WO2022233115A1 - 一种增强Er离子光致发光的无铅双钙钛矿及其制备方法和应用 - Google Patents

一种增强Er离子光致发光的无铅双钙钛矿及其制备方法和应用 Download PDF

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WO2022233115A1
WO2022233115A1 PCT/CN2021/128247 CN2021128247W WO2022233115A1 WO 2022233115 A1 WO2022233115 A1 WO 2022233115A1 CN 2021128247 W CN2021128247 W CN 2021128247W WO 2022233115 A1 WO2022233115 A1 WO 2022233115A1
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lead
free double
double perovskite
ion
photoluminescence
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French (fr)
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王静
甘伟江
楼孙棋
曹鲁豫
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中山大学
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7704—Halogenides
    • C09K11/7705—Halogenides with alkali or alkaline earth metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • 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
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    • 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

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  • the present invention relates to the technical field of luminescent materials, and more particularly, to a lead-free double perovskite capable of enhancing Er ion photoluminescence and a preparation method and application thereof.
  • Near-infrared light sources have good penetrability to organic matter, so they have great application potential in optoelectronics, food detection, anti-counterfeiting technology and biology.
  • traditional near-infrared light sources such as tungsten filament lamps and halogen lamps are hindered from their applications due to their low quantum efficiency, high operating temperature and long response time. Therefore, we urgently need an efficient and sustainable near-infrared material for light sources. .
  • Rare earth doped semiconductor materials have broad application prospects in the field of optoelectronics, so they have received keen attention.
  • Modern telecommunications networks that transmit data at the speed of light worldwide are based on fiber optic cables and rely on the transmission and processing of optical signals.
  • the energy level transition of 4 I 13/2 - 4 I 15/2 in Er ions results in a wavelength emission of 1.5 ⁇ m, which is just in the low-loss window in optical fiber communication, and because the luminescence of Er ions at 1.5 ⁇ m is the 4f shell of Er
  • the energy position of the luminescence peak is basically not affected by the matrix material, nor does it depend on the ambient temperature. application.
  • due to the ff forbidden transition of Er ion itself its quantum efficiency and absorption coefficient are low, and the emission intensity of near-infrared light cannot meet the requirements, which limits its application and must be excited with high pump power density to obtain optical gain.
  • CN112480921A discloses a phosphor powder with different emission peaks doped with rare earth ions in the same host and a preparation method.
  • the phosphor powder is based on NaY(MoO 4 ) 2 , and is double-doped with Dy 3+ and Er 3+ under the excitation of different wavelengths of near-infrared light and near-ultraviolet light to obtain characteristic up-conversion and down-conversion fluorescence emission, and Er 3+ green Luminescence (at 525nm and 553nm) and blue (at 479nm) and green (at 574)nm) light of Dy 3+ , real
  • the above phosphors can improve the characteristic peak luminous intensity of Er 3+ by increasing the amount of Dy 3+ ion doping, but it is only aimed at the green light emission intensity at 553 nm, and cannot solve the near-infrared light emission intensity of Er ion phosphor materials. The problem of not meeting the requirements.
  • the technical problem to be solved by the present invention is to overcome the defects and deficiencies that the existing rare earth Er ion light conversion materials cannot achieve strong near-infrared emission in the ultraviolet to visible light region, and provide a lead-free double perovskite that enhances Er ion photoluminescence .
  • Another object of the present invention is to provide a preparation method of a lead-free double perovskite with enhanced Er ion photoluminescence.
  • Another object of the present invention is to provide an application of a lead-free double perovskite that enhances Er ion photoluminescence in the fields of near-infrared LEDs, low-loss optical fiber communications and germanium-based solar cells.
  • a lead-free double perovskite capable of enhancing Er ion photoluminescence the chemical formula of the lead-free double perovskite is: Cs 2 AgIn 1-xy Cr x E y Cl 6 , 0.00 ⁇ x ⁇ 1.00, 0.00 ⁇ y ⁇ 1.00.
  • x and y are the molar percentages of doping ions Cr 3+ and Er 3+ respectively relative to the host ions In 3+ .
  • the enhanced Er ion photoluminescence lead-free double perovskite of the present invention uses Cs 2 AgInCl 6 as a host, and Cs 2 AgInCl 6 is a direct band gap semiconductor and has excellent stability.
  • the lead-free double perovskite enhancing Er ion photoluminescence of the present invention is based on the lead-free double perovskite Cs 2 AgInCl 6 , the luminescent centers are trivalent Cr 3+ and Er 3+ ions respectively, and the light conversion material is at 250 Under excitation at ⁇ 900nm , trivalent Cr 3+ ions generate infrared light with a peak at 1010 nm in the matrix, and Er 3+ ions generate infrared light with a peak at 1540 nm .
  • the emission is at 1010 nm, which is close to the absorption of 4 I 15/2 ⁇ 4 I 11/2 of Er ions, which can produce efficient energy transfer, so that the luminescence of the activated ion Er is enhanced, with broadband excitation and strong excitation in the ultraviolet to visible light region.
