CN113106550B - Electrochemical preparation method of frequency doubling crystal - Google Patents
Electrochemical preparation method of frequency doubling crystal Download PDFInfo
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Abstract
The invention discloses an electrochemical preparation method of a frequency doubling crystal, which specifically comprises the following steps: preparing an electrolyte solution containing organic target molecules; the invention uses electrochemical three-electrode system and transition metal sulfide as working electrode to make electrochemical intercalation reaction, and inserts the organic target molecule between transition metal sulfide layers to form the frequency doubling crystal.
Description
Technical Field
The invention belongs to the technical field of frequency doubling crystals, and particularly relates to an electrochemical preparation method of a frequency doubling crystal.
Background
The photoelectronic technology is a novel combination technology in the photon and electron fields, and relates to the core technology of the information industry in the fields of optical display, laser and the like. In the development of this field of technology, much attention has been paid to the study of coherent laser emission light sources. Nonlinear optics is a nonlinear optical phenomenon generated by researching a medium under the action of strong coherent light and application thereof. The nonlinear optical correlation research plays an important role in various photon and photoelectric devices, and particularly relates to the correlation application of high-power laser. When strong light enters a medium with a nonlinear effect, higher harmonics are generated besides the original natural frequency. By utilizing the characteristics of frequency doubling, difference frequency and the like in nonlinear optics, the laser light source can be effectively adjusted, and the application range is widened. According to a large number of reports, the bulk two-dimensional layered semiconductor crystal material which grows naturally is known to be mostly of an AB stacked central symmetry structure, and has small or even impossible response to second harmonic. If the exfoliation is a single layer crystal structure, the central symmetry can be broken. According to reports, a single-layer material of two-dimensional layered transition metal sulfide shows a high-efficiency nonlinear optical effect, and the defect is that the light absorption efficiency of the single-layer material is low and is often less than five percent.
The frequency doubling crystal mainly comprises lithium niobate, potassium dihydrogen phosphate, gallium arsenide and borate crystals, most of the existing artificial frequency doubling crystals are prepared by a chemical vapor deposition method, the cost is high, the size of the final crystal is large, the two-dimensional layered transition metal sulfide crystal prepared by the chemical vapor deposition method is symmetrical in space inversion (central symmetry) and has no frequency doubling effect, and therefore the two-dimensional layered transition metal sulfide crystal cannot be prepared into the frequency doubling crystal by a direct chemical vapor deposition method.
Therefore, in order to solve the above technical problems, it is necessary to provide an electrochemical preparation method of frequency doubling crystal.
Disclosure of Invention
The invention aims to provide a method and a solution for preparing frequency doubling crystals so as to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme: an electrochemical preparation method of a frequency doubling crystal specifically comprises the following steps:
preparing an electrolyte solution containing organic target molecules;
in an electrolyte solution, an electrochemical three-electrode system is adopted for electrochemical intercalation reaction, wherein two-dimensional layered transition metal sulfide is used as a working electrode, and the organic target molecules are inserted between transition metal sulfide layers to form the frequency doubling crystal.
As a preferable technical scheme of the invention, the electrolyte solution comprises an organic solvent, target organic molecules and conductive salt, wherein the content of the target organic molecules in the electrolyte solution is 0.1-1 g/L.
As a preferable technical scheme of the invention, the target organic molecule is one of hexadecyl trimethyl ammonium bromide, perylene tetracarboxylic dianhydride, tetrabutyl ammonium bromide, anthracene, fullerene, 7,8, 8-tetracyano p-benzoquinodimethane and rubrene.
As a preferable technical scheme of the invention, the organic solvent is one of dimethyl sulfoxide, dimethylformamide, isopropanol, cyclohexane, acetone and acetonitrile.
As a preferable technical scheme of the invention, the conductive salt is one of sodium dodecyl sulfate and sodium acetate.
As a preferable technical scheme of the invention, the content of the conductive salt in the electrolyte solution is 0-15 g/L.
As a preferable technical scheme of the invention, the electrolyte solution is obtained by adding an organic target molecule and a conductive salt into an organic solvent and carrying out ultrasonic treatment under the conditions of sealing and 50-60 ℃.
