TW200804561A - Silicate fluorescent material and fabricating method thereof and light-emitting device using the same - Google Patents

Abstract

The present invention relates to a silicate fluorescent material that can be excited by an exciting light source from ultraviolet to green light zone and fabricating method thereof, more particularly relates to a light-emitting device of white light or multi-colors. The material have light-emitting color from blue to red color zone, and the fluorescent material is composed by aMO.bM'O.SiO2.cR:xEu.yLn.zLv, in which M is one or more elements selected from the group consisting of Sr, Ca, Ba and Zn; M' is one or more elements selected from the group consisting of Mg, Cd and Be; R is one or both elements selected from the group consisting of B2O3 and P2O5; Ln is one or more elements selected from the group consisting of Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Sn, Y, Lu, Ga, Sb, Tb and Mn; Lv is one or more element irons selected from the group consisting of Cl-, F-, Br-, I- and S2-; a, b, c, x, y and z are molar coefficients.

Description

200804561 IX. Description of the Invention: [Technical Field] The present invention relates to a fluorescent material, and more particularly to a fluorescent device comprising a white light-based and multi-color light-emitting device using a semiconductor light-emitting device (LED) Material, which can be used as an excitation source for the emission spectrum at 240~

The illuminating element of the ultraviolet ray-green region of V 510 nm is excited to absorb at least a part of the emitted light of the excitation light source, emitting at least 420 to 70 〇 nm, and at least one of the peaks emitting in the range of 43 〇 to 63 〇 nm The spectrum belongs to the field of optoelectronics and lighting technology. [Prior Art] The breakthrough of the nitriding of the second generation semiconductor materials of I1, and the advent of blue, green and white light-emitting diodes, known as "the technology that illuminates the future, LED (semiconductor light-emitting diode, Light- Emitting Diode), gradually entering our daily life, and will lead us to a brighter future. With the second-generation semiconductor material GaN as a semiconductor illumination source, the power consumption is only ordinary at the same brightness. 1/10 of incandescent lamps, life can reach 80,000 hours Φ or more 'A semiconductor lamp can be used for more than 50 years under normal conditions. As a new lighting technology, LEDs will be triggered by its flexible application, environmental protection and convenient adjustment. A revolution in the field of lighting. The output of white LEDs is now a substantial step from the identification function to the illumination function. The white LED is closest to daylight and better reflects the true color of the illuminated object. Look, white LED is undoubtedly the most advanced technology of LED. The application market of white LED will be very wide. Therefore, there is an urgent need for efficient camping materials. Ultraviolet light emitted from a light-emitting element including an LED to green 5 200804561 Light is efficiently converted into visible light, thereby realizing a white light system and a multi-color light-emitting device. Currently, in the prior art, a white LED is realized to pass an ultraviolet wafer. Or the method of exciting the fluorescent material by the blue light wafer. However, these methods have certain limitations due to the limitation of the fluorescent material. H. For example, in the patents US 5998925, US 6998771, and ZL00801494.9, all use the blue light wafer. A rare earth garnet fluorescent material (such as Y3A15012: Ce, (Y, Gd) 3 (A Bu Ga) 5012 · · Ce, referred to as YAG I; or Tb-garnet, TAG for short) excited by erbium, excited by a blue light wafer The material emits yellow light and blue light of some blue wafers to combine white light. In this method, the fluorescent materials used have great limitations in the application and performance of white LEDs. First, the excitation of such fluorescent materials The range is in the range of 420~ 490nm, the most effective excitation is in the range of 450~470nm, for the ultraviolet region and the short-wavelength side region and the green region of visible light. Secondly, the emission spectrum of the rare earth stone weight structure of the phosphor powder can only be up to 540 nm, and the red component is lacking, resulting in a low color rendering index of the white LED. For example, patents US 6649946, USPA 20040135504, CN 1522291A, CN 1705732A, CN 1596292A, CN 1596478A, and μ US 6680569 relate to rare earth-activated nitride or oxynitride phosphors that are effectively excited by the UV-blue region. The effective excitation wavelength of the fluorescent material of this method is increased, and the emission range can also be from green light to red light, but the light-emitting material of the camping material has low luminance and high manufacturing cost, and is practical. LED phosphor powder has a great limit 6 200804561 sex. For example, in the patent USPA 6351069, a sulfide red fluorescent material is used, which can be added as a complementary color component to a white LED to compensate for the color rendering index and lower the color temperature. However, the fluorescein fluorescent material has a low luminance, and although the color rendering index is improved, the lumen efficiency of the LED is lowered. Moreover, its chemical stability and aging resistance are poor, and the wafer is etched, and the LED is shortened. Service life. For example, the patents USPA20060027781, USPA20060028122, and USPA20060027785 refer to a phthalate fluorescent material, but the material is limited to a ruthenium phthalate-containing structure, and the excitation spectrum is in the range of 280 to 490 nm, and the emission spectrum is in the range of 460 to 590 nm. The light is only in the range of green to yellow, and it lacks red light, and the luminous intensity is poor, and it cannot be compared with the YAG fluorescent material. For example, patent CN 1585141A relates to a hafnium phthalate green fluorescent material and a red fluorescent material of pyroantimonate and orthosilicate. The green fluorescent material described in the patent has a wide excitation spectrum, but the luminescent color is single; and the red fluorescent material described has a weak luminescence intensity and cannot be matched with the existing fluorescent powder, and has a large practical application. Limitations. SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a phthalate fluorescent material having a wide excitation range (240 to 510 nm), a wide emission range (43 0 to 630 nm), high light conversion efficiency, and aging resistance. A fluorescent material excellent in performance 〇 Another object of the present invention is to provide a method for producing a >5 bismuth silicate fluorescent material 7 200804561. It is still another object of the present invention to provide a light-emitting device comprising the phthalate fluorescent material of the present invention, and more particularly to a white LED. The main chemical composition of the phthalate fluorescent material of the present invention can be expressed by the formula (1): aM0· bM^ 〇. Si〇2- cR: xEu· yLn- ZLv (1) wherein M is selected from Sr, Ca a combination of one or more of Ba, Zn; Μ - one or more elements selected from the group consisting of Mg, Cd, and Be, and cr, R being selected from one or both of B2〇3, P2〇5 ingredient;

Ln is a combination of one or more of Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Sn, Y, £u, 6a, Sb, Tb, Mn; Lv is selected from C1_, F -, Br-, ", s2 - a combination of one or more element ions; a, b, C, d, x, y, z are the molar coefficients, 0.5 $ as 5 · 0; 0 $ 3.0; OS eg 〇·5 ; 〇·〇〇1$χ$〇·2; 〇^υ$〇·5; 〇$ζ<0·5; where i< (a + b ) $ 6, and when (a + b ) = 2, M / a total of Mg; the material can be used as an excitation spectrum of the excitation source in the UV-green region of the 240 ~ 510nm light-emitting element excitation, absorbing at least a part of the excitation light source, emitting 420 ~ 7OOnm range Within, there is at least one emission spectrum with a peak in the range of 430 to 63 Onm, which can exhibit luminescence of blue, green, green, yellowish green, yellow, yellow red, red, and white colors. According to a preferred embodiment of the present invention An acid salt fluorescent material in which, in order to obtain blue light emission, when K ( a + b) < 2, and a > b, 〇.5^a^l.5^ 〇.4^b^l.〇, O^c^O.5^ 0.001^x^ 200804561 0.2,0$yS〇.5,0$ζ<0·5, and M^Ca; when 2≪(a + b) $4, and agb, 1·0$ 2,1·0$ 2·0 , 0SC$0.5,0·001$χ$0·2,0$y$0.5,0Sz<0.5 ο according to this A preferred embodiment of the phthalate phosphor material, wherein < (a + b) < 2, and a > b, in order to obtain blue-green luminescence,

" 0.5$ 1·5,0.4$ 1·0,0$ 0·5,0.001S 0.2,0$ y $ 0.5,OS z< 0.5, and the molar content I of Ca and the molar content of Sr The ratio is between 0.2 and 0.5. A phthalate fluorescent material according to a preferred embodiment of the present invention, wherein 1 < ( a + b ) < 2, 0.5 S 1.5, 0.2 $ bS 1.0, OScSO. 5, 0.001 $x$0.2,0Sy S 0.5,OS z< 0.5, and the ratio of the molar content of Ca element to the molar content of Si* element is between 〇·6~1·5; when 2< ( a + b) $ 5 When, 0.5SaS3.0, 0$b$3.0, OScSO.5, 0.001S χ$〇·2,0$yS0.5,0$ζ<0·5. • A phthalate fluorescent material according to a preferred embodiment of the present invention, wherein in order to obtain yellow-green luminescence, when 1 < ( a + b) < 2, 0.5 $ a gl. 5, 0 SbS 1.0, 0$ cS0.5, 0.001 ^ x ^ 0.2 ^ 0 e $ y S 0.5,0$ z< 0.5, and the ratio of the molar content of Ca element to the molar content of Sr element is between 2.8 and 3. 3; when 2 < (a+b) $6, and, at the time, 1.5$a$3,0$b$3.0,0Sc$0.5,0·001$χ$0·2,0Sy$0.5,0$ζ<0·5; when (a+b)= 2,1 $ 2,0$ b S 1.0,0$ 0.5,0.001 $ 200804561 〇$ 〇·5, and when b妾0, the ratio of the molar content of ΜΤSr element to the molar content of Ba element is 〇· 8~1 · 6

