CN105238302A - EVA film used in solar cell packaging - Google Patents

EVA film used in solar cell packaging Download PDF

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CN105238302A
CN105238302A CN201510718821.3A CN201510718821A CN105238302A CN 105238302 A CN105238302 A CN 105238302A CN 201510718821 A CN201510718821 A CN 201510718821A CN 105238302 A CN105238302 A CN 105238302A
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fluorescent material
ultrasonic vibration
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CN105238302B (en
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严梅霞
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Hangzhou Fu Mao photovoltaic materials Co., Ltd.
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严梅霞
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E10/50—Photovoltaic [PV] energy

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Abstract

The invention discloses an EVA film used in solar cell packaging. he EVA film is prepared from the following components, by mass: 80-90 parts of an ethylene-vinyl acetate-based copolymer, 1-2 parts of a crosslinking curing agent, 0.5-2 parts of a silane coupling agent, 0.05-1 part of an antioxidant, 0.5-1 part of a light stabilizer and 6-8 parts of a red-light fluorescent composition. The red-light fluorescent composition accounts for 8% of the total mass of the ethylene-vinyl acetate-based copolymer. The red-light fluorescent composition is YVO4: Eu<3+>, Sr<2+> @ YVO4: Eu<3+>, Bi<3+> or YVO4: Eu<3+>, Sr<2+> @ YVO4: Eu<3+>, Bi<3+> @ Ag @ SiO2 red-light fluorescent composition. The EVA film filled with the red-light fluorescent composition and used in solar cell packaging has high transmittance and low yellowing rate. The red-light fluorescent composition has good dispersion in the EVA film. With the EVA film, solar cell photoelectric conversion rate can be improved.

Description

A kind of EVA adhesive film for solar cell package
Technical field
The present invention relates to a kind of EVA adhesive film for solar cell package being filled with ruddiness fluorescent composition.
Background technology
Theoretical Calculation shows, the limit photoelectric conversion rate of traditional silicon battery is 29%, so only be difficult to improve its effciency of energy transfer further by the improvement of material treatment processes.Solar cell expert B.S.Richards once pointed out, following photoelectric transformation efficiency improves further modulates the solar spectrum mainly relied on input.Because silicon semiconductor has fixing band gap (1.12eV), traditional crystal-silicon solar cell cannot absorb the natural solar energy of conversion completely.The energy arriving the solar infrared spectrum district on ground accounts for 50% of whole solar spectrum energy, but the sunlight only having wavelength to be less than 1100nm could realize opto-electronic conversion in silicon crystal, wavelength be greater than UV-light that the infrared light of 1100nm and wavelength be less than 400nm all cannot utilize by silicon solar cell.Conversion or down-conversion luminescent material in utilization, can modulate the solar spectrum of input, realize the utilization of silicon solar cell to all wave band sunlight, Theoretical Calculation shows: under conventional solar irradiance (AM1.5), and in utilization, the limit efficiency of conversion of silicon solar cell can be improved more than 10% by conversion or lower conversion luminescence.
Existing employing transforms in luminescent material, cannot to absorb completely the UV-light lower than 400nm and the spectrum launched is strong, obvious raising cannot be played to the transformation efficiency of silica-based solar cell, cause the application limitation of up-conversion luminescent material.Meanwhile, when upper conversion luminescent material is applied to EVA adhesive film, there is the shortcoming that dispersion is easily uneven, and the performances such as light transmission are not good.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of EVA adhesive film for solar cell package being filled with ruddiness fluorescent composition, it has high permeability, low xanthate ratio, ruddiness fluorescent composition has good dispersiveness in EVA adhesive film, improves the photoelectric conversion rate of solar cell simultaneously.
Technical problem to be solved by this invention is achieved by the following technical programs:
A kind of EVA adhesive film for solar cell package, composed of the following components according to mass parts: ethylene-vinyl acetate base co-polymer 80 ~ 90 parts, crosslinking and curing agent 1 ~ 2 part, silane coupling agent 0.5 ~ 2 part, antioxidant 0.05 ~ 1 part, photostabilizer 0.5 ~ 1 part and ruddiness fluorescent composition 6 ~ 8 parts, this ruddiness fluorescent composition accounts for 8% of ethylene-vinyl acetate copolymer total mass; Described ruddiness fluorescent composition is YVO 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+or YVO 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+agSiO 2ruddiness fluorescent composition.
The present invention has following beneficial effect: the present invention has following beneficial effect: the EVA adhesive film with light conversion characteristic, the ruddiness fluorescent composition filled fully can absorb the light of 200 ~ 400nm in sunlight, and be converted into ruddiness fluorescence, luminosity is higher, be conducive to the absorption of silicon based cells, improve the photoelectric transformation efficiency of silicon single crystal or polysilicon solar cell, also improve weather-proof resistance to UV aging.