In the electrochemical three-electrode system, a platinum wire is used as a counter electrode, Ag/AgCl is used as a reference electrode, and electrochemical intercalation reaction is carried out in a reaction chamber made of PDMS material.
As a preferred technical solution of the present invention, the electrolysis conditions in the electrochemical intercalation reaction are as follows: the electrochemical scanning potential interval is 0 to-3V, and the scanning speed is 20 mV/s.
As a preferred technical scheme of the invention, after the electrochemical intercalation reaction is finished, the pressure is 5 x 10 -6 Pa, and the temperature is 80-100 ℃.
Compared with the prior art, the invention has the beneficial effects that: the two-dimensional layered transition metal sulfide crystal naturally growing is subjected to interlayer decoupling through an electrochemical intercalation technology, the symmetrical structure of the crystal is broken, the second harmonic signal generation in a layer-by-layer addition mode is realized for a single-layer material with high nonlinear coefficient, and the ultrathin high-efficiency frequency doubling crystal is prepared through a simple method.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic diagram of an apparatus for carrying out the process of the present invention;
FIG. 2 is a graph of a crystal optical topography test in one embodiment of the present application;
FIG. 3 is a data diagram illustrating the results of a second harmonic generation signal test according to one embodiment of the present application;
FIG. 4 is a schematic diagram illustrating the operation principle of an interlayer frequency doubling crystal according to an embodiment of the present disclosure;
FIG. 5 is a schematic diagram illustrating the principles of electrochemical intercalation according to one embodiment of the present application;
FIG. 6 is a graphical representation of electrochemical current versus conductance of a two-dimensional material during electrochemical intercalation in accordance with an embodiment of the present application.
Detailed Description
The present invention will be described in detail below with reference to embodiments shown in the drawings. The embodiments are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to the embodiments are included in the scope of the present invention.
As shown in fig. 1 to 6, an electrochemical preparation method of a frequency doubling crystal specifically comprises:
preparing an electrolyte solution containing organic target molecules;
the electrolyte comprises an organic solvent, a target organic molecule and a conductive salt, wherein the content of the target organic molecule in the solution is 0.1-1 g/L, and the preparation method specifically comprises the steps of adding the organic target molecule and the conductive salt into the organic solvent, and carrying out ultrasonic treatment for 30min at the temperature of 50-60 ℃ in a sealed manner to complete the preparation of the electrolyte solution.
Wherein the target organic molecule is one of cetyl trimethyl ammonium bromide, perylene tetracarboxylic dianhydride, tetrabutyl ammonium bromide, anthracene, fullerene, 7,8, 8-tetracyano-p-phenylenediamine dimethane and rubrene.
Wherein the organic solvent is one of dimethyl sulfoxide, dimethylformamide, isopropanol, cyclohexane, acetone and acetonitrile.
The conductive salt is one of sodium dodecyl sulfate and sodium acetate, and plays a role in improving the conductivity of the solution and reducing the reaction potential.
Preferably, the content of the sodium dodecyl sulfate or the sodium acetate in the solution is 0-15 g/L.
The content ranges of the target organic molecules and the conductive salt in the solution are the optimal concentration ranges according to the solubility of the target organic molecules and the conductive salt in the organic solvent and the electrochemical intercalation reaction rate.
Next, in an electrolyte solution, an electrochemical three-electrode system is adopted for electrochemical intercalation reaction, wherein two-dimensional layered transition metal sulfide is taken as a working electrode, and the organic target molecules are inserted between transition metal sulfide layers to form the frequency doubling crystal;
the specific steps are that a platinum wire is used as a counter electrode, Ag/AgCl is used as a reference electrode, electrochemical intercalation reaction is carried out in a reaction chamber prepared from PDMS (polydimethylsiloxane), the electrochemical scanning potential interval is 0-3V, the scanning speed is 20mV/s, the quantity of organic target molecules and the reaction end point are judged according to an oxidation reduction peak and the electrochemical reaction electric quantity, the judging method is shown in figure 6, 6a is an electrochemical linear scanning curve, 6b is a curve that the electric conductance changes along with the electrochemical potential, the electrochemical current is increased when the electrochemical intercalation reaction is carried out, the electric conductance of a two-dimensional material is increased in order of magnitude, and the electrochemical intercalation reaction is stopped when the electric conductance stops increasing.
