CN112331793A - Light-emitting diode based on zero-dimensional metal halide and preparation method thereof - Google Patents
Light-emitting diode based on zero-dimensional metal halide and preparation method thereof Download PDFInfo
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- 229910001507 metal halide Inorganic materials 0.000 title claims abstract description 30
- 150000005309 metal halides Chemical class 0.000 title claims abstract description 30
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims abstract description 34
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920000144 PEDOT:PSS Polymers 0.000 claims abstract description 20
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims description 99
- 239000010408 film Substances 0.000 claims description 60
- 238000004528 spin coating Methods 0.000 claims description 35
- 238000000137 annealing Methods 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001704 evaporation Methods 0.000 claims description 20
- 230000008020 evaporation Effects 0.000 claims description 20
- 238000002347 injection Methods 0.000 claims description 19
- 239000007924 injection Substances 0.000 claims description 19
- 230000005525 hole transport Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000007738 vacuum evaporation Methods 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims 1
- 238000005286 illumination Methods 0.000 abstract description 3
- 239000002346 layers by function Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 42
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- -1 (4-phenyl) (4-butylphenyl) amine Chemical class 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 8
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- ZPJTXKYUASWFBE-UHFFFAOYSA-N C(C=C1)=CC=C1P(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.Cl Chemical compound C(C=C1)=CC=C1P(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.Cl ZPJTXKYUASWFBE-UHFFFAOYSA-N 0.000 description 1
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- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Abstract
The invention discloses a light-emitting diode based on zero-dimensional metal halide and a preparation method thereof. The light emitting diode comprises a solution and a device structure, wherein the solution comprises PEDOT PSS, a Poly-TPD solution dissolved in chlorobenzene and Ph dissolved in DMSO4PCl and SbCl3Solution of Ph4PCl and SbCl3In a molar ratio of 2: 1. the device structure is ITO/PEDOT: PSS/Poly-TPD/(Ph)4P2)SbCl5TPBi/LiF/Al. Thereby realizing the orange electroluminescent device of the zero-dimensional metal halide to promote the application of the zero-dimensional metal halide in display illumination. The functional layers in the invention are environment-friendly, the preparation method is simple and convenient, and the invention is simultaneously suitable for other zero-dimensional metal halides and has good application prospect.
Description
Technical Field
The invention belongs to the field of electroluminescent devices, and particularly relates to a light-emitting diode based on zero-dimensional metal halide and a preparation method thereof.
Background
In recent years, organic-inorganic hybrid zero-dimensional metal halide materials have attracted extensive attention due to their superior photoelectric properties, and have shown great potential in light emitting diodes, solar cells, sensors, and the like.
At present, the fluorescence quantum yield of organic-inorganic hybrid zero-dimensional metal halides can reach 100% at most (J.Am.chem.Soc.2020,142,31,13582-13589), wherein the lead-halogen perovskite is most used for research, but the lead-halogen perovskite material is unstable in air and is easily decomposed by the influence of water and oxygen. Although many researchers now improve the chemical stability of lead-halo-perovskites by reducing their dimensions, the lead atoms contained therein have serious effects on the environment and humans, thereby limiting their practical applications. To solve this problem, most researchers have looked at lead-free metal halides, and it is common to replace the lead Pb atom with copper Cu, bismuth Bi, manganese Mn, antimony Sb, etc. (adv. Mater.2017, 1605739; chem. Mater.2018,30,7, 2374-. There are many reports on both of the blue-emitting Cu-based metal halide and the green-emitting Mn-based metal halide, but no study has been made on the Sb-based orange-emitting light emitting diode. Therefore, the research on the light emitting diode based on the Sb-based metal halide has a very important research value, which will promote the further development of the display illumination field.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a light-emitting diode based on a zero-dimensional metal halide material and a preparation method thereof.
