CN117835778A - Preparation method of patterned quantum dot film, photoelectric device and electronic equipment - Google Patents

Preparation method of patterned quantum dot film, photoelectric device and electronic equipment Download PDF

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Publication number
CN117835778A
CN117835778A CN202211175684.XA CN202211175684A CN117835778A CN 117835778 A CN117835778 A CN 117835778A CN 202211175684 A CN202211175684 A CN 202211175684A CN 117835778 A CN117835778 A CN 117835778A
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quantum dot
layer
ligand
quantum dots
group
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张昊
付钟
周礼宽
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Tsinghua University
TCL Technology Group Co Ltd
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Tsinghua University
TCL Technology Group Co Ltd
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Priority to CN202211175684.XA priority Critical patent/CN117835778A/en
Priority to PCT/CN2023/120673 priority patent/WO2024067394A1/en
Publication of CN117835778A publication Critical patent/CN117835778A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning

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  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The application discloses a preparation method of a patterned quantum dot film, a photoelectric device and electronic equipment, wherein the preparation method comprises the following steps: the preparation method has the advantages of high pattern resolution, high universality, simple preparation process, no damage to the quantum dots, and suitability for large-scale industrial production, can be applied to the preparation of the luminescent layer of the photoelectric device, can construct a luminescent layer with a single-layer structure or a multilayer structure containing quantum dots with different luminescent colors, and is applied to electronic equipment to facilitate the improvement of the display definition and the service life of the electronic equipment.

Description

Preparation method of patterned quantum dot film, photoelectric device and electronic equipment
Technical Field
The application relates to the technical field of photoelectricity, in particular to a preparation method of a patterned quantum dot film, a photoelectric device and electronic equipment.
Background
Quantum Dots (QDs), also known as semiconductor nanocrystals, are nanocrystals with a radius that is less than or near the bohr radius of an exciton, typically between 1nm and 20nm in size. The quantum dot has unique fluorescent nanometer effect, the luminous wavelength of the quantum dot can be regulated and controlled by changing the size and the composition of components, and the quantum dot has the advantages of narrow half-peak width of a luminous spectrum, high color purity, good light stability, wide excitation spectrum and controllable emission spectrum, and has wide application prospect in the technical fields of photovoltaic power generation, photoelectric display, biological probes and the like.
In the field of electro-optical display technology, quantum dots can be used as luminescent materials, and quantum dots are typically used as luminescent layers in the form of thin films, such as patterned quantum dot thin films. The conventional quantum dot film patterning method has the defects that: compared with the quantum dot film before patterning, the quantum dot film after patterning has the problem that the luminous quantum yield is obviously reduced, so that the luminous performance of the quantum dot film is negatively influenced.
Disclosure of Invention
The application provides a preparation method of a patterned quantum dot film, a photoelectric device and electronic equipment, so as to solve the problem that the luminous quantum yield of the patterned quantum dot film is obviously reduced.
The technical scheme of the application is as follows:
in a first aspect, the present application provides a method for preparing a patterned quantum dot film, including the steps of:
providing a substrate, forming a quantum dot film layer on one side of the substrate, wherein the quantum dot film layer comprises quantum dots and a ligand remover, and the surface of each quantum dot is connected with a ligand;
carrying out partial exposure treatment on the quantum dot film layer so that the quantum dot film layer comprises an exposed part and an unexposed part, wherein the ligand of the exposed part is separated from the quantum dot; and
removing the unexposed part to obtain a patterned quantum dot film;
wherein the ligand remover is a compound shown in the following general formula (I):
in the general formula (I), R 2 At least one selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group; in the partial exposure treatment, the ligand remover in the exposed portion loses the R 1 And forming electrophilic groups such that the ligands in the exposed portion bind to the electrophilic groups and are detached from the quantum dots.
Optionally, the R 1 A group selected from the group that can be detached from the ligand-removing agent in the partial exposure treatment;
and/or, the R 1 The pKa value of the conjugate acid formed after the proton is obtained in water at 25 ℃ is between-10 and 9;
and/or, said removing said unexposed portions comprises the steps of: and eluting the quantum dot film layer by using an eluent, wherein the unexposed part can be dissolved in the eluent.
Optionally, the R 1 Selected from the group consisting of a halogen atom, p-toluenesulfonyl, p-toluenesulfonyloxy, mercapto, cyano, azido, thiocyano or alkoxycarbonyl.
Optionally, the substituted or unsubstituted alkyl group has 1 to 10 carbon atoms;
alternatively, the substituted or unsubstituted alkoxy group has 1 to 10 carbon atoms;
alternatively, the substituted or unsubstituted aryl group has 6 to 20 ring atoms;
alternatively, the substituted or unsubstituted heteroaryl group has a number of ring atoms of 5 to 20.
Optionally, the illumination wavelength of the partial exposure treatment is 200nm to 500nm;
and/or, the illumination energy of the partial exposure treatmentThe amount was 50mJ/cm 2 To 6000mJ/cm 2 。
And/or the molar absorptivity of the ligand remover at the illumination wavelength of the partial exposure treatment is 10cm -1 M -1 To 10 5 cm -1 M -1 。
Optionally, the ligand remover is selected from at least one of triphenylchloromethane, triphenylbromomethane, triphenyliodomethane, triphenylacetonitrile or triphenylmethyl mercaptan.
Optionally, the ligand is at least one selected from an amine ligand having 6 to 20 carbon atoms in the main chain, a carboxyl ligand having 6 to 20 carbon atoms in the main chain, and a thiol ligand having 6 to 20 carbon atoms in the main chain.
Optionally, the forming a quantum dot film layer on one side of the substrate includes the steps of: and applying a solution containing quantum dots and a ligand remover on one side of the substrate to form the quantum dot film layer.
Optionally, in the solution, the concentration of the quantum dots is 1mg/mL to 1000mg/mL;
and/or, in the solution, the quantum dots: the mass ratio of the ligand remover is 1: (0.01-2).
Optionally, the quantum dot is selected from at least one of single component quantum dot, core-shell structure quantum dot, inorganic perovskite quantum dot, organic perovskite quantum dot or organic-inorganic hybrid perovskite quantum dot;
for the single component quantum dot and the core-shell structure quantum dot, the material of the single component quantum dot, the material of the core-shell structure quantum dot, and the material of the shell of the core-shell structure quantum dot are selected from at least one of group II-VI compound, group III-V compound, group IV-VI compound, or group I-III-VI compound independently of each other, wherein the group II-VI compound is selected from CdS, cdSe, cdTe, znS, znSe, znTe, znO, hgS, hgSe, hgTe, cdSeS, cdSeTe, cdSTe, znSeS, znSeTe, znSTe, hgSeS, hgSeTe, hgSTe, cdZnS, cdZnSe, cdZnTe, cdHgS, cdHgSe, cdHgTe, hgZnS, hgZnSe, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSe Te, cdHgSTe, hgZnSeS, hgZnSeTe or HgZnSTe, said III-V compound being selected from at least one of GaN, gaP, gaAs, gaSb, alN, alP, alAs, alSb, inN, inP, inAs, inSb, gaNP, gaNAs, gaNSb, gaPAs, gaPSb, alNP, alNAs, alNSb, alPAs, alPSb, inNP, inNAs, inNSb, inPAs, inPSb, gaAlNP, gaAlNAs, gaAlNSb, gaAlPAs, gaAlPSb, gaInNP, gaInNAs, gaInNSb, gaInPAs, gaInPSb, inAlNP, inAlNAs, inAlNSb, inAlPAs or InAlPSb, said IV-VI compound being selected from at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe or SnPbSTe, said I-III-VI compound being selected from CuInS 2 、CuInSe 2 Or AgInS 2 At least one of (a) and (b);
and/or the dielectric constant of the eluent is less than 10.
Optionally, the eluent is selected from at least one of toluene, chlorobenzene, n-hexane, n-octane, n-heptane, cyclohexane, dichloromethane, chloroform and tetrahydrofuran.
In a second aspect, the present application provides an optoelectronic device comprising:
an anode;
a cathode disposed opposite the anode; and
A light-emitting layer disposed between the anode and the cathode;
the light-emitting layer comprises a plurality of quantum dot layers, at least one quantum dot layer in the plurality of quantum dot layers is prepared by the preparation method according to any one of the first aspect, and the material of each quantum dot layer in the plurality of quantum dot layers comprises quantum dots with at least one light-emitting color.
Optionally, the optoelectronic device further comprises an electronic functional layer disposed between the cathode and the light emitting layer; the electron functional layer comprises an electron transport layer and/or an electron injection layer, and for the electron functional layer comprising the electron transport layer and the electron injection layer, the electron transport layer is closer to the light emitting layer than the electron injection layer, and the electron injection layer is closer to the cathode than the electron transport layer;
and/or the photoelectric device further comprises a hole functional layer, wherein the hole functional layer is arranged between the light-emitting layer and the anode, the hole functional layer comprises a hole injection layer and/or a hole transport layer, and for the hole functional layer comprising the hole injection layer and the hole transport layer, the hole injection layer is closer to the anode than the hole transport layer, and the hole transport layer is closer to the light-emitting layer than the hole injection layer;
And/or the materials of the anode and the cathode are selected from at least one of metal, carbon material or first metal oxide independently of each other, wherein the metal is selected from at least one of Al, ag, cu, mo, au, ba, ca or Mg, the carbon material is selected from at least one of graphite, carbon nano tube, graphene or carbon fiber, and the first metal oxide is selected from at least one of indium tin oxide, fluorine doped tin oxide, tin antimony oxide, aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide or magnesium doped zinc oxide.
Optionally, the material of the electron transport layer comprises a second metal oxide selected from ZnO and TiO 2 、SnO 2 、BaO、Ta 2 O 3 、ZrO 2 At least one of TiLiO, znGaO, znAlO, znMgO, znSnO, znLiO, inSnO, alZnO, znOCl, znOF or ZnMgLiO;
and/or the material of the electron injection layer comprises at least one of an alkali metal halide, an alkali metal organic complex or an organic phosphine compound selected from at least one of an organic phosphorus oxide, an organic thiophosphine compound or an organic selenophosphine compound;
and/or the material of the hole injection layer is selected from poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid), copper phthalocyanine, titanyl phthalocyanine, 4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine, 4' -tris [ 2-naphthylphenylamino ] triphenylamine, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, transition metal oxide, or transition metal chalcogenide selected from at least one of an oxide of nickel, an oxide of molybdenum, an oxide of tungsten, an oxide of vanadium, an oxide of chromium, or an oxide of copper, the transition metal chalcogenide selected from at least one of a sulfide of molybdenum, a selenide of molybdenum, a sulfide of tungsten, a selenide of tungsten, or a sulfide of copper;
And/or the material of the hole transport layer is selected from poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), 3-hexyl substituted polythiophene, poly (9-vinylcarbazole), poly [ bis (4-phenyl) (4-butylphenyl) amine]Poly (N, N '-bis (4-butylphenyl) -N, N' -diphenyl-1, 4-phenylenediamine-CO-9, 9-dioctylfluorene), 4',4 "-tris (carbazol-9-yl) triphenylamine, 4' -bis (9-carbazol) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid), doped or undoped graphene, C60, niO, moO 3 、WO 3 、V 2 O 5 、CrO 3 At least one of CuO or P-type gallium nitride.
