization phases.

As mentioned above, clear all fluor with high emission intensity that obtain in the present invention comprise above-mentioned specific crystallization phases.Thus, can determine that they are the fluor that comprise the crystallization phases of alkaline-earth silicate, described alkaline-earth silicate comprises at least a element that is selected among Ba, Sr, Ca and the Mg and with fluor that to comprise above-mentioned definite crystallization phases be feature.

In the present invention, the first twinkler emission wavelength with the above-mentioned fluor of rayed is the light of 350nm-430nm.Preferably, use can be launched the twinkler with the long light of spike in the 350nm-430nm wavelength region.The particular instance of described first twinkler comprises photodiode (LED), laser diode (LD) etc.According to low power consumption, more preferably laser diode.Especially, preferably use GaN compounds semi-conductive GaN class LED or LD.This is that described GaN class LED or LD have significantly higher emission output and external quantum efficiency because compare with SiC class LED luminous in this zone etc., and by in conjunction with above-mentioned fluor, can obtain very bright luminous under very low electric power.For example, for the current loading of 20mA, described GaN-base LED or LD have the emissive porwer of the described SiC-base that is equal to or greater than 100 times usually.In described GaN-base LED or LD, preferably has Al _xGa _yN luminescent layer, GaN luminescent layer or In _xGa _yThe described GaN-base LED or the LD of N luminescent layer.In described GaN-base LED,, and especially preferably has In wherein owing to extra high emissive porwer _xGa _yThe GaN-base LED of N luminescent layer.In described GaN-base LD, especially preferably has described In because of extra high emissive porwer _xGa _yThe GaN-base LD of the multi-quantum pit structure of N layer and described GaN layer.In above-mentioned, the value of X+Y is generally the value of 0.8-1.2.In described GaN-base LED, according to the control emission characteristic, preferably wherein luminescent layer mixes with Zn or Si or undoped GaN-base LED.Described GaN-base LED has luminescent layer, p layer, n layer, electrode and substrate as underlying dimension.Preferably have wherein said luminescent layer owing to high emission efficiency and be clipped in described n type and p type Al _xGa _yN layer, GaN layer, In _xGa _yLED such as base such as the GaN-of the assorted structure between the N layer etc. is because higher emission efficiency and more preferably wherein said assorted structure forms the GaN-base LED of quantum well structure.

In the present invention, especially preferably use the surface-emitting type twinkler, particularly surface-emitting type GaN-based laser diode is as described first twinkler, because it has improved the emission efficiency of whole light-emitting device.Described surface-emitting type twinkler is to have strong luminous twinkler on the face direction of film.In described surface-emitting type GaN-based laser diode, the crystal growth by controlling described luminescent layer etc. and good design reflecting layer etc. can make luminous on the face direction of described luminescent layer more be better than luminous on edge direction.Compare with type, can increase the luminous sectional area of each unit luminous quantity by using described surface-emitting type twinkler from the edge-lit of luminescent layer.As a result, when using the fluor of described second twinkler of rayed, under the light of same amount, can extremely increase irradiated area to improve illumination efficiency.Therefore, from the fluor of described second twinkler, can obtain stronger luminous.

When described surface-emitting type twinkler was used as first twinkler, second twinkler was preferably membranaceous.The result, light from described surface-emitting type twinkler has enough big sectional area, thereby, the irradiation sectional area of described fluor has been increased the per unit amount of described fluor from described first twinkler on its cross-wise direction when second twinkler being made when membranaceous.Therefore, can further increase luminous intensity from described fluor.

In addition, when with described surface-emitting type twinkler as first twinkler and with membranaceous twinkler when second twinkler, the preferred form that adopts the second membranaceous twinkler wherein directly to contact the light-emitting area of first twinkler.Here used described term " contact " means that first twinkler wherein closely contacts each other with second twinkler and do not have the state of air entrainment or gas.As a result, can avoid reflecting the light loss that leaks into the outside from the film surface of second twinkler, therefore can improve the emission efficiency of whole device from the light of first twinkler.

The schematic isometric that has shown first twinkler among the embodiment who is illustrated in light-emitting device of the present invention and the position between second twinkler relation among Fig. 1.In Fig. 1,1 expression has the second membranaceous twinkler of above-mentioned fluor, and 2 expressions are as the surface-emitting type GaN-base LD and the 3 expression substrates of first twinkler.In order to produce the state that contacts with each other, prepare described LD 2 and described second twinkler 1 respectively, and its face is contacted with each other, or on the light-emitting area of described LD 2, form described second twinkler as film (moulding) by adhesion or additive method.As a result, can make described LD 2 and described second twinkler 1 be in contact condition.

Usually launch to all directions from the light of first twinkler with from the light of second twinkler.Yet, when the powder with the described second twinkler fluor is dispersed in the resin, reflected light partly when light leaves described resin, but therefore its direction of alignment to a certain extent.Therefore, described light can be directed into efficient direction to a certain extent, and therefore preferred the use wherein is dispersed with the twinkler of above-mentioned fluorophor powder as the 2nd twinkler in described resin.In addition, when described fluor is dispersed in the described resin, increased the total irradiated area of light on second twinkler from first twinkler.Also therefore has the advantage that can increase from the emissive porwer of second twinkler.The described resin that can be used in this situation comprises various kinds of resin such as silicon resin, Resins, epoxy, polyvinyl resin, polyethylene kind (polyethylenic) resin, polypropylene-base (polypropylenic) resin and polyester resin.Yet, according to the good dispersion of described fluorophor powder, preferred silicon resin or Resins, epoxy.

When being dispersed in the described second twinkler powder in the described resin, the weight ratio of the described second twinkler powder and all powder and described resin is generally 10%-95%, is preferably 20%-90% and 30%-80% more preferably.When described fluor is too much, because the congregation of described powder can reduce emission efficiency sometimes.When it is very few, because the photoabsorption or the scattering of described resin can decrease emission efficiency sometimes.

Described light-emitting device of the present invention comprises the luminous element as the above-mentioned fluor of material for transformation of wave length and emission 350nm-430nm.Above-mentioned fluor absorbs the light of the 350nm-430nm that described luminous element sends, has good color rendering and does not depend on environment for use and can launch the described light-emitting device of high strength visible light to provide.Shine by being used for the light of first twinkler of self-emission 350nm-430nm light, the fluor of the present invention that constitutes light-emitting device and have a described crystallization phases is transmitted in the light in the red or white wavelength region of expression.Therefore, described light-emitting device of the present invention is applicable to the luminous source of backlight, traffic signals etc., image-displaying member such as colour liquid crystal display device, and means of illumination such as face are luminous etc.

Described light-emitting device of the present invention is described with reference to the accompanying drawings, Fig. 2 is the schematic cross-sectional view that shows an example of the light-emitting device with first twinkler (350nm-430nm twinkler) and second twinkler, the 4th, light-emitting device, the 5th, lead is installed, the 6th, inner lead, 7 is first twinkler (twinklers of 350nm-430nm), the 8th, as the resin part that contains fluor of second twinkler, the 9th, conductor wire and 10 is profile members.

The light-emitting device of one embodiment of the invention has as being shown in the conventional artillery type form among Fig. 2, and first twinkler (350nm to 430nm twinkler) 7 of the described GaN of comprising class photodiode etc. by with the formation that contains fluor as the resin of described second twinkler partly cover be fixed on described installation lead 5 on cover, by mix at tackiness agent as silicon resin, Resins, epoxy or acrylic resin and disperse as described in fluor, and described dispersion poured in the cup and form described second twinkler.On the other hand, first twinkler 7 and described installation lead 5, and first twinkler 7 conducts electricity with described conductor wire 9 separately each other mutually with described inner lead 6, and cover and protect them whole with the profile member 10 that comprises Resins, epoxy etc.

In addition, as shown in Figure 3, incorporate into therein in the face litillumination devices 11 of luminous element 1, the lighttight square that a plurality of light-emitting devices 13 placement internal surfaces are made as white smooth surface keeps on the basal surface of container 12, the (not shown)s such as power supply, circuit that will be used to drive described light-emitting device 13 are placed on its outside, with scatterer panel 14 as oyster white acrylic panel etc. be fixed to be equivalent to as described on the part of lid of container 12, be used to make luminous evenly.

Then, drive described litillumination devices 11 and apply voltage, launch the light of 350nm-430nm thus with described first twinkler to luminous element 13.Described luminous component ground is absorbed with visible emitting at the described above-mentioned fluor that contains conduct second twinkler in the fluor resin part.On the other hand, by with the colour mixture of blue light that is not absorbed etc. by described fluor, can obtain to have the luminous of high color rendering.The described scatterer panel 14 of these light transmissions, and above drawing, penetrate.Therefore, can obtain scatterer panel 14 lip-deep illumination light with uniform luminance at described maintenance container (holding case) 12.

Embodiment

Reference example illustrates in greater detail the present invention, but should not think the present invention only limit within its main points below embodiment.

