CN107460452A - Organo-aluminium, the miscible formula in gallium source prepare the device of gallium aluminium acid bismuth thin film - Google Patents

Organo-aluminium, the miscible formula in gallium source prepare the device of gallium aluminium acid bismuth thin film Download PDF

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CN107460452A
CN107460452A CN201710579305.6A CN201710579305A CN107460452A CN 107460452 A CN107460452 A CN 107460452A CN 201710579305 A CN201710579305 A CN 201710579305A CN 107460452 A CN107460452 A CN 107460452A
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gas
organo
source
automatic valve
gallium aluminium
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尹海宏
宋长青
王志亮
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Nantong University
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Abstract

One kind is used to prepare Bi (AlxGa1‑x)O3The device of thin-film material, Bi (AlxGa1‑x)O3Thin-film material is grown on backing material, reacts to obtain from restricted adsorption using presoma time-division formula, and aluminium, gallium organic source mixed dissolution are in a solvent.By using the preparation Bi (Al of the present inventionxGa1‑x)O3The device of thin-film material, it is possible to achieve Bi (AlxGa1‑x)O3The controllable precise of film growth thickness, and Bi (AlxGa1‑x)O3Thin film surface planeness is significantly better than prior art.

Description

Organo-aluminium, the miscible formula in gallium source prepare the device of gallium aluminium acid bismuth thin film
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. CN201510765158.2 divisional application.
Pb(Zr1-xTix)O3(lead zirconate titanate, being abbreviated as PZT) is a kind of ferroelectric material of excellent performance.PZT is PbZrO3 And PbTiO3Solid solution, there is perovskite structure.PbTiO3And PbZrO3It is the Typical Representative of ferroelectric and antiferroelectric, Because Zr and Ti belong to same subgroup, PbTiO3And PbZrO3With similar space lattice form, but both macroscopic propertieies There is very big difference, lead titanates is ferroelectric, and its Curie temperature is 492 DEG C, and lead zirconates is antiferroelectric, and Curie temperature is 232 DEG C, so big difference causes the extensive concern of people.Study PbTiO3And PbZrO3Solid solution after find PZT tool There are a piezoelectric and dielectric properties more excellent than other ferroelectrics, the PZT series ferroelectric ceramics of PZT and doping turns into be ground in recent years The focus studied carefully.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, and this greatly influences PZT utilization.In recent years, Baettig has theoretically foretold Bi (AlxGa1-x)O3(gallium aluminium acid bismuth, be abbreviated as BAG) has With Pb (Zr1-xTix)O3Same excellent ferroelectricity and dielectric properties, because BAG is lead-free, becomes the potential of PZT and replace The person of changing.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 space-time for accurately controlling film thickness Bi (the Al that separate type is prepared from the reaction of restricted adsorptionxGa1-x)O3The method and device of thin-film material, described Bi (AlxGa1-x)O3The space group of thin-film material is Pcca.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 is using organo-bismuth source, oxygen presoma, gallium aluminium Organic source mixes source (hereinafter referred to as organic gallium aluminium source), and organic gallium aluminium source is the mixture of organic silicon source and organic gallium source, organo-aluminium The ratio of source and organic gallium source is by desired Bi (AlxGa1-x)O3The component of film, used organic gallium source, organo-aluminium Source category determines.
In the present invention, organic gallium aluminium source with a certain proportion of triethyl aluminum and triethyl-gallium by being dissolved in dimethylbenzene Obtain, the ratio is by required obtained Bi (AlxGa1-x)O3Component determine that the dimethylbenzene includes：Ortho-xylene, Meta-xylene or paraxylene, can be therein a kind of or two of which or three kinds of mixture.Normally, two Toluene is by three kinds of 45%~70% meta-xylene, 15%~25% paraxylene and 10%~15% ortho-xylene isomeries The mixture that body is formed.
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 gallium aluminium source container 2, organic gallium aluminium source capsule road hand Dynamic valve K2, organic gallium aluminium source capsule road automatic valve AK2, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma Source container 3, oxygen presoma pipeline hand-operated valve K3, oxygen presoma pipeline automatic valve AK3, oxygen presoma gas-carrier pipeline mass flow control Device MFC3 processed, inert gas container 4, inert gas piping hand-operated valve K4, vacuum reaction chamber, vacuum meter, vavuum pump, vavuum pump enter Gas port automatic valve AK4, device controller, electric heater and temperature sensor are provided with vacuum reaction chamber, device controller can With the circuit system for being PLC or FPGA or SCM system or computer or specially designing；Organo-bismuth source container 1, organic gallium aluminium Source container 2, the container of oxygen precursor source containers 3 are 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 gallium aluminium source container 2 are consecutively connected to organic gallium aluminium source by gas piping Pipeline hand-operated valve K2, organic gallium aluminium source capsule road automatic valve AK2, vacuum reaction chamber, the outlet of oxygen precursor source containers 3 passes through gas Pipeline is consecutively connected to oxygen presoma pipeline hand-operated valve K3, oxygen presoma pipeline automatic valve AK3, vacuum reaction chamber, inert gas The outlet of container 4 is connected to inert gas piping hand-operated valve K4 by gas piping, then has been connected respectively to by branch line Machine bismuth source gas-carrier pipeline mass flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen forerunner Body gas-carrier pipeline mass flow controller MFC3, organo-bismuth source gas-carrier pipeline mass flow controller MFC1 outlet pass through threeway Connector is connected on the gas piping between organo-bismuth source capsule road automatic valve AK1 and vacuum reaction chamber, the carrier gas of organic gallium aluminium source Pipeline quality flow controller MFC2 outlet by three-way connector be connected to organic gallium aluminium source capsule road automatic valve AK2 with it is true On gas piping between empty reaction chamber, oxygen presoma gas-carrier pipeline mass flow controller MFC3 outlet is connected by threeway Part is connected on the gas piping between organo-bismuth source capsule road automatic valve AK3 and vacuum reaction chamber, and the outlet of vacuum reaction chamber leads to Cross pipeline and be consecutively connected to air-inlet of vacuum pump automatic valve AK4, the air inlet of vavuum pump；Vacuum meter is provided with vacuum chamber；
Organo-bismuth source capsule road hand-operated valve K1, organic gallium aluminium source capsule road hand-operated valve K2, oxygen presoma pipeline hand-operated valve K3, inert gas Pipeline hand-operated valve K4 is controlled by operating personnel's manual unlocking, uncontrolled device, and 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 gallium aluminium Source capsule road automatic valve AK2, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen precursor source containers 3, oxygen presoma Pipeline automatic valve AK3, oxygen presoma gas-carrier pipeline mass flow controller MFC3, vacuum reaction chamber, vavuum pump, vavuum pump air inlet Mouth automatic valve AK4, the electric heater in vacuum reaction chamber, temperature sensor and the organo-bismuth source container 1, organo-aluminium Gallium source container 2, the electric heater of oxygen precursor source containers 3 and semiconductor cooler are equal to device controller by cable connection By cable connection to device controller, by the respective working condition of device controller centralized Control；
