CN108485658A - The manufacturing method of fluorophor - Google Patents
The manufacturing method of fluorophor Download PDFInfo
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- CN108485658A CN108485658A CN201810390956.5A CN201810390956A CN108485658A CN 108485658 A CN108485658 A CN 108485658A CN 201810390956 A CN201810390956 A CN 201810390956A CN 108485658 A CN108485658 A CN 108485658A
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Abstract
The present invention provides a kind of manufacturing method of fluorophor, the fluorophor includes that composition formula is constituent shown in lower formula (I), wherein, M is selected from magnesium, barium, the group that beryllium and zinc are formed, A is selected from aluminium, gallium, indium, scandium, yttrium, lanthanum, the group that gadolinium and gold-plating are formed, B is selected from silicon, germanium, tin, titanium, the group that zirconium and hafnium are formed, Z elements are the group that is formed selected from europium and cerium, 0 ＜ p ＜ 1, 0 ＜ q ＜ 1, 0≤m ＜ 1, 0≤t≤0.3, 0.00001≤r≤0.1, a=1, 0.8≤b≤1.2, 2.7≤n≤3.1；And, the regular strontium dissolution content of the fluorophor is 1~20ppm, and obtain wave and be longer than the fluorophor that the regions 600~680nm reach high briliancy, in addition, the present invention also provides the fluorophor manufactured by this method and the light-emitting device with high briliancy including the fluorophor simultaneously.CapSrqMm‑Aa‑Bb‑Ot‑Nn：Zr………(I)。
Description
It is on October 27th, 2010 and entitled " glimmering that the application, which is application No. is the 201510704966.8, applying date,
The divisional application of the application for a patent for invention of body of light and light-emitting device ".
Technical field
The present invention relates to the nitrogen used in the lighting units such as display, liquid crystal backlight, fluorescent lamp, light emitting diode
Compound fluorophor forms more particularly, to the nitride phosphor and uses the light-emitting device of the fluorophor.The invention further relates to
The manufacturing method of the fluorophor.
Background technology
In recent years, it is widely used using the light-emitting device of semiconductor light emitting, especially light emitting diode is successfully opened
Hair, the luminaires such as the more conventional cold cathode tube of this light-emitting device, incandescent lamp, high, the small, low power consumption with luminous efficiency
The advantages that power is with low cost, therefore various light sources are can be used as to use.And semiconductor light-emitting apparatus includes semiconductor luminous assembly
With fluorophor, fluorophor can absorb and converts the light that semiconductor luminous assembly is sent out, sent out by semiconductor luminous assembly
Both the light that sends out of light and fluorophor conversion be used in mixed way.Such light-emitting device can be used as fluorescent lamp, car lighting, display
Device, LCD backlight show etc. that various fields use, wherein most widely used with white light emitting device.Existing white luminous dress
It is the YAG fluorophor (Y for using cerium as activated centre to set3Al5O12：Ce it) and arranges in pairs or groups and sends out the semiconductor luminous assembly institute group of blue light
At.However, using Y3Al5O12：Ce fluorophor and arrange in pairs or groups send out the mixed light that the semiconductor luminous assembly of blue light is sent out, color
Degree coordinate is located at the chromaticity coordinate and Y for the semiconductor luminous assembly for sending out blue light3Al5O12：The chromaticity coordinate of Ce fluorophor connects
Online, thus, the mixed light sent out be lack red light white light, color rendering is obviously insufficient with color saturation.In addition,
Y3Al5O12：The preferable excitation spectrum region of Ce and the light-emitting zone of semiconductor luminous assembly are not consistent, therefore, exciting light
Transfer efficiency is bad, is not easy to obtain the white light source of high briliancy.Such tone is bad and the low phenomenon of glorious degrees to solve,
In recent years active development is by YAG：The fluorophor of feux rouges can be sent out by being mixed into Ce fluorophor, and improve the fluorophor that can send out feux rouges
Quality, to improve glorious degrees.
However, absorb blue light and then send out red light or the fluorophor of inclined red light is more rare, industry is opened at present
Hair research is based on nitride, nitrogen oxides fluorophor.It is the Sr in activated centre it has been known that there is europium (Eu) is used2Si5N8：Eu fluorescence
Body, CaAlSiN3：Eu fluorophor and general expression are MgSi12-(m+n)Alm+nOnN16-n：The Sialon phosphor of Eu.However, Sr2Si5N8：
Eu fluorophor has the shortcomings that briliancy and color rendering decline when used for a long time since crystal heat resistance itself is bad；Sialon phosphor
Although itself without endurance issues, light-emitting phosphor briliancy is obviously insufficient, is not popularized using upper commercially.CaAlSiN3：
Although Eu fluorophor has preferable durability, and the briliancy being preferred compared with Sialon phosphor, but industry still expects energy further
The glorious degrees for improving fluorophor, so that light-emitting device can have higher luminous efficiency.
Invention content
In view of the above problems, therefore the purpose of the present invention is to provide the fluorescent material of a high briliancy and its manufacturers
Method, the fluorescent material can be used for arranging in pairs or groups semiconductor luminous assembly and make the light-emitting device of a high briliancy.
Therefore, inventor etc. put that carefulness is studied as a result, especially novel red-emitting phosphors carry out regarding to the issue above
Research and probe.Inventor's sharp study result learns, CapSrqAlSiN3：In Eu (p ＞ 0, q ＞ 0) fluorophor, raw material strontium nitride
Nitridation to glorious degrees have significant impact.And according to inventor's result of study, condition meeting when strontium nitride synthesizes
The regular strontium for influencing synthesized fluorophor dissolves out content, and finds that regular strontium dissolves out content for CapSrqAlSiN3：Eu(p
＞ 0, q ＞ 0) fluorophor glorious degrees have especially significant influence.Therefore spirit of that invention system be by fluorophor just
Ruleization strontium dissolution content is controlled in a certain range, thus reaches the luminosity of high briliancy, and by fluorophor collocation half
Conductor luminescence component is combined as light-emitting device.
