CN110424054B - Preparation method and application of two-dimensional layered GeP single crystal nano film - Google Patents

Preparation method and application of two-dimensional layered GeP single crystal nano film Download PDF

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CN110424054B
CN110424054B CN201910826293.1A CN201910826293A CN110424054B CN 110424054 B CN110424054 B CN 110424054B CN 201910826293 A CN201910826293 A CN 201910826293A CN 110424054 B CN110424054 B CN 110424054B
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王善朋
陶绪堂
于童童
赵淑琪
张百涛
何京良
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Shandong University
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    • C30B29/10—Inorganic compounds or compositions
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
    • C30B9/12—Salt solvents, e.g. flux growth
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    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/10—Controlling the intensity, frequency, phase, polarisation or direction of the emitted radiation, e.g. switching, gating, modulating or demodulating
    • H01S3/11—Mode locking; Q-switching; Other giant-pulse techniques, e.g. cavity dumping
    • H01S3/1106—Mode locking
    • H01S3/1112—Passive mode locking
    • H01S3/1115—Passive mode locking using intracavity saturable absorbers
    • H01S3/1118—Semiconductor saturable absorbers, e.g. semiconductor saturable absorber mirrors [SESAMs]; Solid-state saturable absorbers, e.g. carbon nanotube [CNT] based

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Abstract

A preparation method and application of a two-dimensional layered GeP single crystal nano film are disclosed, the preparation steps are as follows: (1) weighing Ge, P and Bi, filling the Ge, P and Bi into a quartz tube, and sealing the quartz tube; (2) carrying out combination reaction on Ge and P; (3) centrifugally separating the quartz tube to obtain GeP bulk single crystals; (4) GeP putting the monocrystal in dilute hydrochloric acid and cleaning; (5) putting the mixture into a centrifugal tube filled with absolute ethyl alcohol for ultrasonic treatment to obtain an ethyl alcohol suspension; (6) centrifuging; (7) taking out the supernatant, and diluting with ethanol to obtain a dilute solution of GeP nanometer film. The prepared two-dimensional layered GeP monocrystal nano film is used for passive Q-switching or mode-locking modulation of laser by a saturable absorber and manufacturing of negative electrode materials of photon or photoelectron devices, catalysis and lithium batteries. According to the invention, large-size and high-quality GeP bulk single crystals are grown, the prepared GeP nano film is a direct band gap semiconductor, and Q-switching and mode-locked laser are realized by adopting pure GeP, so that higher pulse peak power and pulse energy are obtained in an infrared broadband of 1-3 mu m.

Description

Preparation method and application of two-dimensional layered GeP single crystal nano film
Technical Field
The invention relates to a flux method for growing a two-dimensional layered GeP bulk single crystal and a preparation method of a nano film, and application of a GeP nano film photoelectric device, belonging to the technical field of application of two-dimensional layered materials and photoelectric functional devices thereof.
Background
Two-dimensional layered nanomaterials (referred to as "two-dimensional materials") refer to materials in which electrons are free to move in only two dimensions, with large lateral dimensions and only one or a few atomic layers thick in the thickness direction. Since the advent of graphene in 2004, this field has continued to grow at a high rate. Two-dimensional materials have been found to date to cover different types from insulators, semiconductors, conductors to superconductors, such as: graphene, silylene, black phosphorus, transition metal chalcogenides, hexagonal boron nitride. The two-dimensional material has important application value in the fields of energy conversion and storage such as photoelectric devices, spintronic devices, photo/electro-catalysts, lithium batteries, solar batteries, super capacitors and the like, and is expected to be widely applied in the fields of information transmission devices and energy storage devices of new generations.
Graphene has attracted extensive attention because of its excellent properties such as ultra-high carrier mobility, extremely low resistivity and ultra-high specific surface area, and has made a great deal of valuable research, but its application in the field of photoelectricity has been greatly limited due to its "zero band gap" characteristic.
