CN104861970B - The near-infrared long after glow luminous material of the perovskite structure of a kind of Cr doping and preparation method - Google Patents

Abstract

The invention discloses the near-infrared long after glow luminous material of the perovskite structure of a kind of Cr doping, matrix material is ABO₃, described A is Ca, Sr or Ba；Described B is Sn or Ti；The Cr of doping 0.001～5mol% in described matrix material³⁺.The preparation method that the invention also discloses above-mentioned near-infrared long after glow luminous material, weighs material including (1): weigh respectively containing A compound, containing Ti compound, containing Cr compound；(2) take out after pre-burning in going back air/reducing atmosphere after the ground mixing of material, after regrinding, in firing hour in air/reducing atmosphere.The near-infrared long after glow luminous material of the present invention is launched band and is positioned at 650-850 nanometer, and emission peak is positioned at 760 nanometers, and persistence was up to 100 minutes；The preparation method technique of the present invention is simple, low in raw material price, it is easy to megatechnics is promoted.

Description

A kind of Cr-doped perovskite structure near-infrared long afterglow luminescent material and preparation method

technical field

The invention relates to a nano near-infrared long afterglow luminescent material, in particular to a Cr-doped perovskite structure near-infrared long afterglow luminescent material and a preparation method.

Background technique

Optical imaging, using photons as an information source, represents a rapidly expanding field with direct applications in pharmacology, molecular cell biology, and diagnostics. However, this technique still has many limitations, especially the tissue autofluorescence produced by in vivo illumination and the weak tissue permeability under short-wave excitation light irradiation. In order to overcome these difficulties, scientists have studied a series of inorganic light-emitting materials, which emit light in the near-infrared region (NIR). Molecules emit near-infrared light (700-1100nm), which can be used for the detection of living molecular targets, because biological blood and Tissue is relatively transparent in this wavelength range, reducing the difficulty of in vivo background interference. However, since the excitation light of many fluorescent materials is located in the short-wavelength region, it is not convenient to excite the fluorescent materials, let alone observe the phenomenon. Therefore, many researchers have proposed to use near-infrared long-lasting materials to replace ordinary fluorescent materials, so as to achieve in vitro excitation, and the afterglow that still exists after injection into the body can still be used as biological fluorescent markers. Since the near-infrared fluorescent markers emit light in the near-infrared light region, and biomolecules do not emit light in this light region, there is no interference caused by spectral overlap, and the detection background is low. Near-infrared fluorescent markers can use shorter wavelengths of visible light or near-infrared light. Excited by ultraviolet light, the Stokes shift of the spectrum is large, which helps to avoid the influence of excitation light scattering and obtain higher sensitivity. In addition, the components in biological living tissues have little absorption of near-external light, and near-infrared light has a large penetration depth in biological tissues, and can generate optical signals in deep tissues without affecting the tissues themselves, which helps to obtain more Multi-organism information. Therefore, near-infrared fluorescent markers have become a current research hotspot. Long afterglow materials are used for imaging, which can well remove the background of non-specific imaging. The previous long afterglow materials were mainly concentrated in the visible light region and used as night vision materials. The development of long afterglow materials in the near-infrared region is extremely slow, which limits the application of long afterglow materials in biological imaging. Therefore, vigorously developing near-infrared long-lasting materials can further promote the development of medical imaging and tumor treatment.

Contents of the invention

In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the object of the present invention is to provide a near-infrared long afterglow luminescent material with a Cr-doped perovskite structure, the emission band is located at 650-850 nanometers, the emission peak is located at 760 nanometers, and the afterglow The time is up to 100 minutes.

Another object of the present invention is to provide a method for preparing the above-mentioned Cr-doped perovskite structure near-infrared long-lasting luminescent material, which has a simple preparation process and is easy to promote large-scale technology.

The object of the present invention is achieved through the following technical solutions:

A Cr-doped perovskite structure near-infrared long-lasting luminescent material, the matrix material is ABO ₃ , the A is Ca, Sr or Ba; the B is Sn or Ti; the matrix material is doped with 0.001 -5 mol% Cr ³⁺ .

The base material is also doped with 0-20 mol% Bi ³⁺ .

The preparation method of single-doped Cr ³⁺ ATiO ₃ comprises the following steps:

(1) Weighing materials: weigh A-containing compounds, Ti-containing compounds, and Cr-containing compounds respectively;

(2) After the material is ground and mixed, it is pre-fired at 600-900°C for 1-3 hours in a reducing atmosphere, then taken out, and after grinding again, it is fired at 1300-1450°C for 2-5 hours in a reducing atmosphere.

The reducing atmosphere is composed of 5% H ₂ by volume and 95% N ₂ by volume.