Accompanying drawing explanation
Fig. 1 represents the figure by the determination data of the size distribution of the different fluorescent material obtained, and wherein, 1-1 is that embodiment 1 step 3 obtains YVO 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+the particle size distribution data figure of nucleocapsid fluorescent material; 1-2 is that embodiment 1 step 4 obtains YVO 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+the particle size distribution data figure of ruddiness fluorescent composition; 1-3 is obtained NaYF 4: Yb 3+, Er 3+the particle size distribution data figure of nano-phosphor;
Fig. 2 represents the excitation spectrum of fluorescent material 620nm supervisory wavelength that embodiment 1 to 5 and comparative example 1,2 obtain and the emmission spectrum of 365nm excitation wavelength; Wherein 2-1 to 2-7 represents embodiment 1 to embodiment 5 and the spectrogram corresponding to comparative example 1,2 respectively;
Fig. 3 represents obtained NaYF 4: Yb 3+, Er 3+nano-phosphor is at the emmission spectrum of 980nm excitation wavelength.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be described in detail.
Embodiment 1
One, YVO is prepared 4: Eu 3+, Sr 2+nano-phosphor
(1) by 1.2mmolNa 3vO 412H 2o is dissolved in the mixing solutions containing 5ml ethylene glycol and 2ml distilled water; (2) by above-mentioned solution limit ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir), dropwise instillation contains the Y (NO of the certain proportioning of 1.5mmol below 3) 36H 2o, Eu (NO 3) 3, Sr (NO 3) 2(0.9:0.03:0.07) in 8ml ethylene glycol solution, then ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) 10min clarifies to solution, adds 20ml distilled water; (3) reaction soln is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 200 oinsulation reaction 1h under C, is down to 150 oinsulation reaction 1h under C, after reaction terminates, is cooled to room temperature.Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90 odry 5h under C, obtains the Y of median size 10 ~ 15nm 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor; (5) to Y 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor carries out 500 DEG C of vacuum heat treatment 1h(and is rapidly heated, and heat-treats under preferably fluorescent material being in this annealing temperature when temperature reaches 500 DEG C again), the Y of median size 20 ~ 30nm after acquisition thermal treatment 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor.
Two, YVO is prepared 4: Eu 3+, Bi 3+nano-phosphor
(1) by 1.2mmolNa 3vO 412H 2o is dissolved in the mixing solutions containing 5ml ethylene glycol and 2ml distilled water; (2) above-mentioned solution limit ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) limit is dropwise instilled the Y (NO containing the certain proportioning of 1.5mmol 3) 36H 2o, Eu (NO 3) 3, Bi (NO 3) 3(0.87:0.03:0.1) in 8ml ethylene glycol solution, then ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) 10min clarifies to solution, adds 20ml distilled water; (3) reaction soln is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 180 oinsulation reaction 1.5h under C, after reaction terminates, is cooled to room temperature.Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90 odry 5h under C, obtains the Y that median size is about 10nm 0.87vO 4: Eu 3+ 0.03, Bi 3+ 0.1nano-phosphor.
Three, YVO is prepared 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+nucleocapsid fluorescent material
(1) pre-dispersed: to take the heat treated YVO of 0.1g 4: Eu 3+, Sr 2+nano-phosphor is placed in 10ml ethanol, and carries out ultrasonic agitation (100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) dispersion 30min, obtained solution A; Take 0.008gYVO 4: Eu 3+, Bi 3+nano-phosphor is placed in 10ml ethanol, and carries out ultrasonic agitation (80KHz ultrasonic vibration and 1000r/min centrifugal speed stir) dispersion 15min, obtained solution B; (2) limit ultrasonic agitation (60KHz ultrasonic vibration and 500r/min centrifugal speed stir) solution A, limit dropwise instills solution B; Continue ultrasonic agitation (50KHz ultrasonic vibration and 100r/min centrifugal speed stir) 5min and leave standstill 5min again, centrifugal and clean 3 times with acetone and obtain white precipitates; (4) this is deposited in 90 odry 5h under C, obtains the YVO of median size 40 ~ 60nm 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+nucleocapsid fluorescent material.
Four, YVO is prepared 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+ruddiness fluorescent composition
(1) nucleocapsid fluorescent material ultrasonic agitation (100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) is scattered in ethanol, obtained solution C; Add a certain proportion of (4:1) water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and nucleocapsid fluorescent material after stirring is 1.5:1, and adjust ph is 9, and temperature of reaction is 20 DEG C, reacts 5 hours; Carry out centrifugal and clean 3 acquisition white precipitates with acetone; This is deposited in 90 odry 5h under C, to obtain being coated with SiO 2nucleocapsid fluorescent material; (2) this is coated with SiO 2nucleocapsid fluorescent material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1h, obtain fluorescent material mixture; (3) the fluorescent material mixture of step (2) is immersed in ultrasonic 1h in hydrofluoric acid, removes silicon-dioxide, centrifugal and dry, obtain the YVO of median size 60 ~ 80nm 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+ruddiness fluorescent composition.
Embodiment 2
On basis based on embodiment 1, by the YVO in step 3 4: Eu 3+, Sr 2+with YVO 4: Eu 3+, Bi 3+weight ratio change 1:0.5 into, all the other are identical with embodiment 1.
Embodiment 3
On basis based on embodiment 1, by the YVO in step 3 4: Eu 3+, Sr 2+with YVO 4: Eu 3+, Bi 3+weight ratio change 1:0.001 into, all the other are identical with embodiment 1.