Embodiment A-1

With Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 0.64: 0.96: 0.2: 0.2: 1) in the platinum container, mix and dry.Then, by heating 2 hours described mixture fired with preparation fluor Ba in 1050 ℃ under the nitrogen gas stream that comprises 4% hydrogen _0.64Ca _0.96Eu _0.2Mn _0.2SiO ₄(fluor that uses in second twinkler).Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength of GaN-based light-emitting diode in the UV-light zone.The wavelength of its emission peak, described emission peak intensity (hereinafter referred to as relative intensity) and half breadth when the emission peak intensity of the Comparative Examples A that will describe later-2 is considered as 100 are shown in Table 1.This fluor has enough wide half breadth, has obtained good color rendering, and sends and have the pale red coloured light of peak wavelength in the 590nm-620nm scope.This shows that this fluor launches the bright red light of sensation.

Comparative Examples A-1

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Eu (NO ₃) ₃6H ₂O and SiO ₂Mol ratio be 0.72: 1.08: 0.2: 1) as outside the starting soln, with embodiment A-1 in same way as make fluor Ba _0.72Ca _1.08Eu _0.2SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength of GaN-based light-emitting diode in the UV-light zone.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 1.Demonstration red peak do not occur when in the composition that Mn is not joined embodiment A-1.

Comparative Examples A-2

Remove Ba (NO ₃) ₂The aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 1.6: 0.2: 0.2: 1) as outside the starting soln, with embodiment A-1 in same way as make fluor Ba _1.6Eu _0.2Mn _0.2SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength of GaN-based light-emitting diode in the UV-light zone.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 1.Demonstration red peak do not occur when in the composition that Ca is not joined embodiment A-1.

Comparative Examples A-3

Remove Ca (NO ₃) ₂4H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ca (NO ₃) ₂4H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 1.6: 0.2: 0.2: 1) as outside the starting soln, with embodiment A-1 in same way as make fluor Ca _1.6Eu _0.2Mn _0.2SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength of GaN-based light-emitting diode in the UV-light zone.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 1.Demonstration red peak do not occur when in the composition that Ba is not joined embodiment A-1.

Embodiment A-2

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 0.84: 0.56: 0.3: 0.3: 1) as outside the starting soln, with embodiment A-1 in same way as make fluor Ba _0.84Ca _0.56Eu _0.3Mn _0.3SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength of GaN-based light-emitting diode in the UV-light zone.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 1.This fluor has enough wide half breadth, has obtained good color rendering, and sends and have the light red of peak wavelength in the 590nm-620nm scope.This shows that this fluor launches the bright red light of sensation.

Embodiment A-3

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 0.75: 0.5: 0.3: 0.45: 1) as outside the starting soln, with embodiment A-1 in same way as make fluor Ba _0.75Ca _0.5Eu _0.3Mn _0.45SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength of GaN-based light-emitting diode in the UV-light zone.Described emmission spectrum is shown among Fig. 4.In order to eliminate the influence of excitation light source, introduce the wave filter that is used for blocking the light that is equal to or less than 420nm and measure described emmission spectrum.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 1.This fluor has enough wide half breadth, has obtained good color rendering, and sends and have the light red of peak wavelength in the 590nm-620nm scope.This shows that this fluor launches the bright red light of sensation.

Table 1

Embodiment or comparative example	The chemical constitution of fluor	The wavelength of emission peak (nm)	The relative intensity of emission peak	The half breadth of emission peak (nm)	The mol ratio of Mn	The ratio (mol ratio) of Ca and the summation of Ba and Ca
Embodiment or comparative example	The chemical constitution of fluor	The wavelength of emission peak (nm)	The relative intensity of emission peak	The half breadth of emission peak (nm)	The mol ratio of Mn	The ratio (mol ratio) of Ca and the summation of Ba and Ca	Embodiment A-1	Ba _0.64Ca _0.96Eu _0.2Mn _0.2SiO ₄	605	108	80	0.2	0.6
Embodiment A-2	Ba _0.84Ca _0.56Eu _0.3Mn _0.3SiO ₄	603	75	79	0.3	0.4	Embodiment A-1	Ba _0.64Ca _0.96Eu _0.2Mn _0.2SiO ₄	605	108	80	0.2	0.6
Embodiment A-2	Ba _0.84Ca _0.56Eu _0.3Mn _0.3SiO ₄	603	75	79	0.3	0.4	Embodiment A-3	Ba _0.75Ca _0.5Eu _0.3Mn _0.45SiO ₄	607	36	79	0.45	0.4
Comparative Examples A-1	Ba _0.72Ca _1.08Eu _0.2SiO ₄	448	99	104	0	0.6	Embodiment A-3	Ba _0.75Ca _0.5Eu _0.3Mn _0.45SiO ₄	607	36	79	0.45	0.4
Comparative Examples A-1	Ba _0.72Ca _1.08Eu _0.2SiO ₄	448	99	104	0	0.6	Comparative Examples A-2	Ba _1.6Eu _0.2Mn _0.2SiO ₄	509	100	62	0.2	0
Comparative Examples A-3	Ca _1.6Eu _0.2Mn _0.2SiO ₄	512	25	85	0.2	1	Comparative Examples A-2	Ba _1.6Eu _0.2Mn _0.2SiO ₄	509	100	62	0.2	0

Embodiment A-4

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 1.11: 0.74: 0.06: 0.09: 1) as outside the starting soln, with embodiment A-1 in same way as make fluor Ba _1.11Ca _0.74Eu _0.06Mn _0.09SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength of GaN-based light-emitting diode in the UV-light zone.

Its emmission spectrum is shown among Fig. 5.The wavelength of the x of tristimulus coordinates of expression color and y value, maximum peak, the intensity (hereinafter referred to as the relative intensity of maximum peak) of this fluor maximum peak when the maximum peak intensity of fluor in the Comparative Examples A that will describe later-5 is considered as 100, at the ratio of intensity with the intensity of described maximum peak at 600nm place, which kind of degree is the red component that its expression exists reach, and the half breadth at one group of peak is shown in Table 2.All abundant the existence becomes the non-constant width of described spectrum width thereby these demonstrations have obtained its Smalt, green and red component, and the very high white light emission of color rendering.

Maximum peak means that when having a plurality of peak in emmission spectrum at peak the highest on the intensity with in unimodal situation, described maximum peak is itself.In addition, as shown in Figure 6, how wide the half breadth at one group of peak represents that emmission spectrum distributes and how high color rendering is, and it is defined as the total width of the wavelength region of the half intensity with the intensity that is equal to or greater than maximum peak in the spectrum.For example, in Fig. 6, the described half breadth at one group of peak becomes the summation of width B and width C.

Embodiment A-5

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 0.68: 1.02: 0.2: 0.1: 1) as outside the starting soln, with embodiment A-1 in same way as make fluor Ba _0.68Ca _1.02Eu _0.2Mn _0.1SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength of GaN-based light-emitting diode in the UV-light zone.The wavelength of the x of tristimulus coordinates and y value, maximum peak, the relative intensity of maximum peak, at the ratio of intensity with the intensity of described maximum peak at 600nm place, and the half breadth at one group of peak is shown in Table 2.Thereby these demonstrations have obtained wherein red component and have fully existed and become the non-constant width of described spectrum width, and the very high white light emission of color rendering.

Comparative Examples A-4

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Eu (NO ₃) ₃6H ₂O and SiO ₂Mol ratio be 0.72: 1.08: 0.2: 1) as outside the starting soln, with embodiment A-1 in same way as make fluor Ba _0.72Ca _1.08Eu _0.2SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength of GaN-based light-emitting diode in the UV-light zone.The wavelength of the x of tristimulus coordinates and y value, maximum peak, the relative intensity of maximum peak, at the ratio of intensity with the intensity of described maximum peak at 600nm place, and the half breadth at one group of peak is shown in Table 2.These demonstrations do not obtain white spectrum when in the composition that Mn is not joined embodiment A-5.

Comparative Examples A-5

Remove Ba (NO ₃) ₂The aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 1.7: 0.2: 0.1: 1) as outside the starting soln, with embodiment A-1 in same way as make fluor Ba _1.7Eu _0.2Mn _0.1SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength of GaN-based light-emitting diode in the UV-light zone.The wavelength of the x of tristimulus coordinates and y value, maximum peak, the relative intensity of maximum peak, at the ratio of intensity with the intensity of described maximum peak at 600nm place, and the half breadth at one group of peak is shown in Table 2.These demonstrations do not obtain white spectrum when in the composition that Ca is not joined embodiment A-5.

Comparative Examples A-6

Remove Ca (NO ₃) ₂4H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ca (NO ₃) ₂4H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 1.7: 0.2: 0.1: 1) as outside the starting soln, with embodiment A-1 in same way as make fluor Ca _1.7Eu _0.2Mn _0.1SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength of GaN-based light-emitting diode in the UV-light zone.The wavelength of the x of tristimulus coordinates and y value, maximum peak, the relative intensity of maximum peak, at the ratio of intensity with the intensity of described maximum peak at 600nm place, and the half breadth at one group of peak is shown in Table 2.These demonstrations do not obtain white spectrum when in the composition that Ba is not joined embodiment A-5.

Embodiment A-6

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 0.93: 0.62: 0.3: 0.15: 1) as outside the starting soln, with embodiment A-1 in same way as make fluor Ba _0.93Ca _0.62Eu _0.3Mn _0.15SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength of GaN-based light-emitting diode in the UV-light zone.The wavelength of the x of tristimulus coordinates and y value, maximum peak, the relative intensity of maximum peak, at the ratio of intensity with the intensity of described maximum peak at 600nm place, and the half breadth at one group of peak is shown in Table 2.Thereby these demonstrations have obtained wherein red component and have fully existed and become the non-constant width of described spectrum width, and the very high white light emission of color rendering.