At any one moment, make organo-bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic by device controller control Valve AK2, oxygen presoma pipeline automatic valve AK3 at most only one is in opening, and remaining is in closed mode；It is or organic Bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve AK2, oxygen presoma pipeline automatic valve AK3 are completely in closing shape State；
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；
Added by the electricity of container of device controller control organo-bismuth source container 1, organic gallium aluminium source container 2, oxygen precursor source containers 3 The working condition of hot device and semiconductor cooler, so that organo-bismuth source container 1, organic gallium aluminium source container 2, oxygen precursor source containers 3 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：Gallium aluminium has Machine source with a certain proportion of triethyl aluminum and triethyl-gallium by being dissolved in dimethylbenzene；
The dimethylbenzene includes：Ortho-xylene, meta-xylene or paraxylene can be therein a kind of or wherein Two or three of mixture；Usually dimethylbenzene is meta-xylene, 15%~25% paraxylene by 45%~70% The mixture formed with 10%~15% ortho-xylene, three kinds of isomers；
Because triethyl aluminum, triethyl-gallium, dimethylbenzene are inflammable and explosive dangerous material, therefore, make during mixed dissolution It is essential with vacuum glove box；
B) by organo-bismuth source, step A) obtained organic gallium aluminium source, oxygen precursor source, inert gas be filled into organo-bismuth source respectively Container 1, organic gallium aluminium source container 2, oxygen precursor source containers 3, inert gas container 4, then install and connect with respective pipeline；
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 AK4, is vacuumized to vacuum reaction chamber；
E organo-bismuth source container 1, organic gallium aluminium source container 2, the temperature of oxygen precursor source containers 3) are set on device controller, By device controller control organo-bismuth source container 1, organic gallium aluminium source container 2, oxygen precursor source containers 3 container electric heater And/or the working condition of semiconductor cooler, so that organo-bismuth source container 1, organic gallium aluminium source container 2, oxygen precursor source containers 3 The constant temperature value in setting of temperature, make under the temperature value of set each presoma, organo-bismuth source container 1, organo-aluminium Gallium source container 2, oxygen precursor source containers 3 steam pressure be more than inert gas container 4 by mass flow controller MFC1, Pressure after MFC2, MFC3 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；
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 gallium aluminium source gas-carrier pipeline gas flow rate, oxygen presoma gas-carrier pipeline Gas flow rate, inert gas flow velocity, organo-bismuth source gas pulses length, organic gallium aluminium source gas pulses length, oxygen precursor gas Body pulse length, inert purge gas pulses length；Manual unlocking organo-bismuth source capsule road hand-operated valve K1, organic gallium aluminium source capsule road hand-operated valve K2, oxygen presoma pipeline hand-operated valve K3, inert gas piping hand-operated valve K4；
G organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic gallium aluminium source gas-carrier pipeline matter) are controlled by device controller Measure flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 so that in each gas piping gas according to Step F) in setting value be passed through vacuum reaction chamber, vacuum reaction chamber each leads into indifferent gas according to certain gas pulses sequential Body, organic bismuth source gas, oxygen precursor gas and organic gallium aluminium source gas；All precursor gas respectively use indifferent gas Body is transported；
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 gallium aluminium source capsule road automatic valve are closed by device controller AK2, oxygen presoma pipeline automatic valve AK3, stopping are passed through organo-bismuth source, organic gallium aluminium source, oxygen presoma, continue to be passed through indifferent gas Body, stop powering to electric heater, stop heating vacuum chamber；
I) manual-lock organo-bismuth source capsule road hand-operated valve K1, organic gallium aluminium source capsule road hand-operated valve K2, oxygen presoma pipeline hand-operated valve K3, inert gas piping hand-operated valve K4, air-inlet of vacuum pump automatic valve AK4 are remained on, and vacuum reaction chamber is carried out certainly So cooling；
J) vacuum chamber reaches or during close to room temperature, and air-inlet of vacuum pump automatic valve AK4 is closed by device controller；
K air-inlet of vacuum pump automatic valve AK4) is closed, vacuum reaction chamber, which is inflated, makes its air pressure reach an atmospheric pressure, Vacuum reaction chamber inner and outer air pressure reaches poised state；
L) take out and deposited to obtain Bi (AlxGa1-x)O3The substrate of thin-film material, close inert gas piping hand-operated valve K4；
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：
Organo-bismuth source capsule road hand-operated valve K1, organic gallium aluminium source capsule road hand-operated valve K2, oxygen presoma pipeline hand-operated valve K3 is kept to locate In closed mode, then,
Air-inlet of vacuum pump automatic valve AK4 is in open mode by device controller control, made by device controller control Organo-bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve AK2, oxygen presoma pipeline automatic valve AK3 are in opening State；When the vacuum meter in vacuum reaction chamber no longer changes, air-inlet of vacuum pump automatic valve is made by device controller control AK4 is closed, and organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic gallium aluminium source are controlled by device controller Gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 so that each gas piping Middle inert gas is passed through vacuum reaction chamber according to certain value；When the air pressure in vacuum reaction chamber reaches 0.5 atmospheric pressure, again Air-inlet of vacuum pump automatic valve AK4 is in open mode by device controller control, made by device controller control organic Bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve AK2, oxygen presoma pipeline automatic valve AK3 are in open shape State；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, oxygen precursor gas Body pulse and organic gallium aluminium source gas pulses composition, if representing inert purge gas pulses, organo-bismuth source gas respectively with N, B, O, G Body pulse, the pulse of oxygen precursor gas and organic gallium aluminium source gas pulses, then：
Pulse N is realized by following action：
