Quantum dot glass raw material as well as preparation method and application thereof

Abstract

The invention discloses a quantum dot glass raw material as well as a preparation method and application thereof, and belongs to the technical field of optics. Raw materials of the quantum dot glass comprise the following elements by mole percent: 12.63%-21.05% of Si element; 1.36%-8.2% of an Al element; 1.03%-7.19% of a Zn element; 0.03%-0.68% of a Pb element; the element O accounts for 36.33%-76.36%; 0.34%-2.04% of a G element; 10.7% to 21.41% of an element M; 1.03%-5.13% of an element N; 0.5%-3.4% of an element X; wherein the G element is sulfur, selenium or tellurium; m is an alkali metal element; n is an alkaline earth metal element; x is a halogen element. The halogen elements and the alkali metal elements form alkali metal halide crystals and are located on the surfaces of the PbG quantum dots, so that surface defects of the PbG quantum dots are passivated, and the luminous efficiency is improved.

Description

Technical Field

[0001] The present disclosure relates to the field of optics, and particularly to quantum dot glass raw materials, their preparation methods and applications. Background Art

[0002] IV-VI group semiconductor quantum dots, such as PbS, PbSe, etc., have advantages such as small band gap energy, large exciton Bohr radius, and the fluorescence wavelength can be adjusted below 3 μm and 4.4 μm, making them widely used in many fields.

[0003] The preparation methods of quantum dots include chemical synthesis method, sol-gel method, melting method, etc. Among them, the melting method grows quantum dots in a glass matrix through a heat treatment process, which can not only prevent the aggregation of quantum dots, but also help improve the chemical stability, thermal stability and mechanical stability of quantum dots.

[0004] However, due to the large specific surface area of quantum dots, there are many surface defects, such as many dangling bonds, resulting in low luminescence efficiency of current quantum dots such as PbS and PbSe.

[0005] Disclosure

[0006] On the one hand, a quantum dot glass raw material is provided. The quantum dot glass raw material includes the following elements in mole percentages: Si element: 12.63% - 21.05%; Al element: 1.36% - 8.2%; Zn element: 1.03% - 7.19%; Pb element: 0.03% - 0.68%; O element: 36.33% - 76.36%; G element: 0.34% - 2.04%; M element: 10.7% - 21.41%; N element: 1.03% - 5.13%; X element: 0.5% - 3.4%.

[0007] Among them, the G element is sulfur element S, selenium element Se or tellurium element Te; the M element is an alkali metal element; the N element is an alkaline earth metal element; the X element is a halogen element.

[0008] The quantum dot glass raw material provided by the embodiments of the present disclosure can be used to prepare a quantum dot glass containing PbG quantum dots. The PbG quantum dots can be PbS quantum dots, PbSe quantum dots or PbTe quantum dots. That is to say, when the G element is sulfur element S, the quantum dot glass raw material is used to prepare a quantum dot glass containing PbS quantum dots; when the G element is selenium element Se, the quantum dot glass raw material is used to prepare a quantum dot glass containing PbSe quantum dots; when the G element is tellurium element Te, the quantum dot glass raw material is used to prepare a quantum dot glass containing PbTe quantum dots.

[0009] The quantum dot glass raw materials provided by the embodiments of the present disclosure can be used to prepare quantum dot glass products. Based on the synergistic effect of the above elements in specific molar percentages, the prepared quantum dot glass products have at least the following advantages: PbG quantum dots are formed in situ in the glass matrix, which not only facilitates the uniform dispersion of PbG quantum dots, but also helps to improve the thermal stability, chemical stability and mechanical stability of PbG quantum dots. By adding a certain amount of halogen elements and alkali metal elements to cooperate with each other, alkali metal halide crystals can be formed. On the one hand, the alkali metal halide crystals also help to reduce the melting temperature and viscosity of the glass melt and improve the uniformity of the glass matrix. On the other hand, the alkali metal halide crystals exist on the surface of PbG quantum dots and are connected to each other through halogen lead bonds to passivate the defects on the surface of PbG quantum dots, thereby effectively reducing the capture of carriers by the defects on the surface of PbG quantum dots and improving the luminescence efficiency of PbG quantum dots.

[0010] In some possible implementation manners, the M element is selected from at least one of Na element, K element, and Li element.

[0011] In some possible implementation manners, the N element is selected from at least one of Sr element, Ca element, and Ba element.

[0012] In some possible implementation manners, the X element is selected from at least one of Cl element, Br element, and I element.

[0013] Cl element, Br element, and I element are selected as the X element, and they are compounded with the alkali metal element M to form alkali metal halide crystals and bind to the outer surface of PbG quantum dots, thereby passivating the surface defects of PbG quantum dots and improving the luminescence efficiency.

[0014] In some possible implementation manners, the Si element exists in the form of silicon oxide;

[0015] The Al element exists in the form of aluminum oxide;

[0016] The G element exists in at least one of the form of ZnG and the form of G simple substance;

[0017] The Pb element exists in at least one of the form of lead oxide and the form of lead simple substance;

[0018] The alkaline earth metal element N exists in at least one of the form of alkaline earth metal carbonate compound and the form of alkaline earth metal halide;

[0019] The alkali metal element M exists in at least one of the form of alkali metal carbonate compound, the form of alkali metal sulfide, and the form of alkali metal halide;

[0020] The halogen element X exists in at least one of the forms of alkaline earth metal halide and alkali metal halide.

[0021] In some possible implementation manners, the element G is sulfur element S, and the sulfur element S exists in at least one of the forms of ZnS and elemental sulfur.

[0022] On the other hand, a preparation method of quantum dot glass is provided, and the preparation method of the quantum dot glass includes:

[0023] Providing raw materials for preparing quantum dot glass, wherein the elemental composition of the raw materials for preparing the quantum dot glass conforms to the elemental composition in any one of the above-mentioned quantum dot glass raw materials;

[0024] Performing melting treatment on the raw materials for preparing the quantum dot glass, obtaining molten glass liquid, placing the molten glass liquid in a mold and cooling and shaping to obtain a glass precursor;

[0025] Performing annealing treatment on the glass precursor to obtain a glass intermediate;

[0026] Performing heat treatment on the glass intermediate, thereby precipitating quantum dots in the glass matrix to obtain the quantum dot glass.

[0027] The preparation method of the quantum dot glass provided by the embodiments of the present disclosure can precipitate a uniformly dispersed quantum dot system in the glass matrix by sequentially performing melting treatment, annealing treatment and heat treatment on the raw materials for preparing the quantum dot glass. The quantum dot system includes PbG quantum dots and alkali metal halide crystals located on the surface of the PbG quantum dots. This method is simple and convenient to operate. On the premise that the prepared quantum dot glass has good stability (including mechanical stability, thermal stability and chemical stability), its luminous efficiency is improved compared with the related art.

[0028] In some possible implementation manners, the temperature of the melting treatment is 1350 °C to 1500 °C, and the time of the melting treatment is 30 minutes to 60 minutes;

[0029] The temperature of the annealing treatment is 250 °C to 450 °C, and the time of the annealing treatment is 2 hours to 10 hours.

[0030] In some possible implementation manners, the temperature of the heat treatment is 450 °C to 600 °C, and the time of the heat treatment is 1 hour to 48 hours.

[0031] Through the above heat treatment process, not only can PbG quantum dots precipitate in the glass matrix, but also, on the basis of the PbG quantum dots as crystal nuclei, alkali metal halide crystals MX gradually precipitate.

[0032] During the heat treatment process, by adjusting the heat treatment temperature and time, the particle size and distribution density of PbG quantum dots, as well as the particle size and distribution density of alkali metal halide crystal MX, can be adjusted.

[0033] On the other hand, a method for preparing a quantum dot optical fiber core is provided, and the method for preparing the quantum dot optical fiber core includes:

[0034] Providing raw materials for preparing quantum dot glass, wherein the elemental composition of the raw materials for preparing the quantum dot glass conforms to the elemental composition in any of the above-mentioned quantum dot glass raw materials;

[0035] Performing melting treatment on the raw materials for preparing the quantum dot glass, placing the molten glass liquid in a mold for cooling and forming to obtain a glass precursor;

[0036] Performing optical fiber drawing treatment on the glass precursor to obtain a first optical fiber core preform;

[0037] Performing annealing treatment on the first optical fiber preform to obtain a second optical fiber core preform;

[0038] Performing heat treatment on the second optical fiber core preform, thereby precipitating quantum dots in the glass matrix to obtain the quantum dot optical fiber core.

[0039] In some possible implementation manners, the temperature of the melting treatment is 1350 °C to 1500 °C, and the time of the melting treatment is 30 minutes to 60 minutes;

[0040] The temperature of the annealing treatment is 250 °C to 450 °C, and the time of the annealing treatment is 2 hours to 10 hours;

[0041] The temperature of the heat treatment is 450 °C to 600 °C, and the time of the heat treatment is 1 hour to 48 hours.

[0042] On the other hand, a quantum dot glass is provided, and the quantum dot glass is prepared by using the above-mentioned quantum dot glass raw materials, or by using the above-mentioned method for preparing quantum dot glass;

[0043] The quantum dot glass includes a glass matrix and a quantum dot system located in the glass matrix. The quantum dot system includes PbG quantum dots and alkali metal halide crystals located on the outer surface of the PbG quantum dots. The alkali metal halide crystals are composed of element M and element X. Element G is sulfur element S, selenium element Se or tellurium element Te. Correspondingly, the PbG quantum dots are PbS quantum dots, PbSe quantum dots or PbTe quantum dots.