A phthalate fluorescent material according to a preferred embodiment of the present invention, wherein, in order to obtain yellow luminescence, when 1 < (a + b) < 2, 0.5 S'aS 1.5, 〇.4 $ b'i. 〇'c€〇5 ' 〇·〇〇ι$χ$〇·2' 〇'y $ 0·5, 〇$ z< 〇·5, and Sr ; when 2< ( a + b) $ 6, and When a$b, 2'a$4, 〇$b$3.〇' 〇Sc$CL5' 0.001

$x$CL2,〇'y$CL5,0$z<〇·5,·When (a+b) = 2, l$a$2,0'bSl.O,0$c'〇.5,〇 .〇01$x$〇.2, 0$y$0.5,〇'ζ<0·5, and when b弇〇, ^Mg, when b=〇, the molar content of Sr element and BaS elemental The ratio of the contents is between 1.8 and 2.2. A luminescent acid material according to a preferred embodiment of the present invention, wherein

〇·2, 〇$ y $ 〇·5 Off Mg, in order to obtain a yellow-red glow when b = o, 2 < ( a + b ) $ 5 ' and a > b, l.〇$a$3. 〇,〇$b'2.0,〇'c'〇·5' 〇·0〇ι$χ$〇7 ,〇SyS0.5,〇^z<0.5, and Sr*/or (^ elemental molar content More than the molar content of the Ba element. wherein 5 a ξ ' 〇 $ according to the preferred embodiment of the present invention, the bismuth fluorite precursor material, in order to obtain red luminescence, when 1 < (a + b) <: 1 · 5 Time, 〇·2 1.2, 0.2$ ι·2, 〇$ eg 0·5 , 0·001 $ 〇·2 y $ 0.5,0$ ζ<〇·5; when 1.5 < ( a + b ) < 2, 〇δ 1.8, 0.5$ 1.8, 〇$ 0.5,0·001 g xg 〇gy $ 0.5,0$ z<〇·5; when 2< ( a + b ) $ 5, ίο 200804561 a^3.0 ^ 1.0^b^3^ 0^c^〇.5» 〇.〇〇l^x^0.2* y^0.5^0 ^z<0.5 矽 a phthalate fluorescent material according to a preferred embodiment of the present invention, The Shishi g long salt light-receiving material is excited by the light of the excitation light source having an emission peak in the range of 24 〇 to η 〇 nm, and the emission peak wavelength of the fluorescent material is larger than the long-wave side of the excitation light source. The wavelength of the emission peak.

In the present invention, the wavelength of the broad excitation peak of the fluorescent material is achieved by finely adjusting the content and combination of the alkaline earth metal lanthanum and/or of the phthalate fluorescent material. The transition characteristics between the energy levels of rare earth ions have a well-defined dependence on the crystal structure. By using this relationship, the light emission of different colors is formed by adjusting the wavelength of the rare earth ions. In particular, for the wavelength of the excitation ▼ in the range of 5G 51Gnm, the excitation wavelength range of the fluorescent material of the semiconductor wafer suitable for white LED illumination, which is particularly involved in the present invention, is 3^, which is used in the crystal. The crystal: the influence of the brother on its 5d energy state and 4f-Sd transition is very obvious, the maximum absorption and emission center position of the transition changes with the change of the substrate crystal environment, and the emission wavelength can be from ultraviolet to Fine adjustment changes in the red silk domain. And by finely adjusting the content and combination of the soil strontium and/or strontium of the soil salt fluorescing material, in some heterogeneous crystal series compounds, the position of the center of the chemistry can be regularly changed with the change of the chemical composition of the matrix. Long or short wave direction moves. In the present invention, when a 4f shell layer partially filled with a charge transfer (cts) transition l, fi is used, a wider electric charge d is generated in the spectrum, so that the position of the taste band changes with the environment. 11 200804561 Further, the change in the concentration of strontium ions affects the shift of the main peak position of the emitted light of the phosphor powder in the present invention. The main peak position of the emitted light of the fluorescent material can also be finely adjusted by adjusting the concentration ratio of the Eu and Ln ions. The purpose of introducing Ln in the present invention is to utilize energy transfer between rare earth ions, that is, when the luminescent center is excited, the excitation energy can be transmitted from one place to another or from one illuminating center. Another illuminating center, «and pays for fluorescent materials with high brightness. The Ln ions involved in the present invention, such as Mn, Ce, Bi, etc., can generate highly efficient radiation-free energy transfer between Eu ions and Eu ions. When the phthalate fluorescent material of the present invention is produced, the raw material used is a compound representing each element in the formula (1), and generally, the compound of M, Μ / , Ln, Eu is used as the carbonic acid of the element represented by the element. Salt, sulfate, nitrate, dish salt, >5 pate, acetate, oxalate, citrate or its oxide, hydroxide, halide; Si compound is Si 2 Niobic acid, tannin, sec-second or tantalum nitride; R is a compound of boron and phosphorus; the elemental molar ratio of the raw materials used is: Μ: 0.5~5; Μ / : 0~3·〇; Si : hO ; R : 〇 ~ 〇 5 ; Eu : 0.001 ~ 0.2 ; Ln : 0 ~ 〇 · 5 ; Lv : 〇 ~ 〇 · 5 ; ' Among them: Μ represents a compound of one or more of Sr, Ca, Ba, ζη ; 1VT represents a compound of one or more elements of Mg, Cd, Be; R represents a compound of one or both of B, P;

Si represents a compound of Si; 12 200804561

Ell represents a compound of Eu;

Ln stands for Nd, Dy, Ho, Tm, La, Ce, Er, Pr,

a compound of one or more of Bi, Sm, Sn, Y, Lu, Ga, Sb, Tb, Mix;

Lv represents a compound of one or more of C1, F, Br, I, s; ^ The working force is a high-temperature solid-phase reaction method, and the raw materials of each element are weighed according to the molar ratio, and uniformly mixed. The mixture is first sintered in an oxidizing gas atmosphere at 7 〇〇 〇 (rC for 2 to 6 hours, and then in a reducing atmosphere (the reducing atmosphere is hydrogen, ammonia, nitrogen, hydrogen or carbon particles, or in the above atmosphere). Next, bismuth contains no more than i 〇% of hydrogen sulphide ()), according to the furnace capacity and material weight and material type and formulation, at 1000-1300C firing temperature, sintering 2~6 hours

The production method of the present invention is an oxidation and reduction two-stage reaction. This manufacturing method facilitates the diffusion of rare earth promoter ions in the phthalate fluorescent material and facilitates crystal growth of the fluorescent material. In order to improve the quality of the material, a small amount (not more than 30% by weight of the raw material) of other compounds such as NH4Ci, nh4f, (NH4)2HP〇4, glucose, urea, c仏, ZnF2, ZnS' SiS may be added to the raw material. CaS, SrS〇4, _ρ〇4 or CaHp〇4,

Li2C〇3 participates in the solid phase reaction. After sintering, it is cooled, pulverized, and sieved, and sieved into particles of various sizes according to the requirements of use. The invention also relates to a light-emitting device having a light-emitting element as an excitation light source, and a fluorescent material capable of converting at least a part of the light source of the excitation light source, wherein: the emission spectrum of the light-emitting element has a peak value of ultraviolet light of 24 〇 51 51 〇 ηηι And converting the wavelength of the first illuminating spectrum of at least a portion of said illuminating elements into a fluorescing of at least one second emission spectrum having a peak wavelength in the wavelength range of 430 to 63 〇 nm; A luminescent device of the same material, wherein at least one of the phosphor materials is a phthalate phosphor material of any of the invention. A light-emitting device according to a preferred embodiment of the present invention, wherein the light-emitting element as the excitation light source has at least one or more light-emitting bee wavelengths in a range of 24 to 510 nm of the ultraviolet-green light region of the fluorescent material absorbing light-emitting element. According to a preferred embodiment of the present invention, the light-emitting layer of the light-emitting element is a nitride semiconductor or a nitride semiconductor containing In. According to a preferred embodiment of the light-emitting device of the present invention, the fluorescent material used is any of the phthalate fluorescent materials of the present invention. According to a preferred embodiment of the present invention, the emission spectrum of the light-emitting element of the excitation source is in the ultraviolet range, and the fluorescent material used is one of the phthalate fluorescent materials of the present invention or a combination of two or more; the fluorescent material absorbs at least a portion of the illumination of the excitation source and/or other phosphors in the combination, converting at least a portion of the wavelength of the illumination spectrum of the illumination element to a different one or more peak wavelengths An emission spectrum in the wavelength range of 43 〇 to 630 jim to obtain mixed white light or I light, or green light, or green light, or yellow green light, or yellow light, or yellow 14 200804561 red light, or red light. According to a preferred embodiment of the present invention, the luminescent device used as the excitation light source has an emission spectrum peak in the range of blue to green light. The fluorescent material used is one of the phthalate fluorescent materials of the present invention or a combination of two or more; the fluorescent material absorbs the excitation source and/or the combination thereof