The reaction chamber is a hollow annular tube, the bottom end of the annular tube is fixed on a silicon wafer, and the surface of the silicon wafer is covered with two-dimensional layered transition metal sulfide by adopting methods such as photoetching and the like and is used as a working electrode.
Finally, when the electrochemical intercalation reaction is finished, the pressure is 5 multiplied by 10 -6 Pa, and the temperature is 80-100 ℃, and the annealing is performed for 30min in vacuum, and the annealing is used for desorbing residual solvent molecules on the surface of the prepared frequency doubling crystal.
Some terms of expertise in the present invention will be explained below:
second harmonic generation: when laser light is applied to a second-order nonlinear material, in addition to light having the same incident frequency ω (linear portion), frequency-doubled light having a frequency of 2 ω and an electrostatic field having a frequency of 0 (nonlinear portion) are generated, which generates frequency-doubled light called second-harmonic generation effect.
Frequency doubling crystal: a nonlinear optical crystal for frequency doubling effect.
Two-dimensional material: two-dimensional materials are an emerging class of materials, and materials with thicknesses ranging from a single atomic layer to several atomic layers are referred to as two-dimensional materials. The layers of two-dimensional materials are mainly connected by Van der Waals force, and atoms in the layers are connected by covalent bonds.
Metal sulfide: transition and Metal Dichalcogenides (TMDC) have the chemical formula MX2, M represents a Transition metal element (e.g., molybdenum, tungsten, niobium, rhenium, titanium), and X represents a chalcogen element (e.g., sulfur, selenium, tellurium). The single-layer transition metal sulfide is of a sandwich structure of X-M-X. The bulk TMDC layers are connected by weak van der waals forces, while the in-plane atoms are strongly covalently bonded, so that TMDC can be exfoliated into single or multiple layered nanoplatelets. Many TMDCs exhibit semiconductor characteristics in which the energy band of a multilayer material is an indirect band gap, and when peeled off as a single layer, the energy band structure is converted to a direct band gap.
Electrochemical intercalation: is a unique two-dimensional material performance regulating and controlling method. The method utilizes the intrinsic van der Waals interlayer spacing of the two-dimensional material, inserts target molecules with specific performance between the two-dimensional material layers under proper electrochemical potential, and carries out controllable regulation and control on the electrical, magnetic, optical and other performances of the two-dimensional material.
In the case of the example 1, the following examples are given,
weighing 0.5g of hexadecyl trimethyl ammonium bromide and adding into 1L of dimethyl sulfoxide, weighing 7g of lauryl sodium sulfate and adding into the solution, sealing, performing ultrasonic treatment at 50 ℃ for 30min to obtain an electrolyte solution, taking out 100ml of the prepared electrolyte solution and pouring into a reaction chamber made of PDMS (polydimethylsiloxane) material, wherein the bottom of the reaction chamber is a silicon wafer (f in figure 1), a two-dimensional layered transition metal molybdenum sulfide on the silicon wafer is used as a working electrode (e in figure 1), a platinum wire is used as a counter electrode (c in figure 1), Ag/AgCl is used as a reference electrode (d in figure 1), and the counter electrode and the reference electrode are inserted into the reaction chamberIn the electrolyte solution of the chamber, the electrochemical scanning potential interval is 0 to-3V, the scanning speed is 20mV/s, electrochemical intercalation reaction is carried out, the amount of cetyl trimethyl ammonium bromide and the reaction end point are judged according to the oxidation reduction peak and the electrochemical reaction electric quantity, after the reaction is finished, the electrolyte solution is poured out, the reaction chamber made of PDMS (polydimethylsiloxane) material is dismantled, and the silicon wafer attached with the working electrode is pressed at the pressure of 5 multiplied by 10 -6 Pa and the temperature of 90 ℃ for 30min, and finally obtaining the frequency doubling crystal of the two-dimensional layered transition metal molybdenum sulfide on the surface of the silicon wafer.
And (3) optical appearance testing:
as shown in fig. 2, 2(a) in the figure is an optical photograph of a crystal of two-dimensional layered transition metal molybdenum sulfide that is not subjected to electrochemical treatment, and 2(b) in the figure is an optical photograph of a frequency-doubled crystal of two-dimensional layered transition metal molybdenum sulfide that is subjected to electrochemical treatment.