In a third aspect, the present application provides an electronic device comprising an optoelectronic device according to any one of the second aspects.
The application provides a preparation method of a patterned quantum dot film, a photoelectric device and electronic equipment, and the preparation method has the following technical effects:
the preparation method of the patterned quantum dot film can prepare the quantum dots with different structures to form the patterned film, has the advantages of high pattern resolution, high universality, simple preparation process and suitability for large-scale industrial production, and the whole patterning process does not involve the process of damaging the quantum dots, such as ligand exchange, so that the photoelectric properties of the quantum dots before and after patterning are not obviously changed, for example: the luminous quantum yield of the red quantum dots before and after patterning is kept consistent; the luminous quantum yield of the green quantum dots after patterning is 90% of the luminous quantum yield of the green quantum dots before patterning; for blue quantum dots with poor stability and sensitive surface, the luminous quantum yield of the blue quantum dots after patterning is 70% of the luminous quantum yield of the blue quantum dots before patterning.
The preparation method of the patterned quantum dot film can be applied to the preparation of the light-emitting layer of the photoelectric device, and can construct a single-layer structure light-emitting layer or a multi-layer structure light-emitting layer containing quantum dots with different light-emitting colors (such as red, green and blue), and compared with the photoelectric device containing the unpatterned quantum dot film, the photoelectric performance (such as light-emitting brightness, external quantum efficiency, service life and starting voltage) of the photoelectric device containing the patterned quantum dot film is very small.
The photoelectric device is applied to the electronic equipment, and is beneficial to improving the display definition and prolonging the service life of the electronic equipment.
Drawings
Technical solutions and other advantageous effects of the present application will be made apparent from the following detailed description of specific embodiments of the present application with reference to the accompanying drawings.
Fig. 1 is a schematic flow chart of a first method for preparing a patterned quantum dot film according to an embodiment of the present disclosure;
FIG. 2 is a schematic diagram of a mechanism of patterning a quantum dot film in an embodiment of the present application;
fig. 3 is a schematic flow chart of a second method for preparing a patterned quantum dot film according to an embodiment of the present disclosure;
fig. 4 is a schematic structural diagram of a first photoelectric device provided in an embodiment of the present application;
FIG. 5 is an optical photograph of a patterned quantum dot film under a fluorescence microscope provided in example 1 of the present application;
FIG. 6 is an optical photograph of a patterned quantum dot film under a fluorescence microscope as provided in example 2 of the present application;
FIG. 7 is an optical photograph of a patterned quantum dot film under a fluorescence microscope as provided in example 3 herein;
FIG. 8 is an optical photograph of a patterned quantum dot film under a fluorescence microscope as provided in example 4 herein;
fig. 9 is a graph showing the variation of the luminescence quantum yield of the red, green and blue quantum dots of example 4 before and after patterning;
FIG. 10 is an optical photograph of a patterned quantum dot film under a bright field optical microscope as provided in example 5 of the present application;
FIG. 11 is an optical photograph of a patterned quantum dot film under a fluorescence microscope as provided in example 6 herein;
FIG. 12 is an optical photograph of a patterned quantum dot film under a fluorescence microscope as provided in example 7 herein;
fig. 13 is a schematic structural diagram of a second photoelectric device provided in an embodiment of the present application;
fig. 14 is an optical photograph of a light emitting layer of an optoelectronic device according to embodiment 8 of the present application under a fluorescence microscope, wherein the light emitting layer has a quantum dot array structure;
FIG. 15 is an optical photograph of a quantum dot film provided in comparative example 1 of the present application under a fluorescence microscope;
fig. 16 is a graph of characteristics of the photoelectric devices in example 11 and comparative example 2 in the present application, wherein a is a graph of current density-electroluminescence intensity-voltage characteristics of the photoelectric devices in example 11 and comparative example 2, B is a graph of external quantum efficiency-electroluminescence intensity characteristics of the photoelectric devices in example 11 and comparative example 2, and C is a graph of luminescence quantum yield-time characteristics of the photoelectric devices in example 11 and comparative example 2;
fig. 17 is a graph of characteristics of the photoelectric devices in example 12 and comparative example 3 in the present application, wherein D is a graph of current density-electroluminescence intensity-voltage characteristics of the photoelectric devices in example 12 and comparative example 3, E is a graph of external quantum efficiency-electroluminescence intensity characteristics of the photoelectric devices in example 12 and comparative example 3, and F is a graph of luminescence quantum yield-time characteristics of the photoelectric devices in example 12 and comparative example 3;
fig. 18 is a graph of characteristics of the photovoltaic devices in example 13 and comparative example 4 in the present application, wherein G is a graph of current density-electroluminescence intensity-voltage characteristics of the photovoltaic devices in example 13 and comparative example 4, H is a graph of external quantum efficiency-electroluminescence intensity characteristics of the photovoltaic devices in example 13 and comparative example 4, and I is a graph of luminescence quantum yield-time characteristics of the photovoltaic devices in example 13 and comparative example 4.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present invention. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the scope of the present application.
The following description of the embodiments is not intended to limit the preferred embodiments. Various embodiments of the present application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the ranges, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the description of the present application, the term "comprising" means "including but not limited to".
The term "at least one" means one or more, and "plurality" means two or more. The terms "at least one," "at least one of," or the like, refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c" or "at least one (individual) of a, b, and c" may each be expressed as: a. b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c, respectively, may be single or multiple.
In the present application, the description of "the a layer is formed on the side of the B layer" or "the a layer is formed on the side of the B layer away from the C layer" may mean that the a layer is directly formed on the side of the B layer or the side of the B layer away from the C layer, that is, the a layer is in direct contact with the B layer; it may also mean that the grounding between layers a is formed on one side of layer B or on one side of layer B away from layer C, i.e. other film layers may also be formed between layers a and B.
The scope of the term "and/or" includes any one of the two or more items listed in relation to each other as well as any and all combinations of items listed in relation to each other, including any two items listed in relation to each other, any more items listed in relation to each other, or all combinations of items listed in relation to each other. For example, "a and/or B" includes A, B and a+b three parallel schemes. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical scheme of "logical or" connection), and also include any and all combinations of A, B, C, D, i.e., any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical scheme of "logical and" connection).
The term "substituted or unsubstituted" means that the groups defined may or may not be substituted. When a defined group is substituted, it is understood that any position of the hydrogen atom in the defined group may be substituted with one or more substituents R selected from, but not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 20 carbon atoms, heterocyclyl containing 3 to 20 ring atoms, aromatic containing 6 to 20 ring atoms, heteroaromatic containing 5 to 20 ring atoms, -NR' R ", silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, and which may be further substituted with substituents acceptable in the art. It is understood that R 'and R "in-NR' R" are each independently selected from, but not limited to, H, deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 10 carbon atoms, heterocyclyl containing 3 to 20 ring atoms, aromatic containing 6 to 20 ring atoms, heteroaromatic containing 5 to 20 ring atoms. Preferably, R is selected from, but not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 20 carbon atoms, heterocyclyl containing 3 to 20 ring atoms, aromatic containing 6 to 20 ring atoms, heteroaromatic containing 5 to 20 ring atoms, silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, and which may be further substituted with substituents acceptable in the art.
The term "heteroatom" is a non-carbon atom and may be an N atom, an O atom, an S atom, etc.
The term "number of ring atoms" means the number of ring atoms constituting the ring itself, i.e., the number of ring-forming atoms, in a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atom contained in the substituent is not included in the ring atom. The same applies to the "number of ring atoms" described below, unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
The term "aryl" refers to an aromatic hydrocarbon radical derived from the removal of one hydrogen atom on the basis of an aromatic ring compound, which may be a monocyclic aryl radical, or a fused ring aryl radical, or a polycyclic aryl radical, at least one of which is an aromatic ring system for a polycyclic species. For example, "a substituted or unsubstituted aryl group having 6 to 20 ring atoms" refers to an aryl group containing 6 to 20 ring atoms, and a hydrogen atom at any position on the aryl group may be further substituted. Aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthryl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, perylenyl, acenaphthylenyl, and derivatives thereof. It will be appreciated that a plurality of aryl groups may also be interrupted by short non-aromatic units (e.g. <10% of non-H atoms, such as C, N or O atoms), and in particular such acenaphthene, fluorene, 9-diaryl fluorene, triarylamine, diaryl ether systems should also be included in the definition of aryl groups.
The term "heteroaryl" refers to an aryl group in which at least one carbon atom is replaced by a non-carbon atom, which may be an N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 20 ring atoms" refers to heteroaryl having 5 to 20 ring atoms, heteroaryl including, but not limited to, thienyl, furyl, pyrrolyl, diazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothioyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, phthalazinyl, phenanthridinyl, primary pyridyl, quinazolinonyl, dibenzothienyl, dibenzofuranyl, and derivatives thereof.
The term "alkyl" may denote straight, branched and/or cyclic alkyl groups. The number of carbon atoms of the alkyl group may be 1 to 20, 1 to 10, or 1 to 6. A phrase including the term(s), non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl 3, 7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, n-hexyleicosyl, 2-octyleicosyl, n-eicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, etc.
The term "alkoxy" refers to a group of the structure "-O-alkyl", i.e. an alkyl group as defined above is attached to other groups via an oxygen atom. Phrases containing this term, suitable examples include, but are not limited to: methoxy (-O-CH) 3 or-OMe), ethoxy (-O-CH 2 CH 3 or-OEt) and t-butoxy (-O-C (CH) 3 ) 3 or-OtBu).
The embodiment of the application provides a preparation method of a patterned quantum dot film, as shown in fig. 1, comprising the following steps:
s1, providing a substrate, forming a quantum dot film layer on one side of the substrate, wherein the quantum dot film layer comprises quantum dots and a ligand remover, and the surface of the quantum dots is connected with a ligand;
s2, carrying out partial exposure treatment on the quantum dot film layer so that the quantum dot film layer comprises an exposed part and an unexposed part, wherein a ligand in the exposed part is separated from the quantum dot;
s3, removing the unexposed part to obtain the patterned quantum dot film.
When the quantum dot film layer is in a wet film state or a partially cured state, the preparation method of the patterned quantum dot film before the step S3 further comprises the following steps: and drying the quantum dot film to obtain a solidified quantum dot film.
The ligand remover is a compound shown in the following general formula (I):
In the general formula (I), R 2 At least one selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group.
