CN114990358B - Arsenic-doped alkene nanosheet, and preparation method and application thereof - Google Patents
Arsenic-doped alkene nanosheet, and preparation method and application thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 91
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 81
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 35
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 238000002791 soaking Methods 0.000 claims abstract description 22
- 239000012071 phase Substances 0.000 claims abstract description 21
- 239000007791 liquid phase Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 17
- 230000005540 biological transmission Effects 0.000 claims abstract description 16
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000006228 supernatant Substances 0.000 claims abstract description 16
- 239000002019 doping agent Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 8
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004065 semiconductor Substances 0.000 claims abstract description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 239000011630 iodine Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 33
- 239000010453 quartz Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 239000002064 nanoplatelet Substances 0.000 claims description 4
- 206010040844 Skin exfoliation Diseases 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- -1 arsenic alkene Chemical class 0.000 abstract description 11
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 27
- 239000007789 gas Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 16
- 230000003287 optical effect Effects 0.000 description 13
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 238000003917 TEM image Methods 0.000 description 6
- 238000013507 mapping Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002055 nanoplate Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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- B82—NANOTECHNOLOGY
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- H01L31/0321—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 characterised by the doping material
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Abstract
The invention provides a preparation method of an arsenic-doped alkene nanosheet, which comprises the following steps: s1, calcining a dopant, a transport agent and elemental arsenic by adopting a gas phase transport method to obtain a precursor; wherein the dopant is elemental bismuth or elemental tellurium; the transmission agent is elementary iodine or iodide; and S2, sequentially carrying out soaking treatment, grinding treatment, dispersing treatment, ultrasonic liquid phase stripping treatment and solid-liquid separation treatment on the precursor to obtain a supernatant, wherein the supernatant is a dispersion containing the arsenic-doped alkene nanosheets. The invention completes the modification of the arsenic-doped alkene nanosheet, effectively obtains the arsenic-doped alkene nanosheet material, not only dopes new elements into the arsenic-doped alkene nanosheet, but also enables the arsenic-doped alkene nanosheet material to keep a lamellar structure; and when the doped arsenic alkene nano sheet is thicker, the doped arsenic alkene nano sheet still has a band gap, so that the application of the doped arsenic alkene nano sheet as a semiconductor material is facilitated.
Description
Technical Field
The invention relates to an arsenic alkene material, in particular to an arsenic alkene-doped nanosheet, and a preparation method and application thereof.
Background
The III-V group element two-dimensional material is widely researched in the last decade due to the characteristics of quantum-constrained electronic band structure, adjustable band gap along with the number of layers, excellent electron transfer performance and the like. However, to date, all reported two-dimensional semiconductors have a characteristic bandgap of less than 2.0eV, which greatly limits their applications, particularly in optoelectronic devices that are photoresponsive in the blue and ultraviolet range.
Researchers find that the single-layer arsenic alkene nano sheet material in the V-group element has the advantages of super large band gap, super high carrier mobility, super large on-off ratio and the like, and is expected to make up for the defects of other materials in semiconductor application; however, the arsenic alkene nano-sheet has special layer number dependency, that is, when the layer number of the arsenic alkene nano-sheet is more than or equal to three layers, the nano-sheet material presents a gapless structure, thereby greatly limiting the application value of the arsenic alkene nano-sheet.
In order to improve the performance and the applicability of the arsenic-olefin nanosheet, the arsenic-olefin nanosheet needs to be doped and modified to make up for the defects of the traditional arsenic-olefin nanosheet, so that the layer number of the arsenic-olefin nanosheet is still in a band gap structure when the layer number is more than or equal to three layers; however, no related preparation process of arsenic-doped olefin nanosheets exists in the prior art so far, so that research on arsenic-doped olefin nanosheets has not made a substantial breakthrough.
In view of the above, there is a need to provide an arsenic-doped alkene nanosheet, and a preparation method and an application thereof, so as to solve or at least alleviate the problems of poor performance of the arsenic-doped alkene nanosheet, inability to effectively obtain the arsenic-doped alkene nanosheet, and the like.
Disclosure of Invention
The invention mainly aims to provide an arsenic-doped alkene nanosheet, and a preparation method and application thereof, and aims to solve or at least relieve the problems that the arsenic-doped alkene nanosheet is poor in performance, cannot be effectively obtained and the like.
