CN102395649A - Red phosphor and method for producing same - Google Patents
Red phosphor and method for producing same Download PDFInfo
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- CN102395649A CN102395649A CN2010800166312A CN201080016631A CN102395649A CN 102395649 A CN102395649 A CN 102395649A CN 2010800166312 A CN2010800166312 A CN 2010800166312A CN 201080016631 A CN201080016631 A CN 201080016631A CN 102395649 A CN102395649 A CN 102395649A
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Abstract
Disclosed is a red phosphor which is obtained by activating a titanate represented by the following general formula: M2TiO4 (wherein M represents one or more alkaline earth metal elements) with Mn, and has an Si content of not more than 24,000 ppm. The red phosphor can be produced by a process including a step of mixing an alkaline earth metal source, a manganese source and a titanium source, a step of firing the resultant mixture to obtain a fired body, and a step of annealing the thus-obtained fired body. As the above-mentioned metal sources, those metal sources each having such an Si purity that the Si content in the resulting red phosphor is not more than 24,000 ppm are used.
Description
Technical field
The present invention relates to a kind of is the red-emitting phosphors and the method for manufacture thereof of mother metal with the titanate.
Background technology
In recent years, blue diode obtains practicability, and existing many is the research of the white light-emitting diode of photogen with this diode.Photodiode has light weight, does not use mercury and long-life advantage.
For example known have, with Y
3Al
5O
12: Ce coats the white light-emitting diode that blue light emitting device forms.Yet say that tightly this photodiode is not a white, turquois white is arranged but mix.Following scheme has been proposed thus: mix Y
3Al
5O
12: Ce sends the red-emitting phosphors of red fluorescence with absorbing blue light, thus the adjustment tone.The report of sending the red-emitting phosphors of red fluorescence about absorbing blue light, the report of organic system material aspect is more, but the report of inorganic based material aspect is few.
On the other hand, as general red-emitting phosphors, proposed inorganic based materials such as oxide phosphor, oxysulfide fluor, sulphide phosphor, nitride phosphor, also having proposed with the titanate is the fluor of mother metal.For example, in following patent documentation 1, proposed: to by formula M
2TiO
4Give the red light-emitting phosphor that Eu and the activation of 3 valencys obtain in the titanate shown in (M representes alkali earth metal).In addition, in following patent documentation 2, proposed: by formula M e
I xMe
II yTi
1-aO
4X
m: Mn
z(in the formula, Me
IBe divalence or tervalent positively charged ion, Me
IIBe the univalent positively charged ion, but X is the Cl or the F of balancing charge, 0≤x≤4,0≤y≤4,0≤m≤4,0≤a≤1,0＜z≤0.5) shown in red-emitting phosphors etc.
These are of the prior art to be that the fluor of mother metal obtains as follows with the titanate: through with dry type or wet mixing alkaline earth metal source, metatitanic acid source and activating component; Obtain the uniform mixture of these raw materials; Thereby carrying out roasting then obtains; There is the problem of luminous intensity aspect in the emitting red light body that is obtained, and quantum yield is also low.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-232948 communique
Patent documentation 2: TOHKEMY 2007-297643 communique
Summary of the invention
The problem that invention will solve
Therefore, the present invention provide a kind of through blue light excite and with high luminous intensity send red light red-emitting phosphors, with and industry go up favourable method of manufacture.
The scheme that is used to deal with problems
The inventor etc. further investigate in view of such truth repeatedly, and the result finds, for being mother metal with the titanate of being represented by certain formula and giving Mn and for the red-emitting phosphors that activation obtains, impurity impacts luminous intensity.The result who further studies, the inventor etc. have found that it is Si that luminous intensity is caused the impurity of big influence.
The present invention is based on aforementioned opinion and carry out, a kind of red-emitting phosphors is provided, it is characterized in that,
In by the titanate shown in the formula (1), give Mn and activation obtains, and Si content is below the 24000ppm,
M
2TiO
4 (1)
In the formula, M representes the alkali earth metal more than a kind or 2 kinds.
