CN104630894B - Two-dimensional carbon nitrogen single crystal alloy and preparation method thereof - Google Patents
Two-dimensional carbon nitrogen single crystal alloy and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of Two-dimensional Carbon nitrogen single crystal alloy, carbon skeleton of the Two-dimensional Carbon nitrogen single crystal alloy comprising Graphene and doping nitrogen-atoms, wherein described doping nitrogen-atoms replaces part carbon atom to form the two-dimensional superlattice structure of nitrogen in the carbon skeleton of the Graphene, and the lattice size of the superlattices is 0.4 nanometer to 0.5 nanometer.The present invention also provides a kind of preparation method of Two-dimensional Carbon nitrogen single crystal alloy, the described method comprises the following steps：A) metal substrate surface is processed, to obtain smooth clean surface；B) the smooth clean surface is heated；C) one layer of precursor molecule is deposited on the surface heated；D) continue to heat to maintain temperature to form Two-dimensional Carbon nitrogen single crystal alloy；Wherein described precursor molecule is perhalogeno Pyridine Molecules.
Description
Technical field
The invention belongs to the technical field of carbon material, and in particular to a kind of Two-dimensional Carbon nitrogen single crystal alloy and preparation method thereof.
Background technology
Graphene (Graphene) is a kind of novel nano-material of single layer of carbon atom in hexagoinal lattice arrangement.English in 2004
Two scientist An Deliegaimu (Andre Geim) and Constantine Nuo Woxiaoluofu of University of Manchester of state
(Konstantin Novoselov) has obtained single-layer graphene (referring to document by " micromechanics stripping method "
K.S.Novoselvo et a1., Electric Field Effect in Atomically Thin Carbon Films,
Science, 2004,306,666-669.), and therefore obtain 2010 years Nobel Prizes in physics.Graphene has much not
It is same as the special property of conventional semiconductor material, such as high heat conductance (~5000W/mK), high carrier mobility (~
200000cm2V-1s-1) etc..These properties cause grapheme material in energy stores, electro-catalysis, sensor and electronic product side
Face has a very wide range of applications prospect.
But for intrinsic Graphene, although with mobility high, but its carrier concentration is very low, thus
Limit Graphene application in the semiconductor device.In the last few years, scientific research personnel wished to regulate and control graphite by various means
The carrier concentration of alkene.In the middle of this, it is always a kind of important regulation and control method that chemical doping and modification are carried out to Graphene.It is logical
Chemical doping is crossed, the doping of such as nitrogen can effectively adjust position and the load of Graphene of the Fermi surface of Graphene
Stream subtype etc..(referring to document Theanne Schiros et al., Connecting Dopant Bond Type with
Electronic Structure in N-Doped Graphene.Nano Letters, 2012,12,4025-4031.).
Nitrogen atom doping enters in the lattice of Graphene generally three kinds of bonding modes, including graphite mould nitrogen, pyridine type nitrogen and
Pyrroles's type nitrogen is (referring to document D.Uhachov et al., Nitrogen-Doped Graphene：Efficient Growth,
Structure, and Electronic Properties.Nano Letters, 2011,11,5401-5407.).Work as at this
In, graphite mould nitrogen is most common N doping mode, and it refers to the carbon atom that nitrogen-atoms instead of in benzene hexatomic ring.At present will
Nitrogen atom doping enters in Graphene can be by approach such as segregation growing method, solvent-thermal method and arc discharge methods.But these sides
Method has disadvantages that the doping content of such as nitrogen is few, and the doping position of nitrogen is unordered etc..Unordered N doping can also make carrier exist
Scattered in transport process, so as to the carrier mobility for causing material is reduced.
The content of the invention
One embodiment of the invention is a kind of Two-dimensional Carbon nitrogen single crystal alloy, and the Two-dimensional Carbon nitrogen single crystal alloy includes stone
The carbon skeleton and doping nitrogen-atoms of black alkene, wherein the doping nitrogen-atoms replaces part carbon former in the carbon skeleton of the Graphene
Son forms the two-dimensional superlattice structure of nitrogen, and the lattice size of the superlattices is 0.4 nanometer to 0.5 nanometer.
In one embodiment of the invention, the superlattices are made up of hexagoinal lattice.
In one embodiment of the invention, nitrogen-atoms is entrained in the skeleton of Graphene in order.
It is a kind of preparation method of Two-dimensional Carbon nitrogen single crystal alloy in another embodiment of the invention, methods described includes
Following steps：A) metal substrate surface is processed, to obtain smooth clean surface；B) the smooth clean table is heated
Face；C) one layer of precursor molecule is deposited on the surface heated；D) continue to heat to maintain temperature to form Two-dimensional Carbon nitrogen monocrystalline
Alloy；Wherein described precursor molecule is perhalogeno Pyridine Molecules.
