WO2022134810A1 - 光电器件 - Google Patents

光电器件 Download PDF

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WO2022134810A1
WO2022134810A1 PCT/CN2021/125535 CN2021125535W WO2022134810A1 WO 2022134810 A1 WO2022134810 A1 WO 2022134810A1 CN 2021125535 W CN2021125535 W CN 2021125535W WO 2022134810 A1 WO2022134810 A1 WO 2022134810A1
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optoelectronic device
layer
electrode layer
indium
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PCT/CN2021/125535
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English (en)
French (fr)
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张振琦
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京东方科技集团股份有限公司
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Priority to US17/800,655 priority Critical patent/US20230102357A1/en
Publication of WO2022134810A1 publication Critical patent/WO2022134810A1/zh

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • 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
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations
    • 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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • 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]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present disclosure relates to the field of display technology, and in particular, to an optoelectronic device.
  • PEDOT polyethylenedioxythiophene
  • EDOT 3,4-ethylenedioxythiophene
  • PSS water-soluble polymer electrolyte polystyrene sulfonic acid
  • PEDOT:PSS materials are very efficient hole injection materials. However, due to the acidity of PEDOT:PSS itself, it will corrode the ITO in the optoelectronic device, and the indium ions released after the decomposition of ITO enter the device, which will cause the degradation of the device performance and life.
  • Embodiments of the present disclosure provide an optoelectronic device, including:
  • a first electrode layer located on one side of the base substrate, and the material of the first electrode layer includes an oxide containing indium;
  • a modification layer located on the surface of the first electrode layer away from the base substrate, the modification layer includes: an indium ion capture group, a siloxane group, and a group connected to the indium ion capture group and A connecting group between the siloxane groups, and the siloxane groups are fixed on the surface of the first electrode layer.
  • the indium ion capturing group includes three pyridine groups.
  • the siloxane group is formed by the silane group connected to the connecting group and the surface of the indium-containing oxide.
  • the hydroxyl group reacts to generate the silane group, and the molecular formula of the silane group is Si-R2R3R4, wherein the R2 group, the R3 group and the R4 group include one of methoxy, ethoxy, tert-butyl, and chloride ion.
  • the R2 group, the R3 group, and the R4 group are the same group.
  • the R2 group, the R3 group and the R4 group are all methoxy groups.
  • the linking group includes one of an alkyl group and an aromatic group.
  • the aromatic group includes at least one of a phenyl group, a naphthyl group, and a thienyl group.
  • the number of C atoms contained in the carbon chain of the linking group is 6-10.
  • the thickness of the modification layer is 1 nm-2 nm.
  • the material of the first electrode layer includes one of ITO and IZO.
  • the above-mentioned optoelectronic device provided by the embodiment of the present disclosure further includes: a hole injection layer, located on the side of the first electrode layer away from the base substrate, the hole injection layer The material of the injection layer is acidic.
  • the material of the hole injection layer includes PEDOT:PSS.
  • the optoelectronic device is a light-emitting device, and the optoelectronic device further comprises a hole injection layer on the side away from the modification layer. light-emitting layer.
  • the material of the light-emitting layer is quantum dots or organic substances.
  • the optoelectronic device is a photovoltaic device, and the optoelectronic device further comprises a hole injection layer on the side away from the modification layer. active layer.
  • FIG. 1 is a schematic structural diagram of an optoelectronic device provided by an embodiment of the present disclosure
  • FIG. 2 is another schematic structural diagram of the optoelectronic device provided by the embodiment of the present disclosure.
  • FIG. 3 is the general structural formula of the modification material in the optoelectronic device provided by the embodiment of the present disclosure
  • FIG. 4 is a schematic diagram of the principle of capturing indium ions by indium ion capturing groups of the modified material in the optoelectronic device provided by the embodiment of the present disclosure
  • FIG. 5 is a specific molecular structure of the modification material in the optoelectronic device provided by the embodiment of the present disclosure
  • FIG. 6 is a schematic diagram of the functional principle of the modification layer and the first electrode layer in the optoelectronic device provided by the embodiment of the present disclosure
  • FIG. 7 is a chemical reaction formula produced by a modification material in an optoelectronic device provided by an embodiment of the present disclosure
  • FIG. 8 is a schematic flowchart of a method for fabricating an optoelectronic device according to an embodiment of the present disclosure.
  • the most classic structure is: ITO/PEDOT:PSS/TFB/QD/ZnO/Al, and the EQE of the device can reach more than 20%.
