CN111334780A - Black phosphorus film, preparation method and application thereof - Google Patents

Black phosphorus film, preparation method and application thereof Download PDF

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Publication number
CN111334780A
CN111334780A CN202010134516.0A CN202010134516A CN111334780A CN 111334780 A CN111334780 A CN 111334780A CN 202010134516 A CN202010134516 A CN 202010134516A CN 111334780 A CN111334780 A CN 111334780A
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phosphorus
black phosphorus
reaction chamber
film
growth substrate
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张凯
徐轶君
史鑫尧
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Priority to PCT/CN2020/078188 priority patent/WO2021174527A1/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/28—Deposition of only one other non-metal element
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C30B25/183—Epitaxial-layer growth characterised by the substrate being provided with a buffer layer, e.g. a lattice matching layer
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements

Abstract

The invention relates to the technical field of two-dimensional materials, in particular to a preparation method of a black phosphorus film, which is characterized by comprising the following steps: placing a growth substrate, a phosphorus-containing precursor, and a mineralizer in a vacuum-sealed reaction chamber, wherein the growth substrate and the phosphorus-containing precursor are placed in different regions within the vacuum-sealed reaction chamber; heating the reaction chamber, then preserving heat, enabling the mineralizer to react with phosphorus-containing gas partially derived from a phosphorus-containing precursor, and forming an induced nucleation point or an induced nucleation layer for inducing black phosphorus crystallization on the growth substrate; and reducing the temperature of the reaction chamber, depositing the phosphorus-containing gas on the growth substrate, and forming the black phosphorus film by epitaxial growth under the induction of the induced nucleation points or the induced nucleation layers. The black phosphorus film prepared by the method has high quality, high crystallinity and strong repeatability, is suitable for large-area and batch production of the black phosphorus film, and meets the industrial requirements in practical application.

Description

Black phosphorus film, preparation method and application thereof
Technical Field
The invention relates to the technical field of two-dimensional materials, in particular to a black phosphorus film, and a preparation method and application thereof.
Background
In recent years, two-dimensional materials have attracted much attention and research enthusiasm in the academic and industrial fields due to their excellent properties. The graphene has excellent mechanical, optical, thermal and electrical properties, so that the graphene has great application potential in various fields such as electronics, sensing, energy storage, photoelectricity and semiconductors. However, graphene has some disadvantages, and since the band gap of graphene is zero, it has limited applications in fields such as semiconductor logic devices, photo-detection, and the like. To address this problem, scientists have developed other two-dimensional materials, such as transition metal chalcogenides (TMDCs), including MoS2、WSe2、WS2And the like. The two-dimensional TMDCs material has a band gap width of 1-2 eV, and makes up for the defect of zero band gap of graphene. But the carrier mobility of TMDCs is low (<500cm2Vs) far below graphene, also cannot match existing silicon materials [ s.z. butler, et. al, ACSNANO,2013,7,2898.]. Therefore, there is an urgent need to develop a two-dimensional semiconductor material having both band gap and high carrier mobility.
The black phosphorus is a new member born by a two-dimensional material family in recent years, has the room-temperature carrier mobility of 1000cm2/Vs [ L.Li, et.al, nat. nanotechnol.2014,9,372 ], is far higher than TMDCs, can be compared with the traditional silicon semiconductor material, also has excellent performances such as high current on-off ratio of 105 and the like, and has wide application prospect in the field of semiconductor devices. In addition, the black phosphorus has a direct band gap (band gap range: 0.3-2 eV) which can be tuned along with the thickness change, and the gap blank between graphene and TMDCs is filled, so that the photoelectric detector based on the black phosphorus material can realize the detection of ultraviolet-visible light-near infrared broadband [ M.Buscoma, et.al, Nano Lett.2014,14,3347 ] [ J.Wu, et.al, ACS NANO,2015,9,8070 ], and the limitation of traditional semiconductors such as GaN, silicon, InGaAs, HgCdTe and the like and novel two-dimensional materials such as TMDCs and the like on the detection waveband is overcome. As the focus comment "phosphorus exsites materials scientists" written by the official news commentator Eugenie Samuel Reich in his grasping, the article "e.s. Reich, et al, Nature,2004,506,19.], black phosphorus, a new crystal with atomic layer thickness, which is a material that, following graphene, is exciting to semiconductor technology and industry, has brought about eosin for the development of new semiconductor materials.
