CN108538707A - A kind of two dimension black phosphorus crystal preparation method - Google Patents
A kind of two dimension black phosphorus crystal preparation method Download PDFInfo
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Abstract
The invention discloses a kind of two-dimentional black phosphorus crystal preparation methods, belong to field of material preparation, high temperature specifically will be heated to after phosphorous vapor and nitrogenous gas mixing to be allowed to decompose, then gas-phase decomposition object is deposited on weak interaction substrate surface and is generated with black phosphorus nucleus；Core is extended to single layer black phosphorus by the phosphorous vapor of sustainable supply pyrolytic after being nucleated；This method does not need body block black phosphorus required before as raw material when preparing two-dimentional black phosphorus, but directly prepares two-dimentional black phosphorus using non-black squama raw material, has saved cost of material；Solve the problems, such as that chemical vapour deposition technique grows black phosphorus.
Description
Technical field
The invention belongs to field of material preparation, in particular to a kind of two-dimentional black phosphorus crystal preparation methods.
Background technology
Two-dimensional material has the property that certain block materials do not have, as the electronics in graphene becomes massless dirac
Fermion.In addition, graphene also has high electron mobility, high heat conductance, the properties such as room temperature Hall effect.However, due to stone
Black alkene is without energy gaps（Hereinafter referred to as energy gap）, the logic switch function of semi-conducting material, does not limit it in information apparatus
The application in field.Two-dimentional transient metal sulfide has the characteristic of many similar even better than graphenes.By taking molybdenum disulfide as an example,
Single layer molybdenum disulfide has the energy gap close with silicon, can be used for manufacturing opening up and closes very high field-effect transistor.But transition group gold
It is too low to belong to sulfide carrier mobility so that it is difficult to find application prospect high-frequency electron device field.
Black phosphorus is a kind of two-dimensional material of direct gap.Not only carrier moves the field-effect transistor made from two-dimentional black phosphorus
Shifting rate is too low, and on-off ratio also reaches the value of conventional transistor.In addition, the size of black phosphorus energy gap can be adjusted by the number of plies, from
0.3 e V（Block）To 1.51 e V（Single layer）Between consecutive variations.In terms of optical property, black phosphorus is from visible light to near-infrared
There is response in the range of wavelength.Therefore, black phosphorus is expected to become good two-dimensional semiconductor material, in following optoelectronic areas
Foreground is gratifying.
Black phosphorus has numerous allotropes, wherein blue phosphorus with it with similar energy, and equally there is layer structure.But
Blue phosphorus is indirect gap material, needs phonon to assist in optical transition so that its optical property is far inferior to black phosphorus.In addition, blue
The electric conductivity of phosphorus is also low compared with black phosphorus, and the every abnormity of the electronics for not having black phosphorus.It attempts to use molecular beam epitaxy in the past
Black phosphorus is grown on the metallic substrate, but what is obtained is blue phosphorus.
Preparing two-dimentional black phosphorus method at present has mechanical stripping method, liquid phase stripping method, pulsed laser deposition.Mechanical stripping method
Yield and yield rate are undesirable；Two-dimentional black phosphorus size prepared by liquid phase stripping method is small, and organic solvent is difficult to remove；Pulse laser
Black phosphorus prepared by sedimentation is noncrystal.In addition, above-mentioned three kinds of methods are both needed to using body block black phosphorus as raw material, raw material need additionally at
This.
Invention content
The present invention is directed to problems of the prior art, discloses a kind of two-dimentional black phosphorus crystal preparation method, proposes single
Layer black phosphorus crystal chemical gas-phase deposition process for preparing and preparation principle directly prepare two-dimentional crystalline substance using common high-purity phosphorus as raw material
Body black phosphorus is not limited to black phosphorus raw material, and is expected to develop into preparation large area, the unique channel of high quality black phosphorus single layer, and
Solves above-mentioned technological deficiency.
