CN102585811B - Fluoroaluminate near-infrared quantum cutting material, and preparation method and application thereof - Google Patents
Fluoroaluminate near-infrared quantum cutting material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN102585811B CN102585811B CN201210002237.4A CN201210002237A CN102585811B CN 102585811 B CN102585811 B CN 102585811B CN 201210002237 A CN201210002237 A CN 201210002237A CN 102585811 B CN102585811 B CN 102585811B
- Authority
- CN
- China
- Prior art keywords
- fluoroaluminate
- infrared quantum
- preparation
- raw materials
- quantum tailoring
- 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.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 5
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 6
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 claims description 6
- 229910001637 strontium fluoride Inorganic materials 0.000 claims description 6
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229940118662 aluminum carbonate Drugs 0.000 claims description 2
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 2
- 229940075624 ytterbium oxide Drugs 0.000 claims description 2
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000000265 homogenisation Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 238000000295 emission spectrum Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000000695 excitation spectrum Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000013590 bulk material Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000006862 quantum yield reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 101150027751 Casr gene Proteins 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- -1 rare earth ions Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
本发明公开了一种氟铝酸盐近红外量子剪裁材料及其制备方法与应用。该氟铝酸盐近红外量子剪裁材料，其化学组成式为：Sr3(0.99-x)AlO4F:0.01Ce3+，xYb3+，(0≤x≤0.1)。该氟铝酸盐近红外量子剪裁材料的制备方法，包括如下步骤：按上述化学组成式的摩尔配比，称取锶原料、铝原料、氟原料、铈原料和镱原料；各种原料研磨混匀后，在CO的还原气氛下，以600℃/h升温到1200℃，在1200℃下恒温4小时，冷却后，得到粉末状的氟铝酸盐近红外量子剪裁材料。本发明的氟铝酸盐近红外量子剪裁材料发光强度高，稳定性好，量子效率高，环保。
The invention discloses a fluoroaluminate near-infrared quantum tailoring material, a preparation method and application thereof. The chemical composition formula of the fluoroaluminate near-infrared quantum tailoring material is: Sr 3 (0.99-x) AlO 4 F:0.01Ce 3+ , xYb 3+ , (0≤x≤0.1). The preparation method of the fluoroaluminate near-infrared quantum tailoring material comprises the following steps: weighing strontium raw materials, aluminum raw materials, fluorine raw materials, cerium raw materials and ytterbium raw materials according to the molar ratio of the above chemical composition formula; various raw materials are ground and mixed After homogenization, in a reducing atmosphere of CO, the temperature was raised to 1200°C at 600°C/h, and the temperature was kept at 1200°C for 4 hours. After cooling, a powdered fluoroaluminate near-infrared quantum tailoring material was obtained. The fluoroaluminate near-infrared quantum tailoring material of the invention has high luminous intensity, good stability, high quantum efficiency and environmental protection.
Description
技术领域 technical field
本发明涉及一种新型的近红外量子剪裁材料及其制备方法与应用，尤其涉及一种氟铝酸盐近红外量子剪裁材料及其制备方法与应用。The invention relates to a novel near-infrared quantum tailoring material and its preparation method and application, in particular to a fluoroaluminate near-infrared quantum tailoring material and its preparation method and application.
背景技术 Background technique
量子剪裁(下转换)型近红外发光材料：它将一个高能量光子(波长范围通常为300-500nm)裁剪为多个波长λ≈1000nm近红外光子量子。剪裁效应能够通过单一离子的能级跃迁、离子对之间的能量传递、离子和基质之间的能量传递实现剪裁过程。Quantum clipping (down-conversion) near-infrared luminescent material: it clips a high-energy photon (usually in the wavelength range of 300-500nm) into multiple near-infrared photon quanta with wavelength λ≈1000nm. The tailoring effect can realize the tailoring process through the energy level transition of a single ion, the energy transfer between ion pairs, and the energy transfer between ions and substrates.
