CN117186890B - Yttria-based luminescent material capable of emitting ultraviolet excitation in broadband and emitting red and blue light in dual bands and preparation method thereof - Google Patents
Yttria-based luminescent material capable of emitting ultraviolet excitation in broadband and emitting red and blue light in dual bands and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a yttrium oxide-based luminescent material with ultraviolet excitation in a wide wave band and emission in a red and blue wave bandAnd a preparation method thereof, the luminescent material is represented by the following formula:（100‑x‑y‑z）mol%Y 2 O 3 :xmol%Eu 3+ ,ymol%Bi 3+ ,zmol%TM, wherein,x=0.1‑5，y=0.1‑5，z=0.1-5; the invention can realize peak emphasis control of blue light and red light by changing the doping proportion of TM ions, bi ions and Eu ions, can be excited by 190-275nm and 300-400nm broadband ultraviolet, simultaneously emits blue light and red light, has an internal quantum yield of more than 80%, and has the advantages of simple preparation method, controllable process, low cost, wide adaptability and high popularization value.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and relates to a yttrium oxide-based luminescent material capable of emitting ultraviolet excitation in a broadband and emitting red and blue light in a dual-band and a preparation method thereof.
Background
Sunlight is critical to plant growth, and plants pass through chloroplasts and utilize light energy to convert CO 2 And H 2 Conversion of O to organic matter, release of O 2 . However, the plant has a low solar light utilization rate, and about 5% of solar light can be theoretically fixed through photosynthesis. The sunlight utilization rate of the plants is improved, namely the blue-red light absorbed by the plants through photosynthesis is mainly improved, and the photosynthetic pigments (chlorophyll and carotenoid) for photosynthesis of the plants mainly absorb the blue light wavelength of 400-510nm and the red light wavelength of 610-750 nm. The light conversion film can be used for converting ultraviolet light harmful to plants and green light which cannot be absorbed into red and blue light, so that the absorption of the plants to sunlight is improved, and the purposes of promoting early ripening and improving yield are achieved. At present, the light conversion film is mainly a single light conversion film, namely ultraviolet light is converted into red light or blue light, green light is converted into red light, and ultraviolet light waves are converted into green lightThe absorption of the section is narrower, and can not realize the regulation and control of the red and blue light dual-band, and the practicality is relatively poor.
The ion co-doped rare earth oxide-based phosphor is an important component in luminescent materials. A large number of researches prove that the co-doping system can generate phenomena such as electron transfer, energy transfer and the like, thereby generating rare earth ions with abnormal valence and sensitization, and different matrixes and different synthesis methods can influence the luminous property of the material. Therefore, the luminescent performance of the red fluorescent powder is greatly improved by selecting proper rare earth matrix ions, activating ions and sensitizing ions. Y is Y 2 O 3 Eu fluorescent powder is used as a typical traditional red fluorescent powder and has the advantages of high quantum efficiency, short decay time, high chemical stability and the like, wherein Y 2 O 3 Is a common rare earth metal oxide, is in a body-centered cubic structure, and has a plurality of advantages as a luminescent material matrix, such as low phonon energy, and can effectively inhibit non-radiative transition probability; the chemical stability is high, and the performance is not influenced by the external environment; the Y ions are trivalent ions and most of them are doped without charge compensation problems. In the cubic phase Y 2 O 3 In crystals, Y ions have two lattice sites: c (C) 2 And S is 6 . Wherein C is 2 In the center of non-inversion symmetry, allowing the electric dipole to transition; s is S 6 In the inversion symmetry center, allowing the magnetic dipole to transition, non-radiative relaxation may occur, reducing the luminous efficiency. Eu ions exist as an activation center, and Eu ions replace Y ions to occupy C 2 When the lattice is in, it occurs 5 D 0 → 7 F 2 The transition, i.e. around 610nm, emits red light, is the strongest emission peak position; occupy S 6 When the lattice is in, it occurs 5 D 0 → 7 F 4 The transition, i.e. around 710nm, emits deep red light, the peak intensity is weaker, and there is non-radiative relaxation affecting the luminescence intensity. Due to Y 2 O 3 The coordination degree of the emission spectrum of Eu and the absorption spectrum of plant chlorophyll is higher, so that the Eu-chlorophyll film can be applied to the field of light conversion greenhouse films. But single Y 2 O 3 Eu luminescent material has narrower absorption spectrum in ultraviolet band, and can only emit red light band, but can not emit blue light band, so that it is necessary toDoping other ions is required to be developed to realize broadband excitation in the ultraviolet region and dual-band emission in the red and blue light region so as to adapt to the application of the practical light conversion greenhouse film.
Disclosure of Invention
The invention aims to overcome the technical problems, and provides a yttrium oxide-based luminescent material capable of emitting ultraviolet light in a broadband range and emitting red light and blue light in a dual range and a preparation method thereof, wherein the luminescent material can realize peak emphasis control of blue light and red light by changing the doping proportion of TM ions and Eu ions, can be excited by ultraviolet light in the broadband range of 190-275nm and 300-400nm, emits blue light and red light at the same time, and has an internal quantum yield of more than 80 percent; the preparation method is simple, the process is controllable, the cost is low, and the prepared luminescent material has wide adaptability and high popularization value.
The technical scheme provided by the invention is as follows:
a broadband ultraviolet excited, red-blue dual-band emitted yttria-based luminescent material, the luminescent material being represented by the formula:(100-x-y-z）mol%Y 2 O 3 : xmol%Eu 3+ ,ymol%Bi 3+ ,zmol%TM，wherein the method comprises the steps of，x=0.1-5，y=0.1-5，z=0.1-5; TM is one of Mn, cu, co, ti, V, zn, W, ta, ni.
