A type of Cr 3+ Doped broadband near-infrared luminescent materials and their preparation methods

Abstract

This invention belongs to the field of luminescent materials technology and discloses a Cr 3+ Doped broadband near-infrared luminescent materials and their preparation methods. This Cr... 3+ Doped broadband near-infrared luminescent materials, with the general chemical formula A 1或4 M 4‑x EO 12 :xCr 3+ Wherein, A is selected from at least one of Zn, Sr, Mg, or Ba; M is selected from at least one of Ga, Al, In, or B; E is selected from at least one of Ge, Si, Sn, Zr, or Hf; and 0 < x ≤ 2. The Cr... 3+ Doped broadband near-infrared luminescent materials are materials that can be effectively excited by blue light chips, achieve coverage of a wider wavelength range (especially extending to longer wavelengths), and possess both high luminous efficiency and excellent thermal stability.

Description

Technical Field

[0001] This invention belongs to the field of luminescent materials technology, and specifically relates to a Cr... 3+ Doped broadband near-infrared luminescent materials and their preparation methods. Background Technology

[0002] Near-infrared (NIR, especially in the 700-1700 nm band) light sources, due to their invisibility to the human eye, strong tissue penetration, and unique molecular fingerprint absorption characteristics, show broad application prospects in cutting-edge fields such as biomedical imaging, non-invasive detection, night vision monitoring, food quality analysis, and next-generation optical communication. Among the many implementation paths, the phosphor-converting light-emitting diode (pc-LED) technology based on the coupling of blue LED chips and near-infrared phosphors is considered one of the most practically promising solutions due to its compact structure, controllable cost, mature process, and stable performance.

[0003] However, there are still significant technical bottlenecks in the near-infrared luminescent materials that can be used for blue light excitation. It is difficult to achieve both high-efficiency excitation and ultra-wideband emission and long wavelength extension, which restricts their further application in high-end fields.

[0004] On the one hand, with Nd 3+ Yb 3+ Er 3+ Traditional rare-earth ion-doped materials, represented by Cr, emit near-infrared light from forbidden ff transitions of inner-shell 4f electrons. While these materials can produce near-infrared light at specific wavelengths, the emission bands are typically sharp and narrow due to transition selection rules, with a full width at half maximum (FWHM) generally less than 50 nm. This narrow-band emission characteristic makes it difficult to cover a wide spectral range, failing to meet the demands of multi-wavelength simultaneous detection in applications such as spectral analysis and broadband optical communication. On the other hand, Cr... 3+ Transition metal ion-doped phosphors, represented by Cr, have attracted much attention in recent years. 3+ It possesses a 3d³ electronic configuration and is highly sensitive to the crystal field environment, theoretically enabling broadband emission. Studies have shown that some Cr... 3+ Doped materials can exhibit broadband near-infrared emission under blue light excitation, but their emission peak is mostly concentrated around 800 nm, with limited ability to extend to longer wavelengths. Furthermore, in the pursuit of long-wavelength emission with ultra-wide full width at half maximum (FWHM), high luminous efficiency, and good thermal stability, most Cr... 3+ The system still faces the dilemma of not being able to achieve a balance in terms of overall performance.

[0005] Therefore, developing a novel broadband near-infrared luminescent material that can be effectively excited by blue light chips, can cover a wider wavelength range (especially extending to longer wavelengths), and has both high luminous efficiency and excellent thermal stability has become a key technical problem that urgently needs to be solved in this field. Summary of the Invention

[0006] The present invention aims to at least solve one of the technical problems existing in the prior art described above. To this end, the present invention proposes a Cr... 3+ Doped broadband near-infrared luminescent materials and their preparation methods.

[0007] The Cr of the present invention 3+ Doped broadband near-infrared luminescent materials are materials that can be effectively excited by blue light chips, cover a wider wavelength range (especially extending to longer wavelengths), have high luminous efficiency and excellent thermal stability, and have a simple preparation process and controllable cost.

[0008] This invention utilizes Cr 3+ By doping with a multi-metal oxide material, a luminescent material suitable for excitation by blue LED chips was synthesized, achieving efficient broadband near-infrared luminescence.

[0009] The first aspect of the present invention provides a Cr 3+ Doped with broadband near-infrared luminescent materials.

[0010] Specifically, a type of Cr 3+ Doped broadband near-infrared luminescent materials, with the general chemical formula A 1或4 M 4-x EO 12 :xCr 3+ ;

[0011] Wherein, A is selected from at least one of Zn, Sr, Mg or Ba;

[0012] M is selected from at least one of Ga, Al, In or B;

[0013] The E is selected from at least one of Ge, Si, Sn, Zr or Hf;

[0014] And 0 < x ≤ 2.

[0015] Preferably, A is Mg or Mg 0.9 Zn 0.1 Mg 0.5 Zn 0.5 Mg 0.9 Sr 0.1 Mg 0.9 Ba 0.1、 Zn, Mg 0.98 Ba 0.02 At least one of them.

