WO2020015424A1 - Poudre fluorescente de nitrure et son procédé de préparation, et appareil électroluminescent contenant une poudre fluorescente de nitrure - Google Patents

Poudre fluorescente de nitrure et son procédé de préparation, et appareil électroluminescent contenant une poudre fluorescente de nitrure Download PDF

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WO2020015424A1
WO2020015424A1 PCT/CN2019/084589 CN2019084589W WO2020015424A1 WO 2020015424 A1 WO2020015424 A1 WO 2020015424A1 CN 2019084589 W CN2019084589 W CN 2019084589W WO 2020015424 A1 WO2020015424 A1 WO 2020015424A1
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elements
lial
yeu
xyz
nitride phosphor
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Chinese (zh)
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林金填
陈磊
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旭宇光电（深圳）股份有限公司
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    • C—CHEMISTRY; METALLURGY
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • H01L33/504—Elements with two or more wavelength conversion materials

Definitions

  • the invention belongs to the technical field of LED lighting, in particular to a high-light-emitting nitride phosphor and a preparation method thereof, and a light-emitting device containing the high-light-emitting nitride phosphor.
  • LED has the advantages of high efficiency, energy saving, environmental protection, long life, small size, and easy maintenance. It has attracted widespread attention from researchers at home and abroad. At present, LED is gradually replacing traditional light sources as the mainstream of lighting sources, and is widely used in commercial lighting, industrial lighting, outdoor lighting, indoor lighting, special lighting and other fields. At present, the mainstream way to realize white LEDs is to excite phosphors through chips to emit light. Phosphors, as an important part of white LEDs, are the key to achieving high light efficiency, high display index, and high stability of white LEDs.
  • the purpose of the present invention is to provide a nitride phosphor with high light efficiency, good stability, and simple preparation method, and a method for preparing the same. Low problem.
  • Another aspect of the present invention provides a light-emitting device containing a high-efficiency nitride phosphor.
  • a nitride phosphor whose chemical formula is A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR), wherein, A is selected from one or more of Ca, Sr, Ba, Mg, Zn elements, M is selected from one or more of La, Y, Lu, Gd elements, and D is selected from Si, Ge, Ti, Sn One or more of Se element, N is nitrogen element, C is carbon element, R is selected from one or more of Ce, Tb, Pr element,
  • a method for preparing a nitride phosphor includes the following steps:
  • nitrides of A alloys containing elements M and D, alloys containing elements Li and Al, nitrides of Al 4 C 3 , EuN and R, or fluorides of R, wherein A is selected from Ca, Sr, One or more of Ba, Mg, Zn elements, M is selected from one or more of La, Y, Lu, Gd elements, D is selected from one of Si, Ge, Ti, Sn, Se elements Or more, N is a nitrogen element, C is a carbon element, and R is selected from one or more of Ce, Tb, and Pr elements; the alloy containing the M and D elements is heated to 600-800 ° C in a nitrogen atmosphere Pre-nitriding treatment is performed to obtain intermediate material 1. The alloy containing Li and Al elements is heated to 600-800 ° C. in a nitrogen atmosphere to perform pre-nitriding treatment to obtain intermediate material 2;
  • the intermediate material 1, the intermediate material 2, the nitride of A, the nitrides of Al 4 C 3 , EuN, and R or the fluoride of R at a stoichiometric ratio is obtained a mixed raw material system;
  • the raw material system is placed in a heating device and sintered in a N 2 / H 2 mixed atmosphere at a temperature of 900-950 ° C.
  • a light emitting device includes a fluorescent substance and an excitation light source, the fluorescent substance is a nitride phosphor, and the chemical formula of the nitride phosphor is A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR), wherein A is selected from one or more of Ca, Sr, Ba, Mg, and Zn, and M is selected from La, Y, Lu Or one or more of Gd element, D is selected from one or more of Si, Ge, Ti, Sn, Se element, N is nitrogen element, C is carbon element, and R is selected from Ce, Tb, Pr One or more of the elements,
  • the nitride phosphor provided by the present invention has a molecular formula of A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR), and the structure contains A, M, D, C, R elements, wherein A is selected from one or more of Ca, Sr, Ba, Mg, Zn elements, M is selected from one or more of La, Y, Lu, Gd elements, D One or more selected from Si, Ge, Ti, Sn, and Se elements, C is a carbon element, and R is selected from one or more of Ce, Tb, and Pr elements.
