CN105386006A - Method for manufacturing BiGaO3 film in precursor time division manner - Google Patents

Method for manufacturing BiGaO3 film in precursor time division manner Download PDF

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CN105386006A
CN105386006A CN201510766400.8A CN201510766400A CN105386006A CN 105386006 A CN105386006 A CN 105386006A CN 201510766400 A CN201510766400 A CN 201510766400A CN 105386006 A CN105386006 A CN 105386006A
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gas
presoma
bismuth
gallium
pipeline
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CN105386006B (en
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尹海宏
王志亮
宋长青
张金中
史敏
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Nantong University Technology Transfer Center Co ltd
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Nantong University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—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 deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/409—Oxides of the type ABO3 with A representing alkali, alkaline earth metal or lead and B representing a refractory metal, nickel, scandium or a lanthanide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—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 deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • 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
    • C23C16/52—Controlling or regulating the coating process
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/16—Controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides

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Abstract

The invention provides a method for manufacturing a BiGaO3 film in a precursor time division manner. According to the method for manufacturing a BiGaO3 film material in the precursor time division manner through a self-restrictive surface adsorption reaction, the BiGaO3 film material grows on a substrate material, the space group of the BiGaO3 film material is Pcca, the lattice constant a is equal to 5.626 A, b is equal to 5.081 A, and c is equal to 10.339 A, the BiGaO3 film material grows on a selected substrate, the obtained preferred orientation is (112), and the BiGaO3 film material is obtained in the precursor time division manner through the self-restrictive surface adsorption reaction, wherein the surface adsorption reaction particularly refers to an irreversible chemical adsorption reaction of a Langmuir adsorption mechanism. By the adoption of the method for manufacturing the BiGaO3 film, the growth thickness of the BiGaO3 film can be accurately controlled, and the surface flatness of the BiGaO3 film is greatly superior to that in the prior art.

Description

Presoma time division formula prepares the method for gallic acid bismuth thin film
Technical field
The present invention relates to a kind of bismuth-based oxide thin-film material, specifically a kind of BiGaO 3ferroelectric thin-flim materials and preparation method thereof.
Background technology
Recently it is found that bismuth-based ferroelectric material is as bismuth ferrite (BiFeO 3), bismuth titanates (Bi 4ti 3o 12), Bismuth Aluminate (BiAlO 3) etc. the ferroelectric oxide of uhligite or counterfeit perovskite structure have that electric leakage is little, fatigue resistance is strong, specific inductivity is large and the feature such as environmentally friendly and receiving much concern.In recent years, people are to bismuth ferrite (BiFeO 3) and bismuth titanates (Bi 4ti 3o 12) design, preparation, physicochemical property and produce and life in application had general understanding and understanding, the people such as Baettig in 2005 have foretold gallic acid bismuth (BiGaO theoretically 3) there is excellent ferroelectric properties equally, but current people are to gallic acid bismuth (BiGaO 3) technology of preparing of material also very lacks, and only has report to adopt High Temperature High Pressure solid reaction process (pressure is more than 1,000 degree Celsius in GPa magnitude, temperature) to prepare gallic acid bismuth (BiGaO 3) block materials, and such high temperature, high pressure working condition, obviously be not suitable for applying to the production that microelectronic industry carries out device, unicircuit, its block materials also cannot be applied to the microelectronic more and more microminiaturized, integrated level is more and more higher, and the preparation technology being applicable to the gallic acid bismuth thin film of microelectronic not yet has report.
In document CN103880078A, we have disclosed a kind of chemical solution spin-coating method that adopts and prepare GaBiO 3the method of thin-film material.But in preparation big area height thickness evenness, thickness nano level exact controllability, chemical solution spin-coating method is really helpless, is also difficult to integrated, compatible with semiconductor fabrication process.
Summary of the invention
In order to solve prior art problem, the object of the present invention is to provide a kind of BiGaO of space-time separate type from restricted surface adsorption reaction preparation that accurately can control film thickness 3the method of thin-film material.Realizing the concrete technical scheme of the object of the invention is:
A kind of BiGaO 3the preparation method of thin-film material, adopt custom-designed device, described device has following feature:
Include bismuth precursor source 1, bismuth presoma pipeline manual valve K1, bismuth presoma pipeline self-acting valve AK1, bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium precursor source 2, gallium presoma pipeline manual valve K2, gallium presoma pipeline self-acting valve AK2, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen precursor source 3, oxygen presoma pipeline manual valve K3, oxygen presoma pipeline self-acting valve AK3, oxygen presoma gas-carrier pipeline mass flow controller MFC3, inert gas source 4, inert gas piping manual valve K4, vacuum reaction chamber, vacuum pump, air-inlet of vacuum pump automatic valve AK4, device control unit, electric heater and temperature sensor is provided with in vacuum reaction chamber, device control unit can be PLC, SCM system, computer or custom-designed Circuits System, the container of bismuth precursor source 1, gallium precursor source 2, oxygen precursor source 3 is equipped with electric heater and semiconductor cooler,
The outlet of bismuth precursor source 1 is connected to bismuth presoma pipeline manual valve K1 successively by gas piping, bismuth presoma pipeline self-acting valve AK1, vacuum reaction chamber, the outlet of gallium precursor source 2 is connected to gallium presoma pipeline manual valve K2 successively by gas piping, gallium presoma pipeline self-acting valve AK2, vacuum reaction chamber, the outlet of oxygen precursor source 3 is connected to oxygen presoma pipeline manual valve K3 successively by gas piping, oxygen presoma pipeline self-acting valve AK3, vacuum reaction chamber, the outlet of inert gas source 4 is connected to inert gas piping manual valve K4 by gas piping, bismuth presoma gas-carrier pipeline mass flow controller MFC1 is connected respectively to again by branch line, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3, the outlet of bismuth presoma gas-carrier pipeline mass flow controller MFC1 is connected on the gas piping between bismuth presoma pipeline self-acting valve AK1 and vacuum reaction chamber by three-way connector, the outlet of gallium presoma gas-carrier pipeline mass flow controller MFC2 is connected on the gas piping between gallium presoma pipeline self-acting valve AK2 and vacuum reaction chamber by three-way connector, the outlet of oxygen presoma gas-carrier pipeline mass flow controller MFC3 is connected on the gas piping between bismuth presoma pipeline self-acting valve AK3 and vacuum reaction chamber by three-way connector, the outlet of vacuum reaction chamber is connected to air-inlet of vacuum pump automatic valve AK4 successively by pipeline, the inlet mouth of vacuum pump,