Therefore, other novel two-dimensional materials have been explored, and the transition metal chalcogenide is a graphene-like material with the chemical formula MX2(M is transition metal elements such as Mo and W, X is S, Se and Te), the single-layer transition metal chalcogenide is a sandwich structure consisting of covalent bonds of X-M-X, M atoms are sandwiched between two X atomic layers, and van der Waals force is acted between the layers. Wherein, MoS2Is a widely studied transition metal chalcogenide, MoS2Bandgap tunable, bulk MoS2Is an indirect bandgap semiconductor with a bandgap of about 1.2eV and a single-layer MoS2The direct band gap semiconductor has a band gap of 1.9eV, and the photoelectric conversion efficiency of the direct band gap material is higher, so that MoS2Has very wide application prospect in the photoelectric field. The black phosphorus is a novel direct band gap two-dimensional semiconductor material, has adjustable band gap and very high electron mobility (1000 cm)2Vs), and a very high leakage current modulation rate (10000 times that of graphene), black phosphorus has important application prospects in photoelectricity, catalysis, biosensing, spintronics, lithium ion batteries, supercapacitors and solar cells. However, since phosphorus has a pair of lone-pair electrons and is easy to react with water, the black phosphorus with few layers is extremely unstable in air, and the prepared device has poor stability althoughHowever, the stability of the black phosphorus can be improved by means of surface modification or coating, but the problem of poor stability of the black phosphorus cannot be fundamentally solved, so that the application of the black phosphorus in the field of optoelectronic devices is greatly limited.
GeP belongs to IV-V family binary compound, which is a new type two-dimensional layered material. GeP has two structures of tetragonal phase and monoclinic phase, wherein GeP of the monoclinic phase is a two-dimensional layered structure, [ Ge ]2P6]The structural units form a two-dimensional plane through roof-sharing connection, and the layers are arranged along [20-1 ] through Van der Waals force]The directions stack to form GeP. GeP compared with black phosphorus, the air stability is greatly improved because the Ge element which is more stable replaces the general phosphorus element and the Ge plays a role in protecting the phosphorus in the inner layer.
The GeP of the bulk is an indirect bandgap semiconductor with a bandgap width of 0.51eV, and the GeP nanometer film of the single layer is a direct bandgap semiconductor material with a bandgap width of 1.58 eV. GeP is a p-type semiconductor, most of which is an n-type semiconductor, and has good air stability against black phosphorus, which is also a p-type semiconductor. GeP has important application value in optoelectronic devices due to its excellent semiconductor properties and excellent air stability.
GeP crystals were grown by high temperature and high pressure methods at the earliest, and the crystals obtained were of smaller size and of poorer quality. The film prepared by the gas phase method has the same low quality, a large amount of defects and crystal boundaries exist, and the performance of the device is seriously influenced.
Researchers can grow GeP Crystal blocks (Journal of Crystal Growth,443,2016,75-80) by a high-pressure melt method, the method requires a harsh process condition with a high pressure of 0.5-1GPa, so that the requirement on Growth equipment is high, high-temperature and high-pressure Growth equipment is required, and the method has poor quality of the grown Crystal and small size of the complete single Crystal.
The existing preparation method of GeP nano-film comprises mechanical stripping, CVD method and the like, wherein the nano-film prepared by the mechanical stripping method has small size, is only suitable for being used as a micro-nano device and is not suitable for preparing a large-area saturated absorption mirror; although the CVD method can prepare a large-area film, a large number of grain boundaries and defects exist, and the crystal quality is relatively poor.
Disclosure of Invention
Aiming at the defects of the conventional GeP bulk crystal growth and two-dimensional layered film preparation technology, the invention provides a preparation method capable of obtaining a large-size high-quality GeP bulk single crystal and a two-dimensional layered nano film, and application of the preparation method in the aspect of photoelectric devices.
The preparation method of the two-dimensional layered GeP single crystal nano film comprises the following steps:
(1) according to a molar ratio Ge: p: weighing Ge, P and Bi according to the proportion of 1: 2-5, putting the Ge, P and Bi into a quartz tube, uniformly mixing, vacuumizing the quartz tube, and sintering and sealing the quartz tube, wherein Bi is a metal fluxing agent.
The vacuum degree of the quartz tube for vacuumizing is 3-5 multiplied by 10-4Pa。
(2) Heating the quartz tube filled with the raw materials in stages to enable Ge and P to be subjected to full combination reaction;
the step-wise heating is carried out, namely, the temperature is raised to 350-450 ℃ within 15-20 hours, and the temperature is kept constant for 30-50 hours; then heating to 800-1000 ℃ for 20-30 hours, and keeping the temperature for 20-30 hours to ensure that Ge and P are subjected to full combination reaction; this prevents the quartz tube from exploding.
(3) Then cooling to 600-700 ℃ after 100-200 hours, and centrifugally separating a quartz tube to separate GeP single crystals obtained by growth from a metal fluxing agent Bi to obtain GeP block single crystals;
(4) taking out GeP mass single crystals, placing in dilute hydrochloric acid (10-20% of hydrochloric acid with mass fraction lower than 20%), removing flux Bi attached to the surface, and cleaning with deionized water to obtain GeP mass crystals;
the obtained GeP block single crystal has a size of 2-5 × 5-15 × 1-2 mm3。
(5) Placing GeP block single crystal into a centrifugal tube filled with absolute ethyl alcohol, and carrying out ultrasonic treatment to obtain an ethyl alcohol suspension containing GeP nano films;
the ultrasonic treatment frequency is 40Hz, and the ultrasonic time is 0.5-4 hours.