To meet aforementioned expected purpose, system of the present invention provides a kind of fluorophor, including composition formula is CapSrqMm-Aa-Bb-
Ot-Nn：ZrConstituent (composition), wherein M is the group that is formed selected from magnesium, barium, beryllium and zinc, A be selected from aluminium,
The group that gallium, indium, scandium, yttrium, lanthanum, gadolinium and gold-plating are formed, B are the group formed selected from silicon, germanium, tin, titanium, zirconium and hafnium, Z members
Element is the group that is formed selected from europium and cerium, 0 ＜ p ＜ 1,0 ＜ q ＜ 1,0≤m ＜ 1,0≤t≤0.3,0.00001≤r≤
0.1, a=1,0.8≤b≤1.2,2.7≤n≤3.1；And the regular strontium dissolution content of the fluorophor is 1~20ppm；It is aforementioned
Regular strontium dissolution content system is measured with following methods：200 μ s/cm fluorophor below of electrical conductivity is taken to be washed to 200 μ of electrical conductivity
S/cm hereinafter, according to fluorophor than pure water be 1：100 weight ratio adds pure water, forms the mixed solution of fluorophor and water,
The container is sealed after mixing, after 80 DEG C, heating in 40 hours, the cooling mixed solution takes the water phase of the mixed solution to room temperature,
Measure its regular strontium dissolution content.
The present invention also provides fluorophor below：
Above-mentioned fluorophor, wherein regular strontium dissolution content is 3~17ppm/ moles.
Above-mentioned fluorophor, wherein preferably 0.05≤p≤0.9,0.1≤q≤0.95.
Above-mentioned fluorophor, wherein：
M is the group that is formed selected from magnesium and zinc；
A is the group that is formed selected from aluminium and gallium；
B is the group that is formed selected from silicon and germanium.
Above-mentioned fluorophor, wherein when preferably 455nm light sources being used to irradiate, light-emitting phosphor wavelength is 600~680nm,
Its 1931 chromaticity coordinate (x, y) of CIE for shining tone is 0.45≤x≤0.72,0.2≤y≤0.5.
Above-mentioned fluorophor, when more preferably 455nm light sources being used to irradiate, the cie color coordinate (x, y) of light-emitting phosphor tone
It is 0.6≤x≤0.7,0.3≤y≤0.4.
The present invention also provides a kind of light-emitting device, including：
Semiconductor luminescence component；And
Foregoing fluorophor, wherein the fluorophor can be excited by the light that the semiconductor luminous assembly is sent out, and be turned
Change out the light for being different from exciting light.
Foregoing light-emitting device, wherein the semiconductor luminous assembly can send out the light of 300~550nm wavelength.
The present invention obtains high briliancy mainly by the regular strontium dissolution content of control fluorophor in a certain range
Fluorophor.The present invention and the semiconductor luminous assembly that the fluorophor can be arranged in pairs or groups, and obtain the light-emitting device of high briliancy.
In one aspect, the purpose of the present invention is realized by following entry：
A kind of manufacturing method of 1. fluorophor of entry, the method includes：
Prepare strontium raw metal, wherein the strontium raw metal is to be burnt by system by the way that strontium metal to be placed under nitrogen atmosphere
Standby, firing heating rate is 3-5 DEG C/minute when 150 DEG C of strontium melting point metal is following, and firing temperature is 600~1000 DEG C, and
Nitrogen flow rate is 70-90 liters/min；
By the strontium element raw material, CaCl2, the oxide of element A and/or nitride, the oxide and/or nitrogen of B element
Compound, the oxide of Z elements, nitride and/or metallic monomer and/or the oxide of M element weigh respectively, mixes and is placed into
In crucible, wherein A is the group that is formed selected from aluminium, gallium, indium, scandium, yttrium, lanthanum, gadolinium and gold-plating, B be selected from silicon, germanium, tin,
The group that titanium, zirconium and hafnium are formed, Z elements are the group formed selected from europium and cerium, and M is selected from magnesium, barium, beryllium and zinc institute
The group of composition；And
It is 1200 DEG C or more 2200 DEG C or less and liter that the raw material of aforementioned mixing, which is placed in high temperature furnace together with firing temperature,
The condition that warm speed is 3~15 DEG C/minute is burnt into, and the fluorophor is made；
Wherein, the composition formula of the fluorophor is CapSrqMm-Aa-Bb-Ot-Nn:Zr, wherein 0 ＜ p ＜, 1,0 ＜ q ＜ 1,0
≤ m ＜ 1,0≤t≤0.3,0.00001≤r≤0.1, a=1,0.8≤b≤1.2,2.7≤n≤3.1.
The manufacturing method of 2. fluorophor according to claim 1 of entry, wherein the firing temperature of the strontium element raw material
Degree is 700~900 DEG C.
The manufacturing method of fluorophor of the entry 3. according to entry 1, wherein the nitrogen flow rate is 80~90 liters/min.
The manufacturing method of fluorophor of the entry 4. according to entry 1, wherein during the firing of the strontium metal, from
Heating rate when room temperature is started to warm up to medium temperature is 10 DEG C/minute, when being started to warm up from medium temperature to maintenance temperature
Heating rate is 3-5 DEG C/minute, wherein the medium temperature is 620 DEG C, it is 750~900 DEG C to maintain temperature.
The manufacturing method of fluorophor of the entry 5. according to entry 1, wherein the firing time of the strontium element raw material is 3
~24 hours.
The manufacturing method of fluorophor of the entry 6. according to entry 1, wherein the firing time of the strontium element raw material is 5
~24 hours.
The manufacturing method of fluorophor of the entry 7. according to entry 1, wherein nitrogen gas purity are up to 99.99% or more.
