CN111575787B - Method for growing single-layer silicon phosphide crystal - Google Patents

Method for growing single-layer silicon phosphide crystal Download PDF

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Publication number
CN111575787B
CN111575787B CN202010312686.3A CN202010312686A CN111575787B CN 111575787 B CN111575787 B CN 111575787B CN 202010312686 A CN202010312686 A CN 202010312686A CN 111575787 B CN111575787 B CN 111575787B
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raw material
quartz tube
substrate
silicon phosphide
crystal
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CN111575787A (en
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邱海龙
武羽
胡章贵
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Tianjin University of Technology
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Tianjin University of Technology
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    • 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
    • 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
    • C30B29/10—Inorganic compounds or compositions
    • 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
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/64—Flat crystals, e.g. plates, strips or discs

Abstract

The invention discloses a method for growing single-layer silicon phosphide crystals, which comprises the following steps: preparing a quartz tube, wherein two ends of the quartz tube are respectively a raw material end and a substrate end, placing a substrate in the substrate end of the quartz tube, placing a raw material and a transport agent in the raw material end of the quartz tube, vacuumizing the quartz tube, and sealing the quartz tube after vacuumizing, wherein the raw material is a mixture of elemental silicon and red phosphorus, and the transport agent is elemental iodine; and simultaneously heating the raw material end and the substrate end of the quartz tube for 5-36 hours, cooling the raw material end and the substrate end to room temperature of 20-25 ℃ along with the furnace after heating, and obtaining a single-layer silicon phosphide crystal on the substrate, wherein the heating temperature of the raw material end is 1000-1150 ℃, and the heating temperature of the substrate end is 600-950 ℃. The invention realizes the growth of the monolayer silicon phosphide two-dimensional crystal for the first time by utilizing the chemical vapor transport method, which is a great breakthrough in the growth of the monolayer SiP two-dimensional crystal and provides a favorable support for the chemical vapor transport method to produce the two-dimensional crystal material.

