CN111129355B - Preparation method of quantum dot film and preparation method of quantum dot light-emitting diode - Google Patents
Preparation method of quantum dot film and preparation method of quantum dot light-emitting diode Download PDFInfo
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- CN111129355B CN111129355B CN201811289692.0A CN201811289692A CN111129355B CN 111129355 B CN111129355 B CN 111129355B CN 201811289692 A CN201811289692 A CN 201811289692A CN 111129355 B CN111129355 B CN 111129355B
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
Abstract
The invention belongs to the technical field of quantum dots, and particularly relates to a preparation method of a quantum dot film and a preparation method of a quantum dot light-emitting diode. The preparation method of the quantum dot film comprises the following steps: providing a quantum dot solution, wherein the quantum dot solution contains quantum dots of which the surfaces are combined with surface ligands; depositing the quantum dot solution on a substrate to obtain an initial quantum dot film; and heating the initial quantum dot film, and then placing the initial quantum dot film in an atmosphere containing water and/or oxygen for ultraviolet irradiation treatment to obtain the quantum dot film. The preparation method has simple and easy process and low preparation cost, can not only effectively remove the surface ligand combined on the quantum dots in the quantum dot film, but also passivate the surface of the quantum dots to reduce the surface defects, thereby improving the luminous intensity of the quantum dot film.
Description
Technical Field
The invention belongs to the technical field of quantum dots, and particularly relates to a preparation method of a quantum dot film and a preparation method of a quantum dot light-emitting diode.
Background
The quantum dots have great application potential in high color quality display due to the excellent characteristics of high quantum efficiency, narrow excitation spectrum, unique size dependence excitation spectrum, good solution processing compatibility and the like. With the continuous and deep research on quantum efficiency improvement and electroluminescent principle, exciton decay mechanism, device structure optimization, effective charge transport and the like, the luminous efficiency of the QLED is improved from less than 0.01% to 20.5%, and is close to the efficiency of the commercial OLED.
At present, quantum dots prepared in an organic phase have the advantages of high fluorescence quantum yield, narrow fluorescence half-peak width, good monodispersity and stability, controllable particle size and the like. The preparation of quantum dots in the organic phase mainly employs an organometallic method, i.e., a method for preparing quantum dots by pyrolysis of a precursor in an organic solvent with a high boiling point. And injecting the organic metal precursor solution into the ligand solution at the temperature of 250-300 ℃, wherein the precursor is rapidly pyrolyzed and nucleated under the high-temperature condition, and the crystal nucleus slowly grows into the quantum dot. The crystal nucleus is prevented from growing by the adsorption of the ligand and is stably present in the solvent. However, these ligands form an insulating layer around the quantum dots, preventing efficient charge injection in optoelectronic devices. At present, most researches adopt a method of adding a polar solvent to wash quantum dots for multiple times to control the ligand density on the surfaces of the quantum dots, so that the overall performance of the quantum dots in a device is improved. However, multiple washes may result in severe agglomeration and mass loss of the quantum dots, resulting in a decrease in the luminescence intensity of the quantum dots. Common quantum dot surface ligands are carboxylic acids, amines, alkyl phosphides, alkyl phosphine oxides, alkyl phosphoric acids, thiols, and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a preparation method of a quantum dot film and a preparation method of a quantum dot light-emitting diode, and aims to solve the technical problem that the surface ligand bound on the surface of the existing quantum dot influences the light-emitting performance of a device.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a quantum dot film on one hand, which comprises the following steps:
providing a quantum dot solution, wherein the quantum dot solution contains quantum dots of which the surfaces are combined with surface ligands;
depositing the quantum dot solution on a substrate to obtain an initial quantum dot film;
and heating the initial quantum dot film, and then placing the initial quantum dot film in an atmosphere containing water and/or oxygen for ultraviolet irradiation treatment to obtain the quantum dot film.
The preparation method of the quantum dot film provided by the invention comprises the following steps of firstly heating the initial quantum dot film prepared on the substrate, so that the surface ligand combined on the surface of the quantum dot can be cracked and evaporated along with the heating process, and the surface ligand in the initial quantum dot film is removed; after the surface ligand is evaporated, the quantum dots are in an exposed state and have surface defects, and at the moment, the quantum dots may have agglomeration and a phenomenon of reducing the luminous intensity, so that the initial quantum dot film is subjected to heating treatment and then placed in an atmosphere containing water and/or oxygen for ultraviolet light irradiation treatment, the water and/or oxygen can react with the surface of the exposed quantum dots under the light activation action of ultraviolet light to form a layer of oxide, the oxide can passivate the quantum dots, the outward migration of electrons of the quantum dots is reduced, and the luminous intensity of the quantum dot film is finally improved by repairing and smoothing the surface defects of the quantum dots. In a word, the preparation method has simple and easy process and low preparation cost, not only can effectively remove the surface ligand combined on the quantum dots in the quantum dot film, but also can passivate the surfaces of the quantum dots to reduce the surface defects, thereby improving the luminous intensity of the quantum dot film.
The invention also provides a preparation method of the quantum dot light-emitting diode, which comprises the following steps:
providing a substrate;
preparing a quantum dot light emitting layer on the substrate; the method for preparing the quantum dot light-emitting layer on the substrate is the preparation method of the invention.
In the preparation method of the quantum dot light-emitting diode provided by the invention, the quantum dot light-emitting layer is prepared by the special preparation method, and the preparation of the quantum dot light-emitting layer not only can effectively remove the surface ligands combined on the quantum dots, but also can passivate the surface of the quantum dots to reduce the surface defects, so that the luminous intensity of the quantum dot light-emitting layer is improved, and the luminous intensity of the quantum dot light-emitting diode is finally improved.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, an embodiment of the present invention provides a method for preparing a quantum dot thin film, including the following steps:
s01: providing a quantum dot solution, wherein the quantum dot solution contains quantum dots of which the surfaces are combined with surface ligands;
s02: depositing the quantum dot solution on a substrate to obtain an initial quantum dot film;
s03: and heating the initial quantum dot film, and then placing the initial quantum dot film in an atmosphere containing water and/or oxygen for ultraviolet irradiation treatment to obtain the quantum dot film.
According to the preparation method of the quantum dot film, the initial quantum dot film prepared on the substrate is heated, so that the surface ligand combined on the surface of the quantum dot can be cracked and evaporated along with the heating process, and the surface ligand in the initial quantum dot film is removed; after the surface ligand is evaporated, the quantum dots are in a naked state and have surface defects, and the quantum dots may have agglomeration and a phenomenon of reducing the luminous intensity, so that the quantum dots are heated and then placed in an atmosphere containing water and/or oxygen for ultraviolet irradiation treatment, the water and/or oxygen can react with the surfaces of the naked quantum dots under the action of ultraviolet light activation to form a layer of oxide, the oxide (cations in the oxide are cations on the surfaces of the quantum dots, such as CdSe quantum dots, the oxide is cadmium oxide) can passivate the quantum dots, the outward migration of electrons of the quantum dots is reduced, and the luminous intensity of the quantum dot film is finally improved by repairing and smoothing the surface defects of the quantum dots. The preparation method has simple and easy process and low preparation cost, can not only effectively remove the surface ligand combined on the quantum dots in the quantum dot film, but also passivate the surface of the quantum dots to reduce the surface defects, thereby improving the luminous intensity of the quantum dot film.
In the above preparation method of the embodiment of the present invention, the heating treatment is to evaporate and remove the surface ligands bound to the quantum dots, and the degree of evaporation of the surface ligands herein does not mean that all the surface ligands bound to the quantum dots are completely evaporated and removed, that is, as long as part of the surface ligands of the quantum dots are subjected to the heating treatment, a certain degree of evaporation is generated, and the light emission intensity of the quantum dot thin film is further improved to a certain degree by the ultraviolet light. Therefore, the degree of surface ligand removal in the quantum dot thin film is within the scope of the embodiments of the present invention.
Further, in the above step S01: quantum dots include, but are not limited to, one or more of group II-VI compounds, group III-V compounds, group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, group II-IV-VI compounds, or group IV elements. In particular, the quantum dots are selected from CdSe, CdS, ZnSe, ZnS, PbSe, PbS, CdTe, CdZnSe, CdSeS, PbSeS, ZnCdTe, CdS/ZnS, CdZnS/ZnS, CdZnSe/ZnSe, CdSeS/CdSeS/CdS, CdSe/CdZnSe/CdZnSe/ZnSe, CdS/CdZnS/CdZnS/ZnS, CuInS2、CuInSe2、CsPbCl3、CsPbBr3And CsPbI3At least one of (1). The surface ligand is selected from thiol and carboxylic acidAt least one of an amine-based compound, alkyl phosphorus, alkyl phosphine oxide and alkyl phosphoric acid, but is not limited thereto. Further, the thiol is selected from at least one of a mono-thiol, a di-thiol, a mercapto alcohol, a mercaptoamine, and a mercapto acid; for example, the monothiol is selected from at least one of hexanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecanethiol, tetradecanethiol, hexadecanethiol, and octadecanethiol; the dithiol is at least one selected from 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 4-butanedithiol, 1, 5-pentanethiol, 1, 6-hexanedithiol, 1, 8-octanethiol and 1, 10-decanedithiol; the mercaptoalcohol is at least one selected from the group consisting of 2-mercaptoethanol, 3-mercapto-1-propanol, 4-mercapto-1-butanol, 5-mercapto-1-pentanol, 6-mercapto-1-hexanol and 8-mercapto-1-octanol; the mercapto acid is selected from at least one of 2-mercaptoacetic acid, 3-mercaptopropionic acid, 4-mercaptobutyric acid, mercaptosuccinic acid, 6-mercaptohexanoic acid, 4-mercaptobenzoic acid and cysteine; the mercaptoamine is at least one selected from 2-mercaptoethylamine, 3-mercaptopropylamine, 4-mercaptobutylamine, 5-mercaptopentylamine, 6-mercaptohexylamine, 2-amino-3-mercaptopropionic acid, 2-aminothiophenol and mercaptoundecanamine. The amine compound comprises at least one of oleylamine, octylamine, dioctylamine, trioctylamine, nonylamine, dinonylamine, trinonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine and octadecylamine. The alkyl phosphoric acid is at least one selected from the group consisting of dodecyl phosphoric acid, undecyl phosphoric acid, dodecyl phosphoric acid, tridecyl phosphoric acid, tetradecyl phosphoric acid, pentadecyl phosphoric acid, hexadecyl phosphoric acid and octadecyl phosphoric acid. The alkyl phosphorus is selected from at least one of tributyl phosphine, tripentyl phosphine, trihexyl phosphine, triheptyl phosphine, trioctyl phosphine, trinonyl phosphine and tridecyl phosphine. The alkyl phosphine oxide is at least one selected from tributyl phosphine oxide, tripentyl phosphine oxide, trihexyl phosphine oxide, triheptyl phosphine oxide, trioctyl phosphine oxide, trinonyl phosphine oxide and tridecyl phosphine oxide.
The quantum dot solution is synthesized and prepared by the conventional method, and specifically, after synthesis, the quantum dot mother liquor is centrifuged at 7000-9000rpm for 5min to remove larger impurity particles in the reaction process, the upper layer solution is taken and added with 20-30ml of anti-solvent to extract substances which are not completely reacted in the quantum dot mother liquor, finally 5-10ml of precipitator (such as methanol, ethanol and the like) is added, the quantum dot solid is obtained by centrifugation, and the solid is dissolved in an ink solvent after vacuum drying, so that the quantum dot solution is obtained. The ink solvent comprises one or more of chloroform, n-hexane, cyclohexane, heptane, octane, toluene, chlorobenzene, dichlorobenzene, carbon tetrachloride, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, cyclodecane, cycloundecane and the like.
Further, in the step S02, the substrate may be a glass substrate, and the deposition method may be a spin coating method, specifically, a quantum dot solution is spin coated on a glass substrate at 1500-.
Further, in the step S03, the temperature of the heating treatment is 100-200 ℃; the time of the heating treatment is 5-50 min. In the heating temperature and heating time range, the surface ligand can be better evaporated and removed.
Furthermore, the time of the ultraviolet irradiation treatment is 5-20 min. The ultraviolet light has the effect of photooxidizing the surface of the quantum dot to improve the luminous intensity of the quantum dot, and the initial quantum dot film after the heating treatment is placed in the atmosphere containing water and/or oxygen for ultraviolet irradiation treatment for 5-20min, so that the quantum dot can be photooxidized more effectively to repair the surface defect.
More preferably, the atmosphere containing water specifically refers to an atmosphere having a relative humidity of 65 to 85%; namely, the initial quantum dot film is heated and then placed in an atmosphere with the relative humidity of 65-85% for ultraviolet irradiation treatment. Within the relative humidity range, the ultraviolet light photo-oxidation effect is better. In addition, the temperature of ultraviolet irradiation is not particularly required, and the temperature is generally 20-30 ℃.
In the above step 03: in order to optimize the luminous intensity of the final quantum dot film, the surface ligands bonded on the quantum dots are completely removed as much as possible; in an embodiment of the present invention, in order to characterize and determine whether the surface ligand is completely removed, before performing the ultraviolet irradiation treatment, the method further includes detecting the content of the quantum dot surface ligand in the initial quantum dot thin film after the heating treatment, and performing the ultraviolet irradiation treatment after the mass percentage content of the target element in the initial quantum dot thin film is less than 1%; wherein the target element is a remaining surface ligand element free of carbon elements and the quantum dot elements. That is, when characterizing whether the surface ligand bound to the quantum dot is completely removed, the target element detected in the embodiment of the present invention refers to an element specific to the surface ligand itself, and the target element does not contain a carbon element and the surface ligand element does not repeat with an element in the quantum dot, for example, the surface of CdS does not use a thiol ligand. For example: the S element-containing ligand comprises a sulfhydryl-containing ligand; the N element-containing ligand comprises an amino compound, mercaptoamine and the like; the P-containing element ligand comprises alkyl phosphoric acid, alkyl phosphorus and the like; the ligand containing O element includes oleic acid, mercapto acid, etc. In one embodiment of the present invention, when the surface of the equivalent quantum dot is bound with an amine compound, oleic acid and alkyl phosphoric acid, the detected surface ligand element is O, N, P element.
The detection is characterized by an initial quantum dot film, and if the mass percentage of the target element is less than 1%, the surface ligand is considered to be removed completely; and if the mass percentage of the target element is equal to or more than 1%, carrying out the heating treatment again and then removing the surface ligand. Specifically, the steps of detecting the content of the quantum dot surface ligand in the initial quantum dot film after the heating treatment, and performing ultraviolet irradiation treatment after the mass percentage content of the target element in the initial quantum dot film is less than 1% are divided into two cases: (1) after the content of the quantum dot surface ligand in the initial quantum dot film subjected to the first heating treatment is detected, if the mass percentage of the target element is less than 1%, directly placing the quantum dot film subjected to the first heating treatment in an atmosphere containing water and/or oxygen for ultraviolet irradiation treatment; (2) after the content of the quantum dot surface ligand in the initial quantum dot film subjected to the first heating treatment is detected, if the mass percentage of the target element is equal to or more than 1%, performing second heating treatment, then detecting the content of the quantum dot surface ligand in the quantum dot film subjected to the second heating treatment, and if the mass percentage of the target element is less than 1%, placing the quantum dot film subjected to the second heating treatment in an atmosphere containing water and/or oxygen for ultraviolet irradiation treatment; and if the mass percentage of the target element is equal to or more than 1%, continuing repeating the steps of heating treatment and quantum dot surface ligand content detection until the mass percentage of the target element is less than 1%, and then performing ultraviolet irradiation treatment. It will be appreciated that the purpose is to remove the quantum dot surface ligands by heat treatment. The mass percentage of the target element is not necessarily reduced to less than 1% by one or more heat treatments (it is considered that the quantum dot surface ligand is removed), and therefore, the quantum dot surface ligand content in the quantum dot thin film after each heat treatment needs to be detected until the mass percentage of the target element is reduced to less than 1%, and then the heat treatment is stopped.
Specifically, the method for detecting the content of the ligand on the surface of the quantum dot in the initial quantum dot film after the heating treatment is a scanning electron microscope analysis method or a transmission electron microscope analysis method.
On the other hand, the embodiment of the invention also provides a preparation method of the quantum dot light-emitting diode, which comprises the following steps:
t01: providing a substrate;
t02: preparing a quantum dot light emitting layer on the substrate; the method for preparing the quantum dot light-emitting layer on the substrate is the preparation method of the invention.
In the preparation method of the quantum dot light-emitting diode provided by the embodiment of the invention, the quantum dot light-emitting layer is prepared by the preparation method of the specific quantum dot film provided by the embodiment of the invention, and the preparation of the quantum dot light-emitting layer not only can effectively remove the surface ligands combined on the quantum dots, but also can passivate the surface of the quantum dots to reduce the surface defects, so that the light-emitting intensity of the quantum dot light-emitting layer is improved, and finally, the light-emitting intensity of the quantum dot light-emitting diode is improved.
Further, in the above step T01, the upper surface of the substrate is provided with a bottom electrode, so that the quantum dot light emitting layer can be directly fabricated on the bottom electrode; preferably, the substrate may also include a bottom electrode and a functional layer that are sequentially prepared from bottom to top, so that the quantum dot light emitting layer may be directly prepared on the functional layer. Specifically, if the bottom electrode is an anode, the functional layer is a hole functional layer, and the quantum dot light-emitting layer is prepared on the hole functional layer, and if the bottom electrode is a cathode, the functional layer is an electron functional layer, and the quantum dot light-emitting layer is prepared on the electron functional layer.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
A preparation method of a quantum dot film comprises the following steps:
(1) synthesizing CdSe quantum dots (surface ligands comprise oleic acid, oleylamine and trihexylphosphine), centrifuging the synthesized quantum dot mother liquor for 5min at 7500rpm, removing larger impurity particles in the reaction process, taking the upper layer solution, adding 25ml of ethyl acetate into the upper layer solution to extract substances which are not completely reacted in the quantum dot mother liquor, finally adding 5ml of ethanol, centrifuging to obtain quantum dot solids, and dissolving the quantum dot solids in n-octane after vacuum drying to prepare CdSe quantum dot ink;
(2) spin-coating CdSe quantum dot ink on a glass substrate at 2000rpm, and drying for 2h under a vacuum condition to obtain a CdSe quantum dot film;
(3) under the nitrogen atmosphere, the CdSe quantum dot film is placed on a heating plate at 150 ℃ and heated for 20min, and after the CdSe quantum dot film is cooled, the O, N, P elements on the surface of the quantum dot are quantitatively analyzed by adopting a scanning electron microscope:
the accelerating voltage is set at 15kV, and the working distance is set to 10 mm. And (3) carrying out amplification analysis on the sample, firstly setting the amplification factor to be 300 times, and carrying out focusing element collection analysis on the uniform area of the quantum dot film to obtain the element content.
(4) When the mass ratio of the elements (namely O, N, P elements) is less than 1%, the CdSe quantum dot film with the removed ligands is placed in the air, and is irradiated for 5min under the ultraviolet light at the temperature of 25 ℃ and the relative humidity of 70% to perform the light activation of the CdSe quantum dot film, so that the luminous intensity of the quantum dot film is improved.
Example 2
A preparation method of a quantum dot film comprises the following steps:
(1) synthesis of CsPbCl3The method comprises the steps of (1) centrifuging synthesized quantum dot mother liquor for 5min at 8000rpm for quantum dots (surface ligands comprise octanethiol, decaalkylphosphoric acid and pentadecamine), removing larger impurity particles in the reaction process, adding 30ml of heptane into the upper layer solution to extract substances which are not completely reacted in the quantum dot mother liquor, finally adding 7ml of methanol, centrifuging to obtain quantum dot solid, dissolving the solid in dichlorobenzene after vacuum drying, and preparing CsPbCl3Quantum dot inks.
(2) Mixing CsPbCl3The quantum dot ink is spun on a glass substrate at 3000rpm and dried for 1h under a vacuum condition to obtain CsPbCl3A quantum dot film.
(3) Under nitrogen atmosphere, CsPbCl was added3The quantum dot film is placed on a heating plate at 110 ℃ and heated for 20 min. After cooling, the S, P, N element on the surface of the quantum dot is quantitatively analyzed by a transmission electron microscope:
dissolving CsPbCl on glass substrate with chloroform solution3And (3) cleaning the glass substrate for multiple times to completely dissolve the quantum dots, dripping 8 drops of a small amount of quantum dot solution on a copper mesh, and then placing the copper mesh in a transmission electron microscope analyzer for test analysis. Setting the accelerating voltage to be 100kV, the emission current to be 20 muA, the working distance to be 10mm, carrying out amplification analysis on the sample, firstly setting the amplification factor to be 80000 times, and carrying out focusing analysis on the region with concentrated and uniformly dispersed quantum dots to obtain the element content.
(4) When the mass ratio of the above element (i.e., S, P, N element) is less than 1%, CsPbCl from which the ligand has been removed3The quantum dot film is placed in the air, the light activation of the quantum dot film is carried out by irradiating the quantum dot film for 10min under the conditions of 20 ℃ and relative humidity of 80 percent, and the luminous intensity of the quantum dot film is improved.
Example 3
A preparation method of a QLED device comprises a substrate, an anode, a hole transport layer, a quantum dot light emitting layer, an electron transport layer and a cathode from bottom to top in sequence. The substrate is made of a glass sheet, the anode is made of an ITO (indium tin oxide) substrate, the hole transport layer is made of TFB, the electron transport layer is made of ZnO, and the cathode is made of Al.
The preparation method of the QLED device comprises the following steps:
a: firstly, growing a hole transport layer on an anode substrate;
b: depositing a quantum dot light-emitting layer on the hole transport layer by using the preparation method of the above embodiment 1 or embodiment 2;
c: and finally, depositing an electron transmission layer on the quantum dot light-emitting layer, and evaporating a cathode on the electron transmission layer to obtain the quantum dot light-emitting diode.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the quantum dot film is characterized by comprising the following steps:
providing a quantum dot solution, wherein the quantum dot solution contains quantum dots of which the surfaces are combined with surface ligands;
depositing the quantum dot solution on a substrate to obtain an initial quantum dot film;
heating the initial quantum dot film to crack and evaporate the surface ligand, and placing the initial quantum dot film in an atmosphere containing water and/or oxygen for ultraviolet irradiation treatment after the mass percentage of a target element in the initial quantum dot film is less than 1% to obtain the quantum dot film; wherein the target element is a remaining surface ligand element free of carbon elements and the quantum dot elements.
2. The method as claimed in claim 1, wherein the temperature of the heat treatment is 100-200 ℃; and/or
The time of the heating treatment is 5-50 min.
3. The method according to claim 1, wherein the ultraviolet light treatment is carried out for 5 to 20 min;
and/or, the atmosphere containing water specifically refers to an atmosphere with a relative humidity of 65-85%.
4. The preparation method of claim 1, further comprising detecting the content of the quantum dot surface ligand in the initial quantum dot thin film after the heating treatment before the ultraviolet irradiation treatment, and performing the ultraviolet irradiation treatment after the content of the target element in the initial quantum dot thin film is less than 1% by mass.
5. The preparation method according to claim 4, wherein the method for detecting the content of the ligand on the surface of the quantum dot in the initial quantum dot thin film after the heating treatment is a scanning electron microscope analysis method or a transmission electron microscope analysis method.
6. The preparation method of claim 4, wherein the step of detecting the content of the quantum dot surface ligand in the initial quantum dot thin film after the heating treatment, and after the content of the target element in the initial quantum dot thin film is less than 1% by mass, performing ultraviolet irradiation treatment comprises:
after the content of the quantum dot surface ligand in the initial quantum dot film subjected to the first heating treatment is detected, if the mass percentage of the target element is less than 1%, directly placing the quantum dot film subjected to the first heating treatment in an atmosphere containing water and/or oxygen for ultraviolet irradiation treatment;
after the content of the quantum dot surface ligand in the initial quantum dot film subjected to the first heating treatment is detected, if the mass percentage of the target element is equal to or more than 1%, performing second heating treatment, detecting the content of the quantum dot surface ligand in the quantum dot film subjected to the second heating treatment, and if the mass percentage of the target element is less than 1%, placing the quantum dot film subjected to the second heating treatment in an atmosphere containing water and/or oxygen for ultraviolet irradiation treatment; and if the mass percentage of the target element is equal to or more than 1%, continuing repeating the steps of heating treatment and quantum dot surface ligand content detection until the mass percentage of the target element is less than 1%, and then performing ultraviolet irradiation treatment.
7. The production method according to any one of claims 1 to 6, wherein the surface ligand is at least one selected from the group consisting of thiol, carboxylic acid, amine-based compound, alkyl phosphorus, alkyl phosphine oxide and alkyl phosphoric acid; and/or
The quantum dots are selected from CdSe, CdS, ZnSe, ZnS, PbSe, PbS, CdTe, CdSZnSe, CdSeS, PbSeS, ZnCdTe, CdS/ZnS, CdZnS/ZnS, CdZnSe/ZnSe, CdSeS/CdSeS/CdS, CdSe/CdZnSe/ZnSe, CdZnSe/CdZnSe/ZnSe, CdS/CdZnS/ZnSe, CuInS2、CuInSe2、CsPbCl3、CsPbBr3And CsPbI3At least one of (1).
8. The method according to claim 7, wherein the thiol is at least one selected from the group consisting of a monothiol, a dithiol, a mercaptoalcohol, a mercaptoamine, and a mercaptoacid; and/or
The amine compound comprises at least one of oleylamine, octylamine, dioctylamine, trioctylamine, nonylamine, dinonylamine, trinonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine and octadecylamine; and/or
The alkyl phosphoric acid is selected from at least one of dodecyl phosphoric acid, undecyl phosphoric acid, dodecyl phosphoric acid, tridecyl phosphoric acid, tetradecyl phosphoric acid, pentadecyl phosphoric acid, hexadecyl phosphoric acid and octadecyl phosphoric acid; and/or
The alkyl phosphorus is selected from at least one of tributyl phosphine, tripentyl phosphine, trihexyl phosphine, triheptyl phosphine, trioctyl phosphine, trinonyl phosphine and tridecyl phosphine; and/or
The alkyl phosphine oxide is at least one selected from tributyl phosphine oxide, tripentyl phosphine oxide, trihexyl phosphine oxide, triheptyl phosphine oxide, trioctyl phosphine oxide, trinonyl phosphine oxide and tridecyl phosphine oxide.
9. The method according to claim 8, wherein the monothiol is at least one selected from the group consisting of hexanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecanethiol, tetradecanethiol, hexadecanethiol, and octadecanethiol; and/or
The dithiol is at least one selected from 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 4-butanedithiol, 1, 5-pentanethiol, 1, 6-hexanedithiol, 1, 8-octanethiol and 1, 10-decanedithiol; and/or
The mercaptoalcohol is at least one selected from the group consisting of 2-mercaptoethanol, 3-mercapto-1-propanol, 4-mercapto-1-butanol, 5-mercapto-1-pentanol, 6-mercapto-1-hexanol and 8-mercapto-1-octanol; and/or
The mercapto acid is selected from at least one of 2-mercaptoacetic acid, 3-mercaptopropionic acid, 4-mercaptobutyric acid, mercaptosuccinic acid, 6-mercaptohexanoic acid, 4-mercaptobenzoic acid and cysteine; and/or
The mercaptoamine is at least one selected from 2-mercaptoethylamine, 3-mercaptopropylamine, 4-mercaptobutylamine, 5-mercaptopentylamine, 6-mercaptohexylamine, 2-amino-3-mercaptopropionic acid, 2-aminothiophenol and mercaptoundecanamine.
10. A preparation method of a quantum dot light-emitting diode is characterized by comprising the following steps:
providing a substrate;
preparing a quantum dot light emitting layer on the substrate; wherein the method for producing a quantum dot light-emitting layer on the substrate is the production method according to any one of claims 1 to 9.
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| WO2012138410A1 (en) * | 2011-04-02 | 2012-10-11 | Qd Vision, Inc. | Device including quantum dots |
| CN105140411A (en) * | 2015-08-17 | 2015-12-09 | Tcl集团股份有限公司 | Indium tin oxide (ITO)-free quantum light emitting diode (QLED) and fabrication method thereof |
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| CN101420016A (en) * | 2007-09-28 | 2009-04-29 | 大日本印刷株式会社 | Electroluminescent device fabrication with ligand removal after quantum dot electroluminescent layer coating |
| WO2012138410A1 (en) * | 2011-04-02 | 2012-10-11 | Qd Vision, Inc. | Device including quantum dots |
| CN105140411A (en) * | 2015-08-17 | 2015-12-09 | Tcl集团股份有限公司 | Indium tin oxide (ITO)-free quantum light emitting diode (QLED) and fabrication method thereof |
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