Manganese-doped phantom nanocluster as well as preparation method and application thereof

Abstract

The invention provides a manganese-doped phantom nanocluster as well as a preparation method and application thereof, and belongs to the technical field of semiconductor luminescent materials. According to the invention, a manganese ion source, a selenium precursor, a zinc precursor and a reaction medium are used as raw materials to prepare the manganese-doped ZnSe phantom nanocluster. The fluorescence emission peak wavelength of the manganese-doped ZnSe phantom nanocluster disclosed by the invention is about 600nm, and the characteristic fluorescence emission has excellent stability on light, heat and chemistry. Compared with a traditional II-VI group cadmium semiconductor nanocrystal, the manganese-doped ZnSe magic number nanocluster not only has outstanding fluorescence characteristics, but also can solve the problems of light stability, toxicity of the cadmium semiconductor nanocrystal and the like to a certain extent, and has a good application prospect as a red light emitting material.

Description

Technical Field

[0001] The present invention belongs to the technical field of semiconductor light-emitting materials, and in particular relates to a manganese-doped magic number nanocluster and a preparation method and application thereof. Background Art

[0002] Semiconductor luminescent materials are the core components of modern optoelectronic devices and are widely used in devices such as light-emitting diodes (LEDs), lasers, and photodetectors. Semiconductor luminescent materials can be divided into red light-emitting materials, green light-emitting materials, blue light-emitting materials, and yellow light-emitting materials according to their luminescent colors and application fields. The optical properties and physicochemical characteristics of these materials make them important applications in display technology, lighting, and biomedicine. As an important part of nanomaterial scientific research, semiconductor nanocrystals are widely used in optoelectronics, nanoelectronics, photonics, quantum computers, and life sciences because of their excellent physical and chemical properties.

[0003] Among them, the emission range of red light emitting materials is usually at the long-wave end of visible light, approximately between 610-700 nanometers (nm). Red light emitting materials have important applications in display, lighting equipment, and biological imaging. Common red light emitting materials include rare earth europium complexes, metal porphyrin complexes, and metal ruthenium complexes.

[0004] Magic-Size Clusters (MSCs) are a class of semiconductor nanomaterials with a specific number of atoms and precise spatial structure. They are closely related to the formation path of colloidal semiconductor quantum dots (QDs) during the synthesis process, which is crucial for understanding and controlling the optical and electronic properties of semiconductor nanomaterials. The study of magic clusters helps to enrich and improve the classical and non-classical nucleation theory of semiconductor QDs, explore the structure-activity relationship of semiconductor nanomaterials, and promote the application research of semiconductor QDs. Magic clusters are regarded as precursors of colloidal semiconductor quantum dots. They are generated during the induction period before nucleation and can be converted into MSCs with characteristic optical absorption.

[0005] Manganese doping, as a unique means of regulating the physical and chemical properties of semiconductor nanocrystals, is to introduce a small amount of paramagnetic manganese ions (S=5 / 2) into the main semiconductor nanocrystals to generate a nanomaterial called "diluted magnetic semiconductor (DMS)".

[0006] The photoluminescence of manganese-doped ZnSe semiconductor nanocrystals originates from Mn 2+ The dd-orbit light-forbidden transition ( 4 T1- 6A1), the peak wavelength of fluorescence emission is at ~585nm, and it has a stronger characteristic fluorescence emission than the intrinsic ZnSe semiconductor nanocrystals. This characteristic fluorescence emission has good stability to light, heat and chemistry. Compared with traditional II-VI group cadmium semiconductor nanocrystals, manganese-doped ZnSe semiconductor nanocrystals not only have outstanding fluorescence properties, but also can solve the problems of photostability and toxicity of cadmium semiconductor nanocrystals to a certain extent. Transition metal ion manganese-doped zinc selenide semiconductor nanocrystals (Mn:ZnSeQDs) have attracted widespread attention from scientists due to their unique magnetic and optical properties.

[0007] Although there have been many studies on the synthesis and optical properties of manganese-doped ZnSe quantum dots, the existing manganese-doping methods have harsh conditions, high reaction temperatures, low fluorescence efficiency, and difficult preparation of anion precursors, which require strict control. Summary of the invention

[0008] In view of the problems existing in the prior art, the object of the present invention is to provide a manganese-doped magic number nanocluster and a preparation method and application thereof.

[0009] The invention provides a manganese-doped magic number nanocluster, which is obtained by reacting a manganese ion source, a selenium precursor and a zinc precursor as raw materials in a reaction medium, wherein the molar ratio of the manganese ion source, the selenium precursor and the zinc precursor is 1:50-70:10-30.

[0010] Furthermore, the molar ratio of the manganese ion source, the selenium precursor and the zinc precursor is 1:60:20.

[0011] Further, the manganese ion source is selected from manganese chloride tetrahydrate or manganese acetate tetrahydrate;

[0012] The selenium precursor is selected from selenium powder, selenourea or Se / CO-OLA precursor; the Se / CO-OLA precursor is obtained by mixing selenium powder and oleylamine in carbon monoxide;

[0013] The zinc precursor is selected from zinc acetate dihydrate or oleylamine zinc precursor; the oleylamine zinc precursor is obtained by mixing zinc acetate dihydrate and oleylamine;

[0014] The reaction medium is selected from one or a mixture of two or more of oleylamine, octylamine and dodecylamine.

[0015] Further, when the selenium precursor is selected from selenium powder, the magic nanocluster has a double absorption peak at 311-337nm and 337-360nm;

[0016] Or, when the selenium precursor is selected from selenourea, the magic nanocluster has a double absorption peak at 318-338nm and 338-360nm;

[0017] Or, when the selenium precursor is selected from Se / CO-OLA, the magic nanocluster has double absorption peaks at 313-338nm and 338-362nm.

[0018] Further, when the selenium precursor is selected from selenium powder and the zinc precursor is selected from zinc acetate, the magic nanocluster has a double absorption peak at 312-338nm and 338-358nm;

[0019] Or, when the selenium precursor is selected from selenium powder and the zinc precursor is selected from zinc oleylamine, the magic nanocluster has absorption double peaks at 311-337nm and 337-360nm;

[0020] Or, when the selenium precursor is selected from selenourea and the zinc precursor is selected from zinc oleylamine, the magic nanocluster has a double absorption peak at 318-338nm and 338-360nm;

[0021] Or, when the selenium precursor is selected from Se / CO-OLA and the zinc precursor is selected from zinc oleylamine, the magic nanocluster has double absorption peaks at 313-338nm and 338-362nm.

