WO2017114281A1

WO2017114281A1 - Phosphor powder of garnet-type structure and light-emitting device prepared therewith

Info

Publication number: WO2017114281A1
Application number: PCT/CN2016/111495
Authority: WO
Inventors: 庄卫东; 郑亚玲; 刘荣辉; 钟继有; 徐会兵; 李彦峰; 刘元红; 陈磊
Original assignee: 有研稀土新材料股份有限公司
Priority date: 2015-12-31
Filing date: 2016-12-22
Publication date: 2017-07-06
Also published as: CN106929017A; CN106929017B

Abstract

The present invention provides a phosphor powder with garnet-type structure and a light-emitting device prepared therewith. The phosphor powder has the chemical formula Ca_aLn_b-kM¹ _cSc_dAl_eM² _fO₁₂:Ce_k, wherein Ln represents a trivalent rare earth element, the trivalent rare earth element being at least one of Lu, Y and Gd; M¹ represents at least one of Zr and Hf; M²represents at least one of Ge and Si; 1.8 ≤ a ≤ 2.2; 0.78 ≤ b ≤ 1.2; 0.8 < c < 1.2; 0.8 < d < 1.2; 1.8 ≤ e < 2.2; 0.8 < f < 1.2; and 0 < k ≤ 0.15. An emission peak wavelength and a spectral coverage area of the phosphor powder can be adjusted by modifying the identity and ratio of the trivalent rare earth elements and by modifying the concentration of a luminescence center element Ce, thereby allowing the phosphor powder to meet practical requirements of different light-emitting devices with respect to the photochromic properties of light-emitting materials.

Description

Garnet-type phosphor and light-emitting device therefor

Technical field

The present invention relates to the field of fluorescent materials, and in particular to a garnet-type phosphor and a light-emitting device therefor.

Background technique

In 1993, Japan Nichia Corporation successfully developed blue GaN light-emitting diodes (LEDs), which led the era of semiconductor lighting. The semiconductor white LED lighting device has the advantages of small size, fast response, high luminous efficiency, energy saving, environmental protection and long life, and is the most promising illumination source. There are three options for implementing white LEDs: fluorescent conversion, multi-chip combination, and single-chip multi-quantum well. (1) Fluorescence conversion type: According to the semiconductor chip, the light-emitting wavelength is blue light or near-ultraviolet light, which is divided into two types. One is that the blue LED chip excites the yellow light phosphor to be combined into white light, and the other is the near-ultraviolet light LED chip that excites red. The green, blue and blue primary phosphors are combined into white light. (2) Multi-chip combination type: Red, green and blue LED chips are assembled to realize white light. (3) Single-chip multiple quantum well type: The same semiconductor chip emits visible light of a plurality of colors and combines into white light.

At present, fluorescent conversion white LEDs are the mainstream of solid white light illumination development. The earliest commercial white LED was realized by Japan's Nichia Corporation using a combination of GaN-based blue LED chips and yellow phosphors to realize white LED lighting devices. A very important reason is that YAG yellow powder with garnet structure has extremely stable physical and chemical properties and unmatched high luminous efficiency. However, such a combination of a blue chip and a yellow phosphor has poor color rendering properties, that is, a color rendering index is low, and a color temperature is high, and in the illumination device produced therefrom, there is a problem that the peak intensity of blue light is high and the sleep disorder is easily caused. It is the so-called "blue light problem."

In recent years, a light-emitting device using a combination of a near-ultraviolet chip and a three-primary phosphor has a good light color performance, a wide adjustable range, and a wider range of selectable phosphors. At this stage, in the conventional trichromatic phosphor, the phosphor emitting blue light is mainly BaMgAl ₁₀ O ₁₇ :Eu ²⁺ (BAM) and Ca ₅ (PO ₄ ) ₃ Cl:Eu ²⁺ , however, these two phosphors There has always been a problem of low near-ultraviolet excitation efficiency. Therefore, starting from the matrix material, it is a good research and development idea to find a blue phosphor for white LEDs that is compatible with the ultraviolet chip and has good chemical stability, luminous intensity and high efficiency.

