WO2023178852A1 - Nanoparticle printing method and light-emitting element - Google Patents

Nanoparticle printing method and light-emitting element Download PDF

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Publication number
WO2023178852A1
WO2023178852A1 PCT/CN2022/099871 CN2022099871W WO2023178852A1 WO 2023178852 A1 WO2023178852 A1 WO 2023178852A1 CN 2022099871 W CN2022099871 W CN 2022099871W WO 2023178852 A1 WO2023178852 A1 WO 2023178852A1
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nanoparticle
nanoparticles
light source
printing
quantum dots
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PCT/CN2022/099871
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French (fr)
Chinese (zh)
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林琳涵
刘少峰
孙洪波
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清华大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/435—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by selective application of radiation to a printing material or impression-transfer material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/04—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
    • H01L33/06—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier

Definitions

  • the present application relates to the field of printing technology, specifically to nanoparticle printing methods and light-emitting elements.
  • Quantum dots are a typical nanomaterial with excellent optoelectronic properties such as adjustable luminescence wavelength, narrow half-peak width, high luminescence purity and high luminescence quantum yield. They are used in lighting, QLED displays, flexible devices, photoelectric detection, solar cells, etc. The field has very important application prospects.
  • Quantum dot printing is to print quantum dots on a substrate to prepare functional optoelectronic devices. The development of this technology is a key link in making quantum dot applications practical and commercial.
  • the mainstream technologies for quantum dot printing include photolithography and extrusion ink printing. On the one hand, photolithography technology has complex manufacturing processes, and the photocuring process often causes damage to quantum dots. On the other hand, this technology is limited to 2D quantum dot printing.
  • extrusion ink printing can achieve 2D and 3D printing
  • this technology requires ink preparation.
  • the requirements are high, it is difficult to prepare complex 3D structures, and the processing resolution is low.
  • both technologies require the introduction of additional organic polymers.
  • the presence of polymers reduces the quantum dot components in the printed structure and hinders the charge transfer process between quantum dots, thus seriously affecting the optoelectronic properties and development applications of quantum dots.
  • a method of nanoparticle printing in which the nanoparticles in the nanoparticle solution are excited by a light source, so that the nanoparticles are assembled along the scanning path of the light source.
  • the nanoparticle printing method involved in this application assembles the nanoparticles in the nanoparticle solution through the excitation of the light source. There is no need to introduce polymers into the nanoparticle solution during the process, and there is no need to perform any specificity on the nanoparticle solution during the process. Designed to achieve nanoparticle 2D, 2.5D and 3D printing of any complex structure.
  • the method of nanoparticle printing according to the example of this application may also have the following additional technical features:
  • the nanoparticles have ligands on their surfaces, and the nanoparticles are assembled along the scanning path of the light source by exciting the nanoparticles so that the ligands interact with the adjacent nanoparticles. This is achieved by bonding the particles.
  • the light source is a laser or an incoherent light source.
  • the laser includes at least one of continuous laser, nanosecond laser, picosecond laser and femtosecond laser.
  • the nanoparticles include at least one of quantum dots, metal nanoparticles, and dielectric nanoparticles.
  • the quantum dots are semiconductor quantum dots.
  • the ligand includes: HS-R1-R2, wherein R1 is selected from any one of alkyl groups and peptide bonds, and R2 is selected from any one of carboxyl groups and amino groups.
  • the ligand has a molecular weight of no greater than 2,000.
  • the ligand is selected from at least one of mercaptopropionic acid, mercaptoethylamine and glutathione.
  • the quantum dots are selected from at least one of cadmium selenide, cadmium sulfide and cadmium selenide/zinc sulfide.
  • the quantum dots have a core-shell structure.
  • the concentration of the quantum dot solution is not less than 1 nmol/ml.
  • the method of nanoparticle printing further includes: (1) placing the nanoparticle solution in a closed chamber, the closed chamber having a substrate and a cover; (2) scanning the light source The nanoparticle solution allows the nanoparticles in the nanoparticle solution to assemble along the scanning path of the light source; (3) uncover the cover and wash away the unassembled nanoparticle solution; ( 4) Dry to obtain the assembled structure.
  • a light-emitting element including a light-emitting layer including a nanoparticle material, and the light-emitting layer is formed by the aforementioned method. Therefore, the light-emitting element has all the features and advantages brought by the aforementioned nanoparticle printing method, which will not be described in detail here. Generally speaking, it at least has the advantages of simple preparation process, low cost and high luminous efficiency.
  • Figure 1 shows a schematic structural diagram of an example of a quantum dot in this application
  • Figure 2 shows a schematic structural diagram of an example of a quantum dot in this application
  • Figure 3 shows a schematic structural diagram of another example of a quantum dot in this application.
  • Figure 4 shows a schematic diagram of the shape of quantum dot printing of an example of this application
  • Figure 5 shows a schematic diagram of the shape of quantum dot printing of another example of this application.
  • Figure 6 shows a schematic flow chart of quantum dot printing in an example of this application
  • Figure 7 shows the test chart before and after quantum dot printing of an example of this application
  • Figure 8 shows a schematic flow chart of quantum dot printing in an example of this application.
  • the nanoparticle printing method proposed in this application has at least one of the following advantages:
  • Free-space 3D multi-color nanodisplay can be realized, which has broad application prospects in 3D display.
  • the nanoparticle printing method proposed in this application uses a light source to excite the nanoparticles for assembly. Since the nanoparticles are only assembled in the area scanned by the light source, by controlling the scanning path of the light source, different patterns composed of nanoparticles can be obtained to achieve 2D, 2.5 Printing of 3D and 3D structures.
  • the type of light source is not particularly limited, as long as the light emitted by the light source meets a certain power intensity and can excite quantum dots to achieve the functions of assembly and printing.
  • the light source can be a laser or an incoherent light source.
  • the laser may further include at least one of continuous laser, nanosecond laser, picosecond laser and femtosecond laser. Therefore, after the laser is focused by the objective lens, a spot of a certain size can be produced. Since the quantum dots are only assembled in the area scanned by the laser, a pattern equivalent to the spot size can be formed after scanning. By controlling the spot size after the laser is focused, that is The processing resolution can be controlled to achieve fine printing.
  • femtosecond laser can be selected as the laser.
  • quantum dots When using femtosecond laser for scanning, quantum dots have a nonlinear absorption threshold for femtosecond laser.
  • the focused laser satisfies Gaussian distribution. The closer to the center of the spot, the smaller the light intensity. The higher the intensity, by adjusting the light intensity of the laser, the laser light intensity only at the center of the spot is greater than the printing threshold, that is, printing can only be achieved in the area scanned by the light at the center of the spot.
  • the light in the area near the center of the spot can Quantum dots are excited, but the quantum dots cannot be assembled, so the printing function cannot be realized. Therefore, quantum dot structures at the submicron level or even the sub-hundred nanometer level can be prepared, surpassing the optical diffraction limit, and achieving nanopixelization of quantum dots. and super-resolution printing.
