WO2024041462A1 - 纳米晶复合物及其制备方法和应用 - Google Patents

纳米晶复合物及其制备方法和应用 Download PDF

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WO2024041462A1
WO2024041462A1 PCT/CN2023/113820 CN2023113820W WO2024041462A1 WO 2024041462 A1 WO2024041462 A1 WO 2024041462A1 CN 2023113820 W CN2023113820 W CN 2023113820W WO 2024041462 A1 WO2024041462 A1 WO 2024041462A1
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group
substituted
unsubstituted
nanocrystalline
formula
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French (fr)
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李哲
高远
丁仙予
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华为技术有限公司
纳晶科技股份有限公司
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    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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    • C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
    • C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
    • C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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    • 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
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    • H10K50/14—Carrier transporting layers
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    • H10K50/14—Carrier transporting layers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds

Definitions

  • the embodiments of the present application relate to the technical field of nanocrystalline film preparation, and in particular to a nanocrystalline composite and its preparation method and application.
  • AR Augmented Reality, augmented reality
  • VR Virtual Reality, virtual reality
  • Quantum dots are a new type of display material that has the characteristics of high luminous efficiency and narrow peak width, and can achieve low power consumption, high collimation light emission, and small volume requirements.
  • preparing quantum dot materials into ultra-high-resolution display devices requires fine patterning of the quantum dot (QD) layer of a quantum dot light-emitting device (QLED) to obtain a pixel array (as shown in Figure 1).
  • QD quantum dot
  • QLED quantum dot light-emitting device
  • the industry's main methods for finely patterning the quantum dot layer include: (1) Transfer method, see Figure 2. The transfer method uses a patterned template to stick the quantum dot layer formed on the substrate A according to the target pattern. Go and transfer to substrate B to obtain a patterned quantum dot layer.
  • Photoresist etching method see Figure 3, photoresist etching The method is to coat a layer of photoresist on the quantum dot layer, and then obtain a patterned quantum dot layer through exposure, development, and etching. This method has many process steps, and the developer and etching solution have a negative impact on the quantum dot layer and Functional layers (such as hole transport layer, hole injection layer, electron transport layer) have influence. In order to obtain high-quality patterned quantum dot layers more conveniently, the industry has begun to try to directly synthesize quantum dot materials with patterning functions. See Figure 4. Quantum dot materials with patterning functions can be directly exposed and exposed to the quantum dot layer.
  • the patterned quantum dot layer is obtained in two steps of solvent development.
  • some of the currently developed quantum dot materials with patterning functions do not have high photosensitivity and require long exposure times and high exposure doses; some have too high thermal cross-linking activity, and cross-linking will occur under heating. , causing the quantum dot layer to easily undergo partial cross-linking during the annealing step before exposure, causing the quantum dot layer in the non-exposed area to be unable to be completely developed and eluted, resulting in the remaining quantum dot layer in the non-exposed area.
  • embodiments of the present application provide a nanocrystal composite that has higher photo-crosslinking activity and higher thermal stability (that is, lower thermal cross-linking activity).
  • the nanocrystal composite The composites can be used to prepare patterned films.
  • the first aspect of the embodiments of the present application provides a nanocrystalline composite.
  • the nanocrystalline composite includes nanocrystalline particles and a ligand coordinated on the surface of the nanocrystalline particle.
  • the ligand includes a compound having the formula (I ) and/or a photosensitive ligand with a structure shown in formula (II),
  • the X is a coordination group that coordinately binds to the nanocrystal particles
  • the Y is a connecting group
  • the other is a group containing a carbon-carbon double bond
  • the R and R' are independently a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or One of unsubstituted alkylcarbonyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted aryloxy;
  • the X is a coordination group that coordinately binds to the nanocrystal particles
  • the Y and Y' are connecting groups
  • the R, R' and R" are independently hydrogen atoms. , halogen atom, nitro, hydroxyl, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aromatic group
  • halogen atom nitro, hydroxyl, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aromatic group
  • n 1, 2 or 3.
  • photosensitive ligands with structures shown in formula (I) and/or formula (II), which have higher photo-crosslinking activity and lower thermal cross-linking activity are obtained by coordinating and combining on the surface of nanocrystalline particles.
  • Nanocrystalline composites with high light-sensitive properties and high thermal stability were developed.
  • the nanocrystalline composite has a patterning function. When the nanocrystalline composite is used to prepare a patterned nanocrystalline film, patterning can be achieved directly through exposure and solvent development. During the patterning process, the nanocrystalline composite can be formed in a smaller size. Photo-crosslinking can be achieved under the exposure dose and short exposure time.
  • cross-linking between nanocrystalline composites is achieved through photosensitive ligands, and the process of achieving photo-crosslinking does not require the use of additional photoinitiators; and the nanocrystalline composite will not undergo thermal cross-linking when undergoing a heating annealing process, thus It can avoid the problem of incomplete elution of non-exposed areas during the development process, improve the reliability of the patterning process, and help achieve refined preparation of patterns.
  • the ligands 102 on the surface of the nanocrystalline particles 101 may include one or more photosensitive ligands having the structure shown in formula (I); in some embodiments of the present application, the ligands 102 on the surface of the nanocrystalline particles 101
  • the ligand 102 may include one or more photosensitive ligands having the structure shown in formula (II); in some embodiments of the present application, the ligand 102 on the surface of the nanocrystal particle 101 may include one or more photosensitive ligands having the structure shown in formula (II).
  • the ligands 102 on the surface of the nanocrystal particles 101 may also include ligands with other structures or other functions.
  • the coordination group includes any one of a carboxyl group, an amino group, a phosphate group, a phospholipid group, and a sulfhydryl group.
  • the connecting group Y includes a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylene alkyl group, a substituted or unsubstituted alkylene group Aryl, substituted or unsubstituted alkyleneoxy, substituted or unsubstituted aryleneoxy, substituted or unsubstituted alkylenearyloxy, substituted or unsubstituted arylenealkoxy, carbonyl-containing One or more of groups, groups containing ester groups and/or ether oxygen bonds, and groups containing imine groups.
  • the number of carbon atoms of the connecting group Y is 1-30.
  • the connecting group Y has a suitable number of carbon atoms and can better balance the dispersion of quantum dots and the conductivity of the quantum dot layer.
  • the connecting group Y' includes an oxygen atom, a sulfur atom, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, an ester group-containing group, an amide bond-containing group.
  • the number of carbon atoms of the connecting group Y' is 0-30.
  • the substituted or unsubstituted alkyl group is a substituted or unsubstituted C1-C20 alkyl group
  • the substituted or unsubstituted alkoxy group is a substituted Or unsubstituted C1-C20 alkoxy
  • the substituted or unsubstituted alkylcarbonyl is a substituted or unsubstituted C1-C20 alkylcarbonyl
  • the substituted or unsubstituted cycloalkyl is substituted or unsubstituted C3-C20 cycloalkyl group
  • the substituted or unsubstituted aryl group is a substituted or unsubstituted C6-C20 aryl group
  • the substituted or unsubstituted aryloxy group is a substituted or unsubstituted C6-C20 aryloxy group.
  • the photosensitive ligand having the structure represented by formula (I) includes any compound represented by formula (I-1) to formula (I-14):
  • m is an integer greater than or equal to 0.
  • the photosensitive ligand having the structure represented by formula (II) includes any compound represented by formula (II-1) to formula (II-12):
  • m is an integer greater than or equal to 0.
  • the nanocrystal particles include II-VI compounds, IV-VI compounds, III-V compounds, III-VI compounds, VIB-VIA compounds, VIII-VI compounds, I- One or more of Group VI compounds, Group I elements, Group IV elements, Groups I-IV-VII compounds, and perovskite compounds.
  • the particle size of the nanocrystalline particles is 5 nm-20 nm. Suitable nanocrystal particle size is conducive to obtaining better luminescence properties.
  • the total mass of the ligands on the surface of the nanocrystalline particles is 1%-30% of the mass of the nanocrystalline particles.
  • a suitable coordination amount of photosensitive ligands is conducive to making the nanocrystalline composite have higher photosensitivity properties and higher thermal stability, and at the same time, it can better exert the performance of the nanocrystalline particles themselves.
  • the second aspect of the embodiments of the present application provides a method for preparing the nanocrystalline composite described in the first aspect, including:
  • nanocrystalline particles with the first ligand coordinated on the surface are dispersed in a solvent, and then a photosensitive ligand having a structure shown in formula (I) and/or formula (II) is added, and after stirring and reaction, the ligand-exchanged solution is obtained. Nanocrystalline particles are used to obtain the nanocrystalline composite.
  • the first ligand includes a saturated or unsaturated aliphatic carboxylic acid ligand.
  • the solvent includes one or more of chloroform, chlorobenzene, and ethyl benzoate.
  • the preparation method of the nanocrystalline composite provided in the embodiments of the present application is simple and easy to achieve quantitative production.
  • the third aspect of the embodiments of this application provides a nanocrystal composition, which includes the nanocrystal composite described in the first aspect of the embodiments of this application and a solvent.
  • the mass concentration of the nanocrystal complex is 1 mg/mL-100 mg/mL.
  • a suitable concentration of the nanocrystalline composite can make the nanocrystalline film prepared by using the nanocrystalline composition have better comprehensive properties.
  • the solvent includes one or more of chloroform, chlorobenzene, and ethyl benzoate.
  • the fourth aspect of the embodiments of the present application provides a method for preparing a patterned film, including:
  • a solution containing the nanocrystalline composite described in the first aspect of the embodiments of the present application or the nanocrystalline composition described in the third aspect of the embodiments of the present application is provided on the substrate, and a mask is used for exposure and development.
  • the nanocrystalline composition in the exposed area The crystalline composite is photo-cross-linked and attached to the substrate, and the nanocrystalline composite in unexposed areas is removed by development to form a patterned film.
  • ultraviolet light is used for the exposure, and the light intensity is 0.001mW/cm 2 -1000mW/cm 2 .
  • the exposure time is 0.1 seconds to 600 seconds.
  • the development is solvent development, and the development uses an organic solvent that can elute the nanocrystal composite.
  • the preparation method of the patterned film in the embodiment of the present application can achieve a good cross-linking effect through a short exposure time, and can only use solvent development.
  • the process is relatively simple, which can not only save energy and time, but also obtain higher resolution. picture of.
  • the fifth aspect of the embodiments of the present application provides a patterned film formed by cross-linking the nanocrystalline composite described in the first aspect of the embodiments of the present application; or a patterned film prepared by the preparation method described in the fourth aspect of the embodiments of the present application. film.
  • a sixth aspect of the embodiment of the present application provides an electronic device.
  • the electronic device includes a first electrode and a second electrode arranged oppositely, and a functional layer located between the first electrode and the second electrode.
  • the functional layer includes the cross-linked product of the nanocrystalline composite described in the first aspect of the embodiments of this application; or the functional layer includes the patterned film described in the fifth aspect of the embodiments of this application.
  • the electronic device includes any one of LED, QLED, Mini-LED, Micro-LED, Nano-LED, and QD-OLED.
  • the seventh aspect of the embodiment of the present application further provides a display device, which includes the electronic device described in the sixth aspect of the embodiment of the present application.
  • An embodiment of the present application also provides an electronic device, which includes the display device described in the seventh aspect.
  • Figure 1 is a schematic diagram of a quantum dot layer undergoing fine patterning to obtain a pixel array
  • Figure 2 is a schematic diagram of the process of patterning the quantum dot layer by transfer printing method
  • Figure 3 is a schematic diagram of the process of patterning the quantum dot layer using photoresist etching
  • Figure 4 is a schematic diagram of the process of patterning a quantum dot layer formed of a quantum dot material with patterning function
  • Figure 5 is a schematic structural diagram of the nanocrystalline composite 100 provided by the embodiment of the present application.
  • Figure 6 is a schematic diagram of photo-crosslinking between nanocrystalline composite particles according to the embodiment of the present application.
  • Figure 7 is a schematic flow chart of the preparation method of the patterned film according to the embodiment of the present application.
  • Figure 8 is a schematic structural diagram of the electronic device 200 according to the embodiment of the present application.
  • Figure 9 is a schematic structural diagram of the display device 300 according to the embodiment of the present application.
  • Figure 10 is a schematic structural diagram of an electronic device 400 according to an embodiment of the present application.
  • Figure 11 is the nuclear magnetic resonance spectrum of the photosensitive ligand ChalBen prepared in Example 1 of the present application.
  • Figure 12 is the nuclear magnetic resonance spectrum of the photosensitive ligand ChalC5 prepared in Example 2 of the present application.
  • Figure 13 is the nuclear magnetic resonance spectrum of the photosensitive ligand ChalC8 prepared in Example 3 of the present application.
  • Figure 14 is a nuclear magnetic resonance spectrum of the photosensitive ligand ChalC13 prepared in Example 4 of the present application.
  • Figure 15 is the nuclear magnetic resonance spectrum of the photosensitive ligand CouC2 prepared in Example 5 of the present application.
  • Figure 16 is the nuclear magnetic resonance spectrum of the photosensitive ligand CouC8 prepared in Example 6 of the present application.
  • Figure 17 is the nuclear magnetic resonance spectrum of the photosensitive ligand CouC13 prepared in Example 7 of the present application.
  • Figures 18 and 19 are UV-VIS (ultraviolet-visible) absorption curves at different stages of the quantum dot film samples in the embodiments of the present application;
  • Figures 20 and 21 are UV-VIS (ultraviolet-visible) absorption curves at different stages of the quantum dot film sample of the comparative example.
  • Preparing quantum dot materials into ultra-high-resolution display devices requires the improvement of the quantum dot (QD) layer of quantum dot light-emitting devices (QLED). Rows are finely patterned to obtain pixel arrays.
  • the industry's main methods for finely patterning quantum dot layers include transfer printing and photoresist etching. However, the transfer method has limited processing size and poor processing yield; the photoresist etching method has many process steps. , and the developer and etching solution have an impact on the quantum dot layer and functional layer.
