Sulfur coordination manganese halide complex as well as preparation method and application thereof

Abstract

The invention provides a sulfur coordination manganese halide complex as well as a preparation method and application thereof, and belongs to the technical field of luminescent materials. The complex is an ionic luminous complex which is formed by taking triphenyl sulfosalt as an organic ligand and coordinating and combining with manganese halide ions. The preparation process is simple, the cost is low, and the complex has excellent photophysical properties, weaker self-absorption and higher light quantum yield, and emits green light in a solid state; the fluorescent powder can be applied to the fields of anti-counterfeit printing, lighting display and the like; a thin film prepared on the basis of the complex can also be used as a light-emitting layer to be applied to an OLED (Organic Light Emitting Diode) device; and the complex has excellent X-ray response performance, so that the complex has certain potential in the fields of X-ray imaging and detection, and has wide application prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of luminescent materials, and in particular relates to a type of sulfur-coordinated manganese halide complex and a preparation method and application thereof. Background Art

[0002] In recent years, due to the increasing application demand in various fields, X-ray detection technology has aroused widespread research interest and has developed rapidly. X-ray detectors can be divided into direct detectors and indirect detectors according to their working principles. In indirect detectors, scintillators convert high-energy X-ray photons into visible light signals, which can be further detected and imaged by amorphous silicon photodiodes or photomultiplier tubes. Therefore, scintillator materials are the core components of X-ray detectors.

[0003] At present, commercial scintillators can be divided into inorganic scintillators and organic scintillators. High-efficiency inorganic single crystal scintillators, such as Bi4Ge3O 12 (BGO), Lu3A5O 12 :Ce 3+ (LuAG:Ce) and CsI:TI are widely used in X-ray detection due to their advantages such as high light yield, suppression of optical crosstalk and strong light capability. However, traditional inorganic scintillator materials usually appear in the form of large-sized crystals, and have defects such as complex manufacturing process, high temperature in the preparation process, long time consumption and difficulty in tuning the luminescence. At the same time, organic scintillator materials with fast decay time and low-cost preparation process have attracted the attention of technicians in this field, but the low X-ray absorption coefficient often leads to poor performance of organic scintillators. Therefore, there is an urgent need to explore a new scintillator material with simple preparation process and high X-ray detection efficiency.

[0004] Organic-inorganic hybrid metal halides have triggered a research boom in the field of scintillators due to their simple low-temperature solution preparation process, excellent scintillation performance and rich crystal structure flexibility. Among them, halide materials based on metallic manganese have the advantages of high photoluminescence efficiency, easy synthesis, excellent photoelectric properties, high stability, low toxicity and high abundance. On this basis, the selection of organic cations is particularly important for the construction of manganese-based halide luminescent materials. At present, the organic ligands of organic-inorganic hybrid metal halides are mostly organic molecules containing nitrogen, phosphorus or phosphorus oxide. The selection of ligand organic cations is still in the stage of a large number of attempts and blind selection. There is still a lot of room for research on such complex materials.

[0005] Therefore, it is still a major challenge to select suitable organic molecules for the construction of high-performance manganese-based metal halide luminescent materials. The development of corresponding complexes can provide new ideas for expanding the types of complexes and scintillators, which has important theoretical research significance and practical application value. Summary of the invention

[0006] The purpose of the present invention is to solve the deficiencies in the prior art and provide a class of sulfur-coordinated manganese halide complexes and a preparation method thereof. The present application specifically selects triphenylsulfonate as an organic ligand, which is combined with a manganese halide to form an ionic luminescent manganese halide complex. Such a complex has weak self-absorption, high radiation luminescence intensity, and excellent X-ray imaging performance, and has broad application potential in many fields.

[0007] The specific technical scheme of the present invention is: a type of sulfur-coordinated manganese halide complex, which is an ionic luminescent complex formed by triphenylsulfonium salt as an organic ligand coordinated with a manganese halide ion, and its general structural formula is as follows:

[0008]

[0009] Wherein, A is selected from any one of the following groups:

[0010]

[0011] B is selected from any one of the following groups:

[0012]

[0013] Furthermore, the sulfur-coordinated manganese halide complex emits green light in the solid state and has weak self-absorption and high irradiation luminescence intensity.