  • the advantages of NIR emission are at 1010 nm, which is close to the absorption of 4 I 15/2 ⁇ 4 I 11/2 of Er ions, which can produce efficient energy transfer, so that the luminescence of the activated ion Er is enhanced, with broadband excitation and strong excitation in the ultraviolet to visible light region.
  • the Er ion photoconversion material of the present invention uses co-doping to form a sensitization method for energy transfer, and Cr 3+ ions are used as sensitizing ions, Strengthen the near-infrared luminous intensity of activated ions Er 3+ ions, increase the absorption rate by sensitizing ions, increase the quantum efficiency of Er ions near-infrared by energy transfer, and can use lower intensity or lower energy light sources (such as different wavelengths).
  • the light-emitting diode (LED) to excite and modulate the light source, so as to meet the application requirements of optical fiber communication.
  • the chemical formula of the lead-free double perovskite is: Cs 2 AgIn 1-xy Cr x E y Cl 6 , 0.1 ⁇ x ⁇ 0.8, 0.1 ⁇ y ⁇ 0.8.
  • the invention also specifically protects a preparation method of a lead-free double perovskite that enhances Er ion photoluminescence, comprising the following steps: mixing compounds containing Ag, In, Cr and Er, adding hydrochloric acid, stirring and dissolving, and then adding The Cs-containing compound initiates a precipitation reaction, the reaction temperature is 30-100° C., the reaction is complete, and the lead-free double perovskite is obtained by cooling, separation, cleaning, and drying.
  • the reaction temperature of the present invention needs to be controlled at 30-100° C., and if the reaction temperature is too high, impurity phases will be formed, and at the same time, the luminescence of the material will be reduced.
  • the reason why the temperature is controlled at 30-100 °C is that high-purity and high-performance materials can be prepared within this temperature range.
  • the Cs-containing compound of the present invention is an oxide, carbonate, hydroxide, nitrate or chloride of Cs;
  • Ag-containing compounds are oxides, carbonates, hydroxides, nitrates or chlorides of Ag;
  • the compound containing In is an oxide, carbonate, hydroxide, nitrate or chloride of In;
  • Cr-containing compounds are oxides, carbonates, hydroxides, nitrates or chlorides of Cr;
  • the Er-containing compound is an oxide, carbonate, hydroxide, nitrate or chloride of Er.
  • the mass percentage concentration of hydrochloric acid is 36-38%, and the hydrochloric acid is fully stirred and dissolved at 30-100 DEG C.
  • the cooling is natural cooling to room temperature.
  • the drying is maintained at 50-100° C. for 1-24 hours to complete drying.
  • the compound containing Ag, In, Cr and Er is the chloride of Ag, In, Cr and Er.
  • Chloride can provide both cations and anions required for the reaction, which can better prepare pure phases and obtain lead-free double perovskites with enhanced Er ion photoluminescence.
  • the purity of the chlorides of Ag, In, Cr and Er is ⁇ 99.9%.
  • the reaction temperature is 80°C.
  • the luminescent properties of the material are better at this temperature.
  • the function of cleaning is to remove the remaining reaction raw materials after the reaction in the product, so as not to affect the luminescence performance of the product.
  • the cleaning of the present invention can use organic solvents such as isopropanol, methanol, acetone, and ethanol.
  • the cleaning is ethanol flushing.
  • ethanol has a low boiling point, is volatile, has low toxicity, is low in cost, and easily dissolves residual reaction raw materials.
  • the washing is 1-5 times with ethanol, in order to remove the residual reaction raw materials more thoroughly.
  • the lead-free double perovskite material of the present invention has superior strong near-infrared emission properties, and can be widely used in the fields of near-infrared LEDs, low-loss optical fiber communications and germanium-based solar cell materials, and the present invention especially protects the enhanced Er ion photoinduced Luminescent lead-free double perovskites for applications in near-infrared LEDs, low-loss fiber-optic communications, and germanium-based solar cells.
  • the Er ion photoconversion material of the present invention obtains an emission wavelength of 1540 nm through the energy level transition of 4 I 13/2 - 4 I 15/2 in the Er ion, which is just in the low-loss window of optical fiber communication, and the excitation spectrum is the same as that of commercial 365 nm, 535nm, 620nm LED chips are matched, so it can be widely used in the field of low-loss optical fiber communication.
  • the Er 3+ ion infrared emission of this material is located at about 1540 nm, which is very matched with the forbidden band width of germanium, and the excitation spectrum of this material basically covers the entire visible light region, and can emit light that can be absorbed by germanium-based solar cells.
  • the near-infrared light is a potential light conversion material to improve the efficiency of germanium-based solar cells.
  • the excitation wavelength of the lead-free double perovskite in the application is 250-900 nm.
  • the present invention also specifically protects a germanium-based solar cell, wherein the light conversion material of the germanium-based solar cell is the lead-free double perovskite that enhances Er ion photoluminescence.
