WO2022143820A1 - Light-emitting device and preparation method therefor - Google Patents
Light-emitting device and preparation method therefor Download PDFInfo
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- WO2022143820A1 WO2022143820A1 PCT/CN2021/142723 CN2021142723W WO2022143820A1 WO 2022143820 A1 WO2022143820 A1 WO 2022143820A1 CN 2021142723 W CN2021142723 W CN 2021142723W WO 2022143820 A1 WO2022143820 A1 WO 2022143820A1
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- light
- layer
- emitting device
- preparing
- electron transport
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- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
Definitions
- the present application relates to the technical field of display devices, and in particular, to a light-emitting device and a preparation method thereof.
- Quantum dots are nanocrystalline particles with a radius smaller than or close to the Bohr exciton radius, and their size and diameter are generally between one. Quantum dots have quantum confinement effect and can emit fluorescence when excited. Moreover, quantum dots have unique luminescence characteristics such as wide excitation peak, narrow emission peak, and tunable luminescence spectrum, which make quantum dot materials have broad application prospects in the field of optoelectronic luminescence. Quantum dot light-emitting diode (QLED) is a new type of display technology that has emerged rapidly in recent years. Quantum dot light-emitting diode is a device that uses colloidal quantum dots as the light-emitting layer. The quantum dot light-emitting layer is introduced between different conductive materials to obtain the required wavelength of light. Quantum dot light-emitting diodes have the advantages of high color gamut, self-luminescence, low startup voltage, and fast response speed.
- OLED devices generally adopt a multi-layer device structure, and the quantum dot light-emitting layer mostly adopts quantum dot nanomaterials with a core-shell structure.
- the organic surface ligands of quantum dot nanoparticles and the refined core-shell structure inside them make the annealing temperature not too high, so the interface roughness of the formed quantum dot layer is relatively high.
- the annealing temperature of the quantum dot layer also limits the annealing temperature of its adjacent electron transport layer ETL, making it difficult for the electron transport material to achieve a good crystallization temperature, resulting in discontinuous internal structure of the electron transport layer and reducing the electron transport mobility.
- the charge accumulation center is easily formed at the interface gap, which accelerates the aging of the material and seriously affects the life of the device.
- One of the purposes of the embodiments of the present application is to provide a light-emitting device and a preparation method thereof, aiming at solving the problem of carrier recombination imbalance in optoelectronic devices.
- the present application provides a method for preparing a light-emitting device, comprising the following steps:
- preparing a light-emitting device including an anode, a hole functional layer, a quantum dot light-emitting layer, an electronic functional layer and a cathode that are stacked in sequence; wherein the electronic functional layer includes a metal oxide transport material;
- the light-emitting device is subjected to ultraviolet light irradiation treatment.
- a light-emitting device is provided, and the light-emitting device is manufactured by the above-mentioned method.
- the beneficial effect of the method for preparing a light-emitting device is that: a pair of light-emitting devices including an anode, a hole functional layer, a quantum dot light-emitting layer, an electronic functional layer and a cathode are subjected to ultraviolet light irradiation treatment, and the ultraviolet light irradiation treatment is performed by
- the electrons of O in the metal oxide transport material in the electron transport layer (ETL) are excited to form complexes with active metal elements such as Zn in the adjacent quantum dot light-emitting layer (QD), so that the QD-ETL interface is formed.
- More fusion is conducive to electron injection into the light-emitting layer, and since the electrons of O in the metal oxide are coordinated with the quantum dot material, the bonding defects inside the transport layer are increased, and the electron mobility in the transport layer is improved.
- the formed complexes and metal oxide transport materials have a strong absorption effect on UV light, so that the temperature at the interface between the electron transport layer and the light-emitting layer increases, the crystal bonding electrons in the transport layer are activated, and the crystal grows again.
- the beneficial effect of the light-emitting device provided by the embodiments of the present application is that: since the light-emitting device is subjected to ultraviolet light irradiation treatment, the electrons of O in the metal oxide transport material in the electron transport layer are excited to form a coordination with active metal elements such as Zn in the quantum dot light-emitting layer. At the same time, the metal oxide material has a good fusion effect with the cathode after being excited by ultraviolet light.
- the internal physical structure defects and surface roughness of the electron transport layer are reduced, the electron transport and migration efficiency is high, and the quantum dot light-emitting layer is closely combined with the electron transport layer and the cathode interface, and the electron injection efficiency is high, avoiding the accumulation of charges at the interface of the functional layer, and the device is stable. Good, long lifespan.
- FIG. 1 is a schematic flowchart of a method for preparing a light-emitting device provided in an embodiment of the present application
- FIG. 2 is a schematic structural diagram of a light-emitting device provided by an embodiment of the present application
- FIG. 3 is a schematic diagram of a positive structure of a quantum dot light-emitting diode provided by an embodiment of the present application;
- FIG. 4 is a schematic diagram of an inversion structure of a quantum dot light-emitting diode provided by an embodiment of the present application.
- Example 5 is a graph of the efficiency of the quantum dot light-emitting diodes provided in Example 1 and Comparative Example 1 of the present application;
- Example 6 is a current density-voltage graph of the quantum dot light-emitting diodes provided in Example 1 and Comparative Example 1 of the present application;
- Example 7 is a graph of the brightness of the quantum dot light-emitting diodes provided in Example 1 and Comparative Example 1 of the present application;
- Example 8 is a graph showing the efficiency of the quantum dot light-emitting diodes provided in Example 7, Example 10, Comparative Example 2 and Comparative Example 3 of the present application;
- Example 9 is a current density-voltage graph of the quantum dot light-emitting diodes provided in Example 7, Example 10, Comparative Example 2 and Comparative Example 3 of the present application;
- FIG. 10 is a graph showing the brightness of the quantum dot light-emitting diodes provided in Example 7, Example 10, Comparative Example 2 and Comparative Example 3 of the present application.
- At least one means one or more
- plural items means two or more.
- At least one item(s) below” or similar expressions thereof refer to any combination of these items, including any combination of single item(s) or plural items(s).
- at least one (one) of a, b, or c or, “at least one (one) of a, b, and c” can mean: a,b,c,a-b( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple respectively.
- ⁇ E HTL-HIL E HOMO,HTL -E HIL
- ⁇ E EML-HTL E HOMO,EML -E HTL
- all energy level/work function values are absolute values, and the absolute value of the energy level is large The energy level is deep, and the absolute value of the energy level is small, the energy level is shallow.
- a first aspect of an embodiment of the present application provides a method for preparing a light-emitting device, including the following steps:
- a light-emitting device comprising an anode, a hole functional layer, a quantum dot light-emitting layer, an electronic functional layer, and a cathode that are sequentially stacked; wherein, the electronic functional layer includes a metal oxide transport material;
- a light-emitting device comprising an anode, a hole functional layer, a quantum dot light-emitting layer, an electronic functional layer and a cathode is subjected to ultraviolet light irradiation treatment, and through the ultraviolet light irradiation treatment, on the one hand,
- the electrons of O in the metal oxide transport material in the electron transport layer (ETL) are excited to form complexes with active metal elements such as Zn in the adjacent quantum dot light-emitting layer (QD), so that the QD-ETL interface is more fused.
- the bonding defects inside the transport layer are increased, and the electron mobility in the transport layer is improved.
- the formed complexes and metal oxide transport materials have a strong absorption effect on UV light, so that the temperature at the interface between the electron transport layer and the light-emitting layer increases, the crystal bonding electrons in the transport layer are activated, and the crystal grows again.
- the injection rate of electrons in the light-emitting layer is faster than that of holes, resulting in the negative charge of the quantum dot material.
- Factors such as bulk binding, Coulomb blocking effect, uneven charge distribution, and charge accumulation in the interface layer are maintained.
- the QD-ETL interface has a large electric field intensity distribution, a high charge distribution density, and a large charge accumulation at the QD-ETL interface.
- the negatively charged state of the quantum dot material makes the injection of electrons more and more difficult during the continuous operation of the QLED device, resulting in an imbalance between the actual injection of electrons and holes in the light-emitting layer. Furthermore, when the QLED device continues to light up and work to a stable state, the negatively charged state of the quantum dot material also tends to be stable, that is, the electrons newly captured and bound by the quantum dots reach a dynamic balance with the electrons consumed by the radiative transition. At this time, the injection rate of electrons into the light-emitting layer is much lower than that in the initial state, and the hole injection rate required to achieve the balance of charge injection in the light-emitting layer is actually relatively low.
- the quantum dot light-emitting layer includes a quantum dot material with a core-shell structure, and the valence band top energy level difference between the outer shell layer material of the quantum dot material and the hole transport material in the hole transport layer is greater than or equal to 0.5 eV.
- the hole injection barrier by constructing a hole injection barrier with a valence band top energy level difference of greater than or equal to 0.5 eV between the outer shell layer material of the quantum dot material and the hole transport material, the hole injection barrier is increased and the hole injection efficiency is reduced, thereby Balance the injection balance of holes and electrons in the light-emitting layer.
- the hole injection barrier with ⁇ E EML-HTL ⁇ 0.5 eV constructed in the examples of the present application does not cause holes to be unable to be injected. Because the energy level of the outer shell layer of quantum dots will bend in the energized state, carriers can be injected through the tunneling effect; therefore, although the increase in the energy level barrier will reduce the carrier injection rate, But it does not completely hinder the final injection of carriers.
- the core material determines the luminescence performance
- the shell material protects and facilitates carrier injection
- electrons and holes are injected into the core through the shell layer to emit light.
- the band gap of the inner core is narrower than that of the outer shell, so the energy level difference between the valence band of the hole transport material and the inner core of the quantum dot is smaller than the energy level difference of the valence band of the hole transport material and the outer shell of the quantum dot. Therefore, the ⁇ E EML-HTL is greater than or equal to 0.5 eV, which can simultaneously ensure the effective injection of hole carriers into the inner core of the quantum dot material.
- the valence band top energy level difference between the outer shell layer material of the quantum dot material and the hole transport material in the hole transport layer is 0.5-1.7 eV, that is, the ⁇ E EML-HTL is 0.5 eV-1.7 eV, and the quantum dot material is 0.5-1.7 eV.
- the energy level barrier in this range constructed between the outer shell material and the hole transport material can be applied to device systems constructed of different hole transport materials and quantum dot materials to optimize the injection of electrons and holes in different device systems. balance.
- ⁇ E EML-HTL different top valence band energy level differences ⁇ E EML-HTL can be set according to the specific material properties, and the carrier injection rate of holes and electrons on both sides of the light-emitting layer can be finely adjusted to balance the injection of holes and electrons.
- the absolute value of the valence band top energy level of the hole transport material is less than or equal to 5.3 eV.
- the absolute value of the top energy level of the valence band is adopted in the examples of the present application.
- the shell energy level of conventional quantum dot light-emitting materials is often relatively deep (6.0eV or deeper). The energy level difference is greater than or equal to 0.5eV.
- the mobility of the hole transport material is higher than 1 ⁇ 10 ⁇ 4 cm 2 /Vs.
- the embodiments of the present application use hole transport materials with a mobility higher than 1 ⁇ 10 -4 cm 2 /Vs to further ensure the hole transport and migration effect, prevent charge accumulation, eliminate interface charges, and better reduce the device driving voltage and improve Device life.
- the hole transport material is selected from at least one of: a polymer containing an aniline group, a copolymer containing a fluorene group and an aniline group, and these hole transport materials have high hole transport efficiency, It has the advantages of good stability and easy access.
- the hole transport material includes: at least one of TFB, poly-TPD, P10, P11, P15, P12, P09, and P13, wherein the structural formula of P13 is:
- the structural formula of P09 is:
- the structural formula of P11 is:
- the structural formula of poly-TPD is:
- the structural formula of TFB is:
- the structural formula of P12 is:
- the structural formula of P15 is:
- the valence band top energy level difference between the outer shell material of the quantum dot material and the hole transport material is 0.5eV ⁇ 0.7eV, in this case, the applicable hole transport material is TFB, and the quantum dot shell material is ZnSe, TFB -ZnSe device system.
- the valence band top energy level difference between the outer shell material of the quantum dot material and the hole transport material is 0.7 eV to 1.0 eV, and the applicable hole transport material is P09, and the outer shell material of the quantum dot is ZnSe, P09 -ZnSe device system.
- the valence band top energy level difference between the shell layer material of the quantum dot material and the hole transport material is 1.0eV ⁇ 1.4eV, and the applicable hole transport material is TFB, P13, P14, and the quantum dot shell material For ZnSe, ZnS, such as: TFB-ZnS, P13/P14-ZnSe and other device systems.
- the valence band top energy level difference between the outer shell layer material of the quantum dot material and the hole transport material is greater than 1.4eV-1.7eV, and the device system of P09-ZnS and P13/P14-ZnS is applicable.
- the quantum dot light-emitting layer includes a core-shell structure quantum dot material, and the outer shell layer of the quantum dot material contains zinc. Since most of the current quantum dot synthesis uses II-VI group elements, Zn element and VI group elements have better matching in terms of lattice matching and band gap, which can cover the entire visible light band, and the outer shell of the quantum dot material
- the zinc-containing outer shell layer has suitable chemical activity, high flexibility and controllability, wide band gap, good exciton binding, high quantum efficiency, and good water-oxygen stability. In addition, the coordination effect of zinc element and O electrons is better and more stable.
- the electrons of O of the metal oxide transport material in the electron transport layer are excited, and it is easy to form a complex with the Zn element in the QD, that is, a ZnO complex.
- the formation of ZnO complex bonds facilitates electron injection and improves electron mobility in the electron transport layer.
- the ZnO complex has a strong absorption effect on the wavelength of ultraviolet light, which is conducive to activating the bonding electrons, making the crystal in the ETL grow again, reducing the internal physical structure defects and surface roughness of the ETL, which is conducive to the injection of electrons and reduces the accumulation of electrons. , slow down the material aging, and help to improve the life of the device.
- the outer shell layer of the quantum dot material includes: at least one of ZnS, ZnSe, ZnTe, CdZnS, ZnCdSe, or an alloy material formed by at least two kinds of the outer shell materials, all of which contain zinc element, and the zinc element has high activity, It has a good coordination effect with the excited O electrons in the electron transport material.
- the step of preparing the electronic functional layer includes: sequentially preparing the first sub-electron transport layer to the N-th sub-electron transport layer on the surface of the cathode away from the substrate to form an electron transport layer; At least one sub-electron transport layer in the transport layer includes an organic transport material, at least the N-th sub-electron transport layer includes a metal oxide transport material, and N is a positive integer greater than or equal to 2.
- an electron transport layer of a multi-layered composite structure is prepared in the device, which includes both a metal oxide sub-transport layer with high electron mobility and an organic sub-transport layer with wide energy level regulation.
- the electron transport layer of the composite structure has the characteristics of high electron mobility and energy level matching at the same time, realizes the flexible regulation of the energy level and electron mobility of the electron transport layer, and optimizes the injection and recombination efficiency of electrons and holes in the light-emitting layer.
- the first sub-electron transport layer close to the cathode and the N-th sub-electron transport layer close to the quantum dot light-emitting layer each independently comprise a metal oxide transport material, N It is a positive integer greater than or equal to 3 and less than or equal to 9. If the value of N is too large, the electron transport layer will be too thick, which is not conducive to electron transport.
- the optoelectronic devices prepared in the examples of the present application are treated with ultraviolet light to promote the coordination of the metal oxide transport material in the N-th electron transport layer with the active metal elements in the quantum dots, and at the same time promote the oxidation of metals in the first electron transport layer.
- the material transport material is coordinated with the metal element in the metal cathode to improve the fusion between the QD-ETL and the ETL-cathode interface, which is more conducive to electron injection.
- a schematic structural diagram of the light-emitting device prepared in the embodiment of the present application includes an anode, a hole transport layer, a quantum dot light-emitting layer, and an electron transport layer that are stacked in sequence from top to bottom. (From top to bottom, it includes the Nth electron transport layer, the N-1th electron transport layer...the first electron transport layer) and the cathode, wherein the Nth electron transport layer near the quantum dot light-emitting layer is a metal oxide layer.
- the particle size of the metal oxide transport material in the N-th electron transport layer is 2 to 4 nm, and the metal oxide particles with small particle size have a larger specific surface area and higher surface activity, and are more effective when irradiated with ultraviolet light. It is easy to cooperate with active metals in quantum dots to form a better QD-ETL interface. In addition, the metal oxide particles with small particle size have a wider band gap, which reduces the quenching of exciton emission in the light-emitting layer and improves the device efficiency.
- the electron transport layer includes at least one sub-electron transport layer of a metal oxide transport material with a particle size of 4-8 nm.
- the metal oxide with this particle size has high electron transfer efficiency and is conducive to electron injection and light emission. It is easier to disperse in the solution and has better film-forming properties.
- the electron transport layer includes at least one sub-electron transport layer with a metal oxide transport material having a particle size of 4-8 nm, and the particle size of the metal oxide transport material in the Nth sub-electron transport layer is 2 to 4 nm. Since the electron mobility of metal oxides with small particle size is relatively small, which affects electron injection, and has relatively poor stability and film-forming performance, which reduces device performance, the embodiments of the present application use QD/2-4nm small particle size The combination of metal oxide/4-8nm large particle size metal oxide makes the electron transport layer have high electron migration and injection efficiency, film formation stability, QD-ETL interface fusion and other characteristics, and improves device performance.
- the metal oxide transport material is selected from at least one of ZnO, TiO 2 , Fe 2 O 3 , SnO 2 , Ta 2 O 3 ; these metal oxide materials have high electron mobility, and Among them, the excited electrons of O have a good coordination effect with the zinc element in the QD shell.
- the metal oxide transport material is selected from one of ZnO, TiO 2 , Fe 2 O 3 , SnO 2 , and Ta 2 O 3 , or a mixture of two or more.
- the metal oxide transport material is selected from at least one of ZnO, TiO 2 , Fe 2 O 3 , SnO 2 , Ta 2 O 3 doped with metal elements, wherein the metal elements include aluminum, magnesium , at least one of lithium, lanthanum, yttrium, manganese, gallium, iron, chromium, and cobalt.
- the metal oxide transport materials of the embodiments of the present application are doped with metal elements such as aluminum, magnesium, lithium, lanthanum, yttrium, manganese, gallium, iron, chromium, cobalt, etc., which are beneficial to improve the electron transport and migration efficiency of the materials.
- the metal oxide transport material is doped with one metal element of aluminum, magnesium, lithium, lanthanum, yttrium, manganese, gallium, iron, chromium, and cobalt, or two or more of them are simultaneously doped metal element.
- the electron mobility of the organic transport material is greater than or equal to 10 -4 cm 2 /Vs, and the organic transport material with high mobility can ensure the transfer efficiency of electrons in the transport layer, improve the injection efficiency of electrons, and avoid charges The effect of accumulation on device lifetime.
- the organic transport material is selected from the group consisting of 8-quinolinolato-lithium (Alq 3 ), aluminum octaquinolate, fullerene derivatives PCBM, 3,5-bis(4-tert-butylphenyl) - At least one of 4-phenyl-4H-1,2,4-triazole (BPT), 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi) A sort of.
- These organic transport materials can realize energy level regulation in a wide range, which is more conducive to regulating the energy levels of each functional layer of the device and improving the stability and photoelectric conversion efficiency of the device.
- the electron transport layer has a thickness of 10-200 nm. In some specific embodiments, the thickness of the Nth sub-electron transport layer is 2 ⁇ 8 nm. This thickness satisfies device performance requirements and structural requirements. In some specific embodiments, when the thickness of the electron transport layer is less than 80 nm, the duration of the ultraviolet light irradiation treatment is 15 minutes to 45 minutes. In the examples of the present application, when the thickness of the electron transport layer is less than 80 nm, the light wave energy of the low-thickness material layer is relatively easy to penetrate. At this time, the irradiation time required to achieve the treatment effect is short, and the duration of the ultraviolet light irradiation treatment is 15 minutes to 45 minutes. minutes are appropriate.
- the duration of the ultraviolet light irradiation treatment is 30 minutes to 90 minutes.
- the thickness of the electron transport layer is higher than 80 nm, the light wave energy of the thick material layer is difficult to penetrate, and at this time, the illumination time required to achieve the treatment effect is longer, and the duration of the ultraviolet light irradiation treatment is 30 minutes to 90 minutes. minutes are appropriate.
- the method further includes the step of: preparing a hole transport layer on the surface of the quantum dot light-emitting layer away from the electron transport layer, and on the surface of the hole transport layer away from the quantum dot light-emitting layer The anode is prepared on the surface.
- a schematic structural diagram of the light-emitting device prepared in the embodiment of the present application includes an anode, a hole transport layer, a quantum dot light-emitting layer, and an electron transport layer that are stacked in sequence from top to bottom. (From top to bottom, it includes the Nth electron transport layer, the N-1th electron transport layer...the first electron transport layer) and the cathode, wherein the Nth electron transport layer near the quantum dot light-emitting layer is a metal oxide layer.
- step S20 the step of performing ultraviolet light irradiation treatment on the light-emitting device includes: after preparing a composite layer of the quantum dot light-emitting layer and the electron transport layer between the anode and the cathode, performing ultraviolet light irradiation treatment on the composite layer .
