CN109280551B - Fluorine oxide fluorescent powder of high photosynthetic efficiency and preparation method thereof and semiconductor light-emitting apparatus - Google Patents
Fluorine oxide fluorescent powder of high photosynthetic efficiency and preparation method thereof and semiconductor light-emitting apparatus Download PDFInfo
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- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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Abstract
The invention belongs to luminescent material technical fields, and in particular to a kind of fluorine oxide fluorescent powder of high photosynthetic efficiency and preparation method thereof and semiconductor light-emitting apparatus.The chemical general formula of the fluorine oxide fluorescent powder is AxM2‑xD1‑y‑zSeyF6‑xOx:zMn4+；Wherein, A be selected from Ba, Mg, Sr and Zn at least one of, M is selected from least one of Li, Na and K, and D is selected from least one of Si, Ge and Ti, and 0.01≤x≤1,0.001≤y≤0.2,0.01≤z≤0.2.The fluorescent powder has Photochromic Properties controllable, and the feature that luminous efficiency is high.
Description
Technical field
The invention belongs to luminescent material technical fields, and in particular to a kind of fluorine oxide fluorescent powder of high photosynthetic efficiency and its preparation
Method and semiconductor light-emitting apparatus.
Background technique
In recent years, with the fast development in the markets such as automotive lighting, street lighting, to the light emitting diode of high power white light
(Light Emitting Diode, LED) performance requirement is gradually promoted, and the stability of light efficiency and device is that restriction is high-power at present
The bottleneck of white light LEDs development.Large power white light LED realizes that the mode of high photosynthetic efficiency mainly uses chip to match fluorescent powder at present,
In, the promotion of the external quantum efficiency and stability of fluorescent powder is the key that obtain high-efficient large power white light LEDs.It is high-power at present
Phosphor combination used by LED is mainly the green or yellow fluorescent powder collocation nitride red fluorescent powder of garnet system；
Since the external quantum efficiency of garnet structure fluorescent powder and nitride red fluorescent powder has evolved to bottleneck stage, light efficiency is promoted
It is extremely difficult.Research shows that Mn4+The K of activation2SiF6Or K2GeF6The external quantum efficiency of red fluorescence powder can reach 90% with
On, if other fluorescent powders can be arranged in pairs or groups using such fluorescent powder packaging, it can effectively promote the light efficiency of device.But it is such glimmering
Relatively late, external quantum efficiency still has very big room for promotion to light powder study on the industrialization, and the material stability is relatively poor, at present
Applied to power-type LED, there are still certain difficulties at present.
Based on the above issues, there is not effective solution mode yet at present.
Summary of the invention
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, a kind of fluorine oxide fluorescent powder of high photosynthetic efficiency is provided
And preparation method thereof and semiconductor light-emitting apparatus, it is intended to the technical issues of solving existing red light emitting phosphor low efficiency.
For achieving the above object, The technical solution adopted by the invention is as follows:
One aspect of the present invention provides a kind of fluorine oxide fluorescent powder, and the chemical general formula of the fluorine oxide fluorescent powder is
AxM2-xD1-y-zSeyF6-xOx:zMn4+；Wherein, A be selected from Ba, Mg, Sr and Zn at least one of, M is in Li, Na and K
At least one, D are selected from least one of Si, Ge and Ti, and 0.01≤x≤1,0.001≤y≤0.2,0.01≤z≤0.2.
In fluorine oxide fluorescent powder provided by the invention, element A and O element are introduced simultaneously in fluorescent powder lattice, is passed through
Its biggish doping can regulate and control the Photochromic Properties of fluorine oxide fluorescent powder, have under the precondition of balance crystal lattice stress
Effect maintains the stability of lattice；Meanwhile by introducing Se element on D element position, inoxidizability enhances after Se is introduced, energy
Enough promote Mn7+Effectively it is reduced to Mn4+, and suitable Se and M element can further promote Mn4+It is efficiently entering fluorescence powder crystal
In lattice, based on the synergistic effect of each element in chemical general formula, the luminous efficiency of fluorescent powder can be effectively promoted.