At least a portion of the phosphor powder emits light, converting at least a portion of the wavelength of the illuminating light of the illuminating element into a different emission spectrum having at least one wavelength range of 430 to 63 nm, to obtain mixed white light, Or blue light, or blue-green light, or green light, or yellow-green light, or yellow light, or yellow red light, or red light. According to a preferred embodiment of the present invention, the luminescent device further comprises a second luminescent material, and/or a third luminescent material, for use with more than one phthalate phosphor of the present invention. And/or a fourth fluorescent material; the second fluorescent material, and/or the third fluorescent material, and/or the fourth fluorescent material will have a portion of the light from the excitation source, and/or from the present invention At least a portion of the light of the phthalate phosphor material is wavelength converted 'and has an emission spectrum having at least one emission peak wavelength in the visible region of the blue to red light. According to a preferred embodiment of the present invention, the emission spectrum of the light-emitting element as the gas-emitting source is in the range of ultraviolet light, and at least a portion of the light from the phosphoric acid material of the present invention is from the second The material and/or the third fluorescent material and/or the light of the first loyalty material are mixed with > two or more lights to obtain white light, or blue light, or, or green light, or yellow-green light, or yellow. Light, or yellow red, or red light. 15 200804561 A light-emitting device according to a preferred embodiment of the present invention, the emission spectrum peak of the light-emitting element as the excitation light source is in the range of blue light to green light, at least a part of the light from the excitation light source, and the phthalate fluorescent material from the present invention Mixing at least a portion of the light, at least two or more beams of light from the second phosphor material and/or the third phosphor material and/or the fourth phosphor material to obtain white light, or blue light, or blue-green light, or Green, or yellow-green, or yellow, or yellow-red, or red. According to a preferred embodiment of the present invention, the second fluorescent material and/or the third fluorescent material and/or the fourth fluorescent material is a rare earth-activated oxynitride phosphor, and/or Or a rare earth-doped nitride phosphor, and/or a rare earth-doped hafnium silicate phosphor, and/or a rare earth-initiated garnet-structured phosphor roll, and/or doped rare earth Activated sulfide phosphor, and/or rare earth-doped oxide phosphor, and/or rare earth-doped germanium oxide phosphor, and/or rare earth-doped starter Powdered, and/or doped yttrium-activated fluoroarsenic magnesium fluorite powder, and/or rare earth-activated borate phosphor, and/or rare earth-doped % acid salt phosphor, And/or a rare earth-activated halophosphate glazing powder, and/or a rare earth-doped titanate phosphor, and/or a rare earth-activated thiogallate fluorite. A light emitting device according to a preferred embodiment of the present invention, wherein the first edge light material and/or the third phosphor material and/or the fourth phosphor material will be part of the light from the excitation source, and/or from the present invention The at least a portion of the light of the bismuth salt illuminating material is wavelength converted and has an illuminating spectrum having at least one emission peak in the visible region of light from blue to red 16 200804561. According to a preferred embodiment of the illuminating device 4 of the present invention, the illuminating device is a luminescence conversion LED in which the phosphor material is in direct or indirect contact with the wafer. According to a preferred embodiment of the invention, the illumination device is an illumination device comprising at least one lED using a fluorescent material. The excitation and emission spectra of the twilight materials in this month were tested using an F- 4500 fluorescence spectrometer.

The relative spectral power distribution and chromaticity coordinates of the LEDs were tested using a PMS-5 紫外-UV-visible-near-infrared spectroscopy system. The above and other technical contents, features, and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments of the preferred embodiments. The embodiments of the present invention are described below, and it is necessary to point out

The invention is not limited by these examples. Example 1

Each of the above-mentioned raw materials was sufficiently ball-milled, placed in a collapsed state, and placed in an electric furnace at 900. (: Sintered in an oxidizing atmosphere for 4 hours, cooled and then sintered in a furnace with a mixture of 95% hydrogen, 3% nitrogen and 2% hydrogen sulfide, and incubated at ll ° ° C Sintering for 4 hours. Sintering 17 200804561 Edition, after pulverization, grinding with a ball mill, and then the size of the citron, the: sieve into the 仃-minute' to obtain the blue-emitting phosphor material Sr0· 〇·6 in the present invention. MgO· Si02· 〇.02p2〇5 : 〇〇3 Eu2+·»The excitation light reading of the material is in the range of 240~45Onm, excitation, peak 4 is placed, the emission light is in the range of 420~560nm, and the emission main peak position is 467 nm. v Example 2-8 The excitation spectrum was prepared in the range of 240 to 450 nm by using the mixing method of the fluorescent material of Preparation Example 1 and the firing formula φ (the main peak position of the excitation varies with the composition in the range of 350 to 410 nm) Fluorescent materials of Examples 2-8 having blue emission colors in the range of 420 to 56 Å (the main peak position of the emission varies with the composition in the range of 440 to 475 nm). Table 1 shows the examples. Composition of the fluorescent material. Table 1 Example No. Example Composition 2 1 .3SrO· 0·4 MgO· Si02· 0·08Β2〇3 : 0.003 Eu2+· 0.05Tm3+ · 0.005C1- 3 0.8SrO. 0.5MgO· Si02· 0·01Β2〇3 : 〇·〇2 Eu2+· 0.001Ce3+ · 0.05 F· 4 SrO· 〇.9MgO· Si02· 〇〇2B2〇3 : 〇·1 Eu2, 0.002Tm3 + 5 SrO· 0.5BaO· 1 .OMgO· Si02. 0·2Β2Ο3 : 〇·〇〇1 Ειι2+· 0.0001Γ 6 〇.6SrO· 〇.4BaO· 〇.〇5CaO· 1.2MgO· Si02·0.5B2〇3 : 0-2 Eu2+· 0.001S2· 7 SrO· BaO · 2.0 MgO· Si02 · 0·02Β2Ο3 : 0.003 18 200804561

Eji_0.45Br Ευ2+· 0.45C1 〇5SrO. 2Ba〇· ιο Mg〇. si〇2. 〇〇π 2 + Λ一—ζ w: :0.05 The composition of which is composed of the fluorescent material with blue luminescence of the present invention The influence of the change on the variation of the emission wavelength is: When Shi 1 < (a+b) < 2, M#Ca, when Ba is taken

When Sr is substituted, the excitation emission wavelength of the phosphor powder moves toward the long-wave direction as the content increases, and the excitation emission wavelength of the phosphor powder moves toward the short-wave direction as the Sr content increases. The ratio of the coefficient & b to the large: a > b), the excitation emission wavelength shifts to the short-wave direction more obviously when 2 < ( a + b ) g 4 , the excitation emission wavelength is affected by the ratio of Ba to Sr content and the ratio of a to b. Here, b, and when Ba < Sr, the excitation emission wavelength shifts to the long wave with the increase of the Ba content; when Ba > Sr, the excitation emission wavelength shifts to the short wave as the Ba content increases. Figure 1 illustrates an excitation emission spectrum of the phosphor of Example 1. It can be seen from Fig. 1 that the excitation light 4 of the fluorescent material having blue luminescence of the present invention is entangled, and can form effective excitation γ in the long-wave uv~blue-violet spectral region, and its effective excitation range is higher than that of the prior art. The fluorescent material has a large excitation range and high luminous efficiency, and is very suitable for preparing an LED using an ultraviolet or violet wafer as an excitation light source. Example 9

