CN112176320A - Method for growing two-dimensional semiconductor film in controllable mode through supercritical carbon dioxide pulse - Google Patents
Method for growing two-dimensional semiconductor film in controllable mode through supercritical carbon dioxide pulse Download PDFInfo
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Abstract
A method for growing a two-dimensional semiconductor film in a controllable way by supercritical carbon dioxide pulse belongs to the field of nano composite material film preparation. The method adopts supercritical carbon dioxide as a transport medium, increases the concentration of a precursor, reduces the growth temperature and reduces the environmental pollution; the flow of the precursor is accurately regulated and controlled by the pulse control area, so that the using amount of the precursor is reduced, and the preparation cost is reduced; seed crystals are formed by utilizing rapid pressure relief, which is beneficial to the growth of a two-dimensional semiconductor film and improves the growth efficiency; different precursors and proper carriers are selected to achieve the purpose of preparing the heterogeneous composite membrane; can solve the problems of higher reaction temperature, uncontrollable film quality and low ALD film forming efficiency of the CVD method.
Description
Technical Field
The invention relates to the field of nano composite material film preparation, in particular to a method for controllably growing a two-dimensional semiconductor film by supercritical carbon dioxide pulse.
Technical Field
The two-dimensional semiconductor film is used as a branch of the nano material, has adjustable band gap, good stability, higher carrier mobility and on-off ratio due to accurate preparation on atomic scale, and has huge application prospect in the fields of integrated circuits, photoelectric devices and the like. As such, the development of two-dimensional semiconductor thin films has become a focus of attention in the scientific research community and the industrial community.
High-quality two-dimensional semiconductor films are mostly prepared by Chemical Vapor Deposition (CVD). The traditional CVD technology has mature process and high deposition rate, but has a contradiction: the substrate material often cannot withstand higher temperatures, but the reaction temperature must be increased in order to ensure a certain deposition rate; meanwhile, the thermal decomposition of the precursor is easily caused under the high-temperature condition, the conveying speed of the precursor is reduced, and the performance of the film is influenced. To solve the above-mentioned contradiction, several vapor deposition methods, such as Low Pressure Chemical Vapor Deposition (LPCVD), Plasma Chemical Vapor Deposition (PCVD), and Laser Chemical Vapor Deposition (LCVD), have been derived from CVD. However, the three methods solve the contradiction between the deposition rate and the temperature in the CVD by modifying the angle of equipment, have more or less defects, and have the common problems of higher deposition temperature, lower raw material utilization rate and incapability of accurately regulating and controlling the components of the film. In addition to CVD, Atomic Layer Deposition (ALD), a self-limiting method for depositing thin films by chemical reaction, is a well-established method for preparing two-dimensional semiconductor thin films. The precursor vapor is alternately deposited on the carrier, and the precursor molecules and the carrier are subjected to chemical self-limiting reaction through physical and chemical adsorption to accurately regulate and control the quality of the film. But compared with the CVD method, the deposition rate is too slow to reach the mass production level; since the control of the atomic layer is due to the self-limiting effect under low temperature conditions, the selection of the precursor is limited.
The method adopts supercritical carbon dioxide as a transport medium, increases the concentration of a precursor, reduces the growth temperature and reduces the environmental pollution; the flow of the precursor is accurately regulated and controlled by the pulse control area, so that the using amount of the precursor is reduced, and the preparation cost is reduced; seed crystals are formed by utilizing rapid pressure relief, which is beneficial to the growth of a two-dimensional semiconductor film and improves the growth efficiency; different precursors and proper carriers are selected to achieve the purpose of preparing the heterogeneous composite membrane; can solve the problems of higher reaction temperature, uncontrollable film quality and low ALD film forming efficiency of the CVD method.
