CN108075020B - Light-emitting diode based on cesium-lead halogen perovskite thin film material and preparation method thereof - Google Patents
Light-emitting diode based on cesium-lead halogen perovskite thin film material and preparation method thereof Download PDFInfo
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- CN108075020B CN108075020B CN201711447809.9A CN201711447809A CN108075020B CN 108075020 B CN108075020 B CN 108075020B CN 201711447809 A CN201711447809 A CN 201711447809A CN 108075020 B CN108075020 B CN 108075020B
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- -1 cesium-lead halogen Chemical class 0.000 title claims abstract description 55
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 51
- 239000010409 thin film Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 65
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 34
- 239000012159 carrier gas Substances 0.000 claims abstract description 32
- 239000011812 mixed powder Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000004820 halides Chemical class 0.000 claims abstract description 17
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 230000005525 hole transport Effects 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 238000013329 compounding Methods 0.000 claims description 8
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 5
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical group [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 5
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical group Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 3
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 238000002347 injection Methods 0.000 abstract description 7
- 239000007924 injection Substances 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000002096 quantum dot Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IWDXBHSUFKRAQP-UHFFFAOYSA-N [Cs].[Pb] Chemical compound [Cs].[Pb] IWDXBHSUFKRAQP-UHFFFAOYSA-N 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910002601 GaN Inorganic materials 0.000 description 2
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 2
- NCFBWCVNPJEZMG-UHFFFAOYSA-N [Br].[Pb].[Cs] Chemical compound [Br].[Pb].[Cs] NCFBWCVNPJEZMG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
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- Electroluminescent Light Sources (AREA)
- Chemical Vapour Deposition (AREA)
- Led Devices (AREA)
Abstract
The invention provides a preparation method of a cesium-lead halogen perovskite thin film material, which comprises the following steps: A) mixing cesium halide containing the same halogen element with lead halide and then grinding to obtain mixed powder; B) and (2) placing the mixed powder in a CVD (chemical vapor deposition) tube furnace, introducing carrier gas, placing a substrate in the downstream direction of the carrier gas, raising the temperature in a furnace cavity of the tube furnace to 500-700 ℃ at the speed of 10-30 ℃/min under the condition of 100-200 Pa, keeping the temperature for 5-30 min, cooling, and growing a cesium-lead halogen perovskite thin film material on the surface of the substrate. The cesium-lead-halogen perovskite thin film material prepared by the chemical vapor deposition method provided by the invention has good crystallization quality and optical quality, and the prepared light-emitting diode has high injection current and brightness.
Description
Technical Field
The invention belongs to the technical field of light-emitting diodes, and particularly relates to a cesium-lead halogen perovskite thin film material, a light-emitting diode and a preparation method thereof.
Background
The light emitting diode can be applied to personal or commercial equipment such as display, illumination, stages, advertisement and the like, and has extremely wide application prospect and requirement. However, in order to realize different emission wavelengths, complicated synthesis or growth processes are required to prepare different systems or types of light-emitting layer materials, which increases difficulty and cost. Therefore, it is necessary to develop materials with the same system of light emitting layers with adjustable wavelength to realize light emitting diodes with different colors.
The perovskite material has ultra-fast charge generation speed, high mobility, long carrier life, higher exciton confinement energy and defect tolerance. Compared with the traditional material, the perovskite is easier to prepare the luminescent layer material with narrow emission spectrum and high luminescent efficiency by a simple and economic method. These excellent optoelectronic properties have made perovskite materials recently attract the attention of a great number of researchers, and have raised a hot rush of research on optoelectronic devices based on perovskite materials. Because of their energy band properties that can be adjusted by their composition, perovskite materials are ideal for new luminescent materials with continuously adjustable wavelengths in the visible range, and for low-cost color light emitting diodes. Recent reports have been made on organic-inorganic composite perovskite materials (methylamine lead halides, etc.), and there are also luminescence wavelengths covered by the full spectrum. However, the organic portion of the organic-inorganic composite perovskite material is decomposed at a slightly high temperature and humidity, which affects the stability of the material. Therefore, the preparation of the all-inorganic perovskite material becomes an ideal way for realizing the high-performance homogeneous luminescent material.
