CN107460450A - For the device for the gallium aluminium acid bismuth thin film for preparing content gradually variational - Google Patents
For the device for the gallium aluminium acid bismuth thin film for preparing content gradually variational Download PDFInfo
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- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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- C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
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- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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Abstract
A kind of Bi (Al for being used to prepare content gradually variationalxGa1‑x)O3The device of thin-film material, thin-film material uses to react to obtain from restricted adsorption.In by programme controlled each growth cycle, two counters are set to be respectively used to set and control organic silicon source gas pulses, the quantity of organic gallium source gas pulses in each growth cycle, in gradually growth course, the value of one of counter gradually increases, and the value of another counter is gradually reduced.Bi (Al are prepared by using the device of the present inventionxGa1‑x)O3The method of thin-film material, it is possible to achieve content gradually variational, the Bi (Al across quasi- homotype phase boundaryxGa1‑x)O3Thin-film material, and Bi (AlxGa1‑x)O3The controllable precise of film growth thickness.
Description
Technical field
The present invention relates to a kind of preparation facilities of bismuth-based oxide thin-film material, specifically a kind of Bi (AlxGa1-x)O3
The preparation facilities of ferroelectric thin-flim materials.
Background technology
The present invention is Application No. CN201510764503.0 divisional application.
Pb(Zr1-xTix)O3It is a kind of ferroelectricity of excellent performance, piezoelectric.
However, because PZT contains lead element, cause to easily cause the pollution to environment during its production, use.
In American-European many national laws, clear stipulaties limit or prohibit the use of leaded electronic component, this
It greatly affected PZT utilization.
In recent years, Baettig has theoretically foretold Bi (AlxGa1-x)O3(gallium aluminium acid bismuth, be abbreviated as BAG) has and Pb
(Zr1-xTix)O3Same excellent ferroelectricity and dielectric properties, because BAG is lead-free, become PZT potential replacement person.
At room temperature, BiGaO3The space group of (gallic acid bismuth, be abbreviated as BGO) is Pcca, BiAlO3(bismuth aluminate, it is abbreviated as
BAO space group) is R3c, when BGO and BAO forms solid solution Bi (Al according to a certain percentagexGa1-x)O3When, it can also be formed similar
The quasi- homotype phase boundary of PZT material.
But there has been no the Bi (Al of maturation at presentxGa1-x)O3The technology of preparing of material.
The content of the invention
In order to solve prior art problem, it is an object of the invention to provide a kind of Bi for preparing content gradually variational
(AlxGa1-x)O3The device of thin-film material.
Realizing the object of the invention concrete technical scheme is：
A kind of Bi (AlxGa1-x)O3The preparation method of thin-film material, this method raw material using organo-bismuth source, oxygen precursor gas,
Organic silicon source, organic gallium source gas.
Bi (the AlxGa1-x)O3The preparation method of thin-film material, completed using the device specially designed.
Described device includes but is not limited to：Organo-bismuth source container 1, organo-bismuth source capsule road hand-operated valve K1, organo-bismuth source capsule road
Automatic valve AK1, organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas container 2, organic silicon source flue
Road hand-operated valve K2, organic silicon source gas piping automatic valve AK2, organic silicon source gas carrier pipeline quality flow controller MFC2,
Organogallium silicon source container 3, organic gallium source gas piping hand-operated valve K3, organic gallium source gas piping automatic valve AK3, organic gallium source gas
Body gas-carrier pipeline mass flow controller MFC3, oxygen precursor gas source container 4, oxygen precursor gas pipeline hand-operated valve K4, oxygen
Precursor gas pipeline automatic valve AK4, oxygen precursor gas gas-carrier pipeline mass flow controller MFC4, inert gas container 5,
Inert gas piping hand-operated valve K5, vacuum reaction chamber, vacuum meter, vavuum pump, air-inlet of vacuum pump automatic valve AK5, equipment control
Device processed, is provided with electric heater and temperature sensor in vacuum reaction chamber, device controller can be by PLC or FPGA or CPLD or
SCM system or computer or the circuit system specially designed are formed；Organo-bismuth source container 1, organic silicon source gas container 2, oxygen
The container of precursor gas source container 3 is equipped with electric heater and semiconductor cooler；
The outlet of organo-bismuth source container 1 is consecutively connected to organo-bismuth source capsule road hand-operated valve K1, organo-bismuth source capsule by gas piping
Road automatic valve AK1, vacuum reaction chamber, the outlet of organic silicon source gas container 2 are consecutively connected to organic silicon source by gas piping
Gas piping hand-operated valve K2, organic silicon source gas piping automatic valve AK2, vacuum reaction chamber, the outlet of organic gallium source gas container 3
Organic gallium source gas piping hand-operated valve K3, organic gallium source gas piping automatic valve AK3, vacuum are consecutively connected to by gas piping
Reaction chamber, the outlet of oxygen precursor gas source container 4 are consecutively connected to oxygen precursor gas pipeline hand-operated valve by gas piping
K4, oxygen precursor gas pipeline automatic valve AK4, vacuum reaction chamber, the outlet of inert gas container 5 is connected to by gas piping
Inert gas piping hand-operated valve K5, then organo-bismuth source gas-carrier pipeline mass flow controller is connected respectively to by branch line
MFC1, organic silicon source gas carrier pipeline quality flow controller MFC2, the control of organic gallium source gas carrier pipeline quality flow
Device MFC3, oxygen precursor gas gas-carrier pipeline mass flow controller MFC4, organo-bismuth source gas-carrier pipeline mass flow controller
MFC1 outlet is connected to the gas piping between organo-bismuth source capsule road automatic valve AK1 and vacuum reaction chamber by three-way connector
On, organic silicon source gas carrier pipeline quality flow controller MFC2 outlet is connected to organic silicon source gas by three-way connector
On gas piping between body pipeline automatic valve AK2 and vacuum reaction chamber, organic gallium source gas-carrier pipeline mass flow controller
MFC3 outlet is connected to the gas between organic silicon source gas piping automatic valve AK3 and vacuum reaction chamber by three-way connector
On pipeline, oxygen precursor gas gas-carrier pipeline mass flow controller MFC4 outlet is connected to organo-bismuth by three-way connector
On gas piping between source capsule road automatic valve AK4 and vacuum reaction chamber, the outlet of vacuum reaction chamber is sequentially connected by pipeline
To air-inlet of vacuum pump automatic valve AK5, the air inlet of vavuum pump；
Vacuum meter is provided with vacuum chamber；
Organo-bismuth source capsule road hand-operated valve K1, organic silicon source gas piping hand-operated valve K2, organic gallium source gas piping hand-operated valve K3, oxygen
Precursor gas pipeline hand-operated valve K4, inert gas piping hand-operated valve K5 are by operating personnel's manual unlocking, uncontrolled device institute
Control, this design may insure safety；
Vacuum meter, organo-bismuth source capsule road automatic valve AK1, organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source
Pipeline automatic valve AK2, organic silicon source gas carrier pipeline quality flow controller MFC2, organic gallium source gas piping automatic valve
AK3, organic gallium source gas carrier pipeline quality flow controller MFC3, oxygen precursor gas source container 4, oxygen precursor gas pipe
Road automatic valve AK4, oxygen precursor gas gas-carrier pipeline mass flow controller MFC4, vacuum reaction chamber, vavuum pump, vavuum pump enter
