CN104403666B - Tetravalent manganese ion doping red fluorescence material and preparation method thereof - Google Patents
Tetravalent manganese ion doping red fluorescence material and preparation method thereof Download PDFInfo
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- CN104403666B CN104403666B CN201410732825.2A CN201410732825A CN104403666B CN 104403666 B CN104403666 B CN 104403666B CN 201410732825 A CN201410732825 A CN 201410732825A CN 104403666 B CN104403666 B CN 104403666B
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Abstract
The invention provides novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material and preparation method thereof, the crystalline structure of this red fluorescence material is hexagonal system, and molecular formula is LiRGe
2-xo
6: xMn
4+, R is expressed as: aluminium (Al) and gallium (Ga); Accurately take the raw materials of compound containing lithium respectively, containing aluminium (Al) or the raw materials of compound of gallium (Ga), germanic raw materials of compound and the raw materials of compound containing manganese, after being ground, control temperature 450 ~ 600 DEG C, pre-burning 3 ~ 5 hours; Taken out by sample after pre-burning, after being again ground, in atmosphere, high-temperature firing 3 ~ 6 hours, control temperature 850 ~ 1000 DEG C, cools to room temperature with the furnace, can obtain.
Description
Technical field
The present invention relates to red fluorescence material field, particularly tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material and preparation method thereof.
Background technology
Along with blue gan and long wave ultraviolet laser diode (LED) technical breakthrough and industrialization, solid-state illumination light source has attracted the interest of people again.In lighting industry, white light LEDs has many clear superiorities relative to traditional incandescent light and luminescent lamp etc.Such as: white light LEDs in theory only needs the energy consumption of 50% of incandescent light 10% and luminescent lamp, its life-span is 10 times of luminescent lamp and 100 times of incandescent light, and LED light source breaks overflow the secondary pollution etc. of mercury without the radiation such as ultraviolet and infrared light, unstressed configuration fluorescent tube.At present, substantial contribution, man power and material have poured in the developed countries such as Japan, the U.S. and European Union, have set up functional body and have formulated strategic objective and plan to research and develop solid-state white LED; China starts " semi-conductor (LED) Lighting Industry technological development major project ", set up the Semiconductor Lighting coordinating leading group be made up of eight ministries and commissions, and determined that Shenzhen, Shanghai, Dalian, Nanchang, big city, Xiamen five are industry Demonstration Base.
Two primary colours white light LEDs of current commercialization mainly adopt blue light for InGaN chip to excite Y
3al
5o
12: Ce
3+(YAG:Ce
3+) yellow fluorescent powder.Owing to lacking red fluorescence powder, make it more weak in red spectral region luminescence, thus cause its colour temperature higher, colour rendering index is on the low side.In order to solve this limitation, can consider in two primary colours white light LEDs, increase a kind of red fluorescence powder that can be excited by blue LED die, thus form the white light LEDs of a kind of three primary colours (blue, yellow, red); Commercial three primary colours white light LEDs mainly adopts (closely) ultraviolet chip to excite red, blue and green fluorescence powder composition.Thus, white light LEDs must have: effectively can be excited by blue light or UV-light, the excellent property such as temperature, high thermostability is gone out in ultraviolet light resistant, high hot-quenching, luminous efficiency is high, "dead", nontoxic, harmless and red fluorescence powder to human-body safety.
Nearly ten years, the red fluorescence pruinescence that can be used in white light LEDs is reported in succession, as: sulfuric acid alkaline earth salt and phosphorus boric acid base earth metal salt etc. that the rare earth ion doped nitride, oxynitride, silicate, aluminate etc., tetravalent manganese ion doping aluminate etc. such as europium, samarium, praseodymium adulterates with divalence bismuth ion.Wherein, rear-earth-doped nitride, oxynitride luminescent properties are superior, and quantum yield, more than 70%, obtains application.But the preparation condition of nitride, oxynitride is usually harsher, need high temperature (> 1700 DEG C), high pressure (> 5 normal atmosphere) and special conditions, these conditions are very high to the requirement of equipment, thus the price affecting fluorescent material can not reduce, so significant to the research of the simple red fluorescence powder of preparation method.