The technical scheme of the invention is realized in the following mode: a light-emitting diode based on zero-dimensional metal halide material comprises an ITO substrate and a thin film layer coated on the ITO substrate, wherein the thin film layer is formed by the modes of solution spin coating, high-temperature annealing and evaporation;
the device structure of the light-emitting diode is ITO/PEDOT: PSS/Poly-TPD/(Ph)4P)2SbCl5/TPBi/LiF/Al；
Comprises a solution and a device structure, wherein the solution comprises poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT: PSS), poly [ bis (4-phenyl) (4-butylphenyl) amine dissolved in chlorobenzene](Poly-TPD) solution and tetraphenylphosphine chloride Ph dissolved in dimethyl sulfoxide (DMSO)4PCl and SbCl3Solution of Ph4PCl and SbCl3In a molar ratio of 2: 1.
preferably, the light emitting diode is an orange light emitting diode.
In order to better realize the device, the invention also provides a preparation method of the light-emitting diode based on the zero-dimensional metal halide, which comprises the following specific steps:
s1, selecting raw materials:
by Ph4PCl,SbCl3The powder is prepared by the following steps: 1 molar ratio, the sample is taken and dissolved in DMSO solution.
S2: ITO substrate processing
Putting the ITO substrate into a polytetrafluoroethylene beaker, adding a cleaning agent D90 and deionized water, ultrasonically oscillating for 15min, taking out the ITO, and repeatedly washing the ITO substrate for 3 or 4 times by using the deionized water; sequentially placing the washed ITO substrate into a beaker filled with deionized water, absolute ethyl alcohol, acetone and isopropanol and polytetrafluoroethylene, and respectively carrying out ultrasonic oscillation for 15 min; the cleaned ITO substrate was blow-dried with a nitrogen gun and treated with ultraviolet plasma for 15 min.
S3: preparation of hole injection layer
And (3) placing the ITO substrate processed in the step S2 in a spin coater, spin-coating at 4000rpm for 45S to obtain a hole injection layer PEDOT/PSS film, and annealing the spin-coated PEDOT/PSS film at 150 ℃ for 30min to obtain the ITO substrate covered by the PEDOT/PSS.
S4: preparation of hole transport layer
And (3) placing the ITO substrate spin-coated by S3 in a spin coater in a glove box, then spin-coating at 2000rpm for 45S to obtain a hole transport layer Poly-TPD film, and annealing the Poly-TPD film obtained by spin coating at 120 ℃ for 20min to obtain the ITO substrate coated with PEDOT: PSS and covered by the Poly-TPD film.
S5: light emitting layer (Ph)4P)2SbCl5Preparation of the film
The ITO substrate spin-coated in S4 was placed in a spin coater in a glove box, followed by spin coating (Ph)4P)2SbCl5Film, finally annealing to obtain (Ph)4P)2SbCl5Film-coated ITO substrate coated with Poly-TPD and PEDOT: PSS.
S6: preparation of thin film of electron transport layer TPBi
Placing the ITO substrate treated by S5 on an organic mask plate and placing the ITO substrate in a vacuum evaporation machine, and then controlling the evaporation rate of TPBi
Finally, a coating (Ph) covered with a TPBi film is obtained4P)2SbCl5Poly-TPD and PEDOT: ITO substrate of PSS.
S7: preparation of electron injection layer LiF and electrode Al
Placing the ITO substrate treated by S6 on an electrode mask plate and placing the electrode mask plate in a vacuum evaporation machine, and then respectively controlling the evaporation rate of LiF to be
The evaporation rate of the electrode Al is in
Finally obtaining the product with the structure of ITO/PEDOT: PSS/Poly-TPD/(Ph)4P)2SbCl5a/TPBi/LiF/Al device.
Preferably, in the S1 step, the size of the ITO substrate is 1.5cm by 1.5 cm.
Preferably, in step S4, the oxygen value of the ambient water in the glove box is less than 1 pmm.
Preferably, in the step S5, the spin-coating speed is 4000rpm, the spin-coating time is 70S, the annealing temperature is 100 ℃, and the annealing time is 30 min.
Preferably, in step S6, the pressure of the vacuum evaporator is less than 4 × 10-6And (4) supporting.