[0044] The quantum dot glass provided by the embodiments of the present disclosure has at least the following advantages: PbG quantum dots are formed in situ in the glass matrix, which is not only beneficial to the uniform dispersion of PbG quantum dots, but also beneficial to improving the thermal stability, chemical stability and mechanical stability of PbG quantum dots. By adding a certain amount of halogen elements and alkali metal elements to cooperate with each other, alkali metal halide crystals can be formed. On the one hand, the alkali metal halide crystals are also beneficial to reducing the melting temperature and viscosity of the glass melt and improving the uniformity of the glass matrix. On the other hand, the alkali metal halide crystals exist on the surface of the PbG quantum dots and are connected by halogen-lead bonds to passivate the defects on the surface of the PbG quantum dots, thereby effectively reducing the capture of carriers by the defects on the surface of the PbG quantum dots and improving the luminescence efficiency of the PbG quantum dots.

[0045] On the other hand, a quantum dot optical fiber is provided. The quantum dot optical fiber includes a quantum dot optical fiber core, and the quantum dot optical fiber core is made of the above-mentioned quantum dot glass raw materials or is prepared by using the preparation method of the above-mentioned quantum dot glass;

[0046] The quantum dot optical fiber core includes a glass matrix and a quantum dot system located in the glass matrix. The quantum dot system includes PbG quantum dots and alkali metal halide crystals located on the outer surface of the PbG quantum dots. The alkali metal halide crystals are composed of element M and element X, and the G element is sulfur element S, selenium element Se or tellurium element Te. Description of the Drawings

[0047] Figure 1 Absorption spectra of the glass intermediate and a series of quantum dot glasses provided for Comparative Example 1;

[0048] Figure 2 Emission spectra of a series of quantum dot glasses provided for Comparative Example 1;

[0049] Figure 3 Absorption spectra of the glass intermediate and a series of quantum dot glasses provided for Example 1;

[0050] Figure 4 Emission spectra of a series of quantum dot glasses provided for Example 1;

[0051] Figure 5 Absorption spectra of the glass intermediate and a series of quantum dot glasses provided for Example 2;

[0052] Figure 6 Emission spectra of a series of quantum dot glasses provided for Example 2;

[0053] Figure 7 Absorption spectra of the glass intermediate and a series of quantum dot glasses provided for Example 3;

[0054] Figure 8 Emission spectra of a series of quantum dot glasses provided for Example 3;

[0055] Figure 9 Graph showing the variation of the luminescence efficiency with the quantum dot diameter of a series of quantum dot glasses provided for Comparative Example 1, Example 1, Example 2, and Example 3 under the excitation condition of 600 nm;

[0056] Figure 10 Graph showing the variation of the luminescence efficiency with the quantum dot diameter of a series of quantum dot glasses provided for Comparative Example 1, Example 1, Example 2, and Example 3 under the excitation condition of 700 nm;

[0057] Figure 11 Absorption spectra of the glass intermediate and a series of quantum dot glasses provided for Example 4;

[0058] Figure 12 Emission spectra of a series of quantum dot glasses provided for Example 4;

[0059] Figure 13 Luminescence efficiency test chart of a quantum dot glass provided for Example 4 under the excitation condition of 900 nm;

[0060] Figure 14 Luminescence efficiency test chart of a quantum dot glass provided for Example 5 under the excitation condition of 600 nm;

[0061] Figure 15 Luminescence efficiency test chart of a quantum dot glass provided for Example 6 under the excitation condition of 600 nm;

[0062] Figure 16 Luminescence efficiency test chart of a quantum dot glass provided for Example 7 under the excitation condition of 600 nm;

[0063] Figure 17 Luminescence efficiency test chart of a quantum dot glass provided for Example 8 under the excitation condition of 600 nm;

[0064] Figure 18 Structural layout diagram of an exemplary amplifier provided by an embodiment of the present disclosure.

[0065] Among them, Figure 1 , Figure 3 , Figure 5 , Figure 7 , Figure 11 In the absorption spectra shown, the abscissa Wavelength (nm) refers to the wavelength, and the ordinate Absorption coefficient (cm -1 ) refers to the absorption coefficient, representing the absorption of light per unit length in the medium.

[0066] Figure 2 、 Figure 4 、 Figure 6 、 Figure 8 、 Figure 12 In the emission spectrum diagrams shown, the abscissa Wavelength (nm) refers to the wavelength, and the ordinate PL intensity (a.u.) refers to the photoluminescence intensity.

[0067] Figure 9 、 Figure 10 In the curve diagram of the emission efficiency varying with the quantum dot diameter shown, the abscissa D avg (nm) refers to the average diameter of the quantum dot glass, and the ordinate Quantum yields (%) refers to the emission efficiency;

[0068] Figure 13 、 Figure 14 、 Figure 15 、 Figure 16 、 Figure 17 In the emission efficiency test diagrams shown, the abscissa Wavelength (nm) refers to the wavelength, and the ordinate Intensity (a.u.) refers to the intensity. Detailed implementation manners

[0069] For PbS quantum dots, their preparation methods include chemical synthesis method, sol-gel method, melting method, etc. For the PbS colloidal quantum dots synthesized by chemical method, the surface modification of the quantum dots is simple and the operability is high. However, the quantum dots dispersed in the solution are prone to agglomeration, photooxidation, and have poor thermal stability, which limits their applications. The melting method grows quantum dots in a glass matrix through a heat treatment process, which can not only prevent the agglomeration of quantum dots, but also help improve the chemical stability, thermal stability, and mechanical stability of quantum dots.

[0070] However, due to the small size and large specific surface area of quantum dots, there are many surface defects, such as many dangling bonds, resulting in low emission efficiency. It can be seen that it is very necessary to passivate the surface defects of quantum dots.

[0071] Compared with the chemically synthesized PbS quantum dots, for the quantum dot glass (also known as quantum dot-dispersed glass) synthesized by the melting method, since the PbS quantum dots are coated by the glass matrix, after the synthesis of PbS quantum dots, it is impossible to passivate the surface defects of PbS quantum dots by means of surface ligands, etc., resulting in serious surface defects of PbS quantum dots. Photo-traps generate electrons and vacancies, seriously reducing the emission efficiency of PbS quantum dots and limiting their applications.

[0072] In view of the technical problems existing in the related art, the embodiments of the present disclosure provide a quantum dot glass raw material, which includes the following elements in molar percentages: Si element: 12.63% - 21.05%; Al element: 1.36% - 8.2%; Zn element: 1.03% - 7.19%; Pb element: 0.03% - 0.68%; O element: 36.33% - 76.36%; G element: 0.34% - 2.04%; M element: 10.7% - 21.41%; N element: 1.03% - 5.13%; X element: 0.5% - 3.4%. Among them, the G element is sulfur element S, selenium element Se or tellurium element Te; the M element is an alkali metal element; the N element is an alkaline earth metal element; the X element is a halogen element.

[0073] The quantum dot glass raw material provided by the embodiments of the present disclosure can be used to prepare a quantum dot glass containing PbG quantum dots, and the PbG quantum dots can be PbS quantum dots, PbSe quantum dots or PbTe quantum dots. That is to say, when the G element is sulfur element S, the quantum dot glass raw material is used to prepare a quantum dot glass containing PbS quantum dots; when the G element is selenium element Se, the quantum dot glass raw material is used to prepare a quantum dot glass containing PbSe quantum dots; when the G element is tellurium element Te, the quantum dot glass raw material is used to prepare a quantum dot glass containing PbTe quantum dots.

[0074] The quantum dot glass raw material provided by the embodiments of the present disclosure can be used to prepare a quantum dot glass product. Based on the synergistic effect of the above various elements in specific molar percentages, the prepared quantum dot glass product has at least the following advantages: The PbG quantum dots are in-situ formed in the glass matrix, which is not only beneficial to the uniform dispersion of the PbG quantum dots, but also beneficial to improving the thermal stability, chemical stability and mechanical stability of the PbG quantum dots. By adding a certain amount of halogen element to cooperate with the alkali metal element, alkali metal halide crystals can be formed. On the one hand, the alkali metal halide crystals are also beneficial to reducing the melting temperature and viscosity of the glass melt and improving the uniformity of the glass matrix. On the other hand, the alkali metal halide crystals exist on the surface of the PbG quantum dots and are connected by lead halide bonds to achieve passivation of the surface of the PbG quantum dots, thereby effectively reducing the capture of carriers by the surface defects of the PbG quantum dots and improving the luminescence efficiency of the PbG quantum dots.

[0075] Taking the G element as an example of sulfur element S, PbS quantum dots are in-situ formed in the glass matrix, which is not only beneficial to the uniform dispersion of PbS quantum dots, but also conducive to improving the thermal stability, chemical stability and mechanical stability of PbS quantum dots. By adding a certain amount of halogen elements and alkali metal elements to cooperate to form alkali metal halide crystals, which exist on the surface of PbG quantum dots and are connected by halogen-lead bonds to passivate the surface of PbS quantum dots, thereby effectively reducing the capture of carriers by surface defects of PbS quantum dots and improving the luminescence efficiency of PbS quantum dots.

[0076] In some examples, in the quantum dot glass raw materials provided by the embodiments of the present disclosure, the sum of the molar percentages of Si element, Al element, Zn element, G element, Pb element, O element, N element, M element, and X element is 100%.

[0077] Combined with the molar percentages of the respective elements in the quantum dot glass raw materials involved above, the following are exemplary illustrations of some applicable molar percentages of these elements.

[0078] Exemplarily, the molar percentage of Si element includes but is not limited to: 12.7%, 12.8%, 12.9%, 13%, 13.1%, 13.2%, 13.3%, 13.4%, 13.5%, 13.6%, 13.7%, 13.8%, 13.9%, 14%, 14.2%, 14.4%, 14.5%, 14.6%, 14.8%, 14.9%, 15%, 15.2%, 15.3%, 15.5%, 15.7%, 15.8%, 16%, 16.2%, 16.5%, 16.8%, 17%, 17.3%, 17.5%, 17.7%, 18%, 18.3%, 18.5%, 18.7%, 19%, 19.5%, 20%, 20.1%, 20.2%, 20.3%, 20.4%, 20.5%, 20.6%, 20.7%, 20.8%, 20.9%, 21%, etc.