Embodiment A-7

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Zn (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Zn (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 1.133: 0.378: 0.189: 0.2: 0.1: 1) as outside the starting soln, with embodiment A-1 in same way as make fluor Ba _1.133Ca _0.378Zn _0.189Eu _0.2Mn _0.1SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength of GaN-based light-emitting diode in the UV-light zone.The wavelength of the x of tristimulus coordinates and y value, maximum peak, the relative intensity of maximum peak, at the ratio of intensity with the intensity of described maximum peak at 600nm place, and the half breadth at one group of peak is shown in Table 2.Thereby these demonstrations have obtained wherein red component and have fully existed and become the non-constant width of described spectrum width, and the very high white light emission of color rendering.

Table 2

Embodiment or comparative example	The chemical constitution of fluor	Tristimulus coordinates		The wavelength of maximum peak (nm)	The relative intensity of maximum peak	The intensity of the intensity/maximum peak at 600nm place	The half breadth at one group of peak (nm)	The mol ratio of Mn	The ratio (mol ratio) of Ca and Ba and Ca summation
		Tristimulus coordinates								x	y
		Embodiment A-4	Ba _1.11Ca _0.74Eu _0.06Mn _0.09SiO ₄							x	y	0.34 6	0.34	597	157	0.984	208	0.09	0.4
Embodiment A-5	Ba _0.68Ca _1.02Eu _0.2Mn _0.1SiO ₄	Embodiment A-4	Ba _1.11Ca _0.74Eu _0.06Mn _0.09SiO ₄	0.37 5	0.37	597	115	0.997	194	0.1	0.6	0.34 6	0.34	597	157	0.984	208	0.09	0.4
Embodiment A-5	Ba _0.68Ca _1.02Eu _0.2Mn _0.1SiO ₄	Embodiment A-6	Ba _0.93Ca _0.62Eu _0.3Mn _0.15SiO ₄	0.37 5	0.37	597	115	0.997	194	0.1	0.6	0.35 1	0.353	600	89	1	206	0.15	0.4
Embodiment A-7	Ba _1.133Ca _0.378Zn _0.189Eu _0.2Mn _0.1 SiO ₄	Embodiment A-6	Ba _0.93Ca _0.62Eu _0.3Mn _0.15SiO ₄	0.36 3	0.37	598	60	1	193	0.1	0.25	0.35 1	0.353	600	89	1	206	0.15	0.4
Embodiment A-7	Ba _1.133Ca _0.378Zn _0.189Eu _0.2Mn _0.1 SiO ₄	Comparative Examples A-4	Ba _0.72Ca _1.08Eu _0.2SiO ₄	0.36 3	0.37	598	60	1	193	0.1	0.25	0.19	0.229	448	110	0.12	104	0	0.6
Comparative Examples A-5	Ba _1.7Eu _0.2Mn _0.1SiO ₄	Comparative Examples A-4	Ba _0.72Ca _1.08Eu _0.2SiO ₄	0.16 7	0.527	504	100	0.042	63	0.1	0	0.19	0.229	448	110	0.12	104	0	0.6
Comparative Examples A-5	Ba _1.7Eu _0.2Mn _0.1SiO ₄	Comparative Examples A-6	Ca _1.7Eu _0.2Mn _0.1SiO ₄	0.16 7	0.527	504	100	0.042	63	0.1	0	0.25 4	0.421	504	42	0.27	92	0.1	1

Embodiment A-8

With mol ratio 1.08: 0.72: 0.075: 0.05: 1 weighing BaCO ₃, CaCO ₃, Eu ₂O ₃, MnCO ₃NH ₂O and SiO ₂, and add NH ₄Cl mixed 1 hour in ball mill then as solder flux.The powder of so preparation is put into alumina crucible, is put in the crucible that carbon makes together with this crucible in addition, and under the nitrogen gas stream that comprises 4% hydrogen in 1200 ℃ of heating 6 hours, make fluor Ba thus _1.08Ca _0.72Eu _0.15Mn _0.05SiO ₄Carrying out the X-ray diffraction of this fluor under the following conditions measures.Use comprise CuK α as X-ray source (with its in described diffraction angle error optical adjustment of sweep limit to Δ 2 θ=0.05 ° or littler) Prague-Brentano type powder x-ray diffraction instrument, use therein under the condition of 111 peaks of the standard silicon diffraction angle error relevant as Δ 2 θ=0.05 ° or the littler angle guaranteed reproducibility and carry out the powder x-ray diffraction measurement with the sample excentricity.In addition, the angle of divergence of regulating divergent slit makes the irradiating width of described X-ray not exceed the sample width in the measurement, and for described diffraction peak position (summit) and diffracted intensity (highly), reads out in the value of the measuring result in the fixing slit mode.The X-ray diffraction measuring result is shown among Fig. 7.Table 3 shows that the gained fluor satisfies the condition of describing in the claim 6, and confirms that it comprises above-mentioned specific phase.Emmission spectrum when exciting this fluor at the 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode is shown among Fig. 8.In order to eliminate the influence of excitation light source to described emmission spectrum, blocking-up is equal to or less than the light of 420nm.The wavelength of the emission peak of the x of tristimulus coordinates and y value, this fluor and the intensity of emission peak are shown in Table 4.

Embodiment A-9

Divided by mol ratio 1.35: 0.45: 0.075: 0.05: 1 weighing BaCO ₃, CaCO ₃, Eu ₂O ₃, MnCO ₃NH ₂O and SiO ₂Make fluor Ba with same way as outward, with embodiment A-8 _1.35Ca _0.45Eu _0.15Mn _0.05SiO ₄The X-ray diffraction measuring result is shown in Table 3, and this embodiment satisfies the condition of claim 6.Emmission spectrum is shown among Fig. 8, and characteristic is summarised in the table 4.

Embodiment A-10

Divided by mol ratio 1.20: 0.4: 0.2: 0.075: 0.05: 1 weighing BaCO ₃, CaCO ₃, SrCO ₃, Eu ₂O ₃, MnCO ₃NH ₂O and SiO ₂Make fluor Ba with same way as outward, with embodiment A-8 _1.20Ca _0.4Sr _0.2Eu _0.15Mn _0.05SiO ₄The X-ray diffraction measuring result is shown in Table 3, and this embodiment satisfies the condition of claim 6.Emmission spectrum is shown among Fig. 8, and characteristic is summarised in the table 4.

Embodiment A-11

Divided by mol ratio 1.08: 0.36: 0.36: 0.075: 0.05: 1 weighing BaCO ₃, CaCO ₃, SrCO ₃, Eu ₂O ₃, MnCO ₃NH ₂O and SiO ₂Make fluor Ba with same way as outward, with embodiment A-8 _1.08Ca _0.36Sr _0.36Eu _0.15Mn _0.05SiO ₄The X-ray diffraction measuring result is shown in Table 3, and this embodiment satisfies the condition of claim 6.Emmission spectrum is shown among Fig. 8, and characteristic is summarised in the table 4.

Table 3

Embodiment A-8

With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring
With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring	21.366	R1	29.537	30.148	30.061	78.1
Intensity	R2	30.490	31.122	30.864	100.0	21.366	R1	29.537	30.148	30.061	78.1
Intensity	R2	30.490	31.122	30.864	100.0	54.5	R3	36.122	36.878	36.562	12.2
	R4	37.432	38.217	37.914	25.6	54.5	R3	36.122	36.878	36.562	12.2
	R4	37.432	38.217	37.914	25.6	R5	43.071	43.986	43.712	31.8

Embodiment A-9

With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring
With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring	21.553	R1	29.799	30.415	30.227	73.7
Intensity	R2	30.761	31.398	31.085	100.0	21.553	R1	29.799	30.415	30.227	73.7
Intensity	R2	30.761	31.398	31.085	100.0	49.4	R3	36.446	37.209	36.666	17.6
	R4	37.767	38.560	38.130	26.6	49.4	R3	36.446	37.209	36.666	17.6
	R4	37.767	38.560	38.130	26.6	R5	43.463	44.387	43.857	28.4

Embodiment A-10

With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring
With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring	21.614	R1	29.884	30.502	30.331	93.0
Intensity	R2	30.849	31.488	31.173	100.0	21.614	R1	29.884	30.502	30.331	93.0
Intensity	R2	30.849	31.488	31.173	100.0	51.3	R3	36.551	37.317	36.856	13.2
	R4	37.877	38.672	38.248	31.7	51.3	R3	36.551	37.317	36.856	13.2
	R4	37.877	38.672	38.248	31.7	R5	43.590	44.518	44.035	38.4

Embodiment A-11

With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring
With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring	21.702	R1	30.007	30.628	30.448	100.0
Intensity	R2	30.976	31.618	31.262	96.7	21.702	R1	30.007	30.628	30.448	100.0
Intensity	R2	30.976	31.618	31.262	96.7	42.7	R3	36.512	37.276	37.243	16.3
	R4	38.035	38.834	38.381	29.4	42.7	R3	36.512	37.276	37.243	16.3
	R4	38.035	38.834	38.381	29.4	R5	43.775	44.706	44.197	32.2

