CN101705087A - Ultraviolet excited warm white luminous fluorescent thin film and method for preparing same - Google Patents
Ultraviolet excited warm white luminous fluorescent thin film and method for preparing same Download PDFInfo
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- CN101705087A CN101705087A CN200910233450A CN200910233450A CN101705087A CN 101705087 A CN101705087 A CN 101705087A CN 200910233450 A CN200910233450 A CN 200910233450A CN 200910233450 A CN200910233450 A CN 200910233450A CN 101705087 A CN101705087 A CN 101705087A
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Abstract
The invention relates to an ultraviolet excited warm white illuminating fluorescent thin film and a method for preparing the same, and belongs to the technical field of solid state illumination. The method comprises the following steps of: firstly, preparing Li-doped ZnO colloidal solution; then impregnating a cleaned substrate into the colloidal solution, and slowly pulling so as to coat a layer of even colloidal film on the substrate; performing drying preprocessing on the colloidal film to remove an organic solvent in the film; repeating the steps for many times, and obtaining ZnO: Li thin films with different thicknesses; and finally, carrying out thermal treatment at the helium gas atmosphere to obtain a ZnO: Li fluorescent thin film. The method has the advantages that: a sol-gel method used for preparing the thin film has the advantages of simple equipment, low consumption, available large-area thin film and the like. Because the thin film is prepared by pulling in even sol, the doping uniformity can reach a molecular level. The thin film prepared by the method can emit intense warm white light when excited by the ultraviolet light after the thermal treatment, and the warm white light has warmer and more comfortable visual effect than standard white light.
Description
Technical field
The present invention relates to solid-state illumination (Solid state lighting) technical field, be specifically related to a kind of ZnO:Li fluorescence membrane that under ultraviolet excitation, can launch warm white and preparation method thereof.
Background technology
Modern times, lighting industry was lighted human night because of coming out one after another of incandescent light, luminescent lamp and high-voltage gas discharging light.White light emitting diode has advantages such as volume is little, the life-span long, response is fast, energy-conserving and environment-protective and is regarded as surmounting the former of new generation pollution-free green solid-state illumination light source owing to it.Comparatively sophisticated at present white light LEDs technology is the white light emitting device that utilizes gan (GaN) blue light-emitting diode to make in conjunction with yellow fluorescent material by Japanese Ri Ya chemical company.With yellow fluorescent powder Y
3Al
5O
12: Ce
3+Be coated on the GaN diode of emission blue light, fluorescent material be subjected to the blue-light excited sodium yellow that sends, with the white light that can produce high brightness after blue light that blue light diode is sent mixes.In addition, adopt the UV-light tube core to excite three primary colors fluorescent powder can also realize white light emission.Three primary colors fluorescent powder generally adopts the blended way to make, owing to exist color to absorb between the mixture and proportioning regulation and control problem, makes the luminous efficiency and the color rendition performance of the white light LEDs that this method of employing obtains be a greater impact again.Therefore, the panchromatic single white emitting fluorescent powder of preparation near ultraviolet excitation becomes at present the research and development focus in this field in the world.Literature search shows that the white light single-phase phosphor of succeeding in developing mostly is the multi-component oxide system (as Chinese patent ZL200710045887.6) that contains activator both at home and abroad.
Generally speaking, fluorescent material is coated on the use that relates to polymer bonding agent in the process on semiconductor diode surface.If powder can be made film and directly is coated on the ultraviolet-ray diode surface, the use that then can save organic bond promotes the luminous efficiency of white light LEDs simultaneously.
ZnO as a kind of traditional green fluorescent material, is that the existence because of intrinsic oxygen room has occupied the deep energy level in the forbidden band, but thereby its transmitting green light under the exciting of UV-light.Theoretical Calculation shows, has multiple native defect among the ZnO, except that causing the green emission, also can cause blue light, gold-tinted and red emission (Appl.Phys.Lett.79,2001,943.).How to coordinate the various defect luminescences of ZnO, the single phase fluorescence membrane of preparing the white light emission that covers visible spectrum is with significant.
