CN113265115B - Nitrogen-aluminum co-doped carbon dot film laser protection material and preparation method and application thereof - Google Patents
Nitrogen-aluminum co-doped carbon dot film laser protection material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a nitrogen-aluminum co-doped carbon dot film laser protection material and a preparation method and application thereof. Adding mono-substituted alkylamine and anhydrous aluminum trichloride into a benzene solvent, fully dispersing and uniformly mixing, and performing reflux pyrolysis at 130-190 ℃; and then cooling to room temperature, separating by a silica gel column, and drying in vacuum to obtain the nitrogen-aluminum co-doped hydrophobic carbon dots. Then dissolving polymethyl methacrylate in dichloromethane, adding a dichloromethane dispersion liquid of nitrogen-aluminum co-doped hydrophobic carbon dots, fully dispersing and uniformly mixing to obtain a mixed solution, and forming a film to obtain the nitrogen-aluminum co-doped carbon dot thin film laser protection material; the laser protection material has the advantages of simple preparation method, low dynamic optical limiting threshold, good nonlinear optical performance and good laser protection effect.
Description
Technical Field
The invention relates to a nitrogen-aluminum co-doped carbon dot film laser protection material and a preparation method and application thereof, belonging to the field of new materials.
Background
With the continuous widening of the application scenes of the laser technology in the fields of scientific research, life, industry and the like, the potential dangerousness of the laser is gradually known by people. Because the laser has the characteristics of good unidirectionality and high energy, the human eyes and optical sensitive devices can be damaged in a short time, and the condition that people are injured due to improper use of a high-energy laser also frequently occurs. In view of the threat brought by laser in the aspects of national defense, civil use, scientific research and the like, the research on the novel laser protection material can provide safety protection for optical sensitive elements in workers, scientific research personnel and expensive optical instruments under the high-intensity laser exposure risk, ensure the safety of the personnel and the durability of the instruments, and has important significance for the application of the strong laser. The laser protection system using the band-pass filter as a main component is a main protection component on the market at present, but the protection means has no pertinence to the light intensity of different incident lasers, so that the optical device cannot timely capture effective signals of a protection waveband under the condition of weak light. In order to solve the disadvantage, nonlinear laser protection is provided, which has a strong protection effect on light with high light intensity and has high transmissivity on light with low light intensity. Nonlinear optical clipping will be the dominant trend in future optical countermeasure studies.
Today, many carbon materials have shown remarkable nonlinear optical properties, such as fullerenes, carbon nanotubes, graphene, etc., showing strong nonlinear optical clipping effects. Carbon dots are carbon nanomaterials with the size less than 10 nanometers, and have been applied to the fields of biological imaging, detection, photocatalysis and the like. However, researches on preparing the nonlinear laser protection material by utilizing the nonlinear optical property of the carbon dot under the pulse laser are less, and the researches are mainly focused on a solution area, so that the processing requirements of the device and the working requirements of the device are not facilitated.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nitrogen-aluminum co-doped carbon dot film laser protection material and a preparation method and application thereof. The laser protection material has the advantages of simple preparation method, low dynamic light amplitude limiting threshold value and good laser protection effect.
The invention is realized by the following technical scheme:
the utility model provides a nitrogen aluminium codope carbon dot film laser protection material, laser protection material for the film of doping carbon dot in the polymethyl methacrylate, carbon dot be the hydrophobic carbon dot of nitrogen aluminium codope.
Preferably, according to the invention, the weight average molecular weight of the polymethyl methacrylate is 300000-400000, preferably 350000.
According to the invention, the thickness of the film is preferably 7.20-11.0 microns; the particle size of the carbon dots is 1 to 10 nm, preferably 4 to 5 nm.
According to the invention, the doping amount of the carbon dots in the film is preferably 0.8% to 4.5%, preferably 2% to 3%. The doping amount is the percentage of the mass of the carbon dots in the total mass of the film.
