CN111944516A - High-color-purity red light up-conversion nanoparticle material and preparation method thereof - Google Patents
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Abstract
The invention discloses a high-color-purity red light up-conversion nanoparticle material and a preparation method thereof, belonging to the technical field of luminescent materials. The high-color-purity red light up-conversion nano particle material has a chemical formula of LiErF4:Tm3+@LiYF4，LiErF4:Tm3+@LiYF4Is prepared from LiErF4:Tm3+Being a nucleus, LiYF4Core-shell structure being a shell, LiErF4:Tm3+Tm in nanoparticles3+Has a doping molar weight of Er3+And Tm3+The total molar amount of the component (a) is 0.5-20%.The invention dopes Tm in the red light up-conversion nano-particles3+To reduce the loss of energy migration inside the nanoparticle by adjusting Tm3+To adjust the red up-conversion intensity and by means of LiErF4:Tm3+Synthesizing inert shell LiYF on the surface of nano-particle4The core-shell structure is formed to reduce surface defects and achieve the purpose of up-conversion nanoparticle high-color purity red light emission.
Description
Technical Field
The invention relates to a high-color-purity red light up-conversion nano-particle material and a preparation method thereof, belonging to the technical field of luminescent materials.
Background
The up-conversion nano material is a material capable of converting invisible near infrared light into visible light, has the advantages of sharp spectral line, photobleaching resistance, multicolor adjustability and the like in luminescence, and has wide application prospect in the fields of full-color display, biological marking, advanced anti-counterfeiting technology and coding science. Especially, the nanometer material with red light or near infrared luminescence is more concerned by researchers. The red fluorescent material has the advantages of biological background fluorescence interference resistance, small damage to cells, strong penetrating power and the like, and has great application requirements in biological fluorescence imaging. However, the fluorescence efficiency of the up-conversion nanomaterial is reduced by the presence of cross-relaxation and energy transfer.
Currently, high power excitation can effectively suppress luminescence quenching in up-conversion nanomaterials caused by cross-relaxation. The inert layer can be coated to reduce surface defects and reduce energy transfer loss. However, the above method cannot suppress quenching of luminescence caused by energy transfer from the activator to the internal lattice quenching point.
Disclosure of Invention
The invention provides a high-color-purity red light up-conversion nano-particle material and a preparation method thereof, wherein the Tm is used for passing through3+Doped LiErF4Nanoparticles, incorporating Tm3+Reduction of LiErF as an energy capture center4Energy migration loss in the nanocrystalline is adjusted to Er3+The lattice structure of the 4f/5d orbital of (2) is determined by the structure in LiErF4:Tm3+Surface synthesis of inert shell LiYF4Formation of core-shell structures for LiErF4The defects on the surface of the nanocrystalline are effectively passivated, and the luminescence is further enhanced. Up-conversion nanocrystalline LiErF4:Tm3+@LiYF4Red emission (lambda)em654nm) due to Er3+Of ions4F9/2→4I15/2Transition, while the spectrogram of the upconverted nanoparticle shows LiErF4:Tm3+@LiYF4Middle Tm3+The doping content affects the luminescence intensity of the nanomaterial.
A high-color-purity red light up-conversion nano-particle material with a chemical formula of LiErF4:Tm3+@LiYF4，LiErF4:Tm3 +@LiYF4Is prepared from LiErF4:Tm3+Being a nucleus, LiYF4Core-shell structure being a shell, LiErF4:Tm3+Tm in nanoparticles3+Has a doping molar weight of Er3+And Tm3+The total molar amount of the component (a) is 0.5-20%.