In addition, phosphor matrix materials with garnet structure have been favored by researchers because of their outstanding physical stability. In particular, Ce ³⁺ ions act as activators, which have strong excitation peaks in the ultraviolet and blue regions in the garnet structure, which can well match the ultraviolet, near-ultraviolet or blue light chips. The garnet structure is of the formula A ₃ B ₂ X ₃ O ₁₂ , and A, B and X are generally a dodecahedral structure representing eight oxygen atoms, an octahedral structure coordinated by six oxygen atoms, and four oxygens. A tetrahedral structure of atomic coordination. For garnet-based phosphor materials, the B-site usually has divalent metal elements (such as Mg in Lu ₂ CaMg ₂ (Si, Ge) ₃ O ₁₂ phosphor) and trivalent metal elements (such as Al in the YAG phosphor; Sc) in the Ca ₃ Sc ₂ Si ₃ O ₁₂ phosphor, and tetravalent metal elements (such as Y _3-x Ca _x Al _5-x (Zr/Hf) _x O ₁₂ phosphor Zr, Hf; Zr) in a Ca ₂ LaZr ₂ Ga ₃ O ₁₂ phosphor, and a pentavalent metal element (such as Ta in a Li ₅ La ₂ Ta ₂ O ₁₂ phosphor). It has also been reported in the literature that a divalent metal element and a tetravalent metal element are simultaneously incorporated in the B site, such as (Y/La/Lu) in the Yr-Mg replacement (Y/La/Lu) ₃ Al ₅ O ₁₂ phosphor. And Al.

Summary of the invention

The main object of the present invention is to provide a garnet-type phosphor and a light-emitting device thereof, which can provide a fluorescent powder with excellent wide range of emission peak wavelengths for matching with an ultraviolet chip to prepare a white LED. .

In order to achieve the above object, according to an aspect of the invention, there is provided a garnet-type phosphor having a chemical formula of Ca _a Ln _bk M ¹ _c Sc _d Al _e M ² _f O ₁₂ :Ce _k , Wherein Ln represents a trivalent rare earth element, the trivalent rare earth element is at least one of Lu, Y and Gd; M ¹ represents at least one of Zr and Hf; M ² represents at least one of Ge and Si; 1.8 ≤ a ≤ 2.2; 0.78 ≤ b ≤ 1.2; 0.8 < c <1.2; 0.8 < d <1.2; 1.8 ≤ e <2.2; 0.8 < f <1.2; 0 < k ≤ 0.15.

Further, Ln is Lu.

Further, M ¹ is Zr.

Further, a+b+k=3, c+d=2, and e+f=3.

Further, a=2, b+k=1, c=1, d=1, e=2, and f=1.

Further, 0.01 ≤ k ≤ 0.04.

In order to achieve the above object, according to an aspect of the invention, there is provided a light-emitting device comprising a light source and a phosphor, the phosphor comprising a phosphor of any of the garnet-type structures described above.

Further, the phosphor is a phosphor of any of the above-described garnet type structures.

Further, the light source is a semiconductor solid state light-emitting element having an emission peak in a wavelength range of 325 nm to 480 nm.

Further, the phosphor is a phosphor that emits an emission peak having a wavelength of 450 nm to 550 nm under excitation of a light source.

By applying the technical solution of the present invention, a portion (Y/La/Gd) and (Y/La/Gd) ₃ Al ₅ O ₁₂ are replaced by Ca-(Zr/Hf), Ca-Sc-(Ge/Si) Al is convenient for adjusting the emission peak wavelength and the spectral coverage area of the phosphor by adjusting the kind and ratio of the rare earth element Lu, Y or Gd rare earth element represented by the above Ln and the concentration of the luminescent center element Ce element. Since the luminescent center element has strong excitation peaks in the ultraviolet region and the blue region, it can well match the ultraviolet, near-ultraviolet or blue-light chips, and introduce Ge and/or Si, Ge-ion electricity into the phosphor. The negative polarity is large and its radius is very close to the Al ion, which makes the phosphor structure more stable and compact. The addition of Si can greatly improve the luminous efficiency of the phosphor. Therefore, the phosphor can meet the application requirements of different light-emitting devices for the light color performance of the light-emitting material.