In one embodiment of the invention, perhalogeno Pyridine Molecules are penta chloropyridine molecule, pentabromo- Pyridine Molecules, five
Iodine pyridine molecule, preferably penta chloropyridine molecule.
In one embodiment of the invention, metal substrate is copper.
In one embodiment of the invention, the treatment in step a) is argon ion sputtering treatment.
In one embodiment of the invention, the surface of copper substrate is (111) crystal face.
In one embodiment of the invention, the smooth clean surface to 100 to 400 is heated in step b)
℃。
In one embodiment of the invention, step a)-d) completed in high vacuum environment, vacuum is 1 × 10-3To 1
×10-8Handkerchief.
In one embodiment of the invention, when driving body molecule before deposition, the air pressure of precursor molecule is controlled 1
Handkerchief is to 1 × 10-7Handkerchief.
In one embodiment of the invention, heating and continuous 5 minutes to 2 hours in step d).
In one embodiment of the invention, there are following characteristics：
1. by under high vacuum environment, (vacuum is 1 × 10-3To 1 × 10-8Handkerchief) growth, it is possible to reduce impurity is mixed into
In the sample of growth, be conducive to obtaining the Two-dimensional Carbon nitrogen single crystal alloy of high-purity.
2., by controlling precursor molecule beam intensity, Two-dimensional Carbon nitrogen single crystal alloy film thickness can be controlled.Presoma
The intensity of molecular beam can be determined by the switch size of microleak valve.
In one embodiment of the invention, the Two-dimensional Carbon nitrogen single crystal alloy and biography for being grown using the method for the present invention
The nitrogen-doped graphene of the technology growth of system is compared, and there is following advantage：
1. by the penta chloropyridine molecule that is used carbon-halogen bond there is relatively low bond energy, this programme can be greatly lowered instead
Answer temperature.Such as in document Xinran Wang et al., N-Doping Graphene Through Electrothermal
Reactions with Ammonio.Science, described in 2009,324,768-771, traditional growth N doping graphite
Alkene needs the high temperature at 1000 degree or so, and this programme only needs to relatively low temperature, i.e., 100 to 400 degree just can grow described
Two-dimensional Carbon nitrogen single crystal alloy.
2. presoma penta chloropyridine molecule can be in the orderly self assembly in surface.Due to relatively strong and long-range between binding molecule
Coulomb repulsion is acted on, and precursor molecule can realize oriented and ordered self assembly on substrate.So as to finally obtain high-quality
Orderly nitrogen-doped graphene, i.e. Two-dimensional Carbon nitrogen single crystal alloy.Nitrogen-atoms therein is formed in the carbon skeleton of original Graphene
Superlattices, its lattice parameter includes but is not limited to 0.42 nanometer.The lattice parameter of the superlattices can be by growing Two-dimensional Carbon nitrogen
Precursor molecule and substrate regulation are changed during single crystal alloy.Unordered N doping can make carrier be subject to dissipate in transport process
Penetrate, causing the carrier mobility of material is reduced, and the generation of scattering can be reduced when adulterating in order, so as to greatly increase carrier
Mobility.
3. compared with the unordered nitrogen-doped graphene being previously reported by, previously the Graphene of random N doping was because of nitrogen impurity scattering
And electron mobility is reduced, and described Two-dimensional Carbon nitrogen single crystal alloy has orderly distribution of electron's density, so as to graphite can be made
Alkene obtains big carrier concentration while the electron mobility for having kept.
In one embodiment of the invention, a kind of preparation method of New Two Dimensional carbon nitrogen single crystal alloy is disclosed, should
The features such as single crystal alloy has high carrier concentration, high conductivity and high mobility.And described New Two Dimensional carbon nitrogen monocrystalline
Alloy also has the advantages that nitrogen element content is high, nitrogen-atoms aligned orderly.The preparation of the single crystal alloy mainly make use of pentachloro- pyrrole
Pyridine molecule as precursor molecule, and using the crystal face of metal single crystal (111) as substrate, using the sequential 2 D of molecule from group
Fill to realize the ordered arrangement of the nitrogen-atoms of doping in the carbon skeleton of original Graphene, that is, the nitrogen-atoms for adulterating is original
Superlattices are formed in the carbon skeleton of Graphene, so as to construct this New Two Dimensional carbon nitrogen single crystal alloy.It is of the invention public
The preparation method of the New Two Dimensional carbon nitrogen single crystal alloy opened is sunk on processed clean metal single crystal (111) face of heating
Product one layer of precursor molecule, and heat a period of time after can construct this New Two Dimensional carbon nitrogen single crystal alloy.Due to system
Carbon-halogen bond bond energy in the precursor molecule of standby described this New Two Dimensional carbon nitrogen single crystal alloy is low, therefore anti-when preparing
Answer temperature low, method is simple and easy to apply.Described New Two Dimensional carbon nitrogen single crystal alloy can be widely used for the semiconductor electronic of a new generation
Device, design and the manufacture of high-conductivity transparent electrode and spin electric device.