In addition, the present invention provides a kind of method of manufacture of red-emitting phosphors, it is characterized in that, it is the preferred method that is used to make aforementioned red-emitting phosphors,
Comprise: mixed alkaline earth source metal, manganese source and titanium source, the mixture roasting that is obtained is obtained the roasting body, then this roasting body is carried out the operation of anneal,
The material that uses as aforesaid each source metal has following purity: the amount of contained Si becomes amount such below the 24000ppm for the Si content that can make the red-emitting phosphors that is obtained in them.
The effect of invention
According to the present invention, a kind of high red-emitting phosphors of luminous intensity of red light can be provided.In addition, manufacturing method according to the invention can go up advantageous method through industry and make this red-emitting phosphors.
Description of drawings
Fig. 1 is the fluorescence spectrum (excitation wavelength 460nm) of the red-emitting phosphors of acquisition among the embodiment 1.
Embodiment
Below, based on preferred implementation the present invention is described.
Red-emitting phosphors of the present invention excites through blue light basically and sends red light.Particularly, the exciting light through 270～550nm, preferred 380～490nm excites at least.In addition, has luminous zone (promptly having red spectrum) in the zone of 600～750nm, preferred 650～700nm.
Red-emitting phosphors of the present invention is for giving the material that the Mn activation obtains in by the titanate shown in the formula (1).
M
2TiO
4 (1)
(in the formula, M representes the alkali earth metal more than a kind or 2 kinds.)
M in the general formula (1) is the alkali earth metal more than a kind or 2 kinds that is selected from the group of being made up of calcium, magnesium, strontium and barium, in the middle of these, from the light of the wavelength through blue region be excited, and the viewpoint of sending red light efficiently consider that preferred M is a magnesium.Explain that when M was the alkali earth metal more than 2 kinds, general formula (1) became M
I X1M
II X2M
N XnTiO
4, X1, X2 ... Xn is for satisfying X1+X2+ ... The positive number of+Xn=2.
Making titanate activatory Mn is more than a kind or 2 kinds of divalent～4 valencys, particularly considers and the Mn of preferred 4 valencys from the high viewpoint of the luminous intensity of red area.As far as carrying out the content of activatory Mn, the viewpoint high from luminous efficiency, that luminous intensity is excellent considers, with respect to titanate, is preferably 0.01～2.5mol%, is preferably 0.25～1.0mol% especially in the Mn atom.
Red-emitting phosphors of the present invention is characterised in that it has aforementioned component, and does not contain Si in fact, and particularly Si content is below the 24000ppm.Si content is preferably below the 15000ppm, further is preferably below the 100ppm.In red-emitting phosphors of the present invention, because Si is the reduction luminous intensity, so Si content is few more preferred more.Si content can be reduced to about 20ppm at present.If the Si content of this level then shows fully high luminous intensity.
The red-emitting phosphors that activation obtains in by the titanate shown in the general formula (1), to give Mn is representative, in the past as red-emitting phosphors and in the known inorganic based material, generally comprise the various impurity of source metal of being derived from as raw material etc.Yet, the report that all the time the red-emitting phosphors performance is not impacted about impurity.The inventor etc. particularly in by the titanate shown in the general formula (1), giving Mn and the performance of the red-emitting phosphors that activation obtains, pay close attention to impurity and study, and the result has found that impurity impacts luminous intensity.Further advance research and known that Si causes big influence to luminous intensity among the impurity.Knownly in the past in by the titanate shown in the general formula (1), give Mn and in the red-emitting phosphors that activation obtains (material that the method for record is prepared in for example through patent documentation 2), contain the Si about 25000ppm.If it is made for below the 24000ppm according to mode given to this invention, aspect luminous intensity, confirm to improve significantly effect so.
For the Si content in the red-emitting phosphors of the present invention, for example can analyze quantitatively through fluorescent x-ray analyzer (ZSX100e) that uses the Rigaku corporate system and the interior K α line peak intensity value of scope of utilizing 108～110 degree.In addition, though also indeterminate, can think that Si is with Si in red-emitting phosphors of the present invention
4+Form exist with the state of solid solution in the fluor crystal.