19 200804561

Si02 ___ ζυ.16 60 09 H3BO3 2.47 The raw materials of the above composition are fully ball milled, placed in an electric furnace, and sintered in an oxidizing atmosphere at mrc for 6 hours. After cooling, they are placed in a hydrogen atmosphere. The gas was sintered in a furnace and sintered at 4 Torr for 4 hours. After the sintered body is cooled, it is pulverized, ground by a ball mill, and sieved by a 325 mesh sieve to obtain a fluorescent material having blue-green luminescence in the present invention. S2Ca〇. 〇5Mg〇. si 〇2 • 0.02B203. 〇.2P2〇5 : 0.01 Eu2+. The excitation spectrum of the material is in the range of 250 to 470 (10), the main peak position of the excitation is 362 nm, and the emission spectrum is in the range of 420 to 590 nm. The emission main peak position is 485 nm. Example 10-12 The excitation spectrum was prepared in the range of 250 to 470 nm by using the mixing method of the fluorescent material of Preparation Example 9 and the firing method (the excitation main front position varied with the composition in the range of 360 to 42 〇 nm) The emission material of the embodiment 10-12 having a blue-green luminescent color in the range of 420 to 59 Å (the main peak position of the emission varies with the composition in the range of 470 to 490 nm). Table 2 shows the composition of the phosphor materials of the respective examples. Table 2 Example No. Example Composition 10 〇.7SrO·〇.3CaO· 0.4 MgO· Si〇9 · 0·〇〇8Β^~ 20 200804561 0.005 Ειι2+· 0.005Μη2+· 0·005(:Γ11 〇.7Sr〇 〇.2Ba〇· 0.2CaO · 〇.6MgO· Si02·〇-〇1B7〇3 : 0.03 Eu2+* 0.001Ho3+e 〇〇5F' 12 SrO· 0.2Ca〇·〇.8MgO· Si02· 0.02 P2〇5 ············································································································· When the ratio of the content is between 0.2 and 〇·5, when Ba and/or Ca are partially substituted for Sr, the excitation emission wavelength of the phosphor powder moves toward the long wave direction as the content of Ba and/or Ca increases. The excitation emission spectrum of the fluorescent material of Example 9 is illustrated. It can be seen from analysis 2 that the excitation spectrum of the fluorescent material having blue-green luminescence of the present invention covers the effective excitation from the long-wave UV to blue spectral region, and can be used. For the preparation of using an ultraviolet wafer or a violet wafer or a blue wafer as an excitation source LED of the optical element. Example 13 Weight of raw material (g) SrC〇3 73.82 CaC03 50.05 MgO 12.09 Si02 60.09 H3BO3 1.24 Ευ203 1.76 Mn304 0.076 The raw materials of the above composition were sufficiently ball-milled, placed in a crucible, and placed in an electric furnace. Sintering in a deuterated atmosphere at 1000 ° C for 2 hours, cooling 21 200804561 and then placing it in a furnace with hydrogen gas to be sintered, and under the generation of 蚝 蚝 纟 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Grinding, grinding with a ball mill, and sieving with a 325 mesh sieve to obtain a green light-emitting fluorescent material 〇5Sr〇. 〇5Ca〇. 〇.狗〇. si〇2 0'01B2C)3 〇·〇ι Eu2+· 〇〇〇lMn2+e The excitation spectrum of the material is in the range of 260~48〇nm, and the main peak position is 422; the emission spectrum is in the range of 43〇~60〇nm, and the emission main peak is at 499nm. . Example 14 - 16 • The excitation spectrum was prepared by the mixing method and the firing method using the phosphorescent material of Preparation Example 13 in the range of 26 G to 48 Gnm (the position of the excitation main front varies with the composition in the range of 370 to 43 〇 nm), The emission spectrum of the light-emitting material of Example 14·12 having a green luminescent color in the range of 43 〇 to just (10) (the position of the emission main front varies with the composition in the range of 49 〇 to 51 〇 nm). Table 3 shows the composition of the fluorescent materials of the respective examples. ° Example of the example of the example number 0.6SrO· 〇 4Sr〇. 〇-6Ca〇.^MgO-^7^7i7 0.001Sm2+· 〇·〇〇75^^

2.0BaO. 2.〇8M^1T〇2. 0.0^7^^·^ 0.3Mn2+· 〇.2La3+· 〇.45 ～ U For this hair ^ Green luminescence with fluorescence ^μ, change for emission wavelength The law of influence is: When 1 < ( a + b ) < 2, the condition that the ratio of Mo 2 22 200804561 content of Ca 兀 与 and the molar content of Sr element is between 〇·6 and 15 is guaranteed. The excitation emission wavelength of the lower fluorescent powder moves toward the long wave direction as the Ca content increases. When 2 < ( a + b ) $ 5, the excitation emission wavelength is affected by the ratio of Ba to Sr content and the ratio of a to b. As the Ba content increases, the excitation emission wavelength shifts to a short wave; as the Sr content increases, the excitation emission wavelength shifts toward a long wave.

Figure 3 illustrates an excitation emission spectrum of the phosphor of Example 13. It can be seen from analysis of FIG. 3 that the excitation spectrum of the green light-emitting fluorescent material of the present invention covers effective excitation from the long-wave UV to blue-green spectral region, and can be used for preparation using an ultraviolet wafer or a violet wafer or a blue wafer. The LED that excites the light source of the light source. Example 17

The raw materials of the above composition are sufficiently ball-milled, loaded into a crucible, placed in an electric furnace, sintered in an oxidizing atmosphere at 1000 Torr for 3 hours, cooled, and then placed in a furnace through which a mixed gas of nitrogen and hydrogen is sintered, and Insulation sintering at 13001 for 2 hours. After the sintered body is cooled, it is pulverized, ground by a ball mill 23 200804561, and sieved by a 325 mesh sieve to obtain a fluorescent material having κ green luminescence in the present invention. 2SrO· 〇.6CaO· 0.4 MgO • Si 〇 2. 〇.〇2B203 ·· 0·02 Ειι2+· 0.00lCe3+. 〇〇〇6F-. The excitation spectrum of the material is in the range of 240~500nm, the main peak position is 430nm; the emission spectrum is in the range of 450~600nm, and the emission main peak is at 512nm. 实施 Example 18-22

The excitation spectrum was prepared in the range of 240 to 510 nm by using the mixing method of the fluorescent material of Preparation Example 17 and the firing method (the main peak position of the excitation was varied in the range of 370 to 440 nm with the composition), and the emission spectrum was 45 〇 to 6 〇〇. The phosphor material of Examples 18-22 having a yellow-green luminescent color in the nm range (the main peak position of the emission varies with the composition in the range of 505 to 525 nm). Table 4 shows the composition of each of the examples of fluorescent materials. Table 4 Example No. Example Composition 18 〇.3SrO· 〇.95CaO· 0.7 MgO· Si02. 0·003ρ2〇5 : 0.13 Eu2+· 0.005Dy3+· 〇.〇〇5Γ 19 〇.36SrO· l.〇5CaO· 0.2 MgO· SiO2: 0 06 Eu2+— 0.001Sn2+· 0-0005S' 20 SrO· BaO· Si02* 0.01B203^ 0.008^〇5 : 〇Λ〇6^ Eu2+· 0·05 F· 21 2.0BaO· MgO· Si02 : 0:025 Eii2;^75Mn2+·~^ 0.45CT 22 ---~------ 0.25SrO· 1.5BaO· 0.25CaO· 2Mg〇. SioT^Tu Eu2+· 〇·〇1Μη2+·0.01Ce3+· 〇η7ςη For the composition of the fluorescent material having yellow-green luminescence of the present invention, the variation of the variation of the group TM 24 200804561 on the emission wavelength is: when 1 < ( a + b ) < 2, in ensuring Ca Under the condition that the ratio of the molar content of the element to the molar content of the Sr element is between 28 and 3:3, the excitation emission wavelength of the fluorescent powder moves toward the long wave direction as the Ca content increases. When 2 ‘( a + b ) $ 6 and a b , the excitation wave is excited

The ratio of the long text to the ratio of Ba to Sr and the ratio of a to b. As the Ba content increases, the excitation emission wavelength shifts to a short wave; as the Sr content increases, the excitation emission wavelength shifts to a long wave. The larger the ratio of the coefficients a to b (a > b ), the more the excitation emission wavelength shifts toward the short-wave direction. 4, 5, and 6 are excitation emission spectra of the phosphors of Examples 17, 20, and 21, respectively. The emission spectrum of Fig. 5 was obtained by using an excitation light source of 47 〇 nm as the detection wavelength. It can be seen from the analysis of the spectrogram that the excitation spectrum of the fluorescent material having yellow-green luminescence of the present invention covers the effective excitation from the long-wave uv~ illuminating green spectral region, and can be used for preparing an ultraviolet wafer or a violet wafer or a blue wafer. LED as an excitation light source illuminating element Example 23

25 200804561 The raw materials of the above composition are fully ball-mixed, put into a crucible, placed in an electric furnace, sintered in an oxidizing atmosphere under TC for 4 hours, and then cooled to a volume ratio of nitrogen to hydrogen. Sintered in a furnace of 97:3 mixed gas, and sintered at 123 (rc) for 6 hours. After sintering the cold part of the body, pulverizing, grinding with a ball mill, and sieving with a sieve of 325 mesh size, the present invention is obtained. Fluorescent material with yellow luminescence 〇.85CaO·0.55Mg〇·SiO2 · 0.02B2O3 : 0.015 Eu2+ · LOGISCe · 〇.〇〇6F—The excitation spectrum of the material is excited in the range of 24〇~52〇nm The main peak position is at 432 nm; the emission spectrum is in the range of 450 to 630 nm, and the emission main peak position is at 534 nm. Examples 24-28 The excitation spectrum was prepared in the range of 240 to 520 nm by using the mixing method and the firing method of Preparation Example 23 fluorescent material. Inside (the position of the main peak of the excitation varies with the composition in the range of 400 to 470 nm), and the emission spectrum is in the range of 450 to 640 ηπ (the main peak position of the emission varies with the composition in the range of 515 to 540 nm) with yellow luminescence. Colors of the fluorescent materials of Examples 24-28. Table 5 shows the composition of the fluorescent materials of the respective examples. Table 5 Example No. Example Composition 24 CaO· 0.15BaO · 0.6 MgO· Si〇2· 〇·〇 5Ρ205 : 〇·〇3 Ευ2 + 25 1.3SrO·〇.6Ca〇· O.SBaO* 0.4MgO* Si02* 0·002Β2〇3· 0.005 P205 : 0.2 Ειι2+· 0·028Μη2+· 0.035Dy3+· 0.3C1" 26 0.25 Sr〇·0.25Ca〇·1.5Ba〇· 2.0Mg〇· Si02 : 0.14 26 200804561 Εβ2+·〇.〇78Μη2+·0.035Bi3+·〇08Γ“'~27 0.25Sr〇·〇.25CaO· 1.5Ba〇· 2. 〇Mg〇^ Si〇2 ; Eu2+· 0.〇78Mn2+· 0.035Ce3 + 28 1.3SrO·〇.7BaO· Si〇2·〇·01Β2〇3· 〇.0〇76 p2〇—^ ____0.023 Eu2+· 0.05F* ---------- For the composition of the phosphor material having yellow luminescence of the present invention, the influence of the change in composition on the variation of the emission wavelength is: when 1 < ( a + b) < At 2 o'clock, under the condition of Sr, the excitation emission wavelength of the phosphor powder moves toward the long wave direction as the content of Ca increases. When 2$U+b)$6 and a b, the excitation emission wavelength is affected by the ratio of Ba, Sr, Ca content and the ratio of a to b. As the Ba content increases, the excitation emission wavelength shifts to the short wave; the excitation emission wavelength shifts to the long wave as the content increases, and the excitation emission wavelength shifts to the long wave as the Ca content increases. The effect of the three on the direction of the long-wave direction is Ca>Sr>Ba. //