In order to achieve the purpose, the invention provides a preparation method of an arsenic-doped alkene nano sheet, which comprises the following steps:
s1, calcining a dopant, elemental arsenic and a transport agent by adopting a gas phase transport method to obtain a precursor;
wherein the dopant comprises elemental bismuth or elemental tellurium; the transport agent comprises elemental iodine or iodide;
s2, sequentially performing soaking treatment, grinding treatment, dispersing treatment, ultrasonic liquid-phase stripping treatment and solid-liquid separation treatment on the precursor to obtain a supernatant, wherein the supernatant is a dispersion containing the arsenic-doped alkene nanosheets;
wherein the soaking treatment comprises: soaking the precursor into a first organic solvent;
the grinding treatment comprises the following steps: drying and grinding the precursor after soaking treatment in sequence to obtain precursor powder;
the dispersion treatment includes: dispersing the precursor powder into a second organic solvent.
Further, in the step S1, the molar ratio of the dopant, the elemental arsenic and the transport agent is 1-10:50:0.5-1.
Further, in step S1, the operation process of the gas phase transport method includes: and placing the dopant, the elemental arsenic and the transport agent in a quartz tube, then placing the quartz tube in a double-temperature-zone tube furnace after vacuum sealing, and calcining under a set temperature field.
Further, the temperature field adopted by the gas phase transmission method is 500-550 ℃ or 550-600 ℃; the calcination time is 0.5-3h.
Further, the operation process of the gas phase transmission method also comprises the following steps: and after the calcination is finished, reducing the temperature in the quartz tube to room temperature at a cooling rate of 0.5-5 ℃/min.
Further, in the step S2, the first organic solvent and the second organic solvent each include nitrogen-methyl pyrrolidone;
in the dispersion treatment, the mass-to-volume ratio of the precursor powder to the second organic solvent is 100 to 400mg.
Further, the power of the ultrasonic liquid phase stripping treatment is 100-130W, and the treatment time of the ultrasonic liquid phase stripping treatment is 15-18h.
Further, the purity of the simple substance arsenic is not less than 99.999%; the purity of the simple substance bismuth or the simple substance tellurium is not less than 99.99 percent; the duration of the soaking treatment is 1-3 days.
The invention also provides an arsenic-doped alkene nanosheet, which is prepared by the preparation method.
The invention also provides an application of the arsenic-doped alkene nano sheet as a semiconductor material.
Compared with the prior art, the invention has the following advantages:
according to the invention, the modification of the arsenic-doped graphene nanosheet is completed, the arsenic-doped graphene nanosheet material is effectively obtained, new elements are doped into the arsenic-doped graphene nanosheet, and the arsenic-doped graphene nanosheet material can keep a lamellar structure; and when the arsenic-doped alkene nano sheet is thicker and is multi-layered, the arsenic-doped alkene nano sheet still has a band gap, so that the application of the arsenic-doped alkene nano sheet as a semiconductor material is facilitated.
Specifically, bismuth and tellurium are selected as doping elements, iodine is selected as a transmission agent, and a precursor of the arsenic-doped alkene nano-sheet is successfully synthesized by using a gas phase transmission method, so that the doping material is ensured to be still in a lamellar structure, and the arsenic-doped alkene nano-sheet can be conveniently obtained by using an ultrasonic liquid phase stripping method. Moreover, the preparation method adopted by the invention is simple and is convenient for large-scale popularization and use.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings 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 of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a TEM and AFM image of an arsenene nanoplate of comparative example 1;
FIG. 2 is an optical photograph of the precursor of example 1 and a TEM image of bismuth-doped arsene nanoplatelets; wherein (a) is an optical photograph of the precursor in example 1; (b) is a TEM image of the bismuth-doped arsene nanoplatelets of example 1;
FIG. 3 is a mapping diagram of the elements of bismuth-doped arsalene nanosheets of example 1;
FIG. 4 is an optical photograph of the precursor of example 2 and a TEM image of a tellurium-doped arsenene nanoplate; wherein (a) is an optical photograph of the precursor in example 2; (b) is a TEM image of the tellurium-doped arsenene nanosheets of example 2;
FIG. 5 is a mapping diagram of the elements of the tellurium-doped arsenene nanosheets of example 2;
FIG. 6 is an optical photograph of bismuth-doped arsalene nanoplatelets from examples 3-5;
FIG. 7 is an optical photograph of the tellurium-doped arsenene nanoplates of examples 6-7.