Due to the requirements of reducing the preparation cost and the process difficulty, the preparation method of the perovskite material is required to be capable of simply, conveniently and efficiently realizing the mass synthesis of the luminescent material. The prepared luminescent material is required to have pure three primary colors, stable luminescence and higher electroluminescent efficiency. Most of the high-performance inorganic perovskite materials prepared at the present stage are cesium-lead halide (CsPbX)3X = Cl, Br or I) quantum dots, which achieve the advantages of pure color development and high quantum yield. However, in the light emitting diode, the quantum dots need to be spin-coated to form a thin film structure, and due to the existence of the ligand on the surface of the quantum dots, the organic ligand on the surface of the quantum dots can still affect the injection of carriers even after multiple cleaning treatments. In addition, due to the cleaning of the surface ligands, the lifetime of the quantum dots can be affected, which is easily transformed into a non-luminescent non-perovskite phase, which seriously affects the performance and lifetime of the light emitting diode.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a cesium-lead-halogen perovskite thin film material and a preparation method thereof, and a light emitting diode and a preparation method thereof, wherein the present invention provides a uniform cesium-lead-halogen thin film directly grown on a substrate by using a Chemical Vapor Deposition (CVD) method, so that not only is the rapid and simple preparation of the perovskite thin film material realized, but also the influence of defects in the perovskite quantum dot thin film and surface ligands on the performance of the light emitting diode is avoided.
The invention provides a preparation method of a cesium-lead halogen perovskite thin film material, which comprises the following steps:
A) mixing cesium halide containing the same halogen element with lead halide and then grinding to obtain mixed powder;
B) and (2) placing the mixed powder in a CVD (chemical vapor deposition) tube furnace, introducing carrier gas, placing a substrate in the downstream direction of the carrier gas, raising the temperature in a furnace cavity of the tube furnace to 500-700 ℃ at the speed of 10-30 ℃/min under the condition of 100-200 Pa, keeping the temperature for 5-30 min, cooling, and growing a cesium-lead halogen perovskite thin film material on the surface of the substrate.
Preferably, the molar ratio of the cesium halide to the lead halide is (1-5): 1.
preferably, the carrier gas is selected from high-purity nitrogen or high-purity argon, and the carrier gas flow is 50-400 sccm.
Preferably, the substrate is selected from glass, gallium nitride, zinc oxide or ITO.
Preferably, the thickness of the cesium-lead halogen perovskite thin film material is 1-10 micrometers.
The invention also provides a preparation method of the light-emitting diode, which comprises the following steps:
a) sequentially compounding a cathode and an electron transport layer on the surface of a substrate to obtain an electron transport layer/cathode/substrate composite layer;
b) mixing cesium halide containing the same halogen element with lead halide and then grinding to obtain mixed powder;
placing the mixed powder in a CVD (chemical vapor deposition) tube furnace, introducing carrier gas, taking an electron transport layer/negative electrode/substrate composite layer as a substrate, placing the substrate in the downstream direction of the carrier gas, raising the temperature in a furnace cavity of the tube furnace to 500-700 ℃ at the speed of 10-30 ℃/min under the condition of 100-200 Pa, keeping the temperature for 5-30 min, cooling, and growing a cesium-lead halogen perovskite thin film material on the surface of an electron transport layer of the substrate to obtain the cesium-lead halogen perovskite thin film/electron transport layer/negative electrode/substrate composite layer;
c) and sequentially compounding a hole transport layer and a positive electrode on the surface of the cesium-lead-halogen perovskite film/electron transport layer/negative electrode/substrate composite layer to obtain the light-emitting diode.
Preferably, in step a), the substrate is selected from glass, the negative electrode is selected from ITO, and the electron transport layer is selected from a zinc oxide layer.
Preferably, in step c), the hole transport layer is selected from a 4,4 '-bis (N-carbazole) -1,1' -biphenyl layer, and the positive electrode is selected from gold.
The present invention also provides a light emitting diode, comprising:
a substrate;
the negative electrode is compounded on the surface of the substrate;
the electron transmission layer is compounded on the surface of the negative electrode;
the cesium-lead halogen perovskite thin film is compounded on the surface of the electron transport layer and is prepared by adopting a chemical vapor deposition method;
a hole transport layer compounded on the surface of the cesium-lead halide perovskite thin film;
and the positive electrode is compounded on the surface of the hole transport layer.