Compared with the prior art, the invention adopting the technical scheme has the following technical effects:
(1) this scheme proves (Ph)4P)2SbCl5The material can be used for a light-emitting layer in a light-emitting diode, which is a first example of the light-emitting diode of the electrically-trapped exciton based on zero-dimensional organic-inorganic hybrid metal halide under the room temperature condition, a hole injection layer, a hole transport layer and a light-emitting layer of the light-emitting diode are all prepared by a solution method, orange light is emitted at the room temperature, the light is turned on at 3.8V, and the brightness of the light-emitting diode at 6V exceeds 80Cd/m2。
(2) The preparation method of the light-emitting diode is simple, each functional layer is environment-friendly, and the light-emitting diode does not contain toxic heavy metals such as lead and the like, and is suitable for mass production; this utilization (Ph)4P)2SbCl5The preparation method of the device with the material as the luminescent layer is also suitable for other zero-dimensional metal halides so as to promote the development of the future display illumination field.
Drawings
Fig. 1 is a schematic structural view of an LED device of embodiment 1 of the present invention;
FIG. 2 shows (Ph) in example 1 of the present invention4P)2SbCl5Normalized PL and EL spectra of (a);
fig. 3 is a graph of the Current density (Current D) and luminance (L) output characteristics as a function of voltage for the LED device of embodiment 1 of the present invention;
fig. 4 is a graph of External Quantum Efficiency (EQE) as a function of L for an LED device of example 1 of the present invention.
Detailed Description
The technical solution in the embodiments of the present invention will be fully and clearly described below with reference to the embodiments of the present invention and the accompanying drawings. It should be noted that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Example 1
The zero-dimensional metal halide-based light emitting diode of the present example comprises a solution and a device structure, wherein the solution comprises PEDOT PSS, a solution of Poly-TPD dissolved in chlorobenzene, and Ph dissolved in DMSO4PCl and SbCl3Solution of Ph4PCl and SbCl3In a molar ratio of 2: 1. the device structure is shown in FIG. 1 and is ITO/PEDOT: PSS/Poly-TPD/(Ph)4P2)SbCl5TPBi/LiF/Al. The light emitting diode is an orange light emitting diode.
The preparation method of the zero-dimensional metal halide-based light-emitting diode comprises the following steps:
s1: selecting raw materials:
by Ph4PCl、SbCl3The powder is prepared by the following steps: 1 molar ratio, wherein Ph422.8mg of SbCl are weighed out in PCl375.0mg was weighed and dissolved in 1.956mL of DMSO solution;
12mg of Poly-TPD was weighed out and dissolved in 2mL of chlorobenzene solution.
S2: ITO substrate processing
Putting the ITO substrate into a polytetrafluoroethylene beaker, adding a cleaning agent D90 and deionized water, ultrasonically oscillating for 15min, taking out the ITO, and repeatedly washing the ITO substrate for 3 or 4 times by using the deionized water; sequentially placing the washed ITO substrate into a beaker filled with deionized water, absolute ethyl alcohol, acetone and isopropanol and polytetrafluoroethylene, and respectively carrying out ultrasonic oscillation for 15 min; the cleaned ITO substrate was blow-dried with a nitrogen gun and treated with ultraviolet plasma for 15 min.
S3: preparation of hole injection layer
And (3) placing the ITO substrate processed in the step S2 in a spin coater, spin-coating at 4000rpm for 45S to obtain a hole injection layer PEDOT/PSS film, and annealing the spin-coated PEDOT/PSS film at 150 ℃ for 30min to obtain the ITO substrate covered by the PEDOT/PSS.
S4: preparation of hole transport layer
And (3) placing the ITO substrate spin-coated by S3 in a spin coater in a glove box, then spin-coating at 2000rpm for 45S to obtain a hole transport layer Poly-TPD film, and annealing the Poly-TPD film obtained by spin coating at 120 ℃ for 20min to obtain the ITO substrate coated with PEDOT: PSS and covered by the Poly-TPD film.