Bismuth precursor source 1, bismuth presoma pipeline self-acting valve AK1, bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium precursor source 2, gallium presoma pipeline self-acting valve AK2, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen precursor source 3, oxygen presoma pipeline self-acting valve AK3, oxygen presoma gas-carrier pipeline mass flow controller MFC3, vacuum reaction chamber, vacuum pump, air-inlet of vacuum pump automatic valve AK4, electric heater in vacuum reaction chamber, temperature sensor, the electric heater of described container and semiconductor cooler are all connected to device control unit by cable and are all connected to device control unit by cable, by device control unit centralized Control working order separately,
The image data of temperature sensor to device control unit by cable transmission, is controlled (proportional integral differential control) with the PID realizing temperature, the temperature of vacuum reaction chamber can be made to reach the temperature value of setting rapidly, exactly;
Bismuth presoma pipeline manual valve K1, gallium presoma pipeline manual valve K2, oxygen presoma pipeline manual valve K3, inert gas piping manual valve K4 are by operator's manual unlocking, and uncontrolled device controlled, and this design can guarantee safety;
Bismuth precursor source 1, gallium precursor source 2, the electric heater of container of oxygen precursor source 3 and the working order of semiconductor cooler is controlled, to make the temperature of bismuth precursor source 1, gallium precursor source 2, oxygen precursor source 3 can the constant temperature value in setting by device control unit;
Described BiGaO 3the preparation method of thin-film material, includes but not limited to following concrete steps:
A) the substrate material rare gas element of cleaning is dried up, be placed in substrate pallet;
B) pallet moves into vacuum reaction chamber together with substrate, opens vacuum pump by device control unit, and then opens air-inlet of vacuum pump automatic valve AK4, vacuumizes vacuum reaction chamber;
C) on device control unit, bismuth precursor source 1 is set, gallium precursor source 2, the temperature of oxygen precursor source 3, bismuth precursor source 1 is controlled by device control unit, gallium precursor source 2, the electric heater of the container of oxygen precursor source 3 and/or the working order of semiconductor cooler, to make bismuth precursor source 1, gallium precursor source 2, the homo(io)thermism of oxygen precursor source 3 is at the temperature value of setting, make under the temperature value of set each presoma, bismuth precursor source 1, gallium precursor source 2, the vapor pressure of oxygen precursor source 3 is greater than inert gas source 4 by mass flow controller MFC1, MFC2, pressure after MFC3 in gas piping,
Control electric heater by device control unit to heat vacuum chamber, make the pallet in vacuum chamber and substrate temperature in whole thin film growth process, maintain a suitable temperature window;
Selected suitable temperature window refers to: in suitable temperature range, namely substrate temperature higher than a lowest temperature lower than a upper temperature limit, and the flow velocity of precursor gas supply is when being greater than minimum limit value, the growth velocity of film is a substantially invariable value, the flow velocity that the growth velocity of film and precursor gas are supplied, the flow velocity of carrier gas and rare gas element, the temperature of presoma, substrate temperature, the vacuum tightness of the compartment of vacuum chamber is substantially irrelevant, " substantially irrelevant " described here refers to: even if the growth velocity of film has fluctuation in this temperature window, also be slight fluctuations, when growth temperature exceeds this temperature window namely lower than lowest temperature or higher than upper temperature limit, the growth velocity of film can increase significantly or reduce,
In temperature window, sedimentation rate does not vary with temperature; When temperature is not high enough, presoma condensation causes multilayer absorption to cause too high sedimentation rate, or causes absorption not exclusively, and reactive behavior is poor; When temperature is too high, presoma decomposes and causes extra CVD formula growth, or due to too high hot kinetic energy, presoma desorption;
D) when after vacuum chamber homo(io)thermism for some time, be generally 5 ~ 30 minutes, device control unit sets the cycle index of film growth, bismuth presoma gas-carrier pipeline gas flow rate, gallium presoma gas-carrier pipeline gas flow rate, oxygen presoma gas-carrier pipeline gas flow rate, rare gas element flow velocity; Manual unlocking bismuth presoma pipeline manual valve K1, gallium presoma pipeline manual valve K2, oxygen presoma pipeline manual valve K2, inert gas piping manual valve K4;
E) bismuth presoma gas-carrier pipeline mass flow controller MFC1 is controlled by device control unit, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber, vacuum reaction chamber passes into rare gas element respectively according to certain gas pulses sequential, three (2, 2, 6, 6-tetramethyl--3, the acid of 5-heptadione) bismuth (III) or other bismuth precursor gas, oxygen precursor gas and trimethyl-gallium gas or other gallium precursor gas, all precursor gas adopt rare gas element to transport respectively,
F) when film growth cycle index reaches the number of times of setting, film thickness reaches desirable value, obtains certain thickness BiGaO 3thin-film material, bismuth presoma pipeline self-acting valve AK1, gallium presoma pipeline self-acting valve AK2, oxygen presoma pipeline self-acting valve AK3 is closed by device control unit, stop passing into bismuth presoma, gallium presoma, oxygen presoma, continue to pass into rare gas element, stop powering to electric heater, stop heating vacuum chamber;
G) manual-lock bismuth presoma pipeline manual valve K1, gallium presoma pipeline manual valve K2, oxygen presoma pipeline manual valve K3, inert gas piping manual valve K4, air-inlet of vacuum pump automatic valve AK4 stay open state, and vacuum reaction chamber carries out naturally cooling;
H) vacuum chamber reach or close to room temperature time, close air-inlet of vacuum pump automatic valve AK4 by device control unit;
I) close air-inlet of vacuum pump automatic valve AK4, carry out inflation to vacuum reaction chamber and make its air pressure reach a normal atmosphere, vacuum reaction chamber inner and outer air pressure reaches equilibrium state;
J) taking-up has deposited and has obtained BiGaO 3the substrate of thin-film material, closes inert gas piping manual valve K4;
K) BiGaO is attached with by what obtain in step J 3the substrate of thin-film material, puts into quick anneal oven, carries out quick thermal annealing process, takes out after naturally cooling;
The step of rapid thermal annealing is:
A () maintains 1-10 minute at 180-220 DEG C;
B () maintains 1-10 minute at 390-400 DEG C;
C () be high temperature annealing 1-10 minute at 700 DEG C-750 DEG C;
In step e) in, described gas pulses sequential is by inert purge gas pulses, three (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) bismuth (III) or other bismuth precursor gas pulses, the pulse of oxygen precursor gas and trimethyl-gallium gas or other gallium precursor gas pulses composition, if represent inert purge gas pulses, three (2 with N, B, O, G respectively, 2,6, the acid of 6-tetramethyl--3,5-heptadione) bismuth (III) or other bismuth precursor gas pulses, the pulse of oxygen precursor gas and trimethyl-gallium gas or other gallium precursor gas pulses, then:
Pulse N is realized by following action:
Controlled to make bismuth presoma pipeline self-acting valve AK1, gallium presoma pipeline self-acting valve AK2, oxygen presoma pipeline self-acting valve AK3 all be in closing condition by device control unit, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make rare gas element in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
Pulse B is realized by following action:
Controlled to make bismuth presoma pipeline self-acting valve AK1 be in open mode by device control unit, gallium presoma pipeline self-acting valve AK2, oxygen presoma pipeline self-acting valve AK3 are all in closing condition, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
Pulse O is realized by following action:
Controlled to make oxygen presoma pipeline self-acting valve AK3 be in open mode by device control unit, bismuth presoma pipeline self-acting valve AK1, gallium presoma pipeline self-acting valve AK2 are all in closing condition, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
Pulse G is realized by following action:
Controlled to make gallium presoma pipeline self-acting valve AK2 be in open mode by device control unit, bismuth presoma pipeline self-acting valve AK1, oxygen presoma pipeline self-acting valve AK3 are all in closing condition, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
The rule of these gas pulses sequential aforementioned is as follows:
Any one three (2,2,6, the acid of 6-tetramethyl--3,5-heptadione) before or after bismuth (III) gas pulses or the pulse of oxygen precursor gas or trimethyl-gallium gas pulses, all there is an inert purge gas pulses, namely, such as: BN ..., or GN ..., or ON ... or ... NBN ... or ... NGN ..., or ... NON ..., suspension points " ... " represents other possible collating sequences herein; And when meeting above-mentioned condition,
Any one three (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) the secondary adjacent place of bismuth (III) gas pulses or trimethyl-gallium gas pulses, all also there is the pulse of an oxygen precursor gas, that is, such as: ... NONBN ... or ... NONGN ... or ... NBNON ..., or ... NGNON ..., suspension points " ... " represents other possible collating sequences herein; And when meeting above-mentioned condition,
Three (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) bismuth (III) gas pulses, the pulse of oxygen precursor gas, trimethyl-gallium gas pulses, inert purge gas pulses can arrange with any order, can be multiple three (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) bismuth (III) gas pulses or the pulse of oxygen precursor gas or trimethyl-gallium gas pulses and inert purge gas pulses continuous distribution successively, then one or more groups all the other precursor gas pulses adjacent, in other words, one or morely pass into trimethyl-gallium gas pulses, one or morely pass into three (2, 2, 6, 6-tetramethyl--3, the acid of 5-heptadione) bismuth (III) pulse, one or morely pass into the pulse of oxygen precursor gas and can arrange with any order, for example, the pulse of bismuth precursor gas, the pulse of oxygen precursor gas, the pulse of gallium precursor gas, the sequence of inert purge gas pulses can be ... BNONBNONBNONGNONBNONGNON also can be ... BNONGNONBNONBNONBNONBNONGNON can also be ... GNONGNONBNONBNONBNONBNONBNON or ... GNONBNONBNONBNONBNONGNONBNON ... etc., suspension points " ... " represents other possible collating sequences herein,
These gas pulses sequences are controlled the open and close of corresponding self-acting valve to realize by device control unit, and are performed the growth cycle circulation of particular sequence by program.
In a growth cycle, the quantity of each gas pulses is the multiple of 4 and is not less than 8, such as: 4,8,12,16 ... etc.; Each gas pulses is passed in vacuum reaction chamber successively by pipeline, and pallet and substrate are exposed in the atmosphere of these gas pulses formation successively; And,
In a growth cycle, the quantity sum of the pulse of bismuth precursor gas and the pulse of gallium precursor gas equals the quantity of oxygen presoma pulse, and the quantity sum of the pulse of bismuth precursor gas, the pulse of gallium precursor gas and the pulse of oxygen precursor gas equals the quantity of inert purge gas pulses;
Consider the space steric effect of organic precursor molecule, the quantity of bismuth precursor gas pulse might not be equal with the quantity of gallium precursor gas pulse, but distribute according to following principle:
In a growth cycle, the bismuth that deposited on substrates obtains, the stoichiometric ratio of gallium are close to 1:1, allow the positive error of less than 10%, namely the stoichiometric ratio of bismuth, gallium is in the scope of 1:1 ~ 1:1.1, and this is the adequate compensation of making owing to needing consideration bismuth element in step K rapid thermal annealing easily to volatilize;
When meeting above-mentioned requirements, the pulse of bismuth precursor gas, the pulse of gallium precursor gas the time are as much as possible uniformly distributed arrangement in a growth cycle.
In membrane-film preparation process, the temperature of choose reasonable vacuum reaction chamber, three (2, 2, 6, 6-tetramethyl--3, the acid of 5-heptadione) bismuth (III), trimethyl-gallium, the flow velocity of rare gas element, pressure, make substrate material be exposed to three (2 at every turn, 2, 6, 6-tetramethyl--3, the acid of 5-heptadione) bismuth (III), trimethyl-gallium, time in oxygen presoma atmosphere, substrate material surface all can be made intactly to adsorb a unimolecular layer three (2, 2, 6, 6-tetramethyl--3, the acid of 5-heptadione) bismuth (III) or trimethyl-gallium, its absorption mechanism is Langmuir (Langmuir) absorption, when substrate is exposed in the atmosphere of two kinds of presomas successively, complete a thin film deposition, such as, substrate, through BNON pulse sequence, deposits one deck Bi 2o 3.
If we define precursor molecule in the absorption fraction of coverage on solid substrate surface is θ, adsorbing filament technique k a(r a=k ap (1-θ)) and desorption rate constants k d(r d=k dθ)), so adsorb fraction of coverage and can be expressed as d θ/dt over time, have:
d θ d t = r a - r d = k a p ( 1 - θ ) - k d θ - - - ( 1 )
After absorption reaches capacity, fraction of coverage reaches steady state value, d θ/dt=0, and so we just can obtain equation:
θ e q = k a p k a p + k d = 1 1 + ( K p ) - 1 , ( K = k a k d ) - - - ( 2 )
Namely fraction of coverage is the function of reactant gas dividing potential drop.The Langmuir equation that precursor molecule that Here it is is adsorbed at chemistry of solid surfaces.
In order to realize from restricted reaction, adsorption is necessarily required to be irreversible, i.e. k d=0, at this moment K will trend towards infinity, have:
lim K → ∞ θ e q = 1 - - - ( 3 )
This means that absorption fraction of coverage just can trend towards 100% gradually.Time required so is in theory tending towards infinite, and in reality, when we often think that the increase of fraction of coverage becomes very slow, it is exactly saturated.
In the present invention, 2 ~ 8s is got in the pulse of bismuth precursor gas, and 0.1 ~ 2s is got in the pulse of gallium precursor gas, and 0.1 ~ 6s is got in the pulse of oxygen precursor gas, substantially think and each precursor molecule can enough complete once complete surface adsorption in the chemisorption of substrate surface, fraction of coverage is close to 100%.