Therefore, the difference of the obvious optical appearance between the frequency doubling crystal of the two-dimensional layered transition metal molybdenum sulfide treated by the electrochemical intercalation method and the crystal of the two-dimensional layered transition metal molybdenum sulfide not treated by the electrochemical intercalation method can be obviously seen.
Second Harmonic Generation (SHG) signal test:
and performing SHG signal test on the frequency doubling crystal of the two-dimensional layered transition metal molybdenum sulfide obtained by the preparation and the two-dimensional layered transition metal molybdenum sulfide crystal which is not subjected to electrochemical treatment. Using 780nm femtosecond pulse laser as a light source to compare SHG test results shown before and after intercalation, as shown in fig. 3, wherein 3a is test data of two-dimensional layered transition metal molybdenum sulfide after completing electrochemical intercalation reaction, and 3b is test data of two-dimensional layered transition metal molybdenum sulfide crystal without electrochemical intercalation, so as to obtain that SHG signal intensity of two-dimensional layered transition metal molybdenum sulfide after completing intercalation reaction is obviously enhanced.
In the case of the example 2, the following examples are given,
as shown in figure 1, 1g of perylenetetracarboxylic dianhydride is weighed and added into 1L of acetonitrile, 5g of sodium acetate is weighed and added into the solution, sealing is carried out, ultrasonic treatment is carried out at the temperature of 50 ℃ for 30min to obtain electrolyte solution, and then the electrolyte solution is connected with the electrolyte solutionThen 100ml of the prepared electrolyte solution is taken out and poured into a reaction chamber made of PDMS (polydimethylsiloxane) material, the bottom of the reaction chamber is a silicon wafer (f in figure 1), two-dimensional layered transition metal molybdenum sulfide on the silicon wafer is used as a working electrode (e in figure 1), then a platinum wire was used as a counter electrode (c in FIG. 1), Ag/AgCl was used as a reference electrode (d in FIG. 1) and inserted into the electrolyte solution of the reaction chamber, electrochemical scanning potential interval is 0 to-3V, scanning speed is 20mV/s, electrochemical intercalation reaction is carried out, and the amount of the perylene tetracarboxylic dianhydride and the reaction end point are judged according to the redox peak and the electrochemical reaction electric quantity, after the reaction, the electrolyte solution was poured off, and the reaction chamber made of PDMS (polydimethylsiloxane) material was removed, and the silicon wafer with the working electrode attached was pressed at 5 × 10. -6 Pa and the temperature of 80 ℃ for 30min, and finally obtaining the frequency doubling crystal of the two-dimensional layered transition metal molybdenum sulfide on the surface of the silicon wafer.
Performing a sum optical appearance test on the two-dimensional layered transition metal molybdenum sulfide crystal and the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal prepared by the reaction, wherein the sum optical appearance test is obviously different from the previous two-dimensional layered transition metal molybdenum sulfide crystal; and performing SHG signal test on the two-dimensional layered transition metal molybdenum sulfide crystal and the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal prepared by the reaction, wherein the SHG signal test of the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal obtained by the electrochemical method is obviously stronger than the SHG signal of the two-dimensional layered transition metal molybdenum sulfide crystal.
In the case of the embodiment 3, the following examples,
weighing 0.7g of tetrabutylammonium bromide and adding into 1L of acetone, weighing 10g of sodium acetate and adding into the solution, sealing, performing ultrasonic treatment at 52 ℃ for 30min to obtain an electrolyte solution, taking 100ml of the prepared electrolyte solution and pouring into a reaction chamber made of PDMS (polydimethylsiloxane) material, wherein the bottom of the reaction chamber is a silicon wafer (f in figure 1), a two-dimensional layered transition metal molybdenum sulfide on the silicon wafer is used as a working electrode (e in figure 1), a platinum wire is used as a counter electrode (c in figure 1), Ag/AgCl is used as a reference electrode (d in figure 1), and the counter electrode is inserted into the solutionCarrying out electrochemical intercalation reaction in an electrolyte solution in a reaction chamber with an electrochemical scanning potential interval of 0 to-3V and a scanning speed of 20mV/s, judging the amount of tetrabutyl ammonium bromide and a reaction end point according to an oxidation reduction peak and electrochemical reaction electric quantity, pouring the electrolyte solution after the reaction is finished, dismantling the reaction chamber made of PDMS (polydimethylsiloxane) material, and placing a silicon wafer attached with a working electrode at a pressure of 5 multiplied by 10 -6 Pa and the temperature of 95 ℃ for 30min, and finally obtaining the frequency doubling crystal of the two-dimensional layered transition metal molybdenum sulfide on the surface of the silicon wafer.
