WO2018001372A1 - 氧化镍薄膜及其制备方法、功能材料、薄膜结构的制作方法及电致发光器件 - Google Patents

氧化镍薄膜及其制备方法、功能材料、薄膜结构的制作方法及电致发光器件 Download PDF

Info

Publication number
WO2018001372A1
WO2018001372A1 PCT/CN2017/091265 CN2017091265W WO2018001372A1 WO 2018001372 A1 WO2018001372 A1 WO 2018001372A1 CN 2017091265 W CN2017091265 W CN 2017091265W WO 2018001372 A1 WO2018001372 A1 WO 2018001372A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
nickel oxide
oxide film
organic molecule
nickel
Prior art date
Application number
PCT/CN2017/091265
Other languages
English (en)
French (fr)
Inventor
金一政
梁骁勇
陈超
Original Assignee
浙江大学
纳晶科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 浙江大学, 纳晶科技股份有限公司 filed Critical 浙江大学
Priority to KR1020197003406A priority Critical patent/KR20190028460A/ko
Priority to EP17819368.6A priority patent/EP3480865A4/en
Priority to US16/313,900 priority patent/US20210234100A1/en
Priority to JP2018569158A priority patent/JP2019522367A/ja
Publication of WO2018001372A1 publication Critical patent/WO2018001372A1/zh

