CN109370588B - Nitride phosphor powder for semiconductor light emitting, its preparation method and light emitting device - Google Patents
Nitride phosphor powder for semiconductor light emitting, its preparation method and light emitting device Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 60
- 239000000126 substance Substances 0.000 claims abstract description 82
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 12
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 10
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 4
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 101
- 229910052727 yttrium Inorganic materials 0.000 abstract description 4
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 description 60
- 239000000543 intermediate Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 11
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- 229910004709 CaSi Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
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- 150000002222 fluorine compounds Chemical class 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
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- 230000002427 irreversible effect Effects 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域technical field
本发明属于发光材料技术领域,具体涉及一种半导体发光用的氮化物荧光粉及其制备方法和发光装置。The invention belongs to the technical field of light-emitting materials, and in particular relates to a nitride fluorescent powder for semiconductor light-emitting, a preparation method thereof, and a light-emitting device.
背景技术Background technique
大功率发光二极管(Light Emitting Diode,LED)具有体积小、寿命长、电光转换效率高、响应速度快、节能、环保等优良特性,被广泛应用于商业照明、路灯、汽车灯、探照灯等领域。近年来,白光LED在小功率照明领域得到了广泛普及,技术和应用领域均达到相对成熟的阶段。但在大功率技术和应用领域仍处于起步和发展阶段,主要原因是在高能量激发下,高的热辐射以及强射线辐射对荧光粉造成较大的不可逆伤害,降了器件的使用寿命、稳定性和光效。因此,开发耐高能量密度用LED荧光粉是实现高光效、高稳定性大功率LED器件的关键。High-power light-emitting diodes (Light Emitting Diode, LED) have excellent characteristics such as small size, long life, high electro-optical conversion efficiency, fast response, energy saving, and environmental protection, and are widely used in commercial lighting, street lights, car lights, searchlights and other fields. In recent years, white LEDs have been widely popularized in the field of low-power lighting, and both technology and application fields have reached a relatively mature stage. However, in the field of high-power technology and application, it is still in its infancy and development stage. The main reason is that under high-energy excitation, high thermal radiation and strong ray radiation cause great irreversible damage to the phosphor, which reduces the service life and stability of the device. sex and light effects. Therefore, the development of LED phosphors with high energy density resistance is the key to realize high light efficiency, high stability and high power LED devices.
La3Si6N11:Ce3+荧光粉因其高热稳定性能在大功率LED应用中具有明显的优势。然而由于制备条件相对苛刻,且热稳定性和外量子效率仍需进一步提升,目前尚未在大功率LED中进行广泛应用。因此,开发制备方法简单、热稳定性和外量子效率较高的氮化物荧光粉能够应用于大功率LED器件非常关键。La 3 Si 6 N 11 : Ce 3+ phosphor has obvious advantages in high-power LED applications because of its high thermal stability. However, due to the relatively harsh preparation conditions, and the thermal stability and external quantum efficiency still need to be further improved, it has not yet been widely used in high-power LEDs. Therefore, it is very important to develop nitride phosphors with simple preparation method, high thermal stability and high external quantum efficiency that can be applied to high-power LED devices.
发明内容Contents of the invention
本发明的目的在于克服现有技术的上述不足,提供一种半导体发光用的氮化物荧光粉及其制备方法和发光装置,旨在解决现有荧光粉光效低、耐高能量密度差的技术问题。The purpose of the present invention is to overcome the above-mentioned deficiencies of the prior art, to provide a nitride phosphor powder for semiconductor light-emitting and its preparation method and a light-emitting device, aiming to solve the low light efficiency and poor resistance to high energy density of the existing phosphor powder technology question.
为实现上述发明目的,本发明采用的技术方案如下:For realizing above-mentioned purpose of the invention, the technical scheme that the present invention adopts is as follows:
本发明一方面提供一种氮化物荧光粉,所述氮化物荧光粉的化学通式为A3-x-y- zMxD6(N11-xCx):(yCe,zR);其中,A选自La、Y、Lu和Gd中的至少一种,M选自Ca、Sr和Ba中的至少一种,D选自Si、Ge、Ti、Se和Hf中的至少一种,R选自Pr、Tb、Nd和Dy中的至少一种,且0.001≤x≤2,0.005≤y≤0.2,0.001≤z≤0.1。One aspect of the present invention provides a nitride phosphor, the general chemical formula of the nitride phosphor is A 3-xy- z M x D 6 (N 11-x C x ):(yCe,zR); wherein, A is selected from at least one of La, Y, Lu and Gd, M is selected from at least one of Ca, Sr and Ba, D is selected from at least one of Si, Ge, Ti, Se and Hf, and R is selected from At least one of Pr, Tb, Nd and Dy, and 0.001≤x≤2, 0.005≤y≤0.2, 0.001≤z≤0.1.
本发明提供的氮化物荧光粉中,通过适量M2+和C4-离子分别替代A3+和N3-,从而提升了荧光粉发光中心周围的晶格稳定性和晶体场环境,使得荧光粉的光色性能可控可调,且热稳定性得到大幅度提升;同时本发明氮化物荧光粉中引入R3+,通过能量传递方式,进一步地提升了荧光粉的发光效率(外量子效率),最终,基于化学通式中各元素的协同作用,使得该氮化物荧光粉的光效较高且热稳定性较好,非常适合应用于大功率LED器件中。In the nitride phosphor powder provided by the present invention, A 3+ and N 3- are replaced by an appropriate amount of M 2+ and C 4- ions, respectively, thereby improving the lattice stability and crystal field environment around the luminescent center of the phosphor powder, making the fluorescence The light color performance of the powder is controllable and adjustable, and the thermal stability is greatly improved; at the same time, the introduction of R 3+ into the nitride phosphor powder of the present invention further improves the luminous efficiency of the phosphor powder (external quantum efficiency ), finally, based on the synergistic effect of each element in the general chemical formula, the nitride phosphor has higher luminous efficiency and better thermal stability, and is very suitable for application in high-power LED devices.