[0079] Exemplarily, the molar percentage of Al element includes but is not limited to: 1.4%, 1.45%, 1.5%, 1.55%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, 5%, 5.3%, 5.5%, 5.7%, 6%, 6.3%, 6.4%, 6.5%, 7%, 7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8%, 8.1%, 8.2%, etc.

[0080] Exemplarily, the molar percentage of Zn element includes but is not limited to: 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%, 7.1%, etc.

[0081] Exemplarily, the molar percentage of G element includes but is not limited to: 0.34%, 0.35%, 0.36%, 0.37%, 0.38%, 0.39%, 0.4%, 0.41%, 0.42%, 0.43%, 0.44%, 0.45%, 0.46%, 0.47%, 0.48%, 0.49%, 0.5%, 0.51%, 0.52%, 0.53%, 0.54%, 0.55%, 0.56%, 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%, 0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 071%, 0.72%, 0.73%, 0.74%, 0.75%, 0.76%, 0.77%, 0.78%, 0.79%, 0.8%, 0.81%, 0.82%, 0.83%, 0.84%, 0.85%, 0.86%, 0.87%, 0.88%, 0.89%, 0.9%, 0.91%, 0.92%, 0.93%, 0.94%, 0.95%, 0.96%, 0.97%, 0.98%, 0.99%, 1%, 1.1%, 1.15%, 1.2%, 1.25%, 1.3%, 1.35%, 1.4%, 1.45%, 1.5%, 1.55%, 1.6%, 1.65%, 1.7%, 1.75%, 1.8%, 1.85%, 1.9%, 1.95%, 2%, etc. In some examples, the G element is the S element.

[0082] Exemplarily, the molar percentages of the Pb element include but are not limited to: 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, 0.2%, 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, 0.3%, 0.31%, 0.32%, 0.33%, 0.34%, 0.35%, 0.36%, 0.37%, 0.38%, 0.39%, 0.4%, 0.41%, 0.42%, 0.43%, 0.44%, 0.45%, 0.46%, 0.47%, 0.48%, 0.49%, 0.5%, 0.51%, 0.52%, 0.53%, 0.54%, 0.55%, 0.56%, 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%, 0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, etc.

[0083] Exemplarily, the molar percentages of the alkaline earth metal N element include but are not limited to: 1.03%, 1.05%, 1.08%, 1.1%, 1.12%, 1.24%, 1.25%, 1.26%, 1.27%, 1.28%, 1.3%, 1.32%, 1.35%, 1.36%, 1.37%, 1.38%, 1.4%, 1.42%, 1.43%, 1.44%, 1.45%, 1.46%, 1.47%, 1.5%, 1.55%, 1.58%, 1.6%, 1.63%, 1.64%, 1.65%, 1.66%, 1.67%, 1.69%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, etc.

[0084] Exemplarily, the molar percentage of the alkali metal element M includes but is not limited to: 10.7%, 10.8%, 10.9%, 11%, 11.3%, 11.5%, 11.7%, 12%, 12.3%, 12.5%, 12.8%, 13%, 13.3%, 13.5%, 13.8%, 14%, 14.3%, 14.5%, 14.8%, 15%, 15.2%, 15.5%, 15.7%, 16%, 16.2%, 16.5%, 16.7%, 17%, 17.2%, 17.5%, 17.7%, 17.9%, 18%, 18.1%, 18.2%, 18.3%, 18.5%, 18.7%, 18.9%, 19%, 19.3%, 19.5%, 19.7%, 19.9%, 20%, 20.1%, 20.2%, 20.3%, 20.4%, 20.5%, 20.6%, 20.7%, 20.8%, 20.9%, 21%, 21.1%, 21.2%, 21.3%, 21.4%, etc.

[0085] Exemplarily, the molar percentage of the halogen element X includes but is not limited to: 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, etc.

[0086] In the embodiments of the present disclosure, the alkaline earth metal element N is selected from at least one of Sr element, Ca element, and Ba element, that is, the alkaline earth metal element N can be any one of them, or any two of them, or all three of them can be used simultaneously. Selecting Sr element, Ca element, and Ba element as the alkaline earth metal element N, which exists in the form of a glass network intermediate in the quantum dot glass product, can improve the thermal stability and chemical stability of the quantum dot glass product.

[0087] The alkali metal element M is selected from at least one of Na element, K element, and Li element, that is, the alkali metal element M can be any one of them, or any two of them, or all three of them can be used simultaneously.

[0088] Select Na element, K element, and Li element as the alkali metal element M. Moreover, the molar percentage of the alkali metal element M is greater than the molar percentage of the halogen element X. In this way, a part of the alkali metal element M is compounded with the halogen element X to form an alkali metal halide crystal and binds to the outer surface of the PbG quantum dots, thereby passivating the surface defects of the PbG quantum dots and improving the luminescence efficiency. Another part of the alkali metal element M exists in the form of a glass network intermediate in the quantum dot glass product and also acts as a flux.

[0089] The halogen element X is selected from at least one of Cl element, Br element, and I element, that is, the halogen element X can be any one of them, or any two of them, or all three can be used simultaneously.

[0090] Select Cl element, Br element, and I element as the X element. They are compounded with the alkali metal element M to form an alkali metal halide crystal and bind to the outer surface of the PbG quantum dots, thereby passivating the surface defects of the PbG quantum dots and improving the luminescence efficiency.

[0091] In the quantum dot product involved in the embodiments of the present disclosure, the alkali metal halide crystals are distributed in a dispersed state on the outer surface of the PbG quantum dots, and the alkali metal halide and the PbG quantum dots are connected by a halogen lead bond. Herein, the "dispersed state" involved can include a single alkali metal halide crystal being dispersed, or multiple alkali metal halide crystals agglomerating or combining into a cluster and being dispersed in the form of a cluster. Both of the above two forms can achieve the passivation of the surface defects of the PbG quantum dots.

[0092] The quantum dot glass raw material provided by the embodiments of the present disclosure has each element existing in at least one of the form of a simple substance and a compound, so as to facilitate the acquisition of the quantum dot glass raw material and thus facilitate the preparation of the glass product. The existing forms of each element are described exemplarily as follows.

[0093] In the preparation raw material of the quantum dot glass, the Si element exists in the form of a silicon oxide, for example, in the form of silicon dioxide (SiO 2 ). In the glass product, the Si element combines with the O element and acts as a glass former.

[0094] In the preparation raw material of the quantum dot glass, the Al element exists in the form of an aluminum oxide, for example, in the form of aluminum oxide (Al 2 O 3 ). In the glass product, the Al element combines with the O element and acts as a glass former.

[0095] In the preparation raw material of the quantum dot glass, the Zn element exists in at least one of the forms of ZnO and ZnS. In the glass product, the Zn element combines with the O element and acts as a glass intermediate.

[0096] In the raw materials for preparing quantum dot glass, the G element exists in at least one of the ZnG form and the G single substance form. For example, the ZnG form can be ZnS, ZnSe, etc. In the glass product, the G element exists in the form of PbG quantum dots.

[0097] For example, taking element G as sulfur element S, the sulfur element S exists in at least one of the form of ZnS and the form of sulfur element. One example is that the sulfur element S is introduced into the raw materials for preparing quantum dot glass in the form of ZnS.

[0098] Since sulfur element S is easily volatile, the molar percentage of sulfur element S can be made greater than the molar percentage of Pb element. For example, the ratio of the molar percentage of sulfur element S to the molar percentage of Pb element is 2 to 30:1, including but not limited to 2 to 25:1, 2 to 20:1, 2 to 15:1, etc.

[0099] In the raw materials for preparing quantum dot glass, the Pb element exists in at least one of the form of lead oxide and the form of single lead. For example, the lead oxide can be lead oxide (PbO). In the glass product, the Pb element exists in the form of PbG quantum dots.

[0100] The alkaline earth metal element N exists in at least one of the form of an alkaline earth metal carbonate compound and an alkaline earth metal halide. For example, the alkaline earth metal carbonate compound may be strontium carbonate (SrCO 3 ), calcium carbonate (CaCO 3 ), barium carbonate (BaCO 3 ) at least one of which, for example, an alkaline earth metal halide, may be strontium chloride (SrCl 2 ), strontium bromide (SrBr 2 ), strontium iodide (SrI 2 ), calcium chloride (CaCl 2 ), calcium bromide (CaBr 2 ), calcium iodide (CaI 2 ), barium chloride (BaCl 2 ), barium bromide (BaBr 2 ), barium iodide (BaI 2 ) At least one of the above. During the melting process, the C element evaporates in the form of gas. In addition, in the glass product, the alkaline earth metal element N is combined with the O element and serves as a glass intermediate.

[0101] In the raw materials for preparing quantum dot glass, the alkali metal element M exists in at least one of the forms of alkali metal carbonate, alkali metal sulfide and alkali metal halide. For example, the alkali metal carbonate may be sodium carbonate (Na2 CO 3 ) potassium carbonate (K 2 CO 3 ), lithium carbonate (Li 2 CO 3 ), at least one of which, taking alkali metal sulfides as an example, can be sodium sulfide (Na2S), potassium sulfide (K 2 S), lithium sulfide (Li 2 S), at least one of which. Among them, during the melting process, the C element volatilizes in the form of gas. And, in the glass product, part of the alkali metal element M is compounded with the halogen element X to form an MX crystal and passivate the surface of the PbG quantum dots, and the remaining part of the alkali metal element serves as a glass network intermediate.

[0102] In the preparation raw materials of the quantum dot glass, the halogen element X exists in at least one of the forms of alkaline earth metal halides and alkali metal halides. Taking alkaline earth metal halides as an example, this can be strontium chloride (SrCl 2 ), strontium bromide (SrBr 2 ), strontium iodide (SrI 2 ), calcium chloride (CaCl 2 ), calcium bromide (CaBr 2 ), calcium iodide (CaI 2 ), barium chloride (BaCl 2 ), barium bromide (BaBr 2 ), barium iodide (BaI 2 ), at least one of which. Taking alkali metal halides as an example, this can be sodium chloride (NaCl), sodium bromide (NaBr), sodium iodide (NaI), potassium chloride (KCl), potassium bromide (KBr), potassium iodide (KI), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), at least one of which.