Mn
4+ion outer shell electron distribution is d
3structure is under the optical excitation of ultraviolet region in excitation wavelength, can produce the broad-band illumination including narrow peak in red light region (600-750nm).Mn
4+ion doping red fluorescence powder can in the white light LEDs of UV LED chip+red, green, blue three primary colors fluorescent powder combination.Nineteen forty-seven, the first time such as Williams finds Mn
4+doping germanic acid magnesium transmitting red fluorescence (from: J.Opt.Soc.Am.37 (1947) 302-307); Nineteen sixty, Kemeny etc. find 3.5MgO.0.5MgF
2.GeO
2: Mn
4+fluorescent material can launch red fluorescence (from: J.Chem.Phys.33 (1960) 783-789), and 3.5MgO.0.5MgF
2.GeO
2: Mn
4+fluorescent material becomes the commercial powder of existing redness commercially.Because germanium cost of material is high, make the cost of this red fluorescence powder higher.In order to reduce the production cost of red fluorescence powder and improve luminous efficiency, Mn
4+the research of ion doping red fluorescence powder has been concerned and has reported, as: Mn
4+ion doping aluminate fluorescent powder (CaAl
2o
4: Mn
4+, CaAl
12o
19: Mn
4+, Sr
4al
14o
25: Mn
4+, SrMgAl
10o
17: Mn
4+and Sr
2mgAl
22o
36: Mn
4+deng) (from: Opt.Mater.38 (2014) 53-56; J.Am.Ceram.Soci.96 (9) (2013) 2870-2876.; J.Electrochem.Soc.118 (1971) 1166-1171; JMaterSci:MaterElectron.25 (2014) 2676 – 2681; ECS.J.SolidState.Sci.Technol.1 (4) (2012) R123-R126), Mn
4+ion doping fluorochemical fluorescent material (A
2rF
6: Mn
4+(A=Li, Na, K and R=Si, Ti, Ge), A
2rF
5: Mn
4+(A=Li, Na, K and R=Al, Ga, In) etc.) (from: US2007/0205712A1), Mn
4+ion doping titanate fluorescent powder (ATiO
3: Mn
4+(A=Mg, Ca, Sr, Ba), A
2tiO
3: Mn
4+(A=Li, Na, K)) etc. and luminescent properties research etc. (from: TW2010/42006A1).
Summary of the invention
In order to overcome the above-mentioned shortcoming of prior art with not enough, the object of the present invention is to provide a kind of novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material, have and absorb in UV-light and blue spectral region, ultraviolet and blue-light excited under, have the interval and luminescence center of covering 600 ~ 750nm at about 670nm red fluorescence, its fluorescence has good heat resistanceheat resistant quenching feature.
Another object of the present invention is to the preparation method that above-mentioned novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material is provided.The present invention utilizes cheap tetravalent manganese ion as active ions, in air atmosphere, adopts high temperature solid-state method preparation to have novel tetravalent manganese ion doping germanic acid (aluminium or gallium) the lithium red fluorescence material of good heat resistanceheat resistant quenching feature.
Object of the present invention is achieved through the following technical solutions:
Novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material, the crystalline structure of this red fluorescence material is hexagonal system, and molecular formula is LiRGe
2-xo
6: xMn
4+, by elemental mole ratios Li:R:Ge:Mn=1:1:(2-x): x, wherein 0.001≤x≤0.1, R is expressed as: aluminium (Al) or gallium (Ga).
The preparation method of novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material, comprises the following steps:
(1) raw material is taken: by elemental mole ratios Li:R:Ge:Mn=1:1:(2-x): x, wherein 0.001≤x≤0.1, R is expressed as: aluminium (Al) or gallium (Ga), accurately takes the raw materials of compound containing lithium respectively, containing aluminium (Al) or the raw materials of compound of gallium (Ga), germanic raw materials of compound and the raw materials of compound containing manganese;
(2) pre-burning: the raw material that step (1) takes after being ground, pre-burning 3 ~ 5 hours at temperature is 450 ~ 600 DEG C;
(3) fire: taken out by the sample after pre-burning, after being again ground, firing 3 ~ 6 hours, cool to room temperature with the furnace at temperature is 850 ~ 1000 DEG C, can obtain chemical constitution is LiRGe
2-xo
6: xMn
4+novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material, R is expressed as: aluminium (Al) or gallium (Ga).