(6) Centrifuging the obtained ethanol suspension to obtain supernatant with the Tyndall effect;
the centrifugation was carried out at 4000rpm for 30 minutes.
(7) Taking out GeP supernatant, diluting with ethanol to obtain dilute solution of GeP nanometer film; the diluted solution is dropped on a substrate, and after volatilization and drying, a two-dimensional layered GeP single crystal nano film is formed.
The volume ratio of the GeP supernatant to the ethanol is 1: 10-15.
The thickness of the GeP nanometer film in the solution is 0.5-10 nm, and the band gap is 0.43-1.58 eV.
The two-dimensional layered GeP single crystal nano film prepared by the method has the following purposes:
1. the laser is passively Q-switched or mode-locked and modulated by the saturable absorber, and the output of the 1-3 mu m ultrashort pulse laser is realized.
2. The method is used for manufacturing negative electrode materials of photon or photoelectronic devices, catalysis and lithium batteries.
According to the invention, metal Bi is used as a fluxing agent, and the growth of 2-5 multiplied by 5-15 multiplied by 1-2 mm is controlled by controlling various crystal growth parameters3The prepared single-layer GeP nano film is a direct band gap semiconductor, the band gap is about 1.58eV, two or more layers of GeP with the thickness of 0.43eV are indirect band gap semiconductors, and the band gap of the bulk GeP is 0.43eV, so that the band gap can be adjusted and controlled within the range of 0.43-1.58eV by changing the thickness of the GeP nano film, and the infrared band broadband laser modulation can be realized, can be used for Q and mode locking laser, and adopts simple GeP to realize Q and mode locking laser instead of a compound of organic matters and GeP in the prior art, and higher pulse peak power and pulse energy are obtained. In addition, the material can be used for photoelectronic devices, radiation detectors, catalysis, lithium ion battery cathode materials and the like.
Drawings
FIG. 1 is a photograph of a large size GeP bulk single crystal material grown according to the present invention.
Fig. 2 is a structural diagram of a two-dimensional layered GeP nanofilm grown in accordance with the present invention.
FIG. 3 is an AFM picture of GeP nm film obtained by ultrasonic liquid phase exfoliation in accordance with the present invention.
Fig. 4 is a schematic diagram of a passive Q-switched laser experiment on GeP saturable absorbers.
FIG. 5 is a schematic diagram of the results of the 1-3 μm passive Q-switching performance test of the GeP saturable absorber prepared by the present invention. Wherein: (a) the pulse width and repetition frequency of the laser pump with the diameters of 1 micron, 2 microns and 3 microns are respectively changed along with the power of the pump light; (d) and (e) the single pulse energy and the peak power of the laser pump with the wavelength of 1 micron, 2 microns and 3 microns are respectively changed along with the power of the pump light.
Detailed Description
Example 1
(1) According to a molar ratio Ge: p: weighing Ge, P and Bi according to the proportion of 1:2:2, wherein Bi is a metal fluxing agent, then putting the accurately weighed raw materials into a quartz tube, uniformly mixing, and vacuumizing to 3 multiplied by 10-4Pa vacuum degree, sintering and sealing the tube;
(2) putting the quartz tube filled with the raw materials into a resistance furnace, adopting a staged heating program to heat the quartz tube to 350 ℃ within 15 hours, and keeping the temperature for 30 hours; heating to 800 ℃ within 20 hours, and keeping the temperature for 20 hours to ensure that Ge and P are fully combined and reacted;
(3) then the temperature is reduced to 600 ℃ after 100 hours, and GeP nucleates and grows gradually in the process; after the crystal growth is finished, the quartz tube is quickly taken out from the hearth at high temperature and is centrifugally separated, so that GeP single crystal obtained by growth is separated from the metal fluxing agent Bi, and GeP bulk single crystal with larger size is obtained.
(4) Breaking the quartz tube, taking out a single crystal block containing GeP blocks, dissolving the single crystal block in 10-20% diluted hydrochloric acid to remove Bi fluxing agent attached to the surface of GeP, and cleaning the single crystal block with deionized water to obtain silvery white flaky GeP block crystals with the size of 2-5 × 5-15 × 1-2 mm3. The object is shown in figure 1.