Another aspect of the present invention provides a kind of preparation method of above-mentioned fluorine oxide fluorescent powder, includes the following steps:
The fluoride of A, the fluoride of M or oxide, the fluoride of Mn or oxide are dissolved in HF respectively, obtain first
Solution, the second solution and third solution；
The fluoride of D is dissolved in HF acid, H is formed2DF6Solution；
By H2SeO3Solution or H2SeF3Solution and the H2DF6Solution, the first solution, the second solution and the mixing of third solution
Afterwards, H is added2O2, heated, obtain the fluorine oxide fluorescent powder.
The preparation method of fluorine oxide fluorescent powder provided by the invention, simple process and low cost, final fluorescent powder obtained
For A of the inventionxM2-xD1-y-zSeyF6-xOx:zMn4+, which has Photochromic Properties controllable, and the spy that luminous efficiency is high
Point.
Finally, the present invention provides a kind of semiconductor light-emitting-diode, including be cascading substrate, blue chip and
Fluorescent powder glue-line, the semiconductor light-emitting-diode further include flexible fluorescent glass layer, and the flexibility fluorescent glass layer coats institute
State blue chip and fluorescent powder glue-line and seamless connection on the substrate, the flexibility fluorescent glass layer contains institute of the present invention
The fluorine oxide fluorescent powder that the fluorine oxide fluorescent powder or preparation method of the present invention stated obtain.
Fluorine oxide fluorescent powder of the invention is uniformly sealed in flexible fluorescence glass by semiconductor light-emitting-diode of the invention
In glass, the heat and moisture in air can be effectively obstructed, on the one hand, because the fluorine oxide fluorescent powder has Photochromic Properties adjustable
Control and the high feature of luminous efficiency, can significantly promote the encapsulation light efficiency of device, and on the other hand, fluorine oxide fluorescent powder is sealed up for safekeeping
The stability that power-type encapsulates such fluorescent powder can be effectively improved in flexible fluorescent glass.
Detailed description of the invention
Fig. 1 is the excitation and emission spectra of the fluorine oxide fluorescent powder of the embodiment of the present invention 26；
Fig. 2 is white LED spectrum after the fluorine oxide fluorescent powder of the embodiment of the present invention 26 encapsulates；
Fig. 3 is structure chart of the embodiment of the present invention 34 using fluorine oxide fluorescent powder lens packages light emitting diode；
Fig. 4 is the structure chart that comparative example 6 of the present invention does not use fluorine oxide fluorescent powder lens packages light emitting diode；
Fig. 5 is the structure chart that comparative example 7 of the present invention coats encapsulating light emitting diode using fluorine oxide fluorescent powder；
Wherein, each appended drawing reference in figure:
110 be substrate, and 111 be blue chip, and 112 be fluorescent powder glue-line, and 113 be flexible fluorescent glass layer, and 114 be fluorine oxygen
Compound fluorescent powder.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
Term " first ", " second ", " third ", " the 4th " are used for description purposes only, and are not understood to indicate or imply
Relative importance or the quantity for implicitly indicating indicated technical characteristic.Define as a result, " first ", " second ", " third ",
The feature of " the 4th " can explicitly or implicitly include one or more of the features.
On the one hand, the embodiment of the invention provides a kind of fluorine oxide fluorescent powder, the chemistry of the fluorine oxide fluorescent powder
General formula is AxM2-xD1-y-zSeyF6-xOx:zMn4+；Wherein, A be selected from Ba (barium), Mg (magnesium), in Sr (strontium) and Zn (zinc) at least
One kind, M are selected from least one of Li (lithium), Na (sodium) and K (potassium), D in Si (silicon), Ge (germanium) and Ti (titanium) at least
One kind, and 0.01≤x≤1,0.001≤y≤0.2,0.01≤z≤0.2.
In fluorine oxide fluorescent powder provided in an embodiment of the present invention, element A and O (oxygen) are introduced simultaneously in fluorescent powder lattice
Element can regulate and control the light of fluorine oxide fluorescent powder under the precondition of balance crystal lattice stress by its biggish doping
Color performance effectively maintains the stability of lattice；Meanwhile by introducing Se (selenium) element on D element position, Se resists after introducing
Oxidisability enhancing, can promote manganese ion Mn7+Effectively it is reduced to Mn4+, and suitable Se and M element can further promote
Mn4+It is efficiently entering in fluorescent powder lattice, based on the synergistic effect of each element in chemical general formula, can effectively promote the hair of fluorescent powder
Light efficiency.