[0022] Further, when the selenium precursor is selected from selenium powder, the zinc precursor is selected from zinc acetate, and the reaction medium is selected from OLA, the absorption peaks of the magic clusters are at 312-338nm and 338-358nm;

[0023] Or, when the selenium precursor is selected from selenium powder, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA, the absorption peaks of the magic clusters are at 311-337nm, 337-360nm;

[0024] Or, when the selenium precursor is selected from selenourea, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA, the absorption peaks of the magic clusters are at 318-338nm, 338-355nm;

[0025] Or, when the selenium precursor is selected from selenourea, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA-OTA, the absorption peak of the magic cluster is 318-338nm, 338-355nm;

[0026] Or, when the selenium precursor is selected from selenourea, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA-DDA, the magic cluster absorption double peaks are at 320-338nm and 338-360nm;

[0027] Or, when the selenium precursor is selected from Se / CO-OLA, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA, the absorption peaks of the magic clusters are at 313-338nm and 338-362nm.

[0028] Further, when the doping ion source is selected from MnCl2, the selenium precursor is selected from selenium powder, the zinc precursor is selected from zinc acetate, and the reaction medium is selected from OLA, the magic nanocluster absorbs 312-338nm, 338-358nm, and the emission front is at 560-660nm;

[0029] Or, when the doping ion source is selected from Mn(OAc)2, the selenium precursor is selected from selenium powder, the zinc precursor is selected from zinc acetate, and the reaction medium is selected from OLA, the magic nanocluster has absorption peaks at 312-338nm, 338-357nm, and an emission peak at 570-650nm;

[0030] Or, when the doping ion source is selected from MnCl2, the selenium precursor is selected from selenium powder, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA, the magic nanocluster has absorption peaks at 311-337nm, 337-358nm, and an emission peak at 560-660nm;

[0031] Or, when the doping ion source is selected from Mn(OAc)2, the selenium precursor is selected from selenium powder, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA, the magic nanocluster has absorption peaks at 312-338nm, 338-358nm, and an emission peak at 570-640nm;

[0032] Or, when the doping ion source is selected from MnCl2, the selenium precursor is selected from selenourea, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA, the magic nanocluster has absorption peaks at 318-338nm, 338-355nm, and an emission peak at 550-670nm;

[0033] Or, when the doping ion source is selected from MnCl2, the selenium precursor is selected from selenourea, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA-OTA, the magic nanocluster has absorption double peaks at 318-338nm, 338-355nm, and an emission front at 560-650nm;

[0034] Or, when the doping ion source is selected from MnCl2, the selenium precursor is selected from selenourea, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA-DDA, the magic nanocluster has absorption double peaks at 320-338nm, 338-360nm, and an emission front at 550-670nm;

[0035] Or, when the doping ion source is selected from MnCl2, the selenium precursor is selected from Se / CO-OLA, the zinc precursor is selected from zinc acetate, and the reaction medium is selected from OLA, the magic nanocluster has absorption double peaks at 315-338nm, 338-362nm, and an emission front at 550-680nm;

[0036] Or, when the doping ion source is selected from MnCl2, the selenium precursor is selected from Se / CO-OLA, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA, the magic nanocluster has absorption double peaks at 315-338nm, 338-362nm, and an emission front at 550-680nm;

[0037] Or, when the doping ion source is selected from Mn(OAc)2, the selenium precursor is selected from Se / CO-OLA, the zinc precursor is selected from zinc acetate, and the reaction medium is selected from OLA, the magic nanocluster has absorption double peaks at 318-338nm, 338-360nm, and an emission front at 540-680nm.

[0038] Or, when the doping ion source is selected from Mn(OAc)2, the selenium precursor is selected from Se / CO-OLA, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA, the magic nanocluster has absorption double peaks at 313-338nm, 338-355nm, and an emission front at 570-640nm.

[0039] Further, when the doping ion source is selected from MnCl2, the selenium precursor is selected from selenium powder, the zinc precursor is selected from zinc acetate, and the reaction medium is selected from OLA, the magic nanocluster absorbs 327nm±1%, 345nm±1%, and the emission front is at 600nm±1%;

[0040] Or, when the doping ion source is selected from Mn(OAc)2, the selenium precursor is selected from selenium powder, the zinc precursor is selected from zinc acetate, and the reaction medium is selected from OLA, the magic nanocluster has absorption double peaks at 327nm±1%, 345nm±1%, and an emission front at 600nm±1%;

[0041] Or, when the doping ion source is selected from MnCl2, the selenium precursor is selected from selenium powder, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA, the magic nanocluster has absorption double peaks at 327nm±1%, 345nm±1%, and an emission front at 600nm±1%;

[0042] Or, when the doping ion source is selected from Mn(OAc)2, the selenium precursor is selected from selenium powder, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA, the magic nanocluster has absorption double peaks at 327nm±1%, 345nm±1%, and an emission front at 600nm±1%;

[0043] Or, when the doping ion source is selected from MnCl2, the selenium precursor is selected from selenourea, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA, the magic nanocluster has absorption double peaks at 327nm±1%, 345nm±1%, and an emission front at 600nm±1%;

[0044] Or, when the doping ion source is selected from MnCl2, the selenium precursor is selected from selenourea, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA-DDA, the magic nanocluster has absorption double peaks at 327nm±1%, 345nm±1%, and an emission front at 600nm±1%;

[0045] Or, when the doping ion source is selected from MnCl2, the selenium precursor is selected from Se / CO-OLA, the zinc precursor is selected from zinc acetate, and the reaction medium is selected from OLA, the magic nanocluster has absorption double peaks at 327nm±1%, 345nm±1%, and an emission front at 600nm±1%;

[0046] Or, when the doping ion source is selected from MnCl2, the selenium precursor is selected from Se / CO-OLA, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA, the magic nanocluster has absorption double peaks at 327nm±1%, 345nm±1%, and an emission front at 600nm±1%;

[0047] Or, when the doping ion source is selected from Mn(OAc)2, the selenium precursor is selected from Se / CO-OLA, the zinc precursor is selected from zinc acetate, and the reaction medium is selected from OLA, the magic nanocluster has absorption double peaks at 327nm±1%, 345nm±1%, and an emission front at 600nm±1%;

[0048] Or, when the doping ion source is selected from Mn(OAc)2, the selenium precursor is selected from Se / CO-OLA, the zinc precursor is selected from zinc oleylamine, and the reaction medium is selected from OLA, the magic nanocluster has absorption double peaks at 327nm±1%, 345nm±1%, and an emission front at 600nm±1%.

