CN115755245A - Saturable absorber, preparation method thereof and saturable absorber device - Google Patents
Saturable absorber, preparation method thereof and saturable absorber device Download PDFInfo
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Abstract
The invention discloses a saturable absorber, a preparation method thereof and a saturable absorber device, wherein the saturable absorber comprises graphene and composite nanosheets loaded on the graphene; the composite nanoplatelets comprise: bi 2 Te 3 Nanosheets; is surrounded by Bi 2 Te 3 Annular Sb around and connected with nanosheets to form heterojunction 2 Te 3 Nanosheets. Bi in the invention 2 Te 3 Nanosheet and cyclic Sb 2 Te 3 Bi is formed at the interface where the nano sheets are connected 2 Te 3 /Sb 2 Te 3 The transverse heterojunction is beneficial to realizing the rapid transfer of charges and the rapid recombination of electron hole pairs, and effectively shortens the relaxation time, thereby achieving the purpose of rapid saturated absorption. Meanwhile, the composite nanosheet is compounded with the graphene, and the defects that the two-dimensional layered material is easily oxidized by air and easily agglomerated and the like are effectively overcome by utilizing the characteristics of high thermal conductivity, strong oxidation resistance, large-size film-forming property and the like of the graphene, so that the stability of the saturable absorber is improved.
Description
Technical Field
The invention relates to the technical field of saturable absorbers, in particular to a saturable absorber, a preparation method thereof and a saturable absorber device.
Background
Two-dimensional layered topological insulator material such as Bi 2 Te 3 、Sb 2 Te 3 The material has many unique properties, such as special properties of magnetic monopoles, quantum abnormal Hall effect, macelan fermions, giant magnetoelectric effect and the like, so that the material is suitable for various electric, optical and thermoelectric devices, and is a research hotspot in the field of current condensed state physics and material preparation. In addition, the topological insulator material has proved to be an excellent saturable absorber material, but has the problems of easy agglomeration, uneven film formation, easy oxidation and the like, and the saturable absorption performance of the topological insulator material is required to be further improved.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the present invention aims to provide a saturable absorber, a preparation method thereof, and a saturable absorber device, and aims to solve the problems that the existing two-dimensional layered topological insulator material is easy to agglomerate and oxidize, and the saturable absorption performance needs to be further improved.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, a saturable absorber is provided, which includes graphene and composite nanosheets supported on the graphene;
the composite nanoplatelets comprise:
Bi 2 Te 3 a nanosheet;
and, surrounding the Bi 2 Te 3 Around the nanosheet and with said Bi 2 Te 3 Circular Sb with nanosheets connected to form heterojunction 2 Te 3 A nanosheet.
In a second aspect of the present invention, there is provided a method for preparing the saturable absorber of the present invention, which comprises the steps of:
provided are a graphene oxide dispersion liquid and Bi 2 Te 3 A nanosheet;
adding an antimony source, a tellurium source, a second reducing agent and a second surfactant into a second solvent to obtain a second mixed solution;
and adding the first mixed solution and the graphene oxide dispersion solution into the second mixed solution, and reacting at a second preset temperature for a second preset time to obtain the saturable absorber.
Optionally, the Bi 2 Te 3 The preparation method of the nano sheet comprises the following steps:
adding a bismuth source, a tellurium source, a first reducing agent and a first surfactant into a first solvent, and reacting at a first preset temperature for a first preset time to obtain a first mixed solution, wherein the first mixed solution contains Bi 2 Te 3 A nanosheet.
Optionally, the preparation method of the graphene oxide dispersion liquid includes the steps of:
providing graphene oxide and a third solvent;
and adding the graphene oxide into a third solvent, and performing ultrasonic dispersion to obtain the graphene oxide dispersion liquid.
Optionally, the bismuth source is selected from at least one of bismuth chloride, bismuth nitrate, bismuth oxide;
the tellurium source is selected from at least one of simple substance tellurium, sodium tellurite and potassium tellurite;
the antimony source is at least one of antimony chloride, antimony potassium tartrate and antimony oxide.
Optionally, the first reducing agent and the second reducing agent are respectively and independently selected from at least one of hydrazine hydrate, ammonia water, sodium hydroxide, sodium borohydride, hydroxylamine and ethylenediamine; the first surfactant and the second surfactant are respectively and independently selected from at least one of ethylene diamine tetraacetic acid, cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate and polyvinylpyrrolidone.
Optionally, the step of adding the bismuth source, the tellurium source, the first reducing agent, and the first surfactant into the first solvent, and reacting at a first preset temperature for a first preset time to obtain a first mixed solution specifically includes:
according to Bi 2 Te 3 Adding a bismuth source, a tellurium source, a first reducing agent and a first surfactant into a first solvent according to the stoichiometric ratio, stirring until the bismuth source and the tellurium source are completely dissolved, then placing the mixture into a reaction kettle, and reacting for 12-40h at the temperature of 140-200 ℃ to obtain a first mixed solution.
Optionally, the step of adding the antimony source, the tellurium source, the second reducing agent, and the second surfactant to the second solvent to obtain the second mixed solution specifically includes:
according to Sb 2 Te 3 Adding the antimony source, the tellurium source, the second reducing agent and the second surfactant into the second solvent according to the stoichiometric ratio, and stirring until the antimony source and the tellurium source are completely dissolved to obtain a second mixed solution.
