Summary of the invention
In order to solve prior art problem, the object of the present invention is to provide a kind of Bi (Al of space-time separate type from restricted surface adsorption reaction preparation that accurately can control film thickness
xga
1-x) O
3the method of thin-film material, described Bi (Al
xga
1-x) O
3the spacer of thin-film material is Pcca.Realizing the concrete technical scheme of the object of the invention is:
A kind of Bi (Al
xga
1-x) O
3the preparation method of thin-film material, the method raw material adopts organo-bismuth source, oxygen presoma, organoaluminum source, organic gallium source.
Described Bi (Al
xga
1-x) O
3the preparation method of thin-film material, adopts custom-designed device.
Described device includes but not limited to: organo-bismuth source container 1, organo-bismuth source capsule road manual valve K1, organo-bismuth source capsule road self-acting valve AK1, organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organoaluminum source container 2, organoaluminum source capsule road manual valve K2, organoaluminum source capsule road self-acting valve AK2, organoaluminum source gas-carrier pipeline mass flow controller MFC2, Organogallium aluminium source container 3, organic gallium source pipeline manual valve K3, organic gallium source pipeline self-acting valve AK3, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen precursor source containers 4, oxygen presoma pipeline manual valve K4, oxygen presoma pipeline self-acting valve AK4, oxygen presoma gas-carrier pipeline mass flow controller MFC4, inert gas container 5, inert gas piping manual valve K5, vacuum reaction chamber, vacuumometer, vacuum pump, air-inlet of vacuum pump automatic valve AK5, device control unit, is provided with electric heater and temperature sensor in vacuum reaction chamber, device control unit can be made up of PLC or FPGA or CPLD or SCM system or computer or custom-designed Circuits System, the container of organo-bismuth source container 1, organoaluminum source container 2, oxygen precursor source containers 3 is equipped with electric heater and semiconductor cooler,
The outlet of organo-bismuth source container 1 is connected to organo-bismuth source capsule road manual valve K1 successively by gas piping, organo-bismuth source capsule road self-acting valve AK1, vacuum reaction chamber, the outlet of organoaluminum source container 2 is connected to organoaluminum source capsule road manual valve K2 successively by gas piping, organoaluminum source capsule road self-acting valve AK2, vacuum reaction chamber, the outlet of organic gallium source container 3 is connected to organic gallium source pipeline manual valve K3 successively by gas piping, organic gallium source pipeline self-acting valve AK3, vacuum reaction chamber, the outlet of oxygen precursor source containers 4 is connected to oxygen presoma pipeline manual valve K4 successively by gas piping, oxygen presoma pipeline self-acting valve AK4, vacuum reaction chamber, the outlet of inert gas container 5 is connected to inert gas piping manual valve K5 by gas piping, organo-bismuth source gas-carrier pipeline mass flow controller MFC1 is connected respectively to again by branch line, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4, the outlet of organo-bismuth source gas-carrier pipeline mass flow controller MFC1 is connected on the gas piping between organo-bismuth source capsule road self-acting valve AK1 and vacuum reaction chamber by three-way connector, the outlet of organoaluminum source gas-carrier pipeline mass flow controller MFC2 is connected on the gas piping between organoaluminum source capsule road self-acting valve AK2 and vacuum reaction chamber by three-way connector, the outlet of organic gallium source gas-carrier pipeline mass flow controller MFC3 is connected on the gas piping between organoaluminum source capsule road self-acting valve AK3 and vacuum reaction chamber by three-way connector, the outlet of oxygen presoma gas-carrier pipeline mass flow controller MFC4 is connected on the gas piping between organo-bismuth source capsule road self-acting valve AK4 and vacuum reaction chamber by three-way connector, the outlet of vacuum reaction chamber is connected to air-inlet of vacuum pump automatic valve AK5 successively by pipeline, the inlet mouth of vacuum pump,
Vacuumometer is provided with in vacuum chamber;
Organo-bismuth source capsule road manual valve K1, organoaluminum source capsule road manual valve K2, organic gallium source pipeline manual valve K3, oxygen presoma pipeline manual valve K4, inert gas piping manual valve K5 are by operator's manual unlocking, uncontrolled device controlled, and this design can guarantee safety;
Vacuumometer, organo-bismuth source capsule road self-acting valve AK1, organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organoaluminum source capsule road self-acting valve AK2, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source pipeline self-acting valve AK3, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen precursor source containers 4, oxygen presoma pipeline self-acting valve AK4, oxygen presoma gas-carrier pipeline mass flow controller MFC4, vacuum reaction chamber, vacuum pump, air-inlet of vacuum pump automatic valve AK5, electric heater in vacuum reaction chamber, temperature sensor and described organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3, the electric heater of oxygen precursor source containers 4 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,
