Sb < 3 + > activated zinc-based zero-dimensional organic-inorganic hybrid metal halide near-infrared luminescent material and preparation method thereof

Abstract

The invention discloses a Sb < 3 + > activated zinc-based zero-dimensional organic-inorganic hybrid metal halide and a preparation method thereof. The chemical formula of the Sb < 3 + > activated zero-dimensional organic-inorganic hybrid metal halide is A2ZnBr4: xSb < 3 + >, wherein A < + > is a cation of benzyl triethyl ammonium bromide (C13H22NBr) or a cation of isopropyl triphenyl phosphorus bromide (C21H22BrP); 0 lt; xlt; and 40 mol%. The excitation wavelength of the organic-inorganic hybrid metal halide ranges from 250 nm to 500 nm, the emission wavelength ranges from 550 nm to 800 nm, emission peaks are located at 720 nm and 730 nm respectively, and the organic-inorganic hybrid metal halide can be matched with blue light LED chips, can be used for manufacturing near-infrared light-emitting devices and can be applied to the fields of biological imaging, agricultural product nondestructive quality analysis and the like.

Description

Technical Field

[0001] This invention relates to the field of luminescent materials technology, and particularly to Sb 3+ Activated zinc-based zero-dimensional organic-inorganic hybrid metal halide near-infrared luminescent materials and their preparation methods. Background Technology

[0002] The near-infrared band is generally defined as electromagnetic waves with wavelengths between 700 nm and 2500 nm, with some frequency bands approaching the visible light region. Due to its advantages such as low thermal effect, strong non-destructive testing capabilities, and good tissue penetration, near-infrared light has received widespread attention in recent years in fields such as luminescent devices, bioimaging, and non-destructive quality analysis of agricultural products, becoming one of the rapidly developing key technologies. In particular, near-infrared emission within the first biological window (650 nm to 950 nm) is often used to construct optical probes and conduct bioimaging research due to its high penetration ability in biological tissues. However, traditional near-infrared light sources mainly rely on thermal radiation principles (such as halogen lamps and tungsten lamps), which suffer from low luminous efficiency and poor controllability, limiting their development in high-performance applications. Therefore, the development of novel, efficient, and tunable near-infrared luminescent materials has become a research hotspot in this field.

[0003] In recent years, zero-dimensional organic-inorganic hybrid metal halides have emerged as a new class of semiconductor luminescent materials. Due to their unique "host-guest" lattice structure, formed by the self-assembly of organic ligands and inorganic polyhedra, they exhibit excellent properties such as high luminous efficiency, no self-absorption, good carrier transport capability, ease of synthesis, and low cost, leading to their widespread application in photoelectric detection, light-emitting diodes, and solar cells. This is especially true for Sb-based materials. 3+ Zero-dimensional organic-inorganic hybrid metal halides of ions, their luminescence properties and the energy level distribution of self-trapped excitons, Sb 3+ The local coordination environment and lattice structure of ions are closely related; by finely controlling Sb... 3+ The coordination environment of ions can further optimize their luminescence characteristics, thereby achieving high-quality near-infrared emission.

[0004] By employing a coordination structure optimization strategy, Sb32-S ... 3+ Ion activation of zero-dimensional organic-inorganic hybrid metal halides is of great scientific significance and has broad application prospects for promoting their application in fields such as bioimaging, light-emitting devices, and non-destructive testing of agricultural products. Summary of the Invention

[0005] One of the objectives of this invention is to provide Sb 3+Activating zinc-based zero-dimensional organic-inorganic hybrid metal halides can enable the fabrication of near-infrared light-emitting devices and applications in fields such as bioimaging and non-destructive quality analysis of agricultural products.