Optionally, the step of mixing the Bi 2 Te 3 Adding the nanosheet and the graphene oxide dispersion liquid into the second mixed liquid, and reacting at a second preset temperature for a second preset time to obtain the saturable absorber, wherein the steps of:
the Bi is added 2 Te 3 And adding the nanosheet and graphene oxide dispersion liquid into the second mixed liquid, then placing the nanosheet and graphene oxide dispersion liquid into a reaction kettle, and reacting at the temperature of 140-200 ℃ for 12-40h to obtain the saturable absorber.
The third aspect of the present invention provides a saturable absorber device, wherein the saturable absorber device comprises an optical fiber and a saturable absorber carried on an end face of a fiber core of the optical fiber, or the saturable absorber device comprises a broadband dielectric film and a saturable absorber arranged on the broadband dielectric film;
the saturable absorber is the saturable absorber of the invention and/or the saturable absorber prepared by the preparation method of the invention.
Has the advantages that: bi in the invention 2 Te 3 Nanosheet and Bi enclosed therein 2 Te 3 Nanosheet period cyclic Sb 2 Te 3 Nano-sheetA composite nanosheet (i.e., bi) is formed 2 Te 3 /Sb 2 Te 3 Composite nanosheets), bi 2 Te 3 /Sb 2 Te 3 Bi in composite nanosheet 2 Te 3 Nanosheet and cyclic Sb 2 Te 3 Bi is formed at the interface where the nano sheets are connected 2 Te 3 /Sb 2 Te 3 A lateral heterojunction. In Bi 2 Te 3 /Sb 2 Te 3 In the lateral heterojunction, the energy distribution and band edge position of the whole material are changed due to rearrangement and combination of Sb and Bi atoms. At the heterojunction interface, the stronger internal electric field can improve the carrier mobility, and the higher carrier mobility can promote the absorption between electrons and photons, thereby realizing Bi 2 Te 3 /Sb 2 Te 3 Further optimization of modulation depth of the composite nanosheets, i.e. Bi 2 Te 3 /Sb 2 Te 3 The one-dimensional interface effect of the transverse heterojunction is beneficial to realizing the rapid transfer of charges and the rapid recombination of electron hole pairs, effectively shortens the relaxation time, thereby achieving the purpose of rapid saturation absorption and improving the Bi content of the single two-dimensional layered nano material 2 Te 3 Or Sb 2 Te 3 Saturable absorption properties of (a). At the same time, bi 2 Te 3 /Sb 2 Te 3 The composite nanosheet is compounded with the graphene, and the characteristics of high thermal conductivity, strong oxidation resistance, large-size film forming property and the like of the graphene are further utilized, so that the problems that the two-dimensional layered material is easily oxidized by air, easily agglomerated, uneven in film forming and the like at high temperature in optical application can be well solved, and the stability of the saturable absorber is greatly improved. In addition, bi 2 Te 3 /Sb 2 Te 3 Bi in composite nanosheet 2 Te 3 Nanosheet and cyclic Sb 2 Te 3 Synergistic effect of nanosheets, bi 2 Te 3 /Sb 2 Te 3 The synergistic effect of the composite nanosheets and the graphene can effectively avoid the limitation of single material application, and the nonlinear optical performance of the saturable absorber is greatly improved. The saturable absorber provided by the invention utilizes Bi 2 Te 3 /Sb 2 Te 3 The transverse heterojunction one-dimensional interface effect improves the carrier mobility, increases the modulation depth, and simultaneously considers the characteristics of high thermal conductivity, strong oxidation resistance and large-size film forming performance of the graphene.
Drawings
FIG. 1 is a schematic diagram of the growth process of the saturable absorber in example 1 of the present invention.
Figure 2 is an XRD pattern of the saturable absorber of example 1 of the present invention.
FIG. 3 is an SEM photograph and an EDS photograph of a selective area of a saturable absorber in example 1 of the present invention; wherein (a) is an SEM picture of the saturable absorber in example 1 of the present invention, (b) is an EDS picture of a selected region in the picture (a) of the saturable absorber in example 1 of the present invention, (c) is an EDS picture of Sb elements in a corresponding region in (b), (d) is an EDS picture of Te elements in a corresponding region in (b), and (e) is an EDS picture of Sb elements in a corresponding region in (b).
In FIG. 4, (a) is Bi in comparative example 1 2 Te 3 /Sb 2 Te 3 XPS pattern of composite nanosheets, (b) is an XPS pattern of saturable absorber in example 1 of the present invention.
FIG. 5a shows Bi in comparative example 2 2 Te 3 The near-infrared nonlinear transmittance curve of the nanosheets; FIG. 5b shows Sb in comparative example 3 2 Te 3 The near-infrared nonlinear transmittance curve of the nanosheet; FIG. 5c shows Bi in comparative example 1 2 Te 3 /Sb 2 Te 3 The near-infrared nonlinear transmittance curve of the composite nanosheet; FIG. 5d is a plot of the near infrared nonlinear transmission of the saturable absorber of example 1.