The invention is realized in this way：
A kind of two dimension black phosphorus crystal preparation method, which is characterized in that the method and step is as follows：
Step 1：Device empties, and hydrogen is passed through so that air or vacuumize process is discharged in use device；
Step 2：Purity is placed at steam source generator and is higher than 95% phosphorus source, is heated solid-state phosphorus source, is generated phosphorous vapor；
Step 3：It is passed through nitrogenous current-carrying gas, control throttle valve makes N/P ratio be no more than 1：4；
Step 4：It is heated at high temperature mixed gas, high temperature makes nitrogen exist with atomic form；
Step 5：Mixed gas cooling after being decomposed in step 4 is less than 800 DEG C, makes phosphorus atoms under the auxiliary of nitrogen in weak phase
Crystallization is the nucleus with black phosphorus lattice in interaction substrate；Due to there is the presence of nitrogen, mixed gas is in substrate with black phosphorus
Structure is nucleated.The phosphorus of surrounding is grown by starting point of this core as single layer black phosphorus.
Step 6：Nitrogenous current-carrying gas is cut off after nucleation, is continually fed into and is steamed through the high-purity phosphorus more than 1000 DEG C of pyrolytics
Gas makes black phosphorus nucleus be extended to single layer black phosphorus.Since the interface between the black phosphorus and black phosphorus of doping nitrogen can reach atom cascade
Continuous, the growth of nucleated areas just follows strictly the structure of black phosphorus.Due to the induced growth at interface, the regions transform newly grown is it
The structure of its type phosphorus is kinetically being suppressed.In growth course, the nucleation density of nucleus is very crucial, and nucleation density is low to be had
Conducive to the black phosphorus of growth high quality；Can by physics polish or make annealing treatment improve substrate surface roughness, and then control at
Cuclear density.
This method is that a kind of new black phosphorus preparation method is proposed on the basis of first-principles calculations result.Result of calculation
Disclose black phosphorus has almost the same stability with blue phosphorus；But after equivalent N doping, black phosphorus BELAND phosphorus is obviously more stable.Weak phase
Interaction substrate further stablizes the black phosphorus of N doping, and then stability is worse for blue phosphorus.Based on these as a result, in weak interaction
It is nucleated using N doping help in substrate, to utilize chemical vapor deposition growth black phosphorus.
Further, the phosphorus source includes solid white phosphorus and/or red phosphorus, and the present invention can also be using other phosphorus simple substance
Raw material using N doping and weak interaction substrate, can also generate two-dimentional black phosphorus as long as being heated to pyrolytic, but its at
This relatively common red phosphorus and white phosphorus are high.
Further, the source of nitrogen includes ammonia either hydrazine steam or hydrazine steam, ammonia in the nitrogen current-carrying gas
Mixed gas either hydrogen, the mixed gas of ammonia or nitrogen phosphorus compound steam.
Further, the weak interaction substrate is hexagonal boron nitride or graphene, graphite, silica, Buddha's warrior attendant
Stone or sodium chloride.
Further, the temperature parameter of heating solid-state phosphorus source is in the step two：Red phosphorus is higher than 420 DEG C, and white phosphorus is higher than
280 DEG C, step 4 high temperature heating mixed gas temperature parameter be：1000℃±200℃.
The advantageous effect of the present invention and the prior art is：
1. the protection nitrogen doped aid crystal using the present invention is nucleated, and stablizes black phosphorus nucleus using weak interaction substrate
This method does not need body block black phosphorus required before as raw material when preparing two-dimentional black phosphorus, but directly uses non-black squama
Raw material prepares two-dimentional black phosphorus, has saved cost of material；
2. solving the problems, such as that chemical vapour deposition technique grows black phosphorus by this method, this method is based on accurate ab iitio and mould
It is quasi-, propose single layer black phosphorus crystal chemical gas-phase deposition process for preparing and preparation principle, it is direct as raw material using common high-purity phosphorus
Two dimensional crystal black phosphorus is prepared, black phosphorus raw material is not limited to, and is expected to develop into preparation large area, high quality black phosphorus single layer is only
One approach.