Links

Images

Classifications

    • 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
    • H10K85/115—Polyfluorene; Derivatives thereof
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • 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
    • H10K71/10—Deposition of organic active material
    • 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
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • 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
    • H10K2102/301—Details of OLEDs
    • H10K2102/361—Temperature
    • 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
    • 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
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
    • 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 invention relates to the field of optoelectronic devices, and in particular to a nickel oxide film, a preparation method thereof, a functional material, a method for fabricating a film structure, and an electroluminescent device.
  • ITO Indium tin oxide
  • OLED Organic Light-Emitting Diode
  • QLED Quantum Dot Light-Emitting Diode
  • OLED Organic Photovoltaic
  • the surface work function of conventional ITO is 4.5eV ⁇ 4.8eV, which is lower than the highest electron occupying orbit of most OLED organic functional layers (Homod Occupied Molecular Orbital, referred to as HOMO), which leads to the need to overcome the hole injection as an anode.
  • HOMO Hemod Occupied Molecular Orbital
  • the higher barrier leads to the need to apply a high operating voltage to the OLED device, and the hole injection efficiency is not high, which ultimately leads to low luminous intensity and luminous efficiency of the device, and poor device stability.
  • a hole injection layer such as polyethylene dioxythiophene/polystyrene sulfonate (PEDOT:PSS) is generally introduced on the ITO to match the functional layer.
  • PEDOT:PSS polyethylene dioxythiophene/polystyrene sulfonate
  • the HOMO level is related to the surface work function of ITO, thereby enabling efficient injection of holes.
  • PEDOT:PSS is acidic, which will corrode the ITO film during long-term use and eventually lead to a decrease in luminous efficiency and lifetime of the device.
  • Nickel oxide is a P-type semiconductor material with Ni 2+ vacancies in its crystal lattice, so it exhibits hole conduction properties.
  • the Chinese Patent Application Publication No. CN 103840047A discloses a method for preparing a nickel oxide colloid film on the surface of ITO, and uses it as a hole transport layer to assemble an OLED device which is superior in performance to the same structural condition.
  • the surface work function of the nickel oxide film is about 5.0 eV, which is higher than the surface work function of ordinary ITO, but most of the organic hole transport materials are especially suitable for HOMO of hole transport materials for OLED devices and QLED devices. There is still a large gap between the energy levels and the ability to improve the hole injection of the film is limited. Therefore, how to improve the surface work function of the nickel oxide conductive film to apply it to OLED devices and QLED devices is still an urgent problem to be solved.
  • the main object of the present invention is to provide a nickel oxide film, a preparation method thereof, a functional material, a method for fabricating a film structure, and an electroluminescent device, so as to solve the problem that the surface work function of the nickel oxide conductive film in the prior art cannot satisfy the OLED device and QLED device requirements.
  • a nickel oxide film comprising: a nickel oxide film layer; an organic molecule having an electron withdrawing group, the organic molecule being bonded to the nickel oxide film layer On the surface.
  • the above organic molecule has the following structural formula (I): RR 0 -(CH 2 ) n -P, wherein: P is one of a carboxyl group, a thiol group, a phosphoric acid group, a siloxy group, an amine group, and P is oxidized.
  • n is an integer and 0 ⁇ n ⁇ 15, preferably 0 ⁇ n ⁇ 6, and R is an electron withdrawing group and is one or more selected from the group consisting of halogen, perfluoroalkyl, carbonyl, Carboxyl, cyano, ammonium, nitro, sulfinyl, sulfonyl, amido, pyridinium, phosphonium, pyridyl, thiazolyl, oxadiazolyl and triazolyl, wherein the O atom of the amide group R 0 is bonded and R 0 is an alkyl group, an alkenyl group, a dienyl group or a phenyl group.
  • the above organic molecule has the following structural formula (I): RR 0 -(CH 2 ) n -P, wherein: P is one of a carboxyl group, a thiol group, a phosphoric acid group, a siloxy group, an amine group, and P is oxidized.
  • Nickel oxide linkage of the nickel film layer n is an integer and 0 ⁇ n ⁇ 15, preferably 0 ⁇ n ⁇ 6,
  • R contains at least one electron withdrawing group and the electron withdrawing group is selected from one or more of the following groups: Halogen, perfluoroalkyl, carbonyl, carboxyl, cyano, ammonium, nitro, sulfinyl, sulfonyl, amido, pyridinium, phosphonium, pyridyl, thiazolyl, oxadiazolyl and triazolyl
  • the O atom of the amide group is bonded to R 0 and R 0 is an alkyl group, an alkenyl group, a dienyl group or a phenyl group.
  • the above organic molecule has the following structural formula: Wherein R 0 is C or a phenyl group, and R 1 , R 2 and R 3 are each independently selected from any one of CF 3 , F, CN, NO 2 , Cl, Br and I, and COOH is oxidized by COO- The nickel film layer is connected.
  • the above organic molecule has the following structural formula (II): Wherein Q is any group, R comprises at least one electron withdrawing group and the electron withdrawing group is selected from one or more of the group consisting of halogen, perfluoroalkyl, carbonyl, carboxyl, cyano, ammonium, Nitro, sulfinyl, sulfonyl, amido, pyridinium, phosphonium, pyridyl, thiazolyl, oxadiazolyl and triazolyl.
  • n is an integer greater than or equal to 1.
  • a functional material comprising nickel oxide and an organic molecule having an electron withdrawing group, the organic molecule being bonded to the nickel oxide.
  • the above organic molecule has the following structural formula (I): RR 0 -(CH 2 ) n -P, wherein: P is one of a carboxyl group, a thiol group, a phosphate group, and P is bonded to nickel oxide; n is an integer and 0 ⁇ n ⁇ 15, preferably 0 ⁇ n ⁇ 6, R is an electron withdrawing group and is selected from one or more of the following groups: halogen, perfluoroalkyl, carbonyl, carboxyl, cyano, ammonium, nitrate a sulfinyl group, a sulfonyl group, an amido group, a pyridinium group, a phosphonium group, a pyridyl group, a thiazolyl group, an oxadiazolyl group, and a triazolyl group, wherein the O atom of the amide group is bonded to R 0 and the R 0 is an
  • the above organic molecule has the following structural formula (I): RR 0 -(CH 2 ) n -P, wherein: P is one of a carboxyl group, a thiol group, a phosphate group, and P is bonded to nickel oxide; n is an integer and 0 ⁇ n ⁇ 15, preferably 0 ⁇ n ⁇ 6, R contains at least one electron withdrawing group and is selected from one or more of the following groups: halogen, perfluoroalkyl, carbonyl, carboxyl, cyano, ammonium , nitro, sulfinyl, sulfonyl, amido, pyridinium, phosphonium, pyridyl, thiazolyl, oxadiazolyl and triazolyl, wherein the O atom of the amide group is bonded to R 0 , and R 0 is Alkyl, alkenyl, dienyl or phenyl.
  • R 0 is C or a phenyl group
  • R 1 , R 2 and R 3 are each independently selected from any one of CF 3 , F, CN, NO 2 , Cl, Br and I, and COOH is oxidized by COO- Nickel connection.
  • the above organic molecule has the following structural formula (II): Wherein Q is any group, R comprises at least one electron withdrawing group and the electron withdrawing group is selected from one or more of the group consisting of halogen, perfluoroalkyl, carbonyl, carboxyl, cyano, ammonium, Nitro, sulfinyl, sulfonyl, amido, pyridinium, phosphonium, pyridyl, thiazolyl, oxadiazolyl and triazolyl, wherein COOH is linked to nickel oxide by COO-.
  • Q is any group
  • R comprises at least one electron withdrawing group and the electron withdrawing group is selected from one or more of the group consisting of halogen, perfluoroalkyl, carbonyl, carboxyl, cyano, ammonium, Nitro, sulfinyl, sulfonyl, amido, pyridinium, phosphonium, pyridyl, thiazo
  • n is an integer greater than or equal to 1.
  • a method for preparing a nickel oxide film comprising: disposing a nickel oxide precursor solution on a carrier, and performing a first step on the nickel oxide precursor solution Sub-annealing Forming a nickel oxide film layer; disposing an organic molecule having an electron withdrawing group on the surface of the nickel oxide film layer; and performing a second annealing treatment on the nickel oxide film layer provided with the organic molecule in a nitrogen or inert gas atmosphere to obtain a nickel oxide film.
  • the nickel oxide precursor solution is an aqueous solution comprising a water-soluble nickel salt and glycine, and preferably the water-soluble nickel salt is nickel nitrate, wherein a molar ratio of nickel nitrate to glycine is 1:10 to 1:1; or a nickel oxide precursor
  • the bulk solution is an alcohol solution comprising a water-soluble nickel salt and ethanolamine, and preferably the water-soluble nickel salt is nickel acetate.
  • the temperature of the first annealing treatment is 130 to 300 ° C, and the treatment time is 10 to 90 min.
  • the temperature of the second annealing treatment is 80 to 180 ° C, and the time is 1 to 60 min.
  • the nickel oxide precursor solution is disposed on the carrier by coating, printing or printing.
  • the preparation method further comprises performing ultraviolet-ozone treatment on the nickel oxide film layer, preferably ultraviolet-ozone treatment time is 5 to 60 minutes, and the ultraviolet lamp The irradiation power is 50 to 250 W.
  • a method for preparing any of the above nickel oxide films comprising: disposing a nickel oxide solution prepared in advance on a carrier to form a nickel oxide film layer; After the film is subjected to ultraviolet-ozone treatment, an organic molecule having an electron withdrawing group is disposed on the surface of the nickel oxide film layer; and the nickel oxide film layer provided with the organic molecule is subjected to a second annealing treatment in a nitrogen or inert gas atmosphere, A nickel oxide film is obtained.
  • a method for fabricating a thin film structure includes a hole injection layer, a first conductive layer, and a substrate which are sequentially stacked, and a first conductive layer is disposed on the substrate, and the manufacturing method includes A substrate provided with a first conductive layer is used as a carrier; a nickel oxide film is prepared on the first conductive layer by any of the above preparation methods, and the nickel oxide film is a hole injection layer.
  • an electroluminescent device comprising a substrate, a first conductive layer, a hole injecting layer, a light emitting layer and a second conductive layer which are sequentially stacked, wherein the hole injecting layer is A nickel oxide film in which a nickel oxide film layer of a nickel oxide film is contacted is disposed on a first conductive layer, and an organic molecule having an electron withdrawing group is disposed on a surface of the nickel oxide film layer remote from the first conductive layer.
  • an organic molecule having an electron withdrawing group is disposed on the surface of the nickel oxide film, and it is presumed that the anion of the organic molecule forms a chemical bond with the nickel of the nickel oxide film layer according to the analysis, and since the electron withdrawing group is present
  • the presence of an organic molecule is equivalent to establishing an electric field of reverse nickel oxide on the surface of the nickel oxide, thereby increasing the surface work function of the nickel oxide film.
  • the nickel oxide film having a high surface work function of the present application is applied to the QLED device and the OLED device, the hole injection rate is improved, thereby avoiding the use of PEDOT:PSS which is harmful to the device, thereby improving the performance and stability of the device. Sex.
  • Example 1 is a UPS spectrum of the ITO/nickel oxide film of Example 1;
  • Figure 5 is a graph showing the external quantum efficiency (EQE) of the devices of Example 17 and Comparative Example 2 as a function of operating voltage;
  • Figure 6 is a graph showing brightness versus operating voltage of the devices of Example 17 and Comparative Example 2;
  • Figure 8 is a UPS spectrum of the ITO/nickel oxide film of Comparative Example 3.
  • Figure 9 is a UPS spectrum of the ITO/nickel oxide film of Example 19;
  • Figure 10 is a graph showing the brightness of the devices of Example 34 and Comparative Example 3 as a function of operating voltage
  • Figure 11 is a graph showing the external quantum efficiency (EQE) of the devices of Example 34 and Comparative Example 3 as a function of operating voltage;
  • Figure 12 is a graph showing brightness versus operating voltage of the devices of Example 34 and Comparative Example 4;
  • Figure 13 is a graph showing the external quantum efficiency (EQE) of the devices of Example 34 and Comparative Example 4 as a function of operating voltage;
  • Figure 14 is a graph showing brightness versus operating voltage of the devices of Example 35 and Comparative Example 3;
  • Figure 15 is a graph showing the external quantum efficiency (EQE) of the devices of Example 35 and Comparative Example 3 as a function of operating voltage;
  • Figure 16 is a graph showing brightness versus operating voltage of the devices of Example 35 and Comparative Example 4.
  • Figure 17 is a graph showing the external quantum efficiency (EQE) of the devices of Example 35 and Comparative Example 4 as a function of operating voltage.
  • a nickel oxide film comprising a nickel oxide film layer and an organic molecule having an electron withdrawing group, the organic molecule being connected to the surface of the nickel oxide film layer.
  • the nickel oxide of the present application is not specifically referred to as NiO, that is, not specifically referred to as a nickel atom: the molar ratio of oxygen atoms is 1:1, and may be nickel oxide of various molar ratios.
  • Nickel oxide in the present application refers to nickel oxide nanocrystals.
  • the surface of the nickel oxide film provided by the present application is provided with an organic molecule having an electron withdrawing group.
  • the anion of the organic molecule forms a chemical bond with the nickel of the nickel oxide film layer, and the organic group having the electron withdrawing group
  • the presence of a molecule is equivalent to establishing an electric field of reverse nickel oxide on the surface of the nickel oxide, thereby increasing the surface work function of the nickel oxide film.
  • the hole injection rate is improved, thereby avoiding the use of PEDOT:PSS which is harmful to the device, thereby improving the performance and stability of the device.
  • Organic molecules having electron-withdrawing groups may also cause some organic molecules to enter the interior of the nickel oxide film layer due to different preparation processes.
  • the organic molecule has the following structural formula: R-R0-(CH 2 ) nP, wherein: P is one of a carboxyl group, a thiol group, a phosphate group, and a P and a nickel oxide film layer n; n is an integer and 0 ⁇ n ⁇ 15, preferably 0 ⁇ n ⁇ 6, R is an electron withdrawing group and is selected from one or more of the following groups: halogen, perfluoroalkyl, carbonyl, carboxyl, cyanide a group, an ammonium group, a nitro group, a sulfinyl group, a sulfonyl group, an amido group, a pyridinium group, a phosphonium group, a pyridyl group, a thiazolyl group, an oxadiazolyl group, and a triazolyl group, wherein the O atom of the amide group is
  • the above organic molecule has the following structural formula: Wherein R 0 is C or a phenyl group, and R 1 , R 2 and R 3 are each independently selected from any one of CF 3 , F, CN, NO 2 , Cl, Br and I, and COOH is oxidized by COO- The nickel film layer is connected.
