CN108559973A - A kind of method that two dimension hexagonal boron nitride film doping obtains p-type conductance - Google Patents
A kind of method that two dimension hexagonal boron nitride film doping obtains p-type conductance Download PDFInfo
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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Abstract
A kind of method that two dimension hexagonal boron nitride film doping obtains p-type conductance, is related to semiconductive thin film p-type conductance.Three-temperature-zone dual circuit chemical gas-phase deposition system is set；First the first pipeline of warm area places BN predecessors, and second the second pipeline of warm area places the sources Mg predecessor, third warm area placing response substrate；Vacuum degree control is first extremely less than 10 by growth phase before starting‑4torr；800~1000 DEG C of annealings are carried out to substrate in the atmosphere of hydrogen and argon gas；Three-temperature-zone is heated up to setting temperature respectively, and the first warm area is low-temperature space, 70~100 DEG C of temperature；Second warm area is middle warm area, 400~900 DEG C of temperature；Third warm area is high temperature reaction zone, 900~1200 DEG C of temperature；First pipeline and the second pipeline lead to carrier gas, carry predecessor and impurity source to reaction zone hybrid reaction；Growth terminates, and room temperature is naturally cooled in protective gas, obtains two-dimentional hexagonal boron nitride film doping and obtains p-type conductance.
Description
Technical field
The present invention relates to semiconductive thin film p-type conductances, and p is obtained more particularly, to a kind of two-dimentional hexagonal boron nitride film doping
The method of type conductance.
Background technology
Two-dimentional hexagonal boron nitride (h-BN) and graphene have similar two-dimensional structure, it is excellent broad stopband again simultaneously
Semi-conducting material, energy gap reach 6eV, possess huge exploitation potential in the following sub- device of short wavelength's 2 D photoelectric and wide answer
Use foreground.It is analyzed from the manufacture angle of opto-electronic device, in order to realize that photoelectric converting function, electrical pumping and pn-junction are still main
Flow structure, that is to say, that move towards practical devices application from materials synthesis, the preparation of p, N-shaped conductive layer usually all plays key
Role, therefore to realize the following h-BN 2 D photoelectrics device application, the research of p/n conductivity type thin layers occupies the most extremely
Close important strategic hinge status.Once the pn-junction structure of high quality is achieved, will be easy to be prepared into receiving for h-BN films
Rice photoelectric device.
But the intrinsic defect (dislocation, vacancy etc.) of two-dimentional h-BN films forms deeper alms giver, acceptor-type defect energy level
(>2.0eV), activation energy is very high, it is difficult to obtain n/p type electric conductivities, therefore adulterate just become that h-BN film conductances realize must
By road.Had some relevant documents theoretically discuss the n of h-BN, p-type doping possibility (V.Wang, N.Ma,
H.Mizuseki,Y.Kawazoe.First-principles study of intrinsic defect properties in
hexagonal BN bilayer and monolayer[J].Solid State Communications,2012,152(9):
816-820), the doping but really in two-dimensional film is successful not yet.More representative example is texas,U.S industry
Jiang seminar of university (S.Majety, J.Li, X.K.Cao, R.Dahal, B.N.Pantha, J.Y.Lin,
H.X.Jiang.Epitaxial growth and demonstration of hexagonal BN/AlGaN p-n
junctions for deep ultraviolet photonics[J].Applied Physics Letters,2012,100
(6):4.) it, recently using the BN epitaxial layers (300nm) of Mg doping, successfully instead of the p-type layer of AlGaN and applies dark purple
In outer AlGaN bases LED, prepared by the device to succeed, show lower resistivity (2.3 Ω cm；And AlN:The resistance of Mg
Rate is then up to 104 Ω cm), to solve the problems, such as that the p-type contact in AlN devices is difficult to realize propose new direction.This demonstrate
There is the feasibility that conductance is realized in doping in the intrinsic propesties of the h-BN materials, and have on p-type Effective Conductivity and be better than passing
The characteristic of system wide bandgap semiconductor (such as AlGaN).But h-BN forbidden bands are very wide (up to 5~6eV), depth is more readily formed in impurity
Energy level, ionization difficulty are big.And when its Spatial Dimension is reduced to the scale of atomic monolayer 2D, degree of difficulty is by bigger.This is mesh
The huge challenge of preceding h-BN research work.
