CN116426270A - Nanoparticle and preparation method thereof, photoelectric device and preparation method thereof - Google Patents
Nanoparticle and preparation method thereof, photoelectric device and preparation method thereof Download PDFInfo
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- CN116426270A CN116426270A CN202111666102.3A CN202111666102A CN116426270A CN 116426270 A CN116426270 A CN 116426270A CN 202111666102 A CN202111666102 A CN 202111666102A CN 116426270 A CN116426270 A CN 116426270A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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Abstract
The application discloses a nanoparticle and a preparation method thereof, and an optoelectronic device and a preparation method thereof. The nanoparticle comprises quantum dots, and ligands of the quantum dots contain groups which can be crosslinked with side chain crosslinking groups of the hole transport material. When the nano particles are applied to photoelectric devices, and a mixed layer containing the nano particles and a crosslinkable hole transport material is prepared between a hole transport layer and a light emitting layer, the hole transport material and the nano particles can be tightly crosslinked together, so that potential barriers between HOMO energy levels of the hole transport material and HOMO energy levels of quantum dots can be reduced, holes can be favorably injected into the quantum dots from the hole transport material, and the injection of electrons and holes is more balanced, thereby improving the efficiency and the service life of the QLED device.
Description
Technical Field
The present disclosure relates to the field of semiconductor light emitting devices, and more particularly, to a nanoparticle and a method for preparing the nanoparticle, a photoelectric device and a method for preparing the photoelectric device.
Background
The quantum dots have the advantages of high light color purity, high luminous quantum efficiency, adjustable luminous color, high quantum yield and the like, and the quantum dots can be prepared by a printing process, so that the light emitting diode (quantum dot light emitting diode, QLED) based on the quantum dots has recently received general attention. At present, the external quantum efficiency of the QLED with red and green colors is more than 20%, and the service life of the device basically meets the requirements. However, the lack of blue, which is an indispensable three primary color, is still low with respect to red and green QLEDs in terms of brightness, efficiency, and device lifetime, which becomes a major factor that hinders the blue QLEDs as well as the three primary QLEDs from coming into practical use. Therefore, how to further improve the luminous efficiency and the service life of the blue QLED and realize the blue QLED with high efficiency, high brightness and long service life becomes a key scientific problem which needs to be solved urgently at present.
The main reasons for the low efficiency and the low service life of the blue QLED device are that a larger injection barrier exists between the material of the hole transmission layer and the material of the quantum dot luminescent layer compared with red and green quantum dots, so that the hole injection is insufficient, the electron injection is excessive, and the carrier injection into the quantum dot of the luminescent layer is unbalanced, so that the carrier recombination efficiency is low, the quantum yield is reduced due to the electrification of the quantum dot of the luminescent layer, and the efficiency and the service life of the blue QLED device are finally influenced.
Disclosure of Invention
In order to improve the defects, the application provides a nanoparticle and an optoelectronic device, wherein the nanoparticle contains a crosslinkable group and can be tightly connected with a carrier transmission material, so that the carrier transmission balance can be improved when the nanoparticle is applied to the optoelectronic device, and the efficiency and the service life of the device are improved.
Embodiments of the present application are thus implemented, providing a nanoparticle comprising a first quantum dot and a first ligand attached to a surface of the first quantum dot, the first ligand comprising a first crosslinkable group.
In some embodiments, the first ligand further comprises a coordinating group through which the first ligand is coordinately bound to the first quantum dot;
And/or the first crosslinkable group comprises at least one of a vinyl group, a boric acid group.
In some embodiments, the coordinating group contains a coordinating atom selected from at least one of N, P or S, the coordinating atom being directly attached to the first crosslinkable group via a chemical bond.
In some embodiments, the coordinating group is a heterocyclic group having 5 to 10 ring atoms, the heteroatom of the heterocyclic group comprising N or S, at least one hydrogen atom of the heterocyclic group being substituted with the first crosslinkable group.
In some embodiments, the coordinating group is selected from at least one of an amine group or a phosphate group or a sulfhydryl group.
In some embodiments, the coordinating group comprises at least one of a pyridinyl, pyrrolyl, thiophenyl.
In some embodiments, the first quantum dot is selected from CdS, cdSe, cdTe, inP, agS, pbS, pbSe, hgS, zn X Cd 1-X S、Cu X In 1-X S、Zn X Cd 1-X Se、Zn X Se 1-X S、Zn X Cd 1-X Te、PbSe X S 1-X 、Zn X Cd 1-X S/ZnSe、Cu X In 1-X S/ZnS、Zn X Cd 1-X Se/ZnS、CuInSeS、Zn X Cd 1-X Te/ZnS、PbSe X S 1-X At least one of ZnS, 0<X<1。
In some embodiments, the mass ratio of the first quantum dot to the first ligand is 1 (0.01-0.1).
The embodiment of the application provides a preparation method of nano particles, which comprises the following steps:
providing a solution comprising first quantum dots, wherein the first quantum dot surface is attached to an initial ligand;
Mixing the solution with a first ligand, carrying out ligand exchange reaction to obtain nano particles,
wherein the first ligand comprises a coordinating group and a first crosslinkable group, and the nanoparticle comprises a first quantum dot with a surface coordinately bound to the first ligand.
In some embodiments, the starting ligand is selected from at least one of trioctylphosphine, trioctylphosphine oxide, oleic acid, stearic acid, oleylamine, thioglycollic acid, mercaptopropionic acid;
and/or the reaction temperature of the ligand exchange reaction is 20-30 ℃;
and/or the reaction time of the ligand exchange reaction is 3-5 h.
The embodiment of the application further provides an optoelectronic device, which comprises an anode, a hole transport layer, a light emitting layer and a cathode which are stacked, wherein a mixed layer is further arranged between the hole transport layer and the light emitting layer, and the mixed layer comprises nano particles and a first hole transport material.
In some embodiments, the first hole transport material comprises a second crosslinkable group, the first crosslinkable group being capable of undergoing a crosslinking reaction with the second crosslinkable group.