Red-emitting phosphors of the present invention is a powder, and its particle shape does not receive special restriction.Particle shape for example can be spherical, polyhedral, spindle shape, needle-like, can also be for amorphous.Consider from the viewpoint of the assimilated efficiency of further raising exciting light etc., preferably spherical.
The median size of red-emitting phosphors of the present invention is preferably 1～30 μ m, is preferably 10～25 μ m especially.If median size less than 1 μ m, the easy scattering of exciting light so, the assimilated efficiency of exciting light is tended to reduce.If median size surpasses 30 μ m, granule surface area is easy to diminish so, and the absorption of same exciting light is easy to become insufficient.Explain that the median size of being sayed among the present invention all is meant primary particle cohesion and the median size of the second particle that forms.This median size is a median particle diameter.The median size of second particle (median particle diameter) for example can be made made laser diffraction/diffuse transmission type particle size distribution device (model LA920) by the hole field and measured, and is 1.81, is 1.33 with the specific refractory power of dispersion medium that with the specific refractory power of sample by volume benchmark is calculated.
Median size for example can be regulated as following.That is, through automatic mortar or ball mill etc. to by after the roasting body that obtains of the calcining process stated implement pulverization process, according to circumstances use the sieve of the mesh that conforms to target grain size to carry out classification, thereby can obtain to have the powder of desirable median size.
The BET specific surface area of red-emitting phosphors of the present invention is preferably 0.05～1.0m
2/ g is preferably 0.1～0.5m especially
2/ g.If the not enough 0.05m of BET specific surface area
2/ g, the absorption of exciting light is easy to become insufficient so.If the BET specific surface area surpasses 1.0m
2/ g follows surface-area big and median size is little so, so the absorption that scattering and exciting light take place exciting light sometimes becomes insufficient sometimes.The BET specific surface area for example can be measured through the BET method Monosorb specific area measuring device (Flow Sorb II 2300) that uses Shimadzu Seisakusho Ltd.'s system.
The BET specific surface area for example can be regulated as following.That is, through automatic mortar or ball mill etc. to by after the roasting body that obtains of the calcining process stated implement pulverization process, according to circumstances use the sieve of the mesh that conforms to target grain size to carry out classification, thereby can obtain to have the powder of desirable BET specific surface area.
Then, the preferable production process to red-emitting phosphors of the present invention describes.
The method of manufacture of red-emitting phosphors of the present invention comprises: mixed alkaline earth source metal, manganese source and titanium source, the mixture roasting that is obtained is obtained the roasting body, and then this roasting body is carried out the operation of anneal.That is, the method for manufacture of red-emitting phosphors of the present invention is roughly distinguished and is comprised (a) mixed processes, (b) calcining process and (c) anneal operation.
(a) in the mixed processes, thereby uniform mixture is prepared in uniform mixing alkaline earth metal source, manganese source and titanium source.
As the alkaline earth metal source of the 1st raw material, for example can use oxide compound, oxyhydroxide, carbonate, nitrate salt, vitriol, organic acid salt of earth alkali metal etc.Can use in these compounds more than a kind or 2 kinds.From the not viewpoint of residual impurity and raw material reactive high viewpoint consideration to each other after roasting, preferred oxyhydroxide in the middle of these.Alkaline earth metal source is not that the state with solution such as the aqueous solution uses, but uses with the state of solid (powder).As alkaline earth metal source, consider that from carrying out mixed uniformly viewpoint easily preferably using median size is the material that 5 μ m are following, be in particular 0.2～2 μ m.
As the manganese source of the 2nd raw material, for example can use oxide compound, oxyhydroxide, carbonate, nitrate salt, vitriol, organic acid salt of manganese etc.Can use in these compounds more than a kind or 2 kinds.From the viewpoint of residual impurity and consider preferred manganous carbonates in the middle of these not after roasting with respect to the viewpoint that parent is formed easy solid solution.Also use with the state of solid (powder) in the manganese source.As the manganese source, consider that from carrying out mixed uniformly viewpoint easily preferably using median size is the material that 10 μ m are following, be in particular 1～9 μ m.