The larger the ratio of the coefficients a to b (a > b), the more the excitation emission wavelength shifts toward the short-wave direction. Figure 8 Figure 9 are excitation emission spectra of the phosphors of Examples 23, 25 and 28, respectively. The emission spectrum of Fig. 9 is obtained by using the excitation light source of (10) as the monitoring wavelength. It can be seen from the analysis of the spectrogram that the excitation spectrum of the fluorescent material of the present invention and having yellow luminescence covers from long-wave UV to blue.

The green light spectral region forms an effective excitation, and the material B ^ ^ 疋 疋 has a higher excitation intensity in the region of the illuminating spectrum. 'Can be used for He Bei # _ ^ Clothing using I outer wafer 3 Ge violet wafer as an excitation light source The LEDs of the components, necks, ζιΙ, & m 1 & are not suitable for white LEDs using a blue light wafer as the light source illuminating element. In a white LED, the phosphor material of the present invention is used to absorb the emission of a portion of the blue radiation source to be excited; and its emission is combined with the remaining blue radiation to form white light. This white LED has good lumen efficiency and color rendering index as well as low color temperature. Example 29 Starting material Weight (g) SrC03 295.26 BaC03 15.78 CaC03 3 MgO 34.26 Si02 60.09 Eu203 10.56 NH4C1 16.05

The raw materials of the above composition were sufficiently ball-milled, placed in a crucible, placed in an electric furnace, sintered at 1100 ° C for 3 hours in an oxidizing atmosphere, and then cooled and then placed in a volume ratio of nitrogen to hydrogen of 95:5. The mixed gas was sintered in a furnace and sintered at 1250 ° C for 5 hours. After the sintered body is cooled, it is pulverized, ground by a ball mill, and sieved by a 325 mesh sieve to obtain a phosphorescent material having a yellow-red luminescence in the present invention. 2.0SrO · 0.08BaO · 0.03CaO · 0.85MgO · Si02 : 0.06 Eu2+· 0.3C1—. The excitation spectrum of the material is in the range of 200 to 530 nm, the main peak of the excitation is at 432 nm, the emission spectrum is in the range of 480 to 640 nm, and the main peak of the emission is at 558 nm. Examples 30-31 The excitation spectra were prepared in the range of 200 to 530 nm by using the mixing method and the firing method of Preparation Example 29, and the emission peaks were changed in the range of 400 to 485 nm with the group 28 200804561. The phosphor material of Examples 30-31 having a yellow-red luminescent color in the range of 480 to 640 nm (the emission main peak position varies with the composition in the range of 535 to 580 nm). Table 6 shows the composition of the phosphor materials of the respective examples. EXAMPLES Example Composition 30 l-9SrO·0.〇6Ca〇·0.6 Mg〇· Si02·0.4Β2Ο3·〇·〇03Ρ2〇5 : 〇·08 eu2+· 〇.〇2Mn2+· 〇.〇〇4Dy3 + 31 2.3Sr〇·〇.2BaO·〇.〇6CaO· MgO· Si02 : 0.06 Eu2 + • 0.25F· For the composition of the phosphor material having yellow-red luminescence of the present invention, the influence of the composition change on the change of the emission wavelength is : When 2 < ( a + b ) $ 5, and a > b, the effect of the ratio of the emission wavelength to the ratio of Ba, Sr, and Ca is excited. As the Ba content increases, the excitation emission wavelength shifts to the short wave; as the Sr content increases, the excitation emission wavelength shifts to the long wave; as the Ca content increases, the excitation emission wavelength shifts to the long wave. The effect of the three on the influence of the excitation wavelength on the long-wave direction is Ca > Sr > Ba. The figure shows the excitation emission spectrum of the fluorescent material of Example 29. It can be seen from the analysis of the spectrogram that the range of the aperture of the fluorescent material with yellow-red luminescence of the present invention is effectively excited from the long-wave uv~green spectral region, and the 4-inch aperture is in the wavelength range of 360 to 480 nm. The excitation intensity is high and the basic "Yantian, sitting is not axis-flat", and can be used for preparing a light-emitting element using an enamel wafer or a violet wafer as an excitation light source @LED, which is particularly suitable for using a blue light wafer 29 200804561 as an excitation light source. In the white light led, the fluorescent light source of the present invention absorbs the emission of a portion of the blue light source and is excited; and the emission is combined with the remaining blue light to form white light. Since the emission main peak of the fluorescent material is located Between the yellow spectral region and the red spectral region, therefore

The prepared white LEDs were aged at a temperature of Example 32 - color index and low color temperature. The raw materials of the above composition are fully ball-mixed, loaded into a crucible, placed in an electric furnace, sintered in an oxidizing atmosphere under a loocrc for 6 hours, cooled, and then placed in a mixture having a nitrogen gas to hydrogen volume ratio of 95:5. The gas was sintered in a furnace and sintered at 13 Torr (rc for 5 hours. After the cold portion of the sintered body, pulverized, ground with a ball mill, and then sieved with a 325 mesh sieve for 4 minutes), the red color of the present invention was obtained. Luminescent fluorescent material 〇.25Sr〇. 1.25BaO· 1.5 Mg〇· Si02 : 〇.〇25 Ευ2+· 〇Λ ΜΠ · 〇.5C1·. The excitation spectrum of the material is in the range of 230~500nm, and the main peak position is excited. 429 nm; the emission spectrum has two emission main peaks of a red light region and a blue light region, the red light region emission spectrum is in the range of 480 to 640 nm, and the red light emission main peak position is at 609 nm. Examples 33 to 35 30 200804561 By using Preparation Example 32 Fluorescent material mixing method and firing method to prepare excitation pupil in the range of 200~530nm (excitation main peak position varies with composition in the range of 400 485nm), emission spectrum in the range of 々go ~ 640nm (emission main peak) Fluorescent materials of Examples 33-35 having a yellow-red luminescent color as the composition varied from 580 to 63 Å. Table 7 shows the composition of the phosphor materials of the various examples.

15Ba〇· 2.0 MgO· Si02· 0.〇1B2〇3 : 〇.2 Ευ2 Μη2+· 0.0002Pr^>n in- 〇34 〇.8Ba〇. MMgO. Si02. : 〇.〇6 Eu2. 0.03 Mn2+ · 0.25F' 35 - 9BaO 0.9Mg 〇 · Si02 : 0. 〇〇 3 Eu 2+ · 0.006 Mn 0.005F ' For the composition of the phosphor material having red luminescence of the present invention, the change in composition affects the variation of the emission wavelength Yes: In addition to adjusting the excitation and emission spectra of Eu2+ by using a double earth metal ion bond that produces a difference in the nature of the soil metal content in the matrix, it also effectively utilizes the energy transfer control and adjustment between Eu and Ln ions (especially Mn2+). Emission spectrum and energy. When the content of Mn2+ is fixed, the content of red emission main peak of the emission spectrum increases with the increase of 2 + content, while the intensity of the emission main peak of blue + region decreases. When the content of Eu2+ is fixed, the Mn content increases, and the intensity of the red emission main peak of the emission spectrum decreases. 11 is the excitation emission spectrum of the Μ 32 f light material. Emission light 31 200804561 Two horse red region emission spectrum. It can be seen that the excitation light wavelength range of the present invention and ==Mm_28()~475 nm is excited by using an ultraviolet wafer or a violet wafer or a blue crystal = white light (four) + as an excitation (four) light-emitting element, which is The j-light of the red light area is suitable for the color rendering index, the color temperature, and the skin damage of the human eye.

