阅读说明：本技术 纳米材料及其制备方法和印刷显示材料 (Nano material, preparation method thereof and printing display material ) 是由 叶炜浩 于 2019-08-21 设计创作，主要内容包括：本发明属于平板显示技术领域,具体涉及一种纳米材料及其制备方法和印刷显示材料。本发明所提供的纳米材料的制备方法,包括以下步骤：提供含有掺杂元素的反应物和碳源,将含有掺杂离子元素的反应物与碳源加入水中,进行混合,制备混合液；含有掺杂元素的反应物为硼源、磷源或硫源；调节混合液的pH为2-5,加入引发剂,进行加热反应,制备硼、磷或硫掺杂的碳化聚合物点。由此制得的纳米材料为硼、磷或硫掺杂的碳化聚合物点。与未进行掺杂的碳化聚合物相比,本发明提供的纳米材料不仅具有磁性,还具有优异的发光性能,可显著提高电致发光器件的显示性能。(The invention belongs to the technical field of panel display, and particularly relates to a nano material, a preparation method thereof and a printing display material. The preparation method of the nano material provided by the invention comprises the following steps: providing a reactant containing a doping element and a carbon source, adding the reactant containing the doping ion element and the carbon source into water, and mixing to prepare a mixed solution; the reactant containing the doping element is a boron source, a phosphorus source or a sulfur source; adjusting the pH value of the mixed solution to 2-5, adding an initiator, and carrying out heating reaction to prepare the boron, phosphorus or sulfur doped carbonized polymer dots. The nano material prepared by the method is a boron, phosphorus or sulfur doped carbonized polymer dot. Compared with the undoped carbonized polymer, the nano material provided by the invention not only has magnetism, but also has excellent luminescence property, and can remarkably improve the display performance of an electroluminescent device.)

1. The preparation method of the nano material is characterized by comprising the following steps of:

providing a reactant containing a doping element and a carbon source, adding the reactant containing the doping element and the carbon source into water, and mixing to prepare a mixed solution; the reactant containing the doping element is a boron source, a phosphorus source or a sulfur source;

and adjusting the pH value of the mixed solution to 2-5, adding an initiator, and carrying out heating reaction to prepare the boron, phosphorus or sulfur doped carbonized polymer dots.

2. The method according to claim 1, wherein the heating reaction is carried out at a temperature of 150 to 300 ℃ for 6 to 12 hours.

3. The method according to claim 1, wherein the molar ratio of the dopant element-containing reactant to the carbon source is (0.005-0.05): (1-2); and/or

The molar ratio of the initiator to the carbon source is (0.1-0.5) to (1-2).

4. The production method according to any one of claims 1 to 3, characterized in that the boron source is at least one of trialkylboron, triphenylboron, and phenylboronic acid; and/or

The phosphorus source is at least one of phytic acid, diphenylphosphine, trioctylphosphine and phosphoramide; and/or

The sulfur source is at least one of methionine, cystine, cysteine and thioglycolic acid.

5. The production method according to any one of claims 1 to 3, wherein the carbon source is at least one of citric acid, glucose, sucrose and oleic acid; and/or

The initiator is azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide or potassium persulfate.

6. The method according to any one of claims 1 to 3, wherein the step of adjusting the pH of the mixed solution to 2 to 5 is carried out with a dilute acid.

7. The production method according to any one of claims 1 to 3, characterized by further comprising, after the step of performing the heating reaction: cooling the reaction liquid, and then dialyzing, purifying and drying the reaction liquid, wherein the dialyzing and purifying adopt a dialysis bag with the molecular weight cutoff of 3500-10000.

8. A nanomaterial characterized by a single element doped carbonized polymer dot and the doping element being boron, phosphorus or sulfur.

9. The nanomaterial according to claim 8, wherein the molar percentage of the doping element in the nanomaterial is 0.5% -5%; and/or

The particle size of the nano material is 5-15 nm.

10. A printed display material, comprising: nanomaterial produced by the production method according to any one of claims 1 to 7 or nanomaterial according to claim 8 or 9.

Technical Field

The invention belongs to the technical field of panel display, and particularly relates to a nano material, a preparation method thereof and a printing display material.

Background

The printing display technology refers to the application of the printing electronic technology in the field of flat panel display, and specifically, metal, inorganic materials and organic materials are transferred onto a substrate by adopting a printing method such as ink-jet printing and the like to manufacture a light-emitting display device. Theoretically, "thin film Dot matrix coating" of a QLED (Quantum Dot Light Emitting diode) is more suitable for a printing technology, and compared with a conventional vacuum evaporation technology, the yield is higher, the material cost is lower, and the increase of the technical difficulty of large-size is limited, so that the printing display technology becomes a new direction for the current research of preparing an electroluminescent device.

When the electroluminescent device is prepared by using the printing display technology, materials with different colors need to be sprayed on the same layer, so that one screen can display a gorgeous picture. However, when different color materials are sprayed on the same layer, due to the small distance between different color regions, the different color materials are easily mixed with each other during spraying, which causes color crosstalk between adjacent color regions and affects the display performance of the electroluminescent device.

Disclosure of Invention

The invention mainly aims to provide a preparation method of a nano material and the nano material prepared by the method, which is used as a printing display material.

Another object of the present invention is to provide a printed display material.

In order to achieve the above purpose, the specific technical scheme of the invention is as follows:

the preparation method of the nano material comprises the following steps:

providing a reactant containing a doping element and a carbon source, adding the reactant containing the doping ion element and the carbon source into water, and mixing to prepare a mixed solution; the reactant containing the doping element is a boron source, a phosphorus source or a sulfur source;

and adjusting the pH value of the mixed solution to 2-5, adding an initiator, and carrying out heating reaction to prepare the boron, phosphorus or sulfur doped carbonized polymer dots.

According to the preparation method of the nano material, the boron source, the phosphorus source or the sulfur source is used as a reactant to be mixed with a carbon source, and heating reaction is carried out in an acid environment and in the presence of an initiator, so that the boron, phosphorus or sulfur-doped carbonized polymer dots are prepared.

Correspondingly, the nano material prepared by the preparation method is a single element doped carbonized polymer dot, and the doped element is boron, phosphorus or sulfur.

The nanometer material provided by the invention is a boron, phosphorus or sulfur doped carbonized polymer dot, on one hand, the carbonized polymer dot is used as one member of a carbon dot material, has good luminescent property, high water solubility, stable chemical property, low toxicity, good printability and manufacturability, is easy to form a film, and can be used as a good printing display material; on the other hand, boron, phosphorus or sulfur is used as a doping element to dope the carbonized polymer points, so that carbon lattices with a graphite structure are prevented from being formed, and under the induction of an external electric field, electronic circulation is easily formed to generate an induction magnetic field. Therefore, the nano material provided by the invention can be used as a printing display material for preparing an electroluminescent device, and the printing display materials with different colors can be controlled to a specified color area by adjusting the intensity of an external electric field, so that the mutual blending of the materials with different colors is avoided, and the good display performance of the electroluminescent device is ensured. Different from the undoped carbonized polymer, the nano material provided by the invention not only has good luminescence property, but also has magnetism, and can remarkably improve the display property of an electroluminescent device.

Accordingly, a printed display material comprising: the nano material prepared by the preparation method or the nano material.

The printing display material provided by the invention comprises the boron, phosphorus or sulfur doped carbonized polymer dots, and the nano material has magnetism and can improve the display performance of a printing electroluminescent device.

Drawings

Fig. 1 is a flowchart of a method for preparing a nanomaterial provided in 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 further described in detail 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.

A method for preparing nano-materials, as shown in fig. 1, comprising the following steps:

s01, providing a reactant containing a doping element and a carbon source, adding the reactant containing the doping element and the carbon source into water, and mixing to prepare a mixed solution; the reactant containing the doping element is a boron source, a phosphorus source or a sulfur source;

s02, adjusting the pH value of the mixed solution to 2-5, adding an initiator, and carrying out heating reaction to prepare the boron, phosphorus or sulfur doped carbonized polymer dots.

According to the preparation method of the nano material provided by the embodiment of the invention, the boron source, the phosphorus source or the sulfur source is used as a reactant to be mixed with a carbon source, and the mixture is heated and reacted in an acidic environment in the presence of an initiator to prepare the boron, phosphorus or sulfur doped carbonized polymer dots, so that the process is optimized, the carbonization degree of the reactant is effectively controlled, and the formation of the polymer on the surface of the luminescent carbon core is promoted.

Specifically, in step S01, the reactant containing the doping element and the carbon source are used as reaction raw materials for preparing the nanomaterial. In some embodiments, the carbon source is at least one of citric acid, glucose, sucrose and oleic acid, the citric acid, glucose and sucrose belong to a small molecular structure, and generally the small molecules are polymerized initially to form a polymer chain when forming a carbonized polymer, while the material is similar to a long chain molecule of oleic acid, and due to steric hindrance, the difficulty is greater than that of the small molecules when forming the polymer at the initial stage, so that the polymerization is not sufficient, and the later-stage carbonization is insufficient, the carbon core is small, and the luminescence performance is poor. In other embodiments, the boron source is at least one of trialkylboron, triphenylboron and phenylboronic acid, preferably trialkylboron, and trialkylboron has a small molecular volume, is favorable for entering a carbon chain polymer formed by a carbon source, and has a good doping effect; in still other embodiments, the phosphorus source is at least one of phytic acid, diphenylphosphine, trioctylphosphine and phosphoramide, preferably trioctylphosphine, which is easy to enter into carbon chain polymer formed by carbon source and has better doping effect; in still other embodiments, the sulfur source is at least one of methionine, cystine, cysteine, and thioglycolic acid, preferably thioglycolic acid, with superior doping effects.

And adding the reactant containing the doping elements and the carbon source into water, and mixing to dissolve the reactant containing the doping elements and the carbon source into the water. It is to be understood that the mixing is preferably stirring mixing in order to allow the reactant containing the doping element and the carbon source to be sufficiently dissolved in water. Further, the stirring and mixing are performed at room temperature, and the stirring is performed until the reactant containing the doping element and the carbon source are completely dissolved, for example, the stirring is performed at room temperature for 1 hour or more.

Specifically, in step S02, the pH of the mixed solution is adjusted to 2 to 5, so that the reaction system is in an acidic environment, and the small molecular carbon source is promoted to polymerize and carbonize into carbon nuclei. In the embodiment of the present invention, in the step of adjusting the pH of the mixed solution to 2 to 5, it is preferable to perform adjustment with a dilute acid. In some embodiments, the dilute acid is at least one of dilute hydrochloric acid, dilute sulfuric acid, dilute acetic acid; in other embodiments, the dilute acid has a free hydrogen ion molar concentration of 0.02 to 0.05 mol/L.

In the present examples, the initiator was added for lowering the activation energy of the reaction. The heating reaction is carried out under the conditions of an acid environment and the existence of an initiator, the carbonization degree of reactants in the subsequent heating reaction can be effectively controlled, the polymerization degree of the polymer on the surface of the luminescent carbon core in the later period is prevented from being influenced by excessive carbonization, and the good magnetism and luminescence property of the prepared boron, phosphorus or sulfur doped carbonized polymer dot are ensured. In some embodiments, the initiator is azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, or potassium persulfate, which facilitates the polymerization of long carbon chains from small carbon sources and is removable by washing after the polymerization reaction is complete.

Under the conditions of acidic water environment and initiator existence, the reactants containing doping elements and carbon source are heated to react, and at the initial stage of the reaction, the reactants are dehydrated and condensed to form longer molecular chains. As the reaction proceeds, the activation energy of some potential reactions is reduced under high temperature and pressure conditions, and thus more reactions proceed, facilitating further growth and localized carbonization of the polymer clusters, while at the same time, portion B, P or S carbonizes with the polymer clusters, doping into the carbon lattice to form large pi bonds with carbon atoms to generate magnetism, forming carbonized with certain lattice and external amorphous non-carbonized components (functional groups or polymer chains), eventually forming B, P or S doped carbonized polymer dots.

In the embodiment of the present invention, the temperature of the heating reaction is preferably 150 to 300 ℃, and the reaction time is preferably 6 to 12 hours, so as to control the reaction degree of carbonizing the polymer dots, and when the reaction time is longer and the temperature is higher, the carbonization degree is higher, and the carbon quantum dots are easily formed, so that the properties of the polymer are lost. As a preferred embodiment, the temperature of the heating reaction is preferably 190-230 ℃ and the reaction time is preferably 7-9 hours. In some embodiments, the heating reaction is performed in a stainless steel autoclave with a teflon liner, such that the reaction is performed in a high temperature, high pressure environment, reducing the time for carbon lattice formation.

As a preferred embodiment, the molar ratio of the doping element-containing reactant to the carbon source is (0.005-0.05): 1-2.

As another preferred embodiment, the molar ratio of the initiator to the carbon source is (0.1-0.5): (1-2) to promote the polymerization reaction of the carbon chain, so as to avoid the influence of the initiator on the performance of the carbonized polymer dot due to the participation of the initiator in the reaction at high temperature and high pressure.

In still another preferred embodiment, the concentration of the reactant containing the doping element in the mixed solution is 0.1 to 0.5mmol/L, and the concentration of the carbon source is 3 to 6 mmol/L.

As another preferred embodiment, after the step of performing the heating reaction, the method further comprises: cooling the reaction liquid, and then dialyzing, purifying and drying the reaction liquid, wherein a dialysis bag with the molecular weight cutoff of 3500-10000 is adopted for dialysis and purification so as to remove part of unreacted polymeric carbon chains and initiator molecules. In one example, after the reaction was cooled to room temperature, the reaction was transferred to a dialysis bag with a molecular weight cut-off of 3500 for dialysis purification for 24 hours.

Correspondingly, the nano material prepared by the preparation method is a single element doped carbonized polymer dot, and the doped element is boron, phosphorus or sulfur.

The nano material provided by the embodiment of the invention is a boron, phosphorus or sulfur doped carbonized polymer dot, and on one hand, the carbonized polymer dot is used as one member of a carbon dot material, has good luminescent property, high water solubility, stable chemical property, low toxicity, good printability and manufacturability, is easy to form a film and can be used as a good printing display material; on the other hand, boron, phosphorus or sulfur is used as a doping element to dope the carbonized polymer points, so that carbon lattices with a graphite structure are prevented from being formed, and under the induction of an external electric field, electronic circulation is easily formed to generate an induction magnetic field. Therefore, the nano material provided by the invention can be used as a printing display material for preparing an electroluminescent device, and the printing display materials with different colors can be controlled to a specified color area by adjusting the intensity of an external electric field, so that the mutual blending of the materials with different colors is avoided, and the good display performance of the electroluminescent device is ensured. Different from the undoped carbonized polymer, the nano material provided by the invention not only has good luminescence property, but also has magnetism, and can remarkably improve the display property of an electroluminescent device.

Specifically, the carbonized polymer dots are used as one member of a carbon dot material, have a hybrid structure between a polymer and a traditional carbon dot, take a core of a highly dehydrated and crosslinked carbon skeleton as a luminescent center, and connect a polymer with a certain crosslinking structure on the surface of the carbon core. In embodiments of the invention, the nanomaterial is boron, phosphorus or sulfur doped carbonized polymer dots. The boron atoms only have 3 electrons, and cannot form bonds like carbon atoms after entering carbon lattices, so that the carbon lattices of the graphite structure are damaged, the original large conjugated pi bonds are cut into a plurality of hexagonal structures similar to benzene rings, a plurality of delocalized pi bonds are formed, and magnetism is generated under the excitation of an electric field. S, P atoms are larger than C atoms in atomic size, when S, P is doped into the crystal lattice, the regular hexagonal crystal lattice of the original graphite structure is deformed, so that the original hybridized sp orbitals of the carbon atoms are not hybridized in the same plane any more, and a plurality of delocalized pi bonds are formed; meanwhile, S has 6 outer electrons, and P has 5 outer electrons, so that the compound can be used as an electron donor to passivate surface defects of partial carbonized polymer dots, and the luminescence property of the carbonized polymer dots is improved to a certain extent. In a preferred embodiment, the molar percentage of the doping element in the nanomaterial is 0.5% to 5%, and when the molar percentage of the doping element is greater than 5%, the basic luminescent characteristic of the nanomaterial is lost by destroying the basic structure of the carbonized polymer dots; when the molar percentage of the doping element is less than 0.5%, the magnetic property is weak. As another preferred embodiment, the particle size of the nano material is 5-15nm, when the particle size is larger than 15nm, the quantum confinement effect of each dimension is reduced, and the energy level of the carbonized polymer is gradually continuous to lose the light-emitting property; when the particle size is less than 5nm, the total surface reaction of the particles tends to occur and particle agglomeration tends to occur. As yet another preferred embodiment, the nanomaterial is a water-soluble carbonized polymer dot.

It can be understood that the nano-material provided by the embodiment of the invention has various application purposes, for example, the nano-material is applied to the fields of printing display with magnetic and/or optical guidance, anti-counterfeiting printing and the like, and is applied to the field of biological medicine as a biological probe.

Accordingly, a printed display material comprising: the nano material or the nano material prepared by the preparation method.

The printing display material provided by the invention comprises the boron, phosphorus or sulfur doped carbonized polymer dots, and the nano material not only has magnetism, but also has excellent luminescence property, and can remarkably improve the display property of a printing electroluminescent device.

In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art, and to make the advanced performance of the nanomaterial and the preparation method thereof and the printed display material of the present invention obviously apparent, the implementation of the present invention is illustrated by the following examples.

Example 1

The embodiment prepares a nano material which is a boron-doped carbonized polymer dot, and the specific process flow is as follows:

s11, weighing trialkylboron and citric acid, wherein the molar ratio of trialkylboron to citric acid is 0.01: 1; then, trialkylboron and citric acid were added to 30mL of deionized water, and mixed to prepare a mixed solution.

S12, adjusting the pH value of the mixed solution obtained in the step S11 to 3 by using dilute hydrochloric acid, adding 0.2mmol of azobisisobutyronitrile, transferring the mixture to a stainless steel reaction kettle with a polytetrafluoroethylene lining, and heating the reaction kettle in an oven at 200 ℃ for 10 hours; and after the reaction liquid is cooled, transferring the liquid into a dialysis bag with the molecular weight cutoff of 3500 for dialysis and purification for 24 hours, and then carrying out rotary evaporation and drying to obtain the product.

Example 2

The embodiment prepares a nano material which is a phosphorus-doped carbonized polymer dot, and the specific process flow is as follows:

s21, weighing phytic acid and sucrose, wherein the molar ratio of the phytic acid to the sucrose is 0.02: 1.5; then, phytic acid and sucrose were added to 30mL of deionized water, and mixed to prepare a mixed solution.

S22, adjusting the pH value of the mixed solution obtained in the step S21 to 5 by using dilute hydrochloric acid, adding 0.5mmol of azobisisobutyronitrile, transferring the mixture to a stainless steel reaction kettle with a polytetrafluoroethylene lining, and heating the stainless steel reaction kettle in an oven at 250 ℃ for 10 hours; and after the reaction liquid is cooled, transferring the liquid into a dialysis bag with the molecular weight cutoff of 3500 for dialysis and purification for 24 hours, and then carrying out rotary evaporation and drying to obtain the product.

Example 3

The embodiment prepares a nano material which is a sulfur-doped carbonized polymer dot, and the specific process flow is as follows:

s31, weighing methionine and oleic acid, wherein the molar ratio of the methionine to the oleic acid is 0.04: 2; then, methionine and oleic acid were added to 30mL of deionized water, and mixed to prepare a mixed solution.

S32, adjusting the pH value of the mixed solution obtained in the step S31 to 2 by using dilute hydrochloric acid, adding 0.25mmol of azobisisobutyronitrile, transferring the mixture to a stainless steel reaction kettle with a polytetrafluoroethylene lining, and heating the stainless steel reaction kettle in an oven at 150 ℃ for 12 hours; and after the reaction liquid is cooled, transferring the liquid into a dialysis bag with the molecular weight cutoff of 3500 for dialysis and purification for 24 hours, and then carrying out rotary evaporation and drying to obtain the product.

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.