CN113668053A - Black phosphorus film reaction device and black phosphorus film preparation method - Google Patents

Black phosphorus film reaction device and black phosphorus film preparation method Download PDF

Info

Publication number
CN113668053A
CN113668053A CN202111238217.2A CN202111238217A CN113668053A CN 113668053 A CN113668053 A CN 113668053A CN 202111238217 A CN202111238217 A CN 202111238217A CN 113668053 A CN113668053 A CN 113668053A
Authority
CN
China
Prior art keywords
phosphorus
reaction chamber
reaction
black phosphorus
source
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111238217.2A
Other languages
Chinese (zh)
Other versions
CN113668053B (en
Inventor
张凯
陈程
陈捷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Institute of Nano Tech and Nano Bionics of CAS
Original Assignee
Suzhou Institute of Nano Tech and Nano Bionics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou Institute of Nano Tech and Nano Bionics of CAS filed Critical Suzhou Institute of Nano Tech and Nano Bionics of CAS
Priority to CN202111238217.2A priority Critical patent/CN113668053B/en
Publication of CN113668053A publication Critical patent/CN113668053A/en
Application granted granted Critical
Publication of CN113668053B publication Critical patent/CN113668053B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • C30B25/14—Feed and outlet means for the gases; Modifying the flow of the reactive gases
    • 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
    • C30B25/16—Controlling or regulating
    • C30B25/165—Controlling or regulating the flow of the reactive gases

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention discloses a black phosphorus film reaction device and a black phosphorus film preparation method, wherein the device comprises a vacuum sealed reaction chamber, a slow release body is arranged in the reaction chamber, the slow release body divides the reaction chamber into a first reaction chamber for placing reactants and a second reaction chamber for placing a growth substrate, capillary channels are formed in the slow release body, and the pressure intensity in the second reaction chamber is controlled to be smaller than the pressure intensity in the first reaction chamber in the heating reaction process. The invention arranges a section of slow release body filling between the reactant and the growth substrate to properly inhibit the transmission of the gaseous source in the first reaction cavity to the second reaction cavity, thereby controlling the pressure at the growth end not to be too high, namely the pressure of the second reaction cavity is less than that of the first reaction cavity, improving the uniformity of source supply in time, effectively inhibiting the formation of excessive nucleation points on the substrate and finally obtaining the single crystal film or the alloy film with high crystallization quality.