Embodiment 4
One, YVO is prepared 4: Eu 3+, Sr 2+nano-phosphor
(1) by 1.2mmolNa 3vO 412H 2o is dissolved in the mixing solutions containing 5ml ethylene glycol and 2ml distilled water; (2) by above-mentioned solution limit ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir), dropwise instillation contains the Y (NO of the certain proportioning of 1.5mmol below 3) 36H 2o, Eu (NO 3) 3, Sr (NO 3) 2(0.9:0.03:0.07) in 8ml ethylene glycol solution, then ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) 10min clarifies to solution, adds 20ml distilled water; (3) reaction soln is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 200 oinsulation reaction 1h under C, is down to 150 oinsulation reaction 1h under C, after reaction terminates, is cooled to room temperature.Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90 odry 5h under C, obtains the Y of median size 10 ~ 15nm 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor; (5) to Y 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor carries out 500 DEG C of vacuum heat treatment 1h(and is rapidly heated, and heat-treats under preferably fluorescent material being in this annealing temperature when temperature reaches 500 DEG C again), the Y of median size 20 ~ 30nm after acquisition thermal treatment 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor.
Two, YVO is prepared 4: Bi 3+nano-phosphor
(1) by 1.2mmolNa 3vO 412H 2o is dissolved in the mixing solutions containing 5ml ethylene glycol and 2ml distilled water; (2) above-mentioned solution limit ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) limit is dropwise instilled the Y (NO containing the certain proportioning of 1.5mmol 3) 36H 2o, Bi (NO 3) 3(0.87:0.1) in 8ml ethylene glycol solution, then ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) 10min clarifies to solution, adds 20ml distilled water; (3) reaction soln is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 180 oinsulation reaction 1.5h under C, after reaction terminates, is cooled to room temperature.Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90 odry 5h under C, obtains the Y that median size is about 10nm 0.87vO 4: Bi 3+ 0.1nano-phosphor.
Three, YVO is prepared 4: Eu 3+, Sr 2+yVO 4: Bi 3+nucleocapsid fluorescent material
(1) pre-dispersed: to take the heat treated YVO of 0.1g 4: Eu 3+, Sr 2+nano-phosphor is placed in 10ml ethanol, and carries out ultrasonic agitation (100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) dispersion 30min, obtained solution A; Take 0.008gYVO 4: Bi 3+nano-phosphor is placed in 10ml ethanol, and carries out ultrasonic agitation (80KHz ultrasonic vibration and 1000r/min centrifugal speed stir) dispersion 15min, obtained solution B1; (2) limit ultrasonic agitation (60KHz ultrasonic vibration and 500r/min centrifugal speed stir) solution A, limit dropwise instills solution B 1; Continue ultrasonic agitation (50KHz ultrasonic vibration and 100r/min centrifugal speed stir) 5min and leave standstill 5min again, centrifugal and clean 3 times with acetone and obtain white precipitates; (4) this is deposited in 90 odry 5h under C, obtains the YVO of median size 40 ~ 60nm 4: Eu 3+, Sr 2+yVO 4: Bi 3+nucleocapsid fluorescent material.
Four, YVO is prepared 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+nucleocapsid fluorescent material
(1) by 0.05mmolEu (NO 3) 36H 2o ultrasonic disperse in 15ml ethanol solution, by YVO obtained for step 3 4: Eu 3+, Sr 2+yVO 4: Bi 3+nucleocapsid fluorescent material presoma is dispersed in above-mentioned solution; (2) (60KHz ultrasonic vibration and 500r/min centrifugal speed stir) after ultrasonic agitation 60min, reaction soln is left standstill 24h, ion exchange process is fully carried out.Wherein, Eu (NO 3) 36H 2the amount of O is according to chemical formula Y (0.9-x)vO 4: Eu 3+ (x), Bi 3+ (0.1)determine, preferably excessive a little.After reaction terminates, centrifugal, and obtain white precipitate 3 times with dehydrated alcohol and distilled water wash.Finally, 90 ounder C, dry 5h, obtains YVO 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+nucleocapsid fluorescent material.
Five, YVO is prepared 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+ruddiness fluorescent composition
(1) nucleocapsid fluorescent material ultrasonic agitation (100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) is scattered in ethanol, obtained solution C; Add a certain proportion of (4:1) water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and nucleocapsid fluorescent material after stirring is 1.5:1, and adjust ph is 9, and temperature of reaction is 20 DEG C, reacts 5 hours; Carry out centrifugal and clean 3 acquisition white precipitates with acetone; This is deposited in 90 odry 5h under C, to obtain being coated with SiO 2nucleocapsid fluorescent material; (2) this is coated with SiO 2nucleocapsid fluorescent material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1h, obtain fluorescent material mixture; (3) the fluorescent material mixture of step (2) is immersed in ultrasonic 1h in hydrofluoric acid, removes silicon-dioxide, centrifugal and dry, obtain the YVO of median size 60 ~ 80nm 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+ruddiness fluorescent composition.
