CN113652232B - High-refractive-index microcrystal-modified phosphor compound and preparation method and composition thereof - Google Patents
High-refractive-index microcrystal-modified phosphor compound and preparation method and composition thereof Download PDFInfo
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Abstract
The invention provides a high-refractive-index microcrystal-modified phosphor compound, and a preparation method and a composition thereof. The phosphor compound of the present invention has a general formula of k1 (M1) 0.04‑a M2 a N b O c R d )·X e N f ：mRe/k2(M3 u M4 v O w ). The crystal introduction of the perovskite structure microcrystal of which the surface or the inner part of the main phase crystal of the fluorescence has good stability and strong capability of refracting/reflecting/transmitting light rays enables the crystal to be improved, the thermal vibration to be improved and the interface luminescence superposition effect to be obtained so as to improve the luminescence performance and the anti-attenuation performance and improve the practical application performance of the phosphor compound. The phosphor compound is prepared by introducing a multi-step high-temperature solid-phase reaction method improved by a high-refractive-index microcrystal crystallization technology after a main phase crystal of fluorescence is broken, can emit light from blue to red after being excited by ultraviolet-blue-green light, and is applied to manufacturing of LED devices.
Description
Technical Field
The invention belongs to the field of phosphors, and particularly relates to a high-refractive-index microcrystal-modified nitride and oxynitride phosphor with improved luminescence performance and a preparation method thereof, in particular to a phosphor for white-light-system and multi-color-system light-emitting devices including semiconductor light-emitting elements (LEDs), and a preparation method and application thereof.
Background
In the general illumination technology of LEDs, blue light chips are mainly used to excite yellow-emitting phosphor to generate yellow light, and the yellow light is mixed with the rest of the blue light to obtain white light, while for display backlights in another field of LED illumination applications, green and red fluorescent materials with high color purity excited by blue light chips are required. The traditional yellow fluorescent powder mainly comprises rare earth ion activated garnet structure materials (Y, gd) 3 (Al，Ga) 5 O 12 : ce, (YAG for short) and rare earth ion activated alkaline earth metal orthosilicate materials (Sr, ba, ca) 2 SiO 4 Eu. In order to obtain a warm white lighting effect with more excellent application performance, fluorescent materials which can be used for complementing the color of the warm white lighting effect and can obtain red luminescence under the excitation of blue light are also found in several nitride matrixes in recent years. The prior art discloses Eu capable of emitting 600-650 nm red light by being excited by ultraviolet-blue-green light 2+ Activated alkaline earth silicon nitride phosphor (Ba, sr, ca) 2 Si 5 N 8 . However, this material has a low lumen efficiency and a large thermal decay. Another Eu capable of emitting 600-700 nm red light by being excited by ultraviolet-blue-green light is disclosed in the prior art 2+ Activated alkaline earth metal nitride phosphor (Ca, sr) AlSiN 3 . The luminescent performance of the material is superior to (Ba, sr, ca) 2 Si 5 N 8 Eu material, the luminous efficiency is improved by about 15%, the thermal attenuation is smaller, and Eu material has become the mainstream red fluorescent material of warm white light illumination scheme. However, the half-height width of the emission spectrum of the red fluorescent material is too wide, and in the range of 75-95nm, the requirement of a display backlight source on high color purity cannot be met, and the red fluorescent material can only be used in the field of illumination light sources but cannot be used in the field of display backlight sources.
Besides obtaining a material emitting red light with small light attenuation in a crystal lattice coordinated by N as an anion, in recent years, an excellent LED fluorescent material emitting from blue to orange is also found in nitride and oxynitride materials coordinated by N and O as anions together. The crystal lattices coordinated by N as anion have a common characteristic that the crystal lattices have strong covalency and stable property, are easy to form larger crystal field energy level splitting under the action of an activating agent to realize red emission, and have stronger structural rigidity, so that materials with better thermal stability and smaller light attenuation, such as blue-green emitting alkaline earth metal oxynitride materials (Ba, sr, ca) Si 2 O 2 N 2 Eu also becomes an ideal blue-green complementary color material in the full spectrum scheme of LED illumination. However, the blue-green part of the luminescent color of the material is not suitable for the requirement of a display backlight source, and the green part is also not suitable for the field of the display backlight source due to the wider half-height width of the emission spectrum and can only be used in the field of LED illumination.
In order to meet the application requirements of LED display backlight sources, people find that the extremely strong covalency of coordination crystal lattices with N or N-O as anions enables atoms to be stacked more tightly, and narrower crystal field energy level splitting is formed under the action of an activator more easily to realize narrow-peak-width emission, so that the requirements of LED backlight and display technologies on purer chromaticity and narrower emission peak width of fluorescent powder can be met. The prior art discloses an orange-emitting alpha-sialon material Ca x (Si,Al) 12 (O,N) 16 yEu (x is more than 0.75 and less than 1.0, and y is more than 0.04 and less than 0.25). The prior art also discloses a green emitting beta-sialon material Si 6- z Al z O z N 8-z Eu (z is more than 0 and less than 4.2). The two materials have common structural characteristics, namely in [ Si, al][O,N] 4 On the basis of a structural matrix formed by tetrahedral three-dimensional corner sharing vertices, the luminescent characteristic is obtained by introducing activator ions or alkaline earth metal ions and the activator ions into structural void channels of the structural matrix. The material has the tightest bonding mode and extremely strong covalency, can generally obtain narrow-peak luminescence, and has the stability and the performanceThe material has excellent attenuation resistance, and thus is a good material for an LED display backlight. However, such [ Si, al ]][O,N] 4 The structure of the tetrahedral three-dimensional corner sharing top compact stacking is mainly synthesized by silicon nitride and aluminum nitride raw materials with extremely high stability, extremely high combination energy is needed to break the stable bond energy of binary nitride to re-bond into a derivative structure with a gap channel, the synthesis conditions of extreme high temperature and high pressure are usually needed, the difficulty in equipment and process control is extremely high, and the industrial mass production is not easy. In addition, the luminescence realized by introducing the activator into the structural void passage has strong randomness and uncertainty, the luminescence intensity of the luminescence is very sensitive to equipment and fine process control, and how to obtain a material with ideal crystallization and high-efficiency activator effect through fine control to realize commercial use always becomes a practical obstacle of the phosphor.
Further develops a nitride or oxynitride fluorescent body excited by a structural gap channel type with better luminous efficiency and smaller thermal attenuation, and develops a manufacturing method which has simple synthesis process, mild conditions and easy industrial scale mass production of the fluorescent body with high application performance, thereby having important significance for the technical progress and the application popularization of the domestic LED display backlight.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a high-refractive-index microcrystal modified phosphor and a preparation method and a composition thereof.
The first aspect of the present invention provides a phosphor modified by crystallites with high refractive index, the composition of the phosphor is represented by the following general formula: k1 (M1) 0.04-a M2 a N b O c R d )·X e N f ：mRe/k2(M3 u M4 v O w ) Wherein:
m1 is at least one element selected from Si, ge, sn, pb, ti, zr, hf, W and Mo, M2 is at least one element selected from B, al, ga, in and Tl, N is nitrogen, O is oxygen, R is F - 、Cl - 、Br - 、I - At least one element ion in (b), X is selected from at least one element of Be, mg, ca, sr, ba, li, lu, la, Y and Gd, re is selected from at least one element of Eu, ce, nd, dy, ho, tm, er, pr, bi, sm, tb and Mn, M3 is selected from at least one element of Be, mg, ca, sr, ba, Y, la, nd and Lu, and M4 is selected from at least one element of Ti, zr and Hf;
k1, a, b, c, d, e, f, m, K2, u, v and w are molar coefficients: k is more than 0.3 and less than 2.2, a is more than or equal to 0 and less than 0.03, b is more than or equal to 0.045 and less than 0.075, c is more than or equal to 0 and less than 0.055, d is more than 0 and less than 0.002, e is more than or equal to 0 and less than 0.025, f is more than or equal to 0 and less than 0.025, m is more than 0 and less than 0.025, k is more than 0 and less than 2 and less than 0.003, u is more than 0.0035 and less than 0.0076, v is more than 0.005 and less than 0.008, w is more than 0.01 and less than 0.03;
preferably, the high refractive index crystallite-modified phosphor is composed of a main phase of fluorescence crystal and a second phase of high refractive index crystallite filled in crystal boundaries and internal cracks, defects and holes, wherein the main phase of fluorescence is a group of nitride or oxynitride luminophores with a crystal structure of [ Si, al ] [ O, N ]4 tetrahedron three-dimensional common angle vertex forming frame, alkaline earth metal ions and rare earth metal ions filled in tetrahedral channels, and the second phase of crystallite is a group of perovskite structure rare earth metal titanate or zirconate or hafnate;
more preferably, the high refractive index microcrystal-modified fluorescent body emits one or more peak light emission spectrums with peak wavelength within the range of 450-700 nm after being excited by ultraviolet-blue-green light with peak wavelength within the range of 250-550 nm.