Summary of the invention
The object of the present invention is to provide a kind of ZnO:Li fluorescence membrane that under ultraviolet excitation, can launch warm white, to obtain the single-phase white luminous fluorescent thin film.
For achieving the above object, in the technical scheme of the present invention, adopt sol-gel method to prepare the ZnO:Li film.At first prepare Li doping ZnO colloidal solution; Then cleaned substrate is impregnated in the above-mentioned colloidal solution, slowly rises with a constant speed subsequently, thereby on substrate, apply the layer of even colloidal film.Colloidal film is carried out further dry pre-treatment to remove the organic solvent in the striping.Repeat the above-mentioned steps several times, obtain the ZnO:Li film of different thickness.Last under helium atmosphere the thermal treatment some hrs can obtain the ZnO:Li fluorescence membrane of emission warm white under ultraviolet excitation.
The preparation method of above-mentioned a kind of ZnO:Li warm white fluorescence membrane, concrete steps are:
1, the preparation of ZnO:Li colloidal solution
A certain amount of analytical pure zinc acetate and lithium hydroxide are under agitation added dehydrated alcohol, add an amount of diethanolamine again. continue to stir 1～2 hour, obtain the precursor colloidal solution of a transparent and stable.
2, substrate cleans
Place deionized water, acetone, dehydrated alcohol to carry out ultrasonic cleaning successively substrate, use a large amount of deionized water rinsings then, place baking oven to dry substrate at last.
3, film preparation
Cleaned in advance Si sheet or other substrates (silica glass, sapphire etc.) are impregnated in the above-mentioned transparent colloidal solution, slowly rise with a constant speed then, thereby on substrate, apply the layer of even colloidal film.Colloidal film is carried out pre-treatment to remove the organic solvent in the striping at 300～400 ℃.Repeat the above-mentioned steps several times, obtain the ZnO:Li film of different thickness.
4, the thermal treatment of film
The ZnO:Li film that obtains is placed tube furnace, under the protection of helium atmosphere, heat-treat, slowly cool to room temperature then at 800 ℃.
Among the above-mentioned preparation method, Zn in the step 1
2+Volumetric molar concentration is 0.3～1.0mol/L; Li/Zn atomic percent ratio is 0.5%～5.0%:1; Zn
2+With the molar concentration rate of diethanolamine be 1: 1.
Among the above-mentioned preparation method, the pull rate of substrate from colloidal sol is 0.1～1.0mm/s in the step 3; Colloidal film is 10 minutes～1 hour at 300～400 ℃ pretreatment time; Multiplicity is 6～12 times; Film thickness is 300nm～1 μ m.
Among the above-mentioned preparation method, heat-up rate is 5～10 ℃/minute in the step 4, and soaking time is 1～2 hour.
The invention has the advantages that sol-gel method that film preparation is adopted has that equipment is simple, low cost, be easy to obtain advantage such as large-area film.Make owing to lift in the colloidal sol of film by homogeneous, can be so that adulterated degree of uniformity reaches the molecular level level.The film that method obtained after heat treatment can be launched the intensive warm white under ultraviolet excitation thus, and with respect to the standard white light, its visual effect is snugness more.
Description of drawings
Fig. 1 is the emmission spectrum figure of embodiment 1 under 325nm He-Cd laser excitation.
Fig. 2 is the emmission spectrum figure of embodiment 2 under 325nm He-Cd laser excitation.
Fig. 3 is the emmission spectrum figure of embodiment 3 under 325nm He-Cd laser excitation.