  • the Er ion photoconversion material of the present invention takes Cs 2 AgInCl 6 as the host, and the luminescent centers are trivalent Cr 3+ , Er 3+ ions, Er 3+ ions generate infrared light with a peak at 1540 nm, Cr 3+ ions As sensitizing ions, the ions enhance the near-infrared luminescence intensity of the activated ions Er 3+ ions, and the quantum efficiency can reach 22.6%, which is 60 times higher than that of single-doped materials, and has stronger near-infrared light emission.
  • the Er ion photoconversion material of the present invention has a very wide excitation spectrum, has effective absorption in the range of 250-900 nm, and can effectively absorb ultraviolet light and visible light.
  • the Er ion photoconversion material of the present invention has strong near-infrared light emission, and the energy is just in the low-loss window of optical fiber communication, and can be widely used in the fields of near-infrared LED, low-loss optical fiber communication and germanium-based solar cell materials .
  • Example 1 is the XRD patterns of the lead-free double perovskite with enhanced Er ion photoluminescence of Example 1 and the lead-free double perovskite of Comparative Examples 1-3.
  • Fig. 2 is the excitation and emission spectra of the luminescent material of Comparative Example 2;
  • Example 4 is an excitation and emission spectrum diagram of the luminescent material of Example 1;
  • FIG. 5 is an emission spectrum diagram of the luminescent materials of Examples 1-5 and Comparative Example 3.
  • FIG. 5 is an emission spectrum diagram of the luminescent materials of Examples 1-5 and Comparative Example 3.
  • FIG. 6 is the infrared emission spectra of the luminescent materials doped with Er alone in Comparative Example 3 and Cr and Er co-doped in Example 5, respectively, under the excitation of 356 nm, 580 nm, and 808 nm light.
  • the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
  • a lead-free double perovskite capable of enhancing Er ion photoluminescence the chemical formula of the lead-free double perovskite is: Cs 2 AgIn 0.8 Cr 0.1 Er 0.1 Cl 6 .
  • the preparation method is as follows:
  • CsCl cesium chloride
  • a lead-free double perovskite capable of enhancing Er ion photoluminescence the chemical formula of the lead-free double perovskite is: Cs 2 AgIn 0.6 Cr 0.1 Er 0.3 Cl 6 .
  • the preparation method is as follows:
  • CsCl cesium chloride
  • a lead-free double perovskite capable of enhancing Er ion photoluminescence the chemical formula of the lead-free double perovskite is: Cs 2 AgIn 0.4 Cr 0.1 Er 0.5 Cl 6 .
  • the preparation method is as follows:
  • CsCl cesium chloride
  • a lead-free double perovskite capable of enhancing Er ion photoluminescence the chemical formula of the lead-free double perovskite is: Cs 2 AgIn 0.2 Cr 0.1 Er 0.7 Cl 6 .
  • the preparation method is as follows:
  • CsCl cesium chloride
  • a lead-free double perovskite capable of enhancing Er ion photoluminescence the chemical formula of the lead-free double perovskite is: Cs 2 AgIn 0.1 Cr 0.1 Er 0.8 Cl 6 .
  • the preparation method is as follows:
  • CsCl cesium chloride
  • a lead-free double perovskite the chemical formula of the lead-free double perovskite is: Cs 2 AgInCl 6 .
  • the preparation method is as follows:
  • a lead-free double perovskite the chemical formula of the lead-free double perovskite is: Cs 2 AgIn 0.2 Cr 0.8 Cl 6 .
  • the preparation method is as follows:
  • CsCl cesium chloride
  • a lead-free double perovskite the chemical formula of the lead-free double perovskite is: Cs 2 AgIn 0.2 Er 0.8 Cl 6 .
  • the preparation method is as follows:
  • Fig. 1 is the XRD patterns of the light conversion materials of Example 1 and Comparative Example 1, Comparative Example 2, and Comparative Example 3. It can be seen that the light conversion materials of Example 1 and Comparative Example 1, Comparative Example 2, and Comparative Example 3 have The XRD pattern has a face-centered cubic structure, and the phosphor powder has high crystallinity. The high crystallinity of the material will enhance the near-infrared emission.
  • Fig. 2 is the excitation and emission spectra of Comparative Example 2. It can be seen from Fig. 2 that the obtained photoconversion material has near-infrared emission at 1010 nm, and the excitation spectrum presents 250-450 nm ( 4 A 2 ⁇ 4 T 1 ( 4 P )), three broadband absorptions of Cr ions at 500-650 nm ( 4 A 2 ⁇ 4 T 1 ( 4 F)), 700-900 nm ( 4 A 2 ⁇ 4 T 2 ( 4 F)).