[0014] The preparation method of the above-mentioned sulfur-coordinated manganese halide complex is: weigh manganese halide MnX2 and triphenylsulfonium salt, mix them, fully dissolve them in an organic solvent, heat and evaporate them, and precipitate crystals to obtain the sulfur-coordinated manganese halide complex. The preparation route is as follows:

[0015]

[0016] Wherein, X is Cl or Br.

[0017] Furthermore, the molar ratio of MnX2 to triphenyl sulfide is 1-4:2-8.

[0018] Furthermore, the organic solvent is ethanol, and the evaporation temperature is 60-80°C.

[0019] The scintillator film prepared using the above-mentioned sulfur-coordinated manganese halide complex does not emit light under sunlight, but emits green light under ultraviolet and X-ray irradiation. Based on its responsiveness to X-rays, the scintillator film can be successfully applied to the field of X-ray detection and imaging.

[0020] The sulfur-coordinated manganese halide complex can be applied to OLED devices. Specifically, the sulfur-coordinated manganese halide complex can be prepared into a thin film by vacuum evaporation, and then the thin film can be applied to OLED devices as a light-emitting layer.

[0021] Based on the solid-state luminescence properties of the above-mentioned sulfur-coordinated manganese halide complexes, such materials can also be ground into powder and used as phosphors in the field of solid-state lighting or optoelectronic display.

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

[0023] 1. The sulfur-coordinated manganese halide complex disclosed in the present application has excellent photophysical properties, green light emission in the solid state, weak self-absorption and high light quantum yield;

[0024] 2. The sulfur-coordinated manganese halide complex disclosed in the present application has excellent response performance to X-rays, low detection limit, high light yield, and can be prepared into scintillator films for application in the field of X-ray detection and imaging;

[0025] 3. The sulfur-coordinated manganese halide complex disclosed in the present application is prepared into a thin film and used as a light-emitting layer in an OLED device to emit green light;

[0026] 4. Based on the solid-state luminescence characteristics of the sulfur-coordinated manganese halide complex disclosed in this application, it can be ground into powder and used as phosphor in the field of solid lighting or optoelectronic display, or it can be prepared into powder and mixed with an organic solvent as ink for use in the field of printing or printing;

[0027] 5. The preparation method of the sulfur-coordinated manganese halide complex disclosed in the present application is simple, is synthesized using a "solution method", has low preparation cost, is low toxic and environmentally friendly, and is easy to mass produce and apply. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 is the single crystal structure diagram of complex Ⅰ;

[0029] Figure 2 is the single crystal XRD powder diffraction pattern of complex Ⅰ;

[0030] Figure 3 is the single crystal structure diagram of complex II;

[0031] Figure 4 is the single crystal XRD powder diffraction pattern of complex II;

[0032] Figure 5 The absorption coefficient and photon energy spectrum of complex Ⅰ and complex Ⅱ to high energy X-ray;

[0033] Figure 6 is the normalized solid-state emission spectrum of complex Ⅰ;

[0034] Figure 7 is the normalized solid-state emission spectrum of complex II;

[0035] Figure 8 The emission spectra of complex Ⅰ(a) and complex Ⅱ(b) under different doses of X-rays;

[0036] Fig. 9 X-ray linear response spectra of complex Ⅰ(a) and complex Ⅱ(b);

[0037] Fig.10 is the normalized excitation-emission spectrum of complex Ⅰ;

[0038] Fig.11 is the normalized excitation-emission spectrum of complex II;

[0039] Fig.12 is the CIE 1931 chromaticity diagram of complex Ⅰ;

[0040] Fig.13 is the CIE 1931 chromaticity diagram of complex II;

[0041] Fig.14 The spectrum of the relationship between the attenuation coefficient of complex Ⅰ and complex Ⅱ after X-ray absorption and thickness;

[0042] Fig.15 This is the irradiation luminescence intensity diagram of complex II and inorganic scintillator LuAG:Ce;

[0043] Fig.16 This is an image of the chip made of scintillator film based on complex II under X-ray irradiation;

[0044] Fig.17 The small figures (a) and (b) are images of the springs made of scintillator films based on complex I and complex II under X-ray irradiation, respectively;

[0045] Fig.18 It is a simple schematic diagram of an X-ray imaging device, wherein 1-X-ray tube, 2-sample, 3-scintillator, 4-reflector, 5-camera, 6-computer;

[0046] Fig.19 This is the luminescence image of the thin-film OLED device prepared based on complex II. DETAILED DESCRIPTION

[0047] The technical solution of the present invention is further described below in conjunction with the accompanying drawings, but is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be included in the protection scope of the present invention.