Brief description of the drawings
Fig. 1 is the present invention for preparing the precursor molecule of Two-dimensional Carbon nitrogen single crystal alloy, penta chloropyridine molecule；
Fig. 2 (a) is showing for the structure of the Two-dimensional Carbon nitrogen single crystal alloy that the present invention is prepared using penta chloropyridine precursor molecule
It is intended to；
Fig. 2 (b) is the PSTM figure of the Two-dimensional Carbon nitrogen single crystal alloy less than layer prepared by the present invention.It is empty
Line show the lattice on copper (111) surface, and shown in solid is the lattice of Two-dimensional Carbon nitrogen single crystal alloy.
Fig. 3 is the flow chart that Two-dimensional Carbon nitrogen single crystal alloy scheme is prepared in the present invention.
Fig. 4 is the PSTM of the Two-dimensional Carbon nitrogen single crystal alloy shown in Fig. 2 (a) prepared by the present invention
Figure.
Fig. 5 (a) is the scanning tunnel spectrum of Two-dimensional Carbon nitrogen single crystal alloy prepared by the present invention.
Fig. 5 (b) is the band structure of the Two-dimensional Carbon nitrogen single crystal alloy shown in Fig. 2 (a) of theoretical calculation.
Fig. 6 is to do the scanning tunnel that precursor molecule grows the unordered N doping sample for obtaining under the method using pyridine
Road microscope figure.
Fig. 7 (a) is that air pressure is 10-6Handkerchief, is heated to 300 degree of Two-dimensional Carbon nitrogen monocrystalline grown under conditions of being kept for 20 minutes and closes
The PSTM figure of gold.
Fig. 7 (b) is that air pressure is 10-5Handkerchief, is heated to 300 degree of Two-dimensional Carbon nitrogen monocrystalline grown under conditions of being kept for 20 minutes and closes
The PSTM figure of gold.
Fig. 7 (c) is that air pressure is 10-3Handkerchief, is heated to 300 degree of Two-dimensional Carbon nitrogen monocrystalline grown under conditions of being kept for 20 minutes and closes
The PSTM figure of gold.
Fig. 8 is that air pressure is 10-5Handkerchief, is heated to 500 degree of Two-dimensional Carbon nitrogen single crystal alloys grown under conditions of being kept for 20 minutes
PSTM figure.
Fig. 9 is that air pressure is 10-5Handkerchief, is heated to 300 degree of Two-dimensional Carbon nitrogen single crystal alloys grown under conditions of being kept for 10 minutes
PSTM figure.
Specific embodiment
The objects, technical solutions and advantages of the present invention are illustrated in order to more explicit, below in conjunction with accompanying drawing, to this hair
Bright specific embodiment is described in further detail.
In the specific embodiment of the present invention, can follow the steps below (see Fig. 3)：
Step S1. is processed (111) face of copper single crystal, obtains clean metal single crystal surface；
Step S2. heats the copper single crystal substrate after the treatment；
Copper single crystal surface deposition penta chloropyridine precursor molecules of the step S3. after the heating；
Step S4. maintains copper single crystal substrate temperature 5 minutes to 2 hours, that is, prepare described Two-dimensional Carbon nitrogen monocrystalline and close
Golden material.
It is described in detail below for each step in the specific embodiment of the present invention：
Step S1. is pre-processed in vacuum environment to metal single crystal (111) surface, obtains clean metal single crystal lining
Basal surface.
In the present invention, the metal single crystal surface of atomically flating can be obtained using the treatment of argon ion sputtering rifle.
Step S2. is heated to the metal substrate after the treatment.
The metal substrate that will be handled well is slowly heated to 100 to 400 degrees centigrades.
Substrate surface deposition penta chloropyridine precursor molecules of the step S3. after the heating.Precursor molecule is put into
In sample preparation chamber, sample preparation chamber air pressure is set to reach 1 handkerchief to 1 × 10-7Handkerchief or so.
Step S4. maintain metal single crystal temperature 100 to 400 degrees Celsius about 5 minutes to 2 hours.