Whether black phosphorus can be applied in the fields of electronics, photoelectricity and the like depends to a great extent on whether a reliable method for preparing two-dimensional black phosphorus on a large scale can be developed. At present, the preparation method for obtaining the black phosphorus film mainly comprises a mechanical stripping method, a liquid phase dispersion method, a plasma etching method, a chemical deposition method and the like. The mechanical peeling method is a method of separating the black phosphorus nanosheet layer from the black phosphorus crystal by applying mechanical force (friction, tension, etc.) to the black phosphorus block, and is simple and easy to implement, but the thickness and size of the black phosphorus film cannot be controlled, and the preparation efficiency is low [ l.li, et.al, nat. nanotechnol.2014,9,372 ]. The liquid phase dispersion method is to disperse black phosphorus crystals by means of ultrasound, centrifugation and the like to prepare black phosphorus nano-flakes [ P.Yasaei, et.al, adv.Mater.,2015,27: 1887-. Plasma etching is to thin black phosphorus by reacting plasma groups with phosphorus atoms to generate volatile products [ Jiajie Pei, et al nat. Commun.,2016,7:10450 ], but physical bombardment of the plasma groups can damage the black phosphorus, and residual chemical impurities can introduce pollution to influence the performance of the black phosphorus. The method is difficult to realize the large-scale preparation and industrialization of the black phosphorus material and the device. Therefore, a method for preparing a black phosphorus thin film with high quality and industrialization is needed to solve the above technical problems.
Disclosure of Invention
Aiming at the problems in the prior art, the invention utilizes Van der Waals epitaxial growth technology, adopts a one-step preparation method with simple operation and low cost, and controllably synthesizes the black phosphorus film.
In order to solve the problems, the invention provides a black phosphorus film, a preparation method and application thereof, and the specific technical scheme is as follows:
in a first aspect, the present invention provides a method for preparing a black phosphorus thin film, comprising:
placing a growth substrate, a phosphorus-containing precursor, and a mineralizer in a vacuum-sealed reaction chamber, wherein the growth substrate and the phosphorus-containing precursor are placed in different regions within the vacuum-sealed reaction chamber;
heating the reaction chamber, then preserving heat, enabling the mineralizer to react with phosphorus-containing gas partially derived from a phosphorus-containing precursor, and forming an induced nucleation point or an induced nucleation layer for inducing black phosphorus crystallization on the growth substrate;
and reducing the temperature of the reaction chamber, depositing the phosphorus-containing gas on the growth substrate, and forming the black phosphorus film by epitaxial growth under the induction of the induced nucleation points or the induced nucleation layers.
In a second aspect, the present invention provides a black phosphorus thin film comprising two-dimensional black phosphorus single crystal cells prepared by the above method.
In a third aspect, the present invention provides an optoelectronic material or an electronic material, wherein the optoelectronic material or the electronic material comprises the black phosphorus thin film.
In a fourth aspect, the present invention provides an optoelectronic device, wherein the optoelectronic device comprises an optoelectronic material, and the optoelectronic material comprises the black phosphorus thin film.
In a fifth aspect, the invention provides a battery, including a solar battery, a lithium-sulfur battery, a lithium ion battery or a sodium ion battery, wherein the battery includes a conductive material, and the conductive material includes the black phosphorus thin film.
In a sixth aspect, the present invention provides an electronic device, wherein the electronic device includes an electronic material, and the electronic material includes the black phosphorus thin film described above.
In a seventh aspect, the present invention provides a catalytic system, comprising a catalyst, wherein the catalyst comprises the black phosphorus thin film described above.
In an eighth aspect, the present invention provides a nano material, wherein the nano material comprises the black phosphorus thin film.
Due to the technical scheme, the invention has the following beneficial effects:
the invention provides a preparation method of a black phosphorus film, which realizes the growth of the black phosphorus film with high quality and high crystallinity by adding a mineralizer and forming an induced nucleation point or an induced nucleation layer on a growth substrate. The method has the advantages of low raw material price, low production equipment cost, simple operation, high feasibility and strong repeatability. The controllable growth of the size and the thickness of the black phosphorus film can be realized through simple condition control, and the method is suitable for different application requirements. In addition, the method is suitable for large-area and batch production of the black phosphorus film, and meets the industrial requirement in practical application.