Description

Method for growing single-layer silicon phosphide crystal
Technical Field
The invention belongs to the technical field of preparation of single-layer silicon phosphide crystals, and particularly relates to a method for growing single-layer silicon phosphide crystals.
Background
The existing known two-dimensional materials have the advantages and disadvantages, for example, although graphene has high thermal conductivity and high carrier mobility, the zero band gap of graphene makes the graphene incapable of realizing the logic switch of a semiconductor, and the application of the graphene in the field of semiconductors is greatly limited; molybdenum disulfide is taken as a typical transition metal chalcogenide two-dimensional semiconductor compound, a monolayer of which has a direct band gap of 1.8eV, so that the molybdenum disulfide is not restricted by a zero band gap, and the current switching ratio of the molybdenum disulfide is as high as 108However, the room temperature carrier mobility of the material is only 200cm2v-1s-1Too low mobility limits its application in the semiconductor field. It can be seen that a two-dimensional semiconductor material having a suitable bandgap, high carrier mobility and being more stable is soughtStill is an important research topic in the field of two-dimensional materials. The silicon phosphide crystal is a typical representative of a novel two-dimensional material IVA-VA, has excellent anisotropic characteristics and photoelectric properties, and has great application potential in a plurality of fields such as microelectronics, energy, catalysis, nonlinear optics and the like.
Two-dimensional silicon phosphide crystals are usually obtained by a mechanical stripping method, but the two-dimensional silicon phosphide crystals with controllable layer number and size are difficult to obtain, and the yield is low. It is difficult to prepare by the conventional two-dimensional crystal growth method because of its unstable physicochemical properties. The thin-layer silicon phosphide crystal prepared by the liquid phase stripping method is easy to pollute a sample, the property of the sample is easy to change, and the thickness is not easy to control in the transverse direction and the longitudinal direction; because phosphorus has higher saturated vapor pressure and silicon has higher melting point, the preparation of the silicon phosphide crystal by using a Chemical Vapor Deposition (CVD) method is difficult to realize; the cost for preparing silicon phosphide crystals by film epitaxy is high; the Physical Vapor Deposition (PVD) method for preparing the silicon phosphide crystals can be synthesized, but firstly, the raw material synthesis steps are complex, and secondly, impurities are easily introduced.
Disclosure of Invention
Aiming at the problem of difficulty in preparing two-dimensional silicon phosphide crystals, the invention aims to provide a method for growing single-layer silicon phosphide crystals, which can prepare single-layer silicon phosphide crystals in one step by improving the traditional Chemical Vapor Transport (CVT) method for growing crystals.
The purpose of the invention is realized by the following technical scheme.
A method of growing a single layer of silicon phosphide crystal comprising the steps of:
1) preparing a quartz tube, wherein two ends of the quartz tube are respectively a raw material end and a substrate end, placing a substrate in the substrate end of the quartz tube, placing a raw material and a transport agent in the raw material end of the quartz tube, vacuumizing the quartz tube, and sealing the quartz tube after vacuumizing to ensure that the pressure in the quartz tube is 4 multiplied by 10-6～4×10-4Pa, wherein the raw material is a mixture of elemental silicon and red phosphorus, and the transport agent is elemental iodine;
in the step 1), the substrate is sapphire.
In the step 1), the length of the quartz tube is 15-50 cm, and the inner diameter is 10-20 mm.
In the step 1), the ratio of the raw materials to the transport agent is (2-6) in parts by mass: (1-3).
In the technical scheme, the mass of the raw material is 2-6 mg.
In the step 1), the ratio of the simple substance silicon to the red phosphorus is (1-6): 1 in parts by mass.
2) And simultaneously heating the raw material end and the substrate end of the quartz tube for 5-36 hours, cooling the heated raw material end and the substrate end to room temperature of 20-25 ℃ along with the furnace, and obtaining a single-layer silicon phosphide crystal on the substrate, wherein the heating temperature of the raw material end is 1000-1150 ℃, and the heating temperature of the substrate end is 600-950 ℃.
In the step 2), the temperature gradient between the raw material end and the substrate end is 1.6-14 ℃/cm.
The invention realizes the growth of the monolayer silicon phosphide (SiP) two-dimensional crystal for the first time by utilizing the chemical vapor transport method, which is a great breakthrough for the growth of the monolayer SiP two-dimensional crystal and provides a favorable support for the chemical vapor transport method to produce the two-dimensional crystal material.
Drawings
FIG. 1 is an optical micrograph of a single-layer silicon phosphide crystal obtained in example 1 of the present invention;
FIG. 2 is a photograph taken by an Atomic Force Microscope (AFM) of a single-layer silicon phosphide crystal obtained in example 1 of the present invention;
FIG. 3 shows a Raman spectrum of a single-layer silicon phosphide crystal obtained in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
Elemental silicon (Si): purity is more than or equal to 99.999 percent and Alfa Aesar
Red phosphorus (P): purity is more than or equal to 99.999 percent and Alfa Aesar
Elemental iodine (I)2): purity is more than or equal to 99.999 percent and Alfa Aesar
OLYMPUS-bx53 m-microscope
WiTec confocal Raman and atomic force microscope system (Raman-AFM)
Because the phosphorus simple substance has higher saturated vapor pressure and the silicon simple substance has higher melting point, the synthesis is carried out in a closed container, the CVT method can realize closed and high-vacuum reaction, and the preparation of the silicon phosphide is accurately controlled by adjusting thermodynamic and kinetic influencing factors.
Example 1
A method of growing a single layer of silicon phosphide crystal comprising the steps of:
1) preparing a quartz tube, wherein the length of the quartz tube is 30cm, the inner diameter of the quartz tube is 11mm, two ends of the quartz tube are respectively a raw material end and a substrate end, a substrate is placed in the substrate end of the quartz tube, the substrate is sapphire, raw materials and a transport agent are placed in the raw material end of the quartz tube, vacuumizing is performed on the quartz tube, and the quartz tube is sealed after vacuumizing so that the pressure intensity in the quartz tube of the quartz tube is 2 x 10- 4Pa, wherein the ratio of the raw material to the transport agent is 1:1 in parts by mass. The raw material is a mixture of simple substance silicon and red phosphorus, the mass of the raw material is 2mg, the ratio of the simple substance silicon to the red phosphorus is 1:1 according to the mass parts, and the transport agent is simple substance iodine;
2) and (2) simultaneously heating the raw material end and the substrate end of the quartz tube for 36h by using a tubular furnace, cooling to room temperature of 20-25 ℃ along with the furnace after heating, and obtaining the single-layer silicon phosphide crystal on the substrate, wherein the heating temperature of the raw material end is 1025 ℃, the heating temperature of the substrate end is 950 ℃, and the temperature gradient between the raw material end and the substrate end is 2.5 ℃/cm.
Example 2
A method of growing a single layer of silicon phosphide crystal comprising the steps of:
1) preparing a quartz tube, wherein the length of the quartz tube is 30cm, the inner diameter of the quartz tube is 11mm, two ends of the quartz tube are respectively a raw material end and a substrate end, a substrate is placed in the substrate end of the quartz tube, the substrate is sapphire, raw materials and a transport agent are placed in the raw material end of the quartz tube, vacuumizing is performed on the quartz tube, and the quartz tube is sealed after vacuumizing so that the pressure intensity in the quartz tube of the quartz tube is 2 x 10- 4Pa, wherein, by massThe ratio of the raw materials to the transport agent is 1:1 in parts by weight. The raw material is a mixture of simple substance silicon and red phosphorus, the mass of the raw material is 6mg, the ratio of the simple substance silicon to the red phosphorus is 1:1 according to the mass parts, and the transport agent is simple substance iodine;
2) and simultaneously heating the raw material end and the substrate end of the quartz tube for 10 hours by using a tubular furnace, cooling to room temperature of 20-25 ℃ along with the furnace after heating, and obtaining the single-layer silicon phosphide crystal on the substrate, wherein the heating temperature of the raw material end is 1050 ℃, the heating temperature of the substrate end is 870 ℃, and the temperature gradient between the raw material end and the substrate end is 6 ℃/cm.
Example 3
A method of growing a single layer of silicon phosphide crystal comprising the steps of:
1) preparing a quartz tube, wherein the length of the quartz tube is 30cm, the inner diameter of the quartz tube is 11mm, two ends of the quartz tube are respectively a raw material end and a substrate end, a substrate is placed in the substrate end of the quartz tube, the substrate is sapphire, raw materials and a transport agent are placed in the raw material end of the quartz tube, vacuumizing is performed on the quartz tube, and the quartz tube is sealed after vacuumizing so that the pressure intensity in the quartz tube of the quartz tube is 2 x 10- 4Pa, wherein the ratio of the raw material to the transport agent is 1:1 in parts by mass. The raw material is a mixture of simple substance silicon and red phosphorus, the mass of the raw material is 2mg, the ratio of the simple substance silicon to the red phosphorus is 1:1 according to the mass parts, and the transport agent is simple substance iodine;
2) and (2) simultaneously heating the raw material end and the substrate end of the quartz tube for 15h by using a tubular furnace, cooling to room temperature of 20-25 ℃ along with the furnace after heating, and obtaining the single-layer silicon phosphide crystal on the substrate, wherein the heating temperature of the raw material end is 1050 ℃, the heating temperature of the substrate end is 925 ℃, and the temperature gradient between the raw material end and the substrate end is 4.17 ℃/cm.
A single layer of silicon phosphide crystal was found on the substrate after the above process was completed.
FIG. 1 is an optical micrograph of a single-layer silicon phosphide crystal obtained in example 1 of the present invention;
FIG. 2 is a photograph taken by an Atomic Force Microscope (AFM) of a single-layer silicon phosphide crystal obtained in example 1 of the present invention, and the measured thickness was 0.83nm, which is approximately equal to 0.78nm calculated theoretically, whereby it was confirmed that a single-layer silicon phosphide crystal was produced;
FIG. 3 shows a Raman spectrum obtained in example 1 of the present invention, which shows that silicon phosphide crystals were obtained.
Examples 1 and 2 can obtain the technical effect consistent with example 1.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (5)