  • R-R0-(CH 2 ) nP wherein: P is one of a carboxyl group, a sulfhydryl group, a phosphoric acid group, and P is bonded to nickel oxide of the nickel oxide film layer; n is An integer and 0 ⁇ n ⁇ 15, preferably 0 ⁇ n ⁇ 6, R contains at least one electron withdrawing group and the electron withdrawing group is selected from one or more of the following groups: halogen, perfluoroalkyl, carbonyl, Carboxyl, cyano, ammonium, nitro, sulfinyl, sulfonyl, amido, pyridinium, phosphonium, pyridyl, thiazolyl, oxadiazolyl and triazolyl, wherein the O atom of the amide group R 0 is bonded and R 0 is an alkyl group, an alkenyl group, a dien
  • the above organic molecule has the following structural formula: Wherein R 0 is C or phenyl, R is R 1 , R 2 and R 3 , and R 1 , R 2 and R 3 are each independently selected from the group consisting of CF 3 , F, CN, NO 2 , Cl, Br and I Either one of them, COOH is connected to the nickel oxide film layer by COO-.
  • the above organic molecule may also have the following structural formula (II):
  • R comprises at least one of said electron withdrawing groups and the electron withdrawing group is selected from one or more of the group consisting of halogen, perfluoroalkyl, carbonyl, carboxyl, cyano, ammonium a nitro group, a sulfinyl group, a sulfonyl group, an amido group, a pyridinium group, a phosphonium group, a pyridyl group, a thiazolyl group, an oxadiazolyl group, and a triazolyl group, wherein the COOH is linked to the nickel oxide by COO-.
  • Q contains a group that can be chemically bonded to a C atom.
  • structural formula (II) may be the following chemical structure:
  • n is an integer greater than or equal to 1, preferably n is from 5,000 to 5,000,000, wherein CF 3 is an electron withdrawing group.
  • Suitable organic molecules can also be obtained by changing the position and number of CF 3 in each of the above structural formulas, such as a hydrogen atom in which CF 3 is substituted for an alkyl group; and a suitable organic molecule can also be obtained by changing the number of alkyl groups in each of the above structural formulas.
  • the work function of the nickel oxide thin film can be improved, the hole injection barrier can be reduced, and the hole injection efficiency can be improved.
  • a functional material in another exemplary embodiment of the present application, includes nickel oxide and an organic molecule having an electron withdrawing group attached to the nickel oxide.
  • the nickel oxide in the above functional material provided by the present application is linked with an organic molecule having an electron withdrawing group, and it is presumed that the anion of the organic molecule (anion derived from a P group such as COOH) forms a chemical bond with nickel of nickel oxide according to analysis. Stable connection, and due to the presence of the organic molecule having an electron withdrawing group, is equivalent to establishing an electric field of reverse nickel oxide on the surface of the nickel oxide, and when the film is prepared by using the functional material, the surface work of the nickel oxide film can be improved. function.
  • the hole injection rate is improved, thereby avoiding the use of PEDOT:PSS which is harmful to the device, thereby improving the performance and stability of the device.
  • the above organic molecule has the formula: R-R0-(CH 2 ) nP, wherein: P is one of a carboxyl group, a thiol group, a phosphate group, and P is bonded to nickel oxide; n is an integer and 0 ⁇ n ⁇ 15, preferably 0 ⁇ n ⁇ 6, R is an electron withdrawing group and is selected from one or more of the following groups: halogen, perfluoroalkyl, carbonyl, carboxyl, cyano, ammonium, nitro, sub a sulfuryl group, a sulfonyl group, an amido group, a pyridinium group, a phosphonium group, a pyridyl group, a thiazolyl group, an oxadiazolyl group, and a triazolyl group, wherein the O atom of the amide group is bonded to R 0 , and R 0 is an alkyl group or an alken
  • the above organic molecule has the following structural formula: Wherein R 0 is C or a phenyl group, and R 1 , R 2 and R 3 are each independently selected from any one of CF 3 , F, CN, NO 2 , Cl, Br and I, and COOH is oxidized by COO- Nickel connection.
  • the above organic molecule has the following structural formula (I): R-R0-(CH 2 ) nP, wherein: P is one of a carboxyl group, a fluorenyl group, a phosphoric acid group, and P is bonded to nickel oxide; n is an integer and 0 ⁇ n ⁇ 15, preferably 0 ⁇ n ⁇ 6, R contains at least one electron withdrawing group and the electron withdrawing group is selected from one or more of the following groups: halogen, perfluoroalkyl, carbonyl, carboxyl, cyano An ammonium group, a nitro group, a sulfinyl group, a sulfonyl group, an amido group, a pyridinium group, a phosphonium group, a pyridyl group, a thiazolyl group, an oxadiazolyl group, and a triazolyl group, wherein the O atom of the amide group is
  • the above organic molecule has the following structural formula: Wherein R 0 is C or a phenyl group, and R 1 , R 2 and R 3 are each independently selected from any one of CF 3 , F, CN, NO 2 , Cl, Br and I, and COOH is oxidized by COO- Nickel connection.
  • the above organic molecule may also have the following structural formula (II):
  • R comprises at least one electron withdrawing group and the electron withdrawing group is selected from one or more of the group consisting of halogen, perfluoroalkyl, carbonyl, carboxyl, cyano, ammonium a nitro group, a sulfinyl group, a sulfonyl group, an amido group, a pyridinium group, a phosphonium group, a pyridyl group, a thiazolyl group, an oxadiazolyl group, and a triazolyl group, wherein the COOH is linked to the nickel oxide by COO-.
  • the electron withdrawing group is selected from one or more of the group consisting of halogen, perfluoroalkyl, carbonyl, carboxyl, cyano, ammonium a nitro group, a sulfinyl group, a sulfonyl group, an amido group, a pyridinium group, a phosphonium group,
  • structural formula (II) may be the following chemical structure:
  • n is an integer greater than or equal to 1.
  • the organic molecule in the nickel oxide film may be a mixture or a single compound satisfying each of the above structural formulas.
  • a method for preparing the above nickel oxide film comprising: disposing a nickel oxide precursor solution on a carrier, performing a first annealing to form a nickel oxide a film layer; an organic molecule disposed on a surface of the nickel oxide film layer; and a second annealing treatment of the nickel oxide film layer provided with the organic molecule in a nitrogen gas or an inert gas atmosphere to obtain a nickel oxide film.
  • the nickel oxide precursor solution is first annealed to obtain a nickel oxide film layer; and an organic molecule having an electron withdrawing group at one end is disposed on the nickel oxide film layer, and the organic molecule can be dissolved in a solvent (solvent such as methanol, ethanol, chlorine)
  • a solvent solvent such as methanol, ethanol, chlorine
  • An organic molecular solution is formed in benzene, dimethyl sulfoxide, N,N-dimethylformamide, or acetone or a mixture solvent according to solubility, and the organic molecular solution can be immersed, spin coated, printed , slit coating, etc.
  • the anion of the organic molecule is reacted with nickel on the surface of the nickel oxide, and finally the electron withdrawing group passes through the covalent bond between the anion and the nickel
  • the action is fixed on the surface of the nickel oxide film layer to obtain a functional material of the above nickel oxide film.
  • the resulting film-like functional material retains its original properties after changing its film state.
  • the amount of the above nickel oxide precursor determines the thickness of the formed nickel oxide film layer; since the organic molecules are disposed on the surface of the nickel oxide film layer, the amount of the organic molecules added can be determined according to the area of the nickel oxide film layer.
  • the thickness of the nickel oxide film layer may be from 1 nm to 1000 nm.
  • the nickel oxide precursor solution is an aqueous solution comprising a water-soluble nickel salt and glycine, and further preferably the water-soluble nickel salt is nickel nitrate, wherein a molar ratio of nickel nitrate to glycine is 1:10 to 1:1.
  • the concentration of nickel nitrate in the nickel oxide precursor solution is not particularly required, and the concentration thereof is preferably 0.05 to 0.1 mol/L to prepare a nickel oxide film layer having a conventional thickness.
  • the nickel oxide precursor solution is an alcohol solution comprising a water-soluble nickel salt and ethanolamine, and preferably the water-soluble nickel salt is nickel acetate, wherein the molar ratio of nickel acetate to ethanolamine is 1:5 to 1:0.5.
  • the temperature of the first annealing treatment is preferably 130 to 300 ° C, and the treatment time is 10 to 90 min.
  • the annealing usually includes a heating and a cooling phase, and the temperature of the annealing treatment in the present application refers to the temperature reached after heating, and the processing time refers to the heating time.
  • the temperature of the second annealing treatment is preferably 80 to 180 ° C for 1 to 60 minutes. If the temperature is low, the annealing time can be extended appropriately.
  • the nickel oxide precursor solution is preferably disposed on the carrier by coating, printing or printing. on.
  • the above embodiment can be applied to a large-area substrate without causing damage to the substrate, and has a very important effect on industrialization, and is easy to realize industrial production.
  • the above preparation method further comprises subjecting the nickel oxide film layer to ultraviolet-ozone treatment through ultraviolet-ozone treatment of the nickel oxide film layer.
  • a layer of hydroxyl radical is formed on the surface of the nickel oxide film layer to provide a bonding bond with the organic molecule to strengthen the bonding force with the organic molecule; on the other hand, the nickel oxide film layer is cleaned to improve the combination of the organic molecule and the organic molecule force.
  • the ultraviolet-ozone treatment of the intrinsic properties of the nickel oxide film layer forms a hydroxyl radical on the surface of the nickel oxide film layer. Therefore, those skilled in the art can select the ultraviolet-ozone treatment conditions according to the equipment used and the number of hydroxyl groups.
  • the ultraviolet-ozone treatment time is 5 to 60 minutes, and the ultraviolet lamp irradiation power is 50 to 250 W. Ultraviolet ozone treatment under the above conditions can obtain ideal treatment results in a short period of time.
  • a method for preparing the above-mentioned nickel oxide film comprises: setting a nickel oxide solution prepared in advance (the preparation method thereof can be a method of the prior art) a nickel oxide film layer is formed on the carrier; after the nickel oxide film layer is subjected to ultraviolet-ozone treatment, an organic molecule having an electron withdrawing group is disposed on the surface of the nickel oxide film layer; and the gas is disposed in a nitrogen or inert gas atmosphere The nickel oxide film layer of the organic molecule is subjected to a second annealing treatment to obtain the nickel oxide film.
  • the ligand may be a C 2 - C 30 fatty acid radical
  • the ultraviolet-ozone treatment time is 5 to 60 minutes
  • the ultraviolet lamp irradiation power is 50 to 250W.
  • Ultraviolet ozone treatment under the above conditions can obtain ideal treatment results in a short period of time.
  • the nickel oxide solution on the carrier such as coating, printing, printing, dipping, etc.
  • the second annealed nickel oxide film may be washed, and the cleaning solvent may dissolve the organic molecules.
  • a method for fabricating a thin film structure including a hole injection layer, a first conductive layer, and a substrate stacked in sequence, the first conductive layer being disposed on the substrate comprises: using a substrate provided with a first conductive layer as a carrier; and preparing a nickel oxide film on the first conductive layer by the above-mentioned preparation method, the nickel oxide film being a hole injection layer.
  • the substrate provided with the first conductive layer is used as a carrier, and then a nickel oxide film is prepared on the carrier by using a method for preparing a nickel oxide film, thereby preparing a film structure having a first conductive layer, a substrate and a nickel oxide film, and preparing The method is simple.
  • the structure can be applied to single photon light sources, solar cells, electroluminescent lighting, and display devices.
  • the substrate material used in the above manufacturing method may be a substrate commonly used in the prior art, such as glass, polymer, metal, alloy material, and the foregoing materials.
  • the material used for the first conductive layer may be a conductive oxide film layer commonly used in the prior art, preferably an ITO film.
  • the present application further provides an electroluminescent device comprising a substrate, a first conductive layer, a hole injection layer, a light-emitting layer and a second conductive layer, which are sequentially stacked, the hole injection layer being the above-mentioned nickel oxide film,
  • the nickel oxide film layer of the nickel oxide film is contacted on the first conductive layer, and the organic molecules having electron-withdrawing groups are disposed on the surface of the nickel oxide film layer remote from the first conductive layer.
  • There may be other functional layers between the hole injection layer and the light-emitting layer such as a hole transport layer and a hole blocking layer.
  • There may be other functional layers between the light-emitting layer and the second conductive layer such as one or more layers of the electron blocking layer, the electron transport layer, and the electron injecting layer.
  • the nickel oxide film of the present application has a high surface work function, when it is applied to the electroluminescent device as a hole injecting layer, hole injection is improved, thereby avoiding The PEDOT:PSS which is detrimental to the device is used in the electroluminescent device, thereby improving the performance and stability of the device.
  • the above electroluminescent device may be an OLED device or a QLED device, that is, the above-mentioned light emitting layer may comprise any one or a combination of a group consisting of a quantum dot material, an organic fluorescent material and an organic phosphorescent material.
  • the electroluminescent device includes a substrate, a first conductive layer, and a nickel oxide film (as a hole injecting layer). a hole transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, an electron transport layer, an electron injection layer, and a second conductive layer.
  • Example 17 and Comparative Example 2 were the same batch, and the quantum dot raw materials used in Example 34, Example 35, and Comparative Examples 3 to 4 were another batch having the same composition.
  • Nickel nitrate and glycine were dissolved in water at a molar ratio of 3:5 to prepare a nickel oxide precursor solution, wherein the concentration of nickel nitrate was 0.06 mol/L.
  • the nickel oxide precursor was coated on an ITO substrate by spin coating (rotation speed: 4000 rpm), and the nickel oxide precursor solution was annealed in air at 200 ° C for 60 min to obtain a nickel oxide film layer.
  • the nickel oxide film layer was subjected to ultraviolet-ozone treatment for 20 minutes, wherein the ultraviolet lamp irradiation power was 200 W, and a trifluoromethylbenzoic acid/ethanol solution having a concentration of 3 mmol/L was spin-coated in a glove box of N 2 atmosphere. On ITO/nickel oxide composite film (rotation speed: 2000 rpm).
  • Example 3 The specific steps and materials and apparatus used were the same as in Example 1, except that the annealing temperature in step S3 was 140 °C.
  • the film was tested by ultraviolet photoelectric spectroscopy. The test results are shown in Fig. 3.
  • the ITO/nickel oxide surface work function was 5.7 eV.
