CN107163938A - A kind of Ho doping bismuth silicate green emitting phosphor and preparation method thereof - Google Patents
A kind of Ho doping bismuth silicate green emitting phosphor and preparation method thereof Download PDFInfo
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- CN107163938A CN107163938A CN201710373079.6A CN201710373079A CN107163938A CN 107163938 A CN107163938 A CN 107163938A CN 201710373079 A CN201710373079 A CN 201710373079A CN 107163938 A CN107163938 A CN 107163938A
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- bismuth silicate
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7706—Aluminates
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/34—Silicates
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Abstract
A kind of Ho doping bismuth silicate green emitting phosphor, its molecular formula is (Bi1‑xHox)4Si3O12, x is 0.0005 ~ 0.05.The preparation method of above-mentioned fluorophor is additionally provided, reaction raw materials are weighed, raw material is sufficiently mixed, in 700 750 DEG C of pre-sinterings, raw material is ground after natural cooling, then sintered at 800 850 DEG C, the uniform Ho doping bismuth silicate polycrystal powder sintering feed of component is obtained；The sintering feed of synthesis is fitted into platinum crucible of the bottom equipped with BSO seed crystals, then crucible is fitted into decline stove, being adjusted to appropriate location makes raw material fully be melted in burner hearth high-temperature region；After crystal growth terminates, in-situ annealing processing is carried out, the crucible that will be equipped with growing crystal goes back up to constant temperature zone position in burner hearth, is annealed at a temperature of 800 900 DEG C, produce a kind of Ho doping bismuth silicate green emitting phosphor.By the way that the obtained crystalline material integrality of method of the present invention is good, quality is high.
Description
Technical field
The invention belongs to materialogy field, it is related to a kind of luminescent material, specifically a kind of Ho doping bismuth silicate green glow
Fluorophor and preparation method thereof.
Background technology
LED is light emitting diode（Light Emitting Diode）Abbreviation, with its it is intrinsic the characteristics of, such as work the longevity
Life is long, power consumption is low, the response time is short and is easy to dim, mixes colours, the features such as controllability is big, and the light source made of LED
The environmental contaminants such as mercury, the lead commonly used in the absence of conventional lamp, LED is increasingly becoming first choice " green " light of illumination application
Source.They be widely used in indicator lamp, signal lamp, display screen or used in expect obtain colored light other application in.With it is glimmering
Light powder is compared, and monocrystalline not only has good chemical stability, heat endurance and photostability, and the Cycle-symmetry of crystal
Structure makes the active ions in monocrystalline have higher luminous efficiency.Therefore, using monocrystalline as fluorophor, it can obtain stability more
The good, LED that working life is longer, luminous efficiency is higher.
Bi silicate crystals（Bi4Si3O12, BSO）It is a kind of fast timing weight scintillation crystal, its sunset glow die-away time is short, irradiation
Hardness is high, transparent in visible region.Meanwhile, BSO crystal has good light again as a kind of common multi-functional crystal
Electrical characteristics and outstanding physical and chemical performance, are easier to grow large-size crystals, and process is simple, while cost
It is relatively low.In addition, BSO crystal is due to the particularity of itself crystal structure, is a very good doped substrate material
Material so that it is very suitable for the fluorophor host material applied as LED.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of Ho doping bismuth silicate green emitting phosphors and
Its preparation method, described this Ho doping bismuth silicate green emitting phosphor and preparation method thereof will solve silicic acid of the prior art
Bismuth crystal perfection is not good, quality less high technical problem.
The invention provides a kind of Ho doping bismuth silicate green emitting phosphors, its molecular formula is (Bi1-xHox)4Si3O12, wherein x
For 0.0005 ~ 0.05.
