CN116981311A - Preparation method of light-emitting device, light-emitting device and display device - Google Patents
Preparation method of light-emitting device, light-emitting device and display device Download PDFInfo
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- CN116981311A CN116981311A CN202210394651.8A CN202210394651A CN116981311A CN 116981311 A CN116981311 A CN 116981311A CN 202210394651 A CN202210394651 A CN 202210394651A CN 116981311 A CN116981311 A CN 116981311A
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- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
The application discloses a preparation method of a light-emitting device, the light-emitting device and a display device, wherein the preparation method comprises the following steps: providing a prefabricated device, and applying a solution containing nano metal oxide on one side of the prefabricated device for forming an electron transport precursor layer; and in a preset time range, carrying out electrification treatment on the electron transport precursor layer so as to form an electron transport layer, thereby effectively improving the crystallinity, conductivity and stability of the sub-transport layer.
Description
Technical Field
The application relates to the technical field of photoelectricity, in particular to a preparation method of a light-emitting device, the light-emitting device and a display device.
Background
The Light Emitting device includes, but is not limited to, an Organic Light-Emitting Diode (OLED) and a quantum dot Light-Emitting Diode (Quantum Dot Light Emitting Diodes, QLED), and is of a "sandwich" structure, i.e., includes an anode, a cathode, and a Light Emitting layer, wherein the anode and the cathode are disposed opposite to each other, and the Light Emitting layer is disposed between the anode and the cathode. The light emitting principle of the light emitting device is: electrons are injected into the light-emitting area from the cathode of the device, holes are injected into the light-emitting area from the anode of the device, the electrons and the holes are combined in the light-emitting area to form excitons, and photons are released from the combined excitons in a radiation transition mode, so that light is emitted.
In a light emitting device, an electron transport layer is typically further provided between the cathode and the light emitting layer, and metal oxide nanoparticles are one of the materials used to prepare the electron transport layer. The nano metal oxide has the characteristics of higher electron mobility and wide band gap, but the surface of the nano metal oxide has more defect states, so that the stability of the nano metal oxide is not ideal, and the influence of external environment conditions on the defect density and the conductivity of the nano metal oxide is larger, so that the performance fluctuation of an electron transport layer is larger, and the photoelectric performance and the service life of a light-emitting device are further adversely affected.
Therefore, how to improve the performance stability of the electron transport layer including the nano-metal oxide has important significance for the application and development of the light emitting device.
Disclosure of Invention
The application provides a preparation method of a light-emitting device, the light-emitting device and a display device, so as to improve the photoelectric performance and stability of the light-emitting device.
The technical scheme of the application is as follows:
in a first aspect, the present application provides a method for manufacturing a light emitting device, the method comprising the steps of:
providing a prefabricated device, and applying a solution containing nano metal oxide on one side of the prefabricated device for forming an electron transport precursor layer;
Carrying out electrification treatment on the electron transport precursor layer so as to form an electron transport layer;
when the light-emitting device is of a positive structure, the prefabricated device comprises a bottom electrode and a light-emitting layer which are arranged in a stacked mode, the electron transmission precursor layer is formed on one side, far away from the bottom electrode, of the light-emitting layer, and the bottom electrode is an anode;
alternatively, when the light emitting device is of an inverted structure, the prefabricated device includes a bottom electrode, the electron transport precursor layer is formed on one side of the bottom electrode, and the bottom electrode is a cathode.
Further, the charging treatment is to make the electron transport precursor layer carry positive charges or negative charges, or make the electron transport precursor layer alternately carry positive charges and negative charges.
Further, the electrification process includes the steps of: providing an external power supply, wherein a first end of the external power supply is connected with the bottom electrode, and a second end of the external power supply is grounded; and turning on the external power supply to enable a potential difference to exist between the first end and the second end.
Further, in the process of the electrification treatment, the external power supply applies constant voltage or alternating voltage to the electron transmission precursor layer;
Wherein the constant voltage has a voltage value of 10V to 30V;
the frequency of the alternating voltage is 10Hz to 200Hz, and the value of the effective voltage is 10V to 30V.
Further, the nano metal oxide is 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 or ZnOF;
and/or, the average particle diameter of the nano metal oxide is 2nm to 15nm.
Further, the time of the electrification treatment is 5min to 120min;
the charging treatment is continuous;
or the electrification treatment is intermittent, the time of single electrification treatment is 5min to 20min, and the interval time between adjacent electrification treatments is 5min to 20min.
Further, the electron transport precursor layer is a wet film, and the preparation method further comprises the steps of: and annealing the electron transmission precursor layer.
Further, the annealing treatment temperature is 80 ℃ to 250 ℃;
and/or the annealing treatment is carried out for 5min to 120min.
Optionally, the period of annealing treatment at least partially overlaps with the period of charging treatment, and the manner of annealing treatment and the manner of charging treatment are any of the following cases:
(a1) The annealing treatment is continuous and the charging treatment is continuous;
(a2) The annealing treatment is continuous, and the charging treatment is intermittent;
(a3) The annealing treatment is intermittent and the charging treatment is continuous;
(a4) The annealing treatment is intermittent, and the charging treatment is intermittent.
Further, when the annealing treatment is continuous and the charging treatment is continuous, the overlapping time of the annealing treatment and the charging treatment is 5min to 120min;
or when the annealing treatment is continuous and the charging treatment is intermittent, the overlapping time of the annealing treatment and the charging treatment is 5min to 115min;
or when the annealing treatment is intermittent and the charging treatment is continuous, the interval time between adjacent annealing treatments is 5min to 10min, the time of single annealing treatment is 10min to 30min, and the overlapping time of the annealing treatment and the charging treatment is 5min to 115min;
or when the annealing treatment is intermittent and the charging treatment is intermittent, the interval time between adjacent annealing treatments is 5min to 10min, the time of single annealing treatment is 10min to 30min, and the overlapping time of the annealing treatment and the charging treatment is 5min to 115min.
Optionally, the time period of the annealing treatment and the time period of the charging treatment do not overlap, and the manner of the annealing treatment and the manner of the charging treatment are any of the following cases:
(b1) The annealing treatment and the electrification treatment are alternately performed;
(b2) After the charged treatment is completed on the electron transport precursor layer, the annealing treatment is performed;
wherein, for (b 1), the time of the single annealing treatment is 5min to 20min.
Further, when the light emitting device is of a front structure, the manufacturing method further includes the steps of: after an electron transport layer is formed on one side of the prefabricated device, a top electrode is formed on one side, far away from the light-emitting layer, of the electron transport layer, and the top electrode is a cathode;
alternatively, when the light emitting device is of an inverted structure, the manufacturing method further includes the steps of:
forming an electron transport layer on one side of the prefabricated device, and then forming a light emitting layer on one side of the electron transport layer away from the bottom electrode;
forming a top electrode on one side of the light-emitting layer far away from the electron transport layer, wherein the top electrode is an anode;
and/or the material of the light-emitting layer is an organic light-emitting material or quantum dots;
The organic luminescent material is at least one selected from a diaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative, a fluorene derivative, a TBPe fluorescent material, a TTPA fluorescent material, a TBRb fluorescent material or a DBP fluorescent material;
the quantum dots are selected from at least one of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots or organic-inorganic hybrid perovskite quantum dots; when the quantum dot is selected from a single component quantum dot or a 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 at least one of CuInS2, cuInSe2, or AgInS 2.