In any one moment, controlled to make organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK4 only have at most one to be in opened condition by device control unit, all the other are all in closing condition; Or organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK4 are all in closing condition;
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;
Organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3, the electric heater of container of oxygen precursor source containers 4 and the working order of semiconductor cooler is controlled, to make the temperature of organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3, oxygen precursor source containers 4 can the constant temperature value in setting by device control unit;
Described Bi (Al
xga
1-x) O
3the preparation method of thin-film material, includes but not limited to following concrete steps:
A) in vacuum glove box, rare gas element is filled with, in the atmosphere of inert gases of glove box, complete following operation: organo-bismuth source, organoaluminum source, organic gallium source are filled into organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3 respectively, then install with respective pipeline and be connected;
Because organo-bismuth source, organoaluminum source, organic gallium source are inflammable and explosive hazardous substance, therefore, in pouring process, vacuum glove box is used to be absolutely necessary;
B) oxygen precursor source, rare gas element are filled into oxygen precursor source containers 3, inert gas container 4 respectively, then install with respective pipeline and be connected;
C) the substrate material rare gas element of cleaning is dried up, be placed in substrate pallet;
D) 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 AK5, vacuumizes vacuum reaction chamber;
E) on device control unit, organo-bismuth source container 1 is set, organoaluminum source container 2, organic gallium source container 3, the temperature of oxygen precursor source containers 4, organo-bismuth source container 1 is controlled by device control unit, organoaluminum source container 2, organic gallium source container 3, the electric heater of oxygen precursor source containers 4 and/or the working order of semiconductor cooler, to make organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3, the temperature of oxygen precursor source containers 4 maintains the temperature value of setting, make under the temperature value of set each presoma, organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3, the vapor pressure of oxygen precursor source containers 4 is greater than inert gas container 5 by mass flow controller MFC1, MFC2, MFC3, pressure after MFC4 in gas piping,
Control electric heater by device control unit to heat vacuum chamber, make the pallet in vacuum chamber and substrate temperature constant in a temperature value in whole thin film growth process, described temperature value is in a suitable temperature window;
Described 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; These factors all can cause the growth velocity of film to increase significantly or to reduce;
F) 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, organo-bismuth source gas-carrier pipeline gas flow rate, organoaluminum source gas-carrier pipeline gas flow rate, organic gallium source gas-carrier pipeline gas flow rate, oxygen presoma gas-carrier pipeline gas flow rate, rare gas element flow velocity, organo-bismuth source gas pulses length, organoaluminum source gas pulses length, organic gallium source gas pulses length, oxygen precursor gas pulse length, inert purge gas pulses length; Manual unlocking organo-bismuth source capsule road manual valve K1, organoaluminum source capsule road manual valve K2, organic gallium source pipeline manual valve K3, oxygen presoma pipeline manual valve K4, inert gas piping manual valve K5;
G) organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4 is controlled by device control unit, make gas in each gas piping according to step F) in set(ting)value pass into vacuum reaction chamber, vacuum reaction chamber passes into rare gas element, organic bismuth source gas, organic gallium source gas, oxygen precursor gas and organic aluminum source gas respectively according to certain gas pulses sequential; All precursor gas adopt rare gas element to transport respectively;
For realizing at growth BiGaO
3al doping is realized to obtain Bi (Al in the process of film
xga
1-x) O
3film, in each growth cycle, organic gallium source gas pulses, organoaluminum source gas pulses are inserted in gas pulses sequential according to certain ratio alternatively mixing, and described organic gallium source gas pulses, organoaluminum source gas pulses ratio are by the Bi (Al expecting to obtain
xga
1-x) O
3the component of film, the organic gallium source adopted, organoaluminum source category decide;
Such as, in order to obtain Bi (Al
0.1ga
0.9) O
3film, when organic gallium source, organoaluminum source adopt triethyl-gallium, triethyl aluminum respectively, can arrange organic gallium source gas pulses, the quantitative proportion of organoaluminum source gas pulses is 9:1 in a growth cycle.It needs to be noted: the quantitative proportion of organic gallium source gas pulses, organoaluminum source gas pulses non-immediate equal (1-x): x, also depend on and adopt which kind of organic gallium source, organoaluminum source.