In the partial exposure treatment, the ligand remover in the exposed portion loses R 1 To form triphenylcarbonium ions with strong electrophilicity, the triphenylcarbonium ions are combined with the ligands of the exposed portions so that the ligands of the exposed portions are detached from the quantum dots, and the ligands of the unexposed portions are still connected to the surfaces of the quantum dots, therefore, in the elution treatment step, the ligands are configured to be dissolved in the eluent, the quantum dots of the exposed portions cannot be dissolved in the eluent due to the loss of the ligands, and the exposed portions remain on one side of the substrate, and the unexposed portions are dissolved in the eluent, so that the patterned quantum dot film is obtained. Taking triphenylchloromethane as a ligand remover and oleic acid and oleylamine as an example, as shown in fig. 2, under 254nm light, chlorine atoms in the triphenylchloromethane leave to form triphenylcarbonium ions, the triphenylcarbonium ions are combined with amino groups of the oleylamine to enable the oleylamine ligand to fall off from the quantum dots, and similarly, the triphenylcarbonium ions are combined with carboxyl groups of the oleic acid to enable the oleic acid ligand to fall off from the quantum dots. The triphenylcarbonium is bound to the ligand of the exposed portion The compound formed may or may not be soluble in the eluent, preferably in the eluent.
Specifically, in step S1, the substrate may have a single-layer structure or a multi-layer structure. For example, the substrate may be a single-layer structure, the substrate may be a rigid substrate or a flexible substrate, the material of the rigid substrate may be glass, ceramic, or metal, for example, and the material of the flexible substrate may be at least one of polyimide, polyethylene terephthalate, polyetheretherketone, polystyrene, polyethersulfone, polycarbonate, polyarylate, polyvinyl chloride, polyethylene, polyvinylpyrrolidone, polyacrylate, polyetherimide, polyethylene naphthalate, polyphenylene sulfide, polyallylate, or textile fiber, for example. As another example, the substrate may be a multi-layer structure, the substrate may be a pre-fabricated device comprising a substrate and a bottom electrode, and the solution is applied to the side of the bottom electrode remote from the substrate.
In step S1, the quantum dot film layer may be in a wet film state, a partially cured state, or a fully cured state. For the quantum dot film layer in the wet film state and the partially cured state, a drying treatment step is added before the elution treatment step to form the completely cured quantum dot film layer. The drying treatment may be performed before the partial exposure treatment step or after the partial exposure treatment step.
In some embodiments of the present application, step S1 includes the steps of: s is S 1a And applying a solution containing quantum dots and a ligand remover on one side of the substrate to form a quantum dot film layer, wherein the application mode of the solution comprises at least one of spin coating, ink-jet printing, knife coating, dip-coating, soaking, spraying, roll coating or casting.
Further, the solvent of the solution may be a nonpolar solvent. In some embodiments of the present application, the solvent of the solution is selected from at least one of n-pentane, n-octane, n-hexane, n-heptane, n-nonane, n-decane, n-undecane, cyclohexane, or cyclopentane.
Further, the concentration of the quantum dots in the solution is 1mg/mL to 1000mg/mL, and may be, for example, 1mg/mL to 50mg/mL, 50mg/mL to 100mg/mL, 60mg/mL to 150mg/mL, 140mg/mL to 200mg/mL, 180mg/mL to 250mg/mL, 220mg/mL to 300mg/mL, 270mg/mL to 400mg/mL, 350mg/mL to 500mg/mL, 400mg/mL to 600mg/mL, 500mg/mL to 800mg/mL, 700mg/mL to 900mg/mL, or 850mg/mL to 1000mg/mL.
In order to improve the film forming quality and patterning resolution of the quantum dot film, in some embodiments of the present application, quantum dots in solution: the mass ratio of the ligand remover is 1: (0.01 to 2), for example, 1: (0.01-0.03), 1: (0.02-0.04), 1: (0.03-0.05), 1: (0.04-0.06), 1: (0.05-0.07), 1: (0.06-0.08), 1: (0.07 to 0.09), 1: (0.1 to 0.12), 1: (0.11-0.13), 1: (0.12-0.14), 1: (0.13-0.15), 1: (0.14-0.16), 1: (0.15-0.17), 1: (0.16-0.18), 1: (0.17 to 0.19), or 1: (0.18-0.2).
In some embodiments of the present application, at step S 1a The method further comprises the following steps: s is S 1b And drying the solution containing the quantum dots and the ligand remover on one side of the substrate to obtain a cured quantum dot film layer. Wherein the "drying treatment" includes all the processes capable of obtaining higher energy of the solution containing the quantum dot and the ligand remover on one side of the substrate to be converted into a solid film, including but not limited to at least one of a heat treatment including but not limited to a constant temperature heat treatment or a non-constant temperature heat treatment, for example, the temperature of the heat treatment may be changed in a gradient manner, the temperature of the heat treatment may be not higher than 80 ℃, and the vacuum degree of the vacuum drying treatment may be 10, for example -2 Mpa to 10 -7 The time for the vacuum drying treatment is, for example, 10min to 60min.
In step S1, the luminescent color of the quantum dot includes, but is not limited to, red, blue, or green. Quantum dots include, but are not limited to, single component quantum dots, core-shell structured quantum dots, inorganic perovskite quantum dots, or organic-inorganic hybrid perovskite quantum dots. The average particle size of the quantum dots may be, for example, 5nm to 10nm, for example, 5nm, 6nm, 7nm, 8nm, 9nm or 10nm.
Equivalent weightWhen the quantum dot is a single component quantum dot or a core-shell structure quantum dot, the material of the single component quantum dot, or the material of the core-shell structure quantum dot, or the material of the shell of the core-shell structure quantum dot includes, but is not limited to, at least one of II-VI compound, III-V compound, IV-VI compound or I-III-VI compound, wherein the II-VI compound is selected from at least one of CdS, cdSe, cdTe, znS, znSe, znTe, znO, hgS, hgSe, hgTe, cdSeS, cdSeTe, cdSTe, znSeS, znSeTe, znSTe, hgSeS, hgSeTe, hgSTe, cdZnS, cdZnSe, cdZnTe, cdHgS, cdHgSe, cdHgTe, hgZnS, hgZnSe, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe or HgZnSTe, the III-V compound is selected from at least one of GaN, gaP, gaAs, gaSb, alN, alP, alAs, alSb, inN, inP, inAs, inSb, gaNP, gaNAs, gaNSb, gaPAs, gaPSb, alNP, alNAs, alNSb, alPAs, alPSb, inNP, inNAs, inNSb, inPAs, inPSb, gaAlNP, gaAlNAs, gaAlNSb, gaAlPAs, gaAlPSb, gaInNP, gaInNAs, gaInNSb, gaInPAs, gaInPSb, inAlNP, inAlNAs, inAlNSb, inAlPAs or InAlPSb, the IV-VI compound is selected from at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe or SnPbSTe, and the I-III-VI compound is selected from CuInS 2 、CuInSe 2 Or AgInS 2 At least one of them. The chemical formula provided for the material of the single component quantum dot, the material of the core of the quantum dot of the core-shell structure, or the material of the shell of the quantum dot of the core-shell structure shows only the elemental composition, and the content of each element is not shown, for example: cdZnSe is only composed of three elements of Cd, zn and Se, and if the content of each element is expressed, the Cd is correspondingly obtained x Zn 1-x Se，0<x<1。
For the inorganic perovskite quantum dots, the structural general formula of the inorganic perovskite quantum dots is AMX 3 Wherein A is Cs + Ion, M is a divalent metal cation, M includes but is not limited to Pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、Cd 2+ 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2+ 、Ge 2+ 、Yb 2+ Or Eu 2+ X is a halogen anion including but not limited to Cl - 、Br - Or I - 。
For organic perovskite quantum dots, the structural general formula of the organic perovskite quantum dots is CMX 3 Wherein C is a formamidino group, M is a divalent metal cation, M includes but is not limited to Pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、Cd 2+ 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2+ 、Ge 2+ 、Yb 2+ Or Eu 2+ X is a halogen anion including but not limited to Cl - 、Br - Or I - 。
For the organic-inorganic hybrid perovskite quantum dots, the structural general formula of the organic-inorganic hybrid perovskite quantum dots is BMX 3 Wherein B is selected from organic amine cations including but not limited to CH 3 (CH 2 ) n-2 NH 3+ (n.gtoreq.2) or NH 3 (CH 2 ) n NH 3 2+ (n.gtoreq.2), M is a divalent metal cation, M includes but is not limited to Pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、Cd 2+ 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2+ 、Ge 2+ 、Yb 2+ Or Eu 2+ X is a halogen anion including but not limited to Cl - 、Br - Or I - 。
In step S1, the ligands are native ligands attached to the surface of the quantum dot. In some embodiments of the present application, the ligand is selected from ligands comprising a hydrocarbon chain having 6 to 30 carbon atoms, for example, at least one selected from amine ligands having 6 to 20 carbon atoms in the main chain, carboxyl ligands having 6 to 20 carbon atoms in the main chain, and thiol ligands having 6 to 20 carbon atoms in the main chain. An amine ligand having 6 to 20 carbon atoms in the main chain is, for example, at least one selected from the group consisting of oleylamine, n-butylamine, n-octylamine, octaamine, 1, 2-ethylenediamine and octadecylamine, a carboxyl ligand having 6 to 20 carbon atoms in the main chain is, for example, at least one selected from the group consisting of oleic acid, acetic acid, butyric acid, valeric acid, caproic acid, arachic acid, lauric acid, undecylic acid, myristic acid and stearic acid, and a thiol ligand having 6 to 20 carbon atoms in the main chain is, for example, at least one selected from the group consisting of ethanethiol, propanethiol, mercaptoethanol, benzenethiol, octathiol, octaalkanethiol, dodecylthiol and octadecylthiol.
In step S1, R 1 Selected from the group that can be detached from the ligand remover during the partial exposure process, R in some embodiments of the present application 1 The conjugate acid formed after the proton has a pKa value in water at 25 ℃ of between-10 and 9, such that R 1 Has the characteristics of easy electron acceptance and strong capability of bearing negative charges, thereby being easy to be separated from the ligand remover in partial exposure treatment. R is R 1 For example, selected from a halogen atom, a p-toluenesulfonyl group, a mercapto group, a cyano group, an azido group, a thiocyano group, or an alkoxycarbonyl group, which may be, for example, a methoxycarbonyl group, an ethoxycarbonyl group, or the like.
R in ligand remover with structure shown in general formula (I) 2 For example, from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 20 ring atoms.
In some embodiments of the present application, the ligand-removing agent is selected from at least one of triphenylchloromethane, triphenylbromomethane, or triphenyliodomethane.