The preparation method of Cr ³⁺ and Bi ³⁺ co-doped ATiO ₃ comprises the following steps:

(1) Weighing materials: weigh A-containing compounds, Ti-containing compounds, Cr-containing compounds, and Bi-containing compounds respectively;

(2) After the material is ground and mixed, it is pre-fired at 600-900°C in the air for 1-3 hours, then taken out, and after grinding again, it is fired at 1300-1450°C in the air for 2-5 hours.

The preparation method of single-doped Cr ³⁺ ASnO ₃ comprises the following steps:

(1) Weighing materials: Weigh the A-containing compound, the Sn-containing compound, and the Cr-containing compound respectively;

(2) After the material is ground and mixed, it is pre-fired in a reducing atmosphere at 600-900°C for 1-3 hours, then taken out, and after grinding again, it is fired in a reducing atmosphere at 1350-1500°C for 2-5 hours.

The preparation method of Cr ³⁺ and Bi ³⁺ co-doped ASnO ₃ comprises the following steps:

(1) Weighing materials: weigh A-containing compounds, Sn-containing compounds, Cr-containing compounds, and Bi-containing compounds respectively;

(2) After the material is ground and mixed, it is pre-fired at 600-900°C in the air for 1-3 hours and then taken out. After grinding again, it is fired at 1350-1500°C in the air for 2-5 hours.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

(1) In the near-infrared long-lasting luminescent material of the Cr-doped perovskite structure of the present invention, trivalent Cr ions have received extensive attention due to its excellent long-lasting luminescent performance, and the calcium titanate matrix material is due to its own High carrier mobility is widely used in solar cells. However, since Cr mainly exists in the 4-valent form in calcium titanate, it occupies the octahedral position of Ti atoms. Therefore, it is difficult to obtain long afterglow luminescence of trivalent Cr, and the doping of Bi can effectively stabilize trivalent Cr, increase the content of trivalent Cr ions, thereby effectively improving the long afterglow luminescence of trivalent Cr.

(2) In the near-infrared long-lasting luminescent material of the Cr-doped perovskite structure of the present invention, Bi ions occupy the lattice positions of Ca ions, and because of its unequal substitution, it can also promote the generation of a large number of new defects. Helps prolong the long afterglow glow.

(3) The preparation method of the present invention is simple, the raw materials obtained are cheap, and easy to be popularized on a large scale.

Description of drawings

Fig. 1 (a) is the afterglow spectrum graph of the sample prepared in Example 1 of the present invention.

Fig. 1(b) is a long afterglow decay curve of the sample prepared in Example 1 of the present invention.

Fig. 2(a) is a graph of afterglow spectrum of the sample prepared in Example 2 of the present invention.

Fig. 2(b) is a long afterglow decay curve of the sample prepared in Example 2 of the present invention.

Fig. 3(a) is a graph of the afterglow spectrum of the sample prepared in Example 3 of the present invention.

Fig. 3(b) is a long persistence decay curve of the sample prepared in Example 3 of the present invention.

Fig. 4(a) is a graph of the afterglow spectrum of the sample prepared in Example 4 of the present invention.

Fig. 4(b) is a long persistence decay curve of the sample prepared in Example 4 of the present invention.

detailed description

The present invention will be described in further detail below in conjunction with the examples, but the embodiments of the present invention are not limited thereto.

Example 1

The preparation method of the near-infrared long afterglow luminescent material of the single- ^doped Cr CaTiO _of the present embodiment is as follows:

According to the following components: the matrix is CaTiO ₃ ; the doping amount of Cr ³⁺ is 0.001mol%; titanium oxide, calcium carbonate, and chromium oxide (Cr ₂ O ₃ ) are weighed respectively, and after grinding and mixing, they are placed in a reducing atmosphere (5 %(volume percent) H ₂ +95%(volume percent) N ₂ ) was calcined at 900°C for 3 hours, taken out, ground again, and fired at 1450°C for 2 hours.

The long afterglow spectrum of the near-infrared long-afterglow luminescent material prepared in this embodiment is shown in Figure 1 (a). After irradiating with 254 nm ultraviolet light for 10 minutes, the test was performed after an interval of 30 seconds, and the near-infrared long-afterglow luminescence was obtained. The luminescence peak is located at 766,780 nm. As shown in Figure 1(b), the near-infrared long afterglow luminescence at 766 nm was monitored, and the discovery time was as long as 100 minutes. It shows that this material has excellent near-infrared long afterglow luminescence.

