WO2020134147A1 - 一种量子点发光二极管 - Google Patents
一种量子点发光二极管 Download PDFInfo
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/18—Carrier blocking layers
- H10K50/181—Electron blocking layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
Definitions
- the present disclosure relates to the field of quantum dots, and in particular to a quantum dot light emitting diode.
- the quantum dot light emitting diode is a typical sandwich structure, which is composed of electrodes, functional layers, and light emitting layers. Under the excitation of the applied voltage, the carriers enter the quantum dots from the functional layers through the electrodes at both ends to recombine to form excitons. The recombined excitons release photons in the form of radiation transitions, thereby emitting light. Because colloidal quantum dots have the characteristics of high luminous efficiency, high color purity, wide color gamut, and good stability, QLED not only inherits these excellent properties of quantum dots, but also has self-luminous, wide viewing angle, flexible, etc. Features, showing great commercial application prospects, have become an important research direction in the field of new generation of new and lighting display.
- the quantum dot itself is processed and prepared by the solution method, it is very suitable for configuration as an ink, and then printing, inkjet and other methods are used to achieve large-scale and large-area preparation.
- QLED devices have developed rapidly and achieved remarkable results.
- the alloying of the quantum dot and the growth of the thick shell layer have greatly promoted the performance of QLED devices.
- semiconductor quantum dots generally have a deep HOMO energy level, and there is a large potential barrier for charge transport in each functional layer, resulting in an imbalance between electron and hole injection during device operation.
- a high carrier injection barrier will increase the operating voltage of the device; on the other hand, unbalanced charge injection will greatly reduce the recombination probability of carriers in the light-emitting layer, and easily lead to non-radiative transitions of excitons , Thereby affecting the luminous efficiency and life of the device.
- the purpose of the present disclosure is to provide a quantum dot light-emitting diode, which aims to solve the imbalance of carrier injection in the existing QLED device resulting in a reduction in the recombination probability of carriers in the light-emitting layer, which affects The luminous efficiency and lifespan of the device.
- a quantum dot light-emitting diode includes a cathode, an anode, and a quantum dot light-emitting layer disposed between the cathode and the anode, wherein a functional layer is provided between the cathode and the quantum dot light-emitting layer, and the functional layer includes n-layer stacks
- a functional structural unit provided, the functional structural unit is composed of an electron blocking material layer and an electron transport layer provided in a stack, the electron blocking material layer in the functional structural unit is disposed close to the quantum dot light emitting layer, and the The electron transport layer is disposed near the cathode, and n is an integer greater than or equal to 1.
- the quantum dot light-emitting diode provided by the present disclosure can reduce the transfer rate of electrons to the quantum dot light-emitting layer through the arrangement of the functional layer, thereby balancing the injection rate of electrons and holes, so as to improve carriers in the quantum dot layer Recombination efficiency in the process, thereby improving the luminous efficiency, stability and service life of the quantum dot light-emitting diode; further, the electron blocking material layer in the functional layer can also prevent the orthogonal solvent in the electron transport layer from affecting the quantum dot light emitting layer Has an adverse effect on the optical performance.
- FIG. 1 is a schematic structural diagram of a preferred embodiment of a quantum dot light emitting diode of the present disclosure.
- FIG. 2 is a schematic diagram of the energy band structure of the quantum dot light emitting diode of the present disclosure.
- FIG. 3 is a process flow diagram of a method for manufacturing a sub-point light emitting diode according to an embodiment of the present disclosure.
- the present disclosure provides a quantum dot light emitting diode.
- the present disclosure will be described in further detail below. It should be understood that the specific embodiments described herein are only used to explain the present disclosure and are not intended to limit the present disclosure.
- the quantum dot light emitting diodes are divided into a positive structure and an inverse structure.
- the positive structure quantum dot light emitting diodes include a substrate stacked from bottom to top , Anode, quantum dot light-emitting layer, electron transport layer and cathode.
- the substrate may include a substrate, an anode stacked on the surface of the substrate, and a hole injection layer stacked on the anode; in yet another embodiment of the present disclosure, the The substrate may include a substrate, an anode stacked on the surface of the substrate, a hole injection layer stacked on the surface of the anode, and a hole transport layer stacked on the surface of the hole injection layer.
- the inverted-type quantum dot light-emitting diode may include a substrate, a cathode, a quantum dot light-emitting layer, and an anode layered from bottom to top.
- the substrate may include a substrate, a cathode stacked on the surface of the substrate, and an electron injection layer stacked on the surface of the cathode; in yet another embodiment of the present disclosure, the The substrate may include a substrate, a cathode stacked on the surface of the substrate, an electron injection layer stacked on the surface of the cathode, and an electron transport layer stacked on the surface of the electron injection layer; in still another embodiment of the present disclosure, the The substrate may include a substrate, a cathode stacked on the surface of the substrate, an electron injection layer stacked on the surface of the cathode, an electron transport layer stacked on the surface of the electron injection layer, and a hole blocking layer stacked on the surface of the electron transport layer.
- the present disclosure provides a quantum dot light-emitting diode, which includes a cathode, an anode, and a quantum dot light-emitting layer disposed between the cathode and the anode.
- a functional layer is provided between the cathode and the quantum dot light-emitting layer, and the functional layer includes n
- the electron transport layer in is located close to the cathode, where n is an integer greater than or equal to 1.
- a functional layer is provided between the cathode and the quantum dot light-emitting layer.
- the functional layer includes n layers of stacked functional structural units.
- the functional structural units are composed of stacked electron blocking material layers and electron transport layers.
- the functional structural unit can effectively reduce the electron transmission rate, thereby balancing the injection rate of electrons and holes, so as to improve the recombination efficiency of carriers in the quantum dot light-emitting layer, thereby improving the luminous efficiency and stability of the quantum dot light-emitting diode And service life.
- the material of the electron blocking material layer is selected from one or more of PVK, Poly-TPD, NPB, TCTA, TAPC, CBP, TFB, and DNA, but is not limited thereto.
- the material of the electron blocking material layer is selected from one or more of compound-doped PVK, Poly-TPD, NPB, TCTA, TAPC, CBP, TFB, and DNA, and the compound is selected from One of Li-TFSI, NiO, CuSCN, MoO 3 , CuO, V 2 O 5 or CuS, but is not limited thereto.
- the electron blocking material layer has a LUMO energy level of -2.0 to -5.0 eV.
- the positive-type quantum dot light-emitting diode shown in FIG. 1 will be mainly used as an example for introduction.
- the positive-type quantum dot light-emitting diode includes a substrate 10, an anode 20, a hole transport layer 30, a quantum dot light-emitting layer 40, a functional layer, and a cathode 60 stacked from bottom to top.
