Nonlinear optical glass, method for producing the same, and use thereof

Abstract

The application relates to a nonlinear optical glass, comprising a glass matrix and noble metal nanocrystals doped in the glass matrix, wherein the mass fraction of the glass matrix in the nonlinear optical glass is greater than or equal to 40%, and the composition of the glass matrix is xBi2O3-(66-x)P2O5-yZnO-(34-y)Al2O3 in terms of a mole fraction, 1 < x < 21, and 26 < y < 32. The application further provides a preparation method and application of the nonlinear optical glass. The nonlinear optical glass can realize high-concentration doping of noble metal nanocrystals and improve the third-order nonlinear performance of the nonlinear optical glass.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of nonlinear optical materials, in particular to a nonlinear optical glass, a preparation method and application thereof. BACKGROUND

[0002] Glass fibers with high nonlinearity play an important role in the field of optical communication, and can be used to construct high-performance optical switches and other optical signal modulation devices. Glasses with high nonlinearity and good thermal processing performance are basic materials for manufacturing high-performance nonlinear optical fibers. High nonlinear glasses mainly include chalcogenide glasses, tellurite glasses, lead glasses and bismuthate glasses. Among them, chalcogenide glasses have the highest nonlinear coefficient, but have poor mechanical properties, complex melting process, high manufacturing cost, and need to be protected by atmosphere during fiber drawing, which has relatively high technical difficulty. Tellurite glasses have high nonlinear coefficient, good thermal stability and chemical stability, but poor mechanical properties. Lead glasses have high nonlinear coefficient, good mechanical strength, high thermal stability and chemical stability, and good drawing performance, but the raw materials are highly toxic and the production process has high environmental pressure. Bismuthate glass is relatively the best in comprehensive performance among the above high nonlinear glasses.

[0003] Noble metal nanocrystals have strong localized surface plasmon resonance (LSPR) phenomenon, which can cause extremely high optical nonlinearity. Therefore, doping noble metal nanocrystals in bismuthate glass can further improve its optical nonlinearity, and is expected to be used for the manufacture of high-performance nonlinear optical fibers. However, the improvement of the nonlinear coefficient by this scheme is very limited at present, the main reason being that the solubility of bismuthate glass for noble metal ions is low, making it difficult to achieve high concentration doping. For example, when silver nanocrystals are doped in bismuthate glass, the silver or silver compound doping content has not reached 5wt%, and the silver nanocrystals have already grown excessively, resulting in serious visible absorption and Mie scattering. SUMMARY

[0004] Therefore, it is necessary to provide a nonlinear optical glass, a preparation method and application thereof, which can realize high-concentration doping of noble metal nanocrystals and improve the third-order nonlinear performance of the nonlinear optical glass.

[0005] A nonlinear optical glass comprises a glass matrix and noble metal nanocrystals doped in the glass matrix, wherein the mass fraction of the glass matrix in the nonlinear optical glass is greater than or equal to 40%, and the composition of the glass matrix in terms of mole fraction is xBi2O3-(66-x)P2O5-yZnO-(34-y)Al2O3, 1

[0006] In one of the embodiments, the mass fraction of the noble metal nanocrystals in the nonlinear optical glass is 5% to 20%.

[0007] In one of the embodiments, the noble metal nanocrystals are selected from gold nanocrystals and / or silver nanocrystals.

[0008] A preparation method of a nonlinear optical glass, comprising the following steps:

[0009] Measuring by scale the raw materials containing bismuth, phosphorus, zinc, aluminum and noble metal, and grinding, pre-burning and melting to obtain a glass liquid;

[0010] Preparation of bulk glass by using the glass liquid;

[0011] Sequentially performing annealing treatment and heat treatment on the bulk glass to obtain the nonlinear optical glass.

[0012] In one of the embodiments, the bismuth-containing raw material is selected from at least one of Bi2O3, Bi(NO3)3·5H2O, BiCl3, BiPO4, Bi2(SO4)3 or (BiO)2CO3;

[0013] The phosphorus-containing raw material is selected from at least one of P2O5, BiPO4, Zn3(PO4)2 or AlPO4;

[0014] The zinc-containing raw material is selected from at least one of ZnO, Zn(CH3CO2)2, ZnCO3, ZnSO4, Zn3(PO4)2 or ZnC2O4;

[0015] The aluminum-containing raw material is selected from at least one of Al2O3, Al(OH)3, AlPO4, AlCl3 or Al(NO3)3;

[0016] The noble metal-containing raw material is selected from at least one of gold powder, HAuCl4·4H2O, silver powder, AgNO3 or AgNO2.