Embodiment 5
On basis based on embodiment 1 or 4, coated one deck AgSiO again after the ruddiness fluorescent composition prepared 2nanometer film, specifically comprises the steps:
(1), under room temperature, be that the polyvinylpyrrolidone of 10000 is dissolved in 30ml ethylene glycol by 6g molecular-weight average, add 0.25gAgNO while stirring 3until formation clear solution, solution is placed in autoclave, is warming up to 130 DEG C and is incubated 30min, after being cooled to room temperature, after centrifugation, obtain quantum dot nano aluminium powder;
(2) above-mentioned for 0.15g obtained nanometer silver powder ultrasonic agitation 30min(100KHz ultrasonic vibration and 1000r/min centrifugal speed are stirred) be scattered in 30ml dehydrated alcohol and 10ml distilled water; Be that the ammoniacal liquor of 28% and the tetraethoxy TEOS of 0.15ml add in above-mentioned dispersion soln by 1.5ml massfraction, at 20 DEG C, fully stir 4h; Carry out centrifugal and with distilled water and washes of absolute alcohol 3 times, and 80 odry 3h under C, to obtain being coated with SiO 2the AgSiO of median size about 10 nanometer 2-nanometer powder;
(3) take 0.1g ruddiness fluorescent composition and be placed in 10ml ethanol, and carry out ultrasonic agitation (100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) dispersion 30min, obtained solution A1; Take 0.005gAgSiO 2-nanometer powder is placed in 10ml ethanol, and carries out ultrasonic agitation (80KHz ultrasonic vibration and 1000r/min centrifugal speed stir) dispersion 15min, obtained solution B2; Limit ultrasonic agitation (60KHz ultrasonic vibration and 500r/min centrifugal speed stir) solution A 1, limit dropwise instills solution B 2; Continue ultrasonic agitation mixing solutions 5min(50KHz ultrasonic vibration and 100r/min centrifugal speed to stir) leave standstill 5min again, centrifugal and clean 3 times with acetone, and 90 odry 4h under C, obtains the YVO of median size 70 ~ 80nm 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+agSiO 2ruddiness fluorescent composition.
Comparative example 1
One, YVO is prepared 4: Eu 3+, Sr 2+nano-phosphor
(1) by 1.2mmolNa 3vO 412H 2o is dissolved in the mixing solutions containing 5ml ethylene glycol and 2ml distilled water; (2) by above-mentioned solution limit ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir), dropwise instillation contains the Y (NO of the certain proportioning of 1.5mmol below 3) 36H 2o, Eu (NO 3) 3, Sr (NO 3) 2(0.9:0.03:0.07) in 8ml ethylene glycol solution, then ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) 10min clarifies to solution, adds 20ml distilled water; (3) reaction soln is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 200 oinsulation reaction 1h under C, is down to 150 oinsulation reaction 1h under C, after reaction terminates, is cooled to room temperature.Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90 odry 5h under C, obtains the Y of median size 10 ~ 20nm 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor; (5) to Y 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor carries out 500 DEG C of vacuum heat treatment 1h(and is rapidly heated, and heat-treats under preferably fluorescent material being in this annealing temperature when temperature reaches 500 DEG C again), the Y of median size 20 ~ 30nm after acquisition thermal treatment 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor.
Two, YVO is prepared 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+nucleocapsid fluorescent material
By the Y obtained by the first step 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07fluorescent material (1.6mmol) is dispersed in 10ml ethylene glycol solution, and according to R value (nucleocapsid mol ratio, i.e. R=YVO 4: Eu 3+, Ba 2+/ YVO 4: Eu 3+, Bi 3+) calculate, by the Y (NO of certain molar weight 3) 36H 2o, Eu (NO 3) 3, Bi (NO 3) 35H 2o(mol ratio is 0.87:0.03:0.1) add in above-mentioned solution, and ultrasonic vibration 20min; (2) 1.2mmolNa 3vO 412H 2o adds in the mixing solutions containing 5ml ethylene glycol and 2ml distilled water, dropwise instills in (1) gained solution while stirring, add 20ml distilled water after stirring 5min after dissolving completely; (3) gained reaction soln is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml (compactedness 70%), 200 ounder C, isothermal holding 2h, after reaction terminates, cools to room temperature with the furnace.Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) finally this is deposited in 80 ounder C, dry 8h, obtains YVO 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+nano-phosphor.
Three, YVO is prepared 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+ruddiness fluorescent composition
(1) nucleocapsid fluorescent material ultrasonic agitation (100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) is scattered in ethanol, obtained solution C; Add a certain proportion of (4:1) water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and nucleocapsid fluorescent material after stirring is 1.5:1, and adjust ph is 9, and temperature of reaction is 20 DEG C, reacts 5 hours; Carry out centrifugal and clean 3 acquisition white precipitates with acetone; This is deposited in 90 odry 5h under C, to obtain being coated with SiO 2nucleocapsid fluorescent material; (2) this is coated with SiO 2nucleocapsid fluorescent material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1h, obtain fluorescent material mixture; (3) the fluorescent material mixture of step (2) is immersed in ultrasonic 1h in hydrofluoric acid, removes silicon-dioxide, centrifugal and dry, obtain ruddiness fluorescent composition.
Comparative example 2
On basis based on embodiment 1, remove step 3, and in step 4, by heat treated for 1g YVO 4: Eu 3+, Sr 2+nano-phosphor and 0.05gYVO 4: Eu 3+, Bi 3+nano-phosphor mixing ultrasonic agitation (100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) is scattered in ethanol, obtained solution C; All the other are identical with embodiment 1.
Performance test analysis:
The ruddiness fluorescent composition that embodiment 1 is obtained carries out XRD diffraction, bragg peak positions all in diffractogram, relative intensity all with YVO 4standard card (JCPDS17-0341) is consistent, can be characterized by pure Tetragonal YVO 4crystalline structure, does not find other assorted peaks.