  • the nitride phosphor that meets the above structural requirements has a suitable element composition, and the content between each element is appropriate, so that the basic structure of the material is similar to that of SrLiAl 3 N 4 nitride red powder, and it has a good configuration and crystallinity. Therefore, the physical and chemical stability is good, and the weather resistance is improved.
  • the nitride phosphor A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR ) provided by the present invention has stable crystal structure and weather resistance. Good, high luminous efficiency.
  • an alloy nitriding method is used to first pre-nitrate an alloy containing M and D elements, and an alloy containing Li and Al elements to avoid Li at a high temperature during the preparation process.
  • the nitride phosphor can be prepared under relatively mild conditions; at the same time, it is beneficial to improve the stability of the crystal structure in the subsequent preparation process.
  • elements A, M, D, C, and R through high-temperature doping, nitride phosphors with stable crystal structure, good weather resistance, and high luminous efficiency can be obtained.
  • the light-emitting device provided by the present invention contains the above-mentioned nitride phosphor, so the advantages of stable crystal structure, good weather resistance, and high light-emitting efficiency of the nitride phosphor can be fully utilized, thereby further improving the light-emitting efficiency and stability of the light-emitting device.
  • Example 1 is an XRD pattern of a nitride phosphor obtained in Example 31 of the present invention.
  • Example 31 is a SEM image of a nitride phosphor provided in Example 31 of the present invention.
  • FIG. 4 is a comparison chart of the excitation spectrum and the emission spectrum of the nitride phosphor obtained in Example 31 of the present invention.
  • first and second are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as “first” and “second” may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "plurality” is two or more, unless specifically defined otherwise.
  • An embodiment of the present invention provides a nitride phosphor.
  • the chemical formula of the nitride phosphor is A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu , zR), wherein A is selected from one or more of Ca, Sr, Ba, Mg, and Zn elements, M is selected from one or more of La, Y, Lu, Gd elements, and D is selected from Si Or more of Ge, Ti, Sn, Se, N is nitrogen, C is carbon, R is selected from one or more of Ce, Tb, Pr,
  • the nitride phosphor provided by the embodiment of the present invention has a molecular formula of A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR), the structure contains A, M, D, C, and R elements, wherein A is selected from one or more of Ca, Sr, Ba, Mg, and Zn elements, and M is selected from one or more of La, Y, Lu, and Gd elements D is selected from one or more of Si, Ge, Ti, Sn, and Se elements, C is a carbon element, and R is selected from one or more of Ce, Tb, and Pr elements.
  • the nitride phosphor that meets the above structural requirements has a suitable element composition, and the content between each element is appropriate, so that the material has a better configuration on the basis of meeting the basic structural requirements of SrLiAl 3 N 4 nitride red powder. And crystallinity, therefore, good physical and chemical stability and improved weather resistance.
  • Eu and R wherein R is selected from one or more of Ce, Tb, and Pr elements.
  • the nitride phosphor A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR ) provided in the embodiment of the present invention has stable crystal structure, Good weather resistance and high luminous efficiency.
  • the nitride phosphor A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR) contains four types of element sites The points are the first element site, the second element site, the third element site, and the fourth element site, respectively, and have structures similar to SrLiAl 3 N 4 .
  • the first element site is composed of A element, M element, Eu element, and R element (A is selected from one or more of Ca, Sr, Ba, Mg, and Zn elements, and M is selected from La, Y, Lu, One or more of Gd elements, R is selected from one or more of Ce, Tb, Pr elements),
  • the second element site includes the Li element site, and the third element site includes the Al element and
  • the D element and the fourth element site include the N element and the C element.