In any precursor gas pulse, the precursor molecule of a molecular layer is formed except being adsorbed on substrate surface, remaining unnecessary precursor molecule will take away by inert purge gas pulses following closely, discharged outside vacuum reaction chamber by vacuum pump, that is, after substrate surface occurs each time " half-reaction ", substrate surface can form at most certain atoms of precursor of one deck, in fact, typically, due to the steric effect of precursor molecule, or claim the bridging effect of organic group, shade influence, once can not form certain atoms of precursor of one deck at substrate surface after " half-reaction ", but need repeatedly " half-reaction " certain atoms of precursor of one deck can be formed at substrate surface.
Just based on above-mentioned principle, preparation BiGaO of the present invention 3the method of thin-film material, really can realize the controllable precise of thickness during film growth.This is that other any film growth techniques cannot match in excellence or beauty.
In membrane-film preparation process, underlayer temperature is positioned at aforesaid suitable temperature window, be exposed to bismuth precursor gas atmosphere at substrate at every turn, gallium precursor gas atmosphere, during oxygen precursor gas atmosphere, the Chemisorption of substrate surface is " half-reaction " (" half-reaction "), instead of once complete Chemisorption, substrate is only had to be exposed to bismuth precursor gas atmosphere and oxygen precursor gas atmosphere for twice respectively, or gallium precursor gas atmosphere and oxygen precursor gas atmosphere, just complete once complete Chemisorption, obtain the Bi of an atomic shell respectively 2o 3or Ga 2o 3,
Three (2 are exposed to successively with substrate, 2,6, the acid of 6-tetramethyl--3,5-heptadione) bismuth (III) atmosphere and steam atmosphere be example, substrate is three (2,2,6,6-tetramethyl--3,5-heptadione acid) bismuth (III) atmosphere time its chemical absorption of surface reaction be:
※Bi–OH+Bi(tmhd) 3(g)→※Bi–O–Bi(tmhd) 2+Htmhd(4)
Then, substrate again when steam atmosphere its chemical absorption of surface reaction be:
※Bi–tmhd+H 2O(g)→※Bi–OH+Htmhd(5)
Here, ※ represents substrate surface adsorption potential, and the alphabetical g in bracket represents gaseous state.So just complete once complete Chemisorption at substrate surface, obtain the Bi of an atomic shell 2o 3.In fact, actual Chemisorption may more complicated than above described by two equations, such as, and a Bi (tmhd) 3molecule may with more than one hydroxyl (– OH) combine, see equation (4).
In the present invention, the molecular formula of three (acid of 2,2,6,6-tetramethyl--3,5-heptadione) bismuth (III) is expressed as Bi (tmhd) 3, wherein tmhd represents 2,2,6,6-tetramethyl--3,5-heptadione acid-group.
Confirm, through step H through X-ray diffraction (XRD) test and structure refinement) BiGaO that obtains 3the spacer of thin-film material is Pcca, and lattice parameter is described BiGaO 3thin-film material is (112) in the preferred orientation that selected Grown obtains.
Due to thickness controllable precise when method of the present invention can realize film growth, but every secondary growth at most only obtains the material of an atomic shell, and the speed of growth is lower, therefore, is generally used for the BiGaO of the thickness growing several nanometer to tens nanometer 3thin-film material, maximum hundreds of nanometer, is less than 500 nanometers, otherwise its too low speed of growth will become and cannot accept.
In the present invention, described substrate can be Si, LaNiO 3/ Si, Pt/TiO 2/ SiO 2/ Si, Pt/Ti/SiO 2/ Si can also be other suitable substrates, as TiN, SiO 2deng.
In the present invention, term " rare gas element " not only refers to the rare gas element (helium, argon gas etc.) of usual chemical field indication, to be also included in whole membrane-film preparation process can not with other gases of presoma generation chemical reaction, such as: nitrogen.
In the present invention, oxygen precursor gas can be H 2o, O 2, O 3wherein any one, also can be the mixed gas of wherein any two or three, wherein H 2o is deionized water, O 2, O 3purity is all higher than 99.999%.
In the present invention, bismuth presoma, gallium presoma are respectively three (acid of 2,2,6,6-tetramethyl--3,5-heptadione) bismuth (III), trimethyl-gallium; When equipment permission and practical requirement, bismuth presoma also can adopt triphenyl bismuth, trimethyl-bismuthine, three trimethyl carbinol base bismuths, trimethylsilyl bismuth etc., and gallium presoma also can adopt triethyl-gallium, tri-tert gallium.
Preferably, all gas pipeline being connected to vacuum reaction chamber is all coated with heating zone, is heated pipeline by device control unit central current supply, to avoid the condensation of various precursor gas in pipeline;
Preferably, pallet can be connected with the rotating shaft of a motor, is at the uniform velocity rotated in thin film growth process by driven by motor pallet, by the mode of this rotation substrate, the uniformity of film that obtains can be made better.
Preferably, device control unit can be the special circuit of customization, can be made up of PLC (programmable logic controller), can be made up of FPGA (field programmable gate array), also can be made up of CPLD (CPLD), can also be that micro-chip is formed, or PC.
Beneficial effect of the present invention:
By adopting preparation BiGaO of the present invention 3the method of thin-film material, can realize BiGaO 3the controllable precise of film growth thickness, and BiGaO 3thin film surface planeness is better than prior art greatly.
Accompanying drawing explanation
Fig. 1: preparation BiGaO 3the device of thin-film material, in figure: 1, bismuth precursor source; K1, bismuth presoma pipeline manual valve; AK1, bismuth presoma pipeline self-acting valve; MFC1, bismuth presoma gas-carrier pipeline mass flow controller; 2, gallium precursor source; K2, gallium presoma pipeline manual valve; AK2, gallium presoma pipeline self-acting valve; MFC2, gallium presoma gas-carrier pipeline mass flow controller; 3, oxygen precursor source; K3, oxygen presoma pipeline manual valve; AK3, oxygen presoma pipeline self-acting valve; MFC3, oxygen presoma gas-carrier pipeline mass flow controller; 4, inert gas source; K4, inert gas piping manual valve; AK4, air-inlet of vacuum pump automatic valve;
Fig. 2: the suitable temperature window schematic diagram of film growth, in figure, L represents lowest temperature, and H represents upper temperature limit; In temperature window, sedimentation rate does not vary with temperature; When temperature is not high enough, presoma condensation causes multilayer absorption to cause too high sedimentation rate, or causes absorption not exclusively, and reactive behavior is poor; When temperature is too high, presoma decomposes and causes extra CVD formula growth, or due to too high hot kinetic energy, presoma desorption.
Fig. 3,4: represent inert purge gas pulses, the pulse of bismuth precursor gas, the pulse of oxygen precursor gas and the pulse of gallium precursor gas with N, B, O, G respectively.