Disclosure of Invention
The invention aims to provide a method for growing a two-dimensional semiconductor film in a controllable manner by using supercritical carbon dioxide pulses. The method for controllably growing the two-dimensional semiconductor film at a lower temperature by adopting supercritical carbon dioxide as a transport medium and through a periodic growth mode of rapid pressure relief nucleation and accurate pulse feeding.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for growing a two-dimensional semiconductor film in a controllable manner by supercritical carbon dioxide pulse comprises the following steps:
dissolving an excessive metal precursor in supercritical carbon dioxide to reach a saturated state;
step two, introducing a certain amount of the supercritical carbon dioxide containing the metal precursor obtained in the step one at a certain flow rate;
introducing supercritical carbon dioxide into a pressure relief and nucleation reaction zone, so that the temperature and the pressure of the pressure relief and nucleation reaction zone respectively reach 40-80 ℃ and 20-80MPa continuously;
step four, decompressing the decompression nucleation reaction area until the pressure is 0Mpa, and growing seed crystals on the carrier;
step five, locally heating the carrier in the decompression nucleation reaction area, and introducing quantitative supercritical carbon dioxide containing the metal precursor obtained in the step one at a certain flow rate; growing a film;
introducing supercritical carbon dioxide into a decompression nucleation reaction zone for backflushing;
and seventhly, adding the nonmetal precursor by selecting one of the following two modes:
(1) dissolving a nonmetal precursor in supercritical carbon dioxide; introducing supercritical carbon dioxide dissolved with a nonmetal precursor into a decompression nucleation reaction zone; then introducing supercritical carbon dioxide into the pressure relief nucleation reaction zone to ensure that the temperature and the pressure of the pressure relief nucleation reaction zone respectively and continuously reach 40-80 ℃ and 20-80 MPa;
(2) introducing a nonmetal precursor gas into a decompression nucleation reaction zone, so that a certain stoichiometric ratio of metal and nonmetal on the carrier is ensured, and keeping for 1-2 minutes;
step eight, introducing supercritical carbon dioxide into a pressure relief nucleation reaction area for backflushing;
and step nine, decompressing the decompression nucleation reaction area until the pressure is 0Mpa, and generating a periodic thin film.
And step ten, circulating the steps from one step to eight, and continuously forming the film on the basis of the film generated in the previous period.
In the first step, the temperature of the supercritical carbon dioxide in which the metal precursor is dissolved is 40-80 ℃, and the pressure is 10-35 MPa.
In the second step, the flow of the supercritical carbon dioxide containing the metal precursor into the decompression nucleation reaction area is 50-500sccm, and the introduction time is 30-60 s.
In the fourth step and the ninth step, the pressure relief rate is 0.5-2 MPa/s.
In the fifth step, the temperature for locally heating the carrier is 150-300 ℃.
And in the fifth step, introducing the supercritical carbon dioxide containing the metal precursor obtained in the first step into the pressure-relief nucleation reaction region at the flow rate of 50-500sccm for 30-90 s.
In the sixth step and the eighth step, the supercritical carbon dioxide is introduced into the pressure relief nucleation reaction region for backflushing at a flow rate of 300-.
In the seventh step, two modes are as follows:
(1) the temperature of the supercritical carbon dioxide dissolved with the nonmetallic precursor is 40-80 ℃, and the pressure is 10-35 MPa. Introducing the supercritical carbon dioxide dissolved with the nonmetallic precursor into the decompression nucleation reaction region at the flow rate of 50-200sccm for 60-12 s.
(2) And introducing the non-metal precursor gas into the decompression nucleation reaction area at the flow rate of 50-200 sccm.
The metal precursor comprises organic transition metal compounds containing molybdenum, tin, tantalum or tungsten and the like;
the nonmetal precursor comprises inorganic or organic compounds containing sulfur, selenium, nitrogen and the like;
the substrate comprises silicon, silicon dioxide/silicon, sapphire, graphene, mica, or polyimide.
