CN110230039A - A kind of method of single layer molybdenum sulfide regulation lead iodide growth - Google Patents

A kind of method of single layer molybdenum sulfide regulation lead iodide growth Download PDF

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CN110230039A
CN110230039A CN201910588389.9A CN201910588389A CN110230039A CN 110230039 A CN110230039 A CN 110230039A CN 201910588389 A CN201910588389 A CN 201910588389A CN 110230039 A CN110230039 A CN 110230039A
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temperature
single layer
pbi
warm area
growth
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CN110230039B (en
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黄寒
肖君婷
邵子依
刘金鑫
何丙辰
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Central South University
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/305—Sulfides, selenides, or tellurides
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/12—Halides

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Abstract

The present invention provides a kind of methods of single layer molybdenum sulfide regulation lead iodide growth, belong to inorganic matter preparation field.The following steps are included: being dried up with nitrogen gun after substrate successively to be used to acetone, isopropanol and hydrogen peroxide ultrasonic cleaning, obtaining precondition substrate；Under nitrogen protection, by MoO3Powder and S block obtain single layer MoS in the one side progress chemical vapor deposition of the precondition substrate2；Under vacuum conditions, in the single layer MoS2Surface carry out PbI2Physical vapour deposition (PVD).The present invention uses PVD heat deposition PbI under vacuum condition2, in the single layer MoS of CVD growth2Upper epitaxial growth PbI2, the MoS of growth during being somebody's turn to do2Triangle side length is at 20~60 μm, MoS2Area is big, and PbI2In entire single layer MoS2Upper covering, avoids interlayer contamination, can be easier and produce on a large scale, and the device performance of manufacture can be more preferable.

Description

A kind of method of single layer molybdenum sulfide regulation lead iodide growth
Technical field
The present invention relates to inorganic matter preparation technical field more particularly to a kind of sides of single layer molybdenum sulfide regulation lead iodide growth Method.
Background technique
Lead iodide (PbI2) monocrystal be make room temperature x- ray (or gamma-rays) detector one of material, use lead iodide The device of monocrystal production can work within the scope of the even higher temperature of room temperature, to the lead Iodide single crystal of production detector Integrality have high requirement: require first monocrystal have high purity, caused with eliminating foreign atom in monocrystal Defect；Secondly it requires in strict conformity with stoicheiometry, to eliminate crystal defect caused by atom omission.Currently, regulation PbI2's Growth can pass through the single layer MoS of dry robin mechanical stripping2Cover the PbI of low temperature solution polycondensation growth2Film, present in Problem has the single layer MoS of mechanical stripping2Area is smaller, so that being not easy to manufacture device, and can not keep away in this process Impurity can be introduced with exempting from, influence the application of next step.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of methods of single layer molybdenum sulfide regulation lead iodide growth.This hair The growing method of bright offer passes through the large area monolayer MoS that grows in chemical vapour deposition technique2Upper epitaxial growth PbI2, keep away Interlayer contamination is exempted from, can be easier and has produced on a large scale.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of methods of single layer molybdenum sulfide regulation lead iodide growth, comprising the following steps:
After substrate successively to be used to acetone, isopropanol and hydrogen peroxide ultrasonic cleaning, drying obtains precondition substrate；
Under nitrogen protection, by MoO3Powder and S block are obtained in the one side progress chemical vapor deposition of the precondition substrate To single layer MoS2；
Under vacuum conditions, in the single layer MoS2Surface carry out PbI2Physical vapour deposition (PVD).
Preferably, the S block and MoO3The mass ratio of powder is 28~32:1.
Preferably, the chemical vapor deposition carries out in double temperature-area tubular furnaces, and double temperature-area tubular furnaces include right temperature Area and Zuo Wenqu.
Preferably, the quartzy circumference that S block is housed is placed at the center of the left warm area.