Step (2) described pre-burning is carried out in air atmosphere.
Fire described in step (3) and carry out in air atmosphere.
The described lithium-containing compound raw material of step (1) is any one in carbonate, nitrate, muriate, oxide compound, oxalate and acetate.
Step (1) is described is any one in carbonate, nitrate, muriate, oxide compound, oxalate and acetate containing aluminium or gallium compound raw material.
Step (1) is described is any one in carbonate, nitrate, muriate, oxide compound, oxalate and acetate containing manganic compound raw material.
The described germanium-containing compound raw material of step (1) is any one in carbonate, nitrate, muriate, oxide compound, oxalate and acetate.
Novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material of the present invention has following advantage and beneficial effect:
Novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material Heat stability is good of the present invention, fluorescence intensity is high, and color developing is good, is the red fluorescence powder material that can be used in white light LEDs that a kind of performance is very excellent.Fluorescent material prepared by the present invention has in (closely) ultraviolet and blue spectral region absorption, under (closely) ultraviolet and blue light excite, there is the interval and luminescence center of covering 600 ~ 750nm at about 670nm red fluorescence, its fluorescence has good heat resistanceheat resistant quenching feature, temperature is raised to room temperature 300K from 50K, fluorescence intensity and fluorescence lifetime change are less than 5%, can obtain application in fields such as luminescent lamp, solid-state white LED and displays.The present invention adopts high temperature solid-state method to prepare in atmosphere with the fluorescent material that germanic acid (aluminium or gallium) lithium salts is matrix, and this preparation method is simple, adopts suitable heat temperature raising technique, obtains germanic acid (aluminium or gallium) the lithium salts fluorescent material of excellent property.
Accompanying drawing explanation
Fig. 1 is novel tetravalent manganese ion doping germanic acid aluminium lithium (LiAlGe prepared by embodiments of the invention 1
1.994o
6: 0.006Mn
4+) the exciting light spectrogram of red fluorescence material under emission wavelength 671nm.
Fig. 2 is novel tetravalent manganese ion doping germanic acid gallium lithium (LiGaGe prepared by embodiments of the invention 1
1.994o
6: 0.006Mn
4+) the exciting light spectrogram of red fluorescence material under emission wavelength 668nm
Fig. 3 is novel tetravalent manganese ion doping germanic acid aluminium lithium (LiAlGe prepared by embodiments of the invention 1
1.994o
6: 0.006Mn
4+) the utilizing emitted light spectrogram of red fluorescence material under excitation wavelength is 335nm.
Fig. 4 is novel tetravalent manganese ion doping germanic acid gallium lithium (LiGaGe prepared by embodiments of the invention 1
1.994o
6: 0.006Mn
4+) the utilizing emitted light spectrogram of red fluorescence material under excitation wavelength is 337nm.
Fig. 5 is novel tetravalent manganese ion doping germanic acid aluminium lithium (LiAlGe prepared by embodiments of the invention 1
1.994o
6: 0.006Mn
4+) red fluorescence material excitation wavelength be 335 and 465nm under utilizing emitted light spectrogram.
Fig. 6 is novel tetravalent manganese ion doping germanic acid gallium lithium (LiGaGe prepared by embodiments of the invention 1
1.994o
6: 0.006Mn
4+) red fluorescence material excitation wavelength be 337 and 470nm under utilizing emitted light spectrogram.
Fig. 7 is novel tetravalent manganese ion doping germanic acid aluminium lithium (LiAlGe prepared by embodiments of the invention 1
2o
6: Mn
4+) the utilizing emitted light spectrogram of the different manganese ion doping concentration of red fluorescence material under excitation wavelength is 335nm.