Average granulometry: the dispersion liquid obtained with ultrasonic homogenizer process, uses laser diffraction formula particle size distribution device (Shimadzu Seisakusho Ltd.'s system " SALD-7000 ") to measure median size.As can be seen from Figure 1, the YVO of embodiment 1 step 3 acquisition 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+nucleocapsid fluorescent material median size is 40 ~ 60nm; Embodiment 1 step 4 obtains ruddiness fluorescent composition median size 60 ~ 80nm, and nucleocapsid fluorescent material is carried out SiO 2remove again after coated annealing, can effectively prevent fluorescent material agglomeration from occurring and particle increase, the basic median size keeping ruddiness fluorescent composition.
As can be seen from Figure 2, comparative example 1 ruddiness fluorescent composition absorbs with certain broadening, and the band edge of absorption band is to long wavelength's red shift, but it is not very strong in the absorption of the ultraviolet region of short wavelength; Comparative example 2 ruddiness fluorescent composition compares ratio the last 1 in the absorption in short UV light district; Embodiment 1 to 5 ruddiness fluorescent composition absorption band has certain broadening, not only the band edge of absorption band is to long wavelength's red shift, in short UV light district, also there is good absorption at it simultaneously, particularly embodiment 5, absorbing comparatively other embodiments at ultraviolet region absorbs the strongest, is also the strongest equally at the emission peak of 620nm wavelength.
Present invention also offers a kind of EVA adhesive film for solar cell package, it is filled with YVO of the present invention 4: Eu 3+, Ba 2+yVO 4: Eu 3+, Bi 3+ruddiness fluorescent composition or YVO 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+agSiO 2-ruddiness fluorescent composition.This EVA adhesive film is composed of the following components according to mass parts: ethylene-vinyl acetate base co-polymer 80 ~ 90 parts, crosslinking and curing agent 1 ~ 2 part, silane coupling agent 0.5 ~ 2 part, antioxidant 0.05 ~ 1 part, photostabilizer 0.5 ~ 1 part and ruddiness fluorescent composition 6 ~ 8 parts, this ruddiness fluorescent composition accounts for 8% of ethylene-vinyl acetate copolymer total mass.
Embodiment 6 ~ 10, comparative example 3 ~ 5, specifically fills a prescription in table 1.
The preparation method of the EVA adhesive film for solar cell package of embodiment 6 to 9, comparative example 3 to 5, specifically comprises the steps:
(1) ruddiness fluorescent composition is joined in 50ml deionized water, after ultrasonic agitation (80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stir) dispersion 20min, forms solution D, take 1g stearic acid and add in 100ml propyl carbinol and form E solution,
After being mixed by D, E solution, ultrasonic agitation (80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stir) disperses 20min again, put into 120 DEG C of oil bath return stirrings, cool to room temperature after reaction 1h, obtains oil loving ruddiness fluorescent composition after centrifugation, deionized water wash, 90 DEG C of dryings;
(2) after the ruddiness fluorescent composition of ethylene-vinyl acetate base co-polymer, crosslinking and curing agent, silane coupling agent, antioxidant, photostabilizer and oleophylic process being mixed by table 1 weight ratio, drop in casting machine, extrude through plasticizing, stretch, draw, rolling makes EVA adhesive film.
Wherein, the ruddiness fluorescent composition of the ruddiness fluorescent composition of embodiment 6 to 8 obtained by embodiment 1 to 3; The ruddiness fluorescent composition of ruddiness fluorescent composition obtained by embodiment 4 of embodiment 9; The ruddiness fluorescent composition of ruddiness fluorescent composition obtained by embodiment 1 of comparative example 3 to 5.
The preparation method of the EVA adhesive film for solar cell package of embodiment 10: after ethylene-vinyl acetate base co-polymer, crosslinking and curing agent, silane coupling agent, antioxidant, photostabilizer and ruddiness fluorescent composition being mixed by above-mentioned weight ratio, drop in casting machine, extrude through plasticizing, stretch, draw, rolling makes EVA adhesive film.Wherein, the ruddiness fluorescent composition of ruddiness fluorescent composition obtained by embodiment 5.
Invention further provides a kind of EVA adhesive film for solar cell package, it is filled with ruddiness fluorescent composition of the present invention and NaYF 4: Yb 3+, Er 3+fluorescent material.This EVA adhesive film is composed of the following components according to mass parts: ethylene-vinyl acetate base co-polymer 80 ~ 90 parts, crosslinking and curing agent 1 ~ 2 part, silane coupling agent 0.5 ~ 2 part, antioxidant 0.05 ~ 1 part, photostabilizer 0.5 ~ 1 part, ruddiness fluorescent composition 4 ~ 5 parts and NaYF 4: Yb 3+, Er 3+4 ~ 5 parts, fluorescent material.Preferably, ruddiness fluorescent composition and NaYF 4: Yb 3+, Er 3+fluorescent material accounts for 5% of ethylene-vinyl acetate copolymer total mass respectively.
Embodiment 11 ~ 14, specifically fills a prescription in table 1.