  • PEDOT:PSS itself is acidic, it will corrode ITO in the device, and the indium ions released after the decomposition of ITO enter the light-emitting layer, which will cause the degradation of device performance and life.
  • oxides as the hole injection layer, such as NiO, WOx, VOx, MoOx, etc.
  • the energy level and mobility of the oxide are different from those of the PEDOT:PSS/TFB system, and the oxide may also quench the QDs, the final EQE of the devices currently using this scheme is not high, and the current highest EQE is 8.1%, and the device structure is ITO/NiO/Al2O3/QD/ZnO/Al.
  • the optoelectronic device provided by the embodiment of the present disclosure proposes a new idea.
  • a modification layer is inserted between PEDOT:PSS and ITO to slow down the corrosion of PEDOT:PSS to ITO. And trap indium ions to improve device lifetime.
  • the modification layer can form a monomolecular layer during fabrication, its thickness is extremely thin and will not affect the carrier transport properties of the device itself, and therefore, will not affect the device efficiency.
  • an optoelectronic device provided by an embodiment of the present disclosure, as shown in FIG. 1 and FIG. 2 , includes:
  • the first electrode layer 2 is located on one side of the base substrate 1, and the material of the first electrode layer 2 includes an oxide containing indium; the modification layer 21 is located on the surface of the first electrode layer 2 on the side away from the base substrate 1, and is modified
  • the layer 21 includes: an indium ion capture group X, a siloxane group, and a connecting group R1 connected between the indium ion capture group X and the siloxane group, and the siloxane group is fixed to the first electrode surface of layer 2.
  • a modification layer 21 is added to the surface of the first electrode layer 2 on the side away from the base substrate 1 .
  • the existence of the modification layer 21 can prevent the first electrode layer 2 and other
  • the direct contact between the film layers can slow down the corrosion of the indium-containing oxide constituting the first electrode layer 2 .
  • the indium ion trapping group X contained in the modification layer 21 can fix the indium ions released after the indium-containing oxide is corroded on the surface of the first electrode layer 2 to prevent the indium ions from moving to the interior of the optoelectronic device, thereby increasing the lifetime of optoelectronic devices.
  • the material of the first electrode layer 2 may include one of ITO and IZO.
  • the optoelectronic device may further include: a hole injection layer 3 located on the side of the first electrode layer 2 away from the base substrate 1 , The material of the hole injection layer 3 is acidic.
  • the material of the hole injection layer 3 may include PEDOT:PSS.
  • PEDOT:PSS is a mixture of two materials, PEDOT is a polymer of EDOT (3,4-ethylenedioxythiophene monomer), PSS is a polystyrene sulfonate, and PSS has a certain acidity.
  • the acidic hole injection layer 3 in the device will corrode the first electrode layer 2, and the indium ions released after the decomposition of the first electrode layer 2 enter the light-emitting layer, which will cause the degradation of device performance and life. Therefore, a modification layer 21 is inserted between the hole injection layer 3 and the first electrode layer 2. The existence of the modification layer 21 can prevent the direct contact between the first electrode layer 2 and the hole injection layer 3, and can slow down the formation of the first electrode layer 2. There is a problem that the indium-containing oxide of the electrode layer 2 is corroded.
  • the optoelectronic device may be a light-emitting device, and as shown in FIG. Layer 4.
  • the optoelectronic device may further include a second electrode layer 5 , and an electron transport layer 6 located between the second electrode layer 5 and the light-emitting layer 4 , and between the light-emitting layer 4 and the hole injection layer 3 the hole transport layer 7.
  • the material of the light-emitting layer 4 may be quantum dot QD or organic EL.
  • the material of the electron transport layer 6 can be ZnO
  • the material of the hole transport layer 7 can be TFB.
  • the second electrode layer 5 is generally a cathode layer, and its material can be Al.
  • the optoelectronic device when the optoelectronic device is a light-emitting device, the light-emitting device can be applied to a display device, and the display device can be any product with a display function, such as a mobile phone, a tablet computer, a television, a monitor, a notebook computer, a digital photo frame, a navigator, etc. or parts.
  • a display device can be any product with a display function, such as a mobile phone, a tablet computer, a television, a monitor, a notebook computer, a digital photo frame, a navigator, etc. or parts.
  • the optoelectronic device may also be a photovoltaic device.
  • the material of active layer 8 can be PBDT-DTNT: PC71BM.