  • Figure 3 shows the excitation and emission spectra of Comparative Example 3. It can be seen from Figure 3 that the obtained phosphor has near-infrared emission at 1540 nm, and the excitation spectrum exhibits broadband matrix absorption from 250 nm to 350 nm. , 488nm, 520nm, 544nm, 650nm excitation peaks are assigned to Er ions 4 I 15/2 ⁇ 2 G 9/2 , 4 G 11/2 , 2 H 9/2 , 2 F 5/2 , 4 F 7/ 2 , 2 H 11/2 , 4 S 3/2 , 4 F 9/2 energy level absorption.
  • Fig. 4 is the excitation and emission spectra of the luminescent material of Example 1. It can be seen from Fig. 4 that the obtained phosphor has near-infrared emission at 1010 nm and 1540 nm, and the excitation spectrum presents 250-450 nm ( 4 A 2 ⁇ 4 Three broadband absorptions of Cr ions at T 1 ( 4 P)), 500-650 nm ( 4 A 2 ⁇ 4 T 1 ( 4 F)), 700-900 nm ( 4 A 2 ⁇ 4 T 2 ( 4 F)).
  • the quantum efficiency of the lead-free double perovskite with enhanced Er ion photoluminescence of Example 5 was measured by using the absolute photoluminescence quantum efficiency test system (Hamamatsu Photoelectric Co., Ltd., Quantaurus-QY Plus C13534-12), and the results showed that The quantum efficiency can reach 22.6%, which is about 60 times higher than that of single-doped materials.
  • Example 1 achieves the following technical effects: with the addition of Cr element, the luminescent material is Under the excitation of different wavelengths, the 1540nm near-infrared light emission intensity of Er ions is greatly improved.
  • the measurement method of near-infrared light emission intensity is as follows:
  • Example 6 is the infrared emission spectra of the luminescent material doped with Er alone and the Cr and Er co-doped light-emitting materials of Example 5 under the excitation of 356 nm, 580 nm, and 808 nm, respectively, and Table 2 is the enhanced Er ions of Example 5
  • Table 2 is the enhanced Er ions of Example 5
  • the emission intensities of the photoluminescent lead-free double perovskite and the lead-free double perovskite of Comparative Example 3 it can be seen that under different excitation wavelengths, the lead-free double calcium enhanced Er ion photoluminescence of the present invention Titanites have remarkable strong Er ion photoluminescence effect.

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Abstract