[0048] Example 1

[0049] The synthetic route of sulfur-coordinated manganese halide complex Ⅰ is as follows:

[0050]

[0051] The specific preparation process of complex I is as follows:

[0052] Weigh MnCl2 (1 mmol) and triphenylsulfur chloride (1 mmol) into a 20 mL vial, add 5 mL of ethanol to fully dissolve, then slowly evaporate at 60 ° C. After about a week, crystals will precipitate, which is complex I. The single crystal structure of complex I is shown in the figure Figure 1 The single crystal XRD powder diffraction pattern of complex Ⅰ is shown in Figure 2 shown.

[0053] Example 2

[0054] The synthetic route of sulfur-coordinated manganese halide complex II is as follows:

[0055]

[0056] The specific preparation process of complex II is as follows:

[0057] Weigh MnBr2 (1 mmol) and triphenylsulfur bromide (1 mmol) into a 20 mL vial, add 5 mL of ethanol to fully dissolve, then slowly evaporate at 60 ° C. After about a week, crystals will precipitate, which is complex II. The single crystal structure of complex II is shown in the figure Figure 3 The single crystal XRD powder diffraction pattern of complex II is shown in Figure 4 shown.

[0058] Related performance tests

[0059] 1) The absorption coefficient and photon energy spectrum of the complex to high-energy X-rays can be obtained by measuring the irradiation emission spectrum. Figure 5 That is the absorption coefficient and photon energy spectrum of complex I and complex II. It can be seen from the figure that the X-ray energy range is from 0.001MeV to 1MeV, which is at the same order of magnitude as the absorption coefficient of inorganic scintillators LuAG:Ce and CsI:TI.

[0060] 2) Figure 6 , Figure 7 They are the normalized solid-state emission spectra of complex I and complex II, respectively. It can be seen from the figure that the emission characteristic peak of complex I is located at 520nm, and the emission characteristic peak of complex II is located at 518nm.

[0061] 3) Figure 8Panels (a) and (b) are the emission spectra of complex I and complex II under different doses of X-rays, respectively. It can be seen from the figures that both complexes show a monotonically increasing emission spectrum under X-ray irradiation (60 kV, 0.15 μGy / s→3.35 μGy / s), and exhibit a good linear response in the range of 0.15 μGy / s→3.35 μGy / s.

[0062] 4) Fig. 9 The small figures (a) and (b) reflect the relationship between the irradiation intensity and X-ray dose rate of complex I and complex II, respectively. The detection limit is set when the signal-to-noise ratio is equal to 3. The detection limits of complex I and complex II are 81.1nGyaiX / s and 127.2nGyaiX / s, respectively, which are far lower than the standard limit of X-ray medical diagnosis (5.5μGyaiX / s).

[0063] 5) The excitation spectrum and emission spectrum were measured on an Edinburgh FLS-980 spectrophotometer. The emission spectrum was obtained using a 460W xenon lamp in the range of 300nm-800nm. The normalized solid-state excitation-emission spectra of complex I and complex II are shown in Fig.10 , Fig.11 As shown, the emission characteristic peak of complex Ⅰ is located at 520nm, and the emission characteristic peak of complex Ⅱ is located at 518nm. The emission bands are consistent with [MnX4] 2- The tetraligand Mn in the unit 2+ Ions 4 T1(G) to 6 A1 radiation transition, the crystal has only one luminescent center, emitting green light. Both have large Stokes shifts, the Stokes shift of complex I is 70nm, and the Stokes shift of complex II is 48nm, showing weak self-absorption.

[0064] 6) The emission spectra of complexes I and II were calculated using CIE 1931 software. The results are shown in Fig.12 and Fig.13 The chromaticity values ​​of complex Ⅰ and complex Ⅱ were (0.203, 0.670) and (0.148, 0.697), respectively, both of which are green light.

[0065] 7) The material density data of complex I and complex II were obtained by calculating the X-ray absorption coefficient and XRD characterization experiment, and the attenuation coefficient of the two complexes after absorbing X-rays with an energy of 60 keV was plotted as a function of thickness. The results are shown in Fig.14 ,From the figure, it can be seen that the crystal thickness of complex Ⅰ and complex Ⅱ is at the same level as the inorganic scintillator LuAG:Ce after 1 mm.