DRAWINGS

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

1 shows an XRD pattern of a phosphor prepared in Example 1 of the present invention;

2 is a view showing an excitation spectrum of a phosphor prepared in Example 1 of the present invention;

3 is a view showing an emission spectrum of a phosphor prepared in Example 1 of the present invention;

4 shows emission spectra of phosphors prepared in Examples 2 to 5 of the present invention;

Figure 5 is a view showing emission spectra of phosphors prepared in Examples 6 to 10 of the present invention;

Figure 6 is a view showing an emission spectrum of a phosphor prepared in Example 12 of the present invention;

Fig. 7 is a view showing the emission spectrum of the phosphor prepared in Example 13 of the present invention.

detailed description

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

As mentioned in the background section, the phosphors for white LEDs matched with the ultraviolet chips in the prior art are still difficult to meet the market demand. In an exemplary embodiment of the present invention, a garnet structure fluorescence is provided. Powder, the chemical formula of the phosphor is Ca _a Ln _bk M ¹ _c Sc _d Al _e M ² _f O ₁₂ :Ce _k , wherein Ln represents a trivalent rare earth element, and the trivalent rare earth element is at least one of Lu, Y and Gd M1 represents at least one of Zr and Hf; M2 represents at least one of Ge and Si; 1.8 ≤ a ≤ 2.2; 0.8 ≤ b ≤ 1.2; 0.8 < c <1.2; 0.8 < d <1.2; 1.8 ≤ e <2.2; 0.8 < f <1.2; 0 < k ≤ 0.15.

The phosphor provided by the present invention replaces a portion (Y/La/Gd) in (Y/La/Gd) ₃ Al ₅ O ₁₂ by using Ca-(Zr/Hf), Ca-Sc-(Ge/Si) Al makes it possible to adjust the emission peak wavelength and the spectral coverage area of the phosphor by adjusting the kind and ratio of the rare earth element Lu, Y or Gd rare earth element represented by the above Ln and the concentration of the luminescent center element Ce element. Since the luminescent center element has strong excitation peaks in the ultraviolet region and the blue region, it can well match the ultraviolet, near-ultraviolet or blue-light chips, and introduce Ge and/or Si, Ge-ion electricity into the phosphor. The negative polarity is large and the radius is very close to that of the Al ion, which makes the phosphor structure more stable and compact. The addition of Si can greatly improve the luminous efficiency of the phosphor, so that the phosphor can satisfy the light color performance of the luminescent material of different illuminating devices. Application requirements.

The trivalent rare earth element Lu, Y or Gd represented by Ln in the above formula, as the content of Lu element decreases and the content of Y element increases, the emission peak wavelength of the phosphor gradually shifts toward the long wavelength direction, and the luminescent color tends to blue-green. When the concentration (k value) of Ce ³⁺ is increased to more than 0.02, the luminescence of the phosphor will have a concentration quenching effect, and at this time, increasing the concentration of Ce ³⁺ may easily lower the luminescence intensity of the phosphor.

In the above phosphor, Ln is preferably Lu, and for the garnet structure A ₃ B ₂ X ₃ O ₁₂ , the octahedral structure in which the B site element is located is co-edgely connected with the dodecahedral structure in which the A site element is located, and thus the A and B elements are The radius should not be too different. When the B position is selected as Zr (or Hf) or Sc, from the angle matching degree, the A bit is selected to make the structure of the phosphor more stable, thereby improving the fluorescence. The temperature characteristics of the powder. At the same time, it is also possible to replace Ln with other rare earth elements such as La or the like to tune the luminescent properties.

In the above phosphor component, one or two of Zr or Hf are introduced at the same time as the introduction of Sc, and the three elements are matched in ionic radius, especially Zr, Zr and Sc are closer in ionic radius. The lattice distortion caused by the crystal structure is small, and the pure phase compound is more suitable.