  • step S3 was 180 ° C for 2 min.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.7 eV.
  • step S3 The specific steps and materials and apparatus used were the same as in Example 1, except that the annealing temperature in step S3 was 80 ° C and the annealing time was 60 min.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.6 eV.
  • step S3 was 200 °C.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.7 eV.
  • step S3 was 60 ° C and the annealing time was 90 min.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.4 eV.
  • Example 1 The specific procedure and the materials and equipment used were the same as in Example 1, except that the compound used in step S2 was p-trifluoromethylphenylacetic acid.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.4 eV.
  • Example 2 The specific procedure and the materials and equipment used are the same as in Example 1, except that the compound used in step S2 is trifluorobutyric acid. After the treatment, the test was carried out with a UPS. In this example, the ITO surface work function was 5.6 eV.
  • step S1 The specific steps and materials and instruments used were the same as in Example 1, except that the annealing temperature in step S1 was 100 ° C and the annealing time was 90 min.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.7 eV.
  • step S1 the annealing temperature in step S1 was 300 ° C and the annealing time was 10 min.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.7 eV.
  • step S1 The specific steps and materials and instruments used were the same as in Example 1, except that the annealing temperature in step S1 was 80 ° C and the annealing time was 90 min.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.7 eV.
  • Example 2 The specific steps and materials and apparatus used were the same as in Example 1, except that nickel nitrate and glycine in the nickel oxide precursor solution of step S1 were dissolved in water at a molar ratio of 1:10. The film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.6 eV.
  • Example 2 The specific steps and materials and apparatus used were the same as in Example 1, except that nickel nitrate and glycine in the nickel oxide precursor solution of step S1 were dissolved in water at a molar ratio of 1:1.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.7 eV.
  • Example 2 The specific steps and materials and apparatus used were the same as in Example 1, except that nickel nitrate and glycine in the nickel oxide precursor solution of step S1 were dissolved in water at a molar ratio of 1:12.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.6 eV.
  • step S2 The specific steps and materials and apparatus used were the same as in Example 1, except that the ultraviolet-ozone treatment of step S2 was carried out for 60 min, wherein the ultraviolet lamp irradiation power was 50 W.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.6 eV.
  • step S2 The specific steps and materials and apparatus used were the same as in Example 1, except that the ultraviolet-ozone treatment of step S2 was carried out for 5 min, wherein the ultraviolet lamp irradiation power was 250 W.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.6 eV.
  • a quantum dot electroluminescent device having a structure as shown in FIG. 4, the QLED device comprising a substrate 10, an anode 20, and a first functional layer 30 (it is to be explained that 30 in FIG. 4 is divided into two layers, The second functional layer 40, the light-emitting layer 50, the third functional layer 60, and the cathode 70 are merely for explaining that the surface of the nickel oxide film layer has been treated with organic molecules having electron-withdrawing, and there is no actual layering.
  • the substrate is a transparent glass substrate
  • the anode is the ITO layer of the first embodiment
  • the first functional layer 30 is the nickel oxide film of the first embodiment.
  • the two are the surface-modified ITO/nickel oxide composite transparent conductive of the first embodiment. film.
  • the second functional layer is poly-TPD (4-butyl-N,N-diphenylaniline homopolymer) and PVK (polyvinylcarbazole).
  • the luminescent layer 50 is a quantum dot luminescent material.
  • the third functional layer is ZnO nanoparticles. Ag acts as a cathode.
  • step S1 of Example 1 The specific steps and materials and apparatus used were the same as those in step S1 of Example 1, and then the nickel oxide film layer was subjected to ultraviolet-ozone treatment for 20 minutes, wherein the ultraviolet lamp irradiation power was 200 W, and the subsequent step S3 was not performed.
  • the film was tested by ultraviolet photoelectric spectroscopy. The test results are shown in Fig. 2, and the surface work function was 5.0 eV.
  • Example 17 The specific steps and materials and instruments used are the same as those in Example 17, except that the first functional layer is not a nickel oxide film grown on the surface of the ITO, but a PEDOT:PSS organic molecular layer, and the surface work function of the ITO/PEDOT:PSS organic molecule is 5.0eV.
  • the EQE (external quantum efficiency) of the quantum dots electroluminescent devices of Example 17 and Comparative Example 2 was measured using a PR670 spectrophotometric/chroma/radiometer manufactured by PHOTO RESEARCH, at a current density of 2 mA/cm 2 .
  • the test results are shown in Figures 5 and 6, as the operating voltage changes and the brightness varies with the operating voltage.
  • Nickel nitrate and glycine were dissolved in water at a molar ratio of 3:5 to prepare a nickel oxide precursor solution, wherein the concentration of nickel nitrate was 0.06 mol/L.
  • the nickel oxide precursor was coated on an ITO substrate by spin coating (rotation speed: 4000 rpm), and the nickel oxide precursor solution was annealed in air at 200 ° C for 60 min to obtain a nickel oxide film layer.
  • Example 18 The specific steps and materials and apparatus used were the same as in Example 18 except that the annealing temperature in step S3 was 140 °C.
  • the film was tested by ultraviolet photoelectron spectroscopy. The test results are shown in Fig. 9.
  • the ITO/nickel oxide surface work function was 5.5 eV.
  • Example 18 The specific steps and materials and apparatus used were the same as in Example 18 except that the annealing temperature in step S3 was 180 ° C for 2 min.
  • the film was tested by ultraviolet photoelectron spectroscopy.
  • the ITO/nickel oxide surface work function was 5.3 eV.
  • Example 18 The specific steps and materials and apparatus used were the same as in Example 18 except that the annealing temperature in step S3 was 80 ° C and the annealing time was 60 min.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.4 eV.
  • Example 18 The specific steps and materials and apparatus used were the same as in Example 18 except that the annealing temperature in step S3 was 200 °C.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.3 eV.
  • Example 18 The specific steps and materials and apparatus used were the same as in Example 18 except that the annealing temperature was 60 ° C and the annealing time was 90 min in step S3.
  • the film was tested by ultraviolet photoelectric spectroscopy, and the surface work function of the ITO/nickel oxide in this example was 5.4 eV.
  • Example 18 The specific procedure and materials and apparatus used were the same as in Example 18 except that the compound used in step S2 was p-trifluoromethylphenylacetic acid.
  • the film was tested by ultraviolet photoelectron spectroscopy.
  • the ITO/nickel oxide surface work function was 5.4 eV.
  • Example 18 The specific procedure and materials and apparatus used were the same as in Example 18 except that the compound used in step S2 was trifluorobutyric acid. After the treatment, the test was carried out with a UPS. In this example, the surface work function of the ITO/nickel oxide was 5.2 eV.
  • Example 18 The specific steps and materials and apparatus used were the same as in Example 18 except that the annealing temperature in step S1 was 100 ° C and the annealing time was 90 min.
  • the film was tested by ultraviolet photoelectron spectroscopy.
  • the ITO/nickel oxide surface work function was 5.4 eV.
  • Example 18 The specific steps and materials and apparatus used were the same as in Example 18 except that the annealing temperature in step S1 was 300 ° C and the annealing time was 10 min.
  • the film was tested by ultraviolet photoelectron spectroscopy.
  • the ITO/nickel oxide surface work function was 5.4 eV.
  • Example 18 The specific steps and materials and apparatus used were the same as in Example 18 except that the annealing temperature in step S1 was 80 ° C and the annealing time was 90 min.
  • the film was tested by ultraviolet photoelectron spectroscopy.
  • the ITO/nickel oxide surface work function was 5.3 eV.
  • Example 18 The specific steps and materials and apparatus used were the same as in Example 18 except that nickel nitrate and glycine in the nickel oxide precursor solution of step S1 were dissolved in water at a molar ratio of 1:10.
  • the film was tested by ultraviolet photoelectron spectroscopy.
  • the ITO/nickel oxide surface work function was 5.4 eV.
  • Example 18 The specific steps and materials and apparatus used were the same as in Example 18 except that nickel nitrate and glycine in the nickel oxide precursor solution of step S1 were dissolved in water at a molar ratio of 1:1.
  • the film was tested by ultraviolet photoelectron spectroscopy.
  • the ITO/nickel oxide surface work function was 5.3 eV.
  • Example 18 The specific steps and materials and apparatus used were the same as in Example 18 except that nickel nitrate and glycine in the nickel oxide precursor solution of step S1 were dissolved in water at a molar ratio of 1:12.
  • the film was tested by ultraviolet photoelectron spectroscopy.
  • the ITO/nickel oxide surface work function was 5.4 eV.
  • a solution of nickel acetate and ethanolamine in ethanol (also a solution of ethanolamine in methoxyethanol) is dissolved in water at a molar ratio of 3:5 to prepare a nickel oxide precursor solution, wherein the concentration of nickel acetate is 0.06 mol/L.
  • the nickel oxide precursor was coated on the ITO substrate by spin coating (rotation speed: 4000 rpm), and the nickel oxide precursor solution was annealed in air at 200 ° C for 60 min to obtain a nickel oxide film layer.
  • the film is placed on a heating panel, annealed at 120 ° C for 30 min, and then the surface is washed three times with ethanol, and dried to obtain a nickel oxide film, thereby obtaining a surface-modified ITO/nickel oxide composite transparent conductive film.
  • the surface power function of the ITO/nickel oxide in this example was 5.4 eV by ultraviolet photoelectron spectroscopy.
  • the above prepared 100 g/L nickel oxide solution was coated on the ITO substrate, and the ultraviolet-ozone treatment of the step S2 was carried out for 60 minutes, wherein the ultraviolet lamp irradiation power was 50 W.
  • the film was placed on a heating panel, annealed at 150 ° C for 30 min, and then the surface was washed three times with ethanol and dried to obtain a nickel oxide film, thereby obtaining a surface-modified ITO/nickel oxide composite transparent conductive film.
  • the film was tested by ultraviolet photoelectron spectroscopy.
  • the ITO/nickel oxide surface work function was 5.8 eV.
  • a quantum dot electroluminescent device having a structure as shown in FIG. 4, the QLED device comprising a substrate 10, a first conductive layer 20, a first functional layer 30, a second functional layer 40, a light emitting layer 50, and a first The trifunctional layer 60 and the second conductive layer 70.
  • the substrate is a transparent glass substrate
  • the first conductive layer is the ITO layer of the embodiment 18, and the first functional layer 30 is the nickel oxide film of the embodiment 18.
  • the two are the surface-modified ITO/nickel oxide of the embodiment 34.
  • Composite transparent conductive film is poly-TPD (4-butyl-N,N-diphenylaniline homopolymer) and PVK (polyvinylcarbazole).
  • the luminescent layer 50 is a quantum dot luminescent material.
  • the third functional layer is Zn 90 Mg 10 O nanoparticles. Ag serves as a second conductive layer.
  • a quantum dot electroluminescent device having a structure as shown in FIG. 4, the QLED device comprising a substrate 10, a first conductive layer 20, a first functional layer 30, a second functional layer 40, a light emitting layer 50, and a third The functional layer 60 and the second conductive layer 70.
  • the substrate is a transparent glass substrate
  • the first conductive layer is the ITO layer of Embodiment 18
  • the first functional layer 30 is the nickel oxide film of Example 33, which are the surface-modified ITO/nickel oxide of Example 35.
  • Composite transparent conductive film is poly-TPD (4-butyl-N,N-diphenylaniline homopolymer) and PVK (polyvinylcarbazole).
  • the luminescent layer 50 is a quantum dot luminescent material.
  • the third functional layer is Zn 90 Mg 10 O nanoparticles. Ag serves as a second conductive layer.
  • S1 An ethanol solution of nickel acetate and ethanolamine (which may also be a solution of ethanolamine in methoxyethanol) is dissolved in water at a molar ratio of 3:5 to prepare a nickel oxide precursor solution in which the concentration of nickel acetate is 0.06 mol/L.
  • the nickel oxide precursor was coated on the ITO substrate by spin coating (rotation speed: 4000 rpm), and the nickel oxide precursor solution was annealed in air at 200 ° C for 60 min to obtain a nickel oxide film layer.
  • the film is placed on a heating panel, annealed at 120 ° C for 30 min, and then the surface is cleaned three times with toluene, and dried to obtain a nickel oxide film, thereby obtaining a surface-modified ITO/nickel oxide composite transparent conductive film.
  • the surface power function of the ITO/nickel oxide in this example was 5.6 eV by ultraviolet photoelectron spectroscopy.
  • a quantum dot electroluminescent device having a structure as shown in FIG. 4, the QLED device comprising a substrate 10, a first conductive layer 20, a first functional layer 30, a second functional layer 40, a light emitting layer 50, and a first The trifunctional layer 60 and the second conductive layer 70.
  • the substrate is a transparent glass substrate
  • the first conductive layer is the ITO layer of the embodiment 18, and the first functional layer 30 is the nickel oxide film described above in Comparative Example 3.
  • the two are the ITO/nickel oxide composite transparent conductive of Comparative Example 3. film.
  • the second functional layer is poly-TPD (4-butyl-N,N-diphenylaniline homopolymer) and PVK (polyvinylcarbazole).
  • the luminescent layer 50 is a quantum dot luminescent material.
  • the third functional layer is Zn 90 Mg 10 O nanoparticles. Ag serves as a second conductive layer.
  • Example 34 The specific steps and materials and instruments used are the same as those in Example 34, except that the first functional layer is not a nickel oxide film grown on the surface of the ITO, but a PEDOT:PSS organic molecular layer, and the surface work function of the ITO/PEDOT:PSS organic molecule is 5.0eV.
  • step S1 in Example 32 The specific steps and materials and instruments used are the same as step S1 in Example 32, and the subsequent steps S2, S3 are not performed.
  • the film was tested by ultraviolet photoelectron spectroscopy with a surface work function of 4.9 eV.
  • the surface of the nickel oxide film provided by the present application is provided with an organic molecule having an electron withdrawing group, and the anion of the organic molecule forms a stable connection with the nickel atom on the surface of the nickel oxide film, and the organic molecule having an electron withdrawing group
  • the existence of an electric field of reverse nickel oxide is established on the surface of the nickel oxide, thereby increasing the surface work function of the nickel oxide film.
  • the hole injection rate is improved, thereby avoiding the use of PEDOT:PSS which is harmful to the device, thereby improving the performance and stability of the device. Sex.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)
  • Chemically Coating (AREA)