Further, the preparation method further comprises the steps of: forming a hole function layer between the anode and the light emitting layer, wherein the hole function layer comprises a hole injection layer and/or a hole transport layer, when the hole function layer comprises a hole transport layer and a hole injection layer which are stacked, the hole transport layer is close to the light emitting layer, and the hole injection layer is close to the anode;
the material of the hole transport layer is at least one selected from NiO, WO3, moO3, cuO, 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 (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine or N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine;
the hole injection layer is made of poly (3, 4-ethylenedioxythiophene): at least one of poly (styrenesulfonic acid), copper phthalocyanine, 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 is selected from at least one of NiOx, moOx, WOx or CrOx, and the transition metal chalcogenide is selected from at least one of MoSx, moSex, WSx, WSex or CuS.
In a second aspect, the present application provides a light-emitting device manufactured by the manufacturing method according to any one of the first aspects.
In a third aspect, the present application also provides a display apparatus comprising a light-emitting device manufactured by the manufacturing method according to any one of the first aspects, or a light-emitting device according to any one of the second aspects.
The application provides a preparation method of a light-emitting device, the light-emitting device and a display device, which have the following technical effects:
in the preparation method, a solution containing nano metal oxide is applied to one side of the prefabricated device to form an electron transport precursor layer, and the electron transport precursor layer is subjected to electrification treatment to form the electron transport layer, so that the ligand connected to the surface of the nano metal oxide is facilitated to fall off, gaps between adjacent nano particles are effectively shortened, the crystallinity, conductivity and stability of the electron transport layer are improved, and the luminous performance and the service life of the luminous device are greatly improved.
Compared with the existing light-emitting device (the material of the electron transport layer is nano oxide), the electron transport layer (the material of the same kind of nano metal oxide) of the light-emitting device has higher compactness, namely smaller gaps between adjacent nano particles, so that the conductivity and the stability of the electron transport layer are higher, and the comprehensive performance of the light-emitting device is better.
The light-emitting device prepared by the preparation method is applied to the display device, and is beneficial to improving the display effect of the display device and prolonging the service life of the display device.
Drawings
The technical solution and other advantageous effects of the present application will be made apparent by the following detailed description of the specific embodiments of the present application with reference to the accompanying drawings.
Fig. 1 is a schematic flow chart of a method for manufacturing a light emitting device according to an embodiment of the present application.
Fig. 2 is a schematic structural diagram of a first light emitting device according to an embodiment of the present application.
Fig. 3 is a schematic structural diagram of a second light emitting device according to an embodiment of the present application.
Fig. 4 is a schematic structural diagram of a third light emitting device according to an embodiment of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the 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 application. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the application.
The following description of the embodiments is not intended to limit the preferred embodiments. In addition, in the description of the present application, the term "comprising" means "including but not limited to," and the term "plurality" or "multiple layers" means two/more layers. Various embodiments of the 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 application; 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.
The embodiment of the application provides a preparation method of a light-emitting device, as shown in fig. 1, comprising the following steps:
s1, providing a prefabricated device, and applying a solution containing nano metal oxide on one side of the prefabricated device for forming an electron transport precursor layer;
s2, carrying out electrification treatment on the electron transport precursor layer so as to form the electron transport layer.
It should be noted that, in the above preparation method, the electron transport precursor layer may be in a wet film state, or the electron transport precursor layer may be in a dry film state, for example, the electron transport precursor layer may be a wet film formed by applying a solution containing a nano metal oxide to one side of the prefabricated device, and the electron transport precursor layer may be a dry film layer obtained after drying a wet film formed by applying a solution containing a nano metal oxide to one side of the prefabricated device. It will be appreciated that the preparation method may further comprise other treatment steps during or after the charge treatment of the electron transport precursor layer, such as: when the electron transport precursor layer is a wet film, the preparation method may further include a drying process after the electron transport precursor layer is charged, so as to obtain the electron transport layer in a dry film state.
The electron transport precursor layer is prepared by adopting a solution containing nano metal oxide, if the electron transport precursor layer is only subjected to drying treatment to form the electron transport layer, the temperature of the drying treatment is not too high to avoid damage to the luminescent layer and other functional layers, so that the ligand on the surface of the nano metal oxide cannot be sufficiently removed, and the gap between adjacent nano particles cannot be effectively shortened, so that the nano crystal array formed by the nano metal oxide has the characteristic of loose arrangement in the formed electron transport layer, and the problem of lower compactness of the electron transport layer exists. The barrier of electron conduction is formed based on the gaps between adjacent nano particles, and the specific surface area of the nano metal oxide is larger and the property is more active, so that the electron transport layer prepared from the nano metal oxide has poor conductivity and poor stability. Based on the above, in the preparation method, the ligand connected to the surface of the nano metal oxide is dropped under the action of electric energy and high temperature by adopting the technical means of carrying out charged treatment on the electron transport precursor layer, so that the gap between adjacent nano particles is shortened, the crystallinity, the conductivity and the stability of the electron transport layer are further improved, and the photoelectric performance and the service life of the light emitting device are improved.
Specifically, in step S1, the application manner of the solution containing the nano metal oxide includes, but is not limited to, at least one of spin coating, inkjet printing, knife coating, dip-coating, dipping, spray coating, roll coating or casting. When the light emitting device is of a positive structure, the prefabricated device comprises a bottom electrode and a light emitting layer which are stacked, the electron transmission precursor layer is formed on one side, far away from the bottom electrode, of the light emitting layer, and the bottom electrode is an anode, for example: the prefabricated device is composed of a substrate, an anode and a light-emitting layer which are sequentially stacked, and the prefabricated device is as follows: the prefabricated device consists of a substrate, an anode, a hole function layer and a light-emitting layer which are sequentially stacked; when the light emitting device is of an inverted structure, the prefabricated device includes a bottom electrode, an electron transporting precursor layer is formed on one side of the bottom electrode, and the bottom electrode is a cathode, for example: the prefabricated device consists of a substrate and a cathode which are arranged in a stacked manner, and an electron transport precursor layer is formed on one side of the cathode away from the substrate.
The nano metal oxide can be undoped nano metal oxide or doped nano metal oxide. In some embodiments of the application, the nano metal oxide is 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 or ZnOF. The average particle diameter of the nano metal oxide may be, for example, 2nm to 15nm, the average particle diameter of the nano metal oxide may be, for example, 2nm to 4nm, 2nm to 6nm, 2nm to 8nm, 2nm to 10nm, 4nm to 10nm, or 10nm to 15nm, and the average particle diameter of the nano metal oxide may be, for example, 5nm, 6nm, 7nm, 8nm, 9nm, or 10nm.
The solution containing the nano metal oxide may be, for example, a product containing the nano metal oxide prepared by a solution method, wherein the solvent includes, but is not limited to, at least one of water, ethanol, propanol, butanol, hexanol, n-octane, n-hexane, or ethylene glycol monomethyl ether.
Specifically, in step S2, the electrification process is performed in a preset time range, "preset time range" refers to a time range set by the operator, which may be obtained by multiple repeated experiments, and the types of the light emitting devices are different, and the time ranges may be different. In some embodiments of the present application, the time of the charging treatment is 5 to 120min, and the time of the charging treatment may be, for example, 5 to 10min, 10 to 20min, 20 to 30min, 30 to 40min, 40 to 50min, 50 to 60min, 60 to 70min, 70 to 80min, 80 to 90min, 90 to 100min, 100 to 110min, or 110 to 120min.
It will be appreciated that the charging process may be continuous or intermittent over a predetermined time period. In some embodiments of the present application, the charging process is intermittent within a predetermined time range, the time of a single charging process is 5min to 20min, the interval time of adjacent charging processes is 5min to 20min, the time of a single charging process may be, for example, 5min to 8min, 8min to 10min, 10min to 15min, or 15min to 20min, and the interval time of adjacent charging processes may be, for example, 5min to 8min, 8min to 10min, 10min to 12min, 12min to 15min, or 15min to 20min.
In some embodiments of the present application, the "charge treatment" includes all processes that can cause the electron transport precursor layer to carry positive or negative charges, or alternately carry positive and negative charges, and it is understood that the charge treatment may cause the electron transport precursor layer to carry charges only, may cause the entire prefabricated device including the electron transport precursor layer to carry charges, and may cause some layers (including the electron transport precursor layer) in the prefabricated device including the electron transport precursor layer to carry charges.
In some embodiments of the application, the charging process comprises the steps of: an external power supply is provided, a first end of the external power supply is connected with the bottom electrode, a second end of the external power supply is grounded, the external power supply is started, and a potential difference is arranged between the first end and the second section, so that the prefabricated device containing the electron transmission precursor layer wholly carries positive charges or negative charges, or the prefabricated device containing the electron transmission precursor layer wholly alternately carries positive charges and negative charges. The type and the model of the external power supply are not particularly limited, and the external power supply can be selected according to different scales of the light emitting device.
In at least one embodiment of the present application, the "live process" includes the steps of: and fixing the prefabricated device comprising the electron transmission precursor layer on a fixture, connecting a first end of an external power supply with a bottom electrode positioned on one side of the prefabricated device, grounding a second end of the external power supply, and starting the external power supply, wherein a potential difference exists between the first end and the second end.
Further, in the process of the electrification treatment, an external power supply applies a constant voltage or alternating voltage to the electron transport precursor layer. When an external power supply applies constant voltage to the electron transport precursor layer, the first end can be the positive electrode, and the second end can be the negative electrode, so that the whole prefabricated device containing the electron transport precursor layer carries positive charges; or the first electrode is a negative electrode, and the second electrode is a positive electrode, so that the whole prefabricated device containing the electron transport precursor layer carries negative charges. When an external power supply applies alternating voltage to the electron transport precursor layer, the whole prefabricated device containing the electron transport precursor layer alternately carries positive charges and negative charges.
Optionally, when the external power source applies a constant voltage to the electron transport precursor layer, the constant voltage has a voltage value of 10V to 30V, and the constant voltage has a voltage value of, for example, 10V to 15V, 15V to 20V, 20V to 25V, or 25V to 30V. As used herein, a "voltage value" refers only to a specific magnitude of voltage and does not indicate the direction of the voltage. It can be understood that on the premise of constant time of the electrification treatment, the overall performance improvement effect of the light-emitting device is limited due to the fact that the voltage value of the constant voltage is too high or too low, and the ligand removal effect on the surface of the nano metal oxide is limited due to the fact that the voltage value is too low, so that the reduction degree of gaps between adjacent nano particles is limited, and further the improvement effect of the conductivity and the stability of the electron transport layer is limited; if the voltage value is too high, the organic functional layer and/or the light-emitting layer may be damaged to some extent.
Optionally, when an external power source applies an ac voltage to the electron transport precursor layer, the ac voltage has a frequency of 10Hz to 200Hz, the effective voltage has a value of 10V to 30V, the ac voltage has a frequency of, for example, 10Hz to 30Hz, 30Hz to 50Hz, 50Hz to 80Hz, 80Hz to 100Hz, 100Hz to 120Hz, 120Hz to 150Hz, 150Hz to 180Hz, or 180Hz to 200Hz, and the effective voltage has a value of, for example, 10V to 15V, 15V to 20V, 20V to 25V, or 25V to 30V.
In some embodiments of the present application, the electron transport precursor layer is a wet film, and the preparation method further comprises the steps of: and annealing the electron transport precursor layer. The "annealing treatment" includes all the processes capable of obtaining higher energy from the electron transport precursor layer in the wet film state and removing at least a part of the solvent, including but not limited to a constant temperature heat treatment process or a non-constant temperature heat treatment process (e.g., temperature gradient change) process, and in some embodiments of the present application, "annealing treatment" refers to a constant temperature heat treatment at 80 ℃ to 250 ℃ for 5min to 120min, the temperature of the annealing treatment may be, for example, 80 ℃ to 100 ℃, 100 ℃ to 120 ℃, 120 ℃ to 140 ℃, 140 ℃ to 160 ℃, 160 ℃ to 180 ℃, 180 ℃ to 200 ℃, 200 ℃ to 220 ℃, 220 ℃ to 240 ℃, or 240 ℃ to 250 ℃, and the time of the annealing treatment may be, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 110min, or 110min to 120min.
In some embodiments of the application, the period of annealing treatment at least partially overlaps with the period of charging treatment, the manner of annealing treatment and the manner of charging treatment being any of the following:
(a1) The annealing treatment is continuous and the charging treatment is continuous;
(a2) The annealing treatment is continuous, and the charging treatment is intermittent;
(a3) The annealing treatment is intermittent and the charging treatment is continuous;
(a4) The annealing treatment is intermittent, and the charging treatment is intermittent.
In at least one embodiment of the present application, the annealing treatment is continuous and the charging treatment is continuous, and the overlapping time of the annealing treatment and the charging treatment is 5min to 120min, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 110min, or 110min to 120min. The annealing treatment time is, for example, 5min to 120min, the annealing treatment temperature is, for example, 80 ℃ to 250 ℃, and the charging treatment time is, for example, 5min to 120min.
In at least one embodiment of the present application, the annealing treatment is continuous and the charging treatment is intermittent, and the overlapping time of the annealing treatment and the charging treatment is, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 115min. The annealing treatment time is, for example, 5min to 120min, the annealing treatment temperature is, for example, 80 ℃ to 250 ℃, the charging treatment time is, for example, 5min to 120min, the single charging treatment time is, for example, 5min to 20min, and the interval time between adjacent charging treatments is, for example, 5min to 20min.
In at least one embodiment of the present application, the annealing process is intermittent and the charging process is continuous, the interval between adjacent annealing processes is 5min to 10min, the time of a single annealing process is 10min to 30min, the overlapping time of the annealing process and the charging process is 5min to 115min, and the temperature of the annealing process is, for example, 80 ℃ to 250 ℃. The interval time of the annealing treatment is, for example, 5min to 6min, 6min to 7min, 7min to 8min, 8min to 9min, or 9min to 10min, the time of the single annealing treatment is, for example, 10min to 15min, 15min to 20min, 20min to 25min, or 25min to 30min, and the overlapping time of the annealing treatment and the electrification treatment is, for example, 5min to 10min, 10min to 20min, 20min to 30min, 30min to 40min, 40min to 50min, 50min to 60min, 60min to 70min, 70min to 80min, 80min to 90min, 90min to 100min, 100min to 115min. The time of the electrification treatment is, for example, 5min to 120min.
In at least one embodiment of the present application, the annealing process is intermittent, and the charging process is intermittent, the interval between adjacent annealing processes is 5min to 10min, the time of a single annealing process is 10min to 30min, the overlapping time of the annealing process and the charging process is 5min to 115min, and the temperature of the annealing process is, for example, 80 ℃ to 250 ℃. The time of the electrification treatment is, for example, 5min to 120min, the time of the single electrification treatment is, for example, 5min to 20min, and the interval time of the adjacent electrification treatments is, for example, 5min to 20min.
In other embodiments of the present application, the period of annealing treatment does not overlap with the period of charging treatment, and the manner of annealing treatment and the manner of charging treatment are any of the following:
(b1) The annealing treatment and the electrification treatment are alternately carried out;
(b2) And after the charged treatment is completed on the electron transport precursor layer, carrying out the annealing treatment.
It is understood that, for (b 1), the annealing treatment and the charging treatment are both intermittent, the time of the charging treatment is, for example, 5min to 120min, the time of the single charging treatment is, for example, 5min to 20min, the time of the annealing treatment is, for example, 5min to 120min, and the time of the single annealing treatment is, for example, 5min to 20min.
For (b 2), the charging treatment may be continuous or intermittent, and similarly, the annealing treatment may be continuous or intermittent. The time of the electrification treatment is, for example, 5min to 120min, and the time of the annealing treatment is, for example, 5min to 120min.
The annealing treatment and the charging treatment are performed under an inert gas atmosphere, and "inert gas" refers to a gas that is inert in chemical properties, does not react with the electron transport precursor layer and other functional layers, and has characteristics of isolating oxygen and water, and is at least one selected from nitrogen, helium, neon, argon, krypton, and xenon.
In some embodiments of the present application, when the light emitting device is in a front-mounted structure, the manufacturing method further includes the steps of: and forming a top electrode on one side of the electron transport layer far away from the light emitting layer, wherein the top electrode is a cathode. It will be appreciated that when the light emitting device is in a front-up configuration, the prefabricated device may be a stacked configuration comprising an anode, a hole-functional layer and a light emitting layer, and therefore the manufacturing method further comprises the steps of: providing an anode, and sequentially preparing and forming a hole functional layer and a light-emitting layer on one side of the anode, wherein the hole functional layer comprises a hole transport layer and/or a hole injection layer, and when the hole functional layer comprises the hole transport layer and the hole injection layer, the hole injection layer is close to the anode, and the hole transport layer is close to the light-emitting layer.
In at least one embodiment of the present application, when the light emitting device is in a front structure, the manufacturing method includes the steps of:
s1, providing a substrate, and preparing and forming an anode on one side of the substrate;
s2, preparing and forming a hole injection layer on one side of the anode far away from the substrate;
s3, preparing and forming a hole transport layer on one side of the hole injection layer far away from the anode;
s4, preparing a light-emitting layer on one side of the hole transport layer far away from the hole injection layer;
S5, applying a solution containing nano metal oxide on one side of the light-emitting layer far away from the hole transport layer to obtain an electron transport precursor layer in a wet film state, and then carrying out annealing treatment and electrification treatment on the electron transport precursor layer within a preset time range so as to enable the electron transport precursor layer to carry positive charges or negative charges or enable the electron transport precursor layer to alternately carry positive charges and negative charges to obtain the electron transport layer;
and S6, preparing and forming a cathode on one side of the electron transport layer far away from the light emitting layer.
In other embodiments of the present application, when the light emitting device is of an inverted structure, the manufacturing method further includes the steps of:
after forming an electron transport layer on one side of the prefabricated device, forming a light emitting layer on one side of the electron transport layer away from the bottom electrode; and
and preparing and forming a top electrode on one side of the light-emitting layer far away from the electron transport layer, wherein the top electrode is an anode.
Further, when the light emitting device is of an inverted structure, the manufacturing method further includes the steps of: and forming a hole function layer between the anode and the light-emitting layer, wherein the hole function layer comprises a hole injection layer and/or a hole transport layer, and when the hole function layer comprises the hole transport layer and the hole injection layer which are stacked, the hole transport layer is close to the light-emitting layer, and the hole injection layer is close to the anode. It is understood that the "forming a hole function layer between the anode and the light emitting layer" is to prepare a hole function layer on a side of the light emitting layer away from the electron transport layer, and then prepare an anode on a side of the hole function layer away from the light emitting layer; in addition, when the hole functional layer includes a hole injection layer and a hole transport layer, the hole injection layer, and the light emitting layer are sequentially formed on a side of the light emitting layer remote from the electron transport layer.
In at least one embodiment of the present application, when the light emitting device is of an inverted structure, the manufacturing method includes the steps of:
s1', providing a substrate, and preparing and forming a cathode on one side of the substrate;
s2', applying a solution containing nano metal oxide on one side of the cathode, which is far away from the substrate, to obtain an electron transport precursor layer in a wet film state, and then carrying out annealing treatment and electrification treatment on the electron transport precursor layer within a preset time range so as to enable the electron transport precursor layer to carry positive charges or negative charges or enable the electron transport precursor layer to alternately carry positive charges and negative charges, so as to obtain an electron transport layer;
s3', preparing and forming a light-emitting layer on one side of the electron transport layer far away from the cathode;
s4', preparing and forming a hole transport layer on one side of the light-emitting layer far away from the electron transport layer;
s5', preparing and forming a hole injection layer on one side of the hole transport layer far away from the light-emitting layer;
and S6', preparing and forming an anode on one side of the hole injection layer away from the hole transport layer.
Besides the electron transport layer, the preparation method of each other film layer in the light-emitting 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 a light emitting device may also include other steps, such as: after each layer of the light emitting device is completed, the light emitting device is subjected to a packaging process.
The embodiment of the application also provides a light-emitting device, which is manufactured by adopting any one of the manufacturing methods, as shown in fig. 2, the light-emitting device 1 comprises an anode 11, a cathode 12, a light-emitting layer 13 and an electron transport layer 14, wherein the anode 11 and the cathode 12 are arranged oppositely, the light-emitting layer 13 is arranged between the anode 11 and the cathode 12, and the electron transport layer 14 is arranged between the cathode 12 and the light-emitting layer 13. It is understood that the light emitting device includes, but is not limited to, an OLED or QLED, and the light emitting device may be a front-mounted structure, and the light emitting device may also be an inverted structure. Compared with the existing light-emitting device (the material of the electron transport layer is nano metal oxide), the electron transport layer of the light-emitting device in the embodiment of the application has higher compactness, namely the gaps between adjacent nano particles are smaller, so that the conductivity and stability of the electron transport layer are higher, and the light-emitting device in the embodiment of the application has better comprehensive performance.
In the light emitting device of the embodiment of the present application, materials of the anode 11, the cathode 12, and the light emitting layer 13 may be materials common in the art, for example:
The materials of the anode 11 and the cathode 12 are independently selected from at least one of metal, carbon material or 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 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, 40nm to 160nm, and the thickness of the cathode 12 may be, for example, 20nm to 120nm.
The material of the light emitting layer 13 is selected from organic light emitting materials or quantum dots. The thickness of the light emitting layer 13 may be, for example, 20nm to 60nm. The organic light emitting material includes, but is not limited to, at least one of a biaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative, a fluorene derivative, a TBPe fluorescent material, a TTPA fluorescent material, a TBRb fluorescent material, or a DBP fluorescent material.
The quantum dots include, but are not limited to, at least one of red, green, or blue quantum dots, and the quantum dots include, but are not limited to, at least one of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, or organic-inorganic hybrid perovskite quantum dots. The particle size of the quantum dots may be, for example, 5nm to 10nm.
When the quantum dot is selected from single component quantum dot or core-shell structure quantum dot, the single component quantum dotThe material of the dot, the material of the core of the quantum dot with a core-shell structure and the material of the shell of the quantum dot with a core-shell structure 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, 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 them.
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 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 an organic amine cation including, but not limited to, CH 3 (CH 2 ) n -2NH 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 - 。
It is understood that when the material of the light emitting layer includes quantum dots, the material of the light emitting layer further includes a ligand attached to the surface of the quantum dots, the ligand includes, but is not limited to, at least one of amine ligands, carboxylic acid ligands, thiol ligands, (oxy) phosphine ligands, phospholipids, soft phospholipids, or polyvinylpyridines, the amine ligands are selected from at least one of oleylamine, n-butylamine, n-octylamine, octaamine, or 1, 2-ethylenediamine, the carboxylic acid ligands are selected from at least one of oleic acid, acetic acid, butyric acid, valeric acid, caproic acid, arachidic acid, dodecanoic acid, undecylenic acid, tetradecanoic acid, or stearic acid, the thiol ligands are selected from at least one of ethanethiol, propanethiol, mercaptoethanol, benzenethiol, octanethiol, dodecyl mercaptan, or octadecyl thiol, and the (oxy) phosphine ligands are selected from at least one of trioctylphosphine or trioctylphosphine oxide.
In order to obtain better photoelectric performance and lifetime, in some embodiments of the present application, as shown in fig. 3, the light emitting device 1 further includes a hole function layer 15, and the hole function layer 15 is disposed between the anode 11 and the light emitting layer 13. The hole function layer 15 includes a hole injection layer and/or a hole transport layer, and when the hole function layer includes a hole transport layer and a hole injection layer which are stacked, the hole transport layer is close to the light emitting layer, and the hole injection layer is close to the anode. The thickness of the hole function layer 15 may be, for example, 20nm to 100nm.
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]At least one of (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) or N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (abbreviated as NPB, CAS number 123847-85-8); in addition, the material of the hole transport layer can be selected from inorganic materials with hole transport capability, including but not limited to NiO, WO 3 、MoO 3 Or CuO.
The material of the hole injection layer includes, but is not limited to, poly (3, 4-ethylenedioxythiophene): one or more of poly (styrenesulfonic acid) (CAS number 155090-83-8), copper phthalocyanine (abbreviated as CuPc, CAS number 147-14-8), 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone (abbreviated as F4-TCNQ, CAS number 29261-33-4), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene (abbreviated as HATCN, CAS number 105598-27-4), transition metal oxide or transition metal chalcogenide, wherein the transition metal oxide may be NiO x 、MoO x 、WO x Or CrO (CrO) x The metal chalcogenide may be MoS x 、MoSe x 、WS x 、WSe x Or at least one of CuS.
The light emitting device may further include other layer structures, for example, the light emitting device may further include an electron injection layer disposed between the electron transport layer and the cathode, the material of the electron injection layer including, but not limited to, at least one of an alkali metal halide including, but not limited to, liF, an alkali metal organic complex including, but not limited to, lithium 8-hydroxyquinoline, or an 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 embodiment of the application also provides a display device, which comprises the light emitting device manufactured by any one of the manufacturing methods of the embodiment of the application, or any one of the light emitting devices of the embodiment of the application, and the display device can be any electronic product with a 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-mounted display, a television or an electronic book reader, wherein the smart wearable device can be a smart bracelet, a smart watch, a Virtual Reality (VR) helmet, and the like.
The technical scheme and effect of the present application will be described in detail by the following specific examples, which are only some examples of the present application, and are not intended to limit the present application.
Example 1
The embodiment provides a preparation method of a light-emitting device and the prepared light-emitting device, wherein the preparation method comprises the following steps:
s1.1, providing a 0.5mm glass substrate in an atmospheric environment at normal temperature and normal pressure, sputtering ITO on one side of the glass substrate to obtain an ITO layer with the thickness of 40nm, 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 for 15min, acetone for 15min, ethanol for 15min and isopropanol for 15min, and performing ultraviolet-ozone surface treatment for 15min after drying to obtain the glass substrate comprising an anode;
S1.2, spin-coating PEDOT on one side of the anode far away from the glass substrate in the step S1.1 under the atmospheric environment of normal temperature and normal pressure: performing constant temperature heat treatment on the PSS aqueous solution at 150 ℃ for 15min to obtain a hole injection layer with the thickness of 20 nm;
s1.3, spin-coating TFB-chlorobenzene solution on one side of the hole injection layer far away from the anode in the step S1.2 under the nitrogen environment of normal temperature and normal pressure, and then placing the film at a constant temperature of 150 ℃ for heat treatment for 30min to obtain a hole transport layer with the thickness of 30 nm;
s1.4, spin-coating a CdZnSe/CdZnS/ZnS quantum dot-n-octane solution with the concentration of 10mg/mL on one side of the hole transmission layer far away from the hole injection layer in the step S1.3 under the nitrogen environment of normal temperature and normal pressure, and then placing the solution in a constant temperature heat treatment for 5min at the temperature of 100 ℃ to obtain a light-emitting layer with the thickness of 20 nm;
s1.5, under the nitrogen environment of normal temperature and normal pressure, spin-coating a 30mg/mL nano ZnO (particle size of 5 nm) -ethanol solution on one side of the luminescent layer far away from the hole transport layer in the step S1.4 to obtain a laminated structure containing an electron transport precursor layer (wet film);
s1.6, fixing a laminated structure containing an electron transport precursor layer by adopting a clamp under a nitrogen environment at normal temperature and normal pressure, providing an external power supply, connecting a first end of the external power supply with an anode, grounding a second end of the external power supply, continuously annealing at a constant temperature of 150 ℃ for 60min, and applying a constant voltage of positive 25V to the electron transport precursor layer by the external power supply in the annealing process to continuously carry out electrification for 60min, so that the whole prefabricated device containing the electron transport precursor layer carries positive charges in the annealing process to obtain an electron transport layer with the thickness of 50 nm;
S1.7 at an air pressure of 4X 10 -6 In the vacuum environment of mbar, ag is evaporated on the side, far away from the light-emitting layer, of the electron transport layer in the step S1.6 to obtain a cathode with the thickness of 100nm, and then the cathode is packaged by adopting epoxy resin and a glass plate to obtain the light-emitting device with the structure shown in FIG. 4.
Referring to fig. 4, in the bottom-up direction, the light emitting device 1 includes a glass substrate 10, an anode 11, a hole function layer 15, a light emitting layer 13, an electron transport layer 14, and a cathode 12, which are sequentially stacked, wherein the hole function 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 adjacent to the anode 11, and the hole transport layer 152 is adjacent to the light emitting layer 13.
Example 2
The present embodiment provides a method for manufacturing a light emitting device and a manufactured light emitting device, and compared with the method for manufacturing a light emitting device provided in embodiment 1, the method for manufacturing a light emitting device in this embodiment is only different in that: and replacing the step S1.6 with a mode that a laminated structure containing the electron transport precursor layer is fixed by adopting a clamp under the nitrogen environment of normal temperature and normal pressure, providing an external power supply, connecting a first end of the external power supply with an anode, grounding a second end of the external power supply, continuously annealing at a constant temperature of 150 ℃ for 60min, and applying a constant voltage of-25V to the electron transport precursor layer by the external power supply in the annealing process to continuously carry out electrification treatment for 60min, so that the whole prefabricated device containing the electron transport precursor layer carries negative charge in the heating annealing process, and the electron transport layer with the thickness of 50nm is obtained.
Example 3
The present embodiment provides a method for manufacturing a light emitting device and a manufactured light emitting device, and compared with the method for manufacturing a light emitting device provided in embodiment 1, the method for manufacturing a light emitting device in this embodiment is only different in that: and replacing the step S1.6 with a mode that a laminated structure containing the electron transport precursor layer is fixed by adopting a clamp under the nitrogen environment of normal temperature and normal pressure, providing an external power supply, connecting a first end of the external power supply with an anode, grounding a second end of the external power supply, continuously annealing at a constant temperature of 150 ℃ for 60min, and applying a constant voltage of 8V to the electron transport precursor layer by the external power supply in the annealing process to continuously carry out electrification for 60min, so that the prefabricated device containing the electron transport precursor layer integrally carries positive charges, and obtaining the electron transport layer with the thickness of 50 nm.
Example 4
The present embodiment provides a method for manufacturing a light emitting device and a manufactured light emitting device, and compared with the method for manufacturing a light emitting device provided in embodiment 1, the method for manufacturing a light emitting device in this embodiment is only different in that: and replacing the step S1.6 with a mode that a laminated structure containing the electron transport precursor layer is fixed by adopting a clamp under the nitrogen environment of normal temperature and normal pressure, providing an external power supply, connecting a first end of the external power supply with an anode, grounding a second end of the external power supply, continuously annealing at a constant temperature of 150 ℃ for 60min, and applying a constant voltage with a voltage of 40V to the electron transport precursor layer by the external power supply in the annealing process to continuously carry out electrification treatment for 60min, so that the prefabricated device containing the electron transport precursor layer integrally carries positive charges, and obtaining the electron transport layer with a thickness of 50 nm.
Example 5
The present embodiment provides a method for manufacturing a light emitting device and a manufactured light emitting device, and compared with the method for manufacturing a light emitting device provided in embodiment 1, the method for manufacturing a light emitting device in this embodiment is only different in that: and replacing the step S1.6 with a mode that a laminated structure containing the electron transport precursor layer is fixed by adopting a clamp under the nitrogen environment of normal temperature and normal pressure, providing an external power supply, connecting a first end of the external power supply with an anode, grounding a second end of the external power supply, continuously annealing at a constant temperature of 150 ℃ for 60min, and applying a rectangular alternating current voltage (with the frequency of 50 Hz) with the voltage of minus 25V to plus 25V to the electron transport precursor layer in the annealing process by the external power supply to continuously carry out the electrification treatment for 60min, so that the prefabricated device containing the electron transport precursor layer alternately carries positive charges and negative charges, and the electron transport layer with the thickness of 50nm is obtained.
Example 6
The present embodiment provides a method for manufacturing a light emitting device and a manufactured light emitting device, and compared with the method for manufacturing a light emitting device provided in embodiment 1, the method for manufacturing a light emitting device in this embodiment is only different in that: and replacing the step S1.6 with a laminated structure containing an electron transport precursor layer under the nitrogen environment of normal temperature and normal pressure, fixing the laminated structure containing the electron transport precursor layer by using a clamp, providing an external power supply, connecting a first end of the external power supply with an anode, grounding a second end of the external power supply, continuously annealing at a constant temperature of 150 ℃ for 60min, starting the external power supply in the annealing process to intermittently perform constant-voltage (voltage of positive 25V) electrification treatment on the electron transport precursor layer for 60min, wherein the whole prefabricated device containing the electron transport precursor layer in the electrification process carries positive charges, the interval time of adjacent electrification treatment is 10min, the time of single electrification treatment is 10min, and the electron transport layer with the thickness of 50nm is obtained.
Example 7
The present embodiment provides a method for manufacturing a light emitting device and a manufactured light emitting device, and compared with the method for manufacturing a light emitting device provided in embodiment 1, the method for manufacturing a light emitting device in this embodiment is only different in that: and replacing the step S1.6 with a mode that a laminated structure containing an electron transport precursor layer is fixed by adopting a clamp under the nitrogen environment of normal temperature and normal pressure, an external power supply is provided, a first end of the external power supply is connected with an anode, a second end of the external power supply is grounded, then the continuous annealing treatment is carried out for 60 minutes at a constant temperature of 150 ℃, in the annealing treatment process, the external power supply is started, rectangular alternating current voltage (the frequency is 50Hz, the voltage is minus 25V to plus 25V) is applied to the electron transport precursor layer for carrying out intermittent electrification treatment for 60 minutes, the whole prefabricated device containing the electron transport precursor layer in the electrification treatment process alternately carries positive charges and negative charges, the interval time of adjacent electrification treatment is 10 minutes, the time of single electrification treatment is 10 minutes, and the electron transport layer with the thickness of 50nm is obtained.
Example 8
The present embodiment provides a method for manufacturing a light emitting device and a manufactured light emitting device, and compared with the method for manufacturing a light emitting device provided in embodiment 1, the method for manufacturing a light emitting device in this embodiment is only different in that: and S1.6, replacing the step S1.6 with a laminated structure containing an electron transport precursor layer under the nitrogen environment of normal temperature and normal pressure, adopting a clamp to fix the laminated structure, providing an external power supply, connecting a first end of the external power supply with an anode, connecting a second end of the external power supply with the ground, starting the external power supply, applying a constant voltage of 25V to the electron transport precursor layer to carry out continuous electrification treatment for 60min, so that the whole prefabricated device containing the electron transport precursor layer carries positive charges, and carrying out intermittent constant-temperature (150 ℃) annealing treatment for 60min to carry out a heating annealing procedure on the electron transport precursor layer in the electrification treatment process, wherein the interval time of adjacent annealing treatment is 5min, and the time of single annealing treatment is 15min, thereby obtaining the electron transport layer with the thickness of 50 nm.
Example 9
The present embodiment provides a method for manufacturing a light emitting device and a manufactured light emitting device, and compared with the method for manufacturing a light emitting device provided in embodiment 1, the method for manufacturing a light emitting device in this embodiment is only different in that: and S1.6, replacing the step S1.6 with a mode that a laminated structure containing an electron transport precursor layer is fixed by a clamp under the nitrogen environment of normal temperature and normal pressure, an external power supply is provided, a first end of the external power supply is connected with an anode, a second end of the external power supply is grounded, the external power supply is started, rectangular alternating current voltage (with the frequency of 50Hz and the voltage of minus 25V to plus 25V) is applied to the electron transport precursor layer to carry out continuous electrification treatment for 60min, so that the whole prefabricated device containing the electron transport precursor layer alternately carries positive charges and negative charges, and in the electrification treatment process, intermittent constant temperature (150 ℃) annealing treatment is carried out for 60min to carry out a heating annealing process, so that the whole prefabricated device containing the electron transport precursor layer alternately carries the positive charges and the negative charges, the interval time of the adjacent constant temperature heat treatment is 5min, the time of single constant temperature heat treatment is 15min, and the electron transport layer with the thickness of 50nm is obtained.
Example 10
The present embodiment provides a method for manufacturing a light emitting device and a manufactured light emitting device, and compared with the method for manufacturing a light emitting device provided in embodiment 1, the method for manufacturing a light emitting device in this embodiment is only different in that: and S1.6, replacing the step S1.6 with a laminated structure containing an electron transport precursor layer under the nitrogen environment of normal temperature and normal pressure, adopting a clamp to fix the laminated structure, providing an external power supply, connecting a first end of the external power supply with an anode, connecting a second end of the external power supply with the ground, starting the external power supply, applying a constant voltage of 25V to the electron transport precursor layer to carry out intermittent electrification treatment for 60min, carrying positive charges on the whole prefabricated device containing the electron transport precursor layer in the electrification treatment process, and carrying out intermittent constant-temperature (150 ℃) annealing treatment for 60min on the electron transport precursor layer, wherein the electrification treatment and the annealing treatment are alternately carried out, the time of single electrification treatment is 5min, the time of single annealing treatment is 15min, and the electron transport layer with the thickness of 50nm is obtained.
Example 11
The present embodiment provides a method for manufacturing a light emitting device and a manufactured light emitting device, and compared with the method for manufacturing a light emitting device provided in embodiment 1, the method for manufacturing a light emitting device in this embodiment is only different in that: and S1.6, replacing the step S1.6 with a laminated structure containing an electron transport precursor layer under the nitrogen environment of normal temperature and normal pressure, fixing the laminated structure containing the electron transport precursor layer by a clamp, providing an external power supply, connecting a first end of the external power supply with an anode, connecting a second end of the external power supply with the ground, starting the external power supply, applying rectangular alternating voltage (the frequency is 50Hz, the voltage is minus 25V to plus 25V) to the electron transport precursor layer so as to carry out intermittent electrification treatment for 60min, carrying positive charges and negative charges alternately on the whole prefabricated device containing the electron transport precursor layer in the electrification treatment process, carrying out intermittent constant-temperature (150 ℃) annealing treatment for 60min on the electron transport precursor layer, alternately carrying out electrification treatment and annealing treatment, wherein the time of single electrification treatment is 5min, and the time of single annealing treatment is 15min, and obtaining the electron transport layer with the thickness of 50 nm.
Example 12
The present embodiment provides a method for manufacturing a light emitting device and a manufactured light emitting device, and compared with the method for manufacturing a light emitting device provided in embodiment 1, the method for manufacturing a light emitting device in this embodiment is only different in that: and replacing the step S1.6 with a mode of continuously carrying out constant temperature (150 ℃) annealing treatment on the electron transport precursor layer for 60 minutes under the nitrogen environment of normal temperature and normal pressure to form a dry film, then adopting a fixture to fix a laminated structure containing the dry film, providing an external power supply, connecting a first end of the external power supply with an anode, grounding a second end of the external power supply, starting the external power supply, applying rectangular alternating voltage (the frequency is 50Hz and the voltage is minus 25V to plus 25V) on the dry film to carry out continuous electrification treatment for 60 minutes, and carrying positive charges and negative charges alternately on the whole of a prefabricated device containing the dry film in the electrification treatment process to obtain the electron transport layer with the thickness of 50 nm.
Example 13
The present embodiment provides a method for manufacturing a light emitting device and a manufactured light emitting device, and compared with the method for manufacturing a light emitting device provided in embodiment 1, the method for manufacturing a light emitting device in this embodiment is only different in that: and S1.6, replacing the step S1.6 with a laminated structure containing an electron transport precursor layer (wet film) under the nitrogen environment of normal temperature and normal pressure, adopting a clamp to fix the laminated structure, providing an external power supply, connecting a first end of the external power supply with an anode, connecting a second end of the external power supply with the ground, starting the external power supply, applying rectangular alternating voltage (the frequency is 50Hz and the voltage is minus 25V to plus 25V) to the electron transport precursor layer to continuously carry out electrification treatment for 60 minutes, carrying positive charges and negative charges alternately on the whole prefabricated device containing the electron transport precursor layer in the electrification treatment process, and continuously carrying out constant temperature (150 ℃) annealing treatment for 60 minutes on the prefabricated device after the electrification treatment is finished to form the electron transport layer with the thickness of 50 nm.
Comparative example
The present comparative example provides a method of manufacturing a light emitting device and a light emitting device manufactured by the same, which differ from the method of manufacturing a light emitting device provided in example 1 only in that: and replacing the step S1.6 with the step of continuously annealing the electron transport precursor layer at constant temperature (150 ℃) for 60 minutes under the nitrogen environment of normal temperature and normal pressure to obtain the electron transport layer with the thickness of 50 nm.
Experimental example
Performance tests were performed on the light emitting devices of examples 1 to 13 and comparative examples, and the maximum external quantum efficiency (EQE max (wt%) and the time required for the luminance to decay from 100% to 95% (lt95@1000 nit, h), and comparing EQEs for 30 days after placement of the individual light emitting device packages max And LT95@1000nit.
And detecting and obtaining parameters such as voltage, current, brightness, luminescence spectrum and the like of each light-emitting device by using a Friedel-crafts FPD optical characteristic measuring device (an efficiency testing system built by a LabView control QE-PRO spectrometer, keithley 2400 and Keithley 6485), calculating and obtaining key parameters such as external quantum efficiency, power efficiency and the like, and testing the service life of each light-emitting device by using a life testing device.
Specifically, the external quantum efficiency test method is an integrating sphere test method; the lifetime test uses a constant current method, under the drive of a constant current (2 mA current), a silicon optical system is used for testing the brightness change of each light-emitting device, the time (LT 95, h) required for the brightness to decay from 100% to 95% is recorded, and the time (LT95@1000 nit, h) required for the brightness of each light-emitting device to decay from 100% to 95% under the brightness of 1000nit is calculated, and the experimental results are shown in the following table 1:
table 1 results of performance tests of light emitting devices of examples 1 to 13 and comparative examples
As can be seen from Table 1, the overall performance of the light emitting devices of examples 1 to 11 is significantly better than that of the light emitting device of comparative example, and the EQE of the light emitting device of example 5 is as shown in example 5 on the same day of packaging max EQE which is the light emitting device in comparative example max And lt95@1000nit of the light emitting device in embodiment 5 is 3.4 times that of the light emitting device in comparative example; after 30 days of package placement, the EQE of the light emitting device in example 5 max EQE which is the light emitting device in comparative example max And lt95@1000nit of the light emitting device in embodiment 5 is 14.7 times that of the light emitting device in comparative example. Comparing the performance test data on the day of packaging and the day of packaging placement for 30 days, it is known that the light emitting devices in examples 1 to 11 have smaller variation in light emitting performance and operating life, and have ideal stability, while the light emitting devices in comparative example have EQE within 30 days of packaging placement max 51% drop and 75% drop in lt95@1000nit of the light emitting device in the comparative example, fully explaining: in the process of preparing the electron transport layer, annealing treatment and electrification treatment are carried out on the electron transport precursor layer within a preset time range, so that the crystallinity and stability of the electron transport layer can be improved, and the luminous performance and the service life of the luminous device are improved.
As can be seen from the performance test data of the light emitting devices in examples 1 to 4, the overall performance of the light emitting devices in examples 1 and 2 is better than that of examples 3 and 4, and example 2 is optimal, fully explaining: on the premise of constant time of the electrification treatment, the voltage value is properly increased, so that the comprehensive performance of the light-emitting device is further improved.
As can be seen from the performance test data of the light emitting devices in examples 1 and 5, examples 6 and 7, examples 8 and 9, and examples 10 and 11, the charging process is more advantageous to improve the overall performance of the light emitting device than the charging process is under constant voltage condition, which may be: under the condition of alternating voltage, the electric property of charges carried by the nano ZnO continuously oscillates, which is more favorable for ligand shedding on the surface of the nano ZnO and aggregation of phases among nano particles, and is further favorable for improving the compactness and stability of an electron transport layer.
As can be seen from the performance detection data of the light emitting devices in examples 1, 5 and 6 to 11, the continuous constant temperature heat treatment and the continuous charge treatment are adopted to treat the electron transport precursor layer, which is most beneficial to improving the light emitting performance and the service life of the light emitting device; the intermittent constant temperature heat treatment, the continuous type charged treatment, the continuous type constant temperature heat treatment and the intermittent type charged treatment are adopted to treat the electron transmission precursor layer, so that the comprehensive performance of the light-emitting device can be improved to a certain extent, and the energy consumption is saved.
As can be seen from the performance detection data of the light emitting device in examples 5, 12 and 13, compared with the case where the electron transport precursor layer is first annealed and then charged or the electron transport precursor layer is first annealed, the annealing and charging of the electron transport precursor layer within the predetermined time range is more advantageous to improve the overall performance of the light emitting device, which may be due to: under the dual actions of high temperature and electric energy, the ligand connected to the surface of the nano metal oxide is easier to fall off, and the gap between adjacent nano particles is further shortened, so that the crystallinity, conductivity and stability of the electron transport layer are further improved.
The preparation method of the light-emitting device, the light-emitting device and the display device provided by the embodiment of the application are described in detail. The principles and embodiments of the present application have been described herein with reference to specific examples, the description of which is only for aiding in the understanding of 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 (15)
1. A method of manufacturing a light emitting device, comprising the steps of:
providing a prefabricated device, and applying a solution containing nano metal oxide on one side of the prefabricated device for forming an electron transport precursor layer;
carrying out electrification treatment on the electron transport precursor layer so as to form an electron transport layer;
when the light-emitting device is of a positive structure, the prefabricated device comprises a bottom electrode and a light-emitting layer which are arranged in a stacked mode, the electron transmission precursor layer is formed on one side, far away from the bottom electrode, of the light-emitting layer, and the bottom electrode is an anode;
Alternatively, when the light emitting device is of an inverted structure, the prefabricated device includes a bottom electrode, the electron transport precursor layer is formed on one side of the bottom electrode, and the bottom electrode is a cathode.
2. The method according to claim 1, wherein the charging treatment is to cause the electron transport precursor layer to carry positive or negative charges or alternately to carry positive and negative charges.
3. The method of manufacturing according to claim 2, wherein the electrification treatment includes the steps of: providing an external power supply, wherein a first end of the external power supply is connected with the bottom electrode, and a second end of the external power supply is grounded; and turning on the external power supply to enable a potential difference to exist between the first end and the second end.
4. The method according to claim 3, wherein the external power supply applies a constant voltage or an alternating voltage to the electron transport precursor layer during the electrification treatment;
wherein the constant voltage has a voltage value of 10V to 30V;
the frequency of the alternating voltage is 10Hz to 200Hz, and the value of the effective voltage is 10V to 30V.
5. The method according to claim 1, wherein the nano metal oxide is selected from the group consisting of 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;
and/or, the average particle diameter of the nano metal oxide is 2nm to 15nm.
6. The method according to claim 1, wherein the time of the electrification treatment is 5min to 120min;
the charging treatment is continuous;
or the electrification treatment is intermittent, the time of single electrification treatment is 5min to 20min, and the interval time between adjacent electrification treatments is 5min to 20min.
7. The method according to any one of claims 1 to 6, wherein the electron transport precursor layer is a wet film, the method further comprising the step of: and annealing the electron transmission precursor layer.
8. The method of claim 7, wherein the annealing treatment is at a temperature of 80 ℃ to 250 ℃;
and/or the annealing treatment is carried out for 5min to 120min.
9. The method according to claim 8, wherein the period of annealing treatment at least partially overlaps the period of charging treatment, and wherein the manner of annealing treatment and the manner of charging treatment are any of the following:
(a1) The annealing treatment is continuous and the charging treatment is continuous;
(a2) The annealing treatment is continuous, and the charging treatment is intermittent;
(a3) The annealing treatment is intermittent and the charging treatment is continuous;
(a4) The annealing treatment is intermittent, and the charging treatment is intermittent.
10. The production method according to claim 9, wherein when the annealing treatment is continuous and the charging treatment is continuous, an overlapping time of the annealing treatment and the charging treatment is 5min to 120min;
or when the annealing treatment is continuous and the charging treatment is intermittent, the overlapping time of the annealing treatment and the charging treatment is 5min to 115min;
or when the annealing treatment is intermittent and the charging treatment is continuous, the interval time between adjacent annealing treatments is 5min to 10min, the time of single annealing treatment is 10min to 30min, and the overlapping time of the annealing treatment and the charging treatment is 5min to 115min;
or when the annealing treatment is intermittent and the charging treatment is intermittent, the interval time between adjacent annealing treatments is 5min to 10min, the time of single annealing treatment is 10min to 30min, and the overlapping time of the annealing treatment and the charging treatment is 5min to 115min.
11. The production method according to claim 8, wherein the period of the annealing treatment does not overlap with the period of the charging treatment, and the manner of the annealing treatment and the manner of the charging treatment are any of the following:
(b1) The annealing treatment and the electrification treatment are alternately performed;
(b2) After the charged treatment is completed on the electron transport precursor layer, the annealing treatment is performed;
wherein, for (b 1), the time of the single annealing treatment is 5min to 20min.
12. The method of manufacturing according to claim 1, wherein when the light emitting device is of a front-set structure, the method further comprises the steps of: after an electron transport layer is formed on one side of the prefabricated device, a top electrode is formed on one side, far away from the light-emitting layer, of the electron transport layer, and the top electrode is a cathode;
alternatively, when the light emitting device is of an inverted structure, the manufacturing method further includes the steps of:
forming an electron transport layer on one side of the prefabricated device, and then forming a light emitting layer on one side of the electron transport layer away from the bottom electrode;
forming a top electrode on one side of the light-emitting layer far away from the electron transport layer, wherein the top electrode is an anode;
And/or the material of the light-emitting layer is an organic light-emitting material or quantum dots;
the organic luminescent material is at least one selected from a diaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative, a fluorene derivative, a TBPe fluorescent material, a TTPA fluorescent material, a TBRb fluorescent material or a DBP fluorescent material;
the quantum dots are selected from at least one of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots or organic-inorganic hybrid perovskite quantum dots; when the quantum dot is selected from a single component quantum dot or a 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 dotThe materials are independently selected from 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.
13. The method of manufacturing according to claim 12, characterized in that the method of manufacturing further comprises the steps of: forming a hole function layer between the anode and the light emitting layer, wherein the hole function layer comprises a hole injection layer and/or a hole transport layer, when the hole function layer comprises a hole transport layer and a hole injection layer which are stacked, the hole transport layer is close to the light emitting layer, and the hole injection layer is close to the anode;
the hole transport layer is made of NiO or WO 3 、MoO 3 CuO, 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) trisAt least one of aniline, 4' -bis (9-carbazole) biphenyl, N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine, or N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine;
the hole injection layer is made of poly (3, 4-ethylenedioxythiophene): at least one of poly (styrenesulfonic acid), copper phthalocyanine, 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 is selected from NiO x 、MoO x 、WO x Or CrO (CrO) x At least one of the transition metal chalcogenide compounds is selected from MoS x 、MoSe x 、WS x 、WSe x Or at least one of CuS.
14. A light-emitting device, characterized in that the light-emitting device is manufactured by the manufacturing method as claimed in any one of claims 1 to 13.
15. A display device characterized in that the display device comprises the light-emitting device manufactured by the manufacturing method according to any one of claims 1 to 13, or the light-emitting device according to claim 14.
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| CN202210394651.8A CN116981311A (en) | 2022-04-14 | 2022-04-14 | Preparation method of light-emitting device, light-emitting device and display device |
| PCT/CN2022/140059 WO2023197659A1 (en) | 2022-04-14 | 2022-12-19 | Manufacturing method for light emitting device, light emitting device, and display apparatus |
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