The implementation, functional features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be able to be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent, and is not within the protection scope of the present invention.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any number between the two endpoints are optional unless otherwise specified in 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 and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention.
The invention provides a preparation method of an arsenic-doped alkene nanosheet, which is characterized by comprising the following steps:
s1, weighing dopants, simple substance arsenic and a transport agent into a quartz tube according to a required proportion, then carrying out vacuum sealing on the quartz tube, and synthesizing a precursor doped with an arsenic-alkene nanosheet by using a gas phase transport method.
Wherein the molar ratio of the dopant, the elemental arsenic (arsenic block) and the transport agent can be 1-10:50:0.5-1.
The dopant comprises simple substance bismuth or simple substance tellurium, and specifically can be bismuth powder or tellurium powder; the transmission agent comprises elementary iodine or iodide, and particularly, the iodide can be tin iodide; to reduce the introduction of impurities, the iodide may also be bismuth iodide or tellurium iodide.
It is noted that the arsenic lumps used in the present invention have a purity of not less than 99.999%; the purity of the bismuth powder or the tellurium powder used by the invention is not less than 99.99%.
As one of the preferable options, the bismuth powder, arsenic nuggets and tin iodide may be calcined at a molar ratio of 3.
As another preferred option, the tellurium powder, arsenic nuggets and tin iodide may also be calcined at a molar ratio of 3.
As an illustration of the gas phase transport method: the gas phase transmission method is that the dopant, the arsenic block and the transmission agent are subjected to gas phase transmission in a closed vacuum environment; the process can be carried out under the protection of protective gas, and the gas phase transmission method can be generally carried out in a two-temperature-zone tubular furnace.
The gas phase transport process can be understood in particular as: due to the existence of the calcination temperature, the dopant, the transport agent and the arsenic block are converted into gas phase in the calcination process; wherein, according to the set temperature field, the gas phase substance circulates in the reaction vessel due to the temperature difference and the existence of the transmission agent, namely, the gas phase substance migrates from the high temperature area to the low temperature area, and finally is crystallized and deposited in the low temperature area after being cooled.
It is understood that the calcining temperature range formed by the low temperature zone and the high temperature zone can be called as a temperature field; in addition, in the cooling process after the calcination is finished, the cooling rates of the low-temperature area and the high-temperature area can be kept consistent, so that the temperature difference exists continuously until the two ends are cooled to the room temperature.
For the invention, the temperature field of the gas phase transmission can be 500-550 ℃ or 550-600 ℃, and the preferable temperature field can be 550-600 ℃, namely the calcining temperature of the low temperature region is set to be 550 ℃, and the calcining temperature of the high temperature region is set to be 600 ℃; the calcination time period may be 0.5 to 3 hours, and preferably, may be 2 hours. In addition, after the calcination is completed, the temperature in the reaction vessel can be controlled to be reduced to the room temperature at a cooling rate of 0.5-5 ℃/min, and the preferred cooling rate can be 1 ℃/min.
Taking bismuth doping as an example, the specific process for synthesizing and preparing the arsenic-doped alkene nanosheet precursor by using a dual-temperature-zone tube furnace CVT (gas phase transport) method can be as follows: adding simple substance bismuth, simple substance arsenic and a transmission agent into a quartz tube according to a preset proportion, placing the quartz tube into a double-temperature-zone tube furnace after vacuum sealing, and introducing argon gas as protective gas after the quartz tube is installed in the double-temperature-zone tube furnace. Setting the temperature of one end of the double-temperature-zone tubular furnace to be 550 ℃ and the temperature of the other end of the double-temperature-zone tubular furnace to be 600 ℃; and after 2h, respectively heating the temperature of the low-temperature area and the high-temperature area from the room temperature to a set temperature, preserving the heat for 2h at the temperature, then cooling to the room temperature at a cooling speed of 1 ℃/min, finally taking the quartz tube out to a glove box, breaking the quartz tube in the glove box, and collecting the precursor of the bismuth-doped arsenene nanosheet at one side corresponding to the lower temperature.
