CN106409995A - Preparation method of QLED - Google Patents

Preparation method of QLED Download PDF

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Publication number
CN106409995A
CN106409995A CN201610971260.2A CN201610971260A CN106409995A CN 106409995 A CN106409995 A CN 106409995A CN 201610971260 A CN201610971260 A CN 201610971260A CN 106409995 A CN106409995 A CN 106409995A
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qled
preparation
layer
radiation treatment
lamp radiation
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CN201610971260.2A
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CN106409995B (en
Inventor
陈崧
钱磊
杨行
杨一行
曹蔚然
向超宇
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TCL Corp
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TCL Corp
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005Processes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02Semiconductor devices with at least one potential-jump barrier or surface barrier 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
    • H01L33/04Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with a quantum effect structure or superlattice, e.g. tunnel junction
    • H01L33/06Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier

Abstract

The invention provides a preparation method of a QLED. The surface of an electron transmission layer is treated before a light emitting layer is deposited on the electron transmission layer. The method comprises the following steps that oxygen plasma pretreatment or ozone treatment and ultraviolet lamp radiation treatment is carried out on the electron transmission layer, and the photo energy of the ultraviolet lamp radiation treatment is greater than the effective band gap of an electron transmission material. The preparation method of the QLED can be used to reduce the concentration of surface defects of the electron transmission layer material and remove organic residual impurities, further reduce exciton quenching caused by surface defects of the electron transmission layer, and improve the light emitting efficiency and service life of a QLED device effectively.