S5: light emitting layer (Ph)4P)2SbCl5Preparation of the film
The ITO substrate spin-coated in S4 was placed in a spin coater in a glove box, followed by spin coating (Ph)4P)2SbCl5Film, finally annealing to obtain (Ph)4P)2SbCl5Film-coated ITO substrate coated with Poly-TPD and PEDOT: PSS.
S6: preparation of thin film of electron transport layer TPBi
Placing the ITO substrate treated by S5 on an organic mask plate and placing the ITO substrate in a vacuum evaporation machine, and then controlling the evaporation rate of TPBi
Finally, a coating (Ph) covered with a TPBi film is obtained4P)2SbCl5Poly-TPD and PEDOT: ITO substrate of PSS.
S7: preparation of electron injection layer LiF and electrode Al
Placing the ITO substrate treated by S6 on an electrode mask plate and placing the electrode mask plate in a vacuum evaporation machine, and then respectively controlling the evaporation rate of LiF to be
The evaporation rate of the electrode Al is in
Finally obtaining the product with the structure of ITO/PEDOT, PSS (40nm)/Poly-TPD (30 nm)/(Ph)4P)2SbCl5(60-70 nm)/TPBi (50-60 nm)/LiF (1.5nm)/Al (100 nm).
In step S1, the size of the ITO glass substrate is 1.5cm by 1.5 cm. In step S4, the environment of the glove box is such that the water oxygen values are all less than 1 ppm. In the step S5, the spin coating (Ph)4P)2SbCl5Turning of filmThe speed is 4000rpm, and the spin coating time is 70 s; the annealing temperature is 100 ℃, and the annealing time is 30 min. In step S6, the pressure of the vacuum evaporator is 4 × 10-6And (4) supporting.
Wherein (Ph)4P)2SbCl5The preparation method of the film comprises the following steps: according to Ph4PCl:SbCl3Respectively weighing Ph according to the molar ratio of 2:14PCl and SbCl3And dissolving the mixture in a DMSO solution, and stirring the mixture on a magnetic stirrer for 12 hours to completely dissolve the mixture. Dropping 60mL of solution on ITO glass, depositing at 4000rpm for 70s, and annealing at 100 deg.C for 30min to obtain (Ph)4P)2SbCl5A film.
FIG. 2 shows (Ph)4P)2SbCl5The emission spectrum of the film is red-shifted from the electroluminescence spectrum of the device, compared to the spectrum of the photoluminescent film. This is mainly due to the fact that electrons and holes are spatially separated from each other during electroluminescence, which causes a reduction in the energy of the trapped excitons upon recombination compared to photoluminescence, resulting in a red shift of the spectrum.
FIG. 3 is a diagram showing the current density and luminance output characteristics of the device as a function of voltage, and it can be seen from the diagram that when the device is at 3V, the current starts to be injected, the lighting voltage of the device is 3.8V, and when the device is at 6V, the luminance of the device reaches 85Cd/m2The current at this time was 9.5mA/cm2。
Fig. 4 is a functional diagram of external quantum efficiency and luminance of the device, and it can be known that the external quantum efficiency is gradually reduced in the process of gradually increasing luminance of the device, but the reduction range is not large, which indicates that the device is relatively stable.
Example 2
The zero-dimensional metal halide-based light emitting diode of the present example comprises a solution and a device structure, wherein the solution comprises PEDOT, PSS, a mixed solution of Poly-TPD and TPD dissolved in chlorobenzene, and Ph dissolved in DMSO4PCl and SbCl3In which Ph is4PCl and SbCl3In a molar ratio of 2: 1. the device structure is shown in FIG. 1, which is ITO/PEDOT: PSS/Poly-TPD (TPD)/(Ph)4P2)SbCl5TPBi/LiF/Al. The light emitting diode is an orange light emitting diode.