In some embodiments, the mass of the nanoparticles and the first hole transport material in the mixed layer is (3-10): 20, and/or
The thickness of the mixed layer is 5-10nm, and/or
The first hole transport material is selected from at least one of crosslinkable poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), crosslinkable polyvinylcarbazole, crosslinkable poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine) or crosslinkable N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine.
In some embodiments, the second crosslinkable group includes at least one of a vinyl group, a boronic acid group, or a siloxane group.
In some embodiments, the hole transport layer comprises a second hole transport material,
the HOMO level of the first hole transport material is deeper than the HOMO level of the second hole transport material in the hole transport layer.
In some embodiments, the second hole transporting material is selected from one or more of (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4',4 "-tris (carbazol-9-yl) triphenylamine, 4' -bis (9-carbazolyl) 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; and/or
The anode is a composite electrode formed by one or more of a metal electrode, a carbon electrode and a doped or undoped metal oxide electrode; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is at least one selected from graphite, carbon nano tube, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the material of the composite electrode is selected from 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 TiO 2 /Al/TiO 2 At least one of (a) and (b); and/or
The cathode is a composite electrode formed by one or more of a metal electrode, a carbon electrode and a doped or undoped metal oxide electrode; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is selected from graphite and carbon nanoAt least one of rice straw, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the material of the composite electrode is selected from 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 TiO 2 /Al/TiO 2 At least one of (a) and (b); and/or the material of the light-emitting layer comprises second quantum dots, wherein the second quantum dots are blue quantum dots.
The second quantum dot is the same as or different from the first quantum dot; the first quantum dot and/or the second quantum dot is/are selected from CdS, cdSe, cdTe, inP, agS, pbS, pbSe, hgS, zn X Cd 1-X S、Cu X In 1-X S、Zn X Cd 1-X Se、Zn X Se 1-X S、Zn X Cd 1-X Te、PbSe X S 1-X 、Zn X Cd 1-X S/ZnSe、Cu X In 1-X S/ZnS、Zn X Cd 1-X Se/ZnS、CuInSeS、Zn X Cd 1-X Te/ZnS、PbSe X S 1-X At least one of ZnS, 0<X<1。
The embodiment of the application also provides a preparation method of the photoelectric device, which comprises the following steps:
providing a substrate, arranging an anode on the substrate,
providing a hole transport layer ink comprising a second hole transport material and a first organic solvent, disposing the hole transport layer ink on the anode to form a hole transport layer,
providing a mixed layer ink comprising a first hole transport material, nanoparticles and a second organic solvent, disposing the mixed layer ink on the hole transport layer to form a mixed layer,
providing a luminescent layer ink comprising second quantum dots and a third organic solvent, disposing the third precursor solution on the mixed layer to form a luminescent layer,
disposing a cathode on the light emitting layer; or alternatively
Providing a substrate, disposing a cathode on the substrate,
Providing a luminescent layer ink comprising second quantum dots and a third organic solvent, disposing the luminescent layer ink on the cathode to form a luminescent layer,
providing a mixed layer ink comprising a first hole transport material, nanoparticles and a second organic solvent, disposing the mixed layer ink on the light emitting layer to form a mixed layer,
providing a hole transport layer ink comprising a second hole transport material and a first organic solvent, disposing the hole transport layer ink on the mixed layer to form a hole transport layer,
disposing an anode on the hole transport layer;
wherein the nanoparticle comprises a first quantum dot and a first ligand, the first ligand comprising a coordinating group and a first crosslinkable group, the first ligand being coordinately bound to the first quantum dot via the coordinating group.
The present application provides a nanoparticle comprising quantum dots and a ligand comprising a group that can crosslink with a hole transport material side chain crosslinking group. When the nano particles are applied to photoelectric devices, and a mixed layer containing the nano particles and a crosslinkable hole transport material is prepared between a hole transport layer and a luminescent layer, the hole transport material and the nano particles can be tightly crosslinked together through a crosslinking group, so that potential barriers between HOMO energy levels of the hole transport material and HOMO energy levels of quantum dots can be reduced, injection of holes from the hole transport material to the quantum dots is facilitated, and injection of electrons and holes is more balanced, thereby improving efficiency and service life of the QLED device.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly introduced below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of an optoelectronic device according to an embodiment of the present disclosure;
fig. 2 is a schematic structural diagram of another photoelectric device according to an embodiment of the present application;
FIG. 3 is a schematic flow chart of a method for preparing nanoparticles according to an embodiment of the present application;
fig. 4 is a schematic flow chart of a preparation method of a positive-type photoelectric device according to an embodiment of the present application;
fig. 5 is a schematic flow chart of a preparation method of an inversion-structured photoelectric device according to an embodiment of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, based on the embodiments herein, which are within the scope of the protection of the present application, will be within the skill of the art without inventive effort. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and explanation only and is not intended to limit the present application. In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present application, the term "comprising" means "including but not limited to". Various embodiments of the invention 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 range, 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.
[ nanoparticle ]
The embodiment of the application firstly provides a nanoparticle which is mainly used in an optoelectronic device. The nanoparticle includes a first quantum dot and a first ligand including a coordinating group and a first crosslinkable group, wherein the first ligand is coordinately bound to the first quantum dot via the coordinating group included therein.
The first crosslinkable group contained in the nanoparticle can carry out crosslinking reaction with the second crosslinkable group contained in the side chain in the first hole transport material, so as to provide a composite material capable of tightly crosslinking and combining the hole transport material and the nanoparticle.
In one embodiment, the coordinating group may be any coordinating group that can coordinate to the quantum dot, such as one containing at least one of N (nitrogen), P (phosphorus), or S (sulfur), which elements (atoms or groups containing these elements) can coordinate to the quantum dot to form a coordination bond such that the first ligand can be attached to the surface of the quantum dot.