Table 4

Embodiment	The chemical constitution of fluor	Tristimulus coordinates		The wavelength of emission peak (nm)	The intensity of emission peak (arbitrary scale)
		Tristimulus coordinates				x	y
		Embodiment A-8	Ba _1.08Ca _0.72Eu _0.15Mn _0.05SiO ₄			x	y	0.461	0.414	605	113
Embodiment A-9	Ba _1.35Ca _0.45Eu _0.15Mn _0.05SiO ₄	Embodiment A-8	Ba _1.08Ca _0.72Eu _0.15Mn _0.05SiO ₄	0.537	0.389	601	251	0.461	0.414	605	113
Embodiment A-9	Ba _1.35Ca _0.45Eu _0.15Mn _0.05SiO ₄	Embodiment A 1-0	Ba _1.20Ca _0.4Sr _0.2Eu _0.15Mn _0.05SiO ₄	0.537	0.389	601	251	0.538	0.415	605	175
Embodiment A-11	Ba _1.08Ca _0.36Sr _0.36Eu _0.15Mn _0.05SiO ₄	Embodiment A 1-0	Ba _1.20Ca _0.4Sr _0.2Eu _0.15Mn _0.05SiO ₄	0.541	0.427	613	113	0.538	0.415	605	175

Embodiment B-1

With Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 1.133: 0.378: 0.189: 0.2: 0.1: 1) in the platinum container, mix and dry.Then, by heating 2 hours described mixture fired with preparation fluor Ba in 1050 ℃ under the nitrogen gas stream that comprises 4% hydrogen _1.133Ca _0.378Mg _0.189Eu _0.2Mn _0.1SiO ₄(fluor that uses in second twinkler).Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength of its emission peak, described emission peak intensity (hereinafter referred to as relative intensity) and half breadth when the emission peak intensity of the comparative example B-3 that will describe later is considered as 100 are shown in Table 5.This fluor has enough wide half breadth, has obtained good color rendering, and sends and have the light red of peak wavelength in the 590nm-620nm scope.This shows that this fluor launches the bright red light of sensation.

Comparative example B-1

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O and SiO ₂Mol ratio be 1.2: 0.4: 0.2: 0.2: 1) as outside the starting soln, with Embodiment B-1 in same way as make fluor Ba _1.2Ca _0.4Mg _0.2Eu _0.2SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 5.Demonstration red peak do not occur when in the composition that Mn is not joined in the Embodiment B-1.

Comparative example B-2

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Eu (NO ₃) ₃6H ₂O and SiO ₂Mol ratio be 0.72: 1.08: 0.2: 1) as outside the starting soln, with Embodiment B-1 in same way as make fluor Ba _0.72Ca _1.08Eu _0.2SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 5.Demonstration red peak do not occur in crystal when not comprising Mn component or Mg component.

Comparative example B-3

Remove Ba (NO ₃) ₂The aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 1.6: 0.2: 0.2: 1) as outside the starting soln, with Embodiment B-1 in same way as make fluor Ba _1.6Eu _0.2Mn _0.2SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 5.Even show in the crystal to comprise Mn, but when not comprising Ca or Mg, red peak also do not occur.

Comparative example B-4

Remove Ca (NO ₃) ₂4H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ca (NO ₃) ₂4H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 1.6: 0.2: 0.2: 1) as outside the starting soln, with Embodiment B-1 in same way as make fluor Ca _1.6Eu _0.2Mn _0.2SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 5.Even show in the crystal to comprise Mn, but when not comprising Ba or Mg, red peak also do not occur.

Comparative example B-5

Remove Ba (NO ₃) ₂The aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 0.587: 1.173: 0.2: 0.04: 1) as outside the starting soln, with Embodiment B-1 in same way as make fluor Ba _0.587Mg _1.173Eu _0.2Mn _0.04SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 5.Be presented at and fail in the crystal to exist when being the Ca of appropriate amount with respect to Ba, the wavelength of emission peak surpasses 620nm, causes launching the bright ruddiness of sensation.

Table 5

Embodiment or comparative example	The chemical constitution of fluor	The wavelength of emission peak (nm)	The relative intensity of emission peak	The half breadth of emission peak (nm)	The mol ratio of Mn	The ratio (mol ratio) of Mg and dyad, unit price, trivalent and pentad summation except that Eu and Mn	The ratio (mol ratio) of Ca and the summation of Ba and Ca
Embodiment or comparative example	The chemical constitution of fluor	The wavelength of emission peak (nm)	The relative intensity of emission peak	The half breadth of emission peak (nm)	The mol ratio of Mn		The ratio (mol ratio) of Ca and the summation of Ba and Ca	Embodiment B-1	Ba _1.133Ca _0.378Mg _0.189Eu _0.2Mn _0.1SiO ₄	602	147	73	0.1	0.11	0.25
Comparative example B-1	Ba _1.2Ca _0.4Mg _0.2Eu _0.2SiO ₄	496	183	122	0	0.11	0.25	Embodiment B-1	Ba _1.133Ca _0.378Mg _0.189Eu _0.2Mn _0.1SiO ₄	602	147	73	0.1	0.11	0.25
Comparative example B-1	Ba _1.2Ca _0.4Mg _0.2Eu _0.2SiO ₄	496	183	122	0	0.11	0.25	Comparative example B-2	Ba _0.72Ca _1.08Eu _0.2SiO ₄	448	99	104	0	0	0.60
Comparative example B-3	Ba _1.6Eu _0.2Mn _0.2SiO ₄	509	100	62	0.2	0	0.00	Comparative example B-2	Ba _0.72Ca _1.08Eu _0.2SiO ₄	448	99	104	0	0	0.60
Comparative example B-3	Ba _1.6Eu _0.2Mn _0.2SiO ₄	509	100	62	0.2	0	0.00	Comparative example B-4	Ca _1.6Eu _0.2Mn _0.2SiO ₄	512	25	85	0.2	0	1.00
Comparative example B-5	Ba _0.587Mg _1.173Eu _0.2Mn _0.04SiO ₄	630	94	74	0.04	0.67	0.00	Comparative example B-4	Ca _1.6Eu _0.2Mn _0.2SiO ₄	512	25	85	0.2	0	1.00

Embodiment B-2

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 1.173: 0.391: 0.196: 0.2: 0.04: 1) as outside the starting soln, made fluor Ba with same way as with Embodiment B-1 _1.173Ca _0.391Mg _0.196Eu _0.2Mn _0.04SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.Its emmission spectrum is shown among Fig. 9.The wavelength of the x of tristimulus coordinates of expression color and y value, maximum peak, the maximum peak intensity (hereinafter referred to as the relative intensity of maximum peak) of this fluor when the intensity of the fluor maximum peak among the comparative example B-7 that will describe later is considered as 100, at the ratio of intensity with the intensity of described maximum peak at 600nm place, which kind of degree is the red component that its expression exists reach, and the half breadth at one group of peak is shown in Table 6.These demonstrations have obtained its Smalt, green and red component and have all fully existed, thereby become the non-constant width of described spectrum width, and the very high white light emission of color rendering.

Maximum peak means that when having a plurality of peak in emmission spectrum at peak the highest on the intensity with in unimodal situation, described maximum peak is itself.In addition, as shown in Figure 6, the half breadth at one group of peak represents it is how wide that emmission spectrum distributes, and how high color rendering is, and it is defined as the total width of the wavelength region of the half intensity with the intensity that is equal to or greater than maximum peak in the spectrum.

Comparative example B-6

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O and SiO ₂Mol ratio be 1.2: 0.4: 0.2: 0.2: 1) as outside the starting soln, made fluor Ba with same way as with Embodiment B-1 _1.2Ca _0.4Mg _0.2Eu _0.2SiO ₄Measured the emmission spectrum when the 400n as the main wavelength in the UV-light zone of GaN-based light-emitting diode excites this fluor.The wavelength of the x of tristimulus coordinates and y value, maximum peak, the intensity of maximum peak, intensity and the ratio of the intensity of described maximum peak and the half breadth at one group of peak at the 600nm place are shown in Table 6.Its demonstration can not get white spectrum when in the composition that Mn is not joined Embodiment B-5.

Comparative example B-7

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Eu (NO ₃) ₃6H ₂O and SiO ₂Mol ratio be 0.72: 1.08: 0.2: 1), made fluor Ba with same way as with Embodiment B-1 as outside the starting soln _0.72Ca _1.08Eu _0.2SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength of the x of tristimulus coordinates and y value, maximum peak, the intensity of maximum peak, intensity and the ratio of the intensity of described maximum peak and the half breadth at one group of peak at the 600nm place are shown in Table 6.It shows when Mn or Mg are not present in the crystal, can not get white spectrum.

Comparative example B-8

Remove Ba (NO ₃) ₂The aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 0.587: 1.173: 0.2: 0.04: 1) as outside the starting soln, made fluor Ba with same way as with Embodiment B-1 _0.587Mg _1.173Eu _0.2Mn _0.04SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength of the x of tristimulus coordinates and y value, maximum peak, the intensity of maximum peak, be shown in Table 6 at intensity and the ratio of the intensity of described maximum peak and the half breadth at one group of peak of 600n.Be presented in the crystal when failing there is Ca with q.s based on Ba, the wavelength at red peak surpasses 620nm, has obtained not comprising the visible spectrum of the bright red component of sensation.