Preferably, the right warm area, which is placed, is equipped with MoO3The quartzy Noah's ark of powder and precondition substrate, the pretreatment base Bottom is placed in right warm area center, the MoO3Powder is located at the lower section of the precondition substrate.
Preferably, the right warm area is warming up to 720~780 DEG C with the rate of 15~18 DEG C/min, and through-flow speed is 30 cubes The N of cm per minute2, 10~15min is kept, then in N2Flow velocity be 500~520 cc/mins under with -9~-12 DEG C/the cooling 45~50min of the cooling velocity of min.
Preferably, the left warm area is temperature programmed as follows: the temperature of the left warm area is since 50~55 DEG C, Zhi Daosuo The temperature for stating right warm area heats 44~50min, after the temperature of the right warm area reaches 620~650 DEG C, with 25~30 DEG C/min's Heating rate rises to 200~250 DEG C of 15~20min of holding, is then quickly cooled down 30~60min to room temperature.
Preferably, double temperature-area tubular furnaces connect measuring pipette by silicone tube, are inserted into glass drexel bottle, close with rubber plug It seals, absorbs the tail gas that chemical vapor deposition generates equipped with lye in drexel bottle, the drexel bottle gas outlet is run in by silicone tube Fan system.
Preferably, the physical vapour deposition (PVD) is temperature programmed as follows: temperature is since 37~42 DEG C, with 5~8 DEG C/min Rate be warming up to 280~300 DEG C after 30~60min of degasification, then in 280~320 DEG C of 5~20min of holding, then automatic drop It warms to room temperature.
Preferably, PbI in the physical vapour deposition (PVD)2Evaporation rate be 1.6~8nm/min.
The present invention provides a kind of single layer molybdenum sulfide regulation lead iodide growth method, comprising the following steps: by substrate according to After secondary use acetone, isopropanol and hydrogen peroxide ultrasonic cleaning, drying obtains precondition substrate；Under nitrogen protection, by MoO3Powder End and S block obtain single layer MoS in the one side progress chemical vapor deposition of the precondition substrate2；Under vacuum conditions, in institute State single layer MoS2Surface carry out PbI2Physical vapour deposition (PVD).The present invention uses physical vaporous deposition under vacuum conditions (PVD) heat deposition PbI2, in the single layer MoS of aumospheric pressure cvd method (CVD) growth2Upper epitaxial growth PbI2, the process The MoS of middle growth2Triangle side length is at 20~60 μm, MoS2Area is big, and PbI2In entire single layer MoS2Upper covering, avoids Interlayer contamination can be easier and produce on a large scale, and the device performance of manufacture can be more preferable.Embodiment statistics indicate that, this Iodate lead thickness obtained is invented between 10nm~80nm, and single layer MoS2Area it is big.
Detailed description of the invention
Fig. 1 is the device figure of double temperature-area tubular furnaces；
Fig. 2 is that instrument device figure is deposited in PVD；
Fig. 3 is the single layer MoS of embodiment 1CVD growth2Optical picture (a) and AFM phenogram (b)；
Fig. 4 is single layer MoS in embodiment 1Si substrate2Raman figure；
Fig. 5 is single layer MoS in embodiment 1Si substrate2Mapping；
Fig. 6 is that PbI is deposited in embodiment 12(vapor deposition 290 DEG C of temperature, time 6min) single layer MoS in Si substrate afterwards2Raman Figure；
Fig. 7 is that PbI is deposited in embodiment 12(vapor deposition 290 DEG C of temperature, time 6min) single layer MoS in Si substrate afterwards2AFM table Sign figure；
Fig. 8 is that PbI is deposited in embodiment 22(vapor deposition 290 DEG C of temperature, time 10min) single layer MoS in Si substrate afterwards2AFM table Sign figure；
Fig. 9 is that PbI is deposited in embodiment 32(vapor deposition 320 DEG C of temperature, time 10min) single layer MoS in Si substrate afterwards2AFM table Sign figure；
Figure 10 is the single layer MoS of embodiment 4CVD growth2Optical picture.