Gas port automatic valve AK5, the electric heater in vacuum reaction chamber, temperature sensor and the organo-bismuth source container 1, organo-aluminium
Source gas container 2, organic gallium source gas container 3, the electric heater of oxygen precursor gas source container 4 and semiconductor cooler are logical
Cable connection is crossed to device controller by cable connection to device controller, by the respective work of device controller centralized Control
Make state；
At any one moment, organo-bismuth source capsule road automatic valve AK1, organic silicon source gas piping are made certainly by device controller control
Dynamic valve AK2, organic gallium source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK4 at most only one are in and opened
State is opened, remaining is in closed mode；Or organo-bismuth source capsule road automatic valve AK1, organic silicon source gas piping automatic valve AK2,
Organic gallium source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK4 are completely in closed mode；
The gathered data of temperature sensor by cable transmission to device controller, to realize the PID control of temperature (ratio-product
Point-differential control), the temperature of vacuum reaction chamber can be made quickly and accurately to reach the temperature value of setting；
By device controller control organo-bismuth source container 1, organic silicon source gas container 2, organic gallium source gas container 3, oxygen forerunner
The electric heater of the container of gas source container 4 and the working condition of semiconductor cooler, so that organo-bismuth source container 1, organic
Aluminum source gas container 2, organic gallium source container 3, oxygen precursor gas source container 4 temperature can be with the constant temperature value in setting；
Bi (the AlxGa1-x)O3The preparation method of thin-film material, including but not limited to step in detail below：
A inert gas) is filled with vacuum glove box, following operate is completed in the atmosphere of inert gases of glove box：Will be organic
Bismuth source, organic aluminum source gas, organic gallium source gas are filled into organo-bismuth source container 1, organic silicon source gas container 2, organic respectively
Gallium source gas container 3, then install and connect with respective pipeline；
Because organo-bismuth source, organic aluminum source gas, organic gallium source gas are inflammable and explosive dangerous material, therefore, in filling mistake
The use of vacuum glove box is essential in journey；
B oxygen precursor gas source, inert gas) are filled into oxygen precursor gas source container 3, inert gas container 4 respectively, so
Install and connect with respective pipeline afterwards；
C) backing material of cleaning is dried up with inert gas, is placed into substrate pallet；
D) pallet moves into vacuum reaction chamber together with substrate, opens vavuum pump by device controller, then opens vavuum pump again and enter
Gas port automatic valve AK5, is vacuumized to vacuum reaction chamber；
E organo-bismuth source container 1, organic silicon source gas container 2, organic gallium source gas container 3, oxygen) are set on device controller
The temperature of precursor gas source container 4, organo-bismuth source container 1, organic silicon source gas container 2, organic is controlled by device controller
The working condition of gallium source gas container 3, the electric heater of oxygen precursor source containers 4 and/or semiconductor cooler, so that organo-bismuth
Source container 1, organic silicon source gas container 2, organic gallium source gas container 3, the temperature of oxygen precursor gas source container 4 are maintained and set
Fixed temperature value, make under the temperature value of set each presoma, organo-bismuth source container 1, organic silicon source gas container 2, have
Machine gallium source gas container 3, the steam pressure of oxygen precursor gas source container 4 pass through mass flow control more than inert gas container 5
Pressure after device MFC1, MFC2, MFC3, MFC4 processed in gas piping；
Vacuum chamber is heated by device controller control electric heater, makes pallet in vacuum chamber and substrate temperature whole
It is constant in individual thin film growth process to be in a suitable temperature window in a temperature value, the temperature value；
The suitable temperature window refers to：Within the scope of suitable temperature, i.e., substrate temperature higher than a lowest temperature and
Less than one temperature upper limit, and the flow velocity of precursor gas supply, more than in the case of minimum limit value, the growth rate of film is
One substantially invariable value, flow velocity that the growth rate of film is supplied with precursor gas, carrier gas are the flow velocity, preceding of inert gas
Temperature, substrate temperature, the vacuum of the compartment of vacuum chamber of drive body are substantially unrelated, and " substantially unrelated " described here is
Refer to：Even if the growth rate of film has fluctuation, and slight fluctuations in this temperature window, when growth temperature exceeds this temperature window
Mouth less than lowest temperature or can be significantly increased or reduced higher than temperature upper limit, the growth rate of film；
In temperature window, sedimentation rate does not vary with temperature；When temperature is not high enough, presoma condensation causes multilayer absorption to be led
Too high sedimentation rate is caused, or causes absorption incomplete, reactivity is poor；Presoma decomposition causes extra when temperature is too high
CVD formulas grow, or due to too high hot kinetic energy, presoma desorption；These factors can all cause the growth rate of film to show
Increased or decrease with writing；
F after cavity temperature of) taking seriously constant a period of time, usually 5~30 minutes, film growth is set on device controller
Cycle-index, organo-bismuth source gas-carrier pipeline gas flow rate, organic silicon source gas carrier pipeline gas flow velocity, organic gallium source gas carry
Air pipe gas flow rate, oxygen precursor gas gas-carrier pipeline gas flow rate, inert gas flow velocity, organo-bismuth source gas pulses length
Degree, organic silicon source gas gas pulse length, organic gallium source gas pulses length, oxygen precursor gas pulse length, indifferent gas
Body pulse length；Manual unlocking organo-bismuth source capsule road hand-operated valve K1, organic silicon source gas piping hand-operated valve K2, organic gallium source gas
Pipeline hand-operated valve K3, oxygen precursor gas pipeline hand-operated valve K4, inert gas piping hand-operated valve K5；
G organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas carrier pipeline) are controlled by device controller
Mass flow controller MFC2, organic gallium source gas carrier pipeline quality flow controller MFC3, oxygen precursor gas carrier gas pipe
Road mass flow controller MFC4 so that gas is according to step F in each gas piping) in setting value be passed through vacuum reaction chamber,
Vacuum reaction chamber each leads into inert gas, organic bismuth source gas, organic gallium source gas, oxygen according to certain gas pulses sequential
Precursor gas gas and organic aluminum source gas；All precursor gas are respectively transported using inert gas；
To realize in growth BiGaO3Al doping is realized during film to obtain Bi (AlxGa1-x)O3Film, in each life
In long period, when organic gallium source gas pulses, organic silicon source gas pulses are inserted in gas pulses according to certain ratio alternatively mixing
In sequence, the organic gallium source gas pulses, organic silicon source gas pulses ratio are by desired Bi (AlxGa1-x)O3Film
Component, used organic gallium source gas, organic silicon source gaseous species determine；
For example, in order to obtain Bi (Al0.1Ga0.9)O3Film, when triethyl group is respectively adopted in organic gallium source gas, organic aluminum source gas
When gallium, triethyl aluminum, organic gallium source gas pulses, the number of organic silicon source gas pulses can be arranged in a growth cycle
Amount ratio is 9:1.
Of particular note is that：Organic gallium source gas pulses, the quantitative proportion of organic silicon source gas pulses and indirect
Equal to (1-x):Which kind of x, additionally depend on using organic gallium source gas, organic aluminum source gas.