Further, in the chemical general formula of fluorine oxide fluorescent powder described in the embodiment of the present invention, A Ba, because of Ba2+Radius
(149pm) and K+Radius (152pm) is more closely, and O2-Radius (126pm) is with respect to F-(119pm) radius is bigger, works as use
When Ba-O substitutes K-F respectively simultaneously, on the one hand charge can be compensated, keep electroneutral；On the other hand, Ba-O is replaced simultaneously
Mn can effectively be changed for K-F4+The crystalline field of surrounding, and then the Photochromic Properties of Effective Regulation fluorescent powder；Last suitable Ba is replaced
It is able to ascend the binding force between phosphor structure layer for K, promotes the structural stability of fluorescent powder, and then improve ageing properties,
The change of micro-structure can also promote the centre of luminescence to be efficiently entering in lattice simultaneously, and luminescent properties is promoted to enhance.
Further, in the chemical general formula of fluorine oxide fluorescent powder described in the embodiment of the present invention, M is K and Na；In ion
During doping, due to the influence of ionic radius and valence state difference, in order to keep the better stability of fluorescent powder lattice, the present invention
Embodiment introduces suitable K and Na on element A position, is controlled by K/Na ratio, obtains the anti-aging property of fluorescent powder
Certain promotion.Preferably, the molar ratio of K and Na is (9-16): 1.The oxyfluoride fluorescence of K and Na composition i.e. within the scope of this
Powder, anti-aging property are best.
Further, in the chemical general formula of fluorine oxide fluorescent powder described in the embodiment of the present invention, D Ge, or for Si and
Ge.That is D must contain Ge, because introducing Se element on D element position, since the valence state and radius of Se element and Ge are increasingly similar,
Therefore it can promote the centre of luminescence that can incorporate in lattice.Preferably, D is Si and Ge, and the molar ratio of Si and Ge is 1:(6-
8), the luminous intensity of fluorescent powder is best in the proportional region.
Further, in the chemical general formula of fluorine oxide fluorescent powder described in the embodiment of the present invention, 0.1≤x≤0.5,
0.05≤y≤0.1,0.05≤z≤0.1；Suitable Ba-O substitutes K-F element, facilitate the luminous intensity for promoting fluorescent powder and
Ageing properties, but if Ba-O substitution amount is too low, Photochromic Properties regulation is unobvious；And the doping of Ba-O is too high, it can be to fluorescence
Powder structure is affected, so will cause fluorescent powder luminous intensity and ageing properties it is on a declining curve, therefore 0.1≤x≤0.5
In the range of effect it is more excellent, optimal value x=0.3.In addition, the introducing of suitable Se element, can promote Mn4+Conversion effect
Rate, and more centres of luminescence can be promoted to be efficiently entering lattice, promote the luminous efficiency and stability of fluorescent powder；But if
Se doping is very little, and it is unobvious to promote effect, if Se doping is too high, can destroy the crystal structure of fluorescent powder, and then cause
Luminous efficiency and stability decline, therefore effect is more excellent in the range of 0.05≤y≤0.1.
On the other hand, the embodiment of the invention also provides a kind of preparation methods of above-mentioned fluorine oxide fluorescent powder, including such as
Lower step:
S01: the fluoride of A, the fluoride of M or oxide, the fluoride of Mn or oxide are dissolved in HF respectively, respectively
Form the first solution, the second solution and third solution；
S02: the fluoride of D is dissolved in HF acid, H is formed2DF6Solution；
S03: by H2SeO3Solution or H2SeF3Solution and the H2DF6Solution, the first solution, the second solution and third solution
After mixing, H is added2O2, heated to obtain the fluorine oxide fluorescent powder.
The preparation method of fluorine oxide fluorescent powder provided in an embodiment of the present invention, simple process and low cost are final obtained
Fluorescent powder is A of the inventionxM2-xD1-y-zSeyF6-xOx:zMn4+, which has Photochromic Properties controllable, and luminous efficiency
High feature.
Further, in above-mentioned steps S03, preferably H2SeO3Solution, by H2SeO3It is solution and the first solution, second molten
Liquid, third solution, the 4th solution and H2DF6Hybrid Heating stirring is carried out, H is added dropwise in right amount2O2Solution through peroxidating or goes back original shape
At AxM2-xD1-y-zSeyF6-xOx:zMn4+Solution；Preferably, temperature control is stirred 30-60 minutes at 80 DEG C.Finally, by above-mentioned
Solution carries out filtering final acquisition sediment, and sediment is washed using acetone or alcohol, and final acquisition oxyfluoride is red
Color fluorescent powder.