Detailed Description
The present invention provides a saturable absorber, a method for preparing the same, and a saturable absorber device, and the present invention is further described in detail below in order to make the purpose, technical scheme, and effect of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Unless defined otherwise, 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 invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Although graphene has a low modulation depth (the absolute optical modulation depth of single-layer graphene is generally about 1%), although the modulation depth can be increased by increasing the number of graphene layers, unnecessary non-saturation loss increases, which is not preferable in practical laser applications. The two-dimensional layered topological insulator is also proved to be an excellent saturable absorption material, has a wider modulation depth (1.5 mu m wavelength and 70 percent) than graphene, but has the defects of non-uniform film formation (two-dimensional nano materials are easy to agglomerate), easy oxidation and further improvement of saturable absorption performance. Based on this, the embodiment of the present invention provides a saturable absorber, which includes graphene and a composite nanosheet supported on the graphene;
the composite nanoplatelets comprise:
Bi 2 Te 3 nanosheets;
and, surrounding the Bi 2 Te 3 Around the nanosheet and with said Bi 2 Te 3 Circular Sb with nanosheets connected to form heterojunction 2 Te 3 Nanosheets.
In the embodiment of the invention, the Bi 2 Te 3 Nanosheet and cyclic Sb around the nanosheet 2 Te 3 Nanosheets being in the same plane, bi 2 Te 3 Nanosheet and Bi surrounded by the nanosheet 2 Te 3 Cyclic Sb around nanosheets 2 Te 3 The nanosheets forming a composite nanosheet (i.e., bi) 2 Te 3 /Sb 2 Te 3 Composite nanosheets), bi 2 Te 3 /Sb 2 Te 3 Bi in composite nano sheet 2 Te 3 Nanosheet and cyclic Sb 2 Te 3 Bi is formed at the interface where the nano sheets are connected 2 Te 3 /Sb 2 Te 3 A lateral heterojunction. In Bi 2 Te 3 /Sb 2 Te 3 In the lateral heterojunction, the energy distribution and band edge position of the whole material are changed due to rearrangement and combination of Sb and Bi atoms. At the heterojunction interface, the carrier mobility can be improved by a stronger internal electric field, and the absorption between electrons and photons can be promoted by higher carrier mobility, so that Bi is realized 2 Te 3 /Sb 2 Te 3 Further optimization of modulation depth of composite nanosheets, i.e. Bi 2 Te 3 /Sb 2 Te 3 The one-dimensional interface effect of the transverse heterojunction is beneficial to realizing the rapid transfer of charges and the rapid recombination of electron hole pairs, effectively shortens the relaxation time, thereby achieving the purpose of rapid saturation absorption and improving the Bi content of the single two-dimensional layered nano material 2 Te 3 Or Sb 2 Te 3 Saturable absorption properties of (a). At the same time, bi 2 Te 3 /Sb 2 Te 3 The composite nano sheet is compounded with the graphene, and the characteristics of high thermal conductivity, strong oxidation resistance, large-size film forming property and the like of the graphene are further utilized, so that the problem of a two-dimensional layered material (Bi) can be well solved 2 Te 3 Nanosheet, sb 2 Te 3 Nanosheet and Bi 2 Te 3 /Sb 2 Te 3 Composite nano-sheet) is easy to be oxidized by air and agglomerated easily at high temperature in optical application, the film forming is uneven, and the stability of the saturable absorber is greatly improved. In addition, bi 2 Te 3 /Sb 2 Te 3 Bi in composite nano sheet 2 Te 3 Nanosheet and cyclic Sb 2 Te 3 Synergistic effect of nanosheets, bi 2 Te 3 /Sb 2 Te 3 The synergistic effect of the composite nanosheets and the graphene can effectively avoid the limitation of single material application, and greatly improve the nonlinear optical performance of the saturable absorber.
Therefore, the saturable absorber provided by the invention utilizes Bi 2 Te 3 /Sb 2 Te 3 One-dimensional boundary of lateral heterojunctionThe surface effect improves the carrier mobility, increases the modulation depth, and simultaneously considers the characteristics of high thermal conductivity, strong oxidation resistance and large-size film-forming property of the graphene. The saturable absorber provided by the invention has the advantages of high carrier mobility, large modulation depth, good nonlinear optical performance, strong oxidation resistance, difficulty in agglomeration, easiness in film formation and the like.
In one embodiment, the composite nanosheets are uniformly loaded on the graphene, so that agglomeration of the composite nanosheets can be effectively prevented, the film of the saturable absorber can be better formed, the stability of the saturable absorber can be greatly improved, and the saturable absorber can be better applied.
In one embodiment, bi 2 Te 3 /Sb 2 Te 3 The two-dimensional plane direction of the composite nanosheets is parallel to the two-dimensional plane direction of the graphene. I.e. Bi 2 Te 3 /Sb 2 Te 3 The composite nano sheets are loaded on the graphene in parallel, namely Bi 2 Te 3 /Sb 2 Te 3 Bi at the center of the composite nanosheet 2 Te 3 Nanosheet and Bi 2 Te 3 Cyclic Sb around nanosheets 2 Te 3 The nanoplatelets are simultaneously in contact with the graphene.
The embodiment of the present invention further provides a method for preparing the saturable absorber described above in the embodiment of the present invention, as shown in fig. 1, including the steps of:
s1, providing a graphene oxide dispersion liquid
And Bi 2 Te 3 Nanosheets;
s2, adding an antimony source, a tellurium source, a second reducing agent and a second surfactant into a second solvent to obtain a second mixed solution;
s3, mixing the Bi 2 Te 3 And adding the nanosheet and the graphene oxide dispersion liquid into the second mixed liquid, and reacting at a second preset temperature for a second preset time to obtain the saturable absorber.
