CN112909126A - PVK-TMDCs van der Waals heterojunction and preparation method thereof - Google Patents
PVK-TMDCs van der Waals heterojunction and preparation method thereof Download PDFInfo
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- CN112909126A CN112909126A CN202110140994.7A CN202110140994A CN112909126A CN 112909126 A CN112909126 A CN 112909126A CN 202110140994 A CN202110140994 A CN 202110140994A CN 112909126 A CN112909126 A CN 112909126A
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- 239000011261 inert gas Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000010549 co-Evaporation Methods 0.000 claims description 9
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- 238000001704 evaporation Methods 0.000 claims description 8
- 229910052961 molybdenite Inorganic materials 0.000 claims description 8
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010410 layer Substances 0.000 description 14
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- 229910052798 chalcogen Inorganic materials 0.000 description 11
- 150000001787 chalcogens Chemical class 0.000 description 11
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 7
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- 238000002207 thermal evaporation Methods 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a PVK-TMDCs van der Waals heterojunction and a preparation method thereof, belonging to the technical field of photoelectric materials. The invention adopts a chemical vapor deposition method to prepare a transition metal chalcogenide film on a substrate; and preparing a perovskite film on the surface of the transition metal chalcogenide film by adopting a physical vapor deposition method to obtain the PVK-TMDCs Van der Waals heterojunction. The invention adopts the chemical vapor deposition method to prepare the transition metal chalcogenide film on the substrate to obtain the film with high purity, good compactness, small residual stress and good crystallization, and then adopts the physical vapor deposition method to prepare the perovskite film on the surface of the transition metal chalcogenide film, and the transition metal chalcogenide film can play a role in regulating and controlling the growth structure and energy level of the perovskite film, thereby preventing impurities from appearing in the heterojunction interface and improving the photoelectric detection performance of the photoelectric material.
Description
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to a PVK-TMDCs van der Waals heterojunction and a preparation method thereof.
Background
Transition metal chalcogenides (TMDCs, e.g. MoS)2、MoSe2、WS2Etc.) and perovskites (PVKs, such as MAPbX)3(X＝I,Br,Cl)，CsPbX3Etc.) have better photoelectric property, and the heterojunction formed by stacking the heterojunction has excellent photoelectric detection performance. At present, the heterojunction is mainly prepared by adopting a spin-coating method or a fixed-point transfer method, but the interface of the heterojunction prepared by adopting the two methods is often not clean, the experimental repeatability is low, the fixed-point transfer technology based on mechanical stripping can not realize large-scale mass production, and the performance and the application of a subsequent manufactured device are greatly influenced.
Therefore, it is required to provide a method for preparing a heterojunction with a clean interface and strong repeatability, which is suitable for industrial production.
Disclosure of Invention
The invention aims to provide a PVK-TMDCs van der Waals heterojunction and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a PVK-TMDCs van der Waals heterojunction, which comprises the following steps:
(1) preparing a transition metal chalcogenide film on a substrate by adopting a chemical vapor deposition method;
(2) preparing a perovskite film on the surface of the transition metal chalcogenide film obtained in the step (1) by adopting a physical vapor deposition method to obtain a PVK-TMDCs Van der Waals heterojunction.
Preferably, the substrate in the step (1) comprises a Si layer and SiO2And the Si layer is a P-type heavily doped Si layer.
Preferably, the SiO2The thickness of the layer is 100 to 500 nm.
Preferably, the material of the transition metal chalcogenide thin film in step (1) is MoS2、MoSe2Or WS2。
Preferably, the step (1) is performed in an inert gas atmosphere.
Preferably, the inert gas atmosphere is nitrogen, argon or helium.
Preferably, the perovskite thin film in the step (2) is made of MAPbX3Or CsPbX3Said MAPbX3And CsPbX3X in (a) is independently I, Br or Cl.