[0017] In one of the embodiments, in the pre-burning step, the temperature is 200°C to 250°C and the time is 1h to 2h.

[0018] In one of the embodiments, in the melting step, the temperature is 900°C to 1300°C and the time is 10min to 60min.

[0019] In one of the embodiments, in the annealing treatment step, the temperature is 200°C to 300°C and the holding time is 1h to 5h.

[0020] In one of the embodiments, in the heat treatment step, the temperature is 380°C to 450°C and the holding time is 2h to 24h.

[0021] Use of the nonlinear optical glass in the preparation of a nonlinear optical device.

[0022] In the nonlinear optical glass of the present application, by introducing a phosphate matrix component having high ion solubility into a bismuthate glass matrix, a mixed glass matrix is formed, in which the negatively charged [PO4] 3- The tetrahedral units and network formers are conducive to the dispersion and dissolution of noble metal ions, and the mixed glass matrix has high nonlinear performance and self-reducing property, thereby enabling efficient realization of the precipitation of noble metal nanocrystals. Therefore, the nonlinear optical glass of the present application can realize high-concentration doping of noble metal nanocrystals, thereby effectively improving the third-order nonlinear performance of the nonlinear optical glass. BRIEF DESCRIPTION OF DRAWINGS

[0023] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or prior art description will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments described in the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0024] Figure 1 are absorption spectrum diagrams of the nonlinear optical glasses of Examples 1-7 and Comparative Example 1, and b are absorption spectrum diagrams of the nonlinear optical glasses of Examples 9-13 and Comparative Example 2;

[0025] Figure 2 are TEM diagrams of the nonlinear optical glasses, in which a and b are TEM diagrams of the nonlinear optical glass of Example 4, c and d are TEM diagrams of the nonlinear optical glass of Example 7, and e and f are TEM diagrams of the nonlinear optical glass of Example 12, and the insets are diffraction patterns;

[0026] Figure 3 are open-aperture Z-scan test diagrams of the nonlinear optical glasses, in which a are open-aperture Z-scan test diagrams of the nonlinear optical glasses of Example 5 and Example 8, and b are open-aperture Z-scan test diagrams of the nonlinear optical glasses of Example 13 and Example 14. DETAILED DESCRIPTION

[0027] In order to facilitate the understanding of the present application, the present application will be described in more detail below. However, it should be understood that the present application can be realized in many different forms, and is not limited to the embodiments or examples described herein. On the contrary, the purpose of providing these embodiments or examples is to make the disclosure of the present application more thorough and comprehensive.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for describing specific embodiments or examples only and is not intended to be limiting. The use herein of the terms "and / or" and "at least one of" means that any and all possible combinations of the associated listed items are contemplated, whether explicit or implicit.

[0029] The nonlinear optical glass provided by the present application comprises a glass matrix and noble metal nanocrystals doped in the glass matrix, wherein the mass fraction of the glass matrix in the nonlinear optical glass is greater than or equal to 40%, and the composition of the glass matrix in terms of mole fraction is xBi2O3-(66-x)P2O5-yZnO-(34-y)Al2O3, 1 < x < 21, 26 < y < 32.

[0030] In the nonlinear optical glass of the present application, by introducing a phosphate matrix component with high ion solubility into a bismuthate glass matrix, a mixed glass matrix is formed, in which the negatively charged [PO4] 3- The tetrahedral units and network formers are conducive to the dispersion and dissolution of noble metal ions, and at the same time, the mixed glass matrix has high nonlinear performance and self-reducing property, thereby enabling efficient realization of the precipitation of noble metal nanocrystals.

[0031] Therefore, the nonlinear optical glass of the present application can realize high-concentration doping of noble metal nanocrystals, and specifically, the mass fraction of noble metal nanocrystals in the nonlinear optical glass can be as high as 60%, which can be regulated by the proportion of the glass matrix and the introduction mode of the noble metal nanocrystals, thereby effectively improving the third-order nonlinear performance of the nonlinear optical glass.

[0032] In order to ensure the high nonlinear performance of the nonlinear optical glass, preferably, the mass fraction of the noble metal nanocrystals in the nonlinear optical glass is preferably 5% to 20%, and further, the mass fraction is preferably 5% to 15%.