Invention content
The present invention is directed to for the p-type doping that can not effectively carry out h-BN at present, pn-junction in LED be provided, by simple
The method of chemical vapor deposition CVD obtains the h-BN for having stability, it is made to carry out Mg originals on the basis of original excellent performance
The p-type doping of son, applies a kind of two-dimentional hexagonal boron nitride film doping of purpose in pn-junction to obtain to reach as p-type pole
The method for obtaining p-type conductance.
The present invention includes the following steps：
1) three-temperature-zone dual circuit chemical gas-phase deposition system is set；
2) first the first pipeline of warm area places BN predecessors, and second the second pipeline of warm area places the sources Mg predecessor, third temperature
Area's placing response substrate；
3) first by vacuum degree control to less than 10 before growth phase starts-4torr；
4) 800~1000 DEG C of annealings are carried out to substrate in the atmosphere of hydrogen and argon gas；
5) three-temperature-zone is heated up to setting temperature respectively, and the first warm area is low-temperature space, 70~100 DEG C of temperature；Second warm area is
Middle warm area, 400~900 DEG C of temperature；Third warm area is high temperature reaction zone, 900~1200 DEG C of temperature；
6) the first pipeline and the second pipeline lead to carrier gas respectively, carry predecessor and impurity source to reaction zone hybrid reaction；
7) growth terminates, and room temperature is naturally cooled in protective gas, obtains two-dimentional hexagonal boron nitride film doping and obtains p-type
Conductance.
In step 1), setting three-temperature-zone dual circuit chemical gas-phase deposition system, including three independent temperature control warm areas
With two separate gas pipelines, and pipeline, with quartz tube device, tolerable high temperature simultaneously has air-tightness.
In step 2), the BN predecessors can be the solid state reagents of B, N mixing, including borazane, borazine powder
The mixing at one or both of end；The sources Mg predecessor can be nitridation magnesium dust, magnesium powder etc.；Metal can be used in the reaction substrate
Film-substrate or other semiconductor substrates, the metallic film substrate can be the elemental metals substrates such as copper foil, platinum foil, nickel foil, or
Two of which and two or more alloy substrates；The semiconductor substrate can be Si, SiO2, GaAs, sapphire, GaN substrate
Deng.
It is described that vacuum degree control is extremely less than 10 in step 3)-4Torr can utilize mechanical pump and molecular pump by tubular type chamber
Interior air pressure is evacuated to 10-4Torr is hereinafter, ensure that the pollutants such as oxygen are eliminated in air.
In step 4), by third temperature-raising region temperature raising to 800~1000 DEG C, and a certain proportion of hydrogen and argon gas mixing are passed to
Gas is made annealing treatment about 20~60min to substrate surface oxide layer, to improve the crucial skill of two-dimensional film crystal quality
Art.
In step 6), first pipeline and the second pipeline lead to carrier gas respectively, carry predecessor and impurity source to reaction
The specific method of area's hybrid reaction can be：When three warm areas all reach setting reaction temperature, sample preparation reaction starts, respectively
It is passed through H from the first pipeline2The carrier gas of (8sccm) and Ar (20sccm) as conveying Borazane steam, the second pipeline are passed through H2
(4sccm) and Ar (10sccm) are as conveying Mg3N2The carrier gas of steam, gas flow and ratio can be according to doping concentrations and reaction
Speed is necessarily drawn to, and the first pipeline and the second pipeline gas carry predecessor to third warm area part and mix, and carry out anti-
It answers, generates Mg and adulterate h-BN two-dimensional films.
In step 7), after growth, heating schedule is closed, and continue in outer tube to be passed through H2(5~10sccm) and Ar
(10~20sccm) is used as protective gas, and room temperature to be dropped to takes out sample.
The present invention key be：1) present invention designs a kind of chemical vapor deposition CVD equipment conduct of three-temperature-zone dual circuit
Key Experiment device；2) use borazane as B, N predecessor, nitrogenous magnesium source (Mg3N2) as doping predecessor, purity is
99.99% copper foil is as substrate；3) first the first pipeline of warm area setting tubule of three-temperature-zone is ventilated, built-in B, N predecessor,
One sources Mg predecessor is set in second the second pipeline of warm area；4) it is annealed using hydrogen and argon gas as mixed gas, hydrogen
Gas plays the role of removing surface impurity, and argon gas plays the role of the step of protection, annealing terminates to be grown again；5) the first and second pipe
Road controls the mixed carrier gas of certain proportion and flow respectively, and control carries the supply of predecessor；6) growth terminates to pass through protection
The wherein form of Temperature fall.