- a composite layer of a quantum dot light-emitting layer (QD) and an electron transport layer (ETL) is prepared between the anode and the cathode, and the composite layer is treated with ultraviolet light (UV), so that the metal oxide in the electron transport layer is transported
- UV ultraviolet light
- the electrons of O in the material are excited to form complexes with active metal elements such as Zn in the light-emitting layer of quantum dots, which optimizes the ETL-QD interface, reduces interface defects, and facilitates the injection of electrons from the electron transport layer to the interior of the light-emitting layer of quantum dots;
- the bonding defects inside the electron transport layer are increased, the bonding electrons are activated, the crystal regrowth in the electron transport layer is promoted, and the electron mobility in the electron transport layer is improved.
- a thin film transfer method is used to prepare a composite layer of the quantum dot light-emitting layer and the electron transport layer between the anode and the cathode, which specifically includes the steps of: sequentially depositing and preparing the quantum dot light-emitting layer and the electron transport layer on the substrate, After the composite layer of the quantum dot light-emitting layer and the electron transport layer is subjected to ultraviolet light irradiation treatment, the composite layer of the quantum dot light-emitting layer and the electron transport layer is transferred to the substrate prepared with the cathode, and then the surface of the quantum dot light-emitting layer is sequentially prepared.
- a hole transport layer, a hole injection layer and an anode are used to obtain a light-emitting device with an inversion structure.
- the composite layer of the quantum dot light-emitting layer and the electron transport layer is transferred to a substrate prepared in sequence with an anode, a hole injection layer and a hole transport layer, and then a cathode is prepared on the surface of the electron transport layer to obtain a positive-type light-emitting structure. device.
- a solution deposition method is used to prepare a laminated composite structure of a quantum dot light-emitting layer and an electron transport layer between the anode and the cathode.
- the specific steps include: preparing an anode on a substrate; depositing a hole injection layer on the surface of the anode away from the substrate; depositing and preparing holes on the surface of the hole injection layer away from the anode transport layer; deposit and prepare a quantum dot light-emitting layer on one side of the hole transport layer; prepare an electron transport layer on the surface of the quantum dot light-emitting layer away from the hole transport layer, and irradiate the electron transport layer with ultraviolet light to obtain quantum dots
- a composite layer of a light-emitting layer and an electron transport layer; a cathode is deposited on the surface of the electron transport layer to obtain an optoelectronic device.
- the specific steps include: preparing a cathode on a substrate; preparing an electron transport layer on the surface of the cathode; preparing a quantum dot light-emitting layer on the side surface of the electron transport layer away from the cathode, and subjecting the quantum dot light-emitting layer to ultraviolet light Irradiation treatment to obtain a composite layer of the quantum dot light-emitting layer and the electron transport layer; a hole transport layer, a hole injection layer and an anode are sequentially prepared on the surface of the quantum dot light-emitting layer away from the electron transport layer to obtain an optoelectronic device.
- the step of irradiating with ultraviolet light includes: irradiating the light-emitting device for 10-60 minutes under the condition that the wavelength of the ultraviolet light is 250-420 nm and the light wave density is 10-300 mJ/cm 2 .
- the ultraviolet irradiation treatment conditions in the examples of this application can better promote the coordination of O atoms in the metal oxide transport material in the ETL with elements such as zinc in the outer shell layer of the quantum dots, and not only optimize the electron transport layer and the quantum dot light-emitting layer and
- the interface gap between the cathodes can improve the efficiency of electron migration and injection, and can better increase the internal bonding of ETL, promote the re-growth of internal crystals, reduce internal crystal structure defects and surface roughness, and improve electron mobility.
- the conditions of the ultraviolet light irradiation treatment include: performing in an environment where the content of H 2 O is less than 1 ppm and the temperature is 80-120° C.
- the ultraviolet light irradiation treatment is carried out in an environment where the H 2 O content is less than 1 ppm and the temperature is 80-120° C., so as to avoid the excessive water content in the environment, which will cause the surface of the quantum dot material to be hydrolyzed during the light treatment process, which will affect the performance of the material.
- the heating environment of 80-120 °C is conducive to promoting the formation of bonds between the electrons excited by O and the zinc ions, and is also conducive to the activation of the bonding electrons.
- the step of ultraviolet light irradiation treatment includes: using ultraviolet light waves with a wavelength of 320-420 nm and an optical wave density of 10-150 mJ/cm 2 to perform irradiation treatment from the anode side for 10-60 minutes.
- the functional layers such as anode, holes and QDs have little damage to the light wave. Longer, less dense light waves are irradiated.
- the step of irradiating with ultraviolet light includes: using ultraviolet light waves with a wavelength of 250-320 nm and an optical wave density of 100-200 mJ/cm 2 to perform irradiation treatment from the cathode side for 10-60 minutes.
- the metal cathode has a large damage to the UV light wave, and the light wave directly acts on the ETL layer after passing through the cathode layer, and will not affect the materials of other functional layers such as holes.
- the wavelength of ultraviolet light irradiation treatment is 250-355 nm
- the optical wave density is 50-150 mJ/cm 2 .
- the bond energy of ZnS is about 3.5eV
- the bond energy of ZnO is about 3.3eV.
- the transfer of the bonding charges of electron transport materials such as ZnS and ZnO in the material shell makes the zinc element in the shell layer and the O element in the electron transport material have a better coordination effect, forming a complex between the electron transport material and the quantum dot material.
- the wavelength of ultraviolet light irradiation treatment is 280-375 nm, and the optical wave density is 30-120 mJ/cm 2 .
- the bond energy of ZnSe is about 2.9eV, and the bond energy of ZnO is about 3.3eV, and the wavelength of ultraviolet light irradiation treatment is 280 ⁇ 375nm, and the light wave density is 30 ⁇ 120mJ/ cm2 .
- the wavelength of ultraviolet light irradiation treatment is 250-375 nm
- the optical wave density is 30-150 mJ/cm 2 .
- the bond energy of ZnSeS is about 2.7eV
- the bond energy of ZnO is about 3.3eV
- the wavelength of ultraviolet light irradiation treatment is 250 ⁇ 375nm
- the optical wave density is 30 ⁇ 150mJ/ cm2
- the quantum dot light-emitting layer has a thickness of 8-100 nm.
- the hole transport layer has a thickness of 10-150 nm. This thickness satisfies device performance requirements and structural requirements.
- the electron functional layer, the light emitting layer, and the hole functional layer in the device can be designed with appropriate thicknesses according to the characteristics of the device in the above embodiments.
- the thickness of the outer shell layer of the quantum dot material is 0.2-6.0 nm, which ensures the stability of the inner layer material of the quantum dot and the carrier injection effect, and at the same time ensures the zinc element and the metal oxide in the outer shell layer. Coordination effects of O element in transport materials.
- the cathode in the above step S10, in the substrate on which the cathode is deposited, includes at least one metal material or at least two alloy materials of Mg, Ag, Al, and Ca. Under the condition of ultraviolet light irradiation, These cathode metal materials have good fusion effects with metal oxide electron transport materials, which can reduce the electron injection barrier and improve the efficiency of electron injection into optoelectronic devices.
- the preparation of the light-emitting device in the embodiments of the present application includes the steps:
- step S50 in order to obtain a high-quality zinc oxide nanomaterial thin film, the ITO substrate needs to undergo a pretreatment process.
- the basic specific treatment steps include: cleaning the ITO conductive glass with a detergent to preliminarily remove the stains on the surface, and then ultrasonically cleaning in deionized water, acetone, anhydrous ethanol, and deionized water for 20 minutes respectively to remove impurities on the surface. , and finally blow dry with high-purity nitrogen to obtain the ITO positive electrode.
- the step of growing the hole transport layer includes: on the ITO substrate, depositing the prepared solution of the hole transport material through processes such as drop coating, spin coating, soaking, coating, printing, evaporation, etc. Film formation; the film thickness is controlled by adjusting the concentration of the solution, deposition rate and deposition time, and then thermal annealing at an appropriate temperature.
- the step of depositing the quantum dot light-emitting layer on the hole transport layer includes: on the substrate on which the hole transport layer has been deposited, a solution of a light-emitting substance prepared with a certain concentration is applied by drop coating, spin coating, soaking , coating, printing, evaporation and other processes to deposit the film, and control the thickness of the light-emitting layer by adjusting the concentration of the solution, the deposition speed and the deposition time, about 20-60nm, and dry at an appropriate temperature.
- the step of depositing the electron transport layer on the quantum dot light-emitting layer includes: the Nth electron transport layer is a metal oxide transport material: on the substrate on which the quantum dot light-emitting layer has been deposited, a certain amount of The concentrated metal oxide transport material solution is deposited into a film by processes such as drop coating, spin coating, soaking, coating, printing, evaporation, etc.
- the deposition speed for example, the rotation speed is between 3000 and 5000 rpm
- the thickness of the electron transport layer is controlled by the deposition time, about 20 to 60 nm, and then annealed at 150 to 200 °C to form a film to fully remove the solvent.
- Sub-electron transport layers such as organic transport materials and metal oxide transport materials are prepared by redepositing on the surface of the N-th sub-electron transport layer.
- the cathode preparation step includes: placing the substrate on which each functional layer has been deposited into an evaporation chamber and thermally evaporated a layer of 60-100 nm metal silver or aluminum as a cathode through a mask plate.
- step S100 in an environment where the H 2 O content is less than 1 ppm and the temperature is 80-120° C., ultraviolet light with a wavelength of 250-420 nm and an optical wave density of 10-300 mJ/cm 2 is used to vertically conduct the photoelectric device. Irradiate for 10 to 60 minutes.
- the obtained QLED device is packaged, and the package process can be packaged by a common machine or by manual packaging.
- the oxygen content and water content are both lower than 0.1ppm to ensure the stability of the device.
- the preparation steps of the light-emitting device in the embodiments of the present application may also adopt the preparation sequence of the inversion device structure, and the electron transport layer, the quantum dot light-emitting layer, the hole transport layer, the electron transport layer, the quantum dot light-emitting layer, the hole transport layer, the hole injection layer and anode.
- a second aspect of the embodiments of the present application provides a light-emitting device, and the light-emitting device is manufactured by the above method.
- the light-emitting device since the light-emitting device is subjected to ultraviolet light irradiation treatment, the electrons of O in the metal oxide transport material in the electron transport layer are excited to form complexes with active metal elements such as Zn in the quantum dot light-emitting layer, and simultaneously
- the metal oxide material has a good fusion effect with the cathode after being excited by ultraviolet light.
- the internal physical structure defects and surface roughness of the electron transport layer are reduced, the electron transport and migration efficiency is high, and the quantum dot light-emitting layer is closely combined with the electron transport layer and the cathode interface, and the electron injection efficiency is high, avoiding the accumulation of charges at the interface of the functional layer, and the device is stable. Good, long lifespan.
- the light-emitting device is not limited by the device structure, and may be a device with a positive structure or a device with an inversion structure.
- the positive structure light-emitting device includes a stacked structure of oppositely disposed anode and cathode, a light-emitting layer disposed between the anode and the cathode, and the anode is disposed on the substrate.
- a hole functional layer such as a hole injection layer, a hole transport layer, and an electron blocking layer can also be arranged between the anode and the light-emitting layer; an electron transport layer, an electron injection layer, and a hole blocking layer can also be arranged between the cathode and the light-emitting layer.
- the isoelectronic functional layer is shown in Figure 3.
- the light emitting device includes a substrate, an anode disposed on the surface of the substrate, a hole transport layer disposed on the surface of the anode, a light emitting layer disposed on the surface of the hole transport layer, An electron transport layer on the surface of the layer and a cathode disposed on the surface of the electron transport layer.
- the inversion structure light-emitting device includes a stacked structure of an anode and a cathode disposed oppositely, a light-emitting layer disposed between the anode and the cathode, and the cathode disposed on the substrate.
- a hole functional layer such as a hole injection layer, a hole transport layer, and an electron blocking layer can also be arranged between the anode and the light-emitting layer; an electron transport layer, an electron injection layer, and a hole blocking layer can also be arranged between the cathode and the light-emitting layer.
- the isoelectronic functional layer is shown in Figure 4.
- the light emitting device includes a substrate, a cathode disposed on the surface of the substrate, an electron transport layer disposed on the surface of the cathode, a light emitting layer disposed on the surface of the electron transport layer,
- the hole transport layer is an anode disposed on the surface of the hole transport layer.
- the choice of the substrate is not limited, and a rigid substrate or a flexible substrate may be used.
- the rigid substrate includes, but is not limited to, one or more of glass and metal foil.
- the flexible substrate includes, but is not limited to, polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polyetheretherketone (PEEK), polystyrene (PS), polyethersulfone (PES), polycarbonate (PC), polyarylate (PAT), polyarylate (PAR), polyimide (PI), polyvinyl chloride (PV), poly One or more of ethylene (PE), polyvinylpyrrolidone (PVP), and textile fibers.
- PET polyethylene terephthalate
- PEN polyethylene terephthalate
- PEEK polyetheretherketone
- PS polystyrene
- PS polyethersulfone
- PC polycarbonate
- PAT polyarylate
- PAR polyarylate
- PI polyimide
- PV polyviny
- the choice of anode material is not limited and can be selected from doped metal oxides, including but not limited to indium doped tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO), Aluminum-Doped Zinc Oxide (AZO), Gallium-Doped Zinc Oxide (GZO), Indium-Doped Zinc Oxide (IZO), Magnesium-Doped Zinc Oxide (MZO), Aluminum-Doped Magnesium Oxide (AMO) one or more.
- doped metal oxides including but not limited to indium doped tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO), Aluminum-Doped Zinc Oxide (AZO), Gallium-Doped Zinc Oxide (GZO), Indium-Doped Zinc Oxide (IZO), Magnesium-Doped Zinc Oxide (MZO), Aluminum-Doped Magnesium Oxide (AMO)
- the hole injection layer includes, but is not limited to, one or more of organic hole injection materials, doped or undoped transition metal oxides, doped or undoped metal chalcogenides .
- organic hole injection materials include, but are not limited to, poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS), copper phthalocyanine (CuPc), 2,3, 5,6-Tetrafluoro-7,7',8,8'-tetracyanoquinone-dimethane (F4-TCNQ), 2,3,6,7,10,11-hexacyano-1,4,5 One or more of ,8,9,12-hexaazatriphenylene (HATCN).
- PDOT:PSS poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid
- CuPc copper phthalocyanine
- F4-TCNQ 2,3,6,7,10,11-hexacyano-1,
- transition metal oxides include, but are not limited to, one or more of MoO 3 , VO 2 , WO 3 , CrO 3 , and CuO.
- the metal chalcogenide compounds include, but are not limited to, one or more of MoS 2 , MoSe 2 , WS 2 , WSe 2 , and CuS.
- the hole transport layer may be selected from organic materials with hole transport capability and/or inorganic materials with hole transport capability.
- the organic material with hole transport capability includes, but is not limited to, poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) (TFB), poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) Vinylcarbazole (PVK), poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) (poly-TPD), poly(9,9-dioctyl) Fluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4,4"-tris(carbazol-9-yl)triphenylamine (TCTA), 4, 4'-bis
- inorganic materials with hole transport capability include but are not limited to doped graphene, undoped graphene, C60, doped or undoped MoO 3 , VO 2 One or more of , WO 3 , CrO 3 , CuO, MoS 2 , MoSe 2 , WS 2 , WSe 2 , and CuS.
- the light-emitting layer includes the quantum dot material in the above embodiments, the quantum dot material is a core-shell structure quantum dot material, and the outer shell layer of the quantum dot material contains zinc.
- the outer shell layer of the quantum dot material includes: at least one of ZnS, ZnSe, ZnTe, CdZnS, and ZnCdSe, or an alloy material formed by at least two of them.
- the particle size of the quantum dot material is in the range of 2 to 10 nm. If the particle size is too small, the film-forming property of the quantum dot material becomes poor, and the energy resonance transfer effect between the quantum dot particles is significant, which is not conducive to the application of the material. , the particle size is too large, the quantum effect of the quantum dot material is weakened, resulting in a decrease in the optoelectronic properties of the material.
- the material of the electron transport layer adopts the electron transport layer of the above-mentioned laminated composite structure.
- the cathode material may be one or more of various conductive carbon materials, conductive metal oxide materials, and metallic materials.
- conductive carbon materials include, but are not limited to, doped or undoped carbon nanotubes, doped or undoped graphene, doped or undoped graphene oxide, C60, graphite, carbon fiber, many Empty carbon, or a mixture thereof.
- the conductive metal oxide material includes, but is not limited to, ITO, FTO, ATO, AZO, or mixtures thereof.
- the metal materials include, but are not limited to, Al, Ag, Cu, Mo, Au, or their alloys; among the metal materials, their forms include but are not limited to dense films, nanowires, nanospheres, nanometers Rods, nano cones, nano hollow spheres, or their mixtures; the cathode is Ag, Al.
- a light-emitting diode comprising the following preparation steps:
- ITO anode Provides ITO anode, and pre-treat the anode: use alkaline washing solution (preferably PH>10 ultrasonic for 15 min, deionized water ultrasonic for 15 min twice, isopropanol ultrasonic cleaning for 15 min, dry at 80 °C for 2 h, ozone ultraviolet Process for 15min.
- alkaline washing solution preferably PH>10 ultrasonic for 15 min, deionized water ultrasonic for 15 min twice, isopropanol ultrasonic cleaning for 15 min, dry at 80 °C for 2 h, ozone ultraviolet Process for 15min.
- step (2) (2) forming a hole injection layer on the anode of step (1): under an electric field, spin-coating the PEDOT:PSS solution on the anode, spin-coating at 5000 rpm for 40 s, and then annealing at 150° C. for 15 min to form a hole-injecting layer; wherein , the action direction of the electric field is perpendicular to the anode and toward the hole injection layer, and the electric field strength is 10 4 V/cm.
- Al is evaporated on the electron transport layer by an evaporation method to form an Al electrode with a thickness of 60-150 nm.
- UV treatment was performed on the prepared device, under the environment of H 2 O content less than 1 ppm and temperature of 100°C, vertical irradiation from the Al electrode side, UV wavelength 250nm, intensity 300mJ/cm 2 , UV time 30min.
- a light-emitting diode the difference between its preparation steps and Example 1 is: in step (7), UV treatment is performed on the prepared device, vertical irradiation from the ITO anode side, UV wavelength 420nm, intensity 100mJ/cm 2 , UV time 30min .
- a light-emitting diode the preparation steps of which are different from those in Example 1 are: TiO 2 is used in step (5).
- a light-emitting diode the preparation steps of which are different from those in Example 1 are: ZnMgO is used in step (5).
- a light-emitting diode the preparation steps of which are different from those in Example 1 are: CdZnSe/ZnSe is used in step (4).
- the ultraviolet illumination conditions are as follows: UV light with a UV wavelength of 320 nm and an intensity of 300 mJ/cm 2 is used to vertically irradiate the light-emitting layer for 30 minutes.
- a light-emitting diode the preparation steps of which are different from those in Example 1 are: CdZnSe/ZnSeS is used in step (4).
- the ultraviolet light conditions are: 340 nm, UV light with an intensity of 300 mJ/cm 2 vertically irradiates the light-emitting layer for 30 minutes.
- a light-emitting diode comprising the following preparation steps:
- step (2) forming the electron transport layer of the composite structure on the Al cathode of step (1): take the ZnO nanoparticle solution (concentration is 30mg/mL, the solvent is ethanol), put the ZnO nanoparticle solution in a glove box (water oxygen content is less than 0.1ppm), spin-coated on the low electrode at 4000rpm, and annealed at 80°C for 30min to form a ZnO layer. Then, take the Alq3 solution (concentration is 10 mg/mL, the solvent is dimethylformamide), spin-coat the Alq3 solution on the ZnO layer at 1000 rpm, and anneal at 80 °C for 30 min to form the Alq3 layer.
- a hole transport layer on the light-emitting layer under an electric field, spin-coat TFB solution (concentration of 8 mg/mL, solvent is chlorobenzene) on the light-emitting layer, spin-coat at 3000 rpm for 30 s, and then anneal at 80 °C for 30 min.
- a hole transport layer was formed; wherein the direction of action of the electric field was perpendicular to the anode and toward the hole transport layer, and the electric field strength was 104 V/cm.
- An ITO anode is formed on the hole injection layer.
- UV treatment was performed on the prepared device, under the environment of H 2 O content less than 1 ppm and temperature of 100°C, vertical irradiation from the Al electrode side, UV wavelength 250nm, intensity 200mJ/cm 2 , UV time 30min.
- a light-emitting diode the preparation steps of which are different from those in Example 1 are: in step (2), PCBM is used to prepare an organic electron transport layer.
- a light-emitting diode the preparation steps of which are different from those in Example 1 are: in step (2), ZnMgO is used to prepare an inorganic electron transport layer.
- a light-emitting diode the preparation steps of which are different from those in Example 1 are: Alq3+ZnO (particle size is 5.5 nm)+ZnO (particle size is 3 nm) is used in step (2).
- a light-emitting diode the preparation steps of which are different from those in Example 1 are: CdZnSe/ZnSe is used in step (3).
- the ultraviolet illumination conditions are as follows: UV light with a UV wavelength of 320 nm and an intensity of 300 mJ/cm 2 is used to vertically irradiate the light-emitting layer for 30 minutes.
- a light-emitting diode the preparation steps of which are different from those in Example 1 are: CdZnSe/ZnSeS is used in step (3).