The high refractive index microcrystalline-modified phosphor according to the first aspect of the present invention, wherein 0.8 < k1 < 1.2,0 < a < 0.025,0.045 < b < 0.055, 0. Ltoreq.c < 0.005,0 < d < 0.0015, and 0.045 < b + c + d < 0.062, e =0, f =0,0 < m < 0.0015,0 < k2 < 0.003,0.0035 < u < 0.0076,0.005 < v < 0.008,0.01 < w < 0.03;
preferably, M1 is Si, M2 is Al, N is N, O is O, and R is selected from F - 、Cl - At least one element ion, re is selected from Eu or Ce, M3 is La, and M4 is Ti; and/or
Preferably, 0.95. Ltoreq. K1. Ltoreq.1.05, 0.001. Ltoreq. A. Ltoreq.0.02, 0.052. Ltoreq. B.ltoreq.0.054, 0. Ltoreq. C.ltoreq.0.0035, 0. Ltoreq. D.0013 and 0.052. Ltoreq. B + c + d. Ltoreq.0.0588, e =0, f =0, 0. Ltoreq. M.ltoreq.0.0013, 0. Ltoreq. K2. Ltoreq.0.0015, 0.0039. Ltoreq. U.ltoreq.0.0072, 0.0062. Ltoreq. V.ltoreq.0.0072, 0.018. Ltoreq. W.ltoreq.0.022.
The high refractive index microcrystalline-modified phosphor according to the first aspect of the present invention, wherein k1 is 1.8 < 2.2, a is 0 < 0.025, b is 0.045 < 0.055, c is 0. Ltoreq.c < 0.005, d is 0 < 0.002 and 0.05 < b + c + d < 0.055, e is 0 < 0.015, f is 0 < 0.01, m is 0 < 0.0035, k2 is 0 < 0.003, u is 0.0035 < 0.0076, v is 0.005 < 0.008, w is 0.01 < 0.03;
preferably, M1 is selected from Si, M2 is Al, N is N, O is O, and R is selected from F - 、Cl - At least one element ion in (1), re is selected from Eu or Ce, X is at least one element in Mg, ca, la and Y, M3 is La, and M4 is Ti; and/or
Preferably, k1 is not less than 1.95 but not more than 2.05, a is not less than 0.0005 but not more than 0.02, b is not less than 0.052 but not more than 0.054, c is not less than 0 but not more than 0.0033, d is not less than 0.0017 and not more than 0.052 but more than b + c + d is not less than 0.059, e is not less than 0 but not more than 0.0133, f is not less than 0.0089, m is not less than 0 but not more than 0.0033, k2 is not less than 0 but not more than 0.0015, u is not less than 0.0039 but not more than 0.0072, v is not less than 0.0062 but not more than 0.0072, and w is not less than 0.018 but not more than 0.022.
The second aspect of the present invention provides a method for producing the high refractive index crystallite-modified phosphor according to the first aspect, the method comprising the steps of:
(1) Weighing raw materials according to element proportion, mixing uniformly, and preparing fluorescent structure matrix k1 (M1) by high-temperature solid-phase reaction 0.04-a M2 a N b O c R d )·X e N f : mRe, crushing and screening to obtain a primary phosphor sintering material;
(2) The coprecipitation-hydrothermal method is utilized to prepare the material with the mixture ratio of k2 (M3) u M4 v O w ) The perovskite structure microcrystal precursor material;
(3) Respectively weighing the primary phosphor sintered material obtained in the step (1) and the primary phosphor sintered material obtained in the step (2) and the perovskite structure microcrystal precursor material according to the proportion, fully and uniformly mixing the primary phosphor sintered material and the perovskite structure microcrystal precursor material, and then putting the mixture into grinding and crushing equipment for grinding and crushing;
(4) Placing the mixture in high-temperature sintering equipment, and performing secondary high-temperature sintering treatment;
(5) And (4) crushing, screening and post-treating the sintered material obtained in the step (4) to obtain the phosphor compound.
The method according to the second aspect of the present invention, wherein, in the step (1), the atmosphere of the high-temperature solid-phase reaction is a nitrogen atmosphere or a mixed atmosphere of nitrogen and hydrogen; the reaction pressure is 0-2000 atmospheric pressure, preferably 20-200 atmospheric pressure; the reaction temperature is 1200-2500 ℃, preferably 1600-2300 ℃; and/or the reaction time is 4 to 16 hours, preferably 6 to 12 hours; and/or
In the step (4), the atmosphere of the high-temperature solid-phase reaction is nitrogen atmosphere or mixed atmosphere of nitrogen and hydrogen; the reaction pressure is 0-100 atmospheric pressure, preferably 0-10 atmospheric pressure; the reaction temperature is 800-1400 ℃, preferably 1000-1200 ℃; and/or the reaction time is 2 to 12 hours, preferably 4 to 6 hours; and/or
In the step (5), the post-processing step includes: placing the crushed and sieved materials into an acid solution with the molar concentration of 1-10% to be stirred and washed for 1-4 hours, then filtering out the acid solution, washing for 1-4 times by using deionized water or ethanol, and drying to obtain the phosphor compound; preferably, the acid is selected from one or more of: sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid.
The method according to the second aspect of the present invention, wherein in the step (2), the raw materials of the element ratio are respectively selected from nitrate containing M3 element and n-butyl M4 acid containing M4 element;
preferably, the step (2) includes the steps of:
(A) Respectively measuring and weighing N-butyl M4-carboxylate, glacial acetic acid and nitrate of M3 element according to the proportion, dissolving the N-butyl M4-carboxylate and the glacial acetic acid into a uniform mixed solution, and dissolving the nitrate containing the M3 element in deionized water to form a nitrate solution;
(B) Placing the mixed solution of the N-butyl M4-carboxylate and glacial acetic acid in acetic acid for acylation and stirring to obtain a light yellow transparent solution; then slowly adding the mixed solution into a nitrate solution containing M3 element, and magnetically stirring to obtain a transparent mixed solution;
(C) Then dropwise adding NaOH solution to obtain white emulsion;
(D) Transferring the white emulsion obtained in the step (C) into a reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction;
(E) Taking out the slurry after the hydrothermal reaction, washing the slurry by deionized water and ethanol for multiple times, separating a product by adopting a centrifuge, and drying the product in an oven at 80 ℃ to obtain a perovskite structure microcrystal precursor material;
more preferably, in the step (a), the ratio of the amounts of the M3 and M4 elements is 1:1, the amount of n-butyl ester M4 is 0.005mol, the amount of glacial acetic acid is 0.05mol, the amount of nitrate containing M3 element is 0.005mol, and the nitrate solution is formed by dissolving the nitrate in 10ml of deionized water;
in the step (B), the amounts of the mixed solution of the n-butyl M4-carboxylate and the glacial acetic acid and the acetic acid are respectively 0.005mol and 0.05mol, and the stirring time is 30 minutes;
in the step (C), the concentration of the NaOH solution is 0.5-1.5mol/L; and/or
The step (D) is that the hydrothermal reaction condition is that the temperature is kept constant at 200 ℃ for 24 hours;
the method according to the second aspect of the present invention, wherein in the step (3), the time for grinding and crushing the mixture of the primary phosphor sintered material and the perovskite-structure microcrystal precursor material is 10 seconds to 30 minutes, preferably 30 seconds to 15 minutes.