Organo-bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve AK2, oxygen presoma are made by device controller control Pipeline automatic valve AK3 is in closed mode, and organo-bismuth source gas-carrier pipeline mass flow controller is controlled by device controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 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, organic gallium aluminium source capsule road automatic valve by device controller control AK2, oxygen presoma pipeline automatic valve AK3 are in closed mode, and organo-bismuth source gas-carrier pipeline quality is controlled by device controller Flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass 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 O is realized by following action：
Oxygen presoma pipeline automatic valve AK3 is set to be in open mode, organo-bismuth source capsule road automatic valve by device controller control AK1, organic gallium aluminium source capsule road automatic valve AK2 are in closed mode, and organo-bismuth source gas-carrier pipeline matter is controlled by device controller Measure flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline quality stream Amount controller MFC3 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 aluminium source capsule road automatic valve AK2 is set to be in open mode, organo-bismuth source capsule road automatic valve by device controller control AK1, oxygen presoma pipeline automatic valve AK3 are in closed mode, and organo-bismuth source gas-carrier pipeline quality is controlled by device controller Flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow Controller MFC3 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：
Before any one organo-bismuth source gas pulses or the pulse of oxygen precursor gas or organic gallium aluminium gas pulses or it Afterwards, all with an inert purge gas pulses, i.e. for example：BN ..., or GN ..., or ON ..., or ... NBN ..., Or ... NGN ..., or ... NON ..., herein ellipsis " ... " represent other possible collating sequences；And in satisfaction In the case of stating condition,
In the secondary adjacent place of any one organo-bismuth source gas pulses or organic gallium aluminium gas pulses, all also there is an oxygen forerunner Gas pulse, i.e. such as：... NONBN ..., or ... NONGN ..., or ... NBNON ..., or ... NGNON ..., herein ellipsis " ... " represent other possible collating sequences；And in the case where meeting above-mentioned condition,
Organo-bismuth source gas pulses, the pulse of oxygen precursor gas, organic gallium aluminium gas pulses, inert purge gas pulses can be with any Sequential arrangement, can be multiple organo-bismuth sources gas pulses or the pulse of oxygen precursor gas or organic gallium aluminium gas pulses and inertia Gas pulses are continuously distributed successively, then abut remaining one or more groups of precursor gas pulse；In other words, it is one or more organic Gallium aluminium gas pulses, one or more organo-bismuth sources gas pulses, one or more are passed through the pulse of oxygen precursor gas can be with Any order arranges, for example, organo-bismuth source gas pulses, the pulse of oxygen precursor gas, organic gallium aluminium source gas pulses, lazy The sequence of property gas pulses can be ... BNONBNONBNONGNONBNONGNON ... or ... BNONGNONBNONBNONBNONBNONGNON ..., it can also be ... GNONGNONBNONBNONBNONBNONBNON ..., or ... GNONBNONBNONBNONBNONGNONBNON ... etc.； Ellipsis " ... " represents other possible collating sequences herein；
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 8, such as：8,12,16, 20 ... 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, the quantity sum of organo-bismuth source gas pulses and organic gallium aluminium source gas pulses is equal to oxygen forerunner The quantity of body pulse, the quantity sum of organo-bismuth source gas pulses, organic gallium aluminium source gas pulses and oxygen precursor gas pulse Equal to the quantity of inert purge gas pulses；
In view of the space steric effect of organic precursor molecule, quantity and the organic gallium aluminium source gas of organo-bismuth source gas pulses The quantity of pulse 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 gallium aluminium source gas pulses are a growth week Arrangement is uniformly distributed on the time as much as possible in interim.
In membrane-film preparation process, the temperature of reasonable selection vacuum reaction chamber, organo-bismuth source, organic gallium aluminium source, oxygen forerunner Body, the flow velocity of inert gas, pressure so that backing material is every time exposed to organo-bismuth source, organic gallium aluminium source, oxygen presoma atmosphere When middle, substrate material surface can be set intactly to adsorb a monolayer organo-bismuth or organic gallium aluminium, its absorption mechanism is bright Miao Er (Langmuir) is adsorbed；When in the atmosphere that substrate is sequentially exposed to two kinds of presomas, a thin film deposition, example are completed Such as, when substrate passes through BNON pulse trains, one layer of Bi is deposited2O3。
In the present invention, organo-bismuth source gas pulses take 2~8s, and organic gallium aluminium source gas pulses take 0.1~2s, oxygen forerunner Gas pulse takes 0.1~6s, think substantially can each precursor molecule complete one enough in the chemisorbed of substrate surface Secondary complete adsorption, 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 of atoms of precursor, in fact, typically, due to the steric effect of precursor molecule, or the shadowing effect of organic group, Shadow effect, once one layer of certain atoms of precursor can not be formed in substrate surface after " half-reaction ", but needed multiple " half-reaction " can form one layer of certain atoms of precursor 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 gallium aluminium source atmosphere, oxygen precursor gas atmosphere, the Chemisorption of substrate surface It is " half-reaction " (" half-reaction "), rather than once complete Chemisorption, only substrate are sudden and violent respectively twice It is exposed at organo-bismuth source atmosphere and oxygen precursor gas atmosphere, or organic gallium aluminium source atmosphere and oxygen precursor gas atmosphere Enclose, just complete once complete Chemisorption, 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 gallium aluminium source are respectively three (2,2,6,6- tetramethyl -3,5- heptadione acid) bismuths (III), trimethyl gallium；In the case where equipment allows and meets actual demand, organo-bismuth source can also use triphenyl bismuth, three Methyl bismuth, three tert-butyl alcohol base bismuths, trimethylsilyl bismuth etc., organic gallium aluminium source 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 Bi (AlxGa1-x)O3Film The controllable precise of 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 figure：1, organo-bismuth source；K1, organo-bismuth source capsule road hand Dynamic valve；AK1, organo-bismuth source capsule road automatic valve；MFC1, organo-bismuth source gas-carrier pipeline mass flow controller；2, organic gallium aluminium Source；K2, organic gallium aluminium source capsule road hand-operated valve；AK2, organic gallium aluminium source capsule road automatic valve；MFC2, organic gallium aluminium source gas-carrier pipeline Mass flow controller；3, oxygen precursor source；K3, oxygen presoma pipeline hand-operated valve；AK3, oxygen presoma pipeline automatic valve； MFC3, oxygen presoma gas-carrier pipeline mass flow controller；4, inert gas source；K4, inert gas piping hand-operated valve；AK4, very Empty pump steam inlet automatic valve；Semiconductor cooler, the electric heater of vacuum meter source container are not drawn into figure.
