CN101033396A - Fluorescent material capable of emitting strong red light and preparing method thereof - Google Patents
Fluorescent material capable of emitting strong red light and preparing method thereof Download PDFInfo
- Publication number
- CN101033396A CN101033396A CN 200710014516 CN200710014516A CN101033396A CN 101033396 A CN101033396 A CN 101033396A CN 200710014516 CN200710014516 CN 200710014516 CN 200710014516 A CN200710014516 A CN 200710014516A CN 101033396 A CN101033396 A CN 101033396A
- Authority
- CN
- China
- Prior art keywords
- nitrate
- fluorescent material
- ion
- rare earth
- transition metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention provides a fluorescent material of strong red light emission, and the chemical formula of the fluorescent material is LiYZrO:Eu3+, R3+, in which, R is representative of the mixture of one / two kinds of rare earth ions or one / two kinds of transition metal ions or any two kind of B (B3 +) or rare-earth ions, transition metal ions and B. The preparation of the fluorescent material is that it dissolves any one / two kinds of lithium nitrate, yttrium nitrate, zirconium nitrate, Eu nitrate, and rare metal nitrate, transition metal compounds and boric acid in the deionized water, and then it adds the related nitrate and citric acid, and then it stirs the dissolved solution and heats the solution to achieve the material.
Description
Technical field
The present invention relates to fluorescent material of strong red emission and preparation method thereof, belong to the luminescent material technical field.
Technical background
Ri Ya chemical company took the lead in the technical also industrialization that makes a breakthrough of blue GaN LED in 1993, developed white light LEDs in 1996, specific practice is yttrium aluminum garnet (the yttrium aluminum garnet with jaundice spectrum row, YAG) fluorescent material cooperates blue-ray LED to obtain high efficiency white light source, and pushes to market in 1998.Compare with the traditional lighting light source, white light LEDs has many advantages, as: volume is little, less energy consumption, response is fast, the life-span is long, pollution-free etc., therefore be called the 4th generation lighting source.The plurality of advantages of white light LEDs makes it that huge following illumination market and remarkable energy-conservation prospect be arranged.
According to luminescence and colorimetry principle, be that substrate realizes that white light LEDs has multiple scheme with LED, development has following three kinds of schemes faster.
(1) the blue led chip and the jaundice emitting phosphor that can effectively be excited by blue light are in conjunction with forming white light LEDs.Part blue light is absorbed by fluorescent material, excitated fluorescent powder emission gold-tinted, and the gold-tinted of emission and remaining blue light are regulated and control their strength ratio, can obtain white light.The maximum blue-ray LED of current use is the InGaN blue-ray LED, emission peak 450 ~ 480nm.And gold-tinted fluorescent material mainly still is yttrium aluminum garnet series.Though this method can obtain optical throughput and the higher white light LEDs of luminous efficiency, its colour temperature is higher, and color developing is relatively poor.
(2) launch the red, green, blue three primary colors fluorescent powder with can effectively being excited in conjunction with forming white light LEDs with the led chip of sending out UV-light by UV-light.
(3) assembling of red, green, blue three base LED chips is realized white light.But owing to the rising of LED device light output meeting with temperature descends, different LED decline degree difference is very big, consequently causes the aberration of mixed white light, makes and realizes that with the assembling of three base LED chips the application of white light is restricted.
Use fluorescent material and LED combination to realize the technology of white light, therefore emission wavelength that can be by changing fluorescent material, the colourity that fluorescent material thickness is regulated white light LEDs, colour temperature etc. are widely adopted, and development is rapid.Especially second method because the adding of red composition can reduce the colour temperature of device in the spectrum, and improves the color developing of device, but because present red fluorescence powder (Y
2O
3: luminous efficiency Eu) is lower, causes the whole lighting efficiency of device not high.And to prepare the white light LEDs of high color rendering index (CRI), this class red fluorescence powder is absolutely necessary again.
In addition, the preparation method of present fluorescent material mainly concentrates on high temperature solid-state method, but solid phase method synthesis temperature height, the product particle diameter is bigger than normal and size-grade distribution is wide, is difficult to meet the requirements of granularity, and is difficult to obtain the pure phase material, has very big drawback.