As the titanium source of the 3rd raw material, for example can use titanyl compound, oxyhydroxide, halogenide, alkoxide cpd etc.Can use in these compounds more than a kind or 2 kinds.From the not viewpoint of residual impurity and the comparable viewpoint consideration that is easier to obtain after roasting, preferred titanium oxide (TiO in the middle of these
2).Titanium oxide (the TiO that uses
2) can be the material that obtains through sulfuric acid process or chlorine method, in addition, also can not receive restrictedly to use especially the material of Detitanium-ore-type or rutile-type.In addition, also use with the state of solid (powder) in the titanium source.As the titanium source, consider that from carrying out mixed uniformly viewpoint easily preferably using median size is the material that 5 μ m are following, be in particular 0.2～2 μ m.
As previously mentioned, red-emitting phosphors of the present invention particularly is that Si content is the material below the 24000ppm for not containing the material of Si in fact.Therefore, in the mixed processes, the material that uses as aforesaid each source metal has following high purity: the amount of contained Si becomes amount such below the 24000ppm for the Si content that can make the red-emitting phosphors that is obtained in them.
Discoveries such as the inventor, the Si that sneaks into red-emitting phosphors mainly is derived from the titanium source of raw material (for example titanium oxide).In the present invention, as employed titanium source, preferably use Si content as below the 9000ppm, be in particular below the 6000ppm, especially be the highly purified material below the 100ppm.As the titanium source of raw material, can use commercially available article.In the commercially available article, the preferred above-mentioned highly purified titanium source of use of selecting.
Aspect alkaline earth metal source and manganese source, also likewise preferably use the low highly purified material of Si content with the titanium source.But, the Si content in alkaline earth metal source and manganese source is generally low than titanium source, therefore can not become problem usually in the present invention.Alkaline earth metal source preferably uses the material of the purity below the Si content 100ppm, and the material of the purity below the Si content 100ppm is preferably used in the manganese source.About alkaline earth metal source and manganese source, even general commercially available article also can satisfy these Si content.
With regard to the blending ratio in alkaline earth metal source and titanium source; Consider that from obtaining the most excellent viewpoint of single die and internal quantum the alkaline earth metal atom in the alkaline earth metal source (M) is preferably 1.6～2.5, is preferably 1.8～2.2 especially with respect to the mol ratio (M/Ti) of the titanium atom in the titanium source (Ti).
On the other hand, with regard to the blending ratio in manganese source, consider that from absorbing the also excellent viewpoint of exciting light and light conversion efficiency well with respect to the titanate that is obtained, the Mn atom is preferably 0.01～3mol%, is preferably 0.1～1.5mol% especially.
Though the Si content in the final red-emitting phosphors that obtains also receives the influence of the concrete kind of employed each source metal; If but adopt the source metal and the preferred blending ratio of aforesaid preferred purity, then can make the Si content of red-emitting phosphors usually is below the 24000ppm.
Method as alkaline earth metal source, manganese source and the titanium source of mixing the 1st～the 3rd raw material can be any in damp process and the drying process; But consider from the viewpoint that can obtain the mixed uniformly uniform mixture of each raw material easily, preferably carry out with damp process through mechanical.Particularly through carrying out combination treatment as pulverizing simultaneously with the medium grinding machine (media mill) of blended machine and with damp process; Thereby can obtain uniform mixture more easily; In addition, use this uniform mixture and the luminous intensity of the red-emitting phosphors that obtains is high especially.
Further specify the combination treatment of working medium grinding machine.
Combination treatment in the medium grinding machine consists essentially of: the pulp preparation operation, the slurry that is obtained is directed in the medium grinding machine and carries out the mixed processes of combination treatment.
In the pulp preparation operation, alkaline earth metal source, manganese source and titanium source are scattered in dispersion medium and process slurry.As dispersion medium, can make any in water and the nonaqueous dispersion medium.Consider from the viewpoint of handling easy grade, preferably make water as dispersion medium.