Embodiment
Technical scheme of the present invention is specifically introduced below in conjunction with example.
Embodiment 1:
A) the substrate material rare gas element of cleaning is dried up, be placed in substrate pallet;
B) pallet moves into vacuum reaction chamber together with substrate, opens vacuum pump by device control unit, and then opens air-inlet of vacuum pump automatic valve AK4, vacuumizes vacuum reaction chamber;
C) bismuth precursor source 1, gallium precursor source 2, oxygen precursor source 3, rare gas element 4 are respectively three (acid of 2,2,6,6-tetramethyl--3,5-heptadione) bismuth (III), tri-tert gallium, H 2o, the purity N more than 99.9995% 2(nitrogen);
Device control unit sets bismuth precursor source 1, gallium precursor source 2, oxygen precursor source 3 temperature be respectively 180 DEG C, 25 DEG C, 15 DEG C, by the electric heater of container and/or the working order of semiconductor cooler of device control unit control bismuth precursor source 1, gallium precursor source 2, oxygen precursor source 3, to make the homo(io)thermism of bismuth precursor source 1, gallium precursor source 2, oxygen precursor source 3 at the temperature value of setting;
Three (2,2,6, the acid of 6-tetramethyl--3,5-heptadione) bismuth (III) gas produces by a solid source bottle, raw material three (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) at bismuth (III) is in 170-195 DEG C by heating, produce three (2,2,6, the acid of 6-tetramethyl--3,5-heptadione) bismuth (III) gas; H 2o gas is produced by a fluid supply bottle, and deionized water is under room temperature state and suitably lowered the temperature to avoid to produce too high vapour pressure by semiconductor chilling plate; Tri-tert gallium gas is produced by a fluid supply bottle, tri-tert gallium organic solvent is carried out dilution and dissolves and produce tri-tert gallium steam;
Control electric heater by device control unit to heat vacuum chamber, the pallet in vacuum chamber and substrate temperature is made to maintain 330 DEG C in whole thin film growth process, the growth velocity of film is a substantially invariable value at such a temperature, and the vacuum tightness of the compartment of the temperature of the flow velocity that the growth velocity of film and precursor gas are supplied, the flow velocity of carrier gas and rare gas element, presoma, substrate temperature, vacuum chamber is substantially irrelevant;
D) when vacuum chamber homo(io)thermism is after 30 minutes, the inputting interface of device control unit sets the cycle index of film growth:
Three (acid of 2,2,6,6-tetramethyl--3,5-heptadione) bismuth (III) gas pulses, tri-tert gallium gas pulses, H is represented respectively with B, G, O, N 2o gas pulses, pulse of nitrogen, in whole growth cycle, gas pulses cyclic sequence is as shown in Figure 3;
It is 5s that the inputting interface of device control unit sets three (acid of 2,2,6,6-tetramethyl--3,5-heptadione) bismuth (III) gas pulses length, and tri-tert gallium gas pulses length is 2s, H 2o gas pulses length is 0.1s, and pulse of nitrogen length is 4s;
It is 200sccm (standardcubiccentimetersperminute), gallium presoma gas-carrier pipeline gas flow rate 200sccm, oxygen presoma gas-carrier pipeline gas flow rate 250sccm that the inputting interface of device control unit sets bismuth presoma gas-carrier pipeline gas flow rate; Manual unlocking bismuth presoma pipeline manual valve K1, gallium presoma pipeline manual valve K2, oxygen presoma pipeline manual valve K2, inert gas piping manual valve K4;
E) bismuth presoma gas-carrier pipeline mass flow controller MFC1 is controlled by device control unit, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber, vacuum reaction chamber is according to step D) the gas pulses sequential that sets passes into rare gas element respectively, three (2, 2, 6, 6-tetramethyl--3, the acid of 5-heptadione) bismuth (III) or other bismuth precursor gas, oxygen precursor gas and trimethyl-gallium gas or other gallium precursor gas, all precursor gas adopt rare gas element to transport respectively, in film deposition process, in vacuum reaction chamber, maintain air pressure 1 – 10hPa,
Pulse N is realized by following action:
Controlled to make bismuth presoma pipeline self-acting valve AK1, gallium presoma pipeline self-acting valve AK2, oxygen presoma pipeline self-acting valve AK3 all be in closing condition by device control unit, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make rare gas element in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
Pulse B is realized by following action:
Controlled to make bismuth presoma pipeline self-acting valve AK1 be in open mode by device control unit, gallium presoma pipeline self-acting valve AK2, oxygen presoma pipeline self-acting valve AK3 are all in closing condition, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
Pulse O is realized by following action:
Controlled to make oxygen presoma pipeline self-acting valve AK3 be in open mode by device control unit, bismuth presoma pipeline self-acting valve AK1, gallium presoma pipeline self-acting valve AK2 are all in closing condition, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
Pulse G is realized by following action:
Controlled to make gallium presoma pipeline self-acting valve AK2 be in open mode by device control unit, bismuth presoma pipeline self-acting valve AK1, oxygen presoma pipeline self-acting valve AK3 are all in closing condition, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
F) when film growth cycle index reaches the number of times of setting, film thickness reaches desirable value, obtains certain thickness BiGaO 3thin-film material, bismuth presoma pipeline self-acting valve AK1, gallium presoma pipeline self-acting valve AK2, oxygen presoma pipeline self-acting valve AK3 is closed by device control unit, stop passing into bismuth presoma, gallium presoma, oxygen presoma, continue to pass into rare gas element, stop powering to electric heater, stop heating vacuum chamber;
G) manual-lock bismuth presoma pipeline manual valve K1, gallium presoma pipeline manual valve K2, oxygen presoma pipeline manual valve K3, inert gas piping manual valve K4, air-inlet of vacuum pump automatic valve AK4 stay open state, and vacuum reaction chamber carries out naturally cooling;
H) vacuum chamber reach or close to room temperature time, close air-inlet of vacuum pump automatic valve AK4 by device control unit;
I) close air-inlet of vacuum pump automatic valve AK4, carry out inflation to vacuum reaction chamber and make its air pressure reach a normal atmosphere, vacuum reaction chamber inner and outer air pressure reaches equilibrium state;
J) taking-up has deposited and has obtained BiGaO 3the substrate of thin-film material, closes inert gas piping manual valve K4;
K) BiGaO is attached with by what obtain in step J 3the substrate of thin-film material, puts into quick anneal oven, carries out quick thermal annealing process, namely successively through following three rapid thermal annealing (RTA) steps:
A () maintains 3 minutes at 180-220 DEG C;
B () maintains 5 minutes at 390-400 DEG C;
(c) high temperature annealing 5 minutes at 700 DEG C-750 DEG C;
Take out after naturally cooling.
A series of test is carried out to obtained film sample.