Fig. 8 is novel tetravalent manganese ion doping germanic acid gallium lithium (LiGaGe prepared by embodiments of the invention 1
2o
6: Mn
4+) the utilizing emitted light spectrogram of the different manganese ion doping concentration of red fluorescence material under excitation wavelength is 337nm.
Fig. 9 is novel tetravalent manganese ion doping germanic acid aluminium lithium (LiAlGe prepared by embodiments of the invention 1
1.994o
6: 0.006Mn
4+) the utilizing emitted light spectrogram of red fluorescence material under excitation wavelength is 335nm, 50K to 300K temperature.
Figure 10 is novel tetravalent manganese ion doping germanic acid gallium lithium (LiGaGe prepared by embodiments of the invention 1
1.994o
6: 0.006Mn
4+) the utilizing emitted light spectrogram of red fluorescence material under excitation wavelength is 337nm, 50K to 300K temperature.
Figure 11 is novel tetravalent manganese ion doping germanic acid aluminium lithium (LiAlGe prepared by embodiments of the invention 1
1.994o
6: 0.006Mn
4+) fluorescence decay curve of red fluorescence material, monitoring wavelength is 671nm, and excitation wavelength is 335nm.
Figure 12 is novel tetravalent manganese ion doping germanic acid gallium lithium (LiGaGe prepared by embodiments of the invention 1
1.994o
6: 0.006Mn
4+) fluorescence decay curve of red fluorescence material, monitoring wavelength is 668nm, and excitation wavelength is 337nm.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
embodiment 1
Choose the raw materials of compound containing lithium, make starting raw material, according to elemental mole ratios Li:R:Ge:Mn=1:1:(2-x containing aluminium (Al) or the raw materials of compound of gallium (Ga), germanic raw materials of compound and the raw materials of compound containing manganese): x, accurately takes four kinds of raw materials respectively, wherein x gets 0.001 respectively, 0.002,0.004,0.006,0.008,0.01,0.03,0.06,0.1, R is expressed as: aluminium (Al) or gallium (Ga).1. take Quilonum Retard, aluminum oxide, germanium oxide and Manganse Dioxide four kinds of raw materials respectively, controlling mixture total weight is about 50 grams.50 grams of mixtures, after ball milling mixing, are put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, control raw materials of compound decomposition reaction velocity, prevent mixture from overflowing from crucible, sample was 450 DEG C of pre-burnings 5 hours.Taken out by sample after pre-burning, be again ground, put into crucible, burn 4 hours at 900 DEG C, cool to room temperature with the furnace, can obtain chemical constitution is LiAlGe
2-xo
6: xMn
4+novel tetravalent manganese ion doping germanic acid aluminium lithium red fluorescence material; 2. take Quilonum Retard, gallium oxide, germanium oxide and Manganse Dioxide four kinds of raw materials respectively, according to above-mentioned same preparation process, can obtain chemical constitution is LiGaGe
2-xo
6: xMn
4+novel tetravalent manganese ion doping germanic acid gallium lithium red fluorescence material.X-ray diffraction analysis shows that the red fluorescence powder prepared is the pure phase of germanic acid (aluminium or gallium) lithium salts.Novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material LiRGe prepared by the present embodiment
2-xo
6: xMn
4+(x=0.006, R is Al or Ga) within the scope of 200 ~ 550nm, there is 355,357,465 and 470nm excitation peak (see Fig. 1 and Fig. 2) respectively, wherein, match with (closely) ultraviolet chip commercial at present at the excitation peak of 355 or 357nm, match with blue chip commercial at present at the excitation peak of 465 or 470nm; Novel tetravalent manganese ion doping germanic acid aluminium lithium red fluorescence material excites in about 355 and 465nm and can produce the red fluorescence that peak position is positioned at about 671nm down, and fluorescence covers 600-750nm spectral region (see Fig. 3 and Fig. 5); Novel tetravalent manganese ion doping germanic acid gallium lithium red fluorescence material excites in about 357 and 470nm and can produce the red fluorescence that peak position is positioned at about 668nm down, and fluorescence covers 600-750nm spectral region (see Fig. 4 and Fig. 6).Fig. 7 and Fig. 8 illustrates novel tetravalent manganese ion doping germanic acid (aluminium or gallium) the lithium red fluorescence material LiRGe under excitation wavelength is respectively 355 and 357nm