[0016] Preferably, M is Ga 0.9 Al 0.1 Ga 0.9 In 0.1,Ga,Ga 0.8 Al 0.2 At least one of them.

[0017] Preferably, E is Ge, Sn, or Ge 0.9 Si 0.1 、Ge 0.9 Zr 0.1 、Ge 0.9 Hf 0.1 、Ge 0.9 Sn 0.1 、Ge 0.8 Sn 0.2 、Ge 0.8 Sn 0.1 Zr 0.1 At least one of them.

[0018] Preferably, the value of x is in the range of 0 < x ≤ 1; more preferably, the value of x is in the range of 0.1 < x ≤ 0.3. Where x is Cr 3+ Doping content.

[0019] Preferably, the Cr 3+ Doped broadband near-infrared luminescent materials, selected from Mg(Ga) 0.9 Al 0.1 ) 3.9 GeO 12 0.1Cr 3 + 、(Mg 0.9 Zn 0.1 )4(Ga 0.9 Al 0.1 ) 3.9 GeO 12 0.1Cr 3+ Mg4(Ga 0.9 In 0.1 ) 3.85 GeO 12 0.15Cr 3+ 、(Mg 0.5 Zn 0.5 )4(Ga 0.9 Al 0.1 ) 3.9 GeO 12 0.1Cr 3+ Mg4(Ga 0.9 In 0.1 ) 3.8 SnO 12 0.2Cr 3+ Mg4(Ga 0.9 In 0.1 ) 3.8 (Ge 0.9 Si0.1 )O 12 0.2Cr 3+ 、(Mg 0.9 Sr 0.1 )4(Ga 0.9 In 0.1 ) 3.7 (Ge 0.9 Zr 0.1 )O 12 0.3Cr 3+ Mg4Ga 3.8 SnO 12 0.2Cr 3+ 、(Mg 0.9 Ba 0.1 )4Ga 3.8 (Ge 0.9 Hf 0.1 )O 12 0.2Cr 3+ 、(Mg 0.5 Zn 0.5 )4(Ga 0.9 In 0.1 ) 3.9 (Ge 0.9 Zr 0.1 )O 12 0.1Cr 3 + Zn4(Ga 0.8 Al 0.2 ) 3.9 (Ge 0.9 Sn 0.1 )O 12 0.1Cr 3+ Mg4Ga 3.5 (Ge 0.8 Sn 0.2 )O 12 0.5Cr 3+ 、(Mg 0.98 Ba 0.02 )4Ga 3.95 (Ge 0.8 Sn 0.1 Zr 0.1 )O 12 0.15Cr 3+ At least one of them.

[0020] A second aspect of the present invention provides a Cr 3+ Preparation method of doped broadband near-infrared luminescent materials.

[0021] Specifically, a type of Cr 3+ A method for preparing doped broadband near-infrared luminescent materials includes the following steps:

[0022] (1) According to the Cr 3+ Weigh the raw materials according to the stoichiometric ratio of the elements in the general chemical formula of the doped broadband near-infrared luminescent material, mix them, and obtain a mixture.

[0023] (2) The mixture is pre-calcined in air and then calcined to obtain the Cr. 3+ Doped with broadband near-infrared luminescent materials.

[0024] Preferably, the raw material includes zinc-containing compounds, strontium-containing compounds, magnesium-containing compounds, barium-containing compounds, gallium-containing compounds, aluminum-containing compounds, indium-containing compounds, boron-containing compounds, silicon-containing compounds, tin-containing compounds, zirconium-containing compounds, germanium-containing compounds, hafnium-containing compounds, or chromium-containing compounds. The type of raw material depends on the Cr content. 3+ The elemental composition in the general chemical formula of doped broadband near-infrared luminescent materials was determined.

[0025] Preferably, the zinc-containing compound, strontium-containing compound, magnesium-containing compound, and barium-containing compound are carbonates, nitrates, or oxides containing zinc, strontium, magnesium, or barium.

[0026] Preferably, the gallium-containing compound, aluminum-containing compound, indium-containing compound, and boron-containing compound are nitrates, oxalates, or oxides containing gallium, aluminum, indium, or boron.

[0027] Preferably, the silicon-containing compound, tin-containing compound, zirconium-containing compound, germanium-containing compound, and hafnium-containing compound are oxides containing silicon, tin, zirconium, germanium, or hafnium.

[0028] Preferably, the chromium-containing compound is a nitrate, oxide, or oxalate compound containing chromium metal.

[0029] Preferably, the zinc-containing compound is zinc oxide or zinc nitrate.

[0030] Preferably, the strontium-containing compound is strontium carbonate or strontium oxide.

[0031] Preferably, the magnesium-containing compound is magnesium oxide or magnesium nitrate.

[0032] Preferably, the barium-containing compound is barium carbonate or barium oxide.

