CN100532496C - Method for reinforcing fluorescence intensity for rare earth three primary colors phosphor powder - Google Patents
Method for reinforcing fluorescence intensity for rare earth three primary colors phosphor powder Download PDFInfo
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- CN100532496C CN100532496C CNB2006100812495A CN200610081249A CN100532496C CN 100532496 C CN100532496 C CN 100532496C CN B2006100812495 A CNB2006100812495 A CN B2006100812495A CN 200610081249 A CN200610081249 A CN 200610081249A CN 100532496 C CN100532496 C CN 100532496C
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Abstract
The present invention belongs to the field of light emitting and lighting engineering technology, relates to photon crystal applying technology, and is especially method of raising the fluorescence strength of three primary color phosphors and the luminous intensity of lighting device with the Bragg mirror reflection of reverse opal type photon crystal. By means of the forbidden band property of 3D photon crystal, which reflects light in the frequency range of photon forbidden band without transmittance, the reverse opal type photon crystal film is coated with RE phosphor to raise the fluorescence strength by means of the reflecting film of the photon crystal. The present invention has low cost, simple technological process and high light emitting efficiency, and may be applied in display device, auxiliary light source and main light source.
Description
Technical field
The invention belongs to luminous and lighting technical field, relate to the photonic crystal applications technology, relate in particular to the character of utilizing the minute surface reflection of photonic crystal Prague, strengthen the method for fluorescence intensity for rare earth three primary colors phosphor powder, raising illuminating device luminous intensity with counter opal type photonic crystal.
Background technology
Rare-earth trichromatic fluorescent powder be rare-earth ion activated, have light efficiency height, photochromic adjustable characteristics, be one of present most important rare earth luminescent material.The lamp rare-earth trichromatic fluorescent powder is meant mainly that under 254nm is ultraviolet ray excited the emission peak wavelength is near the blue light the 450nm, near the green light the 540nm and near the fluorescent material of the red light the 610nm.
Since nineteen seventies, because energy dilemma, many countries very pay attention to for save energy, and illumination then is an aspect that electricity consumption is more, therefore, carries out research novel, efficient, the power saving lighting source and just becomes a very important problem.Improve the luminous intensity (luminous efficiency) of luminescent material, become improve lighting source one very important approach.
In the process of the luminous efficiency that further improves luminescent material, characteristics such as the physical properties of photonic crystal uniqueness such as forbidden photon band, photon local, for being incorporated into photonic crystal, people provide good theoretical basis in the luminescent device, by changing the geometry of luminescence chip, improve and get optical tech, luminous efficiency is greatly improved.2003, Japanese Matsushita Electric Industrial industry development success luminous efficiency reach original 1.5 times GaN blue LED (LED) chip.This time the blue led chip of exploitation utilizes the modulating properties of the periodic structure of photonic crystal to light, has improved luminous efficiency.The organic luminescent dye of doping perhaps can reach luminous regulation and control and enhancing (Appl.Phys.Lett.2001,79,3573 at its surperficial evaporation luminous organic material in photonic crystal; Chem.Mater.2000,12,2508; Phys.Rev.A, 2000,63,011801.).On the other hand, aspect photonic crystal applications, patent CN:03100044.4 provides the application of a kind of 2 D photon crystal as photoswitch; Patent CN:02159759.6 has invented and can grow the extraordinary two dimensional surface photonic crystal of periodic structure low-light grid on very little space and area, and this grating can be used as light-splitting device in light path; The omnirange that patent CN:200310110550.0 the has invented a kind of photonic crystal film that is all-trans; The patent CN:200510012047.0 of the previous application of the inventor utilizes photonic crystal light in the range of frequency of forbidden photon band not see through and the character that is reflected, the luminous organic material that is complementary at photon crystal surface evaporation and forbidden photon band, thus the luminous efficiency of material improved.And, utilize inverse opal photonic crystal that the raising of inorganic rare earth luminescent material luminous efficiency is not appeared in the newspapers as yet at lighting field.
Summary of the invention
The object of the present invention is to provide a kind of counter opal type photonic crystal to strengthen the method for fluorescence intensity for rare earth three primary colors phosphor powder, the character of utilizing photonic crystal light in the range of frequency of forbidden photon band not see through and being reflected, in order to strengthen the luminous intensity of lamp with rare earth luminescent material, with low cost, technology is simple, luminous efficiency is high, can be applicable to display device, secondary light source and lighting source.