本发明另一方面提供一种上述氮化物荧光粉的制备方法,包括如下步骤:Another aspect of the present invention provides a method for preparing the above-mentioned nitride phosphor, comprising the following steps:
将第一A的氮化物、第一D的氮化物和CeN混合,在N2和H2的还原下,进行第一烧结处理,得到中间体;Mixing the nitride of the first A, the nitride of the first D and CeN, under the reduction of N2 and H2 , performing the first sintering treatment to obtain the intermediate;
将第二A的氮化物、第二D的碳化物、M的氮化物和R的氮化物或氟化物加入所述中间体中,在C还原气氛下,进行第二烧结处理,得到所述氮化物荧光粉;Add the second nitride of A, the second carbide of D, the nitride of M and the nitride or fluoride of R into the intermediate, and carry out the second sintering treatment under the reducing atmosphere of C to obtain the nitrogen Compound phosphor;
其中,所述第一A的氮化物和所述第二A的氮化物的A总摩尔量,所述第一D的氮化物和所述第二D的氮化物的D总摩尔量,分别为所述氮化物荧光粉的化学通式中A和D的摩尔量。Wherein, the total molar weight of A of the nitride of the first A and the nitride of the second A, and the total molar weight of D of the nitride of the first D and the nitride of the second D are respectively The molar amounts of A and D in the general chemical formula of the nitride phosphor.
本发明提供的氮化物荧光粉为两步法制成,该制备方法工艺简单,成本低,先将第一A的氮化物、第一D的氮化物和CeN混合制成中间体,再将中间体与第二A的氮化物、第二D的碳化物、M的氮化物和R的氮化物或氟化物混合,制成最终的氮化物荧光粉,这样两步制成的氮化物荧光粉的不仅光效较高、热稳定性较好,而且具有更好的结晶效果。The nitride phosphor powder provided by the present invention is prepared by a two-step method. The preparation method is simple in process and low in cost. First, the nitride of the first A, the nitride of the first D and CeN are mixed to form an intermediate, and then the intermediate It is mixed with the nitride of the second A, the carbide of the second D, the nitride of M and the nitride or fluoride of R to make the final nitride phosphor, so that the nitride phosphor made in two steps is not only High light efficiency, good thermal stability, and better crystallization effect.
最后,本发明提供一种发光装置,包括激发光源和被所述激发光源激发的荧光物质,所述荧光物质为本发明所述的氮化物荧光粉或本发明所述的制备方法得到的氮化物荧光粉。Finally, the present invention provides a light-emitting device, including an excitation light source and a fluorescent substance excited by the excitation light source, and the fluorescent substance is the nitride phosphor powder described in the present invention or the nitride phosphor obtained by the preparation method described in the present invention Phosphor.
本发明的发光装置中,被激发光源激发的荧光物质为本发明特有的氮化物荧光粉,该氮化物光效较高且热稳定性较好,最终提高了发光装装置的光效和稳定性。In the light-emitting device of the present invention, the fluorescent substance excited by the excitation light source is the unique nitride phosphor powder of the present invention. The nitride has high light efficiency and good thermal stability, and finally improves the light efficiency and stability of the light-emitting device. .
附图说明Description of drawings
图1为本发明实施例40的激发光谱图(检测波长540nm);Fig. 1 is the excitation spectrogram (detection wavelength 540nm) of the embodiment of the present invention 40;
图2为本发明实施例40的发射光谱图(激发波长450nm)Fig. 2 is the emission spectrogram (excitation wavelength 450nm) of embodiment 40 of the present invention
图3(a)为本发明实施例40两步法得到的氮化物荧光粉的扫描电镜图;Fig. 3 (a) is the scanning electron micrograph of the nitride phosphor obtained by the two-step method of Example 40 of the present invention;
图3(b)为本发明实施例44一步法得到的氮化物荧光粉的扫描电镜图;Fig. 3 (b) is the scanning electron micrograph of the nitride phosphor obtained by the one-step method of Example 44 of the present invention;
图4为本发明实施例40和比较例1的热稳定性对比图。Fig. 4 is a thermal stability comparison chart of Example 40 of the present invention and Comparative Example 1.
具体实施方式Detailed ways
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.
术语“第一”、“第二”仅用于描述目的,而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此,限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。The terms "first" and "second" are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. Thus, a feature defined as "first" and "second" may explicitly or implicitly include one or more of these features.
一方面,本发明实施例提供了一种氮化物荧光粉,所述氮化物荧光粉的化学通式为A3-x-y-zMxD6(N11-xCx):(yCe,zR);其中,A选自La(镧)、Y(钇)、Lu(镥)和Gd(钆)中的至少一种,M选自Ca(钙)、Sr(锶)和Ba(钡)中的至少一种,D选自Si(硅)、Ge(锗)、Ti(钛)、Se(硒)和Hf(铪)中的至少一种,R选自Pr(镨)、Tb(铽)、Nd(钕)和Dy(镝)中的至少一种,且0.001≤x≤2,0.005≤y≤0.2,0.001≤z≤0.1。On the one hand, the embodiment of the present invention provides a nitride phosphor, the general chemical formula of the nitride phosphor is A 3-xyz M x D 6 (N 11-x C x ):(yCe,zR); Among them, A is selected from at least one of La (lanthanum), Y (yttrium), Lu (lutetium) and Gd (gadolinium), and M is selected from at least one of Ca (calcium), Sr (strontium) and Ba (barium). One, D is selected from at least one of Si (silicon), Ge (germanium), Ti (titanium), Se (selenium) and Hf (hafnium), R is selected from Pr (praseodymium), Tb (terbium), Nd (neodymium) and Dy (dysprosium), and 0.001≤x≤2, 0.005≤y≤0.2, 0.001≤z≤0.1.
本发明实施例提供的氮化物荧光粉中,通过适量M2+和C4-离子分别替代A3+和N3-,从而提升了荧光粉发光中心周围的晶格稳定性和晶体场环境,使得荧光粉的光色性能可控可调,且热稳定性得到大幅度提升;同时本发明氮化物荧光粉中引入R3+,通过能量传递方式,进一步地提升了荧光粉的发光效率(外量子效率),最终,基于化学通式中各元素的协同作用,使得该氮化物荧光粉的光效较高且热稳定性较好,非常适合应用于大功率LED器件中。In the nitride phosphor powder provided by the embodiment of the present invention, A 3+ and N 3- are replaced by an appropriate amount of M 2+ and C 4- ions, respectively, thereby improving the lattice stability and crystal field environment around the luminescent center of the phosphor, The light color performance of the phosphor is controllable and adjustable, and the thermal stability is greatly improved; at the same time, the introduction of R 3+ into the nitride phosphor of the present invention further improves the luminous efficiency of the phosphor through the energy transfer method (external Quantum efficiency), finally, based on the synergistic effect of each element in the general chemical formula, the nitride phosphor has high light efficiency and good thermal stability, and is very suitable for high-power LED devices.