(5) Selecting high-quality GeP block single crystals, putting the single crystals into a centrifugal tube filled with absolute ethyl alcohol, and performing ultrasonic treatment for 0.5 hour at the frequency of 40Hz to obtain an ethyl alcohol suspension containing GeP nano films;
(6) then putting the obtained suspension into a centrifuge, and centrifuging for 30min at the rotating speed of 4000rpm to obtain a supernatant with the tyndall effect;
(7) taking out GeP supernatant, and diluting with ethanol according to the ratio of 1:10 to obtain a dilute solution of GeP nano-film with the thickness of 0.5-10 nm. The diluted solution contains nano-sheets, the nano-sheets are dropped on a substrate, and after volatilization and drying, GeP nano-films are formed.
Fig. 2 shows the crystal structure of the two-dimensional layered GeP nano-film grown in this example, and fig. 3 shows an AFM photograph of a GeP nano-film, tested with GeP nano-sheet thickness of about 4 nm. The thickness range of the two-dimensional layered GeP nanometer film prepared by the embodiment is 0.5-10 nm, and the band gap is in the range of 0.43-1.58 eV.
The two-dimensional layered GeP nano-film prepared by the embodiment can be made into a saturable absorber. As shown in fig. 4, a passive Q-switched laser experiment was performed, and a pump source, a coupling system, an input mirror, a gain medium, GeP saturable absorber, and an output mirror were sequentially provided.
FIG. 5 shows the results of the GeP saturable absorber 1-3 μm laser passive Q-switching performance test. (a) The pulse width and repetition frequency of the laser pump with the diameters of 1 micron, 2 microns and 3 microns are respectively changed along with the power of the pump light; (d) and (e) the single pulse energy and the peak power of the laser pump with the wavelength of 1 micron, 2 microns and 3 microns are respectively changed along with the power of the pump light.
The two-dimensional layered GeP nano-film prepared by the embodiment can also be used for manufacturing optoelectronic devices, radiation detectors, lithium ion battery cathode materials and the like.
Example 2
(1) According to a molar ratio Ge: p: weighing Ge, P and Bi according to the proportion of 1:5:5, wherein Bi is a metal fluxing agent, then putting the accurately weighed raw materials into a quartz tube, uniformly mixing, and vacuumizing to 5 multiplied by 10-4Pa vacuum degree, sintering and sealing the tube;
(2) putting the quartz tube filled with the raw materials into a resistance furnace, and adopting a staged heating program to heat the quartz tube to 450 ℃ within 20 hours and keeping the temperature for 50 hours in order to avoid the explosion of the quartz tube; heating to 1000 ℃ within 30 hours, and keeping the temperature for 30 hours to ensure that Ge and P are fully combined and reacted;
(3) then cooling to 700 ℃ after 200 hours, and GeP nucleates and grows gradually in the process; after the crystal growth is finished, the quartz tube is quickly taken out from the hearth at high temperature and centrifugally separated, so that the GeP single crystal obtained by growth is separated from the metal fluxing agent Bi to obtain the GeP bulk single crystal with larger size of 2-5 multiplied by 5-15 multiplied by 1-2 mm3；
(4) Breaking the quartz tube, taking out a single crystal block containing GeP blocks, placing the single crystal block into 10-20% diluted hydrochloric acid to dissolve and remove Bi fluxing agent attached to the surface of GeP, and then cleaning the single crystal block by using deionized water to obtain silver-white flaky GeP crystals;
(5) selecting high-quality GeP block single crystals, putting the single crystals into a centrifugal tube filled with absolute ethyl alcohol, and performing ultrasonic treatment for 2 hours at the frequency of 40Hz to obtain an ethyl alcohol suspension containing GeP nano films;
(6) then putting the obtained suspension into a centrifuge, and centrifuging for 30min at the rotating speed of 4000rpm to obtain a supernatant with the tyndall effect;
(7) taking out GeP supernatant, diluting with ethanol at a ratio of 1:12 to obtain GeP nanometer film diluted solution,
the thickness range of the two-dimensional layered GeP nanometer film prepared by the embodiment is 0.5-10 nm, and the band gap is in the range of 0.43-1.58 eV. The passive Q-switching or mode-locking modulation is carried out on the infrared broadband ultrashort pulse laser with the wavelength of 1-3 mu m, the performance is good, and high pulse peak power and pulse energy can be obtained.