Fig. 4 is the emmission spectrum figure of embodiment 4 under 325nm He-Cd laser excitation.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
Take by weighing Zn (Ac)
22H
2O (analytical pure) 10.9745g, LiOH (analytical pure) 0.1049g; Above-mentioned medicine is successively added in the 100mL dehydrated alcohol under stirring condition; Measure the 4.8mL diethanolamine, add under stirring condition in the above-mentioned solution, solution is become colorless transparent gradually by muddiness; Continue to stir 2 hours; obtain the colloidal sol of a transparent and stable. the silica glass that cleans up is impregnated in the above-mentioned precursor colloidal sol; utilize crystal pulling method will propose liquid level with the speed of 0.5mm/s; thereby on silica glass, apply the layer of even dissolved glue film. dissolved glue film was carried out pre-treatment 10 minutes at 400 ℃; repeat the dipping of front then; lift; pre-treatment step totally 12 times; obtaining a thickness is the ZnO:Li film of 600nm. the ZnO:Li film is placed tube furnace; under the protection of helium atmosphere; be warming up to 800 ℃ of insulations 1 hour with 5 ℃/minute speed; naturally cool to room temperature subsequently. Figure 1 shows that the emmission spectrum figure of the film that obtains under the 325nm ultraviolet excitation. as seen from the figure; one more weak band edge emission is arranged at the 383nm place; then there is a wide and strong glow peak in whole visible spectrum zone. replenish standard colorimetric observer's spectral tristimulus value x (λ) according to CIE1964; y (λ); z (λ) can calculate
(wherein I (λ) is for recording luminescent spectrum).The cie color coordinate
Its cie color coordinate is (0.36,0.42) as calculated, and visual effect is a warm white.
Embodiment 2:
Take by weighing Zn (Ac)
22H
2O (analytical pure) 10.9745g, LiOH (analytical pure) 0.0420g; Above-mentioned medicine is successively added in the 100mL dehydrated alcohol under stirring condition; Measure the 4.8mL diethanolamine, add under stirring condition in the above-mentioned solution, solution is become colorless transparent gradually by muddiness; Continue to stir 2 hours, obtain the colloidal sol of a transparent and stable.The Si sheet that cleans up is impregnated in the precursor colloidal sol, adopts crystal pulling method will propose liquid level, thereby on the Si sheet, apply the layer of even dissolved glue film with the speed of 1.0mm/s.Dissolved glue film was carried out pre-treatment 30 minutes at 350 ℃, repeat then the front dipping, lift, pre-treatment step totally 6 times, obtaining a thickness is the ZnO:Li film of 300nm.The ZnO:Li film is placed tube furnace, under the protection of helium atmosphere, be warming up to 800 ℃ of insulations 1 hour, naturally cool to room temperature subsequently with 5 ℃/minute speed.Figure 2 shows that the emmission spectrum figure of the film that obtains under the 325nm ultraviolet excitation.As seen from the figure, at the 383nm place one more weak band edge emission is arranged, then have a wide and strong glow peak in whole visible spectrum zone, its cie color coordinate is (0.35,0.39) as calculated, and visual effect is a warm white.
Embodiment 3:
Take by weighing Zn (Ac)
22H
2O (analytical pure) 21.9490g, LiOH (analytical pure) 0.1049g; Above-mentioned medicine is successively added in the 100mL dehydrated alcohol under stirring condition; Measure the 9.7mL diethanolamine, add under stirring condition in the above-mentioned solution, solution is become colorless transparent gradually by muddiness; Continue to stir 2 hours, obtain the colloidal sol of a transparent and stable.The silica glass that cleans up is impregnated in the precursor colloidal sol, utilizes crystal pulling method will propose liquid level, thereby on silica glass, apply the layer of even dissolved glue film with the speed of 1.0mm/s.Dissolved glue film was carried out pre-treatment 1 hour at 300 ℃, repeat then the front dipping, lift, pre-treatment step totally 10 times, obtain the ZnO:Li film that a thickness is about 1 μ m.The ZnO:Li film is placed tube furnace, under the protection of helium atmosphere, be warming up to 800 ℃ of insulations 2 hours, naturally cool to room temperature subsequently with 10 ℃/minute speed.Figure 3 shows that the emmission spectrum figure of the film that obtains under the 325nm ultraviolet excitation.As seen from the figure, at the 383nm place one more weak band edge emission is arranged, then have a wide and strong glow peak in whole visible spectrum zone, its cie color coordinate is (0.35,0.40) as calculated, and visual effect is a warm white.
