CN114854412B - A near-ultraviolet excited narrow-band deep blue luminescent material and its preparation method - Google Patents
A near-ultraviolet excited narrow-band deep blue luminescent material and its preparation method Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000000227 grinding Methods 0.000 claims description 26
- 239000011812 mixed powder Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 26
- 238000000695 excitation spectrum Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 10
- 229910052727 yttrium Inorganic materials 0.000 abstract description 5
- 229910052765 Lutetium Inorganic materials 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 150000001768 cations Chemical group 0.000 abstract description 3
- 238000006862 quantum yield reaction Methods 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 230000003595 spectral effect Effects 0.000 abstract 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 25
- 229910004298 SiO 2 Inorganic materials 0.000 description 24
- 238000005245 sintering Methods 0.000 description 24
- 238000005286 illumination Methods 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 230000008859 change Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 230000009102 absorption Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 229910003443 lutetium oxide Inorganic materials 0.000 description 1
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 230000009103 reabsorption Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/77062—Silicates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明公开了一种近紫外激发的窄带深蓝发光材料及其制备方法，该材料的化学结构式为：Ln2Si2O7:xBi3+，其中Ln为Sc，Gd，Y，Lu中的至少一种，1≤x≤6，其制备方法包含以下步骤：S1：按照化学式Ln2Si2O7:xBi3+中的化学计量比，分别称取含Ln化合物，含Si化合物，含Bi化合物，将化合物混合后研磨均匀，得到混合物；S2：将步骤S1中得到的混合物加热煅烧，然后冷却，得到近紫外激发的窄带深蓝发光材料。本发明通过阳离子取代，将Ln2Si2O7:xBi3+(Ln＝Sc，Gd，Y，Lu)的荧光从450nm调整到403‑422nm，最强的吸收峰位于n‑UV区(370‑380nm),其中，Sc2Si2O7:Bi3+在372nm n‑UV激发下产生403nm深蓝色发光，FWHM为41nm，量子产率为41.2％，具备良好的热稳定性，其在全光谱照明领域应用潜力巨大。
The invention discloses a near-ultraviolet-excited narrow-band deep blue luminescent material and a preparation method thereof. The chemical structural formula of the material is: Ln 2 Si 2 O 7 :xBi 3+ , where Ln is at least one of Sc, Gd, Y, and Lu. One, 1≤x≤6, and its preparation method includes the following steps: S1: According to the stoichiometric ratio in the chemical formula Ln 2 Si 2 O 7 :xBi 3+ , weigh the Ln-containing compound, Si-containing compound, and Bi-containing compound respectively. , mix the compounds and grind them evenly to obtain a mixture; S2: Heat and calcine the mixture obtained in step S1, and then cool it to obtain a near-ultraviolet-excited narrow-band deep blue luminescent material. The present invention adjusts the fluorescence of Ln 2 Si 2 O 7 :xBi 3+ (Ln=Sc, Gd, Y, Lu) from 450nm to 403-422nm through cation substitution, and the strongest absorption peak is located in the n-UV region (370 -380nm), among which, Sc 2 Si 2 O 7 :Bi 3+ produces 403nm deep blue luminescence under 372nm n-UV excitation, with a FWHM of 41nm and a quantum yield of 41.2%. It has good thermal stability and is widely used throughout the world. The application potential in the field of spectral lighting is huge.
Description
Technical Field
The invention relates to a near ultraviolet excited narrow-band deep blue luminescent material and a preparation method thereof.
Background
White light diodes (W-LEDs) have excellent characteristics of high luminous efficiency, good stability, environmental protection, low power consumption, etc., and have been considered as the next generation illumination light source in the past decades; at present, the fluorescent powder is widely applied to white light illumination and is coated with yellow fluorescent powder (YAG: ce) 3+ ) The blue light (InGaN) emitted by the blue light emitting diode (InGaN) has a negative effect on human health, and near ultraviolet (n-UV) white light emitting diodes (W-LEDs) as alternatives have received a great deal of attention from researchers for health reasons.
Near ultraviolet (n-UV) LED (350-380 nm) chips need to be covered with trichromatic (blue, green, red) phosphors to obtain white light, with blue phosphors having been receiving widespread attention. The current reabsorption of blue phosphor in the visible region limits the development of high quality W-LED lighting applications, and blue phosphor is mostly luminescent with long wavelength of 450nm, and obvious cavities appear in the deep blue region 400-450nm, resulting in a decrease in color rendering index (Ra). Therefore, development of deep blue fluorescent powder has important significance for improving Ra and realizing full spectrum W-LED illumination.
