CN105256287B - The method that presoma space cellular-type prepares aluminic acid bismuth thin film - Google Patents
The method that presoma space cellular-type prepares aluminic acid bismuth thin film Download PDFInfo
- Publication number
- CN105256287B CN105256287B CN201510767278.6A CN201510767278A CN105256287B CN 105256287 B CN105256287 B CN 105256287B CN 201510767278 A CN201510767278 A CN 201510767278A CN 105256287 B CN105256287 B CN 105256287B
- Authority
- CN
- China
- Prior art keywords
- gas
- compartment
- passed
- bismuth
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
A kind of being reacted from restricted adsorption for presoma space cellular-type prepares BiAlO3The method of thin-film material, BiAlO3Thin-film material is grown on backing material, described BiAlO3The space group of thin-film material is R3c, and lattice constant is a=7.611, c=7.942；Obtained using presoma space cellular-type from the reaction of restricted adsorption, the irreversible Chemisorption of Langmuir absorption mechanism is refered in particular in the adsorption reaction.By using the preparation BiAlO of the present invention3The method of thin-film material, it is possible to achieve BiAlO3The controllable precise of film growth thickness, and BiAlO3Thin film surface planeness is significantly better than prior art.Because being passed through for various gases is successive and constant flow rate, the thickness of film is only dependent upon the number of times that substrate is turned over, and technique becomes extremely simple, reliable.
Description
Technical field
The present invention relates to a kind of bismuth-based oxide thin-film material, specifically a kind of BiAlO3Ferroelectric thin-flim materials and its
Preparation method.
Background technology
Recently it is found that bismuth-based ferroelectric material such as bismuth ferrite (BiFeO3), bismuth titanates (Bi4Ti3O12), bismuth aluminate
(BiAlO3) etc. the ferroelectric oxide of perovskite or counterfeit perovskite structure have that the small, fatigue resistance that leaks electricity is strong, dielectric constant is big
And it is environmentally friendly the features such as and receive much concern.In recent years, people are to bismuth ferrite (BiFeO3) and bismuth titanates (Bi4Ti3O12)
Design, prepare, physicochemical properties and the application in production and life have it is universal be appreciated and understood by, 2005 years
Baettig et al. has theoretically foretold bismuth aluminate (BiAlO3) equally with excellent ferroelectric properties, but people couple at present
Bismuth aluminate (BiAlO3) technology of preparing of material also extremely lacks, only using HTHP solid reaction process, (pressure exists report
GPa magnitudes, temperature are more than 1,000 degrees Celsius) prepare bismuth aluminate (BiAlO3) block materials, and so high temperature, high pressure life
Production condition, it is clear that be not suitable for applying to microelectronic industry progress device, the production of integrated circuit, its block materials can not also be applied
In increasingly miniaturization, the higher and higher microelectronic of integrated level, and it is applied to the system of the aluminic acid bismuth thin film of microelectronic
Standby technique has not been reported.
The content of the invention
In order to solve prior art problem, it is an object of the invention to provide a kind of space for accurately controlling film thickness
Separate type reacts the BiAlO prepared from restricted adsorption3The method of thin-film material.Realize the object of the invention particular technique side
Case is：
A kind of BiAlO3The preparation method of thin-film material, the BiAlO3The space group of thin-film material is R3c, lattice constant
For
Including but not limited to step in detail below：
A) backing material of cleaning is dried up with inert gas, is placed into substrate pallet；
B) pallet moves into vacuum reaction chamber together with substrate, opens vavuum pump and vacuum reaction chamber is vacuumized；
C) vacuum chamber is heated, pallet and substrate temperature in vacuum chamber is tieed up in whole thin film growth process
Hold in a stationary temperature value, the temperature value is in a suitable temperature window；
Selected suitable temperature window refers to：Within the scope of suitable temperature, i.e., substrate temperature is higher than a temperature
Spend lower limit and less than temperature upper limit, and precursor gas supply flow velocity be more than minimum limit value in the case of, the life of film
Long speed is a substantially invariable value, and the growth rate of film is inert gas with the flow velocity of precursor gas supply, carrier gas
Flow velocity, substantially unrelated, the described here " base of the temperature of presoma, substrate temperature, the vacuum of the compartment of vacuum chamber
This is unrelated " refer to：It is also slight fluctuations even if the growth rate of film has fluctuation in this temperature window, when growth temperature is super
Go out this temperature window i.e. less than lowest temperature or higher than temperature upper limit, the growth rate of film can be significantly increased or reduced；
In temperature window, sedimentation rate is not varied with temperature；When temperature is not high enough, presoma condensation causes multilayer to be inhaled
It is attached to cause too high sedimentation rate, or cause absorption incomplete, reactivity is poor；Presoma, which is decomposed, when temperature is too high causes additionally
The growth of CVD formulas, or due to too high hot kinetic energy, presoma desorption；
Include multiple compartments in vacuum reaction chamber, be respectively used to be passed through bismuth precursor gas, aluminium precursor gas,
Oxygen precursor gas, inert gas；
D after cavity temperature of) taking seriously constant a period of time, the number of turns that setting pallet is rotated together with substrate, vacuum reaction chamber
The different compartments are each led into before inert gas, three (DPM dpm,dipivalomethane acid) bismuths (III) or other bismuths
Drive body gas, oxygen precursor gas and trimethylaluminum gas or other aluminium precursor gas；All precursor gas are respectively
Transported using inert gas；
E) substrate bracket disk drives backing material to move together, is being passed through three (2,2,6,6- tetramethyl -3,5- heptadione acid)
The compartment of bismuth (III) or other bismuth precursor gas, be passed through the compartment of inert gas, be passed through trimethylaluminum gas or
The compartment of other aluminium precursor gas, it is passed through between four kinds of compartments such as compartment of oxygen precursor gas and passes through；
F) when pallet and substrate, which are rotated, reaches the number of turns of setting, stop operating, film thickness reaches desirable value, obtain one
Determine the BiAlO of thickness3Thin-film material, stopping is passed through bismuth presoma, aluminium presoma, oxygen presoma, continues to be passed through inert gas, stops
Only pallet and substrate, stop the heating progress natural cooling of vacuum chamber；
G) vacuum chamber reaches or during close to room temperature, closes vavuum pump, vacuum reaction chamber, which is inflated, reaches its air pressure
One atmospheric pressure, taking-up, which has been deposited, obtains BiAlO3The substrate of thin-film material；
H) it is attached with BiAlO by what is obtained in step G3The substrate of thin-film material, is put into quick anneal oven, carries out quick
Taken out after thermal anneal process, natural cooling.