  • the elements A, M, Eu, R All are at the first element site.
  • Eu element is the main activator, which is the luminous center of the entire phosphor.
  • the content of Eu element determines the color coordinates, peak wavelength, and stability of the phosphor.
  • a 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR) the content of the Eu element satisfies: 0.005 ⁇ y ⁇ 0.1.
  • the nitride phosphor A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR) has a small number of light-emitting centers and emits light.
  • the intensity is very low; when the value of y is too high, no radiation transition occurs between Eu ions, causing concentration quenching, and both the luminous intensity and the stability performance will decrease.
  • Eu element alone acts as an activator of the nitride phosphor, and the luminous efficiency of the obtained nitride phosphor is relatively low.
  • Eu and R (R is selected from one or more of Ce, Tb, and Pr elements) are jointly used as an activator to improve the luminous efficiency of the nitride phosphor.
  • R as a sensitizer, converts the absorbed light into energy and transfers it to Eu ions, which helps to increase the emission intensity of Eu, thereby improving the luminous efficiency.
  • the content of the R element satisfies: 0.01 ⁇ z ⁇ 0.0. 05.
  • R is selected from one or more of Ce, Tb, and Pr elements.
  • the energy levels of the Ce, Tb, and Pr elements are matched with that of the Eu element, and energy transfer can occur through resonance, which helps to increase the intensity of Eu emission and improve the luminous efficiency of the nitride phosphor.
  • R is a mixed element of Ce element and Tb element. When Ce and Tb are co-doped, the Ce emission effect is significantly enhanced, which further results in the highest energy transfer efficiency of the Ce-Eu phosphor, and the most significant increase in the emission intensity of the phosphor.
  • R is Ce element and Tb Element mixed element
  • the molar ratio of Ce element and Tb element is 2: 1 ⁇ 3: 1.
  • the doping molar ratio of the two is the key.
  • the molar ratio of Ce and Tb is between 2: 1 and 3: 1, Tb-Ce energy transfer efficiency is the largest.
  • the sensitization effect of the Tb element is not obvious; when the molar ratio of the Ce element and the Tb element is too low, there is a probability of no radiation transition between the Tb elements and between the Ce element and the Tb element Increasing it will cause a decrease in the luminous intensity of the phosphor.
  • the A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR), M is selected from La, Y, Lu, One or more of the Gd elements. Because the role of the M element is mainly to promote the R element to enter the lattice more effectively, the M element selection mainly selects +3 valence metal elements closer to the A element and the R element. More preferably, in the A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR), M is a La element. The ionic radius of the La element is more matched with that of the A and R elements, and its crystalline state is more excellent, and the effect of increasing the emission intensity is most obvious.
  • the introduction of D element and the synergy of C element can greatly improve the stability and emission intensity of phosphor. .
  • a 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR) the content of the D element satisfies: 0.5 ⁇ m ⁇ 1.
  • the content of the D element satisfies: 0.8 ⁇ m ⁇ 0.9. This range is the optimal ratio of D element doping into the crystal lattice.
  • the microstructure of the phosphor is the most stable, and the stability of the phosphor and the overall effect of the luminous intensity are the best.
  • the A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR), D is selected from Si, Ge, Ti, One or more of Sn and Se elements. Because the element C (-4 valence) is used to replace the element N (-3 valence), its ionic radius and valence state show a certain mismatch. In order to increase the doping content of the C element, the embodiments of the present invention introduce both the D element and the C element The D element is selected from +4 valence metals, which can balance the crystal charge and reduce the lattice stress caused by ion doping.
  • D is selected from the group consisting of Si, Ge, and Se.
  • One or more because the ionic radii of Si, Ge, and Se elements are closer to those of Al elements, and the radius is slightly smaller than that of A-type elements, it can reduce the stress caused by lattice expansion caused by C element replacing N element, reduce defects, and further improve the crystallinity of phosphors. .
  • D is selected from the Ge element or D is selected from the Se element.