[0049] Furthermore, in the Se / CO-OLA precursor, the mass volume ratio of selenium powder and oleylamine is 1g:40-60ml;

[0050] In the oleylamine zinc precursor, the mass volume ratio of zinc acetate dihydrate to oleylamine is 1g:8-10ml.

[0051] Furthermore, the mass volume ratio of the selenium powder and oleylamine is 1g:50ml;

[0052] The mass volume ratio of the zinc acetate dihydrate and oleylamine is 1 g:9.5 ml.

[0053] Further, the manganese ion source is manganese chloride tetrahydrate;

[0054] The selenium precursor is selenium powder;

[0055] The zinc precursor is zinc acetate dihydrate;

[0056] The reaction medium is oleylamine.

[0057] The present invention also provides a method for preparing the above manganese-doped magic number nanoclusters, the method comprising the following steps: mixing a manganese ion source, a selenium precursor, a zinc precursor and a reaction medium to obtain.

[0058] Furthermore, the reaction conditions are: reacting at 110-130° C. for 0.5-3 hours under vacuum conditions with nitrogen protection.

[0059] Furthermore, the reaction conditions are: reacting at 120°C for 1 to 2 hours under nitrogen protection vacuum conditions.

[0060] The present invention also provides the use of the above manganese-doped magic number nanoclusters in preparing semiconductor light-emitting materials; the semiconductor light-emitting material is preferably a red light-emitting material.

[0061] The present invention uses a manganese ion source, a selenium precursor, a zinc precursor and a reaction medium as raw materials to prepare a manganese-doped ZnSe magic number nanocluster. The peak wavelength of the fluorescence emission of the manganese-doped ZnSe magic number nanocluster of the present invention is at 600nm, and the characteristic fluorescence emission has good stability to light, heat and chemistry. Compared with traditional II-VI group cadmium semiconductor nanocrystals, the manganese-doped ZnSe magic number nanocluster can not only have outstanding fluorescence characteristics, but also can solve the problems of photostability and toxicity of cadmium semiconductor nanocrystals to a certain extent, and has a good application prospect as a red light emitting material.

[0062] The invention prepares ZnSe magic number nanoclusters with absorption peaks at 327nm±1%, 345nm±1% and emission peaks at 600nm, which can effectively expand the application of magic number clusters and can also solve the problems of photostability and toxicity of cadmium-based semiconductor nanocrystals to a certain extent, and has good application prospects as red light emitting materials.

[0063] Obviously, according to the above contents of the present invention, in accordance with common technical knowledge and customary means in the art, without departing from the above basic technical ideas of the present invention, other various forms of modification, replacement or change may be made.

[0064] The above contents of the present invention are further described in detail below through specific implementation methods in the form of examples. However, this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples. All technologies realized based on the above contents of the present invention belong to the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 TEM characterization of the magic number-doped nanoclusters prepared in Example 9.

[0066] Figure 2 The absorption spectra, emission spectra and fluorescence excitation spectra of Examples 1 and 2 at different reaction temperatures are shown.

[0067] Figure 3 The absorption spectra, emission spectra and fluorescence excitation spectra of Examples 3 and 4 at different reaction temperatures are shown.

[0068] Figure 4 The absorption spectra and emission spectra of Examples 5, 6 and 7 at different reaction temperatures are shown.

[0069] Figure 5 The absorption spectra and emission spectra of Examples 3, 5 and 7 at different reaction times are shown.

[0070] Figure 6 The absorption spectra, emission spectra and fluorescence excitation spectra of Examples 8 and 9 at different reaction temperatures are shown.

[0071] Figure 7 The absorption spectra, emission spectra and fluorescence excitation spectra of Example 10 and Example 11 at different reaction temperatures are shown.

[0072] Figure 8 The absorption spectra, emission spectra and fluorescence excitation spectra of Examples 9 and 11 at different reaction times are shown. DETAILED DESCRIPTION

[0073] The raw materials and equipment used in the present invention are all known products, which are obtained by purchasing commercially available products.

[0074] The "room temperature" referred to in the present invention is 25°C.

[0075] Example 1

[0076] Composition: Manganese chloride tetrahydrate (MnCl2·4H2O) is used as a manganese ion source, selenium powder is used as a selenium precursor, zinc acetate dihydrate (Zn(OAc)2·2H2O) is used as a zinc precursor, and oleylamine (OLA) is used as a reaction medium.

[0077] 1. Preparation of manganese-doped magic number nanoclusters

[0078] The method for preparing manganese-doped magic number nanoclusters comprises the following steps:

[0079] (1) Manganese chloride tetrahydrate (0.009 g, 0.044 mmol), zinc acetate dihydrate (0.193 g, 0.88 mmol), selenium powder (0.208 g, 2.64 mmol) and oleylamine (10 ml) were placed in a three-necked flask;

[0080] (2) Evacuate at room temperature and perform vacuum / nitrogen ventilation three times (completed within 30 min);

[0081] (3) Under nitrogen protection, the temperature was raised to 120 °C and the reaction was carried out under vacuum conditions for 1 h to obtain manganese-doped magic number nanoclusters.

[0082] 2. Testing the fluorescence spectrum of manganese-doped magic nanoclusters under elevated temperature conditions

[0083] Under nitrogen protection, the temperature was raised by 20°C at regular intervals. The reaction temperatures were selected at 120, 140, 160, 180, and 200°C. After reacting for 15 minutes at each temperature, 10 ul of the sample was dispersed in 3 mL ToL for testing.