The preparation method of the EVA adhesive film for solar cell package of embodiment 11 to 13:
(1) the ruddiness fluorescent composition of embodiment 1 is joined in 50ml deionized water, solution D is formed after ultrasonic agitation (80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stir) dispersion 20min, take 1g stearic acid to add in 100ml propyl carbinol and form E solution, by D, after the mixing of E solution, ultrasonic agitation (80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stir) disperses 20min again, put into 120 DEG C of oil bath return stirrings, cool to room temperature after reaction 1h, through centrifugation, deionized water wash, oil loving ruddiness fluorescent composition is obtained after 90 DEG C of dryings, to NaYF 4: Yb 3+, Er 3+fluorescent material carries out same oleophylic process,
(2) by table 1 weight ratio by the ruddiness fluorescent composition of ethylene-vinyl acetate base co-polymer, crosslinking and curing agent, silane coupling agent, antioxidant, photostabilizer, oleophylic process and NaYF 4: Yb 3+, Er 3+after fluorescent material mixes, drop in casting machine, extrude through plasticizing, stretch, draw, rolling makes EVA adhesive film.
Embodiment 14 is for the preparation method of the EVA adhesive film of solar cell package: by the NaYF of table 1 weight ratio by ethylene-vinyl acetate base co-polymer, crosslinking and curing agent, silane coupling agent, antioxidant, photostabilizer, ruddiness fluorescent composition and oleophylic process 4: Yb 3+, Er 3+after fluorescent material mixes, drop in casting machine, extrude through plasticizing, stretch, draw, rolling makes EVA adhesive film.Wherein, the ruddiness fluorescent composition of ruddiness fluorescent composition obtained by embodiment 5.
Described NaYF 4: Yb 3+, Er 3+the preparation method of fluorescent material is as follows:
(1) 1.8mmolY (NO is taken 3) 36H 2o, 0.17mmolYb (NO 3) 35H 2o, 0.1mmolEr (NO 3) 35H 2o, with 2mmolNaNO 3mixing is also fully dissolved in 15ml ethylene glycol and forms solution F; By 8mmolNH 4f is fully dissolved in 15ml ethylene glycol and forms solution G; Ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) solution F, G30min respectively, at continuation ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) 30min after two solution mixing; Mixing solutions is poured in polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 180 oinsulation reaction 12h under C, is down to 150 oinsulation reaction 4h under C, after reaction terminates, is cooled to room temperature.Gained suspension is poured out, centrifugal and with distilled water and dehydrated alcohol clean successively 3 times obtain fluorescent material; This is deposited in 80 odry 5h under C, obtains the NaYF of median size 30 ~ 60nm 4: Yb 3+, Er 3+nano-phosphor;
(2) by above-mentioned for 0.3g obtained nano NaY F 4: Yb 3+, Er 3+phosphor powder ultrasonic agitation 30min(100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) be scattered in 40ml dehydrated alcohol and 10ml distilled water; Be that the ammoniacal liquor of 28% and the tetraethoxy TEOS of 0.3ml add in above-mentioned dispersion soln by 2ml massfraction, at 20 DEG C, fully stir 4h, obtained NaYF 4: Yb 3+, Er 3+siO 2-powder; Carry out centrifugal and obtain white precipitate 3 times with distilled water and washes of absolute alcohol; This is deposited in 90 odry 5h under C, to obtain being coated with SiO 2naYF 4: Yb 3+, Er 3+nucleocapsid fluorescent material; By this NaYF 4: Yb 3+, Er 3+siO 2nucleocapsid fluorescent material carries out 800 DEG C of thermal treatment 60min under being placed in argon gas atmosphere, obtains fluorescent material mixture; Fluorescent material mixture is immersed in ultrasonic 1h in hydrofluoric acid, removes silicon-dioxide, centrifugal and dry, obtain the NaYF of median size 40 ~ 70nm 4: Yb 3+, Er 3+nano-phosphor, its particle size determination 1-3 as shown in Figure 1, it launches corresponding characteristic peak under 980nm excitation wavelength, is particularly positioned at the highest peak of 655nm, as shown in Figure 3.
It should be noted that, as preferably, can in advance to NaYF 4: Yb 3+, Er 3+nano-phosphor is coated one deck AgSiO again 2or SiO 2nanometer film.Preferably, can respectively by ruddiness fluorescent composition and NaYF 4: Yb 3+, Er 3+nano-phosphor and part EVA resin are pre-mixed and form EVA master batch, then are mixed to form EVA adhesive film with other EVA resin.
The property indices of each embodiment and comparative example EVA adhesive film is measured by the following method:
1, resistance to ultraviolet(ray) radiation energy
Test sample book is the glued membrane multi-disc of 0.5mm.Uv-radiation ageing testing method is International Electrotechnical Commission IEC61345 standard, and test condition is: temperature 60 ± 5 DEG C, wavelength 200 ~ 400nm, irradiation intensity 15KWh/m2.Determination of light transmittance presses GB/T2410 standard, its printing opacity conservation rate=(sample mean transmittance after irradiation/pre-irradiation sample mean transmittance) × 100%.Yellowness index is analyzed according to GB2409-80.Test result is as shown in table 1.
2, wet and heat ageing resistant performance
Wet and heat ageing resistant testing method presses GB/T2423.3 standard, and test condition is: temperature 85 DEG C, relative humidity 85%, time 2000h.Determination of light transmittance presses GB/T2410 standard, its printing opacity conservation rate=(sample mean transmittance after irradiation/pre-irradiation sample mean transmittance) × 100%.Yellowness index is analyzed according to GB2409-80.Test result is as shown in table 1.