H) when film growth cycle-index reaches the number of setting, film thickness reaches desirable value, obtains certain thickness
Bi (AlxGa1-x)O3Thin-film material, organo-bismuth source capsule road automatic valve AK1, organic silicon source gas piping are closed by device controller
Automatic valve AK2, organic gallium source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK3, stopping are passed through organo-bismuth
Source, organic aluminum source gas, organic gallium source gas, oxygen precursor gas, continue to be passed through inert gas, stop supplying electric heater
Electricity, stop heating vacuum chamber；
I) manual-lock organo-bismuth source capsule road hand-operated valve K1, organic silicon source gas piping hand-operated valve K2, organic gallium source gas piping
Hand-operated valve K3, oxygen precursor gas pipeline hand-operated valve K4, inert gas piping hand-operated valve K5, air-inlet of vacuum pump automatic valve
AK4 is remained on, and vacuum reaction chamber carries out natural cooling；
J) vacuum chamber reaches or during close to room temperature, and air-inlet of vacuum pump automatic valve AK5 is closed by device controller；
K) vacuum reaction chamber, which is inflated, makes its air pressure reach an atmospheric pressure, and vacuum reaction chamber inner and outer air pressure reaches equilibrium-like
State；
L) take out and deposited to obtain Bi (AlxGa1-x)O3The substrate of thin-film material, close inert gas piping hand-operated valve K5；
M Bi (Al) are attached with by what is obtained in step LxGa1-x)O3The substrate of thin-film material, is put into quick anneal oven, carries out
Quick thermal annealing process, take out after natural cooling, the Bi (Al for confirming to obtain by testxGa1-x)O3The space group of thin-film material
For Pcca；
The step of rapid thermal annealing is：
(a) 1-10 minutes are maintained at 180-220 DEG C；
(b) 1-10 minutes are maintained at 360-400 DEG C；
(c) the high annealing 1-10 minutes at 750 DEG C -1050 DEG C；
In order to avoid the air containing steam in pipeline produces unpredictable influence to film growth, in step B) it is logical afterwards
Often should also there is the operation for driving away the air after each material container installation connects in pipeline, specifically, the operation is：
Keep organo-bismuth source capsule road hand-operated valve K1, organic silicon source gas piping hand-operated valve K2, organic gallium source gas piping hand-operated valve
K3, oxygen presoma pipeline hand-operated valve K4 are in closed mode, then,
Air-inlet of vacuum pump automatic valve AK5 is in open mode by device controller control, made by device controller control
Organo-bismuth source capsule road automatic valve AK1, organic silicon source gas piping automatic valve AK2, organic gallium source gas piping automatic valve AK3, oxygen
Precursor gas pipeline automatic valve AK4 is in open mode；When the vacuum meter in vacuum reaction chamber no longer changes, by equipment
Controller control is closed air-inlet of vacuum pump automatic valve AK5, and organo-bismuth source carrier gas is controlled by device controller
Pipeline quality flow controller MFC1, organic silicon source gas carrier pipeline quality flow controller MFC2, organic gallium source gas carry
Air pipe mass flow controller MFC3, oxygen precursor gas gas-carrier pipeline mass flow controller MFC4 so that each flue
Inert gas is passed through vacuum reaction chamber according to certain value in road；When the air pressure in vacuum reaction chamber reaches 0.5 atmospheric pressure, then
It is secondary air-inlet of vacuum pump automatic valve AK5 is in open mode by device controller control, make to have by device controller control
Machine bismuth source capsule road automatic valve AK1, organo-aluminium source capsule road automatic valve AK2, organic gallium source gas piping automatic valve AK3, oxygen presoma
Gas piping automatic valve AK4 is in open mode；Repeat said process 3~6 times.
In step G) in, the gas pulses sequential is by inert purge gas pulses, organo-bismuth source gas pulses, organic gallium source gas
Body pulse, the pulse of oxygen precursor gas and organic silicon source gas pulses composition, if representing indifferent gas respectively with N, B, O, A, G
Body pulse, organo-bismuth source gas pulses, the pulse of oxygen precursor gas, organic silicon source gas pulses, organic gallium source gas pulses,
Then：
Pulse N is realized by following action：
Organo-bismuth source capsule road automatic valve AK1, organic silicon source gas piping automatic valve AK2, Organogallium are made by device controller control
Source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK4 are in closed mode, are controlled by device controller
Organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow controller MFC2, have
Machine gallium source gas carrier pipeline quality flow controller MFC3, oxygen precursor gas gas-carrier pipeline mass flow controller MFC4,
So that inert gas is according to step D in each gas piping) in setting value be passed through vacuum reaction chamber；
Pulse B is realized by following action：
Organo-bismuth source capsule road automatic valve AK1 is set to be in open mode by device controller control, organic silicon source gas piping is automatic
Valve AK2, organic gallium source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK4 are in closed mode, by setting
Preparation controller control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow control
Device MFC2 processed, organic gallium source gas-carrier pipeline mass flow controller MFC3, the control of oxygen precursor gas gas-carrier pipeline mass flow
Device MFC4 so that gas is according to step D in each gas piping) in setting value be passed through vacuum reaction chamber；
Pulse O is realized by following action：
Oxygen precursor gas pipeline automatic valve AK4 is set to be in open mode by device controller control, organo-bismuth source capsule road is automatic
Valve AK1, organic silicon source gas piping automatic valve AK2, organic gallium source gas piping automatic valve AK3 are in closed mode, by setting
Preparation controller control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow control
Device MFC2 processed, organic gallium source gas-carrier pipeline mass flow controller MFC3, the control of oxygen precursor gas gas-carrier pipeline mass flow
Device MFC4 so that gas is according to step D in each gas piping) in setting value be passed through vacuum reaction chamber；
Pulse G is realized by following action：
Organic gallium source gas piping automatic valve AK3 is set to be in open mode by device controller control, organo-bismuth source capsule road is automatic
Valve AK1, oxygen precursor gas pipeline automatic valve AK3 are in closed mode, and organo-bismuth source carrier gas pipe is controlled by device controller
Road mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow controller MFC2, oxygen precursor gas carrier gas
Pipeline quality flow controller MFC3 so that gas is according to step D in each gas piping) in setting value be passed through vacuum reaction
Chamber；
Pulse A is realized by following action：
Organic silicon source gas piping automatic valve AK2 is set to be in open mode by device controller control, organo-bismuth source capsule road is automatic
Valve AK1, organic gallium source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK4 are in closed mode, by setting
Preparation controller control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow control
Device MFC2 processed, organic gallium source gas-carrier pipeline mass flow controller MFC3, the control of oxygen precursor gas gas-carrier pipeline mass flow
Device MFC4 so that gas is according to step D in each gas piping) in setting value be passed through vacuum reaction chamber；
The rule of these foregoing gas pulses sequential is as follows：
In any one organo-bismuth source gas pulses or the pulse of oxygen precursor gas or organo-aluminium gas pulses or Organogallium gas
Before or after pulse, all with an inert purge gas pulses, i.e. for example：BN ..., or GN ..., or ON ..., or
AN ..., or ... NBN ..., or ... NGN ..., or ... NON ..., or ... NAN ..., herein ellipsis
" ... " represents other possible collating sequences；And in the case where meeting above-mentioned condition,
In the secondary adjacent place of any one organo-bismuth source gas pulses or organo-aluminium gas pulses or Organogallium gas pulses, all also
With an oxygen precursor gas pulse, i.e. for example：... NONBN ..., or ... NONGN ..., or ...