The preparation method of the high-color-purity red light up-conversion nanoparticle material comprises the following specific steps:
(1) ErCl3Solution and TmCl3Adding the solution into an organic solvent, and carrying out temperature increasing sectional reaction under the stirring condition to obtain a mixed solution A; wherein the organic solvent is a mixed solvent of oleic acid and octadecene;
(2) cooling the mixed solution A to the temperature of 30-60 ℃, adding the mixed solution B into the mixed solution A, and reacting at the constant temperature for 20-60 min to obtain a mixed solution C; wherein the mixed liquid B contains NH4Methanol solution of F and LiOH;
(3) heating the mixed solution C at a constant speed to remove the methanol solvent to obtain a mixed solution D, heating the mixed solution D at a constant speed to 280-320 ℃, reacting at a constant temperature for 1-3 h, and precipitating with ethanol to obtain Tm3+Doped LiErF4:Tm3+Nanoparticles, LiErF4:Tm3+The nanoparticles are dispersed in cyclohexane;
(4) mixing YCl3Adding the solution into an organic solvent, and reacting for 20-60 min under the stirring condition at the temperature of 140-180 ℃ to obtain a mixed solution E; wherein the organic solvent is the same as the organic solvent of step (1);
(5) cooling the mixed solution E to the temperature of 30-60 ℃, and adding LiErF4:Tm3+Adding the mixed solution B into the mixed solution A, and reacting at constant temperature for 20-60 min to obtain a mixed solution F;
(6) the mixed liquid F is heated at a constant speedRemoving the methanol solvent to obtain a mixed solution G, uniformly heating the mixed solution G to 280-320 ℃, reacting at a constant temperature for 1-3 hours, and precipitating with ethanol to obtain LiErF4:Tm3+@LiYF4Nanoparticles, LiErF4:Tm3+@LiYF4The nanoparticles are dispersed in cyclohexane.
The volume ratio of oleic acid to octadecene in the organic solvent in the step (1) is 2: 3.0-3.5, and ErCl3Solution and TmCl3The volume ratio of the total volume of the solution to the organic solvent is 1: 10.0-11.5;
further, the temperature-increasing step reaction in the step (1) is as follows: the reaction is carried out at 110-112 ℃ for 50-80 min, at 118-122 ℃ for 8-15 min, at 128-132 ℃ for 8-15 min, at 138-142 ℃ for 8-15 min, and at 148-152 ℃ for 20-60 min. The temperature increasing sectional reaction is beneficial to the evaporation of water in the solution, and the excellent optical performance of the nano particles is ensured.
NH in the mixed solution B in the step (2)4F concentration of 0.5-1 mol/L, LiOH concentration of 1-2 mol/L, step (1) ErCl3ErCl in solution3And Tmcl3Tmcl in solution3The molar ratio of the total molar amount of LiOH to LiOH is 1:1,
YCl in the step (4)3The volume ratio of the solution to the organic solvent is 1: 10.0-11.5.
The step (5) LiErF4:Tm3+The molar ratio of the nanoparticle solution to the YCl in the step (4)3YCl in solution3In the mixed solution B, the LiOH and the YCl in the step (4) are mixed according to a molar ratio of 1:13YCl in solution3Is 1: 1.
The invention has the beneficial effects that:
(1) the invention dopes Tm in the red light up-conversion nano-particles3+Synthesis of LiErF to reduce loss of energy migration within nanoparticles4:Tm3+By modulating Tm3+To adjust the red up-conversion intensity and by means of LiErF4:Tm3+Surface synthesis of inert shell LiYF4Forming a core-shell structure to reduce surface defects;
(2) the invention synthesizes the upconversion nanometer particles with uniform particle size and good dispersibility by a thermal cracking method, and the Tm is passed3+Doped LiErF4Nanoparticles, incorporating Tm3+Reduction of LiErF as an energy capture center4Energy migration loss in the nanocrystalline is adjusted to Er3+The 4f/5d orbit of the crystal lattice structure realizes Er3+Is/are as follows4F9/2→4I15/2Transition; by using in LiErF4:Tm3+Surface synthesis of inert shell LiYF4Formation of core-shell structures for LiErF4The defects on the surface of the nanocrystalline are effectively passivated, the luminescence is further enhanced, and the high-color-purity red light emission of the up-conversion nanoparticles is ensured.