Description

The preparation method of QLED
Technical field
The invention belongs to display technology field, more particularly, to a kind of preparation method of QLED.
Background technology
The quantum dot light emitting material of inorganic nano-crystal has the advantages that emergent light color saturation, Wavelength tunable, and photic, electric Photoluminescence quantum yield is high, is suitable for preparing Performance Monitor part.Additionally, in terms of preparation technology angle, quantum dot light emitting material The solution processing mode such as spin coating, printing, printing device preparation film forming can be adopted under non-vacuum condition.So, with quantum dot The light emitting diode with quantum dots (QLED) of film preparation becomes the contenders of Display Technique of future generation.
Common, QLED device includes anode, hole injection, transport layer, luminescent layer, electric transmission, implanted layer and negative electrode. According to the relative position of electrode 1 and electrode 2, i.e. back electrode and top electrode, the structure of QLED can be divided into tradition and transoid device Two kinds.Wherein, hole injection, transport layer are used for providing transportable hole from dispatch from foreign news agency road direction luminescent layer, and electron transfer layer is used for carrying For transportable electronics.Electron-hole forms exciton in quantum dot, and exciton passes through radiation recombination output photon, and then luminous.
Nano zine oxide is commonly used electric transmission in QLED device, injection material, and its conduction level is conducive to electricity Injection from negative electrode to quantum dot for the son, and its deeper valence-band level can play effective effect stopping hole.But how Improve the photoelectric characteristic of nano zine oxide further, thus the device efficiency improving QLED is also an emphasis of current research. The preparation of zinc oxide nanocrystalline (quantum dot) typically adopts the sol-gel process of low temperature.Specific surface due to quantum dot superelevation Long-pending, equally can there is substantial amounts of surface defect state in quantum dot.These defect one side can be by the side of optics and elementary analysis Method is characterized, and another aspect surface defect is effective excitonic luminescence quenching mechanism.Additionally, remain in building-up process is organic Thing is coupled with negative effect to the electricity between interface.Electric transmission, the boundary defect of implanted layer will directly affect QLED device Luminescent properties and its stability.
Content of the invention
It is an object of the invention to provide a kind of preparation method of QLED, and the QLED for preparing in the method it is intended to Solve existing QLED and there is electron transfer layer boundary defect, the impact luminescent properties of QLED device and its problem of stability.
The present invention is achieved in that a kind of preparation method of QLED, on the electron transport layer before depositing light emitting layer, right Described electron transfer layer is surface-treated, and comprises the following steps:Described electron transfer layer is carried out oxygen gas plasma locate in advance Reason or ozone are processed and uviol lamp radiation treatment, and wherein, the photon energy of described uviol lamp radiation treatment is more than electric transmission Effective band gap of material.
And, a kind of QLED, pass including the substrate being cascading, hearth electrode, electron transfer layer, luminescent layer, hole Defeated layer, hole injection layer and top electrode, the electron transfer layer that described electron transfer layer is surface-treated for said method.
The preparation method of the QLED that the present invention provides, by carrying out oxygen-enriched atmosphere to electric transmission layer surface and combining ultraviolet The surface treatment of light radiation, effectively remove part defect state in electron transport material such as Zinc oxide nanoparticle (as reduced colour center, Such as oxygen vacancy concentration), reducing conditional electronic transport layer boundary defect state, removing organic residue impurity, thus reducing minimizing table The excitonic luminescence quenching effect that planar defect produces, improves the luminous efficiency of particularly red, the green QLED device of QLED device and makes Use the life-span.By the QLED of the inventive method preparation, there is preferable luminous efficiency, device stability, longer service life.
Brief description
Fig. 1 is in the preparation method of QLED provided in an embodiment of the present invention, and what electron transfer layer was surface-treated shows It is intended to;
Fig. 2 is QLED structural representation provided in an embodiment of the present invention.
Specific embodiment
In order that the technical problem to be solved in the present invention, technical scheme and beneficial effect become more apparent, below in conjunction with Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only in order to explain The present invention, is not intended to limit the present invention.
In conjunction with Fig. 1, embodiments provide a kind of preparation method of QLED, depositing light-emitting on electron transfer layer 3 Before layer, described electron transfer layer 3 is surface-treated, comprises the following steps:Described electron transfer layer 3 is carried out oxygen etc. Gas ions pretreatment or ozone are processed and uviol lamp radiation treatment, and wherein, the photon energy of described uviol lamp radiation treatment is big Effective band gap in electron transport material.
In view of in traditional QLED, electron transport material has segmental defect state, and then in electron transfer layer 3 and luminescent layer Between formed boundary defect, directly affect luminescent properties and its stability of QLED device.In view of this, the embodiment of the present invention is led to Cross surface treatment electron transfer layer 3 surface being carried out with oxygen-enriched atmosphere and combining ultraviolet radiation, effectively remove electric transmission material In material such as Zinc oxide nanoparticle, part defect state (as reduced colour center, such as oxygen vacancy concentration), reduces conditional electronic transmitting layer 3 Boundary defect state (reduces the defect density of the luminous bed boundary of electron transfer layer 3-), removes organic residue impurity, thus reduce subtracting The excitonic luminescence quenching effect that few surface defect produces, and then improve luminous efficiency and the life-span of QLED device.
Specifically, described oxygen gas plasma pretreatment or ozone process, combine uviol lamp radiation treatment, not only can subtract The concentration of few surface defect, and ultraviolet radiant light can excite free electron in a large number, and these free electrons can fill band gap In defect states so that it is inactivated, reduce quenching effect.Additionally, the electron transport material of sol-gal process synthesis is for example nano oxidized Organic substance residues are usually contained, after film forming, organic substance residues generally contain higher containing in electron transfer layer 3 upper surface in zinc colloid Amount.Pre-processed by oxygen gas plasma or ozone processes and can effectively remove electron transfer layer 3 surface with ultraviolet radiation Organic substance residues, improve the electricity coupling between electron transfer layer 3 and luminescent layer.