[0103] For example, when introducing an alkali metal halide to replace an alkali metal oxide into the preparation raw materials of the quantum dot glass, the method of substituting with an equimolar amount of alkali metal elements is adopted, such as using 2 mol% of NaCl to replace 1 mol% of Na 2 O.

[0104] In some examples, the molar percentage of the halogen element X in the quantum dot glass raw materials is 0.5% - 3.4%, further 0.68% - 2.05%, which can not only achieve the above-mentioned passivation effect, but also prevent problems such as phase separation during the glass formation process.

[0105] On the other hand, the embodiments of the present disclosure also provide a method for preparing a quantum dot glass, and the method for preparing the quantum dot glass includes the following steps:

[0106] Step S11, providing raw materials for preparing quantum dot glass, the element composition of the raw materials for preparing quantum dot glass conforms to the element composition of any of the above-mentioned raw materials for quantum dot glass.

[0107] Step S12, melting the raw materials for preparing quantum dot glass, placing the molten glass liquid in a mold for cooling and forming, and obtaining a glass precursor.

[0108] Step S13, annealing the glass precursor to obtain a glass intermediate.

[0109] Step S14: heat-treating the glass intermediate, thereby precipitating quantum dots in the glass matrix to obtain quantum dot glass.

[0110] The method for preparing quantum dot glass provided in the embodiment of the present disclosure can prepare quantum dot glass by sequentially melting, annealing and heat treating the raw materials for preparing quantum dot glass, thereby precipitating uniformly dispersed PbG quantum dots and alkali metal halide crystals located on the surface of PbG quantum dots in the glass matrix. The method is simple and convenient to operate, and the prepared quantum dot glass has good stability (including mechanical stability, thermal stability and chemical stability), and its luminous efficiency is improved compared with related technologies.

[0111] For step S11, raw materials for preparing quantum dot glass are provided, and the element composition of the raw materials for preparing quantum dot glass conforms to the element composition of any of the above-mentioned raw materials for quantum dot glass.

[0112] As mentioned above, Si element exists in the form of silicon oxide; Al element exists in the form of aluminum oxide; G element exists in at least one of ZnG form and G single substance form; Pb element exists in at least one of lead oxide form and lead single substance form; alkaline earth metal element N exists in at least one of alkaline earth metal carbonate form and alkaline earth metal halide form; alkali metal element M exists in at least one of alkali metal carbonate form, alkali metal sulfide form and alkali metal halide form; halogen element X exists in at least one of alkaline earth metal halide form and alkali metal halide form.

[0113] For each element, determine the existence form of each element and use it as a component in the raw material for preparing quantum dot glass. According to the molar ratio of the elements in the above-mentioned raw material for quantum dot glass, determine the ratio of each component in the raw material for preparing quantum dot glass, so as to obtain the raw material for preparing quantum dot glass.

[0114] In some examples, each component of the raw material for preparing quantum dot glass is accurately weighed according to the ratio, put into a mortar and fully ground to mix evenly, and then step S12 is performed.

[0115] ​For step S12, the raw materials for preparing the quantum dot glass are melted, and the molten glass liquid is placed in a mold to cool and form. For example, the raw materials for preparing the quantum dot glass can be placed in a sealed crucible for melting treatment to obtain a molten glass liquid. Among them, PbG quantum dots are not formed in the molten glass liquid.

[0116] Some applicable temperatures for the melting treatment are 1350°C to 1500°C, including but not limited to: 1350°C, 1360°C, 1370°C, 1380°C, 1390°C, 1400°C, 1410°C, 1420°C, 1430°C, 1440°C, 1450°C, 1460°C, 1470°C, 1480°C, 1490°C, 1500°C, etc. Some applicable times for the melting treatment are 30 minutes to 60 minutes, including but not limited to: 30 minutes, 40 minutes, 50 minutes, 60 minutes, etc.

[0117] For step S13, the glass precursor is annealed to obtain a glass intermediate, thereby eliminating residual stress, and the obtained glass intermediate is yellow and transparent.

[0118] Some applicable temperatures for the annealing treatment are 250°C to 450°C, including but not limited to: 250°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, etc. The time for the annealing treatment is 2 hours to 10 hours, including but not limited to: 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, etc.

[0119] For step S14, the glass intermediate is heat-treated to precipitate quantum dots in the glass matrix to obtain quantum dot glass.

[0120] Exemplarily, the temperature of the heat treatment is 450°C to 600°C, including but not limited to: 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, etc.

[0121] The heat treatment time is from 1 hour to 48 hours, including but not limited to: 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, 36 hours, 37 hours, 38 hours, 39 hours, 40 hours, 41 hours, 42 hours, 43 hours, 44 hours, 45 hours, 46 hours, 47 hours, 48 hours, etc.

[0122] Through the above heat treatment process, not only can PbG quantum dots precipitate in the glass matrix, but also, on the basis of PbG quantum dots as crystal nuclei, alkali metal halide crystals MX gradually precipitate to form a quantum dot system.

[0123] During the heat treatment process, by adjusting the heat treatment temperature and heat treatment time, the particle size and distribution density of PbG quantum dots, as well as the particle size and distribution density of alkali metal halide crystals MX, can be adjusted.

[0124] The heat treatment process is also the glass crystallization process, which includes two stages: crystal nucleus formation and crystal growth. The higher the heat treatment temperature, the faster the crystal nucleus growth rate, and the longer the heat treatment time, the larger the crystal size. Therefore, by controlling the length of the heat treatment time and the height of the heat treatment temperature, PbG quantum dots with high density and required size can be obtained accordingly.

[0125] On the other hand, the embodiments of the present disclosure also provide a method for preparing a quantum dot optical fiber core, and the method for preparing the quantum dot optical fiber core includes the following steps:

[0126] Step S21: Provide the preparation raw materials of the quantum dot glass, and the elemental composition of the preparation raw materials of the quantum dot glass conforms to the elemental composition in any of the above-mentioned quantum dot glass raw materials.

[0127] Step S22: Perform melting treatment on the preparation raw materials of the quantum dot glass, place the molten glass liquid in a mold and cool it to form a glass precursor.

[0128] Step S23: Perform optical fiber drawing treatment on the glass precursor to obtain a first optical fiber core preform.

[0129] Step S24: Perform annealing treatment on the first optical fiber preform to obtain a second optical fiber core preform.

[0130] Step S25: Heat-treat the second optical fiber core preform to precipitate quantum dots in the glass matrix, thereby obtaining a quantum dot optical fiber core.

[0131] The method for preparing a quantum dot optical fiber core provided by the embodiments of the present disclosure can precipitate a uniformly dispersed quantum dot system in the glass matrix by successively performing melting treatment, optical fiber drawing treatment, annealing treatment, and heat treatment on the raw materials for preparing the quantum dot glass, so as to obtain a quantum dot optical fiber core. The quantum dot system includes PbG quantum dots and alkali metal halide crystals located on the surface of the PbG quantum dots. This method is simple and convenient to operate. On the premise that the prepared quantum dot glass has good stability (including mechanical stability, thermal stability, and chemical stability), its luminescence efficiency is improved compared with the related art.

[0132] Exemplarily, the temperature of the melting treatment is 1350°C to 1500°C, and the time of the melting treatment is 30 minutes to 60 minutes; the temperature of the annealing treatment is 250°C to 450°C, and the time of the annealing treatment is 2 hours to 10 hours; the temperature of the heat treatment is 450°C to 600°C, and the time of the heat treatment is 1 hour to 48 hours.

[0133] For steps S21, S22, S24, and S25, reference can be made to the relevant descriptions of steps S11, S12, S13, and S14 above respectively, and details will not be elaborated here.

[0134] For step S23, to perform an optical fiber drawing treatment on the glass precursor to obtain a first optical fiber core preform, the above drawing treatment can be carried out by using the existing optical fiber preform drawing technology.

[0135] On the other hand, the embodiments of the present disclosure also provide a quantum dot glass, which is prepared by using any of the above-mentioned quantum dot glass raw materials or by using the preparation method of any of the above-mentioned quantum dot glasses.

[0136] Among them, the quantum dot glass includes a glass matrix and a quantum dot system located in the glass matrix. The quantum dot system includes PbG quantum dots and alkali metal halide crystals located on the outer surface of the PbG quantum dots. The alkali metal halide crystals are composed of element M and element X. Element G is sulfur element S, selenium element Se, or tellurium element Te. Correspondingly, the PbG quantum dots are PbS quantum dots, PbSe quantum dots, or PbTe quantum dots.

[0137] The quantum dot glass provided by the embodiments of the present disclosure has at least the following advantages: The PbG quantum dots are formed in-situ in the glass matrix, which not only facilitates the uniform dispersion of the PbG quantum dots, but also helps to improve the thermal stability, chemical stability and mechanical stability of the PbG quantum dots. By adding a certain amount of halogen elements and alkali metal elements to cooperate with each other, alkali metal halide crystals can be formed. On the one hand, the alkali metal halide crystals also help to reduce the melting temperature and viscosity of the glass melt and improve the uniformity of the glass matrix. On the other hand, the alkali metal halide crystals exist on the surface of the PbG quantum dots and are connected by halogen-lead bonds to passivate the defects on the surface of the PbG quantum dots, thereby effectively reducing the capture of carriers by the surface defects of the PbG quantum dots and improving the luminescence efficiency of the PbG quantum dots.

[0138] The alkali metal halide crystals are distributed in a dispersed state on the outer surface of the PbG quantum dots, and the two are connected by halogen-lead bonds. Herein, the "dispersed state" involved herein may include the dispersed arrangement of a single alkali metal halide crystal, or may include the aggregation or combination of multiple alkali metal halide crystals into a cluster and the dispersed arrangement in the form of a cluster. Both of the above two forms can achieve the passivation of the surface defects of the PbG quantum dots.