  • embodiments of the present application provide a nanocrystalline composite, which has high photo-crosslinking activity.
  • the nanocrystalline composite is used to prepare patterned films.
  • the process is simple, the patterning effect is good, and it can avoid the damage of the quantum dot layer and the quantum dot layer during the patterning process. Functional layer effects.
  • FIG 5 is a schematic structural diagram of a nanocrystalline composite 100 provided by an embodiment of the present application.
  • the nanocrystalline composite 100 includes nanocrystalline particles 101 and ligands 102 coordinated on the surface of the nanocrystalline particles 101.
  • the ligands 102 include formulas (I) and/or the photosensitive ligand with the structure shown in formula (II),
  • a carbon-carbon double bond group, R and R' are independently a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkyl group
  • R and R' are independently a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkyl group
  • n can be 1, 2 or 3.
  • photosensitive ligands with structures shown in formula (I) and/or formula (II), which have higher photo-crosslinking activity and lower thermal cross-linking activity are obtained by coordinating and combining on the surface of nanocrystalline particles.
  • Nanocrystalline composites with high light-sensitive properties and high thermal stability were developed.
  • the nanocrystalline composite has a patterning function. When the nanocrystalline composite is used to prepare a patterned nanocrystalline film, patterning can be achieved directly through exposure and solvent development. During the patterning process, the nanocrystalline composite can be formed in a smaller size.
  • Photo-crosslinking is achieved under a high exposure dose and short exposure time, specifically through photosensitive ligands to achieve cross-linking between nanocrystal composites, and the process of achieving photo-cross-linking does not require the use of additional photoinitiators; and the nanocrystal composite
  • the object will not undergo thermal cross-linking when undergoing the heating annealing process, thereby avoiding the problem of incomplete elution of non-exposed areas during the development process, improving the reliability of the patterning process, and conducive to achieving refined pattern preparation.
  • the ligands 102 on the surface of the nanocrystalline particles 101 may include one or more photosensitive ligands having the structure shown in formula (I); in some embodiments of the present application, the ligands 102 on the surface of the nanocrystalline particles 101
  • the ligand 102 may include one or more photosensitive ligands having the structure shown in formula (II); in some embodiments of the present application, the ligand 102 on the surface of the nanocrystal particle 101 may include one or more photosensitive ligands having the structure shown in formula (II).
  • the ligands 102 on the surface of the nanocrystal particles 101 may also include ligands with other structures or other functions.
  • X is a coordination group, that is, a group that forms a coordination bond with the surface of the nanocrystal particle 101.
  • the coordination group Coordinated groups are formed on the surface of the nanocrystal particle 101, including but not limited to any one of carboxyl groups (-COOH), amino groups (-NH 2 ), phosphate groups, phospholipid groups, and sulfhydryl groups (-SH). These coordination groups can enable the photosensitive ligand to be better riveted and bound to the surface of inorganic nanocrystal quantum dots.
  • the connecting group Y includes a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted arylene alkyl group.
  • substituted or unsubstituted alkylene aryloxy substituted or unsubstituted alkyleneoxy, substituted or unsubstituted aryleneoxy, substituted or unsubstituted alkylenearyloxy, substituted or unsubstituted alkylene
  • the substituent group in the substituted alkylene group may be, but is not limited to, a halogen atom, and specifically may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • n in formula (I) and formula (II) is 2 or 3. Specifically, when the linking group Y is When , n is 2; when the linking group Y is When, n is 3.
  • the number of carbon atoms of the linking group Y may be 1-30. In some embodiments, the number of carbon atoms of the linking group Y can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30.
  • the connecting group Y has a suitable number of carbon atoms and can better balance the dispersion of quantum dots and the conductivity of the quantum dot layer.
  • the substituted or unsubstituted alkylene group in the linking group Y, can be, for example, a substituted or unsubstituted methylene group (-CH 2 -), a substituted or unsubstituted ethylene group, a substituted or unsubstituted ethylene group, or a substituted or unsubstituted alkylene group.
  • Alkylene is obtained by removing one hydrogen atom from an alkyl group.
  • the substituted or unsubstituted arylene group may be a substituted or unsubstituted arylene group having 6 to 30 carbon atoms. Specifically, it may be a substituted or unsubstituted phenylene group (-C 6 H 4 -), a substituted or unsubstituted arylene group. Unsubstituted biphenylene group, substituted or unsubstituted terphenylene group, substituted or unsubstituted fluorenylene group, substituted or unsubstituted naphthylene group, substituted or unsubstituted anthracene group, etc.
  • the number of carbon atoms of the substituted or unsubstituted alkylene aryl group can be 7-30, specifically it can be an alkylene phenyl group, such as methylene phenyl (-CH 2 -C 6 H 4 -), ethylene group Phenyl (-CH 2 CH 2 -C 6 H 4 -), etc.
  • the number of carbon atoms of the substituted or unsubstituted arylene alkyl group can be 7-30, specifically it can be a phenylene alkyl group, such as phenylene methyl (-C 6 H 4 -CH 2 -), phenylene group Ethyl (-C 6 H 4 -CH 2 CH 2 -), etc.
  • the substituted or unsubstituted alkyleneoxy group may be, for example, a substituted or unsubstituted methyleneoxy group (-CH 2 -O-), a substituted or unsubstituted ethyleneoxy group (-CH 2 CH 2 -O-), Substituted or unsubstituted propyleneoxy (-CH 2 CH 2 CH 2 -O-), substituted or unsubstituted isopropyleneoxy, substituted or unsubstituted butyleneoxy, substituted or unsubstituted isobutylene Oxygen group, substituted or unsubstituted neopentyloxy group, substituted or unsubstituted hexamethyleneoxy group, etc.
  • the number of carbon atoms of the substituted or unsubstituted aryleneoxy group may be 6-30, specifically, it may be a phenyleneoxy group (-C 6 H 4 -O-), etc.
  • the number of carbon atoms of the substituted or unsubstituted alkylene aryloxy group can be 7-30, specifically it can be an alkylene phenoxy group, such as methylene phenoxy (-CH 2 -C 6 H 4 -O- ), ethylene phenoxy (-CH 2 CH 2 -C 6 H 4 -O-), etc.
  • the number of carbon atoms of the substituted or unsubstituted arylene alkoxy group can be 7-30, specifically it can be a phenylene alkoxy group, such as phenylene methoxy (-C 6 H 4 -CH 2 -O- ), phenylene ethoxy (-C 6 H 4 -CH 2 CH 2 -O-), etc.
  • a substituted alkylene group, a substituted arylene group, a substituted arylene alkyl group, a substituted alkylene aryl group, a substituted alkyleneoxy group, a substituted alkylene group a substituted alkylene group
  • the substituent groups in the aryloxy group, substituted alkylene aryloxy group, substituted arylene alkoxy group, and substituted alkylene carbonyl group can be, but are not limited to, halogen atoms, and specifically can be fluorine atoms, chlorine atoms, Bromine or iodine atom.
  • the connecting group Y' may be a group including an oxygen atom, a sulfur atom, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or an ester group-containing group.
  • the substituent group in the substituted alkylene group may be, but is not limited to, a halogen atom, and specifically may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • the number of carbon atoms of the linking group Y' may be 0-30.
  • the carbon atom of the connecting group Y' The number specifically can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30.
  • the linking group Y' is an oxygen atom.
  • A may be connected to the para position of the linking group Y. In some embodiments, A may be attached to the ortho position of the linking group Y. In some embodiments, A may be connected to the meta position of the linking group Y.
  • the substituents R, R', R" can be selected from hydrogen atoms, halogen atoms, nitro groups, hydroxyl groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or Any one of the following: unsubstituted alkylcarbonyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy.
  • R, R', R" When it is a halogen atom, it may specifically be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • the substituted or unsubstituted alkyl group can be a substituted or unsubstituted C1-C20 alkyl group, specifically it can be a substituted or unsubstituted C1, C2, C3, C4 , C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20 alkyl, such as substituted or unsubstituted methyl (-CH 3 ), substituted Or unsubstituted ethyl, substituted or unsubstituted isopropyl, substituted or unsubstituted butyl, etc.; the substituted or unsubstit
  • R among substituted alkyl, substituted alkoxy, substituted alkylcarbonyl, substituted cycloalkyl, substituted aryl, substituted aryloxy
  • the substituent group may be, but is not limited to, a halogen atom (including a fluorine atom, a chlorine atom, a bromine atom or an iodine atom).
  • the substituted alkyl group may be trifluoromethyl, trifluoroethyl, etc.
  • R and R' can be located on any vacant carbon atom (a carbon atom not connected to the connecting group Y, group A, or group B) on the ring structure where it is located.
  • R” can be located on any vacant carbon atom in the ring structure where it is located.
  • the photosensitive ligand having the structure represented by formula (I) may specifically include any compound represented by formula (I-1) to formula (I-14):
  • m is an integer greater than or equal to 0. Specifically, m can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 ,23,24,25,26,27,28,29.
  • the photosensitive ligand having the structure represented by formula (II) may specifically include any compound represented by formula (II-1) to formula (II-12):
  • m is an integer greater than or equal to 0. Specifically, m can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 ,23,24,25,26,27,28,29.
  • the nanocrystalline particles include II-VI compounds, IV-VI compounds, III-V compounds, III-VI compounds, VIB-VIA compounds, VIII-VI compounds, I-VI compounds.
  • the nanocrystalline particles in the embodiments of the present application can be composed of the above material, or they can be composed of two or more materials; the nanocrystalline particles can be single material particles, uniform mixture particles, gradient mixture particles, core Shell structure particles, etc. can also be doped products of the above compounds.
  • nanocrystalline particles may include, but are not limited to, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, PbS, PbSe, PbTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, ZnO,SnO 2 ,TiO 2 ,In 2 O 3 ,Ga 2 O 3 ,SiO 2 ,NiO,MoO 3 ,WO 3 ,Cu 2 O,CuO,Fe 3 O 4 ,Au,Ag, carbon dots, CsPbCl 3 , CsPbBr 3 , CsPbI 3 , CH 3 NH 3 PbCl 3 , CH 3 NH 3 PbBr 3 , CH 3 NH 3 PbI 3 , or a mixture, gradient mixture, core-shell structure of the above substances, or a core-shell structure of a mixture
  • the nanocrystalline particles may be quantum dots, specifically red quantum dots, green quantum dots, or blue quantum dots.
  • the particle size of the nanocrystalline particles may be 5 nm-20 nm. Suitable nanocrystal particle size is conducive to obtaining better luminescence properties. In some embodiments, the particle size of the nanocrystalline particles may be 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm.
  • the total mass of the ligands 102 on the surface of the nanocrystal particle 101 is 1%-30% of the mass of the nanocrystal particle 101. That is, the total mass of the ligand 102 coordinated on the surface of the nanocrystal particle 101 is 1%-30% relative to the mass of the nanocrystal particle 101 . In some embodiments, the total mass of the ligands 102 on the surface of the nanocrystal particle 101 is 1%, 2%, 5%, 10%, 12%, 15%, 20%, 25%, 30% of the mass of the nanocrystal particle 101 wait.
  • the total mass of the photosensitive ligands having the structure shown in formula (I) and/or formula (II) on the surface of the nanocrystal particle 101 is 1%-30% of the mass of the nanocrystal particle 101.
  • a suitable coordination amount of photosensitive ligands is conducive to making the nanocrystalline composite have higher photosensitive properties and It has high thermal stability and can better utilize the properties of nanocrystalline particles.
  • the nanocrystalline composites of the embodiments of the present application can form particles under ultraviolet light irradiation through photosensitive ligands having structures shown in Formula (I) and/or Formula (II) coordinated on the surface of the nanocrystalline particles.
  • Cross-linking with particles allows direct preparation of patterned films using mask exposure and solvent development. Specifically, the nanocrystalline composite in the exposed area undergoes photo-crosslinking to form a thin film after being irradiated with ultraviolet light, while the nanocrystalline composite in the non-exposed area does not undergo photocrosslinking and can be eluted by a solvent, thereby obtaining a patterned thin film.
  • the embodiments of the present application also provide a method for preparing the above-mentioned nanocrystalline composite, including:
  • the stirring reaction may be performed at room temperature.
  • the time of stirring reaction can be 10min-120min.
  • the first ligand may include a saturated or unsaturated aliphatic carboxylic acid ligand, specifically, but is not limited to, an oleic acid ligand.
  • the solvent may include, but is not limited to, one or more of chloroform, chlorobenzene, and ethyl benzoate.
  • the added mass of the photosensitive ligand having the structure shown in formula (I) and/or formula (II) can be equal to the mass of the nanocrystal particles with the first ligand coordinated on the surface, that is, having the formula
  • the added mass of the photosensitive ligand having the structure shown in (I) and/or formula (II) is equal to the total mass of the first ligand and the nanocrystal particles.
  • excess methanol can be used to precipitate once, and the precipitate can be collected to obtain a nanocrystalline composite product in the form of powder; the obtained precipitate can also be redissolved in a solvent to obtain a dispersed nanocrystalline composite.
  • the solvent may include, but is not limited to, one or more of chloroform, chlorobenzene, and ethyl benzoate.
  • the photosensitive ligand having the structure represented by formula (I) can be obtained by using hydroxyl-substituted chalcone as raw material and introducing a target group.
  • the photosensitive ligand with the structure shown in formula (I-1) can be obtained by reacting a hydroxyl-substituted chalcone with a diacid, and the preparation process can be as shown in reaction formula (1):
  • n can be an integer greater than or equal to 0.
  • the photosensitive ligand having the structure represented by formula (II) can be obtained by using hydroxyl-substituted coumarin as a raw material and introducing a target group.
  • the preparation process of the photosensitive ligand with the structure shown in formula (I-1) can be:
  • n can be an integer greater than or equal to 0.
  • the preparation method of the nanocrystalline composite provided in the embodiments of the present application is simple and easy to achieve quantitative production.
  • the embodiments of the present application also provide a nanocrystal composition, which includes the nanocrystal composite mentioned above in the embodiments of the present application and a solvent.
  • the solvent may include, but is not limited to, one or more of chloroform, chlorobenzene, and ethyl benzoate.
  • the mass concentration of the nanocrystal complex in the nanocrystal composition, may be 1 mg/mL-100 mg/mL. In some embodiments, the mass concentration of the nanocrystal complex is 1 mg/mL, 5 mg/mL, 10 mg/mL, 15 mg/mL, 20 mg/mL, 30 mg/mL, 40 mg/mL, 50 mg/mL, 60 mg/mL, 70 mg /mL, 80mg/mL, 90mg/mL, 100mg/mL.
  • a suitable concentration of the nanocrystalline composite can make the nanocrystalline film prepared by using the nanocrystalline composition have better comprehensive properties.
  • embodiments of the present application also provide a method for preparing a patterned film, including:
  • a solution containing the above-mentioned nanocrystalline composite in the embodiment of the present application or the above-mentioned nanocrystalline composition is placed on the substrate 11 to form a coating layer 12.
  • the mask 13 is used for exposure and development, and the nanocrystalline composite in the exposed area is formed. Photo-crosslinking is attached to the substrate 11, and the nanocrystalline composite in the unexposed areas is removed by development to form a patterned film 12'.