Drawings
FIG. 1 shows the different Tm's for comparative example 1 and example 13+An XRD pattern of the upconversion nanoparticles of doping concentration;
FIG. 2 shows the different Tm's for comparative example 1 and example 13+Doping concentration up-conversion nanoparticle LiErF4:Tm3+Spectrogram under 980nm excitation;
FIG. 3 shows LiErF of example 24:1.0％Tm3+And LiErF4:1.0％Tm3+@LiYF4Up-converting the XRD pattern of the nanoparticles;
FIG. 4 shows LiErF of example 24:1.0％Tm3+And LiErF4:1.0％Tm3+@LiYF4A spectrogram of the upconverted nanoparticle under 980nm excitation;
FIG. 5 shows LiErF of example 24:1.0％Tm3+Morphology of up-conversion nanoparticles, in which a is LiErF4:1.0％Tm3+TEM image of nanoparticles, b is LiErF4:1.0％Tm3+High resolution of the nanoparticles, c is LiErF4:1.0％Tm3+The particle size distribution diagram of the nano-particles is shown in the specification, and d is LiErF4:1.0％Tm3+A diffraction speckle pattern of nanoparticles;
FIG. 6 shows LiErF of example 24:1.0％Tm3+@LiYF4Morphology of up-conversion nanoparticles, in which a is LiErF4:1.0％Tm3+@LiYF4TEM image of nanoparticles, b is LiErF4:1.0％Tm3+@LiYF4High resolution of the nanoparticles, c is LiErF4:1.0％Tm3+@LiYF4The particle size distribution diagram of the nano-particles is shown in the specification, and d is LiErF4:1.0％Tm3+@LiYF4Diffraction speckle pattern of nanoparticles.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Comparative example 1: tm-free3+Doped LiErF4The preparation method of the up-conversion nano particles comprises the following specific steps:
(1) ErCl3Adding the solution into an organic solvent, and carrying out temperature increasing sectional reaction under the stirring condition to obtain a mixed solution A; wherein the organic solvent is a mixed solvent of oleic acid and octadecene; wherein the volume ratio of oleic acid to octadecene in the organic solvent is 2:3, ErCl3The volume ratio of the solution to the organic solvent is 1:10, ErCl3The concentration of the solution is 0.5 mol/L; the temperature-increasing stage reaction is as follows: reacting at 110 deg.C for 60min, at 120 deg.C for 10min, at 130 deg.C for 10min, at 140 deg.C for 10min, and at 150 deg.C for 30 min;
(2) cooling the mixed solution A to 50 ℃, adding the mixed solution B into the mixed solution A, and reacting at constant temperature for 30min to obtain a mixed solution C; wherein the mixed liquid B contains NH4Methanol solution of F and LiOH; NH in mixed liquid B4The concentration of F is 0.5mol/L, the concentration of LiOH is 1mol/L, step (1) ErCl3ErCl in solution3The molar ratio of LiOH to LiOH is 1: 1;
(3) heating the mixed solution C at a constant speed to remove the methanol solvent to obtain a mixed solution D, heating the mixed solution D at a constant speed to 290 ℃, reacting at a constant temperature for 2 hours, and precipitating LiErF by using ethanol4Nanoparticles of LiErF4The nanoparticles are dispersed in cyclohexane.
No Tm for this comparative example3+Doped LiErF4The XRD pattern of the up-converted nanoparticles is shown in FIG. 1, and from FIG. 1, no Tm is found3+Doped LiErF4The up-converted nanoparticles were compared to PDF cards and showed diffraction peaks corresponding to standard card JCPDS No.
51-1618, demonstrating synthetic no Tm3+Doped LiErF4The phase of the upconverting nanoparticles is a pure phase.