Description

Black phosphorus film reaction device and black phosphorus film preparation method
Technical Field
The invention relates to the technical field of two-dimensional materials, in particular to a black phosphorus film reaction device and a black phosphorus film preparation method.
Background
In recent years, as a direct band gap two-dimensional semiconductor material, the narrow band gap characteristics of black phosphorus and the advantages of adjustable direct band gap and the like make black phosphorus receive wide attention in the fields of electronics and photoelectric application. In addition, the alloying strategy is utilized to dope the substitutional arsenic atoms in the black phosphorus crystal to form the black arsenic phosphorus alloy, so that the band gap adjustment of the black phosphorus material system can be realized, and the competitive advantage of the black phosphorus material system in the fields of photoelectric devices and the like is further improved.
Although black phosphorus has a great application prospect, the current research progress on the epitaxial growth of the film still faces a plurality of problems, and the scale application in the field of black phosphorus material devices is hindered. At present, the preparation of the black phosphorus film mainly comprises two methods, namely a chemical vapor transport method and a laser pulse deposition method, and the existing two methods can not obtain a single crystal film with high crystallization quality.
For the existing chemical vapor transport method, a reactant and a growth substrate are placed in the same cavity, nucleation is induced on the substrate under certain temperature and pressure by the action of a mineralizer, and then a black phosphorus film is grown, in the heat treatment process, the pressure of the position of the reactant and the position of the growth substrate are the same, and the existing problems at least comprise: the pressure required by the black phosphorus phase transition nucleation epitaxy is high, the formation of nucleation points is difficult to control under the high pressure, and a great number of nucleation points can be easily obtained to grow simultaneously, so that a polycrystalline film with low crystallization quality is finally obtained, and the technology is difficult to expand to the growth of a high-quality black arsenic phosphorus alloy film.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a black phosphorus film reaction device and a black phosphorus film preparation method, which can control the pressure at a growth end not to be too high and improve the uniformity of time source supply.
In order to achieve the above object, an embodiment of the present invention provides a black phosphorus thin film reaction apparatus, which includes a vacuum-tight reaction chamber,
a slow release body is arranged in the reaction chamber, the slow release body divides the reaction chamber into a first reaction cavity for placing reactants and a second reaction cavity for placing a growth substrate,
capillary channels are formed in the slow release body, and the pressure intensity in the second reaction cavity is controlled to be smaller than the pressure intensity in the first reaction cavity in the heating reaction process.
In one or more embodiments of the invention, the slow release carrier is a molecular sieve, and the particle size of particles forming the molecular sieve is 1-2 mm; or the slow release body adopts a quartz column, and the diameter of a capillary channel in the quartz column is 0.2-0.5 mm.
In one or more embodiments of the present invention, the particles constituting the molecular sieve are quartz sand, silicon particles, silica particles, or sapphire particles.
In order to achieve the above object, an embodiment of the present invention further provides a method for preparing a black phosphorus thin film, including:
providing the black phosphorus film reaction device;
placing reactants and a growth substrate in a first reaction chamber and a second reaction chamber respectively, wherein the reactants at least comprise a phosphorus source and a mineralizer;
heating to make the phosphorus-containing gas enter the second reaction chamber from the first reaction chamber and form a black phosphorus film on the surface of the growth substrate.
In one or more embodiments of the invention, the reactants further comprise an arsenic source, the phosphorus source and the arsenic source are located at different locations within the first reaction chamber, and the temperature at the location of the arsenic source is controlled to be greater than the temperature at the location of the phosphorus source during the reaction.
In one or more embodiments of the invention, the temperature difference between the arsenic source and the phosphorus source is 50 ℃ or less.
In one or more embodiments of the invention, the arsenic source is selected from elemental arsenic, or is capable of thermal decomposition to yield As4A compound of a molecule.
In one or more embodiments of the present invention, the mineralizer is selected from any one or more of tin, gold-tin alloy, tin iodide, lead, indium, silver, copper, magnesium, and magnesium-tin-copper alloy.
In one or more embodiments of the present invention, the phosphorus source is selected from one or more of a phosphorus-containing compound capable of decomposing under heat to generate a phosphorus-containing gas, white phosphorus, and red phosphorus.
In one or more embodiments of the present invention, the method further comprises forming a catalyst on the growth substrate, wherein the catalyst is Au or a compound thereof.
Compared with the prior art, the invention has the advantages that:
(1) the invention arranges a section of slow release body filling between the reactant and the growth substrate to properly inhibit the transmission of the gaseous source in the first reaction cavity to the second reaction cavity, thereby controlling the pressure of the growth end not to be too high, namely the pressure of the second reaction cavity is less than the pressure of the first reaction cavity, improving the uniformity of source supply in time, effectively inhibiting the formation of excessive nucleation points on the substrate and finally obtaining the single crystal film with high crystallization quality.
(2) The invention also designs that the arsenic source and the phosphorus source are separately placed to keep the distance difference and the temperature difference and keep constant proportion for continuous supply, and can expand the growth method of the black phosphorus single crystal film provided by the invention to be applied to the growth of the high-quality black arsenic-phosphorus film.
Drawings
FIG. 1 is a schematic structural diagram of a black phosphorus thin film reactor according to an embodiment of the present invention;
FIG. 2 is a schematic diagram illustrating the arrangement of the reactant positions in the black phosphorus thin film reactor according to one embodiment of the present invention;
FIG. 3 is the morphology of a black phosphorus single crystal thin film obtained in example 1 according to the present invention;
FIG. 4 is an electron microscope picture of a sample of a black phosphorus single crystal thin film obtained in example 2 according to the present invention;
FIG. 5 is a SAED characterization of a sample of a black phosphorus single crystal thin film obtained in example 2 according to the present invention;
FIG. 6 is the HRTEM result of a black phosphorus single crystal thin film sample obtained in example 2 according to the present invention;
FIG. 7 is a schematic view showing the distribution of As element in the alloy thin film obtained in example 4 according to the present invention;
FIG. 8 is a schematic view showing the distribution of P element in the alloy thin film obtained in example 4 according to the present invention;
FIG. 9 is XPS results for alloy films of different compositions according to example 5 of the present invention;