In one embodiment, the first crosslinkable group is a group that readily undergoes a crosslinking reaction, such as a vinyl group, an unsaturated carboxylic acid group, an unsaturated ester group, a boric acid group, a siloxane group, or the like.
The first crosslinkable group may be directly attached to the coordinating group, e.g., the first crosslinkable group is directly attached to the N atom or the P atom or the S atom via a chemical bond, forming a shorter ligand chain, which may have a tighter attachment to the hole transporting material, e.g., the first ligand is a trivinyl amine or a vinyl phosphate. The first crosslinkable group can also be connected with a heterocyclic group containing an N atom or an S atom through a chemical bond, namely, the hydrogen atom of any site of the heterocyclic group is replaced by the first crosslinkable group, and at the moment, all large pi bonds of the heterocyclic group can also ensure the tight connection of the nano particles and the hole transport material. The heterocyclic group containing an N atom or S atom may be a heterocyclic group having 5 to 10 ring atoms, for example, a heterocyclic compound having 5 or 6 ring atoms. As an example, the first ligand may be selected from one of vinylpyridine, vinylpyrole, vinylthiophene, pyridylboronic acid, pyrrolylboronic acid, or thienyl boronic acid. It is understood that the types of first ligands listed above refer to a class of compounds having corresponding coordinating groups and first crosslinkable groups. For example, the trivinylamine may be triallylamine (trivinylmonoamine, CAS number: 102-70-5), trivinyldiamine (CAS number: 280-57-9), or other trivinylamine compounds; as another example, the vinyl pyridine may be a pyridine compound substituted with vinyl at an arbitrary site, for example, 1-vinyl pyridine (CAS number: 100-69-6), 4-vinyl pyridine (100-43-6) or another pyridine compound substituted at another site, not limited to any one.
As an example, the first ligand may have a chemical structure represented by the following formula (1), formula (2), or formula (3):
R-X (1)
in formula (1), formula (2) or formula (3), R is a first crosslinkable group, X is an acyclic group containing N, P, or S, for example an amine or phosphate group or a mercapto group, X 1 、X 2 Independently selected from N or S.
Wherein it is understood that the first crosslinkable group in formula (1) is directly bonded to the N atom or the P atom or the S atom via a chemical bond to form a shorter ligand chain. In formula (2) or formula (3), the first crosslinkable group is bonded to a heterocyclic group containing an N atom or an S atom via a chemical bond. The above formula (1), formula (2) or formula (3) is merely illustrative of the chemical bonding manner of the first crosslinkable group and the coordinating group, and does not represent a limitation on the ligand structure.
As an example, the first ligand may be selected from one of vinylpyridine, vinylpyrole, vinylthiophene, pyridylboronic acid, pyrrolylboronic acid, or thienyl boronic acid.
In an embodiment, the kind of the first quantum dot is not particularly limited, and may be a binary phase quantum dot, a ternary phase quantum dot, or a quaternary phase quantum dot known in the art. As an example, the first quantum dot species is selected from CdS, cdSe, cdTe, inP, agS, pbS, pbSe, hgS, zn X Cd 1-X S、Cu X In 1-X S、Zn X Cd 1-X Se、Zn X Se 1-X S、Zn X Cd 1-X Te、PbSe X S 1-X 、Zn X Cd 1-X S/ZnSe、Cu X In 1-X S/ZnS、Zn X Cd 1-X Se/ZnS、CuInSeS、Zn X Cd 1-X Te/ZnS、PbSe X S 1-X At least one of ZnS, 0<X<1。
In one embodiment, the molar ratio of the first quantum dot to the first ligand in the nanoparticle is 1 (1-10), and may be any molar ratio within this range. As an example, the molar ratio of the first quantum dot to the ligand is 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, or any other molar ratio within this range.
In an embodiment, in the nanoparticle, the mass ratio of the first quantum dot to the first ligand is 1 (0.01-0.1), for example, may be 1:0.01, 1:0.05 or 1:0.1 or other mass ratio within the range.
However, the amount of the ligand relative to the first quantum dot may not be too small, and if too small, the number of crosslinkable sites is too small, so that the ligand is difficult to play a role of tightly connecting the hole transport material; if the amount of the ligand relative to the first quantum dot is too large, hole injection into the quantum dot is not favored, which affects the application of the nanoparticle in the optoelectronic device.
[ method for producing nanoparticles ]
Referring to fig. 3, the embodiment of the present application further provides a method for preparing nanoparticles, including the following steps:
s1, providing a solution comprising first quantum dots, wherein the surfaces of the first quantum dots are connected with initial ligands;
S2, mixing the solution comprising the first quantum dots with a first ligand, carrying out ligand exchange reaction to obtain nano particles,
wherein the first ligand comprises a coordinating group and a first crosslinkable group, and the nanoparticle comprises a first quantum dot with a surface coordinately connected with the first ligand.
In some embodiments, the kind of the initial ligand is not particularly limited, and may be a quantum dot long-chain or short-chain ligand known in the art. The initial ligand does not include a crosslinkable group. As an example, the primary ligand is selected from at least one of trioctylphosphine, trioctylphosphine oxide, oleic acid, stearic acid, oleylamine, thioglycollic acid, mercaptopropionic acid;
in some embodiments, the reaction temperature of the ligand exchange reaction is from 20 ℃ to 30 ℃; for example, the reaction may be carried out at room temperature.
In some embodiments, the reaction time of the ligand exchange reaction is not particularly limited, and may be adjusted according to the scale of the reaction system, etc. As an example, the ligand exchange reaction time may be 3 to 5 hours.
It is understood that the method of preparing the nanoparticle of the embodiments of the present application further includes a step of separation and purification after the ligand exchange reaction. Specific methods of separation and purification may be performed using methods of separation and purification of quantum dots known in the art, such as adding precipitants or complexing agents to isolate nanoparticles. And will not be described in detail herein.
The preparation method of this example can be used to prepare nanoparticles as described previously.