In these steps, precursor molecule is in the absorption of metal single crystal (111) substrate surface, dehalogenation, diffusion, connection
Deng.In precursor molecule after adsorption, because carbon-halogen bond bond energy is low, cause precursor molecule carbon-halogen bond at the temperature disclosed above
It is broken and is formed the carbon nitrogen skeleton after dehalogenation.Acted on due to the coulomb repulsion between the carbon nitrogen skeleton after dehalogenation so that after dehalogenation
Carbon nitrogen skeleton can realize that orderly self assembly is arranged and connected on metal single crystal (111) face.Make by above-mentioned course of reaction
Obtain precursor molecule and be interconnected to form described New Two Dimensional carbon nitrogen single crystal alloy.
In order to verify feasibility of the invention, we enter to the preparation method based on Two-dimensional Carbon nitrogen single crystal alloy of the invention
Experiment is gone.Specific embodiment is as follows：
(persursor material is penta chloropyridine molecule, and copper single crystal is (111) crystal face, and argon ion sputtering device is Omicron public
The ISE5Ion Source of department, instrument is the sample of the molecular beam epitaxy in the PSTM device of Createc companies
Prepare cavity)
1. the treatment of pair copper (111) single-crystal surface, obtains clean metal single crystal surface
The single crystal Cu that will be cleaned up is put into vacuum chamber, using argon ion sputtering device to single crystal Cu surface at
Reason, the basic vacuum condition of argon ion sputtering is 1x10-3Pa, accelerating potential is 1KV, and process time is 20 minutes or so.Argon from
Sample after sub- sputter process is again in 500 degree of annealing.The above method can process out the substrate surface of atomically flating.Process
Substrate surface afterwards can be observed with low-energy electron diffraction and PSTM.If surface smoothness or cleaning
Degree is undesirable, can repeatedly circulate above-mentioned steps.
2. the copper single crystal substrate after pair treatment is heated
The single crystalline substrate that will be handled well delivers to sample preparation chamber, and is slowly heated between 100 degree to 400 degree, maintains about 30 points
Clock.
3. the copper single crystal substrate surface after the heating deposits penta chloropyridine molecule
Presoma penta chloropyridine molecule after purification, 100 degree or so is slowly heated in sample room, now in sample room
Precursor molecule is gaseous state.Precursor molecule is slowly put into vacuum chamber by microleak valve, make sample preparation chamber air pressure reach 1 to
1x10-7Handkerchief.The Two-dimensional Carbon nitrogen single crystal alloy of different-thickness will be obtained using different molecule air pressure conditions.
4. the temperature of copper single crystal is maintained
Keep substrate temperature about 5 minutes to 2 hours, that is, complete the preparation of New Two Dimensional carbon nitrogen single crystal alloy.Dimension
The time of holding will influence thickness, quality of forming film of sample for growing etc..
Shown in the structural representation such as Fig. 2 (a) for the Two-dimensional Carbon nitrogen single crystal alloy prepared using methods described.In order to enter one
Step obtains the match condition of this Two-dimensional Carbon nitrogen single crystal alloy and the lattice structure of copper (111) substrate, and we are in relatively low presoma
The Two-dimensional Carbon nitrogen single crystal alloy that molecule grown at atmospheric pressure goes out less than layer is covered in the surface of copper (111), and such as low temperature scanning tunnel shows
Shown in micro mirror Fig. 2 (b), wherein dotted line is the lattice on copper (111) surface, and its lattice parameter is 0.256 nanometer, and solid line is Two-dimensional Carbon
The lattice of nitrogen single crystal alloy, its lattice parameter is 0.44 nanometer.Compared with the schematic diagram of Fig. 2 (a), this Two-dimensional Carbon can be obtained
Nitrogen single crystal alloy has hexagoinal lattice, and nitrogen therein adulterates in order.Two-dimensional Carbon nitrogen single crystal alloy prepared by methods described is larger
Boundary surface pattern is as shown in figure 4, this image is the acquisition on the low-temperature scanning tunneling microscope of Createc companies, experiment
Temperature is liquid nitrogen temperature (- 193 degree).The visible carbon nitrogen single crystal alloy formed on copper (111) surface has hexagonal Mi Dui's in figure
Colloidal particles, the lattice parameter of this structure is 0.44 nanometer, is that can obtain by the tape measure given in STM images,
As described Two-dimensional Carbon nitrogen single crystal alloy.