本发明公开了一种增强Er离子光致发光的无铅双钙钛矿及其制备方法和应用，属于发光材料技术领域。无铅双钙钛矿的化学式为：Cs 2AgIn 1-x-yCr xEr yCl 6，0.00<x≤1.00，0.00<y≤1.00，以Cs 2AgInCl 6为基质，发光中心分别为三价Cr 3+，Er 3+离子，Er 3+离子产生峰位位于1540nm的红外光，量子效率可达22.6％，相对于单掺杂材料提升了约60倍，具有更强的近红外光发射，在250～900nm范围内均有有效吸收，具有非常宽的激发光谱，可有效的吸收紫外光和可见光，能量正好处于光纤通讯中的低损耗窗口，可以广泛应用于近红外LED、低损耗光纤通信和锗基太阳能电池材料领域。

Description

一种增强Er离子光致发光的无铅双钙钛矿及其制备方法和应用 技术领域
本发明涉及发光材料技术领域，更具体地，涉及一种增强Er离子光致发光的无铅双钙钛矿及其制备方法和应用。
背景技术
近红外光源对有机物具有良好的穿透性，所以在光电子，食品检测，防伪技术和生物领域有很大的应用潜力。目前传统的近红外光源钨丝灯、卤素灯，因量子效率低、工作温度高和响应时间长等缺点阻碍了其应用，因此，我们迫切需要一种高效、可持续的近红外材料用于光源。随着LED技术的普遍应用和发展，且用于LED的光转换近红外材料拥有可调节的荧光光谱，高的辐射通量，简单的制备方法，廉价的成本和良好的耐久性，是当今的热点研究方向。
稀土掺杂半导体材料在光电子领域有广阔的应用前景，因而受到热切关注。全球范围内以光速传输数据的现代电信网络是以光纤电缆为基础，依赖于光信号的传输和处理。Er离子中 4I 13/2- 4I 15/2的能级跃迁，得到1.5μm的波长发射，正好处于光纤通讯中的低损耗窗口，且由于Er离子1.5μm处的发光是Er的4f壳层内跃迁的结果，由于受到5s 25p 6外壳电子的屏蔽，发光峰的能量位置基本不受基体材料的影响，也不依赖于所处的环境温度，这样的稳定性更有助于其实际应用。但是，因为Er离子自身的f-f禁阻跃迁，导致其量子效率和吸收系数较低，近红外光发射强度达不到要求，而限制其应用，必须用高泵浦功率密度激发才能获得光增益。
CN112480921A公开了一种不同发射峰稀土离子掺杂同基质的荧光粉及制备方法，荧光粉的表达式为：NaY(97％-x％)(MoO 4) 2:Dy 3+(x％),Er 3+(3％)(x＝1.0～5.0)NaY(98％-y％)(MoO 4)2:Dy 3+(2％),Er 3+(y％)(y＝1.0～10.0，荧光粉以NaY(MoO 4) 2为基质，Dy 3+、Er 3+双掺在不同波长近红外光和近紫外光激发下，得到特征上转换和下转换荧光发射，并获得Er 3+绿色发光(525nm和553nm处)和Dy 3+的蓝(479nm处)绿(574)nm处)光，实现Dy 3+→Er 3+的能量传递过程；测得NaY(92％)(MoO 4) 2:Dy 3+(5％),Er 3+(3％)样品553nm处的发光强度是NaY(96％)(MoO 4) 2:Dy 3+(1％),Er 3+(3％)样品553nm处的发光强度的8倍。上述荧光粉通过Dy 3+离子掺杂量的增 加来提高Er 3+的特征峰发光强度，但其只是针对在553nm处的绿光发射强度，并不能解决Er离子荧光粉材料近红外光发射强度达不到要求的问题。
发明内容
本发明要解决的技术问题是克服现有的稀土Er离子光转换材料不能在紫外至可见光区实现强近红外发射的缺陷和不足，提供一种增强Er离子光致发光的无铅双钙钛矿。
本发明的另一目的在于提供一种增强Er离子光致发光的无铅双钙钛矿的制备方法。
本发明的又一目的在于提供一种增强Er离子光致发光的无铅双钙钛矿在近红外LED、低损耗光纤通信和锗基太阳能电池领域中的应用。
本发明上述目的通过以下技术方案实现：
一种增强Er离子光致发光的无铅双钙钛矿，所述无铅双钙钛矿的化学式为：Cs 2AgIn 1-x-yCr xEr yCl 6，0.00<x≤1.00，0.00<y≤1.00。
其中，需要说明的是：
x，y分别为掺杂离子Cr 3+，Er 3+，相对基质离子In 3+的摩尔百分含量。
其中需要说明的是：
本发明的增强Er离子光致发光无铅双钙钛矿以Cs 2AgInCl 6是为基质，Cs 2AgInCl 6是直接带隙半导体，且具有优异的稳定性。
本发明的增强Er离子光致发光的无铅双钙钛矿以无铅双钙钛矿Cs 2AgInCl 6为基质，发光中心分别为三价Cr 3+，Er 3+离子，光转换材料在250～900nm激发下，三价Cr 3+离子在该基质中产生峰位位于1010nm红外光，Er 3+离子产生峰位位于1540nm的红外光，由于敏化离子Cr离子的 4T 2→ 4A 2的发射在1010nm，与Er离子的 4I 15/2→ 4I 11/2的吸收接近，能够产生有效的能量传递，使得激活离子Er的发光增强，具有紫外至可见光区宽谱带激发和强近红外发射的优点。
为了解决Er离子光转换材料不能在紫外至可见光区实现强近红外发射的问题，本发明的Er离子光转换材料使用共掺杂形成能量传递的敏化方法，Cr 3+离子作为敏化离子，强化了激活离子Er 3+离子的近红外发光强度，通过敏化离子提高吸收率，以能量传递增加Er离子近红外的量子效率，同时可以使用强度较低或者能量较低的光源(如不同波长的发光二极管LED)来激发并调制光源，从而达到光纤通讯的应用需求。
优选地，所述无铅双钙钛矿的化学式为：Cs 2AgIn 1-x-yCr xEr yCl 6，0.1≤x≤0.8，0.1≤y≤0.8。
本发明同时还具体保护一种增强Er离子光致发光的无铅双钙钛矿的制备方法，包括如下步骤：将含Ag、In、Cr、Er的化合物混合，加入盐酸，搅拌溶解，再加入含Cs的化合物引发沉淀反应，反应温度30～100℃，反应完全，冷却、分离、清洗，干燥得到无铅双钙钛矿。