  • the optoelectronic device may further include a second electrode layer 5 on the side of the active layer 8 away from the hole injection layer 3 , and the material of the second electrode layer 5 may be Al.
  • the optoelectronic device is a photovoltaic device
  • the photovoltaic device can be applied to a solar cell.
  • the optoelectronic devices provided by the embodiments of the present disclosure may also be other devices including the direct contact structure of ITO and PEDOT:PSS, and the device life can be increased by adding a modification layer between ITO and PEDOT:PSS.
  • the modification layer 21 is formed by the reaction between the modification material and the hydroxyl group on the surface of the first electrode layer 2 .
  • the siloxane group in the modification layer 21 is generated by the reaction of the silane group Si-R2R3R4 connected with the connecting group R1 and the hydroxyl group existing on the surface of the indium-containing oxide.
  • the modified material specifically includes an indium ion capture group X, a silane group Si-R2R3R4, and a connecting group R1 connected between the indium ion capture group X and the silane group Si-R2R3R4.
  • the general formula is X-R1-Si-R2R3R4, wherein X is an indium ion capturing group, R1 is a linking group, and Si-R2R3R4 is a silane group.
  • the indium ion capturing group X may include three pyridine groups, as shown in FIG. 3 , the N atoms on the three pyridine rings may be combined with indium ions, As shown in FIG. 4 , the diffused indium ions are fixed on the surface of the first electrode layer 2 to prevent the indium ions from entering the device and affecting the device efficiency and life.
  • the molecular formula of the silane group is SiR2R3R4, wherein the R2 group, the R3 group and the R4 group include methoxy, ethoxy, tert-butyl, one of the chloride ions.
  • the function of the silane group Si-R2R3R4 is to react with the hydroxyl groups on the surface of the first electrode layer 2 after hydrolysis, so as to fix the modification layer 21 on the surface of the first electrode layer 2 .
  • the R2 group, the R3 group and the R4 group in the silane group may be the same group or different groups, if they are different groups When different groups are formed, the hydrolysis rate and solubility of different groups will be different to some extent.
  • the arrangement of the R2 group, the R3 group and the R4 group in the silane group is not required.
  • the R2 group, the R3 group and the R4 group may all be methoxy groups (OMe, Me is methyl), and the specific molecular structure is shown in FIG. 5 . Show.
  • the hydrolysis mechanism of the modified material is to hydrolyze to silanol after heating, that is, X-R1-Si(OMe)3 ⁇ X-R1-Si(OH)3, silanol Si(OH) 3 can react with hydroxyl groups on the surface of the first electrode layer 2 to become siloxane, so as to be closely connected with the first electrode layer 2 , as shown in FIG. 6 .
  • the linking group R1 may be an alkyl group, an aromatic group, or the like.
  • the linking group R1 is an alkyl group as an example for illustration.
  • the alkyl group may include groups such as methyl, ethyl, or propyl
  • the aromatic group is a group containing a conjugated unit, which may include phenyl, naphthyl, thienyl, and the like.
  • the linking group R1 has two functions, one is to play a connecting role, connecting the indium ion capture group X and the silane group Si-R2R3R4 together; the other is to play a separation role, increasing the first electrode
  • the distance between layer 2 and hole injection layer 3 slows down the corrosive effect of PEDOT:PSS on ITO.
  • the number of C atoms contained in the carbon chain of the linking group R1 is preferably 6-10.
  • the quantum dot ligands mainly used in QLED devices are mainly octanethiol and dodecanethiol.
  • the overall thickness of the modification layer 21 is about 1 nm, and the hole is minimized. While the injection layer corrodes the first electrode layer, the carrier transport will not be affected.
  • the modification layer 21 is formed on the surface of the first electrode layer 2 in a manner of reacting with the hydroxyl group on the surface of the first electrode layer 2 after the modification material is hydrolyzed, the modification layer is ensured.
  • 21 consists of a monolayer of molecules.
  • the thickness of the modification layer 21 is the molecular length of a modification material, and the film thickness of the modification layer 21 varies according to different molecular lengths.
  • the thickness of the modification layer 21 is generally 1 nm-2 nm.
  • the specific reaction formula is shown in Figure 7.
  • an embodiment of the present disclosure also provides a method for fabricating the above-mentioned optoelectronic device. Since the principle of solving the problem of the fabrication method is similar to that of the aforementioned optoelectronic device, the implementation of the fabrication method can refer to the implementation of the optoelectronic device. The repetition will not be repeated.