以往对量子剪裁效应的研究局限于可见光区域，最近几年已经开始拓展到近红外领域。近红外量子剪裁是指将一个可见光子转化为两个近红外光子，避免了可见光子在向更低能量光子转化过程中的能量损失，它可以有效提高太阳能电池的效率及稳定性，因此把太阳能光谱中的可见光和紫外光转换为近红外光的新型荧光体是目前发光材料研究的主要任务。目前使用最普遍的基质为稀土离子掺杂的氟化物体系。但制备过程中会生产对人体、环境有害的气体，破坏人体健康、污染环境。Previous studies on the quantum tailoring effect were limited to the visible light region, and have begun to expand to the near-infrared region in recent years. Near-infrared quantum tailoring refers to the conversion of one visible photon into two near-infrared photons, avoiding the energy loss in the process of converting visible photons to lower-energy photons. It can effectively improve the efficiency and stability of solar cells, so the solar energy New phosphors that convert visible light and ultraviolet light into near-infrared light in the spectrum are the main tasks in the research of luminescent materials at present. The most common matrix currently used is the fluoride system doped with rare earth ions. However, during the preparation process, gases harmful to the human body and the environment will be produced, which will damage human health and pollute the environment.
发明内容 Contents of the invention
本发明目的在于提供一种发光强度高、稳定性好、量子效率高的氟铝酸盐近红外量子剪裁材料。The purpose of the present invention is to provide a fluoroaluminate near-infrared quantum tailoring material with high luminous intensity, good stability and high quantum efficiency.
本发明所提供的氟铝酸盐近红外量子剪裁材料，其化学组成为化学组成式为：The chemical composition of the fluoroaluminate near-infrared quantum tailoring material provided by the present invention is:
Sr3(0.99-x)AlO4F:0.01Ce3+，xYb3+，(0≤x≤0.1)。Sr 3(0.99-x) AlO 4 F:0.01Ce 3+ , xYb 3+ , (0≤x≤0.1).
其中，0≤x≤0.01，0.01≤x≤0.02，0.02≤x≤0.03，0.03≤x≤0.04，0.04≤x≤0.05，0.05≤x≤0.06，0.06≤x≤0.07，0.07≤x≤0.08，0.08≤x≤0.09或0.09≤x≤0.10。Among them, 0≤x≤0.01, 0.01≤x≤0.02, 0.02≤x≤0.03, 0.03≤x≤0.04, 0.04≤x≤0.05, 0.05≤x≤0.06, 0.06≤x≤0.07, 0.07≤x≤0.08, 0.08≤x≤0.09 or 0.09≤x≤0.10.
本发明的另一个目的是提供一种氟铝酸盐近红外量子剪裁材料的制备方法。Another object of the present invention is to provide a method for preparing a fluoroaluminate near-infrared quantum tailoring material.
本发明所提供的氟铝酸盐近红外量子剪裁材料的制备方法，包括如下步骤：The preparation method of the fluoroaluminate near-infrared quantum tailoring material provided by the present invention comprises the following steps:
按化学组成式Sr3(0.99-x)AlO4F:0.01Ce3+，xYb3+(0≤x≤0.1)的摩尔配比，称取锶原料、铝原料、氟原料、铈原料和镱原料；According to the molar ratio of chemical composition formula Sr 3(0.99-x) AlO 4 F:0.01Ce 3+ , xYb 3+ (0≤x≤0.1), weigh strontium raw material, aluminum raw material, fluorine raw material, cerium raw material and ytterbium raw material;
所述原料研磨混匀后在CO的还原气氛下，以600℃/h升温到1200℃，在1200℃恒温4小时，冷却后，研磨，得到氟铝酸盐近红外量子剪裁材料。After the raw materials are ground and mixed, the temperature is raised to 1200°C at 600°C/h in a reducing atmosphere of CO, and the temperature is kept at 1200°C for 4 hours. After cooling, grind to obtain a fluoroaluminate near-infrared quantum tailoring material.
根据本发明的一个方面，所述锶原料选自碳酸锶、硝酸锶和氧化锶中的任一种或任几种。According to one aspect of the present invention, the strontium raw material is selected from any one or more of strontium carbonate, strontium nitrate and strontium oxide.
根据本发明的一个方面，所述铝原料选自氧化铝、氢氧化铝和碳酸铝中的任一种或任几种。According to one aspect of the present invention, the aluminum raw material is selected from any one or more of aluminum oxide, aluminum hydroxide and aluminum carbonate.
根据本发明的一个方面，所述氟原料选自氟化锶和氟化氨中的任一种或任几种。According to one aspect of the present invention, the fluorine raw material is selected from any one or more of strontium fluoride and ammonium fluoride.
根据本发明的一个方面，所述铈原料选自氧化铈和硝酸铈中的任一种或任几种。According to one aspect of the present invention, the cerium raw material is selected from any one or more of cerium oxide and cerium nitrate.