Summary of the invention
The present invention is directed to red fluorescence powder (Y in the existing white light LEDs manufacturing processed
2O
3: Eu) the low problem of efficiency of conversion, the fluorescent material of the high strong red emission of a kind of efficiency of conversion is provided, a kind of this Preparation of Fluorescent Material method is provided simultaneously.
The chemical formula of the fluorescent material of strong red emission of the present invention is:
LiYZrO:Eu
3+，R
3+
Wherein: R represents one to two kind of rare earth ion or one to two kind of transition metal ion or boron ion (B
3+) or rare earth ion, transition metal ion and boron ion in any two kinds of ions mix altogether.Can adopt any rare earth ion.Can adopt any transition metal ion.
This fluorescent material is compared with existing red fluorescence powder has higher emissive porwer, and efficiency of conversion is higher.
The Preparation of Fluorescent Material method of strong red emission of the present invention may further comprise the steps:
(1) 90: 90: 10 in molar ratio: be dissolved in lithium nitrate, Yttrium trinitrate, zirconium nitrate, europium nitrate and other component in deionized water at 0.1 ~ 10: 0 ~ 10, and other components are meant that any two kinds in one to two kind of rare earth nitrate or one to two kind of transistion metal compound or boric acid or rare earth nitrate, transistion metal compound and the boric acid mix altogether;
(2) add the citric acid of 1 ~ 3 times of the urea of 3 ~ 5 times of relative nitrate mol ratios and mol ratio then in above-mentioned solution, the dissolving back was 100 ℃ ~ 180 ℃ following heated and stirred 10 ~ 50 minutes;
(3) then with above-mentioned solution 600 ℃ ~ 900 ℃ following sintering 5 ~ 40 minutes, can obtain the novel fluorescent material LiYZrO:Eu of Powdered strong red emission
3+, R
3+
The present invention adopts the fluorescent material red emission intensity height of combustion method preparation, and thing is mutually even, and the product granularity is little, belong to nano level, and chemical stability is good.In addition, the fluorescent material that the present invention obtains is nontoxic, radiationless, belongs to the environmental type luminescent material, and preparation technology is simple, safety, production temperature are lower, saves the energy.
Embodiment
Embodiment 1
Take by weighing 100g lithium nitrate, 250.7g Yttrium trinitrate, 69.168g zirconium nitrate (Zr (NO in molar ratio respectively
3)
45H
2O), 0.38g europium nitrate, 550.8g urea and 964.5g citric acid be soluble in water, 100 ℃ of following heated and stirred 40 minutes, 650 ℃ of following sintering 40 minutes, can obtain the white powder fluorescent material then.
Embodiment 2
Take by weighing 100g lithium nitrate, 250.7g Yttrium trinitrate, 69.168g zirconium nitrate (Zr (NO in molar ratio respectively
3)
45H
2O), 7.60g europium nitrate, 5.96g Dysprosium trinitrate, 561.6g urea and 655.6g citric acid be soluble in water, 120 ℃ of heating 35 minutes down, 750 ℃ of following sintering 25 minutes, can obtain the white powder fluorescent material then.
Embodiment 3
Take by weighing 100g lithium nitrate, 250.7 Yttrium trinitrates, 69.168g zirconium nitrate (Zr (NO in molar ratio respectively
3)
45H
2O), 7.60g europium nitrate, 5.39g lanthanum nitrate, 599.0g urea and 786.8g citric acid be soluble in water, 150 ℃ of heating 30 minutes down, 850 ℃ of following sintering 15 minutes, can obtain the white powder fluorescent material then.
Embodiment 4
Take by weighing 100g lithium nitrate, 250.7g Yttrium trinitrate, 69.168g zirconium nitrate (Zr (NO in molar ratio respectively
3)
45H
2O), 7.60g europium nitrate, 5.96g Dysprosium trinitrate, 1.81g cerous nitrate, 562.0g urea and 656.0g citric acid be soluble in water, 120 ℃ of heating 35 minutes down, 800 ℃ of following sintering 20 minutes, can obtain the white powder fluorescent material then.