Example 1: the high color purity red light up-conversion nanoparticle material of this example has the chemical formula LiErF4:Tm3+Wherein Tm is3+Is Er in turn3+And Tm3+0.5%, 1.0%, 5.0%, 10%, 20% of the total molar amount of (A);
Tm3+LiErF with doping concentrations of 0.5%, 1.0%, 5.0%, 10% and 20% in sequence4The preparation method of the up-conversion nano particles comprises the following specific steps:
(1) ErCl3Adding the solution into an organic solvent, and carrying out temperature increasing sectional reaction under the stirring condition to obtain a mixed solution A; wherein the organic solvent is a mixed solvent of oleic acid and octadecene; wherein the volume ratio of oleic acid to octadecene in the organic solvent is 2:3, ErCl3The volume ratio of the solution to the organic solvent is 1:10, ErCl3The concentration of the solution is 0.5 mol/L; ErCl3Solution and TmCl3The volume ratio of the solution is 1.99:0.01, 1.98:0.02, 1.9:0.1, 1.8:0.2 and 1.6:0.4 in sequence; the temperature-increasing stage reaction is as follows: reacting at 110 deg.C for 60min, at 120 deg.C for 10min, at 130 deg.C for 10min, at 140 deg.C for 10min, and at 150 deg.C for 30 min;
(2) cooling the mixed solution A to 50 ℃, adding the mixed solution B into the mixed solution A, and reacting at constant temperature for 30min to obtain a mixed solution C; wherein the mixed liquid B contains NH4Methanol solution of F and LiOH; NH in mixed liquid B4The concentration of F is 0.5mol/L, the concentration of LiOH is 1mol/L, step (1) ErCl3ErCl in solution3The molar ratio of LiOH to LiOH is 1: 1;
(3) heating the mixed solution C at a constant speed to remove the methanol solvent to obtain a mixed solution D, heating the mixed solution D at a constant speed to 290 ℃, reacting at a constant temperature for 2 hours, and precipitating with ethanol to obtain Tm3+Doped LiErF4:Tm3+Nanoparticles of LiErF4:Tm3+The nanoparticles are dispersed in cyclohexane;
different concentrations of Tm3+Doped LiErF4The XRD pattern of the up-converted nanoparticles is shown in FIG. 1, and from FIG. 1, LiErF4:0.5％Tm3+、LiErF4:1.0％Tm3+、LiErF4:5.0％Tm3+、LiErF4:10％Tm3+、LiErF4:20％Tm3+The XRD of the up-conversion nano-particles is compared with the PDF card, and the result shows that the diffraction peak corresponds to the JCPDS No.51-1618 standard card, which proves that the synthesized LiErF4:0.5％Tm3+、LiErF4:1.0％Tm3+、LiErF4:5.0％Tm3+、LiErF4:10％Tm3+、LiErF4:20％Tm3+The phase of the upconverting nanoparticles is pure;
different concentrations of Tm3+Doped LiErF4The spectrum of the upconversion nanoparticles excited at 980nm is shown in FIG. 2. from FIG. 2, the peak of the emission spectrum at 654nm appears as red emission with Tm3+The concentration of the ions is increased, the luminous intensity shows the trend of increasing and then decreasing, LiErF4:1.0％Tm3+The nanoparticle emits the strongest light, indicating Tm3+The optimum doping concentration of (2) is 1.0%.
Example 2: the high color purity red light up-conversion nanoparticle material of this example has the chemical formula LiErF4:Tm3+@LiYF4，LiErF4:Tm3+@LiYF4Is prepared from LiErF4:Tm3+Being a nucleus, LiYF4Core-shell structure being a shell, LiErF4:Tm3+Tm in nanoparticles3+The doping molar weight of the crystal is Er and Tm in sequence3+0.5%, 1.0%, 5.0%, 10.0%, 20.0% of the total molar amount of (A);
Tm3+LiErF with doping concentrations of 0.5%, 1.0%, 5.0%, 10.0% and 20.0% in sequence4:Tm3+@LiYF4The preparation method comprises the following specific steps:
(1) ErCl3Adding the solution into organic solvent under stirringCarrying out temperature increasing sectional reaction to obtain a mixed solution A; wherein the organic solvent is a mixed solvent of oleic acid and octadecene; wherein the volume ratio of oleic acid to octadecene in the organic solvent is 2:3.2, ErCl3The volume ratio of the solution to the organic solvent is 1:11, ErCl3The concentration of the solution is 0.5 mol/L; ErCl3Solution and TmCl3The volume ratio of the solution is 1.99:0.01, 1.98:0.02, 1.9:0.1, 1.8:0.2 and 1.6:0.4 in sequence; the temperature-increasing stage reaction is as follows: reacting at 110 deg.C for 60min, at 120 deg.C for 10min, at 130 deg.C for 10min, at 140 deg.C for 10min, and at 150 deg.C for 30 min;
(2) cooling the mixed solution A to 50 ℃, adding the mixed solution B into the mixed solution A, and reacting at constant temperature for 30min to obtain a mixed solution C; wherein the mixed liquid B contains NH4Methanol solution of F and LiOH; NH in mixed liquid B4The concentration of F is 0.5mol/L, the concentration of LiOH is 1mol/L, step (1) ErCl3ErCl in solution3The molar ratio of LiOH to LiOH is 1: 1;
(3) heating the mixed solution C at a constant speed to remove the methanol solvent to obtain a mixed solution D, heating the mixed solution D at a constant speed to 290 ℃, reacting at a constant temperature for 2 hours, and precipitating with ethanol to obtain Tm3+Doped LiErF4:Tm3+Nanoparticles of LiErF4:Tm3+The nanoparticles are dispersed in cyclohexane;
(4) mixing YCl3Adding the solution into an organic solvent, and reacting for 30min at the temperature of 150 ℃ under the stirring condition to obtain a mixed solution E; wherein the organic solvent is the same as the organic solvent of step (1); YCl3The volume ratio of the solution to the organic solvent is 1:11, YCl3The concentration of the solution is 0.5 mol/L;
(5) cooling the mixture E to 50 deg.C, adding LiErF4:Tm3+Adding the mixed solution B into the mixed solution A, and reacting at constant temperature for 30min to obtain a mixed solution F; wherein LiErF4:Tm3+Li in the nano-particles and YCl in the step (4)3YCl in solution3In the mixed solution B, the LiOH and the YCl in the step (4) are mixed according to a molar ratio of 1:13YCl in solution3In a molar ratio of 1: 1;
(6) the mixed liquid F is uniform in speedHeating to remove the methanol solvent to obtain a mixed solution G, uniformly heating the mixed solution G to 290 ℃, reacting at constant temperature for 2 hours, and precipitating with ethanol to obtain LiErF4:Tm3+@LiYF4Nanoparticles, LiErF4:Tm3+@LiYF4The nanoparticles are dispersed in cyclohexane;
this example LiErF4:1.0％Tm3+And LiErF4:1.0％Tm3+@LiYF4The XRD pattern of the upconversion nanoparticles is shown in FIG. 3, and from FIG. 3, LiErF4:1.0％Tm3+And LiErF4:1.0％Tm3+@LiYF4No miscellaneous peak is found by comparing the up-conversion nano-particles with the PDF card, and the synthesized LiErF is proved4:1.0％Tm3+And LiErF4:1.0％Tm3+@LiYF4The phase of the upconversion nanoparticles is pure;
LiErF4:1.0％Tm3+and LiErF4:1.0％Tm3+@LiYF4The spectrum of the upconverting nanoparticles under 980nm excitation is shown in FIG. 4. from FIG. 4, LiErF4:1.0％Tm3+LiErF with core-shell structure4:1.0％Tm3+@LiYF4The peak values of the emission spectra are all at 654nm and are in LiErF4:1.0％Tm3+Nuclear surface coating shell LiYF4The nano particles show stronger red light;
LiErF4:1.0％Tm3+the TEM image of the up-converted nanoparticles is shown in FIG. 5, and from FIG. 5, LiErF4:1.0％Tm3+The average particle size of the upconversion nanoparticles is 8.0 nm; LiErF4:1.0％Tm3+@LiYF4TEM image of the upconverted nanoparticles is shown in FIG. 6, and from FIG. 6, LiErF4:1.0％Tm3+@LiYF4The average particle size of the upconversion nanoparticles was 15.0nm, and fig. 5 and 6 demonstrate that the core-shell structured LiErF was successfully prepared4:1.0％Tm3+@LiYF4Up-converting the nanoparticles.