Specific embodiment
The present invention provides it is a kind of the present invention provides a kind of single layer molybdenum sulfide regulation lead iodide growth method, including with Lower step:
After substrate successively to be used to acetone, isopropanol and hydrogen peroxide ultrasonic cleaning, drying obtains precondition substrate；
Under nitrogen protection, by MoO3Powder and S block are obtained in the one side progress chemical vapor deposition of the precondition substrate To single layer MoS2；
Under vacuum conditions, in the single layer MoS2Surface carry out PbI2Physical vapour deposition (PVD).
After substrate is successively used acetone, isopropanol and hydrogen peroxide ultrasonic cleaning by the present invention, drying obtains pretreatment base Bottom.The present invention does not have special restriction to the type of the substrate and source, using well known to those skilled in the art commercially available Substrate, specifically, such as SiO2Substrate or Si substrate.The present invention is cleaned by ultrasonic the acetone, isopropanol and hydrogen peroxide And the concrete operations of drying do not have special restriction, using mode well known to those skilled in the art.In the present invention, The drying is preferably dried up with nitrogen gun.
After obtaining precondition substrate, the present invention under nitrogen protection, by MoO3Powder and S block are in the precondition substrate Chemical vapor deposition is carried out on one side, obtains single layer MoS2。
In the present invention, the S block and MoO3The mass ratio of powder is preferably 28~32:1, more preferably 30:1.
In the present invention, the chemical vapor deposition preferably carries out in double temperature-area tubular furnaces, double temperature-area tubular furnaces Preferably include right warm area and Zuo Wenqu.In the present invention, the nitrogen preferably flows to right warm area by left warm area.The present invention is in dual temperature In area's tube furnace, with MoO3Powder prepares single layer MoS as the source S as the source Mo, S block2, right in double temperature-area tubular furnaces by controlling The reaction temperature of warm area, the distance of reaction raw materials, sulphur steam enter the time of right warm area from left warm area in double temperature-area tubular furnaces, Precondition substrate surface grows large-sized single layer MoS2.In the present invention, the distance of the reaction raw materials is preferably 20cm.
In the present invention, it is preferred to place the quartzy circumference that S block is housed at the center of the left warm area.
MoO is housed in the present invention, it is preferred to place in the right warm area3The quartzy Noah's ark of powder and precondition substrate, institute It states precondition substrate and is preferably disposed in right warm area center, the MoO3Powder is preferably placed at the lower section of the precondition substrate.
In the present invention, the right warm area is preferably warming up to 720~780 DEG C with the rate of 15~18 DEG C/min, through-flow speed For the N of 30 cc/mins (s.c.c.m)2, 10~15min is kept, then in N2Flow velocity be 500~520 cubic centimetres/ With the cooling 45~50min of the cooling velocity of -9~-12 DEG C/min under minute, 720 more preferably are warming up to the rate of 15 DEG C/min DEG C, through-flow speed is the N of 30 cc/mins (s.c.c.m)2, 15min is kept, then in N2Flow velocity be 500 cubic centimetres/ With the cooling 45min of the cooling velocity of -9 DEG C/min under minute.
In the present invention, the left warm area is temperature programmed preferably as follows: the temperature of the left warm area is opened from 50~55 DEG C Begin, until the temperature of the right warm area heats 44~50min, after the temperature of the right warm area reaches 620~650 DEG C, with 25~ The heating rate of 30 DEG C/min rises to 200~250 DEG C of 15~20min of holding, then 30~60min of rapid cooling to room temperature, more 220 DEG C are preferably risen to, more preferable temperature is since 50 DEG C, until the temperature of the right warm area heats 44min, the right warm area Temperature reach 620 DEG C after, 200 DEG C of holding 15min are risen to the heating rate of 25 DEG C/min, then be quickly cooled down 30min extremely Room temperature more preferably rises to 220 DEG C.