As a limitation of the present invention, the phosphor has a single cubic yttrium oxide phase, and Eu ions, bi ions and TM ions are completely dissolved in Y 2 O 3 The size of the fluorescent powder particle in the crystal lattice is 5-10 mu m, and the crystal lattice has regular morphology and is approximately spherical.
Bi element and Bi ion 6s are introduced into the luminescent material 2 The 6s6p belongs to electric dipole allowable transition, has higher absorption intensity and wider absorption range in ultraviolet and near ultraviolet bands, and can overcome the problem of lower transition absorption intensity in the rare earth ion 4f configuration. Therefore, bi ions are selected as doping elements for modulating the activation band of the fluorescent powder, so that the proper excitation wavelength is obtained. The ultraviolet broadband absorption band is derived from Bi ions for 6s 2 The 6s6P electric dipole transition is P when 340nm is used as excitation wave 1 Bi ions in an excited state can emit a blue-green bandThe visible photons (400-580 nm) return to the ground state (i.e. Bi ions) 3 P 1 → 1 S 0 Intrinsic transition emission); and the absorption spectrum of Eu ion 4f energy level transition is between 300-500nm, so that the energy between the emission of Bi ions and the absorption of Eu ions is well overlapped, and the excitation energy can be transferred to Eu ions through resonance energy transfer. Therefore, the characteristic emission of Eu ions can be transferred to the excited state energy level of Eu ions by the sensitization of Bi ions to Eu ions, wherein the Bi ions serve as luminescence sensitizer, and the near ultraviolet absorption of the charge transfer band of the Bi ions is utilized, and the energy transfer mode is adopted. Namely: bi ion doping can widen Y 2 O 3 Eu is excited in ultraviolet band, and Y is enhanced 2 O 3 Eu has emission intensity in a red light wave band, but has the defects of unstable valence state and difficult powder synthesis.
Therefore, the invention introduces Transition Metal (TM) with 3d into the luminescent material 1-10 4s 0-2 Electron configuration, when doped into a solid matrix, loses the outer electron orbitals to form a 3d structure n TM ion in electronic configuration. TM ions have degrees of freedom such as charge, self-selection, orbitals, etc., often present in a solid matrix with multiple placeholders, valences and multiple possible transition types, and 3d n The nature of the optical transitions (d-d transitions) within the configuration is strongly dependent on the host and the specific coordination environment in which it is located. Most optically active transition metal ions have multiple valence states and may occupy various coordination environments, which allows the transition metal ions to have broadband characteristics and to be tunable in bandwidth and emission band. The luminescence process of the transition metal ions is as follows: the transition metal ions enter a ligand field and are pumped by an excitation light source, the outer electrons are transited from an excited state to an excited state energy level, the electrons are transited to a metastable state in a non-radiative way due to the unstable excited state energy level, and then the electrons return to a ground state from the metastable state, and the redundant energy is released in the form of photons. For example transition metal Mn 4+ Electronic configuration 3d of (2) 3 Is an ideal activating ion of red fluorescent powder. Mn (Mn) 4+ Usually only in an octahedral environment, because in an octahedral lattice the Mn-3d orbitalsCleavage into three degenerate t 2g Track and two degenerated t eg The electrons on the Mn-3d orbit fill up the low energy t 2g The track is in the state of lowest energy. Whereas in tetrahedral lattices, t is the Mn-3d orbital eg The track is at t 2g Below the track. Except that two electrons occupy t eg Outside the orbit, there is also an electron t which needs to occupy a high energy 2g The rail, which requires higher energy, is thus an unstable state. Due to Mn 4+ The outer layer has no shielding of the closed shell layer, so Mn 4+ The electron motion of (2) is greatly affected by the external crystal field. When Mn is 4+ When located in the octahedral lattice sites, mn 4+ The ions can remain stable, exhibiting broadband absorption in the ultraviolet and blue regions and narrowband emission in the red region. Mn (Mn) 4+ The absorption bands of (2) are derived from spin permission 4 A 2 → 4 T 1 And 4 A 2 → 4 T 2 generated by transition, the red light emission of which is derived from Mn 4+ Spin forbidden resistance of (a) 2 E 1 → 4 A 2 And (5) transition. Transition metal Ni 2+ Besides the light-emitting peak position can be regulated and controlled by the environmental change of the crystal field, the light-emitting device has the characteristic of broadband light emission. Since both the Janh-teller effect and the spin-orbit interaction of the transition metal ions cause the energy level splitting of the d-orbit, the energy level splitting of the d-orbit causes the transition change of the light-emitting energy level, thereby widening the light-emitting spectrum. Transition metal Cr 3+ With d 3 Configuration, generally occupying octahedral sites, two broad excitation bands in the visible region originate from 4 A 2 → 4 T 2 And 4 A 2 → 4 T 2 spin transitions, when they occupy a weaker crystal field environment, can occur 4 A 2 → 4 T 2 Near infrared light emission. Transition metal Mn 2+ With 3d 5 Electronic configuration of 4 T 1 → 6 A 1 The transition can emit red light due to Mn 2+ The d-d transition of (2) is easily affected by an external crystal field, and the luminous color can be adjusted from visible light to near infrared light.
Bi ionThe son is used as sensitization ion, which can widen Y 2 O 3 The Eu fluorescent powder absorbs the spectrum wave band, and simultaneously generates Bi ions, eu ion energy transfer and Bi ions, TM ions MMCT, and simultaneously improves the emission intensity of Eu ions in the red light wave band and the emission intensity of TM ions in the blue light wave band. The selected TM activated ion pair Y of the invention 2 O 3 Eu luminescent material is doped to regulate and control TM ions in Y 2 O 3 The occupation of the base is achieved, so that a controllable and adjustable luminescent material capable of emitting red and blue light in double wave bands is obtained, and the luminescent material is applied to an agricultural light conversion greenhouse film, so that the utilization rate of different plants to sunlight can be improved.