The preparation method of the zero-dimensional metal halide-based light-emitting diode comprises the following steps:
s1: selecting raw materials:
by Ph4PCl、SbCl3The powder is prepared by the following steps: 1 molar ratio, wherein Ph422.8mg of SbCl are weighed out in PCl375.0mg was weighed and dissolved in 1.956mL of DMSO solution;
12mg of Poly-TPD and 2mg of TPD were weighed out and dissolved in 2mL of chlorobenzene solution.
S2: ITO substrate processing
Putting the ITO substrate into a polytetrafluoroethylene beaker, adding a cleaning agent D90 and deionized water, ultrasonically oscillating for 15min, taking out the ITO, and repeatedly washing the ITO substrate for 3 or 4 times by using the deionized water; sequentially placing the washed ITO substrate into a beaker filled with deionized water, absolute ethyl alcohol, acetone and isopropanol and polytetrafluoroethylene, and respectively carrying out ultrasonic oscillation for 15 min; the cleaned ITO substrate was blow-dried with a nitrogen gun and treated with ultraviolet plasma for 15 min.
S3: preparation of hole injection layer
And (3) placing the ITO substrate processed in the step S2 in a spin coater, spin-coating at 3000rpm for 45S to obtain a hole injection layer PEDOT/PSS film, and annealing the spin-coated PEDOT/PSS film at 120 ℃ for 30min to obtain the ITO substrate covered by the PEDOT/PSS.
S4: preparation of hole transport layer
And (3) placing the ITO substrate spin-coated by S3 in a spin coater in a glove box, then spin-coating at 3000rpm for 45S to obtain a mixed film of a hole transport layer Poly-TPD (TPD), and annealing the Poly-TPD film mixed with TPD obtained by spin coating at 120 ℃ for 20min to obtain the ITO substrate coated with PEDOT: PSS and covered by the Poly-TPD film.
S5: light emitting layer (Ph)4P)2SbCl5Preparation of the film
The ITO substrate spin-coated in S4 was placed in a spin coater in a glove box, followed by spin coating (Ph)4P)2SbCl5Film, finally annealing to obtain (Ph)4P)2SbCl5Film-coated ITO substrate coated with Poly-TPD and PEDOT: PSS.
S6: preparation of thin film of electron transport layer TPBi
Placing the ITO substrate treated by S5 on an organic mask plate and placing the ITO substrate in a vacuum evaporation machine, and then controlling the evaporation rate of TPBi
Finally, a coating (Ph) covered with a TPBi film is obtained4P)2SbCl5Poly-TPD and PEDOT: ITO substrate of PSS.
S7: preparation of electron injection layer LiF and electrode Al
Placing the ITO substrate treated by S6 on an electrode mask plate and placing the electrode mask plate in a vacuum evaporation machine, and then respectively controlling the evaporation rate of LiF to be
The evaporation rate of the electrode Al is in
Finally obtaining the product with the structure of ITO/PEDOT, PSS (40-60nm)/Poly-TPD (20-30 nm)/(Ph)4P)2SbCl5(40-80 nm)/TPBi (50-60 nm)/LiF (1.5nm)/Al (100 nm).
In step S1, the size of the ITO glass substrate is 1.5cm by 1.5 cm. In step S4, the environment of the glove box is such that the water oxygen values are all less than 1 ppm. In the step S5, the spin coating (Ph)4P)2SbCl5The rotating speed of the film is 3000rpm, and the spin coating time is 100 s; the annealing temperature is 120 ℃, and the annealing time is 30 min. In step S6, the pressure of the vacuum evaporator is 4 × 10-6And (4) supporting.
The main luminescence spectrum, current-voltage-brightness curve and external quantum efficiency curve are similar to those of example 1.
Example 3
The zero-dimensional metal halide-based light emitting diode of the present example comprises a solution and a device structure, wherein the solution comprises PEDOT PSS, a solution of Poly-TPD in chlorobenzene, and Ph in dichloromethane4PCl and SbCl3In which Ph is4PCl and SbCl3In a molar ratio of 2: 1. the device structure is shown in FIG. 1 and is ITO/PEDOT: PSS/Poly-TPD/(Ph)4P2)SbCl5TPBi/LiF/Al. The light emitting diode is an orange light emitting diode.