Fig. 2：Gas pulses cyclic sequence figure in embodiment 1.
Fig. 3：Gas pulses cyclic sequence figure in embodiment 2.
Fig. 4：Gas pulses cyclic sequence figure in embodiment 3.
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：Weight ratio is weighed as 1：10 triethyl aluminum and triethyl-gallium, is dissolved in dimethylbenzene, and it is the molten of 0.1M to obtain concentration Liquid；
It is that the dimethylbenzene commercial sources are bought, by 45%~70% meta-xylene, 15%~25% paraxylene and The mixture that 10%~15% three kinds of ortho-xylene isomers (toatl proportion is by 100%) forms；
B) organo-bismuth source uses deionization using three (2,2,6,6- tetramethyl -3,5- heptadione acid) bismuths (III), oxygen precursor source Water, inert gas use the nitrogen of more than 99.9995% purity；By organo-bismuth source, step A) obtained organic gallium aluminium source, before oxygen Drive body source, nitrogen is filled into organo-bismuth source container 1, organic gallium aluminium source container 2, oxygen precursor source containers 3, inert gas source respectively Container 4, then install and connect with respective pipeline；
Driving away the air in pipeline, the specifically operation after each material container installation connects is：
Organo-bismuth source capsule road hand-operated valve K1, organic gallium aluminium source capsule road hand-operated valve K2, oxygen presoma pipeline hand-operated valve K3 is kept to locate In closed mode, then,
Air-inlet of vacuum pump automatic valve AK4 is in open mode by device controller control, made by device controller control Organo-bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve AK2, oxygen presoma pipeline automatic valve AK3 are in opening State；When the vacuum meter in vacuum reaction chamber no longer changes, air-inlet of vacuum pump automatic valve is made by device controller control AK4 is closed, and organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic gallium aluminium source are controlled by device controller Gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 so that each gas piping Middle inert gas is passed through vacuum reaction chamber according to certain value；When the air pressure in vacuum reaction chamber reaches 0.5 atmospheric pressure, again Air-inlet of vacuum pump automatic valve AK4 is in open mode by device controller control, made by device controller control organic Bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve AK2, oxygen presoma pipeline automatic valve AK3 are in open shape State；Repeat said process 5 times；
C) the Si backing materials of cleaning are dried up with the nitrogen of 99.9995% purity, are placed into substrate pallet；
D) pallet moves into vacuum reaction chamber together with Si substrates, opens vavuum pump by device controller, then opens vavuum pump again Air inlet automatic valve AK4, is vacuumized to vacuum reaction chamber；
E the temperature point of organo-bismuth source container 1, organic gallium aluminium source container 2, oxygen precursor source containers 3) is set on device controller Wei not be 185 DEG C, 20 DEG C, 20 DEG C, organo-bismuth source container 1, organic gallium aluminium source container 2, oxygen precursor source are controlled by device controller The electric heater of the container of container 3 and/or the working condition of semiconductor cooler, so that organo-bismuth source container 1, organic gallium aluminium source Container 2, the constant temperature value in setting of the temperature of oxygen precursor source containers 3；
Vacuum chamber is heated by device controller control electric heater, makes pallet in vacuum chamber and substrate temperature whole It is constant at 300 DEG C in individual thin film growth process；
F after constant 30 minutes of cavity temperature of) taking seriously, organo-bismuth source gas-carrier pipeline gas is set on the inputting interface of device controller Rate of flow of fluid, organic gallium aluminium source gas-carrier pipeline gas flow rate, oxygen presoma gas-carrier pipeline gas flow rate, inert gas flow velocity are respectively 200sccm(standard cubic centimeters per minute)、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 tri-tert gallium gas pulses length is 2s, H2O gas pulses length is 0.1s, and pulse of nitrogen length is 4s；
Represent three (DPM dpm,dipivalomethane acid) bismuth (III) gas pulses, organic gallium aluminium respectively with B, G, O, N Source gas pulses, H2O gas pulses, pulse of nitrogen,
In whole growth cycle, gas pulses cyclic sequence is as shown in Figure 2：
Manual unlocking organo-bismuth source capsule road hand-operated valve K1, organic gallium aluminium source capsule road hand-operated valve K2, oxygen presoma pipeline hand-operated valve K3, Inert gas piping hand-operated valve K4；
G organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic gallium aluminium source gas-carrier pipeline matter) are controlled by device controller Measure flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 so that in each gas piping gas according to Step F) in setting value be passed through vacuum reaction chamber, vacuum reaction chamber is according to step F) in setting gas pulses sequential difference It is passed through nitrogen, organic bismuth source gas, oxygen precursor gas and organic gallium aluminium source gas；All precursor gas respectively use Nitrogen is transported；In film deposition process, vacuum reaction intracavitary maintains the -10hPa of air pressure 1；
Pulse N is realized by following action：
Organo-bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve AK2, oxygen presoma are made by device controller control Pipeline automatic valve AK3 is in closed mode, and organo-bismuth source gas-carrier pipeline mass flow controller is controlled by device controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 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, organic gallium aluminium source capsule road automatic valve by device controller control AK2, oxygen presoma pipeline automatic valve AK3 are in closed mode, and organo-bismuth source gas-carrier pipeline quality is controlled by device controller Flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass 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 O is realized by following action：
