CN111952459A - One-dimensional/two-dimensional perovskite Van der Waals heterojunction photoelectric device and manufacturing method thereof - Google Patents

One-dimensional/two-dimensional perovskite Van der Waals heterojunction photoelectric device and manufacturing method thereof Download PDF

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CN111952459A
CN111952459A CN202010860334.1A CN202010860334A CN111952459A CN 111952459 A CN111952459 A CN 111952459A CN 202010860334 A CN202010860334 A CN 202010860334A CN 111952459 A CN111952459 A CN 111952459A
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CN111952459B (en
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刘孔
王智杰
曲胜春
贾晓皓
孙明飞
任宽宽
黄志涛
吴玉林
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Abstract

A one-dimensional/two-dimensional perovskite Van der Waals heterojunction photoelectric device and a manufacturing method thereof are provided, the one-dimensional/two-dimensional perovskite Van der Waals heterojunction photoelectric device comprises two-dimensional perovskite nanosheets; the one-dimensional perovskite nano wire is arranged on the two-dimensional perovskite nano sheet; the Van der Waals heterojunction is arranged on the contact surface of the one-dimensional perovskite nanowire and the two-dimensional perovskite nanosheet; the device electrode comprises a first electrode and a second electrode, the first electrode is arranged at the bottom of the two-dimensional perovskite nanosheet, and the second electrode is arranged on the one-dimensional perovskite nanowire; and a substrate, on which a first electrode is provided, at the bottom of the device. According to the invention, two materials with different dimensions form a heterojunction, so that the coupling and regulation of physical effects in the materials with different dimensions can be realized; by combining the advantages of the low-dimensional metal halide perovskite material and the van der Waals heterojunction, an effective means is provided for the preparation of the high-performance photoelectric device, and the method can realize the flexible regulation and control of the photoelectric property in the system.

Description

One-dimensional/two-dimensional perovskite Van der Waals heterojunction photoelectric device and manufacturing method thereof
Technical Field
The invention relates to the field of photoelectric devices, in particular to a one-dimensional/two-dimensional perovskite van der Waals heterojunction photoelectric device and a manufacturing method thereof.
Background
Van der waals heterojunctions have been the hot spot in the research of low dimensional materials due to the simple preparation method and novel physical properties. The Van der Waals heterojunction can be realized by directly stacking low-dimensional materials, and due to the fact that tolerance of the Van der Waals heterojunction to lattice mismatch is high, the Van der Waals heterojunction can be assembled by flexibly selecting units with different physical characteristics and different arrangement modes, and therefore regulation and control of various physical properties in a system are achieved. With the recent increase of research heat of two-dimensional materials, many works related to van der waals heterojunction based on two-dimensional materials have been reported. This structure exhibits some novel physical phenomena such as Hofstetter butterfly spectrum, Moire fringe, strong exciton binding energy, and spin energy valley polarization. The van der waals heterojunction has a promoting effect on researching a new physical theory and developing a novel photoelectric device.
The metal halide perovskite material has a plurality of excellent photoelectric properties and is a leading-edge hot spot material which is widely concerned. In recent years, the research of three-dimensional perovskite materials is gradually transferred to low-dimensional perovskite materials, such as zero-dimensional quantum dots, one-dimensional nanowires, two-dimensional nanosheets and the like. However, van der waals heterojunctions based on one-dimensional/two-dimensional perovskite materials have not been reported. The perovskite low-dimensional Van der Waals heterojunction can provide a new platform for the research of a new physical mechanism and has important significance for the development of a novel photoelectric device in the future. On one hand, the structure is helpful for deeply resolving potential physical mechanisms in materials and devices, such as exciton evolution, charge transfer and transportation and the like; on the other hand, due to the unique structural characteristics and quantum confinement effect of the low-dimensional perovskite material, the method is favorable for further developing high-performance optoelectronic devices with special purposes.
However, the preparation of the one-dimensional/two-dimensional perovskite van der waals heterojunction still faces a plurality of difficulties at present, which relate to the synthesis and the shape and size control of high-quality low-dimensional single crystal perovskite materials, the construction of van der waals heterojunction through dry transfer, and the like.