The preparation method is simple, does not need complex and expensive instruments, adopts a smart preparation method, namely adopts a simple and expensive methodThe saturable absorber is prepared by the two-step solvothermal reaction. First providing a single Bi 2 Te 3 A nanosheet; then using Bi 2 Te 3 Nanosheet as template for transversely growing annular Sb at periphery 2 Te 3 Nanosheet of Bi 2 Te 3 /Sb 2 Te 3 Lateral heterostructure to form Bi 2 Te 3 /Sb 2 Te 3 Composite nano-sheets. Meanwhile, a large amount of Bi is prepared by taking graphene as a framework and a simple self-assembly process 2 Te 3 /Sb 2 Te 3 The nano sheets are loaded on the surface of graphene, so that a saturable absorber (namely graphene-Bi) is formed 2 Te 3 /Sb 2 Te 3 A bi-directional heterojunction composite).
In Bi 2 Te 3 /Sb 2 Te 3 In the lateral heterojunction, the energy distribution and band edge position of the whole material are changed due to rearrangement and combination of Sb and Bi atoms. At the heterojunction interface, the stronger internal electric field can improve the carrier mobility, and the higher carrier mobility can promote the absorption between electrons and photons, thereby realizing Bi 2 Te 3 /Sb 2 Te 3 Further optimization of modulation depth, i.e. Bi 2 Te 3 /Sb 2 Te 3 The one-dimensional interface effect of the transverse heterojunction is beneficial to realizing the rapid transfer of charges and the rapid recombination of electron hole pairs, and effectively shortens the relaxation time, thereby achieving the purpose of rapid saturated absorption. At the same time, bi 2 Te 3 /Sb 2 Te 3 The composite nanosheet is compounded with the graphene, and the characteristics of high thermal conductivity, strong oxidation resistance, large-size film forming property and the like of the graphene are further utilized, so that the problems that the layered material is easily oxidized by air and easily agglomerated at high temperature in optical application can be well solved, and the stability of the saturable absorber is greatly improved. In addition, bi 2 Te 3 /Sb 2 Te 3 Bi in composite nano sheet 2 Te 3 Nanosheet and cyclic Sb 2 Te 3 Synergistic effect of nanosheets, bi 2 Te 3 /Sb 2 Te 3 The synergistic effect of the composite nanosheets and the graphene can effectively avoid the limitation of single material application, and the nonlinear optical performance of the saturable absorber is greatly improved.
Therefore, the saturable absorber utilizes both Bi and Bi 2 Te 3 /Sb 2 Te 3 The transverse heterojunction one-dimensional interface effect improves the carrier mobility, increases the modulation depth, and simultaneously considers the characteristics of high thermal conductivity, strong oxidation resistance and large-size film forming performance of the graphene, so that the saturable absorber has the advantages of high carrier mobility, large modulation depth, strong oxidation resistance, difficult agglomeration, easy film forming and the like.
In step S1, the graphene oxide in the graphene oxide dispersion liquid may be prepared by an improved Hummers method (which is an existing method and is not described herein again), or may be obtained by direct purchase.
In one embodiment, the method for preparing the graphene oxide dispersion liquid includes the steps of:
providing graphene oxide and a third solvent;
and adding the graphene oxide into the third solvent, and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid.
Further, the ultrasonic dispersion time is 1-3h, and graphene oxide dispersion liquid with uniformly dispersed graphene oxide can be obtained.
In one embodiment, the third solvent is selected from at least one of ethylene glycol, isopropyl alcohol, but is not limited thereto.
In one embodiment, the Bi 2 Te 3 The preparation method of the nano-sheet comprises the following steps:
adding a bismuth source, a tellurium source, a first reducing agent and a first surfactant into a first solvent, and reacting at a first preset temperature for a first preset time to obtain a first mixed solution, wherein the first mixed solution contains Bi 2 Te 3 Nanosheets.
In one embodiment, the step of adding the bismuth source, the tellurium source, the first reducing agent, and the first surfactant into the first solvent, and reacting at a first preset temperature for a first preset time to obtain the first mixed solution specifically includes:
according to Bi 2 Te 3 Adding bismuth source, tellurium source, first reducing agent and first surfactant into first solvent according to the stoichiometric ratio, stirring until the bismuth source and the tellurium source are completely dissolved (to prevent component segregation in the reaction process), then placing the mixture into a reaction kettle, and reacting for 12-40h at the temperature of 140-200 ℃ to obtain first mixed solution.
In one embodiment, the bismuth source is selected from at least one of bismuth chloride, bismuth nitrate, bismuth oxide, but is not limited thereto.
In one embodiment, the tellurium source is selected from elemental tellurium, sodium tellurite (Na) 2 TeO 3 ) Potassium tellurite (K) 2 TeO 3 ) But is not limited thereto.
In one embodiment, the first reducing agent is selected from at least one of hydrazine hydrate, ammonia water, sodium hydroxide, sodium borohydride, hydroxylamine, ethylenediamine, but is not limited thereto.