The phosphor provided by the invention introduces Ge or Si, and the Ge ion has a large electronegativity and a radius close to that of the Al ion, which makes the phosphor structure more stable and compact. However, the introduction of Ge may affect the luminous efficiency of Ce ³⁺ ions. Therefore, the addition of Si can greatly improve the luminous efficiency of the phosphor. Therefore, in the above phosphor, M ² is preferably introduced simultaneously with Ge, which is advantageous for obtaining a phosphor having a more stable structure and good luminous efficiency.

The phosphor provided by the present invention is constructed based on a garnet structure with X elements (including Ce and Tb) as luminescent centers. Among them, X (including Ce and Tb) must contain Ce ³⁺ . In the novel garnet structure matrix, Ce ³⁺ has strong excitation peaks in the ultraviolet region and the blue region, which can well match ultraviolet light, A chip that is near-ultraviolet or blue. Moreover, the co-doping of two elements, Ce and Tb, is beneficial to enhance the absorption of the radiant energy of the phosphor by the phosphor, and can transfer the absorbed energy to the luminescent center in the phosphor to increase the luminescence brightness without generating a luminescent center. The phenomenon of competitive absorption or reabsorption is performed to ensure superior luminous efficiency of the phosphor. However, the addition amount k of the X element (including Ce and Tb) is preferably in the range of 0.02 ≤ k ≤ 0.15. Within this range, the luminance of the phosphor is made high, and if the amount is too large, the non-emissive phase is easily generated, and the luminance of the light is impaired.

In the above phosphor, when the content of the component is preferably a+b+k=3, c+d=2, and e+f=3, the obtained phosphor has good stability. More preferably, a = 2, b + k = 1, c = 1, d = 1, e = 2, and f = 1, under these conditions, the stability of the phosphor is better.

In another exemplary embodiment of the present invention, there is further provided a light-emitting device comprising a light source and a phosphor combination, wherein the phosphor combination comprises a phosphor, wherein the phosphor comprises any one of the above-mentioned garnet types Structure of the phosphor. More preferably, the phosphor is a phosphor of any of the above-described garnet type structures. With the above phosphor, the above-mentioned light-emitting device can better tune the intensity of blue light and the color rendering index of white LED by controlling the amount of phosphor.

The light-emitting device comprising the above-mentioned phosphor provided by the present invention, wherein the light source is a semiconductor solid-state light-emitting element having an emission peak in a wavelength range of 325 nm to 480 nm or 325 nm to 410 nm, and the first phosphor is excited by the light source A phosphor having an emission peak in a region of 450 nm to 550 nm.

The light-emitting device comprising the above-mentioned phosphor provided by the present invention uses a light source of the above wavelength range and a phosphor of the above wavelength range, so that the light-emitting device has a lower color temperature and a higher color-developing finger.

The method for preparing the above phosphor of the present invention can be prepared by a high temperature solid phase method. Specifically, a compound containing each element in the chemical expression Ca _a Ln _bk M ¹ _c Sc _d Al _e M ² _f O ₁₂ :Ce _k is used as a raw material, and the raw materials of the phosphor are respectively contained in each element of the chemical expression. As the compound, a compound containing the element can be selected as a raw material according to various elements contained in the chemical expression. The corresponding raw materials are weighed according to the molar ratio of each element in the above chemical expression; the raw material solid powder of each of the above elements is ground and mixed uniformly to obtain a precursor; the precursor is placed in a reducing atmosphere and heated to a temperature of 900 ° C to 1450 ° C. The calcination is carried out 1 or 2 times to obtain a final calcined product, and the calcination time is 3 to 6 hours each time. After each calcination, it is naturally cooled to room temperature for grinding treatment, and the reducing atmosphere is hydrogen (volume content of 5 to 15%) and nitrogen gas. The mixed gas or reducing atmosphere is an air mixture containing carbon monoxide (5 to 15% by volume). The garnet structure phosphor is obtained by post-treatment of the final calcined product by crushing, particle size classification, grinding, washing, drying, and the like.