Compared with the traditional black phosphorus bulk crystal, such as black phosphorus with a tightly stacked layered structure (DSL) structure, the black phosphorus film provided by the invention has higher on-off ratio, photoresponse rate and photoconductive gain, has the advantages of low surface roughness, good photoelectric performance and the like, can be directly subjected to micro-nano processing, and is convenient for large-scale research and development and application of related devices.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the description of the embodiment 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 invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1: the microscope image of the black phosphorus film provided by the embodiment of the invention;
FIG. 2: atomic Force Microscope (AFM) images of the black phosphorus thin film in fig. 1;
FIG. 3: the embodiment of the invention provides a Raman image of the black phosphorus film;
FIG. 4: the X-ray photoelectron spectroscopy (XPS) of the black phosphorus film provided by the embodiment of the invention;
FIG. 5 a: a cross-sectional view of a Transmission Electron Microscope (TEM) of the black phosphorus thin film provided by the embodiment of the invention;
FIG. 5 b: element distribution (mapping) diagram in FIG. 5 a;
fig. 6 to 8: the embodiment of the invention provides a high-resolution transmission electron microscopic image (HRTEM) and an electron diffraction Spectrum (SAED) of the black phosphorus film;
FIG. 9: the black phosphorus film provided by the embodiment of the invention and the infrared absorption spectrogram of the traditional black phosphorus material; in the figure, a represents black phosphorus film, B represents conventional DSL black phosphorus;
FIG. 10: photoluminescence spectrograms of the black phosphorus film and the traditional black phosphorus material provided by the embodiment of the invention; in the figure, a represents black phosphorus film, B represents conventional DSL black phosphorus;
FIG. 11: the embodiment of the invention provides a microscope image of a photoelectric detection device;
FIG. 12: the black phosphorus film provided by the embodiment of the invention has an electrical test curve graph at different temperatures and different bias voltages;
FIG. 13: the black phosphorus film provided by the embodiment of the invention has a carrier mobility curve chart at different temperatures;
FIG. 14: the Hall mobility and Hall concentration curve diagrams of the black phosphorus film provided by the embodiment of the invention at different temperatures;
FIG. 15: the photoelectric performance of the black phosphorus film provided by the embodiment of the invention is tested;
FIG. 16: the photoresponse rate and the photoconductive gain curve of the black phosphorus film provided by the embodiment of the invention;
FIG. 17: the photoelectric performance of the black phosphorus film provided by the embodiment of the invention is tested;
FIG. 18: the photoresponse rate and the photoconductive gain curve of the black phosphorus film provided by the embodiment of the invention;
FIG. 19: a black phosphorus thin film microscope image provided by another embodiment of the present invention;
FIG. 20: AFM images of the black phosphorus film in FIG. 19;
FIG. 21: another embodiment of the present invention provides an AFM image of a black phosphorus film.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious 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.
For the following defined terms, these definitions shall be applied, unless a different definition is given in the claims or elsewhere in this specification. All numerical values, whether explicitly indicated or not, are herein defined as modified by the term "about". The term "about" generally refers to a range of values that one of ordinary skill in the art would consider equivalent to the recited value to produce substantially the same property, function, result, etc. A numerical range indicated by a low value and a high value is defined to include all numbers subsumed within the numerical range and all subranges subsumed within the numerical range.
The invention provides a preparation method of a black phosphorus film, which comprises the following steps:
s100: placing a growth substrate, a phosphorus-containing precursor, and a mineralizer in a vacuum-sealed reaction chamber, wherein the growth substrate and the phosphorus-containing precursor are placed in different regions within the vacuum-sealed reaction chamber;
s200: heating the reaction chamber, then preserving heat, enabling the mineralizer to react with phosphorus-containing gas partially derived from a phosphorus-containing precursor, and forming an induced nucleation point or an induced nucleation layer for inducing black phosphorus crystallization on the growth substrate;
s300: and reducing the temperature of the reaction chamber, depositing the phosphorus-containing gas on the growth substrate, and forming the black phosphorus film by epitaxial growth under the induction of the induced nucleation points or the induced nucleation layers.
In the embodiments of the present disclosure, the induced nucleation point or the induced nucleation layer may be a compound having a similar lattice structure to the black phosphorus thin film, or the induced nucleation point or the induced nucleation layer may have a crystal face capable of forming a lattice match with a crystal face of the black scale single crystal, and the induced nucleation point or the induced nucleation layer may be a wafer structure having a thickness of a crystal nucleus, a fine crystal grain, or an atomic layer distributed on a growth substrate, or may be a continuous or dispersedly grown thin film structure. The induced nucleation points or the induced nucleation layers can induce phosphorus to nucleate on the growth substrate and grow into a black phosphorus film.
In some embodiments, the induced nucleation site or layer may be a phosphorous-containing alloy having a crystal structure. Preferably, the induced nucleation sites or layers are capable of being stably present in a phosphorus-containing gas, the phosphorus-containing alloy may be a binary or multicomponent phosphorus-containing alloy, and the phosphorus-containing alloy may include any one or more of gold, tin, silver, copper, magnesium, tin iodide, lead, and indium.
In some embodiments, the exposed crystal plane of the induced nucleation site or layer is lattice matched to one crystal plane of the black phosphorus single crystal.
In an actual production process, the "arranged in the vacuum-tight reaction chamber" can be directly arranged in a heating chamber of a heating device, such as an inner cavity of a quartz tube used for heating reaction in a tube furnace; or the quartz tube or the glass tube can be placed in a small quartz tube or a small glass tube, then the quartz tube or the glass tube is vacuumized and sealed, and then the processed quartz tube or the glass tube is placed in a heating cavity of the heating device.
It should be noted that the vacuum-tight reaction chamber includes, but is not limited to, the above-described implementation manner, and may be any growth device or growth container of the vacuum-tight reaction chamber capable of implementing the growth of the black phosphorus film.
In some embodiments, the pressure within the vacuum-tight reaction chamber may be less than or equal to 0.1 Pa.