Preferably, the step (2) is carried out in a vacuum environment with a vacuum degree of 10-7～10- 8mbar
Preferably, the physical vapor deposition method in the step (2) is a sequential evaporation method or a co-evaporation method.
The invention provides the PVK-TMDCs van der Waals heterojunction prepared by the preparation method in the technical scheme.
The invention provides a preparation method of a PVK-TMDCs van der Waals heterojunction, which comprises the following steps: (1) preparing a transition metal chalcogenide film on a substrate by adopting a chemical vapor deposition method; (2) preparing a perovskite film on the surface of the transition metal chalcogenide film obtained in the step (1) by adopting a physical vapor deposition method to obtain a PVK-TMDCs Van der Waals heterojunction. The method comprises the steps of firstly preparing the transition metal chalcogenide film on the substrate by adopting a chemical vapor deposition method to obtain the film with high purity, good compactness, small residual stress and good crystallization, and then preparing the perovskite film on the surface of the transition metal chalcogenide film by adopting a physical vapor deposition method, so that the transition metal chalcogenide film can play a role in regulating and controlling the growth structure and energy level of the perovskite film, impurities in a heterojunction interface are prevented, and the photoelectric detection performance of the photoelectric material is improved. From the inventionMoS obtained in example 12-MAPbI3PL Spectrum and energy band alignment of heterojunction and MoS prepared in example 22-MAPbI3PL spectrum and AFM characterization of the heterojunction show that the Van der Waals heterojunction obtained by the preparation method is low in impurity content and excellent in photoelectric property.
Drawings
FIG. 1 shows preparation of MoS according to example 1 of the present invention2A schematic diagram of a film growth device and deposition raw materials;
FIG. 2 shows the preparation of MAPbI in example 1 of the present invention3A schematic diagram of a film growth device and deposition raw materials;
FIG. 3 shows the preparation of MAPbI by sequential evaporation in example 1 of the present invention3A schematic view of a thin film;
FIG. 4 shows the preparation of MAPbI by co-evaporation method in example 2 of the present invention3A schematic view of a thin film;
FIG. 5 is a single layer MoS prepared in example 1 of the present invention2An optical diagram of (a);
FIG. 6 is a single layer MoS prepared in example 1 of the present invention2(ii) a Raman spectrum of;
FIG. 7 is a single layer MoS prepared in example 1 of the present invention2(ii) photoluminescence spectroscopy;
FIG. 8 is a MoS prepared according to example 1 of the present invention2-MAPbI3PL spectrum of the heterojunction;
FIG. 9 is a MoS prepared according to example 1 of the present invention2-MAPbI3The energy band arrangement of the heterojunction;
FIG. 10 is a MoS prepared according to example 2 of the present invention2-MAPbI3PL spectrum of the heterojunction;
FIG. 11 is a MoS prepared according to example 2 of the present invention2-MAPbI3AFM characterization of the heterojunction.
Detailed Description
The invention provides a preparation method of a PVK-TMDCs van der Waals heterojunction, which comprises the following steps:
(1) preparing a transition metal chalcogenide film on a substrate by adopting a chemical vapor deposition method;
(2) preparing a perovskite film on the surface of the transition metal chalcogenide film obtained in the step (1) by adopting a physical vapor deposition method to obtain a PVK-TMDCs Van der Waals heterojunction.
The invention adopts a chemical vapor deposition method to prepare the transition metal chalcogenide film on the substrate.
In the present invention, the material of the transition metal chalcogenide thin film is preferably MoS2、MoSe2Or WS2More preferably MoS2. The thin film prepared by the transition metal chalcogenide has better photoelectric property.
In the present invention, the substrate preferably includes a Si layer and SiO2A layer; the Si layer is preferably a P-type heavily doped Si layer; the SiO2The thickness of the layer is preferably 100 to 500nm, more preferably 200 to 400nm, and most preferably 250 to 350 nm. The source of the substrate is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. The invention adopts the material which is high temperature resistant, has low chemical activity and is not easy to generate chemical reaction with the deposition raw material as the substrate, and can avoid the influence of the substrate on the Van der Waals heterojunction in the preparation process.