- the ultraviolet light conditions are: 340 nm, UV light with an intensity of 300 mJ/cm 2 , vertically irradiating the light-emitting layer for 30 minutes.
- the two kinds of quantum dots used in Examples 13 to 20 of the present application are: blue QD1 with CdZnS outer shell (the inner core is CdZnSe, the middle shell is ZnSe, the outer shell thickness is 1.5 nm, and the top energy level of the valence band is -6.2 eV) , blue QD2 with ZnS outer shell (inner core is CdZnSe, intermediate shell is ZnSe, ZnS shell thickness is 0.3 nm, valence band top energy level is -6.5 eV).
- the blue QD3 with ZnSeS shell (the inner core is CdZnSe, the middle shell is ZnSe) hole transport materials are P9 (E HOMO :-5.1eV), P15 (E HOMO :-5.8eV), the hole injection layer is PEDOT : PSS (E HOMO : -5.1 eV), the electron transport layer adopts ZnO and TiO 2 , as shown in Table 2 below.
- the optoelectronic devices in Examples 13 to 20 of the present application are all UV treated: in an environment where the H 2 O content is less than 1 ppm and the temperature is 100° C., vertical irradiation from the Al electrode side, UV wavelength 250 nm, intensity 300 mJ/cm 2 , UV time 30min.
- Example 2 A light-emitting diode, the difference between its preparation steps and Example 1 is that it does not have step (7) UV treatment). Comparative Example 2
- a light-emitting diode whose preparation steps differ from those of Example 7 in that it is not UV-treated in step (8).
- step (2) the electron transport layer only contains a ZnO metal oxide layer
- a light-emitting diode the preparation steps of which are different from those in Example 1 are: in step (2), the electron transport layer only contains an Alq3 organic transport layer.
- test index and the test method are as follows, and the test results are shown in the following table and accompanying drawings:
- the specific calculation formula is as follows:
- ⁇ e is the optical output coupling efficiency
- ⁇ r is the ratio of the number of recombined carriers to the number of injected carriers
- ⁇ is the ratio of the number of excitons that generate photons to the total number of excitons
- KR is the radiation process rate.
- KNR is the nonradiative process rate. Test conditions: At room temperature, the air humidity is 30-60%.
- Luminance (L) is the ratio (cd/m2) of the luminous flux of the light-emitting surface in the specified direction to the area of the luminous flux perpendicular to the specified direction.
- the life test adopts the constant current method, under the constant current of 50mA/ cm2 , the silicon photosystem is used to test the brightness change of the device, and the time when the brightness of the device starts from the highest point and decays to 95% of the highest brightness is recorded LT95, Then extrapolate the 1000nit LT95S life of the device through the empirical formula:
- This method is convenient for comparing the lifetime of devices with different brightness levels, and has a wide range of applications in practical optoelectronic devices.
- the energy level test method of each material in the examples of the present application after spin-coating each functional layer material to form a film, the energy level test is carried out by UPS (ultraviolet photoelectron spectroscopy) method.
- UPS ultraviolet photoelectron spectroscopy
- Valence band top VB(HOMO): E HOMO E F-HOMO + ⁇ , where E F-HOMO is the difference between the material HOMO(VB) and the Fermi level, corresponding to the first occurrence of the low binding energy end in the binding energy spectrum the starting edge of a peak;
- E LOMO E HOMO -E HOMO-LOMO
- E HOMO-LOMO is the band gap of the material, obtained from UV-Vis (ultraviolet absorption spectrum).
- Example 1 Part number Quantum Dot Shell Electron transport layer (particle size) EQE(%) LT95 (hours) Comparative Example 1 ZnS ZnO(5.5nm) 1.80% 7.19 Example 1 ZnS ZnO(5.5nm) 4.30% 15.2 Example 2 ZnS ZnO(5.5nm) 3.10% 9.8 Example 3 ZnS TiO 2 (5.5nm) 5.10% 10.2 Example 4 ZnS ZnMgO(5.5nm) 6.10% 39 Example 5 ZnSe ZnO(5.5nm) 3.80% 12.4 Example 6 ZnSeS ZnO(5.5nm) 4.00% 13
- the ⁇ E EML-HTL barrier difference increases from 0.4eV to 0.7eV, the device The lifespan has been significantly improved, the 1000nit LT95S lifespan has been increased from 1.2 to 9.3. It can be seen that whether the HTL or EML material is adjusted to increase the valence band top energy level difference ⁇ E EML-HTL to more than 0.5 eV, the device injection balance is optimized, and the device lifetime can be enhanced. It shows that reducing the hole injection efficiency by increasing the hole injection barrier can better balance the injection balance of holes and electrons in the light-emitting layer, and improve the luminous efficiency and luminous life of the device.
Abstract
Disclosed in the present application are a light-emitting device and a preparation method therefor. The preparation method for the light-emitting device comprises the following steps: preparing a light-emitting device comprising an anode, a hole functional layer, a quantum dot light-emitting layer, an electron functional layer, and a cathode that are sequentially stacked, wherein the electron functional layer comprises a metal oxide transport material; and performing ultraviolet irradiation treatment on the light-emitting device. According to the preparation method for the light-emitting device of the present application, ultraviolet irradiation treatment is performed on the light-emitting device so that electrons of O in the metal oxide transport material are excited to form a complex with active metal elements in the quantum dot material, and at the same time, after being excited by ultraviolet light, the metal oxide material fuses well with the cathode. Internal physical structure defects and the surface roughness of the electron transport layer are reduced, the electron transport migration efficiency is high, the quantum dot light-emitting layer is tightly combined with the electron transport layer and cathode interface, the electron injection efficiency is high, the interface charge accumulation of the functional layers is avoided, and the device has good stability and a long service life.
Description
本申请要求于2020年12月31日在中国专利局提交的、申请号为202011636859.3、发明名称为“发光器件及其制备方法”，申请号为202011639283.6、发明名称为“发光器件及其制备方法”，以及申请号为202011639297.8、发明名称为“发光器件及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application is required to be submitted in the China Patent Office on December 31, 2020, the application number is 202011636859.3, the name of the invention is "light-emitting device and its preparation method", the application number is 202011639283.6, and the invention name is "light-emitting device and its preparation method" , and the priority of the Chinese patent application with the application number of 202011639297.8 and the invention titled "Light-emitting device and its preparation method", the entire contents of which are incorporated in this application by reference.
本申请涉及显示设备技术领域，具体涉及一种发光器件及其制备方法。The present application relates to the technical field of display devices, and in particular, to a light-emitting device and a preparation method thereof.
这里的陈述仅提供与本申请有关的背景信息，而不必然构成现有技术。量子点是半径小于或者接近波尔激子半径的纳米晶颗粒，其尺寸粒径一般介于一之间。量子点具有量子限域效应，受激发后可以发射荧光。而且量子点具有激发峰宽、发射峰窄、发光光谱可调等独特的发光特性，使得量子点材料在光电发光领域具有广阔的应用前景。量子点发光二极管(QLED)是近年来迅速兴起的一种新型显示技术，量子点发光二极管是将胶体量子点作为发光层的器件，在不同的导电材料之间引入量子点发光层从而得到所需要波长的光。量子点发光二极管具有色域高、自发光、启动电压低、响应速度快等优点。The statements herein merely provide background information related to the present application and do not necessarily constitute prior art. Quantum dots are nanocrystalline particles with a radius smaller than or close to the Bohr exciton radius, and their size and diameter are generally between one. Quantum dots have quantum confinement effect and can emit fluorescence when excited. Moreover, quantum dots have unique luminescence characteristics such as wide excitation peak, narrow emission peak, and tunable luminescence spectrum, which make quantum dot materials have broad application prospects in the field of optoelectronic luminescence. Quantum dot light-emitting diode (QLED) is a new type of display technology that has emerged rapidly in recent years. Quantum dot light-emitting diode is a device that uses colloidal quantum dots as the light-emitting layer. The quantum dot light-emitting layer is introduced between different conductive materials to obtain the required wavelength of light. Quantum dot light-emitting diodes have the advantages of high color gamut, self-luminescence, low startup voltage, and fast response speed.
目前OLED器件为了平衡载流子注入，一般采用多层的器件结构，量子点发光层多采用核壳结构的量子点纳米材料。量子点发光二极管中，量子点纳米颗粒的有机表面配体和其内部精细化的核壳结构，导致其退火温度不能过高，所以形成的量子点层界面粗糙度较高。另外，量子点层的退火温度也限制了其相邻电子传输层ETL的退火温度，使得电子传输材料难以达到较好的结晶温度，导致电子传输层内部结构不连续，降低了电子传输迁移率，增大了界面粗糙度。然而，量子点发光层和电子传输层之间高的界面粗糙度，影响了载流子注入到量子点发光层的连续性，注入效率低，降低了载流子注入性能。并且，界面缝隙处易形成电荷累积中心，加速材料老化，严重影响了器件寿命。At present, in order to balance the injection of carriers, OLED devices generally adopt a multi-layer device structure, and the quantum dot light-emitting layer mostly adopts quantum dot nanomaterials with a core-shell structure. In quantum dot light-emitting diodes, the organic surface ligands of quantum dot nanoparticles and the refined core-shell structure inside them make the annealing temperature not too high, so the interface roughness of the formed quantum dot layer is relatively high. In addition, the annealing temperature of the quantum dot layer also limits the annealing temperature of its adjacent electron transport layer ETL, making it difficult for the electron transport material to achieve a good crystallization temperature, resulting in discontinuous internal structure of the electron transport layer and reducing the electron transport mobility. Increased interface roughness. However, the high interface roughness between the QD light-emitting layer and the electron transport layer affects the continuity of carrier injection into the QD light-emitting layer, resulting in low injection efficiency and reduced carrier injection performance. In addition, the charge accumulation center is easily formed at the interface gap, which accelerates the aging of the material and seriously affects the life of the device.
本申请实施例的目的之一在于：提供一种发光器件及其制备方法，旨在解决光电器件中载流子复合不平衡的问题。One of the purposes of the embodiments of the present application is to provide a light-emitting device and a preparation method thereof, aiming at solving the problem of carrier recombination imbalance in optoelectronic devices.
为解决上述技术问题，本申请实施例采用的技术方案是：In order to solve the above-mentioned technical problems, the technical solutions adopted in the embodiments of the present application are:
第一方面，本申请提供一种发光器件的制备方法，包括以下步骤：In a first aspect, the present application provides a method for preparing a light-emitting device, comprising the following steps:
制备包括依次叠层设置的阳极、空穴功能层、量子点发光层、电子功能层和阴极的发光器件；其中，所述电子功能层中包括金属氧化物传输材料；preparing a light-emitting device including an anode, a hole functional layer, a quantum dot light-emitting layer, an electronic functional layer and a cathode that are stacked in sequence; wherein the electronic functional layer includes a metal oxide transport material;
对所述发光器件进行紫外光照射处理。The light-emitting device is subjected to ultraviolet light irradiation treatment.
第二方面，提供了一种发光器件，所述发光器件由上述的方法制得。In a second aspect, a light-emitting device is provided, and the light-emitting device is manufactured by the above-mentioned method.
本申请实施例提供的发光器件的制备方法的有益效果在于：一对包括阳极、空穴功能层、量子点发光层、电子功能层和阴极的发光器件进行紫外光照射处理，通过紫外光照射处理，一方面，使电子传输层(ETL)中金属氧化物传输材料中O的电子受激发后与相邻的量子点发光层(QD)中Zn等活泼金属元素形成配合物，使QD-ETL界面更融合，有利于电子注入发光层内部，且由于金属氧化物中O的电 子与量子点材料配位增加了传输层内部成键缺陷，提高了传输层内电子迁移率。另一方面，形成的配合物以及金属氧化物传输材料对UV光具有较强的吸收作用，使电子传输层及发光层界面处温度升高，传输层中晶体成键电子被激活，晶体再次生长，降低了传输层内部物理结构缺陷和表面粗糙度，使电子传输层与相邻的发光层和阴极界面结合更紧密稳定，减少界面缝隙，降低功能层之间的势垒，更有利于电子注入，减少电荷在界面层累积，降低材料老化速率，提高器件寿命。The beneficial effect of the method for preparing a light-emitting device provided by the embodiment of the present application is that: a pair of light-emitting devices including an anode, a hole functional layer, a quantum dot light-emitting layer, an electronic functional layer and a cathode are subjected to ultraviolet light irradiation treatment, and the ultraviolet light irradiation treatment is performed by On the one hand, the electrons of O in the metal oxide transport material in the electron transport layer (ETL) are excited to form complexes with active metal elements such as Zn in the adjacent quantum dot light-emitting layer (QD), so that the QD-ETL interface is formed. More fusion is conducive to electron injection into the light-emitting layer, and since the electrons of O in the metal oxide are coordinated with the quantum dot material, the bonding defects inside the transport layer are increased, and the electron mobility in the transport layer is improved. On the other hand, the formed complexes and metal oxide transport materials have a strong absorption effect on UV light, so that the temperature at the interface between the electron transport layer and the light-emitting layer increases, the crystal bonding electrons in the transport layer are activated, and the crystal grows again. , reduce the internal physical structure defects and surface roughness of the transport layer, make the electron transport layer more closely and stably combine with the adjacent light-emitting layer and the cathode interface, reduce the interface gap, reduce the potential barrier between the functional layers, and is more conducive to electron injection , reduce the accumulation of charges in the interface layer, reduce the material aging rate, and improve the device life.
本申请实施例提供的发光器件的有益效果在于：由于发光器件经过紫外光照射处理，电子传输层中金属氧化物传输材料中O的电子受激发与量子点发光层中Zn等活泼金属元素形成配合物，同时金属氧化物材料受紫外光激发后与阴极融合效果好。降低了电子传输层内部物理结构缺陷和表面粗糙度，电子传输迁移效率高，且量子点发光层与电子传输层和阴极界面结合紧密，电子注入效率高，避免功能层界面电荷累积，器件稳定性好，使用寿命长。The beneficial effect of the light-emitting device provided by the embodiments of the present application is that: since the light-emitting device is subjected to ultraviolet light irradiation treatment, the electrons of O in the metal oxide transport material in the electron transport layer are excited to form a coordination with active metal elements such as Zn in the quantum dot light-emitting layer. At the same time, the metal oxide material has a good fusion effect with the cathode after being excited by ultraviolet light. The internal physical structure defects and surface roughness of the electron transport layer are reduced, the electron transport and migration efficiency is high, and the quantum dot light-emitting layer is closely combined with the electron transport layer and the cathode interface, and the electron injection efficiency is high, avoiding the accumulation of charges at the interface of the functional layer, and the device is stable. Good, long lifespan.
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例或示范性技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。In order to illustrate the technical solutions in the embodiments of the present application more clearly, the following briefly introduces the accompanying drawings that are used in the description of the embodiments or exemplary technologies. Obviously, the drawings in the following description are only for the present application. In some embodiments, for those of ordinary skill in the art, other drawings can also be obtained according to these drawings without any creative effort.
图1是本申请实施例提供的发光器件的制备方法的流程示意图；1 is a schematic flowchart of a method for preparing a light-emitting device provided in an embodiment of the present application;
图2是本申请实施例提供的发光器件的结构示意图；FIG. 2 is a schematic structural diagram of a light-emitting device provided by an embodiment of the present application;
图3是本申请实施例提供的量子点发光二极管的正型结构示意图；3 is a schematic diagram of a positive structure of a quantum dot light-emitting diode provided by an embodiment of the present application;
图4是本申请实施例提供的量子点发光二极管的反型结构示意图；4 is a schematic diagram of an inversion structure of a quantum dot light-emitting diode provided by an embodiment of the present application;
图5是本申请实施例1和对比例1提供的量子点发光二极管的效率曲线图；5 is a graph of the efficiency of the quantum dot light-emitting diodes provided in Example 1 and Comparative Example 1 of the present application;
图6是本申请实施例1和对比例1提供的量子点发光二极管的电流密度-电压曲线图；6 is a current density-voltage graph of the quantum dot light-emitting diodes provided in Example 1 and Comparative Example 1 of the present application;
图7是本申请实施例1和对比例1提供的量子点发光二极管的亮度曲线图；7 is a graph of the brightness of the quantum dot light-emitting diodes provided in Example 1 and Comparative Example 1 of the present application;
图8是本申请实施例7、实施例10、对比例2和对比例3提供的量子点发光二极管的效率曲线图；8 is a graph showing the efficiency of the quantum dot light-emitting diodes provided in Example 7, Example 10, Comparative Example 2 and Comparative Example 3 of the present application;
图9是本申请实施例7、实施例10、对比例2和对比例3提供的量子点发光二极管的电流密度-电压曲线图；9 is a current density-voltage graph of the quantum dot light-emitting diodes provided in Example 7, Example 10, Comparative Example 2 and Comparative Example 3 of the present application;
图10是本申请实施例7、实施例10、对比例2和对比例3提供的量子点发光二极管的亮度曲线图。FIG. 10 is a graph showing the brightness of the quantum dot light-emitting diodes provided in Example 7, Example 10, Comparative Example 2 and Comparative Example 3 of the present application.
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本申请，并不用于限定本申请。In order to make the purpose, technical solutions and advantages of the present application more clearly understood, the present application will be described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application, but not to limit the present application.
本申请中，术语“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。In this application, the term "and/or", which describes the relationship between related objects, means that there can be three relationships, for example, A and/or B, which can mean that A exists alone, A and B exist at the same time, and B exists alone Happening. where A and B can be singular or plural.
本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a,b,或c中的至少一项(个)”，或，“a,b,和c中的至少一项(个)”，均可以表示：a,b,c,a-b(即a和b),a-c,b-c,或a-b-c，其中a,b,c分别可以是单个，也可以是多个。In this application, "at least one" means one or more, and "plurality" means two or more. "At least one item(s) below" or similar expressions thereof refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (one) of a, b, or c", or, "at least one (one) of a, b, and c", can mean: a,b,c,a-b( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple respectively.
应理解，在本申请的各种实施例中，上述各过程的序号的大小并不意味着执行顺序的先后，部分或全部步骤可以并行执行或先后执行，各过程的执行顺序应以其功能和内在逻辑确定，而不应对本申请实 施例的实施过程构成任何限定。在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。It should be understood that, in various embodiments of the present application, the size of the sequence numbers of the above-mentioned processes does not imply the sequence of execution, some or all of the steps may be executed in parallel or sequentially, and the execution sequence of each process should be based on its functions and It is determined by the internal logic and should not constitute any limitation on the implementation process of the embodiments of the present application. The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. As used in the embodiments of this application and the appended claims, the singular forms "a" and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise.
在本申请实施例中，ΔE
HTL-HIL＝E
HOMO,HTL-E
HIL，ΔE
EML-HTL＝E
HOMO,EML-E
HTL，所有能级/功函值均取绝对值，能级绝对值大表示能级深，能级绝对值小表示能级浅。
In the examples of the present application, ΔE HTL-HIL =E HOMO,HTL -E HIL , ΔE EML-HTL =E HOMO,EML -E HTL , all energy level/work function values are absolute values, and the absolute value of the energy level is large The energy level is deep, and the absolute value of the energy level is small, the energy level is shallow.
如附图1所示，本申请实施例第一方面提供一种发光器件的制备方法，包括以下步骤：As shown in FIG. 1 , a first aspect of an embodiment of the present application provides a method for preparing a light-emitting device, including the following steps:
S10.制备包括依次叠层设置的阳极、空穴功能层、量子点发光层、电子功能层和阴极的发光器件；其中，电子功能层中包括金属氧化物传输材料；S10. Prepare a light-emitting device comprising an anode, a hole functional layer, a quantum dot light-emitting layer, an electronic functional layer, and a cathode that are sequentially stacked; wherein, the electronic functional layer includes a metal oxide transport material;
S20.对发光器件进行紫外光照射处理。S20. Perform ultraviolet light irradiation treatment on the light-emitting device.
本申请第一方面提供的发光器件的制备方法，对包括阳极、空穴功能层、量子点发光层、电子功能层和阴极的发光器件进行紫外光照射处理，通过紫外光照射处理，一方面，使电子传输层(ETL)中金属氧化物传输材料中O的电子受激发后与相邻的量子点发光层(QD)中Zn等活泼金属元素形成配合物，使QD-ETL界面更融合，有利于电子注入发光层内部，且由于金属氧化物中O的电子与量子点材料配位增加了传输层内部成键缺陷，提高了传输层内电子迁移率。另一方面，形成的配合物以及金属氧化物传输材料对UV光具有较强的吸收作用，使电子传输层及发光层界面处温度升高，传输层中晶体成键电子被激活，晶体再次生长，降低了传输层内部物理结构缺陷和表面粗糙度，使电子传输层与相邻的发光层和阴极界面结合更紧密稳定，减少界面缝隙，降低功能层之间的势垒，更有利于电子注入，减少电荷在界面层累积，降低材料老化速率，提高器件寿命。In the method for preparing a light-emitting device provided in the first aspect of the present application, a light-emitting device comprising an anode, a hole functional layer, a quantum dot light-emitting layer, an electronic functional layer and a cathode is subjected to ultraviolet light irradiation treatment, and through the ultraviolet light irradiation treatment, on the one hand, The electrons of O in the metal oxide transport material in the electron transport layer (ETL) are excited to form complexes with active metal elements such as Zn in the adjacent quantum dot light-emitting layer (QD), so that the QD-ETL interface is more fused. It is beneficial to inject electrons into the inside of the light-emitting layer, and because the electrons of O in the metal oxide are coordinated with the quantum dot material, the bonding defects inside the transport layer are increased, and the electron mobility in the transport layer is improved. On the other hand, the formed complexes and metal oxide transport materials have a strong absorption effect on UV light, so that the temperature at the interface between the electron transport layer and the light-emitting layer increases, the crystal bonding electrons in the transport layer are activated, and the crystal grows again. , reduce the internal physical structure defects and surface roughness of the transport layer, make the electron transport layer more closely and stably combine with the adjacent light-emitting layer and the cathode interface, reduce the interface gap, reduce the potential barrier between the functional layers, and is more conducive to electron injection , reduce the accumulation of charges in the interface layer, reduce the material aging rate, and improve the device life.