The invention also provides a preparation method of the nitrogen-aluminum co-doped carbon dot film laser protection material, which comprises the following steps:
dissolving polymethyl methacrylate in dichloromethane, adding a nitrogen-aluminum co-doped dichloromethane dispersion liquid of hydrophobic carbon dots, fully dispersing and uniformly mixing to obtain a mixed solution, and forming a film to obtain the nitrogen-aluminum co-doped carbon dot thin film laser protection material;
the preparation of the nitrogen-aluminum co-doped hydrophobic carbon dots comprises the following steps: adding mono-substituted alkylamine and anhydrous aluminum trichloride into a benzene solvent, fully dispersing and uniformly mixing, and performing reflux pyrolysis at 130-190 ℃; and then cooling to room temperature, separating by a silica gel column, and drying in vacuum to obtain the nitrogen-aluminum co-doped hydrophobic carbon dots.
According to the invention, the monosubstituted alkylamine is one of hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine or octadecylamine, and is preferably dodecylamine.
According to the invention, the mass ratio of the mono-substituted alkylamine to the anhydrous aluminum trichloride is 0.5: 1-6: 1, preferably 1.5: 1.
According to the invention, the benzene solvent is preferably one of chlorobenzene, bromobenzene, iodobenzene, o-dichlorobenzene, m-dichlorobenzene or p-dichlorobenzene; the volume ratio of the mass of the monosubstituted alkylamine to the benzene solvent is 0.05-0.5 g/ml.
Preferably, according to the invention, the reflux pyrolysis temperature is 140 ℃.
According to the invention, the reflux pyrolysis time is preferably 24-48 hours.
According to the invention, a silica gel column is adopted to separate and remove unreacted raw materials, solvents and byproducts; the silica gel column separation method is carried out according to the prior art.
According to the invention, the concentration of the nitrogen-aluminum co-doped hydrophobic carbon dots in the mixed solution is preferably 0.23-1.35 mg/ml.
According to the present invention, the concentration of the polymethyl methacrylate in the mixed solution is preferably 25 to 30 mg/ml.
According to the invention, the concentration of the nitrogen-aluminum co-doped hydrophobic carbon dots in the dichloromethane dispersion liquid of the nitrogen-aluminum co-doped hydrophobic carbon dots is 1.38-8.1 mg/mL.
According to the invention, the mass ratio of the polymethyl methacrylate and the nitrogen-aluminum co-doped hydrophobic carbon dots is 21-125:1, preferably 39: 1.
According to the invention, the method preferably comprises the step of removing bubbles by ultrasonic after adding the nitrogen-aluminum co-doped hydrophobic carbon dots to fully disperse and uniformly mix, wherein the ultrasonic time is 10-30 minutes.
According to the invention, the film forming temperature is room temperature, and the film forming time is 24-48 hours.
The invention also provides an application of the nitrogen-aluminum co-doped carbon dot film laser protection material, and the nitrogen-aluminum co-doped carbon dot film laser protection material is applied to laser protection as a protection material.
The invention has the following technical characteristics and beneficial effects:
1. the method comprises the steps of mixing mono-substituted alkylamine with anhydrous aluminum trichloride and a solvent, and performing reflux pyrolysis to obtain nitrogen-aluminum co-doped hydrophobic carbon dots; wherein, alkylamine is used as a carbon source and a nitrogen source, and anhydrous aluminum trichloride is used as an aluminum source. In the process of preparing the carbon dots, the complex processes such as glycidic oxidation carbonization and the like mainly occur, wherein the higher mass ratio of alkylamine to anhydrous aluminum trichloride, the lower reaction temperature and the proper solvent are important conditions for preparing the nitrogen-aluminum co-doped carbon dots. The existence of nitrogen and aluminum in the carbon points greatly improves the optical amplitude limiting effect of the carbon points, enhances the nonlinear optical performance of the material, enables the material to have a larger nonlinear absorption coefficient and a lower optical amplitude limiting threshold, enables the laser transmittance to have dependency on the incident energy of laser, and realizes the laser protection of dynamic optical amplitude limiting.