The present invention preferably sequentially cuts, cleans and dries the substrate before use.
In the present invention, the cutting is preferably performed in the crystal direction of the substrate with a diamond glass knife. The invention can make the substrate have regular shape by cutting. The specific shape of the substrate is not particularly limited in the present invention, and may be determined as needed.
In the invention, the cleaning preferably comprises deionized water ultrasonic cleaning, acetone ultrasonic cleaning, isopropanol ultrasonic cleaning and hydrogen peroxide ultrasonic cleaning in sequence. In the invention, the ultrasonic cleaning time of the deionized water, the acetone and the isopropanol is preferably 10-20 min independently, and more preferably 15 min; the time for ultrasonic cleaning by hydrogen peroxide is preferably 5-15 min, and more preferably 10 min. The ultrasonic power for the ultrasonic cleaning is not particularly limited in the present invention, and may be determined according to the technical common knowledge of those skilled in the art. According to the invention, deionized water is used for ultrasonic cleaning to remove scraps on the surface of the substrate, acetone and isopropanol are used for ultrasonic cleaning to remove organic matters attached to the surface of the substrate, and hydrogen peroxide is used for ultrasonic cleaning to remove residual acetone and isopropanol on the surface of the substrate, so that the surface of the substrate is ensured to be clean.
In the present invention, the drying is preferably performed by blow-drying with a nitrogen gun. The invention adopts a nitrogen gun to blow and dry, and can reduce the content of impurities on the surface of the substrate.
In the present invention, the method for preparing the transition metal chalcogenide thin film preferably includes the steps of:
heating the transition metal oxide to 700-800 ℃ in an inert gas atmosphere, heating the chalcogen element simple substance to 200-300 ℃, and depositing to obtain the transition metal chalcogenide film.
In the present invention, the transition metal oxide and the substrate are preferably heated simultaneously.
In the invention, the deposition device is preferably a dual-temperature-zone slide rail furnace with the model of OTF-1200X-II-80-SL. The specific source of the dual-temperature-zone sliding rail furnace with the type of OTF-1200X-II-80-SL is not specially limited, and the dual-temperature-zone sliding rail furnace can be a commercially available product well known by the technical personnel in the field. In the invention, preferably, the transition metal oxide and the chalcogen simple substance are respectively placed in different temperature areas of the dual-temperature-area slide rail furnace, the substrate is placed in the temperature area where the transition metal oxide is located, one end of the substrate is placed right above the transition metal oxide, and SiO of the substrate2The layer is towards the transition metal oxide. In the invention, when a dual-temperature-zone slide rail furnace is adopted for deposition, the temperature zone of the elemental chalcogen is heated to 200-300 ℃, the temperature zone of the transition metal oxide and the substrate is heated to 700-800 ℃, and the transition metal oxide and the elemental chalcogen are sublimated into gas for reaction.
In the present invention, the transition metal oxide is preferably MoO3Or WO3(ii) a The shape of the transition metal oxide is preferably a powder. In the present invention, the particle size of the transition metal oxide is not particularly limited, and is within the skill of those skilled in the artThe determination of the common sense of art is sufficient. The source of the transition metal oxide is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the elemental chalcogen is preferably sulfur or selenium, and the elemental chalcogen is preferably in the form of a bulk. The source of the chalcogen simple substance is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the present invention, the mass ratio of the transition metal oxide to the chalcogen simple substance is preferably 1: (10-40), more preferably 1: (20 to 35), most preferably 1: (25-30). The specific sources of the transition metal oxide and the chalcogen simple substance are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. The invention controls the mass ratio of the raw materials within the range, and can further improve the photoelectric property of the transition metal chalcogenide film.
In the present invention, the inert gas is preferably nitrogen, argon or helium, and more preferably argon. The invention carries out chemical vapor deposition in the inert gas atmosphere, and can prevent impurities in the air from entering the transition metal chalcogenide film.