Example 2

The preparation method of the near-infrared long afterglow luminescent material of Cr and Bi co- ^{doped SrTiO} _of the present embodiment is as follows:

According to the following composition: the matrix is SrTiO ₃ ; the doping amount of Cr ³⁺ is 5 mol%, and the doping amount of Bi ³⁺ is 20 mol %; titanium oxide, strontium carbonate, chromium oxide (Cr ₂ O ₃ ), oxide Bismuth (Bi ₂ O), after being ground and mixed, pre-fired at 600°C for 1 hour in air, then taken out, and after grinding again, fired at 1300°C for 5 hours.

The long afterglow spectrum of the near-infrared long-lasting luminescent material prepared in this embodiment is shown in Figure 2(a). After irradiating with 254 nm ultraviolet light for 10 minutes, the test was performed after an interval of 30 seconds, and the near-infrared long-lasting luminescence was obtained. The luminescence peak is located at 766 nm. As shown in Figure 2(b), the near-infrared long afterglow luminescence at 766 nm was monitored, and the discovery time was as long as 100 minutes. It shows that this material has excellent near-infrared long afterglow luminescence.

Example 3

The preparation method of the near-infrared long afterglow luminescent material of single-doped Cr ^BaSnO _of the present embodiment is as follows:

According to the following components: the matrix is BaSnO ₃ ; the doping amount of Cr ³⁺ is 5 mol%; tin oxide, barium carbonate, and chromium oxide are weighed respectively, and after grinding and mixing, they are placed in a reducing atmosphere (5% H ₂ +95% N ₂ ) After calcining at 600°C for 1 hour, take it out, grind it again, and fire at 1350°C for 5 hours.

The long afterglow spectrum of the near-infrared long-afterglow luminescent material prepared in this embodiment is shown in Figure 3(a). After being irradiated with 254 nm ultraviolet light for 10 minutes and tested after an interval of 30 seconds, the near-infrared long afterglow luminescence was obtained. The luminescence peak is located at 800 nm. As shown in Figure 3(b), the near-infrared long afterglow luminescence at 800 nm was monitored, and the discovery time was as long as 100 minutes. It shows that this material has excellent near-infrared long afterglow luminescence.

Example 4

The preparation method of the near-infrared long afterglow luminescent material of Cr3 ⁺ and Bi3 ⁺ co-doped BaSnO3 _of the present embodiment is as follows:

According to the following composition: the matrix is BaSnO ₃ ; the doping amount of Cr ³⁺ is 0.001mol%, and the doping amount of Bi ³⁺ is 20mol%; tin oxide, barium carbonate, chromium oxide and bismuth oxide are weighed respectively, and mixed by grinding After homogenizing, pre-fire at 900°C for 3 hours in the air, take it out, grind again, and burn at 1500°C for 2 hours.

The long afterglow spectrum of the near-infrared long-afterglow luminescent material prepared in this embodiment is shown in Figure 4(a). After irradiating with 254 nm ultraviolet light for 10 minutes, it was tested after an interval of 30 seconds, and the near-infrared long afterglow luminescence was obtained. The luminescence peak is located at 800 nm. As shown in Figure 4(b), the near-infrared long afterglow luminescence at 800 nm was monitored, and the discovery time was as long as 100 minutes. It shows that this material has excellent near-infrared long afterglow luminescence.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the embodiment, and any other changes, modifications, substitutions and combinations made without departing from the spirit and principle of the present invention , simplification, all should be equivalent replacement methods, and are all included in the protection scope of the present invention.

Claims (3)

1. A near-infrared long afterglow luminescent material of a Cr-doped perovskite structure, characterized in that the matrix material is ABO ₃ , and the A is Ca, Sr or Ba; the B is Sn or Ti; the The matrix material is doped with 0.001-5 mol% of Cr ³⁺ and 20 mol% of Bi ³⁺ . 2. the preparation method of the near-infrared long afterglow luminescent material of the perovskite structure of Cr doping claimed in claim 1 is characterized in that, the _ATiO of Cr ³⁺ and Bi ³⁺ co-doped The preparation method comprises the following steps : (1) Weighing materials: weigh A-containing compounds, Ti-containing compounds, Cr-containing compounds, and Bi-containing compounds respectively; (2) After the material is ground and mixed, it is pre-fired at 600-900°C in the air for 1-3 hours, then taken out, and after grinding again, it is fired at 1300-1450°C in the air for 2-5 hours. 3. the preparation method of the near-infrared long afterglow luminescent material of the perovskite structure of Cr doping according to claim 1, it is characterized in that, Cr ³⁺ and Bi ³⁺ co-doped ASnO ₃ The preparation method comprises the following step: (1) Weighing materials: weigh A-containing compounds, Sn-containing compounds, Cr-containing compounds, and Bi-containing compounds respectively; (2) After the material is ground and mixed, it is pre-fired at 600-900°C in the air for 1-3 hours and then taken out. After grinding again, it is fired at 1350-1500°C in the air for 2-5 hours.