[0139] The quantum dot glass provided by the embodiments of the present disclosure can adjust the particle size of the PbG quantum dots by adjusting the heat treatment process, so as to realize the regulation of the absorption and luminescence of the quantum dot glass in the wavelength range of 1000nm - 2400nm.

[0140] In some examples, the quantum dot glass provided by the embodiments of the present disclosure includes: PbS quantum dots and alkali metal halide crystals located on the outer surface of the PbS quantum dots.

[0141] On the other hand, the embodiments of the present disclosure also provide a quantum dot optical fiber, which includes a quantum dot optical fiber core. The quantum dot optical fiber core uses the quantum dot glass raw material described in any one of the above, or is prepared by using the preparation method of the quantum dot optical fiber core described in any one of the above. Among them, the quantum dot optical fiber core includes a glass matrix and a quantum dot system located in the glass matrix. The quantum dot system includes PbG quantum dots and alkali metal halide crystals located on the outer surface of the PbG quantum dots. The alkali metal halide crystals are composed of element M and element X. The G element is sulfur element S, selenium element Se or tellurium element Te. Correspondingly, the PbG quantum dots are PbS quantum dots, PbSe quantum dots or PbTe quantum dots.

[0142] The quantum dot optical fiber provided by the embodiments of the present disclosure has at least the following advantages: The PbG quantum dots are formed in situ in the glass matrix, which not only facilitates the uniform dispersion of the PbG quantum dots, but also helps to improve the thermal stability, chemical stability and mechanical stability of the PbG quantum dots. By adding a certain amount of halogen elements and alkali metal elements to cooperate with each other, alkali metal halide crystals can be formed. On the one hand, the alkali metal halide crystals also help to reduce the melting temperature and viscosity of the glass melt and improve the uniformity of the glass matrix. On the other hand, the alkali metal halide crystals are present on the surface of the PbG quantum dots and the two are connected by lead halide bonds to passivate the defects on the surface of the PbG quantum dots, thereby effectively reducing the capture of carriers by the surface defects of the PbG quantum dots and improving the luminescence efficiency of the PbG quantum dots.

[0143] The alkali metal halide crystals are distributed in a dispersed manner on the outer surface of the PbG quantum dots, and the two are connected by lead halide bonds. Regarding the alkali metal halide crystals in the core of the quantum dot optical fiber, reference can be made to the relevant descriptions of the quantum dot glass above.

[0144] The quantum dot optical fiber provided by the embodiments of the present disclosure can adjust the particle size of the PbG quantum dots by adjusting the heat treatment process, so as to realize the regulation of the absorption and luminescence of the core of the quantum dot optical fiber in the wavelength range of 1000nm - 2400nm.

[0145] In some examples, the quantum dot optical fiber provided by the embodiments of the present disclosure includes PbS quantum dots and alkali metal halide crystals located on the outer surface of the PbS quantum dots.

[0146] Of course, the quantum dot glass products involved in the embodiments of the present disclosure can not only be the above-mentioned quantum dot glass and quantum dot optical fiber, but also rod-shaped glass. The quantum dot glass or quantum dot optical fiber provided by the embodiments of the present disclosure can realize the adjustment of the absorption spectrum and luminescence spectrum in the near-infrared to mid-infrared wavelength range, making it have great application potential in the fields of infrared detection and near-infrared fluorescence.

[0147] An optical fiber amplifier is a very important device in an optical fiber communication line. In a backbone long-distance optical communication network, the signal power continuously attenuates as the transmission distance increases. Therefore, an amplifier is needed to amplify the signal every certain transmission distance. A typical amplifier is an erbium-doped optical fiber amplifier, and its working principle is to couple the signal light and the pump light into the erbium-doped optical fiber through a wavelength division multiplexer, and at the same time, an isolator is added to ensure the forward transmission of the optical signal.

[0148] Currently, the noise figure of the erbium-doped optical fiber amplifier is relatively high. One implementation scheme is that the existing erbium-doped optical fiber can be replaced with the quantum dot glass or quantum dot optical fiber provided by the embodiments of the present disclosure to obtain a new type of amplifier, so as to achieve a lower noise figure.

[0149] Among them, the central wavelength of the novel amplifier of the quantum dot glass product based on the embodiments of the present disclosure can be controlled by the central particle size of the quantum dots, the working bandwidth can be controlled by the size distribution of the quantum dots, and the central particle size and size distribution of the quantum dots can be controlled by different heat treatment conditions, thereby providing a new way for expanding the optical fiber communication waveband and industrial applications.

[0150] Exemplarily, referring to Figure 18 , the structure of an amplifier includes: a signal source 1, an isolator 2, a wavelength division multiplexer 3, a pump source 4, and a quantum dot glass product 5 (including quantum dot glass or quantum dot glass optical fiber). The signal light is output from the signal source 1 and enters the isolator 2 to ensure the forward transmission of the optical signal, enters the wavelength division multiplexer 3, and then the signal light enters the quantum dot glass product 5 for optical amplification and outputs the amplified signal light. At the same time, the pump light is output from the pump source 4, enters through the wavelength division multiplexer 3, and then the pump light enters the quantum dot glass product 5 and the pump light enters the quantum dot glass optical fiber 6. Among them, after the signal light and the pump light are coupled in the wavelength division multiplexer, they enter the quantum dot glass product 5 so that the signal can be amplified and output.

[0151] The exemplary embodiments of the present disclosure will be described in more detail below. Although the exemplary embodiments of the present disclosure are described below, it should be understood that the present disclosure can be implemented in various forms and should not be limited by the embodiments set forth herein. For those not specified in the examples in terms of specific technologies or conditions, they shall be carried out according to the technologies or conditions described in the literature in the art or according to the product specifications. For reagents or instruments not specified in terms of the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0152] Examples 1 - 8 and Comparative Example 1 described below all provide a quantum dot glass raw material, and the formulations of these quantum dot glass raw materials are shown in Table 1 respectively.

[0153] Among the raw materials for preparing the quantum dot glass of Examples 1 - 8 and Comparative Example 1, the Si element exists in the form of silicon dioxide (SiO 2 ), the Al element exists in the form of aluminum oxide (Al 2 O 3 ), the Zn element exists in the forms of ZnO and ZnS, the S element exists in the form of ZnS, the Pb element exists in the form of lead oxide (PbO), the Ca element exists in the form of calcium carbonate (CaCO 3 ), the Na element exists in the forms of sodium carbonate (Na 2 CO 3 ) and sodium chloride (NaCl), and the Cl element exists in the form of sodium chloride (NaCl).

[0154] Table 1

[0155]

[0156] Comparative Example 1

[0157] In Comparative Example 1, a quantum dot glass was prepared by the following method: Provide the raw materials for preparing the quantum dot glass that are uniformly mixed, and the elemental composition of the raw materials for preparing the quantum dot glass conforms to the elemental composition in the quantum dot glass raw materials of Comparative Example 1 in Table 1. Place the raw materials for preparing the quantum dot glass in a crucible for melting treatment, with a melting temperature of 1400 °C and a melting time of 40 minutes to obtain a molten glass liquid. After the molten glass liquid cools, a glass precursor is formed, which is transferred to an annealing furnace for annealing treatment, with an annealing temperature of 400 °C and an annealing time of 5 hours to obtain a yellow transparent glass intermediate. After testing, this yellow transparent glass intermediate has no absorption peak in the near-infrared band of visible light.

[0158] Transfer the glass intermediate to a heat treatment furnace for heat treatment, thereby precipitating PbS quantum dots in the glass matrix to obtain a series of quantum dot glasses. Among them, the heat treatment conditions and some test parameters of the quantum dot glass in Comparative Example 1 are shown in Table 2.

[0159] Table 2

[0160] Sample Number Heat Treatment Conditions <![CDATA[λ abs / nm]]> <![CDATA[D avg / nm]]> <![CDATA[λ PL / nm]]> 0 Glass Intermediate / / / 1 510℃ / 10h 724 3.7 980 2 510℃ / 20h 774 3.8 989 3 520℃ / 10h 817 4.0 1023 4 520℃ / 15h 914 4.3 1104 5 520℃ / 20h 973 4.5 1150 6 530℃ / 10h 1117 5.1 1205 7 530℃ / 15h 1142 5.2 1241 8 540℃ / 05h 1180 5.3 1252 9 540℃ / 08h 1329 5.8 1381 10 540℃ / 10h 1423 6.2 1481 11 550℃ / 10h 1674 7.3 1685 12 560℃ / 10h 2004 9.2 1983

[0161] In Table 2, λ abs refers to the central wavelength of the absorption peak of the current quantum dot glass, with the unit of nm; D avg refers to the average diameter of the PbS quantum dots in the current quantum dot glass, with the unit of nm; λ PL refers to the central wavelength of the emission peak of the current quantum dot glass, with the unit of nm.

[0162] Absorption spectrum tests were performed on a series of quantum dot glasses provided in Comparative Example 1. The test results are shown in Table 2 and Appendix Figure 1 , Figure 1 , and the numbers 0 - 12 in it are the sample numbers 0 to 12 described in Table 2. As shown in Appendix Figure 1 , as the heat treatment temperature increases or the heat treatment time prolongs, the absorption peak of the quantum dot glass gradually shifts to the long wavelength band, indicating that PbS quantum dots are precipitated in the glass sample prepared in Comparative Example 1, and the size of the PbS quantum dots gradually increases as the heat treatment temperature increases or the heat treatment time prolongs.

[0163] Emission spectrum tests were performed on a series of quantum dot glasses provided in Comparative Example 1, with an excitation wavelength of 800 nm. The test results are shown in Table 2 and Appendix Figure 2 , Figure 2 , and the numbers 1 → 12 in it are the sample numbers 1 to 12 described in Table 2. As shown in AppendixFigure 2 As shown, with the increase of the heat treatment temperature or the extension of the heat treatment time, the fluorescence peak of the quantum dot glass gradually shifts to the long wavelength band, indicating that PbS quantum dots precipitate in the glass sample prepared in Comparative Example 1, and the size of the PbS quantum dots gradually increases with the increase of the heat treatment temperature or the extension of the heat treatment time.

