WO2021114910A1 - Procédé de transfert de décapage pour nanoréseau d'oxyde métallique de grande surface - Google Patents

Procédé de transfert de décapage pour nanoréseau d'oxyde métallique de grande surface Download PDF

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WO2021114910A1
WO2021114910A1 PCT/CN2020/123985 CN2020123985W WO2021114910A1 WO 2021114910 A1 WO2021114910 A1 WO 2021114910A1 CN 2020123985 W CN2020123985 W CN 2020123985W WO 2021114910 A1 WO2021114910 A1 WO 2021114910A1
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metal oxide
nanoarray
substrate
array
base material
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PCT/CN2020/123985
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English (en)
Chinese (zh)
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杨庭强
梁维源
范涛健
张家宜
康建龙
曾永宏
孟思
张斌
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深圳瀚光科技有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009—Forming specific nanostructures
    • B82B3/0014—Array or network of similar nanostructural elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

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  • the present invention claims the priority of the prior application of the application number 201911288794.5 filed on December 12, 2019 under the title of "A Method for Exfoliating and Transferring Large Area Metal Oxide Nanoarrays", and the content of the foregoing prior application is introduced by way of introduction. Incorporated into this text.
  • the invention relates to a stripping transfer method of a large-area metal oxide nano-array, belonging to the field of manufacturing nano-photoelectric devices.
  • Nanostructures such as metal oxide nanorods and nanosheets are arranged vertically, uniformly, and orderly on the base material to form metal oxide nanoarrays. They exhibit excellent performance in various fields such as solar cells, gas sensors, and photocatalysis. .
  • the preparation process of metal oxide nanoarrays on various substrate materials has been quite mature, but the lift-off transfer process of large-area metal oxide nanoarrays still needs to be developed and improved.
  • the simple and rapid stripping transfer of large-area metal oxide nanoarrays is beneficial to simplify the manufacturing process of optoelectronic devices and improve the integration and stability of the devices.
  • the present invention aims to provide a loose operating environment that can make the metal oxide nanoarray (such as the above-mentioned ZnO nanorod array) spontaneously separate from the base material, thereby achieving simple and rapid peeling And the method of transferring metal oxide nano-arrays.
  • the method of the present invention can realize that the metal oxide nano array prepared by the hydrothermal method is separated from the base material in a large area after annealing, so that the large area metal oxide nano array is simply and quickly transferred to the target substrate. No organic resin encapsulation was used in the transfer process, and no other equipment was used.
  • the exfoliation transfer method of the present invention is simpler than any reported method, and can transfer the metal oxide nanoarray to any target substrate, even a curved substrate, so that it is more suitable for large-scale and low-cost manufacturing of nanodevices.
  • the area of the metal oxide nanoarray that can be peeled and transferred is as high as 1 cm 2 .
  • the present invention provides a method for exfoliating and transferring a large-area metal oxide nanoarray, the method including the following steps:
  • the metal oxide nanoarray is peeled off into an organic binder or sol, and a target substrate is selected to pick up the separated metal oxide nanoarray and attach it to the surface of the target substrate.
  • Heat treatment is performed at a temperature of ⁇ 500° C. in an air atmosphere to remove residual organic matter, so as to realize the transfer of the metal oxide nano-array.
  • the hydrothermal precursor solution is prepared by mixing a nitrate solution of the corresponding metal of the metal oxide with an amine solution; wherein the amine solution includes but is not limited to cyclohexamethylenetetramine (HMTA) solution and Urea solution; wherein the substrate material includes but not limited to glass substrate and Si substrate, preferably FTO glass substrate or Si substrate; wherein the organic binder includes but not limited to Triton and terpineol, the sol is The metal oxide corresponds to a metal acetate sol.
  • HMTA cyclohexamethylenetetramine
  • the feature of the present invention is that the metal oxide nanoarray prepared by the hydrothermal method can be spontaneously separated from the substrate material in a large area, and can be easily peeled off into the organic binder or sol after heat treatment, and the target substrate is used for fishing to achieve a large area. Metal oxide nano-arrays are easily and quickly transferred.
  • the advantage of the patent of the present invention is that the present invention can realize the spontaneous separation of the large-area metal oxide nanoarray from the substrate material without the aid of organic resin and special equipment, so that it can be applied to any target substrate. Even transfer on curved substrates. This method is simpler than previously reported methods, making it more suitable for the preparation of large-scale, low-cost nanodevices.
  • FIG. 1 shows the XRD pattern of the ZnO seed layer prepared on the surface of the common glass substrate of Example 1.
  • Example 2 shows the XRD pattern of the ZnO nanorod array grown on the surface of the common glass substrate of Example 1.
  • Fig. 3 shows a photograph of the ZnO nanorod array of Example 1 being peeled off from a common glass substrate.
  • FIG. 4 shows the FESEM image of the ZnO nanorod array transferred to the surface of the curved ceramic tube of Example 1.
  • a layer of ZnO film was prepared by spin coating and annealing on the surface of a common glass substrate with an area of 4 cm 2 and annealed 5 times (Figure 1 shows the XRD pattern of the ZnO film).
  • the ordinary glass substrate spin-coated with the ZnO film was immersed in the hydrothermal precursor solution and kept at 90°C for 4 hours. After the hydrothermal reaction solution is naturally cooled to room temperature, the ordinary glass substrate is taken out, washed with deionized water, and dried.
  • the ordinary glass substrate on which the ZnO nanorod array was grown was annealed at 400°C for 30 minutes. After the temperature dropped to room temperature, it was found that the area of the ZnO nanorod array separated from the ordinary glass substrate increased significantly, up to 1cm 2 ( Figure 3) Shown).
  • the separated ZnO nanorod array is peeled from the glass substrate into the Triton adhesive.
  • the ZnO nanorod array can be bent freely in the Triton adhesive and exhibits good flexibility.
  • a curved ceramic tube is used to retrieve the ZnO nanorod array, and the ZnO nanorod array is spontaneously attached to the curved ceramic tube.
  • the curved ceramic tube is heat-treated at 400°C to realize the transfer of the large-area ZnO nanorod array to the curved ceramic tube.
  • the FESEM image showed that the structure of the ZnO nanorod array transferred to the curved ceramic tube was not damaged.
  • a layer of CuO film was prepared by spin coating-annealing method on the surface of FTO glass substrate with an area of 4 cm 2 by spin coating and annealing 5 times. Prepare 0.2 mol/L Cu(NO 3 ) 2 and 80 ml of HMTA aqueous solution, and mix these two solutions to obtain a hydrothermal precursor solution.
  • the FTO glass substrate spin-coated with CuO film was immersed in the hydrothermal precursor solution and kept at 90°C for 4 hours. After the hydrothermal reaction solution is naturally cooled to room temperature, the FTO glass substrate is taken out, washed with deionized water, and dried.
  • Figures 5 and 6 are the XRD patterns and FESEM images of the CuO nanoarray, respectively.
  • the FTO glass substrate on which the CuO nano-array is grown is annealed at 400° C. for 30 minutes. After the temperature drops to room temperature, it is found that the area of the CuO nano-array separated from the FTO glass substrate is significantly increased, up to 1 cm 2 .
  • the separated CuO nanoarray is peeled from the FTO glass substrate into the terpineol binder, and the CuO nanoarray can be bent freely in the