H) when film growth cycle index reaches the number of times of setting, film thickness reaches desirable value, obtains certain thickness Bi (Al
xga
1-x) O
3thin-film material, organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK3 is closed by device control unit, stop passing into organo-bismuth source, organoaluminum source, organic gallium source, oxygen presoma, continue to pass into rare gas element, stop powering to electric heater, stop heating vacuum chamber;
I) manual-lock organo-bismuth source capsule road manual valve K1, organoaluminum source capsule road manual valve K2, organic gallium source pipeline manual valve K3, oxygen presoma pipeline manual valve K4, inert gas piping manual valve K5, air-inlet of vacuum pump automatic valve AK4 stay open state, and vacuum reaction chamber carries out naturally cooling;
J) vacuum chamber reach or close to room temperature time, close air-inlet of vacuum pump automatic valve AK5 by device control unit;
K) 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;
L) taking-up has deposited and has obtained Bi (Al
xga
1-x) O
3the substrate of thin-film material, closes inert gas piping manual valve K5;
M) Bi (Al is attached with by what obtain in step L
xga
1-x) O
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 360-400 DEG C;
C () be high temperature annealing 1-10 minute at 750 DEG C-1050 DEG C;
In order to avoid producing unpredictable impact, in step B containing the air of steam to film growth in pipeline) after usually also should have and drive away the operation that each material container installs the air connected in rear pipeline, specifically, this is operating as:
Maintenance organo-bismuth source capsule road manual valve K1, organoaluminum source capsule road manual valve K2, organic gallium source pipeline manual valve K3, oxygen presoma pipeline manual valve K4 are all in closing condition, then,
Controlled to make air-inlet of vacuum pump automatic valve AK5 be in open mode by device control unit, controlled to make organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK4 all be in open mode by device control unit; When the vacuumometer in vacuum reaction chamber no longer changes, controlled to make air-inlet of vacuum pump automatic valve AK5 be in closing condition by device control unit, control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4 by device control unit, make rare gas element in each gas piping pass into vacuum reaction chamber according to certain value; When the air pressure in vacuum reaction chamber reaches 0.5 normal atmosphere, again controlled to make air-inlet of vacuum pump automatic valve AK5 be in open mode by device control unit, controlled to make organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK4 all be in open mode by device control unit; Repeat said process 3 ~ 6 times;
In step G) in, described gas pulses sequential is made up of inert purge gas pulses, organo-bismuth source gas pulses, organic gallium source gas pulses, the pulse of oxygen precursor gas and organoaluminum source gas pulses, if represent inert purge gas pulses, organo-bismuth source gas pulses, the pulse of oxygen precursor gas, organoaluminum source gas pulses, organic gallium source gas pulses with N, B, O, A, G respectively, then:
Pulse N is realized by following action:
Controlled to make organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK4 all be in closing condition by device control unit, control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4 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 organo-bismuth source capsule road self-acting valve AK1 be in open mode by device control unit, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK4 is all in closing condition, organo-bismuth source gas-carrier pipeline mass flow controller MFC1 is controlled by device control unit, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4, 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 AK4 be in open mode by device control unit, organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3 is all in closing condition, organo-bismuth source gas-carrier pipeline mass flow controller MFC1 is controlled by device control unit, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4, 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 organic gallium source pipeline self-acting valve AK3 be in open mode by device control unit, organo-bismuth source capsule road self-acting valve AK1, oxygen presoma pipeline self-acting valve AK3 are all in closing condition, control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organoaluminum source 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 A is realized by following action:
Controlled to make organoaluminum source capsule road self-acting valve AK2 be in open mode by device control unit, organo-bismuth source capsule road self-acting valve AK1, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK4 is all in closing condition, organo-bismuth source gas-carrier pipeline mass flow controller MFC1 is controlled by device control unit, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4, 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:
Before or after any one organo-bismuth source gas pulses or the pulse of oxygen precursor gas or organoaluminum gas pulses or Organogallium gas pulses, all there is an inert purge gas pulses, that is, such as: BN ... or GN ... or ON ..., or AN ..., or ... NBN ... or ... NGN ... or ... NON ..., or ... NAN ..., suspension points " ... " represents other possible collating sequences herein; And when meeting above-mentioned condition,
In the secondary adjacent place of any one organo-bismuth source gas pulses or organoaluminum gas pulses or Organogallium gas pulses, all also there is the pulse of an oxygen precursor gas, namely, such as: ... NONBN ... or ... NONGN ..., or ... NBNON ..., or ... NONAN ... or ... NGNON ..., suspension points " ... " represents other possible collating sequences herein; And when meeting above-mentioned condition,
Organo-bismuth source gas pulses, the pulse of oxygen precursor gas, organoaluminum gas pulses, Organogallium gas pulses, inert purge gas pulses can arrange with any order, can be multiple organo-bismuth source gas pulses or the pulse of oxygen precursor gas or organoaluminum gas pulses or Organogallium 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 more organoaluminum gas pulses, one or more organo-bismuth sources gas pulses, one or more organic gallium source gas pulses, one or morely pass into the pulse of oxygen precursor gas and can arrange with any order, for example, organo-bismuth source gas pulses, the pulse of oxygen precursor gas, organoaluminum source gas pulses, organic gallium source gas pulses, the sequence of inert purge gas pulses can be ... BNONBNONBNONGNONBNONGNONANON also can be ... BNONGNONBNONBNONBNONBNONGNONANONBNONBNON can also be ... GNONGNONBNONBNONANONBNONBNONBNONGNONBNON or ... GNONBNONBNONBNONBNONGNONBNONANONBNONBNON ... 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 12, such as: 12, and 16,20,24 ... 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 organo-bismuth source gas pulses and organoaluminum source gas pulses, organic gallium source gas pulses equals the quantity of oxygen presoma pulse, and the quantity sum of organo-bismuth source gas pulses, organic gallium source gas pulses, organoaluminum source gas pulses 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 organo-bismuth source gas pulses might not be equal with the quantity of organoaluminum source gas pulses+organic gallium source gas pulses, but distribute according to following principle:
In a growth cycle, the stoichiometric ratio of the bismuth that deposited on substrates obtains, aluminium+gallium is 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, organo-bismuth source gas pulses, organoaluminum source gas pulses 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, organo-bismuth source, organoaluminum source, organic gallium source, oxygen presoma, the flow velocity of rare gas element, pressure, when substrate material is exposed in organo-bismuth source, organoaluminum source, organic gallium source, oxygen presoma atmosphere at every turn, substrate material surface all can be made intactly to adsorb a unimolecular layer organo-bismuth or organoaluminum or Organogallium, and 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:
After absorption reaches capacity, fraction of coverage reaches steady state value, d θ/dt=0, and so we just can obtain equation:
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 ALD from restricted reaction, adsorption is necessarily required to be irreversible, i.e. k
d=0, at this moment K will trend towards infinity, have:
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, organo-bismuth source gas pulses gets 2 ~ 8s, organoaluminum source gas pulses gets 0.1 ~ 2s, organic gallium source gas pulses is got the pulse of 0.1 ~ 2s oxygen precursor gas and is got 0.1 ~ 6s, 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 Bi (Al of the present invention
xga
1-x) O