The luminous intensity method of raising rare earth luminescent material of the present invention, its basic demand is on the basis that does not change photon crystal structure, utilize the forbidden photon band character of photonic crystal, spin coating rare-earth trichromatic fluorescent powder film forming on three-dimensional inverse opal photonic crystal film, photonic crystal has the character of reflection to the light of certain wavelength in a certain scope, select for use the rare-earth trichromatic fluorescent powder that is complementary just can reach and make rare-earth trichromatic fluorescent powder fluorescence enhanced effect, thus the luminous intensity of raising rare earth luminescent material.
The method steps that counter opal type photonic crystal of the present invention strengthens fluorescence intensity for rare earth three primary colors phosphor powder comprises:
(1). adopt known technology (method of self-assembly).Select the colloidal crystal emulsion of poly-(vinylbenzene-methyl methacrylate-vinylformic acid) of different-grain diameter for use, concentration is 0.3～0.5wt%, in climatic chamber, it is 70～90 ℃ in temperature, humidity is under 70～90% the condition, adopt the method for self-assembly, the colloidal crystal emulsion is deposited on the opal type photon crystal film that substrate (as glass, silicon chip or stainless steel plate etc.) go up to form different-grain diameter, with this film as template.Film thickness is greatly about 10～20um.
(2). the template that step (1) is obtained immersed in the nano silicasol sol solution (tetraethoxy: dehydrated alcohol: the volume ratio of concentrated hydrochloric acid is 10:4:2) 2～3 hours, took out washing, dried; Or drip at this template surface and to be coated with rare Nano silica sol (tetraethoxy: dehydrated alcohol: the volume ratio of concentrated hydrochloric acid is 3.5:10:0.02); At last at 450～500 ℃ of calcinations of high temperature poly-to remove (vinylbenzene-methyl methacrylate-vinylformic acid) bead, the silicon-dioxide photonic crystal that obtains having the counter opal structure in air aperture is (because silicon sol is in the slit of poly-(vinylbenzene-methyl methacrylate-vinylformic acid) bead, so, can obtain the silicon-dioxide photonic crystal of counter opal structure through sintering).
(3). with binding agent rare-earth trichromatic fluorescent powder is spin-coated on the silicon-dioxide photon crystal surface of the counter opal structure that step (2) obtains, obtains fluorescence intensity enhanced rare-earth trichromatic fluorescent powder.
The mass percent concentration of described rare-earth trichromatic fluorescent powder in the mixture of rare-earth trichromatic fluorescent powder and binding agent is 1～10%.
With barren substrate of glass sample in contrast, fluorescence intensity for rare earth three primary colors phosphor powder increases by 1.5～4.5 times.
The forbidden photon band of the silicon-dioxide photonic crystal of described counter opal structure and the emission peak position of rare-earth trichromatic fluorescent powder are complementary.
The median size of described poly-(vinylbenzene-methyl methacrylate-vinylformic acid) photonic crystal is 320～410nm, is preferably 320nm, 354nm, 400nm or 410nm.
The air aperture average out to 228～321nm of the silicon-dioxide photonic crystal of described counter opal structure is preferably 228nm, 265nm, 315nm or 321nm.
Described rare-earth trichromatic fluorescent powder is selected from a kind of in rare-earth trichromatic blue powder, the green powder of rare-earth trichromatic, rare-earth trichromatic rouge and powder, the long afterglow fluorescent material etc.
The emission main peak position of described rare-earth trichromatic blue powder, the green powder of rare-earth trichromatic, rare-earth trichromatic rouge and powder and long afterglow fluorescent material exists respectively: blue powder: 450nm; Green powder: 487,543,583nm, wherein 543nm is the main peak position; Rouge and powder: 589,610,628nm, wherein 610nm is the main peak position; Long persistence luminescent powder: 501nm.
The chemical constitution of described rare-earth trichromatic blue powder, the green powder of rare-earth trichromatic, rare-earth trichromatic rouge and powder and long afterglow fluorescent material is respectively: blue powder: BaMgAl
10O
11: Eu
2+, green powder: (Ce, Tb) MgAl
11O
19, rouge and powder: Y
2O
3: Eu, long persistence luminescent powder SrAl
2O
4: Eu, Dy.