本发明的反应温度需要控制在30～100℃，反应温度过高会导致形成杂相，同时使得材料的发光降低。控制在30～100℃的原因为此温度范围内均可以制备出高纯度和高性能的材料。
其中，需要说明的是：
本发明的含Cs的化合物为Cs的氧化物、碳酸盐、氢氧化物、硝酸盐或氯化物；
含Ag的化合物为Ag的氧化物、碳酸盐、氢氧化物、硝酸盐或氯化物；
含In的化合物为In的氧化物、碳酸盐、氢氧化物、硝酸盐或氯化物；
含Cr的化合物为Cr的氧化物、碳酸盐、氢氧化物、硝酸盐或氯化物；
含Er的化合物为Er的氧化物、碳酸盐、氢氧化物、硝酸盐或氯化物。
本发明的制备方法中盐酸的质量百分浓度为36-38％，在30-100℃下充分搅拌溶解。
所述冷却是自然冷却至室温。
所述干燥是在50-100℃下保温1-24h至完全干燥。
优选地，所述含Ag、In、Cr、Er的化合物为Ag、In、Cr、Er的氯化物。氯化物既能提供反应所需阳离子，也能提供阴离子，更好的制备纯相，并获得增强Er离子光致发光的无铅双钙钛矿。
反应物的纯度越高，产物越容易制备成纯相，物相越纯发光性能越好。为了制备出高纯度高性能的发光材料，进一步优选地，所述Ag、In、Cr、Er的氯化物的纯度≥99.9％。
优选地，所述反应温度为80℃。在此温度下材料的发光性能更佳。
清洗的作用为清洗掉产物中反应后残留的反应原料，以免影响产物的发光性能。本发明的清洗可以采用、异丙醇，甲醇，丙酮、乙醇等有机溶剂。
优选地，所述清洗为乙醇冲洗。原因是乙醇沸点低，易挥发，毒性低，成本 低，且容易溶解残留的反应原料。
所述清洗是用乙醇冲洗1-5次，为了更彻底地去除残留的反应原料。
本发明的无铅双钙钛矿材料具有优越的强近红外发射性能，可以广泛应用于近红外LED、低损耗光纤通信和锗基太阳能电池材料领域，本发明尤其保护所述增强Er离子光致发光的无铅双钙钛矿在近红外LED、低损耗光纤通信和锗基太阳能电池领域中的应用。
本发明的Er离子光转换材料，通过Er离子中 4I 13/2- 4I 15/2的能级跃迁，得到1540nm的发射波长，正好处于光纤通信的低损耗窗口，激发光谱与商业365nm,535nm,620nm LED芯片相匹配，因此可以广泛应用于低损耗光纤通信领域。
锗基太阳能电池的吸收太阳能最有效的位置为其带隙E＝0.785eV(即λ＝1550nm)附近，与太阳能光谱能量主要集中在可见光区存在严重的光谱能量失配，从而导致太阳能利用效率低，电池热效应严重，最终导致锗基太阳能电池光电转换效率低。而本材料Er 3+离子红外发射，其发射位于约1540nm处，与锗的禁带宽度非常匹配，且本材料的激发光谱基本覆盖整个可见光区，而且能发射出可被锗基太阳能电池所吸收的近红外光，是一种潜在的提高锗基太阳能电池效率的光转换材料。
优选地，所述应用中无铅双钙钛矿的激发波长为250～900nm。
同时，本发明还具体保护一种锗基太阳能电池，所述锗基太阳能电池的光转换材料为所述增强Er离子光致发光的无铅双钙钛矿。
与现有技术相比，本发明的有益效果是：
(1)本发明的Er离子光转化材料以Cs 2AgInCl 6为基质，发光中心分别为三价Cr 3+，Er 3+离子，Er 3+离子产生峰位位于1540nm的红外光，Cr 3+离子作为敏化离子，强化了激活离子Er 3+离子的近红外发光强度，量子效率可达22.6％，相对于单掺杂材料提升了60倍，具有更强的近红外光发射。
(2)本发明的Er离子光转化材料具有非常宽的激发光谱，在250～900nm范围内均有有效吸收，可有效的吸收紫外光和可见光。
(3)本发明的Er离子光转化材料具有较强的近红外光发射，能量正好处于光纤通讯中的低损耗窗口，可以广泛应用于近红外LED、低损耗光纤通信和锗基太阳能电池材料领域。
附图说明
图1为实例1的增强Er离子光致发光的无铅双钙钛矿和对比例1-3的无铅双钙钛矿的XRD图谱。
图2为对比例2的发光材料的激发和发射光谱图；
图3为对比例3的发光材料的激发和发射光谱图；
图4为实施例1的发光材料的激发和发射光谱图；
图5为实施例1-5和对比例3的发光材料的发射光谱图。
图6为对比例3的单独掺入Er以及实施例5的Cr、Er共掺杂发光材料分别在356nm、580nm、808nm光激发下的红外发射光谱图。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规购买的原料试剂。
实施例1
一种增强Er离子光致发光的无铅双钙钛矿，无铅双钙钛矿的化学式为：Cs 2AgIn 0.8Cr 0.1Er 0.1Cl 6。
制备方法如下：
分别称取1mmol氯化银(AgCl)、0.8mmol氯化铟(InCl 3)、0.1mmol六水合三氯化铬(CrCl 3·6H 2O)、0.1mmol六水合三氯化铒(ErCl 3·6H 2O)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml玻璃瓶中，随后加入5ml盐酸(36-38％)，将玻璃瓶放在加热台上恒温80℃加热1小时，搅拌待溶解。待溶解完成，放入2mmol氯化铯(CsCl)以引发白色沉淀，继续恒温加热2小时、自然降至室温。待降至室温后，取出玻璃瓶中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
实施例2
一种增强Er离子光致发光的无铅双钙钛矿，无铅双钙钛矿的化学式为：Cs 2AgIn 0.6Cr 0.1Er 0.3Cl 6。
制备方法如下：