Embodiment 2:
A) the substrate material rare gas element of cleaning is dried up, be placed in substrate pallet;
B) pallet moves into vacuum reaction chamber together with substrate, opens vacuum pump by device control unit, and then opens air-inlet of vacuum pump automatic valve AK4, vacuumizes vacuum reaction chamber;
C) bismuth precursor source 1, gallium precursor source 2, oxygen precursor source 3, rare gas element 4 are respectively trimethyl-bismuthine, trimethyl-gallium, H 2o, the purity N more than 99.9995% 2(nitrogen);
Device control unit sets bismuth precursor source 1, gallium precursor source 2, oxygen precursor source 3 temperature be respectively 25 DEG C, 25 DEG C, 15 DEG C, by the electric heater of container and/or the working order of semiconductor cooler of device control unit control bismuth precursor source 1, gallium precursor source 2, oxygen precursor source 3, to make the homo(io)thermism of bismuth precursor source 1, gallium precursor source 2, oxygen precursor source 3 at the temperature value of setting;
Trimethyl-bismuthine gas is produced by a fluid supply bottle, trimethyl-bismuthine organic solvent is carried out dilution and dissolves and produce trimethyl-bismuthine steam; Trimethyl-gallium gas is produced by a fluid supply bottle, trimethyl-gallium organic solvent is carried out dilution and dissolves and produce trimethyl-gallium steam; H 2o gas is produced by a fluid supply bottle, and deionized water is under room temperature state and suitably lowered the temperature to avoid to produce too high vapour pressure by semiconductor chilling plate;
Control electric heater by device control unit to heat vacuum chamber, the pallet in vacuum chamber and substrate temperature is made to maintain 300 DEG C in whole thin film growth process, the growth velocity of film is a substantially invariable value at such a temperature, and the vacuum tightness of the compartment of the temperature of the flow velocity that the growth velocity of film and precursor gas are supplied, the flow velocity of carrier gas and rare gas element, presoma, substrate temperature, vacuum chamber is substantially irrelevant;
D) when vacuum chamber homo(io)thermism is after 30 minutes, the inputting interface of device control unit sets the cycle index of film growth:
Trimethyl-bismuthine gas pulses, trimethyl-gallium gas pulses, H is represented respectively with B, G, O, N 2o gas pulses, N 2pulse, in whole growth cycle, gas pulses cyclic sequence is as shown in Figure 3;
It is 1s that the inputting interface of device control unit sets trimethyl-bismuthine gas pulses length, and trimethyl-gallium gas pulses length is 1s, H 2o gas pulses length is 0.1s, and pulse of nitrogen length is 4s;
It is 200sccm (standardcubiccentimetersperminute), gallium presoma gas-carrier pipeline gas flow rate 200sccm, oxygen presoma gas-carrier pipeline gas flow rate 230sccm that the inputting interface of device control unit sets bismuth presoma gas-carrier pipeline gas flow rate; Manual unlocking bismuth presoma pipeline manual valve K1, gallium presoma pipeline manual valve K2, oxygen presoma pipeline manual valve K2, inert gas piping manual valve K4;
E) bismuth presoma gas-carrier pipeline mass flow controller MFC1 is controlled by device control unit, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber, vacuum reaction chamber is according to step D) the gas pulses sequential that sets passes into rare gas element respectively, three (2, 2, 6, 6-tetramethyl--3, the acid of 5-heptadione) bismuth (III) or other bismuth precursor gas, oxygen precursor gas and trimethyl-gallium gas or other gallium precursor gas, all precursor gas adopt rare gas element to transport respectively, in film deposition process, in vacuum reaction chamber, maintain air pressure 1 – 10hPa,
Pulse N is realized by following action:
Controlled to make bismuth presoma pipeline self-acting valve AK1, gallium presoma pipeline self-acting valve AK2, oxygen presoma pipeline self-acting valve AK3 all be in closing condition by device control unit, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make rare gas element in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
Pulse B is realized by following action:
Controlled to make bismuth presoma pipeline self-acting valve AK1 be in open mode by device control unit, gallium presoma pipeline self-acting valve AK2, oxygen presoma pipeline self-acting valve AK3 are all in closing condition, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
Pulse O is realized by following action:
Controlled to make oxygen presoma pipeline self-acting valve AK3 be in open mode by device control unit, bismuth presoma pipeline self-acting valve AK1, gallium presoma pipeline self-acting valve AK2 are all in closing condition, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
Pulse G is realized by following action:
Controlled to make gallium presoma pipeline self-acting valve AK2 be in open mode by device control unit, bismuth presoma pipeline self-acting valve AK1, oxygen presoma pipeline self-acting valve AK3 are all in closing condition, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
F) when film growth cycle index reaches the number of times of setting, film thickness reaches desirable value, obtains certain thickness BiGaO 3thin-film material, bismuth presoma pipeline self-acting valve AK1, gallium presoma pipeline self-acting valve AK2, oxygen presoma pipeline self-acting valve AK3 is closed by device control unit, stop passing into bismuth presoma, gallium presoma, oxygen presoma, continue to pass into rare gas element, stop powering to electric heater, stop heating vacuum chamber;
G) manual-lock bismuth presoma pipeline manual valve K1, gallium presoma pipeline manual valve K2, oxygen presoma pipeline manual valve K3, inert gas piping manual valve K4, air-inlet of vacuum pump automatic valve AK4 stay open state, and vacuum reaction chamber carries out naturally cooling;
H) vacuum chamber reach or close to room temperature time, close air-inlet of vacuum pump automatic valve AK4 by device control unit;
I) close air-inlet of vacuum pump automatic valve AK4, carry out inflation to vacuum reaction chamber and make its air pressure reach a normal atmosphere, vacuum reaction chamber inner and outer air pressure reaches equilibrium state;
J) taking-up has deposited and has obtained BiGaO 3the substrate of thin-film material, closes inert gas piping manual valve K4;
K) BiGaO is attached with by what obtain in step J 3the substrate of thin-film material, puts into quick anneal oven, carries out quick thermal annealing process, namely successively through following three rapid thermal annealing (RTA) steps:
A () maintains 3 minutes at 180-220 DEG C;
B () maintains 4 minutes at 390-400 DEG C;
(c) high temperature annealing 4 minutes at 700 DEG C-750 DEG C;
Take out after naturally cooling.
A series of test is carried out to obtained film sample.