进一步地,所述氮化物荧光粉的化学通式中,M为Ca,这是由于Ca2+半径小于La3+半径,C4-离子半径大于N3-半径,当Ca-C同时取代La-N元素,其晶体结构稳定性会更高,发光中心周围晶体场发射变化,光色性能容易调控,热稳定性得到较大幅度提升;更进一步地,A为La和/或Lu,首先当A为La或Lu时,所制备荧光粉相纯度较高,其发光效率更高;适量的Lu替代La元素即同时含有La和Lu时,荧光粉结晶性能更好,发光效率更高,其结构致密性增强,稳定性提高;更进一步地,R为Pr和/或Tb,当选用Pr和/或Tb时,会产生能量传递,进一步提升荧光粉发光效率。Further, in the general chemical formula of the nitride phosphor, M is Ca, this is because the Ca 2+ radius is smaller than the La 3+ radius, and the C 4- ion radius is greater than the N 3- radius, when Ca-C simultaneously replaces La -N element, the stability of its crystal structure will be higher, the field emission of the crystal around the luminescent center will change, the light color performance is easy to control, and the thermal stability is greatly improved; further, A is La and/or Lu, first when When A is La or Lu, the phase purity of the prepared phosphor is higher, and its luminous efficiency is higher; when an appropriate amount of Lu replaces La element, that is, when both La and Lu are contained, the phosphor has better crystallization performance and higher luminous efficiency. The density is enhanced and the stability is improved; furthermore, R is Pr and/or Tb, and when Pr and/or Tb is selected, energy transfer will occur, and the luminous efficiency of the phosphor will be further improved.
进一步地,所述氮化物荧光粉的化学通式中,D选自Si、Ge、Ti、Se中的至少一种,且D包括Si。即D必含有Si,优选地,D为Si和Ge,或者D为Si和Se。以D的摩尔百分含量为100%计,其中,Si的摩尔含量为80-90%。当Si的摩尔含量为100%即D只为Si时,氮化物荧光粉具有更好的发光强度;但是当Si含量太高的时候,Se或Ge替代量太少,这样不利于荧光粉形貌和结晶性能的改善,荧光粉光色性能提升不明显,因此为了提高荧光粉的综合性能,需要适当降低Si的摩尔含量,但当Si含量太低的时候,荧光粉结构会出现畸变,发光效率和稳定性会下降;因此,选择Si的摩尔含量为80-90%之间,这样荧光粉既提升了光色性能又提高了发光效率。Further, in the general chemical formula of the nitride phosphor, D is selected from at least one of Si, Ge, Ti, and Se, and D includes Si. That is, D must contain Si, preferably, D is Si and Ge, or D is Si and Se. Assuming that the molar percentage of D is 100%, the molar content of Si is 80-90%. When the molar content of Si is 100%, that is, when D is only Si, the nitride phosphor has better luminous intensity; but when the Si content is too high, the substitution amount of Se or Ge is too small, which is not conducive to the morphology of the phosphor With the improvement of crystallization properties, the light color performance of the phosphor powder is not significantly improved. Therefore, in order to improve the overall performance of the phosphor powder, it is necessary to appropriately reduce the molar content of Si. However, when the Si content is too low, the structure of the phosphor powder will be distorted, and the luminous efficiency And the stability will decrease; therefore, the molar content of Si is selected to be between 80-90%, so that the phosphor not only improves the light color performance but also improves the luminous efficiency.
进一步地,所述氮化物荧光粉的化学通式中,所述氮化物荧光粉的化学通式中,A为La和Lu,且La和Lu的摩尔比为(4-10):1。通过La和Lu的比例调控,更好地提升荧光粉晶格稳定性,在该比例范围的A组成的氮化物荧光粉的热稳定性最佳;当La/Lu比过低时,荧光粉结构发生变化,荧光粉发光效率会下降,当La/Lu比过高时,荧光粉结晶和结构稳定性提升不明显,光色性能提升不明显,因此La和Lu的摩尔比在(4-10):1的范围内时,荧光粉既提升了光色性能又提高了发光效率。Further, in the general chemical formula of the nitride phosphor, in the general chemical formula of the nitride phosphor, A is La and Lu, and the molar ratio of La and Lu is (4-10):1. By adjusting the ratio of La and Lu, the stability of the phosphor lattice can be better improved. The thermal stability of the nitride phosphor composed of A in this ratio range is the best; when the La/Lu ratio is too low, the phosphor structure changes, the luminous efficiency of the phosphor will decrease. When the La/Lu ratio is too high, the crystallization and structural stability of the phosphor will not be significantly improved, and the light and color performance will not be significantly improved. Therefore, the molar ratio of La to Lu is between (4-10) : In the range of 1, the phosphor not only improves the light color performance but also improves the luminous efficiency.
进一步地,所述氮化物荧光粉的化学通式中,0.01≤x≤1.5,0.01≤y≤0.1,0.005≤z≤0.05;当x值过高时,荧光粉相纯度降低,发光效率和稳定性均呈下降趋势,x值过低时,荧光粉微结构变化不够明显,光色性能调控不明显,其发光效率和热稳定性提升效果较小,因此0.01≤x≤1.5的范围内效果最优;当y值过高时,Ce3+和Ce3+之间会产生无辐射能量传递,进而会导致荧光粉的发光效率和稳定性降低,y值过低时,荧光粉中发光中心浓度太低,发光效率相对较低,因此0.01≤y≤0.1的范围内效果最优;另外,z值偏大会导致激活剂之间发生无辐射能量传递,发生浓度猝灭,且对蓝光吸收较多,会导致Ce3+发射强度降低,z值偏小时,R离子向Ce离子发射能量传递效果不明显,发光效率提升不明显,因此0.005≤z≤0.05的范围内效果最优。Further, in the general chemical formula of the nitride phosphor, 0.01≤x≤1.5, 0.01≤y≤0.1, 0.005≤z≤0.05; when the x value is too high, the phase purity of the phosphor decreases, and the luminous efficiency and stability When the value of x is too low, the change of phosphor microstructure is not obvious enough, the control of light color performance is not obvious, and the improvement effect of its luminous efficiency and thermal stability is small, so the effect in the range of 0.01≤x≤1.5 is the best. Excellent; when the y value is too high, there will be non-radiative energy transfer between Ce 3+ and Ce 3+ , which will lead to a decrease in the luminous efficiency and stability of the phosphor. When the y value is too low, the concentration of luminescent centers in the phosphor will Too low, the luminous efficiency is relatively low, so the effect is optimal in the range of 0.01≤y≤0.1; in addition, a large z value will lead to non-radiative energy transfer between activators, concentration quenching, and more absorption of blue light , will lead to a decrease in Ce 3+ emission intensity, and a small z value, the effect of energy transfer from R ions to Ce ions is not obvious, and the luminous efficiency is not significantly improved, so the effect is best in the range of 0.005≤z≤0.05.