The above grinding can be carried out in an agate mortar or a ball mill. The method of classifying the above particle size is one or more of a sedimentation method, a sieving method, or a gas flow method. The final calcined product is crushed, ground, and classified by particle size, which means that the particle size of the sintered body is finely ground by manual crushing, and is classified by sedimentation method, sieving method or airflow method, and the particle size is 3～. 10 micron solid powder. The above washing and drying are sequentially washed with water and alcohol, and the solid phase is separated by filtration and dried at 100 to 110 °C.

Advantageous effects of the present invention will be further described below in conjunction with specific embodiments.

It should be noted that in the following examples, the XRD pattern was subjected to X-ray diffraction using a Co target (λ = 1.78892 nm). Excitation and emission spectra were acquired using a highly sensitive integrated fluorescence spectrometer from Horiba's FluoroMax-4 model; the luminescence intensity and color coordinates were measured using a high-speed fast spectroradiometer from Hangzhou Yuanfang HAAS-2000. The gamut range and color rendering index and color temperature were detected by the company's ZWL-600 model photoelectric test system.

Example 1: Preparation of Ca ₂ Lu _0.98 ZrScAl ₂ GeO ₁₂ :Ce _0.02 Phosphor

The raw materials containing the respective elements are weighed according to the chemical formula. The purity of each of the above raw materials is 99% or more. Each of the above raw material mixtures was uniformly ground in an agate mortar, and then placed in a corundum crucible, and heated to 1400 ° C at a heating rate of 5 ° C / min under a reducing atmosphere of carbon monoxide gas, and calcined at 1400 ° C for 4 hours. Then, the calcined product was cooled to room temperature. The obtained sintered product was ground and then ground with a ball mill to obtain a sample. The phosphor has an emission wavelength between 450 nm and 550 nm under excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 480 nm. The relative luminous intensity is shown in Table 1.

The X-ray diffraction spectrum (upper row) of the Ce ^{3+ -doped} garnet-structured phosphor prepared in this example is compared with the standard card PDF #75-1853 (lower row) as shown in FIG. As can be seen from Figure 1, the phosphor produced was a garnet structure.

The excitation spectrum (λ _em = 480 nm) of the phosphor prepared in this embodiment is shown in FIG. 2, and the phosphor can be excited by light having a wavelength in the range of 325 nm to 425 nm, which is a white LED application excited by an ultraviolet or near-ultraviolet LED chip. New phosphor. The emission spectrum of the phosphor (λ _ex = 400 nm) is shown in Fig. 3. As can be seen from FIG. 3, the phosphor emits light at a wavelength of between 450 nm and 550 nm under excitation of near-ultraviolet light of 400 nm, and the peak wavelength of the emitted light is 480 nm.

Example 2: Preparation of Ca ₂ Lu _0.98 ZrScAl ₂ Ge _0.9 Si _0.1 O ₁₂ :Ce _0.02 Phosphor

Weigh the raw materials according to the chemical formula. The purity of the above raw materials is above 99%. The raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample. The phosphor has an emission wavelength between 450 nm and 550 nm under excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 483 nm. The relative luminous intensity is shown in Table 1.

The emission spectrum of the phosphor prepared in this example is shown in Fig. 4. As can be seen from FIG. 4, the phosphor has an emission wavelength between 450 nm and 550 nm and an emission peak wavelength of 483 nm under excitation of near-ultraviolet light (λ _ex = 400 nm) of 400 nm.

Example 3: Preparation of Ca ₂ Lu _0.98 ZrScAl ₂ Ge _0.7 Si _0.3 O ₁₂ :Ce _0.02 Phosphor

Weigh the raw materials according to the chemical formula. The purity of the above raw materials is above 99%. The raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample. The fluorescent The light powder has an emission wavelength between 450 nm and 550 nm under excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 485 nm. The relative luminous intensity is shown in Table 1.

The emission spectrum of the phosphor prepared in this example is shown in Fig. 4. As can be seen from FIG. 4, the phosphor has an emission wavelength between 450 nm and 550 nm and an emission peak wavelength of 485 nm under excitation of near-ultraviolet light (λ _ex = 400 nm) of 400 nm.