The present invention utilizes the above key point, contrived experiment scheme, and obtains good desired effect, completes stable h-BN
Growth, and carried out the p-type doping of Mg, and the success of doping is demonstrated by a series of test.
The present invention devises the CVD reaction systems of three-temperature-zone dual circuit, and two are successfully realized in discrete temperature control and single-chamber body
Effective p-type doping of h-BN semiconductive thin films is tieed up, and obtains good p-type electric current, and still can guarantee that h-BN's is a series of
Good characteristic, the p-type electric-conducting layer being properly applied in the following tradition or the sub- device of 2 D photoelectric, can also be used as and graphene phase
The dielectric layer of the electronic device of pass.The present invention is by using Mg3N2Mg impurity sources with N element, as the doped source of Mg,
It is set to evaporate and effectively provide Mg foreign atoms under high temperature.Its heating temperature, separate carrier gas pipe are controlled by independent warm area
Road controls its carrying amount, and Mg atoms, which are introduced h-BN lattices, forms displacement doping, obtains the uniform full two-dimensional of effective p-type conductance
Film.
Description of the drawings
Fig. 1 is the effect simulation figure of experimental facilities of the present invention.
Fig. 2 is the atomistic simulation figure that Mg adulterates h-BN.
Fig. 3 be 30min doped growings after surface condition SEM figure.
Fig. 4 is to prove the successful XPS figures of Mg source dopings.
Fig. 5 is to prove the successful auger electron spectroscopy of Mg source dopings (AES).
The four probe station test result figures that the electric conductivity of sample is done after Fig. 6 adulterates for proof.
Specific implementation mode
Below by taking p-type h-BN doping as an example, in conjunction with attached drawing, the present invention is further illustrated.
1, three-temperature-zone dual circuit chemical gas-phase deposition system.
1) system, including three independent temperature control warm areas and two separate gas pipelines.Each warm area is about 30cm, center
For flat-temperature zone, length about 10cm is filled between warm area with fibrous ceramic insulation, obstructs the mutual hot shadow between adjacent warm area
It rings, each warm area is controlled by independent temperature control module.
2) reaction cavity uses quartz ampoule structure, is constituted with tubule dual pipeline with managing greatly, big pipe provide vacuum environment with
Whole cavity gaseous environment；Tubule constitutes independent ventilation pipeline, point the first pipeline and the second pipeline, directly with independent gas circuit phase
Even, the first pipeline and the second length of pipe pass through the first and second warm areas, outlet setting and third warm area section start.
3) there is mass flow controller to connect gas cylinder outside the first and second pipelines, accurately control gas mass flow,
And do the mixed gas supply of multiple gases.
4) big tube chamber rear end connects vacuum pump, including mechanical pump and molecular pump two-stage vacuum device, can be evacuated to cavity
Required vacuum degree, it is ensured that reaction is protected from airborne pollution, while taking the exhaust gas generated in reaction process and by-product out of cavity.
2, the synthesis of p-type doping h-BN.
1) preparation before reacting：First, predecessor is weighed,
Predecessor is borazane (ammonia borine), and 0.0120g is weighed on counter balance using pan paper,
Holding and then be put into a diameter using the small container of an a height of 4cm0.5cm0.2cm of length and width is about
In tubule built in the first pipeline of 1cm, it is in the first warm area position, there will be the small container of predecessor ammonia borine to shift first onto later
The center of warm area.
The sources Mg are Mg3N2, 0.05g is weighed on counter balance using pan paper, equally using the same small of a length, width and height
Container holds the second warm area position for being placed in the second pipeline.
The Cu foil substrates of certain size are placed in the center of third warm area.
2) stage of reaction is tested：
A, after the completion of above all of preparation, tubular type intracavitary air pressure is evacuated to 10 using mechanical pump and molecular pump- 4Torr is hereinafter, ensure that the pollutants such as oxygen are eliminated in air；Then it by third temperature-raising region temperature raising to 800~1000 DEG C, and passes to
A certain proportion of hydrogen and argon gas mixed gas are made annealing treatment about 20~60min to substrate, remove substrate surface oxide layer
Pollutants etc. are adsorbed with other.