[0164] Example 1

[0165] Example 1 prepared a quantum dot glass, which was prepared by the following method: providing a uniformly mixed raw material for preparing the quantum dot glass, and the elemental composition of the raw material for preparing the quantum dot glass conforms to the elemental composition in the quantum dot glass raw material of Example 1 in Table 1. The raw material for preparing the quantum dot glass was placed in a crucible for melting treatment, the melting temperature was 1400 °C, and the melting time was 40 minutes to obtain a molten glass liquid. After the molten glass liquid was cooled, a glass precursor was formed, which was transferred to an annealing furnace for annealing treatment, the annealing temperature was 400 °C, and the annealing time was 5 hours to obtain a yellow transparent glass intermediate. After testing, the yellow transparent glass intermediate has no absorption peak in the near-infrared band of visible light.

[0166] The glass intermediate was transferred to a heat treatment furnace for heat treatment to precipitate PbS quantum dots in the glass matrix. Among them, NaCl crystals are distributed on the outer surface of the PbS quantum dots, and the two cooperate to form a quantum dot system, thereby obtaining a series of quantum dot glasses. Absorption spectra and emission spectra of the glass intermediate and a series of quantum dot glasses provided in Example 1 were tested. Among them, the excitation wavelength during the emission spectrum test was 800 nm.

[0167] The heat treatment conditions of Example 1 and some test parameters of the quantum dot glass are shown in Table 3.

[0168] Table 3

[0169] Sample Number Heat Treatment Conditions <![CDATA[λ abs / nm]]> <![CDATA[λ PL / nm]]> <![CDATA[D avg / nm]]> 0 Glass Intermediate / / / 1 510℃ / 10h 797 1016 3.9 2 510℃ / 15h 803 1030 4.0 3 510℃ / 20h 917 1112 4.3 4 520℃ / 10h 1046 1168 4.8 5 520℃ / 15h 1164 1252 5.2 6 520℃ / 20h 1285 1330 5.7 7 530℃ / 05h 1176 1234 5.2 8 530℃ / 07h 1316 1396 5.8 9 530℃ / 10h 1476 1502 6.4 10 540℃ / 05h 1531 1556 6.7 11 540℃ / 10h 1825 1810 8.1 12 550℃ / 10h 2276 2069 11.4 13 560℃ / 10h 2321 2075 11.9

[0170] In Table 3, λ abs refers to the central wavelength of the absorption peak of the current quantum dot glass, with the unit of nm; λ PL refers to the central wavelength of the emission peak of the current quantum dot glass, with the unit of nm; D avg refers to the average diameter of the PbS quantum dots in the current quantum dot glass, with the unit of nm.

[0171] Absorption spectra of the glass intermediate and a series of quantum dot glasses provided in Example 1 were tested, and the test results are shown in Table 3 and Appendix Figure 3 , Figure 3 The numbers 0 - 13 in are the sample numbers 0 to 13 described in Table 3. As shown in Appendix Figure 3As shown, there is no absorption peak in the glass intermediate. As the heat treatment temperature increases or the heat treatment time prolongs, the absorption peak of the quantum dot glass gradually shifts towards the long wavelength band, indicating that PbS quantum dots precipitate in the glass sample prepared in Example 1, and the size of the PbS quantum dots gradually increases as the heat treatment temperature increases or the heat treatment time prolongs.

[0172] Luminescence spectra tests were conducted on a series of quantum dot glasses provided in Example 1. The excitation wavelength was 800 nm. The test results are shown in Table 3 and Appendix Figure 4 , Figure 4 The numbers 1 - 13 in it are the sample numbers 1 to 13 described in Table 3. As shown in Appendix Figure 4 As shown, as the heat treatment temperature increases or the heat treatment time prolongs, the fluorescence peak of the quantum dot glass gradually shifts towards the long wavelength band, indicating that PbS quantum dots precipitate in the glass sample prepared in Example 1, and the size of the PbS quantum dots gradually increases as the heat treatment temperature increases or the heat treatment time prolongs.

[0173] Luminescence efficiency tests were conducted on a series of quantum dot glasses provided in Example 1 and Comparative Example 1 respectively. The test results when the excitation wavelength was 600 nm are shown in Figure 9 , and the test results when the excitation wavelength was 700 nm are shown in Figure 10 . As shown in Appendix Figure 9 and Appendix Figure 10 As shown, under the excitation of light sources with wavelengths of 600 nm and 700 nm, the luminescence efficiency of the quantum dot glass in Comparative Example 1 is lower than 30%. Compared with Comparative Example 1, when the average diameter of the PbS quantum dots is the same, the luminescence efficiency of the quantum dot glass provided in Example 1 is improved. This is because Cl ions effectively passivate the surface Pb ion dangling bonds of the PbS quantum dots, thereby effectively improving the luminescence efficiency of the PbS quantum dots.

[0174] Example 2

[0175] Quantum dot glass was prepared in Example 2, which was prepared by the following method: Provide the preparation raw materials of the quantum dot glass that are uniformly mixed. The elemental composition of the preparation raw materials of the quantum dot glass conforms to the elemental composition in the quantum dot glass raw materials of Example 2 in Table 1. Place the preparation raw materials of the quantum dot glass in a crucible for melting treatment. The melting temperature is 1400 °C and the melting time is 40 minutes to obtain a molten glass liquid. After the molten glass liquid cools, a glass precursor is formed and transferred to an annealing furnace for annealing treatment. The annealing temperature is 400 °C and the annealing time is 5 hours to obtain a yellow transparent glass intermediate. After testing, this yellow transparent glass intermediate has no absorption peak in the near-infrared band of visible light.

[0176] Transfer the glass intermediate to a heat treatment furnace for heat treatment, so as to precipitate PbS quantum dots in the glass matrix. There are NaCl crystals distributed on the outer surface of the PbS quantum dots, thereby obtaining a series of quantum dot glasses. The absorption spectra and luminescence spectra of the glass intermediate and the series of quantum dot glasses provided in Example 2 were tested. Among them, the excitation wavelength during the luminescence spectrum test was 800 nm.

[0177] The heat treatment conditions of Example 2 and some test parameters of the quantum dot glasses are shown in Table 4.

[0178] Table 4

[0179] Sample Number Heat Treatment Conditions <![CDATA[λ abs / nm]]> <![CDATA[λ PL / nm]]> <![CDATA[D avg / nm]]> 0 Glass Intermediate / / / 1 510℃ / 10h 848 1012 4.1 2 510℃ / 15h 877 1068 4.2 3 510℃ / 20h 917 1108 4.3 4 520℃ / 10h 1016 1172 4.7 5 520℃ / 15h 1180 1304 5.3 6 520℃ / 20h 1256 1342 5.5 7 530℃ / 05h 1245 1344 5.5 8 530℃ / 07h 1341 1432 5.9 9 530℃ / 10h 1483 1520 6.4 10 540℃ / 05h 1450 1518 6.3 11 540℃ / 10h 1755 1780 7.7 12 550℃ / 10h 1997 1990 9.2 13 560℃ / 10h 2017 2105 9.3

[0180] In Table 4, λ abs refers to the central wavelength of the absorption peak of the current quantum dot glass, with the unit of nm; λ PL refers to the central wavelength of the emission peak of the current quantum dot glass, with the unit of nm; D avg refers to the average diameter of the PbS quantum dots in the current quantum dot glass, with the unit of nm.

[0181] The absorption spectra of the glass intermediate and the series of quantum dot glasses provided in Example 2 were tested. The test results are shown in Table 4 and Appendix Figure 5 , Figure 5 . The numbers 0 - 13 in it are the sample numbers 0 to 13 described in Table 4. As shown in Appendix Figure 5 , the glass intermediate has no absorption peak. As the heat treatment temperature increases or the heat treatment time prolongs, the absorption peak of the quantum dot glass gradually shifts to the long wavelength band. This indicates that PbS quantum dots are precipitated in the glass sample prepared in Example 2, and the size of the PbS quantum dots gradually increases as the heat treatment temperature increases or the heat treatment time prolongs.

[0182] The luminescence spectra of the series of quantum dot glasses provided in Example 2 were tested. The excitation wavelength was 800 nm. The test results are shown in Table 4 and Appendix Figure 6 , Figure 6 . The numbers 1 - 13 in it are the sample numbers 1 to 13 described in Table 4. As shown in Appendix Figure 6 , as the heat treatment temperature increases or the heat treatment time prolongs, the fluorescence peak of the quantum dot glass gradually shifts to the long wavelength band. This indicates that PbS quantum dots are precipitated in the glass sample prepared in Example 2, and the size of the PbS quantum dots gradually increases as the heat treatment temperature increases or the heat treatment time prolongs.

[0183] The luminous efficiency of the series of quantum dot glasses provided in Example 2 and Comparative Example 1 was tested respectively. The test results when the excitation wavelength was 600 nm are shown in Figure 9, see the test results when the excitation wavelength is 700 nm Figure 10 . As shown in the attached Figure 9 and the attached Figure 10 . As shown, under the excitation of light sources with wavelengths of 600 nm and 700 nm, the luminescence efficiency of the quantum dot glass in Comparative Example 1 is lower than 30%. Compared with Comparative Example 1, when the average diameter of the PbS quantum dots is the same, the luminescence efficiency of the quantum dot glass provided in Example 2 is improved. This is because the Cl ions effectively passivate the surface Pb ion dangling bonds of the PbS quantum dots, thereby effectively improving the luminescence efficiency of the PbS quantum dots.