[0084] At 180℃, the absorption curve is as follows Figure 2 As shown in a1, the absorption double peaks are at 312-338nm and 338-358nm, and the fluorescence spectrum is shown in the curve. Figure 2 As shown in a2, the emission range is 560-660nm. The specific absorption / fluorescence peak positions are shown in Table 1:

[0085] Table 1 shows the variation of ZnSe magic number nanoclusters synthesized in Example 1 with reaction temperature

[0086]

[0087] Example 2

[0088] Composition: Manganese acetate tetrahydrate (Mn(OAc)2·4H2O) is used as a manganese ion source, selenium powder is used as a selenium precursor, zinc acetate dihydrate is used as a zinc precursor, and oleylamine is used as a reaction medium.

[0089] 1. Preparation of manganese-doped magic number nanoclusters

[0090] The method for preparing manganese-doped magic number nanoclusters comprises the following steps:

[0091] Referring to the method of Example 1, the only difference is that the manganese chloride tetrahydrate in Example 1 is replaced with manganese acetate tetrahydrate, so as to obtain manganese-doped magic number nanoclusters.

[0092] 2. Testing the fluorescence spectrum of manganese-doped magic nanoclusters under elevated temperature reaction

[0093] Refer to the method of Example 1.

[0094] At 180℃, the absorption curve is as follows Figure 2 As shown in b1, the absorption double peaks are at 312-338nm and 338-357nm, and the fluorescence spectrum is shown in the curve. Figure 2 As shown in b2, the emission range is 560-650nm.

[0095] The specific absorption / fluorescence peak positions are shown in Table 2:

[0096] Table 2 shows the variation of ZnSe magic number nanoclusters synthesized in Example 2 with reaction temperature

[0097]

[0098]

[0099] Example 3

[0100] Composition: Manganese chloride tetrahydrate is used as a manganese ion source, selenium powder is used as a selenium precursor, zinc oleylamine (Zn(OAc)2 / OLA) is used as a zinc precursor, and oleylamine is used as a reaction medium.

[0101] 1. Preparation of manganese-doped magic number nanoclusters

[0102] The method for preparing manganese-doped magic number nanoclusters comprises the following steps:

[0103] 1.1 Preparation of oleylamine zinc precursor

[0104] (1) Zinc acetate dihydrate (1.5834 g, 8.63 mmol) and oleylamine (15 ml) were placed in a three-necked flask;

[0105] (2) Evacuate at room temperature and perform vacuum / nitrogen ventilation three times (completed within 30 min);

[0106] (3) Under nitrogen protection, the temperature was raised to 120°C and the reaction was carried out under vacuum for 2 h;

[0107] (4) Cooling to room temperature and collecting the resulting product is zinc oleylamine precursor (Zn(OAc)2 / OLA).

[0108] 1.2 Preparation of Mn-doped Magic Nanoclusters

[0109] (1) Manganese chloride tetrahydrate (0.009 g, 0.044 mmol), oleylamine zinc precursor (1.54 ml, 0.88 mmol), selenium powder (0.208 g, 2.64 mmol) and oleylamine (10 ml) were placed in a three-necked flask;

[0110] (2) Evacuate at room temperature and perform vacuum / nitrogen ventilation three times (completed within 30 min);

[0111] (3) Under nitrogen protection, the temperature is raised to 120°C and the reaction is carried out under vacuum for 1 h to obtain the product.

[0112] 2. Testing the fluorescence spectrum of manganese-doped magic nanoclusters under elevated temperature reaction

[0113] Refer to the operation of Example 1.

[0114] At 180℃, the absorption curve is as follows Figure 3As shown in a1, the absorption double peaks are at 312-337nm and 337-352nm, and the fluorescence spectrum is shown in the curve. Figure 3 As shown in a2, the emission range is 560-650nm.

[0115] The specific absorption / fluorescence peak positions are shown in Table 3:

[0116] Table 3 shows the variation of ZnSe magic number nanoclusters synthesized in Example 3 with reaction temperature

[0117]

[0118] 3. Testing the fluorescence spectrum of manganese-doped magic nanoclusters under constant temperature reaction

[0119] Under nitrogen protection, the temperature was directly raised to 170°C, and the reaction times were selected as 15, 30, 60, 90, 120, and 150 min. At each reaction time, 10 ul of sample was dispersed into 3 mL ToL for testing.

[0120] Its absorption curve is Figure 5 As shown in a1, the absorption double peaks are at 310-338nm and 338-352nm, and the fluorescence spectrum is shown in the curve. Figure 5 As shown in a2, the emission range is 550-660nm.

[0121] The specific absorption / fluorescence peak positions are shown in Table 4:

[0122] Table 4 shows the change of ZnSe magic number nanoclusters synthesized in Example 3 with reaction time

[0123]

[0124] Example 4

[0125] Composition: Manganese acetate tetrahydrate is used as a manganese ion source, selenium powder is used as a selenium precursor, zinc oleylamine (Zn(OAc)2 / OLA) is used as a zinc precursor, and oleylamine is used as a reaction medium.

[0126] 1. Preparation of manganese-doped magic number nanoclusters

[0127] The method for preparing manganese-doped magic number nanoclusters comprises the following steps:

[0128] 1.1 The preparation of oleylamine zinc precursor is as described in Example 3.

[0129] 1.2 The preparation of manganese-doped magic number nanoclusters is as described in Example 2.

[0130] 2. The fluorescence spectrum of manganese-doped magic nanoclusters was tested under elevated temperature reaction as described in Example 1.

[0131] At 180℃, the absorption curve is as follows Figure 3 As shown in b1, the absorption double peaks are at 312-337nm and 337-352nm, and the fluorescence spectrum is shown in the curve. Figure 3 As shown in b2, the emission range is 565-650nm;

[0132] The specific absorption / fluorescence peak positions are shown in Table 5:

[0133] Table 5 shows the variation of ZnSe magic number nanoclusters synthesized in Example 4 with reaction temperature

[0134]

[0135] The comparison results of the luminescence characteristics of the samples of Examples 1-4 are as follows:

[0136] (1) Temperature-controlled Mn:ZnSe magic number nanoclusters and their luminescence properties

[0137] Figure 2 It is the Mn:ZnSe magic number nanoclusters prepared in Examples 1 and 2. Figure 3 It is the Mn:ZnSe magic number nanoclusters prepared in Examples 3 and 4. Figure 2 a1, a2, b1, b2 are Mn:ZnSe magic number nanoclusters prepared using manganese chloride tetrahydrate and manganese acetate tetrahydrate as manganese ion sources, zinc acetate dihydrate as cation precursor, selenium powder as anion precursor, and oleylamine as reaction medium. Figure 3 a1, a2, b1, b2 are Mn:ZnSe magic number nanoclusters prepared with manganese chloride tetrahydrate as manganese ion source, zinc acetate dihydrate and zinc oleylamine as cation precursors, selenium powder as anion precursors, and oleylamine as reaction medium. As the reaction temperature increases, different doping ion sources and zinc precursors do not affect the growth law of Mn:ZnSe dMSC-345, which appears at 160°C and disappears at 200°C. The characteristic fluorescence emission peak of the doped manganese ion center appears at 180°C, and the fluorescence disappears with the disappearance of Mn:ZnSe dMSC-345.