[0033] Preferably, the gallium-containing compound is gallium oxide.

[0034] Preferably, the aluminum-containing compound is aluminum oxide.

[0035] Preferably, the indium-containing compound is indium oxide.

[0036] Preferably, the boron-containing compound is boron oxide.

[0037] Preferably, the silicon-containing compound is silicon oxide.

[0038] Preferably, the tin-containing compound is tin oxide.

[0039] Preferably, the zirconium-containing compound is zirconium oxide.

[0040] Preferably, the germanium-containing compound is germanium oxide.

[0041] Preferably, the hafnium-containing compound is hafnium oxide.

[0042] Preferably, the chromium-containing compound is chromium oxide, chromium nitrate, or chromium oxalate.

[0043] Preferably, the pre-firing temperature is 400-550℃, and the pre-firing holding time is 3-4 hours.

[0044] Preferably, the calcination temperature is 1350-1450℃, and the calcination holding time is 4-6 hours.

[0045] Preferably, the preparation method includes the following steps:

[0046] (1) Ingredients: Weigh out compounds containing zinc, strontium, magnesium or barium, gallium, aluminum, indium or boron, silicon, tin, zirconium, germanium or hafnium according to the stoichiometric ratio, and mix the above-weighed raw materials thoroughly and grind them until uniform.

[0047] (2) Calcination: The mixture obtained in (1) is transferred to a corundum crucible and pre-calcined at a low temperature in a muffle furnace under an air atmosphere. After naturally cooling to room temperature, it is taken out and ground uniformly again. Then, it is placed in a high-temperature tube furnace for high-temperature calcination. After the reaction is completed and naturally cooled to room temperature, it is taken out and ground again to obtain the Cr. 3+ Doped with broadband near-infrared luminescent materials.

[0048] A third aspect of the present invention provides a Cr 3+ Applications of doped broadband near-infrared luminescent materials.

[0049] A semiconductor device comprising the above-mentioned Cr 3+ Doped with broadband near-infrared luminescent materials.

[0050] Preferably, the semiconductor device includes a near-infrared LED light source.

[0051] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0052] (1) The Cr described in this invention 3+ Doped broadband near-infrared luminescent materials are composed of specific types of elements in specific proportions, such that the Cr... 3+Doped broadband near-infrared luminescent materials are materials that can be effectively excited by blue light chips, cover a wider wavelength range (especially extending to longer wavelengths, specifically 700-1300nm), and have both high luminous efficiency and excellent thermal stability.

[0053] (2) The preparation method described in this invention is simple, cost-controllable, and can be mass-produced industrially.

[0054] (3) The product obtained by the present invention is applicable to blue LED chips and can generate broadband near-infrared light emission, which can meet the needs of fields such as biological imaging, industrial detection, component analysis, and non-destructive abrasion. Attached Figure Description

[0055] Figure 1 The Cr prepared in Example 1 of this invention 3+ X-ray diffraction (XRD) pattern of a broadband near-infrared luminescent material;

[0056] Figure 2 The Cr prepared in Example 2 of this invention 3+ Excitation and emission spectra of doped broadband near-infrared luminescent materials;

[0057] Figure 3 The Cr prepared in Example 3 of this invention 3+ Excitation and emission spectra of doped broadband near-infrared luminescent materials;

[0058] Figure 4 The Cr prepared in Example 4 of this invention 3+ Quantum efficiency diagram of doped broadband near-infrared luminescent materials;

[0059] Figure 5 The Cr prepared in Example 5 of this invention 3+ Excitation and emission spectra of doped broadband near-infrared luminescent materials;

[0060] Figure 6 The Cr prepared in Example 6 of this invention 3+ Excitation and emission spectra of doped broadband near-infrared luminescent materials;

[0061] Figure 7 The Cr prepared in Example 7 of this invention 3+ Results of the luminescence thermal stability of doped broadband near-infrared luminescent materials. Detailed Implementation

[0062] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0063] Unless otherwise specified, the raw materials, reagents or devices used in the following examples are available from conventional commercial sources or can be obtained by existing known methods.

[0064] Example 1

[0065] A type of Cr 3+ Doped broadband near-infrared luminescent materials, with the chemical formula Mg(Ga) 0.9 Al 0.1 ) 3.9 GeO 12 0.1Cr 3+ .

[0066] A type of Cr 3+ A method for preparing doped broadband near-infrared luminescent materials includes the following steps:

[0067] According to the stoichiometric ratio of Mg(Ga) 0.9 Al 0.1 ) 3.9 GeO 12 0.1Cr 3+ Magnesium oxide, gallium oxide, aluminum oxide, germanium oxide, and chromium oxide were accurately weighed as raw materials. The weighed powders were placed in a mortar, thoroughly mixed, and ground until homogeneous. The mixture was then transferred to an alumina crucible, placed in a muffle furnace, and heated to 450 °C at a controlled heating rate (1 °C / min) under air atmosphere. This temperature was maintained for 3 hours for pre-calcination. After the sample cooled naturally to room temperature, it was removed, ground again until homogeneous, and then transferred to a tube furnace. The temperature was raised to 1400 °C (4 °C / min) under air atmosphere and maintained for 5 hours for a high-temperature solid-phase reaction. After the reaction, the sample was allowed to cool naturally to room temperature, removed, and ground again until homogeneous to obtain Cr. 3+ Doped with broadband near-infrared luminescent materials.