The manufacturing method of fluorophor of the entry 8. according to entry 1, wherein the firing temperature of the fluorophor is 1400
DEG C or more 2000 DEG C or less.
The manufacturing method of fluorophor of the entry 9. according to entry 1, wherein the firing time of the fluorophor is 1~10
Hour.
The manufacturing method of fluorophor of the entry 10. according to entry 1, wherein the firing pressure of the fluorophor is
0.5MPa or less.
The manufacturing method of fluorophor of the entry 11. according to entry 1, wherein the firing pressure of the fluorophor is
0.1MPa or less.
The manufacturing method of fluorophor of the entry 12. according to entry 1, wherein the p value is 0.05~0.9, the q values
It is 0.1~0.95.
The manufacturing method of fluorophor of the entry 13. according to entry 1, wherein the p value is 0.2~0.65, the q values
It is 0.342~0.792.
Description of the drawings
Fig. 1 is the use state diagram of briliancy measuring device；
Fig. 2 is the perspective view of light emitting device embodiment of the present invention.
Symbol description
11 babinets；12 sample cells；13 light sources；14 light guide skirts；15 speculums；16 brightness photometers；
21 semiconductor luminous assemblies；211 pedestals；212 loading ends；213 LED crystal particles；
214 connecting lines；215 conducting wires；22 fluorescence coatings；221 fluorophor；23 encapsulated layers.
Specific implementation mode
In order to illustrate the effect of the present invention, spy is illustrated with the following example, is only the preferable possible embodiments of the present invention,
Not to limit the present invention, thus it is all according to modifying or changing made by spirit of that invention scope, it ought to be included in this crime
In bright claim.
A kind of fluorophor of the present invention, including composition formula is CapSrqMm-Aa-Bb-Ot-Nn：ZrConstituent, wherein M be choosing
From the group formed in magnesium, barium, beryllium and zinc, A is the group formed selected from aluminium, gallium, indium, scandium, yttrium, lanthanum, gadolinium and gold-plating, B
For the group formed selected from silicon, germanium, tin, titanium, zirconium and hafnium, Z elements are the group formed selected from europium and cerium, 0 ＜ p ＜
1,0 ＜ q ＜ 1,0≤m ＜ 1,0≤t≤0.3,0.00001≤r≤0.1, a=1,0.8≤b≤1.2,2.7≤n≤3.1；And
The regular strontium dissolution content of the fluorophor is 1~20ppm；Aforementioned normalization strontium dissolution content measures by the following method：It takes
200 μ s/cm fluorophor below of electrical conductivity, according to fluorophor than pure water be 1：100 weight ratio adds pure water, forms fluorescence
The mixed solution of body and water seals the container after mixing, after 80 DEG C, heating in 40 hours, the cooling mixed solution takes to room temperature
The water phase of the mixed solution measures its regular strontium dissolution content.
In aforementioned phosphors, M is the group that is formed selected from magnesium, barium, beryllium and zinc.A be selected from aluminium, gallium, indium, scandium, yttrium,
The group that lanthanum, gadolinium and gold-plating are formed, for example, A can be individually for aluminium element, also can be the mixture of the elements such as aluminium, gallium.B be selected from
In the group that silicon, germanium, tin, titanium, zirconium and hafnium are formed, for example, B can be individually for element silicon, also can be the mixing of the elements such as silicon, germanium
Object.Z elements are the group that is formed selected from europium and cerium.Ca is calcium constituent, Sr is strontium element, O is oxygen element, N is nitrogen.
Composition formula CapSrqMm-Aa-Bb-Ot-Nn：ZrIn, 0 ＜ p ＜ 1,0 ＜ q ＜ 1,0≤m ＜ 1.
Wherein：
M is preferably 0≤m ＜ 1, more preferably 0≤m≤0.1, most preferably 0≤m≤0.05.
A=1.More preferably, when A is aluminium, glorious degrees are more preferably.
B is preferably 0.8≤b≤1.2, more preferably 0.9≤a≤1.1.More preferably, when B is silicon, and b values are 1, shine brightness
Degree is more preferably.
T is preferably 0≤t≤0.3, more preferably 0≤t≤0.1.
N is preferably 2.7≤n≤3.1, more preferably 2.8≤n≤3.1.
M, when a, b, t are in aforementioned the scope of the present invention, glorious degrees are good.
R is preferably 0.00001≤r≤0.1.More preferably, when Z elements are europium (Eu), glorious degrees are more preferably.When r values are small
When 0.00001, since the Eu quantity of the centre of luminescence is few, glorious degrees reduce；When r values are more than 0.1, due to Eu atoms
Between the phenomenon that interfering with each other and cause concentration delustring so that briliancy lower.More preferably, when r values are 0.002~0.03, hair
Brilliant degree is more preferably.
In addition, in the fluorophor composition of the present invention, contain calcium, strontium element simultaneously, wherein 0 ＜ p ＜ 1,0 ＜ q ＜ 1, it is aforementioned
P value is preferable with 0.02~0.95, and q values are preferable, more preferably p=0.05~0.9, q=0.1~0.95 with 0.05~0.98.
Calcium, strontium element relativeness on, preferably 0 ＜ (p+q) ＜ 1, (p/q)=0.1~10.Fluorophor especially of the present invention is just
It is 1~20ppm that ruleization strontium, which dissolves out content, it is found that the light-emitting phosphor briliancy for meeting the range can be obviously improved.