Preferably, the turn-on voltage of the light emitting diode is 4V, and the light emitting wavelengths of the light emitting diode are respectively 400nm, 510nm and 690 nm.
Compared with the prior art, the invention provides a preparation method of a cesium-lead halide perovskite thin film material, which comprises the following steps: A) mixing cesium halide containing the same halogen element with lead halide and then grinding to obtain mixed powder; B) and (2) placing the mixed powder in a CVD (chemical vapor deposition) tube furnace, introducing carrier gas, placing a substrate in the downstream direction of the carrier gas, raising the temperature in a furnace cavity of the tube furnace to 500-700 ℃ at the speed of 10-30 ℃/min under the condition of 100-200 Pa, keeping the temperature for 5-30 min, cooling, and growing a cesium-lead halogen perovskite thin film material on the surface of the substrate. The cesium-lead-halogen perovskite thin film material prepared by the chemical vapor deposition method provided by the invention has good crystallization quality and optical quality, and the prepared light-emitting diode has high injection current and brightness.
The result shows that the turn-on voltage of the manufactured LED is about 4V, and the light-emitting wavelengths of the manufactured LED are respectively positioned at 400nm (CsPbCl)3），510nm（CsPbBr3) And 690nm (CsPbI)3) Corresponding to the primary colors blue, green and red, respectively. The IV curve of the device shows the standard P-N junction characteristics. At 4V, the injection current was about 1.5 mA. The brightness of the device is about 4800cd/m at 4.5V2。
Drawings
Fig. 1 is a schematic structural diagram of a light emitting diode provided in the present invention;
FIG. 2 shows CsPbBr prepared3Scanning electron micrographs of the film (a) and X-ray diffraction patterns of the prepared film (b);
FIG. 3 is a CsPbCl sample prepared3Scanning electron micrographs of the film (a) and X-ray diffraction patterns of the prepared film (b);
FIG. 4 is a CsPbI prepared3Scanning electron micrographs of the film (a) and X-ray diffraction patterns of the prepared film (b);
FIG. 5 shows an I-V curve (a) of a prepared LED and an electroluminescence spectrum (b) of the prepared LED.
Detailed Description
The invention provides a preparation method of a cesium-lead halogen perovskite thin film material, which comprises the following steps:
A) mixing cesium halide containing the same halogen element with lead halide and then grinding to obtain mixed powder;
B) and (2) placing the mixed powder in a CVD (chemical vapor deposition) tube furnace, introducing carrier gas, placing a substrate in the downstream direction of the carrier gas, raising the temperature in a furnace cavity of the tube furnace to 500-700 ℃ at the speed of 10-30 ℃/min under the condition of 100-200 Pa, keeping the temperature for 5-30 min, cooling, and growing a cesium-lead halogen perovskite thin film material on the surface of the substrate.
The invention firstly mixes and grinds cesium halide containing the same halogen element and lead halide to obtain mixed powder.
Wherein the cesium halide (CsX) is selected fromFrom cesium chloride, bromide or iodide; the lead halide (PbX)2) Selected from lead chloride, lead bromide or lead iodide. Wherein the halogen element contained in the cesium halide and the lead halide is the same. The molar ratio of the cesium halide to the lead halide is (1-5): 1, preferably (2-4): 1.
placing the obtained mixed powder in a CVD (chemical vapor deposition) tube furnace, introducing carrier gas, placing a substrate in the downstream direction of the carrier gas, raising the temperature in a furnace cavity of the tube furnace to 500-700 ℃ at the speed of 10-30 ℃/min under the condition of 100-200 Pa, keeping the temperature for 5-30 min, cooling, and growing a cesium-lead halogen perovskite thin film material on the surface of the substrate.
Specifically, the mixed powder was loaded into a ceramic boat and placed in a CVD tube furnace. The substrate was placed in the tube furnace in the downstream direction of the ceramic boat carrying the mixed powder, i.e., in the downstream direction of the carrier gas.