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 organo-bismuth source atmosphere at substrate at every turn, organoaluminum source atmosphere, organic gallium source 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 organo-bismuth source atmosphere and oxygen precursor gas atmosphere for twice respectively, or organoaluminum source atmosphere and oxygen precursor gas atmosphere, or organic gallium source atmosphere and oxygen precursor gas atmosphere, just complete once complete Chemisorption, obtain the Bi of an atomic shell respectively
2o
3or Ga
2o
3/ Al
2o
3,
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 Bi (Al of the thickness growing several nanometer to tens nanometer
xga
1-x) O
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, organo-bismuth source, organoaluminum source are respectively three (acid of 2,2,6,6-tetramethyl--3,5-heptadione) bismuth (III), trimethyl-gallium; When equipment permission and practical requirement, organo-bismuth source also can adopt triphenyl bismuth, trimethyl-bismuthine, three trimethyl carbinol base bismuths, trimethylsilyl bismuth etc., and organoaluminum source 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 Bi (Al of the present invention
xga
1-x) O
3the method of thin-film material, can realize Bi (Al
xga
1-x) O
3the controllable precise of film growth thickness, and Bi (Al
xga
1-x) O
3thin film surface planeness is better than prior art greatly.
Embodiment 1: preparation Bi (Al
0.05ga
0.95) O
3film
A) in vacuum glove box, be filled with the nitrogen of more than 99.9995% purity, in the nitrogen atmosphere of glove box, complete following operation: organo-bismuth source, organoaluminum source, organic gallium source are filled into organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3 respectively, then install with respective pipeline and be connected;
B) organo-bismuth source adopts three (2,2,6, the acid of 6-tetramethyl--3,5-heptadione) bismuth (III), organic gallium source adopts triethyl-gallium, organoaluminum source adopts triethyl aluminum, and oxygen precursor source adopts deionized water, and rare gas element adopts the nitrogen of more than 99.9995% purity; Organo-bismuth source, organoaluminum source, organic gallium source, oxygen precursor source, nitrogen are filled into organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3, oxygen precursor source containers 4, rare gas element source container 5 respectively, then install with respective pipeline and be connected;
Drive away each material container and install the air connected in rear pipeline, specifically this is operating as:
Maintenance organo-bismuth source capsule road manual valve K1, organoaluminum source capsule road manual valve K2, organic gallium source pipeline manual valve K3, oxygen presoma pipeline manual valve K4 are all in closing condition, then,
Controlled to make air-inlet of vacuum pump automatic valve AK5 be in open mode by device control unit, controlled to make organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK4 all be in open mode by device control unit; When the vacuumometer in vacuum reaction chamber no longer changes, controlled to make air-inlet of vacuum pump automatic valve AK5 be in closing condition by device control unit, control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4 by device control unit, make rare gas element in each gas piping pass into vacuum reaction chamber according to certain value; When the air pressure in vacuum reaction chamber reaches 0.5 normal atmosphere, again controlled to make air-inlet of vacuum pump automatic valve AK5 be in open mode by device control unit, controlled to make organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK4 all be in open mode by device control unit; Repeat said process 5 times;
C) the TiN substrate material rare gas element of cleaning is dried up, be placed in substrate pallet;
D) pallet moves into vacuum reaction chamber together with TiN substrate, opens vacuum pump, and then opens air-inlet of vacuum pump automatic valve AK5, vacuumize vacuum reaction chamber by device control unit;
E) set on device control unit organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3, oxygen precursor source containers 4 temperature be respectively 185 DEG C, 20 DEG C, 20 DEG C, 20 DEG C, control organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3, the electric heater of oxygen precursor source containers 4 and/or the working order of semiconductor cooler by device control unit, maintain the temperature value of setting to make the temperature of organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3, oxygen precursor source containers 4;