  • the type of nanoparticles is not particularly limited, as long as they can generate high-energy carriers under the irradiation of a light source.
  • nanoparticles may include but are not limited to quantum dots, metal nanoparticles, dielectric At least one of the nanoparticles, specifically a quantum dot, may be a semiconductor quantum dot.
  • the structure of the nanoparticles is not particularly limited.
  • the high-energy carriers generated inside the nanoparticles are separated and transferred.
  • the holes are transferred to the surface of the nanoparticles and interact with the surface ligands, allowing the ligands to bond with adjacent nanoparticles. And thus the assembly is achieved.
  • nanoparticles After the laser is turned off, the assembled nanoparticles will not be redispersed into the solution, so that the structure remains on the substrate and nanoparticle printing can be achieved. Therefore, coating ligands on the surface of nanoparticles can make it easier to assemble between nanoparticles and increase the assembly and printing speed.
  • the type of ligand is not particularly limited.
  • the ligand may include HS-R1-R2, where R1 is selected from any one of alkyl groups and peptide bonds, and R2 is selected from carboxyl groups and amino groups. any of them.
  • the ligands are connected to the surface of the nanoparticles through thiol groups.
  • the light source irradiates the nanoparticle solution, the holes generated inside the nanoparticles can interact with the ligands, causing the ligands on the surface of the nanoparticles to interact with adjacent nanoparticles. Keying occurs, assembly is achieved, and printing is completed.
  • the molecular weight of the ligand may not be greater than 2000. If the molecular weight of the ligand is too large, the ligands on the surface of the nanoparticles will be larger, which will increase the distance between the nanoparticles. Difficulty of assembly.
  • the ligand may be selected from at least one of mercaptopropionic acid, mercaptoethylamine and glutathione.
  • the quantum dot solution is alkaline
  • the ligand is mercaptopropionic acid
  • the thiol group of the mercaptopropionic acid is connected to the surface of the quantum dot, and the carboxyl group is exposed on the outside of the quantum dot.
  • the high-energy carriers inside the quantum dots are separated and transferred, and the holes are transferred to the surface of the quantum dots and interact with the ligands, allowing the carboxyl groups to bond with adjacent quantum dots, allowing the adjacent quantum dots to assemble . Therefore, the above-mentioned ligands are mostly used for coating water-soluble quantum dots.
  • Water-soluble quantum dots are made through special surface modifications and have good biocompatibility, low non-specific adsorption, high quantum yield, large molar extinction coefficient, It has stable optical properties, narrow emission spectrum, and is easy to couple with biomolecules (antibodies, proteins, nucleic acids, etc.). It is the best choice for a new generation of fluorescently labeled probes.
  • the above-mentioned ligands are short-chain ligands. If The above-mentioned quantum dots are used in the preparation of devices. Compared with long-chain ligands, short-chain ligands have less hindrance to charge transport, and the luminous efficiency of quantum dots is higher.
  • quantum dots can be selected.
  • semiconductor quantum dots can be selected. Compared with other quantum dots, semiconductor quantum dots are more stable in a water and oxygen environment. When irradiated by laser, the quantum dots are not easily damaged. For example, you can choose cadmium selenide, cadmium sulfide and cadmium selenide/zinc sulfide. At least one of the above-mentioned quantum dots has high quantum yield and is more stable.
  • the structure of the quantum dots is not particularly limited.
  • the quantum dots can have a core-shell structure.
  • the preparation process of quantum dots with a core-shell structure is relatively mature, and the quantum dots themselves have better fluorescence effects.
  • the luminescence performance is better, the quantum yield is higher, and the shell of the core-shell quantum dots has a protective effect on the core that generates excitons inside, and the damage to the core is less during the light source irradiation process.
  • the luminescence performance is better after printing. After printing is completed , clean the unassembled quantum dot solution, leaving no residual quantum dots around the printed structure.
  • quantum dots with non-core-shell structures can also be assembled.
  • quantum dots when they have a core-shell structure, that is, cadmium selenide is the core and zinc sulfide is the shell, or Non-core-shell structure (refer to Figure 3), that is, cadmium selenide or cadmium sulfide, quantum dots of both structures can achieve assembly functions.
  • the concentration of the quantum dot solution is not particularly limited.
  • the concentration of the quantum dot solution may not be less than 1 nmol/ml.
  • the content of active ingredients in the quantum dot solution is relatively high, There are more quantum dots within the laser irradiation range, the distance between adjacent quantum dots is closer, and the efficiency of assembly and printing is higher. If the concentration of quantum dots in the quantum dot solution is too low, even if the light source can excite the quantum dots, because the effective components If there are too few, the distance between quantum dots will be large and assembly will be slow, which is not conducive to printing.
  • printing of nanoparticles can be performed through the following process:
  • the nanoparticle solution is placed in a closed chamber with a base and a cover to prevent the nanoparticle solution from volatilizing.
  • the light source scans the nanoparticle solution, causing the nanoparticles in the nanoparticle solution to assemble along the scanning path of the light source. Therefore, by controlling the moving path of the light source, the structure formed by the assembly of the nanoparticles can be controlled.
  • the structure formed by the assembly of the nanoparticles can be controlled. For example, when printing quantum dots, you can scan with an upright light path or an inverted light path. When scanning with an upright light path, a quantum dot structure is formed on the substrate; when scanning with an inverted light path, a quantum dot structure is formed on the cover plate. , thereby reducing the obstruction of the light source by the quantum dot structure formed during the printing process.
  • the cover of the closed chamber is removed and the unassembled nanoparticle solution is washed away.
  • the cover plate can be soaked in a deionized water solution to remove excess nanoparticle solution;
  • the substrate can be soaked in a deionized water solution. , remove excess nanoparticle solution.
  • the assembled structure is obtained.
  • the substrate or cover plate containing the printed structure is dried, and after the liquid on the substrate or cover plate evaporates, the assembled structure can be obtained.
  • the substrate or cover plate containing the printed structure is dried, and after the liquid on the substrate or cover plate evaporates, the assembled structure can be obtained.
  • a light-emitting element including a light-emitting layer including nanoparticle materials, and the light-emitting layer is formed by the aforementioned method. Therefore, the light-emitting unit has all the features and advantages brought by the aforementioned nanoparticle printing method, which will not be described in detail here. Generally speaking, it at least has the advantages of simple preparation process, low cost, and high luminous efficiency.
  • the quantum dots are cadmium selenide/zinc sulfide quantum dots with a core-shell structure.
  • Cadmium selenide is the core
  • zinc sulfide is the shell
  • the quantum dot surface ligand is mercaptopropionic acid
  • the solvent is deionized water.
  • the laser is a femtosecond laser with a wavelength of 780nm, a pulse width of 100fs, and a repetition rate of 80MHz.
  • the cover plate is dried, and the printed quantum dot structure is left after the liquid evaporates.
  • the structure shown in Figure 5 and Figure 6 can be printed.