Example 4: Preparation of Ca ₂ Lu _0.98 ZrScAl ₂ Ge _0.4 Si _0.6 O ₁₂ :Ce _0.02 phosphor

Weigh the raw materials according to the chemical formula. The purity of the above raw materials is above 99%. The raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample. The phosphor has an emission wavelength between 450 nm and 550 nm under the excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 486 nm. The relative luminous intensity is shown in Table 1.

The emission spectrum of the Ce ^{3+ -doped} garnet structure phosphor prepared in this example is shown in FIG. 4 . As can be seen from FIG. 4, the phosphor has an emission wavelength between 450 nm and 550 nm and an emission peak wavelength of 486 nm under excitation of near-ultraviolet light (λ _ex = 400 nm) of 400 nm.

Example 5: Preparation of Ca ₂ Lu _0.98 ZrScAl ₂ SiO ₁₂ :Ce _0.02 phosphor

Weigh the raw materials according to the chemical formula. The purity of the above raw materials is above 99%. The raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample. The phosphor has an emission wavelength between 450 nm and 600 nm under excitation of near-ultraviolet light of 400 nm, an emission peak wavelength of 500 nm, and the relative luminescence intensity is shown in Table 1.

The emission spectrum of the Ce ^{3+ -doped} garnet structure phosphor prepared in this example is shown in FIG. 4 . As can be seen from Fig. 4, the phosphor has an emission wavelength between 450 nm and 600 nm and an emission peak wavelength of 500 nm under excitation of 400 nm of near-ultraviolet light (λ _ex = 400 nm).

Example 6: Preparation of Ca ₂ Lu _0.98 Zr _0.8 Sc _1.2 Al _1.8 Ge _1.2 O ₁₂ :Ce _0.01 phosphor

Weigh the raw materials according to the chemical formula. The purity of the above raw materials is above 99%. The raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample. The phosphor has an emission wavelength between 425 nm and 600 nm under excitation of near-ultraviolet light of 400 nm, an emission peak wavelength of 481 nm, and the relative luminescence intensity is shown in Table 1.

The emission spectrum of the Ce ^{3+ -doped} garnet structure phosphor prepared in this example is shown in FIG. As can be seen from Fig. 5, the phosphor has an emission wavelength between 425 nm and 600 nm and an emission peak wavelength of 481 nm under excitation of near-ultraviolet light (λ _ex = 400 nm) of 400 nm.

Example 7: Preparation of Ca ₂ Lu _0.98 Zr _0.8 Sc _1.2 Al _1.8 Ge _1.2 O ₁₂ :Ce _0.02 Phosphor

Weigh the raw materials according to the chemical formula. The purity of the above raw materials is above 99%. The raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample. The phosphor has an emission wavelength between 425 nm and 600 nm under excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 487 nm. The relative luminescence intensity is shown in Table 1.

The emission spectrum of the Ce ^{3+ -doped} garnet structure phosphor prepared in this example is shown in FIG. As can be seen from Fig. 5, the phosphor has an emission wavelength between 425 nm and 600 nm and an emission peak wavelength of 487 nm under excitation of near-ultraviolet light (λ _ex = 400 nm) of 400 nm.

Example 8: Preparation of Ca ₂ Lu _0.98 Zr _0.8 Sc _1.2 Al _1.8 Ge _1.2 O ₁₂ :Ce _0.04 phosphor

Weigh the raw materials according to the chemical formula. The purity of the above raw materials is above 99%. The raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample. The phosphor has an emission wavelength between 450 nm and 600 nm under excitation of near-ultraviolet light of 400 nm, an emission peak wavelength of 493 nm, and the relative luminescence intensity is shown in Table 1.

The emission spectrum of the Ce ^{3+ -doped} garnet structure phosphor prepared in this example is shown in FIG. As can be seen from FIG. 5, the phosphor has an emission wavelength between 450 nm and 600 nm and an emission peak wavelength of 493 nm under excitation of near-ultraviolet light (λ _ex = 400 nm) of 400 nm.