In the cubic phase Y 2 O 3 In which Y ions are present in two lattice sites: c (C) 2 And S is 6 . Eu ions and TM ions exist as activation centers, and Bi ions serve as sensitizers. Eu ion substituted Y ion occupies C 2 Lattice bit can occur 5 D 0 → 7 F 2 The transition, i.e. around 610nm, emits red light, replacing the S occupied by Y ions 6 Lattice bit can occur 5 D 0 → 7 F 4 The transition, i.e. around 710nm, emits deep red light. 6s of Bi ion 2 The 6s6p electric dipole transition makes the ultraviolet region have a broadband absorption, the energy between the emission band of Bi ions and the absorption band of Eu ions has a good overlap, and the excitation energy can be transferred to Eu ions through resonance energy transfer. Not only broadens the ultraviolet excitation wave band of Eu ions, but also enhances the intensity of emission peaks. When TM ions are doped, the valence and the ionic radius of different TM ions can lead to the change of the matrix lattice environment, and as the ionic radius of the TM ions is far smaller than that of Y ions (0.89A), the lattice environment is easily distorted in the doping process, thereby leading C to be the same as the ion of the Y ions 2 Lattice bit and S 6 The crystal field strength of the lattice site changes. TM ion 3d n The transition of the optical transition (d-d transition) in the configuration is strongly dependent on the matrix and the lattice environment, and the transition of different TM ions in Y is regulated 2 O 3 The occupation ratio of different TM ions in the matrix is obtained in 3d n Transition within the configuration, while there is MMCT (metal-metal charge transfer effect) effect between Bi ions and TM ions, inThe near ultraviolet region may be excited while emitting blue light. Bi ions exist as a sensitizer, and simultaneously sensitize Eu ions and TM ions, so that both red and blue light dual-band emission can be realized, the emission peak intensity of a red and blue light band is improved, and the quantum efficiency is higher.
The invention also provides a preparation method of the yttrium oxide-based luminescent material capable of emitting ultraviolet excitation in a broadband and emitting red and blue light in a dual-band, which is sequentially carried out according to the following steps:
(S1) ball milling
Y is set to 2 O 3 、Eu 2 O 3 、Bi 2 O 3 The transition metal oxide TMO is weighed according to the proportion of the expression of the luminescent material, and is put into a ball milling tank together with a dispersing agent, the ball milling tank is put into a planetary ball mill for ball milling, and the ball milling procedure is carried out according to the following steps: the grinding balls are zirconium beads, the size of the zirconium beads is 5-40mm, and the mass ratio of the ball materials is 1:2-4, the rotating speed is 300-700rpm, and ball milling is carried out for 6-12 h.
Ball milling is the generation of mechanical energy by collisions and friction between reactants, milling balls and tanks, resulting in phase and structural changes in the reactants. The ball milling process can reduce the particle size of the material, small crystal grains have large specific surface area, the larger the specific surface area is, the reaction interface and the diffusion section are increased, the thickness of the reaction product layer is reduced, and the reaction speed is increased. The particle size of the material is controlled within a narrower range by adopting proper grinding ball size and rotating speed, so that the reaction degree of reactants in the sintering process is improved.
(S2) drying and grinding
Drying the material A in an electrothermal constant temperature blast drying oven at 80-200deg.C for 12-48 hr, grinding the dried material, and sieving with 80-300 mesh sieve to obtain material B;
(S3) sintering
And (3) placing the B in a crucible, sintering the B in a resistance furnace under the air atmosphere, sieving the sintered powder with a 80-300-mesh sieve, and placing the sieved fluorescent powder in a drying oven at 80-200 ℃ for storage to obtain the final luminescent material.
As one limitation of the preparation method of the invention, the dispersing agent is ethanol, and the mass ratio of the dispersing agent to the total mass of raw materials is 2-4:1.
As a second limitation of the preparation method of the present invention, in the step (S3), the sintering process is a staged sintering, specifically as follows:
a first temperature rising stage: heating to 800-1000 deg.C from room temperature;
a second temperature rising stage: raising the temperature to 1100-1300 ℃ from the first stage temperature, and preserving the heat by 2-5 h;
and (3) a cooling stage: cooling with furnace or cooling to room temperature at 50-200deg.C/h.
As a further limitation of the present invention, the temperature rising rate of the first temperature rising stage is 5-10 ℃/min; the temperature rising rate of the second temperature rising stage is 1-5 ℃/min.
It is well known that luminescence is a result of electron transitions between ions, and that sintering ensures that doping elements enter the yttria matrix lattice without creating other impurity phases. In the present invention, in the first temperature rising stage, particle rearrangement mainly occurs between powders, bonding starts to occur between the particles, but the total surface is not changed much, so the temperature rising rate is faster in this stage. At this stage, contact is started between the four mixed oxides (yttrium oxide, europium oxide, bismuth oxide, transition metal oxide) and a surface effect is generated; in the second heating stage, the bonding among grains is gradually enhanced, fine grains are gradually grown, and the average grain size is increased. The temperature rising rate is slower in this stage, which is to prevent the phenomenon of uneven chemical reaction and recrystallization caused by too high temperature rising rate. At this stage, europium oxide, bismuth oxide and transition metal oxide begin to permeate into yttrium oxide crystal lattice, the reaction proceeds in the whole particle, the surface layer of the particle is loose and activated, at this time, the dispersity of the reactant is very high, no new crystal phase appears, but crystal nucleus is formed. The sintering stage requires that the powder particle size is uniform and fine, and excessive powder particle size can cause recrystallization phenomenon in the sintering process, so that the crystal grain size is excessive, the morphology is irregular, and the luminous performance is further affected. At this stage, the doped element further enters the matrix lattice, the crystal nucleus further grows up, the crystal structure defect is corrected and regulated, the thermodynamic stable state is gradually reached,gradually forming a main phase (c-Y) 2 O 3 Phase), the other dopant element phases disappear.