2-xo
6: xMn
4+(x=0.006, R are Al or Ga) is at the utilizing emitted light spectrogram of different manganese ion doping concentration.Novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material LiRGe can be found according to Fig. 7 and Fig. 8
2-xo
6: xMn
4+(R is Al or Ga), when manganese ion doping concentration is about x=0.6mol%, luminous intensity is best.Fig. 9 and Figure 10 is envrionment temperature (50-300K) under excitation wavelength is respectively 355 and 357nm and novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material LiRGe
2-xo
6: xMn
4+the utilizing emitted light spectrogram situation of (x=0.006, R are Al or Ga).Can realize that this novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material has good thermostability according to Fig. 9 and Figure 10.Figure 11 and Figure 12 is novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material LiRGe
2-xo
6: xMn
4+the fluorescence decay curve of (x=0.006, R are Al or Ga), their monitoring wavelength is respectively 671nm and 668nm, excitation wavelength is respectively 355 and 357nm, life curve meets single exponent ring-down equation, and degree of fitting can reach 99.5%, and fluorescence lifetime is respectively about 1.15 and 1.06 milliseconds.
embodiment 2
Choose Lithium Oxide 98min, carbonate, carbonic acid germanium and manganous carbonate containing aluminium (Al) or gallium (Ga) make starting raw material, according to elemental mole ratios Li:R:Ge:Mn=1:1:(2-x): x, accurately take four kinds of raw materials respectively, wherein 0.001≤x≤0.1, R is expressed as: aluminium (Al) or gallium (Ga).Controlling mixture total weight is about 50 grams.50 grams of mixtures, after ball milling mixing, are put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, control raw materials of compound decomposition reaction velocity, prevent mixture from overflowing from crucible, sample was 500 DEG C of pre-burnings 5 hours.Taken out by sample after pre-burning, be again ground, put into crucible, burn 5 hours at 850 DEG C, cool to room temperature with the furnace, can obtain chemical constitution is LiRGe
2-xo
6: xMn
4+novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material, R is expressed as: aluminium (Al) or gallium (Ga).X-ray diffraction analysis is indicated as germanic acid (aluminium or gallium) lithium pure phase.The spectral quality of fluorescent material and heat resistanceheat resistant cancellation performance thereof are with similar in embodiment 1.
embodiment 3
Choose lithium nitrate, muriate, carbonic acid germanium and manganous carbonate containing aluminium (Al) or gallium (Ga) make starting raw material, according to elemental mole ratios Li:R:Ge:Mn=1:1:(2-x): x, accurately take four kinds of raw materials respectively, wherein 0.001≤x≤0.1, R is expressed as: aluminium (Al) or gallium (Ga), and controlling mixture total weight is about 50 grams.50 grams of mixtures, after ball milling mixing, are put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, control raw materials of compound decomposition reaction velocity, prevent mixture from overflowing from crucible, sample was 400 DEG C of pre-burnings 5 hours.Taken out by sample after pre-burning, be again ground, put into crucible, burn 3 hours at 1000 DEG C, cool to room temperature with the furnace, can obtain chemical constitution is LiRGe
2-xo
6: xMn
4+novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material, R is expressed as: aluminium (Al) or gallium (Ga).X-ray diffraction analysis is indicated as germanic acid (aluminium or gallium) lithium pure phase.The spectral quality of fluorescent material and heat resistanceheat resistant cancellation performance thereof are with similar in embodiment 1.