分别称取1mmol氯化银(AgCl)、0.6mmol氯化铟(InCl 3)、0.1mmol六水合三氯化铬(CrCl 3·6H 2O)、0.3mmol六水合三氯化铒(ErCl 3·6H 2O)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml玻璃瓶中，随后加入5ml盐酸(36-38％)， 将玻璃瓶放在加热台上恒温80℃加热1小时，搅拌待溶解。待溶解完成，放入2mmol氯化铯(CsCl)以引发白色沉淀，继续恒温加热2小时、自然降至室温。待降至室温后，取出玻璃瓶中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
实施例3
一种增强Er离子光致发光的无铅双钙钛矿，无铅双钙钛矿的化学式为：Cs 2AgIn 0.4Cr 0.1Er 0.5Cl 6。
制备方法如下：
分别称取1mmol氯化银(AgCl)、0.4mmol氯化铟(InCl 3)、0.1mmol六水合三氯化铬(CrCl 3·6H 2O)、0.5mmol六水合三氯化铒(ErCl 3·6H 2O)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml玻璃瓶中，随后加入5ml盐酸(36-38％)，将玻璃瓶放在加热台上恒温80℃加热1小时，搅拌待溶解。待溶解完成，放入2mmol氯化铯(CsCl)以引发白色沉淀，继续恒温加热2小时、自然降至室温。待降至室温后，取出玻璃瓶中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
实施例4
一种增强Er离子光致发光的无铅双钙钛矿，无铅双钙钛矿的化学式为：Cs 2AgIn 0.2Cr 0.1Er 0.7Cl 6。
制备方法如下：
分别称取1mmol氯化银(AgCl)、0.2mmol氯化铟(InCl 3)、0.1mmol六水合三氯化铬(CrCl 3·6H 2O)、0.7mmol六水合三氯化铒(ErCl 3·6H 2O)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml玻璃瓶中，随后加入5ml盐酸(36-38％)，将玻璃瓶放在加热台上恒温80℃加热1小时，搅拌待溶解。待溶解完成，放入2mmol氯化铯(CsCl)以引发白色沉淀，继续恒温加热2小时、自然降至室温。待降至室温后，取出玻璃瓶中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
实施例5
一种增强Er离子光致发光的无铅双钙钛矿，无铅双钙钛矿的化学式为：Cs 2AgIn 0.1Cr 0.1Er 0.8Cl 6。
制备方法如下：
分别称取1mmol氯化银(AgCl)、0.1mmol氯化铟(InCl 3)、0.1mmol六水合三氯化铬(CrCl 3·6H 2O)、0.8mmol六水合三氯化铒(ErCl 3·6H 2O)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml玻璃瓶中，随后加入5ml盐酸(36-38％)，将玻璃瓶放在加热台上恒温80℃加热1小时，搅拌待溶解。待溶解完成，放入2mmol氯化铯(CsCl)以引发白色沉淀，继续恒温加热2小时、自然降至室温。待降至室温后，取出玻璃瓶中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
对比例1
一种无铅双钙钛矿，无铅双钙钛矿的化学式为：Cs 2AgInCl 6。
制备方法如下：
分别称取1mmol氯化银(AgCl)、1mmol氯化铟(InCl 3)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml玻璃瓶中，随后加入5ml盐酸(36-38％)，将玻璃瓶放在加热台上恒温80℃加热1小时，搅拌待溶解。待溶解完成，放入2mmol氯化铯(CsCl)以引发白色沉淀，继续恒温加热2小时、自然降至室温。待降至室温后，取出玻璃瓶中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
对比例2
一种无铅双钙钛矿，无铅双钙钛矿的化学式为：Cs 2AgIn 0.2Cr 0.8Cl 6。
制备方法如下：
分别称取1mmol氯化银(AgCl)、0.2mmol氯化铟(InCl 3)、0.8mmol六水合三氯化铬(CrCl 3·6H 2O)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml玻璃瓶中，随后加入5ml盐酸(36-38％)，将玻璃瓶放在加热台上恒温80℃加热1小时，搅拌待溶解。待溶解完成，放入2mmol氯化铯(CsCl)以引发白色沉淀，继续恒温加热2小时、自然降至室温。待降至室温后，取出玻璃瓶中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
对比例3
一种无铅双钙钛矿，无铅双钙钛矿的化学式为：Cs 2AgIn 0.2Er 0.8Cl 6。
制备方法如下：
分别称取1mmol氯化银(AgCl)、0.2mmol氯化铟(InCl 3)、0.8mmol六水合三氯化铒(ErCl 3·6H 2O)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml 玻璃瓶中，随后加入5ml盐酸(36-38％)，将玻璃瓶放在加热台上恒温80℃加热1小时，搅拌待溶解。待溶解完成，放入2mmol氯化铯(CsCl)以引发白色沉淀，继续恒温加热2小时、自然降至室温。待降至室温后，取出玻璃瓶中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