Table 6

Embodiment or comparative example	The chemical constitution of fluor	Tristimulus coordinates		The wavelength of maximum peak (nm)	The relative intensity of maximum peak	The intensity of the intensity/maximum peak at 600nm place	The half breadth at one group of peak (nm)	The mol ratio of Mn	Mg and the dyad except that Eu and Mn, unit price, the ratio (mol ratio) of trivalent and pentad summation	The ratio (mol ratio) of Ca and Ba and Ca summation
		Tristimulus coordinates									x	y
		Embodiment B-2	Ba _1.173Ca _0.391Mg _0.196Eu _0.2Mn _0.04SiO ₄								x	y	0.376	0.345	598	202	1	158	0.04	0.11	0.25
Comparative example B-6	Ba _1.2Ca _0.4Mg _0.2Eu _0.2SiO ₄	Embodiment B-2	Ba _1.173Ca _0.391Mg _0.196Eu _0.2Mn _0.04SiO ₄	0.184	0.29	496	186	0.08	122	0	0.11	0.25	0.376	0.345	598	202	1	158	0.04	0.11	0.25
Comparative example B-6	Ba _1.2Ca _0.4Mg _0.2Eu _0.2SiO ₄	Comparative example B-7	Ba _0.72Ca _1.08Eu _0.2SiO ₄	0.184	0.29	496	186	0.08	122	0	0.11	0.25	0.19	0.229	448	100	0.12	104	0	0	0.60
Comparative example B-8	Ba _0.587Mg _1.173Eu _0.2Mn _0.04SiO ₄	Comparative example B-7	Ba _0.72Ca _1.08Eu _0.2SiO ₄	0.455	0.291	630	96	0.56	74	0.04	0.67	0.00	0.19	0.229	448	100	0.12	104	0	0	0.60

Embodiment B-3

With mol ratio 1.283: 0.428: 0.09: 0.075: 0.05: 1 weighing BaCO ₃, CaCO ₃, MgCO ₃, Eu ₂O ₃, MnCO ₃NH ₂O and SiO ₂, and add NH ₄Cl mixed 1 hour in ball mill then as solder flux.The powder of so preparation is put into alumina crucible, is put in the crucible that carbon makes together with this crucible in addition, and under the nitrogen gas stream that comprises 4% hydrogen in 1200 ℃ of heating 6 hours, make fluor Ba thus _1.283Ca _0.428Mg _0.09Eu _0.15Mn _0.05SiO ₄Carrying out the X-ray diffraction of this fluor under the following conditions measures.Use comprise CuK α as X-ray source (with its in described diffraction angle error optical adjustment of sweep limit to Δ 2 θ=0.05 ° or littler) Prague-Brentano type powder x-ray diffraction instrument, use therein under the condition of 111 peaks of the standard silicon diffraction angle error relevant as Δ 2 θ=0.05 ° or littler guaranteed angle reproducibility and carry out the powder x-ray diffraction measurement with the sample excentricity.In addition, the angle of divergence of regulating divergent slit make the irradiating width of described X-ray do not exceed in the measurement the sample width and for described diffraction peak position (summit) and diffracted intensity (highly), read out in the value of the measuring result in the fixing slit mode.The X-ray diffraction measuring result is shown among Figure 10.Table 7 shows that the gained fluor satisfies the condition of describing in the claim 6, and confirms that it comprises above-mentioned specific phase.Emmission spectrum when exciting this fluor at the 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode is shown among Figure 11.In order to eliminate the influence of excitation light source to described emmission spectrum, blocking-up is equal to or less than the light of 420nm.The wavelength of the emission peak of the x of tristimulus coordinates and y value, this fluor and the intensity of emission peak are shown in Table 8.

Embodiment B-4

Divided by mol ratio 1.215: 0.405: 0.180: 0.075: 0.05: 1 weighing BaCO ₃, CaCO ₃, MgCO ₃, Eu ₂O ₃, MnCO ₃NH ₂O and SiO ₂Obtain fluor Ba with same way as outward, with Embodiment B-3 _1.215Ca _0.405Mg _0.18Eu _0.15Mn _0.05SiO ₄The X-ray diffraction measuring result is shown in Table 7, and this embodiment satisfies the condition of claim 6.Emmission spectrum is shown among Figure 11, and characteristic is summarised in the table 8.

Embodiment B-5

Divided by mol ratio 0.855: 0.285: 0.57: 0.09: 0.075: 0.05: 1 weighing BaCO ₃, CaCO ₃, SrCO ₃, MgCO ₃, Eu ₂O ₃, MnCO ₃NH ₂O and SiO ₂Obtain fluor Ba with same way as outward, with Embodiment B-3 _0.855Ca _0.285Sr _0.57Mg _0.09Eu _0.15Mn _0.05SiO ₄The X-ray diffraction measuring result is shown in Table 7 and this embodiment satisfies the condition of claim 6.Emmission spectrum is shown among Figure 11 and characteristic is summarised in the table 8.

Embodiment B-6

Divided by mol ratio 0.810: 0.27: 0.54: 0.18: 0.075: 0.05: 1 weighing BaCO ₃, CaCO ₃, SrCO ₃, MgCO ₃, Eu ₂O ₃, MnCO ₃NH ₂O and SiO ₂Obtain fluor Ba with same way as outward, with Embodiment B-3 _0.81Ca _0.27Sr _0.54Mg _0.18Eu _0.15Mn _0.05SiO ₄The X-ray diffraction measuring result is shown in Table 7 and this embodiment satisfies the condition of claim 6.Emmission spectrum is shown among Figure 11, and characteristic is summarised in the table 8.

Table 7

Embodiment B-3

With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring
With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring	21.512	R1	29.741	30.356	30.222	88.0
Intensity	R2	30.701	31.337	31.108	100.0	21.512	R1	29.741	30.356	30.222	88.0
Intensity	R2	30.701	31.337	31.108	100.0	67.5	R3	36.375	37.136	36.723	17.0
	R4	37.694	38.485	38.207	35.9	67.5	R3	36.375	37.136	36.723	17.0
	R4	37.694	38.485	38.207	35.9	R5	43.377	44.299	44.006	43.6

Embodiment B-4

With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring
With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring	21.761	Rl	30.089	30.712	30.523	94.0
Intensity	R2	31.061	31.705	31.396	100.0	21.761	Rl	30.089	30.712	30.523	94.0
Intensity	R2	31.061	31.705	31.396	100.0	70.1	R3	36.806	37.577	37.049	l8.7
	R4	38.141	38.943	38.528	32.4	70.1	R3	36.806	37.577	37.049	l8.7
	R4	38.141	38.943	38.528	32.4	R5	43.898	44.833	44.346	41.1

Embodiment B-5

With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring
With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring	21.834	R1	30.191	30.816	30.641	72.8
Intensity	R2	31.167	31.813	31.572	100.0	21.834	R1	30.191	30.816	30.641	72.8

27.5	R3	36.932	37.706	37.508	23.0
27.5	R3	36.932	37.706	37.508	23.0	R4	38.273	39.077	38.618	24.9
R5	44.052	44.990	44.479	22.2		R4	38.273	39.077	38.618	24.9

Embodiment B-6

With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring
With reference to the diffraction peak angle	Angular region	Start angle	Termination point	Take measurement of an angle	The relative intensity of measuring	21.764	R1	30.094	30.716	30.568	56.3
Intensity	R2	31.066	31.710	31.500	100.0	21.764	R1	30.094	30.716	30.568	56.3
Intensity	R2	31.066	31.710	31.500	100.0	19.2	R3	36.811	37.582	37.433	16.2
	R4	38.147	38.948	38.544	19.1	19.2	R3	36.811	37.582	37.433	16.2
	R4	38.147	38.948	38.544	19.1	R5	43.905	44.839	44.405	15.8

Table 8

Embodiment	The chemical constitution of fluor	Tristimulus coordinates		The wavelength of emission peak (nm)	The intensity of emission peak (arbitrary scale)
		Tristimulus coordinates				x	Y
		Embodiment B-3	Ba _1.283Ca _0.428Mg _0.09Eu _0.15Mn _0.05SiO ₄			x	Y	0.510	0.373	612	439
Embodiment B-4	Ba _1.215Ca _0.405Mg _0.18Eu _0.15Mn _0.05SiO ₄	Embodiment B-3	Ba _1.283Ca _0.428Mg _0.09Eu _0.15Mn _0.05SiO ₄	0.491	0.364	622	404	0.510	0.373	612	439
Embodiment B-4	Ba _1.215Ca _0.405Mg _0.18Eu _0.15Mn _0.05SiO ₄	Embodiment B-5	Ba _0.855Ca _0.285Sr _0.57Mg _0.09Eu _0.15Mn _0.05SiO ₄	0.491	0.364	622	404	0.528	0.429	623	143
Embodiment B-6	Ba _0.81Ca _0.27Sr _0.54Mg _0.18Eu _0.15Mn _0.05SiO ₄	Embodiment B-5	Ba _0.855Ca _0.285Sr _0.57Mg _0.09Eu _0.15Mn _0.05SiO ₄	0.499	0.421	629	100	0.528	0.429	623	143

Embodiment C-1

With Ba (NO ₃) ₂The aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 0.935: 0.935: 0.1: 0.03: 1) in the platinum container, mix and dry.Then, by heating 2 hours described mixture fired with preparation fluor Ba in 1050 ℃ under the nitrogen gas stream that comprises 4% hydrogen _0.935Mg _0.935Eu _0.1Mn _0.03SiO ₄(fluor that uses in second twinkler).Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength of its emission peak, described emission peak intensity (hereinafter referred to as relative intensity) and half breadth when the emission peak intensity of the comparative example C-5 that will describe later is considered as 100 are shown in Table 9.Show the emission of this fluor because the strong ruddiness of the high color rendering that enough high strength and wide half breadth obtain and owing to wavelength this fluorescence physical efficiency in the 615nm-645nm zone of emission peak is launched bright dark red coloured light.The measurement of the excitation spectrum that carries out according to the long 630nm of the spike under 400nm excites place, relative intensity under the excitation wavelength of 254nm, 280nm, 382nm and 400nm be respectively 208,328,351 and 320 and at the stimulated luminescence of about 400nm than being equal to or greater than 1.5 times at the conventional luminous eager to excel in whatever one does of 254nm place.This shows that this fluor is to the very favorable fluor of the light source of GaN-base semiconductor.