B, after the completion of annealing, third warm area reaction chamber temperature is promoted to reaction temperature (900~1200 DEG C), meanwhile,
To the first and second warm area is heated to set-point temperature.First warm area is low-temperature space, selectes preheating temperature in (70~100 DEG C)；The
Two warm areas are middle warm area, and control temperature is in (700~900 DEG C)；
C, when three warm areas all reach setting reaction temperature, sample preparation reaction starts, and is passed through respectively from the first pipeline
H2The carrier gas and the second pipeline of (8sccm) and Ar (20sccm) as conveying Borazane steam are passed through H2(4sccm) and Ar
(10sccm) is as conveying Mg3N2The carrier gas of steam.Gas flow and ratio can be needed according to doping concentration and reaction speed by than
Example regulation and control, two-way gas carry predecessor to third warm area part and mix, reacted, and generate Mg and adulterate h-BN two-dimensional films.
D, it waits for after reaction, closing heating schedule, and continues in outer tube to be passed through H2(5~10sccm) and Ar (10~
20sccm) it is used as protective gas, finally room temperature to be dropped to, closes vacuum pump, open cavity, takes out sample.
3) preservation of laboratory sample：After reaction, growth there is into h-BN:The Cu foils of Mg take out, and differentiate front and do note
Number, it is placed in dry free of contamination environment.
3, composition test analysis is carried out to the two-dimentional h-BN films of p-type doping.
The h-BN samples of Mg doped growings after growth carry out the sight of SEM patterns first after being taken out in quartz ampoule
It examines, analyzes growth situation and mechanism of doping effect.By proving that the introducing in the sources Mg does not influence the growth of h-BN, and need to grow
The h-BN samples of the Mg doping completely covered.So keep other experiment parameters constant, increase growth time to 30min, make its by
It is gradually combined into film, as shown in Fig. 2, the h-BN of Mg doping combines and is covered in Cu foils surface substantially, it can by SEM figures
There is the phenomenon that some fillets are not fully engaged to observe still.This explanation is grown and is stablized by the increase of growth time, after
The long growth time that renews can obtain the h-BN of full single layer:Mg films.
For obtained h-BN:Mg film samples it may first have to prove that Mg elements successfully mix h-BN nanometer thins
Film also needs to determine whether doping is Effective Doping, and whether sample realizes p-type electric-conducting, therefore to h-BN thereafter:Mg film samples into
A series of test experiments of having gone characterize.
It uses XPS spectrum to test first, determines the elemental composition of film.By h-BN:Mg films are transferred on SiO2/Si substrates
It is tested.The peak position of N1s and B1s is obtained in power spectrum respectively in 398.2 and 190.75eV, is tied with obtained by pure h-BN films
Fruit is almost the same, and it is BN to confirm it.In addition to this, also measuring combination can be in the electron spectrum small peak at 305eV, shown in Fig. 3.
It can be corrected in 284.5eV according to the combination of C-C keys, and the peak position obtained by Gauss curve fitting, can corresponded to from xps energy spectrum element
Characterization is found, the Auger peak place which is Mg.Therefore it can tentatively show that h-BN nano thin-films surface has the presence of Mg elements.
Since the measurement area of XPS is larger, still suspect whether this Mg elements peak is to come from surface impurity particle (Mg3N2), rather than incorporation
The Mg atoms of h-BN lattices are contributed.
Therefore Auger electron spectroscopy (AES) is further used, surface layer elemental composition is measured.When due to AES spectral measurements, together
When can use SEM observe surface topography, only selected surface totally agranular region, carried out searching spectrum, avoid impurity particle do
It disturbs.Fig. 4 gives AES spectra measurement result, it can be found that there are three apparent peak positions, corresponds respectively to B KLL, N KLL, Mg
The case where Auger peak position of KLL illustrates that Mg atom contents are less although Mg element peak intensities are weaker, this also complies with impurity doping, this
Data and XPS test results above are mutually coincide, it was demonstrated that Mg impurity is successfully among the lattices of incorporation h-BN films, substantially
The case where eliminating impurity particle.But also one kind may be, and Mg atoms are present in the surfaces h-BN in the form of adsorption, not
Can well and B or N atomic bondings, it is also necessary to more reinforce real data and give to prove.