Disclosure of Invention
In view of the above, one of the main objects of the present invention is to provide a one-dimensional/two-dimensional perovskite van der waals heterojunction photoelectric device and a method for fabricating the same, so as to at least partially solve at least one of the above technical problems.
To achieve the above object, as one aspect of the present invention, there is provided a one-dimensional/two-dimensional perovskite van der waals heterojunction photoelectric device comprising:
a two-dimensional perovskite nanosheet;
the one-dimensional perovskite nano wire is arranged on the two-dimensional perovskite nano sheet;
the Van der Waals heterojunction is arranged on the contact surface of the one-dimensional perovskite nanowire and the two-dimensional perovskite nanosheet;
the device electrode comprises a first electrode and a second electrode, the first electrode is arranged at the bottom of the two-dimensional perovskite nanosheet, and the second electrode is arranged on the one-dimensional perovskite nanowire; and
and the substrate is provided with a first electrode and is positioned at the bottom of the device.
As another aspect of the present invention, there is also provided a method of fabricating a one-dimensional/two-dimensional perovskite van der waals heterojunction photoelectric device, comprising:
transferring the one-dimensional perovskite nano wire to a two-dimensional perovskite nano sheet to form a Van der Waals heterojunction;
transferring the van der waals heterojunction to the substrate on which the first electrode is prepared;
and preparing a second electrode on the one-dimensional perovskite nanowire to obtain the one-dimensional/two-dimensional perovskite Van der Waals heterojunction photoelectric device.
Based on the technical scheme, compared with the prior art, the one-dimensional/two-dimensional perovskite van der waals heterojunction photoelectric device and the manufacturing method thereof have at least one of the following advantages:
(1) the heterojunction formed by the two materials with different dimensions can realize the coupling and regulation of physical effects in the materials with different dimensions;
(2) by combining the advantages of the low-dimensional metal halide perovskite material and the van der Waals heterojunction, an effective means is provided for the preparation of the high-performance photoelectric device, and the method can realize the flexible regulation and control of the photoelectric property in the system;
(3) the weak coulomb shielding of the perovskite materials with two different dimensions and the interface of the Van der Waals heterojunction can be utilized to adjust the exciton binding energy in the system;
(4) the ultra-fast charge transfer and transport in the system can be realized by utilizing quantum confinement effect and a smooth Van der Waals heterojunction interface without a dangling bond.
Drawings
FIG. 1 is a schematic diagram of a one-dimensional/two-dimensional perovskite Van der Waals heterojunction optoelectronic device structure in an embodiment of the invention;
fig. 2 is a flow chart of fabrication of one-dimensional/two-dimensional perovskite van der waals heterojunction photovoltaic devices in an embodiment of the invention.
Description of reference numerals:
the perovskite nanowire structure comprises 1-one-dimensional perovskite nanowire, 2-two-dimensional perovskite nanosheets, 3-van der Waals heterojunction formed by one-dimensional and two-dimensional structures, 41-first electrode, 42-second electrode and 5-substrate.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
The invention provides a one-dimensional/two-dimensional perovskite Van der Waals heterojunction photoelectric device and a manufacturing method thereof, in order to construct a novel low-dimensional photoelectric process research platform and develop a novel photoelectric device. The structure can be used for researching the mutual coupling and regulation of various physical effects in materials with different dimensions, and the advantages of low-dimensional perovskite and van der Waals heterojunction are combined to realize the physical effects of adjustable exciton binding energy, ultrafast charge transfer, high-efficiency photoelectric conversion and the like in the structure, and meanwhile, the structure can also be used for researching a photoelectric detector and a light-emitting diode with specific photoelectric properties.