- the functional layer includes n layers of stacked functional structural units, which are composed of an electron blocking material layer 51 and an electron transport layer 52 stacked, and the electron blocking material layer 51 in the functional structural unit is close to quantum dots
- the light-emitting layer is disposed, the electron transport layer 52 in the functional structural unit is disposed near the cathode, the n is an integer greater than or equal to 2, and the adjacent two functional structural units in the n-layer functional structural unit are located near the cathode
- the LUMO level of the material of the electron blocking material layer is greater than the LUMO level of the material of the electron blocking material layer near the quantum dot light emitting layer.
- the quantum dot light emitting diode can effectively balance the injection rate of electrons and holes through the arrangement of the functional layer, thereby improving the recombination efficiency of carriers in the quantum dot light emitting layer, and thereby improving the luminous efficiency of the quantum dot light emitting diode. Stability and service life.
- the mechanism for achieving the above effect is as follows:
- the functional layer in this embodiment includes n layers of stacked functional structural units, the functional structural unit is composed of stacked electron blocking material layer and electron transport layer Composition, the electron blocking material layer in the functional structural unit is arranged near the quantum dot light emitting layer, the electron transport layer in the functional structural unit is arranged near the cathode, the n is an integer greater than or equal to 2, and the n layer function
- the LUMO energy level of the electron blocking material layer material near the cathode is greater than the LUMO energy level of the electron blocking material layer material near the quantum dot light-emitting layer.
- the electrons when electrons are transferred from the cathode to the quantum dot light-emitting layer, the electrons need to first tunnel through the electron blocking material layer with the largest LUMO energy level, at this time the electron barrier to be overcome is the largest; then The electron-blocking material layer whose tunneling LUMO energy level sequentially decreases reaches the quantum dot light-emitting layer; the stepped electron-blocking material layer is very helpful to alleviate the excessive accumulation of excessive electrons in the quantum dot light-emitting layer, which is conducive to slowing the electron transport performance Therefore, along the direction from the cathode to the anode, as the LUMO level of the electron blocking material layer decreases continuously, the electron transmission efficiency will gradually decrease.
- the quantum dot light emitting diode of the present disclosure can reduce the transfer rate of electrons to the quantum dot light emitting layer through the arrangement of the functional layer, thereby balancing the injection rate of electrons and holes, so as to improve the recombination efficiency of carriers in the quantum dot layer, In turn, the luminous efficiency, stability and service life of the quantum dot light-emitting diode are improved; further, the electron blocking material layer in the functional layer can also prevent the orthogonal solvent in the electron transport layer from detrimental to the optical performance of the quantum dot light emitting layer influences.
- the number of layers of the electron blocking material layer and the electron transport layer are the same, and the number of layers of the electron blocking material layer and the electron transport layer are 2-10 layers. Preferably, the number of layers of the electron blocking material layer and the electron transport layer are 2-5 layers.
- the thickness of each electron blocking material layer is 2-5 nm.
- the electron blocking material layer has a LUMO energy level of -2.0 to -5.0 eV.
- the electron blocking material layer material near the cathode has a LUMO energy level greater than that of the electron blocking material layer near the quantum dot light emitting layer LUMO energy level, and the LUMO energy level difference between adjacent electron blocking material layers is -0.1 ⁇ -0.5eV.
- the electron blocking material layer with a stepped energy level can not only effectively slow down the electron transmission rate, so that the electrons entering the quantum dot light-emitting layer and the holes entering the quantum dot light-emitting layer can reach an equilibrium state, Increasing the recombination probability of electrons and holes; at the same time, it can also effectively reduce the accumulation of excessive electrons in the quantum dot light-emitting layer and cause quantum dot fluorescence attenuation.
- the electron blocking material layer material is selected from one or more of PVK, Poly-TPD, NPB, TCTA, TAPC, CBP, TFB, and DNA, but is not limited thereto.
- the material of the electron blocking material layer is selected from one or more of compound-doped PVK, Poly-TPD, NPB, TCTA, TAPC, CBP, TFB, and DNA, and the compound is selected from One of Li-TFSI, NiO, CuSCN, MoO 3 , CuO, V 2 O 5 or CuS, but is not limited thereto.
- the electron blocking layer material is selected from one of PVK, Poly-TPD, NPB, TCTA, TAPC, CBP, TFB, and DNA and Li-TFSI, NiO, CuSCN, MoO 3 , CuO, V A mixed material composed of 2 O 5 and CuS.
- the purpose of selecting a mixed material compound doped electron blocking material is mainly to adjust the LUMO energy level of the electron blocking material layer material, to achieve a stepped barrier between level energy levels, and thereby to adjust the electron and hole transport rate, Improve the recombination efficiency of excitons.
- the material of the electron blocking material layer is selected from PVK:Li-TFSI, PVK:NiO, PVK:CuSCN, PVK:MoO 3 , PVK:CuO, PVK:V 2 O 5 , PVK:CuS, Poly-TPD, Poly-TPD: Li-TFSI, Poly-TPD: -NiO, Poly-TPD: CuSCN, Poly-TPD: MoO 3 , Poly-TPD: CuO, Poly-TPD: V 2 O 5 , Poly-TPD: CuS, NPB , NPB: Li-TFSI, NPB-TPD: -NiO, NPB-TPD: CuSCN, NPB: MoO 3 , NPB: CuO, NPB: V 2 O 5 , NPB: CuS, TCTA, TCTA: Li-TFSI, TCTA- TPD:-NiO, TCTA-TPD:CuSCN, TCTA:MoO 3 , TC
- the electron transport layer material is selected from one or more of ZnO, TiO 2, Alq 3 , SnO, ZrO, AlZnO, ZnSnO, BCP, TAZ, PBD, TPBI, Bphen, and CsCO 3 , But it is not limited to this.
- the thickness of the electron transport layer is 10-120 nm.
- the quantum dot light-emitting layer material is selected from one or more of group II-VI compounds, group III-V compounds, and group I-III-VI compounds, but is not limited thereto.
- the group II-VI compound is selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS; CdZnSeS, CdZnSeTe and CdZnSTe
- the group III-V compound is selected from one or more of InP, InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, InNP, InNSb, GaAlNP, and InAlNP
- the I -Group III-VI compounds are selected from one or more of InP, In
- the thickness of the quantum dot light emitting layer is 30-120 nm.
- the anode material is selected from one or more of Li, Ca, Ba, LiF, CsN 3 , Cs 2 CO 3 , CsF, Ag, Mo, Al, Cu, and Au, but is not limited to this.
- the thickness of the anode is 20-150 nm.
- the hole transport layer material is selected from TFB, PVK, Poly-TBP, Poly-TPD, NPB, TCTA, TAPC, CBP, PEODT: PSS, MoO 3 , WoO 3 , NiO, CuO, V One or more of 2 O 5 and CuS, but not limited thereto.
- the hole transport layer has a thickness of 30-100 nm.
- the cathode material is selected from one of ITO, FTO, or ZTO. In some embodiments, the thickness of the cathode is 60-130 nm.
- the quantum dot light emitting diode of the present disclosure may further include one or more of the following functional layers: a hole injection layer provided between the anode and the hole transport layer, and a hole injection layer provided between the cathode and the functional layer Electron injection layer.