Embodiment 5
Take by weighing 100g lithium nitrate, 250.7g Yttrium trinitrate, 69.168g zirconium nitrate (Zr (NO in molar ratio respectively
3)
45H
2O), 7.60g europium nitrate, 2.24g manganous nitrate, 4.98g boric acid, 616.3g urea and 809.5g citric acid are soluble in water, heated 35 minutes down at 120 ℃, then 800 ℃ of following sintering 20 minutes, can obtain the Powdered fluorescent material of blush, the product color is deepened with the rising of the doping content of Mn2+.
Embodiment 6
Take by weighing 100g lithium nitrate, 250.7g Yttrium trinitrate, 69.168g zirconium nitrate (Zr (NO in molar ratio respectively
3)
45H
2O), 7.60g europium nitrate, 3.89g cupric nitrate (Cu (NO
3)
23H
2O), 4.98g boric acid, 616.3g urea and 809.5g citric acid be soluble in water, 120 ℃ of heating 35 minutes down, 900 ℃ of following sintering 10 minutes, can obtain little blue powder shape fluorescent material then, the product color is with Cu
2+Doping content rising and deepen.
Embodiment 7
Take by weighing 100g lithium nitrate, 250.7g Yttrium trinitrate, 69.168g zirconium nitrate (Zr (NO in molar ratio respectively
3)
45H
2O), 11.40g europium nitrate, 4.98g boric acid, 559.4g urea and 653.1g citric acid be soluble in water, 130 ℃ of heating 33 minutes down, 700 ℃ of following sintering 30 minutes, can obtain the white powder fluorescent material then.
Embodiment 8
Take by weighing 100g lithium nitrate, 250.7g Yttrium trinitrate, 69.168g zirconium nitrate (Zr (NO in molar ratio respectively
3)
45H
2O), 18.87g europium nitrate, 3.97g Dysprosium trinitrate, 4.98g boric acid, 568.1g urea and 663.2g citric acid be soluble in water, 120 ℃ of heating 35 minutes down, 900 ℃ of following sintering 10 minutes, can obtain the white powder fluorescent material then.
Embodiment 9
Take by weighing 100g lithium nitrate, 250.7g Yttrium trinitrate, 69.168g zirconium nitrate (Zr (NO in molar ratio respectively
3)
45H
2O), 18.87g europium nitrate, 0.39g cupric nitrate (Cu (NO
3)
23H
2O), 659.7g urea and 990.3g citric acid be soluble in water, 120 ℃ of heating 35 minutes down, 850 ℃ of following sintering 15 minutes, can obtain little blue powder shape fluorescent material then, the product color is with Cu
2+Doping content rising and deepen.
Claims (2)
1. the fluorescent material of a strong red emission, it is characterized in that: the chemical formula of this fluorescent material is:
LiYZrO:Eu
3+，R
3+
Wherein on behalf of any two kinds of ions in one to two kind of rare earth ion or one to two kind of transition metal ion or boron ion or rare earth ion, transition metal ion and the boron ion, R mix altogether.
