CN105670621A - Mn<4+>-doped germanate infrared material and preparation method thereof - Google Patents
Mn<4+>-doped germanate infrared material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Mn<4+>-doped germanate infrared material and a preparation method thereof. The material adopts K2Ge4O9 as a matrix and Mn<4+> as an activator, and the chemical composition of the material is K2Ge4O9; Ge<4+> is partially substituted by the Mn<4+>, and the mole doping concentration of the Mn<4+> relative to the matrix K2Ge4O9 is 0.001-1%. The preparation method comprises the following steps: accurately weighing K2CO3, manganese carbonate and germanium oxide used as raw materials according to a stoichiometric ratio, grinding the raw materials, pre-burning the ground raw materials at 300-400DEG C for 1-3h, taking the obtained pre-burnt material out for grinding, sintering the ground pre-burnt material at 500-700DEG C for 2-6h, cooling the sintered material, and taking out the cooled material. The maximum excitation band of the above product is completely matched with blue light emitted by a GaN blue light chip, the emission spectrum of the product is positioned in a red region, and the product can be used in two primary color white light LED to improve the color rendering index. The material has the advantages of stable matrix, simple and environmentally-friendly preparation technology, and suitableness for industrial batch production.
Description
Technical field
The present invention relates to luminescent material, particularly relate to a kind of Mn4+Germanate red light material of doping and preparation method thereof; It is specifically related to a kind of with Mn4+For the centre of luminescence, the red light material and preparation method thereof being substrate with germanate, this material can absorb blue light and launch HONGGUANG.
Background technology
Light emitting diode (LED) is compared with traditional lighting source electric filament lamp and fluorescent lamp, there is the good characteristic that conventional light source is incomparable: efficiently, power saving, the advantage such as long service life, it is a kind of novel green light source, is widely used to the fields such as signal lights, display lamp, display screen and Landscape Lighting. White light LEDs product leading in the market is by by blue light GaN chip and the yellow fluorescent powder YAG:Ce champac two primary colours GaN base white light LEDs formed, this type of white light LEDs efficiency become by champac two colour cell is up to 200lm/W, but owing to spectrum lacking HONGGUANG composition, make its color rendering index too low, it is impossible to be applied to the illumination of room lighting and high-end field. In order to obtain the warm white of low colour temperature (2700 3000K), high colour developing (Ra > 90), adding red color light component in two primary colours white light LEDs is effective solution.
The commercial red light material being currently used for white light LEDs is Eu2+The nitride red light material activated, excellent properties [the X.Q.Piao such as its matrix stability height, Absorber Bandwidth, excitation are high, luminous efficiency is high, temperature quenching is inconspicuous, T.Horikawa, H.Hanzawa, K.Machida, " CharacterizationandluminescencepropertiesofSr2Si5N8:Eu2+phosphorforwhitelight‐emitting‐diodeillumination”,Appl.Phys.Lett.88(2006)161908.Y.Q.Li,DeWithG,H.T.Hintzen,“TheeffectofreplacementofSrbyCaonthestructuralandluminescencepropertiesofthered‐emittingSr2Si5N8:Eu2+LEDconversionphosphor ", J.SolidStateChem.181 (2008) 515 524.]. But the cost of nitride red light material very high (at least 30 ten thousand yuan/kilogram). Therefore, it is still necessary to research and development excellent performance but price, and can by blue-light excited novel two primary colours white light LEDs red light materials far below oxide.