The Two-dimensional Carbon nitrogen single crystal alloy of the growth can be transferred on other substrates with bubble method, comprised the following steps that：
1. a strata methyl methacrylate (PMMA) is covered on the Two-dimensional Carbon nitrogen single crystal alloy/copper surface to be heated to
170 degree, solidify polymethyl methacrylate；
2. polymethyl methacrylate/Two-dimensional Carbon nitrogen single crystal alloy/copper is put into the hydrogen of 0.5-1 mol/Ls as negative electrode
In sodium oxide molybdena electrolyte, and anode is made with platinum, be passed through 1-2 amperes of electric current, the bubble hydrogen produced by electrolysis water makes poly- methyl
Methyl acrylate/Two-dimensional Carbon nitrogen single crystal alloy is stripped down from copper substrate；
3. the polymethyl methacrylate of above-mentioned stripping/Two-dimensional Carbon nitrogen single crystal alloy is transferred on other substrates, passed through
Heating removal polymethyl methacrylate, you can obtain the Two-dimensional Carbon nitrogen single crystal alloy on required substrate.
Embodiment
Embodiment 1
In the present embodiment, persursor material is penta chloropyridine molecule, and copper single crystal is (111) crystal face, argon ion sputtering dress
The ISE5Ion Source of Omicron companies are set to, instrument is the molecule in the PSTM device of Createc companies
The sample preparation cavity of beam epitaxy.
Follow the steps below：
1. the treatment of pair copper (111) single-crystal surface, obtains clean metal single crystal surface
The single crystal Cu that will be cleaned up is put into vacuum chamber, using argon ion sputtering device to single crystal Cu surface at
Reason, the basic vacuum condition of argon ion sputtering is 1x10-3Pa, accelerating potential is 1KV, and process time is 20 minutes or so.Argon from
Sample after sub- sputter process is again in 500 degree of annealing.The above method can process out the substrate surface of atomically flating.Process
Substrate surface afterwards can be observed with low-energy electron diffraction and PSTM.If surface smoothness or cleaning
Degree is undesirable, can repeatedly circulate above-mentioned steps.
2. the copper single crystal substrate after pair treatment is heated
The single crystalline substrate that will be handled well delivers to sample preparation chamber, and is slowly heated to 300 degree, maintenance about 30 minutes.
3. the copper single crystal substrate surface after the heating deposits penta chloropyridine molecule
Presoma penta chloropyridine molecule after purification, 100 degree or so is slowly heated in sample room, now in sample room
Precursor molecule is gaseous state.Precursor molecule is slowly put into vacuum chamber by microleak valve, sample preparation chamber air pressure is reached 10-5
Handkerchief, is kept for 20 minutes.
4. the temperature of copper single crystal is maintained
Keep substrate temperature about 30 minutes, that is, complete the preparation of New Two Dimensional carbon nitrogen single crystal alloy.
5. tunnel microscope experiment is scanned
By in the incoming PSTM device of Two-dimensional Carbon nitrogen single crystal alloy for preparing and completing, liquid nitrogen temperature is cooled to
Degree (- 193 degree).By measurement, the PSTM image of Two-dimensional Carbon nitrogen single crystal alloy atomic resolution can be obtained.
Measure dI, dV signal exported by lock-in amplifier, you can obtain the scanning tunnel spectrum of Two-dimensional Carbon nitrogen single crystal alloy.
Scanning tunnel spectrum such as Fig. 5 (a) institutes of the Two-dimensional Carbon nitrogen single crystal alloy prepared by the method described in embodiment 1
Show there is obvious " gap " structure at -1.2 electron volts, the point is the position of dirac point.For this Two-dimensional Carbon nitrogen monocrystalline
What alloy theory was calculated due to the orderly doping of nitrogen, can be similar to the dirac in Graphene band structure with as shown in Fig. 5 (b)
Point is pulled down to 1.23 electron-volts below Fermi surface of position, " gap " structure at -1.2 electron-volts measured with experiment
It is very identical.Show that this New Two Dimensional carbon nitrogen single crystal alloy is metallicity.Band structure according to theoretical calculation and
The density of states, using formulaThe carrier concentration of this Two-dimensional Carbon nitrogen single crystal alloy is calculated, be 6.4 ×
1014cm-2.Wherein g (E) is the density of states, EfAnd EDIt is respectively the energy of fermi level and dirac point, A is to calculate selected super born of the same parents
Area.
However, traditional nitrogen-doped graphene dirac point is pulled down to 0.3 electron-volt below Fermi surface.According to ideal
Linear response relationship estimation carrier concentration near Graphene dirac point,About 5.4 × 1012cm-2。
Wherein,It is Planck's constant divided by 2 π, VFIt is Fermi velocity 106m/s.(referring to Liuyan Zhao et al.,
Visualizing Individual Nitrogen Dopants in Monolayer Graphene.Science, 2011,
333,999-1003.) carrier concentration of this New Two Dimensional carbon nitrogen single crystal alloy is estimated using this approximation relation, about
It is 1 × 1014cm-2, with the same magnitude of above theoretical calculation, it is far longer than traditional nitrogen-doped graphene.This also indicates that the life
Two-dimensional Carbon nitrogen single crystal alloy long can be applied to high carrier concentration, high conductivity, and (physically high carrier concentration i.e. correspondence is high
Electrical conductivity), the transparency electrode of high mobility and related device.