Disclosure of Invention
The invention aims to provide a novel narrow-band deep blue luminescent material and a preparation method thereof, which solve the technical problem that the blue fluorescent powder has obvious cavity in the deep blue region of 400-450nm to reduce the color rendering index (Ra), so that the blue fluorescent powder can be used in the field of full spectrum illumination, has simple preparation process and easily obtained raw materials, and is suitable for large-scale production.
The technical scheme for realizing the aim of the invention is as follows:
the near ultraviolet excited narrow-band deep blue luminescent material is characterized by having a chemical structural formula: ln (Ln) 2 Si 2 O 7 :xBi 3 + Wherein Ln is at least one of Sc, gd, Y and Lu, and x is more than or equal to 1 and less than or equal to 6.
According to the invention, the cation substitution is adopted, so that the fluorescence range of the material is adjusted to be extended to 403-422nm from the vicinity of 450nm, the problem that the blue fluorescent powder has obvious cavities in the deep blue region of 400-450nm can be effectively solved, the color rendering index of the blue fluorescent powder is stable, and the blue fluorescent powder has important significance for realizing full-spectrum W-LED illumination.
Under PL excitation spectrum, the main emission peak of the near ultraviolet excited narrow-band deep blue luminescent material is 403 nm-422 nm.
The preparation method of the novel near ultraviolet excited narrow-band deep blue luminescent material comprises the following steps:
s1: according to chemical formula Ln 2 Si 2 O 7 :xBi 3+ Respectively weighing Ln-containing compound, si-containing compound and Bi-containing compound, mixing the compounds, and grinding uniformly to obtain a mixture;
and S2, heating and calcining the mixture obtained in the step S1, and then cooling to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
In the step S1, since the degree of mixing of the reactants has a great influence on the uniformity and sufficiency of the reaction, it is necessary to increase the uniformity and sufficiency of the reaction between the raw materials so that the reactants are sufficiently contacted with each other to promote the progress of the reaction.
In step S2, the Ln-containing compound and the Si-containing compound react at a high temperature to form a host lattice, bi at a high temperature 3+ Will enter the matrix lattice to replace Ln in the matrix lattice 3+ The lattice structure is not changed, so that the fluorescence can be adjusted from 422nm to 403nm, the luminescence gap of the original material is made up, and the deep blue luminescence is enhanced.
Further, the Ln-containing compound in the step S1 is at least one of scandium oxide, yttrium oxide, lutetium oxide, and gadolinium oxide.
Further, the Si-containing compound in the step S1 is silica.
Further, the Bi-containing compound in the step S1 is Bi 2 O 3 。
Further, in step S2, the operation method of the heating and calcining is as follows: the mixed powder was heated at 900 ℃ for 4 hours, and then the pre-calcined powder was sintered at 1400 ℃ for 5 hours.
The mixture can be sufficiently calcined at high temperatures to allow for sufficient reaction between the individual compounds.
The preparation method of the preparation steps is simple, the raw materials are easy to obtain, the atmosphere protection is not needed in the preparation process,
by adopting the technical scheme, the invention has the following beneficial effects:
(1) Ln is substituted by cations 2 Si 2 O 7 :xBi 3+ The fluorescence of (Ln=Gd, Y, lu, sc) is adjusted from 450nm to 403-422nm, the strongest absorption peak is located in the n-UV region (370-380 nm), wherein Sc 2 Si 2 O 7 :Bi 3+ Generating 403nm deep blue hair under 372nm n-UV excitationThe light has FWHM of 41nm and quantum yield of 41.2%, has good thermal stability, and has great application potential in the field of full spectrum illumination.
(2) The narrow-band deep blue luminescent material excited by near ultraviolet is prepared by taking Ln-containing compounds, si-containing compounds, bi-containing compounds and the like as raw materials, the raw materials are easy to obtain, and in the operation process, all the compounds are only required to be mixed, ground and calcined, protective atmosphere is not required, and the method is simple to operate and suitable for large-scale production.