Wherein the temperature is increased from room temperature to 550 ℃ and 600 ℃ in order to change the gasification of the raw material in the quartz tube into a gaseous state; the heat preservation at 550 ℃ and 600 ℃ is to fully gasify and transfer the raw materials from a high temperature area to a low temperature area; the cooling is to make the raw material crystallize and deposit at the low temperature end.
And S2, sequentially carrying out soaking treatment, grinding treatment, dispersing treatment, ultrasonic liquid phase stripping treatment and solid-liquid separation treatment on the precursor to obtain a supernatant, wherein the supernatant is a dispersion containing the arsenic-doped alkene nanosheets.
Wherein the soaking treatment comprises: soaking the precursor into a first organic solvent; the duration of the soaking treatment may be 1 to 3 days.
The grinding treatment comprises the following steps: and drying and grinding the precursor after soaking treatment in sequence to obtain precursor powder.
The dispersion treatment comprises: dispersing the precursor powder into a second organic solvent. Wherein, the mass volume ratio of the precursor powder to the second organic solvent may be 100-400mg. The first organic solvent and the second organic solvent may both be nitrogen-methyl pyrrolidone solvents.
The ultrasonic liquid phase stripping treatment comprises the following steps: dispersing the precursor powder to a second organic solvent to obtain a mixed solution; peeling the mixed solution in an ultrasonic cell disruption instrument with the power of 100-130W for 15-18 h; the ultrasonic liquid phase stripping treatment is performed in a circulating cooling environment, generally at-one centigrade.
The solid-liquid separation treatment comprises the following steps: the mixed solution after ultrasonic liquid phase stripping treatment was centrifuged at 2000rpm for 30min.
As an explanation of the above embodiment:
the invention mainly relates to a two-step method for preparing an arsenic-doped alkene nano sheet, which comprises the steps of preparing a precursor of the arsenic-doped alkene nano sheet and stripping the precursor. The preparation of the precursor is mainly that under a certain temperature, raw materials are fully mixed under the condition of being in a gaseous state, and doping elements enter a structure of simple substance arsenic and finally form the doping precursor through crystallization and deposition. And the stripping of the precursor is mainly to break the laminated structure of the precursor by utilizing bubbles and cavities generated in the ultrasonic process, and finally disperse the laminated structure into few layers of arsenic-doped graphene nanosheets.
In order to obtain a high-performance material, the invention further provides an arsenic-doped alkene nano sheet prepared by the preparation method according to any embodiment.
In order to improve the application value of the doped arsenic-alkene nano-sheet, the invention also provides an application of the doped arsenic-alkene nano-sheet as a semiconductor material.
To facilitate a further understanding of the above embodiments, reference will now be made to the following examples:
comparative example 1
1. Adding 200mg of simple substance arsenic powder into 40ml of nitrogen-methyl pyrrolidone solvent to obtain a mixed solution;
2. ultrasonic liquid phase stripping (100-130W) is carried out on the mixed solution for 16.5h under the condition of-1 ℃, and the mixed solution is centrifuged for 30min under the condition of 2000rpm after stripping; and taking the supernatant to finally obtain the dispersion liquid of the arsenic-alkene nano-sheets.
In the comparative example, the thickness of the arsenic alkene nano-sheet is 10nm, the number of layers is about 30, the arsenic alkene nano-sheet does not have a band gap, and TEM and AFM images of the arsenic alkene nano-sheet are shown in FIG. 1.
Example 1
1. 62.694mg bismuth powder, 374.6mg arsenic block and 62.622mg tin iodide (i.e. molar ratio Bi: as: snI) 4 1) adding the bismuth-doped arsenic-alkene nano sheet into a quartz tube, sealing in vacuum, calcining at 550-600 ℃ in a temperature field for 2h, and then cooling to room temperature at the speed of 1 ℃/min to obtain a precursor of the bismuth-doped arsenic-alkene nano sheet;
2. soaking 200mg of the precursor in 40mL of nitrogen-methyl pyrrolidone solvent for three days, taking out, drying and grinding to obtain precursor powder; adding the precursor powder into 40ml of nitrogen-methyl pyrrolidone solvent to obtain a mixed solution;
3. carrying out ultrasonic liquid phase stripping (100-130W) on the mixed solution for 16.5h at the temperature of-1 ℃, and centrifuging the mixed solution for 30min at the rpm of 2000 after stripping; and taking the supernatant to finally obtain the dispersion liquid of the bismuth-doped arsenic-alkene nanosheets.