When measuring regular strontium dissolution content, 200 μ s/cm fluorophor below of electrical conductivity is taken, refers to fluorophor via following
Electrical conductivity detection method detects, and electrical conductivity is 200 μ s/cm or less.Fluorophor electrical conductivity detection method is as follows：Pure water is taken (to lead
Electric degree is less than 1 μ s/cm) the fluorophor detection mixed liquor of 1 weight % of phosphor content, detection mixing are mixed to form with fluorophor
Liquid stirs 30 minutes under 80 DEG C of water-baths, is then allowed to stand to room temperature, and the upper layer clear solution of detection mixed liquor is taken to carry out electrical conductivity
It measures.If measure zeta potential be 200 μ s/cm hereinafter, if the fluorophor be 200 μ s/cm fluorophor below of electrical conductivity；
If measured value is 200 μ s/cm or more, fluorophor pickling processes are first carried out until zeta potential is 200 μ s/cm or less.Fluorescence
Body pickling processes method is as follows：The salpeter solution and fluorophor for taking 0.5 weight % are mixed to form the glimmering of 1 weight % of phosphor content
Body of light pickling mixed liquor, the pickling mixed liquor vibrate 30 minutes via ultrasonic at room temperature, and fluorophor after filtering is added
The step of 100 times of pure water, seals stirring and washing 30 minutes under 80 DEG C of water-baths, then row filtering, and aforementioned pure water cleaning is with filtering
It repeats four times, the fluorophor being finally obtained by filtration measures zeta potential according to above-mentioned electrical conductivity detection method again.
200 μ s/cm fluorophor below of electrical conductivity is with pure water according to 1：100 weight ratio forms fluorophor and the mixing of water is molten
Liquid, the mixed solution are sealed using container, prevent moisture loss in heating process, and heating device is baking oven.By 80
DEG C, after heating in 40 hours, the mixed solution of the cooling fluorophor and water to room temperature.
Regular (normalize) strontium dissolution content refers to being measured in the water phase of mixed solution after foregoing routine
Content of strontium divided by composition formula CapSrqMm-Aa-Bb-Ot-Nn：ZrIn q values after obtained result.
When irradiating the fluorophor using 455nm light sources, which is stimulated and sends out for the fluorophor of the present invention preferably system
The luminous dominant wavelength of light is 600~680nm, and 1931 chromaticity coordinates (x, y) of CIE for the tone that shines are 0.45≤x≤0.72,
0.2≤y≤0.5.Luminous dominant wavelength refers to the maximum wavelength of luminous intensity.
One of implementation form of the present invention is 0 ＜ p ＜ 1,0 ＜ q ＜ 1,0≤m≤0.05,0≤t≤0.3,0.00001≤r≤
0.1, p+q+m+r=[1/ (1+t)], a=1, b=(1-t)/(1+t), n=(3-t)/(1+t)；And the normalization of the fluorophor
It is 1~20ppm that strontium, which dissolves out content,.And the considerations of by glorious degrees, the group of fluorophor become CapSrqMm-Aa-Bb-Ot-Nn：Zr, and
Can exist in the form of single-phase, however, because of pollution, raw material in impurity, processing procedure in the addition of fluxing agent, raw material in building-up process
The factors such as volatilization influence, other crystalline phases or noncrystalline phase (amorphous phase) are may be simultaneously present, as long as not influencing
Under the premise of glorious degrees, the spirit of the present invention is still conformed to.
The composition analysis of this implementation form fluorophor is implemented as a result, finding from the calculated each element of composition analysis result institute
M, a, b, t, n value, and compared to from have slightly deviation using calculated m, a, b, t, n value of material allocation ratio.This phenomenon
It is believed that have a small amount of raw material decomposes or evaporation in firing, or caused by analytical error.Especially it is the deviation of t values, it can
Think such as：From the outset just contained in the oxygen or the oxygen of adhering on surface in raw material, or in raw material weighing, when mixing and
When firing, the mixed oxygen because of raw material surface oxidation, and be adsorbed in after firing moisture or the oxygen etc. of phosphor surface and made
At.In addition, when being burnt into the environment containing nitrogen and/or ammonia, the oxygen in firing in raw material may be also detached from
And replaced by nitrogen, judge that several deviations will occur for t, n.
When the fluorophor manufacture of the present invention, the raw material of strontium element is preferable using nitride.The manufacturing method of nitride is to select
Required divalent metal is selected to be burnt under the atmosphere of high-purity nitrogen.Firing atmosphere is preferred with high-purity nitrogen, high-purity nitrogen
Gas means purity up to 99.99% or more.And nitrogen flow rate must control the state for high flow rate, such as 70~90 liters/min are preferred,
80~90 liters/min more preferably.Too high or too low nitrogen flow rate can not all synthesize strontium nitride appropriate, so that is subsequently synthesized is glimmering
There is body of light the regular strontium in particular range of the present invention to dissolve out content.Firing temperature is preferably between 600~1000 DEG C, more preferably
Between 700~900 DEG C.Firing temperature is less than 600 DEG C or can not all obtain required strontium nitride more than 1000 DEG C.Firing time
Preferably between 3~24 hours, more preferably between 5~24 hours.Firing time is long or very few, can not all obtain required fit
Work as nitride.And the heating rate of firing need to be controlled especially, that is, when being less than 150 DEG C of melting point metal or less, heating rate need to be compared with
It is slow, such as 5 DEG C/minute of heating rate is preferred, more preferably, reason is to carry out nitride metal reaction to 3 DEG C/minute of heating rate
When, if heating rate is too fast near melting point metal, surface metal rapid melting easily occurs and carries out nitridation reaction, and can not
Appropriate strontium nitride needed for obtaining.The container of firing is preferred using BN (boron nitride) crucible, silicon nitride crucible, wherein with BN (nitrogen
Change boron) crucible is best.The nitridation reaction formula of strontium is as follows：
3Sr+N2→Sr3N2
The present invention fluorophor manufacture when, element A (+III valences), B element (+IV valences) raw material respective nitridation can be used
Object, oxide, any type of compound.For example, nitride (AN)/oxide (A of element A can be used in mixed way2O3) or A members
Nitride (AN, B of element, B element3N4).So-called " oxide ", however it is not limited to which the compound only closed with oxidation, other are such as carbonic acid
Salt, oxalates etc. can decompose in firing, and there is the compound containing the element and oxygen for substantially constituting oxide to also belong to
The range of aforementioned " oxide "；The case where nitride also refers to having the element and nitrogen compound.