2. According to the invention, polymethyl methacrylate is used as a matrix to fix and disperse the nitrogen-aluminum co-doped hydrophobic carbon dots, so that the prepared material has high transparency and processability, and the application of the material in devices is facilitated. The polymethyl methacrylate used in the invention has high film forming speed and simple film forming process, and the formed film has good transparency and thermal stability, thereby meeting the requirements of the optical amplitude limiting material of the invention and better playing the characteristics of the optical amplitude limiting material, namely slightly high transmittance to low-light-intensity laser and lower transmittance to high-light-intensity laser. In the process of preparing the film, the high permeability of the film needs to be maintained, so that the control of the proportion of the nitrogen-aluminum co-doped carbon dots doped into the film is important, and the permeability of the film needs to be maintained and the optical limiting performance of the film needs to be improved. The preparation method is simple, short in period and easy to scale.
Drawings
Fig. 1 is a route diagram for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protective material in embodiment 1 of the present invention.
FIG. 2 is a photomicrograph and a high-resolution transmission electron micrograph of carbon dots obtained in example 1.
FIG. 3 is an infrared spectrum of a carbon spot and an infrared spectrum of a raw material obtained in example 1.
FIG. 4 is a fluorescence spectrum of the carbon dots obtained in example 1 dissolved in ethanol at different excitation wavelengths.
FIG. 5 is an X-ray photoelectron spectrum of a carbon spot obtained in example 1.
FIG. 6 shows fluorescence and sunlight photographs of the film obtained in example 1.
FIG. 7 is a Z-scan curve of the film obtained in example 1.
Fig. 8 is an optical limiting curve of the film obtained in example 1.
FIG. 9 is a fluorescent photograph and a sunbeam photograph of the film obtained in comparative example 1.
Fig. 10 is a Z-scan curve of the film obtained in comparative example 2.
Detailed Description
For a better understanding of the present invention, reference is made to the following examples.
The experimental methods used in the examples are all conventional methods unless otherwise specified.
The materials, reagents and the like used in the examples are commercially available unless otherwise specified.
Example 1
A preparation method of a nitrogen-aluminum co-doped carbon dot film laser protection material is shown in figure 1, and comprises the following steps:
(1) respectively weighing 9.3 g of dodecylamine and 6.2 g of anhydrous aluminum trichloride, adding the dodecylamine and the anhydrous aluminum trichloride into a 250 ml three-neck flask, adding 50 ml of o-dichlorobenzene, fully and uniformly mixing, carrying out reflux pyrolysis at 140 ℃ for 48 hours, cooling to room temperature, purifying by using a normal hexane silica gel column to remove a solvent, purifying by using an ethanol silica gel column to remove a raw material and a byproduct, carrying out rotary evaporation to remove an eluent, and carrying out vacuum drying at 50 ℃ for 5 days to obtain a nitrogen-aluminum co-doped hydrophobic carbon dot;
the obtained photomicrograph of the carbon dots and a high-resolution transmission electron microscope are shown in FIG. 2; the figure shows that the prepared nitrogen-aluminum co-doped hydrophobic carbon dots are blocky, and a high-resolution transmission electron microscope shows that the prepared carbon dots have good dispersibility, and the average particle size of the carbon dots is 4.61 nanometers.
The infrared spectrum of the obtained carbon dots is shown in FIG. 3; compared with the red light spectrum of the raw material, the nitrogen-hydrogen stretching vibration peak of the prepared nitrogen-aluminum co-doped hydrophobic carbon dot is from 3333cm-1Moving red to 3170cm-1Meanwhile, the signal intensity is weakened, which indicates that amino in the raw material dodecylamine participates in the generation process of carbon points in the carbonization process; 1500cm in spectrum of nitrogen-aluminum co-doped hydrophobic carbon dot-1，1580cm-1And 1600cm-1The vibration peak of the carbon-carbon double bond or the carbon-nitrogen double bond indicates that the carbon points contain abundant aromatic ring structures; 654cm-1The vibration peak of the aluminum oxide confirms the aluminumSuccessful incorporation of the element.