In the invention, the flow velocity of the inert gas is preferably 20-50 cm3Min, more preferably 30cm3And/min. The invention controls the flow rate of the inert gas, can prevent the steam from being blown away quickly during deposition, and ensures that the film can be deposited and formed.
In the invention, the heating mode of the transition metal oxide is preferably to firstly heat up to 300 ℃, preserve heat for 10-20 min, then heat up to 700-800 ℃, and preserve heat for 10-20 min. In the invention, the heating rate is preferably 10-20 ℃/min, and more preferably 15 ℃/min. The invention heats the transition metal oxide to sublimate the transition metal oxide into gas, and the gas reacts with the sulfur group element simple substance which is sublimated into gas and then is deposited on the substrate to form the transition metal sulfur group compound film.
In the present invention, the chalcogen element is preferably heated by: when the temperature of the transition metal oxide reaches 600-650 ℃, the temperature is raised to 200-300 ℃ at a rate of 20-30 ℃/min. In the present invention, the transition metal oxide and the chalcogen element are preferably simultaneously brought to the respective target temperatures. The invention can further improve the purity of the transition metal chalcogenide compound, reduce the impurity content and improve the photoelectric property by the heating mode.
After the deposition is finished, the temperature of the deposited product is preferably reduced to obtain the transition metal chalcogenide film. In the invention, the cooling mode is preferably that the substrate is cooled to 500-550 ℃ at the speed of 9-10 ℃/min, and then the substrate is naturally cooled to the room temperature. The invention can prevent the structure damage of the transition metal chalcogenide film on the substrate caused by too fast temperature drop rate by the cooling mode.
The invention adopts the chemical vapor deposition method to prepare the transition metal chalcogenide film on the substrate, and can obtain the film with high purity, good compactness, small residual stress and good crystallization.
After the transition metal chalcogenide film is obtained, the perovskite film is prepared on the surface of the transition metal chalcogenide film by adopting a physical vapor deposition method, and the PVK-TMDCs Van der Waals heterojunction is obtained.
In the invention, the apparatus for preparing the perovskite thin film by the physical vapor deposition method is preferably a high vacuum thermal deposition system. The specific source of the high vacuum thermal deposition system is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the present invention, the perovskite thin film is preferably made of MAPbX3Or CsPbX3More preferably MAPbX3(ii) a The MAPbX3And CsPbX3X in (b) is independently preferably I, Br or Cl, more preferably I. The film prepared by perovskite has better photoelectric property.
In the present invention, the physical vapor deposition method is preferably a sequential evaporation method or a co-evaporation method.
In the present invention, the preparation of the perovskite thin film is preferably carried out in a vacuum environmentAnd (6) rows. In the present invention, the degree of vacuum of the vacuum environment is preferably 10-7～10-8mbar. The specific operation mode of the vacuum environment is not particularly limited, and can be determined according to the technical common knowledge of the skilled in the art. The perovskite thin film is prepared under the vacuum condition, and the influence caused by impurities in the air can be reduced.
In the present invention, the method for producing a perovskite thin film using the sequential evaporation method preferably includes the steps of:
I. mixing PbX2Increasing the temperature to 342-348 ℃ at the speed of 3-5 ℃/min, preserving the heat for 3-10 min, then reducing the temperature to 340 ℃ at the speed of 1 ℃/min, and then enabling the substrate to approach PbX2Depositing and cooling to obtain the PbX-plated film2A substrate of a thin film;
II. Heating MAX/CsX to 90-100 ℃ at a speed of 0.5-1 ℃/min, preserving heat for 3-10 min, and then plating PbX obtained in the step I2And (3) depositing a film substrate close to MAX/CsX, and cooling to obtain the perovskite film.