In the invention, it is found that in the preparation process of the fluorescent material, the human (5), ΝΗβ, (nh4)2hpo4, glucose 'urea' BaF2, CaF2, ZnF2, ZnS, SrS, CaS, SrS〇 can be added. 4 'SrHP〇4 or CaHP〇4, Li2C〇3, etc. participate in the solid phase reaction to increase the relative luminance and excitation emission spectrum of the material at different twists, as exemplified below. Example 36 ------- humiliation (2) _- Sr(NCM? 1. -=- \ t? / ----- __ 253.96 __ __ Ca(〇H)? __ 14.8 — __BaC03 ——— ----- __ 157.85 __ Mg ( OH) 2· 4MgC03· ___ 6H20 -------------—.—— 10.07 __ H4Si〇4 ------ —------ __ 9 6 __ __ H3BO3 __0.12 _____ —>_ (NH4)2HP04 ___ 2.64 __ —__Eu(N〇,), _ 16.9 Mn02 0.87 ____ Ce〇2 ——_________—— 8.6 ___ -_ NH4CI —_ 2.68 __ _ ZnS 0.49 32 200804561 Adding 14% of BaF2 and 0.3% of Li2C03, the raw materials of the above composition are fully ball-mixed, put into the crucible, and placed in an electric furnace at 700°. Sintering was carried out for 6 hours under an oxidizing atmosphere in C. After cooling, it was sintered in a furnace containing a mixed gas of a volume of nitrogen and hydrogen and a hydrogen sulfide ratio of 95:3:2, and sintered at 1150 ° C for 5 hours. After the sintered body is cooled, it is pulverized, ground by a ball mill, and sieved by a 325 mesh sieve to obtain a fluorescent material having a yellow luminescence in the present invention. 1.2Sr〇·0.8BaO·0.2Ca〇·0.1 MgO · Si02· 0.〇〇1B2〇3 • 0 · 01Ρ205 : 〇·〇5 Eu2+ · 0·01 Mn2+ · 〇·〇5 Ce3+ · 0.05C1·· 0.005S2·· 0.45F-· 0.05 Li+. The excitation spectrum of the material is in the range of 240~520nm, and the main peak position is excited. There is a strong excitation spectrum at 475 nm; the emission spectrum is in the range of 45 〇 to 63 〇 nm, and the emission main peak is at 537 nm. The manner and method of adding various external raw materials required in the manufacturing method of the present invention are similar to those of the embodiment 36 except that the type and amount of the raw materials to be added are selected according to the excitation emission spectrum range and relative brightness of the fluorescent material to be produced. . The present invention also relates to an illumination device using any one or more of the phosphor materials of the present invention, and more particularly to a semiconductor LED using an emission main peak used as an excitation light source in the range of 240 to 510 nm, particularly an LED emitting white light. The scope of the claimed invention will now be described in the form of a specific embodiment. Referring to Fig. 12, the LED of the present invention comprises a semiconductor light-emitting chip 2, a cathode electrode 2, a positive electrode 3, a pin 4, a fluorescent material 5, a sealing material 6, and a lead 33 200804561 7 reflecting cup 8. The half-body light-emitting chip is a secret wafer or a wafer. The fluorescent material includes at least one or more of the (4) acid salt glazing materials of the present invention. The encapsulating material is a transparent resin, and may be a transparent epoxy resin, such as a transparent stone. & wherein a is a direct contact between the fluorescent material and the semiconductor light-emitting chip, and the fluorescent material is mixed with the transparent resin and then coated on the reflective glass of the semiconductor light-emitting chip. ® b is the way to contact between the fluorescent material and the semiconductor light-emitting chip. The fluorescent material is evenly distributed on the surface of the epoxy resin. Figure 〇 is the way in which the light-emitting material semiconductor light-emitting chip is in indirect contact, and the light-emitting materials are all disposed in the epoxy resin and above the semiconductor light-emitting chip. Example 37 • A white LED was prepared using the LED package of Figure 3 of Figure 12. The specific enthalpy process is to select I g having a matching emission main peak wavelength according to the effective excitation wavelength range of the phosphor powder. In the example of the conjugate of the film, the wavelength of the main peak of the semiconductor light-emitting chip is 460 nm, and the luminescent material is selected as described in Example 29, and the die-bonding, wire bonding, and drying are performed. Weigh a few grams and a transparent epoxy resin in the appropriate proportions. ί over the semiconductor wafer (dispensing). The glued lead cup is glued, the empty chess box is solidified, and then inserted into a mold filled with epoxy resin, and then solidified in a work oven, and finally demolded. The relative spectral power of this $ $ # τ ρη distribution ^ mm Γ , color xum, γ = 0.3292, color rendering index 85. The emission spectrum is formed by the luminescence powder being partially excited by the blue light and emitted by the blue light, and then emitted by the red light spectrum of the first red light and the remaining "second film". Example 38 34 200804561 ^ The white light LED is prepared by using the LED package method in FIG. 12 . In this example, the emission main peak wavelength of the 帛 'body light emitting chip is 385 nm, and the fluorescent material selection embodiment i, the embodiment 13, the embodiment 23, and the embodiment 32 The camping materials are mixed in an appropriate ratio. The package is similar to the embodiment π, but the phosphor material is evenly distributed on the surface of the epoxy resin. The emission spectrum of the white LED is controlled by the above four kinds of phosphors. When the ultraviolet light is emitted, the blue, green, yellow, and red luminescence spectra respectively emitted by the external light and/or part of the emitted light from the fluorescent powder are combined with the remaining 4 minute emission spectrum of the fluorescent powder. The color coordinates are 胄x=03747, Υ=〇.34〇3, and the color temperature is 3874K. Fig. 14 is a (10) diagram of the white light coffee. The point F is the chromaticity seat point of the white LED of the embodiment. Example 39 # Use Figure i 2 in Figure e The white LED is prepared by LED packaging. In the example, the emission main peak wavelength of the semiconductor light-emitting chip is 胄470nm, and the fluorescent material selected in the third embodiment is the fluorescent material (the emission main wavelength is 556ηΐΏ) and the doping rare earth starts. YAG campsite powder of the pumice structure ((Y0.33Gd0.63Ce0.04)3A]5〇] 2' emission main peak wavelength 532(10)) and sulfide-fluorescent fluorescing # (CaS: Eu, emission main peak) The wavelength is 6〇6—mixed in an appropriate ratio. The packaging process is the same as in Example 37(4), but the fluorescent materials are all distributed in the epoxy resin and on the semiconductor light-emitting chip. This _ LED emission spectrum is composed of the above three kinds of camp light. The yellow, yellow-red, and red-emitting spectroscopy spectra of the yellow, yellow, and red luminescence spectra emitted by the luminescence and the luminescence of the remaining portion of the blue ray are respectively emitted by the blue light and the @ part of the luminescent powder. Composite color. Its color coordinates stomach χ = 〇 · 3288, γ = 〇. Qiu, color temperature 5637 Κ 'color rendering index 8 〇. Using Figure a, Figure, (3) (four) package can be used to prepare LED. seal The process is similar to the embodiment η%. However, there are many options for the combination of the phosphor powder. The principle is: The effective excitation wavelength range of the worm phosphor powder and the emission main peak wavelength of the semiconductor wafer and/or together (4) other camp wires The emission main peak wavelength is matched to the core. Under the premise of determining the emission main peak wavelength of the semiconductor wafer, the fluorescent material is selected according to the required luminescent color of the LED product. Under the premise of using at least one of the above-described phthalate fluorescent materials of the present invention At the same time, according to the luminescent color of the LED product, the second fluorescent material and/or the third fluorescent material and/or the fourth fluorescent material are not selected. The types of fluorescent materials that can be used as the first fluorescent material and/or the third fluorescent material and/or the fourth fluorescent material include: rare earth-doped oxynitride phosphors, rare earth-doped nitride phosphors. Photopowder, #杂Rare earth-activated phthalate phosphor powder, rare earth-doped stone structure phosphor powder, rare earth-doped sulfide phosphor powder 4 4 rare earth-activated oxide phosphor powder , doped rare earth-activated sulfur oxide fluorescent powder, rare earth-doped aluminate fluorescent powder, doped activated fluorine arsenic magnesium fluorite powder, doped rare earth activated powder , doped rare earth-activated acid-filled phosphor powder, rare earth-doped functional phosphate phosphor, doped rare earth-activated titanate 36 200804561 Fluorescent powder, rare earth-doped thiogallate Light powder. The LED illumination color of the clothing is determined by the emission spectrum and relative brightness of the semiconductor wafer used and the emission spectrum and phase of the phosphor used. The following are explained by Examples 40 to 48, and the selection of *曰 μ / ugly day, the selection of the phosphor and the color of the LED are shown in Table 8. Table 8

37 200804561 620 46 Gal 400 470 3.5MgO·〇.5MgF2· 655 White nN 530 Ge02: Mn4+ 47 Gal 460 510 (Y〇.95Ce〇>〇5)3Al5〇i2 550 White nN 535 48 Gal nN 410 570 Yellow Red