It will be appreciated that the photon energy of uviol lamp radiation treatment described in the embodiment of the present invention is more than electric transmission Effective band gap of material, the realization of guarantee the effect above, concrete photon energy is different because of electron transport material.Preferably , the wavelength≤300nm of described uviol lamp radiation treatment.
In the embodiment of the present invention, described surface treatment can be accomplished in several ways.Wherein, when adopting oxygen plasma Body pre-processes, it is desirable to provide vacuum environment is improving the purity of oxygen gas plasma, and then reaches preferable plasma and locate in advance Reason effect.
As a preferred embodiment, described surface treatment is oxygen gas plasma pretreatment and ultraviolet under vacuum condition Lamp radiation treatment, and described oxygen gas plasma pre-processes and uviol lamp radiation treatment is carried out simultaneously, process time 30-300s, Wherein, the sputtering power of described oxygen gas plasma pretreatment is 25-250mw/cm2, oxygen flow is 5-1000sccm;Described Power density >=the 100mw/cm of uviol lamp radiation treatment2.
In the embodiment of the present invention, carry out plasma on described electron transfer layer 3 surface, described oxygen gas plasma is located in advance The sputtering power of reason is unsuitable too high or too low, if sputtering power is too low, effectively can not realize plasma, if sputtering power mistake Height, then easily etching electron transport material, so as to performance changes, causes the damage of electron transport material.In above-mentioned sputtering Under the premise of power, likewise, described oxygen flow be difficult too high or too low, if oxygen flow is too low, the cation of plasma Concentration is too low, and surface treatment effect is limited;If oxygen flow is too high, oxygen cannot sufficient plasma, due to wait from Sonization directly occurs on electron transfer layer 3 surface, and therefore, the part oxygen of non-plasma still can be presented in oxygen molecule Electron transfer layer 3 surface, and then affect surface treatment effect.During described uviol lamp radiation treatment, as power density >=100mw/ cm2When, described electron transfer layer 3 could absorb enough uv energies, and then excites substantial amounts of free electron to fill band gap In defect states, and so that it is inactivated.
It is further preferred that described surface treatment is carried out in the prerinse equipment be provided with magnetron.This equipment helps Carry out while the pretreatment of described oxygen gas plasma and uviol lamp radiation treatment, improve surface processing efficiency.
As a preferred embodiment, described surface treatment is oxygen gas plasma pretreatment and ultraviolet under vacuum condition Lamp radiation treatment, wherein, described oxygen gas plasma pretreatment sets in the surface treatment being provided with independent oxonium ion generating means Carry out in standby, the hot-wire coil power of described independent oxonium ion generating means is 10-200W, and sputtering power is 25-250mw/ cm2, oxygen flow is 5-200sccm, process time 15-150s;Power density >=the 100mw/ of described uviol lamp radiation treatment cm2.
In the embodiment of the present invention, it is transported to electron transfer layer 3 surface again after first by oxygen plasma and carries out oxygen etc. Gas ions pre-process, and wherein, the hot-wire coil of described independent oxonium ion generating means is used for oxygen plasma, described live wire The power of circle is 10-200W, both can guarantee that good plasma effect, and can effectively reduce energy consumption again.Embodiment of the present invention institute The sputtering power stating oxygen gas plasma pretreatment can be less than the sputtering power of above-described embodiment, and obtains preferable plasma Effect.Under the premise of above-mentioned sputtering power, described oxygen flow be difficult too high or too low, if oxygen flow is too low, plasma Cation concn too low, surface treatment effect is limited;If oxygen flow is too high, even if carrying out the stroke phase of plasma process To longer, but oxygen it is possible to cannot sufficient plasma, part oxygen still can be transferred to electricity in the form of oxygen molecule Sub- transmitting layer 3 surface, and then affect surface treatment effect.During described uviol lamp radiation treatment, as power density >=100mw/cm2 When, described electron transfer layer 3 could absorb enough uv energies, and then excites substantial amounts of free electron to fill in band gap Defect states, and so that it is inactivated.
As another preferred embodiment, under conditions of or else meeting vacuum, described it is surface-treated at for ozone Reason and uviol lamp radiation treatment.Further, described surface treatment is carried out in UV-ozone generating means.Preferably, described Power >=the 100W of UV-ozone generating means, thus, described electron transfer layer 3 could absorb enough uv energies, and then Excite substantial amounts of free electron to fill the defect states in band gap, and so that it is inactivated.
As a specific embodiment, taking the UV ozone generating means of 100W and zinc oxide electron transfer layer 3 as a example, 15min UV-ozone process can substantially remove the thick Nano zinc oxide film medium wavelength center of 30nm in 520nm about, half Defect luminescence generated by light in peak width 50nm (proves that the defect density of nano zine oxide can be processed by significantly by UV-ozone Reduce), thus improving the conversion efficiency of photovoltaic device.
Electron transport material described in the embodiment of the present invention includes but is not limited to transition group oxide, II-VI group semiconductor, titanium Hydrochlorate, described transition group oxide includes zinc oxide, titanium dioxide, tantalum pentoxide, and wherein, described zinc oxide includes zinc oxide Nanocrystalline (including ball shaped nano crystalline substance (i.e. quantum dot), nanometer rods), undoped zinc oxide, undoped zinc oxide-organic nano are multiple Compound;Described titanate includes bismuth titanates, barium titanate.
Described in the embodiment of the present invention, the preparation method of electron transfer layer 3 includes solution spin coating, printing;Magnetic under vacuum condition Cosputtering etc..Other Rotating fields of the embodiment of the present invention (include substrate 1, hearth electrode 2, luminescent layer, hole transmission layer, hole injection Layer and top electrode) preparation, be referred to this area conventional method and realize.
And, in conjunction with Fig. 2, the embodiment of the present invention additionally provides a kind of QLED, including the substrate 1 being cascading, bottom Electrode 2, electron transfer layer 3, luminescent layer 4, hole transmission layer 5, hole injection layer 6 and top electrode 7, described electron transfer layer 7 is The electron transfer layer that said method is surface-treated.
The preparation method of QLED provided in an embodiment of the present invention, by carrying out oxygen-enriched atmosphere to electric transmission layer surface and tying Close the surface treatment of ultraviolet radiation, effectively remove part defect state in electron transport material such as Zinc oxide nanoparticle and (such as drop Low colour center, such as oxygen vacancy concentration), reducing conditional electronic transport layer boundary defect state, removing organic residue impurity, thus reducing Reduce the excitonic luminescence quenching effect that surface defect produces, improve the luminous efficiency of particularly red, the green QLED device of QLED device And service life.By the QLED of present invention method preparation, there is preferable luminous efficiency, device stability, longer Service life.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.