In the present invention, double temperature-area tubular furnaces connect measuring pipette by silicone tube, are inserted into glass drexel bottle, use glue Plug seals, and absorbs the tail gas that chemical vapor deposition generates equipped with lye in drexel bottle, the drexel bottle gas outlet preferably passes through silicon Sebific duct runs in fan system.
Obtain single layer MoS2Afterwards, the present invention under vacuum conditions, in the single layer MoS2Surface carry out PbI2Physics gas Mutually deposit.
In the present invention, the physical vapour deposition (PVD) is temperature programmed preferably as follows: temperature is since 37~42 DEG C, with 5 30~60min of degasification after the rate of~8 DEG C/min is warming up to 280~300 DEG C, then in 280~320 DEG C of 5~20min of holding, Then it is cooled to room temperature automatically, more preferable temperature is warming up to 300 DEG C of degasification 40min since 42 DEG C, with the rate of 5 DEG C/min, Then in 290 DEG C of 6~10min of holding, bolt down procedure makes temperature be cooled to room temperature automatically after experiment.In the present invention, institute It states physical vapour deposition (PVD) and preferably carries out (instrument is deposited in PVD) in physical vapour deposition (PVD) vapor deposition instrument.
In the present invention, PbI in the physical vapour deposition (PVD)2Evaporation rate be preferably 1.6~8nm/min.
In the present invention, after the completion of the physical vapour deposition (PVD), the present invention keeps 30 preferably at 280~320 DEG C~ 60min can reserve time enough degasification and determine PbI2Evaporation rate, more preferably at 300 DEG C keep 40min remove PbI is determined after gas again2Evaporation rate.
In the present invention, the temperature of different physical vapour deposition (PVD)s is set in the different stages if necessary, is preferably continued to The temperature programmed of the physical vapour deposition (PVD) is set.
In the present invention, after the completion of the degasification, preferably quick turning manipulator makes single layer MoS originally upward2Become Downward towards PbI2Evaporation source finds suitable evaporation position, it can be achieved that not and at the same time manipulator is protruded into growth chamber Physical vapour deposition (PVD) under same position, different temperatures and time.
In the present invention, the vacuum in the PVD vapor deposition instrument is preferably evacuated to high vacuum state, and air pressure is preferably 10-7mbar ~10-8Mbar magnitude preferably uses high-temperature heat-resistance double-sided adhesive before vacuumizing on a robotic arm on the molybdenum plate immediately ahead of bellows Viscous substantial monolayer MoS2。
After the completion of physical vapour deposition (PVD), the present invention opens growth chamber after preferably successively closing molecular pump and mechanical pump, passes through Manipulator takes out sample.
In order to further illustrate the present invention, raw to single layer molybdenum sulfide provided by the invention regulation lead iodide below with reference to example Long method is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
With single layer MoS2To regulate and control PbI2The method of growth, equipment therefor is as illustrated in fig. 1 and 2, and Fig. 1 is double temperature-area tubular furnaces Device figure, including right warm area and Zuo Wenqu, with MoO3Powder prepares single layer MoS as the source S as the source Mo, S block2, Zuo Wenqu's The quartzy circumference that S block is housed is placed at center, and right warm area, which is placed, is equipped with MoO3The quartzy Noah's ark of powder and precondition substrate, pretreatment Substrate is preferably disposed in right warm area center, and nitrogen flows to right warm area from left warm area, and Fig. 2 is that instrument device figure is deposited in PVD, in the single layer MoS2Surface carry out PbI2Physical vapour deposition (PVD).
The specific steps are that:
(1) silicon wafer is cut with glass cutter first along its crystal orientation, graduating with cutter first is carried out to bed perimeter, is clipped later with tweezers It breaks into two with one's hands, substrate will be broken along crystal orientation, the substrate of cut growth bar shaped, can be generated a large amount of fines in cutting process and be fallen in base On bottom, substrate is cleaned in ultrasonator respectively with acetone, isopropanol and hydrogen peroxide, each process time is 15min, is used Nitrogen gun dries up substrate with spare.