In step S3, the quantum dot film layer is exposed by using a mask. In some embodiments of the present application, the illumination wavelength of the partial exposure treatment is 200nm to 500nm; and/or the irradiation energy of the partial exposure treatment is 50mJ/cm 2 To 6000mJ/cm 2 For example, 50mJ/cm 2 To 100mJ/cm 2 、100mJ/cm 2 To 500mJ/cm 2 、300mJ/cm 2 To 600mJ/cm 2 、500mJ/cm 2 To 1000mJ/cm 2 、1000mJ/cm 2 To 2000mJ/cm 2 、2000mJ/cm 2 To 3000mJ/cm 2 、3000mJ/cm 2 To 4000mJ/cm 2 、4000mJ/cm 2 To 5000mJ/cm 2 Or 5000mJ/cm 2 To 6000mJ/cm 2 。
In order to ensure that the ligands of the exposed portions are sufficiently detached from the quantum dots, in some embodiments of the present application, when the illumination wavelength of the partial exposure treatment is 200nm to 500nm, the molar absorption coefficient of the ligand remover at the illumination wavelength of the partial exposure treatment is 10cm -1 M -1 To 10 5 cm -1 M -1 For example, it may be 10cm -1 M -1 To 10 2 cm -1 M -1 、10 2 cm -1 M -1 To 10 3 cm -1 M -1 、10 3 cm -1 M -1 To 10 4 cm -1 M -1 Or 10 4 cm -1 M -1 To 10 5 cm -1 M -1 。
In some embodiments of the present application, step S3 includes the steps of: and eluting the quantum dot film layer by using an eluent, wherein the unexposed part can be dissolved in the eluent. The eluent refers to a solvent which can dissolve the ligand and the quantum dot with the ligand connected to the surface, but can not dissolve the quantum dot with the ligand not connected to the surface. In some embodiments of the present application, the dielectric constant of the eluent is less than 10, including but not limited to at least one of toluene, chlorobenzene, n-hexane, n-octane, n-heptane, cyclohexane, dichloromethane, chloroform, and tetrahydrofuran.
It is understood that the patterned quantum dot film of the present application may be a single layer, and the material of the quantum dot film may include one kind of quantum dot or a plurality of kinds of quantum dots, and when the material of the quantum dot film includes a plurality of kinds of quantum dots, the luminescent colors of the plurality of kinds of quantum dots may be different from each other. The patterned quantum dot film can also be a plurality of layers, the materials of each layer can be quantum dots with different luminous colors or the same luminous color, and the patterns of each layer can be the same or different.
As an example, the quantum dot film is a single layer, and the material of the quantum dot film includes red quantum dots, green quantum dots and blue quantum dots, as shown in fig. 3, and the preparation method of the quantum dot film includes the following steps:
s11, providing a substrate, applying a first solution containing first quantum dots and a first ligand remover on one side of the substrate, wherein the first quantum dots are red quantum dots, and the surfaces of the first quantum dots are connected with first ligands;
s12, drying the first solution positioned on one side of the substrate to obtain a first quantum dot layer;
s13, carrying out partial exposure treatment on the first quantum dot layer so that the first quantum dot layer comprises an exposed part and an unexposed part, wherein a first ligand of the exposed part is separated from the first quantum dot;
s14, eluting the first quantum dot layer by using a first eluent capable of dissolving a first ligand to obtain a red quantum dot pattern;
s21, applying a second solution containing second quantum dots and a second ligand remover on one side of the substrate, wherein the second solution is applied to a blank area on one side of the substrate, the second quantum dots are green quantum dots, and the surfaces of the second quantum dots are connected with second ligands;
s22, drying the second solution positioned on one side of the substrate to obtain a second quantum dot layer, wherein the second quantum dot layer and the red quantum dot pattern are arranged on the same layer;
S23, carrying out partial exposure treatment on the second quantum dot layer so that the second quantum dot layer comprises an exposed part and an unexposed part, wherein a second ligand of the exposed part is separated from the second quantum dot;
s24, eluting the second quantum dot layer by adopting a second eluent capable of dissolving a second ligand to obtain a green quantum dot pattern;
s31, applying a third solution containing third quantum dots and a third ligand remover on one side of the substrate, wherein the third quantum dots are blue quantum dots, the third solution is applied to a blank area on one side of the substrate, and the surface of the third quantum dots is connected with a third ligand;
s32, drying the third solution positioned on one side of the substrate to obtain a third quantum dot layer, wherein the third quantum dot layer, the red quantum dot pattern and the green quantum dot pattern are arranged on the same layer;
s303, carrying out partial exposure treatment on the third quantum dot layer so that the third quantum dot layer comprises an exposed part and an unexposed part, wherein a third ligand of the exposed part is separated from the third quantum dot;
s304, eluting the third quantum dot layer by using a third eluent capable of dissolving a third ligand to obtain a blue quantum dot pattern, wherein the formed quantum dot film has a single-layer structure and comprises a red quantum dot pattern, a green quantum dot pattern and a blue quantum dot pattern which are arranged on the same layer.
As an example, the quantum dot film includes a first patterned quantum dot layer, a second patterned quantum dot layer and a third patterned quantum dot layer, which are stacked, wherein the first patterned quantum dot layer is made of red quantum dots, the second patterned quantum dot layer is made of green quantum dots, and the third patterned quantum dot layer is made of blue quantum dots, and the preparation method of the quantum dot film includes the following steps:
s101, providing a substrate, applying a first solution containing first quantum dots and a first ligand remover on one side of the substrate, wherein the first quantum dots are red quantum dots, and the surfaces of the first quantum dots are connected with first ligands;
s102, drying a first solution positioned on one side of a substrate to obtain a first quantum dot layer;
s103, carrying out partial exposure treatment on the first quantum dot layer so that the first quantum dot layer comprises an exposed part and an unexposed part, wherein a first ligand of the exposed part is separated from the first quantum dot;
s104, eluting the first quantum dot layer by using a first eluent capable of dissolving the first ligand to obtain a patterned first quantum dot layer;
s201, applying a second solution containing second quantum dots and a second ligand remover on one side of the first quantum dot layer away from the substrate, wherein the second quantum dots are green quantum dots, and the surfaces of the second quantum dots are connected with second ligands;
S202, drying a second solution positioned on one side of the first quantum dot layer far away from the substrate to obtain a second quantum dot layer;
s203, performing partial exposure treatment on the second quantum dot layer so that the second quantum dot layer comprises an exposed part and an unexposed part, wherein a second ligand of the exposed part is separated from the second quantum dot;
s204, eluting the second quantum dot layer by adopting a second eluent capable of dissolving a second ligand to obtain a green quantum dot pattern;
s301, applying a third solution containing third quantum dots and a third ligand remover on one side, far away from the first quantum dot layer, of the second quantum dot layer, wherein the third quantum dots are blue quantum dots, and the surfaces of the third quantum dots are connected with third ligands;
s302, drying a third solution positioned on one side of the second quantum dot layer far away from the first quantum dot layer to obtain a third quantum dot layer;
s303, carrying out partial exposure treatment on the third quantum dot layer so that the third quantum dot layer comprises an exposed part and an unexposed part, wherein a third ligand of the exposed part is separated from the third quantum dot;
s304, eluting the third quantum dot layer by using a third eluent capable of dissolving a third ligand to obtain a patterned third quantum dot layer.
Wherein the first to third ligands are described with reference to the previous ligands and the first to third eluents are described with reference to the previous eluents.
The conventional quantum dot film patterning method mainly comprises a photoetching method, an electron beam etching method, an ink-jet printing method and a nano imprinting method, but the applicant finds that the methods are difficult to achieve the indexes of improving pattern resolution, universality, reducing manufacturing cost and the like, and particularly compared with a quantum dot film before patterning, the quantum dot film after patterning has the problem that the luminous quantum yield is obviously reduced. Photolithography requires the use of photoresist that contaminates and degrades the quantum dots, and the solvents used to remove the photoresist dissolve the deposited quantum dot layer. The electron beam etching method needs to etch the pattern by using high-energy electron beams or X rays, but the high-energy electron beams or X rays can cause irreversible damage to the quantum dots. The patterned quantum dot film prepared by the inkjet printing method is easy to generate a coffee ring phenomenon, and has the problems that the inkjet printing method has strict requirements on the viscosity and the concentration of the ink, and the accurate deposition is difficult, so that the pattern resolution of the quantum dot film prepared by the inkjet printing method is difficult to reach less than 50 microns. Compared with the photoetching method, the electron beam etching method and the ink-jet printing method, the pattern resolution of the quantum dot film prepared by the nano-imprinting method is higher, but the quantum dot film has the problems of high manufacturing cost, poor flexibility and unstable pattern quality.
The preparation method of the embodiment of the application starts from the surface chemistry and colloid stabilization mechanism of the quantum dot, carries out chemical design and modification on the original ligand of the quantum dot, and utilizes photosensitive chemistry to construct a patterning method with high precision and high performance, which comprises the following steps: forming a quantum dot film layer on one side of a substrate, wherein the quantum dot film layer comprises a ligand remover with a structure shown in a general formula (I) and quantum dots with ligands connected to the surface, then carrying out partial exposure treatment on the quantum dot film layer, and then carrying out elution treatment on the quantum dot film layer to obtain a patterned quantum dot film, so that the quantum dots with different structures can be prepared to form the patterned film, the pattern resolution can reach 4 microns, and the quantum dot film has the advantages of high pattern resolution, high universality, simple preparation procedure and suitability for large-scale industrial production.
In addition, the whole preparation process does not involve the procedures of ligand exchange and the like for damaging the quantum dots, so that the photoelectric properties of the quantum dots before and after patterning are not obviously changed, for example: the luminous quantum yield of the red quantum dots before and after patterning is kept consistent; the luminous quantum yield of the green quantum dots after patterning is 90% of the luminous quantum yield of the green quantum dots before patterning; for blue quantum dots with poor stability and sensitive surface, the luminous quantum yield of the blue quantum dots after patterning is 70% of the luminous quantum yield of the blue quantum dots before patterning.
The embodiment of the application provides an optoelectronic device, as shown in fig. 4, the optoelectronic device 1 includes an anode 11, a cathode 12, and a light-emitting layer 13, the anode 11 is disposed opposite to the cathode 12, and the light-emitting layer 13 is disposed between the anode 11 and the cathode 12. The light-emitting layer 13 includes a plurality of quantum dot layers, "a plurality of quantum dot layers" means one or more quantum dot layers, "a plurality of" is more than two, that is, the quantum dot layers in the light-emitting layer 13 may be one, two, three, four or more, at least one quantum dot layer in the plurality of quantum dot layers is prepared by using the preparation method of the patterned quantum dot film described in any one of the embodiments of the present application, and the material of each quantum dot layer in the plurality of quantum dot layers contains quantum dots of at least one light-emitting color.
In the photovoltaic device 1 of the embodiment of this application, the materials of the anode 11 and the cathode 12 are selected from at least one of a metal, a carbon material, or a first metal oxide, and the metal is selected from at least one of Al, ag, cu, mo, au, ba, ca or Mg; the carbon material is at least one of graphite, carbon nano tube, graphene or carbon fiber; the first metal oxide may be a doped or undoped metal oxide, for example, at least one selected from Indium Tin Oxide (ITO), fluorine doped tin oxide (FTO), tin antimony oxide (ATO), aluminum doped zinc oxide (AZO), gallium doped zinc oxide (GZO), indium doped zinc oxide (IZO), or magnesium doped zinc oxide (MZO). Anode 11 or cathode 12 may also be selected from a composite electrode of doped or undoped transparent metal oxide sandwiching a metal, the composite electrode including but not limited to AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO 2 /Ag/TiO 2 、TiO 2 /Al/TiO 2 、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO 2 /Ag/TiO 2 Or TiO 2 /Al/TiO 2 At least one of them. The thickness of the anode 11 may be, for example, 20nm to 200nm, and the thickness of the cathode 12 may be, for example, 20nm to 200nm.