根据本发明的一个方面，所述镱原料选自氧化镱和硝酸镱中的任一种或任几种。According to one aspect of the present invention, the ytterbium raw material is selected from any one or more of ytterbium oxide and ytterbium nitrate.
根据本发明的一个方面，0≤x≤0.01，0.01≤x≤0.02，0.02≤x≤0.03，0.03≤x≤0.04，0.04≤x≤0.05，0.05≤x≤0.06，0.06≤x≤0.07，0.07≤x≤0.08，0.08≤x≤0.09或0.09≤x≤0.10。According to one aspect of the invention, 0≤x≤0.01, 0.01≤x≤0.02, 0.02≤x≤0.03, 0.03≤x≤0.04, 0.04≤x≤0.05, 0.05≤x≤0.06, 0.06≤x≤0.07, 0.07 ≤ x ≤ 0.08, 0.08 ≤ x ≤ 0.09, or 0.09 ≤ x ≤ 0.10.
与现有技术相比，本发明的新型的近红外量子剪裁材料可以被200～500nm的近紫外光激发，激发光谱非常宽，在近紫外区(200～500nm)具有强的吸收其发射峰位于近红外(900～1200nm)范围内。经计算得其量子效率最高达185％，是一种适用于太阳能电池的新型近红外量子剪裁材料。本发明的新型的近红外量子剪裁材料采用了常见的氟铝酸盐为基质，合成方法简单，易于操作，环保。Compared with the prior art, the novel near-infrared quantum tailoring material of the present invention can be excited by near-ultraviolet light of 200-500nm, the excitation spectrum is very wide, and it has strong absorption in the near-ultraviolet region (200-500nm), and its emission peak is located at Near infrared (900 ~ 1200nm) range. It is calculated that its quantum efficiency is up to 185%, and it is a new type of near-infrared quantum tailoring material suitable for solar cells. The novel near-infrared quantum tailoring material of the present invention adopts a common fluoroaluminate as a matrix, has a simple synthesis method, is easy to operate, and is environmentally friendly.
附图说明 Description of drawings
图1为本发明的氟铝酸盐近红外量子剪裁材料Sr2.97AlO4F:0.01Ce3+的XRD衍射图谱；Fig. 1 is the XRD diffraction pattern of the fluoroaluminate near-infrared quantum tailoring material Sr 2.97 AlO 4 F:0.01Ce 3+ of the present invention;
图2为本发明的氟铝酸盐近红外量子剪裁材料Sr2.94AlO4F:0.01Ce3+，0.01Yb3+的XRD衍射图谱；Fig. 2 is the XRD diffraction pattern of the fluoroaluminate near-infrared quantum tailoring material Sr 2.94 AlO 4 F:0.01Ce 3+ , 0.01Yb 3+ of the present invention;
图3为本发明的氟铝酸盐近红外量子剪裁材料Sr2.82AlO4F:0.01Ce3+，0.05Yb3+的XRD衍射图谱；Fig. 3 is the XRD diffraction pattern of the fluoroaluminate near-infrared quantum tailoring material Sr 2.82 AlO 4 F:0.01Ce 3+ , 0.05Yb 3+ of the present invention;
图4为本发明的氟铝酸盐近红外量子剪裁材料Sr2.67AlO4F:0.01Ce3+，0.1Yb3+的XRD衍射图谱。Fig. 4 is an XRD diffraction pattern of the fluoroaluminate near-infrared quantum tailoring material Sr 2.67 AlO 4 F:0.01Ce 3+ , 0.1Yb 3+ of the present invention.