- some embodiments of the present disclosure also provide a method for manufacturing a sub-point light emitting diode, including the following steps:
- the functional layer includes n layers of stacked functional structural units.
- the functional structural units are composed of stacked electron blocking material layers and electron transport layers.
- the electron blocking material layer is disposed near the quantum dot light emitting layer
- the electron transport layer in the functional structural unit is disposed near the cathode
- the n is an integer greater than or equal to 2.
- the quantum dot light emitting diode is divided into an upright structure and an inverted structure.
- the upright structure includes an anode, a cathode, and a quantum dot light-emitting layer disposed between the anode and the cathode.
- the anode of the upright structure is disposed on the substrate, and hole transport can also be provided between the anode and the quantum dot light-emitting layer.
- the hole functional layer such as a layer, a hole injection layer, and an electron blocking layer may be provided with an electron functional layer such as an electron transport layer, an electron injection layer, and a hole blocking layer between the cathode and the quantum dot light emitting layer.
- the inverted structure includes an anode, a cathode, and a quantum dot light-emitting layer disposed between the anode and the cathode.
- the cathode of the inverted structure is disposed on the substrate.
- a hole transport layer can also be provided between the anode and the quantum dot light-emitting layer.
- a hole functional layer such as a hole injection layer and an electron blocking layer may be provided with an electron functional layer such as an electron transport layer, an electron injection layer and a hole blocking layer between the cathode and the quantum dot light emitting layer.
- the bottom electrode disposed on the substrate is an anode.
- the substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, and a stacked layer disposed on the bottom Quantum dot light-emitting layer on the surface of the electrode; in other embodiments of the present disclosure, the anode substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, a hole transport layer stacked on the surface of the bottom electrode, and a stack A quantum dot light-emitting layer provided on the surface of the hole transport layer; in still other embodiments of the present disclosure, the anode substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, and a hollow layer stacked on the surface of the bottom electrode A hole injection layer, a hole transport layer stacked on the surface of the hole injection layer, and a quantum dot light emitting layer stacked on the surface of the hole transport layer; in still other embodiments of the present disclosure, the anode substrate may
- the bottom electrode provided on the substrate is a cathode.
- the cathode substrate may be a bottom electrode provided on the substrate; in still other embodiments of the present disclosure, The substrate may include a substrate, a bottom electrode stacked on the surface of the substrate, and an electron injection layer stacked on the surface of the bottom electrode.
- Embodiments of the present disclosure provide an example of a method for manufacturing a quantum dot light-emitting diode having a formal structure as shown in FIG. 1, specifically including the following steps:
- An electron blocking material layer is prepared on the quantum dot light-emitting layer, an electron transporting layer is prepared on the electron blocking material layer, an electron blocking material layer is further prepared on the electron transporting layer, and the above steps are repeated until the predetermined number of countdowns Preparing a final nth electron transport layer on the first electron blocking material layer to obtain the functional layer;
- n is an integer greater than or equal to 2
- the electron blocking material layer material near the cathode has a LUMO energy level greater than that near the quantum dot light emitting layer The LUMO energy level of the electron blocking material layer material.
- each layer preparation method may be a chemical method or a physical method, wherein the chemical method includes but is not limited to one of chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method, and co-precipitation method One or more; physical methods include but are not limited to solution methods (such as spin coating method, printing method, blade coating method, dipping and pulling method, dipping method, spraying method, roll coating method, casting method, slit coating method) Or strip coating method, etc.), evaporation method (such as thermal evaporation method, electron beam evaporation method, magnetron sputtering method or multi-arc ion coating method, etc.), deposition method (such as physical vapor deposition method, atomic layer One or more of deposition method, pulsed laser deposition method, etc.).
- solution methods such as spin coating method, printing method, blade coating method, dipping and pulling method, dipping method, spraying method, roll coating method, casting method, slit coating method
- a quantum dot light-emitting diode comprising a substrate, an anode, a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, a functional layer and a cathode arranged in sequence from bottom to top.
- the lowest layer of the functional layer is an electron blocking material layer and is located near the quantum dot light-emitting layer.
- the highest layer of the functional layer is an electron transport layer and is located near the cathode; along the anode In the direction of the cathode, the material of each electron blocking material layer is PVK, PVK doped with 1.5wt.% Li-TFSI, PVK doped with 3wt.% Li-TFSI, 4.5wt.% Li- TFSI PVK and 6wt.% Li-TFSI PVK; the anode is ITO with a thickness of 100nm; the hole injection layer material is PEDOT:PSS with a thickness of 40nm; the hole transport layer material is TFB with a thickness 80nm; the material of the quantum dot light-emitting layer is InP/ZnS with a thickness of 100nm; the thickness of each electron blocking material layer is 4nm; the material of each electron transport layer is ZnO, each layer The thickness of the electron transport layer is 20 nm; the cathode is Al and the thickness is 50 nm.
- a quantum dot light-emitting diode comprising a substrate, an anode, a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, a functional layer and a cathode arranged in sequence from bottom to top.
- the lowest layer of the functional layer is an electron blocking material layer and is located near the quantum dot light-emitting layer.
- the highest layer of the functional layer is an electron transport layer and is located near the cathode; along the anode In the direction of the cathode, the material of each electron blocking material layer is TFB, TFB doped with 1.5wt.% Li-TFSI, TFB doped with 3wt.% Li-TFSI, 4.5wt.% Li- TFSI TFB and 6wt.% Li-TFSI TFB; the anode is ITO with a thickness of 100nm; the hole injection layer material is PEDOT:PSS with a thickness of 40nm; the hole transport layer material is TFB with a thickness 80nm; the material of the quantum dot light-emitting layer is InP/ZnS, the thickness is 40nm; the thickness of each electron blocking material layer is 4nm; the material of each electron transport layer is SnO, the electron transport of each layer The thickness of the layer is 10 nm; the cathode is Al and the thickness is 50 nm.
- a quantum dot light-emitting diode comprising a substrate, an anode, a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, a functional layer and a cathode arranged in sequence from bottom to top.
- the lowest layer of the functional layer is an electron blocking material layer and is located near the quantum dot light-emitting layer.
- the highest layer of the functional layer is an electron transport layer and is located near the cathode; along the anode to the direction of the cathode, the electron blocking material, each material layer TCTA were doped with TCTA 1.5wt.% MoO 3 and doped with TCTA 3wt.% MoO 3 of, TCTA 4.5wt.% MoO 3 of And 6wt.% MoO 3 TCTA;
- the anode is ITO with a thickness of 100nm;
- the hole injection layer material is PEDOT: PSS with a thickness of 40nm;
- the hole transport layer material is TFB with a thickness of 80nm;
- the material of the quantum dot light emitting layer is InP/ZnS with a thickness of 80 nm;
- the thickness of each electron blocking material layer is 4 nm;
- the material of each electron transport layer is TiO, and the thickness of each electron blocking material layer
- the thickness is 15 nm; the cathode is Al and the thickness is
- a quantum dot light-emitting diode comprising a substrate, an anode, a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, a functional layer and a cathode arranged in sequence from bottom to top.