Finally, the embodiment of the present invention provides a kind of semiconductor light-emitting-diode, including substrate, the blue light being cascading
Chip and fluorescent powder glue-line, the semiconductor light-emitting-diode further include flexible fluorescent glass layer, the flexibility fluorescent glass layer
Coat the blue chip and fluorescent powder glue-line and seamless connection on the substrate, the flexibility fluorescent glass layer contains this
The fluorine oxide fluorescent powder that the invention fluorine oxide fluorescent powder or preparation method of the present invention obtain.
The semiconductor light-emitting-diode of the embodiment of the present invention uniformly seals the fluorine oxide fluorescent powder of the embodiment of the present invention up for safekeeping
In flexible fluorescent glass, the heat and moisture in air can be effectively obstructed, on the one hand, because the fluorine oxide fluorescent powder has
The feature that Photochromic Properties are controllable and luminous efficiency is high can significantly promote the encapsulation light efficiency of device, on the other hand, fluorine oxidation
Matter fluorescent powder, which is sealed in flexible fluorescent glass, can effectively improve the stability that power-type encapsulates such fluorescent powder.
Further, the substrate is metal or ceramic substrate；The emission peak of the blue chip is located at 440-
470nm。
Meanwhile the preparation method of above-mentioned semiconductor light-emitting-diode includes, including be sequentially prepared on substrate blue chip,
Fluorescent powder glue-line and flexible fluorescent glass layer；Blue chip is located on substrate, and fluorescent powder glue-line is coated on blue chip surface, institute
Flexible fluorescent glass layer is stated by solder seamless welding on substrate, and encapsulates cladding blue chip and fluorescent powder glue-line.Wherein
Fluorescent powder glue-line include fluorescent glue, aluminate fluorescent powder, nitride phosphor or nitric oxide fluorescent powder combination, and it is flexible
Fluorescent glass layer includes the mixing of the above-mentioned fluorine oxide fluorescent powder, glass powder and graphene of the embodiment of the present invention.
The present invention successively carried out test of many times, and it is further detailed as reference pair invention progress now to lift A partial experiment result
Thin description, is described in detail combined with specific embodiments below.
Embodiment 1
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.1K1.85Na0.05Ge0.86Se0.05F5.9O0.1:0.09Mn4+。
Preparation method are as follows: according to Ba0.1K1.85Na0.05Ge0.86Se0.05F5.9O0.1:0.09Mn4+Stoichiometric ratio weigh GeO2With
SeO2It is dissolved in HF acid and forms H2(Ge,Se)F6Solution, by KMnO4、BaF2, KF, NaF distinguish in Solution H F acid and form solution, will
Above-mentioned solution and H2SiF6Solution mixing, while H being added dropwise in right amount2O2Solution, 80 DEG C be mixed 40 minutes, by above-mentioned solution into
Row filters final acquisition sediment, and sediment is carried out washing and drying using acetone or alcohol, final to obtain oxyfluoride red
Fluorescent powder.
Embodiment 2
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Mg0.1K1.85Na0.05Ge0.86Se0.05F5.9O0.1:0.09Mn4+。
Preparation method are as follows: according to Mg0.1K1.85Na0.05Ge0.86Se0.05F5.9O0.1:0.09Mn4+Stoichiometric ratio weigh GeO2With
SeO2It is dissolved in HF acid and forms H2(Ge,Se)F6Solution, by KMnO4、MgF2, KF, NaF distinguish in Solution H F acid and form solution, will
Above-mentioned solution and H2SiF6Solution mixing, while H being added dropwise in right amount2O2Solution, 80 DEG C be mixed 40 minutes, by above-mentioned solution into
Row filters final acquisition sediment, and sediment is carried out washing and drying using acetone or alcohol, final to obtain oxyfluoride red
Fluorescent powder.
Embodiment 3
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Sr0.1K1.85Na0.05Ge0.86Se0.05F5.9O0.1:0.09Mn4+。
Preparation method are as follows: according to Sr0.1K1.85Na0.05Ge0.86Se0.05F5.9O0.1:0.09Mn4+Stoichiometric ratio weigh GeO2With
SeO2It is dissolved in HF acid and forms H2(Ge,Se)F6Solution, by KMnO4、SrF2, KF, NaF distinguish in Solution H F acid and form solution, will
Above-mentioned solution and H2SiF6Solution mixing, while H being added dropwise in right amount2O2Solution, 80 DEG C be mixed 40 minutes, by above-mentioned solution into
Row filters final acquisition sediment, and sediment is carried out washing and drying using acetone or alcohol, final to obtain oxyfluoride red
Fluorescent powder.