图5为本发明的氟铝酸盐近红外量子剪裁材料Sr2.97AlO4F:0.01Ce3+在室温下的激发和发射光谱图；Fig. 5 is the excitation and emission spectrum of the fluoroaluminate near-infrared quantum tailoring material Sr 2.97 AlO 4 F:0.01Ce 3+ at room temperature;
图6为本发明的氟铝酸盐近红外量子剪裁材料Sr2.94AlO4F:0.01Ce3+，0.01Yb3+在室温下的用980nm和464nm检测得到激发光谱图；Fig. 6 is the excitation spectrum of the fluoroaluminate near-infrared quantum tailoring material Sr 2.94 AlO 4 F:0.01Ce 3+ , 0.01Yb 3+ at room temperature detected by 980nm and 464nm;
图7为本发明的氟铝酸盐近红外量子剪裁材料Sr2.94AlO4F:0.01Ce3+，0.01Yb3+在室温下401nm激发的发射光谱图；Fig. 7 is the emission spectrum of the fluoroaluminate near-infrared quantum tailoring material Sr 2.94 AlO 4 F:0.01Ce 3+ , 0.01Yb 3+ excited at room temperature at 401 nm;
图8为本发明的氟铝酸盐近红外量子剪裁材料Sr2.82AlO4F:0.01Ce3+，0.05Yb3+在室温下401nm激发的发射光谱图；Fig. 8 is the emission spectrum of the fluoroaluminate near-infrared quantum tailoring material Sr 2.82 AlO 4 F:0.01Ce 3+ , 0.05Yb 3+ excited at room temperature at 401 nm;
图9为本发明的氟铝酸盐近红外量子剪裁材料Sr2.67AlO4F:0.01Ce3+，0.1Yb3+在室温下401nm激发的发射光谱图；Fig. 9 is the emission spectrum of the fluoroaluminate near-infrared quantum tailoring material Sr 2.67 AlO 4 F:0.01Ce 3+ , 0.1Yb 3+ excited at room temperature at 401 nm;
图10为本发明的氟铝酸盐近红外量子剪裁材料Sr2.97AlO4F:0.01Ce3+在室温下Ce3+的寿命衰减图；Fig. 10 is a lifetime decay diagram of Ce 3+ at room temperature for the fluoroaluminate near-infrared quantum tailoring material Sr 2.97 AlO 4 F:0.01Ce 3+ of the present invention;
图11为本发明的氟铝酸盐近红外量子剪裁材料Sr2.94AlO4F:0.01Ce3+，0.01Yb3+在室温下Ce3+的寿命衰减图；Fig. 11 is a lifetime decay diagram of Ce 3+ at room temperature for the fluoroaluminate near-infrared quantum tailoring material Sr 2.94 AlO 4 F:0.01Ce 3+ and 0.01Yb 3+ of the present invention;
图12为本发明的氟铝酸盐近红外量子剪裁材料Sr2.82AlO4F:0.01Ce3+，0.05Yb3+在室温下Ce3+的寿命衰减图；Fig. 12 is a lifetime decay diagram of Ce 3+ at room temperature for the fluoroaluminate near-infrared quantum tailoring material Sr 2.82 AlO 4 F:0.01Ce 3+ and 0.05Yb 3+ of the present invention;
图13为本发明的氟铝酸盐近红外量子剪裁材料Sr2.67AlO4F:0.01Ce3+，0.1Yb3+在室温下Ce3+的寿命衰减图；Fig. 13 is a lifetime decay diagram of Ce 3+ at room temperature for the fluoroaluminate near-infrared quantum tailoring material Sr 2.67 AlO 4 F:0.01Ce 3+ and 0.1Yb 3+ of the present invention;
图14为本发明的氟铝酸盐近红外量子剪裁材料Sr3(0.99-x)AlO4F:0.01Ce3+，xYb3+(0≤x≤0.1)经计算所得能量传递率和量子产率对比图。Figure 14 shows the calculated energy transfer rate and quantum yield of the fluoroaluminate near-infrared quantum tailoring material Sr 3(0.99-x) AlO 4 F:0.01Ce 3+ , xYb 3+ (0≤x≤0.1) of the present invention. rate comparison chart.