- the lowest layer of the functional layer is an electron blocking material layer and is located near the quantum dot light-emitting layer.
- the highest layer of the functional layer is an electron transport layer and is located near the cathode; along the anode In the direction of the cathode, the material of each electron blocking material layer is PVK, PVK doped with 1.5wt.% Li-TFSI, PVK doped with 3wt.% Li-TFSI, 4.5wt.% Li- TFSI PVK and 6wt.% Li-TFSI PVK; the anode is ITO with a thickness of 100nm; the hole injection layer material is PEDOT:PSS with a thickness of 40nm; the hole transport layer material is TFB with a thickness 80nm; the material of the quantum dot light-emitting layer is CdZnS/CdZnSe/ZnS, the thickness is 120nm; the thickness of each electron blocking material layer is 4nm; the material of the electron transport layer is AlZnO, the electron transport of each layer The thickness of the layer is 8 nm; the cathode is Al and the thickness is 50
- a quantum dot light-emitting diode comprising a substrate, an anode, a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, a functional layer and a cathode arranged in sequence from bottom to top.
- the lowest layer of the functional layer is an electron blocking material layer and is located near the quantum dot light-emitting layer.
- the highest layer of the functional layer is an electron transport layer and is located near the cathode; along the anode In the direction of the cathode, the material of each electron blocking material layer is TFB, TFB doped with 1.5wt.% Li-TFSI, TFB doped with 3wt.% Li-TFSI, 4.5wt.% Li- TFSI TFB and 6wt.% Li-TFSI TFB; the anode is ITO with a thickness of 100nm; the hole injection layer material is PEDOT:PSS with a thickness of 40nm; the hole transport layer material is TFB with a thickness 80nm; the material of the quantum dot light-emitting layer is CdZnS/CdZnSe/ZnS with a thickness of 30nm; the thickness of each electron blocking material layer is 4nm; the material of each electron transport layer is TPBI, the The thickness of each electron transport layer is 12 nm; the cathode is Al and the thickness is 50 nm.
- a quantum dot light-emitting diode comprising a substrate, an anode, a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, a functional layer and a cathode arranged in sequence from bottom to top.
- the lowest layer of the functional layer is an electron blocking material layer and is located near the quantum dot light-emitting layer.
- the highest layer of the functional layer is an electron transport layer and is located near the cathode; along the anode to the direction of the cathode, the electron blocking material, each material layer TCTA were doped with TCTA 1.5wt.% MoO 3 and doped with TCTA 3wt.% MoO 3 of, TCTA 4.5wt.% MoO 3 of And 6wt.% MoO 3 TCTA;
- the anode is ITO with a thickness of 100nm;
- the hole injection layer material is PEDOT: PSS with a thickness of 40nm;
- the hole transport layer material is TFB with a thickness of 80nm;
- the material of the quantum dot light-emitting layer is CdZnS/CdZnSe/ZnS, and the thickness is 110 nm;
- the thickness of each electron blocking material layer is 4 nm;
- the material of each electron transport layer is ZnO, and each layer of electrons
- the thickness of the transmission layer is 8