Described binding agent is mineral binder bond or organic binder bond.
Described mineral binder bond is a Nano silica sol, and organic binder bond is the aqueous solution of acrylate.
Among the preparation method of the present invention, basic demand to the selection of inverse opal photonic crystal and fluorescent material is: the forbidden photon band position of photonic crystal and the emission peak position of fluorescent material are complementary, be that the reflection peak position of photonic crystal and the emission peak position of fluorescent material are close, thereby the photonic crystal effect that could have reflection to the fluorescence that fluorescent material sends reach the purpose that strengthens fluorescence intensity like this.The kind of used opal type photonic crystal template has: (emulsion of 320～410nm) poly-(vinylbenzene-methyl methacrylate-vinylformic acid) deposits film forming by self-assembly to the different-grain diameter size; The air pore size of used counter opal silicon-dioxide photonic crystal is 228～321nm.
Among the preparation method of the present invention, the collocation method of used nano silicasol sol solution can be: 10 milliliters tetraethoxy and 4 milliliters of dehydrated alcohols mix, and under agitation slowly splash into 1 milliliter of mass concentration then and be 37% hydrochloric acid, stir several minutes and get final product; Perhaps 3.5 milliliters tetraethoxy and 10 milliliters of dehydrated alcohols mix, and under agitation splash into 0.02 milliliter of mass concentration then and be 37% hydrochloric acid, stir 4 hours.
The present invention mainly is a forbidden photon band character of utilizing three-D photon crystal, the character that promptly can not see through and be reflected for light in the range of frequency of forbidden photon band, spin coating fluorescent RE powder on the inverse opal photonic crystal film, the effect of photonic crystal reflectance coating make the fluorescence intensity of fluorescent material thing that very big enhancing be arranged.The present invention is with low cost, technology is simple, luminous efficiency is high, can be applicable to display device, secondary light source and lighting source.
The invention has the advantages that:
1. the inventive method is simple, with low cost, can prepare luminous flat by larger area.
2. the present invention is greatly improved the fluorescence intensity of rare-earth trichromatic fluorescent powder, luminous efficiency.
3. the present invention has extremely important practical application meaning for the raising of lighting source luminous efficiency.
Description of drawings
Fig. 1. the fluorescent emission spectrogram of the rare-earth trichromatic fluorescent powder that the present invention is used.
Fig. 2. the reflection spectrogram of the counter opal silicon-dioxide photonic crystal that the embodiment of the invention 1,2,3,4,5,6,7 air apertures vary in size.
Fig. 3 A. embodiment of the invention 1 air pore size is the stereoscan photograph of the counter opal silicon-dioxide photonic crystal of 228nm;
Fig. 3 B. embodiment of the invention 2,3 air pore sizes are the stereoscan photograph of the counter opal silicon-dioxide photonic crystal of 265nm;
Fig. 3 C. embodiment of the invention 4,7 air pore sizes are the stereoscan photograph of the counter opal silicon-dioxide photonic crystal of 315nm;
Fig. 3 D. embodiment of the invention 5,6 air pore sizes are the stereoscan photograph of the counter opal silicon-dioxide photonic crystal of 321nm.
Fig. 4. the embodiment of the invention 1 rare-earth trichromatic blue powder is spin-coated on the comparison diagram of brilliant film of light and fluorescence spectrum on glass respectively.
Fig. 5. the embodiment of the invention 2 long afterglow fluorescent material are spin-coated on the comparison diagram of brilliant film of light and fluorescence spectrum on glass respectively.
Fig. 6. the embodiment of the invention 3 long afterglow fluorescent material are spin-coated on the comparison diagram of brilliant film of light and fluorescence spectrum on glass respectively.
Fig. 7. the green powder of the embodiment of the invention 4 rare-earth trichromatics is spin-coated on the comparison diagram of brilliant film of light and fluorescence spectrum on glass respectively.
Fig. 8. the embodiment of the invention 5 rare-earth trichromatic rouge and powder are spin-coated on the comparison diagram of brilliant film of light and fluorescence spectrum on glass respectively.