[0184] Example 3

[0185] Example 3 prepared a quantum dot glass, which was prepared by the following method: Provide the preparation raw materials of the quantum dot glass that are uniformly mixed, and the elemental composition of the preparation raw materials of the quantum dot glass conforms to the elemental composition in the quantum dot glass raw materials of Example 3 in Table 1. Place the preparation raw materials of the quantum dot glass in a crucible for melting treatment, the melting temperature is 1400 °C, and the melting time is 40 minutes to obtain a molten glass liquid. After the molten glass liquid cools, a glass precursor is formed, which is transferred to an annealing furnace for annealing treatment, the annealing temperature is 400 °C, and the annealing time is 5 hours to obtain a yellow transparent glass intermediate. After testing, this yellow transparent glass intermediate has no absorption peak in the near-infrared band of visible light.

[0186] Transfer the glass intermediate to a heat treatment furnace for heat treatment, so that PbS quantum dots are precipitated in the glass matrix. Among them, NaCl crystals are distributed on the outer surface of the PbS quantum dots, thereby obtaining a series of quantum dot glasses. The absorption spectra and luminescence spectra of the glass intermediate and a series of quantum dot glasses provided in Example 3 were tested. Among them, the excitation wavelength during the luminescence spectrum test is 800 nm.

[0187] The heat treatment conditions of Example 3 and some test parameters of the quantum dot glass are shown in Table 5.

[0188] Table 5

[0189] Sample Number Heat Treatment Conditions <![CDATA[λ abs / nm]]> <![CDATA[λ PL / nm]]> <![CDATA[D avg / nm]]> 0 Glass Intermediate / / / 1 510℃ / 10h 817 1016 3.9 2 510℃ / 15h / / / 3 510℃ / 20h 877 1036 4.2 4 520℃ / 10h 974 1136 4.5 5 520℃ / 15h 1091 1200 4.9 6 520℃ / 20h 1165 1260 5.2 7 530℃ / 05h 1260 1312 5.6 8 530℃ / 07h 1345 1420 5.9 9 530℃ / 10h 1414 1478 6.2 10 540℃ / 05h 1395 1436 6.1 11 540℃ / 10h 1717 1700 7.5 12 550℃ / 10h 1971 1984 9.0 13 560℃ / 10h 2115 2080 10.0

[0190] In Table 5, λ abs refers to the central wavelength of the absorption peak of the current quantum dot glass, with the unit of nm; λ PL refers to the central wavelength of the luminescence peak of the current quantum dot glass, with the unit of nm; D avg refers to the average diameter of the PbS quantum dots in the current quantum dot glass, with the unit of nm.

[0191] Absorption spectrum tests were carried out on the glass intermediate and a series of quantum dot glasses provided in Example 3. The test results are shown in Table 5 and Appendix Figure 7 , Figure 7 . The numbers 0 - 13 in it are the sample numbers 0 to 13 described in Table 5. As shown in Appendix Figure 7 , the glass intermediate has no absorption peak. As the heat treatment temperature increases or the heat treatment time prolongs, the absorption peak of the quantum dot glass gradually shifts to the long wavelength band, indicating that PbS quantum dots precipitate in the glass sample prepared in Example 3, and the size of the PbS quantum dots gradually increases as the heat treatment temperature increases or the heat treatment time prolongs.

[0192] Luminescence spectrum tests were carried out on a series of quantum dot glasses provided in Example 3. The excitation wavelength was 800 nm. The test results are shown in Table 5 and Appendix Figure 8 , Figure 8 . The numbers 1 - 13 in it are the sample numbers 1 to 13 described in Table 5. As shown in Appendix Figure 8 , as the heat treatment temperature increases or the heat treatment time prolongs, the fluorescence peak of the quantum dot glass gradually shifts to the long wavelength band, indicating that PbS quantum dots precipitate in the glass sample prepared in Example 3, and the size of the PbS quantum dots gradually increases as the heat treatment temperature increases or the heat treatment time prolongs.

[0193] Luminescence efficiency tests were carried out on a series of quantum dot glasses provided in Example 3 and Comparative Example 1 respectively. The test results when the excitation wavelength was 600 nm are shown in Figure 9 , and the test results when the excitation wavelength was 700 nm are shown in Figure 10 . As shown in Appendix Figure 9 and Appendix Figure 10 , under the excitation of light sources with wavelengths of 600 nm and 700 nm, the luminescence efficiency of the quantum dot glass in Comparative Example 1 is lower than 30%. Compared with Comparative Example 1, when the average diameter of the PbS quantum dots is the same, the luminescence efficiency of the quantum dot glass provided in Example 3 is significantly improved, up to 49.3%. This is because Cl ions effectively passivate the surface Pb ion dangling bonds of the PbS quantum dots, thus effectively improving the luminescence efficiency of the PbS quantum dots.

[0194] Example 4

[0195] Example 4 prepared a quantum dot glass, which was prepared by the following method: providing a uniformly mixed raw material for preparing the quantum dot glass, and the elemental composition of the raw material for preparing the quantum dot glass conforms to the elemental composition in the raw material of the quantum dot glass in Example 4 in Table 1. Placing the raw material for preparing the quantum dot glass in a crucible for melting treatment, the melting temperature is 1400 °C, and the melting time is 40 minutes to obtain a molten glass liquid. After the molten glass liquid cools, a glass precursor is formed, which is transferred to an annealing furnace for annealing treatment, the annealing temperature is 400 °C, and the annealing time is 5 hours to obtain a yellow transparent glass intermediate (numbered AP). After testing, this yellow transparent glass intermediate has no absorption peak in the near-infrared band of visible light.

[0196] Transfer the glass intermediate to a heat treatment furnace for heat treatment, so as to precipitate PbS quantum dots in the glass matrix. Among them, NaCl crystals are distributed on the outer surface of the PbS quantum dots, thus obtaining a series of quantum dot glasses. The heat treatment temperatures of these quantum dot glasses are 520 °C, 530 °C, and 540 °C respectively, and the heat treatment time is 5 hours or 10 hours. The numbers of these quantum dot glasses are defined as: 52010, 53005, 53010, 54010.

[0197] Absorption spectrum tests were carried out on the glass intermediate and a series of quantum dot glasses provided in Example 4, and the test results are attached Figure 11 . As attached Figure 11 shown, the glass intermediate has no absorption peak. As the heat treatment temperature increases or the heat treatment time prolongs, the absorption peak of the quantum dot glass gradually moves to the long wavelength band, which indicates that PbS quantum dots are precipitated in the glass sample prepared in Example 4, and the size of the PbS quantum dots gradually increases as the heat treatment temperature increases or the heat treatment time prolongs.

[0198] Luminescence spectrum tests were carried out on a series of quantum dot glasses provided in Example 4, and the test results are shown in the attached Figure 12 . As attached Figure 12 shown, as the heat treatment temperature increases or the heat treatment time prolongs, the fluorescence peak of the quantum dot glass gradually moves to the long wavelength band, which indicates that PbS quantum dots are precipitated in the glass sample prepared in Example 4, and the size of the PbS quantum dots gradually increases as the heat treatment temperature increases or the heat treatment time prolongs.

[0199] Luminescence efficiency tests were carried out on the quantum dot glass with a heat treatment temperature of 520 °C and a heat treatment time of 10 hours in Example 4, and its excitation wavelength is 900 nm. The test results are shown in Figure 13 , among which, Figure 13 the solid black squares in refer to the luminescence spectrum of the 900 nm excitation light source, and the hollow circles are the above-mentioned quantum dot glass 52010. As attachedFigure 13 As shown, under the excitation of a 900 nm wavelength light source, the luminescence efficiency of this quantum dot glass is as high as 55%. This is because Cl ions effectively passivate the surface Pb ion dangling bonds of PbS quantum dots, thus effectively improving the luminescence efficiency of the quantum dots.

[0200] Example 5

[0201] Example 5 prepared a quantum dot glass, which was prepared by the following method: Provide the preparation raw materials of the quantum dot glass that are uniformly mixed, and the elemental composition of the preparation raw materials of the quantum dot glass conforms to the elemental composition in the quantum dot glass raw materials of Example 5 in Table 1. Place the preparation raw materials of the quantum dot glass in a crucible for melting treatment, with a melting temperature of 1350 °C and a melting time of 40 minutes to obtain a molten glass liquid. After the molten glass liquid cools, a glass precursor is formed, which is transferred to an annealing furnace for annealing treatment, with an annealing temperature of 400 °C and an annealing time of 5 hours to obtain a yellow transparent glass intermediate. After testing, this yellow transparent glass intermediate has no absorption peak in the near-infrared band of visible light.

[0202] Transfer the glass intermediate to a heat treatment furnace and perform heat treatment at 500 °C for 10 hours, so that PbS quantum dots precipitate in the glass matrix. Among them, KBr crystals are distributed on the outer surface of the PbS quantum dots, thus obtaining the quantum dot glass, which is numbered 50010.

[0203] The luminescence efficiency of the quantum dot glass 50010 provided in Example 5 was tested, and its excitation wavelength was 600 nm. The test results are shown in Figure 14 , where Figure 14 the solid black squares in refer to the emission spectrum of the 600 nm excitation light source, and the hollow circles are the emission spectra of the above-mentioned quantum dot glass 50010. Combining with the attached Figure 14 As shown, under the excitation of a 600 nm wavelength light source, the luminescence efficiency of this quantum dot glass is 39%. This is because Br ions effectively passivate the surface Pb ion dangling bonds of PbS quantum dots, thus improving the luminescence efficiency of the quantum dots.

[0204] Example 6

[0205] Example 6 prepared a quantum dot glass, which was prepared by the following method: providing the preparation raw materials of the quantum dot glass that were uniformly mixed, and the elemental composition of the preparation raw materials of the quantum dot glass conforms to the elemental composition in the quantum dot glass raw materials of Example 6 in Table 1. Placing the preparation raw materials of the quantum dot glass in a crucible for melting treatment, the melting temperature was 1400 °C, and the melting time was 40 minutes to obtain a molten glass liquid. After the molten glass liquid cooled, a glass precursor was formed, which was transferred to an annealing furnace for annealing treatment, the annealing temperature was 400 °C, and the annealing time was 5 hours to obtain a yellow transparent glass intermediate. After testing, this yellow transparent glass intermediate had no absorption peak in the near-infrared band of visible light.