The preparation method utilizes the principle of chemical vapor transport, mineralizers are added into reaction raw materials, the mineralizers form an induced nucleation point or an induced nucleation layer on a growth substrate through heating, and meanwhile, phosphorus-containing gas is generated from phosphorus-containing precursors. And after the phosphorus-containing gas reaches the upper part of the growth substrate, a black phosphorus crystal nucleus is epitaxially formed on the induction nucleation point or the induction nucleation layer, and finally, a black phosphorus film is further grown and formed. The method has the advantages of low raw material price, low production equipment cost, simple operation, high feasibility and strong repeatability. The controllable growth of the size and the thickness of the black phosphorus film can be realized by controlling the growth conditions, and the method is suitable for different application requirements. In addition, through the reasonable design of production equipment, the method is suitable for large-area and batch production of the black phosphorus film, and meets the industrial requirements in practical application.
In the embodiments of the present disclosure, the phosphorus-containing precursor includes, but is not limited to, one or more of white phosphorus, red phosphorus, and a phosphorus-containing compound capable of being decomposed by heat to generate a phosphorus-containing gas. The phosphorus-containing compound may be, for example, phosphorus triiodide, phosphorus tribromide, or the like.
In embodiments of the present description, the growth substrate and the phosphorus-containing precursor being disposed in different regions within the vacuum-tight reaction chamber include: the growth substrate is arranged in a temperature zone with higher temperature in the vacuum-sealed reaction chamber, and the phosphorus-containing precursor is arranged in a temperature zone with lower temperature in the vacuum-sealed reaction chamber. Therefore, through the process of inverse temperature growth, the concentration of the phosphorus source near the growth substrate in the growth process can be controlled, the formation of the black phosphorus film is facilitated, and the thickness of the product is controlled.
In an actual production process, a separate heating control system and a separate monitoring system can be provided to provide a heat source for the reaction chamber, and after heating, the temperature in the reaction chamber usually shows a gradient change.
In some embodiments, the temperature of the growth substrate and the temperature of the temperature zone in which the phosphorus-containing precursor is located may differ by 40 ℃ to 200 ℃.
In an embodiment of the present specification, the method further comprises: and limiting the growth space for the diffusion of the phosphorus-containing gas at the growth substrate, and realizing the thickness control of the black phosphorus film through a space confinement effect. Thus, the concentration and the entering amount of the phosphorus source and the growth speed of the black phosphorus film are controlled by arranging a very narrow growth space at the growth substrate, and the thickness of the black phosphorus film is controlled.
Preferably, in one embodiment, several pieces of the growth substrates may be arranged at the same temperature zone apart. Therefore, by increasing the total area of the growth substrate, on one hand, the number of black phosphorus induced nucleation points or layers is increased, which is beneficial to the dispersive growth of black phosphorus; on the other hand, the effective regulation and control of the phosphorus source concentration at the growth substrate is realized through the space confinement effect, and further, the regulation and control of the thickness of the black phosphorus film is realized.
It is noted that limiting the growth space at the growth substrate for diffusion of the phosphorous-containing gas is not limited to the above described implementations, but may also be a very narrow space at the growth substrate where a barrier is placed or where the reaction chamber is designed, as well as other implementations that enable a spatial confinement effect at the growth substrate.
In an actual production process, several growth substrates may be stacked in the reaction chamber, for example, may be longitudinally spaced apart at the same position in a horizontal quartz tube.
In some embodiments, the growth substrate may include, but is not limited to, a silicon dioxide wafer, a sapphire or conductive glass growth substrate, or the like.
In the embodiments of the present disclosure, the mineralizer includes, but is not limited to, any one or more of tin, gold-tin alloy, tin iodide, lead, indium, silver, copper, magnesium, and magnesium-tin-copper alloy.
In some embodiments, the mineralizer comprises tin iodide and/or tin, which may be disposed in the same region within the vacuum-tight reaction chamber as the phosphorus-containing precursor. I.e. can be placed in the same temperature zone.
In some embodiments, any one or more of gold, gold-tin alloy, silver, copper, magnesium, and magnesium-tin-copper alloy in the mineralizer may form a thin film on the growth substrate, and the thickness of the thin film may be 5 to 180 nm.
In practical production, the above-mentioned method of forming a thin film on a growth substrate can be, but is not limited to, deposition, sputtering, evaporation, or spin coating.
In some embodiments, the mineralizer may include tin iodide and tin, and the mass ratio of the tin iodide to the phosphorus-containing precursor is 1 (2-40) to (10-300).
In some embodiments, the mineralizer may include tin iodide and tin, and the mass ratio of the tin iodide to the phosphorus-containing precursor is 1 (2-20) to (10-200), and preferably 1 (2-10) to (10-80).
In an embodiment of the present disclosure, the step S300 of "maintaining the temperature after heating the reaction chamber" may include: the reaction chamber is heated to 650-.
In the actual production process, the temperature rise rate in the heating process can be (3-40) DEG C/min.