The contrast of the reflection spectrum of the counter opal silicon-dioxide photonic crystal that the fluorescence spectrum of Fig. 9 A. embodiment of the invention 1 rare-earth trichromatic blue powder and air aperture are 228nm;
The contrast of the reflection spectrum of the counter opal silicon-dioxide photonic crystal that the fluorescence spectrum of the green powder of Fig. 9 B. embodiment of the invention 4 rare-earth trichromatics and air aperture are 315nm;
The contrast of the reflection spectrum of the counter opal silicon-dioxide photonic crystal that the fluorescence spectrum of Fig. 9 C. embodiment of the invention 5 rare-earth trichromatic rouge and powder and air aperture are 321nm.
Specific embodiments
Below in conjunction with embodiment technical scheme of the present invention is described further.
Embodiment 1
1) used copolymer emulsion ball is that the emulsion of poly-(vinylbenzene-methyl methacrylate-vinylformic acid) 0.3wt% of size average out to 320nm is at climatic chamber (LHS-100CL climatic chamber, Shanghai one permanent Science and Technology Ltd.) it is 70 ℃ in temperature in, humidity is that self-assembly is deposited on the substrate of glass under 70% the condition, obtains opal type photon crystal film.Film thickness is greatly about 5～15um.
2) 10 milliliters of mass concentrations are that tetraethoxy and 4 milliliters of dehydrated alcohols of 28% mix, and under agitation slowly splash into 1 milliliter of mass concentration then and be 37% hydrochloric acid, stir several minutes, promptly prepare silicon sol solution.
3) be template with opal type photon crystal film, immerse in the above-mentioned silicon sol and soaked 3 hours that washing is dried then.
4) in retort furnace in 500 ℃ of calcinations 3 hours, remove polymer globules, promptly obtain having the silicon-dioxide photonic crystal of the counter opal structure in air aperture.
5), measure air pore size average out to 228nm with the surface topography (seeing accompanying drawing 3A) of scanning electron microscopic observation (S of HIT-3000N scanning electronic microscope) counter opal silicon-dioxide photonic crystal.
6) reflection spectrum (UV of Hitachi-4100 ultraviolet-visual spectrometer) of survey counter opal silicon-dioxide photonic crystal is seen accompanying drawing 2.
7) mass percent is accounted for 3% rare-earth trichromatic blue powder (BaMgAl
10O
11: Eu
2+) with acrylate aqueous solution ball milling, be spin-coated on counter opal silicon-dioxide photon crystal surface film forming (the desk-top sol evenning machine of KW4A type, the Microelectronics Center, Academia Sinica) then, simultaneously on blank glass with identical speed also spin-coating film as reference.
8) survey the fluorescence spectrum (F-4500 of Hitachi fluorescence spectrophotometer) of brilliant film of counter opal light and rare-earth trichromatic blue powder on glass respectively, see accompanying drawing 4.
9) fluorescence spectrum of the reflection spectrum of counter opal silicon-dioxide photonic crystal and three primary colours blue powder is contrasted, see accompanying drawing 9A.
From accompanying drawing 4 as can be seen, rare-earth trichromatic blue powder is spin-coated on fluorescence intensity ratio on the brilliant film of counter opal silicon-dioxide light and is spin-coated on tangible enhancing is arranged on the glass surface, its reason is because the photon band gap of the emission peak position (450nm) of blue powder and counter opal silicon-dioxide light crystalline substance just in time is complementary (seeing accompanying drawing 9A), be that the light that sends of blue powder is in the forbidden photon band of light crystalline substance, can not see through and can be reflected, so fluorescence strengthens.Sum up by embodiment 1 that its fluorescence intensity is on glass 4 times behind spin coating three primary colours blue powder on the brilliant film of counter opal silicon-dioxide light.
1) used copolymer emulsion ball is that the emulsion of poly-(vinylbenzene-methyl methacrylate-vinylformic acid) 0.3wt% of size average out to 354nm is 80 ℃ in temperature in climatic chamber, humidity is that self-assembly is deposited on the substrate of glass under 80% the condition, obtains opal type photon crystal film.Film thickness is greatly about 5～15um.
2) 10 milliliters of mass concentrations are that tetraethoxy and 4 milliliters of dehydrated alcohols of 28% mix, and under agitation slowly splash into 1 milliliter of mass concentration then and be 37% hydrochloric acid, stir several minutes, promptly prepare silicon sol solution.
3) be template with opal type photon crystal film, immerse in the above-mentioned silicon sol and soaked 2 hours that washing is dried then.