Firstly, pumping the air pressure in the tubular furnace to 20-50 Pa, then introducing carrier gas of 50-400 sccm into the furnace chamber, keeping the pressure in the furnace chamber at 100-200 Pa after introducing the carrier gas, then raising the temperature in the furnace chamber of the tubular furnace to 500-700 ℃ at the speed of 10-30 ℃/min, keeping for 5-30 min, reacting the mixed powder in the process, growing on the surface of the substrate to obtain the cesium-lead halogen perovskite thin film material, stopping heating after the growth is finished, naturally cooling the inside of the furnace chamber, and keeping the air flow of the carrier gas and the air pressure in the furnace chamber until the temperature in the furnace chamber is reduced to below 150 ℃ to obtain the cesium-lead halogen perovskite thin film material growing on the surface of the substrate.
The carrier gas is preferably high-purity nitrogen (99.99%) or high-purity argon (99.99%), and the flow of the carrier gas is 50-400 sccm, preferably 100-350 sccm.
The heating rate of the cesium-lead halogen perovskite thin film material in the furnace cavity during growth is 10-30 ℃/min, and preferably 15-25 ℃/min. The temperature in the furnace cavity is finally raised to 500-700 ℃, preferably 550-650 ℃, and is kept at the final temperature for 5-30 min, preferably 10-25 min.
The substrate of the present invention is not particularly limited in kind, and is preferably glass, gallium nitride, zinc oxide or ITO.
The thickness of the finally obtained cesium-lead halogen perovskite thin film material is 1-10 micrometers, and preferably 3-7 micrometers.
The invention provides a chemical vapor deposition preparation method of a cesium-lead halogen perovskite thin film material, and the thin film material prepared by the method has good crystallization quality and optical quality and can be used in a light-emitting device and a photoelectric detector device.
The invention also provides a preparation method of the light-emitting diode, which comprises the following steps:
a) sequentially compounding a cathode and an electron transport layer on the surface of a substrate to obtain an electron transport layer/cathode/substrate composite layer;
b) mixing cesium halide containing the same halogen element with lead halide and then grinding to obtain mixed powder;
placing the mixed powder in a CVD (chemical vapor deposition) tube furnace, introducing carrier gas, taking an electron transport layer/negative electrode/substrate composite layer as a substrate, placing the substrate in the downstream direction of the carrier gas, raising the temperature in a furnace cavity of the tube furnace to 500-700 ℃ at the speed of 10-30 ℃/min under the condition of 100-200 Pa, keeping the temperature for 5-30 min, cooling, and growing a cesium-lead halogen perovskite thin film material on the surface of an electron transport layer of the substrate to obtain the cesium-lead halogen perovskite thin film/electron transport layer/negative electrode/substrate composite layer;
c) and sequentially compounding a hole transport layer and a positive electrode on the surface of the cesium-lead-halogen perovskite film/electron transport layer/negative electrode/substrate composite layer to obtain the light-emitting diode.
When the light-emitting diode is prepared, the energy level matching between the hole transport layer and the electron transport layer and the cesium-lead halogen perovskite thin film is required to be met as much as possible, and the hole transport layer and the electron transport layer also have good electrical characteristics.
Therefore, CBP (4,4 '-Bis (N-carbazole) -1,1' -biphenyl, 4,4 '-Bis (N-carbazolyl) -1,1' -biphenol) is selected as a hole transport layer of the light-emitting diode, and zinc oxide is selected as an electron transport layer of the light-emitting diode. And gold and ITO (indium tin oxide) glass are respectively used as electrodes at the positive end and the negative end. The light-emitting surface of the device is ITO glass.
Firstly, sequentially compounding a cathode and an electron transmission layer on the surface of a substrate to obtain an electron transmission layer/cathode/substrate composite layer;
specifically, a negative electrode (ITO (indium tin oxide) glass) is subjected to ultrasonic cleaning by using a solvent, then a zinc oxide nanoparticle solution is coated on the surface of the negative electrode, and then annealing is carried out for 5-25 minutes at 350-500 ℃ to obtain an electron transport layer/negative electrode/substrate composite layer.
Wherein, the solvent is selected from one or more of ethanol, acetone and deionized water. The coating method is selected from spin coating, the speed of the spin coating is 1000-2000 r/min, and the time of the spin coating is 30-60 seconds. The concentration of the zinc oxide nanoparticle solution is 0.05-0.15 g/ml, preferably 0.08-0.12 g/ml. The annealing temperature is preferably 400-450 ℃, and the annealing time is preferably 10-20 minutes.