  • the exposure time may be 0.1 seconds to 600 seconds. In some embodiments, the exposure time may be, for example, 0.1 seconds, 10 seconds, 15 seconds, 30 seconds, 40 seconds, 50 seconds, 60 seconds, or 100 seconds.
  • ultraviolet light is used for exposure, the wavelength of light can be 365nm, and the intensity of light can be 0.001mW/cm 2 -1000mW/cm 2 .
  • the light intensity can be, for example, 0.001mW/cm 2 , 1mW/cm 2 , 5mW/cm 2 , 10mW/cm 2 , 20mW/cm 2 , 30mW/cm 2 , 50mW/cm 2 , 100mW/cm 2 .
  • the nanocrystalline composites in the embodiments of the present application have better light-sensitive properties and can be used under lower irradiation dose and shorter exposure time conditions. Cross-linking is achieved under the conditions to complete the preparation of patterned films, thus saving energy and time.
  • the development is solvent development, and the development uses an organic solvent that can elute the nanocrystal composite.
  • the solvent can be, for example, chloroform.
  • annealing treatment can be performed after forming the coating layer and before exposure and development. Since the nanocrystalline composites in the embodiments of the present application have low heat-sensitive cross-linking activity, coating of the nanocrystalline composites can be avoided. The layers are cross-linked during annealing, affecting the patterning refinement results.
  • the preparation method of the patterned film in the embodiment of the present application can achieve a good cross-linking effect through a short exposure time, and can only use solvent development.
  • the process is relatively simple, which can not only save energy and time, but also obtain higher resolution. picture of.
  • the embodiments of the present application also provide a patterned film formed by cross-linking the nanocrystalline composite described in the embodiments of the present application; or a patterned film prepared by the preparation method described in the embodiments of the present application.
  • the patterned film can achieve high-resolution pattern preparation, such as sub-pixel sizes below 10 microns or even below 3 microns.
  • an embodiment of the present application also provides an electronic device 200.
  • the electronic device 200 includes a first electrode 201 and a second electrode 202 arranged oppositely, and a functional layer located between the first electrode 201 and the second electrode 202.
  • the functional layer 203 includes the cross-linked product of the nanocrystalline composite 100 described in the embodiment of the present application; or the functional layer 203 includes the patterned film described in the embodiment of the present application.
  • the electronic device 200 may include, but is not limited to, any one of LED, QLED, Mini-LED, Micro-LED, Nano-LED, and QD-OLED. In the embodiment of the present application, the electronic device 200 may be an upright device or an inverted device.
  • the first electrode 201 and the second electrode 202 are an anode and a cathode respectively.
  • the constituent materials of the anode and the cathode are conductive materials, which can be independently selected from conductive metals, conductive metal oxides, conductive polymers, etc.
  • the conductive metal may include one or more of magnesium (Mg), aluminum (Al), gold (Au), silver (Ag), platinum (Pt), target (Pd) and other metal elements and their alloys;
  • conductive Metal oxides include but are not limited to indium tin oxide (ITO), indium zinc oxide (IZO), aluminum-doped zinc oxide (AZO), fluorine-doped tin dioxide (FTO), phosphorus-doped tin dioxide (PTO), etc.
  • conductive polymers include but are not limited to polythiophene, polypyrrole, polyaniline, etc.
  • the functional layer 203 includes a light-emitting layer 2031.
  • the light-emitting layer 2031 includes the cross-linked product of the nanocrystal composite 100 described in the embodiment of the present application; or the functional layer 203 includes the patterned film described in the embodiment of the present application.
  • the functional layer 203 also includes a first carrier transport layer 2032 located between the first electrode 201 and the luminescent layer 2031, and a second carrier transport layer 2032 located between the second electrode 202 and the luminescent layer 2031. Transport layer 2033.
  • the first carrier transport layer 2032 may include a hole injection layer 2032a, a hole transport layer 2032b, One or more of the electron blocking layers 2032c.
  • the hole injection layer 2032a is located between the anode 201 and the hole transport layer 2032b
  • the electron blocking layer 2032c is located between the light emitting layer 2031 and the hole transport layer 2032b.
  • the second carrier transport layer 2033 may include one or more of an electron injection layer 2033a, an electron transport layer 2033b, and a hole blocking layer 2033c located between the cathode 202 and the light-emitting layer 2031.
  • the electron injection layer 2033a is located between the cathode 202 and the electron transport layer 2033b
  • the hole blocking layer 2033c is located between the cathode 202 and the hole transport layer 2032b.
  • the electronic device 200 includes an anode 201, a hole injection layer 2032a, a hole transport layer 2032b, an electron blocking layer 2032c, a light emitting layer 2031, a hole blocking layer 2033c, and an electron transport layer arranged in sequence.
  • the functional layer 203 may also include a stacked structure of "light-emitting layer 2031/electron transport layer 2033b" in sequence along the direction from anode 201 to cathode 202, or a stacked structure of "light-emitting layer 2031/electron injection layer 2033a", or include A stacked structure of “hole injection layer 2032a/light-emitting layer 2031/electron transport layer 2033b”, or a stacked structure including “hole injection layer 2032a/light-emitting layer 2031/electron injection layer 2033a”, or a stacked structure including “hole transport layer 2032b” /Light-emitting layer 2031/Electron transport layer 2033b", or a laminate structure including "hole injection layer 2032a/hole transport layer 2032b/light-emitting layer 20
  • the electronic device 200 may also have a substrate 204 (as shown in Figure 8).
  • the substrate 204 may be located on the side of the anode 201 away from the functional layer 203 (as shown in FIG. 8 ), and the substrate 204 may also be located on the side of the cathode 202 away from the functional layer 203 . That is, the electronic device 200 may be a bottom-emitting device or a bottom-emitting device. It is a top-emitting device.
  • the substrate 204 can be used as a supporting part of the entire electronic device 200, and its material can be quartz, glass, elemental silicon, metal, plastic, etc. In some embodiments, substrate 204 is light-transparent glass or plastic.
  • the shape of the substrate 204 can be determined according to the specific application scenario, for example, it can be formed into a plate shape, a film shape, a sheet shape, etc.
  • the thickness of the substrate 204 is not particularly limited.
  • the substrate 204 may include active matrix or passive matrix driving circuits.
  • Physical vapor deposition can be used. It can be prepared by deposition method, chemical vapor deposition method or coating method. Among them, the physical vapor deposition method can include vacuum evaporation methods (such as resistance evaporation source evaporation method, electron beam evaporation source evaporation method, pulse laser deposition method, etc.), sputtering methods (such as magnetron sputtering method), etc.
  • vacuum evaporation methods such as resistance evaporation source evaporation method, electron beam evaporation source evaporation method, pulse laser deposition method, etc.
  • sputtering methods such as magnetron sputtering method
  • One or more coating methods may include solution spin coating, dip coating, blade coating, spray coating, roller coating, inkjet printing, screen printing, etc.
  • the anode 201 and the cathode 202 can be prepared by vacuum evaporation, and each layer of the functional layer 203 can be prepared by vacuum evaporation or coating.
  • the anode 201 can be formed on the substrate 204 first, and then the functional layer 203 including the light-emitting layer 2031 is sequentially formed on the anode 201, and then the cathode 202 is formed on the functional layer 203.
  • the cathode 202 and the functional layer 203 including the light-emitting layer 2031 may be sequentially formed on the substrate 204, and then the anode 201 may be formed on the functional layer 203.
  • the constituent materials of the hole injection layer include, but are not limited to, aniline conductive polymers, polythiophene conductive polymers, and the like.
  • Materials constituting the hole transport layer include, but are not limited to, aromatic amine organic materials (such as TFB).
  • the constituent materials of the electron transport layer may include, but are not limited to, alkaline earth metal oxides (such as zinc oxide) and the like.
  • the preparation process of the quantum dot light-emitting device QLED may be:
  • a metal electrode is prepared on the electron injection layer.
  • the preparation process of the quantum dot light-emitting device QLED can be:
  • red, green, and blue devices in top-emitting devices may require different microcavity structures.
  • Hole transport layers of different thicknesses can be prepared for red, green, and blue sub-pixels as needed (for example, using TFB material) and/or electron transport layer (such as ZnO or other metal oxides with electron transport capabilities).
  • the order of preparing patterned films of red, green, and blue quantum dots can also be changed as needed.
  • an embodiment of the present application further provides a display device 300 .
  • the display device 300 includes the electronic device 200 described above in the embodiment of the present application.
  • the display device 300 can be a mobile phone, a tablet computer, a notebook computer, a wearable device (such as a smart watch, a smart bracelet, etc.), a television, a digital camera, a camcorder, a player, a micro-display device (such as smart glasses, virtual reality (VR) equipment, augmented reality (AR) equipment, telephones, printers, vehicles, household appliances, billboards, information boards, car central control screens, etc.
  • an embodiment of the present application further provides an electronic device 400 .
  • the electronic device 400 includes the display device 300 described above in the embodiment of the present application.
  • the electronic device 400 can be a mobile phone, a tablet computer, a notebook computer, a wearable device (such as a smart watch, a smart bracelet, etc.), a television, a digital camera, a camcorder, a player, a micro-display device (such as smart glasses, virtual reality) (Virtual Reality, VR) equipment, augmented reality (Augmented Reality, AR) equipment, telephones, printers, vehicles, household appliances, billboards, information boards, car central control screens and other electronic products with display functions.
  • virtual reality Virtual Reality
  • AR Augmented Reality
  • FIG. 15 is a nuclear magnetic resonance spectrum of the photosensitive ligand CouC2 prepared in Example 5 of the present application. The reaction process is shown in formula (5):
  • FIG. 16 is a nuclear magnetic resonance spectrum of the photosensitive ligand CouC8 prepared in Example 6 of the present application. The reaction process is shown in formula (6):
  • FIG. 17 is a nuclear magnetic resonance spectrum of the photosensitive ligand CouC13 prepared in Example 7 of the present application. The reaction process is shown in formula (7):
  • the synthesis of green quantum dots includes the following steps:
  • Quantum dot ligand exchange Quantum dot ligand exchange
  • the quantum dot solution obtained above was prepared to obtain a patterned quantum electrical film, and the photo-crosslinking effect and thermal cross-linking performance were evaluated:
  • Exposure Use 365nm LED surface light source (energy density about 30mW/cm 2 ) to illuminate the quantum dot film layer, and the cross-linking time is 15s to 60s;
  • the UV-VIS (ultraviolet-visible) absorption curves of the quantum dot film samples at different stages were measured, and the results are shown in Figures 18 and 19.
  • the UV-VIS absorption curves of the quantum dot film samples of the comparative example at different stages were measured.
  • the results are shown in Figures 20 and 21, in which the development solvent elution is Immerse in chloroform solution and let stand for 1 minute.
  • curve 1 is the UV-VIS absorption curve of a quantum dot film with ChalC8 ligands coordinated on the surface without light cross-linking and development solvent elution (immersed in chloroform solution and left for 1 min) (that is, without any treatment) Blank control experiment results)
  • Curve 2 is the UV-VIS absorption curve of a quantum dot film with ChalC8 ligands coordinated on the surface after annealing at 100°C for 10 minutes and 15 seconds of light cross-linking and elution with a developing solvent.
  • the surface coordination The quantum dots containing ChalC8 ligand were annealed at 100°C for 10 minutes and photo-cross-linked for 15 seconds.
  • curve 1 is the UV-VIS absorption curve of a quantum dot film with linolenic acid ligands coordinated on the surface without light cross-linking and development solvent elution (immersed in chloroform solution and left for 1 min) (that is, without any Processed blank control experimental results)
  • curve 2, curve 3, and curve 4 are respectively the UV-VIS absorption curves of quantum dot films with linolenic acid ligands coordinated on the surface after 5 min, 10 min, and 15 min of light cross-linking and elution with developing solvents.
  • the retention rate of quantum dots with linolenic acid ligands coordinated on the surface is less than 80% after 5 to 15 minutes of light cross-linking.
  • the quantum dots with ChalC8 ligands coordinated on the surface in the examples of the present application can achieve relatively complete cross-linking under shorter illumination conditions, and the photo-cross-linking effect is good.
  • the absorbance of the UV-VIS absorption curve of the quantum dot film sample is significantly lower than that of the quantum dot film sample before exposure and development, it means that the photo-crosslinking effect of the quantum dot composite is poor, resulting in quantum dot composite The object is washed away by the developing solvent; otherwise, it means that the photo-crosslinking effect is better.
  • Curve 1 is the UV-VIS absorption curve of a quantum dot film with ChalC8 ligands coordinated on the surface without light cross-linking, annealing and development solvent elution (immersed in chloroform solution and left for 1 min) (i.e. Blank control experimental results without any treatment)
  • Curve 2 is the UV-VIS absorption curve of a quantum dot film with ChalC8 ligands coordinated on the surface that was only annealed at 100°C for 10 minutes without photo-crosslinking, and then eluted with a developing solvent.
  • Curve 1 is the UV-VIS absorption curve of a quantum dot film with linolenic acid ligands coordinated on the surface without light cross-linking, annealing and development solvent elution (immersed in chloroform solution and left for 1 min) ( That is, the result of the blank control experiment without any treatment), curve 2 shows the quantum dot film with linolenic acid ligands coordinated on the surface after annealing at 100°C for 10 minutes.
  • the UV-VIS absorption curve of developing solvent elution without photo-crosslinking can be seen from Figure 21.
  • the residual amount of quantum dots with linolenic acid ligands coordinated on the surface of the comparative example reaches 50%, indicating that the thermal cross-linking degree of linolenic acid ligand is relatively high.
  • the photosensitive ligands of Examples 1-2 and 4-7 were prepared into quantum dot solutions using the same method as above, and then prepared into patterned quantum dot films. After testing, it was found that the photosensitive ligands of Examples 1-2 and 4-7 were prepared into quantum dot solutions.
  • the photosensitive ligands of 7 can obtain a retention rate of more than 90% after 15s to 60s of light cross-linking; under annealing conditions, the elution residual rates are all less than 20%; it is shown that using Examples 1-2 and implementation
  • the nanocrystalline composite prepared using the photosensitive ligand in Examples 4-7 has high photo-crosslinking activity and low thermal cross-linking activity.
  • At least one refers to one or more
  • plural refers to two or more.
  • At least one of the following” or similar expressions thereof refers to any combination of these items, including any combination of a single item (items) or a plurality of items (items).
  • at least one of a, b, or c or “at least one of a, b, and c” can mean: a, b, c, a-b ( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple respectively.
  • the size of the sequence numbers of the above-mentioned processes does not mean the order of execution. Some or all steps can be executed in parallel or one after another. The execution order of each process should be based on its function and order. The internal logic is determined and should not constitute any limitation on the implementation process of the embodiments of the present application.