另一方面,本发明实施例还提供了一种上述氮化物荧光粉的制备方法,包括如下步骤:On the other hand, the embodiment of the present invention also provides a method for preparing the above-mentioned nitride phosphor, comprising the following steps:
S01:将第一A的氮化物、第一D的氮化物和CeN混合,在N2和H2的还原下,进行第一烧结处理,得到中间体;S01: Mix the nitride of the first A, the nitride of the first D and CeN, and perform the first sintering treatment under the reduction of N2 and H2 to obtain an intermediate;
S02:将第二A的氮化物、第二D的碳化物、M的氮化物和R的氮化物或氟化物加入所述中间体中,在C还原气氛下,进行第二烧结处理,得到所述氮化物荧光粉;S02: Add the second nitride of A, the second carbide of D, the nitride of M and the nitride or fluoride of R into the intermediate, and carry out the second sintering treatment under the reducing atmosphere of C to obtain the obtained The nitride phosphor powder;
其中,所述第一A的氮化物和所述第二A的氮化物的A总摩尔量,所述第一D的氮化物和所述第二D的氮化物的D总摩尔量,分别为所述氮化物荧光粉的化学通式中A和D的摩尔量。Wherein, the total molar weight of A of the nitride of the first A and the nitride of the second A, and the total molar weight of D of the nitride of the first D and the nitride of the second D are respectively The molar amounts of A and D in the general chemical formula of the nitride phosphor.
本发明实施例提供的氮化物荧光粉的制备方法工艺简单,成本低,该制备方法为两步法工艺,即先将原料A的氮化物分成两份:第一A的氮化物和所述第二A的氮化物;原料D的氮化物分成两份:第一D的氮化物和第二D的氮化物;然后将将第一A的氮化物、第一D的氮化物和CeN混合制成中间体,再将中间体与第二A的氮化物、第二D的碳化物、M的氮化物和R的氮化物或氟化物混合,制成最终的氮化物荧光粉,这样两步制成的氮化物荧光粉的不仅光效较高、热稳定性较好,而且具有更好的结晶效果。The preparation method of the nitride phosphor provided by the embodiment of the present invention is simple in process and low in cost. The nitride of the second A; the nitride of the raw material D is divided into two parts: the nitride of the first D and the nitride of the second D; then the nitride of the first A, the nitride of the first D and CeN are mixed to make Intermediate, and then mix the intermediate with the second A nitride, the second D carbide, M nitride and R nitride or fluoride to make the final nitride phosphor, which is made in two steps The nitride phosphor not only has higher light efficiency and better thermal stability, but also has better crystallization effect.
进一步地,在上述步骤S01中,所述第一A的氮化物中的A元素与所述CeN中Ce元素的摩尔量之和与所述第一D的氮化物中的D元素的摩尔量之比为1:3。在该比例范围内,可以更好地制成中间体,从而有利于后续制成氮化物荧光粉。Further, in the above step S01, the sum of the molar weights of the A element in the nitride of the first A and the Ce element in the CeN and the molar weight of the D element in the first D nitride The ratio is 1:3. Within this ratio range, intermediates can be better produced, which is beneficial to the subsequent production of nitride phosphors.
更进一步地,所述第一烧结处理的温度为1300-1500℃,时间为5-7h;第二烧结处理的温度为1500-1700℃,时间为7-9h。在上述温度和时间范围内,可以更好地烧结得到中间体以及最终的氮化物荧光粉。Furthermore, the temperature of the first sintering treatment is 1300-1500°C, and the time is 5-7h; the temperature of the second sintering treatment is 1500-1700°C, and the time is 7-9h. Within the above range of temperature and time, the intermediate and the final nitride phosphor can be better sintered.
具体一实施例中,该氮化物荧光粉的制备方法包括:In a specific embodiment, the preparation method of the nitride phosphor comprises:
(一)将一定比例的A的氮化物、D的氮化物和CeN粉末按照一定的化学计量比均匀混合,并放入钨坩埚中,在N2/H2混合气体的还原下,1400℃保温6h烧结,经过破碎后获得中间体;其中A为La、Y、Lu、Gd的任一种或多种,D为Si、Ge、Ti、Se、Hf的任一种或多种;(1) Mix a certain proportion of nitrides of A, nitrides of D and CeN powder uniformly according to a certain stoichiometric ratio, and put them into a tungsten crucible, and keep it at 1400°C under the reduction of N 2 /H 2 mixed gas 6h sintering, after crushing to obtain an intermediate; wherein A is any one or more of La, Y, Lu, Gd, and D is any one or more of Si, Ge, Ti, Se, Hf;
(二)将获得的中间体添加A的氮化物、M的氮化物、D的碳化物和R的氮化物或氟化物,按照一定的比例混合,并在C还原气氛下,1600℃保温8h烧结,将所获得的荧光物质经过破碎、洗涤、烘干,最终获得目标氮化物荧光粉。(2) Add nitrides of A, nitrides of M, carbides of D, and nitrides or fluorides of R to the obtained intermediate, mix according to a certain ratio, and sinter at 1600°C for 8 hours in a reducing atmosphere of C , crushing, washing and drying the obtained fluorescent substance to finally obtain the target nitride phosphor.
最后,本发明实施例提供一种发光装置,包括激发光源和被所述激发光源激发的荧光物质,所述荧光物质为本发明实施例所述的氮化物荧光粉或本发明实施例所述的制备方法得到的氮化物荧光粉。Finally, an embodiment of the present invention provides a light-emitting device, including an excitation light source and a fluorescent substance excited by the excitation light source. The fluorescent substance is the nitride phosphor powder described in the embodiment of the present invention or the phosphor powder described in the embodiment of the present invention. The nitride phosphor powder obtained by the preparation method.
本发明实施例的发光装置中,被激发光源激发的荧光物质为本发明实施例特有的氮化物荧光粉,该氮化物光效较高且热稳定性较好,最终提高了发光装装置的光效和稳定性。In the light-emitting device of the embodiment of the present invention, the fluorescent substance excited by the excitation light source is the unique nitride phosphor powder of the embodiment of the present invention. The nitride phosphor has high light efficiency and good thermal stability, and finally improves the light emission of the light-emitting device. efficiency and stability.
进一步地,所述激发光源为发射波长范围为330~480nm的半导体芯片。Further, the excitation light source is a semiconductor chip with an emission wavelength range of 330-480 nm.