Abstract

氧化镍薄膜及其制备方法、功能材料、薄膜结构的制作方法及电致发光器件。该氧化镍薄膜包括：氧化镍膜层；具有吸电子基团的有机分子，该有机分子连接设置在氧化镍膜层表面上。由于该具有吸电子基团的有机分子的存在，相当于在氧化镍表面建立起一个反向氧化镍的电场，进而提高了氧化镍薄膜的表面功函数。该具有高表面功函数的氧化镍薄膜应用到QLED器件和OLED器件时，使得空穴注入率提高。

Description

氧化镍薄膜及其制备方法、功能材料、薄膜结构的制作方法及电致发光器件 技术领域
本发明涉及光电器件领域，具体而言，涉及一种氧化镍薄膜及其制备方法、功能材料、薄膜结构的制作方法及电致发光器件。
背景技术
氧化铟锡(Indium tin oxide，简称ITO)透明导电薄膜具有优异的导电能力，并且具有＞90％的透光度，广泛作为如有机电致发光器件(Organic Light-Emitting Diode，简称OLED)、量子点电致发光器件(Quantum Dot Light-Emitting Diode，简称QLED)、有机光伏电池(Organic Photovoltaic，简称OPV)等光电器件的电极使用，还同时兼做透光窗口。
目前，常规ITO的表面功函数为4.5eV～4.8eV，低于大部分OLED有机功能层的最高电子占据轨道(Highest Occupied Molecular Orbital，简称HOMO)，导致其在作为阳极将空穴注入时需要克服较高的势垒，进而导致需要给OLED器件施加很高的工作电压，加之其空穴注入效率不高，最终导致器件的发光强度及发光效率偏低、器件稳定性差。在现有的OLED器件的实际制造技术中，一般会在ITO上引入一层空穴注入层，如聚乙撑二氧噻吩/聚苯乙烯磺酸盐(PEDOT:PSS)用以匹配功能层的HOMO能级与ITO的表面功函数，从而实现空穴的有效注入。但是该方法的不足之处在于PEDOT:PSS呈酸性，在长期使用中会腐蚀ITO薄膜，并最终导致器件的发光效率和寿命的降低。
氧化镍是一种P型半导体材料，其晶格中存在Ni2+空位，所以呈现空穴导电的性能。公开号为CN 103840047A中国专利申请公开了在ITO表面制备一层氧化镍胶体薄膜的方法，并利用其作为空穴传输层组装出一种OLED器件，其在性能表现上优于相同结构条件下的以PEDOT:PSS为空穴传输层的器件。
但是氧化镍薄膜的表面功函数约为5.0eV，该数值虽然高于普通ITO的表面功函数，但是和大部分有机空穴传输材料尤其是适用于OLED器件以及QLED器件的空穴传输材料的HOMO能级相比仍然有较大差距，对提高薄膜的空穴注入能力有限。所以如何提高氧化镍导电薄膜的表面功函数以将其应用于OLED器件以及QLED器件仍是一个亟待解决的问题。
发明内容
本发明的主要目的在于提供一种氧化镍薄膜及其制备方法、功能材料、薄膜结构的制作方法及电致发光器件，以解决现有技术中氧化镍导电薄膜的表面功函数不能满足OLED器件以及QLED器件要求的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种氧化镍薄膜，该氧化镍薄膜包括：氧化镍膜层；具有吸电子基团的有机分子，该有机分子连接设置在氧化镍膜层表面上。
进一步地，上述有机分子具有如下结构式(I)：R-R0-(CH2)n-P，其中：P是羧基、巯基、磷酸基、硅氧基、胺基中的一种，且P与氧化镍膜层连接；n是整数且0≤n≤15，优选0≤n≤6，R是吸电子基团且选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，酰胺基的O原子与R0连接，R0为烷基、烯基、二烯基或苯基。
进一步地，上述有机分子具有如下结构式(I)：R-R0-(CH2)n-P，其中：P是羧基、巯基、磷酸基、硅氧基、胺基中的一种，且P与氧化镍膜层的氧化镍连接；n是整数且0≤n≤15，优选0≤n≤6，R包含至少一个吸电子基团且吸电子基团选自下列基团的一种或多种：卤素、全氟 烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，酰胺基的O原子与R0连接，R0为烷基、烯基、二烯基或苯基。
进一步地，上述有机分子具有如下结构式：
Figure PCTCN2017091265-appb-000001
其中，R0为C或者苯基，R1、R2和R3各自独立地选自CF3、F、CN、NO2、Cl、Br和I中的任意一种，COOH以COO-与氧化镍膜层连接。
进一步地，上述有机分子具有如下结构式(II)：
Figure PCTCN2017091265-appb-000002
其中，Q为任意基团，R包含至少一个吸电子基团且吸电子基团选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基。
进一步地，上述有机分子具有如下结构式：
Figure PCTCN2017091265-appb-000003
n为大于等于1的整数。
根据本申请的另一方面，提供了一种功能材料，包括氧化镍及具有吸电子基团的有机分子，有机分子与氧化镍连接。
进一步地，上述有机分子具有如下结构式(I)：R-R0-(CH2)n-P，其中：P是羧基、巯基、磷酸基中的一种，且P与氧化镍连接；n是整数且0≤n≤15，优选0≤n≤6，R是吸电子基团且选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，酰胺基的O原子与R0连接，R0为烷基、烯基、二烯基或苯基。
进一步地，上述有机分子具有如下结构式(I)：R-R0-(CH2)n-P，其中：P是羧基、巯基、磷酸基中的一种，且P与氧化镍连接；n是整数且0≤n≤15，优选0≤n≤6，R包含至少一个吸电子基团且选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，酰胺基的O原子与R0连接，R0为烷基、烯基、二烯基或苯基。
进一步地，上述有机分子具有如下结构式：
Figure PCTCN2017091265-appb-000004
其中，R0为C或者苯基，R1、R2和R3各自独立地选自CF3、F、CN、NO2、Cl、Br和I中的任意一种，COOH以COO-与氧化镍连接。
进一步地，上述有机分子具有如下结构式(II)：
Figure PCTCN2017091265-appb-000005
其中，Q为任意基团，R包含至少一个吸电子基团且吸电子基团选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，COOH以COO-与氧化镍连接。
进一步地，上述有机分子具有如下结构式：
Figure PCTCN2017091265-appb-000006
Figure PCTCN2017091265-appb-000007
Figure PCTCN2017091265-appb-000008
n为大于等于1的整数。
根据本申请的又一方面，提供了一种上述任一种的氧化镍薄膜的制备方法，该制备方法包括：将氧化镍前驱体溶液设置于载体上，并对氧化镍前驱体溶液进行第一次退火处理，形 成氧化镍膜层；在氧化镍膜层表面设置具有吸电子基团的有机分子；以及在氮气或惰性气体气氛中对设置有有机分子的氧化镍膜层进行第二次退火处理，得到氧化镍薄膜。
进一步地，上述氧化镍前驱体溶液为包括水溶性镍盐与甘氨酸的水溶液，优选水溶性镍盐为硝酸镍，其中硝酸镍与甘氨酸的摩尔比为1：10～1：1；或者氧化镍前驱体溶液为包括水溶性镍盐与乙醇胺的醇溶液，优选水溶性镍盐为醋酸镍。
进一步地，上述第一次退火处理的温度为130～300℃，处理时间为10～90min。
进一步地，上述第二次退火处理的温度为80～180℃，时间为1～60min。
进一步地，采用涂覆、打印或印刷的方式将氧化镍前驱体溶液设置于载体上。
进一步地，在上述氧化镍膜层表面设置具有吸电子基团的有机分子之前，制备方法还包括对氧化镍膜层进行紫外-臭氧处理，优选紫外-臭氧处理的时间为5～60min，紫外灯照射功率为50～250W。
根据本申请的又一方面，提供了一种上述任一种氧化镍薄膜的制备方法，该制备方法包括：将提前制备好的氧化镍溶液设置于载体上，形成氧化镍膜层；将氧化镍膜层经过紫外-臭氧处理后，在氧化镍膜层表面设置具有吸电子基团的有机分子；以及在氮气或惰性气体气氛中对设置有有机分子的氧化镍膜层进行第二次退火处理，得到氧化镍薄膜。
根据本申请的又一方面，提供了一种薄膜结构的制作方法，薄膜结构包括依次叠置的空穴注入层、第一导电层和基板，第一导电层设置在基板上，该制作方法包括：以设置有第一导电层的基板为载体；在第一导电层上利用上述任一种制备方法制备氧化镍薄膜，氧化镍薄膜为空穴注入层。
根据本申请的又一方面，提供了一种电致发光器件，包括依次叠置的基板、第一导电层、空穴注入层、发光层和第二导电层，该空穴注入层为上述任一种的氧化镍薄膜，氧化镍薄膜的氧化镍膜层接触设置在第一导电层上，具有吸电子基团的有机分子设置在氧化镍膜层的远离第一导电层的表面上。
应用本发明的技术方案，氧化镍薄膜表面设置了具有吸电子基团的有机分子，根据分析推测该有机分子的阴离子与氧化镍膜层的镍形成化学键稳定连接，且由于该具有吸电子基团的有机分子的存在，相当于在氧化镍表面建立起一个反向氧化镍的电场，进而提高了氧化镍薄膜的表面功函数。进而将本申请具有高表面功函数的氧化镍薄膜应用到QLED器件和OLED器件时，使得空穴注入率提高，进而可以避免使用对器件有损害的PEDOT：PSS，从而提高了器件的性能和稳定性。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1为实施例1的ITO/氧化镍薄膜的UPS能谱；
图2为对比例1的ITO/氧化镍薄膜的UPS能谱；
图3为实施例2的ITO/氧化镍薄膜的UPS能谱；
图4为实施例17、34和35的量子点电致发光器件的结构示意图；
图5为实施例17和对比例2的器件的外量子效率(EQE)随工作电压变化曲线图；
图6为实施例17和对比例2的器件的亮度随工作电压变化曲线图；
图7为实施例18的ITO/氧化镍薄膜的UPS能谱；
图8为对比例3的ITO/氧化镍薄膜的UPS能谱；
图9为实施例19的ITO/氧化镍薄膜的UPS能谱；
图10为实施例34和对比例3的器件的亮度随工作电压变化曲线图；
图11为实施例34和对比例3的器件的外量子效率(EQE)随工作电压变化曲线图；
图12为实施例34和对比例4的器件的亮度随工作电压变化曲线图；
图13为实施例34和对比例4的器件的外量子效率(EQE)随工作电压变化曲线图；
图14为实施例35和对比例3的器件的亮度随工作电压变化曲线图；
图15为实施例35和对比例3的器件的外量子效率(EQE)随工作电压变化曲线图；
图16为实施例35和对比例4的器件的亮度随工作电压变化曲线图；以及
图17为实施例35和对比例4的器件的外量子效率(EQE)随工作电压变化曲线图。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。
如背景技术所分析的，现有技术氧化镍导电薄膜的表面功函数较低，导致其不能满足OLED器件以及QLED器件要求，为了解决该问题，在本申请一种典型的实施方式中，提供了一种氧化镍薄膜，该氧化镍薄膜包括氧化镍膜层和具有吸电子基团的有机分子，该有机分子连接地设置在氧化镍膜层表面上。需要说明的是本申请的氧化镍并非特指NiO，即并非特指镍原子：氧原子的摩尔比例为1：1，而可以是各种摩尔比组成的氧化镍。本申请中的氧化镍指的是氧化镍纳米晶体。
本申请所提供的氧化镍薄膜表面设置了具有吸电子基团的有机分子，根据分析推测该有机分子的阴离子与氧化镍膜层的镍形成化学键稳定连接，且由于该具有吸电子基团的有机分子的存在，相当于在氧化镍表面建立起一个反向氧化镍的电场，进而提高了氧化镍薄膜的表面功函数。进而将本申请具有高表面功函数的氧化镍薄膜应用到QLED器件和OLED器件时，使得空穴注入率提高，进而可以避免使用对器件有损害的PEDOT：PSS，从而提高了器件的性能和稳定性。具有吸电子基团的有机分子也可能因为不同的制备工艺使得部分有机分子进入氧化镍膜层内部。
在本申请一种优选的实施例中，上述有机分子具有如下结构式：R-R0-(CH2)n-P，其中：P是羧基、巯基、磷酸基中的一种，且P与氧化镍膜层连接；n是整数且0≤n≤15，优选0≤n≤6，R是吸电子基团且选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，酰胺基的O原子与R0连接，R0为烷基、烯基、二烯基或苯基。进一步优选上述有机分子具有如下结构式：
Figure PCTCN2017091265-appb-000009
其中，R0为C或者苯基，R1、R2和R3各自独立地选自CF3、F、CN、NO2、Cl、Br和I中的任意一种，COOH以COO-与氧化镍膜层连接。或者上述有机分子具有如下结构式(I)：R-R0-(CH2)n-P，其中：P是羧基、巯基、磷酸基中的一种，且P与氧化镍膜层的氧化镍连接；n是整数且0≤n≤15，优选0≤n≤6，R包含至少一个吸电子基团且该吸电子基团选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，酰胺基的O原子与R0连接，R0为烷基、烯基、二烯基或苯基。 进一步优选上述有机分子具有如下结构式：
Figure PCTCN2017091265-appb-000010
其中，R0为C或者苯基，R为R1、R2和R3，R1、R2和R3各自独立地选自CF3、F、CN、NO2、Cl、Br和I中的任意一种，COOH以COO-与氧化镍膜层连接。
上述有机分子还可以具有如下结构式(II)：
Figure PCTCN2017091265-appb-000011
其中，Q为任意基团，R包含至少一个所述吸电子基团且吸电子基团选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，COOH以COO-与所述氧化镍连接。Q包含可化学地与C原子连接的基团。
具体地，结构式(II)可以为下述化学结构：
Figure PCTCN2017091265-appb-000012
Figure PCTCN2017091265-appb-000013
n为大于等于1的整数，优选n为5000～500万，其中CF3为吸电子基团。通过改变上述各个结构式中CF3的位置和数量也可以得到合适的有机分子，比如CF3取代烷基的氢原子；还可以通过改变上述各个结构式中烷基的数量得到合适的有机分子。
当有机分子选自上述物质时，能够提高氧化镍薄膜的功函数，减小空穴注入势垒，提高空穴注入效率。
在本申请另一种典型的实施方式中，提供了一种功能材料，该功能材料包括氧化镍及具有吸电子基团的有机分子，有机分子与氧化镍连接。
本申请所提供的上述功能材料中的氧化镍上连接有具有吸电子基团的有机分子，根据分析推测该有机分子的阴离子(阴离子源自P基团，比如COOH)与氧化镍的镍形成化学键稳定连接，且由于该具有吸电子基团的有机分子的存在，相当于在氧化镍表面建立起一个反向氧化镍的电场，当利用该功能材料制备薄膜时，能够提高氧化镍薄膜的表面功函数。进而将 本申请具有高表面功函数的氧化镍薄膜应用到QLED器件和OLED器件时，使得空穴注入率提高，进而可以避免使用对器件有损害的PEDOT：PSS，从而提高了器件的性能和稳定性。
进一步地，优选上述有机分子具有如下结构式：R-R0-(CH2)n-P，其中：P是羧基、巯基、磷酸基中的一种，且P与氧化镍连接；n是整数且0≤n≤15，优选0≤n≤6，R是吸电子基团且选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，酰胺基的O原子与R0连接，R0为烷基、烯基、二烯基或苯基。更优选上述有机分子具有如下结构式：
Figure PCTCN2017091265-appb-000014
其中，R0为C或者苯基，R1、R2和R3各自独立地选自CF3、F、CN、NO2、Cl、Br和I中的任意一种，COOH以COO-与氧化镍连接。或者优选上述有机分子具有如下结构式(I)：R-R0-(CH2)n-P，其中：P是羧基、巯基、磷酸基中的一种，且P与氧化镍连接；n是整数且0≤n≤15，优选0≤n≤6，R包含至少一个吸电子基团且该吸电子基团选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，酰胺基的O原子与R0连接，R0为烷基、烯基、二烯基或苯基。更优选上述有机分子具有如下结构式：
Figure PCTCN2017091265-appb-000015
其中，R0为C或者苯基，R1、R2和R3各自独立地选自CF3、F、CN、NO2、Cl、Br和I中的任意一种，COOH以COO-与氧化镍连接。
上述有机分子还可以具有如下结构式(II)：
Figure PCTCN2017091265-appb-000016
其中，Q为任意基团，R包含至少一个吸电子基团且所述吸电子基团选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，COOH以COO-与所述氧化镍连接。
具体地，结构式(II)可以为下述化学结构：
化合物(1)
Figure PCTCN2017091265-appb-000017
或者化合物(2)
Figure PCTCN2017091265-appb-000018
或者化合物(3)
Figure PCTCN2017091265-appb-000019
或者
化合物(4)
Figure PCTCN2017091265-appb-000020
n为大于等于1的整数。
氧化镍薄膜中的有机分子可以是满足上述各个结构式的混合物或者单一化合物。
在本申请又一种典型的实施方式中，提供了一种上述的氧化镍薄膜的制备方法，该制备方法包括：将氧化镍前驱体溶液设置于载体上，进行第一次退火，形成氧化镍膜层；在氧化镍膜层表面设置有机分子；以及在氮气或惰性气体气氛中对设置有有机分子的氧化镍膜层进行第二次退火处理，得到氧化镍薄膜。
将氧化镍前驱体溶液进行第一次退火，得到氧化镍膜层；在氧化镍膜层上接着设置一端具有吸电子基团的有机分子，有机分子可以溶解于溶剂(溶剂比如甲醇、乙醇、氯苯、二甲基亚砜、N,N-二甲基甲酰胺、或丙酮或混合物溶剂，根据溶解性选择合适的溶剂)中形成有机分子溶液，有机分子溶液可以以浸泡、旋转涂布、打印、狭缝涂布等方式设置到氧化镍膜层上；并通过第二次退火处理，使该有机分子的阴离子与氧化镍表面的镍反应，最终吸电子基团通过阴离子与镍的共价键的作用固定在氧化镍膜层的表面上，进而得到上述氧化镍薄膜状的功能材料。所得到的薄膜状的功能材料在改变其薄膜状态后仍可保持原有性能。
上述氧化镍前驱体用量的多少决定所形成的氧化镍膜层的厚度；由于有机分子设置在氧化镍膜层表面，因此可以根据氧化镍膜层面积确定所加入的有机分子的量。氧化镍膜层的厚度可以是1nm～1000nm。
上述氧化镍前驱体溶液的主要作用是用于生成氧化镍，因此现有技术中用于制备氧化镍的氧化镍前驱体溶液均可考虑应用至本申请中。优选上述氧化镍前驱体溶液为包括水溶性镍盐与甘氨酸的水溶液，进一步优选水溶性镍盐为硝酸镍，其中硝酸镍与甘氨酸的摩尔比为1：10～1：1。其中，氧化镍前驱体溶液中的硝酸镍的浓度没有特殊要求，优选其浓度为：0.05～0.1mol/L，以制备常规厚度的氧化镍膜层。或者氧化镍前驱体溶液为包括水溶性镍盐与乙醇胺的醇溶液，优选水溶性镍盐为醋酸镍，其中醋酸镍与乙醇胺的摩尔比为1：5～1：0.5。
为了保证氧化镍前驱体充分转化为氧化镍，优选第一次退火处理的温度为130～300℃，处理时间为10～90min。通常退火包括加热保温阶段和降温阶段，但本申请中退火处理的温度是指加热后达到的温度，处理时间是指加热时间。
为了快速地使有机分子较为稳定地结合到氧化镍膜层上，优选上述第二次退火处理的温度为80～180℃，时间为1～60min。如果温度较低，可以适当延长退火时间。
将氧化镍前驱体溶液设置于载体上的方法有多种，比如涂覆、打印、印刷、浸渍等，为了便于实施，优选采用涂覆、打印或印刷的方式将氧化镍前驱体溶液设置于载体上。上述实施方式可适用于大面积基板，且对基板不产生损伤，对其产业化有非常重要的作用，易于实现产业化生产。
在氧化镍膜层表面设置具有吸电子基团的有机分子之前，优选上述制备方法还包括对所述氧化镍膜层进行紫外-臭氧处理，通过对氧化镍膜层的紫外-臭氧处理，一方面在氧化镍膜层表面生成一层羟基自由基，以提供与有机分子键合的连接键，加强其与有机分子的结合力；另一方面对氧化镍膜层进行清洁，提高有机分子与其的结合力。利用紫外-臭氧处理氧化镍膜层的固有性质，在氧化镍膜层表面形成羟基自由基，因此，本领域技术人员可以根据所采用的设备以及对羟基数目的要求选择紫外-臭氧处理的条件，优选，上述紫外-臭氧处理的时间为5～60min，紫外灯照射功率为50～250W。在上述条件下进行紫外臭氧处理，能够在较短的时间内得到理想的处理结果。