Comparative example 1
Referring to document Liuyan Zhao et al., Visualizing Individual Nitrogen Dopants in
Monolayer Graphene.Science, 2011,333,999-1003, follow the steps below experiment：
1. copper substrate is heated to 1000 degree in the atmosphere of hydrogen of 0.055torr, is kept for 10 minutes；
2. by air pressure for the mixed gas of the methane, hydrogen and ammonia of 1.9torr are passed through, 1000 degree are heated to, keep 18
Minute；
3. normal temperature is down to.
From the result of above-mentioned document can be seen that the method growth sample nitrogen doped concentration low (0.23%-0.35%) and
Doping is unordered.It is Graphene that the PSTM figure provided by document can be seen that most of within the specific limits, only
A small amount of bright spot represents nitrogen-atoms, illustrates that the sample nitrogen doped concentration of the method growth is low, and the size of bright spot and be distributed
Entirely without rule, the sample nitrogen for illustrating the method growth is unordered doping.
Comparative example 2
In this comparative example, persursor material is Pyridine Molecules, and copper single crystal is (111) crystal face, and argon ion sputtering device is
The ISE5Ion Source of Omicron companies, instrument is outside the molecular beam in the PSTM device of Createc companies
The sample preparation cavity for prolonging.
Follow the steps below：
1. the treatment of pair copper (111) single-crystal surface, obtains clean metal single crystal surface
The single crystal Cu that will be cleaned up is put into vacuum chamber, using argon ion sputtering device to single crystal Cu surface at
Reason, the basic vacuum condition of argon ion sputtering is 1x10-3Pa, accelerating potential is 1KV, and process time is 20 minutes or so.Argon from
Sample after sub- sputter process is again in 500 degree of annealing.The above method can process out the substrate surface of atomically flating.Process
Substrate surface afterwards can be observed with low-energy electron diffraction and PSTM.If surface smoothness or cleaning
Degree is undesirable, can repeatedly circulate above-mentioned steps.
2. the copper single crystal substrate after pair treatment is heated
The single crystalline substrate that will be handled well delivers to sample preparation chamber, and is slowly heated to 500 degree or so, maintenance about 30 minutes.
3. the copper single crystal substrate surface after the heating deposits Pyridine Molecules
Presoma Pyridine Molecules after purification, 100 degree or so are slowly heated in sample room, now the forerunner in sample room
Body molecule is gaseous state.Precursor molecule is slowly put into vacuum chamber by microleak valve, sample preparation chamber air pressure is reached 10-5Handkerchief.
4. the temperature of copper single crystal is maintained
Keep substrate temperature about 20 minutes.
The PSTM of the product prepared by the method described in comparative example 2 is as shown in Figure 6, it can be seen that
The brightness unevenness of image is even, and nitrogen is unordered doping in illustrating the nitrogen-doped graphene of such scheme growth, electronics distribution in sample
It is uneven result in it is bright dark uneven on image.And there is no the periodic structure for stabilization occur to illustrate that the program grows in figure yet
Nitrogen-doped graphene in nitrogen be unordered doping.
Embodiment 2
In the present embodiment, persursor material is penta chloropyridine molecule, and copper single crystal is (111) crystal face, argon ion sputtering dress
The ISE5Ion Source of Omicron companies are set to, instrument is the molecule in the PSTM device of Createc companies
The sample preparation cavity of beam epitaxy.
Follow the steps below：
1. the treatment of pair copper (111) single-crystal surface, obtains clean metal single crystal surface
The single crystal Cu that will be cleaned up is put into vacuum chamber, using argon ion sputtering device to single crystal Cu surface at
Reason, the basic vacuum condition of argon ion sputtering is 1x10-3Pa, accelerating potential is 1KV, and process time is 20 minutes or so.Argon from
Sample after sub- sputter process is again in 500 degree of annealing.The above method can process out the substrate surface of atomically flating.Process
Substrate surface afterwards can be observed with low-energy electron diffraction and PSTM.If surface smoothness or cleaning
Degree is undesirable, can repeatedly circulate above-mentioned steps.
2. the copper single crystal substrate after pair treatment is heated
The single crystalline substrate that will be handled well delivers to sample preparation chamber, and is slowly heated to 300 degree or so, maintenance about 30 minutes.