[0006] The chemical formula of the luminescent material provided by this invention is A2ZnBr4:xSb 3+ A + They are benzyltriethylammonium bromide (C 13 H 22 NBr) cations or isopropyltriphenylphosphine bromide (C 21 H 22 BrP) cation; 0 <x<40mol%。

[0007] In one embodiment, 10 ≤ x ≤ 30 mol%. Within the range of x values, as the x value increases, the chemical compositions of the Sb vary. 3+ The luminescence intensity of activated zinc-based zero-dimensional organic-inorganic hybrid metal halides exhibits a change of first increasing and then decreasing.

[0008] In one implementation, the Sb 3+ The excitation wavelength range of the activated zinc-based zero-dimensional organic-inorganic hybrid metal halide is 250-500 nm, the emission wavelength range is 550-800 nm, and the emission peaks are located at 720 nm and 730 nm, respectively.

[0009] In one implementation, the Sb 3+ Activating zinc-based zero-dimensional organic-inorganic hybrid metal halides into (C 13 H 22 N)2ZnBr4:xSb 3+ It belongs to the triclinic crystal system and has a space group of P-1.

[0010] In one implementation, the Sb 3+ Activating zinc-based zero-dimensional organic-inorganic hybrid metal halides into (C 21 H 22 P)2ZnBr4:xSb 3+ It belongs to the monoclinic crystal system and has the space group P21 / n.

[0011] Another object of the present invention is to provide a method for preparing the above-mentioned Sb 3+ Methods for activating zinc-based zero-dimensional organic-inorganic hybrid metal halides include:

[0012] According to the chemical formula A2ZnBr4:xSb 3+ Weigh C separately 13 H 22 NBr and C 21 H 22One of BrP, a Zn-containing compound, and an Sb-containing compound are added to the reaction vessel as raw materials;

[0013] Add acid or organic solvent to the reaction vessel and stir at 50–60°C to obtain a clear solution;

[0014] By adding a poor solvent to the clarified solution and controlling the cooling rate, the Sb is obtained. 3+ Activation of zinc-based zero-dimensional organic-inorganic hybrid metal halides;

[0015] Among them, A + They are benzyltriethylammonium bromide (C 13 H 22 NBr) cations or isopropyltriphenylphosphine bromide (C 21 H 22 BrP) cation; 0 <x<40mol%。

[0016] In one embodiment, the Zn-containing compound is one or two of Zn-containing carbonates, oxides, hydroxides, nitrates, or bromides, preferably ZnBr2.

[0017] In one embodiment, the Sb-containing compound is one or two of Sb-containing carbonates, oxides, hydroxides, nitrates, or bromides, preferably SbBr3.

[0018] In one embodiment, the acid is one or more of hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, and acetic acid.

[0019] In one embodiment, the organic solvent is one or more of N,N-dimethylformamide, acetonitrile, and dimethyl sulfoxide.

[0020] In one embodiment, the undesirable solvent is one or more of acetone, diethyl ether, and chloroform.

[0021] In one embodiment, the cooling is performed at a cooling rate of 0.01-1 °C / min.

[0022] Compared with the prior art, the present invention has the following advantages:

[0023] The Sb of the present invention 3+ Activated zinc-based zero-dimensional organic-inorganic hybrid metal halides exhibit high brightness, good chemical stability, and a wide excitation and emission range, with the excitation band extending from 250 nm to 500 nm, covering the ultraviolet to cyan region. This luminescent material can be used as a light conversion material for commercial blue LED chips or ultraviolet LED chips to realize a broadband near-infrared light source.

[0024] The preparation method of the present invention is simple, easy to operate, has low equipment cost and no pollution, and is suitable for popularization and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a schematic diagram of the crystal structure of the samples prepared in Example 1, Example 2 and Example 3 of the present invention.

[0026] Figure 2 It is a powder X-ray diffraction spectrum (XRD) diagram of the samples prepared in Example 1, Example 2 and Example 3 of the present invention.

[0027] Figure 3 It is the photoluminescence excitation (PLE) and emission spectrum (PL) of the sample prepared in Example 1 of the present invention.

[0028] Figure 4 It is the photoluminescence excitation (PLE) and emission spectrum (PL) of the sample prepared in Example 2 of the present invention.