[0033] Optionally, the noble metal nanocrystals are selected from silver nanocrystals and / or gold nanocrystals, the silver nanocrystals can be introduced by doping silver powder and / or silver compounds, and the gold nanocrystals can be introduced by doping gold powder and / or gold compounds. Taking silver nanocrystals as an example, silver nanocrystals can be introduced by doping silver powder and / or AgNO3 and other silver compounds.

[0034] Optionally, in the composition of the glass matrix, x is further preferably 6-18 mol%, so that high concentration doping of noble metal nanocrystals can be better achieved.

[0035] The application further provides a preparation method of the nonlinear optical glass, comprising the following steps:

[0036] S1. Measuring by scale bismuth, phosphorus, zinc, aluminum and noble metal raw materials, and grinding, pre-burning and melting to obtain a glass liquid;

[0037] S2. Preparing a bulk glass by using the glass liquid;

[0038] S3. Annealing and heat treating the bulk glass in sequence to obtain the nonlinear optical glass.

[0039] In step S1, the bismuth-containing raw material is selected from at least one of Bi2O3, Bi(NO3)3·5H2O, BiCl3, BiPO4, Bi2(SO4)3 or (BiO)2CO3; the phosphorus-containing raw material is selected from at least one of P2O5, BiPO4, Zn3(PO4)2 or AlPO4; the zinc-containing raw material is selected from at least one of ZnO, Zn(CH3CO2)2, ZnCO3, ZnSO4, Zn3(PO4)2 or ZnC2O4; the aluminum-containing raw material is selected from at least one of Al2O3, Al(OH)3, AlPO4, AlCl3 or Al(NO3)3; and the noble metal-containing raw material is selected from at least one of gold powder, HAuCl4·4H2O, silver powder, AgNO3 or AgNO2.

[0040] According to the mass fraction of the glass matrix in the nonlinear optical glass of the application, in step S1, the mass proportion of the bismuth, phosphorus, zinc and aluminum-containing raw materials is greater than or equal to 40% and less than 100%, and the mass proportion of the noble metal-containing raw material is less than or equal to 60% and greater than 0. Further, the amount of the bismuth, phosphorus, zinc and aluminum-containing raw materials is converted into moles according to the specific selection.

[0041] Specifically, the mass ratio of the raw material containing bismuth, phosphorus, zinc and aluminum and the mass ratio of the raw material containing noble metal can be inversely calculated according to the mass fraction of silver nanocrystals in the nonlinear optical glass. For example, in order to make the mass fraction of silver nanocrystals in the nonlinear optical glass be 5% to 20%, if silver nanocrystals are introduced by silver powder, the mass ratio of the raw material containing bismuth, phosphorus, zinc and aluminum can be selected to be 80% to 95%, and the mass ratio of silver powder can be selected to be 5% to 20%. If silver nanocrystals are introduced by AgNO3 compound, the mass ratio of the raw material containing bismuth, phosphorus, zinc and aluminum can be selected to be 68.5% to 92%, and the mass ratio of AgNO3 compound can be selected to be 8% to 31.5%. Further preferably, in order to make the mass fraction of silver nanocrystals in the nonlinear optical glass be 5% to 15%, if silver nanocrystals are introduced by silver powder, the mass ratio of the raw material containing bismuth, phosphorus, zinc and aluminum can be selected to be 85% to 95%, and the mass ratio of silver powder can be selected to be 5% to 15%. If silver nanocrystals are introduced by AgNO3 compound, the mass ratio of the raw material containing bismuth, phosphorus, zinc and aluminum can be selected to be 76% to 92%, and the mass ratio of AgNO3 compound can be selected to be 8% to 24%.

[0042] Optionally, in the pre-burning step, the temperature increasing rate is preferably 5℃ / min to 10℃ / min, the temperature is preferably 200℃ to 250℃, and the holding time is preferably 1h to 2h. Further preferably, in the pre-burning step, the temperature is increased to 230℃ at a rate of 5℃ / min and is held for 2h.

[0043] Optionally, in the melting step, the temperature is preferably 900℃ to 1300℃, further preferably 1000℃ to 1100℃, and the time is preferably 10min to 60min.

[0044] In step S2, the thickness of the bulk glass is preferably 1mm to 3mm, further preferably 2mm.