  • a method for fabricating an optoelectronic device includes:
  • modification material includes an indium ion capture group, a silane group, and a connecting group connected between the indium ion capture group and the silane group;
  • the ITO substrate was placed on a hot stage and heated at 80° C. for 10 min to make the silane groups of the modified material react with the hydroxyl groups on the ITO surface.
  • the ITO substrate is placed on a hot stage, heated at 80° C. for 10 minutes, and the solvent in the solution of the modification material is removed to form a modification layer.
  • a modification layer is added to the surface of the first electrode layer away from the base substrate of the optoelectronic device.
  • the existence of the modification layer can prevent the direct contact between the first electrode layer and other film layers, and can play a The problem of corrosion of the indium-containing oxide constituting the first electrode layer is alleviated.
  • the indium ion trapping group contained in the modified layer can fix the indium ions released after the indium-containing oxide is corroded on the surface of the first electrode layer, preventing the indium ions from moving into the optoelectronic device, thereby increasing the efficiency of the optoelectronic device. life.

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Abstract

本公开提供了一种光电器件，光电器件在第一电极层远离衬底基板一侧的表面增加一个修饰层，修饰层的存在可以防止第一电极层和其他膜层直接接触，可以起到减缓构成第一电极层的含铟的氧化物被腐蚀的问题。并且，修饰层内含有的铟离子捕获基团可以将含铟的氧化物被腐蚀后释放出来的铟离子固定在第一电极层表面，防止铟离子向光电器件内部移动，从而可以增加光电器件的寿命。

Description

光电器件
相关申请的交叉引用
本申请要求在2020年12月24日提交中国专利局、申请号为202011547998.9、申请名称为“光电器件”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。
技术领域
本公开涉及显示技术领域，尤指一种光电器件。
背景技术
德国拜耳公司在1988年首先合成出了聚噻吩的衍生物聚乙烯二氧噻吩即PEDOT，它以3,4-乙烯二氧噻吩(EDOT)为单体，具有导电率高、环境稳定性好等特点，引起了科学家们的广泛兴趣。PEDOT本身为不溶性聚合物限制了其应用。随后，采用一种水溶性的高分子电解质聚苯乙烯磺酸(PSS)掺杂解决了PEDOT的加工问题，获得的PEDOT：PSS膜具有高电导率、高机械强度、高可见光透射率和优越的稳定性等。此后，PEDOT应用领域得到了快速发展，尤其是以PEDOT为基材而开发出来的新材料、新工艺、新元件等得到了充分发展。