In one embodiment, the first surfactant is selected from at least one of ethylenediaminetetraacetic acid (EDTA), cetyltrimethylammonium bromide (CTAB), sodium Dodecylbenzenesulfonate (SDBS), polyvinylpyrrolidone (PVP), but is not limited thereto.
In one embodiment, the first solvent is selected from at least one of ethylene glycol, isopropyl alcohol, but is not limited thereto.
In step S2, in an embodiment, the step of adding the antimony source, the tellurium source, the second reducing agent, and the second surfactant to the second solvent to obtain the second mixed solution specifically includes:
in one embodiment, according to Sb 2 Te 3 Adding the antimony source, the tellurium source, the second reducing agent and the second surfactant into the second solvent according to the stoichiometric ratio, and stirring until the antimony source and the tellurium source are completely dissolved (so as to prevent component segregation in the reaction process), thereby obtaining a second mixed solution.
In one embodiment, the antimony source is selected from at least one of antimony chloride, antimony potassium tartrate, antimony oxide, but is not limited thereto.
In one embodiment, the tellurium source is selected from at least one of elemental tellurium, sodium tellurite, potassium tellurite, but is not limited thereto.
In one embodiment, the second reducing agent is selected from at least one of hydrazine hydrate, ammonia water, sodium hydroxide, sodium borohydride, hydroxylamine, ethylenediamine, but is not limited thereto.
In one embodiment, the second surfactant is selected from at least one of ethylenediaminetetraacetic acid, cetyltrimethylammonium bromide, sodium dodecylbenzene sulfonate, polyvinylpyrrolidone, but is not limited thereto.
In one embodiment, the second solvent is selected from at least one of ethylene glycol, isopropyl alcohol, but is not limited thereto.
In step S3, the Bi is added 2 Te 3 In the process of mixing and reacting the nano-sheets, the graphene oxide dispersion liquid and the second mixed liquid containing the antimony source and the tellurium source, bi is used 2 Te 3 Nanosheet as template for transversely growing annular Sb at periphery 2 Te 3 Nanosheets of Bi 2 Te 3 /Sb 2 Te 3 Lateral heterostructure to form Bi 2 Te 3 /Sb 2 Te 3 Composite nanosheets; meanwhile, a large amount of Bi is prepared by taking graphene as a framework through a simple self-assembly process 2 Te 3 /Sb 2 Te 3 The composite nanosheets are loaded on the surface of the graphene, so that a saturable absorber is formed.
In step S3, the first mixed solution (containing Bi) may be 2 Te 3 Nanosheet) and graphene oxide dispersion liquid are added into the second mixed liquid to react to obtain the saturable absorber. That is, bi can be converted into Bi in the present invention 2 Te 3 Adding the nanosheet and graphene oxide dispersion liquid into the second mixed liquid, and reacting to obtain the saturable absorber; can also directly contain Bi 2 Te 3 First mixed solution of nanosheets (containing Bi) 2 Te 3 Nanosheet) and graphene oxide dispersion liquid are added into the second mixed solution to react to obtain the graphene oxide nano-particlesA saturable absorber. Furthermore, the molar ratio of the Bi element to the Sb element can be controlled by controlling the dosage of the first mixed solution and the second mixed solution according to actual needs, and the Bi element in the saturable absorber can be further controlled 2 Te 3 And Sb 2 Te 3 In a molar ratio of (a). The amount of the graphene oxide dispersion liquid and the first mixed liquid and the second mixed liquid can be controlled through actual needs to control Bi 2 Te 3 /Sb 2 Te 3 And (3) coverage rate of the composite nanosheets on the graphene surface.
In one embodiment, the Bi is 2 Te 3 Adding the nanosheet and the graphene oxide dispersion liquid into the second mixed liquid, and reacting at a second preset temperature for a second preset time to obtain the saturable absorber, wherein the steps of:
the Bi is added 2 Te 3 And adding the nanosheet and graphene oxide dispersion liquid into the second mixed liquid, then placing the nanosheet and graphene oxide dispersion liquid into a reaction kettle, and reacting at the temperature of 140-200 ℃ for 12-40h to obtain the saturable absorber.
In step S3, the first mixed solution (containing Bi) may be 2 Te 3 Nanosheet) is added into the second mixed solution, ultrasonic stirring is carried out for 0.5-4h, then the graphene oxide dispersion liquid is added, and ultrasonic stirring is carried out for 0.5-4h, so that a uniformly dispersed solution is obtained.
The embodiment of the invention also provides a saturable absorber device, which comprises an optical fiber and a saturable absorber loaded on the end face of the fiber core of the optical fiber; the saturable absorber is the saturable absorber described above in the embodiment of the present invention, or the saturable absorber is the saturable absorber prepared by the preparation method described above in the embodiment of the present invention, or the saturable absorber is the saturable absorber described above in the embodiment of the present invention and the saturable absorber prepared by the preparation method described above in the embodiment of the present invention.
The embodiment of the invention also provides another saturable absorber device, wherein, or the saturable absorber device comprises a broadband dielectric film and a saturable absorber arranged on the broadband dielectric film; the saturable absorber is the saturable absorber described above in the embodiment of the present invention, or the saturable absorber is the saturable absorber prepared by the preparation method described above in the embodiment of the present invention, or the saturable absorber is the saturable absorber described above in the embodiment of the present invention and the saturable absorber prepared by the preparation method described above in the embodiment of the present invention.