[0068] Figure 1 Cr prepared in Example 1 3+ X-ray diffraction (XRD) pattern of a broadband near-infrared luminescent material.

[0069] Example 2

[0070] A type of Cr 3+ Doped broadband near-infrared luminescent materials, with the chemical formula (Mg... 0.9 Zn 0.1 )4(Ga 0.9 Al 0.1 ) 3.9 GeO 12 0.1Cr 3+ .

[0071] A type of Cr 3+A method for preparing doped broadband near-infrared luminescent materials includes the following steps:

[0072] According to the stoichiometry (Mg) 0.9 Zn 0.1 )4(Ga 0.9 Al 0.1 ) 3.9 GeO 12 0.1Cr 3+ Accurately weigh the required amounts of basic magnesium carbonate, zinc oxide, gallium oxide, aluminum oxide, germanium oxide, and chromium oxide as raw materials. Place the weighed powders in a mortar, mix thoroughly, and grind until homogeneous. Then transfer the mixture to an alumina crucible, place it in a muffle furnace, and heat to 500 °C in air at a controlled heating rate (1 °C / min). Maintain this temperature for 3 hours for pre-calcination. After the sample has naturally cooled to room temperature, remove it, grind it again until homogeneous, and then transfer it to a tube furnace. Heat the sample to 1400 °C in air at a heating rate of 4 °C / min and maintain this temperature for 4 hours for a high-temperature solid-phase reaction. After the reaction, allow the sample to cool naturally to room temperature, remove it, and grind it again until homogeneous to obtain Cr. 3+ Doped with broadband near-infrared luminescent materials.

[0073] Figure 2 Cr prepared in Example 2 3+ Excitation and emission spectra of doped broadband near-infrared luminescent materials. From Figure 2 It can be seen that the excitation peaks are 460 nm and 590 nm, the emission peak is 798 nm, and the emission range is 700-1300 nm.

[0074] Example 3

[0075] A type of Cr 3+ Doped broadband near-infrared luminescent material, with the chemical formula Mg4(Ga 0.9 In 0.1 ) 3.85 GeO 12 0.15Cr 3+ .

[0076] A type of Cr 3+ A method for preparing doped broadband near-infrared luminescent materials includes the following steps:

[0077] According to the stoichiometric ratio of Mg4(Ga 0.9 In 0.1 ) 3.85 GeO 12 0.15Cr 3+Accurately weigh the required amounts of basic magnesium carbonate, gallium oxide, indium oxide, germanium oxide, and chromium oxide as raw materials. Place the weighed powders in a mortar, mix thoroughly, and grind until homogeneous. Then transfer the mixture to an alumina crucible, place it in a muffle furnace, and heat to 450 °C in air at a controlled heating rate (1 °C / min). Maintain this temperature for 3 hours for pre-calcination. After the sample has naturally cooled to room temperature, remove it, grind it again until homogeneous, and then transfer it to a tube furnace. Heat the sample to 1450 °C in air at a heating rate of 4 °C / min and maintain this temperature for 5 hours for a high-temperature solid-state reaction. After the reaction, allow the sample to cool naturally to room temperature, remove it, and grind it again until homogeneous to obtain Cr. 3+ Doped with broadband near-infrared luminescent materials.

[0078] Figure 3 Cr prepared in Example 3 3+ Excitation and emission spectra of doped broadband near-infrared luminescent materials. From Figure 3 It can be seen that the excitation peaks are 462 nm and 582 nm, the emission peak is 805 nm, and the emission range is 700-1300 nm.

[0079] Example 4

[0080] A type of Cr 3+ Doped broadband near-infrared luminescent materials, with the chemical formula (Mg... 0.5 Zn 0.5 )4(Ga 0.9 Al 0.1 ) 3.9 GeO 12 0.1Cr 3+ .

[0081] A type of Cr 3+ A method for preparing doped broadband near-infrared luminescent materials includes the following steps:

[0082] According to the stoichiometry (Mg) 0.5 Zn 0.5 )4(Ga 0.9 Al 0.1 ) 3.9 GeO 12 0.1Cr 3+Accurately weigh the required amounts of basic magnesium carbonate, zinc oxide, gallium oxide, aluminum oxide, germanium oxide, and chromium oxide as raw materials. Place the weighed powders in a mortar, mix thoroughly, and grind until homogeneous. Then transfer the mixture to a corundum crucible, place it in a muffle furnace, and heat to 450 °C in air at a controlled heating rate (1 °C / min). Maintain this temperature for 3 hours for pre-calcination. After the sample has naturally cooled to room temperature, remove it, grind it again until homogeneous, and then transfer it to a tube furnace. Heat the sample to 1450 °C in air at a heating rate of 4 °C / min and maintain this temperature for 4 hours for a high-temperature solid-phase reaction. After the reaction, allow the sample to cool naturally to room temperature, remove it, and grind it again until homogeneous to obtain Cr. 3+ Doped with broadband near-infrared luminescent materials.