Oxygen presoma pipeline automatic valve AK3 is set to be in open mode, organo-bismuth source capsule road automatic valve by device controller control AK1, organic gallium aluminium source capsule road automatic valve AK2 are in closed mode, and organo-bismuth source gas-carrier pipeline matter is controlled by device controller Measure flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline quality stream Amount controller MFC3 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 aluminium source capsule road automatic valve AK2 is set to be in open mode, organo-bismuth source capsule road automatic valve by device controller control AK1, oxygen presoma pipeline automatic valve AK3 are in closed mode, and organo-bismuth source gas-carrier pipeline quality is controlled by device controller Flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow Controller MFC3 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 Bi (AlxGa1-x)O3Thin-film material, organo-bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve are closed by device controller AK2, oxygen presoma pipeline automatic valve AK3, stopping are passed through organo-bismuth source, organic gallium aluminium source, oxygen presoma, continue to be passed through indifferent gas Body, stop powering to electric heater, stop heating vacuum chamber；
I) manual-lock organo-bismuth source capsule road hand-operated valve K1, organic gallium aluminium source capsule road hand-operated valve K2, oxygen presoma pipeline hand-operated valve K3, inert gas piping hand-operated valve K4, air-inlet of vacuum pump automatic valve AK4 are remained on, and vacuum reaction chamber is carried out certainly So cooling；
J) vacuum chamber reaches or during close to room temperature, and air-inlet of vacuum pump automatic valve AK4 is closed by device controller；
K air-inlet of vacuum pump automatic valve AK4) is closed, vacuum reaction chamber, which is inflated, makes its air pressure reach an atmospheric pressure, Vacuum reaction chamber inner and outer air pressure reaches poised state；
L) take out and deposited to obtain Bi (AlxGa1-x)O3The substrate of thin-film material, close inert gas piping hand-operated valve K4；
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 step of rapid thermal annealing is：
(a) maintained 3 minutes at 180 DEG C；
(b) maintained 3 minutes at 380 DEG C；
(c) high annealing 5 minutes at 750 DEG C；
Taken out after natural cooling.
A series of test is carried out to resulting film sample.
Embodiment 2：
A the argon gas of more than 99.9995% purity) is filled with vacuum glove box, is completed in the argon atmosphere of glove box following Operation：Weight ratio is weighed as 1：5 triethyl aluminum and triethyl-gallium, is dissolved in dimethylbenzene, obtains the solution that concentration is 0.1M；
It is that the dimethylbenzene commercial sources are bought, by 45%~70% meta-xylene, 15%~25% paraxylene and The mixture that 10%~15% three kinds of ortho-xylene isomers (toatl proportion is by 100%) forms；
B) organo-bismuth source uses triethyl-bismuth, and oxygen precursor source uses deionized water, and inert gas is pure using more than 99.9995% The nitrogen of degree；By organo-bismuth source, step A) obtained organic gallium aluminium source, oxygen precursor source, nitrogen is filled into organo-bismuth source respectively Container 1, organic gallium aluminium source container 2, oxygen precursor source containers 3, inert gas source container 4, then install and connect with respective pipeline；
Driving away the air in pipeline, the specifically operation after each material container installation connects is：
Organo-bismuth source capsule road hand-operated valve K1, organic gallium aluminium source capsule road hand-operated valve K2, oxygen presoma pipeline hand-operated valve K3 is kept to locate In closed mode, then,
Air-inlet of vacuum pump automatic valve AK4 is in open mode by device controller control, made by device controller control Organo-bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve AK2, oxygen presoma pipeline automatic valve AK3 are in opening State；When the vacuum meter in vacuum reaction chamber no longer changes, air-inlet of vacuum pump automatic valve is made by device controller control AK4 is closed, and organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic gallium aluminium source are controlled by device controller Gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 so that each gas piping Middle inert gas is passed through vacuum reaction chamber according to certain value；When the air pressure in vacuum reaction chamber reaches 0.5 atmospheric pressure, again Air-inlet of vacuum pump automatic valve AK4 is in open mode by device controller control, made by device controller control organic Bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve AK2, oxygen presoma pipeline automatic valve AK3 are in open shape State；Repeat said process 5 times；
C) the Si backing materials of cleaning are dried up with the nitrogen of 99.9995% purity, are placed into substrate pallet；
D) pallet moves into vacuum reaction chamber together with Si substrates, opens vavuum pump by device controller, then opens vavuum pump again Air inlet automatic valve AK4, is vacuumized to vacuum reaction chamber；
E the temperature point of organo-bismuth source container 1, organic gallium aluminium source container 2, oxygen precursor source containers 3) is set on device controller Wei not be 190 DEG C, 20 DEG C, 20 DEG C, organo-bismuth source container 1, organic gallium aluminium source container 2, oxygen precursor source are controlled by device controller The electric heater of the container of container 3 and/or the working condition of semiconductor cooler, so that organo-bismuth source container 1, organic gallium aluminium source Container 2, the constant temperature value in setting of the temperature of oxygen precursor source containers 3；
Vacuum chamber is heated by device controller control electric heater, makes pallet in vacuum chamber and substrate temperature whole It is constant at 350 DEG C in individual thin film growth process；
F after constant 25 minutes of cavity temperature of) taking seriously, organo-bismuth source gas-carrier pipeline gas is set on the inputting interface of device controller Rate of flow of fluid, organic gallium aluminium source gas-carrier pipeline gas flow rate, oxygen presoma gas-carrier pipeline gas flow rate, inert gas flow velocity are respectively 200sccm(standard cubic centimeters per minute)、200sccm、220sccm、250sccm；
Triethyl-bismuth gas pulses length is set on the inputting interface of device controller as 0.4s, organic gallium aluminium source gas pulses Length is 0.2s, H2O gas pulses length is 0.1s, and pulse of nitrogen length is 6s；
Represent triethyl-bismuth gas pulses, organic gallium aluminium source gas pulses, H respectively with B, G, O, N2O gas pulses, nitrogen arteries and veins Punching,
In whole growth cycle, gas pulses cyclic sequence is as shown in Figure 3.