[0045] In step S3, in the annealing step, the temperature is preferably 200℃ to 300℃, and the holding time is preferably 1h to 5h. Further preferably, the temperature is 250℃, and the holding time is 2h. In the heat treatment step, the temperature increasing rate is preferably 5℃ / min to 10℃ / min, the temperature is preferably 380℃ to 450℃, and the holding time is preferably 2h to 24h. Further preferably, the temperature is increased to 420℃ at a rate of 5℃ / min and is held, so as to precipitate noble metal nanocrystals by heat treatment.

[0046] The preparation method of the present application is simple, and can realize high concentration doping of noble metal ions, so as to obtain nonlinear optical glass with excellent third-order nonlinear performance.

[0047] Therefore, the application further provides an application of the nonlinear optical glass in preparing nonlinear optical devices, such as a nonlinear optical fiber.

[0048] Hereinafter, the nonlinear optical glass, the preparation method and the application thereof will be further illustrated by the following specific examples.

[0049] Example 1

[0050] Bi2O3, P2O5, ZnO and Al2O3 were weighed according to the molar composition of 11 mol% Bi2O3-55 mol% P2O5-30 mol% ZnO-4 mol% Al2O3 as raw materials for preparing the glass matrix, and AgNO3 was weighed as raw materials for introducing silver nanocrystals, wherein the mass ratio of AgNO3 in all raw materials was 1%, and then the weighed raw materials were placed in a clean agate mortar and ground to no obvious granular shape and mixed uniformly.

[0051] The above mixed raw materials were poured into a clean corundum crucible, covered with a lid, and then placed in a muffle furnace to heat to 230℃ at a heating rate of 5℃ / min and keep for 2h, and then put into a 1100℃ pit furnace, melt for 30min to get glass liquid.

[0052] 5min before discharging, the molten glass liquid was stirred uniformly with a clean quartz glass rod to ensure the uniformity of the glass. Then the fully molten glass liquid was poured on a preheated stainless steel plate and quickly pressed into a 2mm thick bulk glass with another preheated stainless steel plate.

[0053] The bulk glass was quickly transferred to a precision annealing furnace at 250℃ for annealing treatment, and after keeping for 2h, the furnace was cooled to room temperature, and then placed in the precision annealing furnace again, heated to 420℃ at a heating rate of 5℃ / min and kept for 2h for heat treatment and crystallization, and then cooled to room temperature with the furnace, to obtain a nonlinear optical glass, recorded as P11B-1Ag.

[0054] Example 2

[0055] The difference between Example 2 and Example 1 is that Bi2O3, P2O5, ZnO and Al2O3 were weighed according to the molar composition of 11 mol% Bi2O3-55 mol% P2O5-30 mol% ZnO-4 mol% Al2O3 as raw materials for preparing the glass matrix, and AgNO3 was weighed as raw materials for introducing silver nanocrystals, wherein the mass ratio of AgNO3 in all raw materials was 2%, and then the weighed raw materials were placed in a clean agate mortar and ground to no obvious granular shape and mixed uniformly, recorded as P11B-2Ag.

[0056] Example 3

[0057] Example 3 differs from Example 1 in that Bi2O3, P2O5, ZnO and Al2O3 are weighed as raw materials for preparing a glass matrix according to a molar composition of 11 mol% Bi2O3 - 55 mol% P2O5 - 30 mol% ZnO - 4 mol% Al2O3, and AgNO3 is weighed as a raw material for introducing silver nanocrystals, wherein the mass percentage of AgNO3 in all raw materials is 5%, and then the weighed raw materials are placed in a clean agate mortar and ground to no obvious granular state and mixed uniformly, recorded as P11B-5Ag.

[0058] Example 4

[0059] Example 4 differs from Example 1 in that Bi2O3, P2O5, ZnO and Al2O3 are weighed as raw materials for preparing a glass matrix according to a molar composition of 11 mol% Bi2O3 - 55 mol% P2O5 - 30 mol% ZnO - 4 mol% Al2O3, and AgNO3 is weighed as a raw material for introducing silver nanocrystals, wherein the mass percentage of AgNO3 in all raw materials is 7.5%, and then the weighed raw materials are placed in a clean agate mortar and ground to no obvious granular state and mixed uniformly, recorded as P11B-7.5Ag.