3. the copper single crystal substrate surface after the heating deposits penta chloropyridine molecule
Presoma penta chloropyridine molecule after purification, 100 degree or so is slowly heated in sample room, now in sample room
Precursor molecule is gaseous state.Precursor molecule is slowly put into vacuum chamber by microleak valve, sample preparation chamber air pressure is reached respectively
To 1x10-6、1x10-5And 1x10-3Handkerchief, is kept for 20 minutes.The two dimension of different-thickness will be obtained using different molecule air pressure conditions
Carbon nitrogen single crystal alloy.
4. the temperature of copper single crystal is maintained
Keep substrate temperature about 30 minutes, that is, complete the preparation of New Two Dimensional carbon nitrogen single crystal alloy.
By the method described in embodiment 2 in 1x10-6、1x10-5And 1x10-3The scanning-tunnelling of the product that handkerchief is prepared shows
Micro mirror figure is respectively as shown in Fig. 7 (a), (b), (c), it can be seen that in the Two-dimensional Carbon nitrogen single crystal alloy of the different grown at atmospheric pressure
The periodic structure of stabilization is respectively provided with, it is 0.44 nanometer, explanation that lattice parameter can be obtained by scale given in image, after measurement
Nitrogen is orderly to be entrained in described Two-dimensional Carbon nitrogen single crystal alloy.
Embodiment 3
In the present embodiment, persursor material is penta chloropyridine molecule, and copper single crystal is (111) crystal face, argon ion sputtering dress
The ISE5Ion Source of Omicron companies are set to, instrument is the molecule in the PSTM device of Createc companies
The sample preparation cavity of beam epitaxy.
Follow the steps below：
1. the treatment of pair copper (111) single-crystal surface, obtains clean metal single crystal surface
The single crystal Cu that will be cleaned up is put into vacuum chamber, using argon ion sputtering device to single crystal Cu surface at
Reason, the basic vacuum condition of argon ion sputtering is 1x10-3Pa, accelerating potential is 1KV, and process time is 20 minutes or so.Argon from
Sample after sub- sputter process is again in 500 degree of annealing.The above method can process out the substrate surface of atomically flating.Process
Substrate surface afterwards can be observed with low-energy electron diffraction and PSTM.If surface smoothness or cleaning
Degree is undesirable, can repeatedly circulate above-mentioned steps.
2. the copper single crystal substrate after pair treatment is heated
The single crystalline substrate that will be handled well delivers to sample preparation chamber, and is slowly heated to 300 degree and 500 degree, about 30 points of maintenance respectively
Clock.
3. the copper single crystal substrate surface after the heating deposits penta chloropyridine molecule
Presoma penta chloropyridine molecule after purification, 100 degree or so is slowly heated in sample room, now in sample room
Precursor molecule is gaseous state.Precursor molecule is slowly put into vacuum chamber by microleak valve, reaches sample preparation chamber air pressure
1x10-5Handkerchief, is kept for 20 minutes.
4. the temperature of copper single crystal is maintained
Keep substrate temperature about 20 minutes, that is, complete the preparation of New Two Dimensional carbon nitrogen single crystal alloy.
Distinguished in the 300 degree and 500 degree PSTM figures of the product prepared by the method described in embodiment 3
As shown in Fig. 7 (b) and Fig. 8, it can be seen that the Two-dimensional Carbon nitrogen single crystal alloy grown under the different temperatures is respectively provided with stabilization
Periodic structure, lattice parameter can be obtained by scale given in image, after measurement for 0.44 nanometer, illustrate the orderly doping of nitrogen
In described Two-dimensional Carbon nitrogen single crystal alloy.The periodicity of Fig. 8 can be with shadow not as all right bright different temperatures of periodicity of Fig. 7 (b)
Ring the synthesis quality of Two-dimensional Carbon nitrogen single crystal alloy.
Embodiment 4
In the present embodiment, persursor material is penta chloropyridine molecule, and copper single crystal is (111) crystal face, argon ion sputtering dress
The ISE5Ion Source of Omicron companies are set to, instrument is the molecule in the PSTM device of Createc companies
The sample preparation cavity of beam epitaxy.
Follow the steps below：
1. the treatment of pair copper (111) single-crystal surface, obtains clean metal single crystal surface
The single crystal Cu that will be cleaned up is put into vacuum chamber, using argon ion sputtering device to single crystal Cu surface at
Reason, the basic vacuum condition of argon ion sputtering is 1x10-3Pa, accelerating potential is 1KV, and process time is 20 minutes or so.Argon from
Sample after sub- sputter process is again in 500 degree of annealing.The above method can process out the substrate surface of atomically flating.Process
Substrate surface afterwards can be observed with low-energy electron diffraction and PSTM.If surface smoothness or cleaning
Degree is undesirable, can repeatedly circulate above-mentioned steps.