Through X-ray diffraction (XRD) test and structure refinement confirm, by step H) obtained by BiAlO3Thin-film material
Space group is R3c, and lattice constant is
Thickness controllable precise when can realize film growth due to the method for the present invention, but at most only obtain one per secondary growth
The material of atomic layer, the speed of growth is relatively low, therefore, is generally used for growing several nanometers to the BiAlO of tens nanometers of thickness3It is thin
Membrane material, most hundreds of nanometers, less than 500 nanometers, otherwise its too low speed of growth will become to receive.
In the present invention, each compartment is the semienclosed container of semi open model, and these containers are one section and opened
Mouthful, the other end is closed and is provided with gas piping, and gas piping is used to be passed through presoma and/or inert gas；
Pallet is discoid, and has been evenly distributed multiple shallow slots to accommodate substrate, the depth of shallow slot and the thickness of substrate
It is essentially identical, to ensure that substrate does not collide with as principle in motion process with miscellaneous part.
In thin film growth process, pallet is with substrate together in the opening end of the semienclosed container of each semi open model
Motion, and pallet has a certain distance or gap from its vessel port, and the distance is therein to be passed through in grade
Gas is able to discharge from the gap, and ensures that pallet will not collide with during substrate motion with vessel port；
The arrangement rule of these foregoing compartments is as follows：
Represent bismuth precursor gas, aluminium precursor gas, oxygen precursor gas, inert gas respectively with B, A, O, N respectively,
Then：
Three (DPM dpm,dipivalomethane acid) bismuth (III) gases or oxygen precursor gas are passed through at any one
The closest one or both sides of the compartment of body or trimethylaluminum gas, are all also passed through inert gas with one or more
The compartment, be usually one or two compartment, i.e. for example：BN ..., or AN ..., or ON ..., or ...
NBN ..., or ... NAN ..., or ... NON ..., herein ellipsis " ... " represent other possible collating sequences；And
In the case where meeting above-mentioned condition,
Three (DPM dpm,dipivalomethane acid) bismuth (III) gases or trimethyl aluminium gas are passed through at any one
The secondary adjacent side of the compartment of body, all also has one or more compartments for being passed through oxygen precursor gas, and usually one
The individual compartment, i.e. such as：... NONBN ..., or ... NONAN ..., or ... NBNON ..., or ...
NANON ..., herein ellipsis " ... " represent other possible collating sequences；And in the case where meeting above-mentioned condition,
It is passed through the compartment of three (DPM dpm,dipivalomethane acid) bismuths (III), is passed through oxygen precursor gas
The compartment, the compartment that is passed through the compartment of trimethylaluminum gas, is passed through inert gas can arrange with any order
Row can be multigroup compartment for being passed through three (2,2,6,6- tetramethyl -3,5- heptadione acid) bismuths (III) or be passed through oxygen forerunner
The compartment of body gas or be passed through the compartment of trimethylaluminum gas and be passed through inert gas the compartment it is continuous successively
Distribution, then adjacent one or more groups of compartments for being passed through remaining precursor gas；In other words, it is one or more to be passed through trimethyl
The compartment of aluminium gas, one or more separations for being passed through three (DPM dpm,dipivalomethane acid) bismuths (III) are empty
Between, one or more compartments for being passed through oxygen precursor gas can be arranged with any order, for example, be passed through bismuth forerunner
Body gas, oxygen precursor gas, aluminium precursor gas, the sequence of several compartments of inert gas can be ...
BNONBNONBNONANONBNONANON ... or ... BNONANONBNONBNONBNONBNONANON ..., also
Can be ... ANONANONBNONBNONBNONBNONBNON ..., or ...