[0060] Example 5

[0061] Example 5 differs from Example 1 in that Bi2O3, P2O5, ZnO and Al2O3 are weighed as raw materials for preparing a glass matrix according to a molar composition of 11 mol% Bi2O3 - 55 mol% P2O5 - 30 mol% ZnO - 4 mol% Al2O3, and AgNO3 is weighed as a raw material for introducing silver nanocrystals, wherein the mass percentage of AgNO3 in all raw materials is 10%, and then the weighed raw materials are placed in a clean agate mortar and ground to no obvious granular state and mixed uniformly, recorded as P11B-10Ag.

[0062] Example 6

[0063] Example 6 differs from Example 1 in that Bi2O3, P2O5, ZnO and Al2O3 are weighed as raw materials for preparing a glass matrix according to a molar composition of 11 mol% Bi2O3 - 55 mol% P2O5 - 30 mol% ZnO - 4 mol% Al2O3, and AgNO3 is weighed as a raw material for introducing silver nanocrystals, wherein the mass percentage of AgNO3 in all raw materials is 20%, and then the weighed raw materials are placed in a clean agate mortar and ground to no obvious granular state and mixed uniformly, recorded as P11B-20Ag.

[0064] Example 7

[0065] Example 7 differs from Example 1 in that Bi2O3, P2O5, ZnO and Al2O3 are weighed as raw materials for preparing a glass matrix according to a molar composition of 11 mol% Bi2O3 - 55 mol% P2O5 - 30 mol% ZnO - 4 mol% Al2O3, and AgNO3 is weighed as a raw material for introducing silver nanocrystals, wherein the mass ratio of AgNO3 in all raw materials is 30%, and then the weighed raw materials are placed in a clean agate mortar and ground to no obvious granular shape and mixed uniformly, denoted as P11B-30Ag.

[0066] Example 8

[0067] Example 8 differs from Example 5 in that the bulk glass is quickly transferred to a precision annealing furnace at 250°C for annealing treatment, and after holding for 2h, the furnace is cooled to room temperature, and then the bulk glass is again placed in the precision annealing furnace, heated to 420°C at a heating rate of 5°C / min and held for 24h for heat treatment and crystallization, and then the furnace is cooled to room temperature, to obtain a nonlinear optical glass.

[0068] Example 9

[0069] Bi2O3, P2O5, ZnO and Al2O3 are weighed as raw materials for preparing a glass matrix according to a molar composition of 16 mol% Bi2O3 - 50 mol% P2O5 - 30 mol% ZnO - 4 mol% Al2O3, and AgNO3 is weighed as a raw material for introducing silver nanocrystals, wherein the mass ratio of AgNO3 in all raw materials is 1%, and then the weighed raw materials are placed in a clean agate mortar and ground to no obvious granular shape and mixed uniformly.

[0070] The above mixed and uniform raw materials are poured into a clean corundum crucible, covered with a lid, and then placed in a muffle furnace and heated to 230°C at a heating rate of 5°C / min and held for 2h, and then placed in a pit furnace at 1100°C, and melted for 30min to obtain a glass liquid.

[0071] 5min before discharging, the molten glass liquid is stirred uniformly with a clean quartz glass rod to ensure the uniformity of the glass. Then the fully molten glass liquid is poured onto a preheated stainless steel plate and quickly pressed into a 2mm thick bulk glass with another preheated stainless steel plate.

[0072] The bulk glass is quickly transferred into a precision annealing furnace at 250°C for annealing treatment, and after holding for 2h, it is furnace-cooled to room temperature. Then it is placed into the precision annealing furnace again, and heated to 420°C at a heating rate of 5°C / min and held for 2h for heat treatment and crystallization, and then furnace-cooled to room temperature to obtain a nonlinear optical glass, which is recorded as P16B-1Ag.

[0073] Example 10

[0074] Example 10 differs from Example 9 in that Bi2O3, P2O5, ZnO and Al2O3 are weighed according to the molar composition of 16mol% Bi2O3-50mol% P2O5-30mol% ZnO-4mol% Al2O3 as raw materials for preparing the glass matrix, and AgNO3 is weighed as a raw material for introducing silver nanocrystals, wherein the mass ratio of AgNO3 in all raw materials is 2%, and then the weighed raw materials are placed in a clean agate mortar and ground to no obvious granular shape and mixed uniformly, which is recorded as P16B-2Ag.