具体实施方式 Detailed ways
实施例1：氟铝酸盐近红外量子剪裁材料Sr2.97AlO4F:0.01Ce3+的制备Example 1: Preparation of fluoroaluminate near-infrared quantum tailoring material Sr 2.97 AlO 4 F:0.01Ce 3+
分别称取碳酸锶(SrCO3)0.7324g、氟化锶(SrF2)0.1256g、氧化铝(Al2O3)0.1019g、氧化铈(CeO2)0.0034g。将上述原料在玛瑙研钵研磨混匀后，装入刚玉坩埚中，放入高温炉，在CO的还原气氛下，以600℃/h升温到1200℃，在1200℃恒温4小时，冷却，取出块状材料，进行研磨得到粉末状的样品。该样品的XRD衍射图见图1，通过与SrAlO4F的标准卡片对比，发现衍射峰位置完全一致，说明掺杂少量的Ce3+对基质的晶格结构无影响。样品在401nm下激发，该样品的室温激发和发射光谱见图5，近紫外区的发射主峰位于464nm，近红外区无发射。该样品的寿命衰减图谱见图10，通过二次拟合，计算得到Ce3+的荧光寿命为0.035μs。0.7324 g of strontium carbonate (SrCO 3 ), 0.1256 g of strontium fluoride (SrF 2 ), 0.1019 g of aluminum oxide (Al 2 O 3 ), and 0.0034 g of cerium oxide (CeO 2 ) were weighed. Grind and mix the above raw materials in an agate mortar, put them into a corundum crucible, put them into a high-temperature furnace, and raise the temperature to 1200°C at 600°C/h under a reducing atmosphere of CO, keep the temperature at 1200°C for 4 hours, cool, and take out The bulk material is ground to obtain a powder sample. The XRD diffraction pattern of this sample is shown in Figure 1. By comparing with the standard SrAlO 4 F card, it is found that the diffraction peak positions are completely consistent, indicating that doping a small amount of Ce 3+ has no effect on the lattice structure of the matrix. The sample was excited at 401nm. The excitation and emission spectra of the sample at room temperature are shown in Figure 5. The main emission peak in the near-ultraviolet region is located at 464nm, and there is no emission in the near-infrared region. The lifetime attenuation spectrum of this sample is shown in Figure 10. Through quadratic fitting, the fluorescence lifetime of Ce 3+ was calculated to be 0.035 μs.
实施例2：氟铝酸盐近红外量子剪裁材料Sr2.94AlO4F:0.01Ce3+，0.01Yb3+的制备Example 2: Preparation of fluoroaluminate near-infrared quantum tailoring material Sr 2.94 AlO 4 F:0.01Ce 3+ , 0.01Yb 3+
分别称取碳酸锶(SrCO3)0.7279g、氟化锶(SrF2)0.1256g、氧化铝(Al2O3)0.1019g、氧化铈(CeO2)0.0034g和氧化镱(Yb2O3)0.0039g。将上述原料在玛瑙研钵研磨混匀后，装入刚玉坩埚中，放入高温炉，在CO的还原气氛下，以600℃/h升温到1200℃，在1200℃恒温4小时，冷却，取出块状材料，进行研磨得到粉末状的样品。该样品的XRD衍射图见图2，通过与SrAlO4F的标准卡片对比，发现衍射峰位置完全一致，说明掺杂少量的Ce3+，Yb3+对基质的晶格结构无影响。该样品在980nm波长检测下测得的激发光谱与该样品在464nm波长检测下测出的激发光谱见图6，通过对比发现他们的峰型相似，并且主峰都在401nm。说明401nm激发下Ce3+→Yb3+可发生能量传递。样品在401nm下激发，该样品的室温发射光谱见图7，近紫外区的发射主峰位于464nm，近红外区无发射主峰位于980nm。该样品的寿命衰减图谱见图11，通过二次拟合，计算得到Ce3+的荧光寿命为0.029μs。Weigh strontium carbonate (SrCO 3 ) 0.7279g, strontium fluoride (SrF 2 ) 0.1256g, aluminum oxide (Al 2 O 3 ) 0.1019g, cerium oxide (CeO 2 ) 0.0034g and ytterbium oxide (Yb 2 O 3 ) 0.0039g. Grind and mix the above raw materials in an agate mortar, put them into a corundum crucible, put them into a high-temperature furnace, and raise the temperature to 1200°C at 600°C/h under a reducing atmosphere of CO, keep the temperature at 1200°C for 4 hours, cool, and take out The bulk material is ground to obtain a powder sample. The XRD diffraction pattern of this sample is shown in Figure 2. By comparing with the standard SrAlO 4 F card, it is found that the diffraction peak positions are completely consistent, indicating that doping a small amount of Ce 3+ and Yb 3+ has no effect on the lattice structure of the matrix. The excitation spectrum of the sample measured at 980nm wavelength and the excitation spectrum of the sample measured at 464nm wavelength are shown in Figure 6. By comparison, it is found that their peak shapes are similar, and the main peak is at 401nm. It shows that Ce 3+ →Yb 3+ can transfer energy under 401nm excitation. The sample was excited at 401nm. The room temperature emission spectrum of the sample is shown in Figure 7. The main emission peak in the near-ultraviolet region is at 464nm, and the non-emission main peak in the near-infrared region is at 980nm. The lifetime decay spectrum of this sample is shown in Figure 11. Through quadratic fitting, the fluorescence lifetime of Ce 3+ was calculated to be 0.029 μs.