Description of the drawings
Fig. 1 is black phosphorus of the present invention and the molecular structure after blue phosphorus and nitrating；
Various phosphorus compare relative to the stability of black phosphorus in Fig. 2 vacuum and in the case of 5% N doping；
The energy difference of black phosphorus and blue phosphorus in Fig. 3 different bases and in vacuum；
Fig. 4 is the growing method schematic diagram of black phosphorus of the present invention；
Fig. 5 is the experimental provision of black phosphorus growing method in a kind of two-dimentional black phosphorus crystal preparation method of the present invention（Ⅰ）Schematic diagram；
Fig. 6 is the experimental provision of black phosphorus growing method in a kind of two-dimentional black phosphorus crystal preparation method of the present invention（Ⅱ）Schematic diagram.
Specific implementation mode
It is clear to keep the purpose of the present invention, technical solution and effect clearer, referring to the drawings and give an actual example to this
Invention is further described.It should be understood that specific implementation described herein is not used to limit only to explain the present invention
The present invention.
The present invention method be：It is allowed to decompose by high temperature is heated to after phosphorous vapor and nitrogenous gas mixing, then by gas phase
Decomposition product, which is deposited on to generate on weak interaction substrate surface, has black phosphorus nucleus；The phosphorus of sustainable supply pyrolytic after being nucleated
Core is extended to single layer black phosphorus by steam.Vapor phase growing apparatus schematic diagram is as shown in figure 5, triangle symbol is heating device.The figure
A variety of variations may be present in only a kind of possible device, actual device.Growth course is that heating phosphorus source generates phosphorous vapor, through being more than
The high-purity phosphorous vapor of 1000 DEG C of pyrolytics；It is passed through nitrogenous current-carrying gas, control throttle valve makes N/P ratio be no more than 1：4 fully
It, which is heated to high temperature, after mixing makes it resolve into atom level predecessor.Mixed gas deposits to substrate surface, passes through substrate
Induced synthesis black phosphorus nucleus.Close current-carrying gas throttle valve, be continually fed into the phosphorous vapor through pyrolytic so that black phosphorus nucleus into
One step-length is at single layer black phosphorus.It is as follows：
Step 1：Device empties, and is passed through hydrogen in a device so that air or vacuumize process is discharged；
Step 2：Purity is placed at steam source generator and is higher than 95% phosphorus source, and phosphorus source can select solid white phosphorus and/or red phosphorus
（It is raw material to consider that economic factor selects above two, considers safety factor, preferred red phosphorus.Other body block simple substance of phosphorus can also do phosphorus
Source, such as black phosphorus, violet phosphorus, blue phosphorus）, solid-state phosphorus source is heated, specifically, red phosphorus is higher than 416 DEG C, white phosphorus is higher than 281 DEG C, generates phosphorus
Steam；
Step 3：It is passed through nitrogenous current-carrying gas, control throttle valve makes N/P ratio be no more than 1：4；The source of nitrogen can be described
The source of nitrogen includes ammonia either hydrazine steam or hydrazine steam, the mixed gas of ammonia or hydrogen, ammonia in nitrogen current-carrying gas
The mixed gas of gas or the steam of nitrogen phosphorus compound；
Step 4：Temperature is risen to 1000 DEG C, is heated at high temperature mixed gas, high temperature makes nitrogen exist with atomic form；
Step 5：Mixed gas cooling after being decomposed in step 4 is less than 800 DEG C, makes phosphorus atoms under the auxiliary of nitrogen in weak phase
Crystallization is the nucleus with black phosphorus lattice in interaction substrate；Weak interaction substrate can be hexagonal boron nitride, graphene, two
Silica, diamond or sodium chloride.
Step 6：Nitrogenous current-carrying gas is cut off after nucleation, is continually fed into and is steamed through the high-purity phosphorus more than 1000 DEG C of pyrolytics
Gas makes black phosphorus nucleus be extended to single layer black phosphorus.Pratical and feasible value can float up and down 20% in setting value.
Specific embodiment is as follows：
Embodiment 1
Two-dimentional black phosphorus is prepared using experimental provision as shown in Figure 5.Use the substrate that graphene is two-dimentional black phosphorus growth.By substrate
It is put into quartz tube furnace and keeps certain distance with front end.Hydrogen is passed through after quartz ampoule is vacuumized.Quartz tube furnace front end is added
Heat to 1000 DEG C and substrate form temperature gradient.Since front end and substrate keep certain distance, when quartz tube furnace front end is heated to
At 1000 DEG C, temperature gradient is formed so that base reservoir temperature is less than 800 DEG C.