In an embodiment of the present disclosure, the "reducing the temperature of the reaction chamber" in the step S400 may include: and reducing the temperature of the reaction chamber to 300-550 ℃, preserving the heat for 1-8h, and cooling to room temperature.
In the actual production process, the temperature reduction speed in the process of reducing the temperature of the reaction chamber to 450-550 ℃ can be (0.5-3) ° c/min.
The thickness of the black phosphorus film prepared by the method is more than or equal to 1nm, the black phosphorus film is in a crystal structure, and the black phosphorus film is in a single crystal structure or comprises two-dimensional black phosphorus single crystal units.
Wherein the unit size (lateral dimension, such as length, width or diameter) of the two-dimensional black phosphorus single crystal can reach hundreds or microns, and the black phosphorus thin film has high crystallinity and high quality.
Preferably, the black phosphorus thin film has a crystal structure, may be one nanometer to several hundred micrometers, specifically, may be one nanometer to several tens of nanometers, or may also be one hundred nanometers to several hundred micrometers, may be a P-type or n-type semiconductor, has anisotropy, and preferably has bipolarity.
In one embodiment, the interlayer spacing may be 0.45-0.And 55 nm. The carrier mobility can be more than or equal to 200cm2/Vs, preferably 500cm or more2Vs; hall mobility can be more than or equal to 200cm2/Vs, preferably 1000cm or more2Vs; the on-off ratio may be 0.5X10 or more4。
A black phosphorus thin film prepared based on the above method, which includes two-dimensional black phosphorus single crystal cells, is described below.
In the embodiment of the specification, the black phosphorus thin film has anisotropy, and the thickness of the black phosphorus thin film is more than or equal to 1 nm.
Preferably, the thickness of the black phosphorus thin film may range from one nanometer to several hundred micrometers, specifically, from one nanometer to several tens of nanometers, or also from one hundred nanometers to several hundred micrometers.
Preferably, the interlayer distance of the black phosphorus thin film may be 0.45 to 0.55 nm.
In the embodiments of the present description, the black phosphorus film may be a P-type or n-type semiconductor.
Further, the black phosphorus thin film may have a bipolar property.
More specifically, the carrier mobility of the black phosphorus thin film can be greater than or equal to 200cm2/Vs, preferably 500cm or more2Vs; hall mobility can be more than or equal to 200cm2/Vs, preferably 1000cm or more2Vs; the on-off ratio may be 0.5X10 or more4。
In some embodiments, the black phosphorus thin film comprises a plurality of two-dimensional black phosphorus single crystal units with similar morphology and crystal structure, and the size (transverse dimension, such as long diameter) of the two-dimensional black phosphorus single crystal units can be a few nanometers, or tens of nanometers, and even can reach the size of hundreds of nanometers or micrometers.
In some embodiments, a plurality of the two-dimensional black phosphorus single crystal units are stacked to form the black phosphorus thin film, and the stacking is in the form that the edges of every two-dimensional black phosphorus single crystal units are connected to generate the black phosphorus thin film; namely, the edge junction of every two-dimensional black phosphorus single crystal units is a crystal boundary, and the surfaces of a plurality of two-dimensional black phosphorus single crystal units form the surface of the black phosphorus film.
The black phosphorus film has the advantages of high on-off ratio, high photoresponse rate, high photoconductive gain, low surface roughness, good photoelectric performance and the like, can be directly subjected to micro-nano processing, and is convenient for large-scale research and development and application of related devices.
The specification also provides a photoelectric material or an electronic material, and the photoelectric material or the electronic material comprises the black phosphorus film or the black phosphorus film prepared by the method.
The specification also provides a photoelectric device which comprises a photoelectric material, wherein the photoelectric material comprises the black phosphorus film or the black phosphorus film prepared by the method.
The specification also provides a battery, which comprises a solar battery, a lithium-sulfur battery, a lithium ion battery or a sodium ion battery, wherein the battery comprises a conductive material, and the conductive material comprises the black phosphorus film or the black phosphorus film prepared by the method.
The specification also provides an electronic device, which comprises an electronic material, wherein the electronic material comprises the black phosphorus film or the black phosphorus film prepared by the method.
The specification also provides a catalytic system comprising a catalyst, wherein the catalyst comprises the black phosphorus film or the black phosphorus film prepared by the method.
The specification also provides a nano material, and the nano material comprises the black phosphorus film.
Some specific examples of the present specification are listed below based on the above technical solutions.
Example 1
The embodiment discloses a preparation method of a black phosphorus film, which specifically comprises the following steps:
(1) forming induced nucleation sites or layers
a) Providing a plurality of silicon dioxide growth substrates, red phosphorus and a mineralizer, wherein the mineralizer comprises tin iodide, tin and gold, the gold is a layer of gold film uniformly arranged on the silicon dioxide growth substrates, and the thickness of the gold film is 5-180 nm;
b) placing the tin iodide, tin and red phosphorus at a low-temperature end in a vacuum closed reaction chamber, and placing a growth substrate at a high-temperature end in the vacuum closed reaction chamber, wherein a plurality of growth substrates are stacked and spaced;
c) heating the reaction chamber to 750 ℃ at the speed of 10 ℃/min, and preserving heat for 1 h;
wherein the mass ratio of the tin iodide to the tin to the red phosphorus is 1 (2-10) to (10-100).