[0029] Figure 5 It is the photoluminescence excitation (PLE) and emission spectrum (PL) of the sample prepared in Example 3 of the present invention.

[0030] Figure 6 It is a schematic diagram of the crystal structure of the sample prepared in Example 4 of the present invention.

[0031] Figure 7 It is a powder X-ray diffraction spectrum (XRD) diagram of the sample prepared in Example 4 of the present invention.

[0032] Figure 8 It is the photoluminescence excitation (PLE) and emission spectrum (PL) of the sample prepared in Example 4 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0033] The present invention provides Sb 3+ activated zinc-based zero-dimensional organic-inorganic hybrid metal halide, which is a near-infrared luminescent material with the chemical formula A2ZnBr4:xSb 3+ , where A + are respectively the cations of benzyltriethylammonium bromide (C 13 H 22 NBr) or the cations of isopropyltriphenylphosphonium bromide (C 21 H 22 BrP); 0 < x < 40 mol%. The excitation wavelength range of the near-infrared luminescent material is 250 - 500 nm, the emission wavelength range is 550 - 850 nm, and the emission peaks are located at 720 nm and 730 nm respectively. This luminescent material can be matched with a blue LED chip to prepare a near-infrared luminescent device, and can be applied to fields such as biological imaging and non-destructive quality analysis of agricultural products.

[0034] This invention also provides a method for preparing Sb 3+ A method for activating zinc-based zero-dimensional organic-inorganic hybrid metal halides is presented, which is simple and easily scaled up. The method includes the following steps:

[0035] According to the chemical formula A2ZnBr4:xSb 3+ Where A = C 13 H 22 N + C 21 H 22 P + Weigh C respectively 13 H 22 NBr, C 21 H 22 PBr, Zn-containing compounds, and Sb-containing compounds were used as raw materials, and these raw materials were added to the reaction vessel.

[0036] Add acid or organic solvent to the reaction vessel, heat and stir at 50-60°C to obtain a clear solution;

[0037] Adding a poor solvent to the clarified solution and cooling it yields the Sb. 3+ Activate zinc-based zero-dimensional organic-inorganic hybrid metal halides.

[0038] In one implementation, the A + They are benzyltriethylammonium bromide (C 13 H 22 The cations of NBr and isopropyltriphenylphosphine bromide (C 21 H 22 The compound contains Zn (BrP) cations; the Zn-containing compound is one or two of Zn-containing carbonates, oxides, hydroxides, nitrates, or bromides, preferably ZnBr2; the Sb-containing compound is one or two of Sb-containing carbonates, oxides, hydroxides, nitrates, or bromides, preferably SbBr3; in one embodiment, the Zn-containing compound is ZnBr2; the Sb-containing compound is SbBr3. In one embodiment, the acid is one or more of hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, and acetic acid. In one embodiment, the organic solvent is one or more of N,N-dimethylformamide, acetonitrile, and dimethyl sulfoxide. In one embodiment, the undesirable solvent is one or more of acetone, diethyl ether, and chloroform. In one embodiment, the cooling is performed at a cooling rate of 0.01-1°C / min.

[0039] The present invention further provides the Sb 3+ Activate the application of zinc-based zero-dimensional organic-inorganic hybrid metal halides in the preparation of near-infrared light-emitting devices, bioimaging, and non-destructive quality analysis of agricultural products.

[0040] The present invention will be further described in detail below with reference to the embodiments, but the implementation of the present invention is not limited thereto.