In order to further enhance the optoelectronic performance and lifetime of the optoelectronic device, in some embodiments of the present application, with continued reference to fig. 3, the optoelectronic device 1 further comprises an electronic functional layer 14, the electronic functional layer 14 being disposed between the cathode 12 and the light emitting layer 13. The electron functional layer 14 includes an electron transport layer and/or an electron injection layer, and for an electron functional layer including an electron transport layer and an electron injection layer, the electron transport layer is closer to the light emitting layer 13 than the electron injection layer, and the electron injection layer is closer to the cathode 12 than the electron transport layer. The thickness of the electron functional layer 14 is, for example, 10nm to 120nm.
In some embodiments of the present application, the electron functional layer 14 comprises an electron transport layer, the material of which comprises a second metal oxide, either undoped or doped, including but not limited to ZnO, tiO 2 、SnO 2 、BaO、Ta 2 O 3 、ZrO 2 At least one of TiLiO, znGaO, znAlO, znMgO, znSnO, znLiO, inSnO, alZnO, znOCl or ZnOF, it is noted that, for the doped second metal oxide, the chemical formula provided only shows the elemental composition, and does not show the content of the respective elements, for example: znMgO is composed of three elements, zn, mg and O. The average particle diameter of the second metal oxide may be, for example, 2nm to 15nm, exemplified by 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, or 15nm. The thickness of the electron transport layer is, for example, 10nm to 60nm.
In some embodiments of the present application, the electron functional layer 14 comprises an electron injection layer, the material of which includes, but is not limited to, at least one of an alkali metal halide, an alkali metal organic complex, or an organic phosphine compound, the alkali metal halide including, but not limited to, liF, the alkali metal organic complex including, but not limited to, lithium 8-hydroxyquinoline, the organic phosphine compound including, but not limited to, at least one of an organic phosphorus oxide, an organic thiophosphine compound, or an organic selenophosphine compound. The thickness of the electron injection layer is, for example, 10nm to 60nm.
In order to further enhance the optoelectronic performance and lifetime of the optoelectronic device, in some embodiments of the present application, with continued reference to fig. 3, the optoelectronic device 1 further comprises a hole-functional layer 15, the hole-functional layer 15 being disposed between the light-emitting layer 13 and the anode 11, the hole-functional layer 15 comprising a hole-injecting layer and/or a hole-transporting layer. For the hole functional layer 15 including a hole injection layer and a hole transport layer, the hole injection layer is closer to the anode 11 than the hole transport layer, and the hole transport layer is closer to the light-emitting layer 13 than the hole injection layer. The thickness of the hole function layer 15 may be, for example, 10nm to 120nm.
The thickness of the hole injection layer is, for example, 10nm to 60nm, and the material of the hole injection layer includes, but is not limited to, at least one of poly (styrenesulfonic acid), copper phthalocyanine, titan phthalocyanine, 4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine, 4' -tris [ 2-naphthylphenylamino ] triphenylamine, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, transition metal oxide, or transition metal chalcogenide, wherein the transition metal oxide includes, but is not limited to, at least one of nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, chromium oxide, or copper oxide, and the transition metal chalcogenide includes, but is not limited to, at least one of selenium sulfide, molybdenum sulfide, tungsten sulfide, or tungsten sulfide.
The thickness of the hole transport layer is, for example, 10nm to 100nm, and the material of the hole transport layer includes, but is not limited to, poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (abbreviated as TFB, CAS number 220797-16-0), 3-hexyl-substituted polythiophene (CAS number 104934-50-1), poly (9-vinylcarbazole) (abbreviated as PVK, CAS number 25067-59-8), poly [ bis (4-phenyl) (4-butylphenyl) amine](abbreviated as Poly-TPD, CAS number 472960-35-3), poly (N, N '-bis (4-butylphenyl) -N, N' -diphenyl-1, 4-phenylenediamine-CO-9, 9-dioctylfluorene) (abbreviated as PFB, CAS number 223569-28-6), 4 '-tris (carbazol-9-yl) triphenylamine (abbreviated as TCTA, CAS number 139092-78-7), 4' -bis (9-carbazole) biphenyl (abbreviated as CBP, CAS number 58328-31-7), N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (abbreviated as TPD, CAS number 65181-78-4) (abbreviated as NPB, CAS number 123847-85-8), poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid), doped or undoped graphene, C60, niO, moO 3 、WO 3 、V 2 O 5 、CrO 3 At least one of CuO or P-type gallium nitride.
Besides the light-emitting layer, the preparation method of each film layer in the photoelectric device comprises a solution method and a deposition method, wherein the solution method comprises, but is not limited to, spin coating, ink-jet printing, knife coating, dip-coating, dipping, spraying, roll coating or casting; the deposition method includes a chemical method including, but not limited to, a chemical vapor deposition method, a continuous ion layer adsorption and reaction method, an anodic oxidation method, an electrolytic deposition method, or a coprecipitation method, and a physical method including, but not limited to, a thermal evaporation plating method, an electron beam evaporation plating method, a magnetron sputtering method, a multi-arc ion plating method, a physical vapor deposition method, an atomic layer deposition method, or a pulsed laser deposition method. When the film layer is prepared by a solution method, a drying treatment process is added to convert the wet film into a dry film.
It will be appreciated that the method of manufacturing an optoelectronic device may also include other steps, such as: after each film layer of the photoelectric device is prepared, the photoelectric device needs to be packaged.
The embodiment of the application also provides electronic equipment, which comprises any one of the photoelectric devices. The electronic device may be, for example, any electronic product with display function, including but not limited to, a smart phone, a tablet computer, a notebook computer, a digital camera, a digital video camera, a smart wearable device, a smart weighing electronic scale, a vehicle display, a television set, or an electronic book reader, where the smart wearable device may be, for example, a smart bracelet, a smart watch, a Virtual Reality (VR) helmet, or the like.
The technical solutions and technical effects of the present application are described in detail below by means of specific examples, comparative examples and experimental examples, and the following examples are only some examples of the present application and are not intended to limit the present application in any way.
Example 1
The embodiment provides a preparation method of a patterned quantum dot film and the patterned quantum dot film, wherein the material of the patterned quantum dot film comprises red quantum dot CdSe (inner core)/CdS (outer shell), an oleylamine ligand is connected to the surface of the red quantum dot CdSe/CdS, and the preparation method of the red quantum dot CdSe/CdS with the oleylamine ligand connected to the surface is carried out according to the reference (Chaodan Pu, xingliang Dai, yufei Shu, et al, electrochemical-stable ligands bridge the photoluminescence-electroluminescence gap of quantum dots [ J ]. Nat Commun,2020,11 (1): 937).
The preparation method of the patterned quantum dot film in the embodiment comprises the following steps:
s1.1, providing a glass substrate, sequentially ultrasonically cleaning the glass substrate by deionized water for 15min, acetone for 15min, ethanol for 15min and isopropanol for 15min, performing surface treatment by ultraviolet-ozone for 5min after drying, spin-coating a first solution containing CdSe/CdS red quantum dots (the surface of which is connected with an oleylamine ligand) and triphenylchloromethane (a ligand remover) on one side of the glass substrate, wherein the solvent of the first solution is toluene, the concentration of the CdSe/CdS red quantum dots in the first solution is 30mg/mL, and the concentration of the triphenylchloromethane in the first solution is 2mg/mL;
s1.2, performing constant temperature heat treatment on the first solution positioned on one side of the glass substrate at 80 ℃ for 10min to obtain a red quantum dot film with the thickness of 20 nm;
s1.3, carrying out partial exposure treatment on the red quantum dot film by using a mask, wherein a light source adopted in the exposure treatment is ultraviolet light with the wavelength of 254nm, and the illumination energy is 1000mJ/cm 2 The illumination time is 40s, so that the red quantum dot film comprises an exposed part and an unexposed part, and a ligand in the exposed part falls off from the CdSe/CdS red quantum dot;
S1.4, soaking a part of the red quantum dot film subjected to exposure treatment in toluene so as to enable an unexposed part to be dissolved in toluene, keeping the exposed part on one side of a glass substrate, drying the surface of the red quantum dot film by nitrogen after the pattern is developed, and obtaining the patterned red quantum dot film shown in FIG. 5, wherein the circular array pattern of quantum dots emitting red light is developed, and the diameter of a circle is 20 microns.
Example 2
The embodiment provides a preparation method of a patterned quantum dot film and the patterned quantum dot film, wherein the material of the patterned quantum dot film comprises green quantum dot CdSe (core)/Cd with oleic acid ligand connected to the surface 1-x Zn x Se 1-y S y (intermediate Shell)/ZnS (outer Shell), oleic acid ligand being attached to the surfaceReference (Himchan Cho, jia-Ahn Pan, haoqi Wu, et al direct optical patterning of quantum dot light-emitting diodes via in situ ligand exchange [ J)]Adv Mater,2020,32 (46): 2003805).
The preparation method of the patterned quantum dot film in the embodiment comprises the following steps:
s2.1, providing a glass substrate, sequentially ultrasonically cleaning the glass substrate by deionized water, acetone for 15min, ethanol for 15min and isopropanol for 15min, drying, performing ultraviolet-ozone surface treatment for 5min, and spin-coating CdSe/Cd on one side of the glass substrate 1-x Zn x Se 1-y S y A second solution of ZnS green quantum dots (with oleic acid ligand connected to the surface) and triphenylchloromethane (ligand remover), wherein the solvent of the second solution is toluene, and CdSe/Cd in the second solution 1-x Zn x Se 1-y S y The concentration of the Zn green quantum dot is 20mg/mL, and the concentration of triphenylchloromethane in the second solution is 2mg/mL;
s2.2, performing constant-temperature heat treatment on the second solution positioned on one side of the glass substrate at 80 ℃ for 10min to obtain a green quantum dot film with the thickness of 20 nm;
s2.3, carrying out partial exposure treatment on the green quantum dot film by using a mask, wherein a light source adopted in the exposure treatment is ultraviolet light with the wavelength of 254nm, and the illumination energy is 1000mJ/cm 2 The illumination time is 40s, so that the green quantum dot film comprises an exposed part and an unexposed part;
s2.4, soaking the green quantum dot film subjected to partial exposure treatment in toluene so as to enable the unexposed part to be dissolved in toluene, keeping the exposed part on one side of the glass substrate, drying the surface of the green quantum dot film by nitrogen after the pattern is developed, obtaining the patterned green quantum dot film shown in FIG. 6, developing a 'Qinghua school badge' pattern, and embodying the preparation method of the embodiment to have the capability of constructing complex patterns.