Photoelectric device
The embodiment further provides an optoelectronic device 100, which includes a mixed layer 30 including the nanoparticles and the first hole transport material, where the mixed layer 30 is disposed between the hole transport layer 20 and the light emitting layer 40, so that a potential barrier between a HOMO level of the hole transport material and a HOMO level of the quantum dot can be reduced, which is beneficial to injecting holes from the hole transport layer 20 into the light emitting layer 40, improving injection balance of electrons and holes, and improving efficiency and lifetime of the QLED device.
In one embodiment, referring to fig. 1, the optoelectronic device 100 includes an anode 10, a hole transport layer 20, a light emitting layer 40, and a cathode 50 stacked together, and a mixed layer 30 is further disposed between the hole transport layer 20 and the light emitting layer 40, wherein the mixed layer 30 includes nanoparticles and a first hole transport material. Wherein the nanoparticle is a nanoparticle as described above, and will not be described herein.
In one embodiment, the hybrid layer 30 material is comprised of the nanoparticles described above and a first hole transport material.
In the mixed layer 30, the mass ratio of the first hole transport material to the nanoparticles is (3 to 10): 20. Within this mass ratio range, the nanoparticles are able to effectively crosslink together with the first hole transport material. In some embodiments, the mass ratio of the first hole transport material nanoparticles may be 5:20, 6:20, 7:20, 8:20, 9:20, or any ratio within the foregoing ranges. Preferably, the mass ratio of the first hole transport material nanoparticles is (8-10): 20.
In one embodiment, the hybrid layer 30 is of a thinner thickness, at least less than the thickness of the hole transport layer 20 and the light emitting layer 40. In one embodiment, the thickness of the hybrid layer 30 is in the range of 5nm to 10 nm. The mixed layer 30 in this range can achieve a good carrier transport balance. The thinner hybrid layer 30 presents difficulties in the manufacturing process and it is difficult to achieve efficient cross-linking of the first hole transporting material and the nanoparticles; too thick mixed layer 30 may cause too long a transmission distance of hole injection light emitting layer 40, so that the light emitting recombination center shifts into mixed layer 30, causing mixed layer 30 to emit light itself, and reducing the light emitting efficiency of the device.
It will be appreciated by those skilled in the art that the first hole transport material is a crosslinkable hole transport material. Crosslinkable hole-transporting materials mean that the side chains of the compounds having hole-transporting properties comprise crosslinkable groups. In one embodiment, the first hole transport material comprises a second crosslinkable group capable of undergoing a crosslinking reaction with the first crosslinkable group in the nanoparticle. The second crosslinkable group is selected from, but is not limited to, at least one of a vinyl group, an unsaturated carboxylic acid group, an unsaturated ester group, a boric acid group, or a siloxane group. In some embodiments, the compound having hole transporting properties may be any compound known in the art having hole transporting properties, such as one or more of (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4',4 "-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) 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. As an example, the crosslinkable hole transport material in the mixed layer 30 is selected from at least one of crosslinkable poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), crosslinkable polyvinylcarbazole, crosslinkable poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine) or crosslinkable N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine.
In the hole transport layer 20 of the optoelectronic device 100, the material of the hole transport layer 20 comprises a second hole transport material. The second hole transport material in the hole transport layer 20 may be crosslinked or uncrosslinked. The second hole transport material may be a compound having hole transport properties. In some embodiments, the second hole transporting material is selected from, but is not limited to, one or more of (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4',4 "-tris (carbazol-9-yl) triphenylamine, 4' -bis (9-carbazolyl) 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. As an example, the crosslinkable hole transport material in the mixed layer 30 is selected from at least one of crosslinkable poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), crosslinkable polyvinylcarbazole, crosslinkable poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine) or crosslinkable N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine.
The first hole transport material in the mixed layer 30 and the second hole transport material in the hole transport layer 20 may be the same or different from each other. In some embodiments, the HOMO level of the first hole transporting material in the mixed layer 30 is deeper than the HOMO level of the second hole transporting material of the hole transporting layer 20, which is more conducive to hole injection from the hole transporting layer 20 into the mixed layer 30, can greatly improve the ability of hole injection into the light emitting layer 40, and allows for a more balanced injection of electrons and holes, thereby improving the efficiency and lifetime of the QLED device. It will be appreciated by those skilled in the art that the depth of the HOMO level may be determined by the distance of the HOMO level from the datum (0 eV) in the level diagram, with the further distance from the datum indicating a deeper HOMO level. In some embodiments, the HOMO level of the first hole transporting material is 0.1eV to 0.5eV deeper than the HOMO level of the second hole transporting material to provide a better balance of electron and hole injection.
In some embodiments, the hybrid layer 30 includes a first hole transport material therein, wherein the side chains of the first hole transport material have second crosslinkable groups, and the hole transport layer 20 includes a second hole transport material, which may or may not additionally contain crosslinkable groups. The first hole transport material is the same as or different from the second hole transport material, and the HOMO level of the first hole transport material is deeper than the HOMO level of the second hole transport material.
In the above discussion of the types and HOMO levels of the hole transport materials in the mixture layer 30 and the hole transport layer 20, it is only for the types and HOMO levels of the host compounds having hole transport properties in the hole transport material that the hole transport material is crosslinkable or uncrosslinkable. For example, the first hole transporting material is a crosslinked TFB and the second hole transporting material is a non-crosslinked TFB or a crosslinked TFB, where the first hole transporting material is the same as the second hole transporting material.
The thickness of the hole transport layer 20 may be, for example, 10nm to 100nm. The thickness of the hole transport layer 20 may be, for example, 10nm to 100nm, such as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 100nm, and the like.