- the quantum dot light-emitting diode provided by the present disclosure includes a functional layer disposed between the cathode and the quantum dot light-emitting layer, the functional layer includes n-layer stacked functional structural units, and the functional structural units are stacked Composed of an electron blocking material layer and an electron transport layer, the electron blocking material layer in the functional structural unit is disposed near the quantum dot light emitting layer, the electron transport layer in the functional structural unit is disposed near the cathode, and n is greater than or equal to 1 Integer.
- the quantum dot light emitting diode of the present disclosure can reduce the transfer rate of electrons to the quantum dot light emitting layer through the arrangement of the functional layer, thereby balancing the injection rate of electrons and holes, so as to improve the recombination efficiency of carriers in the quantum dot layer, In turn, the luminous efficiency, stability and service life of the quantum dot light-emitting diode are improved; further, the electron blocking material layer in the functional layer can also prevent the orthogonal solvent in the electron transport layer from detrimental to the optical performance of the quantum dot light emitting layer influences.
Abstract
公开一种量子点发光二极管,包括阴极、阳极以及设置在阴极和阳极之间的量子点发光层,所述阴极和量子点发光层之间设置有功能层,所述功能层包括n层层叠设置的功能结构单元,所述功能结构单元由层叠设置的电子阻挡材料层和电子传输层组成,所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置,所述功能结构单元中的电子传输层靠近阴极设置,所述n为大于等于1的整数。本公开量子点发光二极管通过所述功能层的设置能够降低电子传输至量子点发光层的传输速率,从而平衡电子和空穴的注入速率,以提高载流子在量子点层中的复合效率,进而提高量子点发光二极管的发光效率、稳定性和使用寿命。
Description
本公开涉及量子点领域,尤其涉及一种量子点发光二极管。
量子点发光二级管(QLED)为典型的三明治结构,由电极,功能层,发光层等构成。在外加电压的激发下,载流子通过两端电极由各功能层进入到量子点进行复合形成激子,复合后的激子通过辐射跃迁的形式释放光子,从而发光。由于胶体量子点自身具有发光效率高、色纯度高、色域广、稳定性好等特性,QLED不仅承袭了量子点的这些优异的性能,而且QLED还具有自发光、可视角广、可弯曲等特点,表现出极大的商业应用前景,成为新一代新型与照明显示领域的重要研究方向。同时,由于量子点本身是采用溶液法加工制备,非常适合配置成油墨,然后采用印刷、喷墨等方式实现大规模、大面积化制备。目前,经过二十多年的研究与发展,QLED器件得到了迅速发展,并取得了显著的成果。特别是近年来由对功能层的调控转至对量子点自身的调控,对量子点进行合金化和厚壳层的生长极大的推动了QLED器件性能的提升。
现阶段,对于QLED器件而言,如何同步提升器件效率、寿命和稳定性,仍然是一个极具挑战性的难题。通常,半导体量子点普遍具有很深的HOMO能级,电荷在各功能层传输时存在较大的势垒,导致器件在工作时电子和空穴注入不平衡。一方面,高的载流子注入势垒会增加器件的工作电压;另一方面,不平衡的电荷注入会使得载流子在发光层内的复合几率大大降低,容易引发激子的非辐射跃迁,从而影响了器件的发光效率和寿命。
因此,现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足,本公开的目的在于提供一种量子点发光二极管,旨在解决现有QLED器件中载流子注入不平衡导致载流子在发光层内的复合几率降低,影响了器件的发光效率和寿命的问题。
本公开的技术方案如下:
一种量子点发光二极管,包括阴极、阳极以及设置在阴极和阳极之间的量子点发光层,其中,所述阴极和量子点发光层之间设置有功能层,所述功能层包括n层层叠设置的功能结构单元,所述功能结构单元由层叠设置的电子阻挡材料层和电子传输层组成,所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置,所述功能结构单元中的电子传输层靠近阴极设置,所述n为大于等于1的整数。
有益效果:本公开提供的量子点发光二极管通过所述功能层的设置能够降低电子传输至量子点发光层的传输速率,从而平衡电子和空穴的注入速率,以提高载流子在量子点层中的复合效率,进而提高量子点发光二极管的发光效率、稳定性和使用寿命;进一步地,所述功能层中的电子阻挡材料层还可阻止电子传输层中的正交溶剂对量子点发光层的光学性能产生不利影响。
图1为本公开一种量子点发光二极管较佳实施例的结构示意图。
图2为本公开量子点发光二极管的能带结构示意图。
图3为本公开实施方式的一种子点发光二极管的制备方法工艺流程图。
本公开提供一种量子点发光二极管,为使本公开的目的、技术方案及效果更加清楚、明确,以下对本公开进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本公开,并不用于限定本公开。
量子点发光二极管有多种形式,且所述量子点发光二极管分为正型结构和反型结构,在一些实施方式中,所述正型结构的量子点发光二极管包括从下至上层叠设置的基板、阳极、量子点发光层、电子传输层以及阴极。在本公开的又一实施方式中,所述基板可以包括衬底、层叠设置在衬底表面的阳极和层叠设置在阳极的空穴注入层;在本公开的又一种实施方式中,所述基板可以包括衬底、层叠设置在衬底表面的阳极、层叠设置在阳极表面的空穴注入层和层叠设置在空穴注入层表面的空穴传输层。
在一些实施方式中,所述反型结构的量子点发光二极管可包括从下往上层叠设置的基板、阴极、量子点发光层以及阳极。在本公开的一种实施方式中,所述基板可以包括衬底、层叠设置在衬底表面的阴极和层叠设置在阴极表面的电子注入层;在本公开的又一种实施方式中,所述基板可以包括衬底、层叠设置在衬底表面的阴极、层叠设置在阴极表面的电子注入层和层叠设置在电子注入层表面的电子传输层;在本公开的还一种实施方式中,所述基板可以包括衬底、层叠设置在衬底表面的阴极、层叠设置在阴极表面的电子注入层、层叠设置在电子注入层表面的电子传输层和层叠设置在电子传输层表面的空穴阻挡层。