Performing a sum optical appearance test on the two-dimensional layered transition metal molybdenum sulfide crystal and the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal prepared by the reaction, wherein the sum optical appearance test is obviously different from the previous two-dimensional layered transition metal molybdenum sulfide crystal; SHG signal test is carried out on the two-dimensional layered transition metal molybdenum sulfide crystal and the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal prepared by the reaction, and the SHG signal test of the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal obtained by the electrochemical method is obviously stronger than that of the two-dimensional layered transition metal molybdenum sulfide crystal
In the case of the example 4, the following examples are given,
weighing 0.4g of anthracene into 1L of isopropanol, weighing 6g of sodium dodecyl sulfate, continuously adding the solution into the solution, sealing, carrying out ultrasonic treatment at 56 ℃ for 30min to obtain an electrolyte solution, taking 100ml of the prepared electrolyte solution out, pouring the electrolyte solution into a reaction chamber prepared from a PDMS (polydimethylsiloxane) material, wherein the bottom of the reaction chamber is a silicon wafer (f in figure 1), a two-dimensional layered transition metal molybdenum sulfide on the silicon wafer is used as a working electrode (e in figure 1), a platinum wire is used as a counter electrode (c in figure 1), Ag/AgCl is used as a reference electrode (d in figure 1) and is inserted into the electrolyte solution in the reaction chamber, the electrochemical scanning potential interval is 0-3V, the scanning rate is 20mV/s, carrying out electrochemical intercalation reaction, and judging the amount and the reaction end point of the anthracene according to an oxidation reduction peak and the electrochemical reaction electric quantity, after the reaction is finished, the electrolyte solution is poured off, the reaction chamber made of PDMS (polydimethylsiloxane) material is dismantled, and the electrolyte solution is attachedThe silicon wafer with working electrode is at pressure of 5 × 10 -6 Pa and the temperature of 100 ℃ for 30min, and finally obtaining the frequency doubling crystal of the two-dimensional layered transition metal molybdenum sulfide on the surface of the silicon wafer.
The two-dimensional layered transition metal molybdenum sulfide crystal and the two-dimensional layered transition metal molybdenum sulfide double frequency crystal prepared by the reaction are subjected to a sum optical appearance test, and the sum optical appearance test has obvious optical difference with the previous two-dimensional layered transition metal molybdenum sulfide crystal; SHG signal test is carried out on the two-dimensional layered transition metal molybdenum sulfide crystal and the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal prepared by the reaction, and the SHG signal test of the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal obtained by the electrochemical method is obviously stronger than that of the two-dimensional layered transition metal molybdenum sulfide crystal
In the case of the example 5, the following examples were conducted,
weighing 0.1g of fullerene into 1L of dimethylformamide, weighing 15g of sodium dodecyl sulfate, continuously adding the weighed solution into the solution, sealing, carrying out ultrasonic treatment at the temperature of 60 ℃ for 30min to obtain an electrolyte solution, taking 100ml of the prepared electrolyte solution out, pouring the electrolyte solution into a reaction chamber prepared from PDMS (polydimethylsiloxane) material, wherein the bottom of the reaction chamber is a silicon wafer (f in figure 1), a two-dimensional layered transition metal molybdenum sulfide on the silicon wafer is used as a working electrode (e in figure 1), a platinum wire is used as a counter electrode (c in figure 1), Ag/AgCl is used as a reference electrode (d in figure 1) and is inserted into the electrolyte solution in the reaction chamber, the electrochemical scanning potential interval is 0-3V, the scanning rate is 20mV/s, carrying out electrochemical intercalation reaction, and judging the amount and the reaction electric quantity according to an oxidation reduction peak and the electrochemical reaction electric quantity, after the reaction is finished, the electrolyte solution is poured off, the reaction chamber made of PDMS (polydimethylsiloxane) material is disassembled, and the silicon wafer attached with the working electrode is placed under the pressure of 5 multiplied by 10 -6 Pa and the temperature of 85 ℃ for 30min, and finally obtaining the frequency doubling crystal of the two-dimensional layered transition metal molybdenum sulfide on the surface of the silicon wafer.