The invention discloses a one-dimensional/two-dimensional perovskite van der Waals heterojunction photoelectric device, which comprises:
a two-dimensional perovskite nanosheet;
the one-dimensional perovskite nano wire is arranged on the two-dimensional perovskite nano sheet;
the Van der Waals heterojunction is arranged on the contact surface of the one-dimensional perovskite nanowire and the two-dimensional perovskite nanosheet;
the device electrode comprises a first electrode and a second electrode, the first electrode is arranged at the bottom of the two-dimensional perovskite nanosheet, and the second electrode is arranged on the one-dimensional perovskite nanowire; and
and the substrate is provided with a first electrode and is positioned at the bottom of the device.
In some embodiments of the invention, the surface feature size ranges between 100nm to 500 μm, such as 100nm, 200nm, 300nm, 400nm, 500 nm;
in some embodiments of the invention, the thickness ranges between 1nm and 500nm, such as 1nm, 10nm, 20nm, 50nm, 80nm, 100nm, 200nm, 300nm, 400nm, 500 nm.
In some embodiments of the invention, the cross-sectional length or width dimension of the one-dimensional perovskite nanowire ranges between 10nm and 1 μm, for example 10nm, 20nm, 50nm, 80nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm.
In some embodiments of the invention, the length of the one-dimensional perovskite nanowires ranges between 100nm and 10 μm, such as 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm, 2 μm, 5 μm, 8 μm, 10 μm.
In the inventionIn some embodiments, the perovskite adopted by the one-dimensional perovskite nanowire and the two-dimensional perovskite nanosheet is a metal halide perovskite material, and the chemical structure is ABX3Wherein A is any one or a mixture of four cations of methylamine, formamidine, Cs and Rb, B is Pb or Sn, and X is any one or a mixture of three anions of Cl, Br and I.
In some embodiments of the present invention, the cross-sectional shape of the one-dimensional perovskite nanowire comprises at least one of a circle, a triangle, a square, and a rectangle.
In some embodiments of the invention, the exciton binding energy in the van der Waals heterojunction ranges from 0.1eV to 1eV, such as 0.1eV, 0.2eV, 0.5eV, 0.8eV, 1 eV;
in some embodiments of the present invention, the material used for the device electrodes includes any one of Au, Ag, Cu, Al, Cr.
The invention also discloses a manufacturing method of the one-dimensional/two-dimensional perovskite Van der Waals heterojunction photoelectric device, which comprises the following steps:
transferring the one-dimensional perovskite nano wire to a two-dimensional perovskite nano sheet to form a Van der Waals heterojunction;
transferring the van der waals heterojunction to the substrate on which the first electrode is prepared;
and preparing a second electrode on the one-dimensional perovskite nanowire to obtain the one-dimensional/two-dimensional perovskite Van der Waals heterojunction photoelectric device.
In some embodiments of the invention, the preparation method of the one-dimensional perovskite nanowire is prepared by adopting a sound wave auxiliary method;
in some embodiments of the present invention, the length of the nanowires is controlled by controlling the time of the reaction and the reaction temperature.
In some embodiments of the invention, the surface feature size ranges between 100nm to 500 μm, such as 100nm, 200nm, 300nm, 400nm, 500 nm;
in some embodiments of the invention, the thickness ranges between 1nm and 500nm, such as 1nm, 10nm, 20nm, 50nm, 80nm, 100nm, 200nm, 300nm, 400nm, 500 nm.
In some embodiments of the invention, the cross-sectional length or width dimension of the one-dimensional perovskite nanowire ranges between 10nm and 1 μm, for example 10nm, 20nm, 50nm, 80nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm.
In some embodiments of the invention, the length of the one-dimensional perovskite nanowires ranges between 100nm and 10 μm, such as 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm, 2 μm, 5 μm, 8 μm, 10 μm.
In some embodiments of the present invention, the perovskite adopted by the one-dimensional perovskite nano-wire and the two-dimensional perovskite nano-sheet is a metal halide perovskite material, and the chemical structure is ABX3Wherein A is any one or a mixture of four cations of methylamine, formamidine, Cs and Rb, B is Pb or Sn, and X is any one or a mixture of three anions of Cl, Br and I.
In some embodiments of the present invention, the cross-sectional shape of the one-dimensional perovskite nanowire comprises at least one of a circle, a triangle, a square, and a rectangle.