本申请实施例通过研究发现：QLED器件在初始工作状态时，发光层中电子注入速率比空穴快，导致量子点材料带负电，且这种负电状态会因量子点材料的结构特性和表面配体的束缚作用、库仑阻塞效应、电荷分布不均、界面层电荷积累等因素得以保持。另外，当发光层与电子传输层界面存在较多缺陷和较大势垒时，电子向发光层注入困难。在器件工作形成稳定电流时，QD-ETL界面存在较大的电场强度分布，电荷分布密度较高，QD和ETL界面有较大的电荷累积。量子点材料的负电状态使得QLED器件在持续工作过程中，电子的注入变得越来越困难，从而导致发光层中电子与空穴实际注入不平衡。进一步地，QLED器件持续点亮工作至稳定状态的过程中，量子点材料带负电的状态也趋于稳定，即被量子点新捕获束缚的电子与发生辐射跃迁所消耗的电子达到动态平衡。此时电子向发光层的注入速率相比起始状态时要低很多，达到发光层中电荷注入平衡所需的空穴注入速率实际也相对较低。若仍然基于传统OLED器件的理论体系提高空穴的注入效率，采用深能级的空穴传输层只能在QLED器件工作起始阶段形成电荷注入的瞬间平衡，达到起始瞬间的高器件效率。但是，随着QLED器件进入稳定的工作状态，过量的空穴注入反而会加重器件发光层中电子与空穴的不平衡状态，QLED器件效率无法保持，随之降低。且这种电荷的不平衡状态会随着器件持续工作而不断加剧，导致QLED器件寿命也会相应地迅速衰减。Through research in the examples of the present application, it is found that in the initial working state of the QLED device, the injection rate of electrons in the light-emitting layer is faster than that of holes, resulting in the negative charge of the quantum dot material. Factors such as bulk binding, Coulomb blocking effect, uneven charge distribution, and charge accumulation in the interface layer are maintained. In addition, when there are many defects and large potential barriers at the interface between the light-emitting layer and the electron transport layer, it is difficult to inject electrons into the light-emitting layer. When the device operates to form a stable current, the QD-ETL interface has a large electric field intensity distribution, a high charge distribution density, and a large charge accumulation at the QD-ETL interface. The negatively charged state of the quantum dot material makes the injection of electrons more and more difficult during the continuous operation of the QLED device, resulting in an imbalance between the actual injection of electrons and holes in the light-emitting layer. Furthermore, when the QLED device continues to light up and work to a stable state, the negatively charged state of the quantum dot material also tends to be stable, that is, the electrons newly captured and bound by the quantum dots reach a dynamic balance with the electrons consumed by the radiative transition. At this time, the injection rate of electrons into the light-emitting layer is much lower than that in the initial state, and the hole injection rate required to achieve the balance of charge injection in the light-emitting layer is actually relatively low. If the hole injection efficiency is still improved based on the theoretical system of traditional OLED devices, the use of deep-level hole transport layers can only form an instantaneous balance of charge injection in the initial stage of QLED device operation, and achieve high device efficiency at the initial instant. However, as the QLED device enters a stable working state, excessive hole injection will aggravate the unbalanced state of electrons and holes in the light-emitting layer of the device, and the efficiency of the QLED device cannot be maintained, and thus decreases. And this charge imbalance will continue to increase as the device continues to work, resulting in a corresponding rapid decline in the life of the QLED device.
因此，为了实现在器件发光层中载流子的注入平衡，获得更高效率和更长使用寿命的器件。本申请在一些实施例中，量子点发光层中包括核壳结构的量子点材料，量子点材料的外壳层材料与空穴传输层中空穴传输材料的价带顶能级差大于等于0.5eV。本申请实施例通过构建量子点材料的外壳层材料与空穴传输材料的价带顶能级差大于等于0.5eV的空穴注入势垒，提高空穴注入势垒，降低空穴的注入效率， 从而平衡发光层中空穴与电子的注入平衡。Therefore, in order to achieve a balance of carrier injection in the light-emitting layer of the device, a device with higher efficiency and longer lifetime is obtained. In some embodiments of the present application, the quantum dot light-emitting layer includes a quantum dot material with a core-shell structure, and the valence band top energy level difference between the outer shell layer material of the quantum dot material and the hole transport material in the hole transport layer is greater than or equal to 0.5 eV. In the embodiments of the present application, by constructing a hole injection barrier with a valence band top energy level difference of greater than or equal to 0.5 eV between the outer shell layer material of the quantum dot material and the hole transport material, the hole injection barrier is increased and the hole injection efficiency is reduced, thereby Balance the injection balance of holes and electrons in the light-emitting layer.
需要说明的是，本申请实施例构建的ΔE
EML-HTL≥0.5eV的空穴注入势垒并不会导致空穴无法注入。因为量子点在通电工作状态下外壳层的能级会发生能带弯曲，载流子可以通过隧穿效应实现注入；因而这种能级势垒的增加虽然会造成载流子注入速率的降低，但并不会完全阻碍载流子的最终注入。本申请实施例核壳结构的量子点材料中内核材料决定发光性能，外壳材料起到保护和利于载流子注入作用，电子、空穴经过外壳层注入到内核进行发光。一般内核的带隙比外壳窄，所以空穴传输材料与量子点内核价带能级差要小于空穴传输材料与量子点外壳价带能级差。因此，ΔE
EML-HTL大于等于0.5eV能够同时确保空穴载流子有效的注入量子点材料的内核。
It should be noted that the hole injection barrier with ΔE EML-HTL ≥0.5 eV constructed in the examples of the present application does not cause holes to be unable to be injected. Because the energy level of the outer shell layer of quantum dots will bend in the energized state, carriers can be injected through the tunneling effect; therefore, although the increase in the energy level barrier will reduce the carrier injection rate, But it does not completely hinder the final injection of carriers. In the quantum dot materials of the core-shell structure of the embodiments of the present application, the core material determines the luminescence performance, the shell material protects and facilitates carrier injection, and electrons and holes are injected into the core through the shell layer to emit light. Generally, the band gap of the inner core is narrower than that of the outer shell, so the energy level difference between the valence band of the hole transport material and the inner core of the quantum dot is smaller than the energy level difference of the valence band of the hole transport material and the outer shell of the quantum dot. Therefore, the ΔE EML-HTL is greater than or equal to 0.5 eV, which can simultaneously ensure the effective injection of hole carriers into the inner core of the quantum dot material.
在一些实施例中，量子点材料的外壳层材料与空穴传输层中空穴传输材料的价带顶能级差为0.5～1.7eV，即ΔE
EML-HTL为0.5eV～1.7eV，在量子点材料的外壳层材料与空穴传输材料之间构建的该范围的能级势垒，可适用于由不同空穴传输材料和量子点材料构筑的器件体系，优化不同器件体系中电子与空穴的注入平衡。在实际应用中可根据具体的材料性能，设置不同顶价带能级差ΔE
EML-HTL的情形，精细调控发光层两侧空穴和电子的载流子注入速率，使空穴和电子注入平衡。
In some embodiments, the valence band top energy level difference between the outer shell layer material of the quantum dot material and the hole transport material in the hole transport layer is 0.5-1.7 eV, that is, the ΔE EML-HTL is 0.5 eV-1.7 eV, and the quantum dot material is 0.5-1.7 eV. The energy level barrier in this range constructed between the outer shell material and the hole transport material can be applied to device systems constructed of different hole transport materials and quantum dot materials to optimize the injection of electrons and holes in different device systems. balance. In practical applications, different top valence band energy level differences ΔE EML-HTL can be set according to the specific material properties, and the carrier injection rate of holes and electrons on both sides of the light-emitting layer can be finely adjusted to balance the injection of holes and electrons.
在一些实施例中，空穴传输材料的价带顶能级的绝对值小于等于5.3eV。本申请实施例为了构筑ΔE
EML-HTL大于等于0.5eV的能级势垒，实现降低QLED器件内空穴注入速率，调控载流子的注入、复合效率的目的，采用价带顶能级的绝对值小于等于5.3eV的空穴传输材料，常规量子点发光材料的壳层能级往往比较深(6.0eV或更深)，因此，使得浅能级的空穴传输材料与量子点外壳材料之间形成大于等于0.5eV的能级差。
In some embodiments, the absolute value of the valence band top energy level of the hole transport material is less than or equal to 5.3 eV. In order to construct an energy level barrier with ΔE EML-HTL greater than or equal to 0.5 eV, to reduce the hole injection rate in the QLED device, and to regulate the injection and recombination efficiency of carriers, the absolute value of the top energy level of the valence band is adopted in the examples of the present application. For hole transport materials with a value of less than or equal to 5.3eV, the shell energy level of conventional quantum dot light-emitting materials is often relatively deep (6.0eV or deeper). The energy level difference is greater than or equal to 0.5eV.
在一些实施例中，空穴传输材料的迁移率高于1×10
-4cm
2/Vs。本申请实施例采用迁移率高于1×10
-4cm
2/Vs的空穴传输材料，进一步确保空穴的传输迁移效果，防止电荷积累，消除界面电荷，更好的降低器件驱动电压、提升器件寿命。
In some embodiments, the mobility of the hole transport material is higher than 1×10 −4 cm 2 /Vs. The embodiments of the present application use hole transport materials with a mobility higher than 1×10 -4 cm 2 /Vs to further ensure the hole transport and migration effect, prevent charge accumulation, eliminate interface charges, and better reduce the device driving voltage and improve Device life.
在一些实施例中，空穴传输材料选自：含苯胺基团的聚合物、含有芴基团和苯胺基团的共聚物中的至少一种，这些空穴传输材料具有空穴传输效率高，稳定性好，容易获取等优点。在一些具体实施例中，空穴传输材料包括：TFB、poly-TPD、P10、P11、P15、P12、P09、P13中的至少一种，其中，P13的结构式为：
P09的结构式为：
P11 的结构式为：
poly-TPD的结构式为：
TFB的结构式为：
P12的结构式为：
P15的结构式为：
In some embodiments, the hole transport material is selected from at least one of: a polymer containing an aniline group, a copolymer containing a fluorene group and an aniline group, and these hole transport materials have high hole transport efficiency, It has the advantages of good stability and easy access. In some specific embodiments, the hole transport material includes: at least one of TFB, poly-TPD, P10, P11, P15, P12, P09, and P13, wherein the structural formula of P13 is: The structural formula of P09 is: The structural formula of P11 is: The structural formula of poly-TPD is: The structural formula of TFB is: The structural formula of P12 is: The structural formula of P15 is:
在一些具体实施例中，量子点材料的外壳层材料与空穴传输材料的价带顶能级差为0.5eV～0.7eV，此时适用空穴传输材料为TFB，量子点外壳材料为ZnSe，TFB-ZnSe器件体系。在一些具体实施例中，量子点材料的外壳层材料与空穴传输材料的价带顶能级差为0.7eV～1.0eV，此时适用空穴传输材料为P09，量子点外壳材料为ZnSe，P09-ZnSe器件体系。在一些具体实施例中，量子点材料的外壳层材料与空穴传输材料的价带顶能级差为1.0eV～1.4eV，此时适用空穴传输材料为TFB、P13、P14，量子点外壳材料为ZnSe、ZnS，如：TFB-ZnS、P13/P14-ZnSe等器件体系。在一些具体实施例中，量子点材料的外壳层材料与空穴传输材料的价带顶能级差大于1.4eV～1.7eV，此时适用P09-ZnS、P13/P14-ZnS的器件体系。In some specific embodiments, the valence band top energy level difference between the outer shell material of the quantum dot material and the hole transport material is 0.5eV～0.7eV, in this case, the applicable hole transport material is TFB, and the quantum dot shell material is ZnSe, TFB -ZnSe device system. In some specific embodiments, the valence band top energy level difference between the outer shell material of the quantum dot material and the hole transport material is 0.7 eV to 1.0 eV, and the applicable hole transport material is P09, and the outer shell material of the quantum dot is ZnSe, P09 -ZnSe device system. In some specific embodiments, the valence band top energy level difference between the shell layer material of the quantum dot material and the hole transport material is 1.0eV～1.4eV, and the applicable hole transport material is TFB, P13, P14, and the quantum dot shell material For ZnSe, ZnS, such as: TFB-ZnS, P13/P14-ZnSe and other device systems. In some specific embodiments, the valence band top energy level difference between the outer shell layer material of the quantum dot material and the hole transport material is greater than 1.4eV-1.7eV, and the device system of P09-ZnS and P13/P14-ZnS is applicable.
在一些实施例中，量子点发光层中包括核壳结构的量子点材料，量子点材料的外壳层含有锌元素。由于目前的量子点合成大多采用II-VI族的元素，Zn元素与VI族的元素从晶格匹配和带隙方面均有更好的匹配性，能够覆盖整个可见光波段，且量子点材料的外壳层含锌元素的外壳层化学活泼性适合，灵活可控性高，带隙宽，激子束缚性好，量子效率高，水氧稳定性好。另外，锌元素与O的电子的配位效果更好且更稳定。通过UV照射，电子传输层中金属氧化物传输材料的O的电子受激发，易与QD中的 Zn元素形成配合物，即ZnO配合物。ZnO配合键的形成有利于电子注入，提高了电子传输层中电子迁移率。同时，ZnO配合物对紫外光波长有较强的吸收作用，有利于激活成键电子，使ETL中晶体再次生长，降低了ETL内部物理结构缺陷和表面粗糙度，有利于电子注入，减少电子累积，减缓材料老化，有利于提高器件寿命。In some embodiments, the quantum dot light-emitting layer includes a core-shell structure quantum dot material, and the outer shell layer of the quantum dot material contains zinc. Since most of the current quantum dot synthesis uses II-VI group elements, Zn element and VI group elements have better matching in terms of lattice matching and band gap, which can cover the entire visible light band, and the outer shell of the quantum dot material The zinc-containing outer shell layer has suitable chemical activity, high flexibility and controllability, wide band gap, good exciton binding, high quantum efficiency, and good water-oxygen stability. In addition, the coordination effect of zinc element and O electrons is better and more stable. Through UV irradiation, the electrons of O of the metal oxide transport material in the electron transport layer are excited, and it is easy to form a complex with the Zn element in the QD, that is, a ZnO complex. The formation of ZnO complex bonds facilitates electron injection and improves electron mobility in the electron transport layer. At the same time, the ZnO complex has a strong absorption effect on the wavelength of ultraviolet light, which is conducive to activating the bonding electrons, making the crystal in the ETL grow again, reducing the internal physical structure defects and surface roughness of the ETL, which is conducive to the injection of electrons and reduces the accumulation of electrons. , slow down the material aging, and help to improve the life of the device.
在一些实施例中，量子点材料的外壳层包括：ZnS、ZnSe、ZnTe、CdZnS、ZnCdSe中的至少一种或者至少两种形成的合金材料，这些外壳材料均含有锌元素，锌元素活性高，与电子传输材料中受激O电子有较好的配位效果。In some embodiments, the outer shell layer of the quantum dot material includes: at least one of ZnS, ZnSe, ZnTe, CdZnS, ZnCdSe, or an alloy material formed by at least two kinds of the outer shell materials, all of which contain zinc element, and the zinc element has high activity, It has a good coordination effect with the excited O electrons in the electron transport material.
在一些实施例中，上述步骤S10中，制备电子功能层的步骤包括：在阴极背离衬底的表面依次制备第一子电子传输层至第N子电子传输层，形成电子传输层；其中，电子传输层中至少一层子电子传输层包括有机传输材料，至少第N子电子传输层中包括金属氧化物传输材料，N为大于等于2的正整数。本申请实施例在器件中制备了多层叠层复合结构的电子传输层，既包含有具有较高的电子迁移率的金属氧化物子传输层，又包含较宽能级调控的有机子传输层。使复合结构的电子传输层同时具有高电子迁移率和能级匹配特性，实现对电子传输层的能级和电子迁移率的灵活调控，优化发光层内电子与空穴注入及复合效率。In some embodiments, in the above step S10, the step of preparing the electronic functional layer includes: sequentially preparing the first sub-electron transport layer to the N-th sub-electron transport layer on the surface of the cathode away from the substrate to form an electron transport layer; At least one sub-electron transport layer in the transport layer includes an organic transport material, at least the N-th sub-electron transport layer includes a metal oxide transport material, and N is a positive integer greater than or equal to 2. In the examples of the present application, an electron transport layer of a multi-layered composite structure is prepared in the device, which includes both a metal oxide sub-transport layer with high electron mobility and an organic sub-transport layer with wide energy level regulation. The electron transport layer of the composite structure has the characteristics of high electron mobility and energy level matching at the same time, realizes the flexible regulation of the energy level and electron mobility of the electron transport layer, and optimizes the injection and recombination efficiency of electrons and holes in the light-emitting layer.
在一些实施例中，制备的发光器件中，电子传输层中，靠近阴极的第一子电子传输层和靠近量子点发光层的第N子电子传输层分别独立地包含金属氧化物传输材料，N为大于等于3且小于等于9的正整数，N的取值过大，会导致电子传输层过厚，不利于电子传输。本申请实施例制备的光电器件，通过紫外光照射处理，促进第N子电子传输层中金属氧化物传输材料与量子点中活泼金属元素进行配位，同时促进第一子电子传输层中金属氧化物传输材料与金属阴极中金属元素进行配位，提高QD-ETL和ETL-阴极界面间的融合性，更有利于电子注入。In some embodiments, in the prepared light-emitting device, in the electron transport layer, the first sub-electron transport layer close to the cathode and the N-th sub-electron transport layer close to the quantum dot light-emitting layer each independently comprise a metal oxide transport material, N It is a positive integer greater than or equal to 3 and less than or equal to 9. If the value of N is too large, the electron transport layer will be too thick, which is not conducive to electron transport. The optoelectronic devices prepared in the examples of the present application are treated with ultraviolet light to promote the coordination of the metal oxide transport material in the N-th electron transport layer with the active metal elements in the quantum dots, and at the same time promote the oxidation of metals in the first electron transport layer. The material transport material is coordinated with the metal element in the metal cathode to improve the fusion between the QD-ETL and the ETL-cathode interface, which is more conducive to electron injection.
在一些实施例中，本申请实施例制备的发光器件的结构示意图，如附图2所示，从上至下包括依次叠层设置的阳极、空穴传输层、量子点发光层、电子传输层(从上至下依次包括第N子电子传输层、第N-1子电子传输层……第一子电子传输层)和阴极，其中，靠近量子点发光层的第N子电子传输层为金属氧化物层。In some embodiments, a schematic structural diagram of the light-emitting device prepared in the embodiment of the present application, as shown in FIG. 2 , includes an anode, a hole transport layer, a quantum dot light-emitting layer, and an electron transport layer that are stacked in sequence from top to bottom. (From top to bottom, it includes the Nth electron transport layer, the N-1th electron transport layer...the first electron transport layer) and the cathode, wherein the Nth electron transport layer near the quantum dot light-emitting layer is a metal oxide layer.
在一些实施例中，第N子电子传输层中金属氧化物传输材料的粒径为2～4nm，小粒径的金属氧化物颗粒比表面积大，表面活性更高，在紫外光照射处理时更容易与量子点中活泼金属进行配合，形成更优的QD-ETL界面。并且，小粒径的金属氧化物颗粒带隙更宽，减小了发光层中激子发光的淬灭，提高了器件效率。In some embodiments, the particle size of the metal oxide transport material in the N-th electron transport layer is 2 to 4 nm, and the metal oxide particles with small particle size have a larger specific surface area and higher surface activity, and are more effective when irradiated with ultraviolet light. It is easy to cooperate with active metals in quantum dots to form a better QD-ETL interface. In addition, the metal oxide particles with small particle size have a wider band gap, which reduces the quenching of exciton emission in the light-emitting layer and improves the device efficiency.
在一些实施例中，电子传输层中至少包括一层金属氧化物传输材料的粒径为4～8nm的子电子传输层，该粒径大小的金属氧化物电子迁移效率高，有利于电子注入发光层中，且在溶液中更易分散，成膜性能更好。In some embodiments, the electron transport layer includes at least one sub-electron transport layer of a metal oxide transport material with a particle size of 4-8 nm. The metal oxide with this particle size has high electron transfer efficiency and is conducive to electron injection and light emission. It is easier to disperse in the solution and has better film-forming properties.