The phthalate fluorescent material of the present invention is excellent in anti-attenuation performance, and the white LEDs produced in Examples 37, 38, and 39 are subjected to a destructive aging test under the following conditions: ambient temperature 25t: current 100 mA, aging time 1008 hour. The brightness decay curve is shown in Figure 15. As can be seen from the figure, after the destructive test under such conditions, the LED has a light decay of less than 26%, excellent anti-attenuation performance, and good temperature stability. The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a laser emission spectrum of a fluorescent material of Example i having blue light emission; " Excitation of an optical material FIG. 2 is a firefly and emission spectrum of Example 9 having blue-green light emission; The excitation of the material and FIG. 3 is the fluorescene emission spectrum of Example 13 with green luminescence; the excitation of the photonic material of 17 is Example 38 200804561 with emission of yellow-green luminescence and emission spectrum; FIG. 5 is luminescence with yellow-green luminescence Excitation and emission spectra of the fluorescent material of Example 20 wherein the emission spectrum is obtained by using an excitation light source of 470 nm as the detection wavelength; 'Figure 6 is the excitation and emission spectra of the fluorescent material of Example 21 having yellow-green illumination; 7 is an excitation and emission spectrum of the fluorescent material of Example 23 having yellow light emission; • FIG. 8 is an excitation and emission spectrum of the fluorescent material of Example 25 having yellow light emission; FIG. 9 is an Example 28 having yellow light emission. The excitation and emission spectra of the fluorescent material 'where the emission spectrum is obtained by using an excitation light source of 470 nm as the detection wavelength; FIG. 10 is the excitation of Example 29 having yellow-red illumination. Figure 11 is an excitation emission spectrum of Example 3 2 fluorescent material with red emission, emission spectrum is red region emission spectrum; ^ Figure 12 is a schematic diagram of an LED structure; Figure 13 is an embodiment FIG. 14 is a chromaticity coordinate of a white LED of Example 38 in a CiE diagram; and FIG. 15 is a light attenuation diagram of white light 1^0 of Embodiments 37, 38, and 39. 39 200804561 [Explanation of main component symbols] 1 · » _ Semiconductor light-emitting chip 5 _ • · · Fluorescent material 2 · · · · Cathode electrode 6 · · · · Package material 3 · · · * Positive electrode 7 · • •• Lead 4 · · · · Pin 8 · • · · Reflective Cup

40

Claims (1)