Next, depositing a cesium-lead-halogen perovskite thin film material on the surface of the electron transport layer/negative electrode/substrate composite layer by using the chemical vapor deposition method described above, namely:
mixing cesium halide containing the same halogen element with lead halide and then grinding to obtain mixed powder;
placing the mixed powder in a CVD (chemical vapor deposition) tube furnace, introducing carrier gas, taking an electron transport layer/negative electrode composite layer as a substrate, placing the mixed powder in the downstream direction of the carrier gas, raising the temperature in a furnace cavity of the tube furnace to 500-700 ℃ at the speed of 10-30 ℃/min under the condition of 100-200 Pa, keeping the temperature for 5-30 min, cooling, and growing a cesium-lead-halogen perovskite thin film material on the surface of an electron transport layer of the substrate to obtain the cesium-lead-halogen perovskite thin film/electron transport layer/negative electrode composite layer;
the specific process parameters related to the method are the same as those of the method for preparing the cesium-lead-halogen perovskite thin film material, and are not described herein again, but only the substrate is an electron transport layer/negative electrode/substrate composite layer.
And finally, sequentially compounding a hole transport layer and an anode on the surface of the cesium-lead-halogen perovskite film/electron transport layer/cathode/substrate composite layer to obtain the light-emitting diode.
Specifically, a CBP film is coated on the surface of the cesium lead halogen perovskite film/electron transport layer/negative electrode/substrate composite layer.
Wherein, CBP solution is coated on the surface of the film, and the solvent of the CBP solution is chloroform (CHCl)3) The concentration is 5-15 mg/ml, preferably 8-12 mg/ml.
And then, evaporating a gold film with the thickness of 50-100 nm on the CBP film by a vacuum thermal evaporation method to be used as a positive electrode.
The invention also provides a light-emitting diode prepared by the preparation method, which comprises the following steps:
a substrate;
the negative electrode is compounded on the surface of the substrate;
the electron transmission layer is compounded on the surface of the negative electrode;
the cesium-lead halogen perovskite thin film is compounded on the surface of the electron transport layer;
a hole transport layer compounded on the surface of the cesium-lead halide perovskite thin film;
and the positive electrode is compounded on the surface of the hole transport layer.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a light emitting diode provided by the present invention. In fig. 1,1 is a gold electrode, 2 is CBP, 3 is a perovskite thin film, 4 is zinc oxide, 5 is ITO, and 6 is a glass substrate.
The turn-on voltage of the manufactured LED is about 4V, and the light-emitting wavelengths of the manufactured LED are respectively positioned at 400nm (CsPbCl)3），510nm（CsPbBr3) And 690nm (CsPbI)3) Corresponding to the primary colors blue, green and red, respectively. The IV curve of the device shows the standard P-N junction characteristics. At 4V, the injection current was about 1.5 mA. The brightness of the device is about 4800cd/m at 4.5V2。
The invention provides a method for directly growing a uniform cesium-lead halide film on a substrate by using a Chemical Vapor Deposition (CVD) method, so that the rapid and simple preparation of a perovskite film material is realized, and the defects in the perovskite quantum dot film and the influence of surface ligands on the performance of a light-emitting diode are avoided.
The cesium-lead-halogen perovskite thin film material prepared by the chemical vapor deposition method provided by the invention has good crystallization quality and optical quality, and the prepared light-emitting diode has high injection current and brightness.
For further understanding of the present invention, the cesium lead halogen perovskite thin film material and the light emitting diode and the method for manufacturing the same provided by the present invention are described below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
Cesium bromide and lead bromide (CsBr and PbBr)2) In a molar ratio of 2: 1 are mixed together and milled to a uniform powder. The mixed powder was charged into a ceramic boat and placed in a CVD tube furnace. The glass substrate was placed in the downstream direction of the gas flow of a ceramic boat carrying the raw material powder in a tube furnace. Firstly, the air pressure in the tube furnace is pumped to 30 Pa by a mechanical pump, and then high-purity argon (99.99%) of 250sccm is introduced into the furnace chamber to be used as protective gas and carrier gas. After the argon gas was introduced, the pressure in the furnace chamber was kept at 140 Pa. The temperature in the tube furnace chamber was raised to 600 ℃ at a rate of 20 ℃/min and held for 15 minutes. And stopping heating after the growth is finished, naturally cooling the furnace chamber, and keeping the growth airflow and the air pressure until the temperature in the furnace chamber is reduced to below 150 ℃. The thickness of the grown cesium lead bromine perovskite thin film is 5 microns.