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Abstract

一种纳米晶复合物，包括纳米晶颗粒和配位于纳米晶颗粒表面的配体，配体包括具有式(Ⅰ)和/或式(Ⅱ)所示结构的光敏配体，X为配位基团，Y、Y'为连接基团，A、B中一者为-C＝O-，另一者为含有碳碳双键的基团，R、R'、R"独立地为氢原子、卤素原子、硝基、羟基、取代或非取代的烷基、取代或非取代的烷氧基、取代或非取代的烷基羰基、取代或非取代的环烷基、取代或非取代的芳香基、取代或非取代的芳氧基；n为1、2或3。该纳米晶复合物具有较高的光交联活性和热稳定性，用于制备图案化薄膜。

Description

纳米晶复合物及其制备方法和应用
本申请要求于2022年8月22日提交中国专利局、申请号为202211008516.1、申请名称为“纳米晶复合物及其制备方法和应用”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
本申请实施例涉及纳米晶薄膜制备技术领域，特别是涉及一种纳米晶复合物及其制备方法和应用。
背景技术
未来AR(Augmented Reality，增强现实)眼镜、VR(Virtual Reality，虚拟现实)眼镜需要超高分辨率(≥3000ppi)的显示光机，需同时满足超高分辨、低功耗、高准直性发光、小体积等要求。量子点是一类新型显示材料，具有高发光效率、窄峰宽的特征，可以实现低功耗、高准直性发光、小体积要求。
然而，将量子点材料制备成超高分辨率的显示装置，需要对量子点发光器件(QLED)的量子点(QD)层进行精细图案化处理以获得像素阵列(如图1所示)。目前，业界对量子点层进行精细图案化的方法主要有：(1)转印法，参见图2，转印法是利用图案化的模板将形成在基底A上的量子点层按照目标图案粘走，并转移至基底B上获得图案化的量子点层，该方法加工尺寸受限，加工良率具有很大挑战；(2)光刻胶刻蚀法，参见图3，光刻胶刻蚀法是在量子点层上涂覆一层光刻胶，再通过曝光、显影、刻蚀获得图案化的量子点层，该方法工艺步骤较多，而且显影液、刻蚀液对量子点层及功能层(如空穴传输层、空穴注入层、电子传输层)存在影响。为了更方便地获得高质量图案化的量子点层，业界开始尝试直接合成具有图案化功能的量子点材料，参见图4，具有图案化功能的量子点材料可以直接通过对量子点层进行曝光和溶剂显影两步获得图案化的量子点层。然而，现有开发的具有图案化功能的量子点材料有的光敏活性不高，所需曝光时间长、曝光剂量高；有的热交联活性太高，在加热的情况下也会发生交联，导致量子点层在曝光之前的退火步骤中容易发生部分交联，造成非曝光区的量子点层无法被完全显影洗脱，导致非曝光区的量子点层残留。
发明内容
鉴于此，本申请实施例提供一种纳米晶复合物，该纳米晶复合物具有较高的光交联活性，以及较高的热稳定性(即较低的热交联活性)，该纳米晶复合物可用于制备图案化薄膜。
具体地，本申请实施例第一方面提供一种纳米晶复合物，所述纳米晶复合物包括纳米晶颗粒和配位于所述纳米晶颗粒表面的配体，所述配体包括具有式(Ⅰ)和/或式(Ⅱ)所示结构的光敏配体，
式(Ⅰ)中，所述X为与所述纳米晶颗粒配位结合的配位基团，所述Y为连接基团，所述A、B其中一者为-C＝O-，另一者为含有碳碳双键的基团，所述R、R’独立地为氢原子、卤素原子、硝基、羟基、取代或非取代的烷基、取代或非取代的烷氧基、取代或非取代的烷基羰基、取代或非取代的环烷基、取代或非取代的芳香基、取代或非取代的芳氧基中的一种；
式(Ⅱ)中，所述X为与所述纳米晶颗粒配位结合的配位基团，所述Y、Y’为连接基团，所述R、R’、R”独立地为氢原子、卤素原子、硝基、羟基、取代或非取代的烷基、取代或非取代的烷氧基、取代或非取代的烷基羰基、取代或非取代的环烷基、取代或非取代的芳香基、取代或非取代的芳氧基中的一种；
n为1、2或3。
本申请实施例通过在纳米晶颗粒表面配位结合具有较高光交联活性，同时具有较低热交联活性的具有式(Ⅰ)和/或式(Ⅱ)所示结构的光敏配体，获得了具有高光敏感特性和高热稳定性的纳米晶复合物。该纳米晶复合物具有图案化功能，将该纳米晶复合物用于制备图案化纳米晶薄膜，可以直接通过曝光和溶剂显影实现图案化，在图案化过程中，纳米晶复合物可以在较小的曝光剂量和较短的曝光时间下实现光交联， 具体通过光敏配体实现纳米晶复合物之间的交联，且实现光交联的过程无需额外使用光引发剂；而且该纳米晶复合物在经历加热退火工艺时不会发生热交联，从而可以避免显影过程中非曝光区域洗脱不完全的问题，提高图案化工艺的可靠性，有利于实现图案的精细化制备。
本申请一些实施方式中，纳米晶颗粒101表面的配体102可以是包括一种或多种具有式(Ⅰ)所示结构的光敏配体；本申请一些实施方式中，纳米晶颗粒101表面的配体102可以是包括一种或多种具有式(Ⅱ)所示结构的光敏配体；本申请一些实施方式中，纳米晶颗粒101表面的配体102可以是包括一种或多种具有式(Ⅰ)所示结构的光敏配体，和/或一种或多种式(Ⅱ)所示结构的光敏配体。本申请一些实施方式中，纳米晶颗粒101表面的配体102还可以包括具有其他结构或其他功能的配体。
本申请实施方式中，所述配位基团包括羧基、氨基、磷酸基、磷脂基团、巯基中的任意一种。
本申请实施方式中，所述连接基团Y包括取代或非取代的亚烷基、取代或非取代的亚芳基、取代或非取代的亚芳基烷基、取代或非取代的亚烷基芳基、取代或非取代的亚烷氧基、取代或非取代的亚芳氧基、取代或非取代的亚烷基芳氧基、取代或非取代的亚芳基烷氧基、含羰基的基团、含酯基和/或醚氧键的基团、含亚胺基的基团中的一种或多种。
其中，所述含羰基的基团包括-C(＝O)-、-R1-C(＝O)-中的任意一种；所述含酯基和/或醚氧键的基团包括-R2-C(＝O)-O-、 中的任意一种；所述含亚胺基的基团可以是-R3-CH2-NH-、 -R3-C(＝O)-NH-中的任意一种，其中，R1、R2、R3为取代或非取代的亚烷基。
本申请实施方式中，所述连接基团Y的碳原子数为1-30。连接基团Y具有适合的碳原子数，能够较好地兼顾量子点的分散性、量子点层的导电性。
本申请实施方式中，所述连接基团Y’包括氧原子、硫原子、取代或非取代的亚烷基、取代或非取代的亚烷氧基、含酯基的基团、含酰胺键的基团中的一种或多种。其中，含酯基的基团可以是-R1-C(＝O)-O-，含酰胺键的基团可以是-R3-C(＝O)-NH-，其中，R1、R3为取代或非取代的亚烷基。
本申请实施方式中，所述连接基团Y’的碳原子数为0-30。
本申请实施方式中，所述R、R’、R”中，所述取代或非取代的烷基为取代或非取代的C1-C20烷基，所述取代或非取代的烷氧基为取代或非取代的C1-C20烷氧基，所述取代或非取代的烷基羰基为取代或非取代的C1-C20烷基羰基，所述取代或非取代的环烷基为取代或非取代的C3-C20环烷基，所述取代或非取代的芳香基为取代或非取代的C6-C20芳香基，所述取代或非取代的芳氧基为取代或非取代C6-C20芳氧基。
本申请实施方式中，所述具有式(Ⅰ)所示结构的光敏配体包括式(Ⅰ-1)至式(Ⅰ-14)所示的任意一种化合物：