在光电器件中，PEDOT：PSS材料属于非常高效的空穴注入材料。但由于PEDOT：PSS本身呈酸性，会腐蚀光电器件中的ITO，ITO分解后释放出的铟离子进入器件内，会造成器件性能及寿命的衰减。
发明内容
本公开实施例提供了一种光电器件，包括：
衬底基板；
第一电极层，位于所述衬底基板的一侧，所述第一电极层的材料包括含 铟的氧化物；
修饰层，位于所述第一电极层远离所述衬底基板一侧的表面，所述修饰层包括：铟离子捕获基团、硅氧烷基团、以及连接于所述铟离子捕获基团与所述硅氧烷基团之间的连接基团，所述硅氧烷基团固定于所述第一电极层的表面。
在一种可能的实现方式中，在本公开实施例提供的上述光电器件中，所述铟离子捕获基团包括三个吡啶基团。
在一种可能的实现方式中，在本公开实施例提供的上述光电器件中，所述硅氧烷基团由与所述连接基团连接的硅烷基团和所述含铟的氧化物表面存在的羟基反应生成，所述硅烷基团的分子式为Si-R2R3R4，其中，R2基团、R3基团和R4基团包括甲氧基、乙氧基、叔丁基、氯离子中的一个。
在一种可能的实现方式中，在本公开实施例提供的上述光电器件中，所述R2基团、所述R3基团和所述R4基团为相同的基团。
在一种可能的实现方式中，在本公开实施例提供的上述光电器件中，所述R2基团、所述R3基团和所述R4基团均为甲氧基。
在一种可能的实现方式中，在本公开实施例提供的上述光电器件中，所述连接基团包括烷基、芳香基团中的一个。
在一种可能的实现方式中，在本公开实施例提供的上述光电器件中，所述芳香基团至少包括苯基、萘基和噻吩基中的一个。
在一种可能的实现方式中，在本公开实施例提供的上述光电器件中，所述连接基团的碳链中包含的C原子个数为6个-10个。
在一种可能的实现方式中，在本公开实施例提供的上述光电器件中，所述修饰层的厚度为1nm-2nm。
在一种可能的实现方式中，在本公开实施例提供的上述光电器件中，所述第一电极层的材料包括ITO、IZO中的一个。
在一种可能的实现方式中，在本公开实施例提供的上述光电器件中，还包括：空穴注入层，位于所述第一电极层背离所述衬底基板的一侧，所述空 穴注入层的材料呈酸性。
在一种可能的实现方式中，在本公开实施例提供的上述光电器件中，所述空穴注入层的材料包括PEDOT：PSS。
在一种可能的实现方式中，在本公开实施例提供的上述光电器件中，所述光电器件为发光器件，所述光电器件还包括位于所述空穴注入层背离所述修饰层一侧的发光层。
在一种可能的实现方式中，在本公开实施例提供的上述光电器件中，所述发光层的材料为量子点或有机物。
在一种可能的实现方式中，在本公开实施例提供的上述光电器件中，所述光电器件为光伏器件，所述光电器件还包括位于所述空穴注入层背离所述修饰层一侧的活性层。
附图说明
图1为本公开实施例提供的光电器件的一种结构示意图；
图2为本公开实施例提供的光电器件的另一种结构示意图；
图3为本公开实施例提供的光电器件中修饰材料的结构通式；
图4为本公开实施例提供的光电器件中修饰材料的铟离子捕获基团捕获铟离子的原理示意图；
图5为本公开实施例提供的光电器件中修饰材料的一种具体分子结构；
图6为本公开实施例提供的光电器件中修饰层与第一电极层的作用原理示意图；
图7为本公开实施例提供的光电器件中修饰材料制作的化学反应式；
图8为本公开实施例提供的光电器件的制作方法的流程示意图。
具体实施方式
目前，在QD器件中，最经典的结构为：ITO/PEDOT:PSS/TFB/QD/ZnO/Al，器件的EQE可以达到20％以上。但是，由于PEDOT：PSS本身呈酸性，因 此在器件中会腐蚀ITO，ITO分解后释放出的铟离子进入发光层，会造成器件性能及寿命的衰减。
为了代替PEDOT:PSS/TFB的搭配，有人提出采用氧化物作为空穴注入层，例如NiO、WOx、VOx、MoOx等。但是由于氧化物的能级、迁移率都和PEDOT:PSS/TFB体系不同，同时氧化物还可能对QD产生淬灭，因此目前采用这种方案的器件最终EQE都不高，目前最高的EQE为8.1％，器件结构为ITO/NiO/Al2O3/QD/ZnO/Al。另一方面，如果不能彻底取消PEDOT:PSS，另一种思路为将氧化物和PEDOT:PSS组合一起使用，希望通过氧化物隔开PEDOT和ITO以获得较好的寿命，但是由于无机氧化物的能级和迁移率的匹配问题，目前采用这种方案的EQE也不理想，目前最高的器件采用的是ITO/WO3NPs/PEDOT:PSS/TFB/QD/ZnO/Al，EQE是12.47％，仍然和采用PEDOT:PSS的EQE差了约一倍。