The preparation method of the zero-dimensional metal halide-based light-emitting diode comprises the following steps:
s1: selecting raw materials:
by Ph4PCl、SbCl3The powder is prepared by the following steps: 1 molar ratio, wherein Ph422.8mg of SbCl are weighed out in PCl375.0mg was weighed and dissolved in 1.956mL of a mixed solution of dichloromethane and 0.5mL of the surfactant Triton;
12mg of Poly-TPD was weighed out and dissolved in 2mL of chlorobenzene solution.
S2: ITO substrate processing
Putting the ITO substrate into a polytetrafluoroethylene beaker, adding a cleaning agent D90 and deionized water, ultrasonically oscillating for 15min, taking out the ITO, and repeatedly washing the ITO substrate for 3 or 4 times by using the deionized water; sequentially placing the washed ITO substrate into a beaker filled with deionized water, absolute ethyl alcohol, acetone and isopropanol and polytetrafluoroethylene, and respectively carrying out ultrasonic oscillation for 15 min; the cleaned ITO substrate was blow-dried with a nitrogen gun and treated with ultraviolet plasma for 15 min.
S3: preparation of hole injection layer
And (3) placing the ITO substrate processed in the step S2 in a spin coater, spin-coating at 3000rpm for 45S to obtain a hole injection layer PEDOT/PSS film, and annealing the spin-coated PEDOT/PSS film at 100 ℃ for 30min to obtain the ITO substrate covered by the PEDOT/PSS.
S4: preparation of hole transport layer
And (3) placing the ITO substrate spin-coated by S3 in a spin coater in a glove box, then spin-coating at 4000rpm for 45S to obtain a mixed film of a hole transport layer Poly-TPD (TPD), and annealing the Poly-TPD film mixed with TPD obtained by spin coating at 120 ℃ for 20min to obtain the ITO substrate coated with the PEDOT: PSS and covered by the Poly-TPD film.
S5: light emitting layer (Ph)4P)2SbCl5Preparation of the film
The ITO substrate spin-coated in S4 was placed in a spin coater in a glove box, followed by spin coating (Ph)4P)2SbCl5Film, finally annealing to obtain (Ph)4P)2SbCl5Film-coated ITO substrate coated with Poly-TPD and PEDOT: PSS.
S6: preparation of thin film of electron transport layer TPBi
Placing the ITO substrate treated by S5 on an organic mask plate and placing the ITO substrate in a vacuum evaporation machine, and then controlling the evaporation rate of TPBi
Finally, a coating (Ph) covered with a TPBi film is obtained4P)2SbCl5Poly-TPD and PEDOT: ITO substrate of PSS.
S7: preparation of electron injection layer LiF and electrode Al
Placing the ITO substrate treated by S6 on an electrode mask plate and placing the electrode mask plate in a vacuum evaporation machine, and then respectively controlling the evaporation rate of LiF to be
The evaporation rate of the electrode Al is in
Finally obtaining the product with the structure of ITO/PEDOT, PSS (40-60nm)/Poly-TPD (20-30 nm)/(Ph)4P)2SbCl5(40-80 nm)/TPBi (50-60 nm)/LiF (1.5nm)/Al (100 nm).
In step S1, the size of the ITO glass substrate is 1.5cm by 1.5 cm. In step S4, the environment of the glove box is such that the water oxygen values are all less than 1 ppm. In the step S5, theSpin coating (Ph)4P)2SbCl5The rotating speed of the film is 3000rpm, and the spin coating time is 100 s; the annealing temperature is 120 ℃, and the annealing time is 30 min. In step S6, the pressure of the vacuum evaporator is 4 × 10-6And (4) supporting.
The main luminescence spectrum, current-voltage-brightness curve and external quantum efficiency curve are similar to those of example 1.