Control electric heater by device control unit to heat vacuum chamber, make the pallet in vacuum chamber and substrate temperature constant in 300 DEG C in whole thin film growth process;
F) when vacuum chamber temperature after constant 30 minutes, device control unit sets the cycle index of film growth, organo-bismuth source gas-carrier pipeline gas flow rate, organoaluminum source gas-carrier pipeline gas flow rate, organic gallium source gas-carrier pipeline gas flow rate, oxygen presoma gas-carrier pipeline gas flow rate, rare gas element flow velocity, organo-bismuth source gas pulses length, organoaluminum source gas pulses length, organic gallium source gas pulses length, oxygen precursor gas pulse length, inert purge gas pulses length at 300 DEG C; Manual unlocking organo-bismuth source capsule road manual valve K1, organoaluminum source capsule road manual valve K2, organic gallium source pipeline manual valve K3, oxygen presoma pipeline manual valve K4, inert gas piping manual valve K5;
The inputting interface of device control unit sets organo-bismuth source gas-carrier pipeline gas flow rate, organoaluminum source gas-carrier pipeline gas flow rate, organic gallium source gas-carrier pipeline gas flow rate, oxygen presoma gas-carrier pipeline gas flow rate be respectively 200sccm (standardcubiccentimetersperminute), 200sccm, 200sccm, 250sccm;
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 triethyl aluminum gas pulses length is 0.4s, and triethyl-gallium gas pulses length is 0.4s, H
2o gas pulses length is 0.1s, and pulse of nitrogen length is 4s;
Three (acid of 2,2,6,6-tetramethyl--3,5-heptadione) bismuth (III) gas pulses, triethyl aluminum gas pulses, triethyl-gallium gas pulses, H is represented respectively with B, A, G, O, N
2o gas pulses, pulse of nitrogen, in whole growth cycle, gas pulses cyclic sequence as shown in Figure 2.
G) organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4 is controlled by device control unit, make gas in each gas piping according to step F) in set(ting)value pass into vacuum reaction chamber, vacuum reaction chamber passes into rare gas element, organic bismuth source gas, organic gallium source gas, oxygen precursor gas and organic aluminum source gas respectively according to certain gas pulses sequential; All precursor gas adopt nitrogen to transport respectively;
Described gas pulses sequential is made up of inert purge gas pulses, organo-bismuth source gas pulses, organic gallium source gas pulses, the pulse of oxygen precursor gas and organoaluminum source gas pulses, if represent inert purge gas pulses, organo-bismuth source gas pulses, the pulse of oxygen precursor gas, organoaluminum source gas pulses, organic gallium source gas pulses with N, B, O, A, G respectively, then:
Pulse N is realized by following action:
Controlled to make organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK4 all be in closing condition by device control unit, control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4 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 organo-bismuth source capsule road self-acting valve AK1 be in open mode by device control unit, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK4 is all in closing condition, organo-bismuth source gas-carrier pipeline mass flow controller MFC1 is controlled by device control unit, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4, 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 AK4 be in open mode by device control unit, organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3 is all in closing condition, organo-bismuth source gas-carrier pipeline mass flow controller MFC1 is controlled by device control unit, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4, 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 organic gallium source pipeline self-acting valve AK3 be in open mode by device control unit, organo-bismuth source capsule road self-acting valve AK1, oxygen presoma pipeline self-acting valve AK3 are all in closing condition, control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organoaluminum source 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 A is realized by following action:
Controlled to make organoaluminum source capsule road self-acting valve AK2 be in open mode by device control unit, organo-bismuth source capsule road self-acting valve AK1, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK4 is all in closing condition, organo-bismuth source gas-carrier pipeline mass flow controller MFC1 is controlled by device control unit, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4, make gas in each gas piping according to step D) in set(ting)value pass into vacuum reaction chamber,