Claims (9)

1. reacting from restricted surface adsorption of a presoma time division formula prepares BiGaO 3the method of thin-film material, BiGaO 3thin-film material growth is on substrate material, and described substrate comprises Si, LaNiO 3/ Si, Pt/TiO 2/ SiO 2/ Si, Pt/Ti/SiO 2/ Si, TiN, SiO 2deng, described BiGaO 3the spacer of thin-film material is Pcca, and lattice parameter is a=5.626, b=5.081, c=10.339, described BiGaO 3thin-film material is (112) in the preferred orientation that selected Grown obtains;
It is characterized in that:
Described BiGaO 3thin-film material thickness is less than 500 nanometers;
Adopt being obtained by reacting from restrictive surface adsorption of presoma time division formula;
The irreversible Chemisorption of Langmuir absorption mechanism is refered in particular in described surface adsorption reaction;
Chemisorption carries out in vacuum reaction chamber, and the pulse of bismuth precursor gas, the pulse of gallium precursor gas, the pulse of oxygen precursor gas, inert purge gas pulses pass in vacuum reaction chamber successively according to certain order;
Described bismuth presoma is three (acid of 2,2,6,6-tetramethyl--3,5-heptadione) bismuth (III);
Described gallium presoma is trimethyl-gallium;
Described oxygen precursor gas can be H 2o, O 2, O 3wherein any one, also can be the mixed gas of wherein any two or three;
Described " rare gas element " not only refers to the rare gas element (helium, argon gas etc.) of usual chemical field indication, to be also included in whole membrane-film preparation process can not with other gases of presoma generation chemical reaction, such as: nitrogen;
In whole thin film growth process, all precursor gas adopt rare gas element to transport respectively;
The method includes but not limited to following concrete steps:
A) the substrate material rare gas element of cleaning is dried up, be placed in substrate pallet;
B) pallet moves into vacuum reaction chamber together with substrate, opens vacuum pump and vacuumizes vacuum reaction chamber;
C) set the temperature of bismuth precursor source, gallium precursor source, oxygen precursor source, make the homo(io)thermism of bismuth precursor source, gallium precursor source, oxygen precursor source at the temperature value of setting;
Vacuum chamber is heated, makes the pallet in vacuum chamber and substrate temperature in whole thin film growth process, maintain a suitable temperature window;
Selected suitable temperature window refers to: in suitable temperature range, namely substrate temperature higher than a lowest temperature lower than a upper temperature limit, and the flow velocity of precursor gas supply is when being greater than minimum limit value, the growth velocity of film is a substantially invariable value, the flow velocity that the growth velocity of film and precursor gas are supplied, the flow velocity of carrier gas and rare gas element, the temperature of presoma, substrate temperature, the vacuum tightness of the compartment of vacuum chamber is substantially irrelevant, " substantially irrelevant " described here refers to: even if the growth velocity of film has fluctuation in this temperature window, also be slight fluctuations, when growth temperature exceeds this temperature window namely lower than lowest temperature or higher than upper temperature limit, the growth velocity of film can increase significantly or reduce,
D) when vacuum chamber homo(io)thermism is after 5 ~ 30 minutes, cycle index, bismuth presoma gas-carrier pipeline gas flow rate, gallium presoma gas-carrier pipeline gas flow rate, the oxygen presoma gas-carrier pipeline gas flow rate of setting film growth;
E) bismuth presoma gas-carrier pipeline mass flow controller, gallium presoma gas-carrier pipeline mass flow controller, oxygen presoma gas-carrier pipeline mass flow controller is controlled, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber, vacuum reaction chamber passes into rare gas element, bismuth precursor gas, oxygen precursor gas and gallium precursor gas respectively according to certain gas pulses sequential;
Described gas pulses sequential is by inert purge gas pulses, three (2, 2, 6, 6-tetramethyl--3, the acid of 5-heptadione) bismuth (III) or other bismuth precursor gas pulses, the pulse of oxygen precursor gas and trimethyl-gallium gas or other gallium precursor gas pulses composition, respectively with N, B, O, G represents inert purge gas pulses, three (2, 2, 6, 6-tetramethyl--3, the acid of 5-heptadione) bismuth (III) or other bismuth precursor gas pulses, the pulse of oxygen precursor gas and trimethyl-gallium gas or other gallium precursor gas pulses, then the rule of described gas pulses sequential is as follows:
Before or after any one three (acid of 2,2,6,6-tetramethyl--3,5-heptadione) bismuth (III) gas pulses or the pulse of oxygen precursor gas or trimethyl-gallium gas pulses, all there is an inert purge gas pulses; And when meeting above-mentioned condition,
In the secondary adjacent place of any one three (2,2,6,6-tetramethyl--3,5-heptadione acid) bismuth (III) gas pulses or trimethyl-gallium gas pulses, all also there is the pulse of an oxygen precursor gas; And when meeting above-mentioned condition,
These gas pulses sequences are controlled the open and close of the self-acting valve in respective line to realize by device control unit, and are performed the growth cycle circulation of particular sequence by program;
In a growth cycle, the quantity of each gas pulses is the multiple of 4 and is not less than 8;
Each gas pulses is passed in vacuum reaction chamber successively by pipeline, and pallet and substrate are exposed in the atmosphere of these gas pulses formation successively; And,
In a growth cycle, the quantity sum of the pulse of bismuth precursor gas and the pulse of gallium precursor gas equals the quantity of oxygen presoma pulse, and the quantity sum of the pulse of bismuth precursor gas, the pulse of gallium precursor gas and the pulse of oxygen precursor gas equals the quantity of inert purge gas pulses;
F) when film growth cycle index reaches the number of times of setting, film thickness reaches desirable value, obtains certain thickness BiGaO 3thin-film material, stops passing into bismuth presoma, gallium presoma, oxygen presoma, continues to pass into rare gas element, stop heating vacuum chamber;
G) vacuum reaction chamber carries out naturally cooling;
H) vacuum chamber reach or close to room temperature time, close air-inlet of vacuum pump valve;
I) carrying out inflation to vacuum reaction chamber makes its air pressure reach a normal atmosphere, and vacuum reaction chamber inner and outer air pressure reaches equilibrium state;
J) taking-up has deposited and has obtained BiGaO 3the substrate of thin-film material, closes inert gas piping manual valve K4;
K) BiGaO is attached with by what obtain in step J 3the substrate of thin-film material, puts into quick anneal oven, carries out quick thermal annealing process, takes out after naturally cooling.
2. prepare BiGaO as claimed in claim 1 for one kind 3the method of thin-film material, is characterized in that: bismuth presoma also can adopt triphenyl bismuth, trimethyl-bismuthine, three trimethyl carbinol base bismuths, trimethylsilyl bismuth.
3. prepare BiGaO as claimed in claim 1 for one kind 3the method of thin-film material, is characterized in that: gallium presoma also can adopt triethyl-gallium, tri-tert gallium.