Comparative example C-1

Remove Ba (NO ₃) ₂The aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O and SiO ₂Mol ratio be 0.95: 0.95: 0.1: 1), made fluor Ba with same way as with Embodiment C-1 as outside the starting soln _0.95Mg _0.95Eu _0.1SiO ₄Measured the emmission spectrum when the 400nm as the main wavelength in the UV-light zone of GaN-based light-emitting diode excites this fluor.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 9.This demonstration red peak do not occur when in the composition that Mn is not joined in the Embodiment C-1.

Embodiment C-2

Remove Ba (NO ₃) ₂The aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 0.623: 1.247: 0.1: 0.03: 1) as outside the starting soln, made fluor Ba with same way as with Embodiment C-1 _0.623Mg _1.247Eu _0.1Mn _0.03SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 9.This shows the emission of this fluor because the strong ruddiness of the high color rendering that enough high strength and wide half breadth obtain and owing to wavelength this fluorescence physical efficiency in the 615nm-645nm zone of emission peak is launched bright dark red coloured light.

Comparative example C-2

Remove Ba (NO ₃) ₂The aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O and SiO ₂Mol ratio be 0.633: 1.267: 0.1: 1), made fluor Ba with same way as with Embodiment C-1 as outside the starting soln _0.633Mg _1.267Eu _0.1SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 9.This demonstration red peak do not occur when in the composition that Mn is not joined in the Embodiment C-2.

Embodiment C-3

Remove Ba (NO ₃) ₂The aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 0.587: 1.173: 0.2: 0.04: 1) as outside the starting soln, made fluor Ba with same way as with Embodiment C-1 _0.587Mg _1.173Eu _0.2Mn _0.04SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.Its emmission spectrum is shown among Figure 12.In order to eliminate the influence of excitation light source to emmission spectrum, introducing is used to block the wave filter that is equal to or less than 420nm light and measures.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 9.This shows the emission of this fluor because the strong ruddiness of the high color rendering that enough high strength and wide half breadth obtain and owing to wavelength this fluorescence physical efficiency in the 615nm-645nm zone is launched bright dark red coloured light.

Comparative example C-3

Remove Ba (NO ₃) ₂The aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O and SiO ₂Mol ratio for O.6: 1.2: 0.2: 1) as outside the starting soln, made fluor Ba with same way as with Embodiment C-l _0.6Mg _1.2Eu _0.2SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 9.This demonstration red peak do not occur when in the composition that Mn is not joined in the Embodiment C-3.

Comparative example C-4

Remove Ba (NO ₃) ₂The aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂And SiO ₂Mol ratio be 1.7: 0.2: 0.1: 1), made fluor Ba with same way as with Embodiment C-1 as outside the starting soln _1.7Eu _0.2Mn _0.1SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 9.Even this demonstration comprises Mn in crystal, when not containing Mg, red peak does not appear yet.

Comparative example C-5

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 0.567: 0.567: 0.566: 0.2: 0.1: 1) as outside the starting soln, made fluor Ba with same way as with Embodiment C-1 _0.567Ca _0.567Mg _0.566Eu _0.2Mn _0.1SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength of its emission peak, relative intensity and half breadth are shown in Table 9.When it showed that amount as Ca is far more than Ba, the wavelength of emission peak became less than 615nm, cause can not emitting bright dark red coloured light.

Table 9

Embodiment or comparative example	The chemical constitution of fluor	The wavelength of emission peak (nm)	The relative intensity of emission peak	The half breadth of emission peak (nm)	The mol ratio of Eu	The mol ratio of Mn	The ratio (mol ratio) of Mg and the summation of dyad, unit price, trivalent and pentad except that Eu and Mn	The ratio (mol ratio) of Ca and the summation of Ba and Ca
Embodiment or comparative example	The chemical constitution of fluor	The wavelength of emission peak (nm)	The relative intensity of emission peak	The half breadth of emission peak (nm)	The mol ratio of Eu	The mol ratio of Mn		The ratio (mol ratio) of Ca and the summation of Ba and Ca	Embodiment C-1	Ba _0.935Mg _0.935Eu _0.1Mn _0.03SiO ₄	630	320	74	0.1	0.03	0.5	0
Embodiment C-2	Ba _0.623Mg _1.247Eu _0.1Mn _0.03SiO ₄	633	191	73	0.1	0.03	0.67	0	Embodiment C-1	Ba _0.935Mg _0.935Eu _0.1Mn _0.03SiO ₄	630	320	74	0.1	0.03	0.5	0
Embodiment C-2	Ba _0.623Mg _1.247Eu _0.1Mn _0.03SiO ₄	633	191	73	0.1	0.03	0.67	0	Embodiment C-3	Ba _0.587Mg _1.173Eu _0.2Mn _0.04SiO ₄	630	127	74	0.2	0.04	0.67	0
Comparative example C-1	Ba _0.95Mg _0.95Eu _0.1SiO ₄	442	246	117	0.1	0	0.5	0	Embodiment C-3	Ba _0.587Mg _1.173Eu _0.2Mn _0.04SiO ₄	630	127	74	0.2	0.04	0.67	0
Comparative example C-1	Ba _0.95Mg _0.95Eu _0.1SiO ₄	442	246	117	0.1	0	0.5	0	Comparative example C-2	Ba _0.633Mg _1.267Eu _0.1SiO ₄	443	162	97	0.1	0	0.67	0
Comparative example C-3	Ba _0.6Mg _1.2Eu _0.2SiO ₄	438	323	42	0.2	0	0.67	0	Comparative example C-2	Ba _0.633Mg _1.267Eu _0.1SiO ₄	443	162	97	0.1	0	0.67	0
Comparative example C-3	Ba _0.6Mg _1.2Eu _0.2SiO ₄	438	323	42	0.2	0	0.67	0	Comparative example C-4	Ba _1.7Eu _0.2Mn _0.1SiO ₄	504	122	63	0.2	0.1	0	0
Comparative example C-5	Ba _0.567Ca _0.567Mg _0.566Eu _0.2Mn _0.1SiO ₄	602	100	95	0.2	0.1	0.33	0.5	Comparative example C-4	Ba _1.7Eu _0.2Mn _0.1SiO ₄	504	122	63	0.2	0.1	0	0

Embodiment C-4

Remove Ba (NO ₃) ₂The aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 0.92: 0.92: 0.1: 0.06: 1) as outside the starting soln, made fluor Ba with same way as with Embodiment C-1 _0.92Mg _0.92Eu _0.1Mn _0.06SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.Its emmission spectrum is shown among Figure 13.Be equal to or greater than the wavelength at peak (red component peak) of 590nm and relative intensity, be shown in Table 10 less than the x and the y value of the tristimulus coordinates of the half breadth at the wavelength of the maximum peak of 590nm and relative intensity, group peak and expression color.Its demonstration has obtained comprising the wherein scarlet component of spike length in the 615nm-645nm zone, and the wide spectrum that also comprises blue and green color component, has obtained high color rendering, has caused bright white light emission.

Less than the maximum peak of 590nm be meant when in emmission spectrum less than the region memory of 590nm during at a plurality of peak, at peak the highest on the intensity with in unimodal situation, described maximum peak is itself.In addition, as shown in Figure 6, how wide the half breadth at one group of peak represents that emmission spectrum distributes and how high color rendering is, and it is defined as the total width of the wavelength region of the half intensity with the intensity that is equal to or greater than maximum peak in the spectrum.

Comparative example C-6

Remove Ba (NO ₃) ₂The aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O and SiO ₂Mol ratio be 0.95: 0.95: 0.1: 1), made fluor Ba with same way as with Embodiment C-1 as outside the starting soln _0.95Mg _0.95Eu _0.1SiO ₄Measured the emmission spectrum when exciting this fluor at 400n place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength at red component peak and relative intensity, be shown in Table 10 less than wavelength and relative intensity, the half breadth at group peak and the x and the y value of tristimulus coordinates of the maximum peak of 590nm.Demonstration red peak do not occur when in the component that Mn is not joined Embodiment C-4.