Manual unlocking organo-bismuth source capsule road hand-operated valve K1, organic gallium aluminium source capsule road hand-operated valve K2, oxygen presoma pipeline are manual Valve K3, inert gas piping hand-operated valve K4；
G organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic gallium aluminium source gas-carrier pipeline matter) are controlled by device controller Measure flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 so that in each gas piping gas according to Step F) in setting value be passed through vacuum reaction chamber, vacuum reaction chamber is according to step F) in setting gas pulses sequential difference It is passed through nitrogen, organic bismuth source gas, oxygen precursor gas and organic gallium aluminium source gas；All precursor gas respectively use Nitrogen is transported；In film deposition process, vacuum reaction intracavitary maintains the -10hPa of air pressure 1；
Pulse N is realized by following action：
Organo-bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve AK2, oxygen presoma are made by device controller control Pipeline automatic valve AK3 is in closed mode, and organo-bismuth source gas-carrier pipeline mass flow controller is controlled by device controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 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, organic gallium aluminium source capsule road automatic valve by device controller control AK2, oxygen presoma pipeline automatic valve AK3 are in closed mode, and organo-bismuth source gas-carrier pipeline quality is controlled by device controller Flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass 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 O is realized by following action：
Oxygen presoma pipeline automatic valve AK3 is set to be in open mode, organo-bismuth source capsule road automatic valve by device controller control AK1, organic gallium aluminium source capsule road automatic valve AK2 are in closed mode, and organo-bismuth source gas-carrier pipeline matter is controlled by device controller Measure flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline quality stream Amount controller MFC3 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 aluminium source capsule road automatic valve AK2 is set to be in open mode, organo-bismuth source capsule road automatic valve by device controller control AK1, oxygen presoma pipeline automatic valve AK3 are in closed mode, and organo-bismuth source gas-carrier pipeline quality is controlled by device controller Flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow Controller MFC3 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 Bi (AlxGa1-x)O3Thin-film material, organo-bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve are closed by device controller AK2, oxygen presoma pipeline automatic valve AK3, stopping are passed through organo-bismuth source, organic gallium aluminium source, oxygen presoma, continue to be passed through indifferent gas Body, stop powering to electric heater, stop heating vacuum chamber；
I) manual-lock organo-bismuth source capsule road hand-operated valve K1, organic gallium aluminium source capsule road hand-operated valve K2, oxygen presoma pipeline hand-operated valve K3, inert gas piping hand-operated valve K4, air-inlet of vacuum pump automatic valve AK4 are remained on, and vacuum reaction chamber is carried out certainly So cooling；
J) vacuum chamber reaches or during close to room temperature, and air-inlet of vacuum pump automatic valve AK4 is closed by device controller；
K air-inlet of vacuum pump automatic valve AK4) is closed, vacuum reaction chamber, which is inflated, makes its air pressure reach an atmospheric pressure, Vacuum reaction chamber inner and outer air pressure reaches poised state；
L) take out and deposited to obtain Bi (AlxGa1-x)O3The substrate of thin-film material, close inert gas piping hand-operated valve K4；
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 step of rapid thermal annealing is：
(a) maintained 3 minutes at 200 DEG C；
(b) maintained 3 minutes at 400 DEG C；
(c) high annealing 4 minutes at 850 DEG C；
Taken out after natural cooling.
A series of test is carried out to resulting film sample.
Embodiment 3：
A the argon gas of more than 99.9995% purity) is filled with vacuum glove box, is completed in the argon atmosphere of glove box following Operation：Weight ratio is weighed as 1：1 triethyl aluminum and triethyl-gallium, is dissolved in dimethylbenzene, obtains the solution that concentration is 0.1M；
It is that the dimethylbenzene commercial sources are bought, by 45%~70% meta-xylene, 15%~25% paraxylene and The mixture that 10%~15% three kinds of ortho-xylene isomers (toatl proportion is by 100%) forms；
B) organo-bismuth source uses triethyl-bismuth, and oxygen precursor source uses O2、O3Mixed gas, inert gas use The nitrogen of more than 99.9995% purity；By organo-bismuth source, step A) obtained organic gallium aluminium source, oxygen precursor source, nitrogen difference Be filled into organo-bismuth source container 1, organic gallium aluminium source container 2, oxygen precursor source containers 3, inert gas source container 4, then with respectively Install and connect from pipeline；
Drive away the air in pipeline after each material container installation connects：
Organo-bismuth source capsule road hand-operated valve K1, organic gallium aluminium source capsule road hand-operated valve K2, oxygen presoma pipeline hand-operated valve K3 is kept to locate In closed mode, then,
Air-inlet of vacuum pump automatic valve AK4 is in open mode by device controller control, made by device controller control Organo-bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve AK2, oxygen presoma pipeline automatic valve AK3 are in opening State；When the vacuum meter in vacuum reaction chamber no longer changes, air-inlet of vacuum pump automatic valve is made by device controller control AK4 is closed, and organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic gallium aluminium source are controlled by device controller Gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 so that each gas piping Middle inert gas is passed through vacuum reaction chamber according to certain value；When the air pressure in vacuum reaction chamber reaches 0.5 atmospheric pressure, again Air-inlet of vacuum pump automatic valve AK4 is in open mode by device controller control, made by device controller control organic Bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve AK2, oxygen presoma pipeline automatic valve AK3 are in open shape State；Repeat said process 5 times；