  • Ge 4+ ion radius is 67pm
  • Se 4+ ion radius is 64pm
  • its radius is closer to Al 3+ radius (67.5pm)
  • using Ge element or Se element instead of Al element its crystallinity is better, and phosphor luminous intensity The improvement is even more pronounced.
  • A is selected from Ca, Sr, Ba, One or more of Mg and Zn elements.
  • the A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR) is selected from Ca and Sr elements. One or two. Since the Eu element mainly occupies the lattice position of the element A, the radius of the selected Ca and Sr and the Eu element are more matched.
  • A is Ca or Sr
  • the crystallinity of the matrix is the best. More preferably, in the A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR), A is selected from Sr elements. Because the radius of the Sr element and the Eu element is more matched, it can promote the luminous center into the lattice. After doping the rare earth element, the phosphor has better crystallinity and higher emission intensity.
  • the nitride near-infrared fluorescent material A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR) contains a C element, Because C 4- has a lower electronegativity than N 3- , when C element replaces part of N element, it helps to adjust the light color performance of the phosphor on the one hand; on the other hand, the introduction of C element and D element at the same time, The formation of a DC tetrahedron structure helps to improve the stability of the crystal structure and the reliability of the phosphor.
  • the doping content of the C element is mainly affected by two aspects, one is The D element forms a DC bond instead of the Al-N bond. This part of the doping content is the same as the D element doping content. The second is to compensate the charge mismatch caused by the M element replacing the A element. The doping amount depends on the M element. Doping amount.
  • A is selected from Sr elements, and M is selected from La element;
  • D is selected from Ge element or Se element, R is a mixed element of Ce element and Tb element, and the molar ratio of Ce element and Tb element is 2: 1 to 3: 1.
  • the combined phosphor has high luminous intensity, and has the best aging performance at high temperature and high humidity.
  • the range of values that can be satisfied is: 0.05 ⁇ x ⁇ 0.15, 0.01 ⁇ y ⁇ 0.03, 0.01 ⁇ z ⁇ 0.0.05, 0.5 ⁇ m ⁇ 1.
  • the value range of x and m satisfies: 0.08 ⁇ x ⁇ 0.1, 0.8 ⁇ m ⁇ 0.9.
  • the nitride phosphor provided in the embodiment of the present invention can be prepared by the following method.
  • a method for preparing a nitride phosphor includes the following steps:
  • a nitride of A an alloy containing M and D elements, an alloy containing Li and Al elements, Al 4 C 3 , a nitride of EuN and R, or a fluoride of R, wherein A is selected from Ca, One or more of Sr, Ba, Mg, Zn elements, M is selected from one or more of La, Y, Lu, Gd elements, D is selected from Si, Ge, Ti, Sn, Se elements One or more, N is nitrogen, C is carbon, and R is selected from one or more of Ce, Tb, Pr elements; the alloy containing M and D elements is heated to 600- under nitrogen atmosphere Perform pre-nitriding treatment at 800 ° C to obtain intermediate material 1. The alloy containing Li and Al elements is heated to 600-800 ° C under a nitrogen atmosphere to perform pre-nitriding treatment to obtain intermediate material 2;
  • an alloy nitriding method is used to first pre-nitrate an alloy containing M and D elements and an alloy containing Li and Al elements to avoid Li during the preparation It is volatilized under high temperature conditions, so that the nitride phosphor can be prepared under relatively mild conditions; at the same time, it is beneficial to improve the stability of the crystal structure in the subsequent preparation process.
  • elements A, M, D, C, and R through high-temperature doping, nitride phosphors with stable crystal structure, good weather resistance, and high luminous efficiency can be obtained.
  • step S01 the nitride of A, the alloy containing M and D elements, the alloy containing Li and Al elements, Al 4 C 3 , EuN and R nitrides, or R fluoride reference nitrides Phosphor A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR) (where x, y, z, and m range of values satisfy: 0.001 ⁇ x ⁇ 0.2, 0.005 ⁇ y ⁇ 0.1, 0.001 ⁇ z ⁇ 0.1, 0.1 ⁇ m ⁇ 1) are provided in stoichiometric ratios.