[0066] 8) A comparison of the light yield of complex II and the inorganic scintillator LuAG:Ce was obtained under X-ray irradiation at the same dose rate. The results are shown in Fig.15 As can be seen from the figure, the light yield of complex II is more than twice that of the inorganic scintillator LuAG:Ce, which can meet the application requirements in many fields such as space detection and medical imaging.

[0067] Application Example 1

[0068] Based on the unique green light emission and high luminescence quantum efficiency characteristics of complexes I and II, attempts were made to make these two complexes into scintillator films for use in the field of X-ray imaging.

[0069] The film preparation process is as follows: 1g of polymethyl methacrylate (PMMA) is dissolved in 10g of toluene to form a pre-clear solution, which is then mixed with the powder of complex II (0.4g) ground three times, stirred evenly, and then dripped onto a glass slide and evaporated at room temperature to obtain a 1.8mm thick scintillator film.

[0070] The scintillator film prepared based on complex II does not emit light under sunlight, but emits green light under ultraviolet and X-ray irradiation. Since different metals have different absorption of X-rays, the spatial saturation on the scintillator is different, so it can be used for optical imaging, such as Fig.16 As shown, the chip is imaged using the film under X-ray irradiation, and the clear internal structure of the chip can be observed.

[0071] Based on the same method, a scintillator film prepared using complex Ⅰ can be obtained. Fig.17 The small figures (a) and (b) are images of the springs made of scintillator films based on complex I and complex II under X-ray irradiation, respectively. Very clear images of the springs can be observed.

[0072] Application Example 2

[0073] The complex II was ground into powder, and the powder was placed in an evaporation boat. The ITO substrate (ITO side facing down) was placed in a vacuum evaporation chamber, and the corresponding mask was rotated to the bottom of the substrate. The ITO surface was covered with a baffle, and the chamber was evacuated. The evaporation power was turned on to vacuum coat the evaporation boat. The obtained film was applied as a light-emitting layer to an OLED device for a light-emitting experiment. Fig.19 The luminescence image shows green light emission. The same phenomenon is observed when the film made of complex I is applied to OLED devices.

[0074] It can be seen from this that the thin film material made by vacuum evaporation based on complex I and complex II can be used as a light-emitting layer in OLED devices.

[0075] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A sulfur-coordinated manganese halide complex characterized by: It is an ionic luminescent complex formed by triphenylsulfonate as an organic ligand and coordinated with manganese halide ions. Its general structural formula is as follows: Wherein, A is selected from any one of the following groups: B is selected from any one of the following groups:

2. The sulfur-coordinated manganese halide complex according to claim 1, characterized in that: The sulfur-coordinated manganese halogen complex emits green light in the solid state and has weak self-absorption and high irradiation luminescence intensity.

3. The method for preparing the sulfur-coordinated manganese halide complex according to any one of claims 1 to 2, characterized in that: Weigh manganese halide MnX2 and triphenylsulfonium salt, mix them, fully dissolve them in an organic solvent, heat and evaporate them, and precipitate crystals to obtain a sulfur-coordinated manganese halide complex. The preparation route is as follows: Wherein, X is Cl or Br.

4. The method for preparing the sulfur-coordinated manganese halide complex according to claim 3, characterized in that: The molar ratio of MnX2 to triphenyl sulfide is 1-4:2-8.

5. The method for preparing the sulfur-coordinated manganese halide complex according to claim 4, characterized in that: The organic solvent is ethanol, and the evaporation temperature is 60-80°C.

6. Use of the sulfur-coordinated manganese halide complex according to any one of claims 1 to 2 in X-ray detection and imaging.

7. Use of the sulfur-coordinated manganese halide complex according to any one of claims 1 to 2 in an OLED device, characterized in that: The sulfur-coordinated manganese halide complex is prepared into a thin film by vacuum evaporation, and the thin film is used as a light-emitting layer in an OLED device.

8. Use of the sulfur-coordinated manganese halide complex according to any one of claims 1 to 2 in solid lighting or optoelectronic display.

9. A scintillator film, characterized in that: It is prepared based on the sulfur-coordinated manganese halide complex described in any one of claims 1 to 2. The scintillator film does not emit light under sunlight, but emits green light under ultraviolet and X-ray irradiation.

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