In some embodiments of the invention, the exciton binding energy in the van der Waals heterojunction ranges from 0.1eV to 1eV, such as 0.1eV, 0.2eV, 0.5eV, 0.8eV, 1 eV;
in some embodiments of the present invention, the material used for the device electrodes includes any one of Au, Ag, Cu, Al, Cr.
The technical solution of the present invention is further illustrated by the following specific embodiments in conjunction with the accompanying drawings. It should be noted that the following specific examples are given by way of illustration only and the scope of the present invention is not limited thereto.
The chemicals and raw materials used in the following examples were either commercially available or self-prepared by a known preparation method.
As shown in fig. 1, a one-dimensional/two-dimensional perovskite van der waals heterojunction photoelectric device comprises a one-dimensional perovskite nanowire 1, a two-dimensional perovskite nanosheet 2, a van der waals heterojunction 3 formed by one-dimensional and two-dimensional structures, device electrodes (comprising a first electrode 41 and a second electrode 42), and a substrate 5; the perovskite is a metal halide perovskite, and the photoelectric device comprises a light emitting diode and a photoelectric detector.
The perovskite is a metal halide perovskite material and has a chemical structure of ABX3Wherein A is methylamine, formamidine, Cs, Rb or mixed cation of four, B is Pb or Sn, etc., X is Cl, Br, I or mixture of anions of the three. The band gap of the metal halide perovskite material is adjustable within the range of 1.2eV to 3 eV.
The cross-sectional shape of the one-dimensional perovskite nanowire 1 can be circular, triangular, square, rectangular and the like, the cross-sectional dimensions (such as the length and width of the rectangle, the diameter of the circle and the side length of the triangle) range from 10nm to 1 μm, and the length of the one-dimensional perovskite nanowire 1 ranges from 100nm to 10 μm.
The surface characteristic size range of the two-dimensional perovskite nano sheet 2 is between 100nm and 500 mu m, and the thickness range of the two-dimensional nano sheet is between 1nm and 500 nm. The two-dimensional perovskite may also be a two-dimensional layered structure formed of multiple layers of Ruddlesden-Popper (RP) type perovskites.
The Van der Waals heterojunction 3 is positioned on the contact surface of the structures of the one-dimensional perovskite nanowire 1 and the two-dimensional perovskite nanosheet 2, the exciton binding energy in the Van der Waals heterojunction is adjustable within the range of 0.1eV to 1eV, and the interface charge transfer time reaches 10 picoseconds. The device electrode comprises a surface electrode (namely a first electrode 41) directly contacted with the two-dimensional perovskite nanosheet 2 on the substrate 5 and a patterned electrode (namely a second electrode 42) deposited on the surface of the one-dimensional perovskite, wherein the main materials are Au, Ag, Cu, Al, Cr and the like.
As shown in fig. 2, a method for fabricating a one-dimensional/two-dimensional perovskite van der waals heterojunction photoelectric device includes:
step 1: preparing a one-dimensional perovskite nanowire;
step 2: preparing a two-dimensional perovskite nanosheet;
and step 3: transferring the nanowires to the surfaces of the nanosheets to form van der waals heterojunctions; and 4, step 4: and (3) transferring the Van der Waals heterojunction formed in the step (3) to a substrate with a prepared first electrode, and then preparing a second electrode by using the one-dimensional perovskite nanowire to obtain the one-dimensional/two-dimensional perovskite Van der Waals heterojunction photoelectric device.
The one-dimensional perovskite nanowire in the step 1 is prepared by a sound wave auxiliary method, and the size of the nanowire (such as the length and width of a rectangle, the diameter of a circle and the side length of a triangle) is regulated and controlled by accurately controlling the reaction time and the temperature of a reaction system. The ultrasonic wave functions to disperse the reactants in the nonpolar solvent and help them increase contact with each other, thereby increasing the reaction rate, and secondly, the ultrasonic wave energy has a part that can provide activation energy required for the reaction instead of an external heating device. Compared with the traditional thermal injection method, the ultrasonic assisted method has the advantages of high atom utilization rate, short reaction time, high yield, no need of inert gas protection and the like.