  • the alloys containing M and D elements and the alloys containing Li and Al elements are respectively heated to 600-800 ° C. in a nitrogen atmosphere for pre-nitriding treatment.
  • the Li element participates in the heating reaction in the following steps in the form of an alloy raw material, which effectively avoids the volatilization of the Li element, so that the reaction can be performed under mild conditions.
  • the crystallinity of the nitride phosphor can be improved.
  • the temperature of the pre-nitriding treatment is 600-800 ° C, and more preferably 700 ° C. If the temperature of the pre-nitriding treatment is too high, the Li element in the alloy will volatilize. If the temperature of the pre-nitriding treatment is too low, the alloy will not participate in the reaction completely, and the elements in the alloy will be difficult to integrate into the phosphor lattice. The pre-nitrided sample is crushed and processed into powder.
  • the intermediate material 1, the intermediate material 2, the nitride of A, the nitrides of Al 4 C 3 , EuN and R, or the fluoride of R are added in proportion and mixed to obtain a mixed raw material. system.
  • the mixed raw material system is placed in a heating device, preferably in a BN crucible, and sintered under the conditions of 900-950 ° C and N 2 / H 2 mixed gas.
  • a reaction temperature of 900-950 ° C is favorable for obtaining a stable crystal structure during the reaction. If the temperature is too high, it will cause over-burning and the volatilization of Li element. If the temperature is too low, the phosphor phase structure will be impure and the crystallinity will be poor.
  • the N 2 / H 2 mixed atmosphere can ensure the normal progress of the reaction reduction reaction, and provide a reducing atmosphere to avoid the oxidation reaction of each element, deviate from the reaction route, introduce impurities or directly obtain the expected SrLiAl 3 N 4 crystal structure.
  • the volume ratio of H 2 is 5% -10%, so as to ensure a good inert environment and avoid the occurrence of heterogeneous side reactions under the condition that a suitable reducing gas is provided.
  • the Li element participates in the reaction in the form of an alloy. Therefore, it is not necessary to pay special attention to the evaporation of Li during the reaction, and the reaction conditions are relatively mild.
  • it is heated to the reaction temperature at a heating rate of 5-10 ° C / min. More preferably, the time for the sintering treatment is 7-10 hours, and more preferably 8 hours. The sample obtained after sintering is crushed and covered with post-treatment, and finally the phosphor is obtained.
  • an embodiment of the present invention provides a light emitting device, the light emitting device includes a fluorescent substance and an excitation light source, the fluorescent substance is a nitride phosphor, and the chemical formula of the nitride phosphor is A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR), where A is selected from one or more of Ca, Sr, Ba, Mg, Zn elements, and M is selected From one or more of La, Y, Lu, and Gd elements, D is selected from one or more of Si, Ge, Ti, Sn, and Se elements, N is a nitrogen element, C is a carbon element, and R is selected From one or more of Ce, Tb, Pr elements,
  • the light-emitting device provided by the embodiment of the present invention includes the above-mentioned nitride phosphor, which is the above-mentioned A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR), therefore, the advantages of stable crystal structure, good weather resistance, and high luminous efficiency of the nitride phosphor powder can be brought into full play, thereby improving the luminous efficiency and stability of the light emitting device.
  • the above-mentioned nitride phosphor which is the above-mentioned A 1-xyz M x LiAl 3-m D m N 4-m C m + (x + z) / 4 : (yEu, zR)
  • A is selected from one of Ca and Sr elements or Both.
  • M is selected from the La element.
  • D is selected from one or more of Si, Ge, and Se elements.
  • R is a mixed element of Ce element and Tb element.
  • R is a mixed element of Ce element and Tb element, and The molar ratio of the Ce element and the Tb element is 2: 1 to 3: 1.
  • D is selected from a Ge element or a Se element.
  • A is selected from Sr elements.