NBNON ..., or ... NONAN ..., or ... NGNON ..., herein ellipsis " ... " represent other possible arrangements
Sequence；And in the case where meeting above-mentioned condition,
Organo-bismuth source gas pulses, the pulse of oxygen precursor gas, organo-aluminium gas pulses, Organogallium gas pulses, inert gas
Pulse can be arranged with any order, can be multiple organo-bismuth sources gas pulses or the pulse of oxygen precursor gas or organo-aluminium gas
Body pulse or Organogallium gas pulses and inert purge gas pulses are continuously distributed successively, then abut remaining one or more groups of precursor gas
Body pulse；In other words, one or more organo-aluminium gas pulses, one or more organo-bismuth sources gas pulses, one or more
Organic gallium source gas pulses, one or more are passed through the pulse of oxygen precursor gas and can arranged with any order, for example, are had
The pulse of machine bismuth source gas, the pulse of oxygen precursor gas, organic silicon source gas pulses, organic gallium source gas pulses, inert gas arteries and veins
The sequence of punching can be ... BNONBNONBNONGNONBNONGNONANON ... or ...
BNONGNONBNONBNONBNONBNONGNONANONBNONBNON ..., it can also be ...
GNONGNONBNONBNONANONBNONBNONBNONGNONBNON ..., or ...
GNONBNONBNONBNONBNONGNONBNONANONBNONBNON ... etc.；Ellipsis " ... " represents that other may herein
Collating sequence；
These gas pulses sequences control the open and close of corresponding automatic valve to realize by device controller, and perform spy by program
The growth cycle circulation of sequencing row.
In a growth cycle, the quantity of each gas pulses is 4 multiple and not less than 12, such as：12,16,20,
24 ... etc.；Each gas pulses are passed through in vacuum reaction chamber successively by pipeline, and pallet and substrate are sequentially exposed to these
In the atmosphere that gas pulses are formed；And
In a growth cycle, organo-bismuth source gas pulses and organic silicon source gas pulses, the number of organic gallium source gas pulses
Measure the quantity that sum is equal to oxygen precursor gas pulse, organo-bismuth source gas pulses, organic gallium source gas pulses, organic silicon source gas
The quantity sum of body pulse and oxygen precursor gas pulse is equal to the quantity of inert purge gas pulses；
In view of the space steric effect of organic precursor molecule, the quantity of organo-bismuth source gas pulses and organic aluminum source gas arteries and veins
The quantity of punching+organic gallium source gas pulses might not be equal, but is allocated according to following principle：
The bismuth that deposits to obtain in a growth cycle, on substrate, the stoichiometric proportion of aluminium+gallium are close to 1:1, it is allowed to have 10%
Following positive error, i.e. bismuth, the stoichiometric proportion of gallium are 1:1~1:In the range of 1.1, this is due to need to consider in step K
Bismuth element is readily volatilized in rapid thermal annealing and the adequate compensation made；
In the case where meeting above-mentioned requirements, organo-bismuth source gas pulses, organic silicon source gas pulses are in a growth cycle
In in be uniformly distributed arrangement on the time as much as possible.
In order to facilitate control growth circulation, typically, with BNON pulse trains, GNON pulse trains, ANON pulse sequences
The cycling element fragment for forming growth cycle is classified as, these cycling element fragments are arranged with any order in time, according to choosing
The species of organo-bismuth source, organic aluminum source gas and the organic gallium source gas selected is different, in these cycling element fragments some or
It is multiple can also circulate alone repeatedly after, then with other these cycling element fragments successively be arranged to make up a growth cycle, such as：
BNONGNONANON, or GNONANONBNON or BNONBNONGNONGNONANON, or
BNONBNONBNONBNONBNONGNONANONGNON。
In order to obtain content gradually variational and cross over the Bi (Al of quasi- homotype phase boundaryxGa1-x)O3Thin-film material, by programme controlled
In each growth cycle, two counters are set respectively, two counters are respectively used to set and control each growth cycle
In organic silicon source gas pulses, the quantity of organic gallium source gas pulses, in gradually growth course, the value of one of counter
Gradually increase, the value of another counter are gradually reduced；
It is described both to be realized by the hardware circuit comprising counter specially designed by programme-control, can also be by monolithic
Machine or PC control the running of growth apparatus by software；The counter, in specially designed hardware circuit, refer to generally
The digital counter circuit of meaning, in the system that single-chip microcomputer or PC are formed, refer to two variables in software program.
It is the temperature of reasonable selection vacuum reaction chamber, organo-bismuth source, organic aluminum source gas, organic in membrane-film preparation process
Gallium source gas, oxygen presoma, the flow velocity of inert gas, pressure so that backing material is every time exposed to organo-bismuth source, organic silicon source
When in gas, organic gallium source gas, precursor gas atmosphere, substrate material surface can be made intactly to adsorb a monolayer
Organo-bismuth or organo-aluminium or Organogallium, its absorption mechanism adsorb for Langmuir (Langmuir)；When substrate is sequentially exposed to two kinds
When in the atmosphere of presoma, a thin film deposition is completed, for example, when substrate passes through BNON pulse trains, deposits one layer of Bi2O3。
In the present invention, organo-bismuth source gas pulses take 2~8s, and organic silicon source gas pulses take 0.1~2s, organic gallium source
Gas pulses take 0.1~2s oxygen precursor gas pulses to take 0.1~6s, think substantially can each precursor molecule in substrate surface
Chemisorbed complete once complete adsorption enough, coverage rate is close to 100%.
In any precursor gas pulse, the presoma of a molecular layer is formed in substrate surface except adsorbing
Molecule, remaining unnecessary precursor molecule will be taken away by inert purge gas pulses followed by, be discharged by vavuum pump true
Outside empty reaction chamber, that is to say, that each time substrate surface occur " half-reaction " after, substrate surface can at most be formed one layer certain
Kind atoms of precursor.
In fact, typically, due to the steric effect of precursor molecule, or the shadowing effect of organic group, shade
Effect, once one layer of certain atoms of precursor can not be formed in substrate surface after " half-reaction ", but needed repeatedly " partly anti-
Should " one layer of certain atoms of precursor can be formed in substrate surface.
It is based on above-mentioned principle, preparation Bi (Al of the inventionxGa1-x)O3The method of thin-film material, can really it realize
The controllable precise of thickness when film grows.
This is that other any film growth techniques can not match in excellence or beauty.