The invention also has the limit that the luminescent material can be excited by 190-275nm and 300-400nm broadband ultraviolet, simultaneously emit blue light and red light, and the internal quantum yield reaches more than 80 percent
The steps of the invention are closely related and inseparable as a whole, which together affect the properties of the final luminescent material.
By adopting the technical scheme, the beneficial effects obtained by the invention are as follows:
(1) The luminescent material is prepared by a solid phase method, the preparation process is simple, the process is controllable, and the prepared product has single cubic Y 2 O 3 Structure, no impurity phase, eu ion and TM ion occupying C 2 Lattice bit and S 6 The lattice sites have the grain size of 5-10 mu m, are less in agglomeration and easy to disperse, and are ideal optical functional materials for agricultural greenhouse films.
(2) The luminescent material prepared by the invention can be excited by 190-275nm and 300-400nm broadband ultraviolet and is Eu 3+ -O 2- CTB and 6s of Bi ion of (c) 2 A 6s6p electric dipole transition, wherein the emission of the red light wave band is Eu ion occupying C 2 Lattice bit generation 5 D 0 → 7 F 2 The transition and blue light wave band emission are caused by the fact that TM (Mn, gd, cu, co, ti, V, zn, W, ta, ni) ions occupy different lattice positions to cause the change of crystal field intensity, so that blue light emission is generated, and the sensitizer Bi ions sensitize Eu ions and TM ions simultaneously, so that the red and blue light emission intensity is improved.
(3) The invention regulates and controls the proportion of the doped TM (Mn, cu, co, ti, V, zn, W, ta, ni) ions and the doped Eu ions in Y 2 O 3 Occupying space in the matrix to realize the regulation and control of blue light wave band and peak intensity, such as Mn 3+ ：Eu 3+ When the ratio of red to blue light intensity is about 4:1 (mol percent), the internal quantum yield reaches 80.6%, and the broadband ultraviolet excitation and the red and blue light emission can be realizedMeanwhile, the material has high quantum yield, and is an agricultural greenhouse film light functional material with application prospect.
The invention is suitable for preparing luminescent materials, and is further used in optical functional materials of agricultural greenhouse films.
The technical scheme of the invention will be further described in detail below with reference to the attached drawings and the detailed description.
Drawings
FIG. 1 is Y 2 O 3 :Eu 3+ ，Bi 3+ ，TM（TM= Mn 3+ 、Mn 4+ 、 Cu 2+ 、 Co 2+ 、 Ti 4+ 、 V 3+ 、 Zn 2+ 、 W 4+ 、 Ta 5+ 、Ni 2+ ) XRD pattern of luminescent material;
FIG. 2 is a schematic diagram of a commercial blue phosphor, a commercial red phosphor, and Y 2 O 3 :5mol%Eu 3+ , 5mol%Bi 3+ ,5mol%Mn 3+ A spectrum of luminescent material, wherein: (a) -excitation profile, (b) -emission profile;
FIG. 3 is Y 2 O 3 :Eu 3+ ，Bi 3+ ，Mn 3+ SEM images of luminescent materials;
FIG. 4 is Y 2 O 3 :Eu 3+ ，Bi 3+ ，Mn 3+ Particle size diagram of luminescent material;
FIG. 5 is Y 2 O 3 Emission patterns of Eu, bi and Mn luminescent materials;
FIG. 6 is Y 2 O 3 :Eu，Bi，TM（TM= Mn 3+ 、Mn 4+ 、 Cu 2+ 、 Co 2+ 、 Ti 4+ 、 V 3+ 、 Zn 2+ 、 W 4+ 、 Ta 5+ 、Ni 2 + ) Emission spectrum of luminescent material.
Detailed Description
The following examples are only some, but not all, of the examples of the invention. Accordingly, the detailed description of the embodiments of the invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.
In the present invention, all the equipment, raw materials and the like are commercially available or commonly used in the industry unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1: y (Y) 2 O 3 Eu, bi and Mn luminescent material and preparation method thereof
The preparation of the invention93.5mol%Y 2 O 3 : 5mol%Eu 3+ ,1mol%Bi 3+ ,0.5mol%Mn 3+ The luminescent material is prepared by the following steps:
(S1) Y is 2 O 3 、Eu 2 O 3 、Bi 2 O 3 、Mn 2 O 3 The molecular formula ratio of the luminescent materials is calculated well, the luminescent materials and the dispersing agent (absolute ethyl alcohol) are put into a ball milling tank together, the mass ratio of the total mass of ingredients to the dispersing agent is 1:3, the ball milling tank is put into a planetary ball mill for ball milling 6h, and the ball milling procedure is as follows: the grinding balls are zirconium beads, the sizes of the zirconium beads are 10mm, 20mm and 30mm, the mass ratio of the three balls is 3:4:3, the mass ratio of the balls is 1:3, and the rotating speed is 450rpm.
(S2) after ball milling is completed, pouring the materials into a beaker, and putting the beaker into an electrothermal constant-temperature blast drying box to dry 24h at 80 ℃. The dried material was ground and then sieved through an 80 mesh screen.
(S3) pouring the sieved materials into a crucible, placing the crucible into a resistance furnace for phase-forming sintering, wherein the sintering is performed according to a step-by-step sintering process, and the first temperature rising stage: heating to 1000 ℃ from room temperature at a heating rate of 5 ℃/min; a second temperature rising stage: heating to 1100 ℃ from 1000 ℃ at a heating rate of 2 ℃/min, and preserving heat for 3 h; and (3) a cooling stage: cooling to room temperature at a cooling rate of 100 ℃/h. And (3) sieving the sintered precursor powder with a 100-mesh sieve, and placing the sieved fluorescent powder into a drying oven for storage.