[0083] Figure 4 Cr prepared in Example 4 3+ Quantum efficiency plot of doped broadband near-infrared luminescent materials. From Figure 4 It can be seen that the Cr 3+ The internal quantum efficiency of the doped broadband near-infrared luminescent material is 98.2%.

[0084] Example 5

[0085] A type of Cr 3+ Doped broadband near-infrared luminescent material, with the chemical formula Mg4(Ga 0.9 In 0.1 ) 3.8 SnO 12 0.2Cr 3+ .

[0086] A type of Cr 3+ A method for preparing doped broadband near-infrared luminescent materials includes the following steps:

[0087] According to the stoichiometric ratio of Mg4(Ga 0.9 In 0.1 ) 3.8 SnO 12 0.2Cr 3+ Accurately weigh the required amounts of basic magnesium carbonate, gallium oxide, indium oxide, tin oxide, and chromium oxide as raw materials. Place the weighed powders in a mortar, mix thoroughly, and grind until homogeneous. Then transfer the mixture to an alumina crucible, place it in a muffle furnace, and heat to 450 °C in air at a controlled heating rate (1 °C / min). Maintain this temperature for 3 hours for pre-calcination. After the sample has naturally cooled to room temperature, remove it, grind it again until homogeneous, and then transfer it to a tube furnace. Heat the sample to 1450 °C in air at a heating rate of 4 °C / min and maintain this temperature for 5 hours for a high-temperature solid-state reaction. After the reaction, allow the sample to cool naturally to room temperature, remove it, and grind it again until homogeneous to obtain Cr. 3+Doped with broadband near-infrared luminescent materials.

[0088] Figure 5 Cr prepared in Example 5 3+ Excitation and emission spectra of doped broadband near-infrared luminescent materials. From Figure 5 It can be seen that the excitation peaks are 460 nm and 580 nm, the emission peak is 835 nm, and the emission range is 700-1300 nm.

[0089] Example 6

[0090] A type of Cr 3+ Doped broadband near-infrared luminescent material, with the chemical formula Mg4(Ga 0.9 In 0.1 ) 3.8 (Ge 0.9 Si 0.1 )O 12 0.2Cr 3+ .

[0091] A type of Cr 3+ A method for preparing doped broadband near-infrared luminescent materials includes the following steps:

[0092] According to the stoichiometric ratio of Mg4(Ga 0.9 In 0.1 ) 3.8 (Ge 0.9 Si 0.1 )O 12 0.2Cr 3+ Accurately weigh the required amounts of magnesium oxide, gallium oxide, indium oxide, germanium oxide, silicon oxide, and chromium oxide as raw materials. Place the weighed powders in a mortar, mix thoroughly, and grind until homogeneous. Then transfer the mixture to an alumina crucible, place it in a muffle furnace, and heat to 550 °C in air at a controlled heating rate (1 °C / min). Maintain this temperature for 3 hours for pre-calcination. After the sample has naturally cooled to room temperature, remove it, grind it again until homogeneous, and then transfer it to a tube furnace. Heat the sample to 1450 °C in air at a heating rate of 4 °C / min and maintain this temperature for 6 hours for a high-temperature solid-state reaction. After the reaction, allow the sample to cool naturally to room temperature, remove it, and grind it again until homogeneous to obtain Cr. 3+ Doped with broadband near-infrared luminescent materials.

[0093] Figure 6 Cr prepared in Example 6 3+ Excitation and emission spectra of doped broadband near-infrared luminescent materials. From Figure 6 It can be seen that the excitation peaks are 465 nm and 560 nm, the emission peak is 845 nm, and the emission range is 700-1300 nm.

[0094] Example 7

[0095] A type of Cr 3+ Doped broadband near-infrared luminescent materials, with the chemical formula (Mg... 0.9 Sr 0.1 )4(Ga 0.9 In 0.1 ) 3.7 (Ge 0.9 Zr 0.1 )O 12 0.3Cr 3+ .