Present invention also offers a kind of preparation method of above-mentioned Ho doping bismuth silicate green emitting phosphors, including following step
Suddenly：
1) one the step of weigh reaction raw materials, described raw material is Bi2O3、SiO2And Ho2O3, according to molecular formula (Bi1-xHox)4Si3O12In each element chemical composition carry out dispensing, x span is 0.0005 ~ 0.05；
2) one uses the step of two-step sintering method prepares polycrystal raw material, and above-mentioned initial feed is sufficiently mixed uniformly, in 700-
750 DEG C of pre-sintering 8-12 h, naturally cool to after room temperature and to be ground raw material, then sinter at 800-850 DEG C 8-12 h,
Obtain the uniform Ho doping bismuth silicate polycrystal powder sintering feed of component；
3) the step of use Bridgman-Stockbarge method for growing Ho doping bi silicate crystals, by step 2）The sintering feed of synthesis loads bottom
In platinum crucible of the portion equipped with BSO seed crystals, crucible is fitted into decline stove, being adjusted to appropriate location makes raw material be in burner hearth high temperature
Area, Control for Kiln Temperature is at 1075 DEG C -1200 DEG C, and temperature gradient of solid-liquid interface is 35-50 DEG C/cm, and growth rate is controlled in 0.25-
0.5mm/h；After crystal growth terminates, in-situ annealing processing is carried out, the crucible that will be equipped with growing crystal goes back up to perseverance in burner hearth
Warm area position, the 12-15h that annealed at a temperature of 800-900 DEG C produces a kind of Ho doping bismuth silicate green emitting phosphor.
Specifically, described raw material Bi2O3、SiO2And Ho2O3Mol ratio be（1-x）/2：3：X, x span is
0.0005~0.05。
Further, many crucibles can be laid simultaneously in described decline stove stove, realize a stove while growing many crystal.
A kind of preparation method of the monocrystalline of Ho doping bismuth silicate green emitting phosphor of the present invention, using Bridgman-Stockbarger method, thermal field
Stable, production equipment is simple, and easy to operate, production cost is low, and a stove can be put into many crucibles simultaneously（Crucible shape is variable, than
Such as cylinder, rectangular shaped post, tabular）, realize that many crystal grow simultaneously.
The present invention is compared with prior art, and its technological progress is significant.Ho doping bismuth silicate green glows prepared by the present invention
Fluorescence monocrystal material, crystal perfection is good, quality is high, and bright green glow can be sent under ultraviolet irradiation.The system of the present invention
Preparation Method is simple, can be mass, efficiency high, the Ho doping bismuth silicate green emitting phosphor materials that descent method for growing is obtained, crystal
Integrality is good, quality is high, and bright green glow can be sent under ultraviolet irradiation.
Brief description of the drawings
The Ho doping bismuth silicate green emitting phosphor monocrystal material Powder XRD patterns that Fig. 1 is obtained by embodiment 2.
The launching light spectrogram for the Ho doping bismuth silicate green emitting phosphor monocrystalline that Fig. 2 is obtained by embodiment 2.
The CIE diagram for the Ho doping bismuth silicate green emitting phosphor monocrystalline that Fig. 3 is obtained by embodiment 2.
Embodiment
The present invention is further illustrated below by embodiment, but does not limit the present invention.
Embodiment 1
With high-purity Bi2O3、SiO2And Ho2O3For initial feed, by (Bi0.9995Ho0.0005)4Si3O12Molecular formula carries out dispensing, will just
Beginning raw material is sufficiently mixed uniformly, in 700 DEG C of pre-burning 8h.Then raw material is ground, then in 800 DEG C of pre-burning 8h, obtains polycrystalline
Raw material.To be oriented to<001>BSO crystal be seed crystal, the polycrystal material and seed crystal of pre-burning are fitted into cylinder platinum crucible, crucible
It is airtight, it is placed in decline stove and carries out crystal growth.Control for Kiln Temperature at 1075 DEG C, temperature gradient of solid-liquid interface maintain 35 DEG C/
Cm, growth rate is controlled in 0.25mm/h.After end to be grown, crystal is annealed 12h at a temperature of 800 DEG C, with 30 DEG C/h's
Rate of temperature fall, which is cooled to after room temperature, takes out crucible, can obtain transparent cylinder, and molecular formula is (Bi0.9995Ho0.0005)4Si3O12
Green-emitting fluorescent monocrystalline.