Performing a sum optical appearance test on the two-dimensional layered transition metal molybdenum sulfide crystal and the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal prepared by the reaction, wherein the sum optical appearance test is obviously different from the previous two-dimensional layered transition metal molybdenum sulfide crystal; SHG signal test is carried out on the two-dimensional layered transition metal molybdenum sulfide crystal and the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal prepared by the reaction, and the SHG signal test of the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal obtained by the electrochemical method is obviously stronger than that of the two-dimensional layered transition metal molybdenum sulfide crystal
In the case of the example 6, it is shown,
as shown in fig. 1, 0.6g of tcnq (7,7,8, 8-tetracyanoquinodimethane) is weighed and added into 1L of cyclohexane, 2g of sodium dodecyl sulfate is weighed and added into the solution, then sealing is carried out, ultrasonic treatment is carried out at the temperature of 58 ℃ for 30min to obtain an electrolyte solution, then 100ml of the prepared electrolyte solution is taken out and poured into a reaction chamber made of PDMS (polydimethylsiloxane) material, the bottom of the reaction chamber is a silicon wafer (f in fig. 1), two-dimensional layered transition metal molybdenum sulfide on the silicon wafer is used as a working electrode (e in fig. 1), then a platinum wire is used as a counter electrode (c in fig. 1), Ag/AgCl is used as a reference electrode (d in fig. 1) and is inserted into the electrolyte solution in the reaction chamber, the electrochemical scanning potential interval is 0 to-3V, the scanning rate is 20mV/s, performing electrochemical intercalation reaction, judging the amount of TCNQ (7,7,8, 8-tetracyano-p-quinodimethane) and the reaction end point according to the oxidation reduction peak and the electrochemical reaction electricity, pouring the electrolyte solution after the reaction is finished, removing the reaction chamber made of PDMS (polydimethylsiloxane) material, and placing the silicon wafer attached with the working electrode under the pressure of 5 × 10 -6 Pa and the temperature of 90 ℃ for 30min, and finally obtaining the frequency doubling crystal of the two-dimensional layered transition metal molybdenum sulfide on the surface of the silicon wafer.
Performing a sum optical appearance test on the two-dimensional layered transition metal molybdenum sulfide crystal and the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal prepared by the reaction, wherein the sum optical appearance test is obviously different from the previous two-dimensional layered transition metal molybdenum sulfide crystal; SHG signal test is carried out on the two-dimensional layered transition metal molybdenum sulfide crystal and the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal prepared by the reaction, and the SHG signal test of the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal obtained by the electrochemical method is obviously stronger than that of the two-dimensional layered transition metal molybdenum sulfide crystal
In the case of the embodiment 7, the following examples,
weighing 0.2g of rubrene and adding into 1L of dimethyl sulfoxide as shown in figure 1, weighing 4g of sodium acetate and continuously adding into the solution, sealing, carrying out ultrasonic treatment at 53 ℃ for 30min to obtain an electrolyte solution, taking 100ml of the prepared electrolyte solution out and pouring into a reaction chamber made of PDMS (polydimethylsiloxane) material, wherein the bottom of the reaction chamber is a silicon wafer (f in figure 1), a two-dimensional layered transition metal molybdenum sulfide on the silicon wafer is used as a working electrode (e in figure 1), a platinum wire is used as a counter electrode (c in figure 1), Ag/AgCl is used as a reference electrode (d in figure 1) and is inserted into the electrolyte solution in the reaction chamber, the electrochemical scanning potential interval is 0-3V, the scanning rate is 20mV/s, carrying out electrochemical intercalation reaction, and judging the amount and the reaction end point of rubrene according to an oxidation reduction peak and the electrochemical reaction electric quantity, after the reaction is finished, the electrolyte solution is poured off, the reaction chamber made of PDMS (polydimethylsiloxane) material is disassembled, and the silicon wafer attached with the working electrode is placed under the pressure of 5 multiplied by 10 -6 And (3) carrying out vacuum annealing for 30min at the temperature of 96 ℃ under Pa, and finally obtaining a frequency doubling crystal of the two-dimensional layered transition metal molybdenum sulfide on the surface of the silicon wafer.