4. the preparation BiGaO as described in any one of claim 1-3 3the method of thin-film material, is characterized in that: the quantity of bismuth precursor gas pulse and the quantity of gallium precursor gas pulse are distributed according to following principle:
In a growth cycle, the bismuth that deposited on substrates obtains, the stoichiometric ratio of gallium are close to 1:1, allow the positive error of less than 10%, namely the stoichiometric ratio of bismuth, gallium is in the scope of 1:1 ~ 1:1.1, and excessive bismuth will in step K) in volatilization and substantially removing.
5. prepare BiGaO as claimed in claim 1 for one kind 3the method of thin-film material, is characterized in that: in step K) in, the step of rapid thermal annealing is:
A () maintains 1-10 minute at 180-220 DEG C;
B () maintains 1-10 minute at 390-400 DEG C;
C () be high temperature annealing 1-10 minute at 700 DEG C-750 DEG C.
6. the preparation BiGaO as described in any one of claim 1-3 3the method of thin-film material, is characterized in that:
Pallet is driven by motor, drives substrate to rotate evenly.
7. one kind for realizing the preparation BiGaO as described in any one of claim 1-4 3the device of the method for thin-film material, is characterized in that:
Device includes but not limited to: bismuth precursor source 1, bismuth presoma pipeline manual valve K1, bismuth presoma pipeline self-acting valve AK1, bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium precursor source 2, gallium presoma pipeline manual valve K2, gallium presoma pipeline self-acting valve AK2, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen precursor source 3, oxygen presoma pipeline manual valve K3, oxygen presoma pipeline self-acting valve AK3, oxygen presoma gas-carrier pipeline mass flow controller MFC3, inert gas source 4, inert gas piping manual valve K4, vacuum reaction chamber, vacuum pump, air-inlet of vacuum pump automatic valve AK4, device control unit, electric heater and temperature sensor is provided with in vacuum reaction chamber,
The container of bismuth precursor source 1, gallium precursor source 2, oxygen precursor source 3 is equipped with electric heater and semiconductor cooler; Bismuth precursor source 1, gallium precursor source 2, the electric heater of container of oxygen precursor source 3 and the working order of semiconductor cooler is controlled, to make the temperature of bismuth precursor source 1, gallium precursor source 2, oxygen precursor source 3 can the constant temperature value in setting by device control unit;
The outlet of bismuth precursor source 1 is connected to bismuth presoma pipeline manual valve K1 successively by gas piping, bismuth presoma pipeline self-acting valve AK1, vacuum reaction chamber, the outlet of gallium precursor source 2 is connected to gallium presoma pipeline manual valve K2 successively by gas piping, gallium presoma pipeline self-acting valve AK2, vacuum reaction chamber, the outlet of oxygen precursor source 3 is connected to oxygen presoma pipeline manual valve K3 successively by gas piping, oxygen presoma pipeline self-acting valve AK3, vacuum reaction chamber, the outlet of inert gas source 4 is connected to inert gas piping manual valve K4 by gas piping, bismuth presoma gas-carrier pipeline mass flow controller MFC1 is connected respectively to again by branch line, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3, the outlet of bismuth presoma gas-carrier pipeline mass flow controller MFC1 is connected on the gas piping between bismuth presoma pipeline self-acting valve AK1 and vacuum reaction chamber by three-way connector, the outlet of gallium presoma gas-carrier pipeline mass flow controller MFC2 is connected on the gas piping between gallium presoma pipeline self-acting valve AK2 and vacuum reaction chamber by three-way connector, the outlet of oxygen presoma gas-carrier pipeline mass flow controller MFC3 is connected on the gas piping between bismuth presoma pipeline self-acting valve AK3 and vacuum reaction chamber by three-way connector, the outlet of vacuum reaction chamber is connected to air-inlet of vacuum pump automatic valve AK4 successively by pipeline, the inlet mouth of vacuum pump,
Bismuth precursor source 1, bismuth presoma pipeline self-acting valve AK1, bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium precursor source 2, gallium presoma pipeline self-acting valve AK2, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen precursor source 3, oxygen presoma pipeline self-acting valve AK3, oxygen presoma gas-carrier pipeline mass flow controller MFC3, vacuum reaction chamber, vacuum pump, air-inlet of vacuum pump automatic valve AK4, electric heater in vacuum reaction chamber, temperature sensor, the electric heater of described container and semiconductor cooler are all connected to device control unit by cable and are all connected to device control unit by cable, by device control unit centralized Control working order separately,
The image data of temperature sensor to device control unit by cable transmission, is controlled (proportional integral differential control) with the PID realizing temperature, the temperature of vacuum reaction chamber can be made to reach the temperature value of setting rapidly, exactly;
Bismuth presoma pipeline manual valve K1, gallium presoma pipeline manual valve K2, oxygen presoma pipeline manual valve K3, inert gas piping manual valve K4 are by operator's manual unlocking, and uncontrolled device controlled;
Inert purge gas pulses, three (2 is represented respectively with N, B, O, G, 2,6,6-tetramethyl--3, the acid of 5-heptadione) bismuth (III) or other bismuth precursor gas pulses, the pulse of oxygen precursor gas and trimethyl-gallium gas or other gallium precursor gas pulses, then:
Pulse N is realized by following action:
Controlled to make bismuth presoma pipeline self-acting valve AK1, gallium presoma pipeline self-acting valve AK2, oxygen presoma pipeline self-acting valve AK3 all be in closing condition by device control unit, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make rare gas element in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
Pulse B is realized by following action:
Controlled to make bismuth presoma pipeline self-acting valve AK1 be in open mode by device control unit, gallium presoma pipeline self-acting valve AK2, oxygen presoma pipeline self-acting valve AK3 are all in closing condition, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
Pulse O is realized by following action:
Controlled to make oxygen presoma pipeline self-acting valve AK3 be in open mode by device control unit, bismuth presoma pipeline self-acting valve AK1, gallium presoma pipeline self-acting valve AK2 are all in closing condition, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber;
Pulse G is realized by following action:
Controlled to make gallium presoma pipeline self-acting valve AK2 be in open mode by device control unit, bismuth presoma pipeline self-acting valve AK1, oxygen presoma pipeline self-acting valve AK3 are all in closing condition, control bismuth presoma gas-carrier pipeline mass flow controller MFC1, gallium presoma gas-carrier pipeline mass flow controller MFC2, oxygen presoma gas-carrier pipeline mass flow controller MFC3 by device control unit, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber.
8. prepare BiGaO as claimed in claim 7 for one kind 3the device of thin-film material, is characterized in that:
Device control unit can be the special circuit of customization, can be by PLC(programmable logic controller) form, can by FPGA(field programmable gate array) form, also can by CPLD(CPLD) form, can also be that micro-chip is formed, or PC be formed.
9. prepare BiGaO as claimed in claim 7 or 8 for one kind 3the device of thin-film material, is characterized in that:
The all gas pipeline being connected to vacuum reaction chamber is all coated with heating zone, is heated pipeline by device control unit central current supply.
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