[0041] Example 1: Preparation of a chemical formula (C 13 H 22 N)2ZnBr4:0.1Sb 3+ Sb 3+ Activation of zinc-based zero-dimensional organic-inorganic hybrid metal halides

[0042] According to the chemical formula (C) 13 H 22 N)2ZnBr4:0.1Sb 3+ Weigh C respectively 13 H 22 NBr, ZnBr2, and SbBr3 powder raw materials were added to a glass reaction vessel, followed by 1 ml of hydrobromic acid. The mixture was heated and stirred at 60°C for 2 hours to obtain a clear solution. Then, diethyl ether, a poor solvent, was added. The vessel was placed in an oven, and the cooling rate was controlled at 0.03°C / min. After slowly cooling to room temperature, the product with the chemical formula (C...) was obtained. 13 H 22 N)2ZnBr4:0.1Sb 3+ The needle-like crystals can be ground into powder by placing them in an agate mortar.

[0043] The Sb prepared in this embodiment 3+ Schematic diagram of activated zinc-based zero-dimensional organic-inorganic hybrid metal halide crystal structure (e.g.) Figure 1 (As shown).

[0044] The Sb prepared in this embodiment was analyzed using a Bruker D2 PHASER X-ray diffractometer. 3+ The Sb prepared in this embodiment was obtained by X-ray diffraction of activated zinc-based zero-dimensional organic-inorganic hybrid metal halide powder. 3+ Powder X-ray diffraction (XRD) patterns of activated zinc-based zero-dimensional organic-inorganic hybrid metal halides (e.g.) Figure 2 (As shown).

[0045] The powder was subjected to fluorescence spectroscopy using an Edinburgh FS5 fluorescence spectrometer. The photoluminescence (PLE) spectrum of the powder under 720 nm excitation and the emission (PL) spectrum under 450 nm excitation are shown below (e.g., ...). Figure 3 (As shown).

[0046] The experimental results show that the excitation wavelength range of the luminescent material in this embodiment is 250-500 nm, with two excitation peaks located at 325 nm and 440 nm. The emission wavelength range is 550-850 nm, with an emission peak located at 720 nm, indicating it is a near-infrared luminescent material. Furthermore, this Sb...3+ The activated zinc-based zero-dimensional organic-inorganic hybrid metal halides exhibit stable physical and chemical properties.

[0047] Example 2: Preparation of a chemical formula (C 13 H 22 N)2ZnBr4:0.2Sb 3+ Sb 3+ Activation of zinc-based zero-dimensional organic-inorganic hybrid metal halides

[0048] According to the chemical formula (C) 13 H 22 N)2ZnBr4:0.2Sb 3+ Weigh C respectively 13 H 22 NBr, ZnCO3, and Sb2O3 powdered raw materials were added to a glass reaction vessel, followed by 3 ml of nitric acid. The mixture was heated and stirred at 50°C for 2 hours to obtain a clear solution. Acetone, a poor solvent, was then added, and the mixture was placed in an oven. The cooling rate was controlled at 0.05°C / min, and the mixture was slowly cooled to room temperature to obtain the product with the chemical formula (C). 13 H 22 N)2ZnBr4:0.1Sb 3+ The flaky crystals can be ground into powder by placing them in an agate mortar.

[0049] The Sb prepared in this embodiment 3+ Schematic diagram of activated zinc-based zero-dimensional organic-inorganic hybrid metal halide crystal structure (e.g.) Figure 1 (As shown).

[0050] The Sb prepared in this embodiment was analyzed using a Bruker D2 PHASER X-ray diffractometer. 3+ The Sb prepared in this embodiment was obtained by X-ray diffraction of activated zinc-based zero-dimensional organic-inorganic hybrid metal halide powder. 3+ Powder X-ray diffraction (XRD) patterns of activated zinc-based zero-dimensional organic-inorganic hybrid metal halides (e.g.) Figure 2 (As shown).

[0051] The powder was subjected to fluorescence spectroscopy using an Edinburgh FS5 fluorescence spectrometer. The photoluminescence (PLE) spectrum of the powder under 720 nm excitation and the emission (PL) spectrum under 450 nm excitation are shown below (e.g., ...). Figure 4 (As shown).