本公开提供一种量子点发光二极管,其包括阴极、阳极以及设置在阴极和阳极之间的量子点发光层,所述阴极和量子点发光层之间设置有功能层,所述功能层包括n层层叠设置的功能结构单元,所述功能结构单元由层叠设置的电子阻挡材料层和电子传输层组成,所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置,所述功能结构单元中的电子传输层靠近阴极设置,所述n为大于等于1的整数。
对于量子点发光二极管而言,电子从阴极传输至量子点发光层的过程中,电子在各传输层的LUMO能级越深,电子传输时的势垒越大,电子隧穿过该传输层时所需要的能量越高,导致电子传输速率越慢。本实施例通过在阴极和量子点发光层之间设置功能层,所述功能层包括n层层叠设置的功能结构单元,所述功能结构单元由层叠设置的电子阻挡材料层和电子传输层组成,所述功能结构单元能够有效降低电子的传输速率,从而平衡电子和空穴的注入速率,以提高载流子在量子点发光层中的复合效率,进而提高量子点发光二极管的发光效率、稳定性和使用寿命。
在一些实施方式中,所述电子阻挡材料层的材料选自PVK、Poly-TPD、NPB、TCTA、TAPC、CBP、TFB和DNA中的一种或多种,但不限于此。
在一些实施方式中,所述电子阻挡材料层的材料选自化合物掺杂的PVK、Poly-TPD、NPB、TCTA、TAPC、CBP、TFB和DNA中的一种或多种,所述化合物选自Li-TFSI、NiO、CuSCN、MoO
3、CuO、V
2O
5或CuS中的一种,但不限于此。
在一些实施方式中,所述电子阻挡材料层的LUMO能级为-2.0~-5.0eV。
本公开的具体实施方式中将主要以如图1所示的正型结构的量子点发光二极管为例进行介绍。具体的,如图1所示,所述正型结构的量子点发光二极管包括从下至上层叠设置的基板10、阳极20、空穴传输层30、量子点发光层40、功能层以及阴极60,所述功能层包括n层层叠设置的功能结构单元,所述功能结构单元由层叠设置的电子阻挡材料层51和电子传输层52组成,所述功能结构单元中的电子阻挡材料层51靠近量子点发光层设置,所述功能结构单元中的电子传输层52靠近阴极设置,所述n为大于等于2的整数,且所述n层功能结构单元中的相邻两层功能结构单元中,靠近阴极的电子阻挡材料层材料的LUMO能级大于靠近量子点发光层的电子阻挡材料层材料的LUMO能级。
本实施例量子点发光二极管通过所述功能层的设置能够有效平衡电子和空穴的注入速率,从而提高载流子在量子点发光层中的复合效率,进而提高量子点发光二极管的发光效率、稳定性和使用寿命。实现上述效果的机理具体如下:
对于量子点发光二级管而言,电子从阴极传输至量子点发光层的过程中,电子在各传输层的LUMO能级越深,电子传输时的势垒越大,电子隧穿过该传输层时所需要的能量越高,导致电子传输速率越慢;本实施例所述功能层包括n层层叠设置的功能结构单元,所述功能结构单元由层叠设置的电子阻挡材料层和电子传输层组成,所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置,所述功能结构单元中的电子传输层靠近阴极设置,所述n为大于等于2的整数,且所述n层功能结构单元中的相邻两层功能结构单元中,靠近阴极的电子阻挡材料层材料的LUMO能级大于靠近量子点发光层的电子阻挡材料层材料的LUMO能级。如图2所示,当电子从阴极传输至量子点发光层的过程中,所述电子需要先隧穿LUMO能级最大的电子阻挡材料层,此时所需要克服的电子势垒最大;然后再隧穿LUMO能级依次减小的电子阻挡材料层到达量子点发光层;所述阶梯式的电子阻挡材料层非常有利于缓解过量电子在量子点发光层中大量积累,有利于减缓电子的传输性能,因此,沿阴极至阳极的方向,随着电子阻挡材料层的LUMO能级的不断减少,电子的传输效率将逐步降低。本公开量子点发光二极管通过所述功能层的设置能够降低电子传输至量子点发光层的传输速率,从而平衡电子和空穴的注入速率,以提高载流子在量子点层中的复合效率,进而提高量子点发光二极管的发光效率、稳定性和使用寿命;进一步地,所述功能层中的电 子阻挡材料层还可阻止电子传输层中的正交溶剂对量子点发光层的光学性能产生不利影响。
在一些实施方式中,所述电子阻挡材料层和电子传输层的层数相同,且所述电子阻挡材料层和电子传输层的层数均为2-10层。优选的,所述电子阻挡材料层和电子传输层的层数均为2-5层。
在一些实施方式中,所述每层电子阻挡材料层的厚度为2-5nm。
在一些实施方式中,所述电子阻挡材料层的LUMO能级为-2.0~-5.0eV。在一些具体的实施方式中,所述n层功能结构单元中的相邻两层功能结构单元中,靠近阴极的电子阻挡材料层材料的LUMO能级大于靠近量子点发光层的电子阻挡材料层材料的LUMO能级,且相邻电子阻挡材料层的LUMO能级差为-0.1~-0.5eV。本实施方式中,呈阶梯式能级的电子阻挡材料层不仅能够有效地减慢电子的传输速率,使得电子进入到量子点发光层和空穴进入到量子点发光层能达到一种平衡态,增加电子和空穴的复合几率;同时,也可以有效地减少过量电子在量子点发光层中积累造成量子点荧光衰减。
在一些实施方式中,电子阻挡材料层材料选自PVK、Poly-TPD、NPB、TCTA、TAPC、CBP、TFB和DNA中的一种或多种,但不限于此。
在一些实施方式中,所述电子阻挡材料层的材料选自化合物掺杂的PVK、Poly-TPD、NPB、TCTA、TAPC、CBP、TFB和DNA中的一种或多种,所述化合物选自Li-TFSI、NiO、CuSCN、MoO
3、CuO、V
2O
5或CuS中的一种,但不限于此。在一些实施方式中,所述电子阻挡层材料选自PVK、Poly-TPD、NPB、TCTA、TAPC、CBP、TFB和DNA中的一种与Li-TFSI,NiO、CuSCN、MoO
3、CuO、V
2O
5和CuS中的一种组成的混合材料。选择混合材料化合物掺杂的电子阻挡材料的目的,主要是为了调整电子阻挡层电子阻挡材料层材料的LUMO能级,实现阶能级间的阶梯势垒,从而调整电子和空穴的传输速率,提高激子的复合效率。作为举例,所述电子阻挡材料层材料选自PVK:Li-TFSI,PVK:NiO、PVK:CuSCN、PVK:MoO
3、PVK:CuO、PVK:V
2O
5、PVK:CuS、Poly-TPD、Poly-TPD:Li-TFSI,Poly-TPD:-NiO,Poly-TPD:CuSCN,Poly-TPD:MoO
3、Poly-TPD:CuO、Poly-TPD:V
2O
5、Poly-TPD:CuS、NPB、NPB:Li-TFSI,NPB-TPD:-NiO,NPB-TPD:CuSCN,NPB:MoO
3、NPB:CuO、NPB:V
2O
5、NPB:CuS、 TCTA、TCTA:Li-TFSI,TCTA-TPD:-NiO,TCTA-TPD:CuSCN、TCTA:MoO
3、TCTA:CuO、TCTA:V
2O
5、TCTA:CuS、TAPC、TAPC:Li-TFSI、TAPC-TPD:-NiO,TAPC-TPD:CuSCN,TAPC:MoO
3、TAPC:CuO、TAPC:V
2O
5、TAPC:CuS、CBP、CBP:Li-TFSI,CBP-TPD:-NiO、CBP-TPD:CuSCN、CBP:MoO
3、CBP:CuO、CBP:V
2O
5、CBP:CuS、TFB、TFB:Li-TFSI、TFB-TPD:-NiO、TFB-TPD:CuSCN、TFB:MoO
3、TFB:CuO、TFB:V
2O
5和TFB:CuS中的一种或多种,但不限于此。
在一些实施方式中,所述电子传输层材料选自ZnO、TiO
2、Alq
3、SnO、ZrO、AlZnO、ZnSnO、BCP、TAZ、PBD、TPBI、Bphen和CsCO
3中的一种或多种,但不限于此。在一些实施方式中,所述电子传输层的厚度为10-120nm。
在一些实施方式中,所述量子点发光层材料选自II-VI族化合物、III-V族化合物和I-III-VI族化合物中的一种或多种,但不限于此。作为举例,所述II-VI族化合物选自CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS;CdZnSeS、CdZnSeTe和CdZnSTe中的一种或多种;所述III-V族化合物选自InP、InAs、GaP、GaAs、GaSb、AlN、AlP、InAsP、InNP、InNSb、GaAlNP和InAlNP中的一种或多种;所述I-III-VI族化合物选自CuInS