(2) load weighted 450mg S block is put into quartzy circumference, 15mg MoO3Powder is put into quartzy Noah's ark, will pre-process Substrate is placed in MoO3Right above powder.
(3) MoO will be housed3The quartzy Noah's ark of powder and precondition substrate is placed in the right warm area of CVD tube furnace, and makes Si Substrate is located at right warm area center, and the quartzy circumference equipped with S block is put into the center of left warm area.Then sealing tube furnace leads to N2It carries Gas body and protective gas.
(4) growth procedure is set when CVD method growth molybdenum sulfide first, places MoO3It is placed on the quartz boat of Si substrate The temperature at the center of right warm area, right warm area first stage warm area is warming up to 720 DEG C with the rate of 15 DEG C/min, and through-flow speed is vertical for 30 The N of square centimeter per minute (s.c.c.m)2, 720 DEG C of holding 15min at a set temperature, this is growth temperature and time, then With the flow velocity of 500s.c.c.m with the cooling velocity Slow cooling 45min of -9 DEG C/min.
Another quartz boat containing S powder is located at the center upstream of left warm area.Left area is temperature programmed as follows: temperature one is opened Beginning is maintained at 50 DEG C, and until right warm area temperature heats 44min, temperature reaches 620 DEG C, then with the heating rate liter of 25 DEG C/min It to 200 DEG C, is quickly cooled down after keeping 15min, finally opens stove and be quickly cooled down 30min to room temperature, can be obtained in substrate at this time To single layer MoS2.Tail gas is connected into measuring pipette by silicone tube from tube furnace, glass drexel bottle is inserted into, is sealed, washed with rubber plug A certain proportion of lye is packed into according to experimental conditions in gas cylinder and absorbs tail gas, and drexel bottle gas outlet is run in fan system by silicone tube System, guarantees that stable gas pressure prevents lye from flowing back.
(5) PVD method hot evaporation PbI is used2When be also required to the temperature program of setting evaporation source, PVD vapor deposition instrument is evacuated to air pressure and is 10-7Mbar, first setting Current Temperatures are 42 DEG C, are then warming up to 300 DEG C with the rate of 5 DEG C/min, are at this time outgassing temperature Maintain 40min to remove intracavitary impurity, then keep 30min at 290 DEG C of set temperature, 30min at this time be reserve it is enough Time determines PbI2The rate 1.6nm/min of vapor deposition, then turning manipulator make MoS2Downward, towards PbI2Evaporation source, when growth Between control in 6min, turning manipulator makes MoS again after the completion of growth2Face-up stop growing PbI2.Then setting is whole Only the controller of program is cooled to room temperature automatically, after the completion of vapor deposition, opens growth after needing successively to close molecular pump and mechanical pump Chamber takes out sample by manipulator, obtained PbI2With a thickness of 3.6nm.
Obtained product is used into optical microscopy (OM), Raman, atomic force microscope (AFM) characterization, the results show that Single layer MoS2PbI is modulated2Growth.Shown in following Fig. 3~7 of characterize data.
Fig. 3 is the single layer MoS of CVD growth2Optical picture (a) and AFM phenogram (b), obtained single layer MoS2Triangle edges A length of 60 μm, Fig. 4 is single layer MoS in Si substrate2Raman figure, Fig. 5 be Si substrate on single layer MoS2Mapping, Fig. 6 be steam Plate PbI2Single layer MoS in Si substrate afterwards2Raman figure, Fig. 7 be vapor deposition PbI2Single layer MoS in Si substrate afterwards2AFM phenogram.
Embodiment 2
Same as Example 1, difference is only that vapor deposition PbI2Time be 10min.AFM phenogram such as Fig. 8 of its product It is shown, as shown in Figure 8, single layer MoS2PbI is modulated2Growth.