A third aspect of the invention provides a phosphor composition comprising at least the phosphor compound according to the first aspect.
The invention aims to provide a group of nitride and oxynitride phosphors which can emit blue, blue-green, yellow and red lights under the excitation of ultraviolet to blue-green lights (particularly 400nm to 470 nm), successfully introduce perovskite structure microcrystals with good stability and strong light refraction/reflection/transmission capabilities into cracks, cavities and defects on the surface or in the fluorescent main phase crystal due to the technical scheme of crushing the fluorescent main phase crystal and introducing high-refractive-index microcrystals so as to remarkably improve the luminous efficiency and the anti-attenuation capability of the phosphors and enable the high-quality production conditions of the phosphors to be more moderate, and a preparation method thereof.
The high-refractive-index microcrystal-modified nitride or oxynitride phosphor with improved luminescence property is an ultraviolet-blue-green light excitable luminescent material, and the general formula of the phosphor is k1 (M1) 0.04-a M2 a N b O c R d )·X e N f ：mRe/k2(M3 u M4 v O w ) Wherein: m1 is at least one element selected from Si, ge, sn, pb, ti, zr, hf, W and Mo, M2 is at least one element selected from B, al, ga, in and Tl, N is nitrogen, O is oxygen, R is F - 、Cl - 、Br - 、I - At least one element ion in (b), X is selected from at least one element of Be, mg, ca, sr, ba, li, lu, la, Y and Gd, re is selected from at least one element of Eu, ce, nd, dy, ho, tm, er, pr, bi, sm, tb and Mn, M3 is selected from at least one element of Be, mg, ca, sr, ba, Y, la, nd and Lu, and M4 is selected from at least one element of Ti, zr and Hf; k1, a, b, c, d, e, f, m, K2, u, v, w are molar coefficients: k is more than 0.3 and less than 2.2, a is more than or equal to 0 and less than 0.03, b is more than or equal to 0.045 and less than 0.075, c is more than or equal to 0 and less than 0.055, d is more than 0 and less than 0.002, e is more than or equal to 0 and less than 0.025, f is more than or equal to 0 and less than 0.025, m is more than 0 and less than 0.025, k is more than 0 and less than 0.003, u is more than 0.0035 and less than 0.0076, v is more than 0.005 and less than 0.008, w is more than 0.01 and less than 0.03. The high-refractive-index microcrystal-modified nitride or oxynitride phosphor is prepared from [ Si, al][O,N] 4 Based on the luminescent structure matrix with tetrahedral three-dimensional common-angle vertex and rare earth active ion filled in the structural void channel, the high-activity LaTiO is introduced by the technology of luminescent main phase crystal breaking-high refractive index microcrystal introduction 3 The amorphous precursor with perovskite structure is fully injected and crystallized on the surface of luminescent main phase crystal or in cracks, holes and defects in the crystal in the second high-temperature sintering and then cooled in a furnace to obtain the nitride or oxynitride phosphor, which is a second phase LaTiO filled in the cracks, holes and defects in the form of points, lines and surfaces on the surface of the fluorescent main phase crystal and the crystal and in the crystal in the form of microscopic crystals 3 Mosaic crystal junction formed by perovskite structure microcrystalsFig. 1 shows a significant innovation in the composition of the technical solution of the present invention.
The principle of the above technical solution is described as follows: the nitride or oxynitride luminescent matrix is formed by Si-N and Al-N bonds in a structural framework, so that the structural stability and the tolerance are extremely high; after a luminescent precursor crystal is obtained by one-time high-temperature high-pressure sintering, the luminescent precursor crystal and a certain proportion of amorphous precursor material with a high-activity perovskite structure are fully mixed, ground and crushed, on one hand, the luminescent precursor crystal further deforms, merges and is communicated with original cracks, holes and defects in the crystal due to full collision, extrusion and shearing, and the cracks, the holes and the defects can be expanded into a dendritic crack structure with an opening on the surface of the crystal, on the other hand, the LaTiO is also enabled to be fully ground and mixed 3 The amorphous precursor with the perovskite structure is fully contacted with the luminescent parent crystal; the LaTiO in the technical scheme 3 The amorphous precursor with perovskite structure can be fully melted and crystallized at 800-1200 ℃ to form LaTiO 3 The perovskite structure microcrystal has extremely high refractive index of 2.5-2.7, excellent light transmission, and melting and crystallization temperature (1000-1200 ℃) which is obviously lower than the preferable synthesis temperature and stable temperature (1800-2300 ℃) of the nitride or oxynitride luminescent matrix; thus, in the second high temperature sintering of the grinding and crushing mixture, the LaTiO is heated to 1000-1200 deg.C 3 The amorphous precursor with the perovskite structure is completely melted into a liquid phase, and the crystal with the dendritic fracture with the surface opening of the luminescent precursor which is sintered once still keeps stable; in the subsequent sintering stage at 1000-1200 deg.c, amorphous molten phase is injected and filled into the crystal crack system comprising points, lines and planes through the crack opening of the luminescent mother crystal and crystallized to form LaTiO 3 The perovskite structure microcrystal finally obtains a second phase LaTiO crystal with a fluorescence main phase crystal and the crystal surface or inside filled in cracks, holes and defects in a point, line and surface mode 3 A novel phosphor having a mosaic crystal structure composed of perovskite crystallites.
Before the technical scheme of the invention, the [ Si, al ] is][O,N] 4 The luminous body with the tetrahedral three-dimensional common-angle vertex and the rare earth active ion filled in the structural gap channel needs the synthesis condition of extreme high temperature and high pressure, has the characteristics of strong luminous randomness and uncertainty, has great difficulty in equipment and process control, and is easy to cause various defects of a luminous crystal to influence the luminous optical performance. In the technical scheme of the invention, various defects in luminescent crystals synthesized under extreme high temperature and high pressure are amplified firstly, and then high-activity LaTiO is utilized 3 The melting-crystallization characteristic of the amorphous material with the perovskite structure eliminates the defects in luminescent crystals to form a mosaic crystal structure consisting of the luminescent crystals and perovskite structure microcrystals filled in the crystals; the implementation of the technical means has the functions of repairing and improving the micro and macro crystallinity of the luminescent crystal on one hand and LaTiO on the other hand 3 The structure has extremely high light reflection/refraction/transmission performance, and the compensation of the crystal defects also plays a role in amplifying emitted light when the luminescent crystal is excited by light, so that the effect of improving the effect of an activator under a specific synthesis condition is obtained, and the luminous efficiency can be further improved; in addition, laTiO inlaid in the form of points, lines and surfaces in the luminescent crystal 3 The existence of the structure microcrystal also plays a role in structure pinning, so that the thermal vibration amplitude of a lattice structure in an excited state is reduced, and the thermal attenuation resistance of the phosphor is improved; the implementation of the above technical solution is easy to realize industrial mass production of high-performance phosphors. The nitride or oxynitride fluorescent body modified by the high-refractive-index microcrystal is prepared by introducing a crystal breaking-high-refractive-index microcrystal crystallization technology through an improved multi-step high-temperature solid-phase reaction method, and is excited by ultraviolet-blue-green light with an emission peak wavelength within a range of 250-550 nm to emit a light emission spectrum with one or more peaks with a peak wavelength within a range of 450-700 nm, so that the blue-red or blue-green or red fluorescent body can emit light from blue to red, and is applied to the manufacturing of LED devices.