式(Ⅰ-1)至式(Ⅰ-14)中，m为大于或等于0的整数。
本申请实施方式中，所述具有式(Ⅱ)所示结构的光敏配体包括式(Ⅱ-1)至式(Ⅱ-12)所示的任意一种化合物：
式(Ⅱ-1)至式(Ⅱ-12)中，m为大于或等于0的整数。
本申请实施方式中，所述纳米晶颗粒包括II-VI族化合物、IV-VI族化合物、III-V族化合物、III-VI族化合物、VIB-VIA族化合物、VIII-VI族化合物、I-VI族化合物、I族单质、IV族单质、I-IV-VII族化合物、钙钛矿化合物中的一种或多种。
本申请实施方式中，所述纳米晶颗粒的粒径为5nm-20nm。适合的纳米晶颗粒粒径尺寸有利于获得较好的发光性能。
本申请实施方式中，所述纳米晶颗粒表面的配体的总质量为所述纳米晶颗粒质量的1％-30％。适合的光敏配体配位量有利于使纳米晶复合物具有较高光敏感特性和较高热稳定性，同时能够较好地发挥纳米晶颗粒本身的性能。
本申请实施例第二方面提供一种第一方面所述的纳米晶复合物的制备方法，包括：
将表面配位有第一配体的纳米晶颗粒分散于溶剂中，再加入具有式(Ⅰ)和/或式(Ⅱ)所示结构的光敏配体，搅拌反应后，得到配体交换后的纳米晶颗粒，即得到所述纳米晶复合物。
本申请实施方式中，所述第一配体包括饱和或不饱和脂肪羧酸配体。
本申请实施方式中，所述溶剂包括氯仿、氯苯、苯甲酸乙酯中的一种或多种。
本申请实施例提供的纳米晶复合物的制备方法工艺简单，易实现量化生产。
本申请实施例第三方面提供一种纳米晶组合物，所述纳米晶组合物包括本申请实施例第一方面所述的纳米晶复合物和溶剂。
本申请实施方式中，所述纳米晶组合物中，纳米晶复合物的质量浓度为1mg/mL-100mg/mL。适合的纳米晶复合物浓度可以使采用该纳米晶组合物制备的纳米晶薄膜具有较好的综合性能。
本申请实施方式中，所述溶剂包括氯仿、氯苯、苯甲酸乙酯中的一种或多种。
本申请实施例第四方面提供一种图案化薄膜的制备方法，包括：
在基底上设置含本申请实施例第一方面所述纳米晶复合物的溶液或本申请实施例第三方面所述的纳米晶组合物，采用掩膜板进行曝光显影，经曝光的区域的纳米晶复合物发生光交联附着在所述基底上，未经曝光的区域的纳米晶复合物经显影去除，形成图案化薄膜。
本申请实施方式中，所述曝光采用紫外光照，光照强度为0.001mW/cm2-1000mW/cm2。
本申请实施方式中，所述曝光的时间为0.1秒-600秒。
本申请实施方式中，所述显影为溶剂显影，所述显影采用能够洗脱所述纳米晶复合物的有机溶剂。
本申请实施例的图案化薄膜的制备方法，可以通过较短的曝光时间实现良好的交联效果，采用溶剂显影即可，过程较简单，不仅可以节约能量和时间，且可以获得较高分辨率的图案。
本申请实施例第五方面提供一种由本申请实施例第一方面所述的纳米晶复合物经交联形成的图案化薄膜；或者由本申请实施例第四方面所述制备方法制得的图案化薄膜。
本申请实施例第六方面提供一种电子器件，所述电子器件包括相对设置的第一电极和第二电极，以及位于所述第一电极和所述第二电极之间的功能层，所述功能层包括本申请实施例第一方面所述的纳米晶复合物的交联产物；或者所述功能层包括本申请实施例第五方面所述的图案化薄膜。
本申请实施方式中，所述电子器件包括LED、QLED、Mini-LED、Micro-LED、Nano-LED、QD-OLED中的任意一种。
本申请实施例第七方面还提供一种显示装置，所述显示装置包括本申请实施例第六方面所述的电子器件。
本申请实施例还提供一种电子设备，所述电子设备包括第七方面所述的显示装置。
附图说明
图1是量子点层进行精细图案化处理以获得像素阵列的示意图；
图2是转印法对量子点层进行图案化的过程示意图；
图3是光刻胶刻蚀法对量子点层进行图案化的过程示意图；
图4是具有图案化功能的量子点材料形成的量子点层进行图案化的过程示意图；
图5是本申请实施例提供的纳米晶复合物100的结构示意图；
图6是本申请实施例的纳米晶复合物颗粒间发生光交联的示意图；
图7是本申请实施例的图案化薄膜的制备方法流程示意图；
图8是本申请实施例的电子器件200的结构示意图；
图9是本申请实施例的显示装置300的结构示意图；
图10是本申请实施例的电子设备400的结构示意图；
图11是本申请实施例1制备的光敏配体ChalBen的核磁共振谱图；
图12是本申请实施例2制备的光敏配体ChalC5的核磁共振谱图；
图13是本申请实施例3制备的光敏配体ChalC8的核磁共振谱图；
图14是本申请实施例4制备的光敏配体ChalC13的核磁共振谱图；
图15是本申请实施例5制备的光敏配体CouC2的核磁共振谱图；
图16是本申请实施例6制备的光敏配体CouC8的核磁共振谱图；
图17是本申请实施例7制备的光敏配体CouC13的核磁共振谱图；
图18和图19是本申请实施例的量子点薄膜样品不同阶段的UV-VIS(紫外-可见)吸收曲线；
图20和图21是对比例的量子点薄膜样品不同阶段的UV-VIS(紫外-可见)吸收曲线。
具体实施方式
下面将结合本申请实施例中的附图，对本申请实施例进行说明。
将量子点材料制备成超高分辨率的显示装置，需要对量子点发光器件(QLED)的量子点(QD)层进 行精细图案化处理以获得像素阵列。目前，业界对量子点层进行精细图案化的方法主要有转印法和光刻胶刻蚀法，但转印法加工尺寸受限，加工良率不佳；光刻胶刻蚀法工艺步骤多，而且显影液、刻蚀液对量子点层及功能层存在影响。为了更方便地获得高质量图案化的量子点层，满足高分辨率显示装置的制备需求，本申请实施例提供一种纳米晶复合物，该纳米晶复合物具有较高的光交联活性，以及较高的热稳定性(即较低的热交联活性)，将该纳米晶复合物用于制备图案化薄膜，工艺简单，图案化效果好，且能够避免图案化过程对量子点层和功能层的影响。
参见图5，图5是本申请实施例提供的纳米晶复合物100结构示意图，纳米晶复合物100包括纳米晶颗粒101和配位于纳米晶颗粒101表面的配体102，配体102包括具有式(Ⅰ)和/或式(Ⅱ)所示结构的光敏配体，
式(Ⅰ)中，X为与纳米晶颗粒101配位结合的配位基团，Y为连接基团，A、B其中A、B其中一者为-C＝O-，另一者为含有碳碳双键的基团，R、R’独立地为氢原子、卤素原子、硝基、羟基、取代或非取代的烷基、取代或非取代的烷氧基、取代或非取代的烷基羰基、取代或非取代的环烷基、取代或非取代的芳香基、取代或非取代的芳氧基中的一种；
式(Ⅱ)中，X为与纳米晶颗粒101配位结合的配位基团，Y、Y’为连接基团，R、R’、R”独立地为氢原子、卤素原子、硝基、羟基、取代或非取代的烷基、取代或非取代的烷氧基、取代或非取代的烷基羰基、取代或非取代的环烷基、取代或非取代的芳香基、取代或非取代的芳氧基中的一种；
n可以是为1、2或3。
本申请实施例通过在纳米晶颗粒表面配位结合具有较高光交联活性，同时具有较低热交联活性的具有式(Ⅰ)和/或式(Ⅱ)所示结构的光敏配体，获得了具有高光敏感特性和高热稳定性的纳米晶复合物。该纳米晶复合物具有图案化功能，将该纳米晶复合物用于制备图案化纳米晶薄膜，可以直接通过曝光和溶剂显影实现图案化，在图案化过程中，纳米晶复合物可以在较小的曝光剂量和较短的曝光时间下实现光交联，具体通过光敏配体实现纳米晶复合物之间的交联，且实现光交联的过程无需额外使用光引发剂；而且该纳米晶复合物在经历加热退火工艺时不会发生热交联，从而可以避免显影过程中非曝光区域洗脱不完全的问题，提高图案化工艺的可靠性，有利于实现图案的精细化制备。
本申请一些实施方式中，纳米晶颗粒101表面的配体102可以是包括一种或多种具有式(Ⅰ)所示结构的光敏配体；本申请一些实施方式中，纳米晶颗粒101表面的配体102可以是包括一种或多种具有式(Ⅱ)所示结构的光敏配体；本申请一些实施方式中，纳米晶颗粒101表面的配体102可以是包括一种或多种具有式(Ⅰ)所示结构的光敏配体，和/或一种或多种式(Ⅱ)所示结构的光敏配体。本申请一些实施方式中，纳米晶颗粒101表面的配体102还可以包括具有其他结构或其他功能的配体。
本申请实施方式中，式(Ⅰ)和式(Ⅱ)中，X是配位基团，即与纳米晶颗粒101表面形成配位结合的基团，配位基团X可以是各种能够与纳米晶颗粒101表面形成配位结合的基团，包括但不限于是羧基(-COOH)、氨基(-NH2)、磷酸基、磷脂基团、巯基(-SH)中的任意一种。这些配位基团可以使光敏配体能够较好地铆定结合在无机物纳米晶量子点表面。
本申请实施方式中，式(Ⅰ)和式(Ⅱ)中，连接基团Y包括取代或非取代的亚烷基、取代或非取代的亚芳基、取代或非取代的亚芳基烷基、取代或非取代的亚烷基芳基、取代或非取代的亚烷氧基、取代或非取代的亚芳氧基、取代或非取代的亚烷基芳氧基、取代或非取代的亚芳基烷氧基、含羰基的基团、含酯基和/或醚氧键的基团、含亚胺基的基团中的一种或多种。其中，所述含羰基的基团包括-C(＝O)-、-R1-C(＝O)-中的任意一种；所述含酯基和/或醚氧键的基团包括-R2-C(＝O)-O-、 中的任意一种；含亚胺基的基团可以是-R3-CH2-NH-、-R3-C(＝O)-NH-中的任意一种，其中，R1、R2、R3为取代或非取代的亚烷基。R1、R2、R3中，取代的亚烷基中的取代基团可以但不限于是卤素原子，具体可以是氟原子、氯原子、溴原子或碘原子。
本申请实施方式中，当连接基团Y具有分支结构时，式(Ⅰ)和式(Ⅱ)中的n为2或3。具体地，当连接基团Y为时，n为2；当连接基团Y为 时，n为3。
本申请一些实施方式中，连接基团Y的碳原子数可以是1-30。一些实施例中，连接基团Y的碳原子数具体可以是1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30。连接基团Y具有适合的碳原子数，能够较好地兼顾量子点的分散性、量子点层的导电性。
本申请实施方式中，连接基团Y中，取代或非取代的亚烷基例如可以是取代或非取代的亚甲基(-CH2-)、取代或非取代的亚乙基、取代或非取代的亚丙基、取代或非取代的亚异丙基、取代或非取代的亚丁基、取代或非取代的亚异丁基、取代或非取代的亚新戊基、取代或非取代的亚己基等。亚烷基是烷基去掉一个氢原子得到。取代或非取代的亚芳基可以是碳原子数为6-30的取代或非取代的亚芳基，具体例如可以是取代或非取代的亚苯基(-C6H4-)、取代或非取代的亚联苯基、取代或非取代的亚三联苯基、取代或非取代的亚芴基、取代或非取代的亚萘基、取代或非取代的亚蒽基等。取代或非取代的亚烷基芳基的碳原子数可以是7-30，具体可以是亚烷基苯基，例如亚甲基苯基(-CH2-C6H4-)、亚乙基苯基(-CH2CH2-C6H4-)等。取代或非取代的亚芳基烷基的碳原子数可以是7-30，具体可以是亚苯基烷基，例如亚苯基甲基(-C6H4-CH2-)、亚苯基乙基(-C6H4-CH2CH2-)等。取代或非取代的亚烷氧基例如可以是取代或非取代的亚甲氧基(-CH2-O-)、取代或非取代的亚乙氧基(-CH2CH2-O-)、取代或非取代的亚丙氧基(-CH2CH2CH2-O-)、取代或非取代的亚异丙氧基、取代或非取代的亚丁氧基、取代或非取代的亚异丁氧基、取代或非取代的亚新戊氧基、取代或非取代的亚己氧基等。取代或非取代的亚芳氧基的碳原子数可以是6-30，具体可以是亚苯氧基(-C6H4-O-)等。取代或非取代的亚烷基芳氧基的碳原子数可以是7-30，具体可以是亚烷基苯氧基，例如亚甲基苯氧基(-CH2-C6H4-O-)、亚乙基苯氧基(-CH2CH2-C6H4-O-)等。取代或非取代的亚芳基烷氧基的碳原子数可以是7-30，具体可以是亚苯基烷氧基，例如亚苯基甲氧基(-C6H4-CH2-O-)、亚苯基乙氧基(-C6H4-CH2CH2-O-)等。
本申请实施方式中，连接基团Y中，取代的亚烷基、取代的亚芳基、取代的亚芳基烷基、取代的亚烷基芳基、取代的亚烷氧基、取代的亚芳氧基、取代的亚烷基芳氧基、取代的亚芳基烷氧基、取代的亚烷基羰基中的取代基团可以但不限于是卤素原子，具体可以是氟原子、氯原子、溴原子或碘原子。
本申请实施方式中，式(Ⅱ)中，连接基团Y’可以是包括氧原子、硫原子、取代或非取代的亚烷基、取代或非取代的亚烷氧基、含酯基的基团、含酰胺键的基团中的一种或多种。其中，含酯基的基团可以是-R1-C(＝O)-O-，含酰胺键的基团可以是-R3-C(＝O)-NH-，其中，R1、R3为取代或非取代的亚烷基。R1、R3中，取代的亚烷基中的取代基团可以但不限于是卤素原子，具体可以是氟原子、氯原子、溴原子或碘原子。
本申请一些实施方式中，连接基团Y’的碳原子数可以是0-30。一些实施例中，连接基团Y’的碳原子 数具体可以是1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30。一些实施例中，连接基团Y’为氧原子。
式(Ⅰ)中，A、B其中一者为(-C(＝O)-)，另一者为含有碳碳双键的基团。含有碳碳双键的基团具体可以是取代或非取代的亚烯基，具体例如可以是取代或非取代的亚乙烯基(-CH＝CH-)。一些实施例中，A为(-C(＝O)-)，B为含有碳碳双键的基团；一些实施例中，A为含有碳碳双键的基团，B为(-C(＝O)-)。一些实施例中，A可以是连接在连接基团Y的对位上。一些实施例中，A可以是连接在连接基团Y的邻位上。一些实施例中，A可以是连接在连接基团Y的间位上。
本申请实施方式中，取代基R、R’、R”均可以是选自氢原子、卤素原子、硝基、羟基、取代或非取代的烷基、取代或非取代的烷氧基、取代或非取代的烷基羰基、取代或非取代的环烷基、取代或非取代的芳香基、取代或非取代的芳氧基中的任意一种基团。其中，当R、R’、R”为卤素原子时，具体可以是氟原子、氯原子、溴原子或碘原子。本申请实施方式中，R、R’、R”中，取代或非取代的烷基可以是取代或非取代的C1-C20烷基，具体可以是取代或非取代的C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20烷基，例如取代或非取代的甲基(-CH3)、取代或非取代的乙基、取代或非取代的异丙基、取代或非取代的丁基等；取代或非取代的烷氧基可以是取代或非取代的C1-C20烷氧基，具体可以是取代或非取代的C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20烷氧基，例如取代或非取代的甲氧基(-OCH3)、取代或非取代的乙氧基(-OCH2CH3)、取代或非取代的丙氧基、取代或非取代的丁氧基等；取代或非取代的烷基羰基可以是取代或非取代的C1-C20烷基羰基，具体可以是取代或非取代的C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20烷基羰基，例如取代或非取代的甲基羰基(CH3-(C＝O)-)、取代或非取代的乙基羰基(CH3CH2-(C＝O)-)、取代或非取代的丙基羰基、取代或非取代的丁基羰基等；取代或非取代的环烷基可以是取代或非取代的C3-C20环烷基，例如取代或非取代的环丙烷基、取代或非取代的环丁烷基、取代或非取代的环戊烷基、取代或非取代的环己烷基等；取代或非取代的芳香基可以是取代或非取代的C6-C20芳香基，具体可以是取代或非取代的C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20芳香基，例如取代或非取代的苯基、萘基、联苯基、三联苯基、芴基、蒽基等；取代或非取代的芳氧基可以是取代或非取代的C6-C20芳氧基，具体可以是取代或非取代的C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20芳氧基，例如取代或非取代的苯氧基等。R、R’、R”中，取代的烷基、取代的烷氧基、取代的烷基羰基、取代的环烷基、取代的芳香基、取代的芳氧基中的取代基团可以但不限于是卤素原子(包括氟原子、氯原子、溴原子或碘原子)。例如取代的烷基可以是三氟甲基、三氟乙基等。式(Ⅰ)中，R、R’可以是位于其所在环结构上的任意空位碳原子(未连接有连接基团Y、基团A、基团B的碳原子)上。式(Ⅱ)中，R”可以是位于其所在环结构上的任意空位碳原子上。
本申请一些实施方式中，具有式(Ⅰ)所示结构的光敏配体具体可以是包括式(Ⅰ-1)至式(Ⅰ-14)所示的任意一种化合物：