200804561 X. Patent application scope: 1. A fluorescent material, in particular, a fluorescent material for a light-emitting device including lED, which is characterized in that it mainly contains citrate and a promoter ion, and its main chemical composition expression is :aMO · bM〆0 · Si〇2 · cR : Ευ yLn zLv ' where μ is selected from one of Sr, Ca, Ba, Zn Or a combination of a plurality of 7G; M / a combination of one or more elements selected from the group consisting of Mg, cd, and Be; R is selected from one or both of B2〇3, P2〇s' Ln is Nd, Dy, Ho , a combination of one or more of Tm, La, Ce, Er, Pr, Bi, Sm, Sn, Y, Lu, Ga, Sb, Tb, Mn 'Lv is selected from the group consisting of cr, F-, Br-, ", S2 -&gt; combination of one or more element ions; a, b, c, x, y, z are the molar coefficients, 〇·5 ~ ~ 5^°; 0 ^ b ^ 3.0 ; 0 ^ c ^ 〇.5 ; 0.001 ^ χ ^ r\ 0 · =0.2, 〇sy ^ 〇·5 ; ο ^ ζ &lt; 〇·5 ,...1 &lt; (a+b) ^ 6, and when (a+b) = 2 When the μ〆&/material can be used as an excitation source, the emission spectrum is excited by a light-emitting element in the ultraviolet-green region of 240 to 510 nm, and a part of the light is emitted from the excitation light source, emitting a range of 420 to 700 nm. Inside, there is more than one emission spectrum in the range of 430~63〇nra, which can be illuminated by blue, blue green, green, yellow green, yellow, yellow red, red and white colors. The molar coefficient of the first item The fluorescent material is characterized by a range of: when i &lt; (a + b) &lt; 2, and a &gt; b ' 0 · 5 g ^ 〇 · 5 , 〇. 〇〇 ! a — 1· 5 ' 0·4 $ b $ 1·0 , ^ x = 0.2 , 0 ^ y $ 0.5 41 200804561 Z &lt; 〇.5 , and M#Ca ; when 2 &lt; (a+b) , and a$b When, 1.0S a S 2,1.0 $ bm 〇$ e ^ q $ ,0.001 SX $ 〇·2, 〇$ y $ 〇5, 〇$ z &lt; 0·5, the illuminating color after excitation is blue. 3. The camping light material according to the scope of claim patent, characterized in that the range of the molar coefficient is: 1 &lt; ( a + b ) &lt; 2, and a &gt; b, 0.5 $ a $ u, 〇 4 gb. 〇, 〇 $ 2 0.5, regardless of gxg 0.2, 〇 $ y, 〇 5, -〇 " &lt; 0.5, and the ratio of the molar content of Ca element to the molar content of Sr element is Between 0.2 and 5., the illuminating color after excitation is blue-green. 4. The range of the moir coefficient according to the fluorescence described in item i of the patent application scope is: when i &lt;u+b/, == 0.5 ^ a ^ 1.5 , 0.2 ^ 5 〇, 〇^ 〇... ....2, 〇S...5 ; &lt; —y — U.5 , 0 $ ζ &lt; 〇·5 ' and the ratio of the molar content of Ca element to the molar content of Sr element is between 〇6 Μ ;; When 2&lt; (...)$5, 0.5 ga $ 3.〇, 0 - b ~3·0 5 〇^ 0.5,〇.〇〇1 ^ x ^ 〇2 :,0 $ Υ “.5 '〇^ Ζ 〇 5 5 ; ; ; 激发 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. b) &lt;2, 〇·5 “ $ 1.5, M b U0 ' 〇$ c $ 〇5, 0 001 ' X ^ 〇-2 Ό ^ Y ^ 0.5 , 〇^ z &lt; 〇.5 , and Ca The ratio of the molar content of the element to the molar content of the Sr element is between 2 8 42 200804561 3.3; when 2 &lt; (a+b) } = 6 and ab, 15 &lt; a ^ 3,0 $ b $3·〇 ,n &lt; ° = =c $ 0·5,Ο.οοι ^ XS 0.2,0 $ y ^ 〇·5 , 〇χ = ζ &lt;〇·5; when (a+b )-2β inch, i^ A^2 η = b $ U,0 ^ c ^ °·5,0-001 ^ X ^ 0.2 , π &lt; ~ ^ =y ^ 0.5 ,〇&lt; z &lt; 0.5 , and when b is off, 丄M off Mg, when b=(), the molar content of the element is in the range of 0.8 to 16 between the Ba element and the 70 element, and the luminescent color after excitation is yellow-green. The range of the molar coefficient described in the item is · a 〆, which is characterized by 〇.5 "...1n +b) &lt;2, 0 001 &lt;&lt; a 〇, 0$cg 0.5, 0 001 $ XS 0·2 , 〇 &lt;&gt; y ^ ο·5 , 〇幺, and ❹ Sr; when 2 &lt; (a ~ &lt; 0.5 b S3.0 , oj =6 and ab, 2 S =c = 0.5 » 0 001 &lt; ^ 0.2 ^ ^ y ^ 0.5 0.001 s X υ$Ζ&lt;〇ς. fire, , =2, iO $ a &lt; ) 0.5 ,, when (a+b) ...0 “ ^1 ·〇, ο &lt; Γ < 〇·5, 〇·_ “ “·2, ο ' == &lt;0.5, and when b is closed,]·, 〇$ζ The molar content of Ba and Ba element The ear is in the L field b = 0 day, the heart of the ear contains the ratio of the name of the 】; the illuminating color after the excitation is yellow. In the range of 1.8 to 2.2, the range of the molar coefficient described in the scope of the patent application is in the form of material, which is characterized by b., .0$ aq〇/ -<(^) ^, And 〇一...".:,::Γ:...... u = yg 0·5,ο ' ζ 43 200804561 &lt; 〇·5 , and the molar content of Sr and / or Ca elements is greater than the molar content of Ba element The luminescent color after excitation is yellow-red. 8. The fluorescent material according to claim 1, wherein the range of the molar coefficient is: when 1 &lt; (a+b) &lt;;1·5, 〇·2 S a ^ 1·2,0·2 S b $ 1·2,0 ^ c ^ 〇·5 ,0.001 S χ S 0·2,0 $ y $ 0·5 , 〇^ ζ< °·5 : When 1·5 &lt; ( a+b) &lt;2, 〇·5 $ a $ L8,〇·5 =b ^ 1.8 ' 〇^ c ^ 0.5,0.001 ^ χ ^ q 2 , 9· 10. 0 ^ y ^ 0.5 ,0 $ Ζ &lt;0.5; when 2 &lt; (a+b) ^ 5, 1·0 ' ag 3·0, ΐ·〇$ b $ 3 , 〇^ c ^ 〇 · 5 ' 〇·〇〇1 $ χ $ 〇·2, Ο $ y $ 〇·5, 〇$ ζ 〈〇·5; the illuminating color after excitation is red. A fluorescent material according to the invention of claim 1, wherein the phthalate fluorescent material is excited by light of an excitation light source having an emission peak in a range of 240 to 510 nm, and the fluorescent material is The emission peak wavelength is greater than the wavelength of the long-wave side emission peak of the excitation light source. It is the maker of the following bM ^ - type of fluorescent material &amp;amp; it is characterized by the compound of each element of the raw material used. Its element is expressed by the following formula: si〇2. cR: xEu. yLn. The ratio is Μ : 0·5~5 ; Μ ^ : 0~3.0 ; Si : 1.0 ; R : 0~2.0 ; Ευ : 0.001-0.2 ; 44 200804561 Ln : 0~0·5 ; Lv : 0~0.5 ; Wherein: Μ represents a compound of one or more of Sr, Ca, Ba, Zn; ^ represents a compound of one or more of Mg, Cd, Be; R represents a compound of one or two of B, P ; Si represents a compound of Si; Ειι stands for a compound of Ειι; Ln represents Nd, Dy, Ho, Tm, La, Ce, &amp;, &amp; 拗, Sm'Sn' Y'LU'Ga'Sb, Tb, Mn a compound of one or more elements; Lv represents a compound of α, F, Br, I, s φ, a compound of one or more elements of b τ; a compound of Μ M Ln, Eu is a carbonate of an element respectively represented by them Salt, sulphate, nitrate, phosphate, borate, acetate, oxalate, citrate or its chlorine servant, Today, lh ^ , telluride telluride, halide; Si compound is Si 〇 2, Shi Xi brew, Gong Wen Bu ^ 2 矽 I 矽., tantalum nitride or bismuth salt; R is boron, phosphorus Compounds; praise for the work of the industrial s - clothing work temperature and solid phase reaction method, the raw materials of each element according to Moer 屮 manganese road, 曰人 ^ this handle is taken, mixed evenly, first in an oxidizing atmosphere 7〇〇-ii〇〇r sintered 2~6 small Japan, i+ person wb small dry, and then in the reducing atmosphere 1000-1300. (: Sintering 2~6 hours, 6% know%! ν, after the cold part, smashing, sifting into 〇11. According to the application of patent item 10, 尸 坏 迷 踅 踅 踅 , , , 45 200804561 It is characterized in that the reducing gas amp &amp; 々 卜 式 虱 虱 虱 。 。 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 The method for producing a light material is characterized in that it is still in existence, and that the original material contains no more than 1% of H2S. 13. According to the fluorescent material described in the patent item! The manufacturing method is characterized in that nh4C1, NH4F, (NH4)2HP〇4, glucose, urea, BaF2, CaF2' ZnF2 ' ZnS ' SrS ' CaS ' SrS〇4 are added to the mixed raw materials. SrHp〇4 or CaHP〇4, Li2C03 participate in the solid phase reaction. 14. A light-emitting device having a light-emitting element as an excitation light source and a fluorescent material capable of converting at least a part of the light of the excitation light source, wherein: the light-emitting element The emission spectrum peaks at 2 In the range of ultraviolet light-green light region of 4〇~51〇nm, and converting the wavelength of the first light-emitting spectrum of at least a part of the light-emitting elements into at least one peak wavelength in the wavelength range of 430 to 63〇nm The second emission spectrum of the fluorescent material. The light-emitting device has at least one of the fluorescent materials described in any one of claims 1 to 13 of the invention. The illuminating device according to claim 2, characterized in that the illuminating element as the excitation light source has at least one or more workers in the ultraviolet-green region of 240 to 510 nm of the luminescent material absorbing illuminating element. The light-emitting layer of the light-emitting element according to the light-emitting device of claim 15, which is a nitride semiconductor, is a nitride semiconductor. The illuminating device according to item 15 of the present invention, wherein the fluorescent material used is the claim ', / in the square; 18. The light-emitting device according to claim 4, wherein the emission spectrum of the light-emitting element as the excitation light source is in the ultraviolet light range, and the fluorescent material used is any one of the claims a combination of two or more of the phosphoric acid materials; the glory material absorbs at least a portion of the other luminescent powders of the excitation source and/or combination of light luminescence spectra of at least a portion of the luminescent elements The wavelength is converted into a different emission spectrum with at least one peak wavelength in the range of (4) to (iv) wavelengths to obtain mixed white light, or illuminating light, or illuminating green light, or bee 廿 廿 ^ 4 light or Green light, or yellow light, or yellow red light, or red light. The illuminating device according to claim 14, wherein the luminescent material used as the excitation spectrum of the illuminating element of the illuminating element is in the range of blue to green light. Any one or a combination of two or more of the (four) acid salt fluorescent materials; the at least a portion of the light-emitting material absorbing at least a portion of the excitation light source and/or other luminescent powders in the combination The wavelength of the luminescence spectrum of the illuminating element is converted into different emission spectra of at least one of the peak wavelengths in the wavelength range of 430 to 630 nm to obtain mixed white light 47 200804561, or illuminating light, or blue-green light, or green light, Or yellow-green light, 廿,, 5 乂 more light, - or red light, or red light. 2. The illuminating device according to the W, 15, 18 or 19 patent application scope is characterized in that the fluorescent material used further contains any of the &lt; δ 胥冋 nuclear claim 1 I3 a second fluorescent material, and/or a third fluorescent material, and/or a fourth fluorescent material, which are used together with more than one phthalate fluorescent material; the second fluorescent material, and/or The third fluorescent material 1 and/or the fourth fluorescent material will be a portion of the light from the excitation source, =/or light from the bismuth silicate material of any of claims 1-13 At least a portion of the wavelength is converted and has an emission spectrum having at least one emission peak wavelength in the visible region of the blue to red light. The illuminating device according to claim 2, characterized in that the emission spectrum peak of the illuminating element as the excitation light source is in the range of ultraviolet light 'at least a part of the light from the citrate fluorescent material Mixing at least two or more lights of the light from the second phosphor material and/or the third phosphor material and/or the fourth phosphor material to obtain white light, or blue light, or blue-green light, or green Light, or yellow-green light, or yellow light, or yellow red light, or red light. 2. The illuminating device according to claim 14, wherein the radiant value of the illuminating element as the excitation light source is in the range of the illuminating to the green light, from the At least a portion of the light from the excitation source, at least a portion of the light from the phthalate phosphor material is from the second phosphor material and/or the third phosphor material and/or the light of the 48 200804561 four egg light material 5 small a soil to J / two or more beams of light to obtain white light, or blue light, or blue-green light, 吱々廿 #上斗, 廿 ^ 70 戎,, light, or green light, or Page light, or yellow red light, or red light. /, 2 3 · According to the patent application, the illuminating device described in paragraph 14, 15, 18 or 19 of the company, is specifically characterized by the second fluorescent material and/or the third fluorescent material. Sizhongguang materials are: rare earth-doped oxynitride phosphors, and/or rare earth-doped nitride phosphors, and/or rare earth-doped i-silicate phosphors, and/or a rare earth-initiated garnet-structured k-powder, and/or a rare earth-doped sulfided phosphor, and/or a t-rare-earthed oxide phosphor, and/or a rare earth-doped sulfur Oxide phosphors, and/or rare earth-doped aluminate phosphors, and/or Mn-doped fluoroquinone fluorite powder, and/or rare earth-doped borate Fluorescent powder, and/or rare earth-doped phosphate tile, and/or rare earth-doped yttrium phosphate phosphor, and/or rare earth-doped titanate phosphor, and/or Or doped with rare earth-activated thiogallate fluorescein. The illuminating device according to claim 14, wherein the second fluorescent material and/or the third fluorescent material and/or the fourth fluorescent material are derived from At least a portion of the light of the excitation light source and/or at least a portion of the light from the phthalate phosphor material of any of claims 1 to 13 having a wavelength of blue to red light An illuminating spectrum having at least one emission peak in the visible light region 〇25. The illuminating device 49 200804561 according to claim 14, claim 15, 18 or 19, wherein the illuminating device is a kind of arsenal A luminescence conversion led that is in direct or indirect contact with the wafer. The illuminating device according to claim 14, wherein the illuminating device is an illuminating device comprising at least one LED using the luminescent material. 50 200804561 VII. Designated representative map: ). Fluorescent material packaging material lead reflector (1) The representative drawing of this case is: (12 (II) The symbol of the symbol of the representative figure is simple: 1 • · · · Semiconductor light-emitting chip 5 · · 2 • · · · Negative electrode 6 · · y 3 • · ••yang electrode 7 · · 4 • · •• Pin 8 · · 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 200804561 Hd j 冲〉 IV. Statement Matters: □ Proposal for the facts as stipulated in the second paragraph or the second paragraph of Article 22 of the Patent Law, the facts of which occur in the following period: year and month. □ Apply for patents from the following countries (regions) before applying : [Format please follow: order of acceptance of country (region), application date, application case number] □ There is a claim for patent law Article 27, the first international priority · 0 No claim patent law Article 27 An international priority: • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • Apply for 曰, Note on the application case number □ Proposal Patent Law Article 30 Biological Materials: □ Those who need to deposit biological materials: Domestic biological materials [Format please follow the instructions of the depository, the period, the number order] Foreign biomaterials [format: please note: country, organization, date, number order note] □ Those who do not need to deposit biomaterials: When the general knowledge in the technical field is easy to obtain, no deposit is required.