本公开实施例提供的光电器件提出一种新的思路，在不改变原有器件结构的前提下，在PEDOT:PSS和ITO之间插入一个修饰层，用于减缓PEDOT:PSS对ITO的腐蚀，并且捕获铟离子，以提高器件寿命。并且，由于修饰层在制作时可以形成单分子层，其厚度极薄，不会影响器件本身的载流子传输性质，因此，不会影响器件效率。
为了使本公开的目的、技术方案和优点更加清楚，下面将结合附图对本公开作进一步地详细描述，显然，所描述的实施例仅是本公开一部分实施例，而不是全部的实施例。基于本公开中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本公开保护的范围。
附图中各部件的形状和大小不反映真实比例，目的只是示意说明本公开内容。
具体地，本公开实施例提供的一种光电器件，如图1和图2所示，包括：
衬底基板1；
第一电极层2，位于衬底基板1的一侧，第一电极层2的材料包括含铟的氧化物；修饰层21，位于第一电极层2背离衬底基板1一侧的表面，修饰层 21包括：铟离子捕获基团X、硅氧烷基团、以及连接于铟离子捕获基团X与硅氧烷基团之间的连接基团R1，硅氧烷基团固定于第一电极层2的表面。
具体地，在本公开实施例提供的上述光电器件中在第一电极层2远离衬底基板1一侧的表面增加了一个修饰层21，修饰层21的存在可以防止第一电极层2和其他膜层直接接触，可以起到减缓构成第一电极层2的含铟的氧化物被腐蚀的问题。并且，修饰层21内含有的铟离子捕获基团X可以将含铟的氧化物被腐蚀后释放出来的铟离子固定在第一电极层2表面，防止铟离子向光电器件内部移动，从而可以增加光电器件的寿命。
可选地，在本公开实施例提供的上述光电器件中，第一电极层2的材料可以包括ITO、IZO中的一个。
可选地，在本公开实施例提供的上述光电器件中，如图1和图2所示，还可以包括：空穴注入层3，位于第一电极层2背离衬底基板1的一侧，空穴注入层3的材料呈酸性。
具体地，空穴注入层3的材料可以包括PEDOT：PSS。PEDOT:PSS是两种材料混合在一起，PEDOT是EDOT(3，4-乙烯二氧噻吩单体)的聚合物，PSS是聚苯乙烯磺酸盐，其中PSS具有一定的酸性。
具体地，在器件中呈酸性的空穴注入层3会腐蚀第一电极层2，第一电极层2分解后释放出的铟离子进入发光层，会造成器件性能及寿命的衰减。因此，在空穴注入层3和第一电极层2之间插入一个修饰层21，修饰层21的存在可以防止第一电极层2和空穴注入层3直接接触，可以起到减缓构成第一电极层2的含铟的氧化物被腐蚀的问题。
可选地，在本公开实施例提供的上述光电器件中，光电器件可以为发光器件，此时如图1所示，光电器件还可以包括位于空穴注入层3背离修饰层21一侧的发光层4。此外，如图1所示，光电器件还可以包括第二电极层5，以及位于第二电极层5与发光层4之间的电子传输层6，位于发光层4与空穴注入层3之间的空穴传输层7。
可选地，在本公开实施例提供的上述光电器件中，发光层4的材料可以 为量子点QD或有机物EL。当发光层4采用量子点材料制作时，电子传输层6的材料可以为ZnO，空穴传输层7的材料可以为TFB。第二电极层5一般为阴极层，其材料可以是Al。
具体地，当光电器件为发光器件时，该发光器件可以应用于显示装置，显示装置可以为：手机、平板电脑、电视机、显示器、笔记本电脑、数码相框、导航仪等任何具有显示功能的产品或部件。
可选地，在本公开实施例提供的上述光电器件中，光电器件也可以为光伏器件，此时如图2所示，光电器件还可以包括位于空穴注入层3背离修饰层21一侧的活性层8，活性层8的材料可以是PBDT-DTNT：PC71BM。此外，如图2所示，光电器件还可以包括在活性层8背离空穴注入层3一侧的第二电极层5，第二电极层5的材料可以是Al。
具体地，当光电器件为光伏器件时，该光伏器件可以应用于太阳能电池。
此外，本公开实施例提供的光电器件还可以是包含ITO和PEDOT:PSS直接接触结构的其他器件，均可以通过在ITO和PEDOT:PSS之间增加修饰层的方式来增加器件寿命。