Embodiment 4:
Take by weighing Zn (Ac)
22H
2O (analytical pure) 10.9745g, LiOH (analytical pure) 0.2098g; Above-mentioned medicine is successively added in the 100mL dehydrated alcohol under stirring condition; Measure the 4.8mL diethanolamine, add under stirring condition in the above-mentioned solution, solution is become colorless transparent gradually by muddiness; Continue to stir 2 hours; obtain the colloidal sol of a transparent and stable. the silica glass that cleans up is impregnated in the precursor colloidal sol; utilize crystal pulling method will propose liquid level with the speed of 0.8mm/s; thereby on silica glass, apply the layer of even dissolved glue film. dissolved glue film was carried out pre-treatment 15 minutes at 400 ℃; repeat the dipping of front then; lift; pre-treatment step totally 10 times; obtaining a thickness is the ZnO:Li film of 500nm. the ZnO:Li film is placed tube furnace; under the protection of helium atmosphere; be warming up to 800 ℃ of insulations 1 hour with 5 ℃/minute speed; naturally cool to room temperature subsequently. Figure 4 shows that the emmission spectrum figure of the film that obtains under the 325nm ultraviolet excitation. as seen from the figure; one more weak band edge emission is arranged at the 383nm place; then there is a wide and strong glow peak in whole visible spectrum zone; its cie color coordinate is (0.38 as calculated; 0.43), visual effect is a warm white.
Claims (10)
1. ultraviolet excited warm white luminous fluorescent thin film is characterized in that: ZnO thin film doped for Li, film can be launched the warm white that covers whole visible spectrum zone under ultraviolet excitation.
2. the described film of claim 1, it is characterized in that: Li/Zn atomic percent ratio is 0.5%～5.0%: 1.
3. the described film of claim 1, it is characterized in that: film thickness is 300nm～1 μ m.
4. the preparation method of the described film of claim 1 is characterized in that: at first prepare Li doping ZnO colloidal solution; Then cleaned substrate is impregnated in the above-mentioned colloidal solution, slowly lifts subsequently, thereby on substrate, apply the layer of even colloidal film; Colloidal film is carried out dry pre-treatment to remove the organic solvent in the striping, repeat the above-mentioned steps several times, obtain the ZnO:Li film of different thickness; Last under helium atmosphere thermal treatment can obtain the ZnO:Li fluorescence membrane of emission warm white under ultraviolet excitation.
5. the preparation method of the described film of claim 4, it is characterized in that: the preparation of colloidal solution is that zinc acetate and lithium hydroxide are under agitation added dehydrated alcohol, adds diethanolamine again, continues to stir 1～2 hour, obtains the precursor colloidal solution of transparent and stable.
6. the preparation method of the described film of claim 5 is characterized in that: Zn
2+Volumetric molar concentration is 0.3～1.0mol/L; Zn
2+With the molar concentration rate of diethanolamine be 1: 1, Li/Zn atomic percent ratio is 0.5%～5.0%: 1.
7. the preparation method of the described film of claim 4 is characterized in that: dip-coating method is adopted in film preparation, and pull rate is 0.1～1.0mm/s.
8. the preparation method of the described film of claim 4, it is characterized in that: the film drying pretreatment temperature is 300～400 ℃, the time is 10 minutes～1 hour.
9. the preparation method of the described film of claim 4 is characterized in that: flood, lift and dry pretreated multiplicity is 6～12 times.
10. the preparation method of the described film of claim 4, it is characterized in that: thermal treatment is: the ZnO:Li film is placed tube furnace, heat-treat at 800 ℃, heat treated heat-up rate is 5～10 ℃/minute, soaking time is 1～2 hour, slowly cools to room temperature then.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102287759A (en) * | 2010-06-15 | 2011-12-21 | 鸿富锦精密工业（深圳）有限公司 | Light guide plate and backlight module |
| CN110655660A (en) * | 2019-09-05 | 2020-01-07 | 北京科技大学 | Preparation method of single fluorescent molecule white light emission hydrogel with stimulus responsiveness |
-
2009
- 2009-10-30 CN CN200910233450A patent/CN101705087A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102287759A (en) * | 2010-06-15 | 2011-12-21 | 鸿富锦精密工业（深圳）有限公司 | Light guide plate and backlight module |
| CN110655660A (en) * | 2019-09-05 | 2020-01-07 | 北京科技大学 | Preparation method of single fluorescent molecule white light emission hydrogel with stimulus responsiveness |
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Application publication date: 20100512 |