[0096] A type of Cr 3+ A method for preparing doped broadband near-infrared luminescent materials includes the following steps:

[0097] According to the stoichiometry (Mg) 0.9 Sr 0.1 )4(Ga 0.9 In 0.1 ) 3.7 (Ge 0.9 Zr 0.1 )O 12 0.3Cr 3+ Accurately weigh the required amounts of magnesium oxide, strontium carbonate, gallium oxide, indium oxide, germanium oxide, zirconium oxide, and chromium oxide as raw materials. Place the weighed powders in a mortar, mix thoroughly, and grind until homogeneous. Then transfer the mixture to an alumina crucible, place it in a muffle furnace, and heat to 450 °C in air at a controlled heating rate (1 °C / min). Maintain this temperature for 3 hours for pre-calcination. After the sample has naturally cooled to room temperature, remove it, grind it again until homogeneous, and then transfer it to a tube furnace. Heat the sample to 1350 °C in air at a heating rate of 4 °C / min and maintain this temperature for 6 hours for a high-temperature solid-state reaction. After the reaction, allow the sample to cool naturally to room temperature, remove it, and grind it again until homogeneous to obtain Cr. 3+ Doped with broadband near-infrared luminescent materials.

[0098] Figure 7 Cr prepared in Example 7 3+ Luminescent thermal stability data of doped broadband near-infrared luminescent materials. From Figure 7 It can be seen that at 423 K, the luminescence intensity remains at 96% of the room temperature intensity.

[0099] Example 8

[0100] A type of Cr 3+ Doped broadband near-infrared luminescent material, with the chemical formula Mg4Ga 3.8 SnO 12 0.2Cr 3+ .

[0101] A type of Cr 3+ A method for preparing doped broadband near-infrared luminescent materials includes the following steps:

[0102] According to the stoichiometric ratio of Mg4Ga 3.8 SnO 12 0.2Cr 3+ Accurately weigh the required amounts of magnesium oxide, gallium oxide, tin oxide, and chromium oxide as raw materials. Place the weighed powders in a mortar, mix thoroughly, and grind until homogeneous. Then transfer the mixture to an alumina crucible, place it in a muffle furnace, and heat to 450°C in air at a controlled heating rate (1°C / min). Maintain this temperature for 3 hours for pre-calcination. After the sample has naturally cooled to room temperature, remove it, grind it again until homogeneous, and then transfer it to a tube furnace. Heat the sample to 1450°C in air at a heating rate of 4°C / min and maintain this temperature for 5 hours for a high-temperature solid-state reaction. After the reaction, allow the sample to cool naturally to room temperature, remove it, and grind it again until homogeneous to obtain Cr. 3+ Doped with broadband near-infrared luminescent materials.

[0103] Example 9

[0104] A type of Cr 3+ Doped broadband near-infrared luminescent materials, with the chemical formula (Mg... 0.9 Ba 0.1 )4Ga 3.8 (Ge 0.9 Hf 0.1 )O 12 0.2Cr 3+ .

[0105] A type of Cr 3+ A method for preparing doped broadband near-infrared luminescent materials includes the following steps:

[0106] According to the stoichiometry (Mg) 0.9 Ba 0.1 )4Ga 3.8 (Ge 0.9 Hf 0.1 )O 12 0.2Cr 3+Accurately weigh the required amounts of magnesium oxide, barium carbonate, gallium oxide, germanium oxide, hafnium oxide, and chromium oxide as raw materials. Place the weighed powders in a mortar, mix thoroughly, and grind until homogeneous. Then transfer the mixture to an alumina crucible, place it in a muffle furnace, and heat to 400 °C in air at a controlled heating rate (1 °C / min). Maintain this temperature for 4 hours for pre-calcination. After the sample has naturally cooled to room temperature, remove it, grind it again until homogeneous, and then transfer it to a tube furnace. Heat the sample to 1450 °C in air at a heating rate of 4 °C / min and maintain this temperature for 6 hours for a high-temperature solid-state reaction. After the reaction, allow the sample to cool naturally to room temperature, remove it, and grind it again until homogeneous to obtain Cr. 3+ Doped with broadband near-infrared luminescent materials.

[0107] Example 10

[0108] A type of Cr 3+ Doped broadband near-infrared luminescent materials, with the chemical formula (Mg... 0.5 Zn 0.5 )4(Ga 0.9 In 0.1 ) 3.9 (Ge 0.9 Zr 0.1 )O 12 0.1Cr 3+ .

[0109] A type of Cr 3+ A method for preparing doped broadband near-infrared luminescent materials includes the following steps:

[0110] According to the stoichiometry (Mg) 0.5 Zn 0.5 )4(Ga 0.9 In 0.1 ) 3.9 (Ge 0.9 Zr 0.1 )O 12 0.1Cr 3+ Accurately weigh the required amounts of magnesium oxide, zinc oxide, gallium oxide, indium oxide, germanium oxide, zirconium oxide, and chromium oxide as raw materials. Place the weighed powders in a mortar, mix thoroughly, and grind until homogeneous. Then transfer the mixture to an alumina crucible, place it in a muffle furnace, and heat to 400 °C in air at a controlled heating rate (1 °C / min). Maintain this temperature for 3 hours for pre-calcination. After the sample has naturally cooled to room temperature, remove it, grind it again until homogeneous, and then transfer it to a tube furnace. Heat the sample to 1400 °C in air at a heating rate of 4 °C / min and maintain this temperature for 5 hours for a high-temperature solid-state reaction. After the reaction, allow the sample to cool naturally to room temperature, remove it, and grind it again until homogeneous to obtain Cr. 3+ Doped with broadband near-infrared luminescent materials.