The invention has the following beneficial effects:
the supercritical carbon dioxide is used as a transport medium, so that the solubility of a precursor is increased, the growth temperature is reduced, and the environmental pollution is reduced; seed crystals are formed by utilizing rapid pressure relief, which is beneficial to the growth of a metal film and improves the growth efficiency; the pulse of the precursor is accurately regulated and controlled through the pulse control area, so that the using amount of the precursor is reduced, and the preparation cost is reduced; and a periodic pulse growth mode is adopted, so that the thickness of the film is accurately controlled.
Drawings
FIG. 1 is a flow chart of a method for growing a two-dimensional semiconductor film in a controllable manner by using supercritical carbon dioxide pulses.
FIG. 2 is a process flow diagram of a semiconductor thin film controlled growth system with supercritical fluid pulsing.
Fig. 3 is a block diagram of a six-way valve in a semiconductor thin film controlled growth system with supercritical fluid pulses.
Fig. 4 is a cross-sectional view of a reactive deposition chamber in a supercritical fluid pulsed semiconductor thin film controlled growth system.
FIG. 5 is a schematic diagram of the flange structure of the inlet of the reaction deposition chamber of the semiconductor thin film controllable growth system with supercritical fluid pulse.
FIG. 6 is a schematic diagram of the structure of the flange at the outlet of the reaction deposition chamber of the semiconductor thin film controllable growth system with supercritical fluid pulse.
In the figure: 11 reaction gas cylinder, 12 reaction gas filter, 13 reaction gas buffer tank, 14 valve A, 15 mass flowmeter A, 21CO2Gas cylinder, 22 condenser, 23CO2Filter, 24 plunger pump, 25 check valve, 26CO2Buffer tank, 27 valve B, 311 pressure reducing valve A, 312 pressure reducing valve B, 321 magnetic stirrer A, 322 magnetic stirrer B, 331 precursor dissolving tank A, 332 precursor dissolving tank B, 341 valve C, 342 valve D, 41 valve E, 42 six-way valve, 43 valve F, 44 mass flowmeter B, 45 ball valve, 5 reaction deposition chamber, 51 inlet through hole, 52 inlet flange, 531 thermocouple inlet A, 532 thermocouple inlet B, 54 cylinder, 55 cavity, 56 outlet flange, 57 outlet through hole A, 58 outlet through hole B, 61 back pressure valve, 62 needle valve, 7 waste gas recovery tank, 71 mass flowmeter C, 72 electric ball valve, 81 pressure control system, 82 temperature control system, 83 flow rate control system.
Detailed Description
The technical solution of the present application is further described below with reference to examples.
Example 1
50mg of molybdenum hexacarbonyl (Mo (CO))6) Putting a metal precursor into a precursor dissolving tank; introducing supercritical carbon dioxide at 40 deg.C and 15MPa for dissolving; mixing 1X 1cm2SiO2the/Si carrier is arranged in a pressure relief nucleation and reaction area; will dissolve Mo (CO)6The supercritical carbon dioxide mixture enters a decompression nucleation and reaction area with the flow rate of 150sccm and the pulse time of 30 s; injecting supercritical carbon dioxide into the decompression nucleation and reaction area, keeping the temperature at 50 ℃ and the pressure at 20MPa, and maintaining for 1 min; opening a quick-opening bypass in 20s to quickly reduce the pressure of a pressure relief nucleation and reaction area from 20MPa to 0 MPa; after the carrier is locally heated to 155 ℃, Mo (CO) is dissolved6The supercritical carbon dioxide mixture enters a decompression nucleation and reaction area with the flow rate of 75sccm and the pulse time of 30 s; backflushing and decompressing the nucleation and reaction area by using supercritical carbon dioxide with the flow of 500sccm for 300 s; introducing H with the flow rate of 100sccm2S to a decompression nucleation and reaction area for 60S; performing back flushing, pressure relief, nucleation and reaction for 300s by using supercritical carbon dioxide with the flow of 500sccm to obtain a periodic molybdenum disulfide filmAfter a plurality of periods, a multilayer molybdenum disulfide film with the required thickness is obtained.