ANONBNONBNONBNONBNONANONBNON ... etc.；Ellipsis " ... " represents other possible collating sequences herein；
The quantity of each compartment in vacuum reaction chamber for 4 multiple and not less than 8, for example：8,12,16,
20 ... etc.；Each compartment is adjacent successively and tandem array forms close ring, and pallet and substrate are in these compartment shapes
Into atmosphere in move；, each compartment is for being passed through bismuth precursor gas, oxygen precursor gas, aluminium precursor gas
Body, inert gas；
The quantity sum of the compartment for being passed through bismuth precursor gas and aluminium precursor gas, which is equal to, to be used to be passed through oxygen
The quantity of the compartment of presoma, the compartment for being passed through bismuth precursor gas, aluminium precursor gas and oxygen presoma
Quantity sum be equal to be used for be passed through inert gas the compartment quantity；
In view of the space steric effect of precursor molecule, for be passed through bismuth precursor gas the compartment quantity with
The quantity of the compartment for being passed through aluminium precursor gas might not be equal, but is allocated according to following principle：
When pallet and substrate are moved one week in the close ring that these compartments are constituted, deposition is obtained on substrate
Bismuth, the stoichiometric proportion of aluminium are close to 1:1, it is allowed to have the stoichiometric proportion of less than 10% positive error, i.e. bismuth, aluminium 1:1~
1:In the range of 1.1, this is due to need to consider in step H) in rapid thermal annealing bismuth element it is readily volatilized and make it is appropriate
Compensation；
In the case where meeting above-mentioned requirements, exist for being passed through bismuth precursor gas, the compartment of aluminium precursor gas
Arrangement is spatially uniformly distributed in above-mentioned close ring as much as possible.
In membrane-film preparation process, the temperature of reasonable selection vacuum reaction chamber, substrate motion speed, three (2,2,6,6- tetra-
Methyl -3,5- heptadione acid) bismuth (III), trimethyl aluminium, the flow velocity of inert gas, pressure so that backing material is every time by logical
When entering three (2,2,6,6- tetramethyl -3,5- heptadione acid) bismuths (III), the compartment of trimethyl aluminium, it can make substrate material
(2,2,6,6- tetramethyl -3, the 5- heptadione acid) bismuth (III) of a monolayer three or trimethyl aluminium are intactly adsorbed in material surface, its
Absorption mechanism adsorbs for Langmuir (Langmuir)；When substrate sequentially passes through the compartment of two kinds of presomas, complete once
Thin film deposition, for example, when substrate passes through BNON, depositing one layer of Bi2O3。
In membrane-film preparation process, underlayer temperature is located in foregoing suitable temperature window, passes through bismuth every time in substrate
When precursor gas atmosphere, aluminium precursor gas atmosphere, oxygen precursor gas atmosphere, the Chemisorption of substrate surface is
" half-reaction " (" half-reaction "), rather than once complete Chemisorption, only substrate is twice respectively through bismuth
Precursor gas atmosphere and oxygen precursor gas atmosphere, or aluminium precursor gas atmosphere and oxygen precursor gas atmosphere, are just completed
Once complete Chemisorption, respectively obtains the Bi of an atomic layer2O3Or Al2O3；
In membrane-film preparation process, temperature, the substrate motion speed of vacuum reaction chamber keep constant, are passed through each separation
Three (DPM dpm,dipivalomethane acid) bismuth (III) gases in space, trimethylaluminum gas, the flow velocity of inert gas,
Pressure, temperature also all keep constant, and are continuously passed through each compartment, and each gas piping is by mass flow
Controller (MFC) controls gas flow rate, pressure.
In membrane-film preparation process, the air pressure that each is passed through the compartment of identical presoma is essentially identical, but is passed through not
With presoma the compartment air pressure then need not identical (can be the same or different), in addition, in order to ensure growing
Journey controllable precise, each pipeline gas flow velocity must be adjusted when being passed through various gases must comply with the air pressure of each compartment
Following rules：
The air pressure for being passed through the compartment of inert gas have to be larger than and neighbouring be passed through bismuth precursor gas, aluminium precursor gas
The air pressure of the compartment of body or oxygen precursor gas, it is allowed to which the inert gas being passed through in the compartment of inert gas has on a small quantity
Part invades neighbouring point for being passed through other precursor gas (i.e. bismuth presoma, aluminium presoma, oxygen presoma) by gap
Every space, opposite situation does not allow then to occur, and in the case, the connotation of " a small amount of " refers to：Although allowing have a small amount of
Inert gas invades the neighbouring compartment by gap, but still may insure substrate every time by bismuth precursor gas,
When aluminium precursor gas, oxygen precursor gas atmosphere, the substrate surface intactly monolayer of chemisorbed one can be made respectively
Bismuth precursor molecule, aluminium precursor molecule, oxygen precursor molecule.
In each compartment for being passed through bismuth precursor gas, aluminium precursor gas, oxygen precursor gas, it is not necessary to it is required that its
In bismuth precursor molecule, aluminium precursor molecule, oxygen precursor molecule even concentration, it is allowed to there is certain concentration gradient, but
It, which is distributed to arrive extensively, may be such that substrate surface intactly the bismuth precursor molecule of the monolayer of chemisorbed one, aluminium presoma point
Son, oxygen precursor molecule.
In the present invention, described substrate can be TiN, SiO2、Si、LaNiO3/Si、Pt/TiO2/SiO2/Si、Pt/
Ti/SiO2/ Si, can also be other suitable substrates.
In the present invention, term " inert gas " refers not only to signified inert gas (helium, the argon gas of usual chemical field
Deng), other gases that will not be chemically reacted in whole membrane-film preparation process with presoma are additionally included in, for example：Nitrogen.
In the present invention, oxygen precursor gas can be H2O、O2、O3Any of which or wherein any two
Kind or three kinds of mixed gas, wherein H2O is deionized water, O2、O3Purity is above 99.999%.
In the present invention, bismuth presoma, aluminium presoma are respectively three (2,2,6,6- tetramethyl -3,5- heptadione acid) bismuths
(III), trimethyl aluminium；In the case where equipment allows and meets actual demand, bismuth presoma can also use triphenyl bismuth, three
Methyl bismuth, three tert-butyl alcohol base bismuths, trimethylsilyl bismuth etc., aluminium presoma can also use triethyl aluminum, tri-tert aluminium.