H) when film growth cycle index reaches the number of times of setting, film thickness reaches desirable value, obtains certain thickness Bi (Al
0.05ga
0.95) O
3thin-film material, organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK3 is closed by device control unit, stop passing into organo-bismuth source, organoaluminum source, organic gallium source, oxygen presoma, continue to pass into rare gas element, stop powering to electric heater, stop heating vacuum chamber;
I) manual-lock organo-bismuth source capsule road manual valve K1, organoaluminum source capsule road manual valve K2, organic gallium source pipeline manual valve K3, oxygen presoma pipeline manual valve K4, inert gas piping manual valve K5, air-inlet of vacuum pump automatic valve AK4 stay open state, and vacuum reaction chamber carries out naturally cooling;
J) vacuum chamber reach or close to room temperature time, close air-inlet of vacuum pump automatic valve AK5 by device control unit;
K) 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;
L) taking-up has deposited and has obtained Bi (Al
0.05ga
0.95) O
3the substrate of thin-film material, closes inert gas piping manual valve K5;
M) Bi (Al is attached with by what obtain in step L
0.05ga
0.95) O
3the substrate of thin-film material, puts into quick anneal oven, carries out quick thermal annealing process, takes out after naturally cooling, confirms the Bi (Al obtained through test
0.05ga
0.95) O
3the spacer of thin-film material is Pcca;
The step of rapid thermal annealing is:
A () maintains 3 minutes at 220 DEG C;
B () maintains 4 minutes at 360 DEG C;
(c) high temperature annealing 4 minutes at 800 DEG C;
Performance test is carried out to sample.
Embodiment 2: preparation Bi (Al
0.2ga
0.8) O
3film
A) in vacuum glove box, be filled with the nitrogen of more than 99.9995% purity, in the nitrogen atmosphere of glove box, complete following operation: organo-bismuth source, organoaluminum source, organic gallium source are filled into organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3 respectively, then install with respective pipeline and be connected;
B) organo-bismuth source adopts three (2,2,6, the acid of 6-tetramethyl--3,5-heptadione) bismuth (III), organic gallium source adopts triethyl-gallium, organoaluminum source adopts triethyl aluminum, and oxygen precursor source adopts deionized water, and rare gas element adopts the nitrogen of more than 99.9995% purity; Organo-bismuth source, organoaluminum source, organic gallium source, oxygen precursor source, nitrogen are filled into organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3, oxygen precursor source containers 4, rare gas element source container 5 respectively, then install with respective pipeline and be connected;
Drive away each material container and install the air connected in rear pipeline, specifically this is operating as:
Maintenance organo-bismuth source capsule road manual valve K1, organoaluminum source capsule road manual valve K2, organic gallium source pipeline manual valve K3, oxygen presoma pipeline manual valve K4 are all in closing condition, then,
Controlled to make air-inlet of vacuum pump automatic valve AK5 be in open mode by device control unit, controlled to make organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK4 all be in open mode by device control unit; When the vacuumometer in vacuum reaction chamber no longer changes, controlled to make air-inlet of vacuum pump automatic valve AK5 be in closing condition by device control unit, control organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4 by device control unit, make rare gas element in each gas piping pass into vacuum reaction chamber according to certain value; When the air pressure in vacuum reaction chamber reaches 0.5 normal atmosphere, again controlled to make air-inlet of vacuum pump automatic valve AK5 be in open mode by device control unit, controlled to make organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK4 all be in open mode by device control unit; Repeat said process 5 times;
C) the TiN substrate material rare gas element of cleaning is dried up, be placed in substrate pallet;
D) pallet moves into vacuum reaction chamber together with TiN substrate, opens vacuum pump, and then opens air-inlet of vacuum pump automatic valve AK5, vacuumize vacuum reaction chamber by device control unit;