C) by the SiO of cleaning2Backing material is dried up with the nitrogen of 99.9995% purity, is placed into substrate pallet；
D) pallet is together with SiO2Substrate moves into vacuum reaction chamber, opens vavuum pump by device controller, then opens vacuum again Pump steam inlet automatic valve AK4, is vacuumized to vacuum reaction chamber；
E respectively 190 DEG C, 20 DEG C of organo-bismuth source container 1, organic gallium aluminium source container 2) are set on device controller, by equipment The working condition of controller control organo-bismuth source container 1, the electric heater of organic gallium aluminium source container 2 and/or semiconductor cooler, So that organo-bismuth source container 1, organic gallium aluminium source container 2, the constant temperature value in setting of the temperature of oxygen precursor source containers 3；
Vacuum chamber is heated by device controller control electric heater, makes pallet in vacuum chamber and substrate temperature whole It is constant at 330 DEG C in individual thin film growth process；
F after constant 30 minutes of cavity temperature of) taking seriously, organo-bismuth source gas-carrier pipeline gas is set on the inputting interface of device controller Rate of flow of fluid, organic gallium aluminium source gas-carrier pipeline gas flow rate, oxygen presoma gas-carrier pipeline gas flow rate, inert gas flow velocity are respectively 200sccm(standard cubic centimeters per minute)、200sccm、250sccm、250sccm；
Triethyl-bismuth gas pulses length is set on the inputting interface of device controller as 0.3s, organic gallium aluminium source gas pulses Length is 0.2s, O2、O3Mixed gas pulse length be 4s, pulse of nitrogen length is 6s；
Represent triethyl-bismuth gas pulses, organic gallium aluminium source gas pulses, H respectively with B, G, O, N2O gas pulses, nitrogen arteries and veins Punching,
In whole growth cycle, gas pulses cyclic sequence is as shown in Figure 4.
Manual unlocking organo-bismuth source capsule road hand-operated valve K1, organic gallium aluminium source capsule road hand-operated valve K2, oxygen presoma pipeline are manual Valve K3, inert gas piping hand-operated valve K4；
G organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic gallium aluminium source gas-carrier pipeline matter) are controlled by device controller Measure flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 so that in each gas piping gas according to Step F) in setting value be passed through vacuum reaction chamber, vacuum reaction chamber is according to step F) in setting gas pulses sequential difference It is passed through nitrogen, organic bismuth source gas, oxygen precursor gas and organic gallium aluminium source gas；All precursor gas respectively use Nitrogen is transported；In film deposition process, vacuum reaction intracavitary maintains the -10hPa of air pressure 1；
Pulse N is realized by following action：
Organo-bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve AK2, oxygen presoma are made by device controller control Pipeline automatic valve AK3 is in closed mode, and organo-bismuth source gas-carrier pipeline mass flow controller is controlled by device controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 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, organic gallium aluminium source capsule road automatic valve by device controller control AK2, oxygen presoma pipeline automatic valve AK3 are in closed mode, and organo-bismuth source gas-carrier pipeline quality is controlled by device controller Flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass 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 O is realized by following action：
Oxygen presoma pipeline automatic valve AK3 is set to be in open mode, organo-bismuth source capsule road automatic valve by device controller control AK1, organic gallium aluminium source capsule road automatic valve AK2 are in closed mode, and organo-bismuth source gas-carrier pipeline matter is controlled by device controller Measure flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline quality stream Amount controller MFC3 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 aluminium source capsule road automatic valve AK2 is set to be in open mode, organo-bismuth source capsule road automatic valve by device controller control AK1, oxygen presoma pipeline automatic valve AK3 are in closed mode, and organo-bismuth source gas-carrier pipeline quality is controlled by device controller Flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow Controller MFC3 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 Bi (AlxGa1-x)O3Thin-film material, organo-bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve are closed by device controller AK2, oxygen presoma pipeline automatic valve AK3, stopping are passed through organo-bismuth source, organic gallium aluminium source, oxygen presoma, continue to be passed through indifferent gas Body, stop powering to electric heater, stop heating vacuum chamber；
I) manual-lock organo-bismuth source capsule road hand-operated valve K1, organic gallium aluminium source capsule road hand-operated valve K2, oxygen presoma pipeline hand-operated valve K3, inert gas piping hand-operated valve K4, air-inlet of vacuum pump automatic valve AK4 are remained on, and vacuum reaction chamber is carried out certainly So cooling；
J) vacuum chamber reaches or during close to room temperature, and air-inlet of vacuum pump automatic valve AK4 is closed by device controller；
K air-inlet of vacuum pump automatic valve AK4) is closed, vacuum reaction chamber, which is inflated, makes its air pressure reach an atmospheric pressure, Vacuum reaction chamber inner and outer air pressure reaches poised state；
L) take out and deposited to obtain Bi (AlxGa1-x)O3The substrate of thin-film material, close inert gas piping hand-operated valve K4；
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 step of rapid thermal annealing is：
(a) maintained 3 minutes at 200 DEG C；
(b) maintained 3 minutes at 400 DEG C；
(c) high annealing 4 minutes at 950 DEG C；
Taken out after natural cooling.
A series of test is carried out to resulting film sample.