  • A is selected from Sr elements, and M is selected from La elements; D is selected from Ge or Se, R is a mixed element of Ce and Tb, and the molar ratio of Ce and Tb is 2: 1 to 3: 1.
  • the value ranges of x, y, z, and m satisfy : 0.05 ⁇ x ⁇ 0.15, 0.01 ⁇ y ⁇ 0.03, 0.01 ⁇ z ⁇ 0.0.05, 0.5 ⁇ m ⁇ 1.
  • the value range of x and m satisfies: 0.08 ⁇ x ⁇ 0.1, 0.8 ⁇ m ⁇ 0.9.
  • the excitation light source is a semiconductor chip having an emission wavelength range of 430-470.
  • the method for preparing the nitride phosphor includes the following steps:
  • a certain amount of lanthanum germanium alloy and lithium aluminum alloy were first weighed according to the stoichiometric ratio, and respectively pre-nitrided in a N 2 atmosphere at a temperature of 700 ° C.
  • the obtained pre-nitrided product was subjected to crushing and post-treatment.
  • the sieve powder is recorded as intermediate material 1 and intermediate material 2 respectively.
  • the method for preparing the nitride phosphor includes the following steps:
  • a certain amount of lanthanum germanium alloy and lithium aluminum alloy were first weighed according to the stoichiometric ratio, and respectively pre-nitrided in a N 2 atmosphere at a temperature of 700 ° C.
  • the obtained pre-nitrided product was subjected to crushing and post-treatment.
  • the sieve powder is recorded as intermediate material 1 and intermediate material 2 respectively.
  • the intermediate materials 1 and 2 and the raw materials of Sr 3 N 2 , Al 4 C 3 , EuN and TbN are mixed in a stoichiometric ratio, put in a BN crucible, and heated to a temperature of 900-950 ° C. at a heating rate of 5 ° C./min.
  • the method for preparing the nitride phosphor includes the following steps:
  • a certain amount of lanthanum germanium alloy and lithium aluminum alloy were first weighed according to the stoichiometric ratio, and respectively pre-nitrided in a N 2 atmosphere at a temperature of 700 ° C.
  • the obtained pre-nitrided product was subjected to crushing and post-treatment.
  • the sieve powder is recorded as intermediate material 1 and intermediate material 2 respectively.
  • the intermediate materials 1 and 2 and the raw materials of Sr 3 N 2 , Al 4 C 3 , EuN and PrN are mixed in a stoichiometric ratio, put into a BN crucible, and heated to a temperature of 900-950 ° C. at a heating rate of 5 ° C./min.
  • the method for preparing the nitride phosphor includes the following steps:
  • a certain amount of lanthanum germanium alloy and lithium aluminum alloy were first weighed according to the stoichiometric ratio, and respectively pre-nitrided in a N 2 atmosphere at a temperature of 700 ° C.
  • the obtained pre-nitrided product was subjected to crushing and post-treatment.
  • the sieve powder is recorded as intermediate material 1 and intermediate material 2 respectively.
  • the intermediate materials 1 and 2 and Sr 3 N 2 , Al 4 C 3 , EuN, CeN, and PrN raw materials are mixed in a stoichiometric ratio, placed in a BN crucible, and heated to a temperature of 5 ° C./min to 900- Sintered at 950 ° C for 8h under the condition of N 2 / H 2 mixed gas (the ratio is 90% / 10%).
  • the sintered product was crushed and coated with post-treatment to obtain Sr 0.875 La 0.1 LiAl 2.5 Ge 0.5 N 3.5 C 0.52875 : (0.01Eu, 0.01Ce, 0.005Pr) phosphor.
  • the method for preparing the nitride phosphor includes the following steps:
  • a certain amount of lanthanum germanium alloy and lithium aluminum alloy were first weighed according to the stoichiometric ratio, and respectively pre-nitrided in a N 2 atmosphere at a temperature of 700 ° C.
  • the obtained pre-nitrided product was subjected to crushing and post-treatment.