2. the copper single crystal substrate after pair treatment is heated
The single crystalline substrate that will be handled well delivers to sample preparation chamber, and is slowly heated to 300 degree or so, maintenance about 30 minutes.
3. the copper single crystal substrate surface after the heating deposits penta chloropyridine molecule
Presoma penta chloropyridine molecule after purification, 100 degree or so is slowly heated in sample room, now in sample room
Precursor molecule is gaseous state.Precursor molecule is slowly put into vacuum chamber by microleak valve, reaches sample preparation chamber air pressure
1x10-5Handkerchief, is kept for 10 minutes and 20 minutes respectively.
4. the temperature of copper single crystal is maintained
Keep substrate temperature 30 minutes, that is, complete the preparation of New Two Dimensional carbon nitrogen single crystal alloy.
By the method holding 10 minutes described in embodiment 4 and the PSTM figure of the product prepared for 20 minutes
Respectively as shown in Fig. 9 and Fig. 7 (b), it can be seen that the Two-dimensional Carbon nitrogen single crystal alloy grown under the different time is respectively provided with surely
Fixed periodic structure, lattice parameter can be obtained by scale given in image, after measurement for 0.44 nanometer, illustrate that nitrogen is orderly
It is entrained in described Two-dimensional Carbon nitrogen single crystal alloy.
Above-described specific implementation method, has been carried out specifically to the purpose of the present invention, technical scheme and beneficial effect
It is bright.Should be understood that and the foregoing is only specific embodiment of the invention and oneself, be not intended to limit the invention, it is all at this
Within the spirit and principle of invention, any modification, equivalent substitution and improvements done etc. should be included in protection model of the invention
Within enclosing.
Claims (10)
1. a kind of Two-dimensional Carbon nitrogen single crystal alloy, carbon skeleton of the Two-dimensional Carbon nitrogen single crystal alloy comprising Graphene and doping nitrogen are former
Son, wherein the doping nitrogen-atoms replaces part carbon atom to form the two-dimensional superlattice knot of nitrogen in the carbon skeleton of the Graphene
Structure, the lattice size of the superlattices is 0.4 nanometer to 0.5 nanometer.
2. the Two-dimensional Carbon nitrogen single crystal alloy described in claim 1, wherein the superlattices are substantially made up of hexagoinal lattice.
3. the Two-dimensional Carbon nitrogen single crystal alloy described in claim 1, wherein nitrogen-atoms is entrained in the skeleton of Graphene in order.
4. a kind of preparation method of Two-dimensional Carbon nitrogen single crystal alloy, the described method comprises the following steps：
A) metal substrate surface is processed, to obtain smooth clean surface；
B) the smooth clean surface is heated；
C) one layer of precursor molecule is deposited on the surface heated；
D) continue to heat to maintain temperature to form Two-dimensional Carbon nitrogen single crystal alloy；
Wherein described precursor molecule is perhalogeno Pyridine Molecules.
5. method according to claim 4, wherein the metal substrate is copper.
6. method according to claim 5, wherein the surface of the copper substrate is (111) crystal face.
7. method according to claim 4, wherein the heating smooth clean surface is to 100 to 400 in step b)
℃。
8. method according to claim 4, wherein step a)-d) completed in high vacuum environment, vacuum is 1 × 10-3To 1
×10-8Handkerchief.
9. method according to claim 4, wherein when driving body molecule before deposition, the air pressure control of precursor molecule is existed
1 handkerchief is to 1 × 10-7Handkerchief.
10. method according to claim 4, heating and continuous 5 minutes to 2 hours in wherein step d).
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| US20200346933A1 (en) * | 2017-09-29 | 2020-11-05 | Japan Science And Technology Agency | Heteroelement-Containing Graphene |
| CN113136548B (en) * | 2020-01-17 | 2022-05-31 | 中国科学院大连化学物理研究所 | Method for preparing nano material layer on surface of metal single crystal by self-assembly of tolane |
| CN114622163B (en) * | 2020-12-10 | 2022-12-27 | 中国科学院大连化学物理研究所 | Simple and controllable molecular evaporation method |
| CN115011923A (en) * | 2022-07-04 | 2022-09-06 | 昆明理工大学 | High-density nitrogen atom doped two-dimensional single-layer covalent grid structure and preparation method thereof |
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| CN102605339A (en) * | 2012-02-22 | 2012-07-25 | 中国科学院化学研究所 | Regular nitrogen doped graphene and preparation method thereof |
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| CN102605339A (en) * | 2012-02-22 | 2012-07-25 | 中国科学院化学研究所 | Regular nitrogen doped graphene and preparation method thereof |
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