In one embodiment, the broadband dielectric film is CaF coated with a reflective film 2 Lens, siO 2 The broadband dielectric film can also be an Ag coating reflecting mirror, an Au coating reflecting mirror and the like.
Further, the saturable absorber device can be applied to a mode-locked laser.
The details are described below by way of specific examples.
Example 1
(1) Adding 10mg of graphene oxide (prepared by a modified Hummers method) into 8mL of ethylene glycol, fully performing ultrasonic treatment for 2h, and continuously stirring until a completely uniformly dispersed graphene oxide dispersion liquid is obtained;
(2) Adding 315mg of bismuth chloride, 332mg of sodium tellurite, 400mg of sodium hydroxide and 500mg of polyvinylpyrrolidone (PVP K-30) into a beaker, adding 40mL of ethylene glycol, stirring until the ethylene glycol is completely dissolved, then transferring the mixture into a polytetrafluoroethylene lining (the specification is 50 mL) of a high-pressure reaction kettle, wherein the filling degree is 80%, placing the high-pressure reaction kettle into a drying box at the temperature of 180 ℃, reacting for 40 hours at constant temperature, and cooling to room temperature after the reaction is finished to obtain gray liquid (containing Bi) 2 Te 3 Nanosheets), without any treatment for use;
(3) Adding 82.4mg of antimony chloride, 117mg of sodium tellurite, 400mg of sodium hydroxide and 500mg of polyvinylpyrrolidone (PVP K-30) into a beaker, adding 26mL of ethylene glycol, stirring until the ethylene glycol is completely dissolved to obtain a mixed solution, accurately transferring 6mL of gray liquid synthesized in the step (2) by using a liquid transfer gun, adding the gray liquid into the mixed solution, stirring for 2 hours by ultrasonic, and uniformly mixing.
(4) Mixing the graphene oxide dispersion liquid obtained in the step (1) with the solution obtained in the step (3), ultrasonically stirring for 0.5h, transferring into a polytetrafluoroethylene lining (with the specification of 50 mL) of a high-pressure reaction kettle, wherein the filling degree is 80%, placing the high-pressure reaction kettle in a drying oven at 180 ℃, and reacting at constant temperature for 30h.
(5) Repeatedly washing the product obtained in the step (4) with deionized water and absolute ethyl alcohol for 5 times, and performing vacuum drying to obtain black powder, namely the saturable absorber, wherein the saturable absorber comprises graphene and Bi loaded on the graphene 2 Te 3 /Sb 2 Te 3 And (3) compounding nano sheets.
A schematic diagram of the growth of the saturable absorber prepared in example 1 is shown in fig. 1. By using Bi 2 Te 3 Sb induction by using nanosheet as template 2 Te 3 And forming a bidirectional heterojunction through self-assembly with the graphene while the epitaxial growth is carried out.
Example 2
This example differs from example 1 in that: adding 20mg of graphene oxide into 8mL of ethylene glycol in the step (1), fully performing ultrasonic treatment for 3h, and continuously stirring until a completely and uniformly dispersed graphene oxide dispersion liquid is obtained.
Comparative example 1
The only difference from example 1 is: step (1) is not carried out; in the step (4), the graphene oxide dispersion liquid is not added, and the Bi is finally obtained 2 Te 3 /Sb 2 Te 3 And (3) compounding nano sheets.
Comparative example 2
Adding 315mg of bismuth chloride, 332mg of sodium tellurite, 400mg of sodium hydroxide and 500mg of polyvinylpyrrolidone (PVP K-30) into a beaker, adding 40mL of ethylene glycol, stirring until the ethylene glycol is completely dissolved, then transferring the mixture into a polytetrafluoroethylene lining (the specification is 50 mL) of a high-pressure reaction kettle, wherein the filling degree is 80%, placing the high-pressure reaction kettle into a drying box at 180 ℃, reacting at a constant temperature for 40 hours, cooling to room temperature after the reaction is finished to obtain gray liquid, and washing, filtering and drying to obtain Bi 2 Te 3 Nanosheets.
Comparative example 3
82.4mg of antimony chloride, 117mg of sodium tellurite, 400mg of sodium hydroxide, 500mg of polyvinylpyrrolidone (PVP K-30) were added to the beaker and 26mL of ethylene glycol were added,stirring until the mixed solution is completely dissolved to obtain a mixed solution, then transferring the mixed solution into a polytetrafluoroethylene lining (with the specification of 50 mL) of a high-pressure reaction kettle, wherein the filling rate is 52%, placing the high-pressure reaction kettle in a drying oven at 180 ℃, carrying out constant-temperature reaction for 30h, washing, filtering and drying the obtained product to obtain Sb 2 Te 3 Nanosheets.
And (3) testing:
(1) The XRD pattern of the saturable absorber prepared in example 1 is shown in FIG. 2, and comparison with standard PDF card shows that the diffraction spectrum contains Bi 2 Te 3 And Sb 2 Te 3 Two sets of diffraction peaks, which indicates that the synthesized product is indeed Bi 2 Te 3 And Sb 2 Te 3 Two substances. The stronger diffraction intensity also fully indicates that the prepared product has better crystallinity. Due to the low content of graphene and Bi 2 Te 3 /Sb 2 Te 3 The composite nanosheets are adsorbed in a large area, and no diffraction peak of graphene is observed in an XRD (X-ray diffraction) pattern.