In membrane-film preparation process, underlayer temperature is located in foregoing suitable temperature window, is exposed to every time in substrate
When organo-bismuth source atmosphere, organic silicon source atmosphere, organic gallium source atmosphere, oxygen precursor gas atmosphere, substrate table
The Chemisorption in face is " half-reaction " (" half-reaction "), rather than once complete Chemisorption, only
There is substrate to be exposed to organo-bismuth source atmosphere and oxygen precursor gas atmosphere, or organic silicon source atmosphere and oxygen respectively twice
Precursor gas atmosphere, or organic gallium source atmosphere and oxygen precursor gas atmosphere, just complete once complete chemisorbed
Reaction, respectively obtain the Bi of an atomic layer2O3Or Ga2O3/Al2O3；
Due to thickness controllable precise when the method for the present invention can realize film growth, but an atom is at most only obtained per secondary growth
The material of layer, the speed of growth is relatively low, therefore, is generally used for growing several nanometers to the Bi (Al of tens nanometers of thicknessxGa1-x)O3
Thin-film material, most hundreds of nanometers, less than 500 nanometers, otherwise its too low speed of growth will become to receive.
In the present invention, described substrate can be Si, LaNiO3/Si、Pt/TiO2/SiO2/Si、Pt/Ti/SiO2/ Si,
Other suitable substrates are can also be, such as TiN, SiO2Deng.
In the present invention, term " inert gas " refers not only to signified inert gas (helium, the argon gas of usual chemical field
Deng), other gases that will not be chemically reacted in whole membrane-film preparation process with presoma are additionally included in, such as：Nitrogen.
In the present invention, oxygen precursor gas can be H2O、O2、O3Any of which or wherein any two
Kind or three kinds of mixed gas, wherein H2O is deionized water, O2、O3Purity is above 99.999%.
In the present invention, organo-bismuth source, organic aluminum source gas are respectively three (2,2,6,6- tetramethyl -3,5- heptadione acid)
Bismuth (III), trimethyl gallium；
In the case where equipment allows and meets actual demand, organo-bismuth source can also use triphenyl bismuth, trimethyl-bismuthine, three uncles
Butanol base bismuth, trimethylsilyl bismuth etc., organic aluminum source gas can also use triethyl-gallium, tri-tert gallium.
Preferably, all gas pipeline for being connected to vacuum reaction chamber is coated with heating tape, is concentrated by device controller
Power supply is heated to pipeline, to avoid condensation of the various precursor gas in pipeline；
Preferably, pallet can be connected with the rotating shaft of a motor, at the uniform velocity be rotated by motor driven pallet in thin film growth process,
By way of this rotation of substrate, the uniformity of film that can make to obtain is more preferable.
Preferably, device controller can be the special circuit of customization, can be by PLC (programmable logic controller (PLC)) structure
Into can be made up of FPGA (field programmable gate array), can also be made up of CPLD (CPLD), may be used also
To be that single-chip microcomputer is formed, or PC.
Beneficial effects of the present invention：
By using the preparation Bi (Al of the present inventionxGa1-x)O3The method of thin-film material, it is possible to achieve content gradually variational, across accurate same
Bi (the Al of type phase boundaryxGa1-x)O3Thin-film material, and Bi (AlxGa1-x)O3The controllable precise of film growth thickness, and Bi
(AlxGa1-x)O3Thin film surface planeness is significantly better than prior art.
Brief description of the drawings
Fig. 1：Prepare Bi (AlxGa1-x)O3The device of thin-film material,
In Fig. 1：1, organo-bismuth source container；K1, organo-bismuth source capsule road hand-operated valve；AK1, organo-bismuth source capsule road automatic valve；MFC1, have
Machine bismuth source gas-carrier pipeline mass flow controller；2, organo-aluminium source container；K2, organic silicon source gas piping hand-operated valve；AK2, have
Machine aluminum source gas pipeline automatic valve；MFC2, organic silicon source gas carrier pipeline quality flow controller；3, organic gallium source gas holds
Device；K3, organic gallium source gas piping hand-operated valve；AK3, organic gallium source gas piping automatic valve；MFC3, organic gallium source gas carrier
Pipeline quality flow controller；4, oxygen precursor gas source；K4, oxygen precursor gas pipeline hand-operated valve；AK4, oxygen precursor gas
Body pipeline automatic valve；MFC4, oxygen precursor gas gas-carrier pipeline mass flow controller；5, inert gas source；K5, inert gas
Pipeline hand-operated valve；AK5, air-inlet of vacuum pump automatic valve；
Semiconductor cooler, vacuum meter, the electric heater of source container are not drawn into Fig. 1.
Fig. 2：Respectively with N, B, O, A, G come represent pulse of nitrogen, organo-bismuth source gas pulses, the pulse of oxygen precursor gas,
Organic silicon source gas pulses, organic gallium source gas pulses.
Fig. 3：Respectively with N, B, O, A, G come represent pulse of nitrogen, organo-bismuth source gas pulses, the pulse of oxygen precursor gas,
Organic silicon source gas pulses, organic gallium source gas pulses.
Embodiment
Technical scheme is specifically introduced with reference to example.
Embodiment 1：
A the nitrogen of more than 99.9995% purity) is filled with vacuum glove box, is completed in the nitrogen atmosphere of glove box following
Operation：Organo-bismuth source, organic aluminum source gas, organic gallium source gas are filled into organo-bismuth source container 1, organic aluminum source gas respectively
Container 2, organic gallium source container 3, then install and connect with respective pipeline；
B) organo-bismuth source uses three second using three (2,2,6,6- tetramethyl -3,5- heptadione acid) bismuths (III), organic gallium source gas
Base gallium, organic silicon source use triethyl aluminum, and oxygen precursor gas source uses deionized water, inert gas use 99.9995% with
The nitrogen of upper purity；
Organo-bismuth source, organic aluminum source gas, organic gallium source gas, oxygen precursor gas source, nitrogen are filled into organo-bismuth respectively
Source container 1, organic silicon source gas container 2, organic gallium source gas container 3, oxygen precursor gas source container 4, inert gas source hold
Device 5, then install and connect with respective pipeline；
Drive away the air in pipeline after each material container installation connects：
Keep organo-bismuth source capsule road hand-operated valve K1, organic silicon source gas piping hand-operated valve K2, organic gallium source gas piping hand-operated valve
K3, oxygen presoma pipeline hand-operated valve K4 are in closed mode, then,
Air-inlet of vacuum pump automatic valve AK5 is in open mode by device controller control, made by device controller control
Organo-bismuth source capsule road automatic valve AK1, organic silicon source gas piping automatic valve AK2, organic gallium source gas piping automatic valve AK3, oxygen
Precursor gas pipeline automatic valve AK4 is in open mode；
When the vacuum meter in vacuum reaction chamber no longer changes, air-inlet of vacuum pump automatic valve is made by device controller control
AK5 is closed, and organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas are controlled by device controller
Body gas-carrier pipeline mass flow controller MFC2, organic gallium source gas carrier pipeline quality flow controller MFC3, oxygen presoma
Gas carrier pipeline quality flow controller MFC4 so that inert gas is passed through vacuum reaction according to certain value in each gas piping
Chamber；
When the air pressure in vacuum reaction chamber reaches 0.5 atmospheric pressure, air-inlet of vacuum pump is made by device controller control again
Automatic valve AK5 is in open mode, makes organo-bismuth source capsule road automatic valve AK1, organo-aluminium source capsule road by device controller control
Automatic valve AK2, organic gallium source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK4 are in open mode；
Repeat said process 5 times；
C) the TiN backing materials of cleaning are dried up with inert gas, are placed into substrate pallet；
D) pallet moves into vacuum reaction chamber together with TiN substrates, opens vavuum pump by device controller, then opens vavuum pump again
Air inlet automatic valve AK5, is vacuumized to vacuum reaction chamber；
E organo-bismuth source container 1, organic silicon source gas container 2, organic gallium source gas container 3, oxygen) are set on device controller
The temperature of precursor gas source container 4 is respectively 185 DEG C, 20 DEG C, 20 DEG C, 20 DEG C, controls organo-bismuth source to hold by device controller