Red light material such as Y for traditional lighting2O3:Eu3+[J.G.Li,X.D.Li,X.D.Sun,T.Ishigaki,“MonodispersedColloidalSpheresforUniformY2O3:Eu3+Red‐PhosphorParticlesandGreatlyEnhancedLuminescencebySimultaneousGd3+Doping "; J.Phys.Chem.C112 (2008) 11707.]; its luminous efficiency is high; excitation is high; absorbs and is predominantly located at short wavelength UV district; can be applicable to electricity-saving lamp, but it absorbs in blue region and cannot be applied to GaN chip very little, therefore finds the key that novel red light material is white light LEDs development.In recent years, it has been found that Mn4+Aluminate with fluoride system are launched HONGGUANG, and has strong absorption in blue region. Due to Mn4+There is 3d3Electron configuration, its excitation spectrum is broadband shape, is conducive to absorbing energy, and its emission spectrum is positioned at 600 700nm scopes and in narrow crest, is conducive to obtaining high color purity HONGGUANG. As adopted Solid phase synthesis red light material CaAl12O19:Mn4+, long wave ultraviolet with blue-light excited under, the HONGGUANG of 650nm can be launched, but its sintering temperature is up to 1600 DEG C. Japanese scholars utilizes etching method, synthesizes multiple Mn4+The fluoride of doping: K2SiF6、Na2SiF6With Na2GeF6Deng [Y.K.Xu, S.Adachia, " PropertiesofNa2SiF6:Mn4+andNa2GeF6:Mn4+redphosphorssynthesizedbywetchemicaletching”,J.Appl.Phys.105(2009)013525.S.Adachia,T.Takahashi,“DirectsynthesisandpropertiesofK2SiF6:Mn4+phosphorbywetchemicaletchingofSiwafer”,Appl.Phys.104(2008)023512.Y.K.Xu,S.Adachi,“PropertiesofMn4+ActivatedHexafluorotitanatePhosphors "; J.Electrochem.Soc., 158 (2011) J58 J65.], material has wide band absorption in blue region; launch the HONGGUANG of narrow spectral line characteristic, is particularly suitable for improving the color rendering index of two primary colours white light LEDs. But in the method synthesizing these materials, the KMnO of the HF solution high concentration of high concentration need to be used4Solution, requires height to synthesis device, is unfavorable for large-scale industrial production.
Summary of the invention
It is an object of the invention to overcome the shortcoming of prior art, it is provided that a kind of low for equipment requirements, be suitable to large-scale production, the HONGGUANG of transmitting is pure, and at the bottom of synthesis temperature, maximum excitation wavelength is positioned at blue region, can efficient absorption GaN chip blue light launch the Mn of HONGGUANG4+The germanate red light material of doping, is a kind of brand-new inorganic red light material.
The purpose of the present invention is achieved through the following technical solutions:
A kind of Mn4+The germanate HONGGUANG material of doping, with K2Ge4O9For substrate, with Mn4+As activator, chemical composition is K2Ge4O9:Mn4+; Mn4+Part replaces Ge4+, relative to substrate K2Ge4O9, Mn4+Mole doping content be 0.001%～1.0%.
Described Mn4+The blue light that the germanate HONGGUANG material of doping is sent out with GaN blue chip mates completely, and its emission spectrum is positioned at red area.
This Mn4+The maximum excitation wavelength of the germanate red light material of doping, in blue region, excites with the blue-ray LED that wavelength is 440～470nm, obtains the HONGGUANG of pure color.
Described a kind of Mn4+The preparation method of the germanate HONGGUANG material of doping: precise alkali metal salt K2CO3, germanium oxide (GeO2), manganese carbonate (MnCO3), grind 10～30 minutes in grinding, after mix homogeneously, be transferred in Muffle furnace by metering ratio; First 300～400 DEG C of pre-burnings 1～3 hour, take out grinding 5～10 minutes, after sinter 2～6 hours at 500～700 DEG C, take out after cooling, obtain product.
Preferably, relative to Ge4+, Mn4+Mole doping content be 0.001%～1.0%.
Preferably, K in composite material+With Ge4+Mol ratio be 1:2.
Preferably, preparation whole process carries out in atmosphere.
Preferably, the temperature of described pre-burning is 350～380 DEG C, and the time of pre-burning is 1.5～2.5 hours.
Preferably, the time grinding middle grinding described in is 10～20 minutes.
The sintering temperature of described crystallization is preferably 550～650 DEG C of sintering times and is preferably 3～5 hours.
Mn of the present invention4+The chemical composition of the germanate red light material of doping is K2Ge4O9:xMn4+, wherein x=0.001%～1.0%. The present invention with alkali metal salt, manganese carbonate, germanium oxide for raw material, stoichiometrically precise, grind 10～30 minutes, 300～400 DEG C of pre-burnings 1～3 hour, take out grinding 5～10 minutes, sinter 2～6 hours at 500～700 DEG C, take out after cooling and obtain product. The blue light that its maximum excitation band of product is sent out with GaN blue chip mates completely, and its emission spectrum is positioned at red area, can be applicable to two primary colours white light LEDs, to improve its color rendering index.Matrix of materials is stable, and preparation technology is simple and environmentally-friendly, is suitable to industrial production.