Example 3
(1) According to a molar ratio Ge: p: weighing Ge, P and Bi according to the proportion of 1:3:3, wherein Bi is a metal fluxing agent, then putting the accurately weighed raw materials into a quartz tube, uniformly mixing, and vacuumizing to 4 multiplied by 10-4Pa vacuum degree, sintering and sealing the tube;
(2) putting the quartz tube filled with the raw materials into a resistance furnace, and adopting a staged heating program to heat the quartz tube to 400 ℃ within 18 hours and keeping the temperature for 40 hours in order to avoid the explosion of the quartz tube; heating to 900 ℃ within 25 hours, and keeping the temperature for 30 hours to ensure that Ge and P are subjected to full combination reaction;
(3) then the temperature is reduced to 650 ℃ after 150 hours, and GeP nucleates and grows gradually in the process; crystal growthAnd finally, quickly taking out the quartz tube from the hearth at high temperature, and centrifugally separating to separate the GeP single crystal and the metal fluxing agent Bi, so as to obtain GeP large-size single crystal blocks with the size of 2-5 multiplied by 5-15 multiplied by 1-2 mm3；
(4) Breaking the quartz tube, taking out a monocrystalline material block containing GeP blocks, dissolving the monocrystalline material block in 10-20% dilute hydrochloric acid to remove Bi fluxing agent attached to the surface of GeP, and cleaning the monocrystalline material block with deionized water to obtain silver-white flaky GeP crystals;
(5) selecting high-quality GeP block single crystals, putting the single crystals into a centrifugal tube filled with absolute ethyl alcohol, and performing ultrasonic treatment for 2 hours at the frequency of 40Hz to obtain an ethyl alcohol suspension containing GeP nano films;
(6) then putting the obtained suspension into a centrifuge, and centrifuging for 30min at the rotating speed of 4000rpm to obtain a supernatant with the tyndall effect;
(7) taking out GeP supernatant, diluting with ethanol at a ratio of 1:15 to obtain a dilute solution of GeP nano-film; dropping on the substrate, evaporating and drying to form GeP nanometer film.
The two-dimensional layered GeP nano film with the thickness of 0.5-10 nm is prepared in the same way, and the band gap is in the range of 0.43-1.58 eV. The passive Q-switching or mode-locking modulation is carried out on the infrared broadband ultrashort pulse laser with the wavelength of 1-3 mu m, the performance is good, and high pulse peak power and pulse energy can be obtained.

Claims (1)

1. A preparation method of a two-dimensional layered GeP single crystal nano film is characterized by comprising the following steps: the method comprises the following steps:
(1) according to a molar ratio Ge: p: weighing Ge, P and Bi according to the proportion of 1: 2-5, putting the Ge, P and Bi into a quartz tube, uniformly mixing, vacuumizing the quartz tube, and sintering and sealing the quartz tube, wherein Bi is a metal fluxing agent;
(2) heating the quartz tube filled with the raw materials in stages to enable Ge and P to be subjected to full combination reaction;
(3) then cooling to 600-700 ℃ after 100-200 hours, and centrifugally separating a quartz tube to separate GeP single crystals obtained by growth from a metal fluxing agent Bi to obtain GeP block single crystals;
(4) taking out GeP mass single crystals, placing the single crystals in dilute hydrochloric acid, removing the flux Bi attached to the surface, and then cleaning the single crystals by using deionized water to obtain GeP mass crystals;
(5) placing GeP block single crystal into a centrifugal tube filled with absolute ethyl alcohol, and carrying out ultrasonic treatment to obtain an ethyl alcohol suspension containing GeP nano films;
(6) centrifuging the obtained ethanol suspension to obtain supernatant;
(7) taking out GeP supernatant, diluting with ethanol to obtain dilute solution of GeP nanometer film; dripping the dilute solution on a substrate, volatilizing and drying to form a two-dimensional layered GeP single crystal nano film;
in the step (1), the vacuum degree of the quartz tube for vacuumizing is 3-5 multiplied by 10-4Pa; the step (2) is a step of heating, wherein the temperature is raised to 350-450 ℃ within 15-20 hours, and the temperature is kept constant for 30-50 hours; then heating to 800-1000 ℃ for 20-30 hours, and keeping the temperature for 20-30 hours to ensure that Ge and P are subjected to full combination reaction; the size of the GeP bulk single crystal obtained in the step (4) is 2-5 x 5-15 x 1-2 mm3；
The ultrasonic treatment in the step (5) has the frequency of 40Hz and the ultrasonic time of 0.5-4 hours; the centrifugation in the step (6) is carried out for 30 minutes at the rotating speed of 4000 rpm; the volume ratio of the GeP supernatant to the ethanol in the step (7) is 1: 10-15.
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CN111334857B (en) * 2020-03-25 2021-04-16 深圳先进技术研究院 SiP crystal growth regulation and control method
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