Drawings
In order that the invention may be more readily understood, a further detailed description of the invention will be rendered by reference to specific embodiments thereof, in which
FIG. 1 shows a near ultraviolet excited narrow-band deep blue light emitting material Sc prepared in example 1 of the present invention 2 Si 2 O 7 :Bi 3+ XRD and SEM spectra of (a);
FIG. 2 shows a narrow-band deep blue phosphor Sc excited by near ultraviolet light prepared in examples 1 to 6 of the present invention 2 Si 2 O 7 :xBi 3+ PL excitation spectrum of (c);
FIG. 3 shows a near ultraviolet excited narrow-band deep blue luminescent material Gd prepared in examples 7 to 12 of the present invention 2 Si 2 O 7 :xBi 3+ PL emission spectrum of (2);
FIG. 4 shows a near ultraviolet excited narrow-band deep blue luminescent material Y prepared in examples 13 to 18 of the present invention 2 Si 2 O 7 :xBi 3+ PL emission spectrum of (2);
FIG. 5 shows a near ultraviolet excited narrow-band deep blue light emitting material Lu prepared in examples 19 to 24 of the present invention 2 Si 2 O 7 :xBi 3+ PL emission spectrum of (2);
Detailed Description
In order to better understand the above technical solution, the following detailed description will explain the above technical solution in conjunction with specific embodiments of the specification.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the invention generally described and illustrated herein may be arranged and designed in a wide variety of different configurations.
Accordingly, the following detailed description of the embodiments of the invention 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 those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: sc (Sc) 2 Si 2 O 7 :Bi 3+ The preparation process comprises the following steps:
s1: according to formula Sc 2 Si 2 O 7 :Bi 3+ Stoichiometric ratio of Sc is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 2
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: sc (Sc) 2 Si 2 O 7 :2Bi 3+ The preparation process comprises the following steps:
s1: according to formula Sc 2 Si 2 O 7 :2Bi 3+ Stoichiometric ratio of Sc is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 3
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: sc (Sc) 2 Si 2 O 7 :3Bi 3+ The preparation process comprises the following steps:
s1: according to the chemical formula SSc 2 Si 2 O 7 :3Bi 3+ Stoichiometric ratio of Sc is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 4
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: sc (Sc) 2 Si 2 O 7 :4Bi 3+ The preparation process comprises the following steps:
s1: according to formula Sc 2 Si 2 O 7 :4Bi 3+ Stoichiometric ratio of Sc is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 5
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: sc (Sc) 2 Si 2 O 7 :5Bi 3+ The preparation process comprises the following steps:
s1: according to formula Sc 2 Si 2 O 7 :5Bi 3+ Stoichiometric ratio of Sc is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Will be combined intoMixing the materials, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 6
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: sc (Sc) 2 Si 2 O 7 :6Bi 3+ The preparation process comprises the following steps:
s1: according to formula Sc 2 Si 2 O 7 :6Bi 3+ Stoichiometric ratio of Sc is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Diffraction peaks of the samples obtained in examples 1 to 6 above were combined with Sc 2 Si 2 O 7 Standard card (PDF # 20-1037) was compared and scanned on its surface to obtain FIG. 1, which is available from FIG. 1, showing Bi 3+ The introduction of the (C) does not cause the change of the crystal structure, and the synthesized sample has a pure cubic phase structure and good chemical stability.
The samples obtained in examples 1 to 6 were tested to obtain PL excitation spectra, which were shown in FIG. 2, with a main emission peak of 403nm, an excitation spectrum of 250 to 400nm, and an excitation intensity of Bi 3+ The concentration change is firstly increased and then decreased, and the near ultraviolet excitation peak is stronger at 372nm and is matched with a commercial n-UV LED chip; the position of the emission peak follows Bi 3+ The concentration variation remained unchanged, indicating Sc 2 Si 2 O 7 :Bi 3+ Can be used as a candidate material for full spectrum W-LED illumination.
The test shows that the FWHM is 41nm, the quantum yield is 41.2%, and the thermal stability is good
In the above test:
XRD testing was performed using a Miniflex 600 x-ray diffractometer from Japan;
SEM test adopts a Czech Apreo S LoVac field emission scanning electron microscope to obtain a transmission electron microscope;
the luminescence performance test adopts an Edinburgh FLS920 spectrometer in England with a 450W xenon lamp and an R928 photomultiplier;
reagents were purchased from manufacturers such as the ALA Ding Huaxue reagent Co.