Prepared in example 1XRD testing of the luminescent material of (2) is carried out, and as shown in FIG. 1, the XRD diffraction pattern of the powder is shown as single cubic Y 2 O 3 Structure, no impurity phase, indicate Eu 3+ 、Bi 3+ And Mn of 3+ Is completely dissolved in Y 2 O 3 In the crystal lattice. The luminescent material prepared in example 1 was subjected to a particle size test, as shown in FIG. 4, with an average particle size of 6. Mu.m. For the emission spectrum of the luminescent material prepared in example 1, the excitation wavelength was 330nm, and the material had a wider blue light emission region and a narrow red light emission peak as shown in fig. 5. The red-blue light integration area ratio is 4:1, the absorption spectrum of the greenhouse cucumber in agricultural planting is identical to that of the greenhouse cucumber, only 15-20% of blue light and the rest of mixed irradiation of green light and red light are needed under the optimal growth condition of the cucumber, and the luminescent material under the proportion can be applied to a yellow light agricultural film of the greenhouse so as to regulate and control the red light and the blue light, so that the optimal growth condition of the cucumber is achieved.
Example 2: y (Y) 2 O 3 Eu, bi and Mn luminescent material and preparation method thereof
The preparation of the invention95mol%Y 2 O 3 : 2mol%Eu 3+ ,2mol%Bi 3+ ,1mol%Mn 4+ The luminescent material is prepared by the following steps:
(S1) Y is 2 O 3 、Eu 2 O 3 、Bi 2 O 3 、MnO 2 The molecular formula ratio of the luminescent materials is calculated well, the luminescent materials and the dispersing agent (absolute ethyl alcohol) are put into a ball milling tank together, the mass ratio of the total mass of ingredients to the dispersing agent is 1:2, the ball milling tank is put into a planetary ball mill for ball milling for 10 hours, and the ball milling procedure is as follows: the grinding balls are zirconium beads, the sizes of the zirconium beads are 10mm, 20mm and 30mm, the mass ratio of the three balls is 3:4:3, the mass ratio of the balls is 1:2, and the rotating speed is 300rpm.
And (S2) after ball milling is finished, pouring the materials into a beaker, and putting the beaker into an electrothermal constant-temperature blast drying box to dry for 30 hours at 100 ℃. The dried material was ground and then sieved through a 100 mesh sieve.
(S3) pouring the sieved materials into a crucible, placing the crucible into a resistance furnace for phase-forming sintering, wherein the sintering is performed according to a step-by-step sintering process, and the first temperature rising stage: heating to 800 ℃ from room temperature at a heating rate of 8 ℃/min; a second temperature rising stage: heating to 1300 ℃ from 800 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2 h; and (3) a cooling stage: cooling to room temperature along with furnace cooling. And (3) sieving the sintered precursor powder with a 150-mesh sieve, and placing the sieved fluorescent powder into a drying oven for preservation.
XRD testing of the luminescent material obtained in example 2 was conducted, and as shown in FIG. 1, the XRD diffraction pattern of the powder was shown to be a single cubic Y 2 O 3 Structure, no impurity phase, indicate Eu 3+ 、Bi 3+ And Mn of 4+ Is completely dissolved in Y 2 O 3 In the crystal lattice. For the emission spectrum of the luminescent material prepared in example 2, the excitation wavelength is 330nm, and as shown in fig. 6, the component has a wider blue light emission region and a narrow red light emission peak, and the ratio of the red to blue light integration area is 1:2.
Example 3: y (Y) 2 O 3 Eu, bi and Cu luminescent material and preparation method thereof
The preparation of the invention94mol%Y 2 O 3 : 2mol%Eu 3+ ,2mol%Bi 3+ ,2mol%Cu 2+ The luminescent material is prepared by the following steps:
(S1) Y is 2 O 3 、Eu 2 O 3 、Bi 2 O 3 The CuO and the dispersing agent (absolute ethyl alcohol) are well calculated according to the molecular formula ratio of the luminescent material, and are placed into a ball milling tank together with the dispersing agent (absolute ethyl alcohol), the mass ratio of the total mass of ingredients to the dispersing agent is 1:4, the ball milling tank is placed into a planetary ball mill for ball milling 12 and h, and the ball milling procedure is as follows: the grinding balls are zirconium beads, the sizes of the zirconium beads are 10mm, 20mm and 30mm, the mass ratio of the three balls is 3:4:3, the mass ratio of the balls is 1:4, and the rotating speed is 700rpm.
(S2) after ball milling is completed, pouring the materials into a beaker, and putting the beaker into an electrothermal constant-temperature blast drying box to dry the materials at 200 ℃ for 12h. The dried material was ground and then sieved through a 300 mesh sieve.
(S3) pouring the sieved materials into a crucible, placing the crucible into a resistance furnace for phase-forming sintering, wherein the sintering is performed according to a step-by-step sintering process, and the first temperature rising stage: heating to 900 ℃ from room temperature at a heating rate of 10 ℃/min; a second temperature rising stage: heating to 1200 ℃ from 900 ℃ at a heating rate of 1 ℃/min, and preserving heat for 5 h; and (3) a cooling stage: cooling to room temperature at a cooling rate of 50 ℃/h. And (3) sieving the sintered precursor powder with a 300-mesh sieve, and placing the sieved fluorescent powder into a drying oven for preservation.
XRD testing of the luminescent material obtained in example 3 was conducted, and as shown in FIG. 1, the XRD diffraction pattern of the powder was shown to be a single cubic Y 2 O 3 Structure, no impurity phase, indicate Eu 3+ 、Bi 3+ And Cu 2+ Is completely dissolved in Y 2 O 3 In the crystal lattice. For the emission spectrum of the luminescent material prepared in example 3, the excitation wavelength is 330nm, and as shown in fig. 6, the component has a wider blue light emission region and a narrow red light emission peak, and the ratio of the red to blue light integration area is 2:5.