[0075] Example 11

[0076] Example 11 differs from Example 9 in that Bi2O3, P2O5, ZnO and Al2O3 are weighed according to the molar composition of 16mol% Bi2O3-50mol% P2O5-30mol% ZnO-4mol% Al2O3 as raw materials for preparing the glass matrix, and AgNO3 is weighed as a raw material for introducing silver nanocrystals, wherein the mass ratio of AgNO3 in all raw materials is 5%, and then the weighed raw materials are placed in a clean agate mortar and ground to no obvious granular shape and mixed uniformly, which is recorded as P16B-5Ag.

[0077] Example 12

[0078] Example 12 differs from Example 9 in that Bi2O3, P2O5, ZnO and Al2O3 are weighed according to the molar composition of 16mol% Bi2O3-50mol% P2O5-30mol% ZnO-4mol% Al2O3 as raw materials for preparing the glass matrix, and AgNO3 is weighed as a raw material for introducing silver nanocrystals, wherein the mass ratio of AgNO3 in all raw materials is 7.5%, and then the weighed raw materials are placed in a clean agate mortar and ground to no obvious granular shape and mixed uniformly, which is recorded as P16B-7.5Ag.

[0079] Example 13

[0080] Example 13 differs from Example 9 in that Bi2O3, P2O5, ZnO and Al2O3 are weighed as raw materials for preparing the glass matrix according to a molar composition of 16 mol% Bi2O3 - 50 mol% P2O5 - 30 mol% ZnO - 4 mol% Al2O3, and AgNO3 is weighed as a raw material for introducing silver nanocrystals, wherein the mass ratio of AgNO3 in all raw materials is 10%, and then the weighed raw materials are placed in a clean agate mortar and ground to no obvious granular shape and mixed uniformly, denoted as P16B-10Ag.

[0081] Example 14

[0082] Example 14 differs from Example 13 in that the bulk glass is quickly transferred to a precision annealing furnace at 250°C for annealing treatment, and after holding for 2 h, the furnace is cooled to room temperature, and then the bulk glass is again placed in the precision annealing furnace, heated to 420°C at a heating rate of 5°C / min and held for 12 h for heat treatment and crystallization, and then the furnace is cooled to room temperature, to obtain a nonlinear optical glass.

[0083] Comparative Example 1

[0084] Comparative Example 1 differs from Example 1 in that Bi2O3, P2O5, ZnO and Al2O3 are weighed as raw materials for preparing the glass matrix according to a molar composition of 11 mol% Bi2O3 - 55 mol% P2O5 - 30 mol% ZnO - 4 mol% Al2O3, and then the weighed raw materials are placed in a clean agate mortar and ground to no obvious granular shape and mixed uniformly, denoted as P11B-Glass.

[0085] Comparative Example 2

[0086] Comparative Example 2 differs from Example 9 in that Bi2O3, P2O5, ZnO and Al2O3 are weighed as raw materials for preparing the glass matrix according to a molar composition of 16 mol% Bi2O3 - 50 mol% P2O5 - 30 mol% ZnO - 4 mol% Al2O3, and then the weighed raw materials are placed in a clean agate mortar and ground to no obvious granular shape and mixed uniformly, denoted as P16B-Glass.

[0087] The absorption spectra of the nonlinear optical glasses of Examples 1-7 and Comparative Example 1 are shown in FIG. a, the absorption spectra of the nonlinear optical glasses of Examples 9-13 and Comparative Example 2 are shown in FIG. b, and the absorption spectra of the nonlinear optical glasses of Examples 14-16 are shown in FIG. c. Figure 1 a, the absorption spectra of the nonlinear optical glasses of Examples 9-13 and Comparative Example 2 are shown in FIG. b, and the absorption spectra of the nonlinear optical glasses of Examples 14-16 are shown in FIG. c. Figure 1 b, and the absorption spectra of the nonlinear optical glasses of Examples 14-16 are shown in FIG. c. Figure 1As can be seen from a, in the 11mol% Bi2O3-55mol% P2O5-30mol% ZnO-4mol% Al2O3 glass of embodiments 1-7, the silver nanocrystal localized surface plasmon resonance absorption intensity at ~425nm first increases and then decreases with the increase of the AgNO3 compound doping amount of 1wt%, 2wt%, 5wt%, 7.5wt%, 10wt%, 20wt%, 30wt%; as can be seen from b, in the 16mol% Bi2O3-50mol% P2O5-30mol% ZnO-4mol% Al2O3 glass of embodiments 9-13, the silver nanocrystal localized surface plasmon resonance absorption intensity at ~425nm also continuously increases with the increase of the AgNO3 compound doping amount, which shows that the high concentration doping of silver ions in the glass matrix is realized, and as can be seen from embodiments 9-13 and embodiments 1-7, increasing the content of Bi2O3 helps to increase the content of silver nanocrystals in the glass. Figure 1 As can be seen from a, in the 11mol% Bi2O3-55mol% P2O5-30mol% ZnO-4mol% Al2O3 glass of embodiments 1-7, the silver nanocrystal localized surface plasmon resonance absorption intensity at ~425nm first increases and then decreases with the increase of the AgNO3 compound doping amount of 1wt%, 2wt%, 5wt%, 7.5wt%, 10wt%, 20wt%, 30wt%; as can be seen from b, in the 16mol% Bi2O3-50mol% P2O5-30mol% ZnO-4mol% Al2O3 glass of embodiments 9-13, the silver nanocrystal localized surface plasmon resonance absorption intensity at ~425nm also continuously increases with the increase of the AgNO3 compound doping amount, which shows that the high concentration doping of silver ions in the glass matrix is realized, and as can be seen from embodiments 9-13 and embodiments 1-7, increasing the content of Bi2O3 helps to increase the content of silver nanocrystals in the glass.