4) in retort furnace in 500 ℃ of calcinations 3 hours, remove polymer globules, promptly obtain having the silicon-dioxide photonic crystal of the counter opal structure in air aperture.
5), measure air pore size average out to 265nm with the surface topography (seeing accompanying drawing 3B) of scanning electron microscopic observation counter opal silicon-dioxide photonic crystal.
6) reflection spectrum of survey counter opal silicon-dioxide photonic crystal is seen accompanying drawing 2.
7) mass percent is accounted for 4% long afterglow fluorescent material (SrAl
2O
4: Eu, Dy), be spin-coated on counter opal silicon-dioxide photon crystal surface film forming then with acrylate aqueous solution ball milling, simultaneously on blank glass with identical speed also spin-coating film as reference.
8) survey the fluorescence spectrum (501nm) of brilliant film of counter opal light and long afterglow fluorescent material on glass respectively, see accompanying drawing 5.
9) fluorescence spectrum of the reflection spectrum of counter opal silicon-dioxide photonic crystal and long afterglow fluorescent material is contrasted.
Sum up by embodiment 2 that its fluorescence intensity is on glass 2.3 times behind spin coating long afterglow fluorescent material on the brilliant film of counter opal silicon-dioxide light.
Embodiment 3
1) used copolymer emulsion ball is that the emulsion of poly-(vinylbenzene-methyl methacrylate-vinylformic acid) 0.3wt% of size average out to 354nm is 80 ℃ in temperature in climatic chamber, humidity is that self-assembly is deposited on the substrate of glass under 80% the condition, obtains opal type photon crystal film.Film thickness is greatly about 5～10um.
2) 10 milliliters of mass concentrations are that tetraethoxy and 4 milliliters of dehydrated alcohols of 28% mix, and under agitation slowly splash into 1 milliliter of mass concentration then and be 37% hydrochloric acid, stir several minutes, promptly prepare silicon sol solution.
3) be template with opal type photon crystal film, immerse in the above-mentioned silicon sol and soaked 3 hours that washing is dried then.
4) in retort furnace in 500 ℃ of calcinations 3 hours, remove polymer globules, promptly obtain having the silicon-dioxide photonic crystal of the counter opal structure in air aperture.
5), measure air pore size average out to 265nm with the surface topography (seeing accompanying drawing 3B) of scanning electron microscopic observation counter opal silicon-dioxide photonic crystal.
6) reflection spectrum of survey counter opal silicon-dioxide photonic crystal is seen accompanying drawing 2.
7) mass percent is accounted for 1% long afterglow fluorescent material (SrAl
2O
4: Eu, Dy), be spin-coated on counter opal silicon-dioxide photon crystal surface film forming then with the Nano silica sol mixing and ball milling, simultaneously on blank glass with identical speed also spin-coating film as reference.
8) survey the fluorescence spectrum (501nm) of brilliant film of counter opal light and long afterglow fluorescent material on glass respectively, see accompanying drawing 6.
9) fluorescence spectrum of the reflection spectrum of counter opal silicon-dioxide photonic crystal and long afterglow fluorescent material is contrasted.
Sum up by embodiment 3 that its fluorescence intensity is on glass 1.5 times behind spin coating long afterglow fluorescent material on the brilliant film of counter opal silicon-dioxide light.
1) used copolymer emulsion ball is that the emulsion of poly-(vinylbenzene-methyl methacrylate-vinylformic acid) 0.5wt% of size average out to 400nm is 80 ℃ in temperature in climatic chamber, humidity is that self-assembly is deposited on the substrate of glass under 70% the condition, obtains opal type photon crystal film.Film thickness is greatly about 10～20um.
2) 3.5 milliliters of mass concentrations are that tetraethoxy and 10 milliliters of dehydrated alcohols of 28% mix, and under agitation splash into 0.02 milliliter of mass concentration then and be 37% hydrochloric acid, stir 4 hours, promptly prepare silicon sol solution.
3) be template with opal type photon crystal film, template vertically placed that silicon sol drips to template surface, till drenching with the surface, dries, and repeats once.
4) in retort furnace in 450 ℃ of calcinations 6 hours, remove polymer globules, promptly obtain having the silicon-dioxide photonic crystal of the counter opal structure in air aperture.