The formula of each embodiment of table 1 and comparative example and make the test-results of EVA adhesive film
As can be seen from Table 1, the stripping strength result of the printing opacity conservation rate of gained embodiment 4 to 14, photoelectric conversion rate and glass thereof is obviously better than comparative example, shows the superiority of formula, particularly with the addition of two fluorescent material of planting and obtains better effect.
The above embodiment only have expressed embodiments of the present invention; it describes comparatively concrete and detailed; but therefore can not be interpreted as the restriction to the scope of the claims of the present invention; in every case the technical scheme adopting the form of equivalent replacement or equivalent transformation to obtain, all should drop within protection scope of the present invention.

Claims (5)

1. for an EVA adhesive film for solar cell package, composed of the following components according to mass parts: ethylene-vinyl acetate base co-polymer 80 ~ 90 parts, crosslinking and curing agent 1 ~ 2 part, silane coupling agent 0.5 ~ 2 part, antioxidant 0.05 ~ 1 part, photostabilizer 0.5 ~ 1 part and ruddiness fluorescent composition 6 ~ 8 parts; Described ruddiness fluorescent composition is YVO 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+or YVO 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+agSiO 2ruddiness fluorescent composition.
2. the EVA adhesive film for solar cell package according to claim 1, is characterized in that, ruddiness fluorescent composition accounts for 8% of ethylene-vinyl acetate copolymer total mass.
3. the EVA adhesive film for solar cell package according to claim 1, is characterized in that, YVO 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+ruddiness fluorescent composition carries out oleophylic process in advance.
4., according to the arbitrary described EVA adhesive film for solar cell package of claims 1 to 3, it is characterized in that, described YVO 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+ruddiness fluorescent composition is obtained by following methods:
One, YVO is prepared 4: Eu 3+, Sr 2+nano-phosphor
(1) by 1.2mmolNa 3vO 412H 2o is dissolved in the mixing solutions containing 5ml ethylene glycol and 2ml distilled water; (2) above-mentioned solution limit 80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed are stirred below the dropwise Y (NO of instillation containing the certain proportioning of 1.5mmol 3) 36H 2o, Eu (NO 3) 3, Sr (NO 3) 28ml ethylene glycol solution in, more simultaneously 80KHz ultrasonic vibration and 300r/min centrifugal speed stir 5 ~ 10min and clarify to solution, add 20ml distilled water; (3) reaction soln is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 200 oinsulation reaction 1h under C, is down to 150 oinsulation reaction 1h under C, after reaction terminates, is cooled to room temperature; Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90 ounder C, dry 5h, obtains Y 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor; (5) to Y 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor carries out 500 DEG C of vacuum heat treatment 1h, and after acquisition thermal treatment, median size is 20 ~ 30nmY 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor;
Two, YVO is prepared 4: Eu 3+, Bi 3+nano-phosphor
(1) by 1.2mmolNa 3vO 412H 2o is dissolved in the mixing solutions containing 5ml ethylene glycol and 2ml distilled water; (2) above-mentioned solution limit 80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stirring limit are dropwise instilled the Y (NO containing the certain proportioning of 1.5mmol 3) 36H 2o, Eu (NO 3) 3, Bi (NO 3) 38ml ethylene glycol solution in, more simultaneously 80KHz ultrasonic vibration and 300r/min centrifugal speed stir 5 ~ 10min and clarify to solution, add 20ml distilled water; (3) reaction soln is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 180 oinsulation reaction 1.5h under C, after reaction terminates, is cooled to room temperature; Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90 odry 5h under C, obtaining median size is 10nmY 0.87vO 4: Eu 3+ 0.03, Bi 3+ 0.1nano-phosphor;
Three, YVO is prepared 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+nucleocapsid fluorescent material
(1) pre-dispersed: to take the heat treated YVO of 1g 4: Eu 3+, Sr 2+nano-phosphor is placed in 10ml ethanol, and disperses 30min, obtained solution A under carrying out 100KHz ultrasonic vibration and the stirring of 1000r/min centrifugal speed; Take 0.05gYVO 4: Eu 3+, Bi 3+nano-phosphor is placed in 10ml ethanol, and disperses 15min, obtained solution B under carrying out 80KHz ultrasonic vibration and the stirring of 1000r/min centrifugal speed; (2) limit 60KHz ultrasonic vibration and 500r/min centrifugal speed stirred solution A, limit dropwise instills solution B; Continue 50KHz ultrasonic vibration and 100r/min centrifugal speed to stir 5min and leave standstill 5min again, centrifugal and clean 3 times with acetone and obtain white precipitates; (4) this is deposited in 90 odry 5h under C, obtaining median size is 40 ~ 60nmYVO 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+nucleocapsid fluorescent material;
Four, YVO is prepared 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+ruddiness fluorescent composition
(1) nucleocapsid fluorescent material is scattered in ethanol under 100KHz ultrasonic vibration and 1000r/min centrifugal speed stir, obtained solution C; Additional proportion is water and the ammoniacal liquor of 4:1 afterwards, and the mass ratio adding tetraethoxy and nucleocapsid fluorescent material after stirring is 1.5:1, and adjust ph is 9, and temperature of reaction is 20 DEG C, reacts 5 hours; Carry out centrifugal and clean 3 acquisition white precipitates with acetone; This is deposited in 90 odry 5h under C, to obtain being coated with SiO 2nucleocapsid fluorescent material; (2) this is coated with SiO 2nucleocapsid fluorescent material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1h, obtain fluorescent material mixture; (3) the fluorescent material mixture of step (2) is immersed in ultrasonic 1h in hydrofluoric acid, removes silicon-dioxide, centrifugal and dry, obtain median size 60 ~ 80nm ruddiness fluorescent composition.