Example 7
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: gd (Gd) 2 Si 2 O 7 :Bi 3+ The preparation process comprises the following steps:
s1: according to chemical formula Gd 2 Si 2 O 7 :Bi 3+ The stoichiometric ratio of Gd is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 8
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: gd (Gd) 2 Si 2 O 7 :2Bi 3+ The preparation process comprises the following steps:
s1: according to chemical formula Gd 2 Si 2 O 7 :2Bi 3+ The stoichiometric ratio of Gd is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 9
This embodimentProvides a near ultraviolet excited narrow-band deep blue luminescent material, which has the chemical structural formula: gd (Gd) 2 Si 2 O 7 :3Bi 3+ The preparation process comprises the following steps:
s1: according to chemical formula Gd 2 Si 2 O 7 :3Bi 3+ The stoichiometric ratio of (1) is respectively weighed to contain Gd 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 10
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: gd (Gd) 2 Si 2 O 7 :4Bi 3+ The preparation process comprises the following steps:
s1: according to chemical formula Gd 2 Si 2 O 7 :4Bi 3+ The stoichiometric ratio of Gd is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 11
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: gd (Gd) 2 Si 2 O 7 :5Bi 3+ The preparation process comprises the following steps:
s1: according to chemical formula Gd 2 Si 2 O 7 :5Bi 3+ The stoichiometric ratio of Gd is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 12
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: gd (Gd) 2 Si 2 O 7 :6Bi 3+ The preparation process comprises the following steps:
s1: according to chemical formula Gd 2 Si 2 O 7 :6Bi 3+ The stoichiometric ratio of Gd is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
The samples of examples 7 to 12 were tested to give different Bi' s 3+ Concentration of + The PL excitation spectrum under the excitation spectrum is shown in figure 3, the excitation intensity of the PL excitation spectrum is firstly increased or decreased along with the change of Bi, the maximum value is obtained when x=5, the main emission peak is 422nm, the excitation spectrum is a wide band of 250-400 nm, and the PL excitation spectrum has a stronger near ultraviolet excitation peak (372 nm) and is matched with a commercial n-UV LED chip; the position of the emission peak is along with Bi 3+ The change in concentration remained unchanged, indicating Gd 2 Si 2 O 7 :xBi 3+ Can be used as a candidate material for full spectrum W-LED illumination.
Example 13
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: y is Y 2 Si 2 O 7 :Bi 3+ The preparation process comprises the following steps:
s1: according to chemical formula Y 2 Si 2 O 7 :Bi 3+ The stoichiometric ratio of Y is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 14
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: y is Y 2 Si 2 O 7 :2Bi 3+ The preparation process comprises the following steps:
s1: according to chemical formula Y 2 Si 2 O 7 :2Bi 3+ The stoichiometric ratio of Y is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 15
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: y is Y 2 Si 2 O 7 :3Bi 3+ The preparation process comprises the following steps:
s1: according to chemical formula Y 2 Si 2 O 7 :3Bi 3+ The stoichiometric ratio of Y is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 16
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: y is Y 2 Si 2 O 7 :4Bi 3+ The preparation process comprises the following steps:
s1: according to chemical formula Y 2 Si 2 O 7 :4Bi 3+ The stoichiometric ratio of Y is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 17
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: y is Y 2 Si 2 O 7 :5Bi 3+ The preparation process comprises the following steps:
s1: according to chemical formula Y 2 Si 2 O 7 :5Bi 3+ The stoichiometric ratio of Y is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 18
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: y is Y 2 Si 2 O 7 :6Bi 3+ The preparation process comprises the following steps:
s1: according to chemical formula Y 2 Si 2 O 7 :6Bi 3+ The stoichiometric ratio of Y is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
The samples of examples 13 to 18 were tested to give different Bi' s 3+ The PL excitation spectrum at the concentration is shown in FIG. 4, and the excitation intensity is dependent on Bi 3+ The change of (a) is a downward trend, the main emission peak is monitored to be 412nm, and the excitation light is detectedThe spectrum is a wide band of 250-400 nm, has hump-shaped ultraviolet spontaneous peak and stronger near ultraviolet excitation peak (378 nm), is matched with a commercial n-UV LED chip, and the position of the emission peak is along with Bi 3+ The change in concentration remained unchanged, indicating Y 2 Si 2 O 7 :xBi 3+ Can be used as a candidate material for full spectrum W-LED illumination.