[0206] Transfer the glass intermediate to a heat treatment furnace and perform heat treatment at 520 °C for 10 hours, so that PbS quantum dots are precipitated in the glass matrix. Among them, NaI crystals are distributed on the outer surface of the PbS quantum dots, thus obtaining a quantum dot glass, and this quantum dot glass was numbered 52010.

[0207] The luminous efficiency of the quantum dot glass 52010 provided in Example 6 was tested, and its excitation wavelength was 600 nm. The test results are shown in Figure 15 , where Figure 15 The solid black squares in refer to the emission spectrum of the 600 nm excitation light source, and the hollow circles are the emission spectra of the above-mentioned quantum dot glass 52010. Combining with the attached Figure 15 As shown, under the excitation of a 600 nm wavelength light source, the luminous efficiency of this quantum dot glass was 38%. This is because the I ions effectively passivated the surface Pb ion dangling bonds of the PbS quantum dots, thereby improving the quantum dot luminous efficiency.

[0208] Example 7

[0209] Example 7 prepared a quantum dot glass, which was prepared by the following method: providing the preparation raw materials of the quantum dot glass that were uniformly mixed, and the elemental composition of the preparation raw materials of the quantum dot glass conforms to the elemental composition in the quantum dot glass raw materials of Example 7 in Table 1. Placing the preparation raw materials of the quantum dot glass in a crucible for melting treatment, the melting temperature was 1400 °C, and the melting time was 40 minutes to obtain a molten glass liquid. After the molten glass liquid cooled, a glass precursor was formed, which was transferred to an annealing furnace for annealing treatment, the annealing temperature was 400 °C, and the annealing time was 5 hours to obtain a yellow transparent glass intermediate. After testing, this yellow transparent glass intermediate had no absorption peak in the near-infrared band of visible light.

[0210] Transfer the glass intermediate to a heat treatment furnace and conduct heat treatment at 530 °C for 10 hours, so as to precipitate PbS quantum dots in the glass matrix. LiI crystals are distributed on the outer surface of the PbS quantum dots, thereby obtaining quantum dot glass, which is numbered 53010.

[0211] The luminous efficiency of the quantum dot glass 53010 provided in Example 7 was tested, and its excitation wavelength was 600 nm. The test results are shown in Figure 16 , where Figure 16 The solid black squares in refer to the emission spectrum of the 600 nm excitation light source, and the hollow circles are the emission spectra of the above-mentioned quantum dot glass 53010. Combining with the attached Figure 16 As shown, under the excitation of a 600 nm wavelength light source, the luminous efficiency of this quantum dot glass is 31%. This is because the I ions effectively passivate the surface Pb ion dangling bonds of the PbS quantum dots, thereby improving the quantum dot luminous efficiency.

[0212] Example 8

[0213] Example 8 prepared quantum dot glass, which was prepared by the following method: Provide the preparation raw materials of the quantum dot glass that are uniformly mixed, and the elemental composition of the preparation raw materials of the quantum dot glass conforms to the elemental composition in the quantum dot glass raw materials of Example 8 in Table 1. Place the preparation raw materials of the quantum dot glass in a crucible for melting treatment, the melting temperature is 1400 °C, and the melting time is 40 minutes to obtain a molten glass liquid. After the molten glass liquid cools, a glass precursor is formed, which is transferred to an annealing furnace for annealing treatment, the annealing temperature is 400 °C, and the annealing time is 5 hours to obtain a yellow transparent glass intermediate. After testing, this yellow transparent glass intermediate has no absorption peak in the near-infrared band of visible light.

[0214] Transfer the glass intermediate to a heat treatment furnace and conduct heat treatment at 515 °C for 10 hours, so as to precipitate PbSe quantum dots in the glass matrix. NaCl crystals are distributed on the outer surface of the PbSe quantum dots, thereby obtaining quantum dot glass, which is numbered 51510.

[0215] The luminous efficiency of the quantum dot glass 52510 provided in Example 8 was tested, and its excitation wavelength was 600 nm. The test results are shown in Figure 17 , where Figure 17 The solid black squares in refer to the emission spectrum of the 600 nm excitation light source, and the hollow circles are the emission spectra of the above-mentioned quantum dot glass 51510. Combining with the attached Figure 17As shown, under the excitation of a 600 nm wavelength light source, the luminescence efficiency of the quantum dot glass is 33%. This is because the I ions effectively passivate the surface Pb ion dangling bonds of the PbSe quantum dots, thereby improving the luminescence efficiency of the quantum dots.

[0216] The above is only for the convenience of those skilled in the art to understand the technical solutions of the present disclosure, and is not intended to limit the present disclosure. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present disclosure shall be included within the protection scope of the present disclosure.

Claims

1. A quantum dot glass raw material, characterized in that: The quantum dot glass raw material comprises the following elements in molar percentage: Si element: 12.63% to 21.05%; Al element: 1.36% to 8.2%; Zn element: 1.03% to 7.19%; Pb element: 0.03% to 0.68%; O element: 36.33% to 76.36%; G Elements: 0.34% to 2.04%; M elements: 10.7% to 21.41%; N elements: 1.03% to 5.13%; X elements: 0.5% to 3.4%; Wherein, the G element is sulfur element S, selenium element Se or tellurium element Te; M element is an alkali metal element; The N element is an alkaline earth metal element; The X element is a halogen element.

2. The quantum dot glass raw material according to claim 1, characterized in that: The M element is selected from at least one of Na element, K element and Li element.

3. The quantum dot glass raw material according to claim 1, characterized in that: The N element is selected from at least one of Sr, Ca and Ba.

4. The quantum dot glass raw material according to claim 1, characterized in that: The X element is selected from at least one of Cl element, Br element and I element.

5. The quantum dot glass raw material according to any one of claims 1 to 4, characterized in that: The Si element exists in the form of silicon oxide; The Al element exists in the form of aluminum oxide; The G element is present in at least one of a ZnG form and a G single substance form; The Pb element is present in at least one of the form of lead oxide and the form of single lead; The alkaline earth metal element N is present in at least one of the form of an alkaline earth metal carbonate compound and an alkaline earth metal halide; The alkali metal element M is present in at least one of the form of an alkali metal carbonate, an alkali metal sulfide and an alkali metal halide; The halogen element X is present in at least one of an alkaline earth metal halide form and an alkali metal halide form.

6. The quantum dot glass raw material according to claim 5, characterized in that: The G element is sulfur element S, and the sulfur element S exists in at least one of the form of ZnS and the form of sulfur element.

7. A method for preparing quantum dot glass, characterized in that: The method for preparing the quantum dot glass comprises: Providing raw materials for preparing quantum dot glass, wherein the element composition of the raw materials for preparing quantum dot glass conforms to the element composition of the raw materials for preparing quantum dot glass according to any one of claims 1 to 6; The raw materials for preparing the quantum dot glass are melted, and the molten glass liquid is placed in a mold for cooling and forming to obtain a glass precursor; Annealing the glass precursor to obtain a glass intermediate; The glass intermediate is heat-treated to precipitate quantum dots in the glass matrix, thereby obtaining the quantum dot glass.

8. The method for preparing quantum dot glass according to claim 7, characterized in that: The temperature of the melting treatment is 1350°C to 1500°C, and the time of the melting treatment is 30 minutes to 60 minutes; The annealing treatment is performed at a temperature of 250° C. to 450° C. and for a time of 2 hours to 10 hours.

9. The method for preparing quantum dot glass according to claim 7, characterized in that: The temperature of the heat treatment is 450° C. to 600° C., and the time of the heat treatment is 1 hour to 48 hours.

10. A method for preparing a quantum dot optical fiber core, characterized in that: The method for preparing the quantum dot optical fiber core comprises: Providing raw materials for preparing quantum dot glass, wherein the element composition of the raw materials for preparing quantum dot glass conforms to the element composition of the raw materials for preparing quantum dot glass according to any one of claims 1 to 6; The raw materials for preparing the quantum dot glass are melted, and the molten glass liquid is placed in a mold for cooling and forming to obtain a glass precursor; Performing optical fiber drawing processing on the glass precursor to obtain a first optical fiber core preform; Annealing the first optical fiber preform to obtain a second optical fiber core preform; The second optical fiber core preform is heat-treated to precipitate quantum dots in the glass matrix to obtain the quantum dot optical fiber core.

11. The method for preparing a quantum dot optical fiber core according to claim 10, characterized in that: The temperature of the melting treatment is 1350°C to 1500°C, and the time of the melting treatment is 30 minutes to 60 minutes; The annealing temperature is 250°C to 450°C, and the annealing time is 2 hours to 10 hours; The temperature of the heat treatment is 450° C. to 600° C., and the time of the heat treatment is 1 hour to 48 hours.

12. A quantum dot glass, characterized in that: The quantum dot glass is prepared by using the quantum dot glass raw material described in any one of claims 1 to 6, or by using the method for preparing the quantum dot glass described in any one of claims 7 to 9; The quantum dot glass includes a glass matrix and a quantum dot system located in the glass matrix, the quantum dot system includes PbG quantum dots and alkali metal halide crystals located on the outer surface of the PbG quantum dots, the alkali metal halide crystals are composed of elements M and elements X, and the G element is sulfur element S, selenium element Se or tellurium element Te.

13. A quantum dot optical fiber, characterized in that: The quantum dot optical fiber comprises a quantum dot optical fiber core, and the quantum dot optical fiber core is prepared by using the quantum dot glass raw material according to any one of claims 1 to 6, or by using the preparation method of the quantum dot optical fiber core according to any one of claims 10 to 11; The quantum dot optical fiber core includes a glass matrix and a quantum dot system located in the glass matrix, the quantum dot system includes PbG quantum dots and alkali metal halide crystals located on the outer surface of the PbG quantum dots, the alkali metal halide crystals are composed of elements M and elements X, and the G element is sulfur element S, selenium element Se or tellurium element Te.

Images