Preferably, full substrate slice can be arranged on pallet to improve production efficiency.
Preferably, it is drum-shaped that vacuum reaction chamber, which removes ventilation with its main part outside the two ends of exhaust,.
Preferably, pallet is discoid, and has been evenly distributed multiple shallow slots to accommodate substrate.
Preferably, pallet is driven by motor, drives substrate evenly to rotate.
Preferably there is provided a control system, thus the number of turns for being set by control system, controlling pallet to rotate controls
Obtain BiAlO3The thickness of thin-film material, the control system can be the special circuit of customization, can be (programmable by PLC
Logic controller) constitute, it can be made up of FPAL (field programmable gate array), can also be by CPLD (complex programmable logics
Device) constitute, it can also be that single-chip microcomputer is constituted, or PC；The number of times of pallet rotation is preset before thin film deposition, when thin
Film deposition starts rear system and started counting up, and pallet is turned over after the number of turns of setting, stops motor and rotates and stop being passed through various forerunners
Body gas.
In implementation process, the size for making pallet, area should be designed bigger than the closed-loop that all compartments are constituted.So
Can make various precursor gas fully with substrate contact, complete a complete chemical absorption of surface.
Beneficial effects of the present invention：
By using the preparation BiAlO of the present invention3The method of thin-film material, it is possible to achieve BiAlO3Film growth thickness
Controllable precise, and BiAlO3Thin film surface planeness is significantly better than prior art.Simultaneously as being passed through for various gases is continuous
Constantly and constant flow rate, the thickness of film is only dependent upon the number of times that substrate is turned over, and technique becomes extremely simple, reliable.
Brief description of the drawings
Fig. 1：L represents lowest temperature in the suitable temperature window schematic diagram of film growth, figure, and H represents temperature upper limit；
In temperature window, sedimentation rate is not varied with temperature；When temperature is not high enough, it is too high that presoma condensation causes multilayer absorption to cause
Sedimentation rate, or cause that absorption is incomplete, reactivity is poor；Presoma, which is decomposed, when temperature is too high causes extra CVD formulas to be given birth to
It is long, or due to too high hot kinetic energy, presoma desorption.
Fig. 2：Three (DPM dpm,dipivalomethane acid) are respectively adopted in bismuth presoma, aluminium presoma, oxygen presoma
Bismuth (III), tri-tert aluminium, H2Represented respectively with B, A, O, N in the arrangement of each compartment, figure during O bismuth precursor gas,
Aluminium precursor gas, oxygen precursor gas, inert gas.
Fig. 3：Trimethyl-bismuthine, trimethyl aluminium, H is respectively adopted in bismuth presoma, aluminium presoma, oxygen presoma2Each separates during O
Represent bismuth precursor gas, aluminium precursor gas, oxygen precursor gas, indifferent gas in the arrangement in space, figure respectively with B, A, O, N
Body.
Fig. 4：Triphenyl bismuth, triethyl aluminum, H is respectively adopted in bismuth presoma, aluminium presoma, oxygen presoma2Each separates during O
Represent bismuth precursor gas, aluminium precursor gas, oxygen precursor gas, indifferent gas in the arrangement in space, figure respectively with B, A, O, N
Body.
Embodiment
Technical scheme is specifically introduced with reference to example.
Embodiment 1：
Include 32 compartments in used vacuum reaction chamber, be respectively used to be passed through three (2,2,6,6- tetramethyls-
3,5- heptadione acid) bismuth (III) steam, tri-tert aluminium steam, H2The N of O steam, purity more than 99.9995%2(nitrogen)；
Represent bismuth precursor gas, aluminium precursor gas, oxygen precursor gas, high-purity nitrogen respectively with B, A, O, N, then these separate
The ordering in space is as shown in Figure 2.
Three (2,2,6,6- tetramethyl -3,5- heptadione acid) bismuth (III) steam are produced by a solid source bottle, raw material three
(2,2,6,6- tetramethyl -3,5- heptadione acid) bismuth (III) is heated and is at 170-195 DEG C, produces three (2,2,6,6- tetramethyls
Base -3,5- heptadione acid) bismuth (III) steam；
H2O steam is produced by a fluid supply bottle, and the raw material is cooled under room temperature state and suitably by semiconductor chilling plate
To avoid producing too high vapour pressure；
Tri-tert aluminium steam is produced by a fluid supply bottle, and tri-tert aluminium is diluted into dissolving with organic solvent simultaneously
Produce tri-tert aluminium steam；
In film deposition process, vacuum reaction intracavitary maintains the -10hPa of air pressure 1；
A) by high-purity nitrogen (purity the is higher than 99.9995%) drying of the Si backing materials of cleaning, it is placed into lining
In bottom tray；
B) pallet moves into vacuum reaction chamber together with substrate by electric moving bar, after the chamber door for closing vacuum chamber, opens vacuum
Pump is vacuumized to vacuum reaction chamber, its vacuum is maintained 1-10hPa；
C) vacuum chamber is heated, pallet and substrate temperature in vacuum chamber is tieed up in whole thin film growth process
Hold at 300 DEG C；
D after cavity temperature of) taking seriously constant a period of time, the number of turns that pallet rotated together with substrate is set as 300, rotating speed is
1rpm；The different compartments of vacuum reaction chamber each lead into high-purity nitrogen, three (DPM dpm,dipivalomethanes
Acid) bismuth (III), H2O gases and tri-tert aluminium gas；All precursor gas are respectively carried out defeated using high-purity nitrogen
Fortune；
It is passed through three (DPM dpm,dipivalomethane acid) bismuth (III) steam, tri-tert aluminium steam, H2O steams