Embodiment 2
With high-purity Bi2O3、SiO2And Ho2O3For initial feed, according to (Bi0.999Ho0.001)4Si3O12Molecular formula carries out dispensing, will
Initial feed is sufficiently mixed uniformly, in 720 DEG C of pre-burning 10h.Then raw material is ground, then in 820 DEG C of pre-burning 10h, obtained
Polycrystal raw material.Platinum crucible selects rectangular shaped post, and other specification descent method for growing technique as described in embodiment 1 carries out crystal life
It is long, transparent rectangular shaped post, molecular formula are can obtain for (Bi0.999Ho0.001)4Si3O12Green-emitting fluorescent monocrystalline.
Embodiment 3
With high-purity Bi2O3、SiO2And Ho2O3For initial feed, by (Bi0.99Ho0.01)4Si3O12Molecular formula carries out dispensing, will be initial
Raw material is sufficiently mixed uniformly, in 730 DEG C of pre-burning 11h.Then raw material is ground again in 830 DEG C of pre-burning 11h, polycrystalline is obtained former
Material.Descent method for growing technique carries out crystal growth as described in embodiment 1, and can obtain transparent cylinder, molecular formula is
(Bi0.99Ho0.01)4Si3O12Ho doping bismuth silicate green-emitting fluorescent monocrystalline.
Embodiment 4
With high-purity Bi2O3、SiO2And Ho2O3For initial feed, by (Bi0.98Ho0.02)4Si3O12Molecular formula carries out dispensing, will be initial
Raw material is sufficiently mixed uniformly, in 840 DEG C of pre-burning 12h.Then raw material is ground, then in 840 DEG C of pre-burning 12h, obtains polycrystalline
Raw material.Platinum crucible selection is tabular, and descent method for growing technique carries out crystal growth as described in embodiment 1, can obtain transparent
Tabular, molecular formula are (Bi0.98Ho0.02)4Si3O12Green-emitting fluorescent monocrystalline.
Embodiment 5
With high-purity Bi2O3、SiO2And Ho2O3For initial feed, by (Bi0.95Ho0.05)4Si3O12Molecular formula carries out dispensing molecular formula
Dispensing is carried out, initial feed is sufficiently mixed uniformly, in 750 DEG C of pre-burning 12h.Then raw material is ground, then it is pre- at 850 DEG C
12h is burnt, polycrystal raw material is obtained.Descent method for growing technique carries out crystal growth as described in embodiment 1, can obtain transparent cylinder
Shape, molecular formula is (Bi0.95Ho0.05)4Si3O12Ho doping bismuth silicate green emitting phosphor monocrystalline.
Embodiment 6
The process conditions as described in embodiment 1,2,3,4,5, will<001>The BSO crystal seeds of orientation are put into 10 platinum crucibles, platinum earthenware
The Ho doping bismuth silicate polycrystal powders of identical or different component ratio are reloaded into crucible, 10 different shapes, no can be grown simultaneously
Congruent Ho doping bismuth silicate green-emitting fluorescent monocrystalline.
Above said content is only the basic explanation under present inventive concept, and according to appointing that technical scheme is done
What equivalent transformation, all should belong to protection scope of the present invention.