实施例3：氟铝酸盐近红外量子剪裁材料Sr2.82AlO4F:0.01Ce3+，0.05Yb3+ Example 3: Fluoroaluminate near-infrared quantum tailoring material Sr 2.82 AlO 4 F: 0.01Ce 3+ , 0.05Yb 3+
分别称取碳酸锶(SrCO3)0.7103g、氟化锶(SrF2)0.1256g、氧化铝(Al2O3)0.1019g、氧化铈(CeO2)0.0034g和氧化镱(Yb2O3)0.0197g。将上述原料在玛瑙研钵研磨混匀后，装入刚玉坩埚中，放入高温炉，在CO的还原气氛下，以600℃/h升温到1200℃，在1200℃恒温4小时，冷却，取出块状材料，进行研磨得到粉末状的样品。该样品的XRD衍射图见图3，通过与SrAlO4F的标准卡片对比，发现衍射峰位置完全一致，说明掺杂少量的Ce3+，Yb3+对基质的晶格结构无影响。样品在401nm下激发，该样品的室温发射光谱见图8，近紫外区的发射主峰位于464nm，近红外区无发射主峰位于980nm。该样品的寿命衰减图谱见图12，通过二次拟合方法，计算得到Ce3+的荧光寿命为0.020μs。Weigh strontium carbonate (SrCO 3 ) 0.7103g, strontium fluoride (SrF 2 ) 0.1256g, aluminum oxide (Al 2 O 3 ) 0.1019g, cerium oxide (CeO 2 ) 0.0034g and ytterbium oxide (Yb 2 O 3 ) 0.0197g. Grind and mix the above raw materials in an agate mortar, put them into a corundum crucible, put them into a high-temperature furnace, and raise the temperature to 1200°C at 600°C/h under a reducing atmosphere of CO, keep the temperature at 1200°C for 4 hours, cool, and take out The bulk material is ground to obtain a powder sample. The XRD diffraction pattern of this sample is shown in Figure 3. By comparing with the standard SrAlO 4 F card, it is found that the diffraction peak positions are completely consistent, indicating that doping a small amount of Ce 3+ and Yb 3+ has no effect on the lattice structure of the matrix. The sample was excited at 401nm. The room temperature emission spectrum of the sample is shown in Figure 8. The main emission peak in the near-ultraviolet region is at 464nm, and the non-emission main peak in the near-infrared region is at 980nm. The lifetime attenuation spectrum of this sample is shown in Figure 12, and the fluorescence lifetime of Ce 3+ was calculated to be 0.020 μs by quadratic fitting method.
实施例4：氟铝酸盐近红外量子剪裁材料Sr2.67AlO4F:0.01Ce3+，0.1Yb3+ Example 4: Fluoroaluminate near-infrared quantum tailoring material Sr 2.67 AlO 4 F: 0.01Ce 3+ , 0.1Yb 3+
分别称取碳酸锶(SrCO3)0.6882g、氟化锶(SrF2)0.1256g、氧化铝(Al2O3)0.1019g、氧化铈(CeO2)0.0034g和氧化镱(Yb2O3)0.0394g。将上述原料在玛瑙研钵研磨混匀后，装入刚玉坩埚中，放入高温炉，在CO的还原气氛下，以600℃/h升温到1200℃，在1200℃恒温4小时，冷却，取出块状材料，进行研磨得到粉末状的样品。该样品的XRD衍射图见图4，通过与SrAlO4F的标准卡片对比，发现衍射峰位置完全一致，说明掺杂少量的Ce3+，Yb3+对基质的晶格结构无影响。样品在401nm下激发，该样品的室温发射光谱见图9，近紫外区的发射主峰位于464nm，近红外区无发射主峰位于980nm。该样品的寿命衰减图谱见图13，通过二次拟合，计算得到Ce3+的荧光寿命为0.016μs。。Weigh strontium carbonate (SrCO 3 ) 0.6882g, strontium fluoride (SrF 2 ) 0.1256g, aluminum oxide (Al 2 O 3 ) 0.1019g, cerium oxide (CeO 2 ) 0.0034g and ytterbium oxide (Yb 2 O 3 ) 0.0394g. Grind and mix the above raw materials in an agate mortar, put them into a corundum crucible, put them into a high-temperature furnace, and raise the temperature to 1200°C at 600°C/h under a reducing atmosphere of CO, keep the temperature at 1200°C for 4 hours, cool, and take out The bulk material is ground to obtain a powder sample. The XRD diffraction pattern of this sample is shown in Figure 4. By comparing with the standard SrAlO 4 F card, it is found that the diffraction peak positions are completely consistent, indicating that doping a small amount of Ce 3+ and Yb 3+ has no effect on the lattice structure of the matrix. The sample was excited at 401nm. The room temperature emission spectrum of the sample is shown in Figure 9. The main emission peak in the near-ultraviolet region is at 464nm, and the non-emission main peak in the near-infrared region is at 980nm. The lifetime decay spectrum of this sample is shown in Figure 13. Through quadratic fitting, the fluorescence lifetime of Ce 3+ was calculated to be 0.016 μs. .