5), measure air pore size average out to 315nm with the surface topography (seeing accompanying drawing 3C) of scanning electron microscopic observation counter opal silicon-dioxide photonic crystal.
6) reflection spectrum of survey counter opal silicon-dioxide photonic crystal is seen accompanying drawing 2.
7) mass percent is accounted for 5% the green powder of rare-earth trichromatic ((Ce, Tb) MgAl
11O
19) with the aqueous solution ball milling of acrylate, be spin-coated on counter opal silicon-dioxide photon crystal surface film forming then, simultaneously on blank glass with identical speed also spin-coating film as reference.
8) survey the fluorescence spectrum of brilliant film of counter opal light and the green powder of rare-earth trichromatic on glass respectively, see accompanying drawing 7.
9) fluorescence spectrum of the reflection spectrum of counter opal silicon-dioxide photonic crystal and the green powder of rare-earth trichromatic is contrasted, see accompanying drawing 9B.
Accompanying drawing 7 as can be seen, the green powder of rare-earth trichromatic is spin-coated on fluorescence intensity ratio on the brilliant film of counter opal silicon-dioxide light and is spin-coated on tangible enhancing is arranged on the glass surface, its reason is because the photon band gap of the emission peak position (543nm) of green powder and counter opal silicon-dioxide light crystalline substance just in time is complementary (seeing accompanying drawing 9B), be that the light that sends of green powder is in the forbidden photon band of light crystalline substance, can not see through and can be reflected, so fluorescence strengthens.Sum up by embodiment 4 that its fluorescence intensity is on glass 4.5 times behind the green powder of spin coating rare-earth trichromatic on the brilliant film of counter opal silicon-dioxide light.
1) used copolymer emulsion ball is that the emulsion of poly-(vinylbenzene-methyl methacrylate-vinylformic acid) 0.5wt% of size average out to 410nm is 90 ℃ in temperature in climatic chamber, humidity is under 90% the condition on the self-assembly deposition substrate of glass, obtains opal type photon crystal film.Film thickness is greatly about 10～20um.
2) 3.5 milliliters of mass concentrations are that tetraethoxy and 10 milliliters of dehydrated alcohols of 28% mix, and under agitation splash into 0.02 milliliter of mass concentration then and be 37% hydrochloric acid, stir 4 hours, promptly prepare silicon sol solution.
3) be template with opal type photon crystal film, template vertically placed that silicon sol drips to template surface, till drenching with the surface, dries, and repeats once.
4) in retort furnace in 450 ℃ of calcinations 6 hours, remove polymer globules, promptly obtain having the silicon-dioxide photonic crystal of the counter opal structure in air aperture.
5), measure air pore size average out to 321nm with the surface topography (seeing accompanying drawing 3D) of scanning electron microscopic observation counter opal silicon-dioxide photonic crystal.
6) reflection spectrum of survey counter opal silicon-dioxide photonic crystal is seen accompanying drawing 2.
7) mass percent is accounted for 2% rare-earth trichromatic rouge and powder (Y
2O
3: Eu), be spin-coated on counter opal silicon-dioxide photon crystal surface film forming then with the aqueous solution ball milling of acrylate, simultaneously on blank glass with identical speed also spin-coating film as reference.
8) survey the fluorescence spectrum of brilliant film of counter opal light and rare-earth trichromatic rouge and powder on glass respectively, see accompanying drawing 8.
9) fluorescence spectrum of the reflection spectrum of counter opal silicon-dioxide photonic crystal and rare-earth trichromatic rouge and powder is contrasted, see accompanying drawing 9C.
Accompanying drawing 8 as can be seen, the green powder of rare-earth trichromatic is spin-coated on fluorescence intensity ratio on the brilliant film of counter opal silicon-dioxide light and is spin-coated on tangible enhancing is arranged on the glass surface, its reason is because the photon band gap of the emission peak position (610nm) of rouge and powder and counter opal silicon-dioxide light crystalline substance just in time is complementary (seeing accompanying drawing 9C), be that the light that sends of rouge and powder is in the forbidden photon band of light crystalline substance, can not see through and can be reflected, so fluorescence strengthens.Sum up by embodiment 5 that its fluorescence intensity is on glass 3.7 times behind spin coating rare-earth trichromatic rouge and powder on the brilliant film of counter opal silicon-dioxide light.