E) set on device control unit organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3, oxygen precursor source containers 4 temperature be respectively 190 DEG C, 20 DEG C, 20 DEG C, 20 DEG C, control organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3, the electric heater of oxygen precursor source containers 4 and/or the working order of semiconductor cooler by device control unit, maintain the temperature value of setting to make the temperature of organo-bismuth source container 1, organoaluminum source container 2, organic gallium source container 3, oxygen precursor source containers 4;
Control electric heater by device control unit to heat vacuum chamber, make the pallet in vacuum chamber and substrate temperature constant in 330 DEG C in whole thin film growth process;
F) when vacuum chamber temperature after constant 30 minutes, device control unit sets the cycle index of film growth, organo-bismuth source gas-carrier pipeline gas flow rate, organoaluminum source gas-carrier pipeline gas flow rate, organic gallium source gas-carrier pipeline gas flow rate, oxygen presoma gas-carrier pipeline gas flow rate, rare gas element flow velocity, organo-bismuth source gas pulses length, organoaluminum source gas pulses length, organic gallium source gas pulses length, oxygen precursor gas pulse length, inert purge gas pulses length at 330 DEG C; Manual unlocking organo-bismuth source capsule road manual valve K1, organoaluminum source capsule road manual valve K2, organic gallium source pipeline manual valve K3, oxygen presoma pipeline manual valve K4, inert gas piping manual valve K5;
The inputting interface of device control unit sets organo-bismuth source gas-carrier pipeline gas flow rate, organoaluminum source gas-carrier pipeline gas flow rate, organic gallium source gas-carrier pipeline gas flow rate, oxygen presoma gas-carrier pipeline gas flow rate be respectively 200sccm (standardcubiccentimetersperminute), 200sccm, 200sccm, 250sccm;
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 triethyl aluminum gas pulses length is 0.4s, and triethyl-gallium gas pulses length is 0.4s, H
2o gas pulses length is 0.1s, and pulse of nitrogen length is 4s;
Three (acid of 2,2,6,6-tetramethyl--3,5-heptadione) bismuth (III) gas pulses, triethyl aluminum gas pulses, triethyl-gallium gas pulses, H is represented respectively with B, A, G, O, N
2o gas pulses, pulse of nitrogen, in whole growth cycle, gas pulses cyclic sequence is as shown in Figure 3;
G) organo-bismuth source gas-carrier pipeline mass flow controller MFC1, organoaluminum source gas-carrier pipeline mass flow controller MFC2, organic gallium source gas-carrier pipeline mass flow controller MFC3, oxygen presoma gas-carrier pipeline mass flow controller MFC4 is controlled by device control unit, make gas in each gas piping according to step F) in set(ting)value pass into vacuum reaction chamber, vacuum reaction chamber passes into rare gas element, organic bismuth source gas, organic gallium source gas, oxygen precursor gas and organic aluminum source gas respectively according to certain gas pulses sequential; All precursor gas adopt nitrogen to transport respectively;
H) when film growth cycle index reaches the number of times of setting, film thickness reaches desirable value, obtains certain thickness Bi (Al
0.2ga
0.8) O
3thin-film material, organo-bismuth source capsule road self-acting valve AK1, organoaluminum source capsule road self-acting valve AK2, organic gallium source pipeline self-acting valve AK3, oxygen presoma pipeline self-acting valve AK3 is closed by device control unit, stop passing into organo-bismuth source, organoaluminum source, organic gallium source, oxygen presoma, continue to pass into rare gas element, stop powering to electric heater, stop heating vacuum chamber;
I) manual-lock organo-bismuth source capsule road manual valve K1, organoaluminum source capsule road manual valve K2, organic gallium source pipeline manual valve K3, oxygen presoma pipeline manual valve K4, inert gas piping manual valve K5, air-inlet of vacuum pump automatic valve AK4 stay open state, and vacuum reaction chamber carries out naturally cooling;
J) vacuum chamber reach or close to room temperature time, close air-inlet of vacuum pump automatic valve AK5 by device control unit;
K) 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;
L) taking-up has deposited and has obtained Bi (Al
0.2ga
0.8) O
3the substrate of thin-film material, closes inert gas piping manual valve K5;
M) Bi (Al is attached with by what obtain in step L
0.2ga
0.8) O
3the substrate of thin-film material, puts into quick anneal oven, carries out quick thermal annealing process, takes out after naturally cooling, carries out performance test to sample.