In some embodiments, the light emitting layer 40 is a quantum dot light emitting layer 40, including second quantum dots. The second quantum dots may be the same or different in kind from the first quantum dots. In one embodiment, the second quantum dot is a blue quantum dot. The second quantum dot may be selected from, but not limited to, at least one of a single structure quantum dot and a core-shell structure quantum dot. For example, the second quantum dot may be selected from, but not limited to, at least one of group II-VI compounds, group III-V compounds, and group I-III-VI compounds. As an example, the second quantum dot may be selected from CdS, cdSe, cdTe, inP, agS, pbS, pbSe, hgS, zn X Cd 1-X S、Cu X In 1-X S、Zn X Cd 1-X Se、Zn X Se 1-X S、Zn X Cd 1-X Te、PbSe X S 1-X 、Zn X Cd 1-X S/ZnSe、Cu X In 1-X S/ZnS、Zn X Cd 1-X Se/ZnS、CuInSeS、Zn X Cd 1-X Te/ZnS、PbSe X S 1-X At least one of ZnS, 0<X<1。
The second quantum dot may be an oily quantum dot, and the surface of the oily quantum dot is connected with a ligand which is easily dissolved in a solvent with lower polarity. The ligand of the second quantum dot may be selected from at least one of an acid ligand, a thiol ligand, an amine ligand, a (oxy) phosphine ligand, a phospholipid, a soft phospholipid, a polyvinylpyridine, and the like. Wherein the acid ligand can be at least one selected from the group consisting of decanoic acid, undecylenic acid, tetradecanoic acid, oleic acid, and stearic acid; the thiol ligand may be at least one selected from octaalkyl thiol, dodecyl thiol, and octadecyl thiol; the amine ligand can be at least one selected from oleylamine, octadecylamine and octamine; the (oxy) phosphine ligand may be at least one selected from trioctylphosphine and trioctylphosphine oxide.
The thickness of the light emitting layer 40 may be, for example, 5nm to 100nm, such as 5nm, 10nm, 30nm, 40nm, 50nm, 60nm, 80nm, 100nm, etc.
In some embodiments, anode 10 and cathode 50 are anode 10, cathode 50 materials of a QLED as known in the art. The material of anode 10 is known in the art as the material for anode 10 and the material of cathode 50 is known in the art as the material for cathodeThe material of the pole 50. The materials of the anode 10 and the cathode 50 may be, for example, one or more of a metal, a carbon material, and a metal oxide, and the metal may be, for example, one or more of Al, ag, cu, mo, au, ba, ca and Mg; the carbon material may be, for example, one or more of graphite, carbon nanotubes, graphene, and carbon fibers; the metal oxide may be doped or undoped metal oxide including one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, and also includes a composite electrode of doped or undoped transparent metal oxide with metal sandwiched therebetween, 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 TiO 2 /Al/TiO 2 One or more of the following. The thickness of the anode 10 may be, for example, 10nm to 200nm, such as 10nm, 50nm, 80nm, 120nm, 150nm, 200nm, etc.; the thickness of the cathode 50 may be, for example, 10nm to 200nm, such as 10nm, 50nm, 80nm, 120nm, 150nm, 200nm, etc. Specifically, a layer of 15-30nm thick metal silver or aluminum can be thermally evaporated through a mask plate to serve as the cathode 50, or nano silver wires or nano copper wires are used, so that the electrode has smaller resistance, and carriers can be smoothly injected.
Referring to fig. 2, it can be appreciated that the optoelectronic device 100 of embodiments of the present application can further include conventional functional layers in an equivalent number of electron-emitting diodes, such as the hole injection layer 60 and/or the electron transport layer 70. The hole injection layer 60 is disposed between the anode 10 and the hole transport layer 20, and the material of the hole injection layer 60 may be selected from materials having hole injection capability, including but not limited to PEDOT: PSS, moO x 、WO x One or more of NiO and CuO. PEDOT PSS is a high molecular polymer, and the Chinese name is poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid). The thickness of the hole injection layer 60 may be 20nm to 200nm. The electron transport layer 70 is disposed between the light emitting layer 40 and the cathode 50, and the electron transport layer 70 material may be composed of inorganic materials including, but not limited to, undoped or doped with aluminum (Al), magnesium (Mg), indium (In) Metal/non-metal oxides doped with lithium (Li), gallium (Ga), cadmium (Cd), cesium (Cs), or copper (Cu) (e.g., tiO 2 、ZnO、ZrO、SnO 2 、WO 3 、Ta 2 O 3 、HfO 3 、Al 2 O 3 、ZrSiO 4 、BaTiO 3 And BaZrO 3 ) The method comprises the steps of carrying out a first treatment on the surface of the In the case of organic materials, these can be selected from, for example, heterogeneous materials
Azole compounds, triazole compounds, isothiazole compounds, and +_in>
The organic material such as diazole compound, thiadiazole compound, perylene compound or aluminum complex is formed. In some embodiments, the material of the electron transport layer 70 is N-doped ZnO. The thickness of the electron transport layer 70 may be 10nm to 200nm, preferably 10nm to 60nm.
[ method for producing photovoltaic device ]
The embodiment of the present application further provides a method for manufacturing the optoelectronic device 100, and fig. 4 shows a method for manufacturing the optoelectronic device 100 with a positive structure according to the embodiment of the present application, including the following steps:
s11, providing a substrate, and arranging an anode 10 on the substrate;
s12, providing hole transport layer ink comprising a second hole transport material and a first organic solvent, and arranging the hole transport layer ink on the anode 10 to form a hole transport layer 20;
s13, providing mixed layer ink comprising a first hole transport material, the nano particles and a second organic solvent, and arranging mixed layer ink liquid on the hole transport layer 20 to form a mixed layer 30;
S14, providing luminescent layer ink comprising second quantum dots and a third organic solvent, and arranging the luminescent layer ink on the mixed layer 30 to form a luminescent layer 40;
s15. a cathode 50 is disposed on the light emitting layer 40.