Gas flow rate in vapour, each pipeline of high-purity nitrogen is respectively 150sccm, 150sccm, 150sccm, 250sccm；It is high-purity
The flow velocity of degree nitrogen is all higher than other precursor gas rates of flow of fluid, it can be ensured that each precursor gas is in the respective compartment
In will not occur crosstalk, it is ensured that the speed of growth controllable precise of film；
E) substrate bracket disk drives backing material to move together, is being passed through three (2,2,6,6- tetramethyl -3,5- heptadione acid)
The compartment of bismuth (III) gas, the compartment for being passed through the compartment of high-purity nitrogen, being passed through tri-tert aluminium gas,
It is passed through H2Pass through between four kinds of compartments such as compartment of O gases；
F) when pallet and substrate, which are rotated, reaches the number of turns 300 of setting, stop operating, obtain certain thickness BiAlO3It is thin
Membrane material, stopping is passed through bismuth presoma, aluminium presoma, oxygen presoma, continues to be passed through high-purity nitrogen, stops pallet and substrate,
Stop vacuum chamber heating, carry out natural cooling；
G) vacuum chamber is reached or during close to room temperature, closes vavuum pump, and high-purity nitrogen inflation is carried out to vacuum reaction chamber to be made
Its air pressure reaches an atmospheric pressure, and now vacuum reaction chamber inner and outer air pressure reaches balance, opens chamber door, and taking-up, which has been deposited, to be obtained
BiAlO3The substrate of thin-film material；
H) it is attached with BiAlO by what is obtained in step G3The substrate of thin-film material, is put into quick anneal oven, carries out quick
Thermal anneal process, that is, sequentially pass through three below rapid thermal annealing (RTA) step：
(a) maintained 3 minutes at 180~220 DEG C；
(b) maintained 5 minutes at 390~400 DEG C；
(c) high annealing 5 minutes at 900 DEG C~1050 DEG C；
Taken out after natural cooling.
A series of test is carried out to resulting film sample.
Embodiment 2：
Include 32 compartments in used vacuum reaction chamber, be respectively used to be passed through trimethyl-bismuthine steam, front three
Base aluminium steam, H2The N of O steam, purity more than 99.9995%2(nitrogen)；Represented respectively with B, A, O, N bismuth precursor gas,
Aluminium precursor gas, oxygen precursor gas, high-purity nitrogen, then the ordering of these compartments is as shown in Figure 3.
Trimethyl-bismuthine steam is produced by a fluid supply bottle, and trimethyl-bismuthine is diluted with organic solvent and dissolves and produces
Trimethyl-bismuthine steam；
Trimethyl aluminium steam is produced by a fluid supply bottle, and trimethyl aluminium is diluted with organic solvent and dissolves and produces
Trimethyl aluminium steam；
H2O steam is produced by a fluid supply bottle, and the raw material is cooled under room temperature state and suitably by semiconductor chilling plate
To avoid producing too high vapour pressure；
In film deposition process, vacuum reaction intracavitary maintains the -10hPa of air pressure 1；
A) by high-purity nitrogen (purity the is higher than 99.9995%) drying of the Si backing materials of cleaning, it is placed into lining
In bottom tray；
B) pallet moves into vacuum reaction chamber together with substrate by electric moving bar, after the chamber door for closing vacuum chamber, opens vacuum
Pump is vacuumized to vacuum reaction chamber, its vacuum is maintained 1-10hPa；
C) vacuum chamber is heated, pallet and substrate temperature in vacuum chamber is tieed up in whole thin film growth process
Hold at 330 DEG C；
D after cavity temperature of) taking seriously constant a period of time, the number of turns that pallet rotated together with substrate is set as 300, rotating speed is
1rpm；The different compartments of vacuum reaction chamber each lead into high-purity nitrogen, trimethyl-bismuthine, H2O gases and trimethyl aluminium
Gas；All precursor gas are respectively transported using high-purity nitrogen；
It is passed through trimethyl-bismuthine, trimethyl aluminium steam, H2Gas flow rate point in O steam, each pipeline of high-purity nitrogen
Wei not 150sccm, 150sccm, 150sccm, 250sccm；The flow velocity of high-purity nitrogen is all higher than other precursor gas streams
Speed, it can be ensured that crosstalk will not occur in the respective compartment for each precursor gas, it is ensured that the speed of growth essence of film
It is really controllable；
E) substrate bracket disk drive backing material move together, be passed through the compartment of trimethyl-bismuthine gas, be passed through it is high-purity
The compartment of nitrogen is spent, the compartment of trimethylaluminum gas is passed through, is passed through H2Four kinds of compartment of O gases etc. separates empty
Between between pass through；
F) when pallet and substrate, which are rotated, reaches the number of turns 300 of setting, stop operating, obtain certain thickness BiAlO3It is thin
Membrane material, stopping is passed through bismuth presoma, aluminium presoma, oxygen presoma, continues to be passed through high-purity nitrogen, stops pallet and substrate,
Stop vacuum chamber heating, carry out natural cooling；
G) vacuum chamber is reached or during close to room temperature, closes vavuum pump, and high-purity nitrogen inflation is carried out to vacuum reaction chamber to be made
Its air pressure reaches an atmospheric pressure, and now vacuum reaction chamber inner and outer air pressure reaches balance, opens chamber door, and taking-up, which has been deposited, to be obtained
BiAlO3The substrate of thin-film material；
H) it is attached with BiAlO by what is obtained in step G3The substrate of thin-film material, is put into quick anneal oven, carries out quick
Thermal anneal process, that is, sequentially pass through three below rapid thermal annealing (RTA) step：
(a) maintained 3 minutes at 180~220 DEG C；
(b) maintained 5 minutes at 390~400 DEG C；
(c) high annealing 5 minutes at 900 DEG C~1050 DEG C；
Taken out after natural cooling.