Comparative example C-7

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂4H ₂O, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O and SiO ₂Mol ratio be 1.2: 0.2: 0.4: 0.2: 1) as outside the starting soln, made fluor Ba with same way as with Embodiment C-1 _1.2Ca _0.2Mg _0.4Eu _0.2SiO ₄Measured the emmission spectrum when exciting this fluor at 400n place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength at red component peak and relative intensity, be shown in Table 10 less than wavelength and relative intensity, the half breadth at group peak and the x and the y value of tristimulus coordinates of the maximum peak of 590nm.Demonstration red peak do not occur when in the component that Mn is not joined Embodiment C-5.

Embodiment C-5

Remove Ba (NO ₃) ₂The aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 0.82: 0.82: 0.3: 0.06: 1) as outside the starting soln, made fluor Ba with same way as with Embodiment C-1 _0.82Mg _0.82Eu _0.3Mn _0.06SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength at red component peak and relative intensity, be shown in Table 10 less than wavelength and relative intensity, the half breadth at group peak and the x and the y value of tristimulus coordinates of the maximum peak of 590nm.Its demonstration has obtained comprising the wherein scarlet component of spike length in the 615nm-645nm zone, and the wide spectrum that also comprises blue and green color component, has obtained high color rendering, has caused bright white light emission.

Comparative example C-8

Remove Ba (NO ₃) ₂The aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O and SiO ₂Mol ratio be 0.85: 0.85: 0.3: 1), made fluor Ba with same way as with Embodiment C-1 as outside the starting soln _0.85Mg _0.85Eu _0.3SiO ₄Measured the emmission spectrum when the 400nm as the main wavelength in the UV-light zone of GaN-based light-emitting diode excites this fluor.The wavelength at red component peak and relative intensity, be shown in Table 10 less than wavelength and relative intensity, the half breadth at group peak and the x and the y value of tristimulus coordinates of the maximum peak of 590nm.Demonstration red peak do not occur when in the component that Mn is not joined Embodiment C-6.

Comparative example C-9

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 0.88: 0.44: 0.44: 0.2: 0.04: 1) as outside the starting soln, made fluor Ba with same way as with Embodiment C-1 _0.88Ca _0.44Mg _0.44Eu _0.2Mn _0.04SiO ₄Measured the emmission spectrum when the 400nm as the main wavelength in the UV-light zone of GaN-based light-emitting diode excites this fluor.The wavelength at red component peak and relative intensity, be shown in Table 10 less than wavelength and relative intensity, the half breadth at group peak and the x and the y value of tristimulus coordinates of the maximum peak of 590nm.The amount that is presented in the crystal as Ca is a half of the amount of Ba, and the spike length of red component becomes less than 615nm, cause can not emitting bright white light.

Comparative example C-10

Remove Ba (NO ₃) ₂The aqueous solution, Ca (NO ₃) ₂4H ₂The O aqueous solution, Mg (NO ₃) ₂6H ₂The O aqueous solution, Eu (NO ₃) ₃6H ₂The O aqueous solution, Mn (NO ₃) ₂6H ₂The O aqueous solution and colloid silica (SiO ₂) suspension (Ba (NO ₃) ₂, Ca (NO ₃) ₂, Mg (NO ₃) ₂6H ₂O, Eu (NO ₃) ₃6H ₂O, Mn (NO ₃) ₂6H ₂O and SiO ₂Mol ratio be 1.144: 0.216: 0.48: 0.01: 0.15: 1) as outside the starting soln, made fluor Ba with same way as with Embodiment C-1 _1.144Ca _0.216Mg _0.48Eu _0.01Mn _0.15SiO ₄Measured the emmission spectrum when exciting this fluor at 400nm place as the main wavelength in the UV-light zone of GaN-based light-emitting diode.The wavelength at red component peak and relative intensity, be shown in Table 10 less than wavelength and relative intensity, the half breadth at group peak and the x and the y value of tristimulus coordinates of the maximum peak of 590nm.This shows that mol ratio as Eu is little to 0.01 the time, and the intensity of red component has slightly and diminishes sometimes.

Table 10

Embodiment or comparative example	The chemical constitution of fluor	Be equal to or greater than the peak (peak of red component) of 590 nm		Maximum peak less than 590nm		The half breadth (nm) at group peak	Tristimulus coordinates		The mol ratio of Eu	The mol ratio of Mn	The ratio (mol ratio) of Mg and the summation of diad, unit price, trivalent and pentad except Eu and Mn	The ratio (mol ratio) of Ca and the summation of Ba and Ca
				Maximum peak less than 590nm			Tristimulus coordinates						Wavelength (nm)	Relative intensity	Wavelength (nm)	Relative intensity	x	y
		Embodiment C-4	Ba _0.92Mg _0.92Eu _0.1Mn _0.06SiO ₄	629	147		521	76					Wavelength (nm)	Relative intensity	Wavelength (nm)	Relative intensity	x	y	101	0.384	0.33	0.1	0.06	0.5	0
Embodiment C-5	Ba _0.82Mg _0.82Eu _0.3Mn _0.06SiO ₄	Embodiment C-4	Ba _0.92Mg _0.92Eu _0.1Mn _0.06SiO ₄	629	147	637	521	76	108	507	72	124	0.373	0.329	0.3	0.06	0.5	0	101	0.384	0.33	0.1	0.06	0.5	0
Embodiment C-5	Ba _0.82Mg _0.82Eu _0.3Mn _0.06SiO ₄	Comparative example C-6	Ba _0.95Mg _0.95Eu _0.1SiO ₄	-	0	637	442	246	108	507	72	124	0.373	0.329	0.3	0.06	0.5	0	119	0.167	0.267	0.1	0	0.5	0
Comparative example C-7	Ba _1.2Ca _0.2Mg _0.4Eu _0.2SiO ₄	Comparative example C-6	Ba _0.95Mg _0.95Eu _0.1SiO ₄	-	0	-	442	246	0	509	465	73	0.199	0.476	0.2	0	0.22	0.14	119	0.167	0.267	0.1	0	0.5	0
Comparative example C-7	Ba _1.2Ca _0.2Mg _0.4Eu _0.2SiO ₄	Comparative example C-8	Ba _0.85Mg _0.85Eu _0.3SiO ₄	-	0	-	507	227	0	509	465	73	0.199	0.476	0.2	0	0.22	0.14	118	0.180	0.284	0.3	0	0.5	0
Comparative example C-9	Ba _0.88Ca _0.44Mg _0.44Eu _0.2Mn _0.04SiO ₄	Comparative example C-8	Ba _0.85Mg _0.85Eu _0.3SiO ₄	-	0	600	507	227	128	470	100	172	0.356	0.333	0.2	0.04	0.25	0.33	118	0.180	0.284	0.3	0	0.5	0
Comparative example C-9	Ba _0.88Ca _0.44Mg _0.44Eu _0.2Mn _0.04SiO ₄	To two Embodiment C-10	Ba _1.144Ca _0.216Mg _0.48Eu _0.01Mn _0.15SiO ₄	637	41	600	429	68	128	470	100	172	0.356	0.333	0.2	0.04	0.25	0.33	101	0.316	0.177	0.01	0.15	0.26	0.16

Although use embodiment to describe the present invention in detail, can make multiple change and variation without departing from the spirit and scope of the present invention, this is obvious to those skilled in the art.

The application is based on the Japanese patent application of submitting on January 16th, 2004 (patent application No.2004-9768), in the patent application (patent application No.2004-9769) of submission on January 16th, 2004, with the patent application of submitting on January 16th, 2004 (patent application No.2004-9770), its full content is incorporated herein by reference.

Industrial applicibility

According to the present invention, high efficiency red light-emitting fluophor and the white phosphor of demonstration or the illumination of the High Efficiency Luminescence that can be provided for combining with light source luminous in black light-visible region.

Claims

1. the fluor that comprises the crystallization phases of arbitrary chemical constitution with following formula [1]-[4]:

Eu _a0Mn _b0M ¹⁰ _c0M ²⁰ _d0M ³⁰O _e0Z ⁰ _f0 [1]

M wherein ¹⁰Be to comprise the dyad that is selected from least a element among Ba, Ca and the Sr that is equal to or greater than 85 moles of %, wherein Ca is 0.1-0.9 with the ratio (mol ratio) of the summation of Ba and Ca; M ²⁰Representative is selected from least a element in unit price, trivalent and the pentad; M ³⁰Represent one group to comprise the Si that is equal to or greater than 90 moles of % total amounts and the quadrivalent element of Ge; Z ⁰It is at least a element that is selected among negative monovalence and negative dyad, H and the N; With a0 be the number that satisfies 0.001≤a0≤0.6, b0 is the number that satisfies 0＜b0≤0.7, c0 and d0 are the numbers that satisfies 0≤d0/ (c0+d0)≤0.2, a0, b0, c0 and d0 satisfy 1.8≤(a0+b0+c0+d0)≤2.2 number, and e0 and f0 are the numbers that satisfies 0≤f0/ (e0+f0)≤0.035 and 3.6≤(e0+f0)≤4.4:

Eu _a1Mn _b1Mg _c1M ¹¹ _d1M ²¹O _e1Z ¹ _f1 [2]