Performing a sum optical appearance test on the two-dimensional layered transition metal molybdenum sulfide crystal and the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal prepared by the reaction, wherein the sum optical appearance test is obviously different from the previous two-dimensional layered transition metal molybdenum sulfide crystal; SHG signal test is carried out on the two-dimensional layered transition metal molybdenum sulfide crystal and the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal prepared by the reaction, and the SHG signal test of the two-dimensional layered transition metal molybdenum sulfide frequency doubling crystal obtained by the electrochemical method is obviously stronger than that of the two-dimensional layered transition metal molybdenum sulfide crystal
In summary, the present invention can make the thick atomic crystal material (such as two-dimensional layered transition metal sulfide) exhibit quasi-monolayer property, form an oriented monolayer assembly, exhibit the characteristics of frequency doubling crystal (as shown in fig. 4), and have the advantage of preparing ultrathin high-efficiency frequency doubling crystal by simple method.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the specification has been described in terms of embodiments, not every embodiment includes every single embodiment, and such description is for clarity purposes only, and it will be appreciated by those skilled in the art that the specification as a whole can be combined as appropriate to form other embodiments as will be apparent to those skilled in the art.
Claims (7)
1. An electrochemical preparation method for crystals generated by frequency doubling is characterized by specifically comprising the following steps:
preparing an electrolyte solution containing organic target molecules;
in an electrolyte solution, an electrochemical three-electrode system is adopted for electrochemical intercalation reaction, wherein two-dimensional layered transition metal sulfide is used as a working electrode, so that the organic target molecules are inserted between transition metal sulfide layers to form a frequency doubling crystal, the electrolyte solution comprises an organic solvent, target organic molecules and conductive salt, the content of the target organic molecules in the electrolyte solution is 0.1-1 g/L,
in the electrochemical three-electrode system, a platinum wire is used as a counter electrode, Ag/AgCl is used as a reference electrode, and electrochemical intercalation reaction is carried out in a reaction chamber prepared from PDMS material;
the electrolysis condition in the electrochemical intercalation reaction is as follows: the electrochemical scanning potential interval is 0 to-3V, and the scanning speed is 20 mV/s;
the chemical formula of the two-dimensional layered transition metal sulfide is MX 2 Wherein M is molybdenum or tungsten, and X is sulfur or selenium.
2. The electrochemical preparation method of a crystal for frequency doubling generation according to claim 1, wherein: the target organic molecule is one of hexadecyl trimethyl ammonium bromide, perylene tetracarboxylic dianhydride, tetrabutyl ammonium bromide, anthracene, fullerene, 7,8, 8-tetracyano-p-benzoquinodimethane and rubrene.
3. The electrochemical preparation method for crystals for frequency doubling generation according to claim 1, characterized in that: the organic solvent is one of dimethyl sulfoxide, dimethylformamide, isopropanol, cyclohexane, acetone and acetonitrile.
4. The electrochemical preparation method of claim 1, applied to frequency doubling produced crystals, characterized in that: the conductive salt is one of sodium dodecyl sulfate and sodium acetate.
5. The electrochemical preparation method of a crystal for frequency doubling generation according to claim 4, wherein: the content of the conductive salt in the electrolyte solution is 0-15 g/L.
6. The electrochemical preparation method for crystals for frequency doubling generation according to claim 1, characterized in that: the electrolyte solution is obtained by adding an organic target molecule and a conductive salt into an organic solvent and carrying out ultrasonic treatment under the conditions of sealing and 50-60 ℃ of temperature.
7. The electrochemical preparation method for crystals produced by frequency doubling according to any of claims 1 to 6, characterized in that: after the electrochemical intercalation reaction is finished, the pressure is 5 multiplied by 10 -6 Pa, at 80-100 deg.CVacuum annealing under the conditions of (1).
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