FIG. 10 is a Raman spectrum of an alloy thin film of different compositions according to example 5 of the present invention;
FIG. 11 is an IR absorption spectrum of an alloy thin film of different compositions according to example 5 of the present invention;
FIG. 12 is a two-dimensional distribution of As element in the alloy thin film obtained in comparative example 1 according to the present invention;
FIG. 13 is a two-dimensional distribution of P element in the alloy thin film obtained in comparative example 1 according to the present invention;
FIG. 14 is an electron microscope picture of an alloy thin film obtained in comparative example 2 according to the present invention.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
As shown in fig. 1, a black phosphorus thin film reaction apparatus 100 according to a preferred embodiment of the present invention includes a vacuum-tight reaction chamber 10, a slow-release body 20 is disposed in the reaction chamber 10, the slow-release body 20 divides the reaction chamber 10 into a first reaction chamber 11 for accommodating a reactant 30 and a second reaction chamber 12 for accommodating a growth substrate 40, capillary channels are formed in the slow-release body 20, and the first reaction chamber 11 and the second reaction chamber 12 are controlled to have different pressures during a heated reaction process.
In the present case, a section of the sustained release body 20 is disposed between the reactant 30 and the growth substrate 40 for filling, so that the pressure at the growth end can be controlled not to be too high, that is, the pressure of the second reaction chamber 12 is less than the pressure of the first reaction chamber 11, and the uniformity of source supply in time is improved, so that the nucleation point is controlled under a relatively low pressure condition, and finally, a single crystal or an alloy film with high crystallization quality is obtained.
In some embodiments, the sustained release body 20 extends between the first reaction chamber and the second reaction chamber for a length of 5 to 10mm, and the internal capillary passage has a diameter of 0.2 to 0.5 mm. In some embodiments, the sustained release body 20 is a molecular sieve, the material of the sustained release body can be quartz sand, and the type of the selected quartz sand particles is 10-20 meshes, i.e. the particle size is 1-2 mm. The material can also be selected from stable solid substances such as silicon particles, sapphire particles and the like which are high temperature resistant and do not react with phosphorus gas. In some embodiments, the delay body 20 may also be a quartz column.
In some embodiments, the reaction chamber 10 may be a quartz tube for heating reactions placed directly in the heating cavity of a heating device, such as 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 reaction chamber 10 includes, but is not limited to, the above-described implementation manner, and may be any growth device or growth container of a vacuum-tight reaction chamber capable of implementing the growth of the black phosphorus film.
A method for preparing a black phosphorus thin film according to a preferred embodiment of the present invention includes:
s1, providing the black phosphorus thin film reactor 100 of FIG. 1;
s2, placing the reactant 30 and the growth substrate 40 in the first reaction chamber 11 and the second reaction chamber 12 respectively, wherein the reactant 30 at least comprises a phosphorus source and a mineralizer;
heating to make the phosphorus-containing gas enter the second reaction chamber 12 from the first reaction chamber 11, and forming a black phosphorus film on the surface of the growth substrate 40.
In some embodiments, the reactants further comprise an arsenic source, the phosphorus source and the arsenic source are located at different positions in the first reaction chamber, and the temperature of the position of the arsenic source is controlled to be higher than that of the position of the phosphorus source during the reaction.
In some embodiments, the temperature difference Δ T between the phosphorus source and the arsenic source is controlled to be in the range of 0-50 ℃. Because the volatilization rate and the diffusion rate of the arsenic source and the phosphorus source are different, and finally the component distribution of the target black arsenic-phosphorus film is difficult to keep uniform, the phosphorus source is placed at a far distance as far as possible, the distance difference is delta x, and a temperature difference delta T exists between the phosphorus source and the phosphorus source. In some embodiments, b-As is grown with a difference Δ x in the range of 0-5cm and a difference Δ T in the range of 0-50 ℃ according to the difference in the composition of the target grown black arsenic-phosphorus thin filmxP1-xThe greater the value of component x in the film, the greater Δ x and Δ T.
In the whole growth temperature control procedure, the reaction device can adopt a quartz tube, and the quartz tube is horizontally placed in a muffle furnace for heat treatment. After heating, the temperature in the reaction chamber may show gradient change, and preferably, the growth substrate may be placed at the position with the highest temperature, and for the growth of the black arsenic phosphorus film, the region between the growth substrate 40 and the As source is As close As possible and kept at a constant temperature As possible, such As the end B in FIG. 2, but the P source is placed at a position As far As possible and at a lower temperature than the As source, such As the end A in FIG. 2, so As to inhibit the gasification rate of the P source to a certain extent, so As to ensure that the supply ratio of the As source and the P source is stable, and the black arsenic phosphorus alloy film grown on the growth substrate 40 has more uniform composition and higher quality. In order to obtain the ideal components of the black arsenic phosphorus alloy film, the distance delta x and the temperature difference delta T between the As source and the P source can be adjusted within a certain range according to the volatilization rate ratio of the As source and the P source.
In some embodiments, the phosphorus source may include elemental forms of phosphorus such as red phosphorus, white phosphorus, or the like, or may be capable of pyrolysis to yield P4Various classes of compounds of the molecule (Sn)4P3、PI3Compounds, etc.).
In some embodiments, the mineralizer may be selected from a variety of combinations of substances containing I and Sn elements, such as elemental I and Sn, or SnI2And I, and the like, and can also be gold, lead, indium, silver, copper, magnesium, and the like or alloys thereof.
In some embodiments, the arsenic source may include gray phosphorus, black phosphorus, and the likeArsenic in the form of a simple substance or capable of pyrolysis to give As4Various classes of compounds of the molecule (As)2S3Compounds, etc.).
In some embodiments, the presence or absence of arsenic has no effect on the desired feed ratio, weight, when an arsenic source is present. No matter whether As exists or not, the molar value of the ratio Sn to I of the raw material mineralizer is 2-10, the ratio is more critical to the growth of black phosphorus or black arsenic phosphorus, and the weight parameters of the raw materials of phosphorus and arsenic are not critical and can be As much As possible.
In some embodiments, a catalyst formed on the growth substrate 40 is also included, the catalyst being Au or a compound thereof, such as an AuSn, AuCr, AuAg, or like alloy thin film or discontinuous island-like particles. In some embodiments, the catalyst is an Au thin film formed on the growth substrate 40 by evaporation, and the Au thin film is formed on the other side of the growth substrate 40 opposite to the growth side. The function of evaporating the metal layer on the surface of the growth substrate 40 is to facilitate the formation of heterogeneous nucleation points, and the evaporated Au film can react with P, Sn and the like at high temperature to obtain AuSn3P7And the precursor is beneficial to the nucleation growth of the black phosphorus, and then P steam in the reaction cavity is induced to react and change phase to obtain black phosphorus nucleation points, so that the black phosphorus film (or the black arsenic phosphorus film) is grown.