It keeps tube furnace temperature-resistant, purity is heated beyond 450 DEG C higher than 95% red phosphorus.It is passed through ammonia and does current-carrying gas, control
Flow processed so that N/P ratio is no more than 1：4.Ammonia is cut off after 0.5 ~ 2 minute, and is continually fed into the red phosphorus air source of heat resolve.
Growth is passed through hydrogen_cooling to room temperature after 240 ~ 480 minutes, obtains two-dimentional black phosphorus.
Embodiment 2
Two-dimentional black phosphorus is prepared using experimental provision as shown in Figure 5.Use the substrate that hexagonal boron nitride is two-dimentional black phosphorus growth.It will
Substrate is put into the quartz tube furnace vacuumized, and quartz tube furnace front end is heated to 1000 DEG C.
It keeps tube furnace temperature-resistant, purity is heated beyond 450 DEG C higher than 95% red phosphorus, while being passed through ammonia, control stream
Amount so that N/P ratio is no more than 1：4.Ammonia and phosphorous vapor are cut off after 0.5 ~ 2 minute, stops heating, make quartz tube furnace temperature certainly
It is so cold to go to 780 DEG C.Heated quarty tube front end is opened phosphorous vapor and is passed through into tube furnace with lasting to 1000 DEG C, and growth 240 ~
Stop heating after 480 minutes, and be passed through hydrogen_cooling to room temperature, obtains two-dimentional black phosphorus.
Embodiment 3
Two-dimentional black phosphorus is prepared using experimental provision as shown in FIG. 6, with the substrate that hexagonal boron nitride is two-dimentional black phosphorus growth.By base
Bottom is put into rear quartz tube furnace, is vacuumized, and device shown in fig. 6 only has single quartz tube furnace different from Fig. 5, the two using
Different cooling methods：Quartz ampoule pyrolysis furnace and quartz ampoule growth furnace before Fig. 6 is provided with.Preceding quartz tube furnace is heated to
820 DEG C, rear quartz tube furnace not temperature control.
Tubular type furnace temperature is constant before keeping, and purity is heated beyond 420 DEG C higher than 95% red phosphorus, at the same be passed through hydrazine steam,
The mixed gas of ammonia controls flow so that N/P ratio is no more than 1：4.Nitrogenous current-carrying gas is cut off after being nucleated after 0.5 ~ 2 minute,
And continue to be passed through phosphorous vapor into tube furnace.Growth is passed through hydrogen_cooling to room temperature after 240 ~ 480 minutes, obtains two-dimentional black phosphorus.
Embodiment 4
Two-dimentional black phosphorus is prepared using experimental provision as shown in Figure 5.Use the substrate that silica is two-dimentional black phosphorus growth.By base
Bottom is put into quartz tube furnace and keeps certain distance with front end, and quartz tube furnace front end is heated to 1200 DEG C.Make base reservoir temperature
Less than 800 DEG C.
It keeps tube furnace temperature-resistant, purity is heated beyond 500 DEG C higher than 95% red phosphorus, while being passed through hydrogen, ammonia
Mixed gas controls flow so that N/P ratio is no more than 1：4.Cut off nitrogenous current-carrying gas after 0.5 ~ 2 minute nucleation, and continue to
Phosphorous vapor is passed through in tube furnace.Growth is passed through hydrogen_cooling to room temperature after 240 ~ 480 minutes, obtains two-dimentional black phosphorus.
Embodiment 5
Two-dimentional black phosphorus is prepared using experimental provision as shown in Figure 5.Use the substrate that sodium chloride is two-dimentional black phosphorus growth.By substrate
It is put into the quartz tube furnace vacuumized, quartz tube furnace front end is heated to 1100 DEG C.
It keeps tube furnace temperature-resistant, purity is heated to 500 DEG C higher than 95% red phosphorus, while being passed through nitrogen phosphorus compound
Steam controls flow so that N/P ratio is no more than 1：4.Nitrogenous current-carrying gas is cut off after 0.5 ~ 2 minute nucleation, and is continued to tubular type
Phosphorous vapor is passed through in stove.Growth is passed through hydrogen_cooling to room temperature after 240 ~ 480 minutes, obtains two-dimentional black phosphorus.