In the embodiment, the thickness of the bismuth-doped arsenene nanosheet is within the range of 20nm-40nm, the band gap is 2.13eV, an optical photograph of the precursor and a TEM of the bismuth-doped arsenene nanosheet are shown in FIG. 2, and element mapping of the bismuth-doped arsenene nanosheet is shown in FIG. 3.
The method proves that the precursor still presents a layered structure after the Bi element is doped, the material after the precursor is stripped is in a nanosheet shape, the element mapping graph also proves the effective doping of the Bi element, and the Bi-doped arsenic-alkene nanosheet can be successfully prepared by the method, and the band gap of the Bi-doped arsenic-alkene nanosheet is 2.13eV.
Example 2
1. 38.28mg of tellurium powder, 3238 mg of 374.6mg of arsenic block and 31.311mg of tin iodide (i.e. molar ratio Te: as: snI) 4 =3, 0.5) was charged into a quartz tube, vacuum-sealed, and then heated in a vacuum vessel at a temperature ofCalcining at 550-600 ℃ for 2h, and then cooling to room temperature at the speed of 1 ℃/min to obtain a precursor of the tellurium-doped arsenic-alkene nanosheet;
2. soaking 200mg of the precursor in 40mL of nitrogen-methyl pyrrolidone solvent for three days, taking out, drying and grinding to obtain precursor powder; adding the precursor powder into 40ml of nitrogen-methyl pyrrolidone solvent to obtain a mixed solution;
3. ultrasonic liquid phase stripping (100-130W) is carried out on the mixed solution for 16.5h under the condition of-1 ℃, and the stripped mixed solution is centrifuged for 30min under the condition of 2000 rpm; and taking the supernatant to finally obtain the dispersion liquid of the tellurium-doped arsenic-alkene nanosheets.
In the embodiment, the thickness of the tellurium-doped arsenic-alkene nanosheet is in the range of 40nm-50nm, the band gap is 1.96eV, an optical photograph of the precursor and a TEM of the tellurium-doped arsenic-alkene nanosheet are shown in FIG. 4, and the element mapping of the tellurium-doped arsenic-alkene nanosheet is shown in FIG. 5.
The method proves that the precursor still presents a layered structure after the Te element is doped, the material stripped from the precursor is in a nanosheet shape, the effective doping of the Te element is also proved by an element mapping diagram, and the method can successfully prepare the Te doped arsenene nanosheet, and the band gap of the Te doped arsenene nanosheet is 1.96eV.
The following are other examples of the invention:
example 3
1. 62.694mg bismuth powder, 374.6mg arsenic block and 62.622mg tin iodide (i.e. molar ratio Bi: as: snI) 4 1) adding the powder into a quartz tube, sealing in vacuum, calcining at 550-600 ℃ for 30min, and cooling to room temperature at a speed of 1 ℃/min to obtain a precursor of bismuth-doped arsenic-ene nanosheets; the optical photo of the precursor is shown in fig. 6, and the shape of the precursor is granular;
2. soaking 200mg of the precursor in 40mL of nitrogen-methyl pyrrolidone solvent for three days, taking out, drying and grinding to obtain precursor powder, and adding the precursor powder into 40mL of nitrogen-methyl pyrrolidone solvent to obtain a mixed solution;
3. and (3) carrying out ultrasonic liquid phase stripping (100-130W) on the mixed solution for 16.5h at the temperature of-1 ℃, centrifuging the stripped mixed solution for 30min at 2000rpm, and taking supernatant to finally obtain the dispersion liquid of the bismuth-doped arsenic-alkene nanosheet.