Example 19
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: lu (Lu) 2 Si 2 O 7 :Bi 3+ The preparation process comprises the following steps:
s1: according to the chemical formula Lu 2 Si 2 O 7 :Bi 3+ Stoichiometric ratio of Lu is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 20
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: lu (Lu) 2 Si 2 O 7 :2Bi 3+ The preparation process comprises the following steps:
s1: according to the chemical formula Lu 2 Si 2 O 7 :2Bi 3+ Stoichiometric ratio of Lu is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 21
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: lu (Lu) 2 Si 2 O 7 :3Bi 3+ The preparation process comprises the following steps:
s1: according to the chemical formula Lu 2 Si 2 O 7 :3Bi 3+ Stoichiometric ratio of Lu is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 22
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: lu (Lu) 2 Si 2 O 7 :4Bi 3+ The preparation process comprises the following steps:
s1: according to the chemical formula Lu 2 Si 2 O 7 :4Bi 3+ Stoichiometric ratio of Lu is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 23
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: lu (Lu) 2 Si 2 O 7 :5Bi 3+ The preparation process comprises the following steps:
s1: according to the chemical formula Lu 2 Si 2 O 7 :5Bi 3+ Stoichiometric ratio of Lu is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
Example 24
The embodiment provides a near ultraviolet excited narrow-band deep blue luminescent material, which has a chemical structural formula as follows: lu (Lu) 2 Si 2 O 7 :6Bi 3+ The preparation process comprises the following steps:
s1: according to the chemical formula Lu 2 Si 2 O 7 :6Bi 3+ Stoichiometric ratio of Lu is respectively weighed 2 O 3 、Bi 2 O 3 And SiO 2 Mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and heating the mixed powder for 4 hours at 900 ℃, and then sintering the pre-calcined powder for 5 hours at 1400 ℃ to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
The samples of examples 19 to 24 were tested to obtain Bi at different concentrations 3+ The PL excitation spectrum under the condition is shown in figure 5, the excitation intensity of the PL excitation spectrum is increased and then reduced along with the change of Bi, the maximum value is obtained near x=5, the main emission peak is monitored to be 408nm, the excitation spectrum is a wide band of 250-400 nm, the PL excitation spectrum has a stronger near ultraviolet excitation peak (372 nm) which is matched with a commercial n-UV LED chip, and the position of the emission peak is along with Bi 3+ The concentration change remained unchanged, indicating Lu 2 Si 2 O 7 :xBi 3+ Can be used as a candidate material for full spectrum W-LED illumination.
In summary, the chemical structural formula of the narrow-band deep blue luminescent material is as follows: ln (Ln) 2 Si 2 O 7 :Bi 3+ Wherein Ln is one or more of Sc, gd, Y and Lu, and the blue-deep area (400-450 nm) cavity phenomenon can be effectively improved through cationic substitution, the fluorescence ranges of the blue-deep area and the Lu are 403-422nm, the strongest absorption peak is positioned in the n-UV area (370-380 nm), and the blue-deep area can be used as a candidate material for full-spectrum W-LED illumination.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (7)
1. The near ultraviolet excited narrow-band deep blue luminescent material is characterized by comprising the following chemical structural formula: ln (Ln) 2 Si 2 O 7 :x%Bi 3 + Wherein Ln is Sc, x is more than or equal to 1 and less than or equal to 6.
2. The near ultraviolet excited narrow-band deep blue luminescent material according to claim 1, wherein the main emission peak is 403nm under PL excitation spectrum.
3. The method for preparing the near ultraviolet excited narrow-band deep blue luminescent material according to claim 1 or 2, comprising the following steps:
s1: according to chemical formula Ln 2 Si 2 O 7 :xBi 3+ Respectively weighing Ln-containing compound, si-containing compound and Bi-containing compound, mixing the compounds, and grinding uniformly to obtain a mixture;
s2: and (3) heating and calcining the mixture obtained in the step (S1), and then cooling to obtain the near ultraviolet excited narrow-band deep blue luminescent material.
4. The method for preparing the near ultraviolet excited narrow-band deep blue luminescent material according to claim 3, wherein the method comprises the following steps: the Ln-containing compound in the step S1 is scandium oxide.
5. The method for preparing the near ultraviolet excited narrow-band deep blue luminescent material according to claim 3, wherein the method comprises the following steps: the Si-containing compound in step S1 is silica.
6. The method for preparing the near ultraviolet excited narrow-band deep blue luminescent material according to claim 3, wherein the method comprises the following steps: the Bi-containing compound in the step S1 is bismuth trioxide.
7. The method for preparing the near ultraviolet excited narrow-band deep blue luminescent material according to claim 3, wherein the method comprises the following steps: the heating and calcining operation in the step S2 is to heat the mixed powder at 900 ℃ for 4 hours, and then sinter the pre-calcined powder at 1400 ℃ for 5 hours.
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Non-Patent Citations (2)
| Title |
|---|
| Lin, Jun et al..Luminescence and energy transfer of Bi3+ and R3+ ions in C-Y2Si2O7 (R = Eu, Dy).High Temperature and Materials Science.1997,第36卷(第2/3期),第117-125页. * |
| XIE Guo-Bo.Luminescence and Energy Transfer in Europium and Bismuth Codoped Trisodium Yttrium Silicates.CHIN. PHYS. LETT..2013,第30卷(第8期),第087802(1-5)页. * |
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