, operability little from treatment scale is easy to viewpoint to be considered, the solid concentration of slurry (total concn in alkaline earth metal source, manganese source and titanium source) is preferably 5～40 weight %, is preferably 10～30 weight % especially.
Can in slurry, add dispersion agent.Through adding dispersion agent, alkaline earth metal source, manganese source and titanium source are scattered in the dispersion medium more equably.Its result can obtain the uniform mixture of these raw materials more easily.With regard to employed dispersion agent, select suitable dispersion agent to get final product according to the kind of dispersion medium.Dispersion medium is under the situation of water, can use various tensio-active agents, poly carboxylic acid ammonium salt etc. as dispersion agent.Consider that from the viewpoint of sufficient dispersion effect the concentration of the dispersion agent in the slurry is preferably 0.01～10 weight %, is preferably 1～5 weight % especially.
Explain; Dispersion medium that uses in the preparation as far as slurry and dispersion agent; Also preferably using Si content is few material of trying one's best; But usually as long as use aforesaid dispersion medium and dispersion agent, the Si that does not have the amount that the luminous intensity to red-emitting phosphors impacts so serves as to originate to sneak in red-emitting phosphors with said dispersion medium and dispersion agent.In addition, in method of manufacture of the present invention, there are not the factor of the Si that causes sneaking into the degree that the luminous intensity to red-emitting phosphors impacts in each source metal of in pulp preparation, using, dispersion medium and the dispersion agent.
Then, through will being directed in the medium grinding machine and carrying out combination treatment, thereby obtain uniform mixture by the slurry that the pulp preparation operation obtains.As the medium grinding machine, can use ball mill, ball mill, paint shaker, masher, sand mill etc.Especially preferably use ball mill.In this case, kind of operating condition, pearl and big I are suitably selected according to the kind in device size, treatment capacity, alkaline earth metal source, manganese source and titanium source etc.
Consider that from obtaining more uniformly the viewpoint of mixture the median size (median size of second particle) that the combination treatment of carrying out through damp process preferably proceeds to solid substance becomes 0.05～1 μ m, preferred especially 0.1～0.5 μ m.
After combination treatment, reclaim from the slurries filtration uniform mixture.Preferably in advance the uniform mixture that is reclaimed is carried out drying treatment before (b) calcining process paying.Drying treatment for example can be carried out under 80～200 ℃ 1～100 hour.
Then, will pay calcining process, thereby obtain the roasting body by the uniform mixture that (a) mixed processes obtains in (b).With regard to roasting condition, maturing temperature is preferably 1150～1600 ℃, is preferably 1200～1350 ℃ especially.If 1150 ℃ of maturing temperature less thaies are difficult to single-phase acquisition parent crystal so, light emitting ionic is difficult to solid solution in addition; On the other hand, if above 1600 ℃, existing particle sintering to each other excessively to carry out so, maturing temperature causes being difficult to obtain the tendency of powder.Roasting time is more than 1 hour, is preferably 3～20 hours especially.The not special restriction of the atmosphere of roasting can be in the oxidizing gas atmosphere such as atmosphere and in the non-active gas atmosphere any.
The roasting body that obtains is crushed to desirable particle diameter as required, pays in the anneal operation of back with the state of powder.Roasting can be carried out repeatedly according to hope.Perhaps, be uniform purpose from making the characteristic of powder, can the article that roasting once obtains are broken, then carry out roasting once more.In addition also can be before carrying out the anneal operation, thus carry out adjustment particle property such as classification as required and in advance.
Then, will pay in (c) anneal operation through the roasting body that (b) calcining process obtains, thereby obtain red-emitting phosphors of the present invention.Through carrying out this anneal, thereby can significantly improve luminous intensity.Through carrying out reason that this anneal makes that luminous intensity uprises and unclear, but can think that this is because convert into luminous efficiently thereby parent crystalline structure is changed to the luminous energy that regular crystal can make light emitting ionic absorb from cube crystalline substance.