M wherein ¹¹Representative is selected from least a element in monogen, the dyad except that Eu, Mn and Mg, trivalent element and the pentad, the ratio of wherein said dyad is equal to or greater than 80 moles of %, the ratio (mol ratio) that the ratio of the summation of Ba, Ca and Sr is equal to or greater than 40 moles of % and Ca and the summation of Ba and Ca is 0.2-0.9; M ²¹Represent one group to comprise the Si that is equal to or greater than 90 moles of % total amounts and the quadrivalent element of Ge; Z ¹It is at least a element that is selected among negative monovalence and negative dyad, H and the N; With a1 be the number that satisfies 0.000≤a1≤0.8, b1 is the number that satisfies 0＜b1≤0.8, c1 and d1 are the numbers that satisfies 0＜c1/ (c1+d1)≤0.2, a1, b1, c1 and d1 satisfy 1.8≤(a1+b1+c1+d1)≤2.2 number, and e1 and f1 are the numbers that satisfies 0≤f1/ (e1+f1)≤0.035 and 3.6≤(e1+f1)≤4.4:

Eu _a2Mn _b2Mg _c2M ¹² _d2M ²²O _e2Z ² _f2 [3]

M wherein ¹²Representative is selected from least a element in monogen, the dyad except that Eu, Mn and Mg, trivalent element and the pentad, the ratio of wherein said dyad is equal to or greater than 80 moles of %, the ratio of the summation of Ba, Ca and Sr is equal to or greater than the ratio (mol ratio) of 40 moles of % and Ca and the summation of Ba and Ca less than 0.2; M ²²Represent one group to comprise the Si that is equal to or greater than 90 moles of % total amounts and the quadrivalent element of Ge; Z ²It is at least a element that is selected among negative monovalence and negative dyad, H and the N; With a2 be the number that satisfies 0.0003≤a2≤0.8, b2 is the number that satisfies 0＜b2≤0.8, c2 and d2 are the numbers that satisfies 0＜c2/ (c2+d2)≤0.2 or 0.3≤c2/ (c2+d2)≤0.8, a2, b2, c2 and d2 satisfy 1.8≤(a2+b2+c2+d2)≤2.2 number, and e2 and f2 are the numbers that satisfies 0≤f2/ (e2+f2)≤0.035 and 3.6≤(e2+f2)≤4.4.

2. the fluor that comprises the crystallization phases of chemical constitution, wherein M with described formula [1] ¹⁰Be to comprise the dyad that is selected from least a element among Ba, Ca and the Sr that is equal to or greater than 85 moles of %, wherein Ca is 0.2-0.8 with the ratio (mol ratio) of the summation of Ba and Ca; M ²⁰Representative is selected from least a element in unit price, trivalent and the pentad; M ³⁰Be Si; Z is at least a element that is selected among negative monovalence and negative dyad, H and the N; With a0 be the number that satisfies 0.02≤a0≤0.5, b0 is the number that satisfies 0＜b0≤0.7, c0 and d0 are the numbers that satisfies 0≤d0/ (c0+d0)≤0.1, a0, b0, c0 and d0 satisfy 1.9≤(a0+b0+c0+d0)≤2.1 number, and e0 and f0 are the numbers that satisfies 0≤f0/ (e0+f0)≤0.01 and 3.8≤(e0+f0)≤4.2.

3. the fluor that comprises the crystallization phases of chemical constitution, wherein M with described formula [2] ¹¹Representative is selected from least a element in monogen, the dyad except that Eu, Mn and Mg, trivalent element and the pentad, wherein comprise at least a element among Ba, Ca and the Sr of being selected from that is equal to or greater than 85 moles of %, and the ratio (mol ratio) of Ca and the summation of Ba and Ca is 0.2-0.8; M ²¹Be Si; Z is at least a element that is selected among negative monovalence and negative dyad, H and the N; With a1 be the number that satisfies 0.01＜a1≤0.5, b1 is the number that satisfies 0＜b1≤0.7, c1 and d1 are the numbers that satisfies 0≤d1/ (c1+d1)≤0.2, a1, b1, c1 and d1 satisfy 1.9≤(a1+b1+c1+d1)≤2.1 number, and e1 and f1 are the numbers that satisfies 0≤f1/ (e1+f1)≤0.01 and 3.8≤(e1+f1)≤4.2.

4. the fluor that comprises the crystallization phases of chemical constitution, wherein M with described formula [3] ¹²Representative is selected from least a element in monogen, the dyad except that Eu, Mn and Mg, trivalent element and the pentad, the ratio of wherein said dyad is equal to or greater than 80 moles of %, the ratio of the summation of Ba, Ca and Sr is equal to or greater than the ratio (mol ratio) of 40 moles of % and Ca and the summation of Ba and Ca less than 0.2; M ²²Represent one group to comprise the Si that is equal to or greater than 90 moles of % total amounts and the quadrivalent element of Ge; Z is at least a element that is selected among negative monovalence and negative dyad, H and the N; With a2 be the number that satisfies 0.01＜a2≤0.5, b2 is the number that satisfies 0＜b2≤0.8, c2 and d2 are the numbers that satisfies 0＜c2/ (c2+d2)≤0.2 or 0.3≤c2/ (c2+d2)≤0.7, a2, b2, c2 and d2 satisfy 1.9≤(a2+b2+c2+d2)≤2.1 number, and e2 and f2 are the numbers that satisfies 0≤f2/ (e2+f2)≤0.01 and 3.8≤(e2+f2)≤4.2.

5. according to each described fluor among the claim 1-4, wherein said fluor comprises the specific crystallization phases that X-ray diffraction measures, condition below wherein said crystallization phases satisfies:

(condition)

In the X-ray diffraction measurement of using CuK α as X-ray source, in 21.30 °-22.50 ° diffraction angle (2 θ) scope (R0), observe diffraction peak, and when with this diffraction peak as the angular range of reference diffraction peak (P0) and 5 diffraction angle that will derive by the Bragg angle (θ s) of P0 as R1, R2, R3, when R4 and R5, at least one diffraction peak is present in these 5 scopes, condition be with respect to described equal or more than 6 from the strongest diffraction peak in the diffraction peak of crystallization phases, in the diffraction peak aspect ratio, P0 has and is equal to or greater than 20% intensity, with in the diffraction peak aspect ratio, other diffraction peak has and is equal to or greater than 9% intensity, wherein when equaling or be present in the angular range more than two diffraction peaks, the peak that selection intensity is higher

R1:2 * arcsin{sin (θ 0)/(0.720 * 1.015) } to 2 * arcsin{sin (θ 0)/(0.720 * 0.985) }

R2:2 * arcsin{sin (θ 0)/(0.698 * 1.015) } to 2 * arcsin{sin (θ 0)/(0.698 * 0.985) }

R3:2 * arcsin{sin (θ 0)/(0.592 * 1.015) } to 2 * arcsin{sin (θ 0)/(0.592 * 0.985) }

R4:2 * arcsin{sin (θ 0)/(0.572 * 1.015) } to 2 * arcsin{sin (θ 0)/(0.572 * 0.985) }

R5:2 * arcsin{sin (θ 0)/(0.500 * 1.015) } to 2 * arcsin{sin (θ 0)/(0.500 * 0.985) }.

6. according to each described fluor among the claim 1-4, wherein said crystallization phases satisfies following conditions:

(condition)

In the X-ray diffraction measurement of using CuK α as X-ray source, in 21.30 °-22.50 ° diffraction angle (2 θ) scope (R0), observe diffraction peak, and when with this diffraction peak as the angular range of reference diffraction peak (P0) and 5 diffraction angle that will derive by the Bragg angle (θ s) of P0 as R1, R2, R3, when R4 and R5, at least one diffraction peak is present in these 5 scopes, condition be with respect to described equal or more than 6 from the strongest diffraction peak in the diffraction peak of H1, in the diffraction peak aspect ratio, P0 has and is equal to or greater than 20% intensity, with in the diffraction peak aspect ratio, other diffraction peak has and is equal to or greater than 9% intensity, wherein when equaling or be present in the angular range more than two diffraction peaks, the peak that selection intensity is higher

7. the fluor that comprises the alkaline earth metal silicate crystallization phases, described alkaline earth metal silicate comprise at least a element that is selected among Ba, Sr, Ca and the Mg, and wherein said crystallization phases is to satisfy the crystallization phases of following condition:

(condition)

R1：2×arcsin{sin(θ0)/(0.720×1.010)}-2×arcsin{sin(θ0)/(0.720×0.990)}

R2：2×arcsin{sin(θ0)/(0.698×1.010)}-2×arcsin{sin(θ0)/(0.698×0.990)}

R3：2×arcsin{sin(θ0)/(0.592×1.010)}-2×arcsin{sin(θ0)/(0.592×0.990)}

R4：2×arcsin{sin(θ0)/(0.572×1.010)}-2×arcsin{sin(θ0)/(0.572×0.990)}

R5：2×arcsin{sin(θ0)/(0.500×1.010)}-2×arcsin{sin(θ0)/(0.500×0.990)}。

8. the light-emitting device that comprises first twinkler and second twinkler, the light of described first twinkler emission 350nm-430nm, and described second twinkler is by from the irradiation of the light of described first twinkler and visible emitting, and wherein said second twinkler comprises according to each fluor among the claim 1-7.

9. described light-emitting device according to Claim 8, wherein said first twinkler is laser diode or photodiode.

10. comprise according to Claim 8 or the means of illumination of 9 described light-emitting device.

11. comprise according to Claim 8 or the image display device of 9 described light-emitting device.