Relative to prior art, the invention have the advantages that and effect:
(1) present invention is compared with the aluminate red light material that known tetravalent manganese is adulterated, absorption efficiency in the region of blue light is higher, and crystallization temperature is far below the aluminate (1600 DEG C) with the tetravalent manganese doping of high temperature solid-state method synthesis developed, this product can obtain the target phase of crystallization at 500 degree of sintering.
(2) present invention is compared with the fluoride red light material that known tetravalent manganese is adulterated, it is not necessary to use the HF of severe corrosive and the KMnO of strong oxidizing property4, synthesis device is required low.
(3) because material is without rare earth, preparation process keeps away oxygen without keeping away water, and whole process carries out in atmosphere, and therefore, cost is far below than business nitride Hydrargyri Oxydum Rubrum.
(4) building-up process does not produce waste water and waste liquid, and sintering temperature is low to moderate 500 DEG C, energy-conserving and environment-protective.
Accompanying drawing explanation
Fig. 1 (a) K2Ge4O9The XRD standard card data of compound, the product K in (b)～(c) respectively embodiment 1～32Ge4O9:Mn4+XRD figure (namely sintering obtains obtaining the XRD figure of product under 500 DEG C, 600 DEG C with 700 DEG C of conditions respectively).
Fig. 2 is K2Ge4O9:Mn4+The excitation spectrum (monitoring wavelength is 635nm) of (embodiment 2) and emission spectrum (excitation wavelength is 467nm).
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the invention will be further described, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
Precise 0.001mol potassium carbonate (K2CO3), 0.004mol germanium oxide (GeO2) with 4 × 10‐8Mol manganese carbonate (MnCO3), in this embodiment, Mn4+Mole doping content (relative to Ge4+) it is 0.001%, grind 10 minutes in grinding, after mix homogeneously, be transferred in Muffle furnace by metering ratio. First 400 DEG C of pre-burnings 1 hour, take out and grind 5 minutes, after sinter 6 hours at 500 DEG C, take out after cooling and obtain product. As shown in Figure 1 b, XRD shows that product is pure K to its XRD (detection of BrukerD8AdvanceX x ray diffractometer x)2Ge4O9Phase. Product issues bright red at uviol lamp. Utilize Fluoromax 4 fluorescence spectrophotometer (HORIBAJobinYvonInc.), detect the luminescent properties of product at ambient temperature, as shown in Figure 2, this material emitted light spectrum is made up of two broadbands being positioned at 361nm and 467nm, the blue light that its maximum excitation band (467nm) is sent out with GaN blue chip mates completely, emission spectrum be positioned at by 5 lay respectively at 646nm, 656nm, 663nm, 667nm and 678nm spike form, summit is positioned at 663nm.
Embodiment 2
Precise 0.001mol potassium carbonate (K2CO3), 0.004mol germanium oxide (GeO2) with 2 × 10‐7Mol manganese carbonate (MnCO3), in this embodiment, Mn4+Mole doping content (relative to Ge4+) it is 0.005%, grind 22 minutes in grinding, after mix homogeneously, be transferred in Muffle furnace by metering ratio. First 300 DEG C of pre-burnings 1.2 hours, take out and grind 7 minutes, after sinter 2 hours at 600 DEG C, take out after cooling and obtain product. As illustrated in figure 1 c, XRD shows that product is pure K to its XRD (detection of BrukerD8AdvanceX x ray diffractometer x)2Ge4O9Phase. Product issues bright red at uviol lamp. Utilizing Fluoromax 4 fluorescence spectrophotometer (HORIBAJobinYvonInc.), detect the luminescent properties of product at ambient temperature, its excitation spectrum is similar to embodiment 1 to the shape of emission spectrum.