Concrete operation step is identical as (1) in embodiment 1~(4), reach need to be deposited temperature be 290 DEG C after, fastly Fast turning manipulator makes single layer MoS originally upward2Become downward towards evaporation source, and at the same time manipulator to growth chamber In protrude into, find suitable evaporation position.Time of vapor deposition controls in 10min, then keeps at 290 DEG C at a set temperature 30min, 30min at this time are to reserve time enough to determine PbI2The rate 1.6nm/min of vapor deposition, then turning manipulator make MoS2Downward towards PbI2Evaporation source, growth time control is in 10min, and turning manipulator makes MoS again after the completion for growth2 Face-up stop growing PbI2, it is that controller is cooled to room temperature automatically that terminator, which is then arranged, after the completion of vapor deposition, need according to Growth chamber is opened after secondary closing molecular pump and mechanical pump, sample is taken out by manipulator, obtained PbI2With a thickness of 16nm.
Embodiment 3
Same as Example 1, difference is only that vapor deposition PbI2Temperature be 320 DEG C, the time is 10min.The AFM of its product Phenogram is as shown in figure 9, as shown in Figure 9, single layer MoS2PbI is modulated2Growth, compare Fig. 8~9, illustrate PVD different At a temperature of have different evaporation rates.
Concrete operation step is identical as (1) in embodiment 1~(4), reach need to be deposited temperature be 320 DEG C after, fastly Fast turning manipulator makes the single layer MoS of 1 Central Plains of embodiment originally upward2Become downward towards evaporation source, and at the same time manipulator It is protruded into growth chamber, finds suitable evaporation position.Time of vapor deposition controls in 10min, and then at a set temperature 320 DEG C Lower holding 60min, preceding 30min is to reserve time enough to carry out degasification at this time, and rear 30min is for determining PbI2The rate of vapor deposition 8nm/min, then turning manipulator make MoS2Downward towards PbI2Evaporation source, growth time are controlled after the completion of 10min, growth Turning manipulator makes MoS again2Face-up stop growing PbI2, it is that controller is cooled to automatically that terminator, which is then arranged, Room temperature after the completion of vapor deposition, needs to open growth chamber after successively closing molecular pump and mechanical pump, takes out sample by manipulator, obtain The PbI arrived2With a thickness of 80nm.
Embodiment 4
(1) silicon wafer is cut with glass cutter first along its crystal orientation, graduating with cutter first is carried out to bed perimeter, is clipped later with tweezers It breaks into two with one's hands, substrate will be broken along crystal orientation, the substrate of cut growth bar shaped, can be generated a large amount of fines in cutting process and be fallen in base On bottom, substrate is cleaned in ultrasonator respectively with acetone, isopropanol and hydrogen peroxide, each process time is 15min.With Nitrogen gun dries up substrate with spare.
(2) load weighted 450mg S block is put into quartzy circumference, 15mg MoO3Powder is put into quartzy Noah's ark, will pre-process Substrate is placed in MoO3Right above powder.
(3) MoO will be housed3The quartzy Noah's ark of powder and precondition substrate is placed in the right warm area of CVD tube furnace, and makes Si Substrate is located at right warm area center, and the quartzy circumference equipped with S block is put into the center of left warm area.Then sealing tube furnace leads to N2It carries Gas body and protective gas.
(4) growth procedure is set when CVD method growth molybdenum sulfide first, places MoO3It is placed on the quartz boat of Si substrate The temperature at the center of right warm area, right warm area first stage warm area is warming up to 720 DEG C with the rate of 15 DEG C/min, and through-flow speed is vertical for 30 The N of square centimeter per minute (s.c.c.m)2, 720 DEG C of holding 10min at a set temperature, this is growth temperature and time, then With the flow velocity of 500s.c.c.m with the cooling velocity Slow cooling 45min of -9 DEG C/min.