Phosphor raw material of the present invention can be various various forms of predecessors, for convenience, below with nitride raw material
Illustrate as embodiment.Though each nitride raw material of element A, B element can be marketable material, because purity gets over Gao Yue
It is good, therefore the raw material for preferably preparing 3N or more is preferred.The grain size of each raw particles is preferably micro- for the viewpoint for promoting reaction
Particle, but with the grain size of raw material, the difference of shape, the grain size of obtained fluorophor, shape will be also varied from.As long as therefore
The grain size that final the obtained fluorophor of cooperation requires, prepares the nitride raw material with approximate grain size.The raw material of Eu elements
It is preferred with commercially available oxide, nitride raw material or metallic monomer, the higher the better for purity, preferably prepares 3N or more, especially with 4N or more
Raw material be preferred.
The hybrid mode of raw material can be dry process, damp process.Such as the wet ball-milling method of dry type ball-milling method or addition liquid
Etc. numerous embodiments, it is not limited to single mode.It weighs, mix Ca3N2、Sr3N2When because these compounds be easier to by
Oxidation, thus operated more suitably in the glove box under inert environment.In addition, because the nitride of each starting material element
It is easier to be influenced by moisture, thus the gas through fully removing moisture removal is preferred in non-active gas.Mixing arrangement can be used
The commonly used device such as ball mill or mortar.
It can be weighed according to certain proportion when preparing fluorophor, mix each raw material, be placed in crucible, be placed in high temperature furnace burn together
At.The stove used when firing, because firing temperature is high temperature, therefore preferably metallic resistance mode of heating or graphite resistance heating side
Formula.Method as firing, it is preferred that normal pressure sintering method or air pressure (with gas pressurized) sintering method etc. do not apply machine from external
The process for calcining of tool pressurization.Crucible is preferably the high-purity material without impurity, such as Al2O3Crucible, Si3N4Crucible, AlN
The crucible that crucible, the grand crucible of match, BN (boron nitride) crucible etc. can use in inert environment, but BN crucibles are preferred,
Because being mixed into can avoid the impurity from crucible.Firing atmosphere is non-oxidizing gas, for example, can be nitrogen, hydrogen, ammonia, argon
Deng or These gases arbitrary combination.The firing temperature of fluorophor be 1200 DEG C or more 2200 DEG C hereinafter, more preferably 1400 DEG C with
Upper 2000 DEG C hereinafter, heating rate is 3~15 DEG C/min.The subtleer fluorophor of grain size, higher temperatures can be obtained compared with firing under low temperature
Lower firing can obtain the larger fluorophor of grain size.Firing time is different according to raw material type and difference, General reactions time have been 1
~10 hours preferably.Pressure when firing under inert environment preferably (is preferred with 0.1MPa or less) in 0.5MPa or less especially
It is burnt into.It after the completion of firing, is cooled to room temperature, the modes such as ball milling or industrial size reduction machinery of can be used crush, and pass through later
Filter, is dry, being classified and etc., you can obtain the fluorophor of the present invention.
In order to obtain the fluorophor of high briliancy, fluorophor is when firing, because of the impurity in the addition of fluxing agent, raw material, place
The influence of the factors such as process contamination is managed, the impurity content being included in the fluorophor composition should be small as far as possible.Especially
The elements such as fluorine element, boron element, chlorine element, carbon when there are a lot, will inhibit to shine.Therefore the original of higher degree may be selected
Material, and control synthesis step avoid polluting so that the content of aforementioned elements is respectively smaller than 1000ppm.
When the present invention fluorophor in the form of powder in use, the average grain diameter of the fluorophor powder preferably 20 μm with
Under.Reason is because the luminous of fluorophor powder takes place mostly on particle surface, if average grain diameter is (so-called in the present invention
" average grain diameter " refers to volume medium particle diameter (D50)) at 20 μm hereinafter, the surface that will can ensure that fluorophor powder per unit weight
Product, avoids briliancy from reducing.In addition, when the fluorophor powder is coated on the upper situation of luminescence component, the fluorophor powder can be improved
The density of body, for this viewpoint, also can avoid briliancy reduces.In addition, according to the discussion of inventor, from the hair of fluorophor powder
For light efficiency viewpoint, it is preferable to learn average grain diameter to be more than 1 μm.According to above-mentioned, the average grain diameter of fluorophor powder of the present invention
Preferably at 1 μm or more and 20 μm hereinafter, being preferred especially with 3.0 μm or more and 15 μm of grain sizes below." average grain diameter so-called herein
(D50) " it is, to utilize Beckman Coulter corporation Multisizer-3, the value of gained is measured with Kurt method.
The fluorophor of the present invention is suitable for fluorescent display tube (VFD), Field Emission Display (FED), plasma display panel
(PDP), cathode-ray tube (CRT), light emitting diode (LED) etc..Especially, when use 455nm light sources irradiate the glimmering of the present invention
When body of light, the luminous dominant wavelength of fluorophor is 600~680nm, and 1931 chromaticity coordinates (x, y) of CIE for the tone that shines are 0.45
≤ x≤0.72,0.2≤y≤0.5, and glorious degrees are high, and therefore, fluorophor of the invention is especially suitable for light emitting diode.