Example 2
Weighing 50mg of Mo (CO)6Is a metal precursor and 10g C2H6S2Respectively placing nonmetal precursors into two precursor dissolving tanks; introducing supercritical carbon dioxide at 40 deg.C and 20MPa for dissolving; mixing 1X 1cm2 SiO2the/Si carrier is arranged in a pressure relief nucleation and reaction area; will dissolve Mo (CO)6The supercritical carbon dioxide mixture enters a decompression nucleation and reaction area with the flow rate of 150sccm and the pulse time of 30 s; injecting supercritical carbon dioxide into the decompression nucleation and reaction area, keeping the temperature at 50 ℃ and the pressure at 40MPa, and keeping for 1.5 min; opening a quick-opening bypass in 80s to quickly reduce the pressure of a pressure relief nucleation and reaction area from 40MPa to 0 MPa; after the carrier is locally heated to 175 ℃, Mo (CO) is dissolved6The supercritical carbon dioxide mixture enters a decompression nucleation and reaction area with the flow rate of 75sccm and the pulse time of 60 s; backflushing and decompressing the nucleation and reaction area for 400s by using supercritical carbon dioxide with the flow of 500 sccm; dissolving in supercritical carbon dioxide C2H6S2Entering a decompression nucleation and reaction area with the flow rate of 150sccm and the pulse time of 60 s; and (3) backflushing and decompressing the nucleation and reaction area for 500s by using supercritical carbon dioxide with the flow of 500sccm to obtain a molybdenum disulfide film in one period, and obtaining a multilayer molybdenum disulfide film with the required thickness after multiple periods.
Example 3
60mg of tungsten hexacarbonyl (W (CO))6) Putting a metal precursor into a precursor dissolving tank; introducing supercritical carbon dioxide at 50 ℃ and 35MPa for dissolution; mixing 1X 1cm2Al2O3The carrier is arranged in a pressure relief nucleation and reaction area; will dissolve W (CO)6The supercritical carbon dioxide mixture enters a pressure relief nucleation and reaction area with the flow rate of 125sccm and the pulse time of 30 s; injecting supercritical carbon dioxide into the decompression nucleation and reaction area, keeping the temperature at 50 ℃ and the pressure at 60MPa, and keeping for 1 min; opening a quick-opening bypass in 90s to quickly reduce the pressure of a pressure relief nucleation and reaction area from 60MPa to 0 MPa; after the carrier is locally heated to 200 ℃, W (CO) is dissolved6The supercritical carbon dioxide mixture enters a pressure relief nucleation and reaction area with the flow rate of 50sccm and the pulse time of 30 s; backflushing and decompressing the nucleation and reaction area by using supercritical carbon dioxide with the flow of 500sccm for 300 s; h with the flow rate of 75sccm is introduced2Se reaches a decompression nucleation and reaction zone for 60 s; and (3) backflushing and decompressing the nucleation and reaction area for 300s by using supercritical carbon dioxide with the flow of 500sccm to obtain a tungsten disulfide film in one period, and obtaining a multilayer tungsten disulfide film with controllable thickness after multiple periods.
Example 4
80mg of bis (N, N' -diisopropylacetamidinyl) tin (II) (Sn (amd))2) Putting a metal precursor into a precursor dissolving tank; introducing supercritical carbon dioxide at 55 ℃ and 30MPa for dissolution; mixing 1X 1cm2SiO2the/Si carrier is arranged in a pressure relief nucleation and reaction area; will dissolve Sn (amd)2The supercritical carbon dioxide mixture enters a decompression nucleation and reaction area with the flow rate of 150sccm and the pulse time of 40 s; injecting supercritical carbon dioxide into the decompression nucleation and reaction area, keeping the temperature at 50 ℃ and the pressure at 50MPa, and keeping for 1.5 min; opening a quick-opening bypass in 25s to quickly reduce the pressure of a pressure relief nucleation and reaction area from 50MPa to 0 MPa; after the carrier is locally heated to 120 deg.C, Sn (amd) will dissolve2The supercritical carbon dioxide mixture enters a decompression nucleation and reaction area with the flow rate of 75sccm and the pulse time of 30 s; backflushing and decompressing the nucleation and reaction area by using supercritical carbon dioxide with the flow of 500sccm for 300 s; introducing H with the flow rate of 150sccm2S to a decompression nucleation and reaction area for 60S; and (3) backflushing and decompressing the nucleation and reaction area for 360s by using supercritical carbon dioxide with the flow of 500sccm to obtain a tin disulfide film in one period, and obtaining a multilayer tin disulfide film with controllable thickness after multiple periods.