FIG. 2 shows CsPbBr prepared in FIG. 23Scanning electron microscope image (a) of the film and X-ray diffraction image (b) of the prepared film. From the scanning electron micrograph of the sample, the grown sample is a dense thin film structure. The sample is a standard cesium lead bromine perovskite structure as can be seen from the X-ray diffraction pattern. The half-peak width of the diffraction peak is narrow, and no impurity peak exists, so that the grown film structure has good crystallization quality.
Example 2
Mixing cesium chloride with lead chloride (CsCl and PbCl)2) In a molar ratio of 2: 1 are mixed together and milled to a uniform powder. Loading the mixed powder into a ceramic boatAnd placed in a CVD tube furnace. The glass substrate was placed in the downstream direction of the gas flow of a ceramic boat carrying the raw material powder in a tube furnace. Firstly, the air pressure in the tube furnace is pumped to 40 Pa by a mechanical pump, and then high-purity argon (99.99%) of 300sccm is introduced into the furnace chamber to be used as a protective gas and a carrier gas. After the argon gas was introduced, the pressure in the furnace chamber was maintained at 150 Pa. The temperature in the tube furnace chamber was raised to 600 ℃ at a rate of 20 ℃/min and held for 15 minutes. And stopping heating after the growth is finished, naturally cooling the furnace chamber, and keeping the growth airflow and the air pressure until the temperature in the furnace chamber is reduced to below 150 ℃. The thickness of the grown cesium lead chloromalctite film is 6 microns.
FIG. 3 shows CsPbCl prepared in FIG. 33Scanning electron microscope image (a) of the film and X-ray diffraction image (b) of the prepared film. From the scanning electron micrograph of the sample, the grown sample is a dense thin film structure. The X-ray diffraction pattern shows that the sample is a standard cesium lead chloromalctite structure. The half-peak width of the diffraction peak is narrow, and no impurity peak exists, so that the grown film structure has good crystallization quality.
Example 3
Mixing cesium iodide with lead iodide (CsI and PbI)2) According to a molar ratio of 3: 1 are mixed together and milled to a uniform powder. The mixed powder was charged into a ceramic boat and placed in a CVD tube furnace. The glass substrate was placed in the downstream direction of the gas flow of a ceramic boat carrying the raw material powder in a tube furnace. Firstly, the air pressure in the tube furnace is pumped to 40 Pa by a mechanical pump, and then high-purity argon (99.99%) of 300sccm is introduced into the furnace chamber to be used as a protective gas and a carrier gas. After the argon gas was introduced, the pressure in the furnace chamber was maintained at 150 Pa. The temperature in the tube furnace chamber was raised to 650 ℃ at a rate of 20 ℃/min and held for 15 minutes. And stopping heating after the growth is finished, naturally cooling the furnace chamber, and keeping the growth airflow and the air pressure until the temperature in the furnace chamber is reduced to below 150 ℃. The thickness of the grown cesium lead iodoperovskite film is 4 microns. FIG. 4 shows CPbI prepared in FIG. 43Scanning electron microscope image (a) of the film and X-ray diffraction image (b) of the prepared film. From the scanning electron micrograph of the sampleThe grown sample is a dense film structure. The X-ray diffraction pattern shows that the sample is a standard cesium lead iodoperovskite structure. The half-peak width of the diffraction peak is narrow, and no impurity peak exists, so that the grown film structure has good crystallization quality.