Example 4
1. 62.694mg bismuth powder, 374.6mg arsenic block and 62.622mg tin iodide (i.e. molar ratio Bi: as: snI) 4 1) adding the bismuth-doped arsenic-alkene nano sheet into a quartz tube, sealing in vacuum, calcining at 550-600 ℃ in a temperature field for 2h, and then cooling to room temperature at the speed of 5 ℃/min to obtain a precursor of the bismuth-doped arsenic-alkene nano sheet; the optical photo of the precursor is shown in fig. 6, and the morphology of the precursor is granular;
2. soaking 200mg of the precursor in 40mL of nitrogen-methyl pyrrolidone solvent for three days, taking out, drying and grinding to obtain precursor powder, and finally adding the precursor powder into 40mL of nitrogen-methyl pyrrolidone solvent to obtain mixed solution;
3. and (3) carrying out ultrasonic liquid phase stripping (100-130W) on the mixed solution for 16.5h at the temperature of-1 ℃, centrifuging the stripped mixed solution for 30min at the speed of 2000rpm, and taking supernatant liquid to finally obtain the dispersion liquid of the bismuth-doped arsenic-ene nanosheets.
Example 5
1. 41.796mg bismuth powder, 374.6mg arsenic block and 62.622mg tin iodide (i.e. molar ratio Bi: as: snI) 4 1) adding the bismuth-doped arsenic-alkene nano sheet into a quartz tube, sealing in vacuum, calcining at 550-600 ℃ in a temperature field for 2h, and then cooling to room temperature at the speed of 1 ℃/min to obtain a precursor of the bismuth-doped arsenic-alkene nano sheet; the optical photo of the precursor is shown in fig. 6, and the shape of the precursor is granular;
2. soaking 200mg of the precursor in 40mL of nitrogen-methyl pyrrolidone solvent for three days, taking out, drying and grinding to obtain precursor powder, and finally adding the precursor powder into 40mL of nitrogen-methyl pyrrolidone solvent to obtain mixed solution;
3. and (3) carrying out ultrasonic liquid phase stripping (100-130W) on the mixed solution for 16.5h at the temperature of-1 ℃, centrifuging the stripped mixed solution for 30min at 2000rpm, and taking supernatant to finally obtain the dispersion liquid of the bismuth-doped arsenic-alkene nanosheet.
Example 6
1. 38.28mg of tellurium powder, 374.6mg of arsenic lumps and 62.622mg of tin iodide (i.e. molar ratio Te: as:SnI 4 1) adding the mixture into a quartz tube, sealing in vacuum, calcining at 550-600 ℃ for 2h, and then cooling to room temperature at the speed of 1 ℃/min to obtain a precursor of a tellurium-doped arsenene nanosheet; the optical photo of the precursor is shown in fig. 7, the surface of the precursor is covered with black and orange blocks in irregular shapes;
2. soaking 200mg of the precursor in 40mL of nitrogen-methyl pyrrolidone solvent for three days, taking out, drying and grinding to obtain precursor powder, and finally adding the precursor powder into 40mL of nitrogen-methyl pyrrolidone solvent to obtain mixed solution;
3. and (3) carrying out ultrasonic liquid phase stripping (100-130W) on the mixed solution for 16.5h at the temperature of-1 ℃, centrifuging the stripped mixed solution for 30min at 2000rpm, and taking supernatant to finally obtain the dispersion liquid of the tellurium-doped arsenic-ene nanosheets.
Example 7
1. 38.28mg of tellurium powder, 3238 mg of 374.6mg of arsenic block and 31.311mg of tin iodide (i.e. molar ratio Te: as: snI) 4 1) adding the mixture into a quartz tube, sealing in vacuum, calcining at 550-600 ℃ for 2h, and then cooling to room temperature at the speed of 1 ℃/min to obtain a precursor of a tellurium-doped arsenene nanosheet; the optical photo of the precursor is shown in fig. 7, and the precursor is a block body with an irregular shape;
2. soaking 200mg of the precursor in 40mL of nitrogen-methyl pyrrolidone solvent for three days, taking out, drying and grinding to obtain precursor powder, and finally adding the precursor powder into 40mL of nitrogen-methyl pyrrolidone solvent to obtain a mixed solution;
3. and (3) carrying out ultrasonic liquid phase stripping (100-130W) on the mixed solution for 16.5h at the temperature of-1 ℃, centrifuging the stripped mixed solution for 30min at 2000rpm, and taking supernatant to finally obtain the dispersion liquid of the tellurium-doped arsenic-ene nanosheets.