Example 5
Weighing 100mg of tri (ethylformamido) (tert-butyl imido) tantalum (V) (TBTDET) serving as a metal precursor and placing the metal precursor into a precursor dissolving tank; introducing supercritical carbon dioxide at 40 deg.C and 20MPa for dissolving; mixing 1X 1cm2Al2O3The carrier is arranged in a pressure relief nucleation and reaction area; the supercritical carbon dioxide mixture with dissolved TBTDET is mixed at a flow rate of 150sccm,The pulse time is 30s, and the pressure is released, the nucleation and the reaction zone are formed; injecting supercritical carbon dioxide into the decompression nucleation and reaction area, keeping the temperature at 50 ℃ and the pressure at 30MPa, and maintaining for 1 min; opening a quick-opening bypass in 30s to quickly reduce the pressure of a pressure relief nucleation and reaction area from 30MPa to 0 MPa; after the carrier is locally heated to 270 ℃, the supercritical carbon dioxide mixture dissolved with TBTDET enters a pressure relief nucleation and reaction area with the flow rate of 50sccm and the pulse time of 30 s; backflushing and decompressing the nucleation and reaction area by using supercritical carbon dioxide with the flow of 500sccm for 300 s; NH with the flow rate of 70sccm is introduced3To a decompression nucleation and reaction zone for 60 s; and (3) backflushing and decompressing the nucleation and reaction area for 300s by using supercritical carbon dioxide with the flow of 500sccm to obtain a tantalum-nitrogen film of one period, and obtaining a multilayer tantalum-nitrogen film with the required thickness after multiple periods.
Example 6
Weighing 100mgMo (CO)6Putting a metal precursor into a precursor dissolving tank; introducing supercritical carbon dioxide at 40 deg.C and 15MPa for dissolving; 2X 2cm2Placing the graphene carrier in a pressure relief nucleation and reaction area; will dissolve Mo (CO)6The supercritical carbon dioxide mixture enters a decompression nucleation and reaction area with the flow rate of 150sccm and the pulse time of 30 s; injecting supercritical carbon dioxide into the decompression nucleation and reaction area, keeping the temperature at 50 ℃ and the pressure at 20MPa, and maintaining for 1 min; opening a quick-opening bypass in 20s to quickly reduce the pressure of a pressure relief nucleation and reaction area from 20MPa to 0 MPa; after the carrier is locally heated to 155 ℃, Mo (CO) is dissolved6The supercritical carbon dioxide mixture enters a decompression nucleation and reaction area with the flow rate of 150sccm and the pulse time of 30 s; backflushing and decompressing the nucleation and reaction area by using supercritical carbon dioxide with the flow of 500sccm for 300 s; introducing H with the flow rate of 200sccm2S to a decompression nucleation and reaction area for 60S; and (3) backflushing and decompressing the nucleation and reaction area for 300s by using supercritical carbon dioxide with the flow of 500sccm to obtain a molybdenum disulfide film in one period, and obtaining the molybdenum disulfide/graphene heterogeneous composite film with the required thickness after multiple periods.