In some embodiments, the growth substrate 40 is a dielectric layer of amorphous silicon oxide, aluminum oxide, magnesium oxide, or the like. The materials are used as insulators, are beneficial to further device construction after thin film growth, and are ideal growth substrates for device application.
In some embodiments, several growth substrates may be stacked within the reaction chamber, for example, may be longitudinally spaced apart at the same location within a horizontal quartz tube.
In some embodiments, the manner of heat treating comprises: heating the reaction chamber to 650-750 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 1-5 h, cooling to 460-520 ℃ at a speed of 0.5-2 ℃/min, preserving heat for 1h, then slowly cooling to 250-350 ℃ at a speed of 0.1-1 ℃/min, and finally cooling to room temperature.
The prepared black phosphorus film (including a black arsenic phosphorus film) can be used as a photoelectric material and can be applied to photoelectric devices, in some embodiments, the photoelectric devices can be batteries and photoelectric devices for infrared detection, infrared light emission and the like, and the batteries can be solar batteries, lithium sulfur batteries, lithium ion batteries or sodium ion batteries and the like.
Some specific examples of the present specification are listed below based on the above technical solutions.
Example 1: preparation of black phosphorus single crystal film
Preparation of reaction apparatus and raw materials:
providing 5 pieces of Si/SiO evaporated with Au metal film with thickness of 5nm-150nm2The sheet serves as a thin film growth substrate. And red phosphorus, tin tetraiodide and tin particles were provided as raw materials, the mass of these raw materials being 50mg, 5mg and 10mg, respectively.
The black phosphorus thin film reaction apparatus shown in fig. 1 is provided, a straight quartz tube is used as a reaction chamber, a columnar buffer section filled with silicon oxide particles is arranged in the middle of the reaction chamber, the reaction chamber is divided into two sections which are communicated with each other through the silicon oxide particles, raw materials are placed in one section of the reaction chamber, and silicon wafers plated with gold layers are stacked in the other section of the reaction chamber.
And (3) growing procedure: the closed quartz tube containing the reactant raw materials and the growth substrate is horizontally placed in a muffle furnace, and all parts of the reaction cavity of the whole quartz tube are kept at a constant temperature by avoiding temperature difference as much as possible. Heating the reaction chamber to 650 ℃ at the speed of 10 ℃/min, preserving heat for 1h, cooling to 500 ℃ at the speed of 0.5 ℃/min, preserving heat for 1h at 550 ℃, slowly cooling to 350 ℃ at the speed of 0.1 ℃/min, and finally cooling to room temperature. And taking out the quartz tube, and growing the black phosphorus film on each silicon substrate.
The high-quality black phosphorus single crystal film can be grown on the growth substrate, the appearance of the black phosphorus single crystal film is shown in fig. 3, the size of the single crystal film can reach 3mm, and the obtained optical microscope picture of the corner of the single black phosphorus film presents the appearance characteristic that the surface of the corner is regular and smooth.
Example 2: preparation of black phosphorus single crystal film
Preparation of reaction apparatus and raw materials:
providing 4 pieces of Si/SiO evaporated with 5nm-150nm thick gold film2The sheet serves as a thin film growth substrate. And red phosphorus, iodine and tin particles were provided as raw materials, the mass of these raw materials being 150mg, 5mg and 50mg, respectively.
The black phosphorus thin film reaction device shown in fig. 1 is provided, a straight quartz tube is used as a reaction chamber, a quartz column is arranged in the middle of the reaction chamber, a capillary channel with the aperture of 0.3 mm is arranged in the quartz column, the quartz column divides the reaction chamber into two sections which are communicated with each other through the capillary channel, raw materials are placed in one section of the reaction chamber, and a silicon wafer coated with a gold layer is stacked and placed in the other section of the reaction chamber.
And (3) growing procedure: the closed quartz tube containing the reactant raw materials and the growth substrate is horizontally placed in a muffle furnace, and all parts of the whole quartz tube reaction cavity are kept at a constant temperature by avoiding temperature difference as much as possible. Heating the reaction chamber to 650 ℃ at the speed of 10 ℃/min, preserving heat for 1h, cooling to 490 ℃ at the speed of 0.5 ℃/min, preserving heat for 1h at 490 ℃, then slowly cooling to 350 ℃ at the speed of 0.5 ℃/min, and finally cooling to room temperature. And taking out the quartz tube reaction chamber, and growing the black phosphorus film on each silicon substrate.
The black phosphorus film is transferred to a micro-grid copper mesh for TEM representation, a low-resolution electron microscope picture of a black phosphorus film sample is shown in FIG. 4, the sample under the electron microscope can be seen to be uniform and flat, and nine positions are selected on the sample in the area for selective area electron diffraction. The diffraction pattern remains nearly uniform as can be seen from the SAED characterization of fig. 5, which is a good illustration of the single crystal nature of the black phosphorus crystal film in this region. The HRTEM results shown in fig. 6 further demonstrate the high quality single crystal properties of the black phosphorus thin film, and are consistent with orthorhombic characteristics, with no crystal defects or grain boundaries observed in the characterized region, further calculated to have an interplanar spacing within the region along its zigzag boundary direction of about 4.63 a and an interplanar spacing along its armchair boundary direction of about 3.35 a.
Example 3: preparation of black arsenic phosphorus alloy film
Preparation of reaction apparatus and raw materials:
providing 5 pieces of vapor depositionSi/SiO of Au metal film with thickness of 5nm-150nm2The sheet serves as a thin film growth substrate. And red phosphorus, gray arsenic, tin tetraiodide and tin particles were supplied as raw materials, the mass of these raw materials being 79mg, 21mg, 5mg and 10mg, respectively.
The black phosphorus thin film reaction device shown in fig. 1 is provided, a straight quartz tube is used as a reaction chamber, a quartz column is arranged in the middle of the reaction chamber, a thin and long pore canal with the aperture of 0.5mm is arranged in the quartz column, the quartz column divides the reaction chamber into two sections which are communicated with each other through a capillary channel, raw materials are placed in one section of the reaction chamber, and a silicon wafer coated with a gold layer is stacked and placed in the other section of the reaction chamber. Wherein, red phosphorus and other raw materials are respectively arranged at different positions in the reaction cavity, and the red phosphorus is far away from the silicon chip compared with the ash arsenic.