[0052] The experimental results show that the excitation wavelength range of the luminescent material in this embodiment is 250-500 nm, with two excitation peaks located at 325 nm and 440 nm. The emission wavelength range is 550-850 nm, with an emission peak located at 720 nm, indicating it is a near-infrared luminescent material. Furthermore, this Sb... 3+The activated zinc-based zero-dimensional organic-inorganic hybrid metal halides exhibit stable physical and chemical properties.

[0053] Example 3: Preparation of a chemical formula (C 13 H 22 N)2ZnBr4:0.3Sb 3+ Sb 3+ Activation of zinc-based zero-dimensional organic-inorganic hybrid metal halides

[0054] According to the chemical formula (C 13 H 22 N)2ZnBr4:0.3Sb 3+ Weigh C respectively 13 H 22 NBr, ZnBr2, and SbBr3 powdered raw materials were added to a glass reaction vessel, followed by 2 ml of dimethyl sulfoxide. The mixture was heated and stirred at 60°C for 2 hours to obtain a clear solution. Then, chloroform, a poor solvent, was added, and the mixture was placed in an oven. The temperature was controlled at a rate of 0.08°C / min and slowly cooled to room temperature to obtain the product with the chemical formula (C...). 13 H 22 N)2ZnBr4:0.1Sb 3+ The granular crystals can be ground in an agate mortar to obtain the corresponding powder.

[0055] The Sb prepared in this embodiment 3+ Schematic diagram of activated zinc-based zero-dimensional organic-inorganic hybrid metal halide crystal structure (e.g.) Figure 1 (As shown).

[0056] The Sb prepared in this embodiment was analyzed using a Bruker D2 PHASER X-ray diffractometer. 3+ The Sb prepared in this embodiment was obtained by X-ray diffraction of activated zinc-based zero-dimensional organic-inorganic hybrid metal halide powder. 3+ Powder X-ray diffraction (XRD) patterns of activated zinc-based zero-dimensional organic-inorganic hybrid metal halides (e.g.) Figure 2 (As shown).

[0057] The powder was subjected to fluorescence spectroscopy using an Edinburgh FS5 fluorescence spectrometer. The photoluminescence (PLE) spectrum of the powder under 720 nm excitation and the emission (PL) spectrum under 450 nm excitation are shown below (e.g., ...). Figure 5 (As shown).

[0058] The experimental results show that the excitation wavelength range of the luminescent material in this embodiment is 250-500 nm, with two excitation peaks located at 325 nm and 440 nm. The emission wavelength range is 550-850 nm, with an emission peak located at 720 nm, indicating it is a near-infrared luminescent material. Furthermore, this Sb... 3+The activated zinc-based zero-dimensional organic-inorganic hybrid metal halides exhibit stable physical and chemical properties.

[0059] Example 4: Preparation of a chemical formula (C 21 H 22 P)2ZnBr4:0.2Sb 3+ Sb 3+ Activation of zinc-based zero-dimensional organic-inorganic hybrid metal halides

[0060] According to the chemical formula (C 21 H 22 P)2ZnBr4:0.2Sb 3+ Weigh C respectively 21 H 22 Powdered raw materials of BrP, ZnCl2, and SbBr3 were added to a glass reaction vessel, followed by 2 ml of hydrobromic acid. The mixture was heated and stirred at 60°C for 2 hours to obtain a clear solution. Acetone, a poor solvent, was then added, and the mixture was placed in an oven. The cooling rate was controlled at 0.1°C / min, and the solution was slowly cooled to room temperature to obtain the product with the chemical formula (C). 13 H 22 N)2ZnBr4:0.1Sb 3+ The blocky crystals can be ground in an agate mortar to obtain the corresponding powder.

[0061] The Sb prepared in this embodiment 3+ Schematic diagram of activated zinc-based zero-dimensional organic-inorganic hybrid metal halide crystal structure (e.g.) Figure 6 (As shown).