Embodiment 3：
Include 32 compartments in used vacuum reaction chamber, be respectively used to be passed through triphenyl bismuth steam, three second
Base aluminium steam, H2The N of O steam, purity more than 99.9995%2(nitrogen)；Represented respectively with B, A, O, N bismuth precursor gas,
Aluminium precursor gas, oxygen precursor gas, high-purity nitrogen, then the ordering of these compartments is as shown in Figure 4.
Triphenyl bismuth steam is produced by a fluid supply bottle, and triphenyl bismuth is diluted with organic solvent and dissolves and produces
Triphenyl bismuth steam；
Triethyl aluminum steam is produced by a fluid supply bottle, and triethyl aluminum is diluted with organic solvent and dissolves and produces
Triethyl aluminum steam；
H2O steam is produced by a fluid supply bottle, and the raw material is cooled under room temperature state and suitably by semiconductor chilling plate
To avoid producing too high vapour pressure；
In film deposition process, vacuum reaction intracavitary maintains the -10hPa of air pressure 1；
A) by high-purity nitrogen (purity the is higher than 99.9995%) drying of the TiN backing materials of cleaning, it is placed into lining
In bottom tray；
B) pallet moves into vacuum reaction chamber together with substrate by electric moving bar, after the chamber door for closing vacuum chamber, opens vacuum
Pump is vacuumized to vacuum reaction chamber, its vacuum is maintained 1-10hPa；
C) vacuum chamber is heated, pallet and substrate temperature in vacuum chamber is tieed up in whole thin film growth process
Hold at 270 DEG C；
D after cavity temperature of) taking seriously constant a period of time, the number of turns that pallet rotated together with substrate is set as 500, rotating speed is
2rpm；The different compartments of vacuum reaction chamber each lead into high-purity nitrogen, triphenyl bismuth, H2O gases and triethyl aluminum
Gas；All precursor gas are respectively transported using high-purity nitrogen；
It is passed through triphenyl bismuth, triethyl aluminum steam, H2Gas flow rate point in O steam, each pipeline of high-purity nitrogen
Wei not 150sccm, 150sccm, 150sccm, 250sccm；The flow velocity of high-purity nitrogen is all higher than other precursor gas streams
Speed, it can be ensured that crosstalk will not occur in the respective compartment for each precursor gas, it is ensured that the speed of growth essence of film
It is really controllable；
E) substrate bracket disk drive backing material move together, be passed through the compartment of triphenyl bismuth gas, be passed through it is high-purity
The compartment of nitrogen is spent, the compartment of triethyl aluminum gas is passed through, is passed through H2Four kinds of compartment of O gases etc. separates empty
Between between pass through；
F) when pallet and substrate, which are rotated, reaches the number of turns 300 of setting, stop operating, obtain certain thickness BiAlO3It is thin
Membrane material, stopping is passed through bismuth presoma, aluminium presoma, oxygen presoma, continues to be passed through high-purity nitrogen, stops pallet and substrate,
Stop vacuum chamber heating, carry out natural cooling；
G) vacuum chamber is reached or during close to room temperature, closes vavuum pump, and high-purity nitrogen inflation is carried out to vacuum reaction chamber to be made
Its air pressure reaches an atmospheric pressure, and now vacuum reaction chamber inner and outer air pressure reaches balance, opens chamber door, and taking-up, which has been deposited, to be obtained
BiAlO3The substrate of thin-film material；
H) it is attached with BiAlO by what is obtained in step G3The substrate of thin-film material, is put into quick anneal oven, carries out quick
Thermal anneal process, that is, sequentially pass through three below rapid thermal annealing (RTA) step：
(a) maintained 3 minutes at 180-220 DEG C；
(b) maintained 5 minutes at 390-400 DEG C；
(c) high annealing 5 minutes at 900 DEG C -1050 DEG C；
Taken out after natural cooling.