In the present invention, the method for producing a perovskite thin film by the co-evaporation method preferably comprises the steps of:
mixing PbX2Heating to 340 ℃ at the speed of 1.5-2.5 ℃/min, heating MAX/CsX to 90-95 ℃ at the speed of 0.5-1 ℃/min, and placing the substrate in PbX2And MAX/CsX, and cooling to obtain the perovskite thin film.
In the present invention, the PbX is2And MAX/CsX preferably reach their respective target temperatures simultaneously.
The deposition time in the present invention is not particularly limited, and may be determined according to the general technical knowledge of those skilled in the art.
The perovskite thin film is prepared on the surface of the transition metal chalcogenide thin film by adopting a physical vapor deposition method, so that the transition metal chalcogenide thin film can play a role in regulating and controlling the growth structure and energy level of the perovskite thin film, impurities in a heterojunction interface are prevented, and the photoelectric detection performance of the photoelectric material is improved.
The invention provides the PVK-TMDCs van der Waals heterojunction prepared by the preparation method in the technical scheme. The prepared PVK-TMDCs Van der Waals heterojunction has a clean interface, no impurities and excellent photoelectric properties.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The substrate is a Si layer and SiO2The composite material formed is a P-type heavily doped Si layer, SiO2The thickness of the layer is 300 nm; the transition metal chalcogenide being MoS2The perovskite is MAPbI3；
The method comprises the following steps of pretreating a substrate: cutting the silicon substrate along the crystal direction by using a diamond glass cutter, cutting the substrate into a rectangle with the size of 3 multiplied by 2cm, and firstly ultrasonically cleaning the substrate by using deionized water for 15min to remove scraps on the surface of the substrate; ultrasonically cleaning with acetone for 15min, ultrasonically cleaning with isopropanol for 15min, and removing organic matter attached to the surface; finally, ultrasonically cleaning the substrate for 10min by using hydrogen peroxide, and blow-drying the surface of the substrate by using a nitrogen gun after cleaning is finished to obtain a substrate with a clean surface;
the preparation method of the PVK-TMDCs van der Waals heterojunction comprises the following steps:
(1)MoO3the mass ratio of the powder to the S simple substance is controlled to be 1: 30, weigh 15mg of MoO3Placing the powder on a large quartz boat, wherein the powder is required to be gathered together when the powder is placed; then placing the S block in a small quartz ark; MoO3The powder and the S block are both placed in the middle of the quartz boat, the substrate is placed on the big quartz square boat at the position to the right of the middle, and the left side of the substrate is at MoO3SiO of the substrate above the powder2Layer oriented to MoO3Powder, as shown in fig. 1;
(2) placing the large quartz square boat in the right temperature zone of the CVD slide rail furnace, MoO3The powder is directly opposite to the heating wire, the small quartz square boat is placed in the left temperature area of the slide rail furnace, the S block is aligned with the heating wire, then the inlet is tightly sealed by a screw, and the distance between the S block and the heating wire is 500cm3Flow of carrier gas/min is introduced into N2Discharging the air in the furnace to obtain an inert gas atmosphere;
(3) the right temperature zone was first ramped to 300 ℃ at a rate of 15 ℃/min, then held for 15min, and N was added2The flow velocity is adjusted to 30cm3Min, avoiding directly taking away sulfur steam due to over-high flow rate; then raising the temperature to 720 ℃ at a rate of 15 ℃/min, raising the temperature of the left temperature zone to 220 ℃ at a rate of 25 ℃/min when the temperature of the right temperature zone reaches 620 ℃, and keeping the temperature for 15min at the time when the temperature of the left temperature zone and the temperature of the right temperature zone reach the deposition temperature, so that sulfur vapor and MoO are allowed to react3Fully depositing the vapor; after the deposition is finished, the right temperature zone is cooled to 550 ℃ at the speed of 9 ℃/min, all growth procedures are finished, the furnace is opened to be cooled to room temperature, the tail gas pipe is connected with a gas washing bottle, alkali liquor is filled in the gas washing bottle to absorb tail gas, the gas outlet of the gas washing bottle is connected with an exhaust system through a silica gel pipe, the air pressure is ensured to be stable, and the single-layer MoS-plated film is obtained2A substrate of (a);