[0111] Example 11

[0112] A type of Cr 3+ Doped broadband near-infrared luminescent material, with the chemical formula Zn4(Ga 0.8 Al 0.2 ) 3.9 (Ge 0.9 Sn 0.1 )O 12 0.1Cr 3+ .

[0113] A type of Cr 3+ A method for preparing doped broadband near-infrared luminescent materials includes the following steps:

[0114] According to the stoichiometry of Zn4(Ga 0.8 Al 0.2 ) 3.9 (Ge 0.9 Sn 0.1 )O 12 0.1Cr 3+ Accurately weigh the required amounts of zinc oxide, gallium oxide, aluminum oxide, germanium oxide, tin oxide, and chromium oxide as raw materials. Place the weighed powders in a mortar, mix thoroughly, and grind until homogeneous. Then transfer the mixture to a corundum crucible, place it in a muffle furnace, and heat to 500 °C in air at a controlled heating rate (1 °C / min). Maintain this temperature for 3 hours for pre-calcination. After the sample has naturally cooled to room temperature, remove it, grind it again until homogeneous, and then transfer it to a tube furnace. Heat the sample to 1450 °C in air at a heating rate of 4 °C / min and maintain this temperature for 5 hours for a high-temperature solid-state reaction. After the reaction, allow the sample to cool naturally to room temperature, remove it, and grind it again until homogeneous to obtain Cr. 3+ Doped with broadband near-infrared luminescent materials.

[0115] Example 12

[0116] A type of Cr 3+ Doped broadband near-infrared luminescent material, with the chemical formula Mg4Ga 3.5 (Ge 0.8 Sn 0.2 )O 12 0.5Cr 3+ .

[0117] A type of Cr 3+ A method for preparing doped broadband near-infrared luminescent materials includes the following steps:

[0118] According to the stoichiometric ratio of Mg4Ga 3.5 (Ge 0.8 Sn 0.2 )O12 0.5Cr 3+ Accurately weigh the required amounts of magnesium oxide, gallium oxide, germanium oxide, tin oxide, and chromium oxide as raw materials. Place the weighed powders in a mortar, mix thoroughly, and grind until homogeneous. Then transfer the mixture to an alumina crucible, place it in a muffle furnace, and heat to 450 °C in air at a controlled heating rate (1 °C / min). Maintain this temperature for 4 hours for pre-calcination. After the sample has naturally cooled to room temperature, remove it, grind it again until homogeneous, and then transfer it to a tube furnace. Heat the sample to 1400 °C in air at a heating rate of 4 °C / min and maintain this temperature for 6 hours for a high-temperature solid-state reaction. After the reaction, allow the sample to cool naturally to room temperature, remove it, and grind it again until homogeneous to obtain Cr. 3+ Doped with broadband near-infrared luminescent materials.

[0119] Example 13

[0120] A type of Cr 3+ Doped broadband near-infrared luminescent materials, with the chemical formula (Mg... 0.98 Ba 0.02 )4Ga 3.95 (Ge 0.8 Sn 0.1 Zr 0.1 )O 12 0.15Cr 3+ .

[0121] A type of Cr 3+ A method for preparing doped broadband near-infrared luminescent materials includes the following steps:

[0122] According to the stoichiometry (Mg) 0.98 Ba 0.02 )4Ga 3.95 (Ge 0.8 Sn 0.1 Zr 0.1 )O 12 0.15Cr 3+ Accurately weigh the required amounts of magnesium oxide, barium oxide, gallium oxide, germanium oxide, tin oxide, zirconium oxide, and chromium oxide as raw materials. Place the weighed powders in a mortar, mix thoroughly, and grind until homogeneous. Then transfer the mixture to an alumina crucible, place it in a muffle furnace, and heat to 400 °C in air at a controlled heating rate (1 °C / min). Maintain this temperature for 4 hours for pre-calcination. After the sample has naturally cooled to room temperature, remove it, grind it again until homogeneous, and then transfer it to a tube furnace. Heat the sample to 1400 °C in air at a heating rate of 4 °C / min and maintain this temperature for 5 hours for a high-temperature solid-state reaction. After the reaction, allow the sample to naturally cool to room temperature, remove it, and grind it again until homogeneous to obtain Cr. 3+ Doped with broadband near-infrared luminescent materials.

[0123] The above describes the Cr provided by the present invention. 3+ The doped broadband near-infrared luminescent materials and their preparation methods are described in detail. The embodiments described above are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to those described above. Any substitutions or combinations made on the basis of the present invention without departing from its essence fall within the scope of protection of the appended claims.