  • Example 1 The quantum dots in Example 1 were tested by Fourier transform infrared spectroscopy before and after assembly. As can be seen from Figure 7, the two asymmetric peaks near 1500cm -1 are the two characteristic peaks of deprotonated carboxyl groups. The difference between the two peak positions reflects the change of its state. Before assembly, the deprotonated carboxyl groups are in contact with the quantum dot aqueous solution. After assembly, some carboxyl groups are connected to the surface of the quantum dot particles through the bidentate chelation mode and become -COOZn , so the difference changes from 170cm -1 to around 140cm -1 .

Abstract

Provided in the present application are a nanoparticle printing method and a light-emitting element. The method comprises: a light source exciting nanoparticles in a nanoparticle solution, such that the nanoparticles are assembled along a scanning path of the light source.

Description

纳米颗粒打印的方法以及发光元件Nanoparticle printing methods and light-emitting components
优先权信息priority information
本申请请求2022年3月22日向中国国家知识产权局提交的、专利申请号为202210286599.4的专利申请的优先权和权益，并且通过参照将其全文并入此处。This application requests the priority and rights of the patent application with patent application number 202210286599.4, which was submitted to the State Intellectual Property Office of China on March 22, 2022, and the full text of which is incorporated herein by reference.
技术领域Technical field
本申请涉及打印技术领域，具体地，涉及纳米颗粒打印的方法以及发光元件。The present application relates to the field of printing technology, specifically to nanoparticle printing methods and light-emitting elements.
背景技术Background technique
量子点是一种典型的纳米材料，具有优异的光电性能如发光波长可调、半峰宽窄、高发光纯度及高发光量子产率等，在照明、QLED显示、柔性器件、光电探测、太阳能电池等领域具有十分重要的应用前景。量子点打印是将量子点印刷在基底上从而制备功能性光电器件，该技术的开发是使量子点应用走向实用化和商业化的关键环节。目前，量子点打印主流技术有光刻和挤出式油墨打印两种。光刻技术一方面制造工序复杂，光固化过程常常对量子点造成破坏，另一方面该技术局限于量子点2D打印；挤出式油墨打印虽然可实现2D及3D打印，但是该技术对油墨制备要求较高，难以制备复杂3D结构，加工分辨率低。此外，两种技术都需要额外引入有机聚合物，聚合物的存在使得打印结构中量子点组分降低并阻碍量子点间的电荷转移过程，从而严重影响量子点的光电性能及发展应用。Quantum dots are a typical nanomaterial with excellent optoelectronic properties such as adjustable luminescence wavelength, narrow half-peak width, high luminescence purity and high luminescence quantum yield. They are used in lighting, QLED displays, flexible devices, photoelectric detection, solar cells, etc. The field has very important application prospects. Quantum dot printing is to print quantum dots on a substrate to prepare functional optoelectronic devices. The development of this technology is a key link in making quantum dot applications practical and commercial. Currently, the mainstream technologies for quantum dot printing include photolithography and extrusion ink printing. On the one hand, photolithography technology has complex manufacturing processes, and the photocuring process often causes damage to quantum dots. On the other hand, this technology is limited to 2D quantum dot printing. Although extrusion ink printing can achieve 2D and 3D printing, this technology requires ink preparation. The requirements are high, it is difficult to prepare complex 3D structures, and the processing resolution is low. In addition, both technologies require the introduction of additional organic polymers. The presence of polymers reduces the quantum dot components in the printed structure and hinders the charge transfer process between quantum dots, thus seriously affecting the optoelectronic properties and development applications of quantum dots.
因此，目前的打印的方法还需进一步改进。Therefore, the current printing method needs further improvement.
申请内容Application content
在本申请的一个方面，提出了一种纳米颗粒打印的方法，通过光源激发纳米颗粒溶液中的纳米颗粒，以令所述纳米颗粒沿所述光源的扫描路径进行组装。In one aspect of the present application, a method of nanoparticle printing is proposed, in which the nanoparticles in the nanoparticle solution are excited by a light source, so that the nanoparticles are assembled along the scanning path of the light source.
本申请所涉及的纳米颗粒打印的方法，通过光源的激发，使纳米颗粒溶液中的纳米颗粒组装，过程中无需在纳米颗粒溶液中引入聚合物，过程中也无需对纳米颗粒溶液进行任何特异性设计，可以实现纳米颗粒2D，2.5D及3D任意复杂结构打印。The nanoparticle printing method involved in this application assembles the nanoparticles in the nanoparticle solution through the excitation of the light source. There is no need to introduce polymers into the nanoparticle solution during the process, and there is no need to perform any specificity on the nanoparticle solution during the process. Designed to achieve nanoparticle 2D, 2.5D and 3D printing of any complex structure.
根据本申请示例的纳米颗粒打印的方法，还可以具有如下附加的技术特征：The method of nanoparticle printing according to the example of this application may also have the following additional technical features:
根据本申请的一些示例，所述纳米颗粒表面具有配体，令所述纳米颗粒沿所述光源的扫描路径进行组装，是通过激发所述纳米颗粒以令所述配体与相邻所述纳米颗粒发生键和而实现的。According to some examples of this application, the nanoparticles have ligands on their surfaces, and the nanoparticles are assembled along the scanning path of the light source by exciting the nanoparticles so that the ligands interact with the adjacent nanoparticles. This is achieved by bonding the particles.
根据本申请的一些示例，所述光源为激光或非相干光源。According to some examples of this application, the light source is a laser or an incoherent light source.
根据本申请的一些示例，所述激光包括连续激光、纳秒激光、皮秒激光和飞秒激光中的 至少一种。According to some examples of the present application, the laser includes at least one of continuous laser, nanosecond laser, picosecond laser and femtosecond laser.
根据本申请的一些示例，所述纳米颗粒包括量子点、金属纳米颗粒、介电纳米颗粒中的至少一种。According to some examples of the present application, the nanoparticles include at least one of quantum dots, metal nanoparticles, and dielectric nanoparticles.
根据本申请的一些示例，所述量子点为半导体量子点。According to some examples of this application, the quantum dots are semiconductor quantum dots.
根据本申请的一些示例，所述配体包括：HS-R1-R2，其中，R1选自烷基和肽键中的任意一种，R2选自羧基和氨基中的任意一种。According to some examples of this application, the ligand includes: HS-R1-R2, wherein R1 is selected from any one of alkyl groups and peptide bonds, and R2 is selected from any one of carboxyl groups and amino groups.
根据本申请的一些示例，所述配体的分子量不大于2000。According to some examples of this application, the ligand has a molecular weight of no greater than 2,000.
根据本申请的一些示例，所述配体选自巯基丙酸、巯基乙胺和谷胱甘肽中的至少一种。According to some examples of the present application, the ligand is selected from at least one of mercaptopropionic acid, mercaptoethylamine and glutathione.
根据本申请的一些示例，所述量子点选自硒化镉、硫化镉和硒化镉/硫化锌中的至少一种。According to some examples of the present application, the quantum dots are selected from at least one of cadmium selenide, cadmium sulfide and cadmium selenide/zinc sulfide.
根据本申请的一些示例，所述量子点具有核壳结构。According to some examples of the present application, the quantum dots have a core-shell structure.