结果检测
图1为实施例1和对比例1、对比例2、对比例3的光转化材料的XRD图谱，可以看出，实施例1和对比例1、对比例2、对比例3的光转化材料的XRD谱图具有面心立方结构，且荧光粉结晶度高，材料的结晶度高会使得近红外发射增强。
图2为对比例2的激发和发射光谱，从图2可以看出，所获得的光转化材料在1010nm处有近红外发射，激发光谱呈现250-450nm( 4A 2→ 4T 1( 4P))、500-650nm( 4A 2→ 4T 1( 4F))、700-900nm( 4A 2→ 4T 2( 4F))的Cr离子的三个宽带吸收。
图3为对比例3的激发和发射光谱，从图3可以看出，所获得的荧光粉在1540nm处有近红外发射，激发光谱呈现从250nm～350nm的宽带基质吸收，在378nm，406nm，450nm，488nm，520nm，544nm，650nm的激发峰归属于Er离子的 4I 15/2→ 2G 9/2， 4G 11/2， 2H 9/2， 2F 5/2， 4F 7/2， 2H 11/2， 4S 3/2， 4F 9/2的能级吸收。
图4为实施例1的发光材料的激发和发射光谱图，由图4可以看出，所获得的荧光粉在1010nm和1540nm处有近红外发射，激发光谱呈现250-450nm( 4A 2→ 4T 1( 4P))、500-650nm( 4A 2→ 4T 1( 4F))、700-900nm( 4A 2→ 4T 2( 4F))的Cr离子的三个宽带吸收。
采用绝对光致发光量子效率测试系统(滨松光电公司，Quantaurus-QY Plus C13534-12)方法对实施例5的增强Er离子光致发光的无铅双钙钛矿的量子效率进行测定，结果显示量子效率可达22.6％，相对于单掺杂材料提升了约60倍。
由图5中实施例1和对比例3所得的发射光谱图及进行发光强度对比可知，通过对比可以看出，上述实施例1实现了如下技术效果：随着Cr元素的加入，该发光材料在不同波长激发下，Er离子的1540nm近红外光发射强度均有很大程度的提升。
采用爱丁堡FLS1000稳态瞬态光谱仪测定具体的Er离子的1540nm近红外光发射强度，具体检测结果见下表1：
其中，近红外光发射强度测定方法如下：
表1.
序号 发射强度
实施例1 14952.71
实施例2 26741.17
实施例3 44384.92
实施例4 59843.64
实施例5 54634.66
对比例1 18.63
对比例2 108.44
对比例3 1779.44
图6为对比例3的单独掺入Er以及实施例5的Cr、Er共掺杂发光材料分别在356nm、580nm、808nm光激发下的红外发射光谱图，表2为实施例5的增强Er离子光致发光的无铅双钙钛矿和对比例3的无铅双钙钛矿的发射强度，可以看出，在不同的激发波长下，本发明的增强Er离子光致发光的无铅双钙钛矿均具有显著的强Er离子光致发光效果。
表2.
激发波长 实施例5发射强度 对比例3发射强度
356nm 75032.71 1779.43
580nm 22562.95 19.439
808nm 26829.26 20.282
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。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，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种增强Er离子光致发光的无铅双钙钛矿，其特征在于，所述无铅双钙钛矿的化学式为：Cs 2AgIn 1-x-yCr xEr yCl 6，0.00<x≤1.00，0.00<y≤1.00。
  2. 如权利要求1所述增强Er离子光致发光的无铅双钙钛矿，其特征在于，所述无铅双钙钛矿的化学式为：Cs 2AgIn 1-x-yCr xEr yCl 6，0.1≤x≤0.8，0.1≤y≤0.8。
  3. 一种权利要求1或2所述增强Er离子光致发光的无铅双钙钛矿的制备方法，其特征在于，包括如下步骤：将含Ag、In、Cr、Er的化合物混合，加入盐酸，搅拌溶解，再加入含Cs的化合物引发沉淀反应，反应温度30～100℃，反应完全，冷却、分离、清洗，干燥得到无铅双钙钛矿。
  4. 如权利要求3所述增强Er离子光致发光的无铅双钙钛矿的制备方法，其特征在于，所述含Ag、In、Cr、Er的化合物为Ag、In、Cr、Er的氯化物。
  5. 如权利要求4所述增强Er离子光致发光的无铅双钙钛矿的制备方法，其特征在于，所述Ag、In、Cr、Er的氯化物的纯度≥99.9％。
  6. 如权利要求3所述增强Er离子光致发光的无铅双钙钛矿的制备方法，其特征在于，所述反应温度为80℃。
  7. 如权利要求3所述增强Er离子光致发光的无铅双钙钛矿的制备方法，其特征在于，所述清洗为乙醇冲洗。
  8. 一种权利要求1或2所述增强Er离子光致发光的无铅双钙钛矿在近红外LED、低损耗光纤通信和锗基太阳能电池领域中的应用。
  9. 如权利要求8所述应用，其特征在于，所述应用中无铅双钙钛矿的激发波长为250～900nm。
  10. 一种锗基太阳能电池，其特征在于，所述锗基太阳能电池的光转换材料为权利要求1或2所述增强Er离子光致发光的无铅双钙钛矿。
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