Claims (6)

1. one kind is used to prepare Bi (AlxGa1-x)O3The device of the method for thin-film material, it is characterised in that：
Device includes but is not limited to：Vacuum reaction chamber, vacuum meter, vavuum pump, organo-bismuth source container 1, organo-bismuth source capsule road are manual Valve K1, organo-bismuth source capsule road automatic valve AK1, organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic gallium aluminium source container 2nd, organic gallium aluminium source capsule road hand-operated valve K2, organic gallium aluminium source capsule road automatic valve AK2, organic gallium aluminium source gas-carrier pipeline mass flow control Device MFC2 processed, oxygen precursor source containers 3, oxygen presoma pipeline hand-operated valve K3, oxygen presoma pipeline automatic valve AK3, oxygen presoma Gas-carrier pipeline mass flow controller MFC3, inert gas container 4, inert gas piping hand-operated valve K4, air-inlet of vacuum pump are certainly Movable valve AK4, device controller, electric heater and temperature sensor are provided with vacuum reaction chamber；It is organo-bismuth source container 1, organic Gallium aluminium source container 2, the container of oxygen precursor source containers 3 are equipped with electric heater and semiconductor cooler；
Organic gallium aluminium source container 2 is for holding organic silicon source, the solution that organic gallium source mixed dissolution obtains in organic solvent；
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 gallium aluminium source container 2 are consecutively connected to organic gallium aluminium source by gas piping Pipeline hand-operated valve K2, organic gallium aluminium source capsule road automatic valve AK2, vacuum reaction chamber, the outlet of oxygen precursor source containers 3 passes through gas Pipeline is consecutively connected to oxygen presoma pipeline hand-operated valve K3, oxygen presoma pipeline automatic valve AK3, vacuum reaction chamber, inert gas The outlet of container 4 is connected to inert gas piping hand-operated valve K4 by gas piping, then has been connected respectively to by branch line Machine bismuth source gas-carrier pipeline mass flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen forerunner Body gas-carrier pipeline mass flow controller MFC3, organo-bismuth source gas-carrier pipeline mass flow controller MFC1 outlet pass through threeway Connector is connected on the gas piping between organo-bismuth source capsule road automatic valve AK1 and vacuum reaction chamber, the carrier gas of organic gallium aluminium source Pipeline quality flow controller MFC2 outlet is connected to organic gallium aluminium source capsule road automatic valve AK2 and vacuum by three-way connector On gas piping between reaction chamber, oxygen presoma gas-carrier pipeline mass flow controller MFC3 outlet passes through three-way connector It is connected on the gas piping between organo-bismuth source capsule road automatic valve AK3 and vacuum reaction chamber, the outlet of vacuum reaction chamber passes through Pipeline is consecutively connected to air-inlet of vacuum pump automatic valve AK4, the air inlet of vavuum pump；Vacuum meter is provided with vacuum chamber；
Organo-bismuth source capsule road hand-operated valve K1, organic gallium aluminium source capsule road hand-operated valve K2, oxygen presoma pipeline hand-operated valve K3, inert gas Pipeline hand-operated valve K4 is controlled by operating personnel's manual unlocking, uncontrolled device；
Vacuum meter, organo-bismuth source capsule road automatic valve AK1, organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organic gallium aluminium Source capsule road automatic valve AK2, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen precursor source containers 3, oxygen presoma Pipeline automatic valve AK3, oxygen presoma gas-carrier pipeline mass flow controller MFC3, vacuum reaction chamber, vavuum pump, vavuum pump air inlet Mouth automatic valve AK4, the electric heater in vacuum reaction chamber, temperature sensor and the organo-bismuth source container 1, organic gallium aluminium Source container 2, the electric heater of oxygen precursor source containers 3 and semiconductor cooler are logical by cable connection to device controller Cable connection is crossed to device controller, by the respective working condition of device controller centralized Control；
Inert purge gas pulses, organo-bismuth source gas pulses, oxygen precursor gas pulse and organic are represented with N, B, O, G respectively Gallium aluminium source gas pulses, then：
Pulse N is realized by following action：
Organo-bismuth source capsule road automatic valve AK1, organic gallium aluminium source capsule road automatic valve AK2, oxygen presoma are made by device controller control Pipeline automatic valve AK3 is in closed mode, and organo-bismuth source gas-carrier pipeline mass flow controller is controlled by device controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3, 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, organic gallium aluminium source capsule road automatic valve by device controller control AK2, oxygen presoma pipeline automatic valve AK3 are in closed mode, and organo-bismuth source gas-carrier pipeline quality is controlled by device controller Flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow Controller MFC3 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 presoma pipeline automatic valve AK3 is set to be in open mode, organo-bismuth source capsule road automatic valve by device controller control AK1, organic gallium aluminium source capsule road automatic valve AK2 are in closed mode, and organo-bismuth source gas-carrier pipeline matter is controlled by device controller Measure flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline quality stream Amount controller MFC3 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 aluminium source capsule road automatic valve AK2 is set to be in open mode, organo-bismuth source capsule road automatic valve by device controller control AK1, oxygen presoma pipeline automatic valve AK3 are in closed mode, and organo-bismuth source gas-carrier pipeline quality is controlled by device controller Flow controller MFC1, organic gallium aluminium source gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow Controller MFC3 so that gas is passed through vacuum reaction chamber according to setting value in each gas piping.
A kind of 2. preparation Bi (Al as claimed in claim 1xGa1-x)O3The device of thin-film material, it is characterised in that：
Pallet is driven by motor, drives substrate evenly to rotate.
A kind of 3. preparation Bi (Al as claimed in claim 1xGa1-x)O3The device of thin-film material, 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 4. preparation Bi (Al as claimed in claim 1xGa1-x)O3The device of thin-film material, 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 5. preparation Bi (Al as claimed in claim 1xGa1-x)O3The device of thin-film material, it is characterised in that：
Device controller is PLC or FPGA or SCM system or computer or the circuit system specially designed.
A kind of 6. preparation Bi (Al as claimed in claim 1xGa1-x)O3The device of thin-film material, it is characterised in that：
Added by the electricity of container of device controller control organo-bismuth source container 1, organic gallium aluminium source container 2, oxygen precursor source containers 3 The working condition of hot device and semiconductor cooler, so that organo-bismuth source container 1, organic gallium aluminium source container 2, oxygen precursor source containers The 3 constant temperature value in setting of temperature；The gathered data of temperature sensor by cable transmission to device controller, to realize The PID control of temperature（Proportional integral differential control）.
CN201710579305.6A 2015-11-11 2015-11-11 Organo-aluminium, the miscible formula in gallium source prepare the device of gallium aluminium acid bismuth thin film Pending CN107460452A (en)

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Application publication date: 20171212