Fig. 5 shows a method for manufacturing an inversion-structured photovoltaic device 100 according to an embodiment of this application, including the following steps:
s21, providing a substrate, and arranging a cathode 50 on the substrate;
s22, providing luminescent layer ink comprising second quantum dots and a third organic solvent, and arranging the luminescent layer ink on the cathode 50 to form a luminescent layer 40;
s23, providing mixed layer ink comprising a first hole transport material, the nano particles and a second organic solvent, and arranging the mixed layer ink on the light-emitting layer 40 to form a mixed layer 30;
s24, providing hole transport layer ink comprising a second hole transport material and a first organic solvent, and arranging the hole transport layer ink on the mixed layer 30 to form a hole transport layer 20;
s25. an anode 10 is provided on the hole transport layer 20.
It will be appreciated that when the optoelectronic device 100 further comprises a hole injection layer 60 and/or an electron transport layer 70, the steps of providing the hole injection layer 60 and the electron transport layer 70, respectively, are further included before the corresponding steps.
In some embodiments, the first organic solvent and the second organic solvent are orthogonal solvents, the second organic solvent and the third organic solvent are orthogonal solvents, and the solvents between adjacent film layers are orthogonal solvents, so that mutual dissolution between the film layers is avoided, and the stability of the film layers can be maintained. It will be appreciated by those skilled in the art that the first, second and third organic solvents may be one or more of those known in the art, such as chlorobenzene, meta-xylene, ortho-xylene, n-octane, n-pentane, and the like. The orthogonal solvent refers to a solvent which is not mutually soluble, that is to say, the second organic solvent is not mutually soluble with the first organic solvent and the third organic solvent. In some embodiments, the second organic solvent is of a different polarity than the first organic solvent and the third organic solvent, and is therefore a mutually orthogonal solvent.
The preparation method of the embodiment of the present application may be used to prepare the optoelectronic device 100 as described above, and accordingly, the materials of each functional film layer in the optoelectronic device 100 are described in detail in the previous embodiment, which is not described herein again.
Other functional layers of the anode 10, the hole transport layer 20, the mixed layer 30, the light emitting layer 40, the cathode 50, the hole injection layer 60, the electron transport layer 70, and the like in the present application can be prepared by conventional techniques in the art, including but not limited to solution methods and deposition methods, wherein the solution methods include but are not limited to spin coating, inkjet printing, knife coating, dip-coating, dipping, spray coating, 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 10 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 solution method is adopted to prepare each film layer, a drying treatment procedure is required to be added.
In some embodiments, the hybrid layer 30 is crosslinked with the crosslinkable first hole transport material under heat or light conditions. For example, heating at 150-180 ℃ for 20-40 minutes causes cross-linking of the material of the hybrid layer 30.
It can be appreciated that the method for manufacturing the optoelectronic device may further include a packaging step, the packaging material may be acrylic resin or epoxy resin, the packaging may be machine packaging or manual packaging, and ultraviolet curing glue packaging may be used, where the concentration of oxygen and water in the environment where the packaging step is performed is less than 0.1ppm, so as to ensure stability of the optoelectronic device.
The technical solutions and technical effects of the present application are described in detail below by means of specific examples and comparative 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.
In the examples herein, materials and reagents used are commercially available unless otherwise specified.
Example 1
The embodiment provides a nanoparticle, firstly 200mg of CdZnSe/ZnSe blue quantum dot (the original ligand is oleic acid) and 10ml of n-hexane are added into a three-neck flask, argon is introduced for protection, stirring is carried out fully at room temperature for 10min to enable the quantum dot to be completely dissolved, then 10mg of trivinyl amine is added into the quantum dot solution, stirring is carried out at room temperature for 4h, and oleic acid on the surface of the quantum dot is fully exchanged. And then adding ethyl acetate and methanol into the exchanged quantum dot mixed solution for centrifugal separation and cleaning for a plurality of times to obtain the CdZnSe/ZnSe quantum dot containing the ligand of the trivinyl amine (CAS number: 102-70-5).
Example 2
This example provides a nanoparticle differing from example 1 only in that 10mg of trivinylamine was replaced with 10mg of vinylphosphoric acid, resulting in CdZnSe/ZnSe quantum dots containing vinylphosphoric acid ligands.
Example 3
This example provides a nanoparticle differing from example 1 only in that 10mg of trivinyl amine was replaced with 10mg of 2-vinyl thiophene, resulting in a CdZnSe/ZnSe quantum dot containing 2-vinyl thiophene ligands.
Example 4
This example provides a nanoparticle that differs from example 1 only in that the trivinyl amine is replaced with 10mg of pyridine-4-boronic acid, resulting in a CdZnSe/ZnSe quantum dot containing pyridine-4-boronic acid ligands.
Example 5
This example provides a nanoparticle differing from example 4 only in that the mass of pyridine-4-boronic acid is 2mg, resulting in a CdZnSe/ZnSe quantum dot containing pyridine-4-boronic acid ligands.
Example 6
This example provides a nanoparticle differing from example 4 only in that the mass of pyridine-4-boronic acid is 20mg, resulting in a CdZnSe/ZnSe quantum dot containing pyridine-4-boronic acid ligands.
Example 7
This example prepares a QLED device.
The patterned ITO substrate is sequentially placed in acetone, deionized water and isopropanol for ultrasonic cleaning, and each step of ultrasonic cleaning needs to last for about 15 minutes. Placing the ITO into a clean oven for drying after the ultrasonic treatment is finished; after the ITO substrate is baked, the ITO surface is treated with ultraviolet ozone for 5 minutes to further remove organic matters attached to the ITO surface and improve the work function of the ITO.