Claims (10)

1. a kind of preparation method of QLED is it is characterised in that on the electron transport layer before depositing light emitting layer, pass to described electronics Defeated layer is surface-treated, and comprises the following steps:Described electron transfer layer is carried out at oxygen gas plasma pretreatment or ozone Reason and uviol lamp radiation treatment, wherein, the photon energy of described uviol lamp radiation treatment is more than the effective of electron transport material Band gap.
2. the preparation method of QLED as claimed in claim 1 is it is characterised in that described surface treatment is the oxygen under vacuum condition The pretreatment of gas plasma and uviol lamp radiation treatment, and the pretreatment of described oxygen gas plasma and uviol lamp radiation treatment are simultaneously Carry out, process time 30-300s, wherein,
The sputtering power of described oxygen gas plasma pretreatment is 25-250mw/cm2, oxygen flow is 5-1000sccm;
Power density >=the 100mw/cm of described uviol lamp radiation treatment2.
3. the preparation method of QLED as claimed in claim 2 is it is characterised in that described surface treatment is being provided with magnetron Carry out in prerinse equipment.
4. the preparation method of QLED as claimed in claim 1 is it is characterised in that described surface treatment is the oxygen under vacuum condition The pretreatment of gas plasma and uviol lamp radiation treatment, wherein,
Described oxygen gas plasma pretreatment is carried out in the surface processing equipment being provided with independent oxonium ion generating means, described Individually the hot-wire coil power of oxonium ion generating means is 10-200W, and sputtering power is 25-250mw/cm2, oxygen flow is 5- 200sccm, process time 15-150s;
Power density >=the 100mw/cm of described uviol lamp radiation treatment2.
5. the preparation method of QLED as claimed in claim 1 is it is characterised in that described surface treatment is processed and ultraviolet for ozone Lamp radiation treatment.
6. the preparation method of QLED as claimed in claim 5 is it is characterised in that described surface treatment occurs in UV-ozone Carry out in device.
7. the preparation method of QLED as claimed in claim 6 is it is characterised in that the power of described UV-ozone generating means ≥100W.
8. the preparation method of described QLED as arbitrary in claim 1-7 was it is characterised in that described electron transport material included Cross race's oxide, II-VI group semiconductor, titanate.
9. QLED as claimed in claim 8 preparation method it is characterised in that described transition group oxide include zinc oxide, Titanium dioxide, tantalum pentoxide, wherein, described zinc oxide includes zinc oxide nanocrystalline, undoped zinc oxide, undoped oxidation Zinc-organic nano compound;Described II-VI group semiconductor includes zinc sulphide, zinc selenide, zinc telluridse, cadmium sulfide;Described titanate Including bismuth titanates, barium titanate.
10. a kind of QLED, including the substrate being cascading, hearth electrode, electron transfer layer, luminescent layer, hole transmission layer, sky Cave implanted layer and top electrode are it is characterised in that what described electron transfer layer was surface-treated for claim 1-9 either method Electron transfer layer.
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CN109994622A (en) * 2017-12-29 2019-07-09 Tcl集团股份有限公司 A kind of QLED device
CN110277498A (en) * 2019-06-10 2019-09-24 储天新能源科技(长春)有限公司 A kind of preparation method of high efficiency perovskite battery
CN110739404A (en) * 2018-07-18 2020-01-31 Tcl集团股份有限公司 Quantum dot light-emitting diode and preparation method thereof
CN111384308A (en) * 2018-12-29 2020-07-07 Tcl集团股份有限公司 Preparation method of quantum dot light-emitting diode
CN111384304A (en) * 2018-12-29 2020-07-07 Tcl集团股份有限公司 Post-processing method of quantum dot light-emitting diode
CN111725440A (en) * 2020-07-01 2020-09-29 合肥福纳科技有限公司 Metal oxide nanoparticle, processing method thereof and QLED device
CN112331784A (en) * 2019-12-17 2021-02-05 广东聚华印刷显示技术有限公司 Film and use thereof
CN112349856A (en) * 2020-11-30 2021-02-09 河南工程学院 Quantum dot light-emitting diode based on corona discharge interface modification and preparation method thereof
CN112802974A (en) * 2020-12-30 2021-05-14 广东聚华印刷显示技术有限公司 Electronic device structure, preparation method thereof, light emitting diode and display device
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WO2022056905A1 (en) * 2020-09-21 2022-03-24 京东方科技集团股份有限公司 Light-emitting device and preparation method therefor, light-emitting substrate and preparation method therefor, and light-emitting apparatus
WO2022143566A1 (en) * 2020-12-31 2022-07-07 Tcl科技集团股份有限公司 Light-emitting device and preparation method therefor
WO2022143438A1 (en) * 2020-12-30 2022-07-07 Tcl科技集团股份有限公司 Quantum dot light-emitting diode device and preparation method therefor
WO2023093791A1 (en) * 2021-11-26 2023-06-01 Tcl科技集团股份有限公司 Thin film processing method, light-emitting diode preparation method, and light-emitting diode