2、CuInSe
2和AgInS
2中的一种或多种。
在一些实施方式中,所述量子点发光层的厚度为30-120nm。
在一些实施方式中,所述阳极材料选自Li、Ca、Ba、LiF、CsN
3、Cs
2CO
3、CsF、Ag、Mo、Al、Cu和Au中的一种或多种,但不限于此。在一些实施方式中,所述阳极的厚度为20-150nm。
在一些实施方式中,所述空穴传输层材料选自TFB、PVK、Poly-TBP、Poly-TPD、NPB、TCTA、TAPC、CBP、PEODT:PSS、MoO
3、WoO
3、NiO、CuO、V
2O
5和CuS中的一种或多种,但不限于此。在一些实施方式中,所述空穴传输层的厚度为30-100nm。
在一些实施方式中,所述阴极材料选自ITO、FTO或ZTO中的一种。在一些实施方式中,所述阴极的厚度为60-130nm。
需要说明的是,本公开量子点发光二极管还可包含以下功能层中的一层或多层:设置于阳极和空穴传输层之间的空穴注入层,设置于阴极和功能层之间的电子注入层。
如图3所示,本公开的一些实施方式还提供一种子点发光二极管的制备方法,包括如下步骤:
S01提供基板;
S02在所述基板上形成功能层,所述功能层包括n层层叠设置的功能结构单元,所述功能结构单元由层叠设置的电子阻挡材料层和电子传输层组成,所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置,所述功能结构单元中的电子传输层靠近阴极设置,所述n为大于等于2的整数。
具体的,量子点发光二极管分正置结构和倒置结构。正置结构包括层叠设置的阳极、阴极和设置在阳极和阴极之间的量子点发光层,正置结构的阳极设置在衬底上,在阳极和量子点发光层之间还可以设置空穴传输层、空穴注入层和电子阻挡层等空穴功能层,在阴极和量子点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。倒置结构包括层叠设置的阳极、阴极和设置在阳极和阴极之间的量子点发光层,倒置结构的阴极设置在衬底上,在阳极和量子点发光层之间还可以设置空穴传输层、空穴注入层和电子阻挡层等空穴功能层,在阴极和量子点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。
对于正置结构而言,设置在衬底上的底电极为阳极,在本公开的一些实施方式中,所述基板可以包括衬底、层叠设置在衬底表面的底电极、和层叠设置在底电极表面的量子点发光层;在本公开的另一些实施方式中,所述阳极基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在底电极表面的空穴传输层和层叠设置在空穴传输层表面的量子点发光层;在本公开的又一些实施方式中,所述阳极基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在底电极表面的空穴注入层、层叠设置在空穴注入层表面的空穴传输层和层叠设置在空穴传输层表面的量子点发光层;在本公开的又一些实施方式中,所述阳极基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在底电极表面的空穴注入层、层叠设置在空穴注入层表面的空穴传输层、层叠设置在空穴传输层表面的电子阻挡层和层叠设置在电子阻挡层表面的量子点发光层;在本公开的又一些实施方式中,所述阳极基板可以包括衬底、层叠设置在衬底表面的底电极、层叠设置在底电极表面的空穴注入层、层叠设置在空穴注入层表面的空穴传输层、层叠设置在 空穴传输层表面的电子阻挡层、层叠设置在电子阻挡层表面的量子点发光层和层叠设置在量子点发光层表面的空穴阻挡层。
对于倒置结构而言,设置在衬底上的底电极为阴极,在本公开的一些实施方式中,所述阴极基板可以为衬底上设置的底电极;在本公开的又一些实施方式中,所述基板可以包括衬底、层叠设置在衬底表面的底电极和层叠设置在底电极表面的电子注入层。
本公开的实施方式提供一种如图1所述正式结构的量子点发光二极管的制备方法的实施例,具体的包括以下步骤:
提供一衬底,在所述衬底上形成阳极;
在所述阳极上制备空穴传输层;
在所述空穴传输层上制备量子点发光层;
在量子点发光层上制备电子阻挡材料层,在所述电子阻挡材料层上制备电子传输层,在所述电子传输层上继续制备有一电子阻挡材料层,重复上述步骤至按预定层数在倒数第一层电子阻挡材料层上制备最后第n层电子传输层,制得所述功能层;
在所述发光层上制备阴极,得到所述量子点发光二极管;
其中,所述n为大于等于2的整数,且所述功能层中,相邻的两层电子阻挡材料层之间,靠近阴极的电子阻挡材料层材料的LUMO能级大于靠近量子点发光层的电子阻挡材料层材料的LUMO能级。
本公开中,各层制备方法可以是化学法或物理法,其中化学法包括但不限于化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法、共沉淀法中的一种或多种;物理法包括但不限于溶液法(如旋涂法、印刷法、刮涂法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法或条状涂布法等)、蒸镀法(如热蒸镀法、电子束蒸镀法、磁控溅射法或多弧离子镀膜法等)、沉积法(如物理气相沉积法、原子层沉积法、脉冲激光沉积法等)中的一种或多种。
下面通过实施例对本公开进行详细说明。
实施例1
一种量子点发光二极管,从下至上依次包括层叠设置的衬底、阳极、空穴注入层、空穴传输层、量子点发光层、功能层和阴极,所述功能层包括交替层叠设 置的5层电子阻挡材料层和5层电子传输层,所述功能层的最底层为电子阻挡材料层且靠近量子点发光层设置,所述功能层的最顶层为电子传输层且靠近阴极设置;沿阳极至阴极的方向,所述每层电子阻挡材料层的材料依次为PVK、掺杂有1.5wt.%Li-TFSI的PVK、掺杂有3wt.%Li-TFSI的PVK、4.5wt.%Li-TFSI的PVK以及6wt.%Li-TFSI的PVK;所述阳极为ITO,厚度为100nm;所述空穴注入层材料为PEDOT:PSS,厚度为40nm;所述空穴传输层材料为TFB,厚度为80nm;所述量子点发光层的材料为InP/ZnS,厚度为100nm;所述每层电子阻挡材料层的厚度为4nm;所述每层电子传输层的材料均为ZnO,所述每层电子传输层的厚度为20nm;所述阴极为Al,厚度为50nm。
实施例2
一种量子点发光二极管,从下至上依次包括层叠设置的衬底、阳极、空穴注入层、空穴传输层、量子点发光层、功能层和阴极,所述功能层包括交替层叠设置的5层电子阻挡材料层和5层电子传输层,所述功能层的最底层为电子阻挡材料层且靠近量子点发光层设置,所述功能层的最顶层为电子传输层且靠近阴极设置;沿阳极至阴极的方向,所述每层电子阻挡材料层的材料依次为TFB、掺杂有1.5wt.%Li-TFSI的TFB、掺杂有3wt.%Li-TFSI的TFB、4.5wt.%Li-TFSI的TFB以及6wt.%Li-TFSI的TFB;所述阳极为ITO,厚度为100nm;所述空穴注入层材料为PEDOT:PSS,厚度为40nm;所述空穴传输层材料为TFB,厚度为80nm;所述量子点发光层的材料为InP/ZnS,厚度为40nm;所述每层电子阻挡材料层的厚度为4nm;所述每层电子传输层材料为SnO,所述每层电子传输层的厚度为10nm;所述阴极为Al,厚度为50nm。
实施例3
一种量子点发光二极管,从下至上依次包括层叠设置的衬底、阳极、空穴注入层、空穴传输层、量子点发光层、功能层和阴极,所述功能层包括交替层叠设置的5层电子阻挡材料层和5层电子传输层,所述功能层的最底层为电子阻挡材料层且靠近量子点发光层设置,所述功能层的最顶层为电子传输层且靠近阴极设置;沿阳极至阴极的方向,所述每层电子阻挡材料层的材料依次为TCTA、掺杂有1.5wt.%MoO
3的TCTA、掺杂有3wt.%MoO