Spin-coating a PEDOT PSS as a hole injection layer with a thickness of about 30nm on the surface of the treated ITO substrate, and heating the substrate on a heating table at 150 ℃ for 30 minutes to remove water, wherein the spin-coating is completed in air;
placing the dried substrate coated with the hole injection layer in nitrogen atmosphere, spin-coating a layer of hole transport layer 20 material TFB with chlorobenzene as solvent, wherein the thickness of the layer is about 20nm, and placing the substrate on a heating table at 150 ℃ for heating for 30 minutes to remove the solvent;
then mixing the crosslinked TFB with vinyl side chains and the quantum dots prepared in the example 1, wherein the concentrations are 8mg/ml and 20mg/ml respectively, the solvent is m-xylene, spin-coating the mixed solution on the hole transport layer 20 to form a mixed layer, and heating the mixed layer on a heating table at 180 ℃ for 30 minutes to crosslink the mixed layer, wherein the thickness of the mixed layer is about 8nm;
after the mixed layer is cooled, spin-coating CdZnSe/ZnSe blue quantum dot (original ligand is oleic acid) solution on the surface of the mixed layer, wherein the solvent is n-octane, the thickness of the quantum dot luminescent layer is about 20nm, and placing the mixed layer on a heating table at 80 ℃ for heating for 10 minutes, so as to remove residual solvent;
spin-coating ethanol solution of ZnO nano particles on a quantum dot luminescent layer to form an electron transport layer with the thickness of about 40nm, and placing the electron transport layer on a heating table at 80 ℃ for heating for 30 minutes after deposition;
And finally, placing the substrate on which the functional layers are deposited in an evaporation bin, and thermally evaporating a layer of aluminum serving as a cathode through a mask plate, wherein the thickness of the aluminum is 100nm. And (5) finishing the preparation of the device.
Through testing, the maximum External Quantum Efficiency (EQE) of the device is 16%, and the maximum brightness can reach 6250cd/m 2 。
Example 8
This example prepares a QLED device. This example differs from example 7 only in that the mixed layer material was replaced with crosslinked TFB having vinyl groups as side chains and the CdZnSe/ZnSe blue quantum dots containing the vinyl phosphate ligand of example 2 at concentrations of 3mg/ml and 20mg/ml, respectively, and the mixed layer thickness was 10nm. Warp yarnTested, the maximum External Quantum Efficiency (EQE) of the device is 15%, and the maximum brightness can reach 5900cd/m 2 。
Example 9
This example prepares a QLED device. This example differs from example 7 only in that the mixed layer material was replaced with crosslinked PVK having vinyl groups as side chains and the CdZnSe/ZnSe blue quantum dots containing 2-vinylthiophene ligands of example 3, the solvent was chlorobenzene at concentrations of 8mg/ml and 20mg/ml, respectively, and the mixed layer thickness was 10nm. Through testing, the maximum External Quantum Efficiency (EQE) of the device is 18.8%, and the maximum brightness can reach 7340cd/m 2 。
Example 10
This example prepares a QLED device. This example differs from example 7 only in that the mixed layer material was replaced with crosslinked PVK with boric acid as the side chain and CdZnSe/ZnSe blue quantum dots containing pyridine-4-boric acid ligand of example 4, the solvent was o-xylene at concentrations of 10mg/ml and 20mg/ml, respectively, and the mixed layer thickness was 10nm. Through testing, the maximum External Quantum Efficiency (EQE) of the device is 18%, and the maximum brightness can reach 7030cd/m 2 。
Example 11
This example prepares a QLED device. The difference between this example and example 7 is that the quantum dots in the mixed layer are replaced with the CdZnSe/ZnSe blue quantum dots containing pyridine-4-boronic acid ligand of example 5, the solvent is o-xylene, the concentrations of the crosslinked PVK and blue quantum dots with side chains of boric acid in the mixed layer solution are respectively 10mg/ml and 20mg/ml, and the thickness of the mixed layer is 10nm. Through testing, the maximum External Quantum Efficiency (EQE) of the device is 12.5%, and the maximum brightness can reach 4900cd/m 2 。
Example 12
This example prepares a QLED device. The difference between this example and example 7 is that the quantum dots in the mixed layer are replaced with the CdZnSe/ZnSe blue quantum dots containing pyridine-4-boronic acid ligand of example 6, the solvent is o-xylene, the concentrations of the crosslinked PVK and blue quantum dots with side chains of boric acid in the mixed layer solution are respectively 10mg/ml and 20mg/ml, and the thickness of the mixed layer is 10nm. Through testing, the maximum External Quantum Efficiency (EQE) of the device is 13.2%, and the maximum brightness can reach 5170cd/m 2 。
Comparative example
This comparative example prepares a QLED device. The only difference of this comparative example from example 5 is that no mixed layer is provided between the hole transport layer 20 and the quantum dot light emitting layer. Tested, the maximum External Quantum Efficiency (EQE) of the device was 12% and the maximum brightness was 4700cd/m 2 。
As can be seen from examples 7 to 12 and comparison examples, after the mixed layer including the crosslinkable hole transporting material and the nanoparticles is provided, the maximum external quantum dot efficiency and the maximum brightness of the device are significantly improved relative to those of the device without the mixed layer, because the hole transporting material and the nanoparticles are crosslinked together in the mixed layer, so that the connection between the hole transporting material and the nanoparticles is tighter, the potential barrier between the HOMO level of the hole transporting material and the HOMO level of the quantum dot is reduced, the transition effect is achieved, the injection of holes from the hole transporting layer 20 into the mixed layer and the further injection into the quantum dot light emitting layer are facilitated, the injection balance of holes and electrons is improved, and the efficiency and the lifetime of the QLED device are improved.
The nanoparticle, the optoelectronic device and the preparation method provided in the embodiments of the present application are described in detail, and specific examples are applied herein to illustrate the principles and embodiments of the present application, and the description of the above examples is only used to help understand the method and core idea of the present application; meanwhile, those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, and the present description should not be construed as limiting the present application in view of the above.
Claims (15)
1. A nanoparticle comprising a first quantum dot and a first ligand attached to a surface of the first quantum dot, the first ligand comprising a first crosslinkable group.
2. The nanoparticle of claim 1, wherein the first ligand further comprises a coordinating group through which the first ligand is coordinately bound to the first quantum dot;
and/or the first crosslinkable group comprises at least one of a vinyl group, a boric acid group.
3. The nanoparticle of claim 2, wherein the coordinating group comprises a coordinating atom selected from at least one of N, P or S, the coordinating atom being directly attached to the first crosslinkable group via a chemical bond.