Embodiment 4
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Zn0.1K1.85Na0.05Ge0.86Se0.05F5.9O0.1:0.09Mn4+。
Preparation method are as follows: according to Zn0.1K1.85Na0.05Ge0.86Se0.05F5.9O0.1:0.09Mn4+Stoichiometric ratio weigh GeO2With
SeO2It is dissolved in HF acid and forms H2(Ge,Se)F6Solution, by KMnO4、ZnF2, KF, NaF distinguish in Solution H F acid and form solution, will
Above-mentioned solution and H2SiF6Solution mixing, while H being added dropwise in right amount2O2Solution, 80 DEG C be mixed 40 minutes, by above-mentioned solution into
Row filters final acquisition sediment, and sediment is carried out washing and drying using acetone or alcohol, final to obtain oxyfluoride red
Fluorescent powder.
Embodiment 5
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.1Li1.85Na0.05Ge0.86Se0.05F5.9O0.1:0.09Mn4 +.Preparation method are as follows: according to Ba0.1Li1.85Na0.05Ge0.86Se0.05F5.9O0.1:0.09Mn4+Stoichiometric ratio weigh GeO2With
SeO2It is dissolved in HF acid and forms H2(Ge,Se)F6Solution, by LiMnO4、BaF2, LiF, NaF distinguish in Solution H F acid and form solution,
By above-mentioned solution and H2SiF6Solution mixing, while H being added dropwise in right amount2O2Solution, 80 DEG C are mixed 40 minutes, by above-mentioned solution
It carries out filtering final acquisition sediment, sediment is subjected to washing and drying using acetone or alcohol, it is red finally to obtain oxyfluoride
Color fluorescent powder.
Embodiment 6
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.1Li1.75Na0.15Ge0.86Se0.05F5.9O0.1:0.09Mn4 +.Preparation method are as follows: according to Ba0.1Li1.75Na0.15Ge0.86Se0.05F5.9O0.1:0.09Mn4+Stoichiometric ratio weigh GeO2With
SeO2It is dissolved in HF acid and forms H2(Ge,Se)F6Solution, by NaMnO4、BaF2, NaF, LiF distinguish in Solution H F acid and form solution,
By above-mentioned solution and H2SiF6Solution mixing, while H being added dropwise in right amount2O2Solution, 80 DEG C are mixed 40 minutes, by above-mentioned solution
It carries out filtering final acquisition sediment, sediment is subjected to washing and drying using acetone or alcohol, it is red finally to obtain oxyfluoride
Color fluorescent powder.
Embodiment 7
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.1K1.9Ge0.86Se0.05F5.9O0.1:0.09Mn4+.It is made
Preparation Method are as follows: according to Ba0.1K1.9Ge0.86Se0.05F5.9O0.1:0.09Mn4+Stoichiometric ratio weigh GeO2And SeO2It is dissolved in HF acid
Middle formation H2(Ge,Se)F6Solution, by KMnO4、BaF2, KF distinguish in Solution H F acid and form solution, by above-mentioned solution and H2SiF6
Solution mixing, while H being added dropwise in right amount2O2Solution, 80 DEG C are mixed 40 minutes, and above-mentioned solution filter and is finally sunk
Sediment is carried out washing and drying using acetone or alcohol by starch, final to obtain oxyfluoride red fluorescence powder.