Intensity rate such as following table when the different triphosphor Fluorescent Powders of the foregoing description are spin-coated on glass and the brilliant film of counter opal light:
| Embodiment | Embodiment 1 | |
|
|
| Fluorescent RE powder | Blue powder | Long persistence luminescent powder | Green powder | Rouge and powder |
| Intensity rate (I The light crystalline substance/I Glass) | 4 | 2.3/1.5 | 4.5 | 3.7 |
Embodiment 6
1) used copolymer emulsion ball is that the emulsion of poly-(vinylbenzene-methyl methacrylate-vinylformic acid) 0.5wt% of size average out to 410nm is 70 ℃ in temperature in climatic chamber, humidity is under 80% the condition on the self-assembly deposition substrate of glass, obtains opal type photon crystal film.Film thickness is greatly about 10～20um.
2) 3.5 milliliters of mass concentrations are that tetraethoxy and 10 milliliters of dehydrated alcohols of 28% mix, and under agitation splash into 0.02 milliliter of mass concentration then and be 37% hydrochloric acid, stir 4 hours, promptly prepare silicon sol solution.
3) be template with opal type photon crystal film, template vertically placed that silicon sol drips to template surface, till drenching with the surface, dries, and repeats once.
4) in retort furnace in 450 ℃ of calcinations 6 hours, remove polymer globules, promptly obtain having the silicon-dioxide photonic crystal of the counter opal structure in air aperture.
5), measure air pore size average out to 321nm with the surface topography (seeing accompanying drawing 3D) of scanning electron microscopic observation counter opal silicon-dioxide photonic crystal.
6) reflection spectrum of survey counter opal silicon-dioxide photonic crystal is seen accompanying drawing 2.
7) mass percent is accounted for 10% rare-earth trichromatic rouge and powder (Y
2O
3: Eu), be spin-coated on counter opal silicon-dioxide photon crystal surface film forming then with the aqueous solution ball milling of acrylate, simultaneously on blank glass with identical speed also spin-coating film as reference.
Other experiment condition is with embodiment 5.
Embodiment 7
1) used copolymer emulsion ball is that the emulsion of poly-(vinylbenzene-methyl methacrylate-vinylformic acid) 0.5wt% of size average out to 400nm is 80 ℃ in temperature in climatic chamber, humidity is under 80% the condition on the self-assembly deposition substrate of glass, obtains opal type photon crystal film.Film thickness is greatly about 10～20um.
2) 3.5 milliliters of mass concentrations are that tetraethoxy and 10 milliliters of dehydrated alcohols of 28% mix, and under agitation splash into 0.02 milliliter of mass concentration then and be 37% hydrochloric acid, stir 4 hours, promptly prepare silicon sol solution.
3) be template with opal type photon crystal film, template vertically placed that silicon sol drips to template surface, till drenching with the surface, dries, and repeats once.
4) in retort furnace in 450 ℃ of calcinations 6 hours, remove polymer globules, promptly obtain having the silicon-dioxide photonic crystal of the counter opal structure in air aperture.
5), measure air pore size average out to 315nm with the surface topography (seeing accompanying drawing 3C) of scanning electron microscopic observation counter opal silicon-dioxide photonic crystal.
6) reflection spectrum of survey counter opal silicon-dioxide photonic crystal is seen accompanying drawing 2.
7) mass percent is accounted for 8% the green powder of rare-earth trichromatic ((Ce, Tb) MgAl
11O
19) with the aqueous solution ball milling of acrylate, be spin-coated on counter opal silicon-dioxide photon crystal surface film forming then, simultaneously on blank glass with identical speed also spin-coating film as reference.
Other experiment condition is with embodiment 4.