[0138] (2) Mn:ZnSe magic number nanoclusters controlled by manganese ion sources and their luminescence properties

[0139] Figure 2 and Figure 3 c1 and c2 in the figure are the UV-visible absorption (UV-vis), fluorescence emission (PL) and fluorescence excitation (PLE) spectra of the samples at 180℃ / 15min under two manganese ion sources. Figure 2 Among c1 and c2, Figure 3In c1 and c2, it can be observed that the doping effect of using MnCl2·4H2O as the doping ion source is significantly better than that of using Mn(OAc)2·4H2O as the doping ion source.

[0140] (3) Zinc precursor-controlled Mn:ZnSe magic number nanoclusters and their luminescence properties

[0141] contrast Figure 2 C1 and Figure 3 Middle c2, Figure 2 C2 and Figure 3 In c2, it can be observed that Zn(OAc)2(OLA) x The doping effect as a zinc ion source is significantly better than that of Zn(OAc)2 as a zinc source.

[0142] In addition, the emission peak half-width is 50nm, and there is no defect-state luminescence.

[0143] The above results show that the selection of MnCl2·4H2O as the manganese ion source and Zn(OAc)2(OLA) x The doping effect as a zinc ion source is even better.

[0144] Example 5

[0145] Composition: Manganese chloride tetrahydrate (MnCl2·4H2O) is used as a manganese ion source, selenourea is used as a selenium precursor, zinc oleylamine (Zn(OAc)2 / OLA) is used as a zinc precursor, and oleylamine is used as a reaction medium.

[0146] 1. Preparation of manganese-doped magic number nanoclusters

[0147] The method for preparing manganese-doped magic number nanoclusters comprises the following steps:

[0148] 1.1 The oleylamine zinc precursor is as described in Example 3.

[0149] 1.2 Preparation of Mn-doped magic number nanoclusters

[0150] (1) Manganese chloride tetrahydrate (0.002 g, 0.01 mmol), oleylamine zinc precursor (350 ul, 0.2 mmol) and oleylamine (6 ml) were placed in a three-necked flask;

[0151] (2) Evacuate at room temperature and perform vacuum / nitrogen ventilation three times (completed within 30 min);

[0152] (3) Under nitrogen protection, the temperature was raised to 120°C and the reaction was carried out under vacuum for 1 hour;

[0153] (4) Add selenourea (0.049 g, 0.4 mmol) under nitrogen protection;

[0154] 2. Testing the fluorescence spectrum of manganese-doped magic nanoclusters under elevated temperature reaction

[0155] Under nitrogen protection, the temperature was raised by 20°C at regular intervals. The reaction temperatures were selected as 80 / 100, 120, 140, 160, 180, 200, 220, and 240°C. After reacting for 15 min at each temperature, 10 ul of the sample was dispersed in 3 mL of cyclohexane (CH) for testing.

[0156] At 180℃, the absorption curve is as follows Figure 4 As shown in a1, the absorption double peaks are at 312-338nm and 338-358nm, and the fluorescence spectrum is shown in the curve. Figure 4 As shown in a2, the emission range is 540-660nm.

[0157] The specific absorption / fluorescence peak positions are shown in Table 6:

[0158] Table 6 shows the variation of ZnSe magic number nanoclusters synthesized in Example 5 with reaction temperature

[0159]

[0160]

[0161] 3. Testing the fluorescence spectrum of manganese-doped magic nanoclusters under constant temperature reaction

[0162] Under nitrogen protection, the temperature was directly raised to 170°C, and the reaction times were selected as 15, 30, 60, and 90 min. At each reaction time, 10 ul of sample was dispersed in 3 mL of cyclohexane (CH) for testing.

[0163] Its absorption curve is Figure 5 As shown in b1, the absorption peak is at 333-360nm, and the fluorescence spectrum is as shown in the curve Figure 5 As shown in b2, the emission range is 545-660nm.

[0164] The specific absorption / fluorescence peak positions are shown in Table 7:

[0165] Table 7 shows the variation of ZnSe magic number nanoclusters synthesized in Example 5 with reaction time

[0166]

[0167] Example 6

[0168] Composition: Manganese chloride tetrahydrate (MnCl2·4H2O) is used as a manganese ion source, selenourea is used as a selenium precursor, zinc oleylamine (Zn(OAc)2 / OLA) is used as a zinc precursor, and a mixture of oleylamine and octylamine (OTA) (OLA-OTA) is used as a reaction medium.

[0169] 1. Preparation of manganese-doped magic number nanoclusters

[0170] The method for preparing manganese-doped magic number nanoclusters comprises the following steps:

[0171] 1.1 The oleylamine zinc precursor is as described in Example 3.

[0172] 1.2 Preparation of Mn-doped magic number nanoclusters

[0173] The reaction medium in Example 5 was replaced with a mixture of oleylamine (4 ml) and octylamine (2 ml).

[0174] 2. Testing the fluorescence spectrum of manganese-doped magic nanoclusters under elevated temperature reaction

[0175] As described in Example 5, after 15 min of reaction at each temperature, 5 μl of sample was dispersed in 3 mL of cyclohexane (CH) for testing.

[0176] At 180℃, the absorption curve is as follows Figure 4 As shown in b1, the absorption double peaks are at 318-338nm and 338-355nm, and the fluorescence spectrum is shown in the curve. Figure 4 As shown in b2, the emission range is 560-650nm.