Example 3: the high color purity red light up-conversion nanoparticle material of this example has the chemical formula LiErF4:Tm3+@LiYF4，LiErF4:Tm3+@LiYF4Is prepared from LiErF4:Tm3+Being a nucleus, LiYF4Core-shell structure being a shell, LiErF4:Tm3+Tm in nanoparticles3+Has a doping molar weight of Er3+And Tm3+1.0% of the total molar amount of (c);
Tm3+LiErF with doping concentration of 1.0%4Upconversion nanoparticles and LiErF4:Tm3+@LiYF4The preparation method comprises the following specific steps:
(1) ErCl3Solution and TmCl3Adding the solution into an organic solvent, and carrying out temperature increasing sectional reaction under the stirring condition to obtain a mixed solution A; wherein the organic solvent is a mixed solvent of oleic acid and octadecene; wherein the volume ratio of oleic acid to octadecene in the organic solvent is 2:3.2, ErCl3Solution and TmCl3The ratio of the total volume of the solution to the volume of the organic solvent was 1:10, ErCl3The concentration of the solution was 0.5mol/L, TmCl3The concentration of the solution was 0.5mol/L, ErCl3Solution and TmCl3The volume ratio of the solution is 1.98: 0.02; the temperature-increasing stage reaction is as follows: reacting at 112 deg.C for 70min, at 122 deg.C for 8min, at 132 deg.C for 9min, at 142 deg.C for 10min, and at 152 deg.C for 25 min;
(2) cooling the mixed solution A to 40 ℃, adding the mixed solution B into the mixed solution A, and reacting at constant temperature for 40min to obtain a mixed solution C; wherein the mixed liquid B contains NH4Methanol solution of F and LiOH; NH in mixed liquid B4The concentration of F is 0.5mol/L, the concentration of LiOH is 1mol/L, step (1) ErCl3ErCl in solution3The molar ratio of LiOH to LiOH is 1: 1;
(3) heating the mixed solution C at a constant speed to remove the methanol solvent to obtain a mixed solution D, heating the mixed solution D at a constant speed to 320 ℃, reacting at a constant temperature for 1.5h, and precipitating with ethanol to obtain LiErF4:1.0％Tm3+Nanoparticles, LiErF4:1.0％Tm3+The nanoparticles are dispersed in cyclohexane;
(4) mixing YCl3Adding the solution into an organic solvent, and reacting for 25min at the temperature of 170 ℃ under the stirring condition to obtain a mixed solution E; wherein the organic solvent andthe organic solvent in the step (1) is the same; YCl3The volume ratio of the solution to the organic solvent is 1:10, YCl3The concentration of the solution is 0.5 mol/L;
(5) cooling the mixture E to 40 deg.C, adding LiErF4:1.0％Tm3+Adding the mixed solution B into the mixed solution A, and reacting at constant temperature for 50min to obtain a mixed solution F; wherein LiErF4:Tm3+Molar ratio of nanoparticles to YCl in step (5)3YCl in solution3In the mixed solution B, the LiOH and the YCl in the step (4) are mixed according to a molar ratio of 1:13YCl in solution3In a molar ratio of 1: 1;
(6) heating the mixed solution F at a constant speed to remove the methanol solvent to obtain a mixed solution G, heating the mixed solution G at a constant speed to 320 ℃, carrying out constant temperature reaction for 1.5h, and precipitating with ethanol to obtain LiErF4:Tm3+@LiYF4Nanoparticles, LiErF4:Tm3+@LiYF4The nanoparticles are dispersed in cyclohexane;
LiErF4:1.0％Tm3+and LiErF4:1.0％Tm3+@LiYF4The XRD pattern of the up-conversion nano-particles shows that LiErF4:1.0％Tm3+And LiErF4:1.0％Tm3+@LiYF4No miscellaneous peak is found by comparing the up-conversion nano-particles with the PDF card, and the synthesized LiErF is proved4:1.0％Tm3+And LiErF4:1.0％Tm3+@LiYF4The phase of the upconversion nanoparticles is pure;
LiErF4:1.0％Tm3+and LiErF4:1.0％Tm3+@LiYF4The spectrogram of the upconversion nano particle under the excitation of 980nm shows that LiErF4:1.0％Tm3+LiErF with core-shell structure4:1.0％Tm3+@LiYF4The peak values of the emission spectra are all at 654nm and are in LiErF4:1.0％Tm3+Nuclear surface coating shell LiYF4The nano particles show stronger red light;
LiErF4:1.0％Tm3+TEM image of the up-converted nanoparticles shows LiErF4:1.0％Tm3+The average particle diameter of the upconversion nanoparticles is 8.5nm；LiErF4:1.0％Tm3+@LiYF4TEM image of the up-converted nanoparticles shows LiErF4:1.0％Tm3+@LiYF4The average particle size of the up-conversion nano particles is 15.5nm, and the LiErF with the core-shell structure is successfully prepared4:1.0％Tm3+@LiYF4Up-converting the nanoparticles.