The light-emitting device of the present invention includes semiconductor luminous assembly and the fluorophor of the present invention.Semiconductor luminous assembly is to send out
The light person for going out 300~550nm wavelength be it is preferable, especially with ultraviolet (or purple) semiconductor luminous assembly that sends out 330~420nm or
The blue semiconductor luminescence component of 420~500nm is preferable.As these luminescence components, semiconductor luminous assembly can be zinc sulphide
Or the various semiconductors such as gallium nitride, and with luminous efficiency for, it is preferable using gallium nitride semiconductor.Gallium nitride light-emitting component can be by
By the methods of Metalorganic chemical vapor deposition method (MOCVD) or hydrite vapor phase epitaxy method (HVPE) in forming nitridation on substrate
Object semiconductor, with InαAlβGa1-α-βIt is best that N (0≤α, 0≤β, (alpha+beta) ＜ 1) is formed by semiconductor luminous assembly.Semiconductor
Construction can be the homophaneous structures such as MIS engagements, PIN engagements, PN engagements, heterojunction construction or double heterojunctions construction.In addition, can
Its emission wavelength is controlled by the material of semiconductor layer or its mixed crystal degree.
In the light-emitting device of the present invention, other than the fluorophor of the present invention is used alone, it can also shine with other
The fluorophor of characteristic is used together, to constitute the light-emitting device that can send out wanted color.For example, using 330~420nm's
Ultraviolet light semiconductor luminous assembly, the blue-fluorescence for being excited and sending out 420nm or more and 500nm or less wavelength in this wavelength
The combination of the fluorophor of body, the green-emitting phosphor for sending out 500nm or more and 570nm or less wavelength and the present invention.Aforementioned blue
Fluorophor citing can be BaMgAl10O17：Eu, green-emitting phosphor can be β-Sialon phosphor.It constitutes according to this, works as semiconductor light emitting
When the ultraviolet light that component is sent out is irradiated in fluorophor, the three coloured light of red, green, blue can be sent out, white is mixed to via it
Light-emitting device.
In addition, still using the blue semiconductor luminescence component of 420~500nm, be excited in this wavelength and send out 550nm
Above and the yellow fluorophor of 600nm wavelength below and the present invention fluorophor combination.Aforementioned yellow fluorophor, example
Such as can be (Y, Gd)3(Al、Ga)5O12：Ce.It constitutes according to this, when the blue light that semiconductor luminous assembly is sent out is irradiated in fluorescence
When body, red, yellow dichroscope can be sent out, the blue light of these and semiconductor luminous assembly itself is mixed to white or band
The luminaire of light bulb color.
In addition, still using the blue semiconductor luminescence component of 420~500nm, be excited in this wavelength and send out 500nm
Above and the combination of the green-emitting phosphor and fluorophor of the present invention of 570nm wavelength below.Such green-emitting phosphor citing can
For β-Sialon phosphor.It constitutes, when the blue light that semiconductor luminous assembly is sent out is irradiated in fluorophor, can send out according to this
The blue light of these and semiconductor luminous assembly itself is mixed to the luminaire of white by red, green dichroscope.
[Examples and Comparative Examples]
Hereinafter, the embodiment of the present invention is illustrated, but the present invention is not limited to this.
Measurement method explanation：
(1) fluorophor briliancy and chromaticity coordinate：Fluorophor is measured with TOPCON brightness photometers SR-3A using 455nm irradiations.Brightness
It is within ± 0.3% that angle value, which measures difference,.
(2) light-emitting phosphor dominant wavelength：It is measured with the Fluoro Max-3 of Jobin YVON.Luminous dominant wavelength refers to
When using 455nm light excited fluophors, the wavelength of fluorophor maximum emission intensity.
(3) analysis of fluorophor component：
(3-1a) instrument：With the ULTIMA-2 type inductively coupled plasma atomic emission spectrometries (ICP) of Jobin YVON into
Row measures.
(3-1b) sample pre-treatments：Na is added in platinum crucible in the accurate sample for weighing 0.1g2CO31g is uniformly mixed
Afterwards, (temperature condition is melted with 1200 DEG C of high temperature furnaces：1200 DEG C are reached by room temperature 2 hours, in 1200 DEG C of constant temperature 5 hours),
Acid solution, such as 25ml HCl (36%) are added after fusant cooling, and dissolves by heating to clarifying, 100ml is placed in after cooling
It is quantitative to graticule with pure water in PFA volumetric bottles.
(3-2a) instrument：The nitrogen oxygen analyzer of Horiba.Model EMGA-620W.
(3-2b) is measured：By in fluorophor 20mg merging tin capsules, it is positioned in crucible, measures.
(4) regular strontium dissolution is fixed containing measuring：
(4-1a) instrument：With the ULTIMA-2 type inductively coupled plasma atomic emission spectrometries (ICP) of Jobin YVON into
Row measures.
(4-2a) pre-treatment：Take 200 μ s/cm fluorophor below of electrical conductivity, according to fluorophor than pure water be 1：100 weight
Amount ratio adds pure water, forms the mixed solution of fluorophor and water, and after 80 DEG C, heating in 40 hours, the cooling mixed solution is extremely
Via the membrane filtration in the apertures 0.45nm, which is directly measured using ICP room temperature.
(5) dionic tester：The sc-170 of suntex.
(6) fluorophor D50Average grain diameter is analyzed：It is measured with Beckman Coulter Multisizer-3.D50Table
Show that grain size accounts for the 50% of particle total volume less than the particle accumulation volume of the value.
Embodiment 1
Strontium metal (2N) needed for preparing, which is placed under pure nitrogen gas atmosphere, to be burnt into, and reaction condition is that nitrogen flow rate is 85 liters/min,
It is started to warm up from room temperature to medium temperature, heating rate is 10 DEG C/minute, and change heating rate is 3 when 620 DEG C of medium temperature
DEG C/minute, until 900 DEG C.It is maintained at constant temperature at 900 DEG C to be burnt into 24 hours, is down to room temperature with 10 DEG C/minute later, can get nitridation
Strontium (Sr3N2) compound.