[0177] The specific absorption / fluorescence peak positions are shown in Table 8:

[0178] Table 8 shows the variation of ZnSe magic number nanoclusters synthesized in Example 6 with reaction temperature

[0179]

[0180]

[0181] Example 7

[0182] Composition: Manganese chloride tetrahydrate (MnCl2·4H2O) is used as a manganese ion source, selenourea is used as a selenium precursor, zinc oleylamine (Zn(OAc)2 / OLA) is used as a zinc precursor, and a mixture of oleylamine and dodecylamine (DDA) (OLA-DDA) is used as a reaction medium.

[0183] 1. Preparation of manganese-doped magic number nanoclusters

[0184] The method for preparing manganese-doped magic number nanoclusters comprises the following steps:

[0185] 1.1 The oleylamine zinc precursor is as described in Example 3.

[0186] 1.2 Preparation of Mn-doped magic number nanoclusters

[0187] The reaction medium in Example 5 was replaced with a mixture of oleylamine (4 ml) and dodecylamine (2 ml).

[0188] 2. Testing the fluorescence spectrum of manganese-doped magic nanoclusters under elevated temperature reaction

[0189] As described in Example 5, after reacting at each temperature for 15 min, 15 μl of sample was dispersed in 3 mL of cyclohexane (CH) for testing.

[0190] At 180℃, the absorption curve is as follows Figure 4 As shown in c1, the absorption double peaks are at 320-338nm and 338-360nm, and the fluorescence spectrum is as shown in the curve Figure 4 As shown in c2, the emission range is 550-670nm.

[0191] The specific absorption / fluorescence peak positions are shown in Table 9:

[0192] Table 9 shows the variation of ZnSe magic number nanoclusters synthesized in Example 7 with reaction temperature

[0193]

[0194] 3. Testing the fluorescence spectrum of manganese-doped magic nanoclusters under constant temperature reaction

[0195] Under nitrogen protection, the temperature was directly raised to 170°C, and the reaction times were selected as 15, 30, 60, 90, 120, 150, 180, and 210 min. At each reaction time, 15 ul of sample was dispersed in 3 mL of cyclohexane (CH) for testing.

[0196] Its absorption curve is Figure 5 As shown in c1, the absorption double peaks are at 320-336nm and 336-350nm, and the fluorescence spectrum is as shown in the curve Figure 5 As shown in c2, the emission range is 545-665nm.

[0197] The specific absorption / fluorescence peak positions are shown in Table 10:

[0198] Table 10 shows the variation of ZnSe magic number nanoclusters synthesized in Example 7 with reaction time

[0199]

[0200] The results of comparing the luminescence characteristics of samples in Examples 5-7 are as follows:

[0201] 1. Temperature-controlled Mn:ZnSe magic number nanoclusters and their luminescence properties

[0202] Figure 4 It is the Mn:ZnSe magic number nanoclusters prepared in Examples 5, 6, and 7. Figure 4 a1, a2, b1, b2, c1, c2 are Mn:ZnSe magic number nanoclusters prepared by using manganese chloride tetrahydrate as manganese ion source, oleylamine zinc as cation precursor, selenourea as anion precursor, oleylamine or oleylamine-octylamine mixed amine or oleylamine-dodecylamine as reaction medium. As the reaction temperature increases, different reaction media do not affect the growth law of Mn:ZnSe dMSC-345, which appears at 160℃ and disappears at 220℃, and begins to appear fluorescence at 180℃. As Mn:ZnSe dMSC-345 disappears, the fluorescence also disappears.

[0203] 2. Reaction medium-controlled Mn:ZnSe magic number nanoclusters and their luminescence properties

[0204] contrast Figure 4 It can be observed from the figures that MSC-315 can be observed at 140°C when pure oleylamine is used as the reaction medium, and the fluorescence reaches the highest at 220°C; MSC-315 cannot be observed when oleylamine-octylamine or oleylamine-dodecylamine mixed solvent is used as the reaction medium, and the fluorescence reaches the highest at 200°C, and the fluorescence of mixed dodecylamine is significantly stronger than that of mixed octylamine. Using oleylamine-dodecylamine mixed amine as the reaction medium can obtain samples with stronger fluorescence at relatively lower temperatures.

[0205] The above results show that using oleylamine-dodecylamine mixed amine as the reaction medium can obtain samples with stronger fluorescence at a relatively lower temperature.

[0206] The results of comparing the luminescence characteristics of the samples in Example 3, Example 5, and Example 7 are as follows:

[0207] (1) Time-controlled Mn:ZnSe magic number nanoclusters and their luminescence properties

[0208] Figure 5 The Mn:ZnSe magic number nanoclusters prepared in Example 3, Example 5, and Example 7. Figure 5 a1, a2, b1, b2, c1, c2 are Mn:ZnSe magic number nanoclusters prepared by using manganese chloride tetrahydrate as manganese ion source, zinc oleylamine as cation precursor, selenium powder or selenourea as anion precursor, and oleylamine or oleylamine-dodecylamine as reaction medium. With the increase of reaction time, only one type of MSCs, dMSC-345, is generated. With the extension of constant temperature reaction time, the number of dMSC-345 in the system remains almost unchanged, and the fluorescence gradually increases to a peak value and then begins to weaken.

[0209] (2) Mn:ZnSe magic number nanoclusters controlled by selenium precursors and reaction media and their luminescence properties

[0210] Comparing Figures a1, a2, and a3, it can be observed that different precursors only generate MSC-345 at 170°C. When selenium powder is used as a selenium precursor and oleylamine is used as a reaction medium or selenourea is used as a selenium precursor and oleylamine-dodecylamine mixed amine is used as a reaction medium, a bimodal dMSC-345 is generated, while when selenourea is used as a selenium precursor and oleylamine is used as a reaction medium, a single-peak MSC-345 is generated. Comparing b1, b2, and b3, it can be observed that when selenourea is used as a selenium precursor and oleylamine is used as a reaction medium, its fluorescence is significantly weaker than the other two cases. When selenium powder is used as a selenium precursor and oleylamine is used as a reaction medium, the fluorescence reaches a maximum value at 90 minutes. When selenourea is used as a selenium precursor and oleylamine is used as a reaction medium, the fluorescence reaches a maximum value at 180 minutes, and its intensity is significantly stronger than the former.