在一些实施例中，电子传输层中，至少包括一层金属氧化物传输材料的粒径为4～8nm的子电子传输层，且第N子电子传输层中金属氧化物传输材料的粒径为2～4nm。由于小粒径的金属氧化物电子迁移率相对较小，影响电子注入，且稳定性能、成膜性能相对较差，降低了器件性能，因此，本申请实施例采用QD/2～4nm小粒径金属氧化物/4～8nm大粒径金属氧化物配合，使电子传输层兼具高电子迁移注入效率、成膜稳定性、QD-ETL界面融合性等特性，提高器件性能。In some embodiments, the electron transport layer includes at least one sub-electron transport layer with a metal oxide transport material having a particle size of 4-8 nm, and the particle size of the metal oxide transport material in the Nth sub-electron transport layer is 2 to 4 nm. Since the electron mobility of metal oxides with small particle size is relatively small, which affects electron injection, and has relatively poor stability and film-forming performance, which reduces device performance, the embodiments of the present application use QD/2-4nm small particle size The combination of metal oxide/4-8nm large particle size metal oxide makes the electron transport layer have high electron migration and injection efficiency, film formation stability, QD-ETL interface fusion and other characteristics, and improves device performance.
在一些实施例中，金属氧化物传输材料选自ZnO、TiO
2、Fe
2O
3、SnO
2、Ta
2O
3中的至少一种；这些金属氧化物材料具有较高的电子迁移率，且其中O的激发电子与QD外壳层中锌元素配位效果好。在具体一些实施例中，金属氧化物传输材料选自ZnO、TiO
2、Fe
2O
3、SnO
2、Ta
2O
3中的一种，或者两种或两种以上的混合物。
In some embodiments, the metal oxide transport material is selected from at least one of ZnO, TiO 2 , Fe 2 O 3 , SnO 2 , Ta 2 O 3 ; these metal oxide materials have high electron mobility, and Among them, the excited electrons of O have a good coordination effect with the zinc element in the QD shell. In some specific embodiments, the metal oxide transport material is selected from one of ZnO, TiO 2 , Fe 2 O 3 , SnO 2 , and Ta 2 O 3 , or a mixture of two or more.
在一些实施例中，金属氧化物传输材料选自掺杂有金属元素的ZnO、TiO
2、Fe
2O
3、SnO
2、Ta
2O
3中的至少一种，其中，金属元素包括铝、镁、锂、镧、钇、锰、镓、铁、铬、钴中至少一种。本申请实施例金属氧化物传输材料中掺杂有铝、镁、锂、镧、钇、锰、镓、铁、铬、钴等金属元素，有利于提高材料的电子传输迁移效率。在具体一些实施例中，金属氧化物传输材料中掺杂铝、镁、锂、镧、钇、锰、镓、铁、铬、钴中一种金属元素，或者同时掺杂两种或两种以上的金属元素。
In some embodiments, the metal oxide transport material is selected from at least one of ZnO, TiO 2 , Fe 2 O 3 , SnO 2 , Ta 2 O 3 doped with metal elements, wherein the metal elements include aluminum, magnesium , at least one of lithium, lanthanum, yttrium, manganese, gallium, iron, chromium, and cobalt. The metal oxide transport materials of the embodiments of the present application are doped with metal elements such as aluminum, magnesium, lithium, lanthanum, yttrium, manganese, gallium, iron, chromium, cobalt, etc., which are beneficial to improve the electron transport and migration efficiency of the materials. In some specific embodiments, the metal oxide transport material is doped with one metal element of aluminum, magnesium, lithium, lanthanum, yttrium, manganese, gallium, iron, chromium, and cobalt, or two or more of them are simultaneously doped metal element.
在一些实施例中，有机传输材料的电子迁移率大于等于10
-4cm
2/Vs，高迁移率的有机传输材料，确保电子在传输层中的迁移传输效率，提高电子的注入效率，避免电荷积累对器件寿命的影响。
In some embodiments, the electron mobility of the organic transport material is greater than or equal to 10 -4 cm 2 /Vs, and the organic transport material with high mobility can ensure the transfer efficiency of electrons in the transport layer, improve the injection efficiency of electrons, and avoid charges The effect of accumulation on device lifetime.
在一些实施例中，有机传输材料选自8-羟基喹啉-锂(Alq
3)、八羟基喹啉铝、富勒烯衍生物PCBM、3,5-双(4-叔丁基苯基)-4-苯基-4H-1,2,4-***(BPT)、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯(TPBi)中的至少一种。这些有机传输材料可以在较宽的范围内实现能级的调控，更有利于调控器件各功能层能级，提高器件的稳定性和光电转化效率。
In some embodiments, the organic transport material is selected from the group consisting of 8-quinolinolato-lithium (Alq 3 ), aluminum octaquinolate, fullerene derivatives PCBM, 3,5-bis(4-tert-butylphenyl) - At least one of 4-phenyl-4H-1,2,4-triazole (BPT), 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi) A sort of. These organic transport materials can realize energy level regulation in a wide range, which is more conducive to regulating the energy levels of each functional layer of the device and improving the stability and photoelectric conversion efficiency of the device.
在一些实施例中，电子传输层的厚度为10～200nm。在一些具体实施例中，第N子电子传输层的厚度为2～8nm。该厚度满足器件性要求和结构要求。在一些具体实施例中，当电子传输层的厚度低于80nm时，紫外光照射处理的时长为15分钟～45分钟。本申请实施例当电子传输层厚度低于80nm时，低厚度的材料层光波能量相对容易穿透，此时达到处理效果所需的光照时间较短，紫外光照射处理的时长为15分钟～45分钟适宜。在另一些具体实施例中，当电子传输层的厚度高于80nm时，紫外光照射处理的时长为30分钟～90分钟。本申请实施例当电子传输层厚度高于80nm时，厚度较厚的材料层光波能量难以穿透，此时达到处理效果所需的光照时间较长，紫外光照射处理的时长为30分钟～90分钟适宜。In some embodiments, the electron transport layer has a thickness of 10-200 nm. In some specific embodiments, the thickness of the Nth sub-electron transport layer is 2˜8 nm. This thickness satisfies device performance requirements and structural requirements. In some specific embodiments, when the thickness of the electron transport layer is less than 80 nm, the duration of the ultraviolet light irradiation treatment is 15 minutes to 45 minutes. In the examples of the present application, when the thickness of the electron transport layer is less than 80 nm, the light wave energy of the low-thickness material layer is relatively easy to penetrate. At this time, the irradiation time required to achieve the treatment effect is short, and the duration of the ultraviolet light irradiation treatment is 15 minutes to 45 minutes. minutes are appropriate. In other specific embodiments, when the thickness of the electron transport layer is higher than 80 nm, the duration of the ultraviolet light irradiation treatment is 30 minutes to 90 minutes. In the embodiment of the present application, when the thickness of the electron transport layer is higher than 80 nm, the light wave energy of the thick material layer is difficult to penetrate, and at this time, the illumination time required to achieve the treatment effect is longer, and the duration of the ultraviolet light irradiation treatment is 30 minutes to 90 minutes. minutes are appropriate.
在一些实施例中，上述步骤S30中，制备量子点发光层后，还包括步骤：在量子点发光层背离电子传输层的表面制备空穴传输层，在空穴传输层背离量子点发光层的表面制备阳极。In some embodiments, in the above step S30, after preparing the quantum dot light-emitting layer, the method further includes the step of: preparing a hole transport layer on the surface of the quantum dot light-emitting layer away from the electron transport layer, and on the surface of the hole transport layer away from the quantum dot light-emitting layer The anode is prepared on the surface.
在一些实施例中，本申请实施例制备的发光器件的结构示意图，如附图2所示，从上至下包括依次叠层设置的阳极、空穴传输层、量子点发光层、电子传输层(从上至下依次包括第N子电子传输层、第N-1子电子传输层……第一子电子传输层)和阴极，其中，靠近量子点发光层的第N子电子传输层为金属氧化物层。In some embodiments, a schematic structural diagram of the light-emitting device prepared in the embodiment of the present application, as shown in FIG. 2 , includes an anode, a hole transport layer, a quantum dot light-emitting layer, and an electron transport layer that are stacked in sequence from top to bottom. (From top to bottom, it includes the Nth electron transport layer, the N-1th electron transport layer...the first electron transport layer) and the cathode, wherein the Nth electron transport layer near the quantum dot light-emitting layer is a metal oxide layer.
在一些实施例中，步骤S20中，对发光器件进行紫外光照射处理的步骤包括：在阳极和阴极之间制备量子点发光层和电子传输层的复合层后，对复合层进行紫外光照射处理。本申请实施例在阳极和阴极之间制备量子点发光层(QD)和电子传输层(ETL)的复合层，该复合层经过紫外光照射(UV)处理，使电子传输层中金属氧化物传输材料中O的电子受激发与量子点发光层中Zn等活泼金属元素形成配合物，优化了ETL-QD界面，减少了界面缺陷，有利于电子从电子传输层向量子点发光层内部的注入；同时增加电子传输层内部成键缺陷，激活成键电子，促进电子传输层中晶体再次生长，提高电子传输层中电子迁移率。In some embodiments, in step S20, the step of performing ultraviolet light irradiation treatment on the light-emitting device includes: after preparing a composite layer of the quantum dot light-emitting layer and the electron transport layer between the anode and the cathode, performing ultraviolet light irradiation treatment on the composite layer . In the examples of the present application, a composite layer of a quantum dot light-emitting layer (QD) and an electron transport layer (ETL) is prepared between the anode and the cathode, and the composite layer is treated with ultraviolet light (UV), so that the metal oxide in the electron transport layer is transported The electrons of O in the material are excited to form complexes with active metal elements such as Zn in the light-emitting layer of quantum dots, which optimizes the ETL-QD interface, reduces interface defects, and facilitates the injection of electrons from the electron transport layer to the interior of the light-emitting layer of quantum dots; At the same time, the bonding defects inside the electron transport layer are increased, the bonding electrons are activated, the crystal regrowth in the electron transport layer is promoted, and the electron mobility in the electron transport layer is improved.
在一些具体实施例中，采用薄膜转移法在阳极和阴极之间制备量子点发光层和电子传输层的复合 层，具体包括步骤：在基板上依次沉积制备量子点发光层和电子传输层，对量子点发光层和电子传输层的复合层进行紫外光照射处理后，将量子点发光层和电子传输层的复合层转移到制备有阴极的衬底上，再在量子点发光层表面依次制备空穴传输层、空穴注入层和阳极，得到反型结构的发光器件。或者，将量子点发光层和电子传输层的复合层转移到依次制备有阳极、空穴注入层和空穴传输层的衬底上，再在电子传输层表面制备阴极，得到正型结构的发光器件。In some specific embodiments, a thin film transfer method is used to prepare a composite layer of the quantum dot light-emitting layer and the electron transport layer between the anode and the cathode, which specifically includes the steps of: sequentially depositing and preparing the quantum dot light-emitting layer and the electron transport layer on the substrate, After the composite layer of the quantum dot light-emitting layer and the electron transport layer is subjected to ultraviolet light irradiation treatment, the composite layer of the quantum dot light-emitting layer and the electron transport layer is transferred to the substrate prepared with the cathode, and then the surface of the quantum dot light-emitting layer is sequentially prepared. A hole transport layer, a hole injection layer and an anode are used to obtain a light-emitting device with an inversion structure. Alternatively, the composite layer of the quantum dot light-emitting layer and the electron transport layer is transferred to a substrate prepared in sequence with an anode, a hole injection layer and a hole transport layer, and then a cathode is prepared on the surface of the electron transport layer to obtain a positive-type light-emitting structure. device.
在另一些实施例中，采用溶液沉积法在阳极和阴极之间制备量子点发光层和电子传输层的叠层复合结构。在正型结构发光器件中，具体包括步骤：在衬底上制备阳极；在阳极远离衬底的一侧表面沉积制备空穴注入层；在空穴注入层远离阳极的一侧表面沉积制备空穴传输层；在空穴传输层的一侧表面沉积制备量子点发光层；在量子点发光层远离空穴传输层一侧表面制备电子传输层，对电子传输层进行紫外光照射处理，得到量子点发光层和电子传输层的复合层；在电子传输层表面沉积制备阴极，得到光电器件。在反型结构发光器件中，具体包括步骤：在衬底上制备阴极；在阴极表面制备电子传输层；在电子传输层远离阴极的侧表面制备量子点发光层，对量子点发光层进行紫外光照射处理，得到量子点发光层和电子传输层的复合层；在量子点发光层远离电子传输层的一侧表面依次制备空穴传输层、空穴注入层和阳极，得到光电器件。In other embodiments, a solution deposition method is used to prepare a laminated composite structure of a quantum dot light-emitting layer and an electron transport layer between the anode and the cathode. In a positive structure light-emitting device, the specific steps include: preparing an anode on a substrate; depositing a hole injection layer on the surface of the anode away from the substrate; depositing and preparing holes on the surface of the hole injection layer away from the anode transport layer; deposit and prepare a quantum dot light-emitting layer on one side of the hole transport layer; prepare an electron transport layer on the surface of the quantum dot light-emitting layer away from the hole transport layer, and irradiate the electron transport layer with ultraviolet light to obtain quantum dots A composite layer of a light-emitting layer and an electron transport layer; a cathode is deposited on the surface of the electron transport layer to obtain an optoelectronic device. In an inverse structure light-emitting device, the specific steps include: preparing a cathode on a substrate; preparing an electron transport layer on the surface of the cathode; preparing a quantum dot light-emitting layer on the side surface of the electron transport layer away from the cathode, and subjecting the quantum dot light-emitting layer to ultraviolet light Irradiation treatment to obtain a composite layer of the quantum dot light-emitting layer and the electron transport layer; a hole transport layer, a hole injection layer and an anode are sequentially prepared on the surface of the quantum dot light-emitting layer away from the electron transport layer to obtain an optoelectronic device.
在一些实施例中，紫外光照射处理的步骤包括：在紫外光波长为250～420nm，光波密度10～300mJ/cm
2的条件下，对发光器件照射10～60min。本申请实施例该紫外光照射处理条件，可以较好的促使ETL中金属氧化物传输材料中O原子与量子点外壳层中锌等元素进行配位，不但优化电子传输层与量子点发光层和阴极之间的界面缝隙，提高电子迁移注入效率，而且可较好的增加ETL内部成键，促使内部晶体再次生长，降低内部晶体结构缺陷和表面粗糙度，提高电子迁移率。
In some embodiments, the step of irradiating with ultraviolet light includes: irradiating the light-emitting device for 10-60 minutes under the condition that the wavelength of the ultraviolet light is 250-420 nm and the light wave density is 10-300 mJ/cm 2 . The ultraviolet irradiation treatment conditions in the examples of this application can better promote the coordination of O atoms in the metal oxide transport material in the ETL with elements such as zinc in the outer shell layer of the quantum dots, and not only optimize the electron transport layer and the quantum dot light-emitting layer and The interface gap between the cathodes can improve the efficiency of electron migration and injection, and can better increase the internal bonding of ETL, promote the re-growth of internal crystals, reduce internal crystal structure defects and surface roughness, and improve electron mobility.
在一些实施例中，紫外光照射处理的条件包括：在H
2O含量小于1ppm，温度为80～120℃的环境下进行。本申请实施例在H
2O含量小于1ppm，温度为80～120℃的环境下进行紫外光照射处理，避免环境中含水量过高导致在光照处理过程中量子点材料表面被水解，影响材料性能。同时80～120℃的加热环境，有利于促进激发O的电子与锌离子成键，也有利于成键电子被激活。
In some embodiments, the conditions of the ultraviolet light irradiation treatment include: performing in an environment where the content of H 2 O is less than 1 ppm and the temperature is 80-120° C. In the examples of the present application, the ultraviolet light irradiation treatment is carried out in an environment where the H 2 O content is less than 1 ppm and the temperature is 80-120° C., so as to avoid the excessive water content in the environment, which will cause the surface of the quantum dot material to be hydrolyzed during the light treatment process, which will affect the performance of the material. . At the same time, the heating environment of 80-120 °C is conducive to promoting the formation of bonds between the electrons excited by O and the zinc ions, and is also conducive to the activation of the bonding electrons.
在一些实施例中，紫外光照射处理的步骤包括：采用波长为320～420nm，光波密度10～150mJ/cm
2的紫外光波从阳极一侧进行照射处理10～60min。本申请实施例当紫外光波从阳极一侧进行照射处理时，阳极、空穴、QD等功能层对光波减损小，同时为避免UV光能量对空穴功能层中有机材料的破坏作用，采用波长较长，密度较小的光波进行照射处理。
In some embodiments, the step of ultraviolet light irradiation treatment includes: using ultraviolet light waves with a wavelength of 320-420 nm and an optical wave density of 10-150 mJ/cm 2 to perform irradiation treatment from the anode side for 10-60 minutes. In the examples of the present application, when the ultraviolet light wave is irradiated from the anode side, the functional layers such as anode, holes and QDs have little damage to the light wave. Longer, less dense light waves are irradiated.
在另一些实施例中，紫外光照射处理的步骤包括：采用波长为250～320nm，光波密度100～200mJ/cm
2的紫外光波从阴极一侧进行照射处理10～60min。本申请实施例当紫外光波从阴极一侧进行照射处理时，金属阴极对UV光波减损大，光波透过阴极层后直接作用在ETL层中，不会对空穴等其他功能层的材料有影响，但为避免光波对有机子电子传输层材料的影响，此时采用波长为250～320nm，光波密度100～200mJ/cm
2的紫外光波处理较为适宜。
In other embodiments, the step of irradiating with ultraviolet light includes: using ultraviolet light waves with a wavelength of 250-320 nm and an optical wave density of 100-200 mJ/cm 2 to perform irradiation treatment from the cathode side for 10-60 minutes. In the embodiment of the present application, when the ultraviolet light wave is irradiated from the cathode side, the metal cathode has a large damage to the UV light wave, and the light wave directly acts on the ETL layer after passing through the cathode layer, and will not affect the materials of other functional layers such as holes. However, in order to avoid the influence of light waves on the organic electron transport layer material, it is more appropriate to use ultraviolet light waves with a wavelength of 250 to 320 nm and a light wave density of 100 to 200 mJ/cm 2 .
在一些具体实施例中，当量子点材料的外壳层为ZnS时，紫外光照射处理的波长为250～355nm，光波密度50～150mJ/cm
2。本申请实施例当外壳层为ZnS时，ZnS键能为3.5eV左右，ZnO键能在3.3eV左右，在波长为250～355nm，光波密度50～150mJ/cm
2的条件下，可引起量子点材料外壳中ZnS和ZnO等电子传输材料成键电荷的转移，使外壳层中锌元素与电子传输材料中O元素有较好的配位效果，形成 电子传输材料与量子点材料的配合物。
In some specific embodiments, when the outer shell layer of the quantum dot material is ZnS, the wavelength of ultraviolet light irradiation treatment is 250-355 nm, and the optical wave density is 50-150 mJ/cm 2 . In the examples of the present application, when the outer shell layer is ZnS, the bond energy of ZnS is about 3.5eV, and the bond energy of ZnO is about 3.3eV. Under the conditions of wavelength of 250-355nm and optical wave density of 50-150mJ/ cm2 , quantum dots can be induced. The transfer of the bonding charges of electron transport materials such as ZnS and ZnO in the material shell makes the zinc element in the shell layer and the O element in the electron transport material have a better coordination effect, forming a complex between the electron transport material and the quantum dot material.
在一些具体实施例中，当量子点材料的外壳层为ZnSe时，紫外光照射处理的波长为280～375nm，光波密度30～120mJ/cm
2。本申请实施例当外壳层为ZnSe时，ZnSe键能为2.9eV左右，ZnO键能在3.3eV左右，在紫外光照射处理的波长为280～375nm，光波密度30～120mJ/cm
2的条件下可引起量子点材料外壳中ZnSe和ZnO等电子传输材料成键电荷的转移，使外壳层中锌元素与电子传输材料中O元素有较好的配位效果，形成电子传输材料与量子点材料的配合物。
In some specific embodiments, when the outer shell layer of the quantum dot material is ZnSe, the wavelength of ultraviolet light irradiation treatment is 280-375 nm, and the optical wave density is 30-120 mJ/cm 2 . In the examples of the present application, when the outer shell layer is ZnSe, the bond energy of ZnSe is about 2.9eV, and the bond energy of ZnO is about 3.3eV, and the wavelength of ultraviolet light irradiation treatment is 280～375nm, and the light wave density is 30～120mJ/ cm2 . It can cause the transfer of bonding charges of electron transport materials such as ZnSe and ZnO in the outer shell of the quantum dot material, so that the zinc element in the outer shell layer and the O element in the electron transport material have a better coordination effect, forming the electron transport material and the quantum dot material. complex.
在一些具体实施例中，当量子点材料的外壳层为ZnSeS时，紫外光照射处理的波长为250～375nm，光波密度30～150mJ/cm
2。本申请实施例当外壳层为ZnSeS时，ZnSeS键能为2.7eV左右，ZnO键能在3.3eV左右，在紫外光照射处理的波长为250～375nm，光波密度30～150mJ/cm
2的条件下可引起量子点材料外壳中ZnSeS和ZnO等电子传输材料成键电荷的转移，使外壳层中锌元素与电子传输材料中O元素有较好的配位效果，形成电子传输材料与量子点材料的配合物。
In some specific embodiments, when the outer shell layer of the quantum dot material is ZnSeS, the wavelength of ultraviolet light irradiation treatment is 250-375 nm, and the optical wave density is 30-150 mJ/cm 2 . In the examples of this application, when the outer shell layer is ZnSeS, the bond energy of ZnSeS is about 2.7eV, and the bond energy of ZnO is about 3.3eV, and the wavelength of ultraviolet light irradiation treatment is 250～375nm, and the optical wave density is 30～150mJ/ cm2 It can cause the transfer of bonding charges of electron transport materials such as ZnSeS and ZnO in the shell of the quantum dot material, so that the zinc element in the shell layer and the O element in the electron transport material have a better coordination effect, forming the electron transport material and the quantum dot material. complex.