式(Ⅰ-1)至式(Ⅰ-14)中，m为大于或等于0的整数。m具体例如可以是0、1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29。
本申请一些实施方式中，具有式(Ⅱ)所示结构的光敏配体具体可以是包括式(Ⅱ-1)至式(Ⅱ-12)所示的任意一种化合物：

式(Ⅱ-1)至式(Ⅱ-12)中，m为大于或等于0的整数。m具体例如可以是0、1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29。
本申请实施方式中，纳米晶颗粒包括II-VI族化合物、IV-VI族化合物、III-V族化合物、III-VI族化合物、VIB-VIA族化合物、VIII-VI族化合物、I-VI族化合物、I族单质、IV族单质、I-IV-VII族化合物、钙钛矿化合物中的一种或多种。本申请实施例的纳米晶颗粒可以是由上一种材质构成，也可以是由两种或两种以上的材质构成；纳米晶颗粒可以是单一材质颗粒、均匀的混合物颗粒、梯度混合物颗粒、核壳结构颗粒等，还可以是上述化合物的掺杂产物。
本申请一些实施方式中，纳米晶颗粒可以但不限于是包括CdS,CdSe,CdTe,ZnS,ZnSe,ZnTe,PbS,PbSe,PbTe,HgS,HgSe,HgTe,GaN,GaP,GaAs,InP,InAs,ZnO,SnO2,TiO2,In2O3,Ga2O3,SiO2,NiO,MoO3,WO3,Cu2O,CuO,Fe3O4,Au,Ag,碳点，CsPbCl3,CsPbBr3,CsPbI3,CH3NH3PbCl3,CH3NH3PbBr3,CH3NH3PbI3，或上述物质的混合物、梯度混合物、核壳结构，或上述物质的混合物的核壳结构，或上述物质的梯度混合物的核壳结构等。本申请实施方式中，纳米晶颗粒可以是根据需要自行制备，也可以通过商购获得。
本申请实施方式中，纳米晶颗粒可以是量子点，具体可以是红色量子点、绿色量子点、蓝色量子点。
本申请实施方式中，纳米晶颗粒的粒径可以是5nm-20nm。适合的纳米晶颗粒粒径尺寸有利于获得较好的发光性能。一些实施例中，纳米晶颗粒的粒径可以是5nm、6nm、7nm、8nm、9nm、10nm、11nm、12nm、13nm、14nm、15nm、16nm、17nm、18nm、19nm、20nm。
本申请实施方式中，纳米晶颗粒101表面的配体102的总质量为纳米晶颗粒101质量的1％-30％。即配位于纳米晶颗粒101表面的配体102的总质量相对纳米晶颗粒101的质量为1％-30％。一些实施例中，纳米晶颗粒101表面的配体102的总质量为纳米晶颗粒101质量的1％、2％、5％、10％、12％、15％、20％、25％、30％等。具体地，纳米晶颗粒101表面的具有式(Ⅰ)和/或式(Ⅱ)所示结构的光敏配体的总质量为纳米晶颗粒101质量的1％-30％。适合的光敏配体配位量有利于使纳米晶复合物具有较高光敏感特性和 较高热稳定性，同时能够较好地发挥纳米晶颗粒本身的性能。
参见图6，本申请实施例的纳米晶复合物，在紫外光照射下，可以通过配位于纳米晶颗粒表面的具有式(Ⅰ)和/或式(Ⅱ)所示结构的光敏配体发生颗粒与颗粒之间的交联，因此可以借助掩模板曝光和溶剂显影，直接实现图案化薄膜的制备。具体地，曝光区域的纳米晶复合物经紫外光照后发生光交联形成薄膜，而非曝光区域的纳米晶复合物没有发生光交联，可以通过溶剂被洗脱，从而获得图案化的薄膜。
本申请实施例还提供一种上述的纳米晶复合物的制备方法，包括：
将表面配位有第一配体的纳米晶颗粒分散于溶剂中，再加入上述具有式(Ⅰ)和/或式(Ⅱ)所示结构的光敏配体，搅拌反应后，得到配体交换后的纳米晶颗粒，即得到所述纳米晶复合物。
本申请实施方式中，搅拌反应可以是在室温下进行。搅拌反应的时间可以是10min-120min。本申请实施方式中，第一配体可以是包括饱和或不饱和脂肪羧酸配体，具体可以但不限于包括油酸配体。本申请实施方式中，溶剂可以但不限于包括氯仿、氯苯、苯甲酸乙酯中的一种或多种。本申请实施方式中，具有式(Ⅰ)和/或式(Ⅱ)所示结构的光敏配体的加入的质量可以是等于表面配位有第一配体的纳米晶颗粒的质量，即具有式(Ⅰ)和/或式(Ⅱ)所示结构的光敏配体的加入的质量等于第一配体和纳米晶颗粒的总质量。
本申请一些实施方式中，搅拌反应完成后，可用过量甲醇沉淀一次，收集沉淀，获得粉体形式的纳米晶复合物产品；也可以是将所得沉淀复溶于溶剂中，得到纳米晶复合物分散液产品。溶剂可以但不限于包括氯仿、氯苯、苯甲酸乙酯中的一种或多种。
本申请实施方式中，具有式(Ⅰ)所示结构的光敏配体可以是以羟基取代的查尔酮为原料，引入目标基团获得。例如，式(Ⅰ-1)所示结构的光敏配体可以是羟基取代的查尔酮与二酸反应获得，制备过程可以是如反应式(1)所示：
其中，m可以是大于或等于0的整数。
本申请实施方式中，具有式(Ⅱ)所示结构的光敏配体可以是以羟基取代的香豆素为原料，引入目标基团获得。例如，式(Ⅰ-1)所示结构的光敏配体的制备过程可以是：
其中，m可以是大于或等于0的整数。
本申请实施例提供的纳米晶复合物的制备方法工艺简单，易实现量化生产。
本申请实施例还提供一种纳米晶组合物，该纳米晶组合物包括本申请实施例上述的纳米晶复合物和溶剂。本申请实施方式中，溶剂可以但不限于包括氯仿、氯苯、苯甲酸乙酯中的一种或多种。
本申请实施方式中，纳米晶组合物中，纳米晶复合物的质量浓度可以是1mg/mL-100mg/mL。一些实施例中，纳米晶复合物的质量浓度为1mg/mL、5mg/mL、10mg/mL、15mg/mL、20mg/mL、30mg/mL、40mg/mL、50mg/mL、60mg/mL、70mg/mL、80mg/mL、90mg/mL、100mg/mL。适合的纳米晶复合物浓度可以使采用该纳米晶组合物制备的纳米晶薄膜具有较好的综合性能。
参见图7，本申请实施例还提供一种图案化薄膜的制备方法，包括：
在基底11上设置含本申请实施例上述纳米晶复合物的溶液或上述的纳米晶组合物，形成涂覆层12，采用掩膜板13进行曝光显影，经曝光的区域的纳米晶复合物发生光交联附着在基底11上，未经曝光的区域的纳米晶复合物经显影去除，形成图案化薄膜12’。
本申请实施方式中，曝光的时间可以是0.1秒-600秒。一些实施例中，曝光的时间例如可以是0.1秒、10秒、15秒、30秒、40秒、50秒、60秒、100秒。本申请实施方式中，曝光采用的是紫外光照，光照波长可以是365nm，光照强度可以是0.001mW/cm2-1000mW/cm2。一些实施例中，光照强度例如可以是0.001mW/cm2、1mW/cm2、5mW/cm2、10mW/cm2、20mW/cm2、30mW/cm2、50mW/cm2、100mW/cm2。
本申请实施例的纳米晶复合物具有较好的光敏感特性，可以在较低的辐照剂量和较短的曝光时间条件 下实现交联，完成图案化薄膜的制备，从而可以节约能量和时间。
本申请实施方式中，显影为溶剂显影，显影采用能够洗脱所述纳米晶复合物的有机溶剂，溶剂例如可以是氯仿等。
本申请实施方式中，形成涂覆层后，曝光显影之前，可以进行退火处理，由于本申请实施例的纳米晶复合物具有较低的热敏感交联活性，因此可以避免纳米晶复合物涂覆层在退火时发生交联，影响图案化的精细化结果。
本申请实施例的图案化薄膜的制备方法，可以通过较短的曝光时间实现良好的交联效果，采用溶剂显影即可，过程较简单，不仅可以节约能量和时间，且可以获得较高分辨率的图案。
本申请实施例还提供一种由本申请实施例上述的纳米晶复合物经交联形成的图案化薄膜；或者由本申请实施例上述制备方法制得的图案化薄膜。该图案化薄膜可以实现高分辨率图案制备，如可以实现10微米以下甚至3微米以下子像素尺寸。
参见图8，本申请实施例还提供一种电子器件200，该电子器件200包括相对设置的第一电极201和第二电极202，以及位于第一电极201和第二电极202之间的功能层203，功能层203包括本申请实施例上述的纳米晶复合物100的交联产物；或者功能层203包括本申请实施例上述的图案化薄膜。
本申请实施方式中，电子器件200可以但不限于包括LED、QLED、Mini-LED、Micro-LED、Nano-LED、QD-OLED中的任意一种。本申请实施方式中，电子器件200可以是正置的器件，也可以是倒置的器件。
本申请实施方式中，第一电极201和第二电极202分别为阳极和阴极。阳极和阴极的构成材料为导电材料，可以独立地选自导电金属、导电金属氧化物、导电聚合物等。其中，导电金属可以包括镁(Mg)、铝(Al)、金(Au)、银(Ag)、铂(Pt)、靶(Pd)等金属单质及其合金中的一种或多种；导电金属氧化物包括但不限于氧化铟锡(ITO)、氧化铟锌(IZO)、掺铝氧化锌(AZO)、掺氟二氧化锡(FTO)、掺磷二氧化锡(PTO)等中的一种或多种；导电聚合物包括但不限于聚噻吩、聚吡咯、聚苯胺等。
本申请实施方式中，功能层203包括发光层2031。发光层2031包括本申请实施例上述的纳米晶复合物100的交联产物；或者功能层203包括本申请实施例上述的图案化薄膜。
本申请实施方式中，功能层203还包括位于第一电极201和发光层2031之间的第一载流子传输层2032，以及位于第二电极202和发光层2031之间的第二载流子传输层2033。以第一电极201为阳极，第二电极202为阴极为例，第一载流子传输层2032可以是包括位于阳极201与发光层2031之间的空穴注入层2032a、空穴传输层2032b、电子阻挡层2032c中的一种或多种。其中，空穴注入层2032a位于阳极201与空穴传输层2032b之间，电子阻挡层2032c位于发光层2031与空穴传输层2032b之间。第二载流子传输层2033可以是包括位于阴极202与发光层2031之间的电子注入层2033a、电子传输层2033b、空穴阻挡层2033c中的一种或多种。其中，电子注入层2033a位于阴极202与电子传输层2033b之间，空穴阻挡层2033c位于阴极202与空穴传输层2032b之间。一些实施例中，如图8所示，电子器件200包括依次设置的阳极201、空穴注入层2032a、空穴传输层2032b、电子阻挡层2032c、发光层2031、空穴阻挡层2033c、电子传输层2033b、电子注入层2033a。需要说明的是功能层203的各层并非全部必需，但发光层2031是必需的。例如，功能层203沿阳极201向阴极202的方向，也可以依次包括“发光层2031/电子传输层2033b”的层叠结构，或者包括“发光层2031/电子注入层2033a”的层叠结构，或者包括“空穴注入层2032a/发光层2031/电子传输层2033b”的层叠结构，或者包括“空穴注入层2032a/发光层2031/电子注入层2033a”的层叠结构，或者包括“空穴传输层2032b/发光层2031/电子传输层2033b”的层叠结构，或者包括“空穴注入层2032a/空穴传输层2032b/发光层2031/电子传输层2033b”的层叠结构，或者包括“空穴注入层2032a/空穴传输层2032b或电子阻挡层2032c/发光层2031/空穴阻挡层2033c或电子传输层2033b/电子注入层2033a”的层叠结构，或者包括“空穴注入层2032a/空穴传输层2032b/电子阻挡层2032c/发光层2031/空穴阻挡层2033c或电子传输层2033b/电子注入层2033a”的层叠结构等。其中“/”表示各层分界。本申请中，对以上各层的厚度没有特定的限制，本领域技术人员可根据实际需要确定。上述各层的材料为本领域的常规选择，本申请无特殊限定。
在一些实施方式中，电子器件200还可以具有基板204(如图8所示)。基板204可以是位于阳极201远离功能层203的一侧(如图8所示)，基板204也可以是位于阴极202远离功能层203的一侧，即电子器件200可以是底发射器件，也可以是顶发射器件。基板204可以作为整个电子器件200的支撑部，其材质可以为石英、玻璃、单质硅、金属、塑料等。在一些实施方式中，基板204为对光透明的玻璃或塑料。基板204的形状可根据具体应用场景而定，例如可以形成为板状、膜状或片状等。基板204的厚度没有特别限定。基板204可以包含主动矩阵(active matrix)或被动矩阵(passive matrix)驱动电路。
本申请中，对阳极201、阴极202及功能层203各层的制备工艺没有特别限制，可以采用物理气相沉 积法、化学气相沉积法或涂布法等方式制备。其中，物理气相沉积法可以包括真空蒸镀法(如电阻蒸发源蒸镀法、电子束蒸发源蒸镀法、脉冲激光沉积法等)、溅镀法(如磁控溅射法)等中的一种或多种；涂布法可以包括溶液旋涂、浸涂、刮涂、喷涂、辊涂、喷墨印刷、丝网印刷法等方式。一般地，阳极201和阴极202可通过真空蒸镀法制备，功能层203的各层可通过真空蒸镀法或涂布法制备。以图8所示的电子器件200的制备为例，可先在基板204上形成阳极201，再在阳极201上依次形成包含发光层2031的功能层203，随后在功能层203上形成阴极202。在本申请其他实施方式中，可以在基板204上依次形成阴极202，包含发光层2031的功能层203，随后在功能层203上形成阳极201。
作为示例，空穴注入层的构成材料包括但不限于苯胺类导电聚合物、聚噻吩类导电聚合物等。空穴传输层的构成材料包括但不限于芳胺类有机材料(如TFB)等。电子传输层的构成材料可以包括但不限于碱土金属的氧化物(如氧化锌)等。此外，本申请中，对以上各层的厚度没有特定的限制，本领域技术人员可根据实际需要确定。
一些实施例中，量子点发光器件QLED的制备过程可以是：
在洗净的ITO阳极基板上制备空穴注入层；
在空穴注入层上制备空穴传输层；
在空穴传输层上按先后顺序制备红、绿、蓝三色图案化量子点膜层；