近红外量子剪裁材料Sr2.97AlO4F:0.01Ce3+、Sr2.94AlO4F:0.01Ce3+，0.01Yb3+、CaSr2.82AlO4F:0.01Ce3+，0.05Yb3+、Sr2.67AlO4F:0.01Ce3+，0.1Yb3+经计算所得的衰减寿命分别为0.035μs，0.029μs，0.020μs，0.016μs；量子产率分别为0，42.28％，78.30％，185.21％。寿命和量子产率相对于Yb3+掺杂量的变化对比如图14所示Near-infrared quantum tailoring materials Sr 2.97 AlO 4 F: 0.01Ce 3+ , Sr 2.94 AlO 4 F: 0.01Ce 3+ , 0.01Yb 3+ , CaSr 2.82 AlO 4 F: 0.01Ce 3+ , 0.05Yb 3+ , Sr 2.67 The calculated decay lifetimes of AlO 4 F:0.01Ce 3+ and 0.1Yb 3+ are 0.035μs, 0.029μs, 0.020μs, and 0.016μs respectively; the quantum yields are 0, 42.28%, 78.30%, and 185.21%, respectively. The comparison of lifetime and quantum yield with respect to Yb 3+ doping amount is shown in Figure 14
由图14可以看出，Ce3+的荧光寿命随着Yb3+掺杂浓度的增加逐渐下降，进一步证明Ce3+的能量传递给了Yb3+。量子产率随Yb3+掺杂浓度的增加逐渐增加，当Yb3+的掺杂浓度为10％Ce3+→Yb3+的下转换量子效率达到185.2％，说明Ce3+、Yb3+共掺的近红外量子剪裁荧光材料，有较高的量子效率，具有应用于单晶硅太阳能电池的潜能。It can be seen from Figure 14 that the fluorescence lifetime of Ce 3+ decreases gradually with the increase of Yb 3+ doping concentration, which further proves that the energy of Ce 3+ is transferred to Yb 3+ . The quantum yield increases gradually with the increase of Yb 3+ doping concentration. When the Yb 3+ doping concentration is 10%, the down-conversion quantum efficiency of Ce 3+ →Yb 3+ reaches 185.2%, indicating that Ce 3+ and Yb 3+ The co-doped near-infrared quantum tailoring fluorescent material has high quantum efficiency and has the potential to be applied to single crystal silicon solar cells.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210002237.4A CN102585811B (en) | 2012-01-05 | 2012-01-05 | Fluoroaluminate near-infrared quantum cutting material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210002237.4A CN102585811B (en) | 2012-01-05 | 2012-01-05 | Fluoroaluminate near-infrared quantum cutting material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102585811A CN102585811A (en) | 2012-07-18 |
| CN102585811B true CN102585811B (en) | 2014-10-22 |
Family
ID=46475055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210002237.4A Expired - Fee Related CN102585811B (en) | 2012-01-05 | 2012-01-05 | Fluoroaluminate near-infrared quantum cutting material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102585811B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977880A (en) * | 2012-12-04 | 2013-03-20 | 中国科学院半导体研究所 | Preparation method of downconversion fluorescent material |
| CN108384536A (en) * | 2018-05-16 | 2018-08-10 | 长春理工大学 | Er3+/Yb3+Codope calcium aluminum fluoride green up conversion luminescent material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090127508A1 (en) * | 2005-04-20 | 2009-05-21 | Etech Ag | Novel materials used for emitting light |
-
2012
- 2012-01-05 CN CN201210002237.4A patent/CN102585811B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| Chromaticity-Tunable Emission of Sr3AlO4F:Ce3+ Phosphor: Correlation with Matrix Structure and Application in LEDs;Wanping Chen et al.;《Journal of The Electrochemical Society》;20100401;第157卷(第5期);第J159-163页 * |
| Mengmeng Shang et al..Tunable Luminescence and Energy Transfer properties of Sr3AlO4F:RE3+ (RE = Tm/Tb, Eu, Ce) Phosphors.《ACS Appl. Mater. Interfaces》.2011,第3卷第2738–2746页. |
| Tunable Luminescence and Energy Transfer properties of Sr3AlO4F:RE3+ (RE = Tm/Tb, Eu, Ce) Phosphors;Mengmeng Shang et al.;《ACS Appl. Mater. Interfaces》;20110614;第3卷;第2738–2746页 * |