embodiment 4
Choose Lithium Oxide 98min, carbonate, nitric acid germanium and manganese oxide containing aluminium (Al) or gallium (Ga) make starting raw material, according to elemental mole ratios Li:R:Ge:Mn=1:1:(2-x): x, accurately take four kinds of raw materials respectively, wherein 0.001≤x≤0.1, R is expressed as: aluminium (Al) or gallium (Ga), and controlling mixture total weight is about 50 grams.50 grams of mixtures, after ball milling mixing, are put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, control raw materials of compound decomposition reaction velocity, prevent mixture from overflowing from crucible, sample was 500 DEG C of pre-burnings 5 hours.Taken out by sample after pre-burning, be again ground, put into crucible, burn 6 hours at 900 DEG C, cool to room temperature with the furnace, can obtain chemical constitution is LiRGe
2-xo
6: xMn
4+novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material, R is expressed as: aluminium (Al) or gallium (Ga).X-ray diffraction analysis is indicated as germanic acid (aluminium or gallium) lithium pure phase.The spectral quality of fluorescent material and heat resistanceheat resistant cancellation performance thereof are with similar in embodiment 1.
embodiment 5
Choose Quilonum Retard, carbonate, carbonic acid germanium and manganous carbonate containing aluminium (Al) or gallium (Ga) make starting raw material, according to elemental mole ratios Li:R:Ge:Mn=1:1:(2-x): x, accurately take four kinds of raw materials respectively, wherein 0.001≤x≤0.1, R is expressed as: aluminium (Al) or gallium (Ga), and controlling mixture total weight is about 50 grams.50 grams of mixtures, after ball milling mixing, are put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, control raw materials of compound decomposition reaction velocity, prevent mixture from overflowing from crucible, sample was 500 DEG C of pre-burnings 5 hours.Taken out by sample after pre-burning, be again ground, put into crucible, burn 6 hours at 850 DEG C, cool to room temperature with the furnace, can obtain chemical constitution is LiRGe
2-xo
6: xMn
4+novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material, R is expressed as: aluminium (Al) or gallium (Ga).X-ray diffraction analysis is indicated as germanic acid (aluminium or gallium) lithium pure phase.The spectral quality of fluorescent material and heat resistanceheat resistant cancellation performance thereof are with similar in embodiment 1.
embodiment 6
Choose Quilonum Retard, nitrate, nitric acid germanium and manganous nitrate containing aluminium (Al) or gallium (Ga) be starting raw material, according to elemental mole ratios Li:R:Ge:Mn=1:1:(2-x): x, accurately take four kinds of raw materials respectively, wherein 0.001≤x≤0.1, R is expressed as: aluminium (Al) or gallium (Ga), and controlling mixture total weight is about 50 grams.50 grams of mixtures, after ball milling mixing, are put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, control raw materials of compound decomposition reaction velocity, prevent mixture from overflowing from crucible, sample was 400 DEG C of pre-burnings 5 hours.Taken out by sample after pre-burning, be again ground, put into crucible, burn 5 hours at 900 DEG C, cool to room temperature with the furnace, can obtain chemical constitution is LiRGe
2-xo
6: xMn
4+novel tetravalent manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material, R is expressed as: aluminium (Al) or gallium (Ga).X-ray diffraction analysis is indicated as germanic acid (aluminium or gallium) lithium pure phase.The spectral quality of fluorescent material and heat resistanceheat resistant cancellation performance thereof are with similar in embodiment 1.
Above-described embodiment is the present invention's preferably embodiment, but embodiments of the present invention are not limited by the examples, as: lithium-containing compound raw material can also be phosphoric acid (hydrogen) salt, acetate etc., phosphoric acid (hydrogen) salt containing aluminium (Al) or gallium (Ga), oxalic acid, acetate etc., can also be hydrophosphate containing manganese and germanium compound raw material, phosphoric acid salt, oxalate and acetate etc., the change done under other any does not deviate from spirit of the present invention and principle, modify, substitute, combination, simplify, all should be the substitute mode of equivalence, except above-mentioned manganese ion doping germanic acid (aluminium or gallium) lithium red fluorescence material, other as LiAlGeO
4: Mn
4+, Li
3alGeO
5: Mn
4+, Li
0.9al
0.9ge
2.1o
6: Mn
4+, Li
6.3al
0.3ge
1.7o7
6: Mn
4+, Li
3.25al
0.25geO
4: Mn
4+, Li
2.875al
0.375geO
6: Mn
4+, LiGaGeO
4: Mn
4+, Li
3gaGeO
5: Mn
4+, Li
0.9ga
0.9ge
2.1o
6: Mn
4+, Li
6.3ga
0.3ge
1.7o7
6: Mn
4+, Li
3.25ga
0.25geO
4: Mn
4+, Li
2.875ga
0.375geO
6: Mn
4+etc. being included within protection scope of the present invention.