在本申请又一种典型的实施方式中，还提供了另一种上述氧化镍薄膜的制备方法，包括：将提前制备好的氧化镍溶液(其制备方法可以为现有技术的方法)设置于载体上，形成氧化镍膜层；将所述氧化镍膜层经过紫外-臭氧处理后，在氧化镍膜层表面设置具有吸电子基团的有机分子；以及在氮气或惰性气体气氛中对设置有所述有机分子的氧化镍膜层进行第二次退火处理，得到所述氧化镍薄膜。与由于提前制备好的氧化镍溶液中的氧化镍具有表面配体(配体可以为C2～C30的脂肪酸根)，为了促进有机分子与镍的化学连接，即除去氧化镍表面配体从而更多地露出镍原子，本领域技术人员可以选择紫外-臭氧处理的条件，优选，上述紫外-臭氧处理的时间为5～60min，紫外灯照射功率为50～250W。在上述条件下进行紫外臭氧处理，能够在较短的时间内得到理想的处理结果。将氧化镍溶液设置于载体上的方法有多种，比如涂覆、打印、印刷、浸渍等，为了便于实施，优选采用涂覆、打印或印刷的方式将氧化镍设置于载体上。为了进一步除掉未结合上去的有机分子，可以清洗第二次退火后的氧化镍薄膜，清洗溶剂只要可以溶解该有机分子即可。
在本申请又一种典型的实施方式中，还提供了一种薄膜结构的制作方法，该薄膜结构包括依次叠置的空穴注入层、第一导电层和基板，第一导电层设置在基板上，该制作方法包括：以设置有第一导电层的基板为载体；在第一导电层上利用上述的制备方法制备氧化镍薄膜，氧化镍薄膜为空穴注入层。
利用设置有第一导电层的基板为载体，进而再利用制备氧化镍薄膜的方法，在载体上制备氧化镍薄膜，从而就可以制备具有第一导电层、基板和氧化镍薄膜的薄膜结构，制备方法简单。该结构可以应用于单光子光源，太阳能电池，电致发光照明及显示设备等。
由于本申请制备氧化镍薄膜的方法条件温和，因此用于上述制作方法的基板材料可以采用现有技术中常用的基板，比如可以为玻璃、聚合物、金属、合金材料、以及前述几种材料形成的复合材料中的一种或多种。同样，用于上述第一导电层的材料可以为现有技术中常用的导电氧化物薄膜层，优选为ITO薄膜。
本申请进一步还提供了一种电致发光器件，包括依次叠置的基板、第一导电层、空穴注入层、发光层和第二导电层，该空穴注入层为上述的氧化镍薄膜，氧化镍薄膜的氧化镍膜层接触设置在第一导电层上，具有吸电子基团的有机分子设置在氧化镍膜层的远离第一导电层的表面上。空穴注入层和发光层之间可以有其他功能层，如空穴传输层、空穴阻挡层。发光层和第二导电层之间可以有其他功能层，如电子阻挡层、电子传输层、电子注入层中的一层或多层。
如前所述，由于本申请的氧化镍薄膜具有较高的表面功函数，因此当将其应用至该电致发光器件中作为空穴注入层时，使得空穴注入了提高，进而可以避免在该电致发光器件中使用对器件有损害的PEDOT：PSS，从而提高了器件的性能和稳定性。
上述电致发光器件可以为OLED器件或者为QLED器件，即上述发光层可以包含量子点材料、有机荧光和有机磷光材料组成的组中的任意一种或几种的组合。
现有技术中的电致发光器件的结构也有多种，以其中一种为例，该电致发光器件包括依次叠置的：基板、第一导电层、氧化镍薄膜(作为空穴注入层)、空穴传输层、空穴阻挡层、发光层、电子阻挡层、电子传输层、电子注入层、第二导电层。
为使本发明的目的、技术方案和优点更加清楚，下面将结合实施例和附图对本发明实施方法进一步详细描述。
实施例17、对比例2采用的量子点原料为同一批次，实施例34、实施例35、对比例3～4采用的量子点原料为组分相同的另一批次。
实施例1
S1：硝酸镍与甘氨酸以3：5的摩尔比溶于水中制备氧化镍前驱体溶液，其中硝酸镍的浓度为0.06mol/L。通过旋涂的方法将氧化镍前驱体涂覆于ITO衬底上(转速：4000rpm)，对氧化镍前驱体溶液在空气中200℃退火60min，得到氧化镍膜层。
S2：将氧化镍膜层经过紫外-臭氧处理20min，其中紫外灯照射功率为200W，在N2气氛的手套箱中，将浓度为3mmol/L的三氟甲基苯甲酸/乙醇溶液旋涂于ITO/氧化镍复合薄膜上(转速：2000rpm)。
S3：在手套箱中，将上述薄膜置于加热面板，120℃退火30min，然后用乙醇将其表面清洗三遍，干燥，获得氧化镍薄膜，即获得经过表面修饰的ITO/氧化镍复合透明导电薄膜。用紫外电子能谱(Ultraviolet photoelectron spectroscopy，简称UPS)测试，测试结果见图1，表面功函数分别5.5eV。
实施例2
具体步骤以及所用材料和仪器同实施例1，不同的是步骤S3中退火温度为140℃。用紫外光电能谱对薄膜进行测试，测试结果见图3，本实施例中ITO/氧化镍表面功函数为5.7eV。
实施例3
具体步骤以及所用材料和仪器同实施例1，不同的是步骤S3中退火温度为180℃，时间为2min。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.7eV。
实施例4
具体步骤以及所用材料和仪器同实施例1，不同的是步骤S3中退火温度为80℃，退火时间为60min。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.6eV。
实施例5
具体步骤以及所用材料和仪器同实施例1，不同的是步骤S3中退火温度为200℃。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.7eV。
实施例6
具体步骤以及所用材料和仪器同实施例1，不同的是步骤S3中退火温度为60℃，退火时间为90min。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.4eV。
实施例7
具体步骤以及所用材料和仪器同实施例1，不同的是步骤S2中所用化合物为对三氟甲基苯乙酸。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.4eV。
实施例8
具体步骤以及所用材料和仪器同实施例1，唯一不同的是步骤S2中所用的化合物是三氟丁酸。处理后用UPS进行测试，本实施例中ITO表面功函数为5.6eV。
实施例9
具体步骤以及所用材料和仪器同实施例1，不同的是步骤S1中退火温度为100℃，退火时间为90min。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.7eV。
实施例10
具体步骤以及所用材料和仪器同实施例1，不同的是步骤S1中退火温度为300℃，退火时间为10min。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.7eV。
实施例11
具体步骤以及所用材料和仪器同实施例1，不同的是步骤S1中退火温度为80℃，退火时间为90min。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.7eV。
实施例12
具体步骤以及所用材料和仪器同实施例1，不同的是步骤S1的氧化镍前驱体溶液中的硝酸镍与甘氨酸以1：10的摩尔比溶于水中制备。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.6eV。
实施例13
具体步骤以及所用材料和仪器同实施例1，不同的是步骤S1的氧化镍前驱体溶液中的硝酸镍与甘氨酸以1：1的摩尔比溶于水中制备。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.7eV。
实施例14
具体步骤以及所用材料和仪器同实施例1，不同的是步骤S1的氧化镍前驱体溶液中的硝酸镍与甘氨酸以1：12的摩尔比溶于水中制备。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.6eV。
实施例15
具体步骤以及所用材料和仪器同实施例1，不同的是步骤S2的紫外-臭氧处理60min，其中紫外灯照射功率为50W。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.6eV。
实施例16
具体步骤以及所用材料和仪器同实施例1，不同的是步骤S2的紫外-臭氧处理5min，其中紫外灯照射功率为250W。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.6eV。
实施例17
一种量子点电致发光器件(QLED)，其结构如图4所示，该QLED器件包括基板10，阳极20、第一功能层30(需要解释的是，图4中30被分成两层，仅仅是为了说明氧化镍膜层表面被具有吸电子的有机分子处理过，并没有实际的分层)，第二功能层40，发光层50、第三功能层60、阴极70。其中，基板是透明玻璃基板，阳极为实施例1的ITO层，第一功能层30为实施例1的氧化镍薄膜，二者即为实施例1的经过表面修饰的ITO/氧化镍复合透明导电薄膜。第二功能层为poly-TPD(4-丁基-N,N-二苯基苯胺均聚物)和PVK(聚乙烯基咔唑)。发光层50为量子点发光材料。第三功能层为ZnO纳米颗粒。Ag作为阴极。
对比例1
具体步骤以及所用材料和仪器同实施例1中步骤S1，然后将氧化镍膜层经过紫外-臭氧处理20min，其中紫外灯照射功率为200W，并未进行其后续步骤S3。用紫外光电能谱对薄膜进行测试，测试结果见图2，其表面功函数为5.0eV。
对比例2
具体步骤以及所用材料和仪器同实施例17，不同之处在于第一功能层不是在ITO表面生长的氧化镍薄膜，而是PEDOT：PSS有机分子层，ITO/PEDOT：PSS有机分子表面功函数为 5.0eV。
采用PHOTO RESEARCH公司生产的PR670光谱光度/色度/辐射度计，在电流密度为2mA/cm2的条件下，检测实施例17和对比例2量子点电致发光器件的EQE(外量子效率)随工作电压变化以及亮度随工作电压变化情况，检测结果见图5和图6。
由图1至3的对比可以看出，采用本申请的方法制备的氧化镍薄膜的表面功函数得到了提高，进而使得QLED器件的EQE和亮度提高(与图5和6显示结果一致)。
实施例18
S1：硝酸镍与甘氨酸以3：5的摩尔比溶于水中制备氧化镍前驱体溶液，其中硝酸镍的浓度为0.06mol/L。通过旋涂的方法将氧化镍前驱体涂覆于ITO基板上(转速：4000rpm)，对氧化镍前驱体溶液在空气中200℃退火60min，得到氧化镍膜层。
S2：将浓度为3mmol/L的三氟甲基苯甲酸/乙醇溶液旋涂于ITO/氧化镍复合薄膜上(转速：2000rpm)。
S3：在手套箱中，将上述薄膜置于加热面板，120℃退火30min，然后用乙醇将其表面清洗三遍，干燥，获得氧化镍薄膜，即获得经过表面修饰的ITO/氧化镍复合透明导电薄膜。用紫外光电子能谱(Ultraviolet photoelectron spectroscopy，简称UPS)测试，测试结果见图7，表面功函数为5.4eV。
实施例19
具体步骤以及所用材料和仪器同实施例18，不同的是步骤S3中退火温度为140℃。用紫外光电子能谱对薄膜进行测试，测试结果见图9，本实施例中ITO/氧化镍表面功函数为5.5eV。
实施例20
具体步骤以及所用材料和仪器同实施例18，不同的是步骤S3中退火温度为180℃，时间为2min。用紫外光电子能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.3eV。
实施例21
具体步骤以及所用材料和仪器同实施例18，不同的是步骤S3中退火温度为80℃，退火时间为60min。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.4eV。
实施例22
具体步骤以及所用材料和仪器同实施例18，不同的是步骤S3中退火温度为200℃。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.3eV。
实施例23
具体步骤以及所用材料和仪器同实施例18，不同的是步骤S3中退火温度为60℃，退火时间为90min。用紫外光电能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.4eV。
实施例24
具体步骤以及所用材料和仪器同实施例18，不同的是步骤S2中所用化合物为对三氟甲基苯乙酸。用紫外光电子能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.4eV。
实施例25
具体步骤以及所用材料和仪器同实施例18，唯一不同的是步骤S2中所用的化合物是三氟丁酸。处理后用UPS进行测试，本实施例中ITO/氧化镍表面功函数为5.2eV。
实施例26
具体步骤以及所用材料和仪器同实施例18，不同的是步骤S1中退火温度为100℃，退火时间为90min。用紫外光电子能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.4eV。
实施例27
具体步骤以及所用材料和仪器同实施例18，不同的是步骤S1中退火温度为300℃，退火时间为10min。用紫外光电子能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.4eV。
实施例28
具体步骤以及所用材料和仪器同实施例18，不同的是步骤S1中退火温度为80℃，退火时间为90min。用紫外光电子能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.3eV。
实施例29
具体步骤以及所用材料和仪器同实施例18，不同的是步骤S1的氧化镍前驱体溶液中的硝酸镍与甘氨酸以1：10的摩尔比溶于水中制备。用紫外光电子能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.4eV。
实施例30
具体步骤以及所用材料和仪器同实施例18，不同的是步骤S1的氧化镍前驱体溶液中的硝酸镍与甘氨酸以1：1的摩尔比溶于水中制备。用紫外光电子能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.3eV。
实施例31
具体步骤以及所用材料和仪器同实施例18，不同的是步骤S1的氧化镍前驱体溶液中的硝酸镍与甘氨酸以1：12的摩尔比溶于水中制备。用紫外光电子能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.4eV。
实施例32
S1：醋酸镍与乙醇胺的乙醇溶液(也可以是乙醇胺的甲氧基乙醇溶液)以3：5的摩尔比溶于水中制备氧化镍前驱体溶液，其中醋酸镍的浓度为0.06mol/L。通过旋涂的方法将氧化镍前驱体涂覆于ITO衬底基板上(转速：4000rpm)，对氧化镍前驱体溶液在空气中200℃退火60min，得到氧化镍膜层。
S2：将浓度为3mmol/L的三氟甲基苯甲酸/乙醇溶液旋涂于ITO/氧化镍复合薄膜上(转速：2000rpm)。
S3：在手套箱中，将上述薄膜置于加热面板，120℃退火30min，然后用乙醇将其表面清洗三遍，干燥，获得氧化镍薄膜，即获得经过表面修饰的ITO/氧化镍复合透明导电薄膜。用紫外光电子能谱测试，本实施例中ITO/氧化镍表面功函数为5.4eV。
实施例33
1)称取1mmol硬脂酸镍、0.2mmol保护配体硬脂酸锂(摩尔比为5:1)、6mmol的十八醇和10ml的1-十八烯置于50ml反应烧瓶中，在惰性保护气氛下，磁力搅拌升温至50℃，然后对反应体系抽真空温30min。
2)在惰性保护气氛下把温度升高至180℃，保温200min，冷却反应溶液至室温，再经离心提纯，得到胶体NiO纳米晶。
3)将上述胶体NiO纳米晶溶解于八烷中形成氧化镍溶液。
将上述制备好的100g/L的氧化镍溶液涂覆于ITO基板上，步骤S2的紫外-臭氧处理60min，其中紫外灯照射功率为50W。将上述薄膜置于加热面板，150℃退火30min，然后用乙醇将其表面清洗三遍，干燥，获得氧化镍薄膜，即获得经过表面修饰的ITO/氧化镍复合透明导电薄膜。用紫外光电子能谱对薄膜进行测试，本实施例中ITO/氧化镍表面功函数为5.8eV。
实施例34
一种量子点电致发光器件(QLED)，其结构如图4所示，该QLED器件包括基板10， 第一导电层20、第一功能层30，第二功能层40，发光层50、第三功能层60、第二导电层70。其中，基板是透明玻璃基板，第一导电层为实施例18的ITO层，第一功能层30为实施例18的氧化镍薄膜，二者即为实施例34的经过表面修饰的ITO/氧化镍复合透明导电薄膜。第二功能层为poly-TPD(4-丁基-N,N-二苯基苯胺均聚物)和PVK(聚乙烯基咔唑)。发光层50为量子点发光材料。第三功能层为Zn90Mg10O纳米颗粒。Ag作为第二导电层。
实施例35
一种量子点电致发光器件(QLED)，其结构如图4所示，该QLED器件包括基板10，第一导电20、第一功能层30，第二功能层40，发光层50、第三功能层60、第二导电层70。其中，基板是透明玻璃基板，第一导电层为实施例18的ITO层，第一功能层30为实施例33的氧化镍薄膜，二者即为实施例35的经过表面修饰的ITO/氧化镍复合透明导电薄膜。第二功能层为poly-TPD(4-丁基-N,N-二苯基苯胺均聚物)和PVK(聚乙烯基咔唑)。发光层50为量子点发光材料。第三功能层为Zn90Mg10O纳米颗粒。Ag作为第二导电层。
实施例36
S1：醋酸镍与乙醇胺的乙醇溶液(也可以是乙醇胺的甲氧基乙醇溶液)以3：5的摩尔比溶于水中制备氧化镍前驱体溶液，其中醋酸镍的浓度为0.06mol/L。通过旋涂的方法将氧化镍前驱体涂覆于ITO衬底基板上(转速：4000rpm)，对氧化镍前驱体溶液在空气中200℃退火60min，得到氧化镍膜层。
S2：将浓度为3mmol/L的前述化合物(1)的甲苯溶液旋涂于ITO/氧化镍复合薄膜上(转速：2000rpm)，其中化合物(1)中的n＝500。
S3：在手套箱中，将上述薄膜置于加热面板，120℃退火30min，然后用甲苯将其表面清洗三遍，干燥，获得氧化镍薄膜，即获得经过表面修饰的ITO/氧化镍复合透明导电薄膜。用紫外光电子能谱测试，本实施例中ITO/氧化镍表面功函数为5.6eV。
对比例3
具体步骤以及所用材料和仪器同实施例18中步骤S1，并未进行其后续步骤S2，S3。用紫外光电子能谱对薄膜进行测试，测试结果见图8，其表面功函数为4.8eV。一种量子点电致发光器件(QLED)，其结构如图4所示，该QLED器件包括基板10，第一导电层20、第一功能层30，第二功能层40，发光层50、第三功能层60、第二导电层70。其中，基板是透明玻璃基板，第一导电层为实施例18的ITO层，第一功能层30为对比例3上述的氧化镍薄膜，二者即为对比例3的ITO/氧化镍复合透明导电薄膜。第二功能层为poly-TPD(4-丁基-N,N-二苯基苯胺均聚物)和PVK(聚乙烯基咔唑)。发光层50为量子点发光材料。第三功能层为Zn90Mg10O纳米颗粒。Ag作为第二导电层。
对比例4
具体步骤以及所用材料和仪器同实施例34，不同之处在于第一功能层不是在ITO表面生长的氧化镍薄膜，而是PEDOT：PSS有机分子层，ITO/PEDOT：PSS有机分子表面功函数为5.0eV。
对比例5
具体步骤以及所用材料和仪器同实施例32中步骤S1，并未进行其后续步骤S2，S3。用紫外光电子能谱对薄膜进行测试，其表面功函数为4.9eV。
采用PHOTO RESEARCH公司生产的PR670光谱光度/色度/辐射度计，在电流密度为2mA/cm2的条件下，检测实施例34、实施例35和对比例3、对比例4量子点电致发光器件的EQE(外量子效率)随工作电压变化以及亮度随工作电压变化情况，检测结果见图10～图17。
由图7至9的对比可以看出，采用本申请的方法制备的氧化镍薄膜的表面功函数得到了提高，进而使得QLED器件的EQE和亮度提高(与图10至图17显示结果一致)。
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：
本申请所提供的氧化镍薄膜表面设置了一层具有吸电子基团的有机分子，该有机分子的阴离子与氧化镍薄膜表面的镍原子形成稳定连接，且由于该具有吸电子基团的有机分子的存在，相当于在氧化镍表面建立起一个反向氧化镍的电场，进而提高了氧化镍薄膜的表面功函数。进而将本申请具有高表面功函数的氧化镍薄膜应用到QLED器件和OLED器件时，使得空穴注入率提高，进而可以避免使用对器件有损害的PEDOT：PSS，从而提高了器件的性能和稳定性。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (21)