Example 4
The zero-dimensional metal halide-based light emitting diode of the present example comprises a solution and a device structure, wherein the solution comprises PEDOT PSS, a solution of poly (9-vinylcarbazole) PVK in chlorobenzene, and Ph in DMSO4PCl and SbCl3In which Ph is4PCl and SbCl3In a molar ratio of 2: 1. the device structure is shown in FIG. 1, and is ITO/PEDOT: PSS/PVK/(Ph)4P2)SbCl5TPBi/LiF/Al. The light emitting diode is an orange light emitting diode.
The preparation method of the zero-dimensional metal halide-based light-emitting diode comprises the following steps:
s1: selecting raw materials:
by Ph4PCl、SbCl3The powder is prepared by the following steps: 1 molar ratio, wherein Ph422.8mg of SbCl are weighed out in PCl3Weighing 75.0mg, and dissolving in 1.956mL of mixed solution of DMSO and 0.5mL of surfactant triton;
10mg of PVK was weighed out and dissolved in 2mL of chlorobenzene solution.
S2: ITO substrate processing
Putting the ITO substrate into a polytetrafluoroethylene beaker, adding a cleaning agent D90 and deionized water, ultrasonically oscillating for 15min, taking out the ITO, and repeatedly washing the ITO substrate for 3 or 4 times by using the deionized water; sequentially placing the washed ITO substrate into a beaker filled with deionized water, absolute ethyl alcohol, acetone and isopropanol and polytetrafluoroethylene, and respectively carrying out ultrasonic oscillation for 15 min; the cleaned ITO substrate was blow-dried with a nitrogen gun and treated with ultraviolet plasma for 15 min.
S3: preparation of hole injection layer
And (3) placing the ITO substrate processed in the step S2 in a spin coater, spin-coating at 3000rpm for 45S to obtain a hole injection layer PEDOT/PSS film, and annealing the spin-coated PEDOT/PSS film at 120 ℃ for 30min to obtain the ITO substrate covered by the PEDOT/PSS.
S4: preparation of hole transport layer
And (3) placing the ITO substrate spin-coated by S3 in a spin coater in a glove box, then spin-coating at 4000rpm for 45S to obtain a mixed film of the hole transport layer PVK, and annealing the PVK obtained by spin-coating at 120 ℃ for 20min to obtain the ITO substrate coated with the PEDOT: PSS and covered by the PVK film.
S5: light emitting layer (Ph)4P)2SbCl5Preparation of the film
The ITO substrate spin-coated in S4 was placed in a spin coater in a glove box, followed by spin coating (Ph)4P)2SbCl5Film, finally annealing to obtain (Ph)4P)2SbCl5Film-coated ITO substrate coated with PVK and PEDOT: PSS.
S6: preparation of thin film of electron transport layer TPBi
Placing the ITO substrate treated by S5 on an organic mask plate and placing the ITO substrate in a vacuum evaporation machine, and then controlling the evaporation rate of TPBi
Finally, a coating (Ph) covered with a TPBi film is obtained4P)2SbCl5PVK and PEDOT ITO substrates of PSS.
S7: preparation of electron injection layer LiF and electrode Al
Placing the ITO substrate treated by S6 on an electrode mask plate and placing the electrode mask plate in a vacuum evaporation machine, and then respectively controlling the evaporation rate of LiF to be
The evaporation rate of the electrode Al is in
Finally obtaining the product with the structure of ITO/PEDOT, PSS (40-60nm)/Poly-TPD (20-30 nm)/(Ph)4P)2SbCl5(40-80 nm)/TPBi (50-60 nm)/LiF (1.5nm)/Al (100 nm).
In step S1, the size of the ITO glass substrate is 1.5cm by 1.5 cm. In step S4, the environment of the glove box is such that the water oxygen values are all less than 1 ppm. In the step S5, the spin coating (Ph)4P)2SbCl5The rotating speed of the film is 3000rpm, and the spin coating time is 100 s; the annealing temperature is 120 ℃, and the annealing time is 30 min. In step S6, the pressure of the vacuum evaporator is 4 × 10-6And (4) supporting.
The main luminescence spectrum, current-voltage-brightness curve and external quantum efficiency curve are similar to those of example 1.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.