具体地，在本公开实施例提供的上述光电器件中修饰层21由修饰材料和第一电极层2表面的羟基反应后生成。具体地，修饰层21中的硅氧烷基团由与连接基团R1连接的硅烷基团Si-R2R3R4和含铟的氧化物表面存在的羟基反应生成。如图3所示，修饰材料具体包括铟离子捕获基团X、硅烷基团Si-R2R3R4、以及连接于铟离子捕获基团X与硅烷基团Si-R2R3R4之间的连接基团R1，其材料通式为X-R1-Si-R2R3R4，其中X是铟离子捕获基团，R1是连接基团，Si-R2R3R4是硅烷基团。
可选地，在本公开实施例提供的上述光电器件中，铟离子捕获基团X可以包括三个吡啶基团，如图3所示，三个吡啶环上的N原子可以和铟离子结合，如图4所示，将扩散出来的铟离子固定在第一电极层2表面，防止铟离子进入器件内部影响器件效率及寿命。
可选地，在本公开实施例提供的上述光电器件中，硅烷基团的分子式为 SiR2R3R4，其中，R2基团、R3基团和R4基团包括甲氧基、乙氧基、叔丁基、氯离子中的一个。
具体地，硅烷基团Si-R2R3R4的作用是水解后与第一电极层2表面的羟基反应，将修饰层21固定在第一电极层2的表面。
可选地，在本公开实施例提供的上述光电器件中，硅烷基团中R2基团、R3基团和R4基团可以为相同的基团，也可以为不同的基团，若为不同基团时，不同基团的水解速度和溶解度都会存在一定的区别。R2基团、R3基团和R4基团在硅烷基团中的排布没有要求。
可选地，在本公开实施例提供的上述光电器件中，R2基团、R3基团和R4基团可以均为甲氧基(OMe，Me为甲基)，其具体分子结构式如图5所示。
具体地，以R2＝R3＝R4＝OMe为例，修饰材料的水解机理为加热后水解为硅醇，即X-R1-Si(OMe)3→X-R1-Si(OH)3，硅醇Si(OH)3可以和第一电极层2表面的羟基反应，变成硅氧烷，从而和第一电极层2紧密连接在一起，如图6所示。
可选地，在本公开实施例提供的上述光电器件中，连接基团R1可以是烷基、芳香基团等，图5中是以连接基团R1为烷基为例进行说明。
具体地，烷基可以包括甲基、乙基或丙基等基团，芳香基团为含有共轭单元的基团，可以包括苯基，萘基，噻吩基，等等。
具体地，连接基团R1有两个作用，一个是起到连接作用，把铟离子捕获基团X与硅烷基团Si-R2R3R4连接在一起；二个是起到分隔作用，增大第一电极层2和空穴注入层3之间的距离，减缓PEDOT：PSS对ITO的腐蚀作用。
具体地，连接基团R1的长度越长，那么修饰材料构成的修饰层21的厚度越厚，空穴注入层3就离第一电极层2越远，腐蚀作用也会越弱，但修饰层21厚度过厚会影响载流子传输。
优选地，在本公开实施例提供的上述光电器件中，连接基团R1的碳链中包含的C原子个数优选为6个-10个。目前主要应用于QLED器件的量子点配体主要是辛硫醇和十二硫醇，C原子个数在6个-10个时，使得修饰层21 的总体厚度在1nm左右，在尽量减小空穴注入层对第一电极层的腐蚀作用的同时，不会影响载流子传输。
可选地，在本公开实施例提供的上述光电器件中，由于采用修饰材料水解后与第一电极层2表面的羟基反应的方式在第一电极层2表面形成修饰层21，保证了修饰层21由单层分子构成。修饰层21的厚度为一个修饰材料的分子长度，根据分子长度不同，修饰层21的膜层厚度也不同，修饰层21的厚度一般为1nm-2nm。
具体地，在本公开实施例提供的上述光电器件中，修饰材料可以采用如下方式制备得到：将三甲氧基(7-辛烯-1-基)硅烷2g，4'-溴-2,2':6',2”-三联吡啶1.5g，溶于干燥甲苯50mL中，加入催化剂量的四三苯基膦钯，氮气保护，回流10小时。反应结束后，将产物旋干，用柱层析(己烷：乙酸乙酯＝3：1)提纯，最终得到该分子，具体反应式如图7所示。
基于同一发明构思，本公开实施例还提供了一种上述光电器件的制作方法，由于该制作方法解决问题的原理与前述一种光电器件相似，因此该制作方法的实施可以参见光电器件的实施，重复之处不再赘述。
具体地，本公开实施例提供的一种光电器件的制作方法，如图8所示，包括：
S1、提供一衬底基板；
S2、在衬底基板上采用含铟的氧化物形成第一电极层；
S3、在第一电极层上涂布修饰材料，修饰材料包括铟离子捕获基团、硅烷基团、以及连接于铟离子捕获基团与硅烷基团之间的连接基团；
S4、加热涂布修饰材料的衬底基板，使硅烷基团水解生成硅醇基团，硅醇基团与含铟的氧化物表面存在的羟基反应生成硅氧烷基团；
S5、去除反应剩余的修饰材料后，在第一电极层的表面形成修饰层。
可选地，在本公开实施例提供的上述制作方法中，如图8所示，还可以包括：
S6、在修饰层上采用PEDOT：PSS形成空穴注入层。
具体地，在制作完成空穴注入层之后，还可以根据需要制作其他膜层，例如以如图1所示的量子点发光器件结构为例，详细说明本公开实施例提供的上述制作方法。具体地，制作过程如下：