3的TCTA、4.5wt.%MoO
3的TCTA以及6wt.%MoO
3的TCTA;所述阳极为ITO,厚度为100nm;所述空穴注入层 材料为PEDOT:PSS,厚度为40nm;所述空穴传输层材料为TFB,厚度为80nm;所述量子点发光层的材料为InP/ZnS,厚度为80nm;所述每层电子阻挡材料层的厚度为4nm;所述每层电子传输层材料均为TiO,所述每层电子阻挡材料层的厚度为15nm;所述阴极为Al,厚度为50nm。
实施例4
一种量子点发光二极管,从下至上依次包括层叠设置的衬底、阳极、空穴注入层、空穴传输层、量子点发光层、功能层和阴极,所述功能层包括交替层叠设置的5层电子阻挡材料层和5层电子传输层,所述功能层的最底层为电子阻挡材料层且靠近量子点发光层设置,所述功能层的最顶层为电子传输层且靠近阴极设置;沿阳极至阴极的方向,所述每层电子阻挡材料层的材料依次为PVK、掺杂有1.5wt.%Li-TFSI的PVK、掺杂有3wt.%Li-TFSI的PVK、4.5wt.%Li-TFSI的PVK以及6wt.%Li-TFSI的PVK;所述阳极为ITO,厚度为100nm;所述空穴注入层材料为PEDOT:PSS,厚度为40nm;所述空穴传输层材料为TFB,厚度为80nm;所述量子点发光层的材料为CdZnS/CdZnSe/ZnS,厚度为120nm;所述每层电子阻挡材料层的厚度为4nm;所述电子传输层材料为AlZnO,所述每层电子传输层的厚度为8nm;所述阴极为Al,厚度为50nm。
实施例5
一种量子点发光二极管,从下至上依次包括层叠设置的衬底、阳极、空穴注入层、空穴传输层、量子点发光层、功能层和阴极,所述功能层包括交替层叠设置的5层电子阻挡材料层和5层电子传输层,所述功能层的最底层为电子阻挡材料层且靠近量子点发光层设置,所述功能层的最顶层为电子传输层且靠近阴极设置;沿阳极至阴极的方向,所述每层电子阻挡材料层的材料依次为TFB、掺杂有1.5wt.%Li-TFSI的TFB、掺杂有3wt.%Li-TFSI的TFB、4.5wt.%Li-TFSI的TFB以及6wt.%Li-TFSI的TFB;所述阳极为ITO,厚度为100nm;所述空穴注入层材料为PEDOT:PSS,厚度为40nm;所述空穴传输层材料为TFB,厚度为80nm;所述量子点发光层的材料为CdZnS/CdZnSe/ZnS,厚度为30nm;所述每层电子阻挡材料层的厚度为4nm;所述每层电子传输层的材料均为TPBI,所述每层电子传输层的厚度为12nm;所述阴极为Al,厚度为50nm。
实施例6
一种量子点发光二极管,从下至上依次包括层叠设置的衬底、阳极、空穴注入层、空穴传输层、量子点发光层、功能层和阴极,所述功能层包括交替层叠设置的5层电子阻挡材料层和5层电子传输层,所述功能层的最底层为电子阻挡材料层且靠近量子点发光层设置,所述功能层的最顶层为电子传输层且靠近阴极设置;沿阳极至阴极的方向,所述每层电子阻挡材料层的材料依次为TCTA、掺杂有1.5wt.%MoO
3的TCTA、掺杂有3wt.%MoO
3的TCTA、4.5wt.%MoO
3的TCTA以及6wt.%MoO
3的TCTA;所述阳极为ITO,厚度为100nm;所述空穴注入层材料为PEDOT:PSS,厚度为40nm;所述空穴传输层材料为TFB,厚度为80nm;所述量子点发光层的材料为CdZnS/CdZnSe/ZnS,且厚度为110nm;所述每层电子阻挡材料层的厚度为4nm;所述每层电子传输层的材料均为ZnO,所述每层电子传输层的厚度为8nm;所述阴极为Al,厚度为50nm。
综上所述,本公开提供的量子点发光二极管包括设置在阴极和量子点发光层之间的功能层,所述功能层包括n层层叠设置的功能结构单元,所述功能结构单元由层叠设置的电子阻挡材料层和电子传输层组成,所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置,所述功能结构单元中的电子传输层靠近阴极设置,所述n为大于等于1的整数。本公开量子点发光二极管通过所述功能层的设置能够降低电子传输至量子点发光层的传输速率,从而平衡电子和空穴的注入速率,以提高载流子在量子点层中的复合效率,进而提高量子点发光二极管的发光效率、稳定性和使用寿命;进一步地,所述功能层中的电子阻挡材料层还可阻止电子传输层中的正交溶剂对量子点发光层的光学性能产生不利影响。
应当理解的是,本公开的应用不限于上述的举例,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,所有这些改进和变换都应属于本公开所附权利要求的保护范围。
Claims (15)
- 一种量子点发光二极管,包括阴极、阳极以及设置在阴极和阳极之间的量子点发光层,其特征在于,所述阴极和量子点发光层之间设置有功能层,所述功能层包括n层层叠设置的功能结构单元,所述功能结构单元由层叠设置的电子阻挡材料层和电子传输层组成,所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置,所述功能结构单元中的电子传输层靠近阴极设置,所述n为大于等于1的整数。
- 根据权利要求1所述的量子点发光二级管,其特征在于,所述电子阻挡材料层的材料选自PVK、Poly-TPD、NPB、TCTA、TAPC、CBP、TFB和DNA中的一种或多种。
- 根据权利要求1所述的量子点发光二级管,其特征在于,所述电子阻挡材料层的材料选自化合物掺杂的PVK、Poly-TPD、NPB、TCTA、TAPC、CBP、TFB和DNA中的一种或多种,所述化合物选自Li-TFSI、NiO、CuSCN、MoO 3、CuO、V 2O 5或CuS中的一种。
- 根据权利要求1所述的量子点发光二级管,其特征在于,所述电子阻挡材料层的LUMO能级为-2.0~-5.0eV。
- 根据权利要求1所述的量子点发光二极管,其特征在于,所述n为大于等于2的整数,且所述n层功能结构单元中的相邻两层功能结构单元中,靠近阴极的电子阻挡材料层材料的LUMO能级大于靠近量子点发光层的电子阻挡材料层材料的LUMO能级。
- 根据权利要求5所述的量子点发光二极管,其特征在于,2≤n≤10。
- 根据权利要求5所述的量子点发光二极管,其特征在于,2≤n≤5。
- 根据权利要求5所述的量子点发光二极管,其特征在于,相邻电子阻挡材料层的LUMO能级差为-0.1~-0.5eV。
- 根据权利要求5所述的量子点发光二极管,其特征在于,所述每层电子阻挡材料层的厚度为2-5nm。
- 根据权利要求5所述的量子点发光二极管,其特征在于,所述每层电子传输层的厚度为10-120nm。
- 根据权利要求5所述的量子点发光二极管,其特征在于,所述电子传输层材料选自ZnO、TiO 2、Alq 3、SnO、ZrO、AlZnO、InZnO、GaZnO、MgZnO、 ZnSnO、BCP、TAZ、PBD、TPBI、Bphen和CsCO 3中的一种或多种。
- 根据权利要求1所述的量子点发光二极管,其特征在于,所述量子点层材料选自II-VI族化合物、III-V族化合物和I-III-VI族化合物中的一种或多种。
- 根据权利要求1所述的量子点发光二极管,其特征在于,所述阳极和量子点发光层之间还设置有空穴传输层,所述空穴传输层材料选自TFB、PVK、Poly-TBP、Poly-TPD、NPB、TCTA、TAPC、CBP、PEODT:PSS、MoO 3、WoO 3、NiO、CuO、V 2O 5和CuS中的一种或多种。
- 根据权利要求13所述的量子点发光二极管,其特征在于,所述空穴传输层的厚度为30-100nm。
- 一种子点发光二极管的制备方法,其特征在于,包括如下步骤:提供基板;在所述基板上形成功能层,所述功能层包括n层层叠设置的功能结构单元,所述功能结构单元由层叠设置的电子阻挡材料层和电子传输层组成,所述功能结构单元中的电子阻挡材料层靠近量子点发光层设置,所述功能结构单元中的电子传输层靠近阴极设置,所述n为大于等于2的整数。
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