Example 4: y (Y) 2 O 3 Eu, bi and Co luminescent material and preparation method thereof
The preparation of the invention92mol%Y 2 O 3 : 2mol%Eu 3+ ,2mol%Bi 3+ ,4mol%Co 2+ The luminescent material is prepared by the following steps:
(S1) Y is 2 O 3 、Eu 2 O 3 、Bi 2 O 3 The CoO is calculated according to the molecular formula ratio of the luminescent material, and is put into a ball milling tank together with a dispersing agent (absolute ethyl alcohol), the mass ratio of the total mass of ingredients to the dispersing agent is 1:2, the ball milling tank is put into a planetary ball mill for ball milling 8h, and the ball milling procedure is as follows: the grinding balls are zirconium beads, the sizes of the zirconium beads are 10mm, 20mm and 30mm, the mass ratio of the three balls is 3:4:3, the mass ratio of the balls is 1:4, and the rotating speed is 600rpm.
And (S2) after ball milling is finished, pouring the materials into a beaker, and putting the beaker into an electrothermal constant-temperature blast drying box to dry for 48 hours at 150 ℃. The dried material was ground and then sieved through a 200 mesh screen.
(S3) pouring the sieved materials into a crucible, placing the crucible into a resistance furnace for phase-forming sintering, wherein the sintering is performed according to a step-by-step sintering process, and the first temperature rising stage: heating from room temperature to 850 ℃ at a heating rate of 7 ℃/min; a second temperature rising stage: heating to 1200 ℃ from 850 ℃ at a heating rate of 3 ℃/min, and preserving heat for 4 h; and (3) a cooling stage: cooling to room temperature at a cooling rate of 200 ℃/h. And (3) sieving the sintered precursor powder with a 80-mesh sieve, and placing the sieved fluorescent powder into a drying oven for storage.
XRD testing of the luminescent material obtained in example 4 was conducted, and as shown in FIG. 1, the XRD diffraction pattern of the powder was shown to be a single cubic Y 2 O 3 Structure, no impurity phase, indicate Eu 3+ 、Bi 3+ And Co 2+ Is completely dissolved in Y 2 O 3 In the crystal lattice. For the emission spectrum of the luminescent material prepared in example 4, the excitation wavelength is 330nm, and as shown in fig. 6, the component has a wider blue light emission region and a narrow red light emission peak, and the ratio of the red to blue light integration area is 1:4.
Example 5: y (Y) 2 O 3 Eu, bi and Ti luminescent material and preparation method thereof
The preparation of the invention88mol%Y 2 O 3 : 4mol%Eu 3+ ,4mol%Bi 3+ ,4mol%Ti 4+ The luminescent material was prepared in a similar manner to example 1, with the only difference that: in the step (S1), the raw material is Y 2 O 3 、Eu 2 O 3 、Bi 2 O 3 、TiO 2 。
XRD testing of the luminescent material obtained in example 5 was conducted, and as shown in FIG. 1, the XRD diffraction pattern of the powder was shown to be a single cubic Y 2 O 3 Structure, no impurity phase, indicate Eu 3+ 、Bi 3+ And Ti is 4+ Is completely dissolved in Y 2 O 3 In the crystal lattice. For the emission spectrum of the luminescent material prepared in example 5, the excitation wavelength is 330nm, and as shown in fig. 6, the component has a wider blue light emission region and a narrow red light emission peak, and the ratio of the red to blue light integration area is 3:2.
Example 6: y (Y) 2 O 3 Eu, bi and V luminescent materials and preparation method thereof
The preparation of the invention89mol%Y 2 O 3 :5mol%Eu 3+ ,3mol%Bi 3+ ,3mol%V 3+ The luminescent material was prepared in a similar manner to example 1, with the only difference that: in the step (S1), the raw material is Y 2 O 3 、Eu 2 O 3 、Bi 2 O 3 、V 2 O 3 。
XRD testing of the luminescent material obtained in example 6 was conducted, and as shown in FIG. 1, the XRD diffraction pattern of the powder was shown to be a single cubic Y 2 O 3 Structure, no impurity phase, indicate Eu 3+ 、Bi 3+ And V 3+ Is completely dissolved in Y 2 O 3 In the crystal lattice. For the emission spectrum of the luminescent material prepared in example 6, the excitation wavelength is 330nm, and as shown in fig. 6, the component has a wider blue light emission region and a narrow red light emission peak, and the ratio of the red to blue light integration area is 1:1.
Example 7: y (Y) 2 O 3 Eu, bi and W luminescent materials and preparation method thereof
The preparation of the invention87mol%Y 2 O 3 : 4mol%Eu 3+ ,4mol%Bi 3+ ,5mol%W 3+ The luminescent material was prepared in a similar manner to example 1, with the only difference that: in the step (S1), the raw material is Y 2 O 3 、Eu 2 O 3 、Bi 2 O 3 、WO 2 。
XRD testing of the luminescent material obtained in example 7 was conducted, and as shown in FIG. 1, the XRD diffraction pattern of the powder was shown to be a single cubic Y 2 O 3 Structure, no impurity phase, indicate Eu 3+ 、Bi 3+ And W is 4+ Is completely dissolved in Y 2 O 3 In the crystal lattice. For the emission spectrum of the luminescent material prepared in example 7, the excitation wavelength is 330nm, and as shown in fig. 6, the component has a wider blue light emission region and a narrow red light emission peak, and the ratio of the red to blue light integration area is 3:2.