本发明先后进行过多次试验,现举一部分试验结果作为参考对发明进行进一步详细描述,下面结合具体实施例进行详细说明。The present invention has been tested many times successively, and a part of the test results are given as a reference to further describe the invention in detail, and will be described in detail below in conjunction with specific examples.
实施例1Example 1
一种大功率用氮化物荧光材料,化学式为La2.445Ba0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物荧光材料的制备方法,包括以下步骤:将一定比例的LaN、Si3N4和CeN按照一定摩尔比均匀混合,并放入钨坩埚中,在N2/H2混合气体的还原下,1400℃保温6h烧结,经过破碎后获得中间体;然后将获得的中间体同LaN、Ba3N2、Si3N4、TbN、SiC按照一定的摩尔比均匀混合,并在C还原气氛下,1600℃保温8h烧结,将所获得的荧光物质经过破碎、洗涤、烘干,最终获得La2.445Ba0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)荧光粉。所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 2.445 Ba 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride fluorescent material comprises the following steps: uniformly mixing a certain proportion of LaN, Si 3 N 4 and CeN according to a certain molar ratio, putting them into a tungsten crucible, and reducing the N 2 /H 2 mixed gas sintering at 1400°C for 6 hours, and the intermediate was obtained after crushing; then the obtained intermediate was uniformly mixed with LaN, Ba 3 N 2 , Si 3 N 4 , TbN, and SiC according to a certain molar ratio, and the intermediate was mixed in a reducing atmosphere of C sintering at 1600° C. for 8 hours, crushing, washing and drying the obtained fluorescent substance to finally obtain La 2.445 Ba 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb) phosphor. The fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
实施例2Example 2
一种大功率用氮化物荧光材料,化学式为La2.445Sr0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物荧光材料的制备方法,包括以下步骤:将一定比例的LaN、Si3N4和CeN按照一定摩尔比均匀混合,并放入钨坩埚中,在N2/H2混合气体的还原下,1400℃保温6h烧结,经过破碎后获得中间体;然后将获得的中间体同LaN、Sr3N2、Si3N4、TbN、SiC按照一定的摩尔比均匀混合,并在C还原气氛下,1600℃保温8h烧结,将所获得的荧光物质经过破碎、洗涤、烘干,最终获得La2.445Sr0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)荧光粉。所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 2.445 Sr 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride fluorescent material comprises the following steps: uniformly mixing a certain proportion of LaN, Si 3 N 4 and CeN according to a certain molar ratio, putting them into a tungsten crucible, and reducing the N 2 /H 2 mixed gas sintering at 1400°C for 6 hours, and the intermediate was obtained after crushing; then the obtained intermediate was uniformly mixed with LaN, Sr 3 N 2 , Si 3 N 4 , TbN, and SiC in a certain molar ratio, and the intermediate was mixed in a reducing atmosphere of C sintering at 1600°C for 8 hours, crushing, washing and drying the obtained fluorescent material to finally obtain La 2.445 Sr 0.5 Si 6 N 10.5 C 0.5 :(0.05Ce, 0.005Tb) fluorescent powder. The fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
实施例3Example 3
一种大功率用氮化物荧光材料,化学式为La2.445Ca0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法,包括以下步骤:将一定比例的LaN、Si3N4和CeN按照一定摩尔比均匀混合,并放入钨坩埚中,在N2/H2混合气体的还原下,1400℃保温6h烧结,经过破碎后获得中间体;然后将获得的中间体同LaN、Ca3N2、Si3N4、TbN、SiC按照一定的摩尔比均匀混合,并在C还原气氛下,1600℃保温8h烧结,将所获得的荧光物质经过破碎、洗涤、烘干,最终获得La2.445Ca0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)荧光粉。所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 2.445 Ca 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material comprises the following steps: uniformly mixing a certain proportion of LaN, Si 3 N 4 and CeN according to a certain molar ratio, putting them into a tungsten crucible, and mixing them in a N 2 /H 2 mixed gas Under the reduction of 1400°C for 6 hours, the intermediate was obtained after crushing; then the obtained intermediate was uniformly mixed with LaN, Ca 3 N 2 , Si 3 N 4 , TbN, and SiC according to a certain molar ratio, and heated at C Under reducing atmosphere, sintering at 1600°C for 8 hours, crushing, washing, and drying the obtained fluorescent substance to finally obtain La 2.445 Ca 0.5 Si 6 N 10.5 C 0.5 :(0.05Ce, 0.005Tb) phosphor. The fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
实施例4Example 4
一种大功率用氮化物荧光材料,化学式为Y2.445Ca0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法,包括以下步骤:将一定比例的YN、Si3N4和CeN按照一定摩尔比均匀混合,并放入钨坩埚中,在N2/H2混合气体的还原下,1400℃保温6h烧结,经过破碎后获得中间体;然后将获得的中间体同YN、Ca3N2、Si3N4、TbN、SiC按照一定的摩尔比均匀混合,并在C还原气氛下,1600℃保温8h烧结,将所获得的荧光物质经过破碎、洗涤、烘干,最终获得Y2.445Ca0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)荧光粉。所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of Y 2.445 Ca 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material includes the following steps: uniformly mix a certain proportion of YN, Si 3 N 4 and CeN according to a certain molar ratio, put them into a tungsten crucible, and mix them in a N 2 /H 2 mixed gas Under the reduction of 1400°C for 6 hours, the intermediate was obtained after crushing; then the obtained intermediate was uniformly mixed with YN, Ca 3 N 2 , Si 3 N 4 , TbN, and SiC according to a certain molar ratio, and heated at C Under reducing atmosphere, heat preservation at 1600° C. for 8 hours for sintering, crush, wash and dry the obtained fluorescent substance to finally obtain Y 2.445 Ca 0.5 Si 6 N 10.5 C 0.5 :(0.05Ce, 0.005Tb) phosphor. The fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
实施例5Example 5
一种大功率用氮化物荧光材料,化学式为Lu2.445Ca0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法,包括以下步骤:将一定比例的LuN、Si3N4和CeN按照一定摩尔比均匀混合,并放入钨坩埚中,在N2/H2混合气体的还原下,1400℃保温6h烧结,经过破碎后获得中间体;然后将获得的中间体同LuN、Ca3N2、Si3N4、TbN、SiC按照一定的摩尔比均匀混合,并在C还原气氛下,1600℃保温8h烧结,将所获得的荧光物质经过破碎、洗涤、烘干,最终获得Lu2.445Ca0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)荧光粉。所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of Lu 2.445 Ca 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material comprises the following steps: uniformly mixing a certain proportion of LuN, Si 3 N 4 and CeN according to a certain molar ratio, putting them into a tungsten crucible, and mixing them in a N 2 /H 2 mixed gas Under the reduction of 1400°C for 6 hours, the intermediate was obtained after crushing; then the obtained intermediate was uniformly mixed with LuN, Ca 3 N 2 , Si 3 N 4 , TbN, and SiC according to a certain molar ratio, and heated at C Under a reducing atmosphere, heat preservation at 1600°C for 8 hours for sintering, crushing, washing and drying the obtained fluorescent substance to finally obtain Lu 2.445 Ca 0.5 Si 6 N 10.5 C 0.5 :(0.05Ce, 0.005Tb) fluorescent powder. The fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