4. The nanoparticle according to claim 2, wherein the coordinating group is a heterocyclic group having 5 to 10 ring atoms, the hetero atoms of the heterocyclic group including N or S, at least one hydrogen atom of the heterocyclic group being substituted with the first crosslinkable group.
5. A nanoparticle according to claim 3, wherein the coordinating group is selected from at least one of an amine group or a phosphate group or a thiol group.
6. The nanoparticle of claim 4, wherein the coordinating group comprises at least one of a pyridyl group, a pyrrolyl group, a thienyl group.
7. The nanoparticle of claim 1, wherein the first quantum dot is selected from CdS, cdSe, cdTe, inP, agS, pbS, pbSe, hgS, zn X Cd 1-X S、Cu X In 1-X S、Zn X Cd 1-X Se、Zn X Se 1-X S、Zn X Cd 1-X Te、PbSe X S 1-X 、Zn X Cd 1-X S/ZnSe、Cu X In 1-X S/ZnS、Zn X Cd 1-X Se/ZnS、CuInSeS、Zn X Cd 1-X Te/ZnS、PbSe X S 1-X At least one of ZnS, 0<X<1, a step of; and/or the mass ratio of the first quantum dot to the first ligand is 1 (0.01-0.1).
8. A method of preparing nanoparticles comprising the steps of:
providing a solution comprising first quantum dots, wherein the first quantum dot surface is attached to an initial ligand;
mixing the solution with a first ligand, carrying out ligand exchange reaction to obtain nano particles,
wherein the first ligand comprises a coordinating group and a first crosslinkable group, and the nanoparticle comprises a first quantum dot with a surface coordinately bound to the first ligand.
9. The method according to claim 8, wherein the primary ligand is at least one selected from trioctylphosphine, trioctylphosphine oxide, oleic acid, stearic acid, oleylamine, thioglycollic acid, and mercaptopropionic acid;
and/or the reaction temperature of the ligand exchange reaction is 20-30 ℃;
And/or the reaction time of the ligand exchange reaction is 3-5 h.
10. An optoelectronic device comprising an anode, a hole transport layer, a light emitting layer, and a cathode, wherein the anode, the hole transport layer, the light emitting layer, and the light emitting layer are stacked, and a mixed layer is further disposed between the hole transport layer and the light emitting layer, wherein the mixed layer comprises the nanoparticle of any one of claims 1-7 and a first hole transport material.
11. The optoelectronic device of claim 10, wherein the first hole transport material comprises a second crosslinkable group, the first crosslinkable group being capable of undergoing a crosslinking reaction with the second crosslinkable group; and/or
The mass ratio of the nanoparticles to the first hole transport material in the mixed layer is (3-10): 20, and/or
The thickness of the mixed layer is 5-10nm.
12. The optoelectronic device of claim 11, wherein the second crosslinkable group comprises at least one of a vinyl group, a boric acid group; and/or
The first hole transport material is selected from at least one of crosslinkable poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), crosslinkable polyvinylcarbazole, crosslinkable poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine) or crosslinkable N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine.
13. The optoelectronic device of claim 10, wherein the material of the hole transport layer comprises a second hole transport material; the HOMO level of the first hole transporting material is deeper than the HOMO level of the second hole transporting material.
14. The optoelectronic device of claim 13, wherein the second hole transporting material is selected from one or more of (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4',4 "-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) 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; and/or
The anode is a composite electrode formed by one or more of a metal electrode, a carbon electrode and a doped or undoped metal oxide electrode; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is at least one selected from graphite, carbon nano tube, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the material of the composite electrode is selected from 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 TiO 2 /Al/TiO 2 At least one of (a) and (b); and/or
The cathode is a composite electrode formed by one or more of a metal electrode, a carbon electrode and a doped or undoped metal oxide electrode; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is at least one selected from graphite, carbon nano tube, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the material of the composite electrode is selected from 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 TiO 2 /Al/TiO 2 At least one of (a) and (b); and/or the material of the luminescent layer comprises second quantum dots, the second quantum dots are blue quantum dots,
the second quantum dot is the same as or different from the first quantum dot; the first quantum dot and/or the second quantum dot is/are selected from CdS, cdSe, cdTe, inP, agS, pbS, pbSe, hgS, zn X Cd 1-X S、Cu X In 1-X S、Zn X Cd 1-X Se、Zn X Se 1-X S、Zn X Cd 1-X Te、PbSe X S 1-X 、Zn X Cd 1-X S/ZnSe、Cu X In 1-X S/ZnS、Zn X Cd 1-X Se/ZnS、CuInSeS、Zn X Cd 1-X Te/ZnS、PbSe X S 1-X At least one of ZnS, 0<X<1。
15. A method of fabricating an optoelectronic device comprising the steps of:
Providing a substrate, arranging an anode on the substrate,
providing a hole transport layer ink comprising a second hole transport material and a first organic solvent, disposing the hole transport layer ink on the anode to form a hole transport layer,
providing a mixed layer ink comprising a first hole transport material, nanoparticles and a second organic solvent, disposing the mixed layer ink on the hole transport layer to form a mixed layer,
providing a luminescent layer ink comprising second quantum dots and a third organic solvent, disposing the third precursor solution on the mixed layer to form a luminescent layer,
disposing a cathode on the light emitting layer; or alternatively
Providing a substrate, disposing a cathode on the substrate,
providing a luminescent layer ink comprising second quantum dots and a third organic solvent, disposing the luminescent layer ink on the cathode to form a luminescent layer,
providing a mixed layer ink comprising a first hole transport material, nanoparticles and a second organic solvent, disposing the mixed layer ink on the light emitting layer to form a mixed layer,
providing a hole transport layer ink comprising a second hole transport material and a first organic solvent, disposing the hole transport layer ink on the mixed layer to form a hole transport layer,
Disposing an anode on the hole transport layer;
wherein the nanoparticle comprises a first quantum dot and a first ligand comprising a first crosslinkable group.
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