Claims

1. A type of Cr 3+ Doped broadband near-infrared luminescent materials, characterized in that, Its general chemical formula is A 1或4 M 4-x EO 12 :xCr 3+ ; Wherein, A is selected from at least one of Zn, Sr, Mg or Ba; M is selected from at least one of Ga, Al, In or B; The E is selected from at least one of Ge, Si, Sn, Zr or Hf; And 0 < x ≤ 2.

2. The Cr according to claim 1 3+ Doped broadband near-infrared luminescent materials, characterized in that, A is Mg, Mg 0.9 Zn 0.1 Mg 0.5 Zn 0.5 Mg 0.9 Sr 0.1 Mg 0.9 Ba 0.1、 Zn, Mg 0.98 Ba 0.02 At least one of them.

3. The Cr according to claim 1 3+ Doped broadband near-infrared luminescent materials, characterized in that, M is Ga 0.9 Al 0.1 Ga 0.9 In 0.1 ,Ga,Ga 0.8 Al 0.2 At least one of them.

4. The Cr according to claim 1 3+ Doped broadband near-infrared luminescent materials, characterized in that, The E is Ge, Sn, Ge 0.9 Si 0.1 、Ge 0.9 Zr 0.1 、Ge 0.9 Hf 0.1 、Ge 0.9 Sn 0.1 、Ge 0.8 Sn 0.2 、Ge 0.8 Sn 0.1 Zr 0.1 At least one of them.

5. The Cr according to claim 1 3+ Doped broadband near-infrared luminescent materials, characterized in that, The range of x is 0 < x ≤ 1.

6. The Cr according to any one of claims 1-5 3+ Doped broadband near-infrared luminescent materials, characterized in that, The Cr 3+ Doped broadband near-infrared luminescent materials, selected from Mg(Ga) 0.9 Al 0.1 ) 3.9 GeO 12 0.1Cr 3+ 、(Mg 0.9 Zn 0.1 )4(Ga 0.9 Al 0.1 ) 3.9 GeO 12 0.1Cr 3+ Mg4(Ga 0.9 In 0.1 ) 3.85 GeO 12 0.15Cr 3+ 、(Mg 0.5 Zn 0.5 )4(Ga 0.9 Al 0.1 ) 3.9 GeO 12 0.1Cr 3+ Mg4(Ga 0.9 In 0.1 ) 3.8 SnO 12 0.2Cr 3+ Mg4(Ga 0.9 In 0.1 ) 3.8 (Ge 0.9 Si 0.1 )O 12 0.2Cr 3+ 、(Mg 0.9 Sr 0.1 )4(Ga 0.9 In 0.1 ) 3.7 (Ge 0.9 Zr 0.1 )O 12 0.3Cr 3+ Mg4Ga 3.8 SnO 12 0.2Cr 3+ 、(Mg 0.9 Ba 0.1 )4Ga 3.8 (Ge 0.9 Hf 0.1 )O 12 0.2Cr 3+ 、(Mg 0.5 Zn 0.5 )4(Ga 0.9 In 0.1 ) 3.9 (Ge 0.9 Zr 0.1 )O 12 :0.1Cr 3+ Zn4(Ga 0.8 Al 0.2 ) 3.9 (Ge 0.9 Sn 0.1 )O 12 :0.1Cr 3+ Mg4Ga 3.5 (Ge 0.8 Sn 0.2 )O 12 :0.5Cr 3+ , (Mg 0.98 Ba 0.02 )4Ga 3.95 (Ge 0.8 Sn 0.1 Zr 0.1 )O 12 :0.15Cr 3+ Very little in the middle.

7. The Cr according to any one of claims 1-6 3+ A method for preparing doped broadband near-infrared luminescent materials, characterized in that, Includes the following steps: (1) According to the Cr 3+ Weigh the raw materials according to the stoichiometric ratio of the elements in the general chemical formula of the doped broadband near-infrared luminescent material, mix them, and obtain a mixture. (2) The mixture is pre-calcined in air and then calcined to obtain the Cr. 3+ Doped with broadband near-infrared luminescent materials.

8. The preparation method according to claim 7, characterized in that, The raw materials include zinc-containing compounds, strontium-containing compounds, magnesium-containing compounds, barium-containing compounds, gallium-containing compounds, aluminum-containing compounds, indium-containing compounds, boron-containing compounds, silicon-containing compounds, tin-containing compounds, zirconium-containing compounds, germanium-containing compounds, hafnium-containing compounds, or chromium-containing compounds.

9. The preparation method according to claim 7, characterized in that, The pre-firing temperature is 400-550℃, and the pre-firing holding time is 3-4 hours; and / or, the calcination temperature is 1350-1450℃, and the calcination holding time is 4-6 hours.

10. A semiconductor device, characterized in that, Including the Cr as described in any one of claims 1-6 3+ Doped with broadband near-infrared luminescent materials.

Images