1. The application of the method for growing the single-layer silicon phosphide crystal in preparing the single-layer silicon phosphide two-dimensional crystal is characterized by comprising the following steps of:
1) preparing a quartz tube, wherein two ends of the quartz tube are respectively a raw material end and a substrate end, placing a substrate in the substrate end of the quartz tube, placing a raw material and a transport agent in the raw material end of the quartz tube, vacuumizing the quartz tube, and sealing the quartz tube after vacuumizing to ensure that the pressure in the quartz tube is 4 multiplied by 10-6~4×10-4Pa, wherein the raw material is a mixture of simple substance silicon and red phosphorus, the transport agent is simple substance iodine, the ratio of the simple substance silicon to the red phosphorus is 1:1 in parts by mass, and the ratio of the raw material to the transport agent is 1: 1;
2) and simultaneously heating the raw material end and the substrate end of the quartz tube for 5-36 hours, cooling the heated raw material end and the substrate end to room temperature of 20-25 ℃ along with the furnace, and obtaining a single-layer silicon phosphide crystal on the substrate, wherein the heating temperature of the raw material end is 1000-1150 ℃, and the heating temperature of the substrate end is 600-950 ℃.
2. Use according to claim 1, wherein in step 1) the substrate is sapphire.
3. The use according to claim 2, wherein in the step 1), the quartz tube has a length of 15 to 50cm and an inner diameter of 10 to 20 mm.
4. Use according to claim 3, wherein the mass of the raw material is 2-6 mg.
5. The use according to claim 4, wherein in the step 2), the temperature gradient between the raw material end and the substrate end is 1.6-14 ℃/cm.
CN202010312686.3A 2020-04-20 2020-04-20 Method for growing single-layer silicon phosphide crystal Expired - Fee Related CN111575787B (en)

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CN114318520A (en) * 2020-10-09 2022-04-12 天津理工大学 Method for preparing needle-shaped silicon phosphide crystals based on chemical vapor transport method
CN113684529B (en) * 2021-08-20 2022-07-22 清华大学 Preparation method of crystalline red phosphorus sheet
CN114457426B (en) * 2021-11-22 2022-11-22 天津理工大学 Ti-doped monolayer molybdenum disulfide single crystal and preparation method and application thereof

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