5., according to the arbitrary described EVA adhesive film for solar cell package of claims 1 to 3, it is characterized in that, described YVO 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+ruddiness fluorescent composition is obtained by following methods:
One, YVO is prepared 4: Eu 3+, Sr 2+nano-phosphor
(1) by 1.2mmolNa 3vO 412H 2o is dissolved in the mixing solutions containing 5ml ethylene glycol and 2ml distilled water; (2) above-mentioned solution limit 80 ~ 100KHz ultrasonic vibration and 300r/min are dropwise instilled the Y (NO containing the certain proportioning of 1.5mmol below 3) 36H 2o, Eu (NO 3) 3, Sr (NO 3) 28ml ethylene glycol solution in, then 80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stir 10min and clarify to solution, add 20ml distilled water; (3) reaction soln is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 200 oinsulation reaction 1h under C, is down to 150 oinsulation reaction 1h under C, after reaction terminates, is cooled to room temperature; Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90 odry 5h under C, obtains the Y of median size 10 ~ 15nm 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor; (5) to Y 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor carries out 500 DEG C of vacuum heat treatment 1h, the Y of median size 20 ~ 30nm after acquisition thermal treatment 0.9vO 4: Eu 3+ 0.03, Sr 2+ 0.07nano-phosphor;
Two, YVO is prepared 4: Bi 3+nano-phosphor
(1) by 1.2mmolNa 3vO 412H 2o is dissolved in the mixing solutions containing 5ml ethylene glycol and 2ml distilled water; (2) above-mentioned solution limit 80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stirring limit are dropwise instilled the Y (NO containing the certain proportioning of 1.5mmol 3) 36H 2o, Bi (NO 3) 38ml ethylene glycol solution in, then 80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stir 10min and clarify to solution, add 20ml distilled water; (3) reaction soln is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 180 oinsulation reaction 1.5h under C, after reaction terminates, is cooled to room temperature; Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90 odry 5h under C, obtains the Y that median size is about 10nm 0.87vO 4: Bi 3+ 0.1nano-phosphor;
Three, YVO is prepared 4: Eu 3+, Sr 2+yVO 4: Bi 3+nucleocapsid fluorescent material
(1) pre-dispersed: to take the heat treated YVO of 0.1g 4: Eu 3+, Sr 2+nano-phosphor is placed in 10ml ethanol, and carries out 100KHz ultrasonic vibration and 1000r/min centrifugal speed dispersed with stirring 30min, obtained solution A; Take 0.008gYVO 4: Bi 3+nano-phosphor is placed in 10ml ethanol, and carries out 80KHz ultrasonic vibration and 1000r/min centrifugal speed dispersed with stirring 15min, obtained solution B1; (2) limit 60KHz ultrasonic vibration and 500r/min centrifugal speed stirred solution A, limit dropwise instills solution B 1; Continue ultrasonic agitation 50KHz ultrasonic vibration and 100r/min centrifugal speed to stir 5min and leave standstill 5min again, centrifugal and clean 3 times with acetone and obtain white precipitates; (4) this is deposited in 90 odry 5h under C, obtains the YVO of median size 40 ~ 60nm 4: Eu 3+, Sr 2+yVO 4: Bi 3+nucleocapsid fluorescent material;
Four, YVO is prepared 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+nucleocapsid fluorescent material
(1) by 0.05mmolEu (NO 3) 36H 2o ultrasonic disperse in 15ml ethanol solution, by YVO obtained for step 3 4: Eu 3+, Sr 2+yVO 4: Bi 3+nucleocapsid fluorescent material presoma is dispersed in above-mentioned solution; (2), after 60KHz ultrasonic vibration and 500r/min centrifugal speed stir 60min, reaction soln is left standstill 24h; After reaction terminates, centrifugal, and obtain white precipitate 3 times with dehydrated alcohol and distilled water wash; 90 ounder C, dry 5h, obtains YVO 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+nucleocapsid fluorescent material;
Five, YVO is prepared 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+ruddiness fluorescent composition
(1) by nucleocapsid fluorescent material 100KHz ultrasonic vibration and 1000r/min centrifugal speed dispersed with stirring in ethanol, obtained solution C; Additional proportion is water and the ammoniacal liquor of 4:1 afterwards, and the mass ratio adding tetraethoxy and nucleocapsid fluorescent material after stirring is 1.5:1, and adjust ph is 9, and temperature of reaction is 20 DEG C, reacts 5 hours; Carry out centrifugal and clean 3 acquisition white precipitates with acetone; This is deposited in 90 odry 5h under C, to obtain being coated with SiO 2nucleocapsid fluorescent material; (2) this is coated with SiO 2nucleocapsid fluorescent material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1h, obtain fluorescent material mixture; (3) the fluorescent material mixture of step (2) is immersed in ultrasonic 1h in hydrofluoric acid, removes silicon-dioxide, centrifugal and dry, obtain the YVO of median size 60 ~ 80nm 4: Eu 3+, Sr 2+yVO 4: Eu 3+, Bi 3+ruddiness fluorescent composition.
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