Device 1, organo-aluminium source container 2, organic gallium source gas container 3, the electric heater and/or semiconductor of oxygen precursor gas source container 4
The working condition of refrigerator, so that organo-bismuth source container 1, organic silicon source gas container 2, organic gallium source gas container 3, oxygen forerunner
The temperature of gas source container 4 maintains the temperature value of setting；
Vacuum chamber is heated by device controller control electric heater, makes pallet in vacuum chamber and substrate temperature whole
It is constant at 320 DEG C in individual thin film growth process；
F cavity temperature of) taking seriously after constant 30 minute, the cycle-index of film growth is set on device controller, is had at 320 DEG C
Machine bismuth source gas-carrier pipeline gas flow rate, organic silicon source gas carrier pipeline gas flow velocity, organic gallium source gas carrier pipeline gas
Flow velocity, oxygen presoma gas-carrier pipeline gas flow rate, inert gas flow velocity, organo-bismuth source gas pulses length, organic aluminum source gas
Pulse length, organic gallium source gas pulses length, oxygen precursor gas pulse length, inert purge gas pulses length；Manual unlocking
Organo-bismuth source capsule road hand-operated valve K1, organic silicon source gas piping hand-operated valve K2, organic gallium source gas piping hand-operated valve K3, oxygen forerunner
Body gas piping hand-operated valve K4, inert gas piping hand-operated valve K5；
Organo-bismuth source gas-carrier pipeline gas flow rate, organic silicon source gas carrier pipeline are set on the inputting interface of device controller
Gas flow rate, organic gallium source gas carrier pipeline gas flow velocity, oxygen precursor gas gas-carrier pipeline gas flow rate are respectively
200sccm(standardcubiccentimetersperminute)、200sccm、200sccm、250sccm；
Setting three (DPM dpm,dipivalomethane acid) bismuth (III) gas arteries and veins on the inputting interface of device controller
It is 5s to rush length, and triethyl aluminum gas pulses length is 0.4s, and triethyl-gallium gas pulses length is 0.4s, H2O gas pulses
Length is 0.1s, and pulse of nitrogen length is 4s；
Represent three (DPM dpm,dipivalomethane acid) bismuth (III) gas pulses, triethyl group respectively with B, A, G, O, N
Aluminium gas pulses, triethyl-gallium gas pulses, H2O gas pulses, pulse of nitrogen, in whole growth cycle, gas pulses follow
Ring sequence is as shown in Figure 2；
G organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas carrier pipeline) are controlled by device controller
Mass flow controller MFC2, organic gallium source gas carrier pipeline quality flow controller MFC3, oxygen precursor gas carrier gas pipe
Road mass flow controller MFC4 so that gas is according to step F in each gas piping) in setting value be passed through vacuum reaction chamber,
Vacuum reaction chamber each leads into inert gas, organic bismuth source gas, organic gallium source gas, oxygen according to certain gas pulses sequential
Precursor gas gas and organic aluminum source gas；All precursor gas are respectively transported using nitrogen；
The gas pulses sequential is by inert purge gas pulses, organo-bismuth source gas pulses, organic gallium source gas pulses, oxygen presoma
Gas gas pulse and organic silicon source gas pulses composition, if representing inert purge gas pulses, organic respectively with N, B, O, A, G
Bismuth source gas pulse, the pulse of oxygen precursor gas, organic silicon source gas pulses, organic gallium source gas pulses, then：
Pulse N is realized by following action：
Organo-bismuth source capsule road automatic valve AK1, organic silicon source gas piping automatic valve AK2, Organogallium are made by device controller control
Source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK4 are in closed mode, are controlled by device controller
Organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow controller MFC2, have
Machine gallium source gas carrier pipeline quality flow controller MFC3, oxygen precursor gas gas-carrier pipeline mass flow controller MFC4,
So that inert gas is according to step D in each gas piping) in setting value be passed through vacuum reaction chamber；
Pulse B is realized by following action：
Organo-bismuth source capsule road automatic valve AK1 is set to be in open mode by device controller control, organic silicon source gas piping is automatic
Valve AK2, organic gallium source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK4 are in closed mode, by setting
Preparation controller control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow control
Device MFC2 processed, organic gallium source gas-carrier pipeline mass flow controller MFC3, the control of oxygen precursor gas gas-carrier pipeline mass flow
Device MFC4 so that gas is according to step D in each gas piping) in setting value be passed through vacuum reaction chamber；
Pulse O is realized by following action：
Oxygen precursor gas pipeline automatic valve AK4 is set to be in open mode by device controller control, organo-bismuth source capsule road is automatic
Valve AK1, organic silicon source gas piping automatic valve AK2, organic gallium source gas piping automatic valve AK3 are in closed mode, by setting
Preparation controller control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow control
Device MFC2 processed, organic gallium source gas-carrier pipeline mass flow controller MFC3, the control of oxygen precursor gas gas-carrier pipeline mass flow
Device MFC4 so that gas is according to step D in each gas piping) in setting value be passed through vacuum reaction chamber；
Pulse G is realized by following action：
Organic gallium source gas piping automatic valve AK3 is set to be in open mode by device controller control, organo-bismuth source capsule road is automatic
Valve AK1, oxygen precursor gas pipeline automatic valve AK3 are in closed mode, and organo-bismuth source carrier gas pipe is controlled by device controller
Road mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow controller MFC2, oxygen precursor gas carrier gas
Pipeline quality flow controller MFC3 so that gas is according to step D in each gas piping) in setting value be passed through vacuum reaction
Chamber；
Pulse A is realized by following action：
Organic silicon source gas piping automatic valve AK2 is set to be in open mode by device controller control, organo-bismuth source capsule road is automatic
Valve AK1, organic gallium source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK4 are in closed mode, by setting
Preparation controller control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow control
Device MFC2 processed, organic gallium source gas-carrier pipeline mass flow controller MFC3, the control of oxygen precursor gas gas-carrier pipeline mass flow
Device MFC4 so that gas is according to step D in each gas piping) in setting value be passed through vacuum reaction chamber；
H) when film growth cycle-index reaches the number of setting, film thickness reaches desirable value, obtains certain thickness BAG
Thin-film material, organo-bismuth source capsule road automatic valve AK1, organic silicon source gas piping automatic valve AK2, organic is closed by device controller
Gallium source capsule road automatic valve AK3, oxygen precursor gas pipeline automatic valve AK3, stopping are passed through organo-bismuth source, organic aluminum source gas, had
Machine gallium source gas, oxygen precursor gas, continue to be passed through inert gas, stop powering to electric heater, stop heating vacuum chamber；
I) manual-lock organo-bismuth source capsule road hand-operated valve K1, organic silicon source gas piping hand-operated valve K2, organic gallium source gas piping
Hand-operated valve K3, oxygen precursor gas pipeline hand-operated valve K4, inert gas piping hand-operated valve K5, air-inlet of vacuum pump automatic valve
AK4 is remained on, and vacuum reaction chamber carries out natural cooling；
J) vacuum chamber reaches or during close to room temperature, and air-inlet of vacuum pump automatic valve AK5 is closed by device controller；
K) vacuum reaction chamber, which is inflated, makes its air pressure reach an atmospheric pressure, and vacuum reaction chamber inner and outer air pressure reaches equilibrium-like
State；
L) take out and deposited to obtain the substrate of BAG thin-film materials, close inert gas piping hand-operated valve K5；
M) the substrate for being attached with BAG thin-film materials that will be obtained in step L, is put into quick anneal oven, carries out rapid thermal annealing
Handle, taken out after natural cooling, the space group for the BAG thin-film materials for confirming to obtain by test is Pcca；
The step of rapid thermal annealing is：
(a) maintained 3 minutes at 220 DEG C；
(b) maintained 4 minutes at 360 DEG C；
(c) high annealing 4 minutes at 950 DEG C；
Performance test is carried out to sample.