[0062] The Sb prepared in this embodiment was analyzed using a Bruker D2 PHASER X-ray diffractometer. 3+ The Sb prepared in this embodiment was obtained by X-ray diffraction of activated zinc-based zero-dimensional organic-inorganic hybrid metal halide powder. 3+ Powder X-ray diffraction (XRD) patterns of activated zinc-based zero-dimensional organic-inorganic hybrid metal halides (e.g.) Figure 7 (As shown).

[0063] The powder was subjected to fluorescence spectroscopy using an Edinburgh FS5 fluorescence spectrometer. The photoluminescence (PLE) spectrum of the powder under 730 nm excitation and the emission (PLE) spectrum under 450 nm excitation were obtained (e.g., ...). Figure 8 (As shown).

[0064] The experimental results show that the excitation wavelength range of the luminescent material in this embodiment is 250-500 nm, with two excitation peaks located at 330 nm and 450 nm. The emission wavelength range is 550-850 nm, with an emission peak located at 730 nm, indicating it is a near-infrared luminescent material. Furthermore, this Sb... 3+The activated zinc-based zero-dimensional organic-inorganic hybrid metal halides exhibit stable physical and chemical properties.

Claims

1. A type of Sb 3+ Activation of zinc-based zero-dimensional organic-inorganic hybrid metal halides, characterized in that, The Sb 3+ The chemical formula for activating zinc-based zero-dimensional organic-inorganic hybrid metal halides is A2ZnBr4:xSb. 3+ , Where A + They are benzyltriethylammonium bromide (C 13 H 22 NBr) cations or isopropyltriphenylphosphine bromide (C 21 H 22 BrP) cation; 0 <x<40mol%。 2. The luminescent material according to claim 1, characterized in that, 10 ≤ x ≤ 30 mol%.

3. The luminescent material according to claim 1, characterized in that, The Sb 3+ The excitation wavelength range of the activated zinc-based zero-dimensional organic-inorganic hybrid metal halide is 250-500 nm, the emission wavelength range is 550-800 nm, and the emission peaks are located at 720 nm and 730 nm, respectively.

4. The luminescent material according to claim 1, characterized in that, The Sb 3+ Activating zinc-based zero-dimensional organic-inorganic hybrid metal halides into (C 13 H 22 N)2ZnBr4:xSb 3+ It belongs to the triclinic crystal system and has a space group of P-1.

5. The luminescent material according to claim 1, characterized in that, The Sb 3+ Activating zinc-based zero-dimensional organic-inorganic hybrid metal halides into (C 21 H 22 P)2ZnBr4:xSb 3+ It belongs to the monoclinic crystal system and has the space group P21 / n.

6. A method for preparing Sb 3+ Methods for activating zinc-based zero-dimensional organic-inorganic hybrid metal halides include: According to the chemical formula A2ZnBr4:xSb 3+ Weigh C separately 13 H 22 NBr and C 21 H 22 One of BrP, a Zn-containing compound, and an Sb-containing compound are added to the reaction vessel as raw materials; Add acid or organic solvent to the reaction vessel and stir at 50–60°C to obtain a clear solution; By adding a poor solvent to the clarified solution and controlling the cooling rate, the Sb is obtained. 3+ Activation of zinc-based zero-dimensional organic-inorganic hybrid metal halides; Among them, A + They are benzyltriethylammonium bromide (C 13 H 22 NBr) cations or isopropyltriphenylphosphine bromide (C 21 H 22 BrP) cation; 0 <x<40mol%。 7. The method as described in claim 6, characterized in that, The Zn-containing compound is a Zn-containing carbonate, oxide, hydroxide, nitrate, or bromide; The Sb-containing compound is an Sb-containing carbonate, oxide, hydroxide, nitrate, or bromide.

8. The method as described in claim 6, characterized in that, The acid is one or more of hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, and acetic acid.

9. The method as described in claim 6, characterized in that, The organic solvent is one or more of N,N-dimethylformamide, acetonitrile, and dimethyl sulfoxide.

10. The method as described in claim 6, characterized in that, The unsuitable solvent is one or more of acetone, diethyl ether, and chloroform.

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