Example 7
Weighing 50mg W (CO)6With 50mg Mo (CO)6Two metal precursors are respectively put in the two precursors to be dissolvedIn a tank; respectively introducing supercritical carbon dioxide with the temperature of 50 ℃ and the pressure of 35MPa for dissolution; mixing 1X 1cm2Placing the graphene carrier in a pressure relief nucleation and reaction area; will dissolve Mo (CO)6The supercritical carbon dioxide mixture enters a decompression nucleation and reaction area with the flow rate of 75sccm and the pulse time of 30 s; injecting supercritical carbon dioxide into the decompression nucleation and reaction area, keeping the temperature at 50 ℃ and the pressure at 20MPa, and maintaining for 1 min; opening a quick-opening bypass in 60s to quickly reduce the pressure of a pressure relief nucleation and reaction area from 40MPa to 0 MPa; after the carrier is locally heated to 155 ℃, Mo (CO) is dissolved6The supercritical carbon dioxide mixture enters a decompression nucleation and reaction area with the flow rate of 75sccm and the pulse time of 30 s; backflushing and decompressing the nucleation and reaction area by using supercritical carbon dioxide with the flow of 500sccm for 300 s; introducing H with the flow rate of 150sccm2S, obtaining a molybdenum disulfide film in one period in a decompression nucleation and reaction area for 60S; obtaining a multilayer molybdenum disulfide film with required thickness after a plurality of cycles; backflushing and decompressing the nucleation and reaction area by using supercritical carbon dioxide with the flow of 500sccm for 300 s; will dissolve W (CO)6The supercritical carbon dioxide mixture enters a decompression nucleation and reaction area with the flow rate of 75sccm and the pulse time of 30 s; injecting supercritical carbon dioxide into the decompression nucleation and reaction area, keeping the temperature at 60 ℃ and the pressure at 40MPa, and maintaining for 1 min; opening a quick-opening bypass in 30s to quickly reduce the pressure of a pressure relief nucleation and reaction area from 20MPa to 0 MPa; after the carrier is locally heated to 200 ℃, W (CO) is dissolved6The supercritical carbon dioxide mixture enters a decompression nucleation and reaction area with the flow rate of 75sccm and the pulse time of 30 s; backflushing and decompressing the nucleation and reaction area by using supercritical carbon dioxide with the flow of 500sccm for 300 s; introducing H with the flow rate of 150sccm2Se reaches a decompression nucleation and reaction zone for 60 s; performing back flushing, pressure relief, nucleation and reaction for 300s by using supercritical carbon dioxide with the flow of 500sccm to obtain a periodic tungsten disulfide film; and obtaining the tungsten diselenide/molybdenum disulfide/graphene heterogeneous composite film with the required thickness after a plurality of cycles.
A semiconductor thin film controllable growth system based on supercritical fluid pulse, which can be used for realizing the method, comprises supercritical CO2A generation module, a precursor dissolution module, a reaction deposition chamber 5, a reaction gas supply module, an exhaust gas recovery tank 7, a six-way valve 42 and a control module;
the supercritical CO2The generation module is connected with the precursor dissolving module to realize the supercritical CO of the precursor2Dissolving; supercritical CO2The generation module and the precursor dissolution module are both connected with the reaction deposition chamber 5 through a six-way valve 42; the reaction deposition chamber 5 is also respectively connected with a reaction gas supply module, a waste gas recovery tank 7 and a control module; the control module adjusts the temperature, the pressure and the flow rate of the reaction deposition chamber 5; the six-way valve 42 can accurately control supercritical CO2Supercritical CO containing precursor2The amount of the compound is used for carrying out controllable growth of the film.
Further, the supercritical CO2The generation module comprises CO connected in sequence through a pipeline2Gas cylinder 21, condenser 22, CO2Filter 23 and CO2 A buffer tank 26; CO 22Filter 23 and CO2A plunger pump 24 and a check valve 25 are arranged on a pipeline between the buffer tanks 26; CO 22The other end of the buffer tank 26 is connected to a three-way valve through a pipeline, and the other two branches of the three-way valve are respectively led to the six-way valve 42 and the precursor dissolving module.