在一些实施例中，量子点发光层的厚度为8～100nm。在一些实施例中，空穴传输层的厚度为10～150nm。该厚度满足器件性要求和结构要求。在实际应用中，器件中的电子功能层、发光层、空穴功能层可根据上述各实施例中器件的特性对应设计合适的厚度。In some embodiments, the quantum dot light-emitting layer has a thickness of 8-100 nm. In some embodiments, the hole transport layer has a thickness of 10-150 nm. This thickness satisfies device performance requirements and structural requirements. In practical applications, the electron functional layer, the light emitting layer, and the hole functional layer in the device can be designed with appropriate thicknesses according to the characteristics of the device in the above embodiments.
在一些实施例中，量子点材料的外壳层厚度为0.2～6.0nm，该厚度确保了量子点内层材料的稳定性和载流子注入效果，同时确保了外壳层中锌元素与金属氧化物传输材料中O元素的配位效果。In some embodiments, the thickness of the outer shell layer of the quantum dot material is 0.2-6.0 nm, which ensures the stability of the inner layer material of the quantum dot and the carrier injection effect, and at the same time ensures the zinc element and the metal oxide in the outer shell layer. Coordination effects of O element in transport materials.
在一些实施例中，上述步骤S10中，沉积有阴极的衬底中，阴极包括Mg、Ag、Al、Ca中的至少一种金属材料或者至少两种的合金材料，在紫外光照射条件下，这些阴极金属材料与金属氧化物电子传输材料融合效果好，可减小电子注入势垒，提高电子注入到光电器件中的效率。In some embodiments, in the above step S10, in the substrate on which the cathode is deposited, the cathode includes at least one metal material or at least two alloy materials of Mg, Ag, Al, and Ca. Under the condition of ultraviolet light irradiation, These cathode metal materials have good fusion effects with metal oxide electron transport materials, which can reduce the electron injection barrier and improve the efficiency of electron injection into optoelectronic devices.
在一些具体实施例中，本申请实施例发光器件的制备包括步骤：In some specific embodiments, the preparation of the light-emitting device in the embodiments of the present application includes the steps:
S50.获取沉积有阳极的基板；S50. Obtain the substrate on which the anode is deposited;
S60.在阳极表面生长空穴传输层；S60. Growing a hole transport layer on the surface of the anode;
S70.接着沉积量子点发光层于空穴传输层上；S70. Then deposit a quantum dot light-emitting layer on the hole transport layer;
S80.然后沉积电子传输层于量子点发光层上；S80. Then deposit an electron transport layer on the quantum dot light-emitting layer;
S90.蒸镀阴极于电子传输层上，得到发光器件；S90. Evaporating a cathode on the electron transport layer to obtain a light-emitting device;
S100.对发光器件进行紫外光照处理。S100. Perform ultraviolet irradiation treatment on the light-emitting device.
具体地，步骤S50中，为了得到高质量的氧化锌纳米材料薄膜，ITO基底需要经过预处理过程。基本具体的处理步骤包括：将ITO导电玻璃用清洁剂清洗，初步去除表面存在的污渍，随后依次在去离子水、丙酮、无水乙醇、去离子水中分别超声清洗20min，以除去表面存在的杂质，最后用高纯氮气吹干，即可得到ITO正极。Specifically, in step S50, in order to obtain a high-quality zinc oxide nanomaterial thin film, the ITO substrate needs to undergo a pretreatment process. The basic specific treatment steps include: cleaning the ITO conductive glass with a detergent to preliminarily remove the stains on the surface, and then ultrasonically cleaning in deionized water, acetone, anhydrous ethanol, and deionized water for 20 minutes respectively to remove impurities on the surface. , and finally blow dry with high-purity nitrogen to obtain the ITO positive electrode.
具体地，步骤S60中，生长空穴传输层的步骤包括：在ITO基板上，将配制好的空穴传输材料的溶液通过滴涂、旋涂、浸泡、涂布、打印、蒸镀等工艺沉积成膜；通过调节溶液的浓度、沉积速度和沉积时间来控制膜厚，然后在适当温度下热退火处理。Specifically, in step S60, the step of growing the hole transport layer includes: on the ITO substrate, depositing the prepared solution of the hole transport material through processes such as drop coating, spin coating, soaking, coating, printing, evaporation, etc. Film formation; the film thickness is controlled by adjusting the concentration of the solution, deposition rate and deposition time, and then thermal annealing at an appropriate temperature.
具体地，步骤S70中，沉积量子点发光层于空穴传输层上的步骤包括：在已沉积上空穴传输层的基片上，将配制好一定浓度的发光物质溶液通过滴涂、旋涂、浸泡、涂布、打印、蒸镀等工艺沉积成膜，通过调节溶液的浓度、沉积速度和沉积时间来控制发光层的厚度，约20～60nm，在适当温度下干燥。Specifically, in step S70, the step of depositing the quantum dot light-emitting layer on the hole transport layer includes: on the substrate on which the hole transport layer has been deposited, a solution of a light-emitting substance prepared with a certain concentration is applied by drop coating, spin coating, soaking , coating, printing, evaporation and other processes to deposit the film, and control the thickness of the light-emitting layer by adjusting the concentration of the solution, the deposition speed and the deposition time, about 20-60nm, and dry at an appropriate temperature.
具体地，步骤S80中，沉积电子传输层于量子点发光层上的步骤包括：第N子电子传输层为金属氧化物传输材料：在已沉积上量子点发光层的基片上，将配制好一定浓度的金属氧化物传输材料溶液通过滴涂、旋涂、浸泡、涂布、打印、蒸镀等工艺沉积成膜，通过调节溶液的浓度、沉积速度(例如，转速在3000～5000rpm之间)和沉积时间来控制电子传输层的厚度，约20～60nm，然后在150℃～200℃的条件下退火成膜，充分去除溶剂。在第N子电子传输层表面再沉积制备有机传输材料、金属氧化物传输材料等子电子传输层。Specifically, in step S80, the step of depositing the electron transport layer on the quantum dot light-emitting layer includes: the Nth electron transport layer is a metal oxide transport material: on the substrate on which the quantum dot light-emitting layer has been deposited, a certain amount of The concentrated metal oxide transport material solution is deposited into a film by processes such as drop coating, spin coating, soaking, coating, printing, evaporation, etc. By adjusting the concentration of the solution, the deposition speed (for example, the rotation speed is between 3000 and 5000 rpm) and The thickness of the electron transport layer is controlled by the deposition time, about 20 to 60 nm, and then annealed at 150 to 200 °C to form a film to fully remove the solvent. Sub-electron transport layers such as organic transport materials and metal oxide transport materials are prepared by redepositing on the surface of the N-th sub-electron transport layer.
具体地，步骤S90中，阴极制备的步骤包括：将沉积完各功能层的衬底置于蒸镀仓中通过掩膜板热蒸镀一层60-100nm的金属银或者铝作为阴极。Specifically, in step S90, the cathode preparation step includes: placing the substrate on which each functional layer has been deposited into an evaporation chamber and thermally evaporated a layer of 60-100 nm metal silver or aluminum as a cathode through a mask plate.
具体地，步骤S100中，在H
2O含量小于1ppm，温度为80～120℃的环境下，采用紫外光波长为250～420nm，光波密度10～300mJ/cm
2的紫外光对光电器件进行垂直照射10～60min。
Specifically, in step S100, in an environment where the H 2 O content is less than 1 ppm and the temperature is 80-120° C., ultraviolet light with a wavelength of 250-420 nm and an optical wave density of 10-300 mJ/cm 2 is used to vertically conduct the photoelectric device. Irradiate for 10 to 60 minutes.
在一些实施例中，将得到的QLED器件进行封装处理，封装处理可采用常用的机器封装，也可以采用手动封装。封装处理的环境中，氧含量和水含量均低于0.1ppm，以保证器件的稳定性。In some embodiments, the obtained QLED device is packaged, and the package process can be packaged by a common machine or by manual packaging. In the packaging process environment, the oxygen content and water content are both lower than 0.1ppm to ensure the stability of the device.
在另一些实施例中，本申请实施例发光器件的制备步骤也可以采用反型器件结构的制备顺序，在沉积有阴极的基板上依次制备电子传输层、量子点发光层、空穴传输层、空穴注入层和阳极。In other embodiments, the preparation steps of the light-emitting device in the embodiments of the present application may also adopt the preparation sequence of the inversion device structure, and the electron transport layer, the quantum dot light-emitting layer, the hole transport layer, the electron transport layer, the quantum dot light-emitting layer, the hole transport layer, the hole injection layer and anode.
本申请实施例第二方面提供一种发光器件，发光器件由上述的方法制得。A second aspect of the embodiments of the present application provides a light-emitting device, and the light-emitting device is manufactured by the above method.
本申请第二方面提供的发光器件，由于发光器件经过紫外光照射处理，电子传输层中金属氧化物传输材料中O的电子受激发与量子点发光层中Zn等活泼金属元素形成配合物，同时金属氧化物材料受紫外光激发后与阴极融合效果好。降低了电子传输层内部物理结构缺陷和表面粗糙度，电子传输迁移效率高，且量子点发光层与电子传输层和阴极界面结合紧密，电子注入效率高，避免功能层界面电荷累积，器件稳定性好，使用寿命长。In the light-emitting device provided in the second aspect of the present application, since the light-emitting device is subjected to ultraviolet light irradiation treatment, the electrons of O in the metal oxide transport material in the electron transport layer are excited to form complexes with active metal elements such as Zn in the quantum dot light-emitting layer, and simultaneously The metal oxide material has a good fusion effect with the cathode after being excited by ultraviolet light. The internal physical structure defects and surface roughness of the electron transport layer are reduced, the electron transport and migration efficiency is high, and the quantum dot light-emitting layer is closely combined with the electron transport layer and the cathode interface, and the electron injection efficiency is high, avoiding the accumulation of charges at the interface of the functional layer, and the device is stable. Good, long lifespan.
本申请实施例中，发光器件不受器件结构的限制，可以是正型结构的器件，也可以是反型结构的器件。In the embodiments of the present application, the light-emitting device is not limited by the device structure, and may be a device with a positive structure or a device with an inversion structure.
在一种实施方式中，正型结构发光器件包括相对设置的阳极和阴极的层叠结构，设置在阳极和阴极之间的发光层，且阳极设置在衬底上。阳极和发光层之间还可以设置空穴注入层、空穴传输层、电子阻挡层等空穴功能层；在阴极和发光层之间还可以设置电子传输层、电子注入层和空穴阻挡层等电子功能层，如附图3所示。在一些具体正型结构器件的实施例中，发光器件包括衬底，设置在衬底表面的阳极，设置在阳极表面的空穴传输层，设置在空穴传输层表面的发光层，设置在发光层表面的电子传输层和设置在电子传输层表面的阴极。In one embodiment, the positive structure light-emitting device includes a stacked structure of oppositely disposed anode and cathode, a light-emitting layer disposed between the anode and the cathode, and the anode is disposed on the substrate. A hole functional layer such as a hole injection layer, a hole transport layer, and an electron blocking layer can also be arranged between the anode and the light-emitting layer; an electron transport layer, an electron injection layer, and a hole blocking layer can also be arranged between the cathode and the light-emitting layer. The isoelectronic functional layer is shown in Figure 3. In some specific embodiments of the positive structure device, the light emitting device includes a substrate, an anode disposed on the surface of the substrate, a hole transport layer disposed on the surface of the anode, a light emitting layer disposed on the surface of the hole transport layer, An electron transport layer on the surface of the layer and a cathode disposed on the surface of the electron transport layer.
在一种实施方式中，反型结构发光器件包括相对设置的阳极和阴极的叠层结构，设置在阳极和阴极之间的发光层，且阴极设置在衬底上。阳极和发光层之间还可以设置空穴注入层、空穴传输层、电子阻挡层等空穴功能层；在阴极和发光层之间还可以设置电子传输层、电子注入层和空穴阻挡层等电子功能层，如附图4所示。在一些反型结构器件的实施例中，发光器件包括衬底，设置在衬底表面的阴极，设置在阴极表面的电子传输层，设置在电子传输层表面的发光层，设置在发光层表面的空穴传输层，设置在空穴传输层表面的阳极。In one embodiment, the inversion structure light-emitting device includes a stacked structure of an anode and a cathode disposed oppositely, a light-emitting layer disposed between the anode and the cathode, and the cathode disposed on the substrate. A hole functional layer such as a hole injection layer, a hole transport layer, and an electron blocking layer can also be arranged between the anode and the light-emitting layer; an electron transport layer, an electron injection layer, and a hole blocking layer can also be arranged between the cathode and the light-emitting layer. The isoelectronic functional layer is shown in Figure 4. In some embodiments of the inversion structure device, the light emitting device includes a substrate, a cathode disposed on the surface of the substrate, an electron transport layer disposed on the surface of the cathode, a light emitting layer disposed on the surface of the electron transport layer, The hole transport layer is an anode disposed on the surface of the hole transport layer.
在一些实施例中，衬底的选用不受限制，可以采用刚性基板，也可以采用柔性基板。在一些具体实施例中，刚性基板包括但不限于玻璃、金属箔片中的一种或多种。在一些具体实施例中，柔性基板包括 但不限于聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸乙二醇酯(PEN)、聚醚醚酮(PEEK)、聚苯乙烯(PS)、聚醚砜(PES)、聚碳酸酯(PC)、聚芳基酸酯(PAT)、聚芳酯(PAR)、聚酰亚胺(PI)、聚氯乙烯(PV)、聚乙烯(PE)、聚乙烯吡咯烷酮(PVP)、纺织纤维中的一种或多种。In some embodiments, the choice of the substrate is not limited, and a rigid substrate or a flexible substrate may be used. In some specific embodiments, the rigid substrate includes, but is not limited to, one or more of glass and metal foil. In some embodiments, the flexible substrate includes, but is not limited to, polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polyetheretherketone (PEEK), polystyrene (PS), polyethersulfone (PES), polycarbonate (PC), polyarylate (PAT), polyarylate (PAR), polyimide (PI), polyvinyl chloride (PV), poly One or more of ethylene (PE), polyvinylpyrrolidone (PVP), and textile fibers.
在一些实施例中，阳极材料的选用不受限制，可选自掺杂金属氧化物，包括但不限于铟掺杂氧化锡(ITO)、氟掺杂氧化锡(FTO)、锑掺杂氧化锡(ATO)、铝掺杂氧化锌(AZO)、镓掺杂氧化锌(GZO)、铟掺杂氧化锌(IZO)、镁掺杂氧化锌(MZO)、铝掺杂氧化镁(AMO)中的一种或多种。也可以选自掺杂或非掺杂的透明金属氧化物之间夹着金属的复合电极，包括但不限于AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO
2/Ag/TiO
2、TiO
2/Al/TiO
2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO
2/Ag/TiO
2、TiO
2/Al/TiO
2中的一种或多种。
In some embodiments, the choice of anode material is not limited and can be selected from doped metal oxides, including but not limited to indium doped tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO), Aluminum-Doped Zinc Oxide (AZO), Gallium-Doped Zinc Oxide (GZO), Indium-Doped Zinc Oxide (IZO), Magnesium-Doped Zinc Oxide (MZO), Aluminum-Doped Magnesium Oxide (AMO) one or more. It can also be selected from doped or undoped transparent metal oxides sandwiched metal composite electrodes, including but not limited to AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS, ZnS/Al/ZnS, TiO 2 /Ag/TiO 2 , One or more of TiO 2 /Al/TiO 2 .
在一些实施例中，空穴注入层包括但不限于有机空穴注入材料、掺杂或非掺杂的过渡金属氧化物、掺杂或非掺杂的金属硫系化合物中的一种或多种。在一些具体实施例中，有机空穴注入材料包括但不限于聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)、酞菁铜(CuPc)、2,3,5,6-四氟-7,7',8,8'-四氰醌-二甲烷(F4-TCNQ)、2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲(HATCN)中的一种或多种。在一些具体实施例中，过渡金属氧化物包括但不限于MoO
3、VO
2、WO
3、CrO
3、CuO中的一种或多种。在一些具体实施例中，金属硫系化合物包括但不限于MoS
2、MoSe
2、WS
2、WSe
2、CuS中的一种或多种。
In some embodiments, the hole injection layer includes, but is not limited to, one or more of organic hole injection materials, doped or undoped transition metal oxides, doped or undoped metal chalcogenides . In some specific embodiments, organic hole injection materials include, but are not limited to, poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS), copper phthalocyanine (CuPc), 2,3, 5,6-Tetrafluoro-7,7',8,8'-tetracyanoquinone-dimethane (F4-TCNQ), 2,3,6,7,10,11-hexacyano-1,4,5 One or more of ,8,9,12-hexaazatriphenylene (HATCN). In some specific embodiments, transition metal oxides include, but are not limited to, one or more of MoO 3 , VO 2 , WO 3 , CrO 3 , and CuO. In some specific embodiments, the metal chalcogenide compounds include, but are not limited to, one or more of MoS 2 , MoSe 2 , WS 2 , WSe 2 , and CuS.
在一些实施例中，空穴传输层可选自具有空穴传输能力的有机材料和/或具有空穴传输能力的无机材料。在一些具体实施例中，具有空穴传输能力的有机材料包括但不限于聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)(TFB)、聚乙烯咔唑(PVK)、聚(N,N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)(poly-TPD)、聚(9,9-二辛基芴-共-双-N,N-苯基-1,4-苯二胺)(PFB)、4,4,4”-三(咔唑-9-基)三苯胺(TCTA)、4,4'-二(9-咔唑)联苯(CBP)、N,N’-二苯基-N,N’-二(3-甲基苯基)-1,1’-联苯-4,4’-二胺(TPD)、N,N’-二苯基-N,N’-(1-萘基)-1,1’-联苯-4,4’-二胺(NPB)中的一种或多种。在一些具体实施例中，具有空穴传输能力的无机材料包括但不限于掺杂石墨烯、非掺杂石墨烯、C60、掺杂或非掺杂的MoO
3、VO
2、WO
3、CrO
3、CuO、MoS
2、MoSe
2、WS
2、WSe
2、CuS中的一种或多种。
In some embodiments, the hole transport layer may be selected from organic materials with hole transport capability and/or inorganic materials with hole transport capability. In some specific embodiments, the organic material with hole transport capability includes, but is not limited to, poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) (TFB), poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) Vinylcarbazole (PVK), poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) (poly-TPD), poly(9,9-dioctyl) Fluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4,4"-tris(carbazol-9-yl)triphenylamine (TCTA), 4, 4'-bis(9-carbazole)biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4, In 4'-diamine (TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB) One or more. In some specific embodiments, inorganic materials with hole transport capability include but are not limited to doped graphene, undoped graphene, C60, doped or undoped MoO 3 , VO 2 One or more of , WO 3 , CrO 3 , CuO, MoS 2 , MoSe 2 , WS 2 , WSe 2 , and CuS.
在一些实施例中，发光层中包括上述实施例中量子点材料，量子点材料为核壳结构的量子点材料，且量子点材料的外壳层含有锌元素。在一些具体实施例中，量子点材料的外壳层包括：ZnS、ZnSe、ZnTe、CdZnS、ZnCdSe中的至少一种或者至少两种形成的合金材料。在一些实施例中，量子点材料的粒径范围为2～10nm，粒径过小，量子点材料成膜性变差，且量子点颗粒之间的能量共振转移效应显著，不利于材料的应用，粒径过大，量子点材料的量子效应减弱，导致材料的光电性能下降。In some embodiments, the light-emitting layer includes the quantum dot material in the above embodiments, the quantum dot material is a core-shell structure quantum dot material, and the outer shell layer of the quantum dot material contains zinc. In some specific embodiments, the outer shell layer of the quantum dot material includes: at least one of ZnS, ZnSe, ZnTe, CdZnS, and ZnCdSe, or an alloy material formed by at least two of them. In some embodiments, the particle size of the quantum dot material is in the range of 2 to 10 nm. If the particle size is too small, the film-forming property of the quantum dot material becomes poor, and the energy resonance transfer effect between the quantum dot particles is significant, which is not conducive to the application of the material. , the particle size is too large, the quantum effect of the quantum dot material is weakened, resulting in a decrease in the optoelectronic properties of the material.
在一些实施例中，电子传输层的材料采用上述叠层复合结构的电子传输层。In some embodiments, the material of the electron transport layer adopts the electron transport layer of the above-mentioned laminated composite structure.