  1. 一种氧化镍薄膜，其特征在于，所述氧化镍薄膜包括：
    氧化镍膜层；
    具有吸电子基团的有机分子，所述有机分子连接设置在所述氧化镍膜层表面上。
  2. 根据权利要求1所述的氧化镍薄膜，其特征在于，所述有机分子具有如下结构式(I)：
    R-R0-(CH2)n-P，
    其中：P是羧基、巯基、磷酸基、硅氧基、胺基中的一种，且P与所述氧化镍膜层连接；n是整数且0≤n≤15，优选0≤n≤6，R是所述吸电子基团且选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，酰胺基的O原子与R0连接，R0为烷基、烯基、二烯基或苯基。
  3. 根据权利要求1所述的氧化镍薄膜，其特征在于，所述有机分子具有如下结构式(I)：
    R-R0-(CH2)n-P，
    其中：P是羧基、巯基、磷酸基、硅氧基、胺基中的一种，且P与所述氧化镍膜层的氧化镍连接；
    n是整数且0≤n≤15，优选0≤n≤6，R包含至少一个所述吸电子基团且所述吸电子基团选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，酰胺基的O原子与R0连接，R0为烷基、烯基、二烯基或苯基。
  4. 根据权利要求2或3所述的氧化镍薄膜，其特征在于，所述有机分子具有如下结构式：
    Figure PCTCN2017091265-appb-100001
    其中，R0为C或者苯基，R1、R2和R3各自独立地选自CF3、F、CN、NO2、Cl、Br和I中的任意一种，所述COOH以COO-与所述氧化镍膜层连接。
  5. 根据权利要求1所述的氧化镍薄膜，其特征在于，所述有机分子具有如下结构式(II)：
    Figure PCTCN2017091265-appb-100002
    其中，Q为任意基团，R包含至少一个所述吸电子基团且所 述吸电子基团选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基。
  6. 根据权利要求5所述的氧化镍薄膜，其特征在于，所述有机分子具有如下结构式：
    Figure PCTCN2017091265-appb-100003
    Figure PCTCN2017091265-appb-100004
    n为大于等于1的整数。
  7. 一种功能材料，其特征在于，包括氧化镍及具有吸电子基团的有机分子，所述有机分子与所述氧化镍连接。
  8. 根据权利要求7所述的功能材料，其特征在于，所述有机分子具有如下结构式(I)：
    R-R0-(CH2)n-P，
    其中：P是羧基、巯基、磷酸基中的一种，且P与所述氧化镍连接；n是整数且0≤n≤15，优选0≤n≤6，R是吸电子基团且选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，酰胺基的O原子与R0连接，R0为烷基、烯基、二烯基或苯基。
  9. 根据权利要求7所述的功能材料，其特征在于，所述有机分子具有如下结构式(I)：
    R-R0-(CH2)n-P，
    其中：P是羧基、巯基、磷酸基中的一种，且P与所述氧化镍连接；
    n是整数且0≤n≤15，优选0≤n≤6，R包含至少一个所述吸电子基团且选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，酰胺基的O原子与R0连接，R0为烷基、烯基、二烯基或苯基。
  10. 根据权利要求8或9所述的功能材料，其特征在于，所述有机分子具有如下结构式：
    其中，R0为C或者苯基，R1、R2和R3各自独立地选自CF3、F、CN、NO2、Cl、Br和I中的任意一种，所述COOH以COO-与所述氧化镍连接。
  11. 根据权利要求7所述的功能材料，其特征在于，所述有机分子具有如下结构式(II)：
    Figure PCTCN2017091265-appb-100006
    其中，Q为任意基团，R包含至少一个所述吸电子基团且所述吸电子基团选自下列基团的一种或多种：卤素、全氟烷基、羰基、羧基、氰基、铵基、硝基、亚硫酰基、磺酰基、酰氨基、吡啶鎓、磷鎓、吡啶基、噻唑基、噁二唑基和三唑基，其中，COOH以COO-与所述氧化镍连接。
  12. 根据权利要求11所述的功能材料，其特征在于，所述有机分子具有如下结构式：
    Figure PCTCN2017091265-appb-100007
    Figure PCTCN2017091265-appb-100008
    n为大于等于1的整数。
  13. 一种权利要求1至6中任一项所述的氧化镍薄膜的制备方法，其特征在于，所述制备方法包括：
    将氧化镍前驱体溶液设置于载体上，并对所述氧化镍前驱体溶液进行第一次退火处理，形成氧化镍膜层；
    在氧化镍膜层表面设置具有吸电子基团的有机分子；以及
    在氮气或惰性气体气氛中对设置有所述有机分子的氧化镍膜层进行第二次退火处理，得到所述氧化镍薄膜。
  14. 根据权利要求13所述的制备方法，其特征在于，所述氧化镍前驱体溶液为包括水溶性镍盐与甘氨酸的水溶液，优选所述水溶性镍盐为硝酸镍，其中所述硝酸镍与甘氨酸的摩尔比为1：10～1：1；或者所述氧化镍前驱体溶液为包括水溶性镍盐与乙醇胺的醇溶液，优选所述水溶性镍盐为醋酸镍。
  15. 根据权利要求13所述的制备方法，其特征在于，所述第一次退火处理的温度为130～300℃，处理时间为10～90min。
  16. 根据权利要求13所述的制备方法，其特征在于，所述第二次退火处理的温度为80～180℃，时间为1～60min。
  17. 根据权利要求13所述的制备方法，其特征在于，采用涂覆、打印或印刷的方式将所述氧化镍前驱体溶液设置于所述载体上。
  18. 根据权利要求13所述的制备方法，其特征在于，在氧化镍膜层表面设置具有吸电子基团的有机分子之前，所述制备方法还包括对所述氧化镍膜层进行紫外-臭氧处理，优选所述紫外-臭氧处理的时间为5～60min，紫外灯照射功率为50～250W。
  19. 一种权利要求1至6中任一项所述的氧化镍薄膜的制备方法，其特征在于，所述制备方法包括：
    将提前制备好的氧化镍溶液设置于载体上，形成氧化镍膜层；
    将所述氧化镍膜层经过紫外-臭氧处理后，在氧化镍膜层表面设置具有吸电子基团的有机分子；以及
    在氮气或惰性气体气氛中对设置有所述有机分子的氧化镍膜层进行第二次退火处理，得到所述氧化镍薄膜。
  20. 一种薄膜结构的制作方法，所述薄膜结构包括依次叠置的空穴注入层、第一导电层和基板，所述第一导电层设置在所述基板上，其特征在于，所述制作方法包括：
    以设置有所述第一导电层的所述基板为载体；
    在所述第一导电层上利用权利要求13至19中任一项所述的制备方法制备氧化镍薄膜，所述氧化镍薄膜为所述空穴注入层。
  21. 一种电致发光器件，包括依次叠置的基板、第一导电层、空穴注入层、发光层和第二导电层，其特征在于，所述空穴注入层为权利要求1至6中任一项所述的氧化镍薄膜，所述氧化镍薄膜的氧化镍膜层接触设置在所述第一导电层上，所述具有吸电子基团的有机分子设置在所述氧化镍膜层的远离所述第一导电层的表面上。
PCT/CN2017/091265 2016-07-01 2017-06-30 氧化镍薄膜及其制备方法、功能材料、薄膜结构的制作方法及电致发光器件 WO2018001372A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020197003406A KR20190028460A (ko) 2016-07-01 2017-06-30 산화니켈 박막 및 그 제조방법, 기능재료, 박막구조의 제조방법 및 전기발광소자
EP17819368.6A EP3480865A4 (en) 2016-07-01 2017-06-30 NICKEL OXIDE FILM AND ITS PREPARATION METHOD, FUNCTIONAL MATERIAL, MANUFACTURING METHOD OF FILM STRUCTURE, AND LIGHT EMITTING DEVICE
US16/313,900 US20210234100A1 (en) 2016-07-01 2017-06-30 Nickel oxide film and preparation method thereof
JP2018569158A JP2019522367A (ja) 2016-07-01 2017-06-30 酸化ニッケル薄膜及びその製造方法、機能性材料、薄膜構造体の作製方法およびエレクトロルミネセンス素子