在红、绿、蓝三色图案化量子点膜层上制备电子注入层；
在电子注入层上制备金属电极。
本申请一具体实施例中，量子点发光器件QLED的制备过程可以是：
(1)取干净ITO基板依次用去离子水，乙醇超声10min；在洗净的ITO基板上旋涂聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(pedot：pss)水溶液，转速2500RPM，加速度800RPM，旋涂时间30s。随后在空气中加热至150℃，保持30min，得到pedot：pss膜层。
(2)在pedot：pss膜层旋涂6mg/ml可交联TFB(聚[(9,9-二辛基芴基-2,7-二基)-共-(4,4'-(N-(4-仲丁基苯基)二苯胺)])氯苯溶液，转速2800rpm，加速度900rpm，旋涂30秒，随后氮气环境下190℃退火30min，得到TFB膜层。
(3)在TFB膜层上继续旋涂本申请实施例的红色量子点溶液，转速2500rpm，加速度800rpm，旋涂30秒，得到量子点膜层；再采用365nm LED面光源(能量密度约30mW/cm2)和对应红色子像素的掩膜版照射量子点膜层，交联时间15s～60s。
(4)采用氯仿溶液在量子点膜层上旋涂，转速2500rpm，加速度800rpm，旋涂30秒，显影去除未曝光的红色量子点层部分；
(5)采用类似上述(3)-(4)的步骤，依次经过曝光、显影步骤制备绿色量子点、蓝色量子点的图案化薄膜；
(6)在红色、绿色、蓝色量子点膜层上旋涂30mg/ml ZnO溶液，转速4000RPM，加速度4000RPM，旋涂时间30s。
(7)最后以0.1nm/S的速率蒸镀100nm银电极。
根据本领域人员所熟知，顶发射器件中红色、绿色、蓝色器件可能需要不同的微腔结构，根据需要可以针对红色、绿色、蓝色子像素制备不同厚度的空穴传输层(例如使用TFB材料)和(或)电子传输层(例如ZnO或其他具有电子传输能力的金属氧化物)。另外，制备红色、绿色、蓝色量子点的图案化薄膜的顺序也可以根据需要进行改变。
参见图9，本申请实施例还提供了一种显示装置300，显示装置300包括本申请实施例上述的电子器件200。
本申请实施方式中，显示装置300可以是手机、平板电脑、笔记本电脑、可穿戴设备(如智能手表、智能手环等)、电视机、数码相机、摄录机、播放机、微显示设备(如智能眼镜、虚拟现实(Virtual Reality，VR)设备、增强现实(Augmented Reality，AR)设备、电话机、打印机、交通工具、家用电器、广告牌、信息板、汽车中控屏等任何具有显示功能的产品或者部件中的视觉显示装置。
参见图10，本申请实施例还提供一种电子设备400，电子设备400包括本申请实施例上述的显示装置300。电子设备400可以是手机、平板电脑、笔记本电脑、可穿戴设备(如智能手表、智能手环等)、电视机、数码相机、摄录机、播放机、微显示设备(如智能眼镜、虚拟现实(Virtual Reality，VR)设备、增强现实(Augmented Reality，AR)设备、电话机、打印机、交通工具、家用电器、广告牌、信息板、汽车中控屏等任何具有显示功能的电子产品。
下面分多个实施例对本申请实施例进行进一步的说明。
实施例1
光敏配体ChalBen的合成：
室温下向羟基取代的查尔酮的DMF(N,N-二甲基甲酰胺)溶液中加入酸反应物对氯苯乙酸及K2CO3，回流1.5h后，待降至室温后，向反应液中加入去离子水，再用盐酸调节其pH至酸性；随后向混合体系加入二氯甲烷DCM以萃取产物，最后以硫酸镁MgSO4干燥有机相；浓缩有机相后，采用硅胶柱层提纯：正己烷与乙酸乙酯的体积比为2：3，得到光敏配体ChalBen。图11是本申请实施例1制备的光敏配体ChalBen的核磁共振谱图。上述反应过程如式(1)所示：
实施例2
光敏配体ChalC5的合成
向羟基取代的查尔酮的DMF溶液中加入K2CO3及戊二酸酐，反应在50℃保持2h左右。反应结束后向混合体系加入2mol/L的盐酸溶液调至pH≈2-3，随后向混合体系加入二氯甲烷DCM以萃取产物，最后以硫酸镁MgSO4干燥有机相；浓缩有机相后，采用硅胶柱层提纯：二氯甲烷与乙酸乙酯的体积比为10：1，得到光敏配体ChalC5。图12是本申请实施例2制备的光敏配体ChalC5的核磁共振谱图。反应过程如式(2)所示：
实施例3
光敏配体ChalC8的合成
将辛二酸与乙腈(ACN)，碳二亚胺(EDAC)与4-二甲氨基吡啶(DMAP)溶液混合，于0℃加入并搅拌，停留1小时；将羟基取代的查尔酮于室温下加入至上述所得混合体系中，之后于42℃反应保持50min。旋蒸去除乙腈，剩余混合物重溶于二氯甲烷，并以2mol/LHCl、NaCl饱和液、去离子水依次洗涤；以硅胶柱提纯：二氯甲烷与乙酸乙酯的体积比为10：1，得到光敏配体ChalC8。图13是本申请实施例3制备的光敏配体ChalC8的核磁共振谱图。反应过程如式(3)所示：
实施例4
光敏配体ChalC13的合成
将十二烷二酸与乙腈(ACN)，碳二亚胺(EDAC)与4-二甲氨基吡啶(DMAP)溶液混合，于0℃加入并搅拌，停留1小时；将羟基取代的查尔酮于室温下加入至上述所得混合体系中，之后于42℃反应保持1h。旋蒸去除乙腈，剩余混合物重溶于二氯甲烷，并以2mol/LHCl、NaCl饱和液、去离子水依次洗涤；以硅胶柱提纯：二氯甲烷与乙酸乙酯的体积比为10：1，得到光敏配体ChalC8。图14是本申请实施例4制备的光敏配体ChalC13的核磁共振谱图。反应过程如式(4)所示：
实施例5
光敏配体CouC2的合成
室温下向羟基取代的香豆素的DMF溶液中加入氯乙酸及碳酸钾K2CO3，于155℃回流1h；随后加入去离子水，以2mol/LHCl调节pH至酸性，过滤后，继续水洗，所得固体蒸干后，即得光敏配体CouC2。图15是本申请实施例5制备的光敏配体CouC2的核磁共振谱图。反应过程如式(5)所示：
实施例6
光敏配体CouC8的合成
将辛二酸与乙腈(ACN)，碳二亚胺(EDAC)与4-二甲氨基吡啶(DMAP)溶液混合，于0℃加入并搅拌，停留1小时；将羟基取代的香豆素溶于乙腈中，于室温下加入至上述所得混合体系中，之后于40℃-45℃反应保持45min。旋蒸去除乙腈，剩余混合物重溶于氯仿，并以2mol/LHCl、NaCl饱和液、去离子水依次洗涤；以硫酸镁MgSO4干燥有机相后除去溶剂氯仿；最后以乙醇重结晶,过滤保留液相，除去乙醇后得到光敏配体ChalC8。图16是本申请实施例6制备的光敏配体CouC8的核磁共振谱图。反应过程如式(6)所示：
实施例7
光敏配体CouC13的合成
将十三烷二酸与乙腈(ACN)，碳二亚胺(EDAC)与4-二甲氨基吡啶(DMAP)溶液混合，于0℃加入并搅拌，停留1小时；将羟基取代的香豆素溶于乙腈中，于室温下加入至上述所得混合体系中，之后于45℃反应保持2h。旋蒸去除乙腈，剩余混合物重溶于氯仿，并以2mol/LHCl、NaCl饱和液、去离子水依次洗涤；以MgSO4干燥有机相后除去溶剂氯仿；最后以乙醇重结晶,过滤保留液相，除去乙醇后得到白色固体产物，即得到光敏配体ChalC13。图17是本申请实施例7制备的光敏配体CouC13的核磁共振谱图。反应过程如式(7)所示：
以绿色量子点为例，绿色量子点的合成包括以下步骤：
(1)取5mmol Se粉和5mmol S粉溶于5ml三辛基膦(TOP)溶液中，得到(Se+S)-TOP前驱体。
(2)取0.14mmol醋酸镉、3.41mmol氧化锌和7ml油酸于50ml三颈瓶中，在氮气保护条件下升温至150℃，加热30min排除醋酸和水。加入15ml十八烯(ODE)并将反应体系升温至310℃。注入2ml(Se+S)-TOP前驱体，三颈瓶回温至300℃，反应15min，得到CdZnSeS/ZnS绿色量子点。
(3)加入过量甲醇和丙酮(体积比3:1)的混合溶液沉淀出量子点，在8000rpm下离心5min。将沉淀物溶于5ml辛烷溶液，用15ml丙酮再次沉淀，8000rpm下离心5min，重复一次。
(4)将得到的量子点沉淀配置成50mg/ml的氯仿溶液，待用。
量子点配体交换：
以将油酸配体交换成实施例3制备的光敏配体ChalC8为例：取1ml上述所得50mg/ml量子点的氯仿溶液，加入与量子点等质量的光敏配体ChalC8(50mg)，室温搅拌30min，得到配体交换后的量子点，即得到表面配位有光敏配体ChalC8的量子点，即量子点复合物，采用过量甲醇沉淀一次，将沉淀复溶于氯仿溶液中，配置成7.5mg/ml的旋涂用量子点溶液。
将上述所得量子点溶液制备得到图案化量子电薄膜，并进行光交联效果和热交联性能的评估：
图案化量子电薄膜的制备：
(1)量子点薄膜制备：在干净的玻璃片上旋涂30mg/ml ZnO乙醇溶液，转速2800rpm，加速度900rpm，旋涂时间30秒。旋涂完成后氮气环境下150℃退火30min，得到ZnO膜；再在ZnO膜上继续旋涂上述所得量子点溶液，转速2500rpm，加速度800rpm，旋涂时间30秒；
(2)将旋涂所得量子点薄膜样品于100℃退火10min；
(3)曝光：用365nm LED面光源(能量密度约30mW/cm2)照射量子点膜层，交联时间15s～60s；
(4)显影：将附有量子点膜层的玻璃片整体浸没于氯仿溶液中，静置1min，曝光区域的量子点复合物经紫外光照后发生光交联形成薄膜，而非曝光区域的量子点复合物没有发生光交联，可以通过溶剂被洗脱，从而获得图案化量子点薄膜。
光交联效果和热交联性能的评估：
测量量子点薄膜样品不同阶段的UV-VIS(紫外-可见)吸收曲线，其结果如图18和图19所示。以表面配位有亚麻酸配体的量子点作为对比例，测量对比例的量子点薄膜样品不同阶段的UV-VIS吸收曲线，其结果如图20和图21所示，其中显影溶剂洗脱为浸没于氯仿溶液中静置1min。
图18中，曲线1为表面配位有ChalC8配体的量子点薄膜不经过光照交联和显影溶剂洗脱(浸没于氯仿溶液中静置1min)的UV-VIS吸收曲线(即不经任何处理的空白对照实验结果)，曲线2为表面配位有ChalC8配体的量子点薄膜经过100℃退火10min和15s光照交联、显影溶剂洗脱的UV-VIS吸收曲线，由图18可知，表面配位有ChalC8配体的量子点经过100℃退火10min和15s光照交联，经显影溶剂洗脱后保留率大于95％，表明ChalC8配体的光交联程度高。图20中，曲线1为表面配位有亚麻酸配体的量子点薄膜不经过光照交联和显影溶剂洗脱(浸没于氯仿溶液中静置1min)的UV-VIS吸收曲线(即不经任何处理的空白对照实验结果)，曲线2、曲线3、曲线4分别为表面配位有亚麻酸配体的量子点薄膜经过5min、10min、15min光照交联、显影溶剂洗脱的UV-VIS吸收曲线，由图20可知，在相同的显影溶剂洗脱条件下，表面配位有亚麻酸配体的量子点经过5min～15min的光照交联，保留率不到80％。相比对比例，本申请实施例的表面配位有ChalC8配体的量子点可以在更短的光照条件下实现较完全的交联，光交联效果好。如果经过曝光-显影之后，量子点薄膜样品的UV-VIS吸收曲线的吸光度相比曝光-显影之前的量子点薄膜样品有明显降低，说明量子点复合物光交联效果较差，导致量子点复合物被显影溶剂洗掉；反之，则说明光交联效果较好。
图19中，曲线1为表面配位有ChalC8配体的量子点薄膜不经过光照交联、不经过退火和显影溶剂洗脱(浸没于氯仿溶液中静置1min)的UV-VIS吸收曲线(即不经任何处理的空白对照实验结果)，曲线2为表面配位有ChalC8配体的量子点薄膜仅经过100℃退火10min，不经过光交联，再进行显影溶剂洗脱的UV-VIS吸收曲线，由图19可知，在100℃、10min的退火条件下，ChalC8配体不易自发交联，洗脱后残留量低于15％，说明ChalC8配体的热交联程度较低。图21中，曲线1为表面配位有亚麻酸配体的量子点薄膜不经过光照交联、不经过退火和显影溶剂洗脱(浸没于氯仿溶液中静置1min)的UV-VIS吸收曲线(即不经任何处理的空白对照实验结果)，曲线2为表面配位有亚麻酸配体的量子点薄膜经过100℃退火10min， 不经过光交联，再进行显影溶剂洗脱的UV-VIS吸收曲线，由图21可知，在100℃、10min的退火条件下，对比例表面配位有亚麻酸配体的量子点残留量达到50％，说明亚麻酸配体的热交联程度较高。
采用上述相同的方法将实施例1-2和实施例4-7的光敏配体制备成量子点溶液，再制备成图案化量子点薄膜，经检测获知，实施例1-2和实施例4-7的光敏配体均可以在经过15s～60s光照交联后，获得大于90％以上的保留率；在退火条件下，洗脱残留率均低于20％；表明采用实施例1-2和实施例4-7的光敏配体制备得到的纳米晶复合物具有高光交联活性和低热交联活性。
应理解，本文中涉及的第一、第二以及各种数字编号仅为描述方便进行的区分，并不用来限制本申请的范围。
本申请中，“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况，其中A,B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。
本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a,b,或c中的至少一项(个)”，或，“a,b,和c中的至少一项(个)”，均可以表示：a,b,c,a-b(即a和b),a-c,b-c,或a-b-c，其中a,b,c分别可以是单个，也可以是多个。
应理解，在本申请的各种实施例中，上述各过程的序号的大小并不意味着执行顺序的先后，部分或全部步骤可以并行执行或先后执行，各过程的执行顺序应以其功能和内在逻辑确定，而不应对本申请实施例的实施过程构成任何限定。