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CN110739404A (en) * 2018-07-18 2020-01-31 Tcl集团股份有限公司 Quantum dot light-emitting diode and preparation method thereof
US11485908B2 (en) 2018-07-18 2022-11-01 Tcl Technology Group Corporation Quantum dot light-emitting diode and method for fabricating the same
CN110739404B (en) * 2018-07-18 2021-04-02 Tcl科技集团股份有限公司 Quantum dot light-emitting diode and preparation method thereof
CN108987258A (en) * 2018-07-19 2018-12-11 京东方科技集团股份有限公司 The preparation method and device of oxide semiconductor layer
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CN111384304B (en) * 2018-12-29 2021-06-29 Tcl科技集团股份有限公司 Post-processing method of quantum dot light-emitting diode
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CN111384308A (en) * 2018-12-29 2020-07-07 Tcl集团股份有限公司 Preparation method of quantum dot light-emitting diode
CN111384304A (en) * 2018-12-29 2020-07-07 Tcl集团股份有限公司 Post-processing method of quantum dot light-emitting diode
CN110277498B (en) * 2019-06-10 2022-08-02 储天新能源科技(长春)有限公司 Preparation method of perovskite battery
CN110277498A (en) * 2019-06-10 2019-09-24 储天新能源科技(长春)有限公司 A kind of preparation method of high efficiency perovskite battery
WO2021092850A1 (en) * 2019-11-14 2021-05-20 Boe Technology Group Co., Ltd. Quantum dots light emitting diode, display apparatus, and method of fabricating quantum dots light emitting diode
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CN111725440B (en) * 2020-07-01 2022-12-09 合肥福纳科技有限公司 Metal oxide nanoparticle, processing method thereof and QLED device
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WO2022056905A1 (en) * 2020-09-21 2022-03-24 京东方科技集团股份有限公司 Light-emitting device and preparation method therefor, light-emitting substrate and preparation method therefor, and light-emitting apparatus
CN112349856B (en) * 2020-11-30 2022-05-20 河南工程学院 Quantum dot light-emitting diode based on corona discharge interface modification and preparation method thereof
CN112349856A (en) * 2020-11-30 2021-02-09 河南工程学院 Quantum dot light-emitting diode based on corona discharge interface modification and preparation method thereof
WO2022143438A1 (en) * 2020-12-30 2022-07-07 Tcl科技集团股份有限公司 Quantum dot light-emitting diode device and preparation method therefor
CN112802974A (en) * 2020-12-30 2021-05-14 广东聚华印刷显示技术有限公司 Electronic device structure, preparation method thereof, light emitting diode and display device
WO2022143566A1 (en) * 2020-12-31 2022-07-07 Tcl科技集团股份有限公司 Light-emitting device and preparation method therefor
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