In summary, in the above technical solutions of the present invention, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all equivalent structural changes made by using the contents of the specification and the drawings of the present invention or other related technical fields directly/indirectly applied thereto are included in the scope of the present invention.
Claims (7)
1. A preparation method of arsenic-doped alkene nano-sheets is characterized by comprising the following steps:
s1, calcining a dopant, elemental arsenic and a transport agent by adopting a gas phase transport method to obtain a precursor;
wherein the dopant comprises elemental bismuth or elemental tellurium; the transport agent comprises elemental iodine or iodide;
the operation process of the gas phase transmission method comprises the following steps: placing the dopant, the elemental arsenic and the transport agent in a quartz tube, then placing the quartz tube in a double-temperature-zone tube furnace after vacuum sealing, and calcining under a set temperature field;
the temperature field adopted by the gas phase transmission method is 500-550 ℃ or 550-600 ℃; the calcining time is 0.5-3h;
the operation process of the gas phase transmission method further comprises the following steps: after the calcination is finished, cooling the temperature in the quartz tube to room temperature at a cooling rate of 0.5-5 ℃/min;
s2, sequentially carrying out soaking treatment, grinding treatment, dispersing treatment, ultrasonic liquid phase stripping treatment and solid-liquid separation treatment on the precursor to obtain a supernatant, wherein the supernatant is a dispersion containing the arsenic-doped alkene nanosheets;
wherein the soaking treatment comprises: soaking the precursor into a first organic solvent;
the grinding treatment comprises the following steps: drying and grinding the soaked precursor in sequence to obtain precursor powder;
the dispersion treatment comprises: dispersing the precursor powder into a second organic solvent.
2. The method according to claim 1, wherein in the step S1, the molar ratio of the dopant, the elemental arsenic and the transport agent is 1-10:50:0.5-1.
3. The production method according to claim 1, characterized in that, in the step S2, the first organic solvent and the second organic solvent each include nitrogen-methylpyrrolidone;
in the dispersion treatment, the mass volume ratio of the precursor powder to the second organic solvent is 100-400mg.
4. The preparation method according to claim 1, wherein the power of the ultrasonic liquid phase peeling treatment is 100-130W, and the treatment time of the ultrasonic liquid phase peeling treatment is 15-18h.
5. The method according to any one of claims 1 to 4, wherein the purity of the elemental arsenic is not less than 99.999%; the purity of the simple substance bismuth or the simple substance tellurium is not less than 99.99 percent; the duration of the soaking treatment is 1-3 days.
6. Arsenic-doped alkene nanosheets, characterized in that they have been prepared by a process according to any one of claims 1 to 5.
7. Use of a doped arsalene nanoplatelet of claim 6 as a semiconductor material.
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| US3392066A (en) * | 1963-12-23 | 1968-07-09 | Ibm | Method of vapor growing a homogeneous monocrystal |
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| CN108145171A (en) * | 2017-12-26 | 2018-06-12 | 深圳大学 | A kind of bismuth alkene nanometer sheet and preparation method thereof |
| CN112008086A (en) * | 2020-08-25 | 2020-12-01 | 沈阳航空航天大学 | Antimonene nanosheet effectively stripped through physical modification and preparation method thereof |
| CN113817927A (en) * | 2021-10-09 | 2021-12-21 | 中南大学 | Method for efficiently preparing arsenic-alkene nanosheets |
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| US3392066A (en) * | 1963-12-23 | 1968-07-09 | Ibm | Method of vapor growing a homogeneous monocrystal |
| JPS6042819A (en) * | 1983-06-08 | 1985-03-07 | ステンカ−・コ−ポレ−シヨン | Foam semiconductor doping agent carrier |
| CN108145171A (en) * | 2017-12-26 | 2018-06-12 | 深圳大学 | A kind of bismuth alkene nanometer sheet and preparation method thereof |
| CN112008086A (en) * | 2020-08-25 | 2020-12-01 | 沈阳航空航天大学 | Antimonene nanosheet effectively stripped through physical modification and preparation method thereof |
| CN113817927A (en) * | 2021-10-09 | 2021-12-21 | 中南大学 | Method for efficiently preparing arsenic-alkene nanosheets |
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