Example 9: Preparation of Ca ₂ Lu _0.98 Zr _0.8 Sc _1.2 Al _1.8 Ge _1.2 O ₁₂ :Ce _0.1 phosphor

Weigh the raw materials according to the chemical formula. The purity of the above raw materials is above 99%. The raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample. The phosphor has an emission wavelength between 450 nm and 600 nm under the excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 499 nm. The relative luminous intensity is shown in Table 1.

The emission spectrum of the Ce ^{3+ -doped} garnet structure phosphor prepared in this example is shown in FIG. As can be seen from FIG. 5, the phosphor has an emission wavelength between 450 nm and 600 nm and an emission peak wavelength of 499 nm under excitation of near-ultraviolet light (λ _ex = 400 nm) of 400 nm.

Example 10: Preparation of Ca ₂ Lu _0.98 Zr _0.8 Sc _1.2 Al _1.8 Ge _1.2 O ₁₂ :Ce _0.15 phosphor

Weigh the raw materials according to the chemical formula. The purity of the above raw materials is above 99%. The raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample. The phosphor has an emission wavelength between 450 nm and 600 nm under the excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 501 nm. The relative luminous intensity is shown in Table 1.

The emission spectrum of the Ce ^{3+ -doped} garnet structure phosphor prepared in this example is shown in FIG. As can be seen from Fig. 5, the phosphor has an emission wavelength between 450 nm and 600 nm under excitation of near-ultraviolet light (λ _ex = 400 nm) of 400 nm, and an emission peak wavelength of 501 nm.

Example 11: Preparation of Ca ₂ Lu _0.98 Zr _0.8 Hf _0.2 ScAl ₂ GeO ₁₂ :Ce _0.02 phosphor

Weigh the raw materials according to the chemical formula. The purity of the above raw materials is above 99%. The raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample. The phosphor has an emission wavelength between 450 nm and 580 nm under excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 475 nm. The relative luminous intensity is shown in Table 1.

Example 12: Preparation of Ca _1.8 Y _0.78 Lu _0.4 Zr _0.8 Sc _1.2 Al ₂ GeO ₁₂ :Ce _0.02 phosphor

Weigh the raw materials according to the chemical formula. The purity of the above raw materials is above 99%. The raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample. The phosphor has an emission wavelength between 450 nm and 650 nm under the excitation of near-ultraviolet light of 430 nm, and an emission peak wavelength of 517 nm. The relative luminous intensity is shown in Table 1.

The emission spectrum of the Ce ^{3+ -doped} garnet structure phosphor prepared in this example is shown in FIG. As can be seen from Fig. 6, the phosphor has an emission wavelength between 450 nm and 650 nm and an emission peak wavelength of 517 nm under excitation of near-ultraviolet light of 430 nm.

Example 13: Preparation of Ca _2.2 Gd _0.68 Lu _0.3 Zr _1.2 Sc _0.8 Al ₂ GeO ₁₂ :Ce _0.02 Phosphor

Weigh the raw materials according to the chemical formula. The purity of the above raw materials is above 99%. The raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample. The phosphor emits at a wavelength of 425 nm to 700 nm under excitation of near-ultraviolet light of 455 nm, and has an emission peak wavelength of 546 nm. The relative luminescence intensity is shown in Table 1.

The emission spectrum of the Ce ^{3+ -doped} garnet-structured phosphor prepared in this example is shown in FIG. As can be seen from FIG. 7, the phosphor emits at a wavelength of 425 nm to 700 nm under excitation of near-ultraviolet light of 455 nm, and has an emission peak wavelength of 546 nm.

Example 14: Preparation of Ca ₂ Lu _0.98 Zr _1.2 Sc _0.8 Al _2.2 Ge _0.8 O ₁₂ :Ce _0.02 phosphor

Weigh the raw materials according to the chemical formula. The purity of the above raw materials is above 99%. The raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample. The phosphor has an emission wavelength between 425 nm and 600 nm under excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 488 nm. The relative luminescence intensity is shown in Table 1.