The Sr of above-mentioned synthesis3N2With commercially available Ca3N2(2N)、AlN(3N)、Si3N4(3N)、Eu2O3(4N), according to Ca3N2It takes
0.2/3 mole, Sr3N2Take 0.792/3 mole, AlN take 1 mole, Si3N4Take 1/3 mole, Eu2O3Take 0.008/2 mole of ratio
Each raw material powder is weighed, and is mixed using mortar in glove box in a nitrogen environment.Each element in raw material mixed powder end
Molar ratio be shown in Table 2.Aforementioned raw material mixed-powder is placed in boron nitride crucible, and this crucible is placed in high temperature furnace, in stove
Atmosphere is the environment of high-purity nitrogen, and 80 liters/min of gas flow is warming up to 1800 DEG C according to the heating rate of 10 DEG C/min, and in
It is kept for 12 hours and is burnt at 1800 DEG C, be down to room temperature according to the speed of 10 DEG C/min later, and via crushing, ball milling, mistake
Filter, is dry, being classified and etc., it can get fluorophor of the present invention.Average grain diameter (D50) analysis result be 8.3 μm.Nitrogen oxygen analyse and
Icp analysis result is Ca：4.75 weight %, Sr：33.79 weight %, Al：16.20 weight %, Si：16.90 weight %, N：
24.02 weight %, O：1.56 weight %, Eu：0.73 weight %, therefore when on the basis of 1 mole of Al, practical composition formula is
Ca0.1974Sr0.6423Al1Si1.0022N2.8562O0.1624：Eu0.0080, that is, CapSrqMm-Aa-Bb-Ot-Nn：Eur, p=in formula
0.1974, q=0.6423, m=0, t=0.1624, r=0.0080, a=1, b=1.0022, n=2.8562.Take electrical conductivity small
In 0.1 gram of 200 μ s/cm fluorophor below, the weight ratio for being 1 to 100 than pure water according to fluorophor adds pure water, after mixing
The glass container is sealed, after 80 DEG C, heating in 40 hours, is cooled to room temperature, detects the content of strontium in the water phase of the mixed solution
For 1.0ppm, regular content of strontium is 1.0/0.6423=1.6ppm.Also, after the fluorophor is excited with 455nm light, it is measured
The dominant wavelength that shines is 616nm, CIE 1931 chromaticity coordinates x=0.634, y=0.364, and glorious degrees are 165% (see table 3).This
The glorious degrees of embodiment and comparative example in invention mean the glorious degrees (100%) relative to 7 fluorophor of following comparative examples
For.
Embodiment 2~4 and comparative example 1~3
Strontium nitride synthesis condition is carried out according to 1 condition of table, and the molar ratio of each element is shown in Table 2 in raw material mixed powder end,
Tail sequence is the same as embodiment 1.The test result of fluorophor physical property is with reference to table 3.It can be found by the experimental result of table 3, be adjusted by nitrogen
Change the firing condition of strontium, regular strontium dissolves out content when within the scope of 1~20ppm, has preferable brightness value.
Embodiment 5~8 and comparative example 4~6
Strontium nitride synthesis condition is carried out according to 1 condition of table, and the molar ratio of each element is shown in Table 2 in raw material mixed powder end,
Tail sequence is the same as embodiment 1.Fluorophor physical property measurement result is with reference to table 3.It can get and above-mentioned identical conclusion by experimental result.Just
Ruleization strontium dissolves out content when within the scope of 1~20ppm, has preferable brightness value.
Embodiment 9~11 and comparative example 7~8
Strontium nitride synthesis condition is carried out according to 1 condition of table, and the molar ratio of each element is shown in Table 2 in raw material mixed powder end, table 2
In, Y uses Y2O3(3N), Ge use GeO2(3N), Zn use ZnO (3N), remaining program is the same as embodiment 1.Fluorophor physical property measurement
As a result with reference to table 3.It can get and above-mentioned identical conclusion by experimental result.Regular strontium dissolves out content within the scope of 1~20ppm
When, there is preferable brightness value.
Table 1
Note："-" indicates that medium temperature is equal to and maintains temperature in table 1.
Table 2
Table 3
The briliancy of fluorophor of the present invention is measured from via a briliancy measuring device, as shown in Figure 1, the briliancy measures dress
Babinet 11, sample groove 12, a light source 13, a light guide skirt 14, a speculum 15 and the brightness photometer 16 for including a black are set,
Wherein, which is seated in the babinet 11, which is that about 5 centimeters of height of the vertical sample cell 12 are arranged, the light
14 diameter of guide wire is about 2 centimeters and is arranged with 13 angle at 45 ° of light source, which is arranged in the light guide skirt 14,
And with the sample cell 12 apart from about 8 centimeters, and the brightness photometer 16 is about 40 centimeters at a distance from the speculum 15, when being placed in the sample
After fluorophor in product slot 12 is irradiated via the light source 13, the fluorescence that fluorophor is sent out can be via the light guide skirt 14 and speculum
15 exposure level is directed to the brightness photometer 16 and carries out briliancy measurement.
Specifically, in foregoing embodiments and comparative example of the present invention, the briliancy measurement of fluorophor is to take sample to be tested 1.3
Gram merging sample cell 12 in, and through flatten so that sample is uniformly distributed in the sample cell 12, the sample cell 12 is then placed in the case
In body 11, the 13 vertical irradiation sample of light source that emission wavelength is 455nm, and brightness photometer 16 (TOPCON systems, the model are used
SR-3A it is) to detect the fluorescent intensity that the fluorophor is sent out after light source irradiates using 1 ° of sense mode of field.
It is noted that the dominant wavelength of the luminescent spectrum of the fluorophor refers to the maximum wavelength of luminous intensity.
Then, this is made after the fluorophor sample of aforementioned various embodiments of the present invention and semiconductor luminous assembly being packaged
The light-emitting device of invention.