With regard to the condition of anneal, treatment temp is preferably 500～800 ℃, is preferably 570～690 ℃ especially.Its reason is, if 500 ℃ of anneal temperature less thaies change just do not cause crystal so; On the other hand, if the anneal temperature surpasses 800 ℃, there is the tendency that reverts to cube crystalline substance once more so.The anneal time is preferably more than 1 hour, is preferably 3～24 hours especially.The not special restriction of the atmosphere of anneal can be in the oxidizing atmospheres such as oxygen, atmosphere and in the non-active gas atmosphere any.Explain, also can carry out anneal repeatedly as required.
Red-emitting phosphors after the anneal also can be crushed to desirable particle diameter as required or carry out classification etc.
The red-emitting phosphors of operating like this and obtaining can be applicable to the for example purposes of the indicating meter of field emission display, plasma display, electroluminescent (electroluminescence) etc.In addition, owing to have near the excitation spectrum the 460nm front and back, therefore excite purposes with fluor applicable to blue led.Be particularly suitable for the purposes of electroluminescent indicating meter.In addition; Through the method for share with the blue excitation green-emitting phosphor; The method of share with blue-led element and blue excitation green-emitting phosphor and using is perhaps share with blue-led element and blue excitation yellow luminescent phosphor and method of using etc., thereby also applicable to White LED.
Embodiment
Below through embodiment the present invention is described, but the present invention is not subject to these embodiment.
Following embodiment and the Si content in the comparative example, median size and BET specific surface area are measured as following respectively.
Si content: use the fluorescent x-ray analyzer (ZSX100e) of Rigaku corporate system and utilize the interior K α line peak intensity value of scope of 108～110 degree to analyze quantitatively.
Median size: make made laser diffraction/diffuse transmission type particle size distribution device (model LA920) by the hole field and measure, be 1.81, be 1.33 that with the specific refractory power of sample by volume benchmark is calculated with the specific refractory power of dispersion medium.
BET specific surface area: use the BET method Monosorb specific area measuring device (Flow Sorb II 2300) of Shimadzu Seisakusho Ltd.'s system to measure.
[embodiment 1]
The titanium oxide (median size 0.64 μ m) and the manganous carbonate (median size 5.2 μ m) that with Marinco H (median size 0.57 μ m), Si content are 4676ppm are according to magnesium: titanium: the mol ratio of manganese is in 2: 0.996: 0.004 the mode weighing and tank filling.In jar, add entry and dispersion agent (flower king (strain) system, Port イ ズ 2100), prepare the slurry that solid concentration is 15 weight %.The concentration of dispersion agent is 2.0 weight %.
Stir slurry on one side, Yi Bian use the zirconia ball of diameter 2.0mm to carry out ball milling 150 minutes, thus carried out pulverizing based on the mixing of damp process.Through the median size that light scattering determining mixes the raw mix in the slurry after pulverizing, it is 0.5 μ m.
Then, reclaim, obtained dry powder 120 ℃ of dryings 10 hours from the slurries filtration mixture.The median size of dry powder is that 0.5 μ m and slope of repose are 45 °.
Then, with the dry powder electric furnace of packing into, under atmosphere 1250 ℃ of roastings 5 hours under static condition.Then, with roasting powder turn back to room temperature (20 ℃) for the time being afterwards, under oxygen atmosphere 600 ℃ of anneal 16 hours.
To the powder after the anneal, analyze based on X-ray diffraction mensuration.Confirm according to analytical results, the powder that is obtained is Mg
2TiO
4: 0.4mol%Mn
4+
[comparative example 1]
Use titanium oxide (median size 0.64 μ m, the BET specific surface area 6.7m of Si content as 9351ppm
2/ g) replace among the embodiment 1 titanium oxide that uses, in addition, according to having obtained powder with embodiment 1 same operation and condition.The powder that is obtained has been carried out the analysis same with embodiment 1.Analytical results and embodiment 1 are same, and confirming the powder that is obtained is Mg
2TiO
4: 0.4mol%Mn
4+
< mensuration of Si content, median size and BET specific surface area >
The fluor sample that obtains in embodiment 1 and the comparative example 1 has been carried out the mensuration of Si content, median size and BET specific surface area.To measure the result and be shown in table 1.