Embodiment 3
Precise 0.001mol potassium carbonate (K2CO3), 0.004mol germanium oxide (GeO2) with 4 × 10‐7Mol manganese carbonate (MnCO3), in this embodiment, Mn4+Mole doping content (relative to Ge4+) it is 0.01%, grind 30 minutes in grinding, after mix homogeneously, be transferred in Muffle furnace by metering ratio.First 360 DEG C of pre-burnings 1.8 hours, take out and grind 6 minutes, after sinter 2 hours at 700 DEG C, take out after cooling and obtain product. As shown in Figure 1 d, XRD shows that product is pure K to its XRD (detection of BrukerD8AdvanceX x ray diffractometer x)2Ge4O9Phase. Product issues bright red at uviol lamp. Utilizing Fluoromax 4 fluorescence spectrophotometer (HORIBAJobinYvonInc.), detect the luminescent properties of product at ambient temperature, its excitation spectrum is similar to embodiment 1 to the shape of emission spectrum.
Embodiment 4
Precise 0.001mol potassium carbonate (K2CO3), 0.004mol germanium oxide (GeO2) with 2 × 10‐6Mol manganese carbonate (MnCO3), in this embodiment, Mn4+Mole doping content (relative to Ge4+) it is 0.05%, grind 16 minutes in grinding, after mix homogeneously, be transferred in Muffle furnace by metering ratio. First 290 DEG C of pre-burnings 2.7 hours, take out and grind 10 minutes, after sinter 4 hours at 680 DEG C, take out after cooling and obtain product. Product issues bright red at uviol lamp, and XRD shows that product is pure K2Ge4O9Phase, utilizes Fluoromax 4 fluorescence spectrophotometer (HORIBAJobinYvonInc.), detects the luminescent properties of product at ambient temperature, and its excitation spectrum is similar to embodiment 1 to the shape of emission spectrum.
Embodiment 5
Precise 0.001mol potassium carbonate (K2CO3), 0.004mol germanium oxide (GeO2) with 4 × 10‐6Mol manganese carbonate (MnCO3), in this embodiment, Mn4+Mole doping content (relative to Ge4+) it is 0.1%, grind 25 minutes in grinding, after mix homogeneously, be transferred in Muffle furnace by metering ratio. First 290 DEG C of pre-burnings 2.7 hours, take out and grind 9 minutes, after sinter 4 hours at 700 DEG C, take out after cooling and obtain product. Product issues bright red at uviol lamp, and XRD shows that product is pure K2Ge4O9Phase, utilizes Fluoromax 4 fluorescence spectrophotometer (HORIBAJobinYvonInc.), detects the luminescent properties of product at ambient temperature, and its excitation spectrum is similar to embodiment 1 to the shape of emission spectrum.
Embodiment 6
Precise 0.001mol potassium carbonate (K2CO3), 0.004mol germanium oxide (GeO2) with 2 × 10‐5Mol manganese carbonate (MnCO3), in this embodiment, Mn4+Mole doping content (relative to Ge4+) it is 0.5%, grind 28 minutes in grinding, after mix homogeneously, be transferred in Muffle furnace by metering ratio. First 370 DEG C of pre-burnings 3 hours, take out and grind 9 minutes, after sinter 4 hours at 600 DEG C, take out after cooling and obtain product. Product issues bright red at uviol lamp, and XRD shows that product is pure K2Ge4O9Phase, utilizes Fluoromax 4 fluorescence spectrophotometer (HORIBAJobinYvonInc.), detects the luminescent properties of product at ambient temperature, and its excitation spectrum is similar to embodiment 1 to the shape of emission spectrum.
Embodiment 7
Precise 0.001mol potassium carbonate (K2CO3), 0.004mol germanium oxide (GeO2) with 4 × 10‐5Mol manganese carbonate (MnCO3), in this embodiment, Mn4+Mole doping content (relative to Ge4+) it is 1.0%, grind 16 minutes in grinding, after mix homogeneously, be transferred in Muffle furnace by metering ratio. First 320 DEG C of pre-burnings 1 hour, take out and grind 7 minutes, after sinter 6 hours at 560 DEG C, take out after cooling and obtain product. Product issues bright red at uviol lamp, and XRD shows that product is pure K2Ge4O9Phase, utilizes Fluoromax 4 fluorescence spectrophotometer (HORIBAJobinYvonInc.), detects the luminescent properties of product at ambient temperature, and its excitation spectrum is similar to embodiment 1 to the shape of emission spectrum.