Example 4
And ultrasonically cleaning the ITO glass by using solvents such as ethanol, acetone, deionized water and the like. Then 0.1g/ml zinc oxide nanoparticle solution was coated on the ITO substrate by spin coating at 1500 r/min for 40 seconds. Subsequently, the substrate on which the zinc oxide nanoparticles were spin-coated was annealed in a tube furnace at a temperature of 400 ℃ for 15 minutes in an atmospheric atmosphere. Cesium bromide and lead bromide (CsBr and PbBr)2) In a molar ratio of 2: 1 are mixed together and milled to a uniform powder. The mixed powder was charged into a ceramic boat and placed in a CVD tube furnace. The substrate was placed in the tube furnace in the downstream direction of the gas flow of a ceramic boat carrying the feedstock powder. Firstly, the air pressure in the tube furnace is pumped to 30 Pa by a mechanical pump, and then high-purity argon (99.99%) of 250sccm is introduced into the furnace chamber to be used as protective gas and carrier gas. After the argon gas was introduced, the pressure in the furnace chamber was kept at 140 Pa. The temperature in the tube furnace chamber was raised to 600 ℃ at a rate of 20 ℃/min and held for 10 minutes. And stopping heating after the growth is finished, naturally cooling the furnace chamber, and keeping the growth airflow and the air pressure until the temperature in the furnace chamber is reduced to below 150 ℃. The CBP film is continuously spin-coated at a speed of 2000-. The solvent of the CBP solution is chloroform (CHCl)3) The concentration was 12mg/ml and the spin coating time was 40 seconds. And (3) evaporating a gold film with the thickness of 80 nm on the CBP film by using a vacuum thermal evaporation method to be used as an electrode.
Referring to fig. 5, fig. 5 shows an I-V curve (a) of the fabricated light emitting diode and an electroluminescence spectrum (b) of the fabricated light emitting diode. As can be seen from FIG. 5, the turn-on voltage of the fabricated LED was 3.5V, the injection current at this voltage was 1.8mA, the emission wavelength of the LED was 510nm, and the luminance was 4920cd/m2。
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 (6)
1. A preparation method of a light-emitting diode is characterized by comprising the following steps:
a) sequentially compounding a cathode and an electron transport layer on the surface of a substrate to obtain an electron transport layer/cathode/substrate composite layer; the electron transport layer is selected from a zinc oxide layer;
b) mixing cesium halide containing the same halogen element with lead halide and then grinding to obtain mixed powder;
the cesium halide is selected from cesium chloride, cesium bromide or cesium iodide; the lead halide is selected from lead chloride, lead bromide or lead iodide;
the molar ratio of the cesium halide to the lead halide is (2-3): 1;
placing the mixed powder in a CVD (chemical vapor deposition) tube furnace, introducing carrier gas, taking an electron transport layer/negative electrode/substrate composite layer as a substrate, placing the tube furnace in the downstream direction of the carrier gas, raising the temperature in a furnace cavity of the tube furnace to 500-700 ℃ at the speed of 10-30 ℃/min under the condition of 100-200 Pa, keeping the temperature for 5-30 min, cooling, and growing a cesium-lead halogen perovskite thin film material on the surface of an electron transport layer of the substrate to obtain the cesium-lead halogen perovskite thin film/electron transport layer/negative electrode/substrate composite layer, wherein the thickness of the cesium-lead halogen perovskite thin film material is 1-10 microns;
the carrier gas is high-purity argon, and the carrier gas flow is 250-300 sccm;
c) and sequentially compounding a hole transport layer and a positive electrode on the surface of the cesium-lead-halogen perovskite film/electron transport layer/negative electrode/substrate composite layer to obtain the light-emitting diode.
2. The preparation method according to claim 1, wherein the molar ratio of cesium halide to lead halide is (1-5): 1.
3. the method according to claim 1, wherein in step a), the substrate is selected from glass and the negative electrode is selected from ITO.
4. The method according to claim 1, wherein in step c), the hole transport layer is selected from a 4,4 '-bis (N-carbazole) -1,1' -biphenyl layer, and the positive electrode is selected from gold.
5. A light-emitting diode prepared by the preparation method of any one of claims 1 to 4, which is characterized by comprising:
a substrate;
the negative electrode is compounded on the surface of the substrate;
the electron transmission layer is compounded on the surface of the negative electrode;
the cesium-lead halogen perovskite thin film is compounded on the surface of the electron transport layer and is prepared by adopting a chemical vapor deposition method;
a hole transport layer compounded on the surface of the cesium-lead halide perovskite thin film;
and the positive electrode is compounded on the surface of the hole transport layer.
6. The LED of claim 5, wherein the turn-on voltage of the LED is 4V, and the light emission wavelengths thereof are 400nm, 510nm and 690nm, respectively.
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| CN114959886A (en) * | 2022-05-30 | 2022-08-30 | 西安交通大学 | Branched CsPbBr prepared by vapor phase growth 3 Method for preparing nanocrystalline thin film |
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