Example 3
The embodiment provides a preparation method of a patterning quantum dot film and patterning quantumDot film, material of patterning quantum dot film contains Cd with oleic acid ligand connected to surface 1-x Zn x S (core)/ZnS (shell) blue quantum dots, preparation method of blue quantum dots with oleic acid ligand attached to surface (Wan Ki Bae, min Ki Nam, kookheon Char, et al gram-Scale One-Pot Synthesis of Highly Luminescent Blue Emitting Cd1-xZnxS/ZnS nanocrys [ J ]]Chem. Mater,2008,20 (16), 5307-13).
The preparation method of the patterned quantum dot film in the embodiment comprises the following steps:
s3.1, providing a glass substrate, sequentially ultrasonically cleaning the glass substrate by deionized water for 15min, acetone for 15min, ethanol for 15min and isopropanol for 15min, drying, performing ultraviolet-ozone surface treatment for 5min, and spin-coating Cd-containing on one side of the glass substrate 1-x Zn x Third solution of S/ZnS blue quantum dot (oleic acid ligand is connected to surface) and triphenylchloromethane (ligand remover), solvent of the third solution is toluene, and Cd in the third solution 1-x Zn x The concentration of the S/ZnS blue quantum dots is 20mg/mL, and the concentration of triphenylchloromethane in the third solution is 0.5mg/mL;
S3.2, performing constant-temperature heat treatment on the third solution positioned on one side of the glass substrate at 80 ℃ for 10min to obtain a blue quantum dot film with the thickness of 20 nm;
s3.3, carrying out partial exposure treatment on the blue quantum dot film by using a mask, wherein a light source adopted in the exposure treatment is ultraviolet light with the wavelength of 254nm, and the illumination energy is 1000mJ/cm 2 The illumination time is 40s, so that the blue quantum dot film comprises an exposed part and an unexposed part;
s3.4, soaking the blue quantum dot film subjected to partial exposure treatment in toluene so as to enable the unexposed part to be dissolved in toluene, keeping the exposed part on one side of the glass substrate, drying the surface of the blue quantum dot film by nitrogen after the pattern is developed, and obtaining the patterned blue quantum dot film shown in FIG. 7, wherein the square array pattern of quantum dots emitting blue light is developed, and the side length of the square is 60 microns.
Example 4
The embodiment provides a preparation method of a patterned quantum dot film and the patterned quantum dot film, wherein the patterned quantum dot film has a single-layer structure, and the material of the patterned quantum dot film comprises red quantum dots CdSe/CdS (same as the embodiment 1) with the surface connected with an oleylamine ligand and green quantum dots CdSe/Cd with the surface connected with an oleic acid ligand 1-x Zn x Se 1-y S y ) ZnS (same as example 2) blue Quantum dot Cd with oleic acid ligand attached to its surface 1-x Zn x S/ZnS (same as in example 3).
The preparation method of the patterned quantum dot film in this embodiment is shown in fig. 3, and includes the following steps:
s4.11, providing a glass substrate, sequentially ultrasonically cleaning the glass substrate by deionized water for 15min, acetone for 15min, ethanol for 15min and isopropanol for 15min, drying, performing surface treatment by ultraviolet-ozone for 5min, spin-coating a first solution containing CdSe/CdS red quantum dots (the surface of which is connected with an oleylamine ligand) and triphenylchloromethane (a ligand remover) on one side (the first surface) of the glass substrate, wherein the solvent of the first solution is toluene, the concentration of the CdSe/CdS red quantum dots in the first solution is 30mg/mL, and the concentration of the triphenylchloromethane in the first solution is 2mg/mL;
s4.12, performing constant temperature heat treatment on the first solution positioned on one side of the glass substrate at 80 ℃ for 10min to obtain a red quantum dot layer with the thickness of 20 nm;
s4.13, carrying out partial exposure treatment on the red quantum dot layer by using a mask, wherein a light source adopted in the exposure treatment is ultraviolet light with the wavelength of 254nm, and the illumination energy is 1000mJ/cm 2 The illumination time is 40s, so that the red quantum dot layer comprises an exposed part and an unexposed part;
S4.14, soaking the red quantum dot layer subjected to partial exposure treatment in toluene so as to enable the unexposed part to be dissolved in the toluene, keeping the exposed part on one side of the glass substrate, and drying the glass substrate with nitrogen after the patterns are developed to obtain the glass substrate with the red light-emitting array patterns formed on the surface;
s4.21 spin coating CdS on the first surface of the glass substratee/Cd 1-x Zn x Se 1-y S y ZnS green quantum dot (oleic acid ligand is connected to the surface) and triphenylchloromethane, wherein the solvent of the second solution is toluene, and the green quantum dot Cd in the second solution 1-x Zn x The concentration of S/ZnS is 20mg/mL, the concentration of triphenylchloromethane in the second solution is 2mg/mL, and the second solution is spin-coated on a blank area of the first surface, which is not provided with a red light emitting array;
s4.22, performing constant temperature heat treatment on the second solution positioned on one side of the glass substrate at 80 ℃ for 10min to obtain a green quantum dot layer with the thickness of 20 nm;
s4.23, carrying out partial exposure treatment on the green quantum dot layer by using a mask, wherein a light source adopted in the exposure treatment is ultraviolet light with the wavelength of 254nm, and the illumination energy is 1000mJ/cm 2 The illumination time is 40s, so that the green quantum dot layer comprises an exposed part and an unexposed part;
s4.24, soaking the green quantum dot layer subjected to partial exposure treatment in toluene so as to enable the unexposed part to be dissolved in the toluene, keeping the exposed part on one side of the glass substrate, and drying the glass substrate by nitrogen after the patterns are developed to obtain the glass substrate with the red light-emitting array patterns, the green light-emitting array patterns and the blue light-emitting array patterns formed on the surface;
S4.31 spin coating Cd-containing glass substrate on the first surface 1-x Zn x S/ZnS blue quantum dot (with oleic acid ligand connected to the surface) and triphenylchloromethane, wherein the solvent of the third solution is toluene, and Cd in the third solution 1-x Zn x The concentration of the S/ZnS blue quantum dots is 20mg/mL, the concentration of triphenylchloromethane in the third solution is 0.5mg/mL, and the third solution is spin-coated on a blank area of the first surface, which is not provided with a red light emitting array and a green light emitting array;
s4.32, performing constant-temperature heat treatment on the third solution positioned on one side of the glass substrate at 80 ℃ for 10min to obtain a blue quantum dot layer with the thickness of 20 nm;
s4.33, carrying out partial exposure treatment on the blue quantum dot layer by using a mask, wherein a light source adopted in the exposure treatment is ultraviolet light with the wavelength of 254nm, and the illumination energy is 1000mJ/cm 2 The illumination time is 40s, so that the blue quantum dot layer comprises an exposed part and an unexposed part;
s4.34, soaking the blue quantum dot layer subjected to partial exposure treatment in toluene so as to enable the unexposed part to be dissolved in toluene, keeping the exposed part on one side of the glass substrate, drying the glass substrate by nitrogen after the patterns are developed, and obtaining the glass substrate with the red light-emitting array pattern, the green light-emitting array pattern and the blue light-emitting array pattern formed on the surface, wherein the red light-emitting array pattern, the green light-emitting array pattern and the blue light-emitting array pattern form a quantum dot film as shown in FIG. 8.
In the process of preparing the quantum dot film, the luminous quantum yields of the red quantum dot layer, the green quantum dot layer and the blue quantum dot layer before the partial exposure treatment are respectively detected and analyzed, and the luminous quantum yields of the red luminous array, the green luminous array and the blue luminous array after the patterning are respectively detected and analyzed. As shown in fig. 9, the light emission quantum yields of the red quantum dots before and after patterning remained consistent; the luminous quantum yield of the green quantum dots after patterning is 90% of the luminous quantum yield of the green quantum dots before patterning; the luminous quantum yield of the blue quantum dots after patterning is 70% of that of the blue quantum dots before patterning, and the preparation method of the embodiment proves that the damage to the quantum dots is small, so that the photoelectric properties of the quantum dots before and after patterning are not obviously changed, and the red quantum dots, the green quantum dots and the blue quantum dots before and after patterning can have high retention rate of fluorescence properties.
Example 5
The embodiment provides a patterned quantum dot film, the pattern of which is shown in fig. 10, the material of the patterned quantum dot film comprises CdSe green quantum dots without core-shell structures, and oleic acid ligands and oleylamine ligands are connected to the surfaces of the CdSe green quantum dots.
Compared with the preparation method of the patterned quantum dot film in example 2, the preparation method of the patterned quantum dot film in this example only differs in that: cdSe/Cd 1-x Zn x Se 1-y S y /ZnThe S green quantum dot (with oleic acid ligand attached to the surface) was replaced with a CdSe green quantum dot with oleic acid ligand and oleylamine ligand attached to the surface.
Example 6
The embodiment provides a patterned quantum dot film, the pattern of which is shown in fig. 11, the material of the patterned quantum dot film comprises perovskite CsPbBr3 quantum dots, the luminescent color of the perovskite CsPbBr3 quantum dots is red, and the surface of the perovskite CsPbBr3 quantum dots is connected with oleic acid ligand and oleylamine ligand.
Compared with the preparation method of the patterned quantum dot film in example 1, the preparation method of the patterned quantum dot film in this example only differs in that: cdSe/CdS red quantum dots (with oleylamine ligands attached to the surface) were replaced with "CsPbBr 3 perovskite quantum dots with oleic and oleylamine ligands attached to the surface".
Example 7
The embodiment provides a patterned quantum dot film, the pattern of which is shown in fig. 12, the material of the patterned quantum dot film comprises lnP (kernel)/ZnS (shell) quantum dots, the luminescent color of the lnP/ZnS quantum dots is red, and the surface of the lnP/ZnS quantum dots is connected with oleic acid ligand.
Compared with the preparation method of the patterned quantum dot film in example 1, the preparation method of the patterned quantum dot film in this example only differs in that: cdSe/CdS red quantum dots (with oleylamine ligands attached to the surface) were replaced with "InP/ZnS red quantum dots with oleic ligands attached to the surface (with oleylamine ligands attached to the surface)".
Example 8
The present example provides a patterned quantum dot film, the patterned quantum dot film pattern is shown in fig. 5, and the material of the patterned quantum dot film comprises CdSe/CdS red quantum dots (same as in example 1) with oil amine ligands attached to the surface.
Compared with the preparation method of the patterned quantum dot film in example 1, the preparation method of the patterned quantum dot film in this example only differs in that: the ligand remover was replaced by "triphenylchloromethane" with "triphenylacetonitrile with CAS number 6639-43-6".
Example 9
The present example provides a patterned quantum dot film, the patterned quantum dot film pattern is shown in fig. 5, and the material of the patterned quantum dot film comprises CdSe/CdS red quantum dots (same as in example 1) with oil amine ligands attached to the surface.