The two-dimensional perovskite nano-sheet in the step 2 is manufactured on an ITO/glass or mica substrate, and a layer of PEDOT is spin-coated on the substrate in advance: PSS is used as a buffer layer, lead acetate and a halogen precursor AX (A is methylamine, formamidine, Cs, Rb or mixed cations thereof, and X is Cl, Br, I or mixed anions thereof) are reacted in an isopropanol solution, the material preparation process is optimized by changing the conditions of different precursor lead salt films, lead salt film buffer layers, growth temperature, chemical reaction solution concentration and the like, and the structure size is adjusted. As for the perovskite nano sheet prepared on the mica sheet, only weak Van der Waals force exists between the perovskite nano sheet and the mica sheet, so that the perovskite nano sheet can be easily separated by utilizing Polydimethylsiloxane (PDMS) adsorption, and the perovskite material is slightly damaged in the transfer process. When transferred to the substrate surface with electrodes, the two-dimensional perovskite will adsorb to the new substrate by van der waals forces.
And 3, preparing the one-dimensional/two-dimensional perovskite van der Waals heterojunction in the step 3 by using a dry transfer technology, firstly adsorbing the nanowire by using PDMS (polydimethylsiloxane), and slightly moving the PDMS after transferring the nanowire to the surface of the two-dimensional perovskite nano sheet, so that the nanowire can be naturally broken and fall off to cover the surface of the nano sheet. On the other hand, chemical vapor deposition process can be adopted to prepare one-dimensional and two-dimensional perovskite materials and realize the different-dimensional epitaxial growth of the materials. Firstly, PbI is added2Mixing with CsBr at a certain ratioPutting the quartz boat into a chemical vapor deposition tube chamber, and placing the cleaned silicon wafer or mica substrate at the downstream of the quartz boat. Then, a flow of high purity argon is introduced to bring the chamber to a reaction pressure of 350-450Torr, for example, 400 Torr. After the temperature of the heating furnace reaches 550 ℃ and 600 ℃, for example 570 ℃, the reaction furnace is pushed to the reaction area, and the reaction is cooled after about 10-20 minutes, for example 15 minutes. The perovskite nano material with high crystal quality and small defects can be obtained by the method. Meanwhile, one-dimensional and two-dimensional perovskite materials with different morphologies can be obtained by changing the growth conditions. And finally, the preparation of the Van der Waals heterojunction of the perovskite materials with different dimensions is realized by using modes of in-situ chemical vapor deposition, dry transfer and the like.
The electrodes in step 4 include a bottom first electrode 41 and an upper second electrode 42, the first electrode 41 is a glass or mica substrate deposited with patterned ITO or metal electrodes, and the second electrode 42 is a metal electrode deposited by using a mask plate or a photolithography process, and finally a light emitting diode or a photodetector is prepared. And regulating and controlling the physical effects by utilizing the basic rule that the physical effects in materials with different dimensions are mutually coupled. The binding effect of the van der Waals heterojunction interface on excitons in the system is regulated and controlled by utilizing the influence rule of various material performance parameters and structure sizes on bound excitons in the heterojunction, so that the photoelectric conversion process in the system is optimized. In addition, the integration of the light emitting diode and the photoelectric detector is realized by depositing low-dimensional perovskite materials with different components and shapes on the same substrate.