(2) Growing black phosphorus film
And (3) controlling the temperature in the reaction chamber to be reduced to 450 ℃ at the speed of 1.5 ℃/min, preserving the temperature for 1.5h, cooling to room temperature, depositing phosphorus-containing gas of a phosphorus source on a growth substrate, and carrying out epitaxial growth under the induction of an induction nucleation point or an induction nucleation layer to form the black phosphorus film.
A typical black phosphorus film prepared by the above method is characterized by having a relatively flat surface with a long diameter of several hundred microns, as shown in the microscope image of fig. 1. And the thickness is ultra thin, which can be as thin as 10nm or less, please refer to the AFM image in fig. 2.
In addition, referring to fig. 3 and 4, AFM was used to characterize three characteristic peaks of black phosphorus, and the characteristic peaks of phosphorus were detected in XPS spectrum, which proves that the product is black phosphorus.
In addition, referring to fig. 5a and 5b, it can be seen from the TEM cross-sectional view and the element mapping diagram analysis of the prepared growth substrate that an induced nucleation point or an induced nucleation layer and a black phosphorus film are sequentially formed on the silicon dioxide growth substrate. Wherein the induced nucleation point or layer is Au3SnP7。
Referring to fig. 6 to 8, HRTEM images and SAED maps demonstrate that the black phosphorus thin film in this example has a crystalline structure and high crystallinity. The black phosphorus film has a unique structure and is formed by stacking two-dimensional black phosphorus single crystal units, and the crystal structure of the two-dimensional black phosphorus single crystal units belongs to an orthorhombic system. The interlayer spacing was about 0.5nm, the interplanar spacing in the direction of its zigzag boundary was about 0.42nm, and the interplanar spacing in the direction of its armchair boundary was about 0.32 nm.
Meanwhile, referring to fig. 9-10, the black phosphorus film has a higher infrared absorption rate than conventional DSL black phosphorus. Also, the photoluminescence spectrum has a narrower full width at half maximum, demonstrating fewer defect structures.
Further, this example prepared a photodetector device by depositing a metal electrode on the surface of the above-described typical black phosphorus film, as shown in fig. 11. The electrical property test shows that the device has excellent electrical property, and the black phosphorus film is a P-type semiconductor and has a bipolar property, please refer to fig. 12. The carrier mobility of the black phosphorus film can reach 1250cm2Vs, average carrier mobility of about 746cm2Vs, on-off ratio of 104-106Hall mobility can reach 2200cm2/Vs, average Hall mobility of about 1162cm2Vs, please refer to fig. 13-14.
In addition, the photoelectric performance of the photo-detector device was tested, and please refer to fig. 15-18, which has high photocurrent and fast response time in both the infrared and communication bands, and the photo-responsivity and photo-conductive gain in the infrared band can reach 32A/W and 110, and the responsivity and photo-conductive gain in the communication band can exceed 60A/W and 580.
Example 2
The embodiment discloses a preparation method of a black phosphorus film, which specifically comprises the following steps:
(1) forming induced nucleation sites or layers
a) Providing a plurality of silicon dioxide growth substrates, white phosphorus and a mineralizer, wherein the mineralizer comprises tin iodide, tin and gold, the gold is a layer of gold film uniformly arranged on the silicon dioxide growth substrates, and the thickness of the gold film is 5-180 nm;
b) placing the tin iodide, tin and red phosphorus at a low-temperature end in a vacuum closed reaction chamber, and placing a growth substrate at a high-temperature end in the vacuum closed reaction chamber, wherein a plurality of growth substrates are stacked and spaced;
c) heating the reaction chamber to 650 ℃ at the speed of 20 ℃/min, and preserving heat for 2.5 h;
wherein the mass ratio of the tin iodide to the tin to the white phosphorus is 1 (2-20) to (10-200).
(2) Growing black phosphorus film
And controlling the temperature in the reaction chamber to be reduced to 500 ℃ at the speed of 1.0 ℃/min, preserving the temperature for 2h, then cooling to room temperature, depositing phosphorus-containing gas on the growth substrate, and carrying out epitaxial growth under the induction of an induction nucleation point or an induction nucleation layer to form the black phosphorus film.
A typical black phosphorus thin film prepared by the method in this embodiment is a black phosphorus crystal, the morphology and crystal structure of which are similar to those in embodiment 1, the long diameter can reach several hundred micrometers, and the thickness can be as thin as 25nm or less, please refer to fig. 19-20.