在一些实施例中，阴极材料可以是各种导电碳材料、导电金属氧化物材料、金属材料中的一种或多种。在一些具体实施例中，导电碳材料包括但不限于掺杂或非掺杂碳纳米管、掺杂或非掺杂石墨烯、掺杂或非掺杂氧化石墨烯、C60、石墨、碳纤维、多空碳、或它们的混合物。在一些具体实施例中，导电金属氧化物材料包括但不限于ITO、FTO、ATO、AZO、或它们的混合物。在一些具体实施例中，金属材料包括但不限于Al、Ag、Cu、Mo、Au、或它们的合金；其中的金属材料中，其形态包括但不限于致密薄膜、纳米线、纳米球、纳米棒、纳米锥、纳米空心球、或它们的混合物；阴极为Ag、Al。In some embodiments, the cathode material may be one or more of various conductive carbon materials, conductive metal oxide materials, and metallic materials. In some embodiments, conductive carbon materials include, but are not limited to, doped or undoped carbon nanotubes, doped or undoped graphene, doped or undoped graphene oxide, C60, graphite, carbon fiber, many Empty carbon, or a mixture thereof. In some embodiments, the conductive metal oxide material includes, but is not limited to, ITO, FTO, ATO, AZO, or mixtures thereof. In some specific embodiments, the metal materials include, but are not limited to, Al, Ag, Cu, Mo, Au, or their alloys; among the metal materials, their forms include but are not limited to dense films, nanowires, nanospheres, nanometers Rods, nano cones, nano hollow spheres, or their mixtures; the cathode is Ag, Al.
为使本申请上述实施细节和操作能清楚地被本领域技术人员理解，以及本申请实施例发光器件及其制备方法的进步性能显著的体现，以下通过多个实施例来举例说明上述技术方案。In order to make the above implementation details and operations of the present application clearly understood by those skilled in the art, and to significantly reflect the improved performance of the light-emitting devices and their preparation methods in the embodiments of the present application, the above technical solutions are exemplified by multiple embodiments below.
实施例1Example 1
一种发光二极管，包括以下制备步骤：A light-emitting diode, comprising the following preparation steps:
(1)提供ITO阳极，对阳极进行前处理：采用碱性洗涤液(优选PH>10超声15min，去离子水超声15min两次，异丙醇超声清洗15min，后80℃烘干2h，臭氧紫外处理15min。(1) Provide ITO anode, and pre-treat the anode: use alkaline washing solution (preferably PH>10 ultrasonic for 15 min, deionized water ultrasonic for 15 min twice, isopropanol ultrasonic cleaning for 15 min, dry at 80 ℃ for 2 h, ozone ultraviolet Process for 15min.
(2)在步骤(1)的阳极上形成空穴注入层：在电场下，将PEDOT:PSS溶液旋涂在阳极上，5000rpm旋涂40s后150℃退火处理15min，形成空穴注入层；其中，电场的作用方向垂直于阳极并朝向空穴注入层，电场强度为10
4V/cm。
(2) forming a hole injection layer on the anode of step (1): under an electric field, spin-coating the PEDOT:PSS solution on the anode, spin-coating at 5000 rpm for 40 s, and then annealing at 150° C. for 15 min to form a hole-injecting layer; wherein , the action direction of the electric field is perpendicular to the anode and toward the hole injection layer, and the electric field strength is 10 4 V/cm.
(3)在空穴注入层上形成空穴传输层：在电场下，将TFB溶液(浓度为8mg/mL，溶剂为氯苯)旋涂在空穴注入层上，3000rpm旋涂30s后80℃退火处理30min，形成空穴传输层；其中，电场的作用方向垂直于阳极并朝向空穴传输层，电场强度为10
4V/cm。
(3) Forming a hole transport layer on the hole injection layer: under an electric field, spin-coat TFB solution (concentration of 8 mg/mL, solvent is chlorobenzene) on the hole injection layer, spin at 3000 rpm for 30 s and then spin at 80 °C After annealing for 30 minutes, a hole transport layer was formed; wherein, the action direction of the electric field was perpendicular to the anode and toward the hole transport layer, and the electric field strength was 10 4 V/cm.
(4)在空穴传输层上形成发光层：取CdSe/ZnS量子点溶液(浓度为30mg/mL，溶剂为正辛烷)，将CdSe/ZnS量子点溶液在手套箱(水氧含量小于0.1ppm)内以3000rpm转速旋涂于空穴传输层上，形成发光层。(4) Form the light-emitting layer on the hole transport layer: take the CdSe/ZnS quantum dot solution (concentration is 30 mg/mL, the solvent is n-octane), put the CdSe/ZnS quantum dot solution in a glove box (water oxygen content is less than 0.1 ppm) and spin-coated on the hole transport layer at a speed of 3000 rpm to form a light-emitting layer.
(5)在发光层上形成电子传输层：在手套箱(水氧含量小于0.1ppm)内，将ZnO溶液(浓度为45mg/mL，溶剂为乙醇)旋涂在发光层上，3000rpm旋涂30s后80℃退火处理30min，形成电子传输层。(5) Forming an electron transport layer on the light-emitting layer: in a glove box (water oxygen content is less than 0.1ppm), spin-coat ZnO solution (concentration of 45mg/mL, solvent is ethanol) on the light-emitting layer, spin-coating at 3000rpm for 30s After annealing at 80° C. for 30 min, an electron transport layer was formed.
(6)在电子传输层上形成阴极：采用蒸镀法将Al蒸镀在电子传输层上，形成厚度为60-150nm的Al电极。(6) Forming a cathode on the electron transport layer: Al is evaporated on the electron transport layer by an evaporation method to form an Al electrode with a thickness of 60-150 nm.
(7)对制备的器件进行UV处理，在H
2O含量小于1ppm，温度为100℃的环境下，从Al电极侧垂直照射，UV波长250nm，强度300mJ/cm
2，UV时间30min。
(7) UV treatment was performed on the prepared device, under the environment of H 2 O content less than 1 ppm and temperature of 100°C, vertical irradiation from the Al electrode side, UV wavelength 250nm, intensity 300mJ/cm 2 , UV time 30min.
实施例2Example 2
一种发光二极管，其制备步骤与实施例1的区别在于：步骤(7)中，对制备的器件进行UV处理，从ITO阳极侧垂直照射，UV波长420nm，强度100mJ/cm
2，UV时间30min。
A light-emitting diode, the difference between its preparation steps and Example 1 is: in step (7), UV treatment is performed on the prepared device, vertical irradiation from the ITO anode side, UV wavelength 420nm, intensity 100mJ/cm 2 , UV time 30min .
实施例3Example 3
一种发光二极管，其制备步骤与实施例1的区别在于：步骤(5)中采用TiO
2。
A light-emitting diode, the preparation steps of which are different from those in Example 1 are: TiO 2 is used in step (5).
实施例4Example 4
一种发光二极管，其制备步骤与实施例1的区别在于：步骤(5)中采用ZnMgO。A light-emitting diode, the preparation steps of which are different from those in Example 1 are: ZnMgO is used in step (5).
实施例5Example 5
一种发光二极管，其制备步骤与实施例1的区别在于：步骤(4)中采用CdZnSe/ZnSe。步骤(7)中，紫外光照条件为：采用UV波长320nm，强度300mJ/cm
2的UV光垂直照射发光层时间30min。
A light-emitting diode, the preparation steps of which are different from those in Example 1 are: CdZnSe/ZnSe is used in step (4). In step (7), the ultraviolet illumination conditions are as follows: UV light with a UV wavelength of 320 nm and an intensity of 300 mJ/cm 2 is used to vertically irradiate the light-emitting layer for 30 minutes.
实施例6Example 6
一种发光二极管，其制备步骤与实施例1的区别在于：步骤(4)中采用CdZnSe/ZnSeS。步骤(7)中，紫外光照条件为：340nm，强度300mJ/cm
2的UV光垂直照射发光层时间30min。
A light-emitting diode, the preparation steps of which are different from those in Example 1 are: CdZnSe/ZnSeS is used in step (4). In step (7), the ultraviolet light conditions are: 340 nm, UV light with an intensity of 300 mJ/cm 2 vertically irradiates the light-emitting layer for 30 minutes.
实施例7Example 7
一种发光二极管，包括以下制备步骤：A light-emitting diode, comprising the following preparation steps:
(1)提供沉积有Al阴极的基板，对基板进行清洁前处理。(1) Provide a substrate on which Al cathode is deposited, and perform pre-cleaning treatment on the substrate.
(2)在步骤(1)的Al阴极上形成复合结构的电子传输层：取ZnO纳米颗粒溶液(浓度为30mg/mL，溶剂为乙醇)，将ZnO纳米颗粒溶液在手套箱(水氧含量小于0.1ppm)内以4000rpm转速旋涂于低电极上，进行80℃30min退火形成ZnO层。然后，取Alq3溶液(浓度为10mg/mL，溶剂为二甲基甲酰胺),将Alq3溶液以1000rpm转速旋涂于ZnO层上，进行80℃30min退火形成Alq3层。(2) forming the electron transport layer of the composite structure on the Al cathode of step (1): take the ZnO nanoparticle solution (concentration is 30mg/mL, the solvent is ethanol), put the ZnO nanoparticle solution in a glove box (water oxygen content is less than 0.1ppm), spin-coated on the low electrode at 4000rpm, and annealed at 80°C for 30min to form a ZnO layer. Then, take the Alq3 solution (concentration is 10 mg/mL, the solvent is dimethylformamide), spin-coat the Alq3 solution on the ZnO layer at 1000 rpm, and anneal at 80 °C for 30 min to form the Alq3 layer.
(3)在电子传输层上形成发光层：取CdSe/ZnS量子点溶液(浓度为30mg/mL，溶剂为正辛烷)，将CdSe/ZnS量子点溶液在手套箱(水氧含量小于0.1ppm)内以3000rpm转速旋涂于电子传输层上，形成发光层。(3) Form the light-emitting layer on the electron transport layer: take the CdSe/ZnS quantum dot solution (concentration is 30mg/mL, the solvent is n-octane), put the CdSe/ZnS quantum dot solution in a glove box (water oxygen content is less than 0.1ppm) ) was spin-coated on the electron transport layer at a speed of 3000 rpm to form a light-emitting layer.
(4)在空穴传输层上形成发光层：取CdSe/ZnS量子点溶液(浓度为30mg/mL，溶剂为正辛烷)，将CdSe/ZnS量子点溶液在手套箱(水氧含量小于0.1ppm)内以3000rpm转速旋涂于空穴传输层上，形成发光层。(4) Form the light-emitting layer on the hole transport layer: take the CdSe/ZnS quantum dot solution (concentration is 30 mg/mL, the solvent is n-octane), put the CdSe/ZnS quantum dot solution in a glove box (water oxygen content is less than 0.1 ppm) and spin-coated on the hole transport layer at a speed of 3000 rpm to form a light-emitting layer.
(5)在发光层上形成空穴传输层：在电场下，将TFB溶液(浓度为8mg/mL，溶剂为氯苯)旋涂在发光层上，3000rpm旋涂30s后80℃退火处理30min，形成空穴传输层；其中，电场的作用方向垂直于阳极并朝向空穴传输层，电场强度为104V/cm。(5) Forming a hole transport layer on the light-emitting layer: under an electric field, spin-coat TFB solution (concentration of 8 mg/mL, solvent is chlorobenzene) on the light-emitting layer, spin-coat at 3000 rpm for 30 s, and then anneal at 80 °C for 30 min. A hole transport layer was formed; wherein the direction of action of the electric field was perpendicular to the anode and toward the hole transport layer, and the electric field strength was 104 V/cm.
(6)在空穴传输层上形成空穴注入层：在电场下，将PEDOT:PSS溶液旋涂在空穴传输层上，5000rpm旋涂40s后150℃退火处理15min，形成空穴注入层；其中，电场的作用方向垂直于阳极并朝向空穴注入层，电场强度为104V/cm。(6) forming a hole injection layer on the hole transport layer: under an electric field, spin-coat the PEDOT:PSS solution on the hole transport layer, spin at 5000 rpm for 40 s, and then anneal at 150°C for 15 minutes to form a hole injection layer; Among them, the action direction of the electric field is perpendicular to the anode and toward the hole injection layer, and the electric field strength is 104V/cm.
(7)在空穴注入层上形成ITO阳极。(7) An ITO anode is formed on the hole injection layer.
(8)对制备的器件进行UV处理，在H
2O含量小于1ppm，温度为100℃的环境下，从Al电极侧垂直照射，UV波长250nm，强度200mJ/cm
2，UV时间30min。
(8) UV treatment was performed on the prepared device, under the environment of H 2 O content less than 1 ppm and temperature of 100°C, vertical irradiation from the Al electrode side, UV wavelength 250nm, intensity 200mJ/cm 2 , UV time 30min.
实施例8Example 8
一种发光二极管，其制备步骤与实施例1的区别在于：步骤(2)中采用PCBM制备有机电子传输层。A light-emitting diode, the preparation steps of which are different from those in Example 1 are: in step (2), PCBM is used to prepare an organic electron transport layer.
实施例9Example 9
一种发光二极管，其制备步骤与实施例1的区别在于：步骤(2)中采用ZnMgO制备无机电子传输层。A light-emitting diode, the preparation steps of which are different from those in Example 1 are: in step (2), ZnMgO is used to prepare an inorganic electron transport layer.
实施例10Example 10
一种发光二极管，其制备步骤与实施例1的区别在于：步骤(2)中采用Alq3+ZnO(粒径为5.5nm)+ZnO(粒径为3nm)。A light-emitting diode, the preparation steps of which are different from those in Example 1 are: Alq3+ZnO (particle size is 5.5 nm)+ZnO (particle size is 3 nm) is used in step (2).
实施例11Example 11
一种发光二极管，其制备步骤与实施例1的区别在于：步骤(3)中采用CdZnSe/ZnSe。步骤(8)中，紫外光照条件为：采用UV波长320nm，强度300mJ/cm
2的UV光垂直照射发光层时间30min。
A light-emitting diode, the preparation steps of which are different from those in Example 1 are: CdZnSe/ZnSe is used in step (3). In step (8), the ultraviolet illumination conditions are as follows: UV light with a UV wavelength of 320 nm and an intensity of 300 mJ/cm 2 is used to vertically irradiate the light-emitting layer for 30 minutes.
实施例12Example 12
一种发光二极管，其制备步骤与实施例1的区别在于：步骤(3)中采用CdZnSe/ZnSeS。步骤(8)中，紫外光照条件为：340nm，强度300mJ/cm
2的UV光垂直照射发光层时间30min。
A light-emitting diode, the preparation steps of which are different from those in Example 1 are: CdZnSe/ZnSeS is used in step (3). In step (8), the ultraviolet light conditions are: 340 nm, UV light with an intensity of 300 mJ/cm 2 , vertically irradiating the light-emitting layer for 30 minutes.
实施例13～20Examples 13 to 20
本申请实施例13～20中采用的两种量子点为：外壳为CdZnS的蓝色QD1(内核为CdZnSe，中间壳层为ZnSe，外壳厚度为1.5nm，价带顶能级为-6.2eV)、外壳为ZnS的蓝色QD2(内核为CdZnSe，中间壳层为ZnSe，ZnS外壳厚度为0.3nm，价带顶能级为-6.5eV)。外壳为ZnSeS的蓝色QD3(内核为CdZnSe，中间壳层为ZnSe)空穴传输材料分别为P9(E
HOMO:-5.1eV)、P15(E
HOMO:-5.8eV)，空穴注入层采用PEDOT:PSS(E
HOMO:-5.1eV)，电子传输层采用ZnO、TiO
2，具体如下表2所示。
The two kinds of quantum dots used in Examples 13 to 20 of the present application are: blue QD1 with CdZnS outer shell (the inner core is CdZnSe, the middle shell is ZnSe, the outer shell thickness is 1.5 nm, and the top energy level of the valence band is -6.2 eV) , blue QD2 with ZnS outer shell (inner core is CdZnSe, intermediate shell is ZnSe, ZnS shell thickness is 0.3 nm, valence band top energy level is -6.5 eV). The blue QD3 with ZnSeS shell (the inner core is CdZnSe, the middle shell is ZnSe) hole transport materials are P9 (E HOMO :-5.1eV), P15 (E HOMO :-5.8eV), the hole injection layer is PEDOT : PSS (E HOMO : -5.1 eV), the electron transport layer adopts ZnO and TiO 2 , as shown in Table 2 below.
本申请实施例13～20中光电器件均进行UV处理：在H
2O含量小于1ppm，温度为100℃的环境下，从Al电极侧垂直照射，UV波长250nm，强度300mJ/cm
2，UV时间30min。
The optoelectronic devices in Examples 13 to 20 of the present application are all UV treated: in an environment where the H 2 O content is less than 1 ppm and the temperature is 100° C., vertical irradiation from the Al electrode side, UV wavelength 250 nm, intensity 300 mJ/cm 2 , UV time 30min.
对比例1Comparative Example 1
一种发光二极管，其制备步骤与实施例1的区别在于：未经步骤(7)UV处理)。对比例2A light-emitting diode, the difference between its preparation steps and Example 1 is that it does not have step (7) UV treatment). Comparative Example 2
一种发光二极管，其制备步骤与实施例7的区别在于：未经步骤(8)UV处理。A light-emitting diode whose preparation steps differ from those of Example 7 in that it is not UV-treated in step (8).
对比例3Comparative Example 3
一种发光二极管，其制备步骤与实施例7的区别在于：步骤(2)中电子传输层仅含有ZnO金属氧化物层A light-emitting diode, the difference between its preparation steps and Example 7 is: in step (2), the electron transport layer only contains a ZnO metal oxide layer
对比例4Comparative Example 4
一种发光二极管，其制备步骤与实施例1的区别在于：步骤(2)中电子传输层仅含有Alq3有机传输层。A light-emitting diode, the preparation steps of which are different from those in Example 1 are: in step (2), the electron transport layer only contains an Alq3 organic transport layer.
对比例5Comparative Example 5
一种发光二极管，其制备步骤与实施例19的区别在于：未经UV处理，具体如表3所示。A light-emitting diode whose preparation steps differ from Example 19 in that it is not UV-treated, as shown in Table 3.
为了验证本申请实施例的进步性，对实施例和对比例进行了如下性能测试，测试指标和测试方法如下，测试结果如下表和附图所示：In order to verify the progress of the embodiment of the present application, the following performance tests were carried out to the embodiment and the comparative example, the test index and the test method are as follows, and the test results are shown in the following table and accompanying drawings:
(1)构建电流密度-电压(J-V)曲线(1) Constructing a current density-voltage (J-V) curve
在室温、空气湿度为30％-60％的环境下，采用LabView控制QE PRO光谱仪、Keithley 2400、Keithley6485搭建的效率测试***进行测试，并测量电压、电流等参数，构建J-V曲线。Under the environment of room temperature and air humidity of 30%-60%, use LabView to control the efficiency test system built by QE PRO spectrometer, Keithley 2400, and Keithley6485 for testing, and measure parameters such as voltage and current to construct J-V curve.
(2)外量子效率(EQE)：(2) External quantum efficiency (EQE):
注入到量子点中的电子-空穴对数转化为出射的光子数的比值，单位是％，是衡量电致发光器件优劣的一个重要参数，采用EQE光学测试仪器测定即可得到。具体计算公式如下：The ratio of the number of electron-hole pairs injected into the quantum dots converted to the number of photons emitted, the unit is %, is an important parameter to measure the quality of electroluminescent devices, and can be obtained by EQE optical testing instrument. The specific calculation formula is as follows:
式中，η
e为光输出耦合效率，η
r为复合的载流子数与注入载流子数的比值，χ为产生光子的激子数与总激子数的比值，KR为辐射过程速率，KNR为非辐射过程速率。测试条件：在室温下进行，空气湿度为30～60％。
In the formula, η e is the optical output coupling efficiency, η r is the ratio of the number of recombined carriers to the number of injected carriers, χ is the ratio of the number of excitons that generate photons to the total number of excitons, and KR is the radiation process rate. , KNR is the nonradiative process rate. Test conditions: At room temperature, the air humidity is 30-60%.
(3)构建亮度-电压(L-V)曲线(3) Constructing a luminance-voltage (L-V) curve
亮度(L)为发光表面在指定方向的光通量与垂直于指定方向的光通量的面积之比(cd/m2)。采用LabView控制校准过的线性硅光管***PDB-C613测量，并结合光谱和视觉函数计算器件亮度，并根据亮度随电压的变化，构建L-V曲线。Luminance (L) is the ratio (cd/m2) of the luminous flux of the light-emitting surface in the specified direction to the area of the luminous flux perpendicular to the specified direction. Using LabView to control the calibrated linear silicon light pipe system PDB-C613 to measure, and combine the spectral and visual functions to calculate the brightness of the device, and construct the L-V curve according to the change of brightness with voltage.
(4)寿命测试(4) Life test
在下列实施例中，寿命测试采用恒流法，在恒定50mA/cm
2电流驱动下，采用硅光***测试器件亮度变化，记录器件亮度从最高点开始，衰减到最高亮度95％的时间LT95，再通过经验公式外推器件1000nit LT95S寿命：
In the following examples, the life test adopts the constant current method, under the constant current of 50mA/ cm2 , the silicon photosystem is used to test the brightness change of the device, and the time when the brightness of the device starts from the highest point and decays to 95% of the highest brightness is recorded LT95, Then extrapolate the 1000nit LT95S life of the device through the empirical formula:
1000nit LT95＝(L
Max/1000)
1.7×LT95；
1000nit LT95＝(L Max /1000) 1.7 ×LT95;
此方法便于不同亮度水平器件的寿命比较，在实际光电器件中有着广泛的应用。This method is convenient for comparing the lifetime of devices with different brightness levels, and has a wide range of applications in practical optoelectronic devices.