Another quartz boat containing S powder is located at the center upstream of left warm area.Left area is temperature programmed as follows: temperature one is opened Beginning is maintained at 50 DEG C, and until right warm area temperature heats 44min, temperature reaches 620 DEG C, then with the heating rate liter of 25 DEG C/min It to 200 DEG C, is quickly cooled down after keeping 15min, finally opens stove and be quickly cooled down 30min to room temperature, can be obtained in substrate at this time To single layer MoS2.Tail gas is connected into measuring pipette by silicone tube from tube furnace, glass drexel bottle is inserted into, is sealed, washed with rubber plug A certain proportion of lye is packed into according to experimental conditions in gas cylinder and absorbs tail gas, and drexel bottle gas outlet is run in fan system by silicone tube System, guarantees that stable gas pressure prevents lye from flowing back.
Step (5) is same as Example 1.
Figure 10 is the single layer MoS of CVD growth2Optical picture, obtained single layer MoS2A length of 20~30 μm of triangle edges.
The above is only a preferred embodiment of the present invention, it is not intended to limit the present invention in any form.It should It points out, for those skilled in the art, without departing from the principle of the present invention, if can also make Dry improvements and modifications, these modifications and embellishments should also be considered as the scope of protection of the present invention.

Claims (10)

1. a kind of method of single layer molybdenum sulfide regulation lead iodide growth, which comprises the following steps:
After substrate successively to be used to acetone, isopropanol and hydrogen peroxide ultrasonic cleaning, drying obtains precondition substrate；
Under nitrogen protection, by MoO3Powder and S block obtain list in the one side progress chemical vapor deposition of the precondition substrate Layer MoS2；
Under vacuum conditions, in the single layer MoS2Surface carry out PbI2Physical vapour deposition (PVD).
2. the method according to claim 1, wherein the S block and MoO3The mass ratio of powder is 28~32:1.
3. the method according to claim 1, wherein the chemical vapor deposition in double temperature-area tubular furnaces into Row, double temperature-area tubular furnaces include right warm area and Zuo Wenqu.
4. according to the method described in claim 3, it is characterized in that, the quartz circle equipped with S block is placed at the center of the left warm area Week.
5. according to the method described in claim 3, it is characterized in that, the right warm area is placed and MoO is housed3Powder and pretreatment base The quartzy Noah's ark at bottom, the precondition substrate are placed in right warm area center, the MoO3Powder is located under the precondition substrate Side.
6. according to the method described in claim 5, it is characterized in that, the right warm area is warming up to the rate of 15~18 DEG C/min 720~780 DEG C, through-flow speed is the N of 30 cc/mins2, 10~15min is kept, then in N2Flow velocity be 500~520 With the cooling 45~50min of the cooling velocity of -9~-12 DEG C/min under cc/min.
7. the method according to claim 4 or 6, which is characterized in that the left warm area it is temperature programmed as follows: the left temperature The temperature in area is since 50~55 DEG C, and until the temperature of the right warm area heats 44~50min, the temperature of the right warm area reaches After 620~650 DEG C, 200~250 DEG C of 15~20min of holding are risen to the heating rate of 25~30 DEG C/min, are then quickly cooled down 30~60min is to room temperature.
8. according to the method described in claim 3, it is characterized in that, double temperature-area tubular furnaces connect scale suction by silicone tube Pipe is inserted into glass drexel bottle, is sealed with rubber plug, absorbs the tail gas that chemical vapor deposition generates equipped with lye in drexel bottle, described Run in fan system by silicone tube drexel bottle gas outlet.
9. the method according to claim 1, wherein the physical vapour deposition (PVD) is temperature programmed as follows: temperature Since 37~42 DEG C, 30~60min of degasification after being warming up to 280~300 DEG C with the rate of 5~8 DEG C/min, then 280~ 320 DEG C of 5~20min of holding, are then cooled to room temperature automatically.
10. according to claim 1 or method described in 9, which is characterized in that PbI in the physical vapour deposition (PVD)2Evaporation rate For 1.6~8nm/min.
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