Claims (28)

  1. 一种纳米晶复合物，其特征在于，所述纳米晶复合物包括纳米晶颗粒和配位于所述纳米晶颗粒表面的配体，所述配体包括具有式(Ⅰ)和/或式(Ⅱ)所示结构的光敏配体，
    式(Ⅰ)中，所述X为与所述纳米晶颗粒配位结合的配位基团，所述Y为连接基团，所述A、B其中一者为-C＝O-，另一者为含有碳碳双键的基团，所述R、R’独立地为氢原子、卤素原子、硝基、羟基、取代或非取代的烷基、取代或非取代的烷氧基、取代或非取代的烷基羰基、取代或非取代的环烷基、取代或非取代的芳香基、取代或非取代的芳氧基中的一种；
    式(Ⅱ)中，所述X为与所述纳米晶颗粒配位结合的配位基团，所述Y、Y’为连接基团，所述R、R’、R”独立地为氢原子、卤素原子、硝基、羟基、取代或非取代的烷基、取代或非取代的烷氧基、取代或非取代的烷基羰基、取代或非取代的环烷基、取代或非取代的芳香基、取代或非取代的芳氧基中的一种；
    n为1、2或3。
  2. 如权利要求1所述的纳米晶复合物，其特征在于，所述配位基团包括羧基、氨基、磷酸基、磷脂基团、巯基中的任意一种。
  3. 如权利要求1或2所述的纳米晶复合物，其特征在于，所述连接基团Y包括取代或非取代的亚烷基、取代或非取代的亚芳基、取代或非取代的亚芳基烷基、取代或非取代的亚烷基芳基、取代或非取代的亚烷氧基、取代或非取代的亚芳氧基、取代或非取代的亚烷基芳氧基、取代或非取代的亚芳基烷氧基、含羰基的基团、含酯基和/或醚氧键的基团、含亚胺基的基团中的一种或多种。
  4. 如权利要求3所述的纳米晶复合物，其特征在于，所述含羰基的基团包括-C(＝O)-、-R1-C(＝O)-中的任意一种；所述含酯基和/或醚氧键的基团包括-R2-C(＝O)-O-、 中的任意一种；所述含亚胺基的基团包括-R3-CH2-NH-、-R3-C(＝O)-NH-中的任意一种，其中，R1、R2、R3为取代或非取代的亚烷基。
  5. 如权利要求3或4所述的纳米晶复合物，其特征在于，所述连接基团Y的碳原子数为1-30。
  6. 如权利要求1所述的纳米晶复合物，其特征在于，所述连接基团Y’包括氧原子、硫原子、取代或非取代的亚烷基、取代或非取代的亚烷氧基、含酯基的基团、含酰胺键的基团中的一种或多种。
  7. 如权利要求6所述的纳米晶复合物，其特征在于，所述连接基团Y’的碳原子数为0-30。
  8. 如权利要求1-7任一项所述的纳米晶复合物，其特征在于，所述R、R’、R”中，所述取代或非取代的烷基为取代或非取代的C1-C20烷基，所述取代或非取代的烷氧基为取代或非取代的C1-C20烷氧基，所述取代或非取代的烷基羰基为取代或非取代的C1-C20烷基羰基，所述取代或非取代的环烷基为取代或非取代的C3-C20环烷基，所述取代或非取代的芳香基为取代或非取代的C6-C20芳香基，所述取代或非取代的芳氧基为取代或非取代C6-C20芳氧基。
  9. 如权利要求1-8任一项所述的纳米晶复合物，其特征在于，所述具有式(Ⅰ)所示结构的光敏配体 包括式(Ⅰ-1)至式(Ⅰ-14)所示的任意一种化合物：

    式(Ⅰ-1)至式(Ⅰ-14)中，m为大于或等于0的整数。
  10. 如权利要求1-8任一项所述的纳米晶复合物，其特征在于，所述具有式(Ⅱ)所示结构的光敏配体包括式(Ⅱ-1)至式(Ⅱ-12)所示的任意一种化合物：

    式(Ⅱ-1)至式(Ⅱ-12)中，m为大于或等于0的整数。
  11. 如权利要求1-10任一项所述的纳米晶复合物，其特征在于，所述纳米晶颗粒包括II-VI族化合物、IV-VI族化合物、III-V族化合物、III-VI族化合物、VIB-VIA族化合物、VIII-VI族化合物、I-VI族化合物、I族单质、IV族单质、I-IV-VII族化合物、钙钛矿化合物中的一种或多种。
  12. 如权利要求1-11任一项所述的纳米晶复合物，其特征在于，所述纳米晶颗粒的粒径为5nm-20nm。
  13. 如权利要求1-12任一项所述的纳米晶复合物，其特征在于，所述纳米晶颗粒表面的配体的总质量为所述纳米晶颗粒质量的1％-30％。
  14. 如权利要求1-13任一项所述的纳米晶复合物的制备方法，其特征在于，包括：
    将表面配位有第一配体的纳米晶颗粒分散于溶剂中，再加入具有式(Ⅰ)和/或式(Ⅱ)所示结构的光敏配体，搅拌反应后，得到配体交换后的纳米晶颗粒，即得到所述纳米晶复合物。
  15. 如权利要求14所述的制备方法，其特征在于，所述第一配体包括饱和或不饱和脂肪羧酸配体。
  16. 如权利要求14或15所述的制备方法，其特征在于，所述溶剂包括氯仿、氯苯、苯甲酸乙酯中的一种或多种。
  17. 一种纳米晶组合物，其特征在于，所述纳米晶组合物包括权利要求1-13任一项所述的纳米晶复合物和溶剂。
  18. 如权利要求17所述的纳米晶组合物，其特征在于，所述纳米晶组合物中，纳米晶复合物的质量浓度为1mg/mL-100mg/mL。
  19. 如权利要求17或18所述的纳米晶组合物，其特征在于，所述溶剂包括氯仿、氯苯、苯甲酸乙酯中的一种或多种。
  20. 一种图案化薄膜的制备方法，其特征在于，包括：
    在基底上设置含权利要求1-13任一项所述纳米晶复合物的溶液或权利要求17-19任一项所述的纳米晶组合物，采用掩膜板进行曝光显影，经曝光的区域的纳米晶复合物发生光交联附着在所述基底上，未经曝光的区域的纳米晶复合物经显影去除，形成图案化薄膜。
  21. 如权利要求20所述的制备方法，其特征在于，所述曝光采用紫外光照，光照强度为0.001mW/cm2-1000mW/cm2。
  22. 如权利要求20或21所述的制备方法，其特征在于，所述曝光的时间为0.1秒-600秒。
  23. 如权利要求20-22任一项所述的制备方法，其特征在于，所述显影为溶剂显影，所述显影采用能够洗脱所述纳米晶复合物的有机溶剂。
  24. 一种由权利要求1-13任一项所述的纳米晶复合物经交联形成的图案化薄膜；或者由权利要求20-23任一项所述制备方法制得的图案化薄膜。
  25. 一种电子器件，其特征在于，所述电子器件包括相对设置的第一电极和第二电极，以及位于所述第一电极和所述第二电极之间的功能层，所述功能层包括权利要求1-13任一项所述的纳米晶复合物的交联产物；或者所述功能层包括权利要求24所述的图案化薄膜。
  26. 如权利要求25所述的电子器件，其特征在于，所述电子器件包括LED、QLED、Mini-LED、Micro-LED、Nano-LED、QD-OLED中的任意一种。
  27. 一种显示装置，其特征在于，所述显示装置包括权利要求25或26所述的电子器件。
  28. 一种电子设备，其特征在于，所述电子设备包括权利要求27所述的显示装置。
PCT/CN2023/113820 2022-08-22 2023-08-18 纳米晶复合物及其制备方法和应用 WO2024041462A1 (zh)

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