[0088] The TEM image of the nonlinear optical glass of embodiment 4 is shown in a, 2b, the TEM image of the nonlinear optical glass of embodiment 7 is shown in c, 2d, the TEM image of the nonlinear optical glass of embodiment 12 is shown in e, 2f, and the TEM image of the nonlinear optical glass of embodiment 13 is shown in g, 2h. Figure 2 The TEM image of the nonlinear optical glass of embodiment 4 is shown in a, 2b, the TEM image of the nonlinear optical glass of embodiment 7 is shown in c, 2d, the TEM image of the nonlinear optical glass of embodiment 12 is shown in e, 2f, and the TEM image of the nonlinear optical glass of embodiment 13 is shown in g, 2h. Figure 2 The TEM image of the nonlinear optical glass of embodiment 4 is shown in a, 2b, the TEM image of the nonlinear optical glass of embodiment 7 is shown in c, 2d, the TEM image of the nonlinear optical glass of embodiment 12 is shown in e, 2f, and the TEM image of the nonlinear optical glass of embodiment 13 is shown in g, 2h. Figure 2 The TEM image of the nonlinear optical glass of embodiment 4 is shown in a, 2b, the TEM image of the nonlinear optical glass of embodiment 7 is shown in c, 2d, the TEM image of the nonlinear optical glass of embodiment 12 is shown in e, 2f, and the TEM image of the nonlinear optical glass of embodiment 13 is shown in g, 2h. Figure 2 As can be seen from a, in the 11mol% Bi2O3-55mol% P2O5-30mol% ZnO-4mol% Al2O3 glass of embodiments 1-7, the silver nanocrystal localized surface plasmon resonance absorption intensity at ~425nm first increases and then decreases with the increase of the AgNO3 compound doping amount of 1wt%, 2wt%, 5wt%, 7.5wt%, 10wt%, 20wt%, 30wt%; as can be seen from b, in the 16mol% Bi2O3-50mol% P2O5-30mol% ZnO-4mol% Al2O3 glass of embodiments 9-13, the silver nanocrystal localized surface plasmon resonance absorption intensity at ~425nm also continuously increases with the increase of the AgNO3 compound doping amount, which shows that the high concentration doping of silver ions in the glass matrix is realized, and as can be seen from embodiments 9-13 and embodiments 1-7, increasing the content of Bi2O3 helps to increase the content of silver nanocrystals in the glass.