1)将ITO基板在去离子水、乙醇、丙酮中依次进行10min的超声波清洗。
2)ITO基板在使用前在氧气等离子清洁器中清洗10min。
3)在ITO基板上以4000r/min的速度旋涂该修饰材料的溶液。
4)将ITO基板放在热台上，80℃下加热10min，使修饰材料的硅烷基团与ITO表面的羟基反应。
5)用正己烷冲洗ITO基板洗去未反应的修饰材料的溶液。
6)将ITO基板放在热台上，80℃下加热10min，除去修饰材料的溶液中的溶剂，形成修饰层。
7)在空气中，以4000r/min的速度在具有修饰层的ITO基板上旋涂PEDOT∶PSS溶液，然后在150℃高温下干燥退火20min，得到空穴注入层。
8)将ITO基板转移到充氮的手套箱中，再以2000r/min的速度旋涂TFB溶液，120℃高温下干燥退火20min，得到空穴传输层。
9)以2000r/min的速度旋涂量子点溶液，120℃高温下干燥退火20min，得到发光层。
10)以2000r/min的速度旋涂氧化锌溶液，120℃高温下干燥退火20min，得到电子传输层。
11)在5×10 -4Pa的高真空度下，使用金属掩模在蒸发设备中沉积铝电极，得到第二电极层。
本公开实施例提供的上述光电器件，光电器件在第一电极层远离衬底基板一侧的表面增加一个修饰层，修饰层的存在可以防止第一电极层和其他膜层直接接触，可以起到减缓构成第一电极层的含铟的氧化物被腐蚀的问题。并且，修饰层内含有的铟离子捕获基团可以将含铟的氧化物被腐蚀后释放出来的铟离子固定在第一电极层表面，防止铟离子向光电器件内部移动，从而可以增加光电器件的寿命。
显然，本领域的技术人员可以对本公开进行各种改动和变型而不脱离本公开的精神和范围。这样，倘若本公开的这些修改和变型属于本公开权利要求及其等同技术的范围之内，则本公开也意图包含这些改动和变型在内。

Claims (15)

  1. 一种光电器件，其中，包括：
    衬底基板；
    第一电极层，位于所述衬底基板的一侧，所述第一电极层的材料包括含铟的氧化物；
    修饰层，位于所述第一电极层远离所述衬底基板一侧的表面，所述修饰层包括：铟离子捕获基团、硅氧烷基团、以及连接于所述铟离子捕获基团与所述硅氧烷基团之间的连接基团，所述硅氧烷基团固定于所述第一电极层的表面。
  2. 如权利要求1所述的光电器件，其中，所述铟离子捕获基团包括三个吡啶基团。
  3. 如权利要求1所述的光电器件，其中，所述硅氧烷基团由与所述连接基团连接的硅烷基团和所述含铟的氧化物表面存在的羟基反应生成，所述硅烷基团的分子式为Si-R2R3R4，其中，R2基团、R3基团和R4基团包括甲氧基、乙氧基、叔丁基、氯离子中的一个。
  4. 如权利要求3所述的光电器件，其中，所述R2基团、所述R3基团和所述R4基团为相同的基团。
  5. 如权利要求4所述的光电器件，其中，所述R2基团、所述R3基团和所述R4基团均为甲氧基。
  6. 如权利要求1所述的光电器件，其中，所述连接基团包括烷基、芳香基团中的一个。
  7. 如权利要求6所述的光电器件，其中，所述芳香基团至少包括苯基、萘基和噻吩基中的一个。
  8. 如权利要求6所述的光电器件，其中，所述连接基团的碳链中包含的C原子个数为6个-10个。
  9. 如权利要求1所述的光电器件，其中，所述修饰层的厚度为1nm-2nm。
  10. 如权利要求1所述的光电器件，其中，所述第一电极层的材料包括ITO、IZO中的一个。
  11. 如权利要求1-10任一项所述的光电器件，其中，还包括：空穴注入层，位于所述第一电极层背离所述衬底基板的一侧，所述空穴注入层的材料呈酸性。
  12. 如权利要求11所述的光电器件，其中，所述空穴注入层的材料包括PEDOT：PSS。
  13. 如权利要求11所述的光电器件，其中，所述光电器件为发光器件，所述光电器件还包括位于所述空穴注入层背离所述修饰层一侧的发光层。
  14. 如权利要求13所述的光电器件，其中，所述发光层的材料为量子点或有机物。
  15. 如权利要求11所述的光电器件，其中，所述光电器件为光伏器件，所述光电器件还包括位于所述空穴注入层背离所述修饰层一侧的活性层。
PCT/CN2021/125535 2020-12-24 2021-10-22 光电器件 WO2022134810A1 (zh)

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