4, electrical testing analysis is carried out to the two-dimentional h-BN films of p-type doping.
The validity that impurity adulterates in a semiconductor material also needs having for the impurity ionization activation needed for test p-type electric-conducting
Effect property, impurity are mixed with lattice, do not necessarily mean that it obtains effective activation, and intrinsic material is enabled to have conductance
Characteristic.And the acquisition of conductance is only the final purpose of doping.Therefore, electric conductivity further is carried out to the h-BN films after doping
Electrical characterization, look at it whether from the semiconductor transition of insulation be p-type electric-conducting film.
Using probe platform, the h-BN comparative to one group and h-BN:Mg samples have carried out electrical testing, such as Fig. 5 respectively
It is shown.It is that h-BN films are transferred to n-Si substrate surfaces first to measure logic, and the IV that its different location is measured by probe is bent
Line, since n-Si is conductive substrate, if I-V curve is insulating properties, it is insulation film that h-BN films, which can be explained,；Secondly,
Again by h-BN:Mg films are transferred to SiO2In/Si dielectric substrates, in this case, if the film I-V curve measured is conduction
Property, then provable h-BN:Mg films are conductive film.
The results are shown in Figure 6 for test, it is clear that the I-V curve for not doing the h-BN films of any doping presents one
Excellent insulation performance is shown until flowing through sample still without electric current under the voltage of 5V or so without corresponding zero straight line,
Show its high-purity and high quality, this is consistent with the result of preceding chapters and sections.Next test h-BN:The I-V curve of Mg films, makes us
It is desirable that even if on an insulating substrate, it still shows an inclined straight line well, illustrate to have in the case where voltage drives steady
Fixed electric current flows through film surface, confirms effective activation of Mg impurity, provides a large amount of holoe carrier, and it is thin to complete h-BN
The conductance of film is modified.Numerically, under 3V voltages, surface current reaches 10 μ A magnitudes, only single former for one
For the extremely thin film of sublayer, this conductance property has belonged to very excellent.
On the other hand, using Single probe rectification method, determine that its conduction type is p-type, i.e., its majority carrier is hole.It is first
First, the h-BN of 1cm × 1cm is made:Mg/SiO2Sample, and in four angle steaming degree Pt electrodes, anneal 10min at 400 DEG C, realizes
Ohmic contact；Then, a tungsten tipped probe contacts Pt metal electrodes, and another tungsten tipped probe is in direct contact h-BN:Mg film surfaces, shape
At Schottky contacts,；It is tested by IV curves, discovery only in the case of negative voltage, electric current occurs, this has turned out it and has led
Electric type is p-type.
So far, the two-dimentional h-BN films of effective p-type conductance are successfully obtained, there is preferable surface current, while can lead to
The mode for crossing control Mg doping regulates and controls its electric conductivity, this, can predictive of its powerful advantages in the following optoelectronic device applications
As the p-type electric-conducting layer in tradition or the sub- device of 2 D photoelectric, the dielectric with the relevant electronic device of graphene can also be used as
Layer etc..
The present invention uses three-temperature-zone dual circuit chemical vapor deposition (CVD) system, by being put in middle part warm area independent pipeline
The mode of solid-state Mg impurity sources is set, realizes the technology for carrying out Effective Doping to h-BN lattices.Using Mg3N2Powder is mixed as Mg's
Miscellaneous source, evaporated under high temperature (>700 DEG C), under high temperature (>900 DEG C) it thermally decomposes, it is former can effectively to provide Mg doping
Son.Control its heating temperature, separate carrier gas pipe control its carrying amount by independent warm area, respectively by the precursor gas of BN and
Mg steam synchronous transport deposits on Cu foil substrates and grows the h-BN films of Mg doping simultaneously into reaction warm area.This method can
Mg atoms are effectively introduced into h-BN lattices and form displacement doping, obtain the uniform full two-dimensional film of effective p-type conductance.Making side
Method is relatively simple and doping efficiency higher, without being chemically treated and can carry out large-scale industrialization manufacture.With extensive two
Tie up optoelectronic device applications foreground and potentiality to be exploited.