根据本申请的一些示例，所述量子点溶液的浓度不小于1nmol/ml。According to some examples of this application, the concentration of the quantum dot solution is not less than 1 nmol/ml.
根据本申请的一些示例，所述纳米颗粒打印的方法进一步包括：(1)将所述纳米颗粒溶液置于密闭腔室内，所述密闭腔室具有基底和盖板；(2)所述光源扫描所述纳米颗粒溶液，使所述纳米颗粒溶液中的所述纳米颗粒沿所述光源的扫描路径进行组装；(3)揭开所述盖板，洗去未组装的所述纳米颗粒溶液；(4)干燥，以获得组装好的结构。According to some examples of the present application, the method of nanoparticle printing further includes: (1) placing the nanoparticle solution in a closed chamber, the closed chamber having a substrate and a cover; (2) scanning the light source The nanoparticle solution allows the nanoparticles in the nanoparticle solution to assemble along the scanning path of the light source; (3) uncover the cover and wash away the unassembled nanoparticle solution; ( 4) Dry to obtain the assembled structure.
在本申请的另一个方面，提出了一种发光元件，包括发光层，所述发光层包括纳米颗粒材料，所述发光层是通过前述方法形成的。由此，该发光元件具有前述的纳米颗粒打印的方法所带来的全部特征以及优点，在此不再赘述，总的来说，至少具有制备工艺简单、成本低和发光效率高的优点。In another aspect of the present application, a light-emitting element is proposed, including a light-emitting layer including a nanoparticle material, and the light-emitting layer is formed by the aforementioned method. Therefore, the light-emitting element has all the features and advantages brought by the aforementioned nanoparticle printing method, which will not be described in detail here. Generally speaking, it at least has the advantages of simple preparation process, low cost and high luminous efficiency.
附图说明Description of the drawings
图1显示了本申请一个示例的量子点的结构示意图；Figure 1 shows a schematic structural diagram of an example of a quantum dot in this application;
图2显示了本申请一个示例的量子点的结构示意图；Figure 2 shows a schematic structural diagram of an example of a quantum dot in this application;
图3显示了本申请另一个示例的量子点的结构示意图；Figure 3 shows a schematic structural diagram of another example of a quantum dot in this application;
图4显示了本申请一个示例的量子点打印的形状示意图；Figure 4 shows a schematic diagram of the shape of quantum dot printing of an example of this application;
图5显示了本申请另一个示例的量子点打印的形状示意图；Figure 5 shows a schematic diagram of the shape of quantum dot printing of another example of this application;
图6显示了本申请一个示例的量子点打印的流程示意图；Figure 6 shows a schematic flow chart of quantum dot printing in an example of this application;
图7显示了本申请一个示例的量子点打印前后测试图；Figure 7 shows the test chart before and after quantum dot printing of an example of this application;
图8显示本申请一个示例的量子点打印的流程示意图。Figure 8 shows a schematic flow chart of quantum dot printing in an example of this application.
具体实施方式Detailed ways
下面详细描述本申请的示例，所述示例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的示例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。Examples of the present application are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The examples described below with reference to the accompanying drawings are illustrative and are only used to explain the application and are not to be understood as limitations of the application.
在本申请的一个方面，提出了一种纳米颗粒打印的方法，通过光源激发纳米颗粒溶液中的纳米颗粒，以令纳米颗粒沿光源的扫描路径进行组装。由此，本申请提出的纳米颗粒打印的方法，具有以下优势的至少之一：In one aspect of the present application, a method of nanoparticle printing is proposed, in which the nanoparticles in the nanoparticle solution are excited by a light source, so that the nanoparticles are assembled along the scanning path of the light source. Therefore, the nanoparticle printing method proposed in this application has at least one of the following advantages:
(1)整个过程不需要在纳米颗粒溶液中引入聚合物，也无需对纳米颗粒溶液进行任何特异性设计，使得打印结构中纳米颗粒组分达到100％，消除了聚合物对纳米颗粒光电性能的影响。(1) The entire process does not require the introduction of polymers into the nanoparticle solution, nor does it require any specific design of the nanoparticle solution, so that the nanoparticle component in the printed structure reaches 100%, eliminating the impact of the polymer on the photoelectric properties of the nanoparticles. Influence.
(2)分辨率高，可以实现纳米颗粒的纳米像素化，实现超分辨显示。(2) The resolution is high, and nano-pixelization of nanoparticles can be realized to achieve super-resolution display.
(3)可以实现纳米颗粒2D、2.5D及3D任意复杂结构打印。(3) Nanoparticle 2D, 2.5D and 3D printing of any complex structures can be realized.
(4)可以通过选择不同颜色的发光纳米颗粒或者调节不同发光纳米颗粒的浓度配比，实现可见光范围任意颜色发光图案的2D及3D异质打印。(4) By selecting luminescent nanoparticles of different colors or adjusting the concentration ratio of different luminescent nanoparticles, 2D and 3D heterogeneous printing of luminescent patterns of any color in the visible light range can be achieved.
(5)可以实现自由空间的3D多色纳米显示，在3D显示中具有广阔的应用前景。(5) Free-space 3D multi-color nanodisplay can be realized, which has broad application prospects in 3D display.
(6)对基底没有选择性，可以在柔性及非柔性基底上制备，在柔性显示器件及片上集成光电器件如微型激光器、光电探测器、QLED、片上光波导等器件中中有很好的应用前景。(6) It has no selectivity for substrates and can be prepared on flexible and non-flexible substrates. It has good applications in flexible display devices and on-chip integrated optoelectronic devices such as micro lasers, photodetectors, QLEDs, on-chip optical waveguides and other devices. prospect.
(7)工艺简单，成本低廉，适用于工业生产。(7) The process is simple, the cost is low, and it is suitable for industrial production.
如前所述，目前纳米颗粒打印的两种方式有光刻和油墨打印两种，但这两种打印方式存在很多不足，例如，对光刻来说，主要存在以下缺点的至少之一：As mentioned before, the current two methods of nanoparticle printing are photolithography and ink printing. However, these two printing methods have many shortcomings. For example, for photolithography, there are at least one of the following shortcomings:
(1)工艺复杂。(1) The process is complex.
(2)高强度紫外曝光往往对部分纳米颗粒，比如量子点造成破坏。(2) High-intensity UV exposure often causes damage to some nanoparticles, such as quantum dots.
(3)依赖于光敏聚合物，聚合物的存在降低量子点组分的含量而且会影响纳米颗粒的光电性能。(3) Dependent on photosensitive polymers, the presence of polymers reduces the content of quantum dot components and affects the photoelectric properties of nanoparticles.
(4)仅仅局限于平面内加工即2D打印。(4) Only limited to in-plane processing, that is, 2D printing.
对油墨打印方式来说，主要存在以下缺点的至少之一：For ink printing methods, there are at least one of the following shortcomings:
(1)打印过程对油墨的制备要求较高。(1) The printing process requires high ink preparation.
(2)加工分辨率低，受限于机械喷嘴的大小。(2) The processing resolution is low and limited by the size of the mechanical nozzle.