| Wanping Chen et al..Chromaticity-Tunable Emission of Sr3AlO4F:Ce3+ Phosphor: Correlation with Matrix Structure and Application in LEDs.《Journal of The Electrochemical Society》.2010,第157卷(第5期),第J159-J163页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102585811A (en) | 2012-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Efficient near-infrared quantum cutting in Ce3+–Yb3+ codoped glass for solar photovoltaic | |
| Liu et al. | An efficient light converter YAB: Cr 3+, Yb 3+/Nd 3+ with broadband excitation and strong NIR emission for harvesting c-Si-based solar cells | |
| CN103113892B (en) | A kind of tungstate rare earth light conversion material, preparation method and application | |
| de Mayrinck et al. | Reassessment of the potential applications of Eu3+-doped Y2O3 photoluminescent material in ceramic powder form | |
| CN103215038B (en) | A kind ofly under ultraviolet excitation, realize near-infrared luminous molybdate material, preparation method and application | |
| Wang et al. | Energy transfer in Ce, Nd, and Yb co-doped YAG phosphors | |
| CN111423881A (en) | Cr (chromium)3+Doped near-infrared luminescent material and preparation method thereof | |
| CN102174323B (en) | Ytterbium and thulium codoped dodecacalcium heptaluminate polycrystal and preparation method thereof | |
| Parauha et al. | Enhancement of photoluminescence and tunable properties for Ce3+, Eu2+ activated Na2CaSiO4 downconversion phosphor: A novel approach towards spectral conversion | |
| CN102268258B (en) | Strontium aluminate based up-conversion luminescent material and preparation method thereof | |
| CN103756679B (en) | Upconversion material capable of being excited by wide-spectrum incoherent light as well as preparation method of upconversion material | |
| CN102585811B (en) | Fluoroaluminate near-infrared quantum cutting material, and preparation method and application thereof | |
| CN103224790B (en) | Material for conversion of ultraviolet light and emission of near-infrared light and its preparation method and use | |
| CN106701074B (en) | A kind of metatitanic acid alkali red up-conversion luminescent material and preparation method thereof | |
| Li et al. | Near-infrared downconversion through host sensitized energy transfer in Yb3+-doped Na2YMg2 (VO4) 3 | |
| CN104818022A (en) | Novel up-conversion fluorescent powder and preparation method thereof | |
| Kumar et al. | Broadband down-conversion of near-infrared emission in Bi3+-Yb3+ co-doped Y3Al5O12 phosphors | |
| CN102515550A (en) | Transparent glass ceramic capable of conversion luminescence under near-infrared quantum cutting and preparation method thereof | |
| Cao et al. | CaMoO4: x% Yb3+: A novel near-infrared quantum-cutting phosphors via cooperative energy transfer | |
| CN102424750B (en) | Tungstate near infrared quantum cutting material and preparation method and application thereof | |
| CN102660273A (en) | Preparation method of rare earth doped nano zirconia up-conversion phosphor powder | |
| Marques-Hueso et al. | Advances in spectral conversion for photovoltaics: up-converting Er3+ doped YF3 nano-crystals in transparent glass ceramic | |
| CN104004519A (en) | Near-infrared down-conversion luminescent material as well as preparation method and application thereof | |
| CN102191049A (en) | Ytterbium erbium double-doped calcium tungstate polycrystal powder green ray up-conversion material and preparation method thereof | |
| CN103450902B (en) | A kind of oxyfluoride red colour conversion material 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141022 Termination date: 20160105 |
|
| EXPY | Termination of patent right or utility model |