Visible from the above, gained Mn of the present invention4+The blue light that the germanate HONGGUANG material of doping is sent out with GaN blue chip mates completely, and its emission spectrum is positioned at red area. This Mn4+The maximum excitation wavelength of the germanate red light material of doping, in blue region, excites with the blue-ray LED that wavelength is 440～470nm, obtains the HONGGUANG of pure color.
Compared with the aluminate red light material of known tetravalent manganese doping, the present invention absorption efficiency in the region of blue light is higher, and crystallization temperature is far below the aluminate (1600 DEG C) with the tetravalent manganese doping of high temperature solid-state method synthesis developed, this product can obtain the target phase of crystallization at 500 degree of sintering.
The present invention is compared with the fluoride red light material that known tetravalent manganese is adulterated, it is not necessary to use the HF of severe corrosive and the KMnO of strong oxidizing property4, synthesis device is required low, is suitable for scale society and produces.
The present invention is because material is without rare earth, and preparation process keeps away oxygen without keeping away water, and whole process carries out in atmosphere, and therefore, cost is far below than business nitride Hydrargyri Oxydum Rubrum.
Building-up process of the present invention does not produce waste water and waste liquid, and sintering temperature is low to moderate 500 DEG C, and energy-conserving and environment-protective have significant advantage compared with existing production method.
Claims (9)
1. a Mn4+The germanate HONGGUANG material of doping, it is characterised in that: this material is with K2Ge4O9For substrate, with Mn4+As activator, chemical composition is K2Ge4O9:Mn4+; Mn4+Part replaces Ge4+, relative to substrate K2Ge4O9, Mn4+Mole doping content be 0.001%～1%.
2. a kind of Mn according to claim 14+The germanate HONGGUANG material of doping, it is characterised in that: described Mn4+The blue light that the germanate HONGGUANG material of doping is sent out with GaN blue chip mates completely, and its emission spectrum is positioned at red area.
3. a kind of Mn according to claim 14+The germanate HONGGUANG material of doping, it is characterised in that: described Mn4+The maximum excitation wavelength of the germanate red light material of doping, in blue region, excites with the blue-ray LED that wavelength is 440～470nm, obtains the HONGGUANG of pure color.
4. a kind of Mn described in claim 1,2 or 34+The preparation method of the germanate HONGGUANG material of doping, it is characterised in that: precise alkali metal salt K2CO3, germanium oxide, manganese carbonate, grind 10～30 minutes in grinding, by metering ratio after mix homogeneously, be transferred in Muffle furnace; First 300～400 DEG C of pre-burnings 1～3 hour, take out grinding 5～10 minutes, after sinter 2～6 hours at 500～700 DEG C, take out after cooling, obtain product.
5. Mn according to claim 44+The preparation method of the germanate HONGGUANG material of doping, it is characterised in that: relative to Ge4+, Mn4+Mole doping content be 0.001%～1.0%.
6. Mn according to claim 44+The preparation method of the germanate HONGGUANG material of doping, it is characterised in that: K in composite material+With Ge4+Mol ratio be 1:2.
7. Mn according to claim 44+The preparation method of the germanate HONGGUANG material of doping, it is characterised in that: preparation whole process carries out in atmosphere.
8. Mn according to claim 44+The preparation method of the germanate HONGGUANG material of doping, it is characterised in that: the temperature of described pre-burning is 350～380 DEG C, and the time of pre-burning is 1.5～2.5 hours.
9. Mn according to claim 44+The preparation method of germanate HONGGUANG material of doping, it is characterised in that: described in grind time of middle grinding be 10～20 minutes.
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| CN109294572A (en) * | 2018-10-18 | 2019-02-01 | 温州大学 | A kind of preparation method of high colour developing white light LEDs red light material |
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| CN104087298A (en) * | 2014-06-20 | 2014-10-08 | 华南理工大学 | Light conversion material and light conversion film, and preparation methods thereof |
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| CN104087298A (en) * | 2014-06-20 | 2014-10-08 | 华南理工大学 | Light conversion material and light conversion film, and preparation methods thereof |
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| CN109294572A (en) * | 2018-10-18 | 2019-02-01 | 温州大学 | A kind of preparation method of high colour developing white light LEDs red light material |
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