Embodiment 8
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.1K1.85Na0.05Si0.86Se0.05F5.9O0.1:0.09Mn4+。
Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 9
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.1K1.85Na0.05Ti0.86Se0.05F5.9O0.1:0.09Mn4+。
Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 10
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.1K1.85Na0.05Si0.1Ge0.76Se0.05F5.9O0.1:
0.09Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 11
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.1K1.85Na0.05Si0.4Ge0.36Se0.05F5.9O0.1:
0.09Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 12
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.01K1.94Na0.05Si0.1Ge0.76Se0.05F5.99O0.01:
0.09Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 13
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.65Na0.05Si0.1Ge0.76Se0.05F5.7O0.3:
0.09Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 14
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.5K1.45Na0.05Si0.1Ge0.76Se0.05F5.5O0.5:
0.09Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 15
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: BaK0.95Na0.05Si0.1Ge0.76Se0.05F5O:0.09Mn4+。
Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 16
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.76Se0.05F5.7O0.3:
0.09Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 17
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.2Ge0.66Se0.05F5.7O0.3:
0.09Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 18
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.53Na0.17Si0.1Ge0.76Se0.05F5.7O0.3:
0.09Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 19
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.615Na0.085Si0.1Ge0.76Se0.05F5.7O0.3:
0.09Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 20
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.71Se0.1F5.7O0.3:0.09Mn4 +.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 21
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.66Se0.15F5.7O0.3:
0.09Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 22
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.61Se0.2F5.7O0.3:0.09Mn4 +.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 23
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.809Se0.001F5.7O0.3:
0.09Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 24
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.8Se0.01F5.7O0.3:0.09Mn4 +.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 25
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.78Se0.03F5.7O0.3:
0.09Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 26
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.73Se0.08F5.7O0.3:
0.09Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.The fluorine oxygen
The excitation and emission spectra of compound fluorescent powder is as shown in Figure 1, white LED spectrum is as shown in Figure 2 after encapsulation.
Embodiment 27
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.81Se0.08F5.7O0.3:
0.01Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 28
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.79Se0.08F5.7O0.3:
0.03Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 29
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.77Se0.08F5.7O0.3:
0.05Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 30
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.75Se0.08F5.7O0.3:
0.07Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 31
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.72Se0.08F5.7O0.3:0.1Mn4 +.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 32
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.67Se0.08F5.7O0.3:
0.15Mn4+.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 33
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.6Na0.1Si0.1Ge0.62Se0.08F5.7O0.3:0.2Mn4 +.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Embodiment 34
A kind of light emitting diode, for encapsulating structure as shown in figure 3,110 be substrate (ceramic substrate), 111 be blue chip,
112 be fluorescent powder glue-line, and 113 be flexible fluorescent glass layer, and therein 114 be the fluorine oxide fluorescent powder of embodiment 26.Wherein
111 blue chip wavelength are 447-450nm, and 112 fluorescent powder glue-lines are fluorescent glue and Y3(Al,Ga)5O12:Ce3+、(Sr,Ca)
AlSiN3:Eu2+The mixing of fluorescent powder；114 fluorine oxide fluorescent powder chemical compositions are Ba0.3K1.6Na0.1Si0.1Ge0.73Se0.08F5. 7O0.3:0.09Mn4+。
Comparative example 1
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: K2Si0.91F6:0.09Mn4+.Preparation method are as follows: according to
K2Si0.91F6:0.09Mn4+Stoichiometric ratio weigh SiO2It is dissolved in HF acid and forms H2SiF6Solution, by KMnO4Distinguish with KF molten
The first and second solution are formed in liquid HF acid, by the first and second solution and H2SiF6Solution mixing, while H being added dropwise in right amount2O2It is molten
Liquid, 80 DEG C are mixed 40 minutes, and above-mentioned solution is carried out to filter final acquisition sediment, sediment is used acetone or alcohol
Washing and drying is carried out, it is final to obtain oxyfluoride red fluorescence powder.
Comparative example 2
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.615Na0.085Si0.1Ge0.81F5.7O0.3:0.09Mn4 +.Corresponding raw materials of compound mixing, preparation method equivalent integers 1-7 are weighed according to stoichiometric ratio.
Comparative example 3
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.7Si0.1Ge0.76Se0.05F5.7O0.3:0.09Mn4+。
Corresponding raw materials of compound mixing, the year-on-year embodiment 1-7 such as preparation method are weighed according to stoichiometric ratio.
Comparative example 4
A kind of oxyfluoride red fluorescence powder, chemical formula are as follows: Ba0.3K1.7Si0.91F5.7O0.3:0.09Mn4+.It is counted according to chemistry
Amount is than weighing corresponding raw materials of compound mixing, preparation method equivalent integers 1-7.