[0211] The above results show that with the increase of reaction time, only dMSC-345 is generated and with the extension of constant temperature reaction time, the amount of dMSC-345 in the system remains almost unchanged, and the fluorescence gradually increases to a peak value and then begins to weaken. In addition, when selenium powder is used as a selenium precursor and oleylamine is used as a reaction medium, the fluorescence reaches a maximum value at 90 minutes, and when selenourea is used as a selenium precursor and oleylamine-dodecylamine mixed amine is used as a reaction medium, the fluorescence reaches a maximum value at 180 minutes, and its intensity is significantly stronger than the former.

[0212] Example 8

[0213] Composition: Manganese chloride tetrahydrate (MnCl2·4H2O) is used as a manganese ion source, Se / CO-OLA is used as a selenium precursor, zinc acetate dihydrate is used as a zinc precursor, and oleylamine is used as a reaction medium.

[0214] 1. Preparation of manganese-doped magic number nanoclusters

[0215] The method for preparing manganese-doped magic number nanoclusters comprises the following steps:

[0216] 1.1 Preparation of Se / CO-OLA Selenium Precursor

[0217] (1) Selenium powder (0.2097 g, 2.64 mmol) and oleylamine (10 ml) were placed in a three-necked flask;

[0218] (2) Add carbon monoxide (CO) at room temperature until the reaction suspension turns into a white suspension (completed within 60 min);

[0219] (3) The product is sealed and stored, and the obtained product is Se / CO-OLA precursor.

[0220] 1.2 Preparation of Mn-doped magic number nanoclusters

[0221] (1) Manganese chloride tetrahydrate (0.025 g, 0.02 mmol), zinc acetate dihydrate (0.073 g, 0.4 mmol) and oleylamine (5 ml) were placed in a three-necked flask;

[0222] (2) Evacuate at room temperature and perform vacuum / nitrogen ventilation three times (completed within 30 min);

[0223] (3) Under nitrogen protection, the temperature was raised to 120°C and the reaction was carried out under vacuum for 1 h;

[0224] (4) Add Se / CO-OLA precursor (1.2 mmol) under nitrogen protection;

[0225] 2. Testing the fluorescence spectrum of manganese-doped magic nanoclusters under elevated temperature reaction

[0226] Under nitrogen protection, the temperature was raised by 20°C at regular intervals. The reaction temperatures were selected at 120, 140, 160, 180, and 200°C. After reacting for 15 minutes at each temperature, 10 ul of the sample was dispersed in 3 mL ToL for testing.

[0227] At 180℃, the absorption curve is as follows Figure 6 As shown in a1, the absorption double peaks are at 320-338nm and 338-360nm, and the fluorescence spectrum is as shown in the curve Figure 6 As shown in a2, the emission range is 550-670nm.

[0228] The specific absorption / fluorescence peak positions are shown in Table 11:

[0229] Table 11 shows the variation of ZnSe magic number nanoclusters synthesized in Example 8 with reaction temperature

[0230]

[0231]

[0232] Example 9

[0233] Composition: Manganese chloride tetrahydrate (MnCl2·4H2O) is used as a manganese ion source, Se / CO-OLA is used as a selenium precursor, zinc oleylamine (Zn(OAc)2 / OLA) is used as a zinc precursor, and oleylamine is used as a reaction medium.

[0234] 1. Preparation of manganese-doped magic number nanoclusters

[0235] The method for preparing manganese-doped magic number nanoclusters comprises the following steps:

[0236] 1.1 The oleylamine zinc precursor is as described in Example 3.

[0237] 1.2 The Se / CO-OLA selenium precursor is as described in Example 8.

[0238] 1.3 Preparation of Mn-doped magic number nanoclusters

[0239] The zinc precursor in Example 8 was replaced with zinc oleylamine.

[0240] 2. Testing the fluorescence spectrum of manganese-doped magic nanoclusters under elevated temperature reaction is as described in Example 8.

[0241] At 180℃, the absorption curve is as follows Figure 6 As shown in b1, the absorption double peaks are at 315-338nm and 338-355nm, and the fluorescence spectrum is shown in the curve. Figure 6 As shown in b2, the emission range is 550-670nm.

[0242] The specific absorption / fluorescence peak positions are shown in Table 12:

[0243] Table 12 shows the variation of ZnSe magic number nanoclusters synthesized in Example 9 with reaction temperature

[0244]

[0245] 3. Testing the fluorescence spectrum of manganese-doped magic nanoclusters under constant temperature reaction

[0246] Under nitrogen protection, the temperature was directly raised to 160°C, and the reaction times were selected as 15, 30, 60, 90, 120, and 150 min. At each reaction time, 10 ul of sample was dispersed in 3 mL of cyclohexane (CH) for testing.

[0247] Its absorption curve is Figure 8 As shown in a1, the absorption double peaks are at 320-338nm and 338-358nm, and the fluorescence spectrum is shown in the curve. Figure 8 As shown in a2, the emission range is 550-670nm.

[0248] The specific absorption / fluorescence peak positions are shown in Table 13:

[0249] Table 13 shows the variation of ZnSe magic number nanoclusters synthesized in Example 9 with reaction time

[0250]

[0251]

[0252] Figure 1 This is a TEM image of the Mn:ZnSe magic number nanoclusters prepared by constant temperature reaction for 60 min in Example 9, showing a 1D structured nanowire with a diameter of ∼1.40 nm.

[0253] Example 10

[0254] Composition: Manganese acetate tetrahydrate is used as a manganese ion source, Se / CO-OLA is used as a selenium precursor, zinc acetate dihydrate is used as a zinc precursor, and oleylamine is used as a reaction medium.

[0255] 1. Preparation of manganese-doped magic number nanoclusters

[0256] The method for preparing manganese-doped magic number nanoclusters comprises the following steps:

[0257] 1.1 The Se / CO-OLA selenium precursor is as described in Example 8.

[0258] 1.2 Preparation of Mn-doped magic number nanoclusters

[0259] The manganese ion source in Example 8 was replaced with manganese acetate tetrahydrate.

[0260] 2. Testing the fluorescence spectrum of manganese-doped magic nanoclusters under elevated temperature reaction is as described in Example 8.