Further, the reaction gas supply module comprises a reaction gas cylinder 11, a reaction gas filter 12, a reaction gas buffer tank 13, a valve A14 and a mass flow meter A15 which are connected in sequence through a pipeline; the mass flow meter A15 is connected with the reaction deposition chamber 5 and the control system respectively.
Further, the precursor dissolving module comprises a precursor dissolving tank A331 and a precursor dissolving tank B332, and the precursor dissolving module is prepared from CO2A valve B27 and a three-way valve are sequentially connected to a pipeline leading to the precursor dissolving tank 26 in the direction, the other two branches of the three-way valve are respectively connected with a precursor dissolving tank A331 and a precursor dissolving tank B332, a pressure reducing valve A311 is arranged on the pipeline between the three-way valve and the precursor dissolving tank A331, and a pressure reducing valve B312 is arranged on the pipeline between the three-way valve and the precursor dissolving tank B332. The outlet pipelines of the precursor dissolving tank A331 and the precursor dissolving tank B332 are respectively provided with a valve C341. A valve D342; the two outlet pipelines are connected with the six-way valve 42 through a three-way valve in a gathering way; a valve F43 is arranged between the three-way valve and the six-way valve 42; the bottom of the precursor dissolving tank A331 and the bottom of the precursor dissolving tank B332 are respectively provided with a magnetic stirrer A321 and a magnetic stirrer B322.
Further, from CO2A valve E41 is arranged on a pipeline of the buffer tank 26 leading to the six-way valve 42; the six-way valve 42 is connected with the reaction deposition chamber 5, and a mass flow meter B44 and a ball valve 45 are sequentially arranged on a pipeline between the six-way valve and the reaction deposition chamber; the mass flow meter B44 is connected to the control module.
Further, the control module comprises a pressure control system 81, a temperature control system 82, and a flow rate control system 83; the temperature, pressure and flow rate of the reaction deposition chamber 5 can be adjusted.
Furthermore, the pipeline between the waste gas recovery tank 7 and the reaction deposition chamber 5 comprises two pipelines, wherein one pipeline is provided with a backpressure valve 61 and a needle valve 62 in sequence; the other one is sequentially provided with a mass flow meter C71 and an electric ball valve 72, and the mass flow meter C71 and the electric ball valve 72 are both connected with a control module;
further, the reactive deposition chamber 5 includes an inlet flange 52, a cylinder 54, and an outlet flange 56; the inlet flange 52 and the outlet flange 56 are respectively fixed at the inlet end and the outlet end of the cylinder 54, and thermocouple inlets are respectively arranged at the inlet end and the outlet end of the cylinder 54 and used for arranging thermocouples; a cavity 55 is arranged in the cylinder 54; the inlet flange 52 is provided with an inlet through hole 51, and the outlet flange 56 is provided with two outlet through holes. The outer wall of the reaction deposition chamber 5 is provided with a heating jacket.
Further, the reaction deposition chamber 5, the precursor dissolving chamber and the supercritical CO2The generating modules are provided with the pressure gauge and the thermocouple.