Referring to Fig.2, light emitting device embodiment of the present invention includes semiconductor luminescence component 21, a fluorescence coating 22 and one encapsulation
Layer 23.
Wherein, which includes a pedestal that is electrically conductive and having the loading end 212 for being in without exception concave
211, LED crystal particle 213, the connecting line 214 for being set to the concave loading end 212 and being electrically connected with the pedestal 211
It is electrically connected with the LED crystal particle 213, a conducting wire 215 is electrically connected with the connecting line 214；Wherein, which leads with this
Line 215 can coordinate from the extraneous electric energy that provides to the LED crystal particle 213, which can be by receiving
Electric energy is converted into luminous energy and sends out.The present embodiment is by a commercially available emission wavelength 455nm, the blue LED of InGaN
213 (manufacturer of crystal grain：Strange power photoelectricity) with conductive silver glue (model：BQ6886, manufacturer：UNINWELL) bonding is in the pedestal
On 211 loading end 212, then extends from 213 top surface of LED crystal particle and be electrically connected with the LED crystal particle 213
The connecting line 214 and the conducting wire 215 connect.
Aforementioned fluorescent layer 22 coats the LED crystal particle 213.Fluorophor 221 is by this contained in fluorescence coating 22
After the excitation for the light that LED crystal particle 213 is sent out, the light sent out different from excitation wavelength can be converted, in the present embodiment
In, which is that the polysilane oxygen resin containing 35 weight % fluorophor 221 is coated on the LED crystal particle 213
Outer surface, and formed after dry harden.
The encapsulated layer 23 coat the pedestal 211 of 21 part of semiconductor luminous assembly, connecting line 214, part conducting wire 215
And the fluorescence coating 22.
In conclusion ratio of the present invention by each element in phosphor structures, and coordinate the normalization of control fluorophor
Strontium dissolves out content between 1~20ppm, you can obtains the high briliancy fluorophor that a luminous dominant wavelength is 600~680nm.And it should
Fluorophor collocation semiconductor luminous assembly, can obtain the light-emitting device of high briliancy simultaneously.
Only as described above, only presently preferred embodiments of the present invention, when the model that cannot be limited the present invention with this and implement
It encloses, i.e., all still belongs to according to simple equivalent changes and modifications made by scope of the present invention patent and invention description content generally
In the range of patent of the present invention covers.
Claims (13)
1. a kind of manufacturing method of fluorophor, which is characterized in that the method includes：
Prepare strontium element raw material, wherein the strontium element raw material is prepared by firing by the way that strontium metal to be placed under nitrogen atmosphere
, firing heating rate is 3-5 DEG C/minute when 150 DEG C of strontium melting point metal is following, and firing temperature is 600~1000 DEG C, and nitrogen
Gas velocity is 70-90 liters/min；
By the strontium element raw material, CaCl2, the oxide of element A and/or nitride, the oxide of B element and/or nitridation
Object, the oxide of Z elements, nitride and/or metallic monomer (simple substance) and/or the oxide of M element are weighed, are mixed simultaneously respectively
Be placed in crucible, wherein A is the group that is formed selected from aluminium, gallium, indium, scandium, yttrium, lanthanum, gadolinium and gold-plating, B for selected from silicon, germanium,
The group that tin, titanium, zirconium and hafnium are formed, Z elements are the group that is formed selected from europium and cerium, M be selected from magnesium, barium, beryllium and
The group that zinc is formed；And
It is 1200 DEG C or more 2200 DEG C or less and heating speed that the raw material of aforementioned mixing, which is placed in high temperature furnace together with firing temperature,
Degree is burnt into for 3~15 DEG C/minute of condition, and the fluorophor is made；
Wherein, the composition formula of the fluorophor is CapSrqMm-Aa-Bb-Ot-Nn:Zr, wherein 0 ＜ p ＜ 1,0 ＜ q ＜ 1,0≤m ＜
1,0≤t≤0.3,0.00001≤r≤0.1, a=1,0.8≤b≤1.2,2.7≤n≤3.1.
2. the manufacturing method of fluorophor according to claim 1, which is characterized in that the firing temperature of the strontium element raw material
It is 700~900 DEG C.
3. the manufacturing method of fluorophor according to claim 1, which is characterized in that the nitrogen flow rate be 80~90 liters/
Point.
4. the manufacturing method of fluorophor according to claim 1, which is characterized in that during the firing of the strontium metal,
Heating rate when being started to warm up from room temperature to medium temperature is 10 DEG C/minute, is started to warm up from medium temperature to when maintaining temperature
Heating rate be 3-5 DEG C/minute, wherein the medium temperature be 620 DEG C, maintain temperature be 750~900 DEG C.
5. the manufacturing method of fluorophor according to claim 1, which is characterized in that the firing time of the strontium element raw material
It is 3~24 hours.
6. the manufacturing method of fluorophor according to claim 1, which is characterized in that the firing time of the strontium element raw material
It is 5~24 hours.
7. the manufacturing method of fluorophor according to claim 1, which is characterized in that nitrogen gas purity is up to 99.99% or more.
8. the manufacturing method of fluorophor according to claim 1, which is characterized in that the firing temperature of the fluorophor is
1400 DEG C or more 2000 DEG C or less.
9. the manufacturing method of fluorophor according to claim 1, which is characterized in that the firing time of the fluorophor is 1
~10 hours.
10. the manufacturing method of fluorophor according to claim 1, which is characterized in that the firing pressure of the fluorophor is
0.5MPa or less.
11. the manufacturing method of fluorophor according to claim 1, which is characterized in that the firing pressure of the fluorophor is
0.1MPa or less.
12. the manufacturing method of fluorophor according to claim 1, which is characterized in that the p value is 0.05~0.9, described
Q values are 0.1~0.95.
13. the manufacturing method of fluorophor according to claim 1, which is characterized in that the p value is 0.2~0.65, described
Q values are 0.342~0.792.
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