The fluorescence emission spectrum of the obtained carbon dots in ethanol (the concentration of the carbon dots is 5 mg/ml) is shown in FIG. 4; the graph shows that the fluorescence of the prepared nitrogen-aluminum co-doped hydrophobic carbon dots has the characteristic of excitation wavelength dependence, the intensity of an emission spectrum shows a trend of increasing first and then decreasing with the increase of the excitation wavelength, and the intensity of the emission spectrum reaches the maximum value at 470 nanometers of the excitation wavelength.
The X-ray photoelectron spectrum of the obtained carbon dot is shown in FIG. 5; from the figure, it is understood that the aluminum element exists mainly in the form of aluminum-oxygen bond and aluminum-nitrogen bond in the carbon dots, and the nitrogen element exists mainly in the form of pyrrole nitrogen and pyridine nitrogen, and amino nitrogen and graphite nitrogen.
(2) Dissolving 86 mg of polymethyl methacrylate (weight average molecular weight is 350000) in 2.5 ml of dichloromethane, performing ultrasonic dispersion uniformly, dissolving 2.20 mg of nitrogen-aluminum co-doped hydrophobic carbon dots in 0.5 ml of dichloromethane, uniformly mixing the carbon dot solution and the polymethyl methacrylate solution, performing ultrasonic treatment for 20 minutes to remove bubbles, pouring into a 60 mm glass culture dish, standing at room temperature to perform solvent volatilization to form a film, and performing volatilization for 24 hours to obtain the nitrogen-aluminum co-doped carbon dot film (the film thickness is 7.20-11.0 microns).
The doping amount, namely the mass content, of the carbon dots in the obtained nitrogen-aluminum co-doped carbon dot film is 2.5%.
The sunlight and fluorescence photographs (left image sunlight, right image fluorescence) of the obtained nitrogen-aluminum co-doped carbon dot film are shown in fig. 6; the left figure shows that the film prepared by the method of the embodiment is placed on white paper written with letters, and the letters can be clearly displayed through the film, which shows that the prepared film has high transparency; the right panel shows fluorescence, and the film appears blue due to the addition of carbon dots.
A neodymium-doped yttrium aluminum garnet solid laser with the wavelength of 532 nanometers, the frequency of 10 Hz and the laser pulse width of 5 nanoseconds is adopted to measure the nonlinear absorption performance of the film under the condition of opening. The Z-scan curve of the obtained nitrogen-aluminum co-doped carbon dot film is shown in fig. 7; the curve shows that when the sample position is equal to 0, the normalized transmittance is lowest, and the nitrogen-aluminum co-doped carbon dot film shows the behavior of reverse saturation absorption. When the incident laser energy is lower, such as 0.1 micro-focus, the normalized transmittance of the nitrogen-aluminum co-doped carbon dot film is 48%, the energy of the incident laser is improved, the normalized transmittance of the nitrogen-aluminum co-doped carbon dot film is gradually reduced, and when the incident laser energy is 3 micro-focus, the normalized transmittance of the nitrogen-aluminum co-doped carbon dot film is 32%, so that the nitrogen-aluminum co-doped carbon dot film has high transmittance under low incident laser energy and low transmittance under high incident laser energy, thereby realizing the rule that the transmittance dynamically changes along with the energy change, and realizing the laser protection of dynamic light amplitude limiting.
Performing data processing on Z scanning curves with different incident laser energies, and drawing optical limiting curves of the nitrogen-aluminum co-doped carbon dot film under different incident laser energies by taking the incident laser energy density as an abscissa and the normalized transmittance as an ordinate, wherein the optical limiting curves are shown in FIG. 8; the incident laser energy density corresponding to the abscissa where the normalized transmittance is equal to 50% is the optical limiting threshold of the material. From the figure, it can be read that the optical clipping threshold corresponding to an incident laser energy of 3 microjoules is 0.03 joules per square centimeter. The optical clipping threshold for an incident laser energy of 1 microjoule corresponds to 0.02 joules per square centimeter. The light clipping threshold corresponding to an incident laser energy of 0.6 microjoules per square centimeter was 0.016 joules per square centimeter. The light clipping threshold for an incident laser energy of 0.1 microjoules is 0.0105 joules per square centimeter. The threshold value of the optical amplitude limit shows the rule of dynamic change along with the change of the incident laser energy, so that the nitrogen-aluminum co-doped carbon dot film has the characteristic of dynamic laser protection. Since the film does not have nonlinear optical properties in itself under this test condition, the optical confinement of the film comes from the nitrogen and aluminum co-doped carbon dots.