(5)能级测试(5) Energy level test
本申请实施例中各材料能级测试方法：将各功能层材料进行旋涂成膜后，采用UPS(紫外光电子能谱)的方法进行能级测试。The energy level test method of each material in the examples of the present application: after spin-coating each functional layer material to form a film, the energy level test is carried out by UPS (ultraviolet photoelectron spectroscopy) method.
功函数Φ＝hν-E
cutoff，其中hv为入射激发光子的能量，E
cutoff为激发的二次电子截止位置；
Work function Φ=hν-E cutoff , where hv is the energy of the incident excitation photon, and E cutoff is the cut-off position of the excited secondary electrons;
价带顶VB(HOMO)：E
HOMO＝E
F-HOMO+Φ，其中E
F-HOMO为材料HOMO(VB)与费米能级差值，对应结合能谱中低结合能端出现的第一个峰的起始边；
Valence band top VB(HOMO): E HOMO =E F-HOMO +Φ, where E F-HOMO is the difference between the material HOMO(VB) and the Fermi level, corresponding to the first occurrence of the low binding energy end in the binding energy spectrum the starting edge of a peak;
导带底(LOMO)：E
LOMO＝E
HOMO-E
HOMO-LOMO，其中，E
HOMO-LOMO为材料的带隙，由UV-Vis(紫外吸收谱)得到。
Bottom of conduction band (LOMO): E LOMO =E HOMO -E HOMO-LOMO , where E HOMO-LOMO is the band gap of the material, obtained from UV-Vis (ultraviolet absorption spectrum).
表1Table 1
| 器件编号Part number | 量子点外壳Quantum Dot Shell | 电子传输层(粒径)Electron transport layer (particle size) | EQE(％)EQE(%) | LT95(小时)LT95 (hours) |
| 对比例1Comparative Example 1 | ZnSZnS | ZnO(5.5nm)ZnO(5.5nm) | 1.80％1.80% | 7.197.19 |
| 实施例1Example 1 | ZnSZnS | ZnO(5.5nm)ZnO(5.5nm) | 4.30％4.30% | 15.215.2 |
| 实施例2Example 2 | ZnSZnS | ZnO(5.5nm)ZnO(5.5nm) | 3.10％3.10% | 9.89.8 |
| 实施例3Example 3 | ZnSZnS | TiO 2(5.5nm) TiO 2 (5.5nm) | 5.10％5.10% | 10.210.2 |
| 实施例4Example 4 | ZnSZnS | ZnMgO(5.5nm)ZnMgO(5.5nm) | 6.10％6.10% | 3939 |
| 实施例5Example 5 | ZnSeZnSe | ZnO(5.5nm)ZnO(5.5nm) | 3.80％3.80% | 12.412.4 |
| 实施例6Example 6 | ZnSeSZnSeS | ZnO(5.5nm)ZnO(5.5nm) | 4.00％4.00% | 1313 |
由实施例1～6和对比例1的表1测试结果，以及实施例1(S2)和对比例1(S1)附图5效率曲线(横坐标为电压，纵坐标为外量子效率)，附图6电流密度-电压曲线(横坐标为电压，纵坐标为电流密度)，附图7亮度曲线(横坐标为时间，纵坐标为亮度)可知，本申请实施例1～6经过UV处理后的器件，相对于未经UV处理的器件，有更好的发光效率和更长的发光寿命。From the test results of Table 1 of Examples 1 to 6 and Comparative Example 1, as well as the efficiency curves of Figure 5 of Example 1 (S2) and Comparative Example 1 (S1) (the abscissa is the voltage, the ordinate is the external quantum efficiency), the attached Fig. 6 current density-voltage curve (abscissa is voltage, ordinate is current density), Fig. 7 brightness curve (abscissa is time, ordinate is brightness), it can be known that Examples 1-6 of the present application after UV treatment The device has better luminous efficiency and longer luminescence lifetime than the device without UV treatment.
表2Table 2
由实施例7～12和对比例2～4的表2测试结果，以及实施例7(S1)、实施例10(S2)、对比例2(S3)和对比例3(S4)附图8效率曲线(横坐标为电压，纵坐标为外量子效率)，附图9电流密度-电压曲线(横坐标为电压，纵坐标为电流密度)，附图10亮度曲线(横坐标为时间，纵坐标为亮度)可知，本申请实施例7～12经过UV处理后的器件，相对于对比例2～4的器件，有更好的发光效率和更长的发光寿命。From the test results of Table 2 of Examples 7 to 12 and Comparative Examples 2 to 4, and the efficiency of Figure 8 of Example 7 (S1), Example 10 (S2), Comparative Example 2 (S3) and Comparative Example 3 (S4) Curve (abscissa is voltage, ordinate is external quantum efficiency), accompanying drawing 9 current density-voltage curve (abscissa is voltage, ordinate is current density), accompanying drawing 10 brightness curve (abscissa is time, ordinate is Brightness), it can be seen that the UV-treated devices of Examples 7 to 12 of the present application have better luminous efficiency and longer luminous life than the devices of Comparative Examples 2 to 4.
表3table 3
由上表3的测试结果可知，对于同一CdZnS(-6.2eV)外壳量子点，将HTL从P15(-5.8eV)改为P9(-5.1eV)，ΔE
EML-HTL势垒差从0.4eV增大至1.0eV，器件寿命得到提高，1000nit LT95S寿命从1.2提高到2.1。另外，对于同一P15(-5.8eV)材料，改变量子点外壳，从CdZnS(-6.2eV)改为ZnS(-6.5eV)，ΔE
EML-HTL势垒差从0.4eV增大至0.7eV，器件寿命得到显著提高，1000nit LT95S寿命从1.2提高到9.3。由此可见，无论是调整HTL或者EML材料，使价带顶能级差ΔE
EML-HTL增大到0.5eV以上，器件注入平衡得到优化，器件寿命都能得到增强。说明通过提高空穴注入势垒来降低空穴的注入效率，能够更好的平衡发光层中空穴与电子的注入平衡，提高器件发光效率和发光寿命。
From the test results in Table 3 above, it can be seen that for the same CdZnS (-6.2eV) shell quantum dot, changing the HTL from P15 (-5.8eV) to P9 (-5.1eV), the ΔE EML-HTL barrier difference increases from 0.4eV. Up to 1.0eV, the device lifetime is improved, and the lifetime of the 1000nit LT95S is increased from 1.2 to 2.1. In addition, for the same P15 (-5.8eV) material, changing the quantum dot shell from CdZnS (-6.2eV) to ZnS (-6.5eV), the ΔE EML-HTL barrier difference increases from 0.4eV to 0.7eV, the device The lifespan has been significantly improved, the 1000nit LT95S lifespan has been increased from 1.2 to 9.3. It can be seen that whether the HTL or EML material is adjusted to increase the valence band top energy level difference ΔE EML-HTL to more than 0.5 eV, the device injection balance is optimized, and the device lifetime can be enhanced. It shows that reducing the hole injection efficiency by increasing the hole injection barrier can better balance the injection balance of holes and electrons in the light-emitting layer, and improve the luminous efficiency and luminous life of the device.
以上仅为本申请的可选实施例而已，并不用于限制本申请。对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的权利要求范围之内。The above are only optional embodiments of the present application, and are not intended to limit the present application. Various modifications and variations of this application are possible for those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of this application shall be included within the scope of the claims of this application.
Claims (30)
- 一种发光器件的制备方法，其特征在于，包括以下步骤：A method for preparing a light-emitting device, comprising the following steps:制备包括依次叠层设置的阳极、空穴功能层、量子点发光层、电子功能层和阴极的发光器件；其中，所述电子功能层中包括金属氧化物传输材料；preparing a light-emitting device including an anode, a hole functional layer, a quantum dot light-emitting layer, an electronic functional layer and a cathode that are stacked in sequence; wherein the electronic functional layer includes a metal oxide transport material;对所述发光器件进行紫外光照射处理。The light-emitting device is subjected to ultraviolet light irradiation treatment.
- 如权利要求1所述的发光器件的制备方法，其特征在于，所述量子点发光层中包括核壳结构的量子点材料，所述量子点材料的外壳层材料与所述空穴传输层中空穴传输材料的价带顶能级差大于等于0.5eV。The method for preparing a light-emitting device according to claim 1, wherein the quantum dot light-emitting layer comprises a core-shell structure quantum dot material, and the outer shell layer material of the quantum dot material and the hole transport layer are hollow The top energy level difference of the valence band of the hole transport material is greater than or equal to 0.5eV.
- 如权利要求2所述发光器件的制备方法，其特征在于，对所述发光器件进行紫外光照射处理的步骤包括：The method for preparing a light-emitting device according to claim 2, wherein the step of irradiating the light-emitting device with ultraviolet light comprises:在阳极和阴极之间制备量子点发光层和电子传输层的复合层后，对所述复合层进行紫外光照射处理；After preparing the composite layer of the quantum dot light-emitting layer and the electron transport layer between the anode and the cathode, the composite layer is subjected to ultraviolet light irradiation treatment;或者，在阴极表面制备电子传输层后进行紫外光照射处理；在所述电子传输层表面制备量子点发光层后进行紫外光照射处理；Alternatively, ultraviolet light irradiation treatment is performed after preparing an electron transport layer on the surface of the cathode; ultraviolet light irradiation treatment is performed after preparing a quantum dot light-emitting layer on the surface of the electron transport layer;或者，制备依次叠层设置的阳极、空穴传输层、量子点发光层、电子传输层和阴极的叠层复合结构，对所述叠层复合进行紫外光照处理。Alternatively, a laminated composite structure of an anode, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer and a cathode that are stacked in sequence is prepared, and the laminated composite is subjected to ultraviolet irradiation treatment.
- 如权利要求2或3所述发光器件的制备方法，其特征在于，所述量子点材料的外壳层材料与所述空穴传输材料的价带顶能级差为0.5～1.7eV。The method for preparing a light-emitting device according to claim 2 or 3, wherein the difference in valence band top energy level between the outer shell layer material of the quantum dot material and the hole transport material is 0.5-1.7 eV.
- 如权利要求2所述发光器件的制备方法，其特征在于，所述空穴传输材料的价带顶能级的绝对值小于等于5.3eV。The method for preparing a light-emitting device according to claim 2, wherein the absolute value of the top energy level of the valence band of the hole transport material is less than or equal to 5.3 eV.
- 如权利要求2所述发光器件的制备方法，其特征在于和/或，所述空穴传输材料的迁移率高于1×10 -4cm 2/Vs。 The method for preparing a light-emitting device according to claim 2, wherein and/or the mobility of the hole transport material is higher than 1×10 -4 cm 2 /Vs.
- 如权利要求5或6所述发光器件的制备方法，其特征在于和/或，所述空穴传输材料选自：含苯胺基团的聚合物、含有芴基团和苯胺基团的共聚物中的至少一种。The method for preparing a light-emitting device according to claim 5 or 6, wherein and/or the hole transport material is selected from the group consisting of: a polymer containing an aniline group, a copolymer containing a fluorene group and an aniline group at least one of.
- 如权利要求7所述发光器件的制备方法，其特征在于，所述空穴传输材料包括：TFB、poly-TPD、P10、P11、P15、P12、P09、P13中的至少一种。The method for preparing a light-emitting device according to claim 7, wherein the hole transport material comprises: at least one of TFB, poly-TPD, P10, P11, P15, P12, P09, and P13.
- 如权利要求2所述的发光器件的制备方法，其特征在于，所述量子点材料的外壳层含有锌元素。The method for preparing a light-emitting device according to claim 2, wherein the outer shell layer of the quantum dot material contains zinc.
- 如权利要求9所述的发光器件的制备方法，其特征在于，所述量子点材料的外壳层包括：ZnS、ZnSe、ZnTe、CdZnS、ZnCdSe中的至少一种或者至少两种形成的合金材料。The method for preparing a light-emitting device according to claim 9, wherein the outer shell layer of the quantum dot material comprises: an alloy material formed by at least one or at least two of ZnS, ZnSe, ZnTe, CdZnS, and ZnCdSe.
- 如权利要求1所述的发光器件的制备方法，其特征在于，制备所述电子功能层的步骤包括：在所述阴极背离衬底的表面依次制备第一子电子传输层至第N子电子传输层，形成电子传输层；其中，所述电子传输层中至少一层子电子传输层包括有机传输材料，至少所述第N子电子传输层中包括金属氧化物传输材料，N为大于等于2的正整数。The method for preparing a light-emitting device according to claim 1, wherein the step of preparing the electronic functional layer comprises: sequentially preparing a first electron transport sub-layer to an N-th electron transport sub-layer on the surface of the cathode facing away from the substrate layer to form an electron transport layer; wherein, at least one sub-electron transport layer in the electron transport layer includes an organic transport material, at least the Nth sub-electron transport layer includes a metal oxide transport material, and N is greater than or equal to 2 positive integer.
- 如权利要求11所述的发光器件的制备方法，其特征在于，所述电子传输层中，所述第一子电子传输层和所述第N子电子传输层分别独立地包含金属氧化物传输材料，N为大于等于3且小于等于9的正整数，优选地，N小于等于9。The method for fabricating a light-emitting device according to claim 11, wherein, in the electron transport layer, the first electron transport sub layer and the Nth electron transport sub layer independently contain a metal oxide transport material. , N is a positive integer greater than or equal to 3 and less than or equal to 9, preferably, N is less than or equal to 9.
- 如权利要求12所述的发光器件的制备方法，其特征在于，所述第N子电子传输层中金属氧化物传输材料的粒径为2～4nm。The method for preparing a light-emitting device according to claim 12, wherein the particle size of the metal oxide transport material in the N-th sub-electron transport layer is 2-4 nm.
- 如权利要求12或13所述的发光器件的制备方法，其特征在于，所述电子传输层中至少包括一层金属氧化物传输材料的粒径为4～8nm的子电子传输层。The method for preparing a light-emitting device according to claim 12 or 13, wherein the electron transport layer comprises at least one sub-electron transport layer of metal oxide transport material with a particle size of 4-8 nm.
- 如权利要求1所述的发光器件的制备方法，其特征在于，所述紫外光照射处理的步骤包括：在紫外光波长为250～420nm，光波密度10～300mJ/cm 2的条件下，对所述发光器件照射10～60min。 The method for preparing a light-emitting device according to claim 1, wherein the step of irradiating the ultraviolet light comprises: under the conditions that the wavelength of the ultraviolet light is 250-420 nm and the light wave density is 10-300 mJ/cm 2 The light-emitting device is irradiated for 10 to 60 minutes.
- 如权利要求15所述的发光器件的制备方法，其特征在于，所述紫外光照射处理的条件还包括：在H 2O含量小于1ppm，温度为80～120℃的环境下进行。 The method for preparing a light-emitting device according to claim 15, wherein the conditions of the ultraviolet light irradiation treatment further include: performing the treatment in an environment where the H 2 O content is less than 1 ppm and the temperature is 80-120°C.
- 如权利要求15或16所述的发光器件的制备方法，其特征在于，所述紫外光照射处理的步骤包括：采用波长为320～420nm，光波密度10～150mJ/cm 2的紫外光波从所述阳极一侧进行照射处理10～60min。 The method for preparing a light-emitting device according to claim 15 or 16, wherein the step of irradiating ultraviolet light comprises: using ultraviolet light waves with a wavelength of 320-420 nm and an optical wave density of 10-150 mJ/cm 2 from the The anode side is irradiated for 10 to 60 minutes.
- 如权利要求15或16所述的发光器件的制备方法，其特征在于，所述紫外光照射处理的步骤包括：采用波长为250～320nm，光波密度100～200mJ/cm 2的紫外光波从所述阴极一侧进行照射处理10～60min。 The method for preparing a light-emitting device according to claim 15 or 16, wherein the step of irradiating ultraviolet light comprises: using ultraviolet light waves with a wavelength of 250-320 nm and an optical wave density of 100-200 mJ/cm 2 from the The cathode side is irradiated for 10 to 60 minutes.
- 如权利要求1～3、5～6、8～13、15、16任一项所述的发光器件的制备方法，其特征在于，所述金属氧化物传输材料选自：ZnO、TiO 2、Fe 2O 3、SnO 2、Ta 2O 3中的至少一种。 The method for preparing a light-emitting device according to any one of claims 1-3, 5-6, 8-13, 15, and 16, wherein the metal oxide transport material is selected from the group consisting of: ZnO, TiO 2 , Fe At least one of 2 O 3 , SnO 2 , and Ta 2 O 3 .
- 如权利要求19所述的发光器件的制备方法，其特征在于，所述金属氧化物传输材料选自：掺杂有金属元素的ZnO、TiO 2、Fe 2O 3、SnO 2、Ta 2O 3中的至少一种，其中，所述金属元素包括铝、镁、锂、镧、钇、锰、镓、铁、铬、钴中至少一种。 The method for preparing a light-emitting device according to claim 19, wherein the metal oxide transport material is selected from the group consisting of: ZnO, TiO 2 , Fe 2 O 3 , SnO 2 , Ta 2 O 3 doped with metal elements At least one of the metal elements, wherein the metal element includes at least one of aluminum, magnesium, lithium, lanthanum, yttrium, manganese, gallium, iron, chromium, and cobalt.
- 如权利要求11所述的发光器件的制备方法，其特征在于，所述有机传输材料的电子迁移率大于等于10 -4cm 2/Vs。 The method for preparing a light-emitting device according to claim 11, wherein the electron mobility of the organic transport material is greater than or equal to 10 -4 cm 2 /Vs.
- 如权利要求12所述的发光器件的制备方法，其特征在于，所述有机传输材料选自：8-羟基喹啉-锂、八羟基喹啉铝、富勒烯衍生物、3,5-双(4-叔丁基苯基)-4-苯基-4H-1,2,4-***、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯中的至少一种。The method for preparing a light-emitting device according to claim 12, wherein the organic transport material is selected from the group consisting of: 8-hydroxyquinoline-lithium, octahydroxyquinoline aluminum, fullerene derivatives, 3,5-bis (4-tert-Butylphenyl)-4-phenyl-4H-1,2,4-triazole, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene at least one of them.
- 如权利要求1所述的发光器件的制备方法，其特征在于，所述电子传输层的厚度为10～200nm。The method for preparing a light-emitting device according to claim 1, wherein the electron transport layer has a thickness of 10-200 nm.
- 如权利要求1所述的发光器件的制备方法，其特征在于，所述量子点发光层的厚度为8～100nm。The method for preparing a light-emitting device according to claim 1, wherein the quantum dot light-emitting layer has a thickness of 8-100 nm.
- 如权利要求2所述的发光器件的制备方法，其特征在于，所述量子点材料的外壳层厚度为0.2～6.0nm。The method for preparing a light-emitting device according to claim 2, wherein the thickness of the outer shell layer of the quantum dot material is 0.2-6.0 nm.
- 如权利要求1所述的发光器件的制备方法，其特征在于，所述空穴传输层的厚度为10～150nm。The method for preparing a light-emitting device according to claim 1, wherein the hole transport layer has a thickness of 10-150 nm.
- 如权利要求1所述的发光器件的制备方法，其特征在于，所述阴极包括Mg、Ag、Al、Ca中的至少一种金属材料或者至少两种的合金材料。The method for manufacturing a light-emitting device according to claim 1, wherein the cathode comprises at least one metal material or at least two alloy materials of Mg, Ag, Al, and Ca.
- 如权利要求23～27任一项所述的发光器件的制备方法，其特征在于，当紫外光波从所述阴极一侧进行照射，且所述电子传输层的厚度低于80nm时，所述紫外光照射处理的时长为15分钟～45分钟。The method for preparing a light-emitting device according to any one of claims 23 to 27, wherein when ultraviolet light waves are irradiated from the cathode side, and the thickness of the electron transport layer is less than 80 nm, the ultraviolet The duration of the light irradiation treatment is 15 minutes to 45 minutes.
- 如权利要求23～27任一项所述的发光器件的制备方法，其特征在于，当紫外光波从所述阴极一侧进行照射，且所述电子传输层的厚度高于80nm时，所述紫外光照射处理的时长为30分钟～90分钟。The method for preparing a light-emitting device according to any one of claims 23 to 27, wherein when ultraviolet light waves are irradiated from the cathode side, and the thickness of the electron transport layer is higher than 80 nm, the ultraviolet The duration of the light irradiation treatment is 30 minutes to 90 minutes.
- 一种发光器件，其特征在于，所述发光器件由如权利要求1～29任一所述的方法制得。A light-emitting device, characterized in that, the light-emitting device is produced by the method according to any one of claims 1-29.
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| CN202011639283.6A CN114695822A (en) | 2020-12-31 | 2020-12-31 | Light emitting device and method of manufacturing the same |
| CN202011639297.8A CN114695737A (en) | 2020-12-31 | 2020-12-31 | Light emitting device and method of manufacturing the same |
| CN202011639297.8 | 2020-12-31 | ||
| CN202011636859.3 | 2020-12-31 | ||
| CN202011636859.3A CN114695820A (en) | 2020-12-31 | 2020-12-31 | Light emitting device and method of manufacturing the same |
| CN202011639283.6 | 2020-12-31 |
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