实施例6Example 6
一种大功率用氮化物荧光材料,化学式为Gd2.445Ca0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法,包括以下步骤:将一定比例的GdN、Si3N4和CeN按照一定摩尔比均匀混合,并放入钨坩埚中,在N2/H2混合气体的还原下,1400℃保温6h烧结,经过破碎后获得中间体;然后将获得的中间体同GdN、Ca3N2、Si3N4、TbN、SiC按照一定的摩尔比均匀混合,并在C还原气氛下,1600℃保温8h烧结,将所获得的荧光物质经过破碎、洗涤、烘干,最终获得Gd2.445Ca0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)荧光粉。所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of Gd 2.445 Ca 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material comprises the following steps: uniformly mixing a certain proportion of GdN, Si 3 N 4 and CeN according to a certain molar ratio, putting them into a tungsten crucible, and mixing them in a N 2 /H 2 mixed gas Under the reduction of 1400°C for 6 hours, the intermediate was obtained after crushing; then the obtained intermediate was uniformly mixed with GdN, Ca 3 N 2 , Si 3 N 4 , TbN, and SiC according to a certain molar ratio, and heated at C Under reducing atmosphere, heat preservation at 1600°C for 8 hours for sintering, crush, wash and dry the obtained fluorescent substance to finally obtain Gd 2.445 Ca 0.5 Si 6 N 10.5 C 0.5 :(0.05Ce, 0.005Tb) fluorescent powder. The fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
实施例7Example 7
一种大功率用氮化物荧光材料,化学式为La2.445Ca0.5Ge6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法,包括以下步骤:将一定比例的LaN、Ge3N4和CeN按照一定摩尔比均匀混合,并放入钨坩埚中,在N2/H2混合气体的还原下,1400℃保温6h烧结,经过破碎后获得中间体;然后将获得的中间体同LaN、Ca3N2、Ge3N4、TbN、SiC按照一定的摩尔比均匀混合,并在C还原气氛下,1600℃保温8h烧结,将所获得的荧光物质经过破碎、洗涤、烘干,最终获得La2.445Ca0.5Ge6N10.5C0.5:(0.05Ce,0.005Tb)荧光粉。所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 2.445 Ca 0.5 Ge 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material comprises the following steps: uniformly mixing a certain proportion of LaN, Ge 3 N 4 and CeN according to a certain molar ratio, putting them into a tungsten crucible, and mixing them in a N 2 /H 2 mixed gas Under the reduction of 1400°C for 6 hours, the intermediate was obtained after crushing; then the obtained intermediate was uniformly mixed with LaN, Ca 3 N 2 , Ge 3 N 4 , TbN, and SiC according to a certain molar ratio, and heated at C Under reducing atmosphere, sintering at 1600°C for 8 hours, crushing, washing, and drying the obtained fluorescent substance to finally obtain La 2.445 Ca 0.5 Ge 6 N 10.5 C 0.5 :(0.05Ce, 0.005Tb) phosphor. The fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
实施例8Example 8
一种大功率用氮化物荧光材料,化学式为La2.445Ca0.5Ti6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 2.445 Ca 0.5 Ti 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例9Example 9
一种大功率用氮化物荧光材料,化学式为La2.445Ca0.5Se6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 2.445 Ca 0.5 Se 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例10Example 10
一种大功率用氮化物荧光材料,化学式为La2.445Ca0.5Hf6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 2.445 Ca 0.5 Hf 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例11Example 11
一种大功率用氮化物荧光材料,化学式为La1.956Lu0.489Ca0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.956 Lu 0.489 Ca 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例12Example 12
一种大功率用氮化物荧光材料,化学式为La2.2005Lu0.2445Ca0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 2.2005 Lu 0.2445 Ca 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例13Example 13
一种大功率用氮化物荧光材料,化学式为La2.145Lu0.3Ca0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 2.145 Lu 0.3 Ca 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例14Example 14
一种大功率用氮化物荧光材料,化学式为La1.845Lu0.6Ca0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.845 Lu 0.6 Ca 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例15Example 15
一种大功率用氮化物荧光材料,化学式为La2.345Lu0.1Ca0.5Si6N10.5C0.5:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 2.345 Lu 0.1 Ca 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例16Example 16
一种大功率用氮化物荧光材料,化学式为La2.935Ca0.01Si6N10.99C0.01:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 2.935 Ca 0.01 Si 6 N 10.99 C 0.01 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例17Example 17
一种大功率用氮化物荧光材料,化学式为La2.845Ca0.1Si6N10.9C0.1:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 2.845 Ca 0.1 Si 6 N 10.9 C 0.1 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例18Example 18
一种大功率用氮化物荧光材料,化学式为La2.645Ca0.3Si6N10.7C0.3:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 2.645 Ca 0.3 Si 6 N 10.7 C 0.3 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例19Example 19
一种大功率用氮化物荧光材料,化学式为La2.145Ca0.8Si6N10.2C0.8:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 2.145 Ca 0.8 Si 6 N 10.2 C 0.8 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例20Example 20
一种大功率用氮化物荧光材料,化学式为La1.945CaSi6N10C:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material, the chemical formula is La 1.945 CaSi 6 N 10 C: (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例21Example 21
一种大功率用氮化物荧光材料,化学式为La1.445Ca1.5Si6N9.5C1.5:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.445 Ca 1.5 Si 6 N 9.5 C 1.5 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例22Example 22
一种大功率用氮化物荧光材料,化学式为LaCa2Si6N9C2:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material, the chemical formula is LaCa 2 Si 6 N 9 C 2 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例23Example 23
一种大功率用氮化物荧光材料,化学式为La1.9305Y0.2145Ca0.8Si6N10.2C0.8:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9305 Y 0.2145 Ca 0.8 Si 6 N 10.2 C 0.8 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例24Example 24
一种大功率用氮化物荧光材料,化学式为La1.9305Gd0.2145Ca0.8Si6N10.2C0.8:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9305 Gd 0.2145 Ca 0.8 Si 6 N 10.2 C 0.8 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例25Example 25