< evaluation of fluorescent characteristic >
Fluor sample to obtaining in embodiment 1 and the comparative example 1 has been measured the very big wavelength of the luminescent spectrum under the excitation wavelength 460nm, luminous intensity and the cie color under this very big wavelength.To measure the result and be shown in table 1.Explain that greatly the luminous intensity under the wavelength is expressed as, the luminous intensity of the fluor sample of comparative example 1 is made as 100 o'clock relative intensity value.In addition, Fig. 1 representes the fluorescence spectrum of the fluor sample of acquisition among the embodiment 1.
The mensuration of luminescent spectrum and cie color is carried out as following.
Luminescent spectrum: use spectrophotofluorometer (Hitachi High-Technologies Corporation system), exciting light is 460nm, and the scope to 430 to 800nm scans and obtained spectrum.
Cie color: obtained xy table chroma color coordinate according to the fluorescence spectrum relative value under the excitation wavelength 460nm and according to JIS Z 8701.
[embodiment 2]
Use Si content to replace the titanium oxide that uses among the embodiment 1 as the titanium oxide (median size 0.64 μ m) of 9.4ppm, in addition, according to having obtained powder with embodiment 1 same operation and condition.The powder that is obtained has been carried out the analysis same with embodiment 1.Analytical results and embodiment 1 are same, and confirming the powder that is obtained is Mg
2TiO
4: 0.4mol%Mn
4+For the powder that obtains, likewise operate with embodiment 1, carried out the mensuration of Si content, median size and BET specific surface area and the evaluation of fluorescent characteristic.The result is shown in table 1.
Table 1
Record according to table 1 can know that obviously Si content impacts the luminous intensity of red-emitting phosphors.When Si content is below the 24000ppm, then confirming has the raising effect to luminous intensity; When Si content be (embodiment 1) below the 15000ppm, in particular for 100ppm below (embodiment 2), then confirm to have extremely high raising effect.
Claims (11)
1. a red-emitting phosphors is characterized in that,
In by the titanate shown in the formula (1), give Mn and activation obtains, and Si content is below the 24000ppm,
M
2TiO
4 (1)
In the formula, M representes the alkali earth metal more than a kind or 2 kinds.
2. red-emitting phosphors according to claim 1, it is luminous through the exciting light of 270～550nm.
3. red-emitting phosphors according to claim 1 and 2, its zone at 600～750nm has luminous zone.
4. according to each described red-emitting phosphors in the claim 1～3, the M in the said general formula (1) is Mg.
5. according to each described red-emitting phosphors in the claim 1～4, its median size is 1～30 μ m.
6. the method for manufacture of a red-emitting phosphors is characterized in that,
It is the method for the described red-emitting phosphors of manufacturing claim 1,
Comprise: mixed alkaline earth source metal, manganese source and titanium source, the mixture roasting that is obtained is obtained the roasting body, then this roasting body is carried out the operation of anneal,
The material that uses as described each source metal has following purity: the amount of contained Si becomes amount such below the 24000ppm for the Si content that can make the red-emitting phosphors that is obtained in them.
7. the method for manufacture of red-emitting phosphors according to claim 6, wherein, the Si content in said titanium source is below the 9000ppm.
8. according to the method for manufacture of claim 6 or 7 described red-emitting phosphors, wherein, the mixing in said alkaline earth metal source, said manganese source and said titanium source is carried out through damp process.
9. according to the method for manufacture of each described red-emitting phosphors in the claim 6～8, wherein, maturing temperature is 1150～1600 ℃.
10. according to the method for manufacture of each described red-emitting phosphors in the claim 6～9, wherein, the temperature of anneal is 500～800 ℃.