And (3) growing procedure: the closed vacuum quartz tube containing the raw materials and the substrate is horizontally placed in a muffle furnace, and all parts of the whole quartz tube reaction cavity are kept at a constant temperature by avoiding temperature difference as much as possible. Heating the reaction chamber to 650 ℃ at the speed of 10 ℃/min, preserving heat for 1h, cooling to 550 ℃ at the speed of 0.5 ℃/min, preserving heat for 1h at 550 ℃, then slowly cooling to 400 ℃ at the speed of 0.5 ℃/min, and finally cooling to room temperature. Taking out the reaction chamber of the quartz tube, and growing on each silicon substrate to obtain b-As with 10% of arsenic atom0.1P0.9And (3) an alloy film.
Example 4: preparation of black arsenic phosphorus alloy film
Preparation of reaction apparatus and raw materials:
providing 5 pieces of Si/SiO evaporated with Au metal film with thickness of 5nm-150nm2The sheet serves as a thin film growth substrate. And red phosphorus, gray arsenic, tin tetraiodide and tin particles were supplied as raw materials, the mass of these raw materials being 38 mg, 62 mg, 5mg and 10mg, respectively.
The black phosphorus thin film reaction device shown in fig. 1 is provided, a straight quartz tube is used as a reaction chamber, a quartz column is arranged in the middle of the reaction chamber, a capillary channel with the aperture of 0.5mm is arranged in the quartz column, the quartz column divides the reaction chamber into two parts which are communicated with each other through the capillary channel, raw materials are placed in one section of the reaction chamber, and a silicon wafer coated with a gold layer is stacked in the other section of the reaction chamber. Wherein, red phosphorus and other raw materials are respectively arranged at different positions in the reaction cavity, and the red phosphorus is far away from the silicon chip compared with the ash arsenic.
And (3) growing procedure: the closed vacuum quartz tube containing the raw materials and the growth substrate is horizontally placed in a muffle furnace, and all parts of the whole quartz tube reaction cavity are kept at a constant temperature by avoiding temperature difference as much as possible. Heating the reaction chamber to 650 ℃ at the speed of 10 ℃/min, preserving heat for 1h, cooling to 550 ℃ at the speed of 0.5 ℃/min, preserving heat for 1h at 550 ℃, then slowly cooling to 400 ℃ at the speed of 0.5 ℃/min, and finally cooling to room temperature. Taking out the reaction chamber of the quartz tube, and obtaining b-As with the arsenic atom proportion of 40 percent on each silicon substrate0.4P0.6And (3) an alloy film.
b-As grown in example 5 was treated with XPS equipment0.4P0.6The alloy thin film characterizes the distribution of As element and P element, and As a result, As shown in FIGS. 7 and 8, it can be confirmed that the alloy thin film has uniformity of the distribution of the arsenic and phosphorus components in a wide range.
Example 5
By adopting the implementation scheme similar to that of the embodiment 3 and the embodiment 4, b-As with different components can be obtained by changing the atomic ratio of arsenic and phosphorus in the raw materials and properly adjusting the placement distance difference and the temperature difference of the arsenic source and the phosphorus sourcexP1-xThe adjusting range of the component x of the alloy film is 0-0.7, XPS results of different alloy components are shown in figure 9, Raman spectra of the alloy film with different components are shown in figure 10, and Raman peak shapes and Raman peak displacement change rules which change along with the alloy components can be obtained. Fig. 11 is an infrared absorption spectrum of different components, which shows the change rule of the band gap of the grown alloy film and the alloy components, and proves that the arsenic-phosphorus alloying can successfully realize the energy band engineering.
Comparative example 1
Preparation of reaction apparatus and raw materials:
providing 5 pieces of Si/SiO evaporated with Au metal film with thickness of 5nm-150nm2The sheet serves as a thin film growth substrate. And red phosphorus, gray arsenic, tin tetraiodide and tin particles were supplied as raw materials, the mass of these raw materials being 38 mg, 62 mg, 5mg and 10mg, respectively.
The black phosphorus thin film reaction device shown in fig. 1 is provided, a straight quartz tube is used as a reaction chamber, a quartz column is arranged in the middle of the reaction chamber, a capillary channel with the aperture of 0.5mm is arranged in the quartz column, the quartz column divides the reaction chamber into two parts which are communicated with each other through the capillary channel, raw materials are placed in one section of the reaction chamber, and a silicon wafer coated with a gold layer is stacked in the other section of the reaction chamber. Wherein the red phosphorus and other raw materials are arranged at the same position in the reaction chamber.
And (3) growing procedure: the closed vacuum quartz tube containing the raw materials and the growth substrate is horizontally placed in a muffle furnace, and all parts of the whole quartz tube reaction cavity are kept at a constant temperature by avoiding temperature difference as much as possible. Heating the reaction chamber to 650 ℃ at the speed of 10 ℃/min, preserving heat for 1h, cooling to 550 ℃ at the speed of 0.5 ℃/min, preserving heat for 1h at 550 ℃, then slowly cooling to 400 ℃ at the speed of 0.5 ℃/min, and finally cooling to room temperature. Taking out the reaction chamber of the quartz tube, and obtaining b-As with the arsenic atom proportion of 40 percent on each silicon substrate0.4P0.6And (3) an alloy film.
The uniformity of element distribution on the surface of the film is characterized by X-ray photoelectron spectroscopy (XPS), a region (500 μm × 500 μm) with a relatively flat film surface is selected for two-dimensional mapping characterization by XPS, and the characterization results of the black arsenic-phosphorus alloy film under the condition that an arsenic source and a phosphorus source are placed together are shown in FIG. 12 and FIG. 13. As can be seen from the figure, since it is difficult to maintain a constant ratio of the arsenic source to the phosphorus source to be continuously supplied, the composition uniformity of the obtained alloy thin film is relatively poor.
Comparative example 2
Preparation of reaction apparatus and raw materials:
providing 4 pieces of Si/SiO evaporated with 5nm-150nm thick gold film2The sheet serves as a thin film growth substrate. And red phosphorus, iodine and tin particles were provided as raw materials, the mass of these raw materials being 150mg, 5mg and 50mg, respectively.
A straight quartz tube is used as a reaction chamber, the reaction chamber is communicated with each other, the inner diameters of different positions are approximately the same, and a slow release body is not arranged in the reaction chamber. Reactant raw materials are placed at one end in the reaction chamber, and the silicon chip plated with the gold layer is stacked at the other end in the reaction chamber.
And (3) growing procedure: the closed quartz tube containing the reactant raw materials and the growth substrate is horizontally placed in a muffle furnace, and all parts of the whole quartz tube reaction cavity are kept at a constant temperature by avoiding temperature difference as much as possible. Heating the reaction chamber to 650 ℃ at the speed of 10 ℃/min, preserving heat for 1h, cooling to 490 ℃ at the speed of 0.5 ℃/min, preserving heat for 1h at 490 ℃, then slowly cooling to 350 ℃ at the speed of 0.5 ℃/min, and finally cooling to room temperature. And taking out the quartz tube reaction chamber, and growing the black phosphorus film on each silicon substrate. FIG. 14 shows a low resolution electron micrograph of a black phosphorus thin film sample, where it can be seen that the surface of the sample under the electron micrograph is stepped, indicating a plurality of nucleation points and non-single crystal nature (the surface of the sample in example 2 is continuously smooth).
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (10)