In addition, an induced nucleation point or an induced nucleation layer and a black phosphorus film are sequentially formed on the silicon dioxide growth substrate. Wherein the induced nucleation point or layer is Au3SnP7。
Meanwhile, compared with the traditional DSL black phosphorus, the black phosphorus film has higher infrared absorptivity and fewer defect structures.
Further, in this example, a metal electrode was deposited on the surface of the typical black phosphorus thin film, and a photodetector device having excellent electrical properties was prepared, where the black phosphorus thin film is a P-type semiconductor and has a bipolar property. And the carrier mobility of the black phosphorus film can reach 1400cm2Vs, average carrier mobility of about 832cm2Vs, on-off ratio of 104-106The Hall mobility can reach 2330cm2/Vs, average Hall mobility of about 1224cm2/Vs。
In addition, the photoelectric properties of the photodetector device were tested, which had high photocurrent and fast response time in both the infrared and communication bands, and which had similar responsivity and photoconductive gain in the communication band to those of example 1.
Example 3
The embodiment discloses a preparation method of a black phosphorus film, which specifically comprises the following steps:
(1) forming induced nucleation sites or layers
a) Providing a plurality of silicon dioxide growth substrates, white phosphorus and a mineralizer, wherein the mineralizer comprises tin iodide, tin and silver, the gold is a silver film uniformly arranged on the silicon dioxide growth substrates, and the thickness of the silver film is 20-180 nm;
b) placing the tin iodide, tin and red phosphorus at a low-temperature end in a vacuum closed reaction chamber, and placing a growth substrate at a high-temperature end in the vacuum closed reaction chamber, wherein a plurality of growth substrates are stacked and spaced;
c) heating the reaction chamber to 850 ℃ at the speed of 10 ℃/min, and keeping the temperature for 5 hours;
wherein the mass ratio of the tin iodide to the tin to the white phosphorus is 1 (2-40) to (10-300).
(2) Growing black phosphorus film
And (3) controlling the temperature in the reaction chamber to be reduced to 350 ℃ at the speed of 1.5 ℃/min, preserving the temperature for 8h, then cooling to room temperature, depositing phosphorus-containing gas on the growth substrate, and carrying out epitaxial growth under the induction of an induction nucleation point or an induction nucleation layer to form the black phosphorus film.
A typical black phosphorus thin film prepared by the method in this example is a black phosphorus crystal, the morphology and crystal structure of which are similar to those in example 1, the long diameter can reach several hundred microns, and the thickness can be grown to about one micron.
In addition, an induced nucleation point or an induced nucleation layer and a black phosphorus film are sequentially formed on the silicon dioxide growth substrate. Wherein the induced nucleation point or layer is a compound formed of silver, tin and phosphorus.
Meanwhile, compared with the traditional DSL black phosphorus, the black phosphorus film has higher infrared absorptivity and fewer defect structures.
Further, in this example, a metal electrode was deposited on the surface of the typical black phosphorus thin film, and a photodetector device having excellent electrical properties was prepared, where the black phosphorus thin film is a P-type semiconductor and has a bipolar property. The carrier mobility of the black phosphorus film can reach 1232cm2Vs, average carrier mobility of about 721cm2Vs, on-off ratio of 104-106Hall mobility can reach 2200cm2Vs, average Hall mobility of about 1192cm2/Vs。
In addition, the photoelectric properties of the photodetector device were tested, which had high photocurrent and fast response time in both the infrared and communication bands, and which had similar responsivity and photoconductive gain in the communication band to those of example 1.
Example 4
The embodiment discloses a preparation method of a black phosphorus film, which specifically comprises the following steps:
(1) forming induced nucleation sites or layers
a) Providing a plurality of silicon dioxide growth substrates, phosphorus triiodide and a mineralizer, wherein the mineralizer comprises tin iodide, tin and gold, the gold is a layer of gold film uniformly arranged on the silicon dioxide growth substrates, and the thickness of the gold film is 20-180 nm;
b) placing the tin iodide, tin and red phosphorus at a low-temperature end in a vacuum closed reaction chamber, and placing a growth substrate at a high-temperature end in the vacuum closed reaction chamber, wherein a plurality of growth substrates are stacked and spaced;
c) heating the reaction chamber to 900 ℃ at the speed of 40 ℃/min, and preserving heat for 3 h;
wherein the mass ratio of the tin iodide to the tin to the white phosphorus is 1 (2-20) to (10-80).
(2) Growing black phosphorus film
And (3) controlling the temperature in the reaction chamber to be reduced to 550 ℃ at the speed of 1.0 ℃/min, preserving the temperature for 6h, then cooling to room temperature, depositing phosphorus-containing gas on the growth substrate, and carrying out epitaxial growth under the induction of an induction nucleation point or an induction nucleation layer to form the black phosphorus film.
A typical black phosphorus thin film prepared by the method of the present embodiment is a black phosphorus crystal, which has a morphology and a crystal structure similar to those of embodiment 1, a long diameter of several hundred micrometers, and a thickness capable of growing about 30nm, as shown in fig. 21.