  • the sieve powder is recorded as intermediate material 1 and intermediate material 2 respectively.
  • the intermediate materials 1 and 2 and the raw materials of Sr 3 N 2 , Al 4 C 3 , EuN, CeN and TbN are mixed in a stoichiometric ratio, put into a BN crucible, and heated to a temperature of 900 ° C. at a heating rate of 5 ° C./min.
  • the method for preparing the nitride phosphor includes the following steps:
  • a certain amount of lanthanum germanium alloy and lithium aluminum alloy were first weighed according to the stoichiometric ratio, and respectively pre-nitrided in a N 2 atmosphere at a temperature of 700 ° C.
  • the obtained pre-nitrided product was subjected to crushing and post-treatment.
  • the sieve powder is recorded as intermediate material 1 and intermediate material 2 respectively.
  • the intermediate materials 1 and 2 and the raw materials of Sr 3 N 2 , Al 4 C 3 , EuN, CeN and TbN are mixed in a stoichiometric ratio, put into a BN crucible, and heated to a temperature of 900 ° C. at a heating rate of 5 ° C./min.
  • the method for preparing the nitride phosphor includes the following steps:
  • a certain amount of lanthanum germanium alloy and lithium aluminum alloy were first weighed according to the stoichiometric ratio, and respectively pre-nitrided in a N 2 atmosphere at a temperature of 700 ° C.
  • the obtained pre-nitrided product was subjected to crushing and post-treatment.
  • the sieve powder is recorded as intermediate material 1 and intermediate material 2 respectively.
  • the intermediate materials 1 and 2 and the raw materials of Sr 3 N 2 , Al 4 C 3 , EuN, CeN and TbN are mixed in a stoichiometric ratio, put into a BN crucible, and heated to a temperature of 900 ° C. at a heating rate of 5 ° C./min.
  • Example 1-7 according to the chemical formula of nitride phosphors in Table 1 below, the corresponding raw materials were weighed to prepare nitride phosphors.
  • the method for preparing the nitride phosphor includes the following steps:
  • a certain amount of lithium aluminum alloy was first weighed according to the stoichiometric ratio, and respectively pre-nitrided at 700 ° C under a N 2 atmosphere at a temperature of 700 ° C.
  • the obtained pre-nitrided product was subjected to crushing and post-treatment, and passed through a 100-mesh sieve. Mesh sieve powder, recorded as intermediate.
  • the intermediate material and Sr 3 N 2 and EuN raw materials are mixed in a stoichiometric ratio, put into a BN crucible, heated to a temperature of 950-1000 ° C.
  • the method for preparing the nitride phosphor includes the following steps:
  • the nitride phosphors provided in Examples 1 to 41 and Comparative Example 1 were measured at room temperature and aging.
  • the test method is as follows:
  • Double 85 aging refers to aging for 300 hours in a high temperature and high humidity (temperature 85 ° C, humidity 85%) aging box, and then tested by the Hass2000 fluorescence fast radiometer.
  • double 85 aging refers to aging under the conditions of temperature 85 ° C and humidity 85%.
  • Example 1 Sr0.88La0.1LiAl2.5Ge0.5N3.5C0.5275: 0.01Eu, 0.01Ce 120 96
  • Example 2 Sr0.88La0.1LiAl2.5Ge0.5N3.5C0.5275: 0.01Eu, 0.01Tb 105 83
  • Example 3 Sr0.88La0.1LiAl2.5Ge0.5N3.5C0.5275: 0.01Eu, 0.01Pr 108 86
  • Example 4 Sr0.875La0.1LiAl2.5Ge0.5N3.5C0.52875: 0.01Eu, 0.01Ce, 0.005Pr 118 91
  • Example 5 Sr0.875La0.1LiAl2.5Ge0.5N3.5C0.52875: 0.01Eu, 0.01Ce, 0.005Tb 130 102
  • Example 6 Ca0.875La0.1LiAl2.5Ge0.5N3.5C0.52875: 0.01Eu, 0.01Ce, 0.005Tb 128 99
  • Example 7 Example 7
  • Example 32, Example 33, and Comparative Example 1 were respectively matched with blue light 452-455nm chip, Lu 3 Al 5 O 12 : Ce green powder, and encapsulated 90Ra and 2700K lamp beads.