Embodiment 6
Two-dimentional black phosphorus is prepared using experimental provision as shown in Figure 5.Use the substrate that graphite is two-dimentional black phosphorus growth.Substrate is put
Enter in the quartz tube furnace vacuumized, quartz tube furnace front end is heated to 1100 DEG C.
It keeps tube furnace temperature-resistant, purity is heated to 281 DEG C higher than 95% white phosphorus, while being passed through nitrogen phosphorus compound
Steam controls flow so that N/P ratio is no more than 1：4.Nitrogenous current-carrying gas is cut off after 0.5 ~ 2 minute nucleation, and is continued to tubular type
Phosphorous vapor is passed through in stove.Growth is passed through hydrogen_cooling to room temperature after 240 ~ 480 minutes, obtains two-dimentional black phosphorus.
When chemical vapour deposition technique grows black phosphorus, know that phosphorus atoms are preferentially combined into energy most according to maximum energy criterion
Low phosphorus phase.As shown in Figure 1, Fig. 1 can be seen that compared with intrinsic situation, the black phosphorus and blue phosphorus holding structure after nitrating are smooth,
And without apparent structural distortion.
As shown in Fig. 2, energy of each phosphorus phase structure relative to black phosphorus in the case of wherein ordinate E expressions are corresponding.Fig. 2 is true
Various phosphorus compare relative to the stability of black phosphorus in the case of aerial and 5% N doping, and Fig. 2 provides different phosphate mutually relative to black phosphorus phase
Unit nuclear energy.In a vacuum, the energy of black phosphorus and blue phosphorus is very nearly the same, i.e., black phosphorus and blue phosphorus are with almost the same steady
It is qualitative.And after nitrating, the energy of blue phosphorus is mixed in nitrogen and is given birth to using chemical vapour deposition technique compared with black phosphorus apparent increase
When long, it is black phosphorus nucleus rather than blue phosphorus nucleus that phosphorus atoms, which are more likely to crystallization,.
Fig. 3 is the energy difference block diagram of black phosphorus and blue phosphorus in different base.ΔE（Energy difference）, vac expression vacuum, gr tables
Show that graphene, h-BN indicate that hexagonal boron nitride, h-BN+N indicate that 3.12% nitrating adds h-BN substrates.Fig. 3's the result shows that, with
Tend to stablize blue phosphorus toward metallic substrates such as widely used copper, gold, platinum, and cannot get black phosphorus.On the contrary, graphene, six side's nitrogen
Change in the weak interactions substrates such as boron, black phosphorus is mutually significantly more more stable than other all phosphorus.Therefore it is grown in chemical vapour deposition technique
When, it is the key that prepare black phosphorus, and N doping can cooperate with these substrates and facilitate the preferential of black phosphorus using weak interaction substrate
Nucleation.
For the schematic process of chemical vapor deposition growth as shown in figure 4, wherein square is nitrogen-atoms, big ball is phosphorus atoms,
Bead is graphene, indicates that nitrogen assists the black phosphorus nucleus to be formed in diamond block frame, the phosphorus and nitrogen reactant after pyrolytic are in base
Deposited on bottom, by absorption, diffusion, combine and etc. nucleation.Since black phosphorus is relative to other allotrope minimum energies, sink
Long-pending atom can be preferentially nucleated in accordance with black phosphorus structure.With the completion of nucleation, stopping is passed through diamond, it is supreme to be only passed through phosphorus source
Temperature is decomposed, to maintain the growth of nitrogenous black phosphorus nucleus.Since there is identical lattice structure, nucleus will continue to for black phosphorus and nitrogenous black phosphorus
It is grown with black phosphorus lattice structure, is finally grown to single layer black phosphorus.