Claims (7)
1. A light-emitting diode based on zero-dimensional metal halide materials is characterized by comprising an ITO (indium tin oxide) substrate and a plurality of thin film layers coated on the ITO substrate, wherein the thin film layers are formed in a mode of solution spin coating-high temperature annealing and evaporation;
the device structure of the light-emitting diode is ITO/PEDOT: PSS/Poly-TPD/(Ph)4P)2SbCl5/TPBi/LiF/Al；
The solution is PEDOT PSS, Poly-TPD dissolved in chlorobenzene and dimethyl sulfoxide Ph dissolved in dimethyl sulfoxide4PCl and SbCl3Solution of, Ph4PCl and SbCl3In a molar ratio of 2: 1.
2. the zero-dimensional halogenated complex-based light-emitting diode according to claim 1, wherein the light-emitting diode is an orange light-emitting diode.
3. A method for preparing a light-emitting diode based on zero-dimensional halogenated complexes according to claim 1 or 2, characterized in that it comprises the following steps:
S1：(Ph4P)2SbCl5preparation of the solution
Ph is4PCl and SbCl3The powder is prepared by the following steps: 1 in DMSO to form (Ph)4P)2SbCl5A solution;
s2: ITO substrate processing
Cleaning an ITO substrate, drying the ITO substrate by a nitrogen gun and treating the ITO substrate by ultraviolet plasma;
s3: preparation of hole injection layer
Placing the ITO substrate processed by S2 in a spin coater, spin-coating at 2000-4000rpm for 30-100S to obtain a cavity injection layer PEDOT (PSS) film, and annealing the obtained PEDOT (PSS) film at 80-150 ℃ for 10-30min to obtain an ITO substrate covered by the PEDOT (PSS);
s4: preparation of hole transport layer
Placing the ITO substrate spin-coated by S3 in a spin coater in a glove box, spin-coating at 2000-4000rpm for 30-60S to obtain a hole transport layer Poly-TPD film, annealing the Poly-TPD obtained by spin-coating at 100-150 ℃ for 10-30min to obtain a Poly-TPD film, and coating the Poly-TPD film on the ITO substrate containing PEDOT: PSS;
s5: light emitting layer (Ph)4P)2SbCl5Preparation of the film
The ITO substrate spin-coated in S4 was placed in a spin coater in a glove box and spin-coated at 2000-4000rpm (Ph)4P)2SbCl5Annealing the film at 80-120 deg.C for 10-30min to obtain final product (Ph)4P)2SbCl5An ITO substrate coated with Poly-TPD and PEDOT, PSS and covered by the film;
s6: preparation of thin film of electron transport layer TPBi
Placing the ITO substrate treated by S5 on an organic mask plate and placing the ITO substrate in a vacuum evaporation machine, and then controlling the evaporation rate of TPBi
Finally, a coating (Ph) covered with a TPBi film is obtained4P)2SbCl5PSS, ITO substrate;
s7: preparation of electron injection layer LiF and electrode Al
Placing the ITO substrate treated by S6 on an electrode mask plate and placing the electrode mask plate in a vacuum evaporation machine, and then respectively controlling the evaporation rate of LiF to be
The evaporation rate of the electrode Al is in
And obtaining the light-emitting diode.
4. The method of claim 3, wherein in the step of S1, the size of the ITO substrate is 1.5cm by 1.5 cm.
5. The zero-dimensional metal halide based light emitting diode as claimed in claim 3, wherein in step S4, the oxygen value of the ambient water in the glove box is less than 1 pmm.
6. The zero-dimensional metal halide-based light emitting diode as claimed in claim 3, wherein in the step S5, the spin-coating speed is 2000-4000rpm, the spin-coating time is 20-70S, the annealing temperature is 80-150 ℃, and the annealing time is 10-30 min.
7. The zero-dimensional metal halide-based light emitting diode as claimed in claim 3, wherein in the step S6, the pressure of the vacuum evaporator is less than 4 x 10-6And (4) supporting.
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