Claims (4)
- The bismuth silicate green emitting phosphor 1. a kind of Ho adulterates, it is characterised in that：Its molecular formula is (Bi1-xHox)4Si3O12, wherein x is 0.0005~0.05。
- The preparation method of bismuth silicate green emitting phosphor 2. a kind of Ho described in claims 1 adulterates, it is characterised in that including such as Lower step：1）One the step of weigh reaction raw materials, described raw material is Bi2O3、SiO2And Ho2O3, according to molecular formula (Bi1-xHox)4Si3O12In each element chemical composition carry out dispensing, x span is 0.0005 ~ 0.05；2）One uses the step of two-step sintering method prepares polycrystal raw material, and above-mentioned initial feed is sufficiently mixed uniformly, in 700- 750 DEG C of pre-sintering 8-12 h, naturally cool to after room temperature and to be ground raw material, then sinter at 800-850 DEG C 8-12 h, Obtain the uniform Ho doping bismuth silicate polycrystal powder sintering feed of component；3）The step of one use Bridgman-Stockbarge method for growing Ho doping bi silicate crystals, by step 2）The sintering feed of synthesis loads bottom In platinum crucible of the portion equipped with BSO seed crystals, crucible is fitted into decline stove, being adjusted to appropriate location makes raw material be in burner hearth high temperature Area, Control for Kiln Temperature is at 1075 DEG C -1200 DEG C, and temperature gradient of solid-liquid interface is 35-50 DEG C/cm, and growth rate is controlled in 0.25- 0.5mm/h；After crystal growth terminates, in-situ annealing processing is carried out, the crucible that will be equipped with growing crystal goes back up to perseverance in burner hearth Warm area position, the 12-15h that annealed at a temperature of 800-900 DEG C produces a kind of Ho doping bismuth silicate green emitting phosphor（Model is provided Enclose）.
- The preparation method of bismuth silicate green emitting phosphor 3. a kind of Ho as claimed in claim 2 adulterates, it is characterised in that：Described Many crucibles can be laid simultaneously by declining in stove stove, realize a stove while growing many crystal.
- The preparation method of bismuth silicate green emitting phosphor 4. a kind of Ho as claimed in claim 2 adulterates, it is characterised in that：Described Crucible is shaped as cylinder, rectangular shaped post or tabular.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710373079.6A CN107163938A (en) | 2017-05-24 | 2017-05-24 | A kind of Ho doping bismuth silicate green emitting phosphor and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710373079.6A CN107163938A (en) | 2017-05-24 | 2017-05-24 | A kind of Ho doping bismuth silicate green emitting phosphor and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108384533A (en) * | 2018-04-27 | 2018-08-10 | 上海应用技术大学 | A kind of thiazole fluorescent crystal material and preparation method thereof |
| CN110331444A (en) * | 2019-07-09 | 2019-10-15 | 同济大学 | A kind of rare earth ion doped silicate eutectic material and preparation method thereof |
| CN110528077A (en) * | 2019-07-11 | 2019-12-03 | 南京同溧晶体材料研究院有限公司 | A kind of neodymium-doped BGSO mixed crystal material and preparation method thereof |
| CN114232094A (en) * | 2021-12-29 | 2022-03-25 | 上海应用技术大学 | Uranium-doped bismuth silicate scintillation crystal and preparation method thereof |
-
2017
- 2017-05-24 CN CN201710373079.6A patent/CN107163938A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 温裕贤等: "Ho3+掺杂Bi4Si3O12 晶体的生长与光谱特性", 《硅酸盐学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108384533A (en) * | 2018-04-27 | 2018-08-10 | 上海应用技术大学 | A kind of thiazole fluorescent crystal material and preparation method thereof |
| CN110331444A (en) * | 2019-07-09 | 2019-10-15 | 同济大学 | A kind of rare earth ion doped silicate eutectic material and preparation method thereof |
| CN110528077A (en) * | 2019-07-11 | 2019-12-03 | 南京同溧晶体材料研究院有限公司 | A kind of neodymium-doped BGSO mixed crystal material and preparation method thereof |
| WO2021004108A1 (en) * | 2019-07-11 | 2021-01-14 | 南京同溧晶体材料研究院有限公司 | Neodymium-doped bgso mixed crystal material and preparation method therefor |
| CN114232094A (en) * | 2021-12-29 | 2022-03-25 | 上海应用技术大学 | Uranium-doped bismuth silicate scintillation crystal and preparation method thereof |
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Application publication date: 20170915 |