Example 2
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that:
the ratio of dodecylamine to anhydrous aluminum trichloride was changed to 3:1 (i.e., 9.3 grams of dodecylamine and 3.1 grams of anhydrous aluminum chloride); the other steps and conditions were identical to those of example 1.
Example 3
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that:
the ratio of dodecylamine to anhydrous aluminum trichloride was changed to 6:1 (i.e., 9.3 grams of dodecylamine and 1.5 grams of anhydrous aluminum chloride); the other steps and conditions were identical to those of example 1.
Example 4
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that:
the ratio of dodecylamine to anhydrous aluminum trichloride was changed to 1:1 (i.e., 9.3 grams of dodecylamine and 9.3 grams of anhydrous aluminum chloride); the other steps and conditions were identical to those of example 1.
Example 5
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that:
the ratio of dodecylamine to anhydrous aluminum trichloride was changed to 0.5:1 (i.e., 9.3 grams of dodecylamine and 18.6 grams of anhydrous aluminum chloride); the other steps and conditions were identical to those of example 1.
Example 6
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: changing 50 ml of o-dichlorobenzene into 186 ml; the other steps and conditions were identical to those of example 1.
Example 7
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: the volume of 50 ml o-dichlorobenzene is changed to 93 ml; the other steps and conditions were identical to those of example 1.
Example 8
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: 50 ml of o-dichlorobenzene was changed to 18.6 ml; the other steps and conditions were identical to those of example 1.
Example 9
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: changing dodecylamine into hexylamine; the other steps and conditions were identical to those of example 1.
Example 10
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: changing dodecylamine into heptylamine; the other steps and conditions were identical to those of example 1.
Example 11
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: changing dodecylamine into octylamine; the other steps and conditions were identical to those of example 1.
Example 12
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: changing dodecylamine into nonylamine; the other steps and conditions were identical to those of example 1.
Example 13
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: changing dodecylamine into decylamine; the other steps and conditions were identical to those of example 1.
Example 14
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: changing dodecylamine into tetradecylamine; the other steps and conditions were identical to those of example 1.
Example 15
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: changing dodecylamine into hexadecylamine; the other steps and conditions were identical to those of example 1.
Example 16
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: changing dodecylamine into octadecylamine; the other steps and conditions were identical to those of example 1.
Example 17
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: the reflux pyrolysis time is changed to 24 hours; the other steps and conditions were identical to those of example 1.
Example 18
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: the reflux pyrolysis time was changed to 32 hours; the other steps and conditions were identical to those of example 1.
Example 19
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: changing the benzene solvent into chlorobenzene; the other steps and conditions were identical to those of example 1.
Example 20
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: changing the benzene solvent into bromobenzene; the other steps and conditions were identical to those of example 1.
Example 21
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: changing benzene solvent into iodobenzene; the other steps and conditions were identical to those of example 1.
Example 22
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: changing benzene solvent into m-dichlorobenzene; the other steps and conditions were identical to those of example 1.
Example 23
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: benzene solvent is changed into p-dichlorobenzene; the other steps and conditions were identical to those of example 1.
Example 24
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: the ratio of carbon dots to polymethylmethacrylate was changed to 1:125 (i.e., 0.69 mg carbon dots and 86 mg polymethylmethacrylate); the other steps and conditions were identical to those of example 1.
Example 25
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: the ratio of carbon dots to polymethylmethacrylate was changed to 1:100 (i.e., 0.86 mg of carbon dots and 86 mg of polymethylmethacrylate); the other steps and conditions were identical to those of example 1.