1. A black phosphorus film reaction device is characterized in that the device comprises a vacuum closed reaction chamber,
a slow release body is arranged in the reaction chamber, the slow release body divides the reaction chamber into a first reaction cavity for placing reactants and a second reaction cavity for placing a growth substrate,
capillary channels are formed in the slow release body, and the pressure intensity in the second reaction cavity is controlled to be smaller than the pressure intensity in the first reaction cavity in the heating reaction process.
2. The black phosphorus film reaction device of claim 1, wherein the slow release body is a molecular sieve, and the particle size of particles constituting the molecular sieve is 1-2 mm; or
The slow release body adopts a quartz column, and the diameter of a capillary channel in the quartz column is 0.2-0.5 mm.
3. The black phosphorus thin film reaction device according to claim 2, wherein the particles constituting the molecular sieve are quartz sand, silicon particles, silica particles, or sapphire particles.
4. A method for preparing a black phosphorus thin film, comprising:
providing the black phosphorus thin film reaction device of claim 1 or 2;
placing reactants and a growth substrate in a first reaction chamber and a second reaction chamber respectively, wherein the reactants at least comprise a phosphorus source and a mineralizer;
heating to make the phosphorus-containing gas enter the second reaction chamber from the first reaction chamber and form a black phosphorus film on the surface of the growth substrate.
5. The method of claim 4, wherein the reactants further comprise an arsenic source,
the phosphorus source and the arsenic source are positioned at different positions in the first reaction cavity, and the temperature of the position of the arsenic source is controlled to be higher than that of the position of the phosphorus source in the reaction process.
6. The method of claim 5, wherein the temperature difference between the arsenic source and the phosphorus source is 50 ℃ or less.
7. The method of claim 5, wherein the arsenic source is selected from elemental arsenic or can be thermally decomposed to obtain As4A compound of a molecule.
8. The method for preparing a black phosphorus thin film according to claim 4, wherein the mineralizer is selected from any one or more of tin, gold-tin alloy, tin iodide, lead, indium, silver, copper, magnesium and magnesium-tin-copper alloy.
9. The method for preparing a black phosphorus film according to claim 4, wherein the phosphorus source is one or more selected from the group consisting of a phosphorus-containing compound capable of decomposing by heat to generate a phosphorus-containing gas, white phosphorus and red phosphorus.
10. The method of claim 4, further comprising a catalyst formed on the growth substrate, wherein the catalyst is Au or a compound thereof.
CN202111238217.2A 2021-10-25 2021-10-25 Black phosphorus film reaction device and black phosphorus film preparation method Active CN113668053B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111238217.2A CN113668053B (en) 2021-10-25 2021-10-25 Black phosphorus film reaction device and black phosphorus film preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111238217.2A CN113668053B (en) 2021-10-25 2021-10-25 Black phosphorus film reaction device and black phosphorus film preparation method