Claims (15)
1. a method that strengthens fluorescence intensity for rare earth three primary colors phosphor powder is characterized in that, this method may further comprise the steps:
(1). select the colloidal crystal emulsion of poly-(vinylbenzene-methyl methacrylate-vinylformic acid) of different-grain diameter for use, concentration is 0.3～0.5wt%, in climatic chamber, it is 70～90 ℃ in temperature, humidity is under 70～90% the condition, adopt the method for self-assembly, the colloidal crystal emulsion is deposited in the substrate opal type photon crystal film that forms different-grain diameter, with this film as template;
(2). the template that step (1) is obtained immerses in the nano silicasol sol solution, takes out washing, dries; Or drip at this template surface and to be coated with rare Nano silica sol; At 450～500 ℃ of calcinations of high temperature poly-to remove (vinylbenzene-methyl methacrylate-vinylformic acid) bead, obtain having the silicon-dioxide photonic crystal of the counter opal structure in air aperture;
(3). with binding agent rare-earth trichromatic fluorescent powder is spin-coated on the silicon-dioxide photon crystal surface of the counter opal structure that step (2) obtains, obtains fluorescence intensity enhanced rare-earth trichromatic fluorescent powder;
Described template submerged nano silicasol sol solution is made up of tetraethoxy, dehydrated alcohol and concentrated hydrochloric acid, wherein tetraethoxy: dehydrated alcohol: the volume ratio of concentrated hydrochloric acid is 10:4:1;
Described is coated with rare Nano silica sol and is made up of tetraethoxy, dehydrated alcohol and concentrated hydrochloric acid, wherein tetraethoxy: dehydrated alcohol: the volume ratio of concentrated hydrochloric acid is 3.5:10:0.02.
2. method according to claim 1 is characterized in that: the mass percent concentration of described rare-earth trichromatic fluorescent powder in the mixture of rare-earth trichromatic fluorescent powder and binding agent is 1～10%.
3. method according to claim 1 is characterized in that: the forbidden photon band of the silicon-dioxide photonic crystal of described counter opal structure and the emission peak position of rare-earth trichromatic fluorescent powder are complementary.
4. method according to claim 1 is characterized in that: the median size of described poly-(vinylbenzene-methyl methacrylate-vinylformic acid) photonic crystal is 320～410nm.
5. method according to claim 4 is characterized in that: the particle diameter of described poly-(vinylbenzene-methyl methacrylate-vinylformic acid) photonic crystal is 320nm, 354nm, 400nm or 410nm.
6. according to claim 1 or 3 described methods, it is characterized in that: the air aperture average out to 228～321nm of the silicon-dioxide photonic crystal of described counter opal structure.
7. method according to claim 6 is characterized in that: the air aperture of the silicon-dioxide photonic crystal of described counter opal structure is 228nm, 265nm, 315nm or 321nm.
8. according to claim 1,2 or 3 described methods, it is characterized in that: described rare-earth trichromatic fluorescent powder is selected from a kind of in rare-earth trichromatic blue powder, the green powder of rare-earth trichromatic, the rare-earth trichromatic rouge and powder.
9. according to claim 1,2 or 3 described methods, it is characterized in that: described rare-earth trichromatic fluorescent powder is a long afterglow fluorescent material.
10. method according to claim 8 is characterized in that: the emission main peak position of described rare-earth trichromatic blue powder, the green powder of rare-earth trichromatic, rare-earth trichromatic rouge and powder exists respectively: blue powder: 450nm; Green powder: 487,543,583nm, wherein 543nm is the main peak position; Rouge and powder: 589,610,628nm, wherein 610nm is the main peak position.
11. method according to claim 9 is characterized in that: the emission main peak position of described long afterglow fluorescent material is at 501nm.
12. method according to claim 8 is characterized in that: the chemical constitution of described rare-earth trichromatic blue powder, the green powder of rare-earth trichromatic, rare-earth trichromatic rouge and powder is respectively: blue powder: BaMgAl
10O
11: Eu
2+Green powder: (Ce, Tb) MgAl
11O
19Rouge and powder: Y
2O
3: Eu.
13. method according to claim 9 is characterized in that: the chemical constitution of described long afterglow fluorescent material is SrAl
2O
4: Eu, Dy.
14. method according to claim 10 is characterized in that: the chemical constitution of described rare-earth trichromatic blue powder, the green powder of rare-earth trichromatic, rare-earth trichromatic rouge and powder is respectively: blue powder: BaMgAl
10O
11: Eu
2+, green powder: (Ce, Tb) MgAl
11O
19, rouge and powder: Y
2O
3: Eu.
15. method according to claim 11 is characterized in that: the chemical constitution of described long afterglow fluorescent material is SrAl
2O
4: Eu, Dy.
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| CN111218279A (en) * | 2019-11-06 | 2020-06-02 | 北京科技大学 | Cr (chromium)3+Doped near-infrared long-afterglow luminescent material and preparation and application methods thereof |
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