[0261] At 180℃, the absorption curve is as follows Figure 7 As shown in a1, the absorption double peaks are at 316-338nm and 338-358nm, and the fluorescence spectrum is shown in the curve. Figure 7 As shown in a2, the emission range is 550-680nm.

[0262] The specific absorption / fluorescence peak positions are shown in Table 14:

[0263] Table 14 shows the variation of ZnSe magic number nanoclusters synthesized in Example 10 with reaction temperature

[0264]

[0265] Embodiment 11

[0266] Composition: Manganese acetate tetrahydrate is used as a manganese ion source, Se / CO-OLA is a selenium precursor, zinc oleylamine (Zn(OAc)2 / OLA) is a zinc precursor, and oleylamine is a reaction medium.

[0267] 1. Preparation of manganese-doped magic number nanoclusters

[0268] The method for preparing manganese-doped magic number nanoclusters comprises the following steps:

[0269] 1.1 The oleylamine zinc precursor is as described in Example 3.

[0270] 1.2 The Se / CO-OLA selenium precursor is as described in Example 8.

[0271] 1.3 Preparation of Mn-doped magic number nanoclusters

[0272] The zinc precursor in Example 10 was replaced with zinc oleylamine.

[0273] 2. Testing the fluorescence spectrum of manganese-doped magic nanoclusters under elevated temperature reaction is as described in Example 9.

[0274] At 180℃, the absorption curve is as follows Figure 7 As shown in b1, the absorption double peaks are at 318-336nm and 336-355nm, and the fluorescence spectrum is shown in the curve. Figure 7 As shown in b2, the emission range is 550-670nm.

[0275] The specific absorption / fluorescence peak positions are shown in Table 15:

[0276] Table 15 shows the variation of ZnSe magic number nanoclusters synthesized in Example 11 with reaction temperature

[0277]

[0278] 3. The fluorescence spectrum of manganese-doped magic nanoclusters was tested under constant temperature reaction as described in Example 9.

[0279] Its absorption curve is Figure 8 As shown in b1, the absorption double peaks are at 316-337nm and 337-360nm, and the fluorescence spectrum is shown in the curve. Figure 8 As shown in b2, the emission range is 540-680nm; the specific absorption / fluorescence peak positions are shown in Table 16:

[0280] Table 16 shows the variation of ZnSe magic number nanoclusters synthesized in Example 11 with reaction time

[0281]

[0282] The above results show that when manganese chloride tetrahydrate is used as the manganese ion source, zinc oleylamine is used as the zinc precursor, selenourea is used as the selenium precursor, and oleylamine-dodecylamine is used as the reaction medium, Mn:ZnSe magic number nanoclusters with good luminescence efficiency can be obtained. The absorption peaks of the ZnSe magic number nanoclusters are located at 327nm±1%, 345nm±1%, and the emission peak is located at 600nm.

[0283] In summary, the present invention provides a manganese-doped magic number nanocluster and its preparation method and application. The present invention uses a manganese ion source, a selenium precursor, a zinc precursor and a reaction medium as raw materials to prepare a manganese-doped ZnSe magic number nanocluster. The peak wavelength of the fluorescence emission of the manganese-doped ZnSe magic number nanocluster of the present invention is at ~600nm, and the characteristic fluorescence emission has good stability to light, heat and chemistry. Compared with traditional II-VI group cadmium-based semiconductor nanocrystals, manganese-doped ZnSe magic number nanocluster can not only have outstanding fluorescence properties, but also can solve the problems of photostability and toxicity of cadmium-based semiconductor nanocrystals to a certain extent, and has a good application prospect as a red light emitting material.

Claims

1. A manganese-doped magic number nanocluster, characterized in that: The invention is obtained by reacting a manganese ion source, a selenium precursor and a zinc precursor as raw materials in a reaction medium, wherein the molar ratio of the manganese ion source, the selenium precursor and the zinc precursor is 1:50-70:10-30.

2. The manganese-doped magic number nanocluster according to claim 1, characterized in that The molar ratio of the manganese ion source, the selenium precursor and the zinc precursor is 1:60:

20.

3. The manganese-doped magic number nanocluster according to claim 1 or 2, characterized in that: The manganese ion source is selected from manganese chloride tetrahydrate or manganese acetate tetrahydrate; The selenium precursor is selected from selenium powder, selenourea or Se / CO-OLA precursor; the Se / CO-OLA precursor is obtained by mixing selenium powder and oleylamine in carbon monoxide; The zinc precursor is selected from zinc acetate dihydrate or oleylamine zinc precursor; the oleylamine zinc precursor is obtained by mixing zinc acetate dihydrate and oleylamine; The reaction medium is selected from one or a mixture of two or more of oleylamine, octylamine and dodecylamine.

4. The manganese-doped magic number nanoclusters according to claim 3, characterized in that: In the Se / CO-OLA precursor, the mass volume ratio of selenium powder and oleylamine is 1g:40-60ml; In the oleylamine zinc precursor, the mass volume ratio of zinc acetate dihydrate to oleylamine is 1g:8-10ml.

5. The manganese-doped magic number nanocluster according to claim 4, characterized in that The mass volume ratio of the selenium powder and oleylamine is 1g:50ml; The mass volume ratio of the zinc acetate dihydrate and oleylamine is 1 g:9.5 ml.

6. The manganese-doped magic number nanoclusters according to claim 3, characterized in that: The manganese ion source is manganese chloride tetrahydrate; The selenium precursor is selenium powder; The zinc precursor is zinc acetate dihydrate; The reaction medium is oleylamine.

7. A method for preparing the manganese-doped magic number nanoclusters according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: mixing a manganese ion source, a selenium precursor, a zinc precursor and a reaction medium for reaction to obtain the product.

8. The method according to claim 7, characterized in that The reaction conditions are: reacting at 110-130° C. for 0.5-3 hours under vacuum conditions with nitrogen protection.

9. The method according to claim 8, characterized in that The reaction conditions are: reacting at 120° C. for 1 to 2 hours under vacuum conditions with nitrogen protection.

10. Use of the manganese-doped magic number nanoclusters according to any one of claims 1 to 6 in preparing semiconductor light-emitting materials; the semiconductor light-emitting material is preferably a red light-emitting material.

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