Embodiment 2：
Basic step is the same as embodiment 1.
Difference is as follows：
Organo-bismuth source uses triethyl-bismuth, and organic gallium source gas uses triethyl-gallium, and organic aluminum source gas use triethyl aluminum, oxygen
Precursor gas source uses deionized water, and inert gas uses the nitrogen of more than 99.9995% purity；
Before organo-bismuth source container 1, organic silicon source gas container 2, organic gallium source gas container 3, oxygen being set on device controller
The temperature for driving gas source container 4 is respectively 25 DEG C, 20 DEG C, 20 DEG C, 20 DEG C；
Organo-bismuth source gas-carrier pipeline gas flow rate, organic silicon source gas carrier pipeline are set on the inputting interface of device controller
Gas flow rate, organic gallium source gas carrier pipeline gas flow velocity, oxygen precursor gas gas-carrier pipeline gas flow rate are respectively
200sccm(standardcubiccentimetersperminute)、200sccm、200sccm、200sccm；
Triethyl-bismuth gas pulses length is set on the inputting interface of device controller as 0.5s, triethyl aluminum gas pulses length
It is 0.4s, H to spend for 0.4s, triethyl-gallium gas pulses length2O gas pulses length is 0.1s, and pulse of nitrogen length is 4s；
Represent triethyl-bismuth gas pulses, triethyl aluminum gas pulses, triethyl-gallium gas pulses, H respectively with B, A, G, O, N2O
Gas pulses, pulse of nitrogen, in whole growth cycle, gas pulses cyclic sequence is as shown in Figure 3；
The substrate for being attached with BAG thin-film materials that will be obtained in step L, is put into quick anneal oven, carries out at rapid thermal annealing
Manage, taken out after natural cooling.
Claims (6)
- A kind of 1. Bi (Al for being used to prepare content gradually variationalxGa1-x)O3The device of thin-film material, it is characterised in that：In the apparatus, Bi (AlxGa1-x)O3Film is anti-from restricted chemical absorption of surface using presoma time-division formula It should obtain, the irreversible Chemisorption of Langmuir absorption mechanism is refered in particular in the chemical absorption of surface reaction；In membrane-film preparation process, underlayer temperature is located in foregoing suitable temperature window, in substrate every time exposed to organic When bismuth source gas atmosphere, organic silicon source atmosphere, organic gallium source atmosphere, oxygen precursor gas atmosphere, substrate surface Chemisorption is " half-reaction ", rather than once complete Chemisorption, and only substrate is exposed to respectively twice Organo-bismuth source atmosphere and oxygen precursor gas atmosphere, or organic silicon source atmosphere and oxygen precursor gas atmosphere, or have Machine gallium source atmosphere and oxygen precursor gas atmosphere, once complete Chemisorption is just completed, respectively obtains an original The Bi of sublayer2O3Or Ga2O3/Al2O3；Described device includes but is not limited to：Organo-bismuth source container 1, organo-bismuth source capsule road hand-operated valve K1, organo-bismuth source capsule road are automatic Valve AK1, organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas container 2, organic silicon source gas piping hand It is dynamic valve K2, organic silicon source gas piping automatic valve AK2, organic silicon source gas carrier pipeline quality flow controller MFC2, organic Gallium silicon source container 3, organic gallium source gas piping hand-operated valve K3, organic gallium source gas piping automatic valve AK3, organic gallium source gas carry Air pipe mass flow controller MFC3, oxygen precursor gas source container 4, oxygen precursor gas pipeline hand-operated valve K4, oxygen forerunner Body gas piping automatic valve AK4, oxygen precursor gas gas-carrier pipeline mass flow controller MFC4, inert gas container 5, inertia Gas piping hand-operated valve K5, vacuum reaction chamber, vacuum meter, vavuum pump, air-inlet of vacuum pump automatic valve AK5, device controller, Electric heater and temperature sensor, organo-bismuth source container 1, organic silicon source gas container 2, oxygen presoma are provided with vacuum reaction chamber The container of gas source container 3 is equipped with electric heater and semiconductor cooler；The outlet of organo-bismuth source container 1 is consecutively connected to organo-bismuth source capsule road hand-operated valve K1, organo-bismuth source capsule by gas piping Road automatic valve AK1, vacuum reaction chamber, the outlet of organic silicon source gas container 2 are consecutively connected to organic silicon source by gas piping Gas piping hand-operated valve K2, organic silicon source gas piping automatic valve AK2, vacuum reaction chamber, the outlet of organic gallium source gas container 3 Organic gallium source gas piping hand-operated valve K3, organic gallium source gas piping automatic valve AK3, vacuum are consecutively connected to by gas piping Reaction chamber, the outlet of oxygen precursor gas source container 4 are consecutively connected to oxygen precursor gas pipeline hand-operated valve by gas piping K4, oxygen precursor gas pipeline automatic valve AK4, vacuum reaction chamber, the outlet of inert gas container 5 is connected to by gas piping Inert gas piping hand-operated valve K5, then organo-bismuth source gas-carrier pipeline mass flow controller is connected respectively to by branch line MFC1, organic silicon source gas carrier pipeline quality flow controller MFC2, the control of organic gallium source gas carrier pipeline quality flow Device MFC3, oxygen precursor gas gas-carrier pipeline mass flow controller MFC4, organo-bismuth source gas-carrier pipeline mass flow controller MFC1 outlet is connected to the gas piping between organo-bismuth source capsule road automatic valve AK1 and vacuum reaction chamber by three-way connector On, organic silicon source gas carrier pipeline quality flow controller MFC2 outlet is connected to organic silicon source gas by three-way connector On gas piping between body pipeline automatic valve AK2 and vacuum reaction chamber, the control of organic gallium source gas carrier pipeline quality flow Device MFC3 outlet is connected to the gas between organic silicon source gas piping automatic valve AK3 and vacuum reaction chamber by three-way connector On body pipeline, oxygen precursor gas gas-carrier pipeline mass flow controller MFC4 outlet is connected to organic by three-way connector On gas piping between bismuth source capsule road automatic valve AK4 and vacuum reaction chamber, the outlet of vacuum reaction chamber is connected successively by pipeline It is connected to air-inlet of vacuum pump automatic valve AK5, the air inlet of vavuum pump；Vacuum meter is provided with vacuum chamber；Organo-bismuth source capsule road hand-operated valve K1, organic silicon source gas piping hand-operated valve K2, organic gallium source gas piping hand-operated valve K3, oxygen Precursor gas pipeline hand-operated valve K4, inert gas piping hand-operated valve K5 are by operating personnel's manual unlocking, uncontrolled device institute Control；Vacuum meter, organo-bismuth source capsule road automatic valve AK1, organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source Gas piping automatic valve AK2, organic silicon source gas carrier pipeline quality flow controller MFC2, organic gallium source gas piping are automatic Valve AK3, organic gallium source gas carrier pipeline quality flow controller MFC3, oxygen precursor gas source container 4, oxygen precursor gas Pipeline automatic valve AK4, oxygen precursor gas gas-carrier pipeline mass flow controller MFC4, vacuum reaction chamber, vavuum pump, vavuum pump It is air inlet automatic valve AK5, the electric heater in vacuum reaction