Claims (8)
1. a kind of being reacted from restricted adsorption for use presoma space cellular-type prepares BiAlO3The method of thin-film material,
The irreversible Chemisorption of Langmuir absorption mechanism is refered in particular in the adsorption reaction；BiAlO3Thin-film material is grown in
On backing material, described substrate includes Si, TiN, LaNiO3/Si、Pt/TiO2/SiO2/Si、Pt/Ti/SiO2/Si、SiO2, institute
The BiAlO stated3The space group of thin-film material is R3c, and lattice constant is a=7.611, c=7.942；The BiAlO3Film material
Expect that thickness is less than 500 nanometers；
It is characterized in that：
Chemisorption is carried out in vacuum reaction chamber, and multiple compartments are included in vacuum reaction chamber, is respectively used to lead to
Enter bismuth precursor gas, aluminium precursor gas, oxygen precursor gas, inert gas；The bismuth presoma used for three (2,2,6,
6- tetramethyls -3,5- heptadione acid) bismuth (III), aluminium presoma is trimethyl aluminium, and oxygen precursor gas can be H2O、O2、O3Its
In any one or wherein any two or three of mixed gas；" inert gas " refers in whole film system
The gas that will not be chemically reacted during standby with presoma；
Air-flow in all gas pipings is constantly passed through in whole film deposition process, and the air-flow of each pipeline
Flow velocity, pressure keep invariable；
The quantity of each compartment in vacuum reaction chamber for 4 multiple and not less than 8, each compartment is adjacent successively and head
Tail is connected to form close ring, and pallet and substrate are moved in the atmosphere that these compartments are formed；For being passed through bismuth forerunner
The quantity sum of the compartment of body gas and aluminium precursor gas is equal to the quantity for the compartment for being used to be passed through oxygen presoma,
The quantity sum of the compartment for being passed through bismuth precursor gas, aluminium precursor gas and oxygen presoma is equal to lazy for being passed through
The quantity of the compartment of property gas；
The arrangement rule of the compartment is as follows：
In any one be passed through three (DPM dpm,dipivalomethane acid) bismuth (III) gases or oxygen precursor gas or
The closest one or both sides of the compartment of trimethylaluminum gas, all also have a separation for being passed through inert gas empty
Between, and in the case where meeting above-mentioned condition,
In any one (DPM dpm,dipivalomethane acid) bismuth (III) gas that are passed through three or trimethylaluminum gas
The secondary adjacent side of the compartment, all also has the compartment for being passed through oxygen precursor gas；
In whole thin film growth process, all precursor gas are respectively transported using inert gas；
This method includes but is not limited to step in detail below：
A）The backing material of cleaning is dried up with inert gas, is placed into substrate pallet；
B）Pallet moves into vacuum reaction chamber together with substrate, opens vavuum pump and vacuum reaction chamber is vacuumized；
C）Vacuum chamber is heated, pallet and substrate temperature in vacuum chamber is maintained in whole thin film growth process
One stationary temperature value；
D）Surely after cavity temperature constant a period of time, the number of turns that setting pallet is rotated together with substrate, the difference of vacuum reaction chamber
The compartment each leads into inert gas, three (DPM dpm,dipivalomethane acid) bismuth (III) gases, oxygen presoma
Gas and trimethylaluminum gas；
E）Substrate bracket disk drives backing material to move together, is being passed through three (2,2,6,6- tetramethyl -3,5- heptadione acid) bismuths
(III) the compartment, the compartment for being passed through the compartment of inert gas, being passed through aluminium precursor gas, it is passed through oxygen forerunner
Pass through between these four compartments of the compartment of body gas；
F）When pallet and substrate, which are rotated, reaches the number of turns of setting, stop operating, film thickness reaches desirable value, stopping is passed through bismuth
Presoma, aluminium presoma, oxygen presoma, continue to be passed through inert gas, stop pallet and substrate, and the heating for stopping vacuum chamber being carried out
Natural cooling；
G）Vacuum chamber reaches or during close to room temperature, closes vavuum pump, vacuum reaction chamber, which is inflated, makes its air pressure reach one
Atmospheric pressure, taking-up, which has been deposited, obtains BiAlO3The substrate of thin-film material；
H）BiAlO is attached with by what is obtained in step G3The substrate of thin-film material, is put into quick anneal oven, carries out fast speed heat and moves back
Fire processing, rapid thermal annealing is concretely comprised the following steps：
（a）Maintained 1 ~ 10 minute at 180 ~ 220 DEG C；
（b）Maintained 2 ~ 5 minutes at 390 ~ 400 DEG C；
（c）The high annealing 2 ~ 10 minutes at 900 DEG C ~ 1050 DEG C；
Taken out after natural cooling.
2. a kind of preparation BiAlO as claimed in claim 13The method of thin-film material, it is characterised in that：Bismuth presoma can also
Using triphenyl bismuth, trimethyl-bismuthine, three tert-butyl alcohol base bismuths, trimethylsilyl bismuth.
3. a kind of preparation BiAlO as claimed in claim 13The method of thin-film material, it is characterised in that：Aluminium presoma can also
Using triethyl aluminum, tri-tert aluminium.
4. a kind of preparation BiAlO as described in claim any one of 1-33The method of thin-film material, it is characterised in that：For leading to
Enter bismuth precursor gas the compartment quantity with for be passed through aluminium precursor gas the compartment quantity according to as follows
Principle is allocated：
When pallet and substrate are moved one week in the close ring that these compartments are constituted, obtained bismuth, aluminium are deposited on substrate
Stoichiometric proportion close to 1:1, it is allowed to have the stoichiometric proportion of less than 10% positive error, i.e. bismuth, aluminium 1:1~1:1.1
In the range of；Excessive bismuth will be in step H）It is middle volatilization and remove substantially.
5. a kind of preparation BiAlO as claimed in claim 43The method of thin-film material, it is characterised in that：Meeting claim 4
In the case of the requirement, for being passed through bismuth precursor gas, the compartment of aluminium precursor gas in close ring as far as possible
Ground is spatially uniformly distributed arrangement.
6. a kind of preparation BiAlO as described in claim any one of 1-33The method of thin-film material, it is characterised in that：
The air pressure of each compartment follows following rules：
Be passed through the compartment of inert gas air pressure have to be larger than it is neighbouring be passed through bismuth precursor gas, aluminium precursor gas or
The air pressure of the compartment of oxygen precursor gas, it is allowed to which the inert gas being passed through in the compartment of inert gas has a small amount of part
Invaded by gap and neighbouring be passed through other precursor gas（That is bismuth presoma, aluminium presoma, oxygen presoma）Separation it is empty
Between, opposite situation does not allow then to occur, and in the case, the connotation of " a small amount of " refers to：Although allowing have a small amount of inertia
Gas invades the neighbouring compartment by gap, but still may insure that substrate passes through before bismuth precursor gas, aluminium every time
When driving body gas, oxygen precursor gas atmosphere, the bismuth of the substrate surface intactly monolayer of chemisorbed one can be made respectively
Precursor molecule, aluminium precursor molecule, oxygen precursor molecule.