Example 15

The blue phosphor obtained in Example 1 and the β-SiAlON:Eu green phosphor and the CaAlSiN3:Eu red phosphor were dispersed in the resin at a mass ratio of 3:6:1, and the UV LED was coated at 405 nm after slurrying. On the chip, the circuit is cured and soldered, and sealed with resin to obtain a white light emitting device with a color coordinate of (0.3956, 0.3779) and a color reproduction range of 80% NTSC.

Example 16

The blue phosphor obtained in Example 5 and the green phosphor obtained in Example 12 and (Sr, Ca) ₂ Si ₅ N ₈ :Eu red phosphor were dispersed in a resin at a mass ratio of 2:8:1. The slurry is coated on a 405 nm UV LED chip, solidified, and soldered to a circuit, and sealed with a resin to obtain a white light emitting device having a color coordinate of (0.3796, 0.3589), a color rendering index of 86.1, and a correlated color temperature. 4198K.

Table 1 The optimal excitation light wavelength and emission peak wavelength position and relative luminescence intensity of the phosphor prepared in Examples 1-14 (selected at 400 nm photoexcitation, the luminescence intensity of Ca ₂ Lu _0.98 ZrScAl ₂ GeO ₁₂ :Ce _0.02 is 100%)

As apparent from the above, the above-described embodiments of the present invention achieve the following technical effects: by using Ca-(Zr/Hf), Ca-Sc-(Ge/Si) replacement (Y/La/Gd) ₃ Al ₅ O ₁₂ The portion (Y/La/Gd) and Al, which adjust the type and proportion of the rare earth element Lu, Y or Gd, which is represented by the above Ln, and the concentration of the luminescent center element Ce element, can realize the peak emission wavelength of the phosphor And the spectral coverage area is adjustable. Since the luminescent center element has strong excitation peaks in the ultraviolet region and the blue region, it can well match the ultraviolet, near-ultraviolet or blue-light chips, and introduce Ge and/or Si, Ge-ion electricity into the phosphor. The negative polarity is large and its radius is very close to the Al ion, which makes the phosphor structure more stable and compact. The addition of Si can greatly improve the luminous efficiency of the phosphor. Therefore, the phosphor can meet the application requirements of different light-emitting devices for the light color performance of the light-emitting material.

As can be seen from the above Table 1, the emission peak wavelength of the Y _3-x Ca _x Al _5-x (Zr/Hf) _x O ₁₂ phosphor in the prior art is adjusted in the range of 530 nm to 560 nm. The phosphor of the invention has a wider range of emission peak wavelengths and is more biased toward the blue light region.

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

Claims

A garnet-type phosphor, characterized in that the chemical formula of the phosphor is Ca a Ln bk M 1 c Sc d Al e M 2 f O 12 :Ce k , wherein Ln represents a trivalent rare earth element, The trivalent rare earth element is at least one of Lu, Y and Gd; M 1 represents at least one of Zr and Hf; M 2 represents at least one of Ge and Si; 1.8 ≤ a ≤ 2.2; 0.78 ≤ b ≤ 1.2; 0.8 < c <1.2; 0.8 < d <1.2; 1.8 ≤ e <2.2; 0.8 < f <1.2; 0 < k ≤ 0.15.
The phosphor according to claim 1, wherein Ln is Lu.
The phosphor according to claim 1, wherein M 1 is Zr.
The phosphor according to claim 1, wherein a+b+k=3, c+d=2, and e+f=3.
The phosphor according to claim 1, wherein a = 2, b + k = 1, c = 1, d = 1, e = 2, and f = 1.
The phosphor according to any one of claims 1 to 5, wherein 0.01 ≤ k ≤ 0.04.
A light-emitting device comprising a light source and a phosphor, the phosphor comprising the garnet-type phosphor according to any one of claims 1 to 5.
The light-emitting device according to claim 7, wherein the phosphor is a garnet-type phosphor according to any one of claims 1 to 5.
The light-emitting device according to claim 8, wherein the light source is a semiconductor solid-state light-emitting element having an emission peak in a wavelength range of 325 nm to 480 nm.
The light-emitting device according to claim 9, wherein the phosphor is a phosphor that emits an emission peak having a wavelength of 450 nm to 550 nm under excitation of the light source.