Publications (2)

Publication Number Publication Date
CN113668053A true CN113668053A (en) 2021-11-19
CN113668053B CN113668053B (en) 2022-01-07

Family

ID=78550993

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111238217.2A Active CN113668053B (en) 2021-10-25 2021-10-25 Black phosphorus film reaction device and black phosphorus film preparation method

Country Status (1)

Country Link
CN (1) CN113668053B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115807211A (en) * 2023-02-08 2023-03-17 中南大学 Preparation method and device of arsenic-phosphorus thin film material
CN116200824A (en) * 2023-05-04 2023-06-02 中国科学院苏州纳米技术与纳米仿生研究所 Preparation method of black phosphorus film

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108538707A (en) * 2018-03-05 2018-09-14 南京航空航天大学 A kind of two dimension black phosphorus crystal preparation method
CN109706520A (en) * 2019-03-06 2019-05-03 中国科学院苏州纳米技术与纳米仿生研究所 Black arsenic phosphorus crystal and preparation method thereof
CN109913946A (en) * 2018-04-18 2019-06-21 清华-伯克利深圳学院筹备办公室 A kind of method that vapor transportation method prepares black arsenic phosphorus monocrystalline
CN111254494A (en) * 2020-03-27 2020-06-09 李旻鸶 Preparation method for realizing cheap black phosphorus single crystal by using low-purity red phosphorus
CN111285339A (en) * 2020-03-15 2020-06-16 湖北中科墨磷科技有限公司 Sn (tin)3P4Preparation method of induced two-dimensional black phosphorus crystal
CN111334780A (en) * 2020-03-02 2020-06-26 中国科学院苏州纳米技术与纳米仿生研究所 Black phosphorus film, preparation method and application thereof
US20200207623A1 (en) * 2018-12-26 2020-07-02 Government Of The United States, As Represented By The Secretary Of The Air Force Method and apparatus for producing a nanometer thick film of black phosphorus
CN112095146A (en) * 2020-07-24 2020-12-18 深圳市中科墨磷科技有限公司 Reactor for black phosphorus crystal amplification preparation and application thereof
CN112830462A (en) * 2021-02-03 2021-05-25 陕西科技大学 Method for safely and efficiently synthesizing high-purity black phosphorus