As a further improvement of the present invention, the present invention provides a high refractive index microcrystalline modified nitride or oxynitride phosphor having improved luminescence properties, wherein M1 is at least one element selected from the group consisting of Si, ge, sn, pb, ti, zr, hf, W and Mo, and M2 is at least one element selected from the group consisting of B, and Mo,At least one element selected from Al, ga, in and Tl, N is nitrogen, O is oxygen, and R is selected from F - 、Cl - 、Br - 、I - X is at least one element selected from Be, mg, ca, sr, ba, li, lu, la, Y and Gd, re is at least one element selected from Eu, ce, nd, dy, ho, tm, er, pr, bi, sm, tb and Mn, M3 is at least one element selected from Be, mg, ca, sr, ba, Y, la, nd and Lu, and M4 is at least one element selected from Ti, zr and Hf; k1, a, b, c, d, e, f, m, K2, u, v and w are molar coefficients: k1 is more than 0.8 and less than 1.2, a is more than 0 and less than 0.025, b is more than 0.045 and less than 0.055, c is more than or equal to 0 and less than 0.005, d is more than 0 and less than 0.0015, b is more than 0.045 and more than c and more than d and less than 0.062, e is less than 0, f is less than 0, m is more than 0 and less than 0.0015, k2 is more than 0 and less than 0.003, u is more than 0.0035 and less than 0.0076, v is more than 0.005 and less than 0.008, and w is more than 0.01 and less than 0.03.
As a further improvement of the present invention, the second phase glass reinforced nitride or oxynitride phosphor with improved luminescence property of the present invention is provided, wherein M1 is at least one element selected from Si, ge, sn, pb, ti, zr, hf, W, mo, M2 is at least one element selected from B, al, ga, in, tl, N is nitrogen, O is oxygen, R is F - 、Cl - 、Br - 、I - X is at least one element selected from Be, mg, ca, sr, ba, li, lu, la, Y and Gd, re is at least one element selected from Eu, ce, nd, dy, ho, tm, er, pr, bi, sm, tb and Mn, M3 is at least one element selected from Be, mg, ca, sr, ba, Y, la, nd and Lu, and M4 is at least one element selected from Ti, zr and Hf; k1, a, b, c, d, e, f, m, K2, u, v, w are molar coefficients: k1 is more than 1.8 and less than 2.2, a is more than 0 and less than 0.025, b is more than 0.045 and less than 0.055, c is more than or equal to 0 and less than 0.005, d is more than 0 and less than 0.002, b + c + d is more than 0.05 and less than 0.055, e is more than 0 and less than 0.015, f is more than 0 and less than 0.01, m is more than 0 and less than 0.0035, k2 is more than 0 and less than 0.003, u is more than 0.0035 and less than 0.0076, v is more than 0.005 and less than 0.008, and w is more than 0.01 and less than 0.03.
As a further improvement of the invention, the invention provides a high-refractive-index microcrystal-modified nitride or oxynitride fluorescent material with improved luminescence property, wherein M1 is Si, M2 is Al, N is N, O is O, and R is selected from F - 、Cl - At least one element ion, re is selected from Eu or Ce, M3 is La, and M4 is Ti; k1, a, b, c, d, e, f, m, K2, u, v and w are molar coefficients: k1 is more than or equal to 0.95 and less than or equal to 1.05, a is more than or equal to 0.001 and less than or equal to 0.02, b is more than or equal to 0.052 and less than or equal to 0.054, c is more than or equal to 0 and less than or equal to 0.0035, d is more than 0 and less than or equal to 0.0013, b + c + d is more than or equal to 0.0588, e is less than or equal to 0, f is less than or equal to 0, m is more than or equal to 0.0013, k2 is more than or equal to 0 and less than or equal to 0.0015, u is more than or equal to 0.0039 and less than or equal to 0.0072, v is more than or equal to 0.0062 and less than or equal to 0.0072, w is more than or equal to 0.018 and less than or equal to 0.022.
As a further improvement of the invention, the invention provides a high-refractive index microcrystal-modified nitride or oxynitride fluorescent body with improved luminescence property, wherein M1 is selected from Si, M2 is Al, N is N, O is O, and R is selected from F - 、Cl - At least one element ion of (1), re is selected from Eu or Ce, X is at least one element of Mg, ca, la and Y, M3 is La, and M4 is Ti; k1, a, b, c, d, e, f, m, K2, u, v and w are molar coefficients: k1 is more than or equal to 1.95 and less than or equal to 2.05, a is more than or equal to 0.0005 and less than or equal to 0.02, b is more than or equal to 0.052 and less than or equal to 0.054, c is more than or equal to 0 and less than or equal to 0.0033, d is more than 0 and less than or equal to 0.0017, b + c + d is more than or equal to 0.059, e is more than 0 and less than or equal to 0.0133, f is more than 0 and less than or equal to 0.0089, m is more than 0 and less than or equal to 0.0033, k2 is more than or equal to 0 and less than or equal to 0.0015, u is more than or equal to 0.0039 and less than or equal to 0.0072, v is more than or equal to 0.0062 and less than or equal to 0.018 and less than or equal to 0.022.
The invention also provides a preparation method of the high-refractive-index microcrystal-modified nitride and oxynitride phosphor with improved luminescence property, and the raw materials are compounds or simple substances of the following elements, wherein the elements are represented by a formula k1 (M1) according to chemical composition 0.04-a M2 a N b O c R d )·X e N f ：mRe/k2(M3 u M4 v O w ) The molar ratio range is as follows:
M1：0.0001～0.09；
M2：0～0.05；
N：0.0001～0.12；
O：0～0.03；
R：0.0001～0.002；
X：0～0.025；
Re：0.0001～0.025；
M3：0.0001～0.002；
M4：0.0001～0.002；
wherein: m1 represents one or more compounds of Si, ge, sn, pb, ti, zr, hf, W and Mo;
m2 represents one or more compounds of B, al, ga, in and Tl;
r represents F - 、Cl - 、Br - 、I - A compound of one or more elements of (a);
x represents one or more elements of Be, mg, ca, sr, ba, li, lu, la, Y and Gd;
re represents one or more compounds of Eu, ce, nd, dy, ho, tm, er, pr, bi, sm, tb and Mn;
m3 represents one or more elements of Be, mg, ca, sr, ba, Y, la, nd and Lu;
m4 represents one or more compounds of Ti, zr and Hf;
the compound of the element represented by M1 adopts the form of nitride and/or oxide and/or metal simple substance as an element source;
the compound of the element represented by M2 is taken as an element source in the form of nitride and/or oxide and/or metal simple substance;
the compound of the element represented by R is taken in the form of fluoride or chloride or bromide or iodide as an element source;
the compound of the element represented by X is taken as an element source in the form of oxide or nitride or carbonate or hydroxide or halide;
the compound of the element represented by Re takes the form of oxide and/or nitride and/or fluoride and/or chloride as an element source;
the compound of the element represented by M3 adopts a nitrate form as an element source;
the compound of the element represented by M4 adopts a form of N-butyl M4-carboxylate as an element source;
the preparation process comprises introducing luminescent main phase crystal crushing-LaTiO 3 The multi-step high-temperature solid-phase reaction method improved by the perovskite structure microcrystal crystallization technology is characterized by comprising the following steps of: first step ofPreparation of fluorescent structural matrix k1 (M1) by high temperature solid phase reaction 0.04-a M2 a N b O c R d )·X e N f : primary sintering of mRe; in the second step, the mixture ratio of k2 (M3) is prepared by a coprecipitation-hydrothermal method u M4 v O w ) The perovskite structure microcrystal precursor material; the third step is that the primary phosphor sintered material obtained in the first step and the primary phosphor sintered material obtained in the second step and the perovskite structure microcrystal precursor material are fully and uniformly mixed and then are placed in grinding and crushing equipment for grinding and crushing; fourthly, performing secondary high-temperature sintering treatment on the mixed crushed material; and a fifth step of crushing, sieving and post-treating the sintered material obtained in the fourth step to obtain the nitride and oxynitride fluorescent body with improved luminous performance.
As a further improvement of the invention, the luminescent performance of the high-refractive index microcrystal modified nitride or oxynitride phosphor provided by the invention is improved, and the luminescent main phase crystal is introduced to be crushed-LaTiO 3 A multi-step high-temperature solid-phase reaction preparation method improved by a microcrystalline crystallization technology with a perovskite structure is characterized in that raw materials of elements M1, M2, R, X1 and Re1 are weighed according to a molar ratio, uniformly mixed, sintered for 4-16 hours at 1200-2200 ℃ in a nitrogen or nitrogen and hydrogen mixed atmosphere with 0-2000 atmospheric pressure, wherein the preferred sintering pressure is 20-200 atmospheric pressure, the preferred sintering temperature is 1600-2100 ℃, and the preferred sintering time is 6-12 hours, and then crushed and sieved to be used as a primary sintering material for standby.
As a further improvement of the invention, the luminescent performance of the high-refractive-index microcrystal-modified nitride or oxynitride phosphor is improved, and luminescent main phase crystal breakage is introduced, namely LaTiO 3 The second step of the multi-step high-temperature solid-phase reaction preparation method improved by the perovskite structure microcrystal crystallization technology is characterized in that the element proportion of M3 and M4 is 1:1, 0.005mol of N-butyl M4 and 0.05mol of glacial acetic acid are mixed to form a mixed solution, then the mixed solution is put into 0.05mol of acetic acid for esterification and stirred for 30 minutes to obtain a light yellow transparent solution, 0.005mol of nitrate of M3 element is dissolved in 10 mol of nitrate of M3 elementForming a nitrate solution in ml deionized water, adding the mixed solution into the nitrate solution, stirring for 10 minutes to obtain a transparent mixed solution, then dropwise adding a NaOH solution with the concentration of 0.5-1.5mol/L into the solution, stirring to obtain a white emulsion, transferring the white emulsion into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 24 hours at 200 ℃, then taking out the slurry, washing with the deionized water and ethanol, separating out a product by using a centrifuge, drying in an oven at 80 ℃, and obtaining LaTiO 3 A microcrystalline precursor material with a perovskite structure.
As a further improvement of the invention, the luminescent performance of the high-refractive index microcrystal modified nitride or oxynitride phosphor provided by the invention is improved, and the luminescent main phase crystal is introduced to be crushed-LaTiO 3 The third step of the multi-step high-temperature solid-phase reaction preparation method improved by the perovskite structure microcrystal crystallization technology is characterized in that the grinding and crushing time of the mixture of the primary phosphor sintering material and the perovskite structure microcrystal precursor material is 10 seconds to 30 minutes, preferably 30 seconds to 15 minutes.
As a further improvement of the invention, the luminescent performance of the high-refractive index microcrystal modified nitride or oxynitride phosphor provided by the invention is improved, and the luminescent main phase crystal is introduced to be crushed-LaTiO 3 The fourth step of the multi-step high-temperature solid-phase reaction preparation method improved by the perovskite structure microcrystalline crystallization technology is characterized in that the crushed mixture obtained in the third step is sintered for 2 to 12 hours at 800 to 1400 ℃ in the atmosphere of nitrogen or the mixture of nitrogen and hydrogen with 0 to 100 atmospheric pressure, wherein the preferred sintering pressure is 0 to 10 atmospheric pressure, the preferred sintering temperature is 1000 to 1200 ℃, and the preferred sintering time is 4 to 6 hours, so that a secondary sintering material is obtained.
As a further improvement of the invention, the luminescent performance of the high-refractive index microcrystal modified nitride or oxynitride phosphor provided by the invention is improved, and the luminescent main phase crystal is introduced to be crushed-LaTiO 3 The fifth step of the multi-step high-temperature solid-phase reaction preparation method improved by the perovskite structure microcrystal crystallization technology is characterized in that the secondary sintering material obtained in the fourth stepCrushing and screening, then placing the materials in a sulfuric acid solution, nitric acid solution, hydrochloric acid solution or hydrofluoric acid solution with the molar concentration of 1-10%, stirring and washing for 1-4 hours, then filtering out the acid solution, washing for 1-4 times by using deionized water or ethanol, and drying to obtain the nitride and oxynitride fluorescent body with improved luminous performance.
The emission spectrum and the thermal characteristics of the phosphor are respectively tested by an F-4500 fluorescence spectrometer and an EX-1000 fluorescent powder thermal quenching analysis system, the components and the morphological characteristics of the phosphor are respectively tested by a TD-3500X-ray diffractometer and a KYKY 2800B scanning electron microscope, and the content of halogen elements in the phosphor is tested by a TAS-986 atomic absorption spectrometer.
In the invention, the luminescent main phase crystal is broken-LaTiO 3 The technological scheme of microcrystal crystallization in perovskite structure includes one group of [ Si, al][O,N] 4 Filling the tetrahedron three-dimensional common-angle vertex and rare earth active ions on the basis of the luminescent structure matrix of the structural void channel to obtain the LaTiO with high activity 3 The amorphous material with the perovskite structure is fully contacted, injected and crystallized on the surface of the broken luminescent main phase crystal or in cracks, holes and defects in the crystal in the second high-temperature sintering, so that the obtained nitride or oxynitride phosphor is a mosaic crystal structure formed by the fluorescent main phase crystal and second-phase perovskite structure microcrystals filled in the cracks, holes and defects on the surface of the crystal or in the crystal in the form of points, lines and surfaces, and a group of nitride or oxynitride phosphors which are obviously different from a pure structure parent phosphor are formed, which is a remarkable innovation of the technical scheme of the invention in composition.
Conventional simple [ Si, al ]][O,N] 4 A phosphor formed by forming a structural matrix by a tetrahedral three-dimensional corner-sharing roof and introducing an activator into a void channel of the phosphor needs extremely high temperature and high pressure harsh synthesis conditions on one hand, fine high temperature and high pressure synthesis equipment and fine process control on the other hand, an undesirable crystalline state is easily formed due to weak deviation of the equipment and the process, and the phenomena of uncontrolled macroscopic and microscopic symmetries such as defects, dislocation, slippage, distortion and the like in a crystal are excessive, correspondingly, the void channel of the structureThe macroscopic and microscopic space occupying environments of the activator ions lose the ideality, and the luminescence formed after the activator ions are excited is weakened, absorbed, counteracted and consumed on the macroscopic and microscopic scales, so that the ideal luminescence cannot be realized, and high luminous efficiency is difficult to obtain, thereby becoming a technical obstacle to the practical application of the single phosphor. Further, [ Si, al][O,N] 4 The structural matrix formed by the tetrahedral three-dimensional corner sharing roof has strong binding force and is usually used in the field of superhard ceramic materials. At very high synthesis temperatures (1800-2200 ℃) and very high synthesis pressures (10-200 MPa), any attempt to improve luminescence by adding other elements by conventional high temperature solid phase doping reactions results in the formation of dense sialon, and fails to achieve the effect of improving the application properties of the phosphor.
In order to solve the technical difficulty, the invention provides a luminescent main phase crystal broken-LaTiO 3 A multi-step control process for preparing the microcrystal with perovskite structure includes such steps as breaking the defects in luminescent crystal, amplifying, and using LaTiO 3 The melting-crystallization characteristic of the amorphous material with the perovskite structure eliminates the defects in luminescent crystals to form luminescent crystals and LaTiO filled in the crystals 3 A mosaic crystal structure formed by the perovskite structure microcrystals forms a group of novel fluorophors; the implementation of the technical means has the functions of repairing and improving the micro and macro crystallinity of the luminescent crystal on one hand and LaTiO on the other hand 3 The microcrystal with the perovskite structure has extremely high light reflection/refraction/transmission performance, not only has the function of remedying crystal defects, but also has the interface effects of multiple directions and multiple angles between the microcrystal and the crystal surface net in the point, line and surface existing forms in the crystal, so that when the luminescent crystal is excited by light, the emitted light can realize the convergence and superposition amplification effects of various reflections, refraction and transmission on the novel crystal surface net/perovskite microcrystal interface with multiple directions and multiple angles, and the luminescent enhancement effect is realized, thereby obtaining the effect of improving the effectiveness of the activator under the existing synthesis condition, and further improving the luminescent efficiency; in addition, the luminescent crystal is formed by dots,The perovskite microcrystal embedded in the line and surface forms also has the pinning effect on the macroscopic and microscopic structure, so that the thermal vibration amplitude of the lattice structure in an excited state is reduced, and the heat attenuation resistance of the phosphor is improved; the implementation of the technical scheme is easy to realize the industrial mass production of the high-performance phosphor under mild conditions.
The present invention may have, but is not limited to, the following beneficial effects:
the main phase crystal is broken by luminescence-LaTiO 3 Compared with the technical scheme of a pure corresponding nitride or oxynitride phosphor, the technical scheme of the novel nitride or oxynitride modified by the high-refractive-index microcrystals introduced into the perovskite-structure microcrystals has fundamental differences in the aspects of composition, manufacturing method, conditions and performance improvement. The technical scheme of the invention not only improves the luminous performance of the product, but also reduces the harsh conditions for synthesizing the product, so that the product is easier to be put into practical mass production, which is an obvious progress in the related technical field.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 is a characteristic diagram of the high refractive index microcrystal-modified nitride or oxynitride phosphor according to the present invention in terms of the microscopic crystal morphology. Wherein, 1 is the crystal domain of the luminous main phase crystal, 2 is the crystal domain boundary of the luminous main phase crystal, 3 is the crystallized perovskite structure microcrystal in the surface defect of the luminous main phase crystal, 4 is the crystallized perovskite structure microcrystal in the defect in the crystal domain of the luminous main phase crystal, and 5 is the crystallized perovskite structure microcrystal at the crystal domain boundary of the luminous main phase crystal;
FIG. 2 is an X-ray diffraction pattern of the samples of example 1 and comparative example 1 of the present invention, wherein A is the sample of comparative example 1 and B is the sample of example 1;
FIG. 3 is an emission spectrum of samples of example 1 and comparative example 1 of the present invention, wherein A is the sample of comparative example 1 and B is the sample of example 1;
FIG. 4 is a graph showing the emission intensity change characteristics at different temperatures of the samples of example 1 and comparative example 1 according to the present invention, wherein A is the sample of comparative example 1 and B is the sample of example 1;
FIG. 5 is a scanning electron micrograph of samples of example 1 and comparative example 1 of the present invention, wherein A is the sample of comparative example 1 and B is the sample of example 1;
FIG. 6 is excitation and emission spectra of samples of example 2 and comparative example 2 of the present invention, wherein A is the sample of comparative example 2 and B is the sample of example 2;
FIG. 7 is a graph showing the emission intensity change characteristics at different temperatures for the samples of example 2 and comparative example 2 according to the present invention, wherein A is the sample of comparative example 2 and B is the sample of example 2;
Detailed Description
The invention is further illustrated by the following specific examples, which, however, are to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever.
This section generally describes the materials used in the testing of the present invention, as well as the testing methods. Although many materials and methods of operation are known in the art for the purpose of carrying out the invention, the invention is nevertheless described herein in as detail as possible. It will be apparent to those skilled in the art that the materials and methods of operation used in the present invention are well within the skill of the art in this context, if not specifically mentioned.
The reagents and instrumentation used in the following examples are as follows:
Si 3 N 4 : high purity grade, available from UBE corporation of japan; alN: high purity grade, available from deshan, japan; al (Al) 2 O 3 : high purity grade, from ZiboKai Euro New materials Co; euf 3 : high purity grade, purchased from Jiangxian Xinzheng New Material Co; siO 2 2 : analytically pure, purchased from chemical reagents of national drug group; caCO 3 And CaO: analytically pure, purchased from chemical reagents of national drug group; caF 2 Analytically pure, purchased from chemical reagents of national medicine group; ca 3 N 2 : high purity grade, available from de sheng ceramics, je, liao nings; eu (Eu) 2 O 3 、CeO 2 : high purity grade, purchased from shoal Henma high New materials company; n-butyl titanate, glacial acetic acid, lanthanum nitrate, acetic acid, sodium hydroxide: analytically pure, purchased from ChinaPharmaceutical group chemical agents.
The emission spectrum and the thermal characteristic of the phosphor are respectively tested by a remote photoelectric F-4500 fluorescence spectrometer and an EX-1000 fluorescent powder thermal quenching analysis system, the components and the appearance characteristics of the phosphor are respectively tested by a TD-3500X-ray diffractometer of Dandongtong and an OXFORD KY 2800B scanning electron microscope of a Chinese instrument, and the content of the halogen element R in the phosphor is tested by a TAS-986 atomic absorption spectrometer of a Beijing Puanalytic general instrument.
Example 1
This example is for explaining the method of producing the phosphor of the present invention.
Firstly, under the protection of inert gas, weighing the following raw materials in proportion: si 3 N 4 1.12 g, alN 0.08 g, al 2 O 3 0.04 g EuF 3 0.02 g, siO 2 0.05 g, weighing the raw materials in a glove box according to the molar ratio, fully grinding and uniformly mixing. The mixture was then charged into a boron nitride crucible and placed in a gas pressure sintering furnace under N 2 Calcining at 1950 deg.C under 125 atm for 6 hr. Cooling the sintered body, pulverizing, and sieving to obtain primary sintered material of fluorescent structure matrix, i.e. Si 0.0383 Al 0.0017 O 0.0006 N 0.0527 F 0.0003 ：0.00013Eu 2+ And is reserved for use.
Then measuring 1.7ml of n-butyl titanate and 2.9ml of glacial acetic acid, fully mixing the two, placing the two into 5.1ml of acetic acid, stirring for 30 minutes to obtain a light yellow transparent solution, then weighing 1.625 g of lanthanum nitrate, dissolving the lanthanum nitrate into 10ml of deionized water to form a nitrate solution, mixing and stirring the two solutions for 10 minutes to obtain a transparent mixed solution, continuously stirring, dropwise adding a 0.7mol/L NaOH solution to obtain a white emulsion, transferring the white emulsion into a reaction kettle, and preserving the heat at 200 ℃ for 24 hours. Then taking out the reaction slurry, washing the reaction slurry with deionized water and ethanol for three times, separating the slurry by adopting a centrifugal machine, and drying the slurry in an oven at the temperature of 80 ℃ to obtain LaTiO 3 The microcrystalline precursor material with the perovskite structure is reserved for use.
Then in an inert gas atmosphereThe weight ratio of 1 g: 0.015 g of the primary sintering material of the fluorescent structure matrix and LaTiO are respectively weighed 3 And uniformly mixing the microcrystalline precursor material with the perovskite structure, and then putting the mixture into a grinding and crushing instrument for grinding for 10 minutes to obtain a grinding and crushing mixture.
Then the grinding and crushing mixture is put into a boron nitride crucible and put into a sintering furnace, and then N 2 The second calcination was carried out in an atmosphere of 1.5 atm at 1100 deg.C for 4 hours.