一种大功率用氮化物荧光材料,化学式为La1.9305Lu0.2145Ca0.8Si6N10.2C0.8:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9305 Lu 0.2145 Ca 0.8 Si 6 N 10.2 C 0.8 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例26Example 26
一种大功率用氮化物荧光材料,化学式为La1.9305Lu0.2145Ca0.8Si5GeN10.2C0.8:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9305 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例27Example 27
一种大功率用氮化物荧光材料,化学式为La1.9305Lu0.2145Ca0.8Si5SeN10.2C0.8:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9305 Lu 0.2145 Ca 0.8 Si 5 SeN 10.2 C 0.8 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例28Example 28
一种大功率用氮化物荧光材料,化学式为La1.9305Lu0.2145Ca0.8Si5TiN10.2C0.8:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9305 Lu 0.2145 Ca 0.8 Si 5 TiN 10.2 C 0.8 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例29Example 29
一种大功率用氮化物荧光材料,化学式为La1.9305Lu0.2145Ca0.8Si5HfN10.2C0.8:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9305 Lu 0.2145 Ca 0.8 Si 5 HfN 10.2 C 0.8 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例30Example 30
一种大功率用氮化物荧光材料,化学式为La1.9305Lu0.2145Ca0.8Si4.8Se1.2N10.2C0.8:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9305 Lu 0.2145 Ca 0.8 Si 4.8 Se 1.2 N 10.2 C 0.8 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例31Example 31
一种大功率用氮化物荧光材料,化学式为La1.9305Lu0.2145Ca0.8Si4.5Se1.5N10.2C0.8:(0.05Ce,0.005Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9305 Lu 0.2145 Ca 0.8 Si 4.5 Se 1.5 N 10.2 C 0.8 : (0.05Ce, 0.005Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例32Example 32
一种大功率用氮化物荧光材料,化学式为La1.9795Lu0.2145Ca0.8Si5SeN10.2C0.8:(0.005Ce,0.001Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9795 Lu 0.2145 Ca 0.8 Si 5 SeN 10.2 C 0.8 : (0.005Ce, 0.001Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例33Example 33
一种大功率用氮化物荧光材料,化学式为La1.9545Lu0.2145Ca0.8Si5SeN10.2C0.8:(0.03Ce,0.001Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9545 Lu 0.2145 Ca 0.8 Si 5 SeN 10.2 C 0.8 : (0.03Ce, 0.001Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例34Example 34
一种大功率用氮化物荧光材料,化学式为La1.9045Lu0.2145Ca0.8Si5SeN10.2C0.8:(0.08Ce,0.001Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9045 Lu 0.2145 Ca 0.8 Si 5 SeN 10.2 C 0.8 : (0.08Ce, 0.001Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例35Example 35
一种大功率用氮化物荧光材料,化学式为La1.8845Lu0.2145Ca0.8Si5SeN10.2C0.8:(0.1Ce,0.001Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.8845 Lu 0.2145 Ca 0.8 Si 5 SeN 10.2 C 0.8 : (0.1Ce, 0.001Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例36Example 36
一种大功率用氮化物荧光材料,化学式为La1.8345Lu0.2145Ca0.8Si5SeN10.2C0.8:(0.15Ce,0.001Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.8345 Lu 0.2145 Ca 0.8 Si 5 SeN 10.2 C 0.8 : (0.15Ce, 0.001Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例37Example 37
一种大功率用氮化物荧光材料,化学式为La1.7845Lu0.2145Ca0.8Si5SeN10.2C0.8:(0.2Ce,0.001Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.7845 Lu 0.2145 Ca 0.8 Si 5 SeN 10.2 C 0.8 : (0.2Ce, 0.001Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例38Example 38
一种大功率用氮化物荧光材料,化学式为La1.9345Lu0.2145Ca0.8Si5GeN10.2C0.8:(0.05Ce,0.001Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material, the chemical formula is La 1.9345 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.001Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例39Example 39
一种大功率用氮化物荧光材料,化学式为La1.9255Lu0.2145Ca0.8Si5GeN10.2C0.8:(0.05Ce,0.01Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9255 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.01Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例40Example 40
一种大功率用氮化物荧光材料,化学式为La1.9055Lu0.2145Ca0.8Si5GeN10.2C0.8:(0.05Ce,0.03Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1,激发光谱图如图1所示,发射光谱图如图2所示,荧光粉的扫描电镜图如图3(a)所示。A high-power nitride fluorescent material with a chemical formula of La 1.9055 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.03Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1, the excitation spectrum is as shown in Figure 1, and the emission spectrum is as shown in Figure 2. The scanning electron microscope image of the phosphor powder is shown in Figure 3(a).
实施例41Example 41
一种大功率用氮化物荧光材料,化学式为La1.8855Lu0.2145Ca0.8Si5GeN10.2C0.8:(0.05Ce,0.05Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.8855 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.05Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例42Example 42
一种大功率用氮化物荧光材料,化学式为La1.8555Lu0.2145Ca0.8Si5GeN10.2C0.8:(0.05Ce,0.08Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.8555 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.08Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例43Example 43
一种大功率用氮化物荧光材料,化学式为La1.8355Lu0.2145Ca0.8Si5GeN10.2C0.8:(0.05Ce,0.1Tb)。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.8355 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.1Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
实施例44Example 44
一种大功率用氮化物荧光材料,化学式为La1.9055Lu0.2145Ca0.8Si5GeN10.2C0.8:(0.05Ce,0.03Tb)。所述氮化物近红外荧光材料的制备方法包括如下步骤:A high-power nitride fluorescent material with a chemical formula of La 1.9055 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.03Tb). The preparation method of the nitride near-infrared fluorescent material comprises the following steps:
将一定比例的LaN、Si3N4、CeN、LuN、Ca3N2、Ge3N4、TbN、SiC按照化学计量比进行均匀混合,并放入钨坩埚中,在N2/H2混合气体的还原下,1600℃保温8h烧结,将所获得的荧光物质经过破碎、洗涤、烘干,最终获得La1.9055Lu0.2145Ca0.8Si5GeN10.2C0.8:(0.05Ce,0.03Tb)荧光粉。最终得到的氮化物荧光粉的扫描电镜图为图3(b),发光特性如表1所示。Mix a certain proportion of LaN, Si 3 N 4 , CeN, LuN, Ca 3 N 2 , Ge 3 N 4 , TbN, and SiC uniformly according to the stoichiometric ratio, put them into a tungsten crucible, and mix them in N 2 /H 2 Under the reduction of gas, sintering at 1600°C for 8 hours, the obtained fluorescent substance was crushed, washed and dried to finally obtain La 1.9055 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.03Tb) phosphor. The scanning electron microscope image of the finally obtained nitride phosphor is shown in FIG. 3( b ), and the luminescence characteristics are shown in Table 1.