  • the same blue light chip + Lu 3 Al 5 O 12 : Ce green powder + (Ca, Sr) AlSiN 3 : Eu red powder is used for packaging for comparison.
  • the lamp bead packaging results and aging results are shown in Table 2 below.
  • the XRD pattern of the nitride phosphor obtained in Example 31 is shown in FIG.
  • Example 31 the SEM image of the nitride phosphor provided in Example 31 is shown in FIG. 2, and the SEM image of the nitride phosphor provided in Comparative Example 1 is shown in FIG. 2.
  • FIG. 3 the excitation spectrum of the nitride phosphor obtained in Example 31 is shown in FIG. 4, and the emission spectrum of the nitride phosphor obtained in Example 31 is shown in FIG. 5.
  • the structure of the phosphor provided in the embodiment of the present invention is the same as the structure of SrLiAl 3 N 4 .
  • Comparing Example 5 and Comparative Example 2 although Comparative Example 2 and Example 5 have the same element type and content composition (both Sr 0.875 La 0.1 LiAl 2.5 Ge 0.5 N 3.5 C 0.52875 : 0.01Eu, 0.01Ce, 0.005Tb ), but due to different methods, the nitride phosphor prepared according to the method of Example 5 of the present invention has better luminous intensity at room temperature and luminous intensity after double 85 aging for 300 h.
  • Example 5 Comparing Example 5, Example 19, Example 20, and Example 21, it can be seen that although the element types of the nitride phosphors in the four examples are the same, there are differences in the luminous intensity due to the different element contents. Specifically, the nitride phosphor ratio of Example 5 that satisfies “the molar ratio of the Ce element and the Tb element is 2: 1 to 3: 1” does not satisfy the “molar ratio of the Ce element and the Tb element is 2: 1 to 3: The nitride phosphors of Example 19, Example 20, and Example 1 of 1 "have better luminous intensity at room temperature and luminous intensity after double 85 aging for 300 h.
  • the crystallinity of the nitride phosphor provided in Example 31 of the present invention is very good.
  • the two-step method of the alloy of the present embodiment has a simple sintering system, large grains, and crystalline properties Good and so on.
  • Example 31 It can be seen from FIG. 4 that the nitride phosphor provided in Example 31 can be effectively excited in the visible light region, and there is a narrow-band emission of light efficiency concentration between 600 nm and 700 nm.

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Abstract

La présente invention concerne une poudre fluorescente de nitrure, la formule chimique de la poudre fluorescente de nitrure étant A1-x-y-zMxLiAl3-mDmN4-mCm+(x+z)/4:(yEu,zR), dans laquelle A est choisi parmi un ou plusieurs des Ca, Sr, Ba, Mg et Zn, M est choisi parmi un ou plusieurs des La, Y, Lu et Gd, D est choisi parmi un ou plusieurs des Si, Ge, Ti, Sn et Se, N représente un azote, C représente un carbone, R est choisi parmi un ou plusieurs des Ce, Tb et Pr, et les plages de valeurs de x, y, z et m dans A1-x-y-zMxLiAl3-mDmN4-mCm+(x+z)/4:(yEu,zR) satisfont à : 0,001≤x≤0,2, 0,005≤y≤0,1, 0,001≤z≤0,1 et 0,1≤m≤1.
PCT/CN2019/084589 2018-11-28 2019-04-26 Poudre fluorescente de nitrure et son procédé de préparation, et appareil électroluminescent contenant une poudre fluorescente de nitrure WO2020015424A1 (fr)

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ZHONG, HAO: "Synthesis and Optimization of Red-emitting Nitride Phosphors with High Performance", DOCT. DISS., 15 October 2018 (2018-10-15), pages 63 - 85 *

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