Comparative example 5
A kind of light emitting diode, for encapsulating structure as shown in figure 3,110 be substrate (ceramic substrate), 111 be blue chip,
112 be fluorescent powder glue-line, and 113 be flexible fluorescent glass layer, wherein 114 be the fluorine oxide fluorescent powder of comparative example 1.Wherein 111
Blue chip wavelength is 447-450nm, and 112 fluorescent powder glue-lines are fluorescent glue and Y3(Al,Ga)5O12:Ce3+、(Sr,Ca)
AlSiN3:Eu2+The mixing of fluorescent powder；114 fluorine oxide fluorescent powder chemical compositions are K2Si0.91F6:0.09Mn4+。
Comparative example 6
A kind of light emitting diode, for encapsulating structure as shown in figure 4,110 be substrate (ceramic substrate), 111 be blue chip,
112 be fluorescent powder glue-line, and 113 be flexible fluorescent glass, does not have fluorine oxide fluorescent powder in 113.Wherein 111 blue chip wavelength
For 447-450nm, 112 fluorescent powder glue-lines are fluorescent glue and Y3(Al,Ga)5O12:Ce3+、(Sr,Ca)AlSiN3:Eu2+Fluorescent powder
Mixing.
Comparative example 7
A kind of light emitting diode, for encapsulating structure as shown in figure 5,110 be substrate (ceramic substrate), 111 be blue chip,
112 be fluorescent powder glue-line, and wherein fluorescent powder glue-line is fluorescent glue, Y3(Al,Ga)5O12:Ce3+、(Sr,Ca)AlSiN3:Eu2+And fluorine
Oxide fluorescent powder Ba0.3K1.6Na0.1Si0.1Ge0.73Se0.08F5.7O0.3:0.09Mn4+Fluorescent powder and mixing.
Table 1
Table 2
| Chemical composition | Coordinate x decaying | Luminous intensity decaying | |
| Embodiment 13 | Ba0.3K1.65Na0.05Si0.1Ge0.76Se0.05F5.7O0.3:0.09Mn4+ | 15% | 14% |
| Embodiment 16 | Ba0.3K1.6Na0.1Si0.1Ge0.76Se0.05F5.7O0.3:0.09Mn4+ | 3% | 5% |
| Embodiment 18 | Ba0.3K1.53Na0.17Si0.1Ge0.76Se0.05F5.7O0.3:0.09Mn4+ | 5% | 7% |
| Embodiment 19 | Ba0.3K1.615Na0.085Si0.1Ge0.76Se0.05F5.7O0.3:0.09Mn4+ | 16% | 15% |
| Comparative example 4 | Ba0.3K1.7Si0.91F5.7O0.3:0.09Mn4+ | 23% | 25% |
| Comparative example 3 | Ba0.3K1.7Si0.1Ge0.76Se0.05F5.7O0.3:0.09Mn4+ | 20% | 21% |
| Comparative example 1 | K2Si0.91F6:0.09Mn4+ | 35% | 39% |
Table 1 is the Photochromic Properties data of comparative example 1-4 and embodiment 1-33.As shown in Table 1, while element A and O member being introduced
Element is affected to the Photochromic Properties of fluorine oxide fluorescent powder, and especially chromaticity coordinates influences maximum, for comparative example, together
When introduce the luminous intensity that element A and O element each contribute to be promoted fluorescent powder.Element A appointing in Ba, Mg, Sr, Zn element
When one or more, select Ba element substitution part K element to promote the luminous intensity of fluorescent powder maximum, mainly due to Ba and
The radius of K is closest, is conducive to the stability for adulterating and keeping lattice；As x=0.3, and A be Ba when, the hair of fluorescent powder
Luminous intensity reaches optimum value.
When D element contains Ge, due to Ge4+Radius relative to Si4+Or Ti4+Radius is closer to Mn4+Radius introduces
Suitable Ge4+The luminous intensity for being able to ascend fluorescent powder is maximally efficient.As suitable Si4+、Ge4+When being collectively incorporated into, fluorescent powder
Luminous efficiency is higher.By embodiment 10 and embodiment 11 it is found that when Si/Ge ratio is less than 1, the luminous efficiency of fluorescent powder is relatively
It is high.From known to embodiment 20-26 and embodiment 27-33: when the molar ratio of Si and Ge is in 1:(6-8) in the range of, fluorescence
The luminous efficiency of powder is best.
By embodiment 19-26 comparative examples 2 it is found that introducing Se element, the luminous intensity of fluorescent powder is obtained by a relatively large margin
Promotion, the mainly introduction due to Se element, can effectively facilitate the conversion of the centre of luminescence and enter lattice in.When Se element
When doping content is 0.08,30% or more light-emitting phosphor strength enhancing.