Claims (10)
1. a kind of method that two dimension hexagonal boron nitride film doping obtains p-type conductance, it is characterised in that include the following steps：
1) three-temperature-zone dual circuit chemical gas-phase deposition system is set；
2) first the first pipeline of warm area places BN predecessors, and second the second pipeline of warm area places the sources Mg predecessor, and third warm area is put
Set reaction substrate；
3) first by vacuum degree control to less than 10 before growth phase starts-4torr；
4) 800~1000 DEG C of annealings are carried out to substrate in the atmosphere of hydrogen and argon gas；
5) three-temperature-zone is heated up to setting temperature respectively, and the first warm area is low-temperature space, 70~100 DEG C of temperature；Second warm area is medium temperature
Area, 400~900 DEG C of temperature；Third warm area is high temperature reaction zone, 900~1200 DEG C of temperature；
6) the first pipeline and the second pipeline lead to carrier gas respectively, carry predecessor and impurity source to reaction zone hybrid reaction；
7) growth terminates, and room temperature is naturally cooled in protective gas, obtains two-dimentional hexagonal boron nitride film doping and obtains p-type electricity
It leads.
2. a kind of method that two-dimentional hexagonal boron nitride film doping obtains p-type conductance as described in claim 1, it is characterised in that
In step 1), setting three-temperature-zone dual circuit chemical gas-phase deposition system, including three independent temperature control warm areas and two independences
Gas piping, and pipeline is with quartz tube device.
3. a kind of method that two-dimentional hexagonal boron nitride film doping obtains p-type conductance as described in claim 1, it is characterised in that
In step 2), the solid state reagents that the BN predecessors mix for B, N, including at least one in borazane, borazine powder
Kind.
4. a kind of method that two-dimentional hexagonal boron nitride film doping obtains p-type conductance as described in claim 1, it is characterised in that
In step 2), the sources Mg predecessor is nitridation magnesium dust, magnesium powder.
5. a kind of method that two-dimentional hexagonal boron nitride film doping obtains p-type conductance as described in claim 1, it is characterised in that
In step 2), the reaction substrate use metallic film substrate or other semiconductor substrates, the metallic film substrate be copper foil,
Platinum foil, nickel foil elemental metals substrate or in which at least two alloy substrates.
6. a kind of method that two-dimentional hexagonal boron nitride film doping obtains p-type conductance as described in claim 1, it is characterised in that
In step 2), the semiconductor substrate is Si, SiO2, GaAs, sapphire, GaN substrate.
7. a kind of method that two-dimentional hexagonal boron nitride film doping obtains p-type conductance as described in claim 1, it is characterised in that
It is described that vacuum degree control is extremely less than 10 in step 3)-4Tubular type intracavitary air pressure is evacuated to 10 by torr using mechanical pump and molecular pump-4Torr or less.
8. a kind of method that two-dimentional hexagonal boron nitride film doping obtains p-type conductance as described in claim 1, it is characterised in that
In step 4), by third temperature-raising region temperature raising to 800~1000 DEG C, and logical hydrogen and argon gas mixed gas, to substrate surface oxide layer
Made annealing treatment about 20~60min.
9. a kind of method that two-dimentional hexagonal boron nitride film doping obtains p-type conductance as described in claim 1, it is characterised in that
In step 6), first pipeline and the second pipeline lead to carrier gas respectively, carry predecessor and impurity source to reaction zone hybrid reaction
Specific method be：When three warm areas all reach setting reaction temperature, sample preparation reaction starts, logical from the first pipeline respectively
Enter 8sccm H2Carrier gas with 20sccm Ar as conveying Borazane steam, the second pipeline are passed through 4sccm H2And 10sccmAr
As conveying Mg3N2The carrier gas of steam, gas flow and ratio can be necessarily drawn to according to doping concentration and reaction speed,
First pipeline and the second pipeline gas carry predecessor to third warm area part and mix, and are reacted, and generate Mg and adulterate h-BN bis-
Tie up film.
10. a kind of method that two-dimentional hexagonal boron nitride film doping obtains p-type conductance as described in claim 1, it is characterised in that
In step 7), after growth, heating schedule is closed, and continue in outer tube to be passed through H2It is used as protective gas with Ar, waits dropping to
Room temperature takes out sample；The H2It is 10~20sccm for 5~10sccm, the Ar.
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