(3)同样依赖于聚合物，聚合物的存在会降低纳米颗粒组分的含量而且会影响纳米颗粒光电性能。(3) Also dependent on polymers, the presence of polymers will reduce the content of nanoparticle components and affect the photoelectric properties of nanoparticles.
(4)难以实现复杂3D结构的打印。(4) It is difficult to print complex 3D structures.
本申请提出的纳米颗粒打印的方法，是通过光源激发纳米颗粒进行组装，由于纳米颗粒仅在光源扫描的区域组装，通过控制光源的扫描路径，可以获得纳米颗粒组成的不同图 案，实现2D、2.5D和3D结构的打印。The nanoparticle printing method proposed in this application uses a light source to excite the nanoparticles for assembly. Since the nanoparticles are only assembled in the area scanned by the light source, by controlling the scanning path of the light source, different patterns composed of nanoparticles can be obtained to achieve 2D, 2.5 Printing of 3D and 3D structures.
根据本申请的一些示例，光源的种类不受特别限制，只要光源发出的光满足一定的功率强度，能够激发量子点，实现组装和打印的功能即可，例如，光源可以为激光或非相干光源，具体地，激光可以进一步包括连续激光、纳秒激光、皮秒激光和飞秒激光中的至少一种。由此，激光通过物镜聚焦后，可产生一定大小的光斑，由于量子点仅在激光扫描的区域发生组装，扫描后即可形成与光斑尺寸相当的图案，通过控制激光聚焦后的光斑大小，即可控制加工的分辨率，以实现精细化打印。为了实现量子点的超分辨显示，激光可以选择飞秒激光，当使用飞秒激光进行扫描时，量子点对飞秒激光具有非线性吸收阈值，此外聚焦激光满足高斯分布，越靠近光斑中心，光强度越高，通过调整激光的光强，使激光仅在光斑中心处的光强大于打印的阈值，即仅在光斑中心处的光扫描的区域才可实现打印，光斑中心附近区域的光虽然可以激发量子点，但是无法使量子点组装，也就无法实现打印的功能，从而可以制备亚微米级别、甚至亚百纳米级别的量子点结构，超越光学衍射极限的限制，实现量子点的纳米像素化以及超分辨打印。According to some examples of this application, the type of light source is not particularly limited, as long as the light emitted by the light source meets a certain power intensity and can excite quantum dots to achieve the functions of assembly and printing. For example, the light source can be a laser or an incoherent light source. , specifically, the laser may further include at least one of continuous laser, nanosecond laser, picosecond laser and femtosecond laser. Therefore, after the laser is focused by the objective lens, a spot of a certain size can be produced. Since the quantum dots are only assembled in the area scanned by the laser, a pattern equivalent to the spot size can be formed after scanning. By controlling the spot size after the laser is focused, that is The processing resolution can be controlled to achieve fine printing. In order to achieve super-resolution display of quantum dots, femtosecond laser can be selected as the laser. When using femtosecond laser for scanning, quantum dots have a nonlinear absorption threshold for femtosecond laser. In addition, the focused laser satisfies Gaussian distribution. The closer to the center of the spot, the smaller the light intensity. The higher the intensity, by adjusting the light intensity of the laser, the laser light intensity only at the center of the spot is greater than the printing threshold, that is, printing can only be achieved in the area scanned by the light at the center of the spot. Although the light in the area near the center of the spot can Quantum dots are excited, but the quantum dots cannot be assembled, so the printing function cannot be realized. Therefore, quantum dot structures at the submicron level or even the sub-hundred nanometer level can be prepared, surpassing the optical diffraction limit, and achieving nanopixelization of quantum dots. and super-resolution printing.
根据本申请的一些示例，纳米颗粒的种类不受特别限制，只要在光源的照射下，能够产生高能载流子即可，例如，纳米颗粒可以包括但不限于量子点、金属纳米颗粒、介电纳米颗粒中的至少一种，具体地，量子点可以半导体为量子点。According to some examples of this application, the type of nanoparticles is not particularly limited, as long as they can generate high-energy carriers under the irradiation of a light source. For example, nanoparticles may include but are not limited to quantum dots, metal nanoparticles, dielectric At least one of the nanoparticles, specifically a quantum dot, may be a semiconductor quantum dot.
根据本申请的一些示例，纳米颗粒结构不受特别限制，例如，参考图1，在纳米颗粒的表面可以具有配体，令纳米颗粒沿光源的扫描路径进行组装，是通过激发纳米颗粒，以令配体与相邻纳米颗粒发生键和实现的。具体地，光源照射纳米颗粒溶液后，纳米颗粒内部产生的高能载流子分离并发生转移，空穴转移至纳米颗粒表面并与表面配体相互作用，使配体可以与邻近的纳米颗粒发生键和从而实现组装，关闭激光后，组装后的纳米颗粒也不会重新分散至溶液中，使结构保留在基底上从而可实现纳米颗粒打印。由此，在纳米颗粒表面包覆配体能够使纳米颗粒之间更容易进行组装，提高组装和打印速率。According to some examples of this application, the structure of the nanoparticles is not particularly limited. For example, with reference to Figure 1, there can be ligands on the surface of the nanoparticles, so that the nanoparticles are assembled along the scanning path of the light source, by exciting the nanoparticles, so that Ligands are bonded to adjacent nanoparticles. Specifically, after the light source irradiates the nanoparticle solution, the high-energy carriers generated inside the nanoparticles are separated and transferred. The holes are transferred to the surface of the nanoparticles and interact with the surface ligands, allowing the ligands to bond with adjacent nanoparticles. And thus the assembly is achieved. After the laser is turned off, the assembled nanoparticles will not be redispersed into the solution, so that the structure remains on the substrate and nanoparticle printing can be achieved. Therefore, coating ligands on the surface of nanoparticles can make it easier to assemble between nanoparticles and increase the assembly and printing speed.
根据本申请的一些示例，配体的种类不受特别限制，例如，配体可以包括HS-R1-R2，其中，R1选自烷基和肽键中的任意一种，R2选自羧基和氨基中的任意一种。由此，配体通过巯基连接在纳米颗粒的表面，当光源照射纳米颗粒溶液时，纳米颗粒内部产生的空穴能够与配体发生相互作用，使纳米颗粒表面的配体与相邻的纳米颗粒发生键和，实现组装，完成打印的功能。According to some examples of this application, the type of ligand is not particularly limited. For example, the ligand may include HS-R1-R2, where R1 is selected from any one of alkyl groups and peptide bonds, and R2 is selected from carboxyl groups and amino groups. any of them. As a result, the ligands are connected to the surface of the nanoparticles through thiol groups. When the light source irradiates the nanoparticle solution, the holes generated inside the nanoparticles can interact with the ligands, causing the ligands on the surface of the nanoparticles to interact with adjacent nanoparticles. Keying occurs, assembly is achieved, and printing is completed.