2. the Preparation of Fluorescent Material method of the described strong red emission of claim 1, the chemical formula of this fluorescent material is: LiYZrO:Eu
3+, R
3+Wherein on behalf of any two kinds of ions in one to two kind of rare earth ion or one to two kind of transition metal ion or boron or rare earth ion, transition metal ion and the boron, R mix altogether; It is characterized in that: may further comprise the steps:
(1) 90: 90: 10 in molar ratio: be dissolved in lithium nitrate, Yttrium trinitrate, zirconium nitrate, europium nitrate and other component in deionized water at 0.1 ~ 10: 0 ~ 10, and other components are meant that any two kinds in one to two kind of rare earth nitrate or one to two kind of transistion metal compound or boric acid or rare earth nitrate, transistion metal compound and the boric acid mix altogether;
(2) add the citric acid of 1 ~ 3 times of the urea of 3 ~ 5 times of relative nitrate mol ratios and mol ratio then in above-mentioned solution, the dissolving back was 100 ℃ ~ 180 ℃ following heated and stirred 10 ~ 50 minutes;
(3) then with above-mentioned solution 600 ℃ ~ 900 ℃ following sintering 5 ~ 40 minutes, can obtain the novel fluorescent material LiYZrO:Eu of Powdered strong red emission
3+, R
3+
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710014516 CN101033396A (en) | 2007-04-11 | 2007-04-11 | Fluorescent material capable of emitting strong red light and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710014516 CN101033396A (en) | 2007-04-11 | 2007-04-11 | Fluorescent material capable of emitting strong red light and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101033396A true CN101033396A (en) | 2007-09-12 |
Family
ID=38730141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710014516 Pending CN101033396A (en) | 2007-04-11 | 2007-04-11 | Fluorescent material capable of emitting strong red light and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101033396A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660273A (en) * | 2012-04-26 | 2012-09-12 | 哈尔滨工程大学 | Preparation method of rare earth doped nano zirconia up-conversion phosphor powder |
-
2007
- 2007-04-11 CN CN 200710014516 patent/CN101033396A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660273A (en) * | 2012-04-26 | 2012-09-12 | 哈尔滨工程大学 | Preparation method of rare earth doped nano zirconia up-conversion phosphor powder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Improved luminescence and energy-transfer properties of Ca 14 Al 10 Zn 6 O 35: Ti 4+, Mn 4+ deep-red-emitting phosphors with high brightness for light-emitting diode (LED) plant-growth lighting | |
| Liu et al. | High efficiency and high color purity blue-emitting NaSrBO 3: Ce 3+ phosphor for near-UV light-emitting diodes | |
| CN1239673C (en) | Red luminescent powder in use for LED, preparing method and electric light source produced | |
| CN1927996A (en) | Fluorescent powder material, preparation method thereof and white light LED electric light source | |
| CN104804738B (en) | Near ultraviolet excited white light LED fluorescent powder and preparation method thereof | |
| Cai et al. | Selectivity of Mn 2+ ion occupancy and energy transfer of Ce 3+→ Mn 2+ ions in garnet solid solution | |
| CN102643644A (en) | Light emitting diode (LED) fluorescent powder with single matrix white light excited by near ultraviolet and preparation method thereof | |
| CN112708422A (en) | High-temperature red fluorescent material and preparation method thereof | |
| CN103865532A (en) | Double-ion-doped antimonate luminescent material and preparation method thereof | |
| CN114181104B (en) | N-acetyl ethylenediamine metal halide low-dimensional perovskite single crystal material, preparation method and application thereof | |
| CN1255506C (en) | Boron-containing luminescent powder for LED, preparing method thereof and electric light source therefrom | |
| CN101054521A (en) | Red luminescence phosphor | |
| CN1760326A (en) | Phosphor powder of composite oxide in use for white light LED and fabricated electric light source | |
| CN101899304B (en) | Europium-doped SrAlSi oxynitride composite fluorescent powder and preparation method thereof | |
| US8591768B2 (en) | Germanate luminescence material and its preparation | |
| CN112852422A (en) | White LED fluorescent material and preparation method thereof | |
| CN112608742A (en) | beta-Al activated by europium2O3Defect structure blue fluorescent powder and preparation method thereof | |
| CN107163943B (en) | Spectrum-adjustable fluorescent powder suitable for near ultraviolet excitation and preparation method thereof | |
| CN1810923A (en) | Luminescent material and its prepn | |
| CN101033396A (en) | Fluorescent material capable of emitting strong red light and preparing method thereof | |
| CN101045861A (en) | Whole color fluorescent material and preparation method thereof | |
| CN103450898A (en) | Titanate base red fluorescent powder for white LED (Light Emitting Diode) and preparation method thereof | |
| CN112063381A (en) | Mn4+ ion activated perovskite fluoride red light material | |
| CN111778022A (en) | Alkali metal enhanced orange light fluorescent powder and preparation method and application thereof | |
| CN101759361A (en) | Rare earth doped luminescent glass and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20070912 |
|
| C20 | Patent right or utility model deemed to be abandoned or is abandoned |