7. a kind of preparation BiAlO as described in claim any one of 1-33The method of thin-film material, it is characterised in that：
Pallet is discoid, and has been evenly distributed multiple shallow slots to accommodate substrate, and the depth of shallow slot and the thickness of substrate are basic
It is identical, to ensure that substrate does not collide with motion process with miscellaneous part.
8. a kind of preparation BiAlO as described in claim any one of 1-33The method of thin-film material, it is characterised in that：
Pallet is driven by motor, drives substrate evenly to rotate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510767278.6A CN105256287B (en) | 2015-11-11 | 2015-11-11 | The method that presoma space cellular-type prepares aluminic acid bismuth thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510767278.6A CN105256287B (en) | 2015-11-11 | 2015-11-11 | The method that presoma space cellular-type prepares aluminic acid bismuth thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105256287A CN105256287A (en) | 2016-01-20 |
| CN105256287B true CN105256287B (en) | 2017-09-22 |
Family
ID=55096211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510767278.6A Active CN105256287B (en) | 2015-11-11 | 2015-11-11 | The method that presoma space cellular-type prepares aluminic acid bismuth thin film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105256287B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3683039D1 (en) * | 1986-04-04 | 1992-01-30 | Ibm Deutschland | METHOD FOR PRODUCING SILICON AND OXYGEN LAYERS. |
| CN1033384C (en) * | 1993-01-15 | 1996-11-27 | 山东大学 | Production method for ferroelectric film of bismuth titanate |
| US8758512B2 (en) * | 2009-06-08 | 2014-06-24 | Veeco Ald Inc. | Vapor deposition reactor and method for forming thin film |
| CN103469173B (en) * | 2013-09-12 | 2015-10-28 | 大连理工大学 | The preparation method of hole conducting properties gallium oxide film and hole conducting properties gallium oxide film |
| CN104451600B (en) * | 2014-12-04 | 2017-01-18 | 华东师范大学 | Preparation method of bismuth oxide thin film material |
-
2015
- 2015-11-11 CN CN201510767278.6A patent/CN105256287B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105256287A (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104812938B (en) | Substrate in ALD reactors is loaded | |
| US10655218B2 (en) | Substrate processing apparatus, method of manufacturing semiconductor device, and recording medium | |
| CN101665924B (en) | Film deposition apparatus and substrate processing apparatus | |
| CN101748391B (en) | Film deposition apparatus and film deposition method | |
| US11421321B2 (en) | Apparatuses for thin film deposition | |
| CN105386006B (en) | The method that presoma time-division formula prepares gallic acid bismuth thin film | |
| CN101620993B (en) | Substrate processing method and substrate processing apparatus | |
| CN101578386A (en) | Method and apparatus for converting precursor layers into photovoltaic absorbers | |
| CN109943826A (en) | A kind of multi-functional composite deposition equipment and its preparation process | |
| KR101505619B1 (en) | Deposition apparatus for organic-inorganic hybrid thin film and method for fabricating organic-inorganic hybrid thin film using same | |
| CN102892921A (en) | A method for producing a deposit and a deposit on a surface of a silicon substrate | |
| CN103866288A (en) | Reaction unit and method for atom layer film deposition | |
| US20120319252A1 (en) | Method for manufacturing semiconductor device, substrate processing apparatus, and semiconductor device | |
| CN103946418A (en) | An atomic layer deposition reactor for processing a batch of substrates and method thereof | |
| CN105296961B (en) | The method that presoma space cellular-type prepares gallic acid bismuth thin film | |
| Clark et al. | Carrier-gas assisted vapor deposition for highly tunable morphology of halide perovskite thin films | |
| CN105256287B (en) | The method that presoma space cellular-type prepares aluminic acid bismuth thin film | |
| CN104451600B (en) | Preparation method of bismuth oxide thin film material | |
| CN109695025A (en) | A kind of covering and preparation method thereof that refractive index is radially successively decreased along sapphire fiber | |
| CN112239849B (en) | Film growth system and method | |
| CN105369216B (en) | The method that presoma time-division formula prepares aluminic acid bismuth thin film | |
| CN103114277A (en) | Atomic layer deposition equipment | |
| CN105386005B (en) | The method for preparing the sour bismuth thin film of gallium aluminium of component across quasi- homotype phase boundary | |
| CN105274492B (en) | Method for preparing bismuth aluminum gallate thin film by pulse mixed insertion | |
| CN105420695B (en) | Method for preparing bismuth aluminum gallate film in organic source mixing and dissolving mode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220419 Address after: 226019 Jiangsu Province, Nantong City Chongchuan District sik Road No. 9 Patentee after: NANTONG University Address before: 226019 Jiangsu Province, Nantong City Chongchuan District sik Road No. 9 Patentee before: NANTONG University Patentee before: Shi Min |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230830 Address after: 226000 No. 9 Siyuan Road, Chongchuan District, Nantong City, Jiangsu Province Patentee after: Nantong University Technology Transfer Center Co.,Ltd. Address before: 226019 Jiangsu Province, Nantong City Chongchuan District sik Road No. 9 Patentee before: NANTONG University |