11. according to the method for manufacture of each described red-emitting phosphors in the claim 6～10, wherein, said titanium source is a titanium oxide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-097381 | 2009-04-13 | ||
| JP2009097381 | 2009-04-13 | ||
| PCT/JP2010/056309 WO2010119800A1 (en) | 2009-04-13 | 2010-04-07 | Red phosphor and method for producing same |
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| Publication Number | Publication Date |
|---|---|
| CN102395649A true CN102395649A (en) | 2012-03-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2010800166312A Pending CN102395649A (en) | 2009-04-13 | 2010-04-07 | Red phosphor and method for producing same |
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| Country | Link |
|---|---|
| JP (1) | JP2010265448A (en) |
| KR (1) | KR20110138370A (en) |
| CN (1) | CN102395649A (en) |
| TW (1) | TW201042006A (en) |
| WO (1) | WO2010119800A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014034635A (en) * | 2012-08-09 | 2014-02-24 | Ube Ind Ltd | Red phosphor and its manufacturing method |
| CN105670622A (en) * | 2016-01-26 | 2016-06-15 | 井冈山大学 | Red fluorescent material for LED lamps for plant growth and preparation method of red fluorescent material |
| CN106456470A (en) * | 2014-07-29 | 2017-02-22 | 堺化学工业株式会社 | Cosmetic material |
| CN111196925A (en) * | 2020-01-08 | 2020-05-26 | 上海应用技术大学 | Mn4+Doped red fluorescent material and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5662821B2 (en) * | 2011-02-10 | 2015-02-04 | パナソニック株式会社 | Phosphor and light emitting device |
| CN103493226B (en) * | 2011-04-22 | 2016-09-28 | 株式会社东芝 | White light source and include the white light source system of described white light source |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10259946A1 (en) * | 2002-12-20 | 2004-07-15 | Tews, Walter, Dipl.-Chem. Dr.rer.nat.habil. | Phosphors for converting the ultraviolet or blue emission of a light-emitting element into visible white radiation with very high color rendering |
| JPWO2006106883A1 (en) * | 2005-03-31 | 2008-09-11 | Ｄｏｗａエレクトロニクス株式会社 | Phosphor, phosphor sheet and method for producing the same, and light emitting device using the phosphor |
| JP2007112951A (en) * | 2005-10-24 | 2007-05-10 | Fujifilm Corp | Inorganic compound, composition and molded body containing the same, light-emitting device, and solid laser device |
| TWI306676B (en) * | 2006-09-12 | 2009-02-21 | Univ Nat Chiao Tung | Highly saturated red-emitting mn(iv) activated phosphors and method of fabricating the same |
-
2010
- 2010-04-07 WO PCT/JP2010/056309 patent/WO2010119800A1/en active Application Filing
- 2010-04-07 CN CN2010800166312A patent/CN102395649A/en active Pending
- 2010-04-07 KR KR1020117023923A patent/KR20110138370A/en not_active Application Discontinuation
- 2010-04-12 JP JP2010091236A patent/JP2010265448A/en active Pending
- 2010-04-13 TW TW099111434A patent/TW201042006A/en unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014034635A (en) * | 2012-08-09 | 2014-02-24 | Ube Ind Ltd | Red phosphor and its manufacturing method |
| CN106456470A (en) * | 2014-07-29 | 2017-02-22 | 堺化学工业株式会社 | Cosmetic material |
| CN106456470B (en) * | 2014-07-29 | 2019-07-16 | 堺化学工业株式会社 | Cosmetic preparation |
| CN105670622A (en) * | 2016-01-26 | 2016-06-15 | 井冈山大学 | Red fluorescent material for LED lamps for plant growth and preparation method of red fluorescent material |
| CN111196925A (en) * | 2020-01-08 | 2020-05-26 | 上海应用技术大学 | Mn4+Doped red fluorescent material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010119800A1 (en) | 2010-10-21 |
| TW201042006A (en) | 2010-12-01 |
| JP2010265448A (en) | 2010-11-25 |
| KR20110138370A (en) | 2011-12-27 |
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Application publication date: 20120328 |