chamber, temperature sensor and the organo-bismuth source container 1, organic Aluminum source gas container 2, organic gallium source gas container 3, the electric heater of oxygen precursor gas source container 4 and semiconductor cooler are equal It is respective by device controller centralized Control by cable connection to device controller by cable connection to device controller Working condition；At any one moment, organo-bismuth source capsule road automatic valve AK1, organic silicon source gas piping are made certainly by device controller control Dynamic valve AK2, organic gallium source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK4 at most only one are in and opened State is opened, remaining is in closed mode；Or organo-bismuth source capsule road automatic valve AK1, organic silicon source gas piping automatic valve AK2, Organic gallium source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK4 are completely in closed mode；The gathered data of temperature sensor by cable transmission to device controller, to realize the PID control of temperature（Ratio-product Point-differential control）；Organo-bismuth source gas pulses, organic silicon source gas pulses, organic gallium source gas pulses, the pulse of oxygen precursor gas, inertia Gas pulses are passed through in vacuum reaction chamber successively according to certain order；In by programme controlled each growth cycle, two counters are set respectively, two counters be respectively used to setting and Organic silicon source gas pulses, the quantity of organic gallium source gas pulses in each growth cycle are controlled, in gradually growth course, The value of one of counter gradually increases, and the value of another counter is gradually reduced；By device controller control organo-bismuth source container 1, organic silicon source gas container 2, organic gallium source gas container 3, oxygen forerunner The electric heater of the container of gas source container 4 and the working condition of semiconductor cooler, so that organo-bismuth source container 1, organic Aluminum source gas container 2, organic gallium source gas container 3, oxygen precursor gas source container 4 temperature can be with the constant temperature in setting Value.
- A kind of 2. device as claimed in claim 1, it is characterised in that：Gas pulses sequence is controlled the open and close of the automatic valve in each gas piping by device controller to realize, and by program Perform the growth cycle circulation of specific gas pulse train.
- A kind of 3. device as claimed in claim 1, it is characterised in that：Pallet is driven by motor, drives substrate evenly to rotate.
- A kind of 4. device as claimed in claim 1, it is characterised in that：The all gas pipeline for being connected to vacuum reaction chamber is coated with heating tape, and pipeline is entered by device controller centrally connected power supply Row heating.
- A kind of 5. device as claimed in claim 1, it is characterised in that：Device controller is made up of PLC or FPGA or CPLD or SCM system or computer or the circuit system specially designed.
- A kind of 6. device as claimed in claim 1, it is characterised in that：Inert purge gas pulses, organo-bismuth source gas pulses, the pulse of oxygen precursor gas, organic are represented with N, B, O, A, G respectively Aluminum source gas pulse, organic gallium source gas pulses, then：Pulse N is realized by following action：Organo-bismuth source capsule road automatic valve AK1, organic silicon source gas piping automatic valve AK2, Organogallium are made by device controller control Source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK4 are in closed mode, are controlled by device controller Organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow controller MFC2, have Machine gallium source gas carrier pipeline quality flow controller MFC3, oxygen precursor gas gas-carrier pipeline mass flow controller MFC4, So that inert gas is passed through vacuum reaction chamber according to setting value in each gas piping；Pulse B is realized by following action：Organo-bismuth source capsule road automatic valve AK1 is set to be in open mode by device controller control, organic silicon source gas piping is automatic Valve AK2, organic gallium source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK4 are in closed mode, by setting Preparation controller control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow control Device MFC2 processed, organic gallium source gas carrier pipeline quality flow controller MFC3, oxygen precursor gas gas-carrier pipeline mass flow Controller MFC4 so that gas is passed through vacuum reaction chamber according to setting value in each gas piping；Pulse O is realized by following action：Oxygen precursor gas pipeline automatic valve AK4 is set to be in open mode by device controller control, organo-bismuth source capsule road is automatic Valve AK1, organic silicon source gas piping automatic valve AK2, organic gallium source gas piping automatic valve AK3 are in closed mode, by setting Preparation controller control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow control Device MFC2 processed, organic gallium source gas carrier pipeline quality flow controller MFC3, oxygen precursor gas gas-carrier pipeline mass flow Controller MFC4 so that gas is passed through vacuum reaction chamber according to setting value in each gas piping；Pulse G is realized by following action：Organic gallium source gas piping automatic valve AK3 is set to be in open mode by device controller control, organo-bismuth source capsule road is automatic Valve AK1, oxygen precursor gas pipeline automatic valve AK3 are in closed mode, and organo-bismuth source carrier gas pipe is controlled by device controller Road mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow controller MFC2, oxygen precursor gas carrier gas Pipeline quality flow controller MFC3 so that gas is passed through vacuum reaction chamber according to setting value in each gas piping；Pulse A is realized by following action：Organic silicon source gas piping automatic valve AK2 is set to be in open mode by device controller control, organo-bismuth source capsule road is automatic Valve AK1, organic gallium source gas piping automatic valve AK3, oxygen precursor gas pipeline automatic valve AK4 are in closed mode, by setting Preparation controller control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic silicon source gas carrier pipeline quality flow control Device MFC2 processed, organic gallium source gas carrier pipeline quality flow controller MFC3, oxygen precursor gas gas-carrier pipeline mass flow Controller MFC4 so that gas is passed through vacuum reaction chamber according to step setting value in each gas piping.
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| CN201710579317.9A CN107460450B (en) | 2015-11-11 | 2015-11-11 | Device for preparing component-gradient bismuth aluminum gallium oxide film |
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| CN201710579317.9A CN107460450B (en) | 2015-11-11 | 2015-11-11 | Device for preparing component-gradient bismuth aluminum gallium oxide film |
| CN201510764503.0A CN105386005B (en) | 2015-11-11 | 2015-11-11 | The method for preparing the sour bismuth thin film of gallium aluminium of component across quasi- homotype phase boundary |
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| CN201710579317.9A Active CN107460450B (en) | 2015-11-11 | 2015-11-11 | Device for preparing component-gradient bismuth aluminum gallium oxide film |
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| CN105386005B (en) | 2017-09-29 |
| CN107460450B (en) | 2021-03-19 |
| CN105386005A (en) | 2016-03-09 |
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