Claims (5)
1. a kind of two dimension black phosphorus crystal preparation method, which is characterized in that the method and step is as follows：
Step 1：Device empties, and is passed through hydrogen in a device so that air or vacuumize process is discharged；
Step 2：Purity is placed at steam source generator and is higher than 95% phosphorus source, is heated solid-state phosphorus source, is generated phosphorous vapor；
Step 3：It is passed through nitrogenous current-carrying gas, control throttle valve makes N/P ratio be no more than 1：4；
Step 4：It is heated at high temperature mixed gas, nitrogen is made to exist with atomic form；
Step 5：Mixed gas cooling after being decomposed in step 4 is less than 800 DEG C, makes phosphorus atoms under the auxiliary of nitrogen in weak phase
Crystallization is the nucleus with black phosphorus lattice in interaction substrate；
Step 6：Nitrogenous current-carrying gas is cut off after nucleation, is continually fed into the high-purity phosphorous vapor of pyrolytic, and black phosphorus nucleus is made to extend
At single layer black phosphorus.
2. a kind of two-dimentional black phosphorus crystal preparation method according to claim 1, which is characterized in that the phosphorus source includes solid
Body white phosphorus and/or red phosphorus.
3. a kind of two-dimentional black phosphorus crystal preparation method according to claim 1, which is characterized in that in the nitrogen current-carrying gas
The source of nitrogen includes the ammonia either gaseous mixture of hydrazine steam or hydrazine steam, the mixed gas of ammonia or hydrogen, ammonia
The steam of body or nitrogen phosphorus compound.
4. a kind of two-dimentional black phosphorus crystal preparation method according to claim 1, which is characterized in that the weak interaction
Substrate is hexagonal boron nitride, graphene, graphite, silica, diamond or sodium chloride.
5. a kind of two-dimentional black phosphorus crystal preparation method according to claim 1, which is characterized in that add in the step two
The temperature parameter of thermosetting state phosphorus source is：Red phosphorus is higher than 420 DEG C, and white phosphorus is higher than 280 DEG C；Step 4 high temperature heats mixed gas
Temperature parameter is：1000℃±200℃.
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Cited By (6)
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| CN110714224A (en) * | 2019-09-17 | 2020-01-21 | 南京理工大学 | Preparation method of large-area high-stability single-layer blue phospholene based on molecular beam epitaxial growth |
| CN110878425A (en) * | 2019-12-06 | 2020-03-13 | 深圳市中科墨磷科技有限公司 | Method for rapidly preparing high-quality two-dimensional black phosphorus crystal by seed crystal induction |
| CN110963474A (en) * | 2019-12-03 | 2020-04-07 | 昆明理工大学 | Preparation method of black phosphorus-based nano material |
| CN112047313A (en) * | 2020-09-21 | 2020-12-08 | 东北大学 | Preparation and hydrogen storage method of calcium-doped modified two-dimensional black phosphorus nanosheet |
| CN113668053A (en) * | 2021-10-25 | 2021-11-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Black phosphorus film reaction device and black phosphorus film preparation method |
| CN115807211A (en) * | 2023-02-08 | 2023-03-17 | 中南大学 | Preparation method and device of arsenic-phosphorus thin film material |
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|---|---|---|---|---|
| CN110714224A (en) * | 2019-09-17 | 2020-01-21 | 南京理工大学 | Preparation method of large-area high-stability single-layer blue phospholene based on molecular beam epitaxial growth |
| CN110963474A (en) * | 2019-12-03 | 2020-04-07 | 昆明理工大学 | Preparation method of black phosphorus-based nano material |
| CN110878425A (en) * | 2019-12-06 | 2020-03-13 | 深圳市中科墨磷科技有限公司 | Method for rapidly preparing high-quality two-dimensional black phosphorus crystal by seed crystal induction |
| CN112047313A (en) * | 2020-09-21 | 2020-12-08 | 东北大学 | Preparation and hydrogen storage method of calcium-doped modified two-dimensional black phosphorus nanosheet |
| CN112047313B (en) * | 2020-09-21 | 2022-03-29 | 东北大学 | Preparation and hydrogen storage method of calcium-doped modified two-dimensional black phosphorus nanosheet |
| CN113668053A (en) * | 2021-10-25 | 2021-11-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Black phosphorus film reaction device and black phosphorus film preparation method |
| CN115807211A (en) * | 2023-02-08 | 2023-03-17 | 中南大学 | Preparation method and device of arsenic-phosphorus thin film material |
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