And cooling the sintered body, crushing and sieving. Washing in 8% hydrochloric acid solution for 1 hr, water washing and stoving to obtain the phosphor Si of the present invention 0.0383 Al 0.0017 O 0.0006 N 0.0527 F 0.0004 ：0.00013Eu/0.0006(La 0.0044 Ti 0.0067 O 0.02 )。
Comparative example 1
Weighing the following raw materials in proportion under the protection of inert gas: si 3 N 4 1.12 g, alN 0.08 g, al 2 O 3 0.04 g EuF 3 0.02 g, siO 2 0.05 g, weighing the raw materials in a glove box according to the molar ratio, fully grinding and uniformly mixing. The mixture was then charged into a boron nitride crucible and placed in a gas pressure sintering furnace under N 2 Calcining at 1950 deg.C under 125 atm for 6 hr. Cooling the sintered body, crushing, sieving, re-placing in a pressure sintering furnace, and reacting in N 2 The second calcination was carried out at 1950 deg.C under 125 atm for 6 hours. And cooling the sintered body, crushing and sieving. Washing in a hydrochloric acid solution having a concentration of 8% for 1 hour, washing with water and drying to obtain the phosphor Si of comparative example 1 0.0383 Al 0.0017 O 0.0006 N 0.0527 F 0.0004 ：0.00013Eu。
Fig. 1 is a characteristic diagram of the high refractive index microcrystal-modified nitride or oxynitride phosphor according to the present invention in terms of the microscopic crystal morphology. As can be seen from fig. 1, it exhibits a mosaic crystal structure composed of a fluorescent main phase crystal and perovskite structure crystallites filled in cracks, pores and defects in the form of points, lines and planes on the crystal surface or in the crystal.
FIG. 2 is an X-ray diffraction pattern of the samples of example 1 and comparative example 1. The diffraction peaks of the two spectra can be combined with (Si.Al) 0.04 (O,N) 0.0533 The diffraction pattern of the sample in example 1 shows weak second phase sharp diffraction peaks at 13.5 degrees, 27.8 degrees and the like, and the diffraction pattern of the sample in example 1 corresponds to the diffraction peaks in the standard diffraction pattern of the sample in perovskite structure LaTiO 3 The material main diffraction peaks are consistent, which indicates that both (A and B spectra) show diffraction peak spectra of pure crystalline phase structures, but the diffraction spectrum of example 1 shows evidence of weak second phase crystallites. The results of the X-ray diffraction analysis prove that the multi-step process technical scheme provided by the invention does not damage the target luminescent structure matrix and shows a crystal state formed by the crystal matrix and the trace amount of microcrystals. In addition, the intensity of the strongest diffraction peak near 27 ° of the sample of example 1 is more than 30% higher than that of the comparative sample, which also shows that the multi-step process carried out on the sample of example 1 also plays a role in healing, repairing and improving the host crystal of the light-emitting structure, so that the crystallization of the phosphor is improved to obtain the diffraction peak characteristic with stronger intensity.
FIG. 3 is a graph showing emission spectra of phosphors of example 1 and corresponding comparative example 1. Fig. 4 is a graph showing the change in emission intensity at different temperatures for the samples of example 1 and comparative example 1. Fig. 5 is a graph of the crystal morphology of the samples of example 1 and comparative example 1. Compared with the comparison sample, the crystal form of the sample of the example 1 is more ideal, the luminous intensity is improved by 12 percent, and the light attenuation at 150 ℃ is reduced by 0.6 percent.
Example 2
This example is for explaining the method of producing the phosphor of the present invention.
Firstly, weighing the following raw materials in proportion under the protection of inert gas: caCO 3 0.14 g, si 3 N 4 0.84 g, alN 0.1 g, euF 3 0.03 g, weighing the raw materials in a glove box according to the molar ratio, fully grinding and uniformly mixing. The mixture was then charged into a boron nitride crucible and placed in a gas pressure sintering furnace under N 2 Calcining at 1900 deg.C under 25 atm for 6 hr. Cooling the sintered body, pulverizing, and sieving to obtain primary sintered material 2 (Si) as fluorescent structure matrix 0.035 Al 0.005 O 0.0029 N 0.0517 F 0.0004 )·Ca 0.0057 N 0.0038 ：0.0005Eu。
Measuring 1.7ml of n-butyl titanate and 2.9ml of glacial acetic acid, fully mixing the two solutions, placing the mixture in 5.1ml of acetic acid, stirring for 30 minutes to obtain a light yellow transparent solution, then weighing 1.625 g of lanthanum nitrate, dissolving the lanthanum nitrate in 10ml of deionized water to form a nitrate solution, mixing and stirring the two solutions for 10 minutes to obtain a transparent mixed solution, continuously stirring, dropwise adding a 0.7mol/L NaOH solution to obtain a white emulsion, transferring the white emulsion into a reaction kettle, and preserving heat at 200 ℃ for 24 hours. Taking out the reaction slurry, washing with deionized water and ethanol for three times, separating the slurry by a centrifuge, and drying the slurry in an oven at 80 ℃ to obtain LaTiO 3 The microcrystalline precursor material with the perovskite structure is reserved for use.
Then under the protection of inert gas, the weight ratio of 1 g: 0.025 g of the primary sintering material of the fluorescent structure matrix and LaTiO are respectively weighed 3 And uniformly mixing the microcrystalline precursor material with the perovskite structure, and then putting the mixture into a grinding and crushing instrument for grinding for 10 minutes to obtain a grinding and crushing mixture.
Then the grinding and crushing mixture is put into a boron nitride crucible and put into a sintering furnace, and then N 2 The second calcination was carried out in an atmosphere of 1.5 atm at 1100 deg.C for 4 hours.
And cooling the sintered body, crushing and sieving. Washing in 8% hydrochloric acid solution for 1 hr, washing with water and oven drying to obtain phosphor 2 (Si) of the present invention 0.035 Al 0.005 O 0.0029 N 0.0517 F 0.0003 )·Ca 0.0057 N 0.0038 ：0.0005Eu/0.0009(La 0.0044 Ti 0.0067 O 0.02 )。
Comparative example 2
Weighing the following raw materials in proportion under the protection of inert gas: caCO 3 0.14 g, si 3 N 4 0.84 g, alN 0.1 g, euF 3 0.03 g, weighing the raw materials in a glove box according to the molar ratio, fully grinding and uniformly mixing.The mixture was then charged into a boron nitride crucible and placed in a gas pressure sintering furnace under N 2 Calcining at 1900 deg.C under 25 atm for 6 hr. Cooling the sintered body, crushing, sieving, putting into a gas pressure sintering furnace again, and sintering in N 2 The second calcination was carried out in an atmosphere of 25 atm at 1900 deg.C for 6 hours. And cooling the sintered body, crushing and sieving. Washed in a hydrochloric acid solution having a concentration of 8% for 1 hour, washed with water and dried to obtain phosphor 2 (Si) of comparative example 2 0.035 Al 0.005 O 0.0029 N 0.0517 F 0.0003 )·Ca 0.0057 N 0.0038 ：0.0005Eu。
FIG. 6 shows excitation and emission spectra of phosphors of example 2 and corresponding comparative example 2. Fig. 7 is a graph showing the change in emission intensity at different temperatures for the samples of example 2 and comparative example 2. Compared with the comparison sample, the luminous intensity of the sample of the example 2 is improved by 20 percent, and the light attenuation at 150 ℃ is reduced by 0.1 percent.
Examples 3 to 18
This example is for explaining the method of producing the phosphor of the present invention.
The phosphors of examples 3 to 18 were prepared in a similar manner to example 1, and the amounts of the raw materials and process parameters thereof are shown in tables 1 to 3, where table 1 shows the amounts (g) of the raw materials and the process parameters for preparing the single phosphor firing materials of examples 3 to 18, and table 2 shows the LaTiO materials of examples 3 to 18 3 Composition and amount of the perovskite structure microcrystalline precursor material, and table 3 shows the amount of the raw material, process parameters and luminescent properties for the preparation of the secondary sintered material of examples 3 to 18.