Example 26
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: the ratio of carbon dots to polymethylmethacrylate was changed to 1:50 (i.e., 1.72 mg carbon dots and 86 mg polymethylmethacrylate); the other steps and conditions were identical to those of example 1.
Example 27
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: the ratio of carbon dots to polymethylmethacrylate was changed to 1:21 (i.e., 4.05 mg carbon dots and 86 mg polymethylmethacrylate); the other steps and conditions were identical to those of example 1.
Example 28
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: the volatilization time of the formed film is changed to 32 hours; the other steps and conditions were identical to those of example 1.
Example 29
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: the film-forming volatilization time is changed to 48 hours; the other steps and conditions were identical to those of example 1.
Comparative example 1
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: the ratio of carbon dots to polymethylmethacrylate was changed to 1:19 (i.e., 4.5 mg carbon dots and 86 mg polymethylmethacrylate); the other steps and conditions were identical to those of example 1.
The sunlight and fluorescence photographs (left image sunlight, right image fluorescence) of the obtained nitrogen-aluminum co-doped carbon dot film are shown in fig. 9; the left picture shows that the film prepared by the method of comparative example 1 is placed on white paper with letters, compared with example 1, the nitrogen-aluminum co-doped carbon dot film has uneven phenomenon due to too large doping amount of nitrogen-aluminum co-doped carbon dots, the edge and the center of the nitrogen-aluminum co-doped carbon dot film have obvious yellow color, the transmittance is poor, and the low transmittance is not beneficial to the application of the light amplitude limiting of the nitrogen-aluminum co-doped carbon dot film. The right picture is fluorescence, and the nitrogen-aluminum co-doped carbon dot film shows uneven blue fluorescence intensity due to the fact that the overall uniformity of the nitrogen-aluminum co-doped carbon dot film is poor, and the edge fluorescence intensity is shown.
Comparative example 2
A method for preparing a nitrogen-aluminum co-doped carbon dot thin film laser protection material, as described in example 1, except that: the ratio of carbon dots to polymethylmethacrylate was changed to 1:200 (i.e., 0.43 mg carbon dots and 86 mg polymethylmethacrylate); the other steps and conditions were identical to those of example 1.
The Z-scan curve of the nitrogen-aluminum co-doped carbon dot film obtained in comparative example 2 is shown in fig. 10; compared with example 1, the curve shows that when the sample position is equal to 0, the normalized transmittance is the lowest, and the nitrogen-aluminum co-doped carbon dot film also shows the behavior of reverse saturation absorption. However, when the incident laser energy is the same, the normalized transmittance value of the comparative example 2 is significantly greater than that of the example 1, for example 1, when the incident laser energy is 3 microjoules, the normalized transmittance of the nitrogen-aluminum co-doped carbon dot film is 32%, and for the comparative example 2, when the incident laser energy is 3 microjoules, the normalized transmittance of the nitrogen-aluminum co-doped carbon dot film is 75%, the nonlinear absorption coefficients of the two are calculated, and the value reflects an index of the nonlinear optical response of the material, and the larger the value, the better the nonlinear optical response. The nonlinear absorption coefficients of the two materials are compared in table 1, and it can be found that the nonlinear absorption coefficient of example 1 is significantly larger than that of comparative example 2 under the condition that the incident laser energy is the same, which indicates that example 1 has better nonlinear optical response and has a larger application space in the field of laser protection, and therefore, the doping amount of the nitrogen-aluminum co-doped carbon dot is an important factor influencing the nonlinear optical response and the optical limiting effect of the nitrogen-aluminum co-doped carbon dot film.