(4) deposition of MAPbI by sequential evaporation3Film, coating with single layer MoS by adhesive tape2The substrate is adhered on a mechanical arm and then is charged, vacuum pumping is started after assembly is finished, and a mechanical pump is started to pump the cavity to 10 degrees-1mbar, then turning on the molecular pump to pump the chamber to 10-7mbar; heating the temperature in the cavity to 345 ℃ at the speed of 4 ℃/min, and preserving the temperature for 5min to carry out PbI treatment2Degassing the raw materials, discharging impurities in the raw materials, reducing the temperature to 340 ℃ at the speed of 1 ℃/min, and using a manipulator to plate the single-layer MoS2The substrate is stretched into the cavity for deposition for 5min, the surface of the substrate faces downwards, the substrate is stretched out after the deposition is finished, and the PbI-plated substrate is obtained after cooling2A substrate of (a); placing MAI into the cavity, heating to 95 deg.C at 0.7 deg.C/min, maintaining for 5min, degassing, and plating with PbI2The substrate is stretched into the cavity for deposition for 7min, the mechanical arm is stretched out after the deposition is finished, the molecular pump is turned off, then the mechanical pump is turned off, and N is introduced2Then opening the cavity to take out the substrate to obtain MoS2-MAPbI3A heterojunction.
Example 2
Example 2 the preparation method in which step (1), step (2) and step (3) are identical to example 1, except that step (4) is carried out to deposit MAPbI by co-evaporation3A film;
(4) deposition of MAPbI by Co-evaporation3Film, coating with single layer MoS by adhesive tape2The substrate is adhered on a mechanical arm and then is charged, vacuum pumping is started after assembly is finished, and a mechanical pump is started to pump the cavity to 10 degrees-1mbar, then turning on the molecular pump to pump the chamber to 10-7mbar；PbI2The temperature is increased to 340 ℃ at the speed of 2 ℃/min, the MAI is increased to 91 ℃ at the speed of 0.5 ℃/min, and then the single-layer MoS is plated by utilizing a manipulator2The substrate is stretched into the cavity, the surface of the substrate is downward, deposition is carried out for 3min, the mechanical arm is stretched out after the deposition is finished, the molecular pump is turned off, then the mechanical pump is turned off, and N is introduced2Then opening the cavity to take out the substrate to obtain MoS2-MAPbI3A heterojunction.
Example 3
Example 3 was prepared exactly as in example 2, except that MAPbI was deposited3The film time was 1.5min to obtain MoS2-MAPbI3A heterojunction.
FIG. 1 shows preparation of MoS according to example 1 of the present invention2A film growing device and a deposition raw material schematic diagram. As can be seen from FIG. 1, the Mo source and the S source are heated by the heating rods respectively, so that the Mo source and the S source can reach the deposition temperature at the same time, and then deposition is carried out to obtain MoS2A film.
FIG. 2 shows the preparation of MAPbI in example 1 of the present invention3A film growing device and a deposition raw material schematic diagram. As can be seen from FIG. 2, the present invention employs PbI2And MAI as starting materials to prepare MAPbI3A film.
FIG. 3 shows the preparation of MAPbI by sequential evaporation in example 1 of the present invention3Schematic representation of the film. As can be seen in FIG. 3, MAPbI was prepared by sequential evaporation3When the film is made, firstly, MoS is used2Preparation of PbI on film surface2Film, then PbI2Film andgradual MAI deposition to MAPbI3Thin film, the process is easy to exist without MAPbI generation3PbI of thin film2。
FIG. 4 shows the preparation of MAPbI by co-evaporation method in example 2 of the present invention3Schematic representation of the film. As can be seen in FIG. 4, the MAPbI was prepared by co-evaporation3In the case of thin films, PbI2Direct generation of MAPbI with MAI deposition3A film.