Claims (8)
1. tetravalent manganese ion doping red fluorescence material, is characterized in that, this red fluorescence material adopts tetravalent manganese ion doping germanic acid aluminium lithium or germanic acid gallium lithium to obtain, and its crystalline structure is hexagonal system, and molecular formula is LiRGe
2-xo
6: xMn
4+, R is expressed as: aluminium (Al) or gallium (Ga), wherein 0.001≤x≤0.1.
2. a preparation method for tetravalent manganese ion doping red fluorescence material described in claim 1, is characterized in that, comprise the following steps:
(1) raw material is taken: by elemental mole ratios Li:R:Ge:Mn=1:1:(2-x): x, wherein 0.001≤x≤0.1, R is expressed as: aluminium (Al) or gallium (Ga), accurately takes the raw materials of compound containing lithium respectively, containing aluminium (Al) or the raw materials of compound of gallium (Ga), germanic raw materials of compound and the raw materials of compound containing manganese;
(2) pre-burning: the raw material that step (1) takes after being ground, pre-burning 3 ~ 5 hours at temperature is 450 ~ 600 DEG C;
(3) fire: the sample after pre-burning is taken out, after being again ground, at temperature is 850 ~ 1000 DEG C, fires 3 ~ 6 hours, cools to room temperature with the furnace.
3. the preparation method of tetravalent manganese ion doping red fluorescence material according to claim 2, it is characterized in that, described pre-burning is carried out in air atmosphere.
4. the preparation method of tetravalent manganese ion doping red fluorescence material according to claim 2, is characterized in that, described in fire and carry out in air atmosphere.
5. the preparation method of tetravalent manganese ion doping red fluorescence material according to claim 2, is characterized in that, described lithium-containing compound raw material is any one in carbonate, nitrate, muriate, oxide compound, oxalate and acetate.
6. the preparation method of tetravalent manganese ion doping red fluorescence material according to claim 2, is characterized in that, described is any one in carbonate, nitrate, muriate, oxide compound, oxalate and acetate containing aluminium or gallium compound raw material.
7. the preparation method of tetravalent manganese ion doping red fluorescence material according to claim 2, is characterized in that, described is any one in saline oxide, muriate, carbonate, oxalate, acetate and nitrate containing manganic compound raw material.
8. the preparation method of tetravalent manganese ion doping red fluorescence material according to claim 2, is characterized in that, described germanium-containing compound raw material is any one in carbonate, nitrate, muriate, oxide compound, oxalate and acetate.
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| CN107163934B (en) * | 2017-07-28 | 2020-03-31 | 江西理工大学 | Quadrivalent manganese ion doped fluorine aluminum oxide lithium red fluorescent powder and preparation method thereof |
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| CN109777413B (en) * | 2019-03-05 | 2021-08-20 | 江南大学 | Luminescent inorganic particle with multiple photoresponse and blue long afterglow and preparation method thereof |
| CN111394097B (en) * | 2020-03-17 | 2021-05-07 | 北京科技大学 | Cr (chromium)3+Doped lithium indium germanate near-infrared luminescent material and preparation method thereof |
| CN112251226B (en) * | 2020-09-23 | 2021-12-21 | 华南理工大学 | Near-infrared luminescent material, preparation method thereof and conversion type LED (light-emitting diode) luminescent device |
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| CN116875307A (en) * | 2023-07-19 | 2023-10-13 | 常熟理工学院 | Tetravalent manganese ion activated titanate-based red luminescent material and preparation method thereof |
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