TABLE 1
Claims (9)
1. The nitrogen-aluminum co-doped carbon dot film laser protection material is characterized in that the laser protection material is a film doped with carbon dots in polymethyl methacrylate, and the carbon dots are nitrogen-aluminum co-doped hydrophobic carbon dots; the doping amount of the carbon dots in the film is 0.8-4.5%, and the doping amount is the percentage of the mass of the carbon dots in the total mass of the film; the thickness of the film is 7.20-11.0 microns; the grain diameter of the carbon dots is 1-10 nanometers;
the preparation method of the nitrogen-aluminum co-doped carbon dot film laser protection material comprises the following steps:
dissolving polymethyl methacrylate in dichloromethane, adding a nitrogen-aluminum co-doped dichloromethane dispersion liquid of hydrophobic carbon dots, fully dispersing and uniformly mixing to obtain a mixed solution, and forming a film to obtain the nitrogen-aluminum co-doped carbon dot thin film laser protection material;
the preparation of the nitrogen-aluminum co-doped hydrophobic carbon dots comprises the following steps: adding mono-substituted alkylamine and anhydrous aluminum trichloride into a benzene solvent, fully dispersing and uniformly mixing, and performing reflux pyrolysis at 130-190 ℃; then cooling to room temperature, separating by a silica gel column, and drying in vacuum to obtain nitrogen-aluminum co-doped hydrophobic carbon dots;
the monosubstituted alkylamine is one of hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine or octadecylamine.
2. The nitrogen-aluminum co-doped carbon dot film laser protective material as claimed in claim 1, wherein the weight average molecular weight of the polymethyl methacrylate is 300000-400000.
3. The nitrogen-aluminum co-doped carbon dot film laser protective material as claimed in claim 1, wherein the doping amount of the carbon dots in the film is 2-3%.
4. The nitrogen-aluminum co-doped carbon dot thin film laser protective material as claimed in claim 1, wherein the preparation method of the nitrogen-aluminum co-doped carbon dot thin film laser protective material comprises one or more of the following conditions:
i. the mono-substituted alkylamine is dodecylamine;
ii. The mass ratio of the mono-substituted alkylamine to the anhydrous aluminum trichloride is 0.5: 1-6: 1;
iii, the benzene solvent is one of chlorobenzene, bromobenzene, iodobenzene, o-dichlorobenzene, m-dichlorobenzene or p-dichlorobenzene; the volume ratio of the mass of the mono-substituted alkylamine to the benzene solvent is 0.05-0.5 g/ml;
iv, the reflux pyrolysis temperature is 140 ℃;
v, the reflux pyrolysis time is 24-48 hours.
5. The nitrogen-aluminum co-doped carbon dot thin film laser protective material as claimed in claim 1, wherein the preparation method of the nitrogen-aluminum co-doped carbon dot thin film laser protective material comprises one or more of the following conditions:
i. in the mixed solution, the concentration of the nitrogen-aluminum co-doped hydrophobic carbon dots is 0.23-1.35 mg/ml;
ii. In the mixed solution, the concentration of the polymethyl methacrylate is 25-30 mg/ml;
iii, in the dichloromethane dispersion liquid of the nitrogen-aluminum co-doped hydrophobic carbon dots, the concentration of the nitrogen-aluminum co-doped hydrophobic carbon dots is 1.38-8.1 mg/mL.
6. The nitrogen-aluminum co-doped carbon dot film laser protective material as claimed in claim 1, wherein in the preparation method of the nitrogen-aluminum co-doped carbon dot film laser protective material, the mass ratio of the polymethyl methacrylate to the nitrogen-aluminum co-doped hydrophobic carbon dots is 21-125: 1.
7. The nitrogen-aluminum co-doped carbon dot film laser protective material as claimed in claim 1, wherein in the preparation method of the nitrogen-aluminum co-doped carbon dot film laser protective material, the step of removing bubbles by ultrasound is further included after the nitrogen-aluminum co-doped hydrophobic carbon dots are added, fully dispersed and uniformly mixed, and the ultrasound time is 10-30 minutes.
8. The nitrogen-aluminum co-doped carbon dot thin film laser protection material as claimed in claim 1, wherein in the preparation method of the nitrogen-aluminum co-doped carbon dot thin film laser protection material, the film forming temperature is room temperature, and the film forming time is 24-48 hours.
9. The application of the nitrogen-aluminum co-doped carbon dot film laser protective material as claimed in any one of claims 1 to 8, which is applied to laser protection as a protective material.
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