(2) Fig. 3 shows Scanning Electron Microscope (SEM) and selected area spectroscopy (EDS) images of the saturable absorber prepared in example 1. It can be seen that a large amount of Bi is attached to the graphene frame 2 Te 3 /Sb 2 Te 3 And (3) compounding nano sheets. Through self-assembly reaction, the composite nanosheet is regular in size, uniform in hexagon, clear in edge and vertex angle, and smooth in surface, and the prepared material has very good crystallinity. Bi 2 Te 3 /Sb 2 Te 3 The composite nano sheets are uniformly dispersed, and no obvious stacking agglomeration phenomenon is observed. It can also be clearly seen that for the inner hexagonal region, it has only Bi and Te elements, and for the outer annular region, it has only Sb and Te elements. Description of Bi 2 Te 3 /Sb 2 Te 3 The composite nanosheets (transverse heterojunction nanosheets) having a center of Bi 2 Te 3 Nanosheets, the periphery of which is annular Sb 2 Te 3 Lateral heterostructures of the nanoplatelets.
(3) Bi prepared in comparative example 1 2 Te 3 /Sb 2 Te 3 The X-ray photoelectron spectroscopy (XPS) graphs of the composite nanosheet and the saturable absorber prepared in example 1 are shown in fig. 4 (a) and (b), respectively. In comparison with the XPS database, the two strong peaks at 162.5eV and 157.2eV in graphs (a) and (b) are associated with Bi 4f 5/2 And Bi 4f 7/2 The binding energy of (a) is uniform. In addition, both shift peaks at 163.9eV and 158.6eV are oxidation peaks due to surface oxidation. By comparing the graphs (a) and (b), the intensity of two shift peaks at 163.9eV and 158.6eV in the graph (b) is lower than that in the graph (a), which indicates that the graphene can protect Bi to a certain extent 2 Te 3 /Sb 2 Te 3 The composite nano sheet prevents the surface thereof from being oxidized and improves Bi 2 Te 3 /Sb 2 Te 3 Stability of the composite nanosheet.
(4) Bi prepared in comparative example 2 2 Te 3 Nanosheet, sb prepared in comparative example 3 2 Te 3 Nanosheet, bi prepared in comparative example 1 2 Te 3 /Sb 2 Te 3 The near infrared nonlinear transmittance graphs of the nanosheets and the saturable absorber prepared in example 1 are shown in fig. 5a-5d, respectively. By comparison, the saturable absorber (FIG. 5 d) prepared in example 1 has saturation intensity and modulation depth compared with Bi 2 Te 3 Nanosheets (FIG. 5 a), sb 2 Te 3 Nanosheet (FIG. 5 b), bi 2 Te 3 /Sb 2 Te 3 The nanosheets (fig. 5 c) are enlarged, and the larger modulation depth and saturation light intensity are beneficial to pulse compression. Thus, bi can be illustrated 2 Te 3 /Sb 2 Te 3 Bi in composite nano sheet 2 Te 3 Nanosheet and cyclic Sb 2 Te 3 Synergistic effect of nanosheets, bi 2 Te 3 /Sb 2 Te 3 Composite nanosheet (Bi) 2 Te 3 /Sb 2 Te 3 Lateral heterojunction) and graphene are beneficial to increasing modulation depth and saturation intensity, saturable absorption performance is optimized, and nonlinear optical performance of a single material is improved.
To sum up, the present inventionA saturable absorber, a method for preparing the same and a saturable absorber device are provided, wherein Bi 2 Te 3 Nanosheet and Bi enclosed therein 2 Te 3 Nanosheet period cyclic Sb 2 Te 3 The nanosheets forming a composite nanosheet (i.e., bi) 2 Te 3 /Sb 2 Te 3 Composite nanosheets), bi 2 Te 3 /Sb 2 Te 3 Bi in composite nanosheet 2 Te 3 Nanosheet and cyclic Sb 2 Te 3 Bi is formed at the interface where the nano sheets are connected 2 Te 3 /Sb 2 Te 3 A lateral heterojunction. In Bi 2 Te 3 /Sb 2 Te 3 In the lateral heterojunction, the energy distribution and band edge position of the whole material are changed due to rearrangement and combination of Sb and Bi atoms. At the heterojunction interface, the stronger internal electric field can improve the carrier mobility, and the higher carrier mobility can promote the absorption between electrons and photons, thereby realizing Bi 2 Te 3 /Sb 2 Te 3 Further optimization of modulation depth of the composite nanosheets, i.e. Bi 2 Te 3 /Sb 2 Te 3 The one-dimensional interface effect of the transverse heterojunction is beneficial to realizing the rapid transfer of charges and the rapid recombination of electron hole pairs, effectively shortens the relaxation time, thereby achieving the purpose of rapid saturation absorption and improving the Bi content of the single two-dimensional layered nano material 2 Te 3 Or Sb 2 Te 3 Saturable absorption properties of (a). At the same time, bi 2 Te 3 /Sb 2 Te 3 The composite nanosheet is compounded with the graphene, and the characteristics of high thermal conductivity, strong oxidation resistance, large-size film forming property and the like of the graphene are further utilized, so that the problems that the two-dimensional layered material is easily oxidized by air, easily agglomerated, uneven in film forming and the like at high temperature in optical application can be well solved, and the stability of the saturable absorber is greatly improved. In addition, bi 2 Te 3 /Sb 2 Te 3 Bi in composite nanosheet 2 Te 3 Nanosheet and cyclic Sb 2 Te 3 Synergistic effect of nanosheets, bi 2 Te 3 /Sb 2 Te 3 Composite nanoRice flake (Bi) 2 Te 3 /Sb 2 Te 3 Transverse heterojunction) and graphene can effectively avoid the limitation of single material application, and greatly improve the nonlinear optical performance of the saturable absorber. The saturable absorber provided by the invention utilizes Bi 2 Te 3 /Sb 2 Te 3 The transverse heterojunction one-dimensional interface effect improves the carrier mobility, increases the modulation depth, and simultaneously considers the characteristics of high thermal conductivity, strong oxidation resistance and large-size film forming performance of the graphene, namely the saturable absorber provided by the invention has the advantages of high carrier mobility, large modulation depth, good nonlinear optical performance, strong oxidation resistance, difficult agglomeration, easy film forming and the like.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A saturable absorber, comprising graphene and composite nanosheets supported on the graphene;
the composite nanoplatelets comprise:
Bi 2 Te 3 a nanosheet;
and, surrounding the Bi 2 Te 3 Around the nanosheet and with said Bi 2 Te 3 Circular Sb with nanosheets connected to form heterojunction 2 Te 3 Nanosheets.