[0089] The open aperture Z-scan test results of the nonlinear optical glass of embodiment 5 and embodiment 8 are shown in a, the open aperture Z-scan test results of the nonlinear optical glass of embodiment 13 and embodiment 14 are shown in b, and the open aperture Z-scan test results of the nonlinear optical glass of embodiment 15 are shown in c. Figure 3 The open aperture Z-scan test results of the nonlinear optical glass of embodiment 5 and embodiment 8 are shown in a, the open aperture Z-scan test results of the nonlinear optical glass of embodiment 13 and embodiment 14 are shown in b, and the open aperture Z-scan test results of the nonlinear optical glass of embodiment 15 are shown in c. Figure 3 The open aperture Z-scan test results of the nonlinear optical glass of embodiment 5 and embodiment 8 are shown in a, the open aperture Z-scan test results of the nonlinear optical glass of embodiment 13 and embodiment 14 are shown in b, and the open aperture Z-scan test results of the nonlinear optical glass of embodiment 15 are shown in c. Figure 3 As can be seen from a, the inverse saturation absorption coefficient of the nonlinear optical glass of embodiment 5 is 1.3×10 -14 m / W, and the saturable absorption coefficient of the nonlinear optical glass of embodiment 13 is 1.1×10 -14 m / W, which shows that the nonlinear optical glass of the present application can realize high concentration doping of silver nanocrystals to improve the third-order nonlinear performance of the glass; prolonging the heat treatment temperature can improve the inverse saturation absorption coefficient of the nonlinear optical glass of embodiment 5 from 1.3×10 -14 m / W to 5.0×10 -12 m / W (embodiment 8); and the saturable absorption coefficient of the nonlinear optical glass of embodiment 13 is improved from 1.1×10 -14 m / W to -14×10-12 m / W (Example 14), indicating that prolonging the heat treatment temperature can further improve the third-order nonlinear optical property of the glass matrix under the condition that the doping concentration of silver nanocrystals is unchanged.

[0090] The technical features of the above-mentioned embodiments can be combined in any manner. In order to make the description simple, all possible combinations of the technical features in the above-mentioned embodiments are not described, however, as long as the combinations of the technical features do not exist contradictory, it should be considered that they are within the scope of the present disclosure.

[0091] The above-mentioned embodiments only express several implementation manners of the present application, and the description is relatively specific and detailed, but it should not be understood as a limitation on the scope of the patent. It should be pointed out that for ordinary skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A nonlinear optical glass, characterized in that, It consists of a glass matrix and noble metal nanocrystals doped in the glass matrix. Among them, in terms of mole fraction, the composition of the glass matrix is xBi2O3-(66-x) P2O5-yZnO-(34-y)Al2O3, where 1 < x < 21 and 26 < y < 32. Among them, the mass fraction of the noble metal nanocrystals in the nonlinear optical glass is 5% - 20%, and the noble metal nanocrystals are selected from gold nanocrystals and / or silver nanocrystals.

2. The nonlinear optical glass according to claim 1, characterized in that, The mass fraction of the noble metal nanocrystals in the nonlinear optical glass is 5% - 15%.

3. A method for preparing nonlinear optical glass as described in any one of claims 1 to 2, characterized in that, It includes the following steps: Weigh the raw materials containing bismuth, phosphorus, zinc, aluminum and noble metals according to the dosage, and carry out grinding, pre-burning and melting to obtain glass liquid; Use the glass liquid to prepare bulk glass; Anneal and heat-treat the bulk glass in sequence to obtain the nonlinear optical glass.

4. The method for preparing nonlinear optical glass according to claim 3, characterized in that, The raw material containing bismuth is selected from at least one of Bi2O3, Bi(NO3)3·5H2O, BiCl3, BiPO4, Bi2(SO4)3 or (BiO)2CO3; The raw material containing phosphorus is selected from at least one of P2O5, BiPO4, Zn3(PO4)2 or AlPO4; The raw material containing zinc is selected from at least one of ZnO, Zn(CH3CO2)2, ZnCO3, ZnSO4, Zn3(PO4)2 or ZnC2O4; The raw material containing aluminum is selected from at least one of Al2O3, Al(OH)3, AlPO4, AlCl3 or Al(NO3)3; The raw material containing noble metal is selected from at least one of gold powder, HAuCl4·4H2O, silver powder, AgNO3, AgNO2.

5. The method for preparing nonlinear optical glass according to claim 3, characterized in that, In the step of pre-burning, the temperature is 200°C - 250°C and the time is 1h - 2h.

6. The method for preparing nonlinear optical glass according to claim 3, characterized in that, In the step of melting, the temperature is 900°C - 1300°C and the time is 10min - 60min.

7. The method for preparing nonlinear optical glass according to claim 3, characterized in that, In the step of annealing treatment, the temperature is 200°C - 300°C and the heat preservation time is 1h - 5h.

8. The method for preparing nonlinear optical glass according to claim 3, characterized in that, In the step of heat treatment, the temperature is 380°C - 450°C and the heat preservation time is 2h - 24h.

9. Application of a nonlinear optical glass according to any one of claims 1 - 2 in the preparation of a nonlinear optical device.

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