根据本申请的一些具体示例，为了使纳米颗粒之间能够快速组装，配体的分子量可以不大于2000，如果配体的分子量过大，纳米颗粒表面的配体较大，会增加纳米颗粒之间组装的难度。According to some specific examples of this application, in order to enable rapid assembly between nanoparticles, the molecular weight of the ligand may not be greater than 2000. If the molecular weight of the ligand is too large, the ligands on the surface of the nanoparticles will be larger, which will increase the distance between the nanoparticles. Difficulty of assembly.
具体地，配体可以选自巯基丙酸、巯基乙胺和谷胱甘肽中的至少一种。例如，参考图7， 当纳米颗粒为量子点且量子点溶液为碱性、配体为巯基丙酸时，巯基丙酸的巯基与量子点表面相连，羧基暴露在量子点的外侧，光源照射后，量子点内部的高能载流子分离并发生转移，空穴转移到量子点的表面并与配体发生相互作用，使羧基可以与相邻的量子点发生键和，使相邻的量子点组装。由此，上述几种配体多用于水溶性量子点的包覆，水溶性量子点经由特殊表面修饰而成，生物相容性好、非特异性吸附小、量子产率高、摩尔消光系数大、光学性能稳定、发射光谱窄、易于和生物分子(抗体、蛋白、核酸等)偶联，是新一代荧光标记探针的较佳选择，而且，上述几种配体是短链配体，如果将上述量子点用于器件的制备，短链配体相对于长链配体来说，对电荷传输的阻碍更小，量子点的发光效率更高。Specifically, the ligand may be selected from at least one of mercaptopropionic acid, mercaptoethylamine and glutathione. For example, referring to Figure 7, when the nanoparticle is a quantum dot, the quantum dot solution is alkaline, and the ligand is mercaptopropionic acid, the thiol group of the mercaptopropionic acid is connected to the surface of the quantum dot, and the carboxyl group is exposed on the outside of the quantum dot. After the light source is irradiated , the high-energy carriers inside the quantum dots are separated and transferred, and the holes are transferred to the surface of the quantum dots and interact with the ligands, allowing the carboxyl groups to bond with adjacent quantum dots, allowing the adjacent quantum dots to assemble . Therefore, the above-mentioned ligands are mostly used for coating water-soluble quantum dots. Water-soluble quantum dots are made through special surface modifications and have good biocompatibility, low non-specific adsorption, high quantum yield, large molar extinction coefficient, It has stable optical properties, narrow emission spectrum, and is easy to couple with biomolecules (antibodies, proteins, nucleic acids, etc.). It is the best choice for a new generation of fluorescently labeled probes. Moreover, the above-mentioned ligands are short-chain ligands. If The above-mentioned quantum dots are used in the preparation of devices. Compared with long-chain ligands, short-chain ligands have less hindrance to charge transport, and the luminous efficiency of quantum dots is higher.
进一步地，根据本申请的一些示例，为了获得巯基丙酸、巯基乙胺和谷胱甘肽包覆的、更稳定、组装效果更好的纳米颗粒，可以选择量子点，例如，可以选择半导体量子点，相对于其他量子点来说，半导体量子点本身在水氧环境中更稳定，激光照射时，不易损坏量子点，例如，可以选择硒化镉、硫化镉和硒化镉/硫化锌中的至少一种，上述几种量子点的量子产率高、更稳定。Further, according to some examples of this application, in order to obtain nanoparticles coated with mercaptopropionic acid, mercaptoethylamine and glutathione, which are more stable and have better assembly effects, quantum dots can be selected. For example, semiconductor quantum dots can be selected. Compared with other quantum dots, semiconductor quantum dots are more stable in a water and oxygen environment. When irradiated by laser, the quantum dots are not easily damaged. For example, you can choose cadmium selenide, cadmium sulfide and cadmium selenide/zinc sulfide. At least one of the above-mentioned quantum dots has high quantum yield and is more stable.
根据本申请的一些具体示例，量子点的结构不受特别限制，参考图2，量子点可以具有核壳结构，核壳类结构的量子点的制备工艺比较成熟，量子点本身荧光效果更好，发光性能更佳，量子产率更高，而且核壳量子点的壳对于内部产生激子的核具有保护作用，光源照射过程中对核的损伤更小，打印后发光性能更优，打印完成后，清洗未组装的量子点溶液，打印结构周围无残留的量子点。需要说明的，非核壳结构的量子点同样可以实现组装，例如，对硒化镉/硫化锌量子点来说，当其为核壳结构时，即硒化镉为核、硫化锌为壳，或者非核壳结构(参考图3)，即硒化镉或硫化镉，两种结构的量子点均可以实现组装功能。According to some specific examples of this application, the structure of the quantum dots is not particularly limited. Referring to Figure 2, the quantum dots can have a core-shell structure. The preparation process of quantum dots with a core-shell structure is relatively mature, and the quantum dots themselves have better fluorescence effects. The luminescence performance is better, the quantum yield is higher, and the shell of the core-shell quantum dots has a protective effect on the core that generates excitons inside, and the damage to the core is less during the light source irradiation process. The luminescence performance is better after printing. After printing is completed , clean the unassembled quantum dot solution, leaving no residual quantum dots around the printed structure. It should be noted that quantum dots with non-core-shell structures can also be assembled. For example, for cadmium selenide/zinc sulfide quantum dots, when they have a core-shell structure, that is, cadmium selenide is the core and zinc sulfide is the shell, or Non-core-shell structure (refer to Figure 3), that is, cadmium selenide or cadmium sulfide, quantum dots of both structures can achieve assembly functions.
根据本申请的一些示例，量子点溶液的浓度不受特别限制，为了实现快速组装、快速打印，量子点溶液的浓度可以不小于1nmol/ml，此时，量子点溶液中有效成分含量较高，激光照射范围内量子点数量较多，相邻量子点之间距离更近，组装和打印的效率更高，如果量子点溶液中量子点的浓度过低，即使光源能够激发量子点，因为有效成分太少，量子点间距离较大，组装较慢，不利于打印的进行。According to some examples of this application, the concentration of the quantum dot solution is not particularly limited. In order to achieve rapid assembly and rapid printing, the concentration of the quantum dot solution may not be less than 1 nmol/ml. At this time, the content of active ingredients in the quantum dot solution is relatively high, There are more quantum dots within the laser irradiation range, the distance between adjacent quantum dots is closer, and the efficiency of assembly and printing is higher. If the concentration of quantum dots in the quantum dot solution is too low, even if the light source can excite the quantum dots, because the effective components If there are too few, the distance between quantum dots will be large and assembly will be slow, which is not conducive to printing.
根据本申请的一些示例，参考图8，纳米颗粒的打印可通过以下过程进行：According to some examples of this application, referring to Figure 8, printing of nanoparticles can be performed through the following process:
S100：准备纳米颗粒溶液S100: Prepare nanoparticle solution
在此过程中，将纳米颗粒溶液置于密闭腔室内，以防止纳米颗粒溶液挥发，密闭腔室具有基底和盖板。During this process, the nanoparticle solution is placed in a closed chamber with a base and a cover to prevent the nanoparticle solution from volatilizing.
S200：光源扫描纳米颗粒溶液S200: Light source scanning nanoparticle solution
在此步骤中，光源扫描纳米颗粒溶液，使纳米颗粒溶液中的纳米颗粒沿光源的扫描路径 进行组装，由此，通过控制光源的移动路径，即可控制纳米颗粒组装形成的结构。例如，进行量子点打印时，可通过正置光路或倒置光路进行扫描，使用正置光路进行扫描时，在基底上形成量子点结构；使用倒置光路进行扫描时，在盖板上形成量子点结构，由此，可减小打印过程中形成的量子点结构对光源的阻挡。进一步地，可以预先撰写想组装的结构图案程序，并将撰写的程序导入控制软件中，从而控制激光在2D或3D空间中的扫描路径，在激光扫描过的区域留下量子点结构。In this step, the light source scans the nanoparticle solution, causing the nanoparticles in the nanoparticle solution to assemble along the scanning path of the light source. Therefore, by controlling the moving path of the light source, the structure formed by the assembly of the nanoparticles can be controlled. For example, when printing quantum dots, you can scan with an upright light path or an inverted light path. When scanning with an upright light path, a quantum dot structure is formed on the substrate; when scanning with an inverted light path, a quantum dot structure is formed on the cover plate. , thereby reducing the obstruction of the light source by the quantum dot structure formed during the printing process. Furthermore, you can pre-write the structural pattern program you want to assemble, and import the written program into the control software to control the scanning path of the laser in 2D or 3D space, leaving a quantum dot structure in the area scanned by the laser.
S300：清洗S300: Cleaning
在此步骤中，揭开密闭腔室的盖板，洗去未组装的纳米颗粒溶液。具体地，如果使用倒置光路进行扫描，可以将盖板浸泡在去离子水溶液中，去除多余的纳米颗粒溶液；如果使用正置光路进行扫描，揭开盖板后，将基底浸泡在去离子水溶液中，去除多余的纳米颗粒溶液。In this step, the cover of the closed chamber is removed and the unassembled nanoparticle solution is washed away. Specifically, if an inverted light path is used for scanning, the cover plate can be soaked in a deionized water solution to remove excess nanoparticle solution; if an upright light path is used for scanning, after uncovering the cover plate, the substrate can be soaked in a deionized water solution. , remove excess nanoparticle solution.
S400：干燥S400: dry
在此步骤中，通过干燥，获得组装好的结构。具体地，将含有打印结构的基底或盖板进行干燥，待基底或盖板上的液体蒸发后，即可获得组装好结构。需要说明的是，对基底的选择没有特殊的限制，可以在柔性及非柔性基底上制备，在柔性显示器件及片上集成光电器件如微型激光器、光电探测器、QLED、片上光波导等器件中具有很好的应用前景。In this step, through drying, the assembled structure is obtained. Specifically, the substrate or cover plate containing the printed structure is dried, and after the liquid on the substrate or cover plate evaporates, the assembled structure can be obtained. It should be noted that there are no special restrictions on the choice of substrate. It can be prepared on flexible and non-flexible substrates. It has the advantages of flexible display devices and on-chip integrated optoelectronic devices such as micro lasers, photodetectors, QLEDs, on-chip optical waveguides and other devices. Very good application prospects.
在本申请的另一个方面，提出了一种发光元件，包括发光层，发光层包括纳米颗粒材料，发光层是通过前述方法形成的。由此，该发光单元具有前述的纳米颗粒打印的方法所带来的全部特征以及优点，在此不再赘述，总的来说，至少具有制备工艺简单、成本低、发光效率高的优点。In another aspect of the present application, a light-emitting element is proposed, including a light-emitting layer including nanoparticle materials, and the light-emitting layer is formed by the aforementioned method. Therefore, the light-emitting unit has all the features and advantages brought by the aforementioned nanoparticle printing method, which will not be described in detail here. Generally speaking, it at least has the advantages of simple preparation process, low cost, and high luminous efficiency.
示例1Example 1
在本示例中，参考图6，量子点为核壳结构的硒化镉/硫化锌量子点，硒化镉为核，硫化锌为壳，量子点表面配体为巯基丙酸，溶剂为去离子水。In this example, referring to Figure 6, the quantum dots are cadmium selenide/zinc sulfide quantum dots with a core-shell structure. Cadmium selenide is the core, zinc sulfide is the shell, the quantum dot surface ligand is mercaptopropionic acid, and the solvent is deionized water.
在本示例中，激光为波长为780nm的飞秒激光，脉宽100fs，重复频率80MHz。In this example, the laser is a femtosecond laser with a wavelength of 780nm, a pulse width of 100fs, and a repetition rate of 80MHz.
取5μL浓度为10nmol/mL的量子点溶液滴加在50μm厚的液体腔室中，将洗好的玻片盖在液滴上方，之后轻压玻片，形成量子点溶液密封腔室；Take 5 μL of quantum dot solution with a concentration of 10 nmol/mL and drop it into a 50 μm thick liquid chamber. Cover the washed glass slide above the droplet, and then press the glass gently to form a sealed chamber of the quantum dot solution;
调节激光功率，使其在物镜前功率为50mW，调整激光焦点z轴位置，找到加工平面；Adjust the laser power so that the power in front of the objective lens is 50mW, adjust the z-axis position of the laser focus, and find the processing plane;
按照预先设置的图案撰写程序并将程序导入控制软件中，从而控制激光在2D或3D空间中的扫描路径，在激光扫描过的区域留下量子点结构；Write a program according to the preset pattern and import the program into the control software to control the scanning path of the laser in 2D or 3D space, leaving a quantum dot structure in the area scanned by the laser;
加工完成后，将盖板浸泡在去离子水溶液中，去除多余的量子点溶液；After processing is completed, soak the cover plate in deionized water solution to remove excess quantum dot solution;
对盖板进行干燥处理，待液体蒸发后留下打印的量子点结构，例如，可以打印如图5 和图6所示的结构。The cover plate is dried, and the printed quantum dot structure is left after the liquid evaporates. For example, the structure shown in Figure 5 and Figure 6 can be printed.
将示例1中的量子点在组装前和组装后分别进行傅里叶红外光谱测试，由图7可以看出，1500cm -1附近的两个非对称峰是去质子化羧基的两个特征峰，两个峰位的差值反映的是其状态的变化，组装前去质子化羧基接触的是量子点水溶液，组装后，部分羧基通过双齿鳌合模式跟量子点颗粒表面相连，变成-COOZn，所以差值从170cm -1变到140cm -1附近。 The quantum dots in Example 1 were tested by Fourier transform infrared spectroscopy before and after assembly. As can be seen from Figure 7, the two asymmetric peaks near 1500cm -1 are the two characteristic peaks of deprotonated carboxyl groups. The difference between the two peak positions reflects the change of its state. Before assembly, the deprotonated carboxyl groups are in contact with the quantum dot aqueous solution. After assembly, some carboxyl groups are connected to the surface of the quantum dot particles through the bidentate chelation mode and become -COOZn , so the difference changes from 170cm -1 to around 140cm -1 .
在本申请的描述中，术语“纵向”、“横向”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请而不是要求本申请必须以特定的方位构造和操作，因此不能理解为对本申请的限制。In the description of this application, the terms "longitudinal", "transverse", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", " The orientations or positional relationships indicated by "top", "bottom", etc. are based on the orientations or positional relationships shown in the drawings. They are only for the convenience of describing the application and do not require that the application must be constructed and operated in a specific orientation. Therefore, it cannot be understood as Limitations on this Application.
在本说明书的描述中，参考术语“一个示例”、“另一个示例”等的描述意指结合该示例描述的具体特征、结构、材料或者特点包含于本申请的至少一个示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的示例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个示例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同示例或示例以及不同示例或示例的特征进行结合和组合。In the description of this specification, reference to the terms "one example," "another example," etc., means that a particular feature, structure, material, or characteristic described in connection with the example is included in at least one example of the application. In this specification, schematic expressions of the above terms do not necessarily refer to the same example or examples. Furthermore, the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more examples or examples. Furthermore, those skilled in the art may combine and combine different examples or examples and features of different examples or examples described in this specification unless they are inconsistent with each other.
尽管上面已经示出和描述了本申请的示例，可以理解的是，上述示例是示例性的，不能理解为对本申请的限制，本领域的普通技术人员在本申请的范围内可以对上述示例进行变化、修改、替换和变型。Although the examples of the present application have been shown and described above, it can be understood that the above examples are illustrative and cannot be understood as limitations of the present application. Those of ordinary skill in the art can make modifications to the above examples within the scope of the present application. Changes, modifications, substitutions and variations.

Claims (14)

  1. 一种纳米颗粒打印的方法，通过光源激发纳米颗粒溶液中的纳米颗粒，以令所述纳米颗粒沿所述光源的扫描路径进行组装。A nanoparticle printing method uses a light source to excite nanoparticles in a nanoparticle solution, so that the nanoparticles are assembled along the scanning path of the light source.
  2. 根据权利要求1所述的纳米颗粒打印的方法，所述纳米颗粒表面具有配体，令所述纳米颗粒沿所述光源的扫描路径进行组装，是通过激发所述纳米颗粒以令所述配体与相邻所述纳米颗粒发生键和而实现的。The method of printing nanoparticles according to claim 1, wherein the nanoparticles have ligands on their surfaces, and the nanoparticles are assembled along the scanning path of the light source by exciting the nanoparticles to cause the ligands to assemble. This is achieved by bonding with adjacent nanoparticles.
  3. 根据权利要求1或2所述的纳米颗粒打印的方法，所述光源为激光或非相干光源。According to the nanoparticle printing method of claim 1 or 2, the light source is a laser or an incoherent light source.
  4. 根据权利要求1～3任一项所述的纳米颗粒打印的方法，所述激光包括连续激光、纳秒激光、皮秒激光和飞秒激光中的至少一种。The method of nanoparticle printing according to any one of claims 1 to 3, wherein the laser includes at least one of a continuous laser, a nanosecond laser, a picosecond laser and a femtosecond laser.
  5. 根据权利要求1～4任一项所述的纳米颗粒打印的方法，所述纳米颗粒包括量子点、金属纳米颗粒、介电纳米颗粒中的至少一种。The method of nanoparticle printing according to any one of claims 1 to 4, wherein the nanoparticles include at least one of quantum dots, metal nanoparticles, and dielectric nanoparticles.
  6. 根据权利要求1～5任一项所述的纳米颗粒打印的方法，所述量子点为半导体量子点。According to the nanoparticle printing method according to any one of claims 1 to 5, the quantum dots are semiconductor quantum dots.
  7. 根据权利要求1～6任一项所述的纳米颗粒打印的方法，所述配体包括：HS-R1-R2，其中，R1选自烷基和肽键中的任意一种，R2选自羧基和氨基中的任意一种。The nanoparticle printing method according to any one of claims 1 to 6, the ligands include: HS-R1-R2, wherein R1 is selected from any one of alkyl groups and peptide bonds, and R2 is selected from carboxyl groups and any one of amino groups.
  8. 根据权利要求1～7任一项所述的纳米颗粒打印的方法，所述配体的分子量不大于2000。According to the nanoparticle printing method according to any one of claims 1 to 7, the molecular weight of the ligand is not greater than 2,000.
  9. 根据权利要求1～8任一项所述的纳米颗粒打印的方法，所述配体选自巯基丙酸、巯基乙胺和谷胱甘肽中的至少一种。According to the nanoparticle printing method according to any one of claims 1 to 8, the ligand is selected from at least one of mercaptopropionic acid, mercaptoethylamine and glutathione.
  10. 根据权利要求1～9任一项所述的纳米颗粒打印的方法，所述量子点选自硒化镉、硫化镉和硒化镉/硫化锌中的至少一种。According to the nanoparticle printing method according to any one of claims 1 to 9, the quantum dots are selected from at least one of cadmium selenide, cadmium sulfide and cadmium selenide/zinc sulfide.
  11. 根据权利要求1～10任一项所述的纳米颗粒打印的方法，所述量子点具有核壳结构。According to the method of nanoparticle printing according to any one of claims 1 to 10, the quantum dots have a core-shell structure.
  12. 根据权利要求1～11任一项所述的纳米颗粒打印的方法，所述量子点溶液的浓度不小于1nmol/ml。According to the nanoparticle printing method according to any one of claims 1 to 11, the concentration of the quantum dot solution is not less than 1 nmol/ml.
  13. 根据权利要求1～12任一项所述的纳米颗粒打印的方法，进一步包括：The method for nanoparticle printing according to any one of claims 1 to 12, further comprising:
    (1)将所述纳米颗粒溶液置于密闭腔室内，所述密闭腔室具有基底和盖板；(1) Place the nanoparticle solution in a closed chamber, which has a base and a cover;
    (2)所述光源扫描所述纳米颗粒溶液，使所述纳米颗粒溶液中的所述纳米颗粒沿所述光源的扫描路径进行组装；(2) The light source scans the nanoparticle solution so that the nanoparticles in the nanoparticle solution are assembled along the scanning path of the light source;
    (3)揭开所述盖板，洗去未组装的所述纳米颗粒溶液；(3) Open the cover and wash away the unassembled nanoparticle solution;
    (4)干燥，以获得组装好的结构。(4) Drying to obtain the assembled structure.
  14. 一种发光元件，包括发光层，所述发光层包括纳米颗粒材料，所述发光层是通过权利要求1～13任一项所述的方法形成的。A light-emitting element includes a light-emitting layer, the light-emitting layer includes nanoparticle material, and the light-emitting layer is formed by the method described in any one of claims 1 to 13.
PCT/CN2022/099871 2022-03-22 2022-06-20 Nanoparticle printing method and light-emitting element WO2023178852A1 (en)

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CN110832618A (en) * 2017-04-18 2020-02-21 芝加哥大学 Photoactive inorganic ligand-capped inorganic nanocrystals
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