Example 8: y (Y) 2 O 3 Eu, bi and Zn luminescent material and preparation method thereof
The preparation of the invention94.8mol%Y 2 O 3 : 5mol%Eu 3+ ,0.1mol%Bi 3+ ,0.1mol%Zn 4+ The luminescent material was prepared in a similar manner to example 1, with the only difference that: in the step (S1), the raw material is Y 2 O 3 、Eu 2 O 3 、Bi 2 O 3 、ZnO 2 。
XRD testing of the luminescent material obtained in example 8 was conducted, and as shown in FIG. 1, the XRD diffraction pattern of the powder was shown to be a single cubic Y 2 O 3 Structure, no impurity phase, indicate Eu 3+ 、Bi 3+ And Zn 4+ Is completely dissolved in Y 2 O 3 In the crystal lattice. For the emission spectrum of the luminescent material prepared in example 8, the excitation wavelength is 330nm, and as shown in fig. 6, the component has a wider blue light emission region and a narrow red light emission peak, and the ratio of the red to blue light integration area is 1:5.
Example 9: y (Y) 2 O 3 Eu, bi and Ta luminescent material and preparation method thereof
The preparation of the invention92.9mol%Y 2 O 3 :2mol%Eu 3+ ,5mol%Bi 3+ ,0.1mol%Ta 5+ The luminescent material was prepared in a similar manner to example 1, with the only difference that: in the step (S1), the raw material is Y 2 O 3 、Eu 2 O 3 、Bi 2 O 3 、Ta 2 O 5 。
XRD testing of the luminescent material obtained in example 9 was conducted, and as shown in FIG. 1, the XRD diffraction pattern of the powder was shown to be a single cubic Y 2 O 3 Structure, no impurity phase, indicate Eu 3+ 、Bi 3+ And Ta 5+ Is completely dissolved in Y 2 O 3 In the crystal lattice. For the emission spectrum of the luminescent material prepared in example 9, the excitation wavelength was 330nm, and as shown in FIG. 6, the component had a wider blue lightThe emission area and a narrow red emission peak, the ratio of the red-blue integration area is 5:1.
Example 10: y (Y) 2 O 3 Eu, bi and Ni luminescent material and preparation method thereof
The preparation of the invention95.9mol%Y 2 O 3 :0.1mol%Eu 3+ ,3mol%Bi 3+ ,1mol%Ni 2+ The luminescent material was prepared in a similar manner to example 1, with the only difference that: in the step (S1), the raw material is Y 2 O 3 、Eu 2 O 3 、Bi 2 O 3 、NiO。
XRD testing of the luminescent material obtained in example 9 was conducted, and as shown in FIG. 1, the XRD diffraction pattern of the powder was shown to be a single cubic Y 2 O 3 Structure, no impurity phase, indicate Eu 3+ 、Bi 3+ And Ta 5+ Is completely dissolved in Y 2 O 3 In the crystal lattice. For the emission spectrum of the luminescent material prepared in example 10, the excitation wavelength is 330nm, and as shown in fig. 6, the component has a wider blue light emission region and a narrow red light emission peak, and the ratio of the red to blue light integration area is 2:1.
Comparative example
Group A: preparation of Y 2 O 3 Eu, bi and Mn fluorescent powder, the chemical formula of which is the same as that of the example 1, is prepared by adopting a chemical precipitation method, and the specific preparation process is as follows:
accurately weigh 0.92mmol of Y 2 O 3 Eu 0.05mmol 2 O 3 Bi of 0.01mmol 2 O 3 Mn of 0.02mmol 2 O 3 The mixed oxide is dissolved in 5ml of dilute nitric acid with the concentration of 6mol/L, the solution is heated for 10 hours at the temperature of 80 ℃, redundant dilute nitric acid is evaporated in the heating process, and finally mixed rare earth nitrate powder is obtained after drying for 24 hours at the temperature of 80 ℃.
Adding vector urea into the obtained mixed powder to prepare 200mL of mixed solution, placing the mixed solution into a water bath kettle at 85 ℃ to react for 5 hours, standing and ageing the precursor obtained by the reaction for 24 hours, performing ultrasonic dispersion, washing the precursor for 10 times by using absolute ethyl alcohol and deionized water, and drying the precursor at 80 ℃ for 24 hours. And (3) placing the dried product into a crucible, sintering for 3 hours at 700 ℃ in a muffle furnace, and cooling to room temperature along with the furnace to obtain the fluorescent powder.
As shown in FIG. 6, the emission peak intensities of the red light wave band and the blue light wave band are reduced, mainly because the reaction rate of the product is faster in the precipitation process, the precipitated product is generally an aggregate of nano particles and has a random morphology, so that the emission intensity is reduced.
Group B: preparation of Y by solid phase method 2 O 3 Bi, mn phosphor, chemical formula and preparation method are similar to example 1, except that Eu is not doped in this group.
The luminescence properties of the materials prepared in this group were measured, as shown in FIG. 6, from which it can be seen that Y 2 O 3 Bi, mn luminescent material (prepared in example 1) has a blue emission band of a broad band at 400nm, which blue emission band is blue shifted, no red emission is generated, and the intensity is lower than that of example one. This is due to the fact that in Y 2 O 3 In the substrate, eu ion doped replaces C in the substrate 2 And S is 6 Lattice sites, eu ion radius (0.095 a) is larger than Y ion radius (0.089 a), and after doping, the crystal volume becomes large, causing the surrounding crystal field environment to change. Mn ions are sensitive to the environment of a crystal field, and the environment of the crystal field where the Mn ions are positioned when Eu ion doping is not available is unfavorable for the Mn ions 5 T 2 → 5 E transitions, MMCT, which is only Bi ions to Mn ions, thus only emitting blue light and being weak in intensity.