Compared with the preparation method of the patterned quantum dot film in example 1, the preparation method of the patterned quantum dot film in this example only differs in that: the ligand remover was replaced by "triphenylchloromethane" with "compound with CAS number 42756-18-3".
Example 10
The present example provides a patterned quantum dot film, the patterned quantum dot film pattern is shown in fig. 5, and the material of the patterned quantum dot film comprises CdSe/CdS red quantum dots (same as in example 1) with oil amine ligands attached to the surface.
Compared with the preparation method of the patterned quantum dot film in example 1, the preparation method of the patterned quantum dot film in this example only differs in that: the ligand remover was replaced by "triphenylchloromethane" with "triphenylmethyl mercaptan having CAS number 3695-77-0".
Example 11
The embodiment provides a photoelectric device and a preparation method thereof, the photoelectric device is a quantum dot light emitting diode with a forward structure, as shown in fig. 13, in a bottom-up direction, the photoelectric device 1 includes a substrate 10, an anode 11, a hole functional layer 15, a light emitting layer 13, an electron functional layer 14 and a cathode 12 which are sequentially stacked, wherein the hole functional layer 15 is composed of a hole injection layer 151 and a hole transport layer 152 which are stacked, the hole injection layer 151 is closer to the anode 11 than the hole transport layer 152, and the hole transport layer 152 is closer to the quantum dot light emitting layer 13 than the hole injection layer 151; the electron functional layer 14 is an electron transport layer.
The materials and thicknesses of the respective layers in the optoelectronic device 1 are as follows:
the material of the substrate 10 is glass with the thickness of 2mm;
the anode 11 is made of ITO and has a thickness of 50nm;
the cathode 12 is made of Al and has a thickness of 100nm;
the hole injection layer 151 is made of PEDOT PSS with thickness of 25nm;
the hole transport layer 152 is made of TFB and has a thickness of 35nm;
the luminescent layer 13 is made of CdSe/CdS red quantum dots with the surfaces connected with oleylamine ligands, and the total luminescent area is 2cm 2 The light emitting layer 13 is of a red light emitting array structure (as shown in fig. 14, each small pixel size is 10 micrometers×50 micrometers), and the thickness of the light emitting layer 13 is 20nm;
the material of the electron functional layer 14 was nano ZnO having an average particle diameter of 20nm and a thickness of 40nm.
The preparation method of the photoelectric device in the embodiment comprises the following steps:
s11.1, providing a substrate, sputtering ITO on one side of the substrate to obtain an ITO layer, dipping a small amount of soapy water on the surface of the ITO layer by using a cotton swab to remove impurities visible to the naked eyes on the surface, sequentially ultrasonically cleaning the substrate comprising the ITO by using deionized water, acetone for 15min, ethanol for 15min and isopropanol for 15min, and performing ultraviolet-ozone surface treatment for 5min after drying to obtain the substrate comprising an anode;
S11.2, in an air environment at normal temperature and normal pressure, printing PEDOT by ink-jet printing on the side of the anode away from the substrate: performing constant temperature heat treatment on the PSS aqueous solution at 150 ℃ for 30min to obtain a hole injection layer;
s11.3, in a nitrogen environment at normal temperature and normal pressure, performing ink-jet printing on a TFB-chlorobenzene solution on one side of the hole injection layer far away from the anode, and then performing constant-temperature heat treatment at 150 ℃ for 30min to obtain a hole transport layer;
s11.4, forming a light-emitting layer on one side of the hole transport layer, which is far away from the hole injection layer, in a nitrogen environment at normal temperature and normal pressure, wherein the forming method of the light-emitting layer is carried out according to the preparation method of the patterned quantum dot film in the embodiment 1;
s11.5, in a nitrogen environment at normal temperature and normal pressure, printing a nano ZnO-ethanol solution on the luminescent layer far away from the hole transport layer by ink jet, and then performing constant temperature heat treatment at 80 ℃ for 30min to obtain an electronic functional layer;
s11.6 placing the prefabricated device comprising the electronic functional layer under an air pressure of 4×10 -6 In an evaporation bin of mbar, al is thermally evaporated on one side of the electronic functional layer far away from the light-emitting layer through a mask plate, so that a cathode is obtained, and then an ultraviolet curing adhesive is adopted for encapsulation, so that a photoelectric device is obtained.
Example 12
The present embodiment provides an optoelectronic device and a method for manufacturing the same, and compared with the optoelectronic device in embodiment 11, the optoelectronic device in this embodiment is only different in that: replacement of the material of the light-emitting layer with CdSe/Cd with oleic acid ligand attached to the surface 1-x Zn x Se 1-y S y The ZnS green quantum dot and the light emitting layer are of a green light emitting array structure.
The method of manufacturing the photovoltaic device in this example differs from the method of manufacturing the photovoltaic device in example 11 only in that: step S11.4 is replaced by "forming a light emitting layer on a side of the hole transport layer away from the hole injection layer in a nitrogen atmosphere at normal temperature and pressure", and the method of forming the light emitting layer is performed with reference to the method of preparing the patterned quantum dot thin film in example 2.
Example 13
The present embodiment provides an optoelectronic device and a method for manufacturing the same, and compared with the optoelectronic device in embodiment 11, the optoelectronic device in this embodiment is only different in that: replacement of the material of the light-emitting layer with CdSe/Cd with oleic acid ligand attached to the surface 1-x Zn x Se 1-y S y The ZnS blue quantum dot and the light emitting layer are of a blue light emitting array structure.
Compared with the preparation method of the photoelectric device in example 1, the preparation method of the photoelectric device in this example is only different in that: step S11.4 is replaced by "forming a light emitting layer on a side of the hole transport layer away from the hole injection layer in a nitrogen atmosphere at normal temperature and pressure", and the method of forming the light emitting layer is performed with reference to the method of preparing the patterned quantum dot thin film in example 3.
Comparative example 1
The present comparative example provides a method for preparing a patterned quantum dot film, which is different from the method for preparing a patterned quantum dot film in example 1 in that: the ligand remover is replaced by "triphenylmethyl chloride" to "triphenylmethyl alcohol".
In this comparative example, the partially exposed red quantum dot film was immersed in toluene, but not developed in a pattern (as shown in fig. 15), probably because: the photo-decomposition rate of the triphenylmethanol is low, and enough photosensitive free radicals are difficult to generate photochemical reaction with the ligands on the surface of the quantum dots, so that the triphenylmethanol cannot pattern the quantum dots.
Comparative example 2
The present comparative example provides an optoelectronic device and a method for manufacturing the same, which differs from the optoelectronic device of example 11 only in that: the light emitting layer is not patterned.
In comparison with the optoelectronic device in embodiment 11, the optoelectronic device in this embodiment is only different in that: the step S11.4 is replaced by ' in the nitrogen environment at normal temperature and normal pressure ', cdSe/CdS red quantum dot (the same as the example 1, the surface of which is connected with an oleylamine ligand) -n-octane solution with the concentration of 30mg/mL is printed by inkjet on the side of the hole transport layer far away from the hole injection layer ', and then the luminescent layer is obtained by heat treatment at the constant temperature of 80 ℃ for 10 min.
Comparative example 3
The present comparative example provides an optoelectronic device and a method for manufacturing the same, which differs from the optoelectronic device of example 11 only in that: replacement of the material of the light-emitting layer with CdSe/Cd with oleic acid ligand attached to the surface 1-x Zn x Se 1-y S y ZnS green quantum dots (same as example 2) and the light emitting layer was not patterned.
In comparison with the optoelectronic device in embodiment 11, the optoelectronic device in this embodiment is only different in that: the step S11.4 is replaced by' CdSe/Cd with the concentration of 30mg/mL is inkjet printed on the side of the hole transport layer far away from the hole injection layer under the nitrogen environment of normal temperature and normal pressure 1-x Zn x Se 1-y S y And (3) a ZnS green quantum dot-n-octane solution, and then placing the solution in a constant temperature heat treatment for 10min at 80 ℃ to obtain the luminescent layer.
Comparative example 4
The present comparative example provides an optoelectronic device and a method for manufacturing the same, which differs from the optoelectronic device of example 11 only in that: replacement of the material of the light-emitting layer with Cd with oleic acid ligand attached to the surface 1- x Zn x S/ZnS blue quantum dots (same as in example 3) and the light emitting layer was unpatterned.
In comparison with the optoelectronic device in embodiment 11, the optoelectronic device in this embodiment is only different in that: the step S11.4 is replaced by 'in the nitrogen environment at normal temperature and normal pressure', the side of the hole transport layer far away from the hole injection layer is subjected to inkjet printing of Cd with the concentration of 30mg/mL 1-x Zn x S/ZnS blue quantum dot-n-octane solution, and then placing the solution in a constant temperature heat treatment for 10min at 80 ℃ to obtain the luminescent layer.
Experimental example
Performance testing of the optoelectronic devices of examples 11 to 13 and comparative examples 2 to 4 was performed, parameters such as the turn-on voltage, current, electroluminescence intensity, luminescence spectrum, etc. of each optoelectronic device were obtained by detecting using a Friedel-crafts FPD optical characteristic measuring apparatus (including a marine optical USB2000, a LabView control QE-PRO spectrometer, a Keithley2400, a high precision digital source table Keithley 6485, an optical fiber with an inner diameter of 50 μm, a device test probe and jig, and an efficiency test system built with various connecting wires and data cards, an efficiency test cassette, a data acquisition system, etc.), key parameters such as external quantum efficiency, power efficiency, etc. were calculated, and the service lives of the above-mentioned individual optoelectronic devices were tested using a life test apparatus, and the maximum electroluminescence intensity (L) of each optoelectronic device was obtained by detecting max ,cd/m 2 ) Maximum External Quantum Efficiency (EQE) max (wt%), the time required for the brightness to decay from 100% to 95% at a brightness of 1000nit (t 95@1000nit, h), and the turn-on voltage (Ut, V).
Wherein L is max The detection method of (1) comprises the following steps: under the driving condition of constant current (2 mA), obtain The maximum electroluminescent intensity of the optoelectronic device in the range of 0V to 8V driving voltage is taken. The service life testing method comprises the following steps: under the drive of constant current (2 mA), carrying out electroluminescence service life analysis on each photoelectric device by adopting a 128-path QLED service life testing system, recording the time (T95, h) required by each photoelectric device for reducing the maximum brightness to 95 percent, and calculating the time (T95@1000nit, h) required by each photoelectric device for reducing the brightness from 100 percent to 95 percent under the brightness of 1000nit by a reduction fitting formula.
The performance test data for each optoelectronic device is detailed in table 1 below:
table 1 list of performance test data for optoelectronic devices of examples 11-13 and comparative examples 2-4
As can be seen from Table 1 and FIG. 16, the overall performance of the photovoltaic devices in example 11 and comparative example 2 is comparable, U t Are all less than 2V, and L max All reach 10000cd/m 2 And EQE (EQE) max All reached 19% and t95@1000nit all reached 7600h, thereby indicating: the patterning method of the light-emitting layer in example 11 does not substantially damage the CdSe/CdS red quantum dots, so that the photoelectric properties of the CdSe/CdS red quantum dots before and after patterning are not significantly changed.