TABLE 1 raw material amounts (g) and process parameters for preparing primary phosphor firing materials in examples 3 to 18
TABLE 2 LaTiO in examples 3 to 18 3 Composition of microcrystalline precursor material with perovskite structure and raw material dosage (g/ml)
| Examples | Perovskite structure precursor composition | Titanium acid n-butyl ester | Glacial acetic acid | | NaOH | |
| 3～18 | La 0.0044 Ti 0.0067 O 0.02 | 1.7ml | 2.9ml | 1.625 | 15ml |
TABLE 3 raw material usage, process parameters and luminescence properties for the preparation of the two-shot materials of examples 3 to 18
Examples 19 to 22
This example is for explaining the method of producing the phosphor of the present invention.
The phosphors of examples 19 to 22 were prepared in a similar manner to example 2, using the following raw materials in the amounts indicated in the following tables 4 to 6:
TABLE 4 raw material usage (g) and process parameters for one-shot firing in examples 19-22
TABLE 5 LaTiO in examples 19 to 22 3 Composition of microcrystalline precursor material with perovskite structure and raw material dosage (g/ml)
| Examples | Perovskite structure precursor composition | Titanium acid n-butyl ester | Glacial acetic acid | | NaOH | |
| 19～22 | La 0.0044 Ti 0.0067 O 0.02 | 1.7ml | 2.9ml | 1.625 | 15ml |
TABLE 6 Secondary sintering materials, amounts of raw materials for preparation, process parameters, and luminescent properties of examples 19 to 22
Although the present invention has been described to a certain extent, it is apparent that appropriate changes in the respective conditions may be made without departing from the spirit and scope of the present invention. It is to be understood that the invention is not limited to the described embodiments, but is to be accorded the scope consistent with the claims, including equivalents of each element described.
Claims (6)
1. A high refractive index crystallite-modified phosphor compound, characterized in that the composition of the phosphor compound is represented by the following general formula: k1 (M1) 0.04-a M2 a N b O c R d )·X e N f ：mRe / k2（M3 u M4 v O w ) Wherein:
m1 is Si, M2 is Al, N is nitrogen, O is oxygen, R is F - X is Ca, re is Eu, M3 is La, and M4 is Ti;
k1 is more than or equal to 1.95 and less than or equal to 2.05, a is more than or equal to 0.0005 and less than or equal to 0.02, b is more than or equal to 0.052 and less than or equal to 0.054, c is more than 0 and less than or equal to 0.0033, d is more than 0 and less than or equal to 0.0017, b + c + d is more than 0.052 and less than or equal to 0.059, e is more than 0 and less than or equal to 0.0133, f is more than 0 and less than or equal to 0.0089, m is more than 0 and less than or equal to 0.0033, k2 is more than 0 and less than or equal to 0.0015, u is more than or equal to 0.0039 and less than or equal to 0.0072, v is more than or equal to 0.0062 and less than or equal to 0.018 and less than or equal to 0.022;
the phosphor modified by the high-refractive-index microcrystal comprises a second phase filled with crystals in the fluorescence main phase crystal and crystal boundaries, internal cracks, defects and holesHigh refractive index microcrystals, wherein the fluorescent main phase has a crystal structure of [ Si, al][O,N] 4 The tetrahedral three-dimensional corner sharing top forms a frame, and a group of nitrogen oxide luminophors with alkaline earth metal ions and rare earth metal ions filled in tetrahedral channels, wherein the second-phase high-refractive-index microcrystal is a group of perovskite-structured rare earth metal titanates;
the phosphor compound emits one or more peak emission spectra with peak wavelength in the range of 450-700 nm after being excited by ultraviolet-blue-green light with emission peak wavelength in the range of 250-550 nm.
2. A method for preparing a phosphor compound according to claim 1, comprising the steps of:
(1) Weighing raw materials according to element proportion, and preparing fluorescent structure matrix k1 (M1) through high-temperature solid-phase reaction 0.04- a M2 a N b O c R d )·X1 e N f : mRe, crushing and screening to obtain a primary sintering material;
(2) The mixture ratio of k2 (M3) is prepared by a coprecipitation-hydrothermal method u M4 v O w ) The perovskite structure microcrystal precursor material;
(3) Respectively weighing the primary phosphor sintered material and the perovskite structure microcrystal precursor material obtained in the steps (1) and (2) according to the proportion, fully and uniformly mixing the primary phosphor sintered material and the perovskite structure microcrystal precursor material, and then putting the mixture into grinding and crushing equipment for grinding and crushing;
(4) Placing the mixture in high-temperature sintering equipment, and performing secondary high-temperature sintering treatment;
(5) And (4) crushing, screening and post-treating the sintered material obtained in the step (4) to obtain the phosphor compound.
3. The method according to claim 2, wherein in the step (1), the atmosphere of the high-temperature solid-phase reaction is a nitrogen atmosphere or a mixed atmosphere of nitrogen and hydrogen; the reaction pressure is 0-2000 atmospheric pressure; the reaction temperature is 1200-2500 ℃; and/or the reaction time is 4 to 16 hours; and/or
In the step (4), the atmosphere of the high-temperature solid-phase reaction is nitrogen atmosphere or mixed atmosphere of nitrogen and hydrogen; the reaction pressure is 0-100 atmospheric pressure; the reaction temperature is 800-1400 ℃; and/or the reaction time is 2 to 12 hours; and/or
In the step (5), the post-processing step includes: placing the crushed and sieved materials into an acid solution with the molar concentration of 1-10% to be stirred and washed for 1-4 hours, then filtering out the acid solution, washing for 1-4 times by using deionized water or ethanol, and drying to obtain the phosphor compound; the acid is selected from one or more of: sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid.
4. The method according to claim 2, wherein in the step (2), the raw materials of the element ratio are respectively selected from nitrate containing M3 element and n-butyl M4 acid containing M4 element;
the step (2) comprises the following steps:
(A) Respectively measuring and weighing N-butyl M4-carboxylate, glacial acetic acid and nitrate of M3 element according to the proportion, dissolving the N-butyl M4-carboxylate and the glacial acetic acid into a uniform mixed solution, and dissolving the nitrate containing the M3 element in deionized water to form a nitrate solution;
(B) Placing the mixed solution of the N-butyl M4-carboxylate and glacial acetic acid in acetic acid for acylation and stirring to obtain a light yellow transparent solution; then slowly adding the mixed solution into a nitrate solution containing M3 element, and magnetically stirring to obtain a transparent mixed solution;
(C) Then dropwise adding NaOH solution to obtain white emulsion;
(D) Transferring the white emulsion obtained in the step (C) into a reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction;
(E) Taking out the slurry after the hydrothermal reaction, washing the slurry for multiple times by using deionized water and ethanol, separating a product by using a centrifugal machine, and drying the product in an oven at the temperature of 80 ℃ to obtain a perovskite structure microcrystal precursor material;
in the step (A), the quantity ratio of the M3 and the M4 elements is 1:1, the amount of n-butyl ester M4 is 0.005mol, the amount of glacial acetic acid is 0.05mol, the amount of nitrate containing M3 element is 0.005mol, and the nitrate solution is formed by dissolving the nitrate in 10ml of deionized water;
in the step (B), the amounts of the mixed solution of the n-butyl M4-carboxylate and the glacial acetic acid and the acetic acid are respectively 0.005mol and 0.05mol, and the stirring time is 30 minutes;
in the step (C), the concentration of the NaOH solution is 0.5-1.5mol/L; and/or
And (D) keeping the hydrothermal reaction at the constant temperature of 200 ℃ for 24 hours.
5. The method according to claim 2, wherein in the step (3), the time for grinding and crushing the mixture of the primary phosphor sintered material and the perovskite-structure microcrystalline precursor material is 10 seconds to 30 minutes.
6. A phosphor composition comprising at least the phosphor compound of claim 1.
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