FIG. 5 is a single layer MoS prepared in example 1 of the present invention2An optical diagram of (a). As can be seen from FIG. 5, the monolayer MoS is prepared on the surface of the substrate according to the invention2A film.
FIG. 6 is a single layer MoS prepared in example 1 of the present invention2The raman spectrum of (a). As can be seen from FIG. 6, the single-layer MoS prepared in example 1 of the present invention2The film was excited at 383.2nm and 403.7nm, indicating MoS2The photoelectric property of the film is good.
FIG. 7 is a single layer MoS prepared in example 1 of the present invention2Photoluminescence spectrum of (a). As can be seen in FIG. 7, the single-layer MoS prepared by the present invention2The film has high purity and good crystallization.
FIG. 8 is a MoS prepared according to example 1 of the present invention2-MAPbI3PL spectrum of the heterojunction. By MoS in FIG. 82Characteristic line positions of/PVK it can be seen that the MoS prepared in example 1 of the invention2-MAPbI3The impurity content in the heterojunction is low.
FIG. 9 is a MoS prepared according to example 1 of the present invention2-MAPbI3The energy band of the heterojunction is aligned. As can be seen from FIG. 9, the MoS prepared in example 1 of the present invention2-MAPbI3The energy band arrangement form of the heterojunction is staggered arrangement and the energy level difference is low, which indicates that MoS2-MAPbI3The heterojunction has excellent photoelectric properties.
FIG. 10 is a MoS prepared according to example 2 of the present invention2-MAPbI3PL spectrum of the heterojunction. As can be seen from FIG. 10, the MoS prepared in example 2 of the present invention2-MAPbI3The heterojunction has transition at the wavelength of 600-700 nm, and the heterojunction prepared by the method has excellent photoelectric property.
FIG. 11 is a MoS prepared according to example 2 of the present invention2-MAPbI3AFM characterization of the heterojunction. As can be seen from FIG. 11, the MoS prepared in example 2 of the present invention2-MAPbI3The surface fluctuation gradient of the heterojunction is between 0 and 4nm, which indicates that the interface of the heterojunction is clean and has no redundant impurities.
As can be seen from the examples 1 to 3 and the figures 1 to 11, the PVK-TMDCs Van der Waals heterojunction prepared by the preparation method provided by the invention has a clean interface, no impurities and excellent photoelectric properties, can be applied to a photoelectric detector and has better photoelectric detection performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of PVK-TMDCs van der Waals heterojunction comprises the following steps:
(1) preparing a transition metal chalcogenide film on a substrate by adopting a chemical vapor deposition method;
(2) preparing a perovskite film on the surface of the transition metal chalcogenide film obtained in the step (1) by adopting a physical vapor deposition method to obtain a PVK-TMDCs Van der Waals heterojunction.
2. The production method according to claim 1, wherein the substrate in the step (1) comprises a Si layer and SiO2And the Si layer is a P-type heavily doped Si layer.
3. The method of claim 2, wherein the SiO is2The thickness of the layer is 100 to 500 nm.
4. The method according to claim 1, wherein the transition metal chalcogenide thin film of step (1) is MoS2、MoSe2Or WS2。
5. The production method according to claim 1, wherein the step (1) is performed in an inert gas atmosphere.
6. The method according to claim 5, wherein the inert gas atmosphere is nitrogen, argon or helium.
7. The method according to claim 1, wherein the perovskite thin film in the step (2) is made of MAPbX3Or CsPbX3Said MAPbX3And CsPbX3X in (a) is independently I, Br or Cl.
8. The method according to claim 1, wherein the step (2) is performed in a vacuum environment having a degree of vacuum of 10-7～10-8mbar。
9. The production method according to claim 1, wherein the physical vapor deposition method in the step (2) is a sequential evaporation method or a co-evaporation method.
10. The PVK-TMDCs van der Waals heterojunction prepared by the preparation method according to any one of claims 1 to 9.
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