Claims (10)
1. A method for growing a two-dimensional semiconductor film in a controllable manner by using supercritical carbon dioxide pulses is characterized by comprising the following steps:
dissolving an excessive metal precursor in supercritical carbon dioxide to reach a saturated state;
step two, introducing a certain amount of the supercritical carbon dioxide containing the metal precursor obtained in the step one at a certain flow rate;
introducing supercritical carbon dioxide into a pressure relief and nucleation reaction zone, so that the temperature and the pressure of the pressure relief and nucleation reaction zone respectively reach 40-80 ℃ and 20-80MPa continuously;
step four, decompressing the decompression nucleation reaction area until the pressure is 0Mpa, and growing seed crystals on the carrier;
step five, locally heating the carrier in the decompression nucleation reaction area, and introducing quantitative supercritical carbon dioxide containing the metal precursor obtained in the step one at a certain flow rate; growing a film;
introducing supercritical carbon dioxide into a decompression nucleation reaction zone for backflushing;
and seventhly, adding the nonmetal precursor by selecting one of the following two modes:
(1) dissolving a nonmetal precursor in supercritical carbon dioxide; introducing supercritical carbon dioxide dissolved with a nonmetal precursor into a decompression nucleation reaction zone; then introducing supercritical carbon dioxide into the pressure relief nucleation reaction zone to ensure that the temperature and the pressure of the pressure relief nucleation reaction zone respectively and continuously reach 40-80 ℃ and 20-80 MPa;
(2) introducing a nonmetal precursor gas into a decompression nucleation reaction zone, so that a certain stoichiometric ratio of metal and nonmetal on the carrier is ensured, and keeping for 1-2 minutes;
step eight, introducing supercritical carbon dioxide into a pressure relief nucleation reaction area for backflushing;
step nine, decompressing the decompression nucleation reaction area until the pressure is 0Mpa, and generating a periodic thin film;
and step ten, circulating the steps from one step to eight, and continuously forming the film on the basis of the film generated in the previous period.
2. The method for the controlled growth of the two-dimensional semiconductor film by the pulse of the supercritical carbon dioxide as claimed in claim 1, wherein in the first step, the temperature of the supercritical carbon dioxide in which the metal precursor is dissolved is 40-80 ℃, and the pressure is 10-35 MPa.
3. The method for the pulse controlled growth of the two-dimensional semiconductor film by the supercritical carbon dioxide as claimed in claim 1, wherein in the second step, the flow rate of the supercritical carbon dioxide containing the metal precursor into the decompression nucleation reaction region is 50-500sccm, and the introduction time is 30-60 s.
4. The method for the controllable growth of the two-dimensional semiconductor film by the supercritical carbon dioxide pulse according to claim 1, wherein in the fourth step and the ninth step, the pressure relief rate is 0.5-2 MPa/s.
5. The method as claimed in claim 1, wherein the temperature for heating the carrier locally in step five is 150-300 ℃.
6. The method for the pulse controlled growth of the two-dimensional semiconductor film by the supercritical carbon dioxide as claimed in claim 1, wherein in the fifth step, the supercritical carbon dioxide containing the metal precursor obtained in the first step is introduced into the decompression nucleation reaction region at a flow rate of 50-500sccm for 30-90 s.
7. The method as claimed in claim 1, wherein in the sixth and eighth steps, the flow rate of the supercritical carbon dioxide introduced into the pressure-releasing nucleation reaction region for backflushing is 300-600s, and the backflushing time is 500-500 sccm.
8. The method for the controlled growth of the two-dimensional semiconductor film by the supercritical carbon dioxide pulse according to claim 1, wherein in the seventh step, two modes are adopted:
(1) the temperature of the supercritical carbon dioxide dissolved with the nonmetallic precursor is 40-80 ℃, and the pressure is 10-35 MPa; introducing supercritical carbon dioxide dissolved with a nonmetal precursor into a decompression nucleation reaction zone at a flow rate of 50-200sccm for 60-12 s;
(2) and introducing the non-metal precursor gas into the decompression nucleation reaction area at the flow rate of 50-200 sccm.
9. The method for the controlled growth of the two-dimensional semiconductor film through the supercritical carbon dioxide pulse according to claim 1, wherein the substrate is silicon, silicon dioxide/silicon, sapphire, graphene, mica or polyimide.
10. The method for the controlled growth of the two-dimensional semiconductor film by the supercritical carbon dioxide pulse according to claim 1, wherein the metal precursor is a compound containing molybdenum, tin, tantalum or tungsten; the nonmetal precursor is an organic compound containing sulfur, selenium and nitrogen.
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| CN113413778A (en) * | 2021-05-19 | 2021-09-21 | 大连理工大学 | Method for preparing MOF (Metal organic framework) membrane by using seed crystal assisted supercritical technology and gas separation application of MOF membrane |
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