It is to be noted that, in the attached drawings or in the description, the implementation modes not shown or described are all the modes known by the ordinary skilled person in the field of technology, and are not described in detail. In addition, the above definitions of the various elements are not limited to the specific structures, shapes or modes mentioned in the embodiments, and those skilled in the art may easily modify or replace them, for example:
(1) directional phrases used in the embodiments, such as "upper", "lower", "front", "rear", "left", "right", etc., refer only to the orientation of the drawings and are not intended to limit the scope of the present disclosure;
(2) the embodiments described above may be mixed and matched with each other or with other embodiments based on design and reliability considerations, i.e. technical features in different embodiments may be freely combined to form further embodiments.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A one/two dimensional perovskite van der waals heterojunction photovoltaic device, comprising:
a two-dimensional perovskite nanosheet;
the one-dimensional perovskite nano wire is arranged on the two-dimensional perovskite nano sheet;
the Van der Waals heterojunction is arranged on the contact surface of the one-dimensional perovskite nanowire and the two-dimensional perovskite nanosheet;
the device electrode comprises a first electrode and a second electrode, the first electrode is arranged at the bottom of the two-dimensional perovskite nanosheet, and the second electrode is arranged on the one-dimensional perovskite nanowire; and
and the substrate is provided with a first electrode and is positioned at the bottom of the device.
2. The one-dimensional/two-dimensional perovskite van der Waals heterojunction optoelectronic device of claim 1,
the surface characteristic size range of the two-dimensional perovskite nano sheet is between 100nm and 500 mu m; the thickness ranges between 1nm and 500 nm.
3. The one-dimensional/two-dimensional perovskite van der Waals heterojunction optoelectronic device of claim 1,
the length or width size range of the section of the one-dimensional perovskite nanowire is between 10nm and 1 mu m;
the length of the one-dimensional perovskite nanowire ranges from 100nm to 10 μm.
4. The one-dimensional/two-dimensional perovskite van der Waals heterojunction optoelectronic device of claim 1,
the perovskite adopted by the one-dimensional perovskite nano wire and the two-dimensional perovskite nano sheet is a metal halide perovskite material, and the chemical structure is ABX3Wherein A is any one or a mixture of four cations of methylamine, formamidine, Cs and Rb, B is Pb or Sn, and X is any one or a mixture of three anions of Cl, Br and I.
5. The one-dimensional/two-dimensional perovskite van der Waals heterojunction optoelectronic device of claim 1,
the cross section of the one-dimensional perovskite nanowire is in at least one of a circle, a triangle, a square and a rectangle.
6. The one-dimensional/two-dimensional perovskite van der Waals heterojunction optoelectronic device of claim 1,
the exciton binding energy in the van der Waals heterojunction ranges from 0.1eV to 1 eV;
the device electrode is made of any one of Au, Ag, Cu, Al and Cr.
7. A manufacturing method of a one-dimensional/two-dimensional perovskite Van der Waals heterojunction photoelectric device comprises the following steps:
transferring the one-dimensional perovskite nano wire to a two-dimensional perovskite nano sheet to form a Van der Waals heterojunction;
transferring the van der waals heterojunction to the substrate on which the first electrode is prepared;
and preparing a second electrode on the one-dimensional perovskite nanowire to obtain the one-dimensional/two-dimensional perovskite Van der Waals heterojunction photoelectric device.
8. The method of manufacturing according to claim 7,
the preparation method of the one-dimensional perovskite nanowire is characterized in that a sound wave auxiliary method is adopted for preparation; the length of the nano-wire is regulated and controlled by controlling the reaction time and the reaction temperature.
9. The method of manufacturing according to claim 7,
the surface characteristic size range of the two-dimensional perovskite nano sheet is between 100nm and 500 mu m; the thickness ranges from 1nm to 500 nm;
the length or width size range of the section of the one-dimensional perovskite nanowire is between 10nm and 1 mu m;
the length of the one-dimensional perovskite nanowire ranges from 100nm to 10 μm.
10. The method of manufacturing according to claim 7,
the perovskite adopted by the one-dimensional perovskite nano wire and the two-dimensional perovskite nano sheet is a metal halide perovskite material, and the chemical structure is ABX3Wherein A is any one or a mixture of four cations of methylamine, formamidine, Cs and Rb, B is Pb or Sn, and X is any one or a mixture of anions of Cl, Br and I;
the cross section of the one-dimensional perovskite nanowire is in a shape of at least one of a circle, a triangle, a square and a rectangle;
the exciton binding energy in the van der Waals heterojunction ranges from 0.1eV to 1 eV;
the device electrode is made of any one of Au, Ag, Cu, Al and Cr.
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