As can be seen from Table 1 and FIG. 17, the overall performance of the photovoltaic devices in example 12 and comparative example 3 is comparable, U t Are all 2V, and L max All reach 56900cd/m 2 And EQE (EQE) max 17.5% were achieved and T95@1000nit was 8700h, thus indicating that: the patterning process of the light-emitting layer in example 12 did not substantially damage CdSe/Cd 1-x Zn x Se 1-y S y Green quantum dot of/ZnS, thereby enabling CdSe/Cd before and after patterning 1-x Zn x Se 1-y S y The photoelectric property of the ZnS green quantum dot is not changed obviously.
As can be seen from Table 1 and FIG. 18, the light in example 13 and comparative example 4The difference of the comprehensive performance of the electric devices is tiny, and U of the electric devices and the electric devices is equal to U t Are all 2.6V, and L max All reach 4200cd/m 2 And EQE (EQE) max All reached 12% and t95@1000nit all reached 61h, thereby indicating: patterning method of light-emitting layer in example 13 vs Cd 1-x Zn x S/ZnS blue quantum dots are less damaged, so that Cd before and after patterning is realized 1-x Zn x The difference of the photoelectric properties of the S/ZnS blue quantum dots is small.
The preparation method of the patterned quantum dot film, the photoelectric device and the electronic equipment provided by the embodiment of the application are described in detail. The principles and embodiments of the present application are described herein with reference to specific examples, the description of which is only for aiding in understanding the technical solution of the present application and its core ideas; those of ordinary skill in the art will appreciate that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the scope of the corresponding technical solutions of the embodiments of the present application.

Claims (16)

1. The preparation method of the patterned quantum dot film is characterized by comprising the following steps of:
providing a substrate, forming a quantum dot film layer on one side of the substrate, wherein the quantum dot film layer comprises quantum dots and a ligand remover, and the surface of each quantum dot is connected with a ligand;
carrying out partial exposure treatment on the quantum dot film layer so that the quantum dot film layer comprises an exposed part and an unexposed part, wherein the ligand in the exposed part is separated from the quantum dot; and
removing the unexposed part to obtain a patterned quantum dot film;
wherein the ligand remover is a compound shown in the following general formula (I):
in the general formula (I), R 2 At least one selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group;
in the partial exposure treatment, the ligand remover in the exposed portion loses the R 1 And forming electrophilic groups such that the ligands in the exposed portion bind to the electrophilic groups and are detached from the quantum dots.
2. The method of claim 1, wherein R is 1 A group selected from the group that can be detached from the ligand-removing agent in the partial exposure treatment;
and/or, the R 1 The pKa value of the conjugate acid formed after the proton is obtained in water at 25 ℃ is between-10 and 9;
and/or, said removing said unexposed portions comprises the steps of: and eluting the quantum dot film layer by using an eluent, wherein the unexposed part can be dissolved in the eluent.
3. The method of claim 2, wherein R is 1 Selected from the group consisting of a halogen atom, p-toluenesulfonyl, p-toluenesulfonyloxy, mercapto, cyano, azido, thiocyano or alkoxycarbonyl.
4. The production method according to claim 1, wherein the substituted or unsubstituted alkyl group has 1 to 10 carbon atoms;
alternatively, the substituted or unsubstituted alkoxy group has 1 to 10 carbon atoms;
alternatively, the substituted or unsubstituted aryl group has 6 to 20 ring atoms;
alternatively, the substituted or unsubstituted heteroaryl group has a number of ring atoms of 5 to 20.
5. The method according to claim 1, wherein the partial exposure treatment has an illumination wavelength of 200nm to 500nm;
and/or the irradiation energy of the partial exposure treatment is 50mJ/cm 2 To 6000mJ/cm 2 。
And/or the molar absorptivity of the ligand remover at the illumination wavelength of the partial exposure treatment is 10cm -1 M -1 To 10 5 cm -1 M -1 。
6. The method according to claim 1, wherein the ligand remover is at least one selected from triphenylchloromethane, triphenylbromomethane, triphenyliodomethane, triphenylacetonitrile and triphenylmethyl mercaptan.
7. The method according to claim 1, wherein the ligand is selected from ligands comprising a hydrocarbon chain having 6 to 30 carbon atoms.
8. The method according to claim 7, wherein the ligand is at least one selected from the group consisting of an amine ligand having 6 to 20 carbon atoms in the main chain, a carboxyl ligand having 6 to 20 carbon atoms in the main chain, and a thiol ligand having 6 to 20 carbon atoms in the main chain.
9. The method of claim 1, wherein forming a quantum dot film layer on one side of the substrate comprises: and applying a solution containing quantum dots and a ligand remover on one side of the substrate to form the quantum dot film layer.
10. The method of claim 9, wherein the concentration of quantum dots in the solution is 1mg/mL to 1000mg/mL;
And/or, in the solution, the quantum dots: the mass ratio of the ligand remover is 1: (0.01-2).
11. The method of claim 1, wherein the quantum dot is selected from at least one of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, organic perovskite quantum dots, or organic-inorganic hybrid perovskite quantum dots;
for the single component quantum dot and the core-shell structure quantum dot, the material of the single component quantum dot, the material of the core-shell structure quantum dot, and the material of the shell of the core-shell structure quantum dot are selected from at least one of group II-VI compound, group III-V compound, group IV-VI compound, or group I-III-VI compound independently of each other, wherein the group II-VI compound is selected from at least one of CdS, cdSe, cdTe, znS, znSe, znTe, znO, hgS, hgSe, hgTe, cdSeS, cdSeTe, cdSTe, znSeS, znSeTe, znSTe, hgSeS, hgSeTe, hgSTe, cdZnS, cdZnSe, cdZnTe, cdHgS, cdHgSe, cdHgTe, hgZnS, hgZnSe, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe or HgZnSTe, the group III-V compound is selected from at least one of GaN, gaP, gaAs, gaSb, alN, alP, alAs, alSb, inN, inP, inAs, inSb, gaNP, gaNAs, gaNSb, gaPAs, gaPSb, alNP, alNAs, alNSb, alPAs, alPSb, inNP, inNAs, inNSb, inPAs, inPSb, gaAlNP, gaAlNAs, gaAlNSb, gaAlPAs, gaAlPSb, gaInNP, gaInNAs, gaInNSb, gaInPAs, gaInPSb, inAlNP, inAlNAs, inAlNSb, inAlPAs or InAlPSb, the group IV-VI compound is selected from at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe or SnPbSTe, and the group I-III-VI compound is selected from CuInS 2 、CuInSe 2 Or AgInS 2 At least one of (a) and (b);
and/or the dielectric constant of the eluent is less than 10.
12. The method according to claim 11, wherein the eluent is at least one selected from toluene, chlorobenzene, n-hexane, n-octane, n-heptane, cyclohexane, dichloromethane, chloroform and tetrahydrofuran.
13. An optoelectronic device, comprising:
an anode;
a cathode disposed opposite the anode; and
a light-emitting layer disposed between the anode and the cathode;
wherein the light-emitting layer comprises a plurality of quantum dot layers, at least one quantum dot layer of the plurality of quantum dot layers is prepared by the preparation method as claimed in any one of claims 1 to 12, and the material of each quantum dot layer of the plurality of quantum dot layers comprises quantum dots of at least one light-emitting color.
14. The optoelectronic device of claim 13, further comprising an electronic functional layer disposed between the cathode and the light emitting layer; the electron functional layer comprises an electron transport layer and/or an electron injection layer, and for the electron functional layer comprising the electron transport layer and the electron injection layer, the electron transport layer is closer to the light emitting layer than the electron injection layer, and the electron injection layer is closer to the cathode than the electron transport layer;
And/or the photoelectric device further comprises a hole functional layer, wherein the hole functional layer is arranged between the light-emitting layer and the anode, the hole functional layer comprises a hole injection layer and/or a hole transport layer, and for the hole functional layer comprising the hole injection layer and the hole transport layer, the hole injection layer is closer to the anode than the hole transport layer, and the hole transport layer is closer to the light-emitting layer than the hole injection layer;
and/or the materials of the anode and the cathode are selected from at least one of metal, carbon material or first metal oxide independently of each other, wherein the metal is selected from at least one of Al, ag, cu, mo, au, ba, ca or Mg, the carbon material is selected from at least one of graphite, carbon nano tube, graphene or carbon fiber, and the first metal oxide is selected from at least one of indium tin oxide, fluorine doped tin oxide, tin antimony oxide, aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide or magnesium doped zinc oxide.
15. An optoelectronic device according to claim 14, wherein the material of the electron transport layer comprises a second metal oxide selected from ZnO, tiO 2 、SnO 2 、BaO、Ta 2 O 3 、ZrO 2 At least one of TiLiO, znGaO, znAlO, znMgO, znSnO, znLiO, inSnO, alZnO, znOCl, znOF or ZnMgLiO;
and/or the material of the electron injection layer comprises at least one of an alkali metal halide, an alkali metal organic complex or an organic phosphine compound selected from at least one of an organic phosphorus oxide, an organic thiophosphine compound or an organic selenophosphine compound;
and/or the material of the hole injection layer is selected from poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid), copper phthalocyanine, titanyl phthalocyanine, 4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine, 4' -tris [ 2-naphthylphenylamino ] triphenylamine, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, transition metal oxide, or transition metal chalcogenide selected from at least one of an oxide of nickel, an oxide of molybdenum, an oxide of tungsten, an oxide of vanadium, an oxide of chromium, or an oxide of copper, the transition metal chalcogenide selected from at least one of a sulfide of molybdenum, a selenide of molybdenum, a sulfide of tungsten, a selenide of tungsten, or a sulfide of copper;
And/or the material of the hole transport layer is selected from poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), 3-hexyl substituted polythiophene, poly (9-vinylcarbazole), poly [ bis (4-phenyl) (4-butylphenyl) amine]Poly (N, N '-bis (4-butylphenyl) -N, N' -diphenyl-1, 4-phenylenediamine-CO-9, 9-dioctylfluorene), 4 '-tris (carbazol-9-yl) triphenylamine, 4' -bis (9-carbazol) biphenyl, N '-diphenyl-N, N' -bis (3-methylbenzene)Phenyl) -1,1 '-biphenyl-4, 4' -diamine, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene) poly (styrenesulfonic acid), doped or undoped graphene, C60, niO, moO 3 、WO 3 、V 2 O 5 、CrO 3 At least one of CuO or P-type gallium nitride.
16. An electronic device, characterized in that it comprises an optoelectronic device as claimed in any one of claims 13 to 15.
CN202211175684.XA 2022-09-26 2022-09-26 Preparation method of patterned quantum dot film, photoelectric device and electronic equipment Pending CN117835778A (en)

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