Table 2 is double 85 (i.e. 85 DEG C of temperature；Relative humidity 85%) the photochromic attenuation data of aging 300h.As shown in Table 2, in body
The aging that Na element (embodiment 13/16/18/19) relatively example 1,3,4 each contributes to be promoted fluorescent powder is suitably introduced into system
Performance, and when K/Na element ratio is between 9-16:1, the ageing properties of fluorescent powder are best.
Embodiment 26 and 1 fluorescent powder of comparative example are packaged according to Fig. 3 package structure diagram, obtain 34 He of embodiment
Comparative example 5；26 fluorescent powder of embodiment is packaged according to Fig. 5 structural schematic diagram simultaneously and is compared, comparative example 7, institute are obtained
It is consistent using other fluorescent powders, chip and material.Encapsulation performance comparing result is as shown in table 3.As shown in Table 3, fluoride and
Fluorine oxide fluorescent powder helps to promote the encapsulation light efficiency of light emitting diode, wherein using the fluorine oxide fluorescent powder of embodiment 26
5% or so are promoted relative to the fluoride rouge and powder encapsulation light efficiency using comparative example 1；Oxyfluoride is encapsulated using flexible fluorescent glass
The reliability of fluorescent powder is preferable, double 85 aging 300h, and light decay performance boost is obvious.
Table 3
| Relative luminous efficiency | Colour rendering index | Double 85,300h light decay | |
| Embodiment 34 | 112 | 92 | 9% |
| Comparative example 5 | 106 | 92 | 9% |
| Comparative example 6 | 100 | 92 | 8% |
| Comparative example 7 | 113 | 92 | 23% |
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (9)
1. a kind of fluorine oxide fluorescent powder, which is characterized in that the chemical general formula of the fluorine oxide fluorescent powder is AxM2-xD1-y- zSeyF6-xOx:zMn4+；Wherein, A be selected from Ba, Mg, Sr and Zn at least one of, M is selected from least one of Li, Na and K,
D is selected from least one of Si, Ge and Ti, and 0.1≤x≤0.5,0.05≤y≤0.1,0.01≤z≤0.2.
2. fluorine oxide fluorescent powder as described in claim 1, which is characterized in that the chemical general formula of the fluorine oxide fluorescent powder
In, A Ba.
3. fluorine oxide fluorescent powder as described in claim 1, which is characterized in that the chemical general formula of the fluorine oxide fluorescent powder
In, M is K and Na；And/or
D is Ge, or is Si and Ge.
4. fluorine oxide fluorescent powder as claimed in claim 3, which is characterized in that the molar ratio of K and Na is (9-16): 1.
5. fluorine oxide fluorescent powder according to any one of claims 1-4, which is characterized in that the fluorine oxide fluorescent powder
In chemical general formula, D is Si and Ge, and the molar ratio of Si and Ge is 1:(6-8).
6. fluorine oxide fluorescent powder according to any one of claims 1-4, which is characterized in that the fluorine oxide fluorescent powder
In chemical general formula, 0.05≤z≤0.1.
7. a kind of preparation method of fluorine oxide fluorescent powder as claimed in any one of claims 1 to 6, which is characterized in that including such as
Lower step:
The fluoride of A, the fluoride of M or oxide, the fluoride of Mn or oxide are dissolved in HF respectively, it is molten to obtain first
Liquid, the second solution and third solution；
The fluoride of D is dissolved in HF acid, H is formed2DF6Solution；
By H2SeO3Solution and the H2DF6After solution, the first solution, the second solution and the mixing of third solution, H is added2O2, carry out
Heat treatment, obtains the fluorine oxide fluorescent powder.
8. a kind of semiconductor light-emitting-diode, including the substrate, blue chip and fluorescent powder glue-line being cascading, feature
It is, the semiconductor light-emitting-diode further includes flexible fluorescent glass layer, and the flexibility fluorescent glass layer coats the blue light
Chip and fluorescent powder glue-line and seamless connection is on the substrate, to contain claim 1-6 any for the flexibility fluorescent glass layer
The fluorine oxide fluorescent powder that fluorine oxide fluorescent powder or preparation method as claimed in claim 7 described in obtain.
9. semiconductor light-emitting-diode as claimed in claim 8, which is characterized in that the emission peak of the blue chip is located at
Between 440-470nm.
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