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610525274.1A CN107565033B (zh) 2016-07-01 2016-07-01 氧化镍薄膜及其制备方法、功能材料、薄膜结构的制作方法及电致发光器件
CN201610525274.1 2016-07-01

Publications (1)

Publication Number Publication Date
WO2018001372A1 true WO2018001372A1 (zh) 2018-01-04

Family

ID=60785332

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/091265 WO2018001372A1 (zh) 2016-07-01 2017-06-30 氧化镍薄膜及其制备方法、功能材料、薄膜结构的制作方法及电致发光器件

Country Status (6)

Country Link
US (1) US20210234100A1 (zh)
EP (1) EP3480865A4 (zh)
JP (1) JP2019522367A (zh)
KR (1) KR20190028460A (zh)
CN (1) CN107565033B (zh)
WO (1) WO2018001372A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022507894A (ja) * 2018-11-21 2022-01-18 ハント ペロヴスカイト テクノロジーズ， エル．エル．シー． 酸化ニッケルゾルゲルインク

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110635053B (zh) * 2018-06-21 2022-06-17 上海和辉光电股份有限公司 p型掺杂材料、包含其的空穴注入材料、空穴注入层和OLED显示面板
CN110970534A (zh) * 2018-09-29 2020-04-07 Tcl集团股份有限公司 一种氧化镍薄膜及其制备方法、量子点发光二极管
CN111384258B (zh) * 2018-12-28 2021-11-19 Tcl科技集团股份有限公司 量子点发光二极管及其制备方法
CN111725408A (zh) * 2019-03-20 2020-09-29 Tcl集团股份有限公司 量子点发光二极管及其制备方法和复合材料
CN111509131B (zh) * 2019-04-28 2022-10-25 广东聚华印刷显示技术有限公司 发光器件及其制备方法和显示装置
ES2800224B2 (es) * 2019-06-19 2021-05-21 Univ Valencia Lamina catalitica de oxido de niquel, procedimiento para su obtencion y sus usos
KR20210034953A (ko) 2019-09-23 2021-03-31 삼성전자주식회사 발광소자, 발광소자의 제조 방법과 표시 장치
WO2021210096A1 (ja) * 2020-04-15 2021-10-21 シャープ株式会社 発光素子
WO2023062840A1 (ja) * 2021-10-15 2023-04-20 シャープディスプレイテクノロジー株式会社 発光素子

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103840047A (zh) * 2014-02-20 2014-06-04 浙江大学 一种以胶体NiO纳米晶薄膜为空穴传输层的光电器件及其制备方法
WO2014088691A1 (en) * 2012-12-03 2014-06-12 Advanced Technology Materials Inc. IN-SITU OXIDIZED NiO AS ELECTRODE SURFACE FOR HIGH k MIM DEVICE

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19805434C2 (de) * 1998-02-11 2000-02-03 Wella Ag Haarbehandlungsmittel mit fluorierten Säuren und Polymeren

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014088691A1 (en) * 2012-12-03 2014-06-12 Advanced Technology Materials Inc. IN-SITU OXIDIZED NiO AS ELECTRODE SURFACE FOR HIGH k MIM DEVICE
CN103840047A (zh) * 2014-02-20 2014-06-04 浙江大学 一种以胶体NiO纳米晶薄膜为空穴传输层的光电器件及其制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SAI, BAI ET AL.: "Low_Temperature Combustion-Synthesized Nickel Oxide Thin Films as Hole-Transport Interlayers for Solution-Processed Optoelectronic Devices", ADVANCED ENERGY MATERIALS, vol. 4, no. 6, 19 November 2013 (2013-11-19), pages 1 - 6, XP055450612 *
See also references of EP3480865A4 *
SONAVANE, A.C. ET AL.: "Simple and Rapid Synthesis of NiO/PPy Thin Films with Improved Electrochromic Performance", ELECTROCHIMICA ACTA, vol. 55, 2 December 2009 (2009-12-02), pages 2344 - 2351, XP026896940 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022507894A (ja) * 2018-11-21 2022-01-18 ハント ペロヴスカイト テクノロジーズ， エル．エル．シー． 酸化ニッケルゾルゲルインク
JP7420806B2 (ja) 2018-11-21 2024-01-23 ハント ペロヴスカイト テクノロジーズ， エル．エル．シー． 酸化ニッケルゾルゲルインク

Also Published As

Publication number Publication date
JP2019522367A (ja) 2019-08-08
CN107565033A (zh) 2018-01-09
EP3480865A1 (en) 2019-05-08
CN107565033B (zh) 2021-02-26
KR20190028460A (ko) 2019-03-18
US20210234100A1 (en) 2021-07-29
EP3480865A4 (en) 2020-02-26

Similar Documents

Publication Publication Date Title
WO2018001372A1 (zh) 氧化镍薄膜及其制备方法、功能材料、薄膜结构的制作方法及电致发光器件
US11245076B2 (en) Perovskite optoelectronic device, preparation method therefor and perovskite material
Ahmad et al. Recent progress in cathode interlayer materials for non‐fullerene organic solar cells
KR101607478B1 (ko) 핵-껍질 구조의 나노입자를 이용한 역구조 유기태양전지 소자와 그 제조방법
Lee et al. Low-cost and efficient perovskite solar cells using a surfactant-modified polyaniline: poly (styrenesulfonate) hole transport material
CN110718637B (zh) 一种量子点发光二极管及其制备方法
Gu et al. Oriented perovskite crystal towards efficient charge transport in FASnI3 perovskite solar cells
Yang et al. Highest‐Efficiency Flexible Perovskite Solar Module by Interface Engineering for Efficient Charge‐Transfer
Lian et al. Inverted perovskite solar cells based on small molecular hole transport material C8‐dioctylbenzothienobenzothiophene
Lan et al. Surface Passivation with Diaminopropane Dihydroiodide for p‐i‐n Perovskite Solar Cells with Over 25% Efficiency
Khan et al. Organic cation–polystyrene sulfonate polyelectrolytes as hole transporting interfacial layers in perovskite solar cells
KR20160020121A (ko) 페로브스카이트 태양전지 및 그 제조방법
Ali et al. Control of aggregation and dissolution of small molecule hole transport layers via a doping strategy for highly efficient perovskite solar cells
KR101578875B1 (ko) 자기조직된 유전체를 포함하는 태양전지 및 그의 제조방법
Muhammad et al. Gaining insight into the underlayer treatment for in situ fabrication of efficient perovskite nanocrystal-based light-emitting diodes
Li et al. Effective interface treatment by zirconium acetylacetonate for inverted methylammonium-rich perovskite solar cells
CN109360898B (zh) 一种同步优化有机聚合物激光性质和电致发光器件载流子注入的方法
CN111029485A (zh) 一种聚合物修饰的石墨烯薄膜及其制备方法与应用
CN114203941A (zh) 薄膜的制备方法和发光二极管
JP2010087104A (ja) 光電変換素子、その製造方法及び太陽電池
KR101479028B1 (ko) 극성용매로 계면처리된 전하선택적 계면전송층 및 이를 이용한 유기전자 소자
KR102258124B1 (ko) 광활성층의 제조방법, 이에 의해 제조된 광활성층을 포함하는 소자
KR102657093B1 (ko) 플라즈마 ald를 이용한 전자수송층을 통한 박막 계면제어 방법
Rostirolla et al. Influence of TiO 2 nanoparticles on the optical and structural properties of PPV thin films converted at low temperatures.
KR102202046B1 (ko) 플렉서블 유기 태양전지 및 이의 제조 방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17819368

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018569158

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2017819368

Country of ref document: EP

Effective date: 20190201

Ref document number: 20197003406

Country of ref document: KR

Kind code of ref document: A