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108538707A (en) * 2018-03-05 2018-09-14 南京航空航天大学 A kind of two dimension black phosphorus crystal preparation method
CN109913946A (en) * 2018-04-18 2019-06-21 清华-伯克利深圳学院筹备办公室 A kind of method that vapor transportation method prepares black arsenic phosphorus monocrystalline
US20200207623A1 (en) * 2018-12-26 2020-07-02 Government Of The United States, As Represented By The Secretary Of The Air Force Method and apparatus for producing a nanometer thick film of black phosphorus
CN109706520A (en) * 2019-03-06 2019-05-03 中国科学院苏州纳米技术与纳米仿生研究所 Black arsenic phosphorus crystal and preparation method thereof
CN111334780A (en) * 2020-03-02 2020-06-26 中国科学院苏州纳米技术与纳米仿生研究所 Black phosphorus film, preparation method and application thereof
CN111285339A (en) * 2020-03-15 2020-06-16 湖北中科墨磷科技有限公司 Sn (tin)3P4Preparation method of induced two-dimensional black phosphorus crystal
CN111254494A (en) * 2020-03-27 2020-06-09 李旻鸶 Preparation method for realizing cheap black phosphorus single crystal by using low-purity red phosphorus
CN112095146A (en) * 2020-07-24 2020-12-18 深圳市中科墨磷科技有限公司 Reactor for black phosphorus crystal amplification preparation and application thereof
CN112830462A (en) * 2021-02-03 2021-05-25 陕西科技大学 Method for safely and efficiently synthesizing high-purity black phosphorus

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115807211A (en) * 2023-02-08 2023-03-17 中南大学 Preparation method and device of arsenic-phosphorus thin film material
CN116200824A (en) * 2023-05-04 2023-06-02 中国科学院苏州纳米技术与纳米仿生研究所 Preparation method of black phosphorus film

Also Published As

Publication number Publication date
CN113668053B (en) 2022-01-07

Similar Documents

Publication Publication Date Title
CN113668053B (en) Black phosphorus film reaction device and black phosphorus film preparation method
Chen et al. Zinc oxide nanotetrapods
CN110228796B (en) Preparation method of thin-layer two-dimensional transition metal tellurium-based solid solution
KR20090101617A (en) Method for manufacturing zinc oxide nanowires
CN110980659A (en) Tungsten ditelluride grown by using new raw material and preparation method thereof
Redkin et al. Aligned arrays of zinc oxide nanorods on silicon substrates
KR101633075B1 (en) 3 dimensional plasmonic nano structure and method for preparing the same
Li et al. The selective synthesis of single-crystalline CdS nanobelts and nanowires by thermal evaporation at lower temperature
US7537659B2 (en) Method of obtaining a CdTe or CdZnTe single crystal and the single crystal thus obtained
CN109023296B (en) Method for growing molybdenum-tungsten-selenium alloy on fluorophlogopite substrate through chemical vapor deposition
CN115341273B (en) Preparation of large-size two-dimensional thermoelectric material bismuth telluride single crystal
Singh et al. Synthesis of zinc oxide nanotetrapods and nanorods by thermal evaporation without catalysis
KR100943977B1 (en) Fabrication Method of Bismuth Single Crystalline Nanowire
CN114182230A (en) Chemical vapor deposition method for preparing two-dimensional tellurine film
Solís-Pomar et al. Growth of ZnO nanowires using Au/Pd nanoparticles as catalyst
Gremenok et al. Investigation of CuInZnSe2 thin films for solar cell applications
CN105019028B (en) A kind of method for the InAs nano wires for preparing specific morphology and crystal structure
KR101118743B1 (en) Apparatus and Method for manufacturing CuInGaSe layer
Choi et al. Synthesis of ZnO nanorods by a hot-wall high-temperature metalorganic chemical vapor deposition process
Hamidinezhad et al. Forest of ultra thin silicon nanowires: realization of temperature and catalyst size
Hu et al. Synthesis and Photoluminscence Properties of Morphology-and Microstructure-Controlled S-Doped ZnO Nanostructures
CN114956011B (en) Preparation method of nano material
Choi et al. Formation Mechanism and Properties of Foam-Structured ZnO Films Prepared Using Catalyst-Free Carbothermal Method
CN113652739B (en) Preparation method of large-size two-dimensional bismuth iodide single crystal
KR20100136185A (en) Fabrication method of twin-free single crystalline ag nano-wire and the twin-free single crystalline ag nano-wire fabricated using thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant