CN109599505B - Preparation method of modified metal chalcogenide and light-emitting device - Google Patents
Preparation method of modified metal chalcogenide and light-emitting device Download PDFInfo
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Abstract
The invention belongs to the field of display devices, and provides a preparation method of a modified metal chalcogenide and a light-emitting device. The invention provides a metal chalcogenide, and the metal chalcogenide is placed in a reaction chamber to carry out a first modification treatment and a second modification treatment to obtain the modified metal chalcogenide. In the preparation process, the first modification treatment reduces the defects of the chalcogen element through sufficient acid treatment, releases charges combined with the defect state of the chalcogen element, and simultaneously removes oxygen species (oxygen species) in the chalcogen compound, thereby obtaining a purer metal chalcogen compound; the second modification treatment enables the chalcogen element defect state and the mercaptan to carry out chemical adsorption in a covalent bond mode through mercaptan treatment, and eliminates the residual defects on the surface of the chalcogen element to the minimum; therefore, the modified metal chalcogenide with higher charge transmission efficiency is obtained, and the luminous efficiency of the device is improved. In addition, the preparation method has simple process and low cost, and can realize large-scale production.
Description
Technical Field
The invention belongs to the field of display devices, and particularly relates to a preparation method of a modified metal chalcogenide and a light-emitting device.
Background
In the existing preparation technology of QLED and OLED, organic matter is generally adopted as a hole transport material, namely PEDOT: PSS is commonly used, however, acidity and water absorbability of an EDOT: PSS hole injection layer cause damage and attenuation to ITO and devices to different degrees, and therefore stability of the devices is still to be improved. At the present time replacing PEODT: PSS, the more used alternatives are metal oxides such as molybdenum oxide, nickel oxide, or copper oxide, etc.; in other reports on solar cells, metal chalcogenides have also been used to replace PEDOT, PSS, such as molybdenum sulfide and copper sulfide. Sulfide has higher carrier mobility (200 cm) due to the sulfide2·V-1·s-1-500cm2·V-1·s-1) Are widely used in photocatalysis, transistors and solar cells. However, although metal chalcogenides can be used as a replacement for PEDOT: PSS in the preparation of solar cells, they are expected to be deficient in the preparation process and in the defect state to a varying degreeWhen the material is used as a hole transport material, the defect that charges are bound on the defect can not be avoided, so that the recombination proportion of the charges is reduced, and the hole transport efficiency is further reduced.
Therefore, the existing metal chalcogenide has poor hole transport capability when applied as a hole transport material due to the existence of more defects and defect states.
Disclosure of Invention
The invention aims to provide a preparation method of a modified metal chalcogenide and a luminescent device, and aims to solve the problem that the existing metal chalcogenide has poor hole transport capability when being applied as a hole transport material due to more defects and defect states.
The invention provides a preparation method of a modified metal chalcogenide, which comprises the following steps:
providing a metal chalcogenide, placing the metal chalcogenide in a reaction chamber;
introducing a non-oxidizing acid to carry out first modification treatment on the metal chalcogenide;
and (3) introducing mercaptan, and carrying out second modification treatment on the metal chalcogenide subjected to the first modification treatment to obtain the modified metal chalcogenide.
The invention provides a light-emitting device comprising a hole-functional layer containing a modified metal chalcogenide prepared as described above.
The preparation method of the modified metal chalcogenide and the luminescent device provided by the invention are characterized in that the metal chalcogenide is provided, the metal chalcogenide is placed in a reaction chamber, non-oxidizing acid is introduced to carry out first modification treatment on the metal chalcogenide, and mercaptan is introduced to carry out second modification treatment on the metal chalcogenide, so that the modified metal chalcogenide is obtained. In the preparation process, the first modification treatment reduces the defects of the chalcogen element through sufficient acid treatment, can release charges combined with the defect state of the chalcogen element, and simultaneously removes oxygen species (oxygen species) in the chalcogen compound, thereby obtaining a purer metal chalcogen compound; the second modification treatment enables the chalcogen element defect state and the mercaptan to carry out chemical adsorption in a covalent bond mode through mercaptan treatment, and eliminates the residual defects on the surface of the chalcogen element to the minimum; therefore, the modified metal chalcogenide with higher charge transmission efficiency is obtained, and the luminous efficiency of the device is improved. In addition, the preparation method has simple process and low cost, and can realize large-scale production.
Drawings
FIG. 1 is a schematic representation of the molecular structure of bis-sulfimides provided in accordance with an embodiment of the invention;
fig. 2 is a schematic diagram of an apparatus for a process for preparing a modified metal chalcogenide according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of a light emitting device provided by an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and 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 the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The embodiment of the invention provides a preparation method of a modified metal chalcogenide. The preparation method comprises the following steps:
step S11: providing a metal chalcogenide and placing the metal chalcogenide in a reaction chamber.
In one embodiment of the present invention, the metal chalcogenide compound has the general formula MS2Wherein M is a metal element, e.g. Mo, W, V, Nb, Ta, etc., and S represents a chalcogen such as S, SeAnd (4) elements. And (3) placing the prepared metal chalcogenide into a reaction chamber for processing, wherein the reaction chamber is a device which can be ventilated and sealed.
Step S12: a first modification treatment is performed on the metal chalcogenide by introducing a non-oxidizing acid.
In an embodiment of the present invention, the passing of the non-oxidizing acid comprises: inert gas is introduced into the non-oxidizing acid solution and flowed into the reaction chamber to entrain gaseous or small amounts of liquid non-oxidizing acid. Wherein, the non-oxidizing acid includes but is not limited to hydrohalic acid and/or bissulfimide, wherein, the hydrohalic acid includes but is not limited to HCl, HBr, HI; the molecular structure of the bis-sulfimide is shown in figure 1 (wherein R is one of alkane, arene, substituted alkane or substituted arene, and the number of carbon atoms in R is less than eight).
Specifically, as shown in fig. 2, the procedure of the first modification process includes: and (3) introducing the a-path gas, namely introducing inert gas into the non-oxidizing acid solution, enabling the inert gas to flow into the reaction chamber, and introducing the non-oxidizing acid into the reaction chamber. Preferably, in order to sufficiently acid-treat the metal chalcogenide, the first modification process further includes: and after the path a gas is ventilated for 5min to 180min, the path a is closed, and the path c is used for introducing inert gas to pressurize the gas in the reaction chamber, so that the treatment gas introduced in the path a is fully contacted with the metal chalcogenide to fully react. Preferably, the pressure is 1.1MPa to 11MPa, and if the pressure is too low (less than 1.1MPa), the pressurization is not performed, whereas if the pressure is too high (more than 11MPa), on the one hand, the complexity of the processing equipment is increased, and on the other hand, the concentration of the reaction gas is diluted by the high pressure obtained by introducing the inert gas, and the reaction cannot be sufficiently performed.
In the embodiment of the invention, the metal chalcogenide is subjected to acid treatment by the non-oxidizing acid, so that on one hand, the defects of the chalcogen elements such as S and Se can be reduced, the charges combined with the defect states of the chalcogen elements such as S and Se can be released, the oxygen species in the chalcogen compounds can be removed and converted into M-S/Se-X, and the S/M value in the chalcogen compounds can be closer to 2 and further closer to pure MS after the acid treatment2(ii) a On the other hand, the first modification adopts a ventilation mode, so that the metal chalcogenide can be prevented from corroding the substrate attached and deposited with the metal chalcogenide in the production application: for example, when the metal chalcogenide is used as the material of the hole transport layer, the metal chalcogenide is treated in a ventilation mode, so that the corrosion to the bottom electrode or the hole injection layer can be avoided in the light-emitting device with the positive structure, and the corrosion to the light-emitting layer can be avoided in the light-emitting device with the reverse structure; when the metal chalcogenide is used as the material of the hole injection layer, the metal chalcogenide is treated in a ventilation mode, so that the bottom electrode can be prevented from being corroded in an upright structure, and the light emitting layer or the hole transport layer can be prevented from being corroded in an inverted structure.
Step S13: and (3) introducing mercaptan, and carrying out second modification treatment on the metal chalcogenide subjected to the first modification treatment to obtain the modified metal chalcogenide.
In an embodiment of the invention, passing the thiol comprises: introducing inert gas into the mercaptan solution, flowing the inert gas into the reaction chamber, and carrying the mercaptan into the reaction chamber. The second modification treatment process uses thiol, and preferably, a thiol gas with a carbon number less than eight in a thiol molecular chain, such as ethanedithiol, is selected, and an excessively long carbon chain may cause a decrease in charge transport efficiency and increase resistance to hole transport.
Specifically, as shown in fig. 2, the process of the second modification treatment includes: and (3) adjusting the pressure after the first modification treatment to normal pressure, and then introducing a path b gas, namely introducing an inert gas into the mercaptan solution, allowing the inert gas to flow into the reaction chamber, and introducing the mercaptan gas into the reaction chamber. Preferably, in order to subject the metal chalcogenide compound to sufficient thiol treatment, the second modification treatment process further includes: and after the gas in the path b is aerated for 5min to 180min, the path b is closed, and the inert gas is introduced through the path c to pressurize the gas in the reaction chamber, so that the treatment gas introduced in the path b is fully contacted with the metal chalcogenide to react more fully. Preferably, the pressure is 1.1MPa to 11MPa, and if the pressure is too low (less than 1.1MPa), the pressurization is not performed, whereas if the pressure is too high (more than 11MPa), on the one hand, the complexity of the processing equipment is increased, and on the other hand, the concentration of the reaction gas is diluted by the high pressure obtained by introducing the inert gas, and the reaction cannot be sufficiently performed.
In the embodiment of the present invention, the path a, the path b, and the path c for introducing the inert gas may be the same path or may be three independent paths. When the paths a, b and c are three independent lines, the inert gases in the paths a, b and c can be inert gases from the same source or different sources, and are respectively introduced into the reaction chamber through the paths a, b and c. When the paths a, b and c are the same pipeline, the non-oxidizing acid and the mercaptan may be placed in the pipeline in sequence, the non-oxidizing acid or the mercaptan may be taken out after the inert gas is introduced to complete the first modification treatment step, and then the inert gas may be introduced, wherein the introduced inert gas may be the same source or different sources of inert gas.
In the embodiment of the invention, the metal chalcogenide compound is sufficiently subjected to thiol treatment by the thiol gas, and the remaining defects on the surface of the metal chalcogenide compound can be eliminated to the minimum after the second modification treatment because the metal chalcogenide compound can be chemically adsorbed with thiol in a covalent bond form due to the existence of the defects of the chalcogen element such as S or Se in the metal chalcogenide compound; on the other hand, the second modification treatment adopts a ventilation mode, so that the metal chalcogenide can be prevented from corroding the substrate attached and deposited by the metal chalcogenide in production application: for example, when the metal chalcogenide is used as the material of the hole transport layer, because the metal chalcogenide is treated in a ventilation mode, the corrosion to the bottom electrode or the hole injection layer can be avoided in the light emitting device with the positive structure, and the corrosion to the light emitting layer or the hole transport layer can be avoided in the light emitting device with the reverse structure; when the metal chalcogenide is used as the material of the hole injection layer, the metal chalcogenide is treated in a ventilation mode, so that the bottom electrode can be prevented from being corroded in an upright structure, and the light emitting layer or the hole transport layer can be prevented from being corroded in an inverted structure.
According to the preparation method of the modified metal chalcogenide provided by the embodiment of the invention, the metal chalcogenide is provided and is placed in a reaction chamber to be subjected to acid treatment and thiol treatment, so that the modified metal chalcogenide is obtained. In the preparation process, on one hand, the defects of the chalcogen are reduced through sufficient acid treatment, the charges combined with the defect state of the chalcogen can be released, and oxygen species (oxygen species) in the chalcogen are removed at the same time, so that purer metal chalcogen is obtained; on the other hand, the sulfur element defect state and the sulfur alcohol are chemically adsorbed in a covalent bond form through mercaptan treatment, and the residual defects on the surface of the sulfur element are eliminated to the minimum; therefore, the modified metal chalcogenide with higher charge transmission efficiency is obtained, and the luminous efficiency of the device is improved. In addition, the preparation method has simple process and low cost, and can realize large-scale production.
Embodiments of the present invention provide a light emitting device comprising a hole functional layer containing a modified metal chalcogenide prepared as described above. Wherein, the hole function layer is a hole injection layer or a hole transmission layer.
In the embodiment of the present invention, the light emitting device may be of an inverted structure or an upright structure, and in an actual production process, the inverted structure is preferred because a small amount of liquid non-oxidizing acid may damage the light emitting layer in the preparation process of the inverted structure.
Taking a light emitting device with an upright structure as an example, as shown in fig. 3, the light emitting device includes a substrate 1, a bottom electrode 2, a hole functional layer 3, a light emitting layer 4 and a top electrode 5, which are sequentially arranged, the hole functional layer 3 is a hole injection layer or a hole transport layer, and the hole functional layer 3 contains a modified metal chalcogenide prepared according to the preparation method of the modified metal chalcogenide. Further, the light emitting device further comprises an electron functional layer 6 disposed between the light emitting layer 4 and the top electrode 5.
In the embodiment of the present invention, the substrate 1 is not limited to be selected, and may be a flexible substrate or a hard substrate, where the flexible substrate includes but is not limited to one or more of polyethylene terephthalate (PET), polyethylene terephthalate (PEN), Polyetheretherketone (PEEK), Polystyrene (PS), Polyethersulfone (PES), Polycarbonate (PC), Polyarylate (PAT), Polyarylate (PAR), Polyimide (PI), polyvinyl chloride (PV), Polyethylene (PE), polyvinylpyrrolidone (PVP), and textile fibers; the hard substrate includes, but is not limited to, one or more of glass, metal foil.
In the embodiment of the present invention, the bottom electrode 2 is made of a conventional anode material, and in order to prevent the electrode from being affected by the acid treatment process, one of an Ag electrode, an Al electrode, a Cu electrode, an Au electrode, a Mo electrode, an alloy electrode, a graphene electrode, and FTO conductive glass is preferably used.
In the embodiment of the present invention, the hole functional layer 3 is a hole injection layer or a hole transport layer, and the hole functional layer 3 contains the modified metal chalcogenide prepared according to the preparation method of the modified metal chalcogenide, and the details of the modified metal chalcogenide are described in the above embodiment and are not repeated herein. Wherein, when the hole function layer 3 is a hole injection layer, the transport material of the hole transport layer may include at least one of NiO, CuO, CuS, VOx, WOx, MoOx, or at least one of TFB, PVK, Poly-TPD, TCTA, CBP, and/or include the modified metal chalcogenide, wherein TFB is preferred, and the thickness of the hole transport layer is preferably 0 to 100 nm. When the hole function layer 3 is a hole transport layer, the injection material of the hole injection layer may be a metal chalcogenide or a common hole injection material.
In the embodiment of the present invention, the material of the light emitting layer 4 includes at least one of an inorganic semiconductor nanocrystal, an inorganic perovskite type semiconductor, an organic-inorganic hybrid perovskite nanocrystal, and an organic light emitting material. According to the choice of the material of the light-emitting layer 4, the light-emitting form of the light-emitting layer 4 may be mainly the light-emitting of organic materials, corresponding to an organic light-emitting (OLED) device; quantum dot material emission may also be dominant, such as at least one of the common red, green, blue, yellow, and infrared and ultraviolet quantum dots, corresponding to quantum dot light emitting (QLED) devices. The thickness of the light-emitting layer 4 is preferably 10nm to 50 nm.
In the present embodiment, the electron function layer 6 is used for transporting electrons, and includes, but is not limited to, an electron transport layer and an electron injection layer disposed on the light emitting layer 4. Wherein the electron transport layer preferably has a thickness of 10nm-60nm, and the material of the electron transport layer is not limited and can beAs oxide electron-transporting materials, e.g. n-type ZnO, TiO2、SnO、Ta2O3、AlZnO、ZnSnO、InSnO、Alq3、Ca、Ba、CsF、LiF、CsCO3Preferably n-type zinc oxide having high electron transport properties. The material of the electron injection layer can be selected from Ca, Ba and other metals with low work function, can also be selected from CsF, LiF, CsCO3 and other compounds, and can also be other electrolyte type electron transport layer materials.
In the embodiment of the present invention, the material of the top electrode 5 is not limited, and may be one of Ag, Al, Cu, Au, and an alloy electrode. The thickness of this layer is preferably 50nm-150nm, and then the device is simply encapsulated.
In the light-emitting device provided by the embodiment of the invention, since the hole functional layer 3 contains the modified metal chalcogenide compound prepared according to the preparation method of the modified metal chalcogenide compound, the hole injection or transmission efficiency is effectively improved, and the performance of the light-emitting device is enhanced.
The light-emitting device provided by the embodiment of the invention can be prepared by the following method:
s21, providing a substrate with a bottom electrode.
S22, depositing a metal chalcogenide on a bottom electrode of the substrate to obtain a metal chalcogenide film; the metal chalcogenide film is modified by the preparation method of the modified metal chalcogenide to prepare the hole functional layer.
In step S21 according to an embodiment of the present invention, the description of the substrate and the bottom electrode is as above, and for brevity, will not be repeated herein.
In step S22 of this embodiment of the present invention, a metal chalcogenide is deposited on the bottom electrode surface of the substrate to obtain a metal chalcogenide thin film. As an example, the metal chalcogenide thin film may be prepared by: and preparing an inorganic salt solution containing the metal chalcogenide acid radicals, depositing the inorganic salt solution on the bottom electrode of the substrate, and carrying out heating annealing treatment to form the metal chalcogenide film. As one specific example thereof, an inorganic compound containing a metal chalcogenideThe salt solution may be (NH)4)2MoS4The aqueous solution is, of course, not limited thereto.
Further, the metal chalcogenide thin film may be formed by depositing an inorganic salt solution on the bottom electrode side of the substrate by a solution processing method including spin coating, drop coating, spray coating, or pulling.
Further, the heating annealing treatment comprises heating treatment at the temperature of 60-100 ℃ in air, wherein the time of the heating treatment is at least 5 min; annealing treatment is carried out in an inert atmosphere at the temperature of 200-400 ℃, and the time of the annealing treatment is at least 5 min. If the annealing temperature is too low and/or the annealing time is too short, the metal oxide film cannot be effectively formed; if the temperature of the annealing treatment is too high, the substrate and/or the bottom electrode are likely to be adversely affected, and the performance of the resulting light-emitting device is affected.
As another example, the metal chalcogenide thin film can be prepared by: providing metal chalcogenide powder, and depositing the metal chalcogenide thin film powder on the bottom electrode surface of the substrate by a vapor deposition method to form the metal chalcogenide thin film.
In the embodiment of the present invention, the thickness of the metal chalcogenide thin film is preferably 5nm to 40 nm. If the thickness of the metal chalcogenide film is too thin and cannot completely cover the bottom electrode, the hole injection performance cannot be effectively improved; if the thickness of the metal chalcogenide thin film is too thick, the resistance of the hole functional layer formed by the metal chalcogenide thin film is too high, and the current is too small, so that on one hand, the injection of holes is influenced, and further the light emitting performance of the light emitting device is influenced, and on the other hand, most of energy is converted into heat energy due to the high resistance of the hole functional layer, and the stability of the light emitting device is influenced.
In step S22 of the embodiment of the present invention, the method for modifying a metal chalcogenide thin film using the above-mentioned method for preparing a modified metal chalcogenide is not described herein again for saving space. Wherein, the modification treatment process adopts a reaction chamber ventilation mode, so that the corrosion to the bottom electrode can be avoided; the direct solvent treatment results in corrosion of the bottom electrode.
In an embodiment of the present invention, after the hole functional layer is obtained, the method for manufacturing a light emitting device further includes sequentially depositing a light emitting layer, an electron functional layer, and a top electrode on the hole functional layer. The method for sequentially depositing the light-emitting layer, the electron transport layer and the top electrode on the hole function layer can be prepared by adopting a conventional method. If a solution processing method is adopted to prepare the luminous layer and the electronic functional layer, the top electrode is thermally evaporated in an evaporation chamber through a mask. Preferably, in order to avoid interference of water and oxygen, the substrate deposited with the hole functional layer is moved into a glove box filled with nitrogen gas to prepare the luminescent layer by solution processing. After deposition of each layer, thermal annealing is performed to remove the solvent and form a dense film. The electronic function layer and the top electrode material are described above, and are not described herein again for brevity.
The following description will exemplify a method for manufacturing a light-emitting device using a hole functional layer as a hole injection layer:
example 1.
(1) Depositing a layer of MoS on a substrate containing silver nanowires2By spin coating (NH)4)2MoS4The aqueous solution is then annealed to obtain MoS2A film (wherein, the heating condition is 80 ℃/15min in the air, and the annealing condition is that inert gas is annealed at 300 ℃/15 min);
(2) mixing MoS2The film was placed in the apparatus shown in FIG. 2, and subjected to the first modification treatment and the second modification treatment. Introducing gas HI from path a, closing path a after introducing gas for 15min, introducing inert gas from path c, and increasing pressure to 5 MPa. And (3) introducing the gas ethanedithiol in the path b after the pressure is reduced to the normal pressure, introducing inert gas in the path c after the gas is introduced for 15min, and increasing the pressure to 5 MPa. After the pressure is reduced to normal pressure, the substrate is moved into a glove box, a hole transport layer is deposited, the hole transport layer can be TFB, spin-coating is carried out at the rotating speed of 3000rpm, and then annealing is carried out for 30min at the temperature of 150 ℃;
(3) depositing a light-emitting layer with the thickness of 40nm on the TFB, wherein the material is red light quantum dots;
(4) sequentially depositing an electron transmission layer with the thickness of 30nm, wherein the material is ZnO;
(5) finally, a top electrode with the thickness of 100nm is deposited, the material is Al, and then the device is simply packaged.
Example 2.
(1) Depositing a layer of MoSe on a FTO-containing substrate2Prepared by CVD to a thickness of 20nm and then MoSe2The film was put into the apparatus shown in FIG. 3 to be subjected to the first modification treatment and the second modification treatment. Firstly introducing gas HBr of a path, closing the path a after introducing the gas for 30min, introducing inert gas through the path c, and increasing the pressure to 5 MPa. When the pressure is reduced to normal pressure, the ethane dithiol path b is introduced, after the gas is introduced for 15min, the inert gas path c is introduced, and the pressure is increased to 5 MPa. After the pressure is reduced to normal pressure, the substrate is moved into a glove box, then a hole transport layer is deposited, the layer is TFB, spin-coated at 3000rpm, and then annealed for 30min at 150 ℃;
(2) depositing a light-emitting layer with the thickness of 40nm on the TFB, wherein the material is red light quantum dots;
(3) sequentially depositing an electron transmission layer with the thickness of 30nm, wherein the material is ZnO;
(4) finally, a top electrode with the thickness of 100nm is deposited, the material is Ag, and then the device is simply packaged.
The preparation method of the light-emitting device provided by the embodiment of the invention only needs to deposit other functional layers in sequence on the basis of the hole functional layer, and the method is mature and easy to realize.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A process for preparing a modified metal chalcogenide compound, comprising the steps of:
providing a metal chalcogenide, placing the metal chalcogenide in a reaction chamber;
introducing a non-oxidizing acid to carry out first modification treatment on the metal chalcogenide;
introducing mercaptan, and carrying out second modification treatment on the metal chalcogenide subjected to the first modification treatment to obtain a modified metal chalcogenide;
wherein the content of the first and second substances,
the introducing of the non-oxidizing acid comprises: introducing inert gas into the non-oxidizing acid solution, allowing the inert gas to flow into the reaction chamber, and introducing the non-oxidizing acid into the reaction chamber;
the introduction of the mercaptan comprises: introducing inert gas into the mercaptan solution, flowing the inert gas into the reaction chamber, and carrying the mercaptan into the reaction chamber.
2. The process for preparing a modified metal chalcogenide compound according to claim 1, further comprising a step of introducing an inert gas before and/or after the introduction of the thiol.
3. The process for preparing a modified metal chalcogenide compound as claimed in claim 1, characterized in that the pressure in the reaction chamber is comprised between 1.1MPa and 11 MPa.
4. The method for preparing a modified metal chalcogenide compound according to claim 1, wherein said non-oxidizing acid comprises a hydrohalic acid and/or a bis-sulfonimide having a molecular structure as follows:
wherein R is one of alkane, arene, substituted alkane or substituted arene, and the number of carbon atoms in R is less than eight.
5. The process for preparing a modified metal chalcogenide compound according to claim 1, characterized in that the number of carbon atoms in the thiol molecular chain is less than eight.
6. The process for the preparation of a modified metal chalcogenide according to any one of claims 1 to 5, characterized in that said metal chalcogenide has the chemical formula MS2Wherein M is a metal element and S is a chalcogen element.
7. A light-emitting device comprising a hole-functional layer, characterized in that said hole-functional layer comprises a modified metal chalcogenide prepared by the preparation process according to any one of claims 1 to 6.
8. The light-emitting device according to claim 7, wherein the hole function layer is a hole injection layer or a hole transport layer.
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| CN103460428A (en) * | 2011-03-28 | 2013-12-18 | 住友化学株式会社 | Electronic device, polymer compound, organic compound, and method of producing polymer compound |
| CN106252522A (en) * | 2016-09-09 | 2016-12-21 | Tcl集团股份有限公司 | The preparation method of QLED hole injection layer, QLED and preparation method thereof |
| CN106784357A (en) * | 2017-01-04 | 2017-05-31 | 纳晶科技股份有限公司 | Luminescent device, the display device containing it and lighting device and solar cell |
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