Claims (7)
1. A high-color-purity red light up-conversion nano-particle material is characterized in that the chemical formula is LiErF4:Tm3+@LiYF4，LiErF4:Tm3+@LiYF4Is prepared from LiErF4:Tm3+Being a nucleus, LiYF4Core-shell structure being a shell, LiErF4:Tm3+Tm in nanoparticles3 +Has a doping molar weight of Er3+And Tm3+The total molar amount of the component (a) is 0.5-20%.
2. A preparation method of a high-color-purity red light up-conversion nanoparticle material is characterized by comprising the following specific steps:
(1) ErCl3Solution and TmCl3Adding the solution into an organic solvent, and carrying out temperature increasing sectional reaction under the stirring condition to obtain a mixed solution A; wherein the organic solvent is a mixed solvent of oleic acid and octadecene;
(2) cooling the mixed solution A to the temperature of 30-60 ℃, adding the mixed solution B into the mixed solution A, and reacting at the constant temperature for 20-60 min to obtain a mixed solution C; wherein the mixed liquid B contains NH4Methanol solution of F and LiOH;
(3) heating the mixed solution C at a constant speed to remove the methanol solvent to obtain a mixed solution D, heating the mixed solution D at a constant speed to 280-320 ℃, reacting at a constant temperature for 1-3 h, and precipitating with ethanol to obtain Tm3+Doped LiErF4:Tm3+Nanoparticles of LiErF4:Tm3+The nanoparticles are dispersed in cyclohexane;
(4) mixing YCl3Adding the solution into an organic solvent, and reacting for 20-60 min under the stirring condition at the temperature of 140-180 ℃ to obtain a mixed solution E; wherein the organic solvent is in phase with the organic solvent of step (1)The same is carried out;
(5) cooling the mixed solution E to the temperature of 30-60 ℃, and adding LiErF4:Tm3+Adding the mixed solution B into the mixed solution A, and reacting at constant temperature for 20-60 min to obtain a mixed solution F;
(6) heating the mixed solution F at a constant speed to remove the methanol solvent to obtain a mixed solution G, heating the mixed solution G at a constant speed to 280-320 ℃, reacting at a constant temperature for 1-3 hours, and precipitating with ethanol to obtain LiErF4:Tm3+@LiYF4Nanoparticles of LiErF4:Tm3+@LiYF4The nanoparticles are dispersed in cyclohexane.
3. The method of preparing high color purity red light up-conversion nanoparticle material as claimed in claim 2, wherein: the volume ratio of oleic acid to octadecene in the organic solvent in the step (1) is 2: 3.0-3.5, and ErCl3Solution and TmCl3The volume ratio of the total volume of the solution to the volume of the organic solvent is 1: 10.0-11.5.
4. The method of preparing high color purity red light up-conversion nanoparticle material as claimed in claim 2, wherein: the temperature-increasing stage reaction is as follows: the reaction is carried out at 110-112 ℃ for 50-80 min, at 118-122 ℃ for 8-15 min, at 128-132 ℃ for 8-15 min, at 138-142 ℃ for 8-15 min, and at 148-152 ℃ for 20-60 min.
5. The method of preparing high color purity red light up-conversion nanoparticle material as claimed in claim 2, wherein: step (1) ErCl3ErCl in solution3And Tmcl3Tmcl in solution3The molar ratio of the total molar amount of (3) to LiOH is 1:1, and NH is contained in the mixed liquid B in the step (2)4The concentration of F is 0.5-1 mol/L, and the concentration of LiOH is 1-2 mol/L.
6. The method of preparing high color purity red light up-conversion nanoparticle material as claimed in claim 2, wherein: YCl in step (4)3The volume ratio of the solution to the organic solvent is 1:10.0 to up to11.5。
7. The method of preparing high color purity red light up-conversion nanoparticle material as claimed in claim 2, wherein: the step (5) LiErF4:Tm3+The molar ratio of the nanoparticle solution to the YCl in the step (4)3YCl in solution3In a molar ratio of 1:1, step (4) YCl3YCl in solution3The molar ratio of (a) to LiOH in the mixed liquid B was 1: 1.
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