比较例5Comparative Example 5
一种大功率用氮化物荧光材料,化学式为La1.9355Lu0.2145Ca0.8Si5GeN10.2C0.8:0.05Ce。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9355 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 :0.05Ce. The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
比较例4Comparative example 4
一种大功率用氮化物荧光材料,化学式为La1.9355Lu0.2145Ca0.8Si5SeN10.2C0.8:0.05Ce。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9355 Lu 0.2145 Ca 0.8 Si 5 SeN 10.2 C 0.8 :0.05Ce. The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
比较例3Comparative example 3
一种大功率用氮化物荧光材料,化学式为La1.9355Lu0.2145Ca0.8Si6N10.2C0.8:0.05Ce。所述氮化物近红外荧光材料的制备方法同实施例1-7基本相同;所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with a chemical formula of La 1.9355 Lu 0.2145 Ca 0.8 Si 6 N 10.2 C 0.8 :0.05Ce. The preparation method of the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescent properties of the obtained phosphor powder are shown in Table 1.
比较例2Comparative example 2
一种大功率用氮化物荧光材料,学式为:La2.95Si6N11:0.05Ce。所述氮化物近红外荧光材料的制备方法,包括以下步骤:将一定比例的LaN、Si3N4和CeN按照化学计量比进行均匀混合,并放入钨坩埚中,在N2/H2混合气体的还原下,1600℃保温8h烧结,将所获得的荧光物质经过破碎、洗涤、烘干,最终获得La2.95Si6N11:0.05Ce荧光粉。所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with the formula: La 2.95 Si 6 N 11 :0.05Ce. The preparation method of the nitride near-infrared fluorescent material includes the following steps: uniformly mix a certain proportion of LaN, Si 3 N 4 and CeN according to the stoichiometric ratio, put them into a tungsten crucible, and mix them in N 2 /H 2 Under the reduction of the gas, it was sintered at 1600°C for 8 hours, and the obtained fluorescent substance was crushed, washed and dried to finally obtain La 2.95 Si 6 N 11 :0.05Ce phosphor. The fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
比较例1Comparative example 1
一种大功率用氮化物荧光材料,化学式为:La2.95Si6N11:0.05Ce。所述氮化物近红外荧光材料的制备方法,包括以下步骤:将一定比例的LaN、Si3N4和CeN按照一定摩尔比均匀混合,并放入钨坩埚中,在N2/H2混合气体的还原下,1400℃保温6h烧结,经过破碎后获得中间体;然后将获得的中间体同LaN、Si3N4按照一定的摩尔比均匀混合,并在C还原气氛下,1600℃保温8h烧结,将所获得的荧光物质经过破碎、洗涤、烘干,最终获得La2.95Si6N11:0.05Ce荧光粉。所得到荧光粉的荧光发光特性见表1。A high-power nitride fluorescent material with the chemical formula: La 2.95 Si 6 N 11 :0.05Ce. The preparation method of the nitride near-infrared fluorescent material comprises the following steps: uniformly mixing a certain proportion of LaN, Si 3 N 4 and CeN according to a certain molar ratio, putting them into a tungsten crucible, and mixing them in a N 2 /H 2 mixed gas Under the reduction of 1400°C for 6 hours, the intermediate was obtained after crushing; then the obtained intermediate was uniformly mixed with LaN and Si 3 N 4 according to a certain molar ratio, and sintered at 1600°C for 8 hours in a reducing atmosphere of C , crushing, washing and drying the obtained fluorescent substance to finally obtain La 2.95 Si 6 N 11 :0.05Ce fluorescent powder. The fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
表1Table 1
图1和图2为实施例40的激发和发射光谱,从图可以看出该实施例的氮化物荧光粉在紫外和蓝光区域均能被有效激发,且发射峰值波长位于540nm,半峰宽较宽,在580nm左右有一个肩峰。根据比较例1和比较例2可知,采用本发明实施例两步法制备的样品的初始强度和热稳定性相对传统方法制备样品具有明显的优势,图3(a)是根据实施例40两步法法得到的氮化物荧光粉的扫描电镜图,图3(b)是根据实施例44一步法得到的氮化物荧光粉的扫描电镜图,从图3中(a)和(b)对比可以看出两步法的结晶性更好。图4为比较例1和实施例40的热稳定性对比图,可以看出本发明实施例40的热稳定性具有明显的提升。Figure 1 and Figure 2 are the excitation and emission spectra of Example 40. It can be seen from the figures that the nitride phosphor powder of this embodiment can be effectively excited in the ultraviolet and blue light regions, and the emission peak wavelength is located at 540nm, and the half maximum width is relatively large. Broad, with a shoulder around 580nm. According to Comparative Example 1 and Comparative Example 2, it can be seen that the initial strength and thermal stability of the sample prepared by the two-step method of the embodiment of the present invention have obvious advantages relative to the sample prepared by the traditional method. The scanning electron micrograph of the nitride phosphor obtained by the method, Fig. 3 (b) is the scanning electron micrograph of the nitride phosphor obtained according to the one-step method of Example 44, as can be seen from the comparison of (a) and (b) in Fig. 3 The crystallinity of the two-step method is better. Fig. 4 is a comparison chart of thermal stability between Comparative Example 1 and Example 40. It can be seen that the thermal stability of Example 40 of the present invention has been significantly improved.
由实施例30和实施例31可知:当Si的摩尔含量大于等于80%,荧光粉具有更好的发光强度。由实施例13和实施例14可知:当La和Lu的摩尔比大于4:1时,荧光粉提高了发光强度,由实施例33-37或实施例38-43可知,当La和Lu的摩尔比在(4:10)-1之间时,效果最佳。It can be seen from Example 30 and Example 31 that when the molar content of Si is greater than or equal to 80%, the phosphor has better luminous intensity. It can be seen from Example 13 and Example 14: when the molar ratio of La and Lu is greater than 4:1, the phosphor improves the luminous intensity. It can be seen from Examples 33-37 or Examples 38-43 that when the molar ratio of La and Lu The effect is best when the ratio is between (4:10)-1.
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. within range.
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