In addition, an induced nucleation point or an induced nucleation layer and a black phosphorus film are sequentially formed on the silicon dioxide growth substrate. Wherein the induced nucleation point or layer is Au3SnP7。
Meanwhile, compared with the traditional DSL black phosphorus, the black phosphorus film has higher infrared absorptivity and fewer defect structures.
Further, in this example, a metal electrode was deposited on the surface of the typical black phosphorus thin film, and a photodetector device having excellent electrical properties was prepared, where the black phosphorus thin film is a P-type semiconductor and has a bipolar property. And the carrier mobility of the black phosphorus film can reach 1550cm2Vs, average carrier mobility of about 1068cm2Vs, on-off ratio of 104-106The Hall mobility can reach 2390cm2Vs, average Hall mobility of about 1048cm2/Vs。
In addition, the photoelectric properties of the photodetector device were tested, which had high photocurrent and fast response time in both the infrared and communication bands, and which had similar responsivity and photoconductive gain in the communication band to those of example 1.
In summary, the present invention provides a method for preparing a black phosphorus thin film, which realizes the growth of a high quality and high crystallinity black phosphorus thin film by adding a mineralizer and forming an induced nucleation point or an induced nucleation layer on a growth substrate. The method can realize the controllable growth of the size and the thickness of the black phosphorus film, is suitable for large-area and batch production of the black phosphorus film, and meets the industrialization requirement in practical application. Compared with the photoelectric detector prepared from the traditional black phosphorus bulk crystal, the photoelectric detector prepared based on the black phosphorus film provided by the invention has higher switching ratio, photoresponse rate and photoconductive gain, and excellent photoelectric properties.
The foregoing description has disclosed fully preferred embodiments of the present invention. It should be noted that those skilled in the art can make modifications to the embodiments of the present invention without departing from the scope of the appended claims. Accordingly, the scope of the appended claims is not to be limited to the specific embodiments described above.

Claims (12)

1. A method for preparing a black phosphorus film is characterized by comprising the following steps:
placing a growth substrate, a phosphorus-containing precursor, and a mineralizer in a vacuum-sealed reaction chamber, wherein the growth substrate and the phosphorus-containing precursor are placed in different regions within the vacuum-sealed reaction chamber;
heating the reaction chamber, then preserving heat, enabling the mineralizer to react with phosphorus-containing gas partially derived from a phosphorus-containing precursor, and forming an induced nucleation point or an induced nucleation layer for inducing black phosphorus crystallization on the growth substrate;
and reducing the temperature of the reaction chamber, depositing the phosphorus-containing gas on the growth substrate, and forming the black phosphorus film by epitaxial growth under the induction of the induced nucleation points or the induced nucleation layers.
2. The method of manufacturing according to claim 1, wherein the induced nucleation point or layer is a phosphorous-containing alloy having a crystal structure.
3. The production method according to claim 1, wherein the exposed crystal face of the induced nucleation point or the induced nucleation layer is lattice-matched to one crystal face of the black phosphorus single crystal.
4. The method of claim 1, wherein the growth substrate and the phosphorus-containing precursor being disposed in different regions within the vacuum-tight reaction chamber comprises: the growth substrate is arranged in a temperature zone with higher temperature in the vacuum-sealed reaction chamber, and the phosphorus-containing precursor is arranged in a temperature zone with lower temperature in the vacuum-sealed reaction chamber.
5. The method of manufacturing according to claim 1, further comprising: and limiting the growth space for the diffusion of the phosphorus-containing gas at the growth substrate, and realizing the thickness control of the black phosphorus film through a space confinement effect.
6. The method according to claim 1, wherein the mineralizer comprises any one or more of tin, gold-tin alloy, tin iodide, lead, indium, silver, copper, magnesium, and magnesium-tin-copper alloy.
7. The production method according to claim 1, wherein the thickness of the black phosphorus thin film is 1nm or more, and the black phosphorus thin film comprises two-dimensional black phosphorus single crystal units.
8. The method according to claim 1, wherein the phosphorus-containing precursor comprises one or more of a phosphorus-containing compound capable of decomposing under heat to generate a phosphorus-containing gas, white phosphorus, and red phosphorus.
9. A black phosphorus thin film produced according to any one of claims 1 to 8, wherein the black phosphorus thin film comprises two-dimensional black phosphorus single crystal units.
10. The black phosphorus thin film according to claim 9, wherein the black phosphorus thin film has anisotropy and a thickness of 1nm or more.
11. An electro-optical material or an electronic material, characterized in that the electro-optical material or the electronic material comprises the black phosphorus thin film according to any one of claims 9 to 10.
12. An optoelectronic device or an electronic device, wherein an optoelectronic material in the optoelectronic device or an electronic material in the electronic device comprises the black phosphorus thin film according to any one of claims 9 to 10.
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