2. A method of making a saturable absorber as claimed in claim 1, comprising the steps of:
provides a graphene oxide dispersion and Bi 2 Te 3 A nanosheet;
adding an antimony source, a tellurium source, a second reducing agent and a second surfactant into a second solvent to obtain a second mixed solution;
the Bi is added 2 Te 3 And adding the nanosheet and graphene oxide dispersion liquid into the second mixed liquid, and reacting at a second preset temperature for a second preset time to obtain the saturable absorber.
3. The method for producing a saturable absorber according to claim 2, wherein the Bi is 2 Te 3 The preparation method of the nano-sheet comprises the following steps: adding a bismuth source, a tellurium source, a first reducing agent and a first surfactant into a first solvent, and reacting at a first preset temperature for a first preset time to obtain a first mixed solution, wherein the first mixed solution contains Bi 2 Te 3 Nanosheets.
4. The method according to claim 2, wherein the graphene oxide dispersion liquid is prepared by a method comprising the steps of:
providing graphene oxide and a third solvent;
and adding the graphene oxide into the third solvent, and performing ultrasonic dispersion to obtain the graphene oxide dispersion liquid.
5. The production method according to claim 3,
the bismuth source is at least one selected from bismuth chloride, bismuth nitrate and bismuth oxide;
the tellurium source is selected from at least one of simple substance tellurium, sodium tellurite and potassium tellurite;
the antimony source is at least one of antimony chloride, antimony potassium tartrate and antimony oxide.
6. The preparation method according to claim 3, wherein the first reducing agent and the second reducing agent are each independently selected from at least one of hydrazine hydrate, ammonia water, sodium hydroxide, sodium borohydride, hydroxylamine and ethylenediamine;
the first surfactant and the second surfactant are respectively and independently selected from at least one of ethylene diamine tetraacetic acid, cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate and polyvinylpyrrolidone.
7. The preparation method of claim 3, wherein the step of adding the bismuth source, the tellurium source, the first reducing agent and the first surfactant into the first solvent, and reacting at a first preset temperature for a first preset time to obtain the first mixed solution specifically comprises:
according to Bi 2 Te 3 Adding a bismuth source, a tellurium source, a first reducing agent and a first surfactant into a first solvent according to the stoichiometric ratio, stirring until the bismuth source and the tellurium source are completely dissolved, then placing the mixture into a reaction kettle, and reacting for 12-40h at the temperature of 140-200 ℃ to obtain a first mixed solution.
8. The preparation method according to claim 2, wherein the step of adding the antimony source, the tellurium source, the second reducing agent, and the second surfactant to the second solvent to obtain the second mixed solution specifically comprises:
according to Sb 2 Te 3 Adding the antimony source, the tellurium source, the second reducing agent and the second surfactant into the second solvent according to the stoichiometric ratio, and stirring until the antimony source and the tellurium source are completely dissolved to obtain a second mixed solution.
9. The method according to claim 2, wherein said reacting Bi 2 Te 3 Adding the nanosheet and the graphene oxide dispersion liquid into the second mixed liquid, and reacting at a second preset temperature for a second preset time to obtain the saturable absorber, wherein the steps of:
the Bi is added 2 Te 3 And adding the nano sheet and the graphene oxide dispersion liquid into the second mixed liquid, then placing the mixture into a reaction kettle, and reacting at the temperature of 140-200 ℃ for 12-40h to obtain the saturable absorber.
10. A saturable absorber device is characterized in that the saturable absorber device comprises an optical fiber and a saturable absorber carried on the end face of a fiber core of the optical fiber, or the saturable absorber device comprises a broadband dielectric film and a saturable absorber arranged on the broadband dielectric film;
the saturable absorber is the saturable absorber described in claim 1 and/or the saturable absorber prepared by the preparation method described in any one of claims 1 to 9.
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