Group C: the high-temperature solid phase method is adopted to prepare YAG Eu, bi and Mn fluorescent powder, the chemical formula of the fluorescent powder is the same as that of the example 1, and the preparation process is as follows:
y is stoichiometrically mixed with 2 O 3 、Ei 2 O 3 、Al(OH) 3 、Mn 2 O 3 The superfine raw material powder is mixed and placed in a nylon ball milling tank according to the molar ratio of 6:9:40:5, absolute ethyl alcohol is added as a dispersing agent, and the mass ratio of the dispersing agent to the material is 2:1. Placing a nylon ball milling tank in a planetary ball mill to obtain a ball-material ratioIs 1: ball milling for 24 hours under the condition of 2. After ball milling is completed, pouring the materials into a beaker, and putting the beaker into an electrothermal constant-temperature blast drying oven for drying for 12 hours, wherein the temperature of the drying oven is 80 ℃. The dried powder was ground and then sieved with an 80 mesh sieve.
Pouring the sieved powder into a crucible, and placing the crucible in a box-type resistance furnace for sintering into a phase. The sintering temperature is 1300 ℃, the heat preservation time is 3 hours, wherein the temperature rise system is 5 ℃/min below 1000 ℃, the temperature above 1000 ℃ is 2 ℃/min, and the temperature reduction system is 100 ℃/h.
As shown in FIG. 6, the light-emitting performance of the materials prepared by the group is measured, and the activator and the sensitizer with the same doping amount have larger change in the emission spectrum of the YAG substrate, only have red light wavelength at 610nm, have lower intensity and no blue light emission, thus proving that the TM ions almost have no transition in the YAG substrate, and the d-d transition of the TM ions is prevented by the field environment of the substrate YAG.
Group D: preparation of Y by high temperature solid phase method 2 O 3 Excitation spectra and emission spectra of Eu, bi, mn phosphors (provided in example 1 of the present invention) and commercial blue phosphors (commercial phosphors purchased from Baotou rare earth institute), commercial red phosphors (commercial phosphors purchased from Baotou rare earth institute), as shown in FIG. 2. As can be seen from the graph, the fluorescence powder prepared by the invention has higher emission peak intensity of the excitation wave Duan Fengjiang in ultraviolet band and red and blue light than commercial blue and red fluorescence powder.
Claims (5)
1. A broadband ultraviolet excited, red and blue dual-band emitted yttria-based luminescent material, characterized in that the luminescent material is represented by the formula:（100-x-y-z）mol%Y 2 O 3: xmol%Eu 3+ ,ymol%Bi 3+ ,zmol%TM ，wherein the method comprises the steps of，x=0.1-5，y=0.1-5，z=0.1-5; TM is one of Mn, cu, co, ti, V, zn, W, ta, ni;
the fluorescent powder has single c-Y 2 O 3 The Eu ions, bi ions and TM ions are completely dissolved in Y 2 O 3 In the crystal lattice, fluorescent powderThe grain size is 5-10 mu m, the shape is regular, and the grain size is approximately spherical;
the preparation method of the yttrium oxide-based luminescent material capable of emitting light in the ultraviolet excitation, red and blue dual-band is carried out sequentially according to the following steps:
(S1) ball milling
Y is set to 2 O 3 、Eu 2 O 3 、Bi 2 O 3 The transition metal oxide TMO is weighed according to the proportion of the expression of the luminescent material, and is put into a ball milling tank together with a dispersing agent, and the ball milling tank is put into a planetary ball mill for ball milling for 6-12 hours to obtain A;
(S2) drying and grinding
Drying the material A in an electrothermal constant temperature blast drying oven at 80-200deg.C for 12-48h, grinding the dried material, and sieving with 80-300 mesh sieve to obtain material B;
(S3) sintering
And (3) placing the B in a crucible, sintering the B in a resistance furnace under the air atmosphere, sieving the sintered powder by 80-300 meshes, and placing the sieved fluorescent powder in a drying oven for storage to obtain the final luminescent material.
2. The method for preparing the yttrium oxide-based luminescent material with ultraviolet excitation and red and blue dual-band emission according to claim 1, wherein the dispersing agent is ethanol, and the mass of the dispersing agent is equal to that of the raw material Y 2 O 3 、Eu 2 O 3 、Bi 2 O 3 The total mass ratio of the transition metal oxide TMO is 2-4:1.
3. The method for preparing the yttria-based luminescent material with ultraviolet excitation in a wide band and emission in both red and blue bands according to claim 1, wherein in the step (S3), the sintering process is a sectional sintering, specifically comprising the following steps:
a first temperature rising stage: heating to 800-1000 deg.C from room temperature;
a second temperature rising stage: raising the temperature from the first stage to 1100-1300 ℃, and preserving the heat by 2-5 h;
and (3) a cooling stage: cooling with furnace or cooling to room temperature at 50-200deg.C/h.
4. The method for preparing the yttrium oxide-based luminescent material with broadband ultraviolet excitation and red and blue dual-band emission according to claim 3, wherein the heating rate of the first temperature stage is 5-10 ℃/min; the temperature rising rate of the second temperature rising stage is 1-5 ℃/min.
5. The method for preparing the yttrium oxide-based luminescent material capable of emitting ultraviolet excitation in a broadband and emitting red and blue light in a dual band according to claim 3, wherein the luminescent material can be excited by ultraviolet excitation in a broadband of 190-275nm and 300-400nm, emits blue light and red light simultaneously, and has an internal quantum yield of more than 80%.
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| JP2013046621A (en) * | 2012-10-03 | 2013-03-07 | Mitsubishi Chemicals Corp | Lighting device for growing plant |
| CN115557709A (en) * | 2022-11-09 | 2023-01-03 | 苏州大学 | Anti-reflection type light conversion glass film layer and preparation method thereof |
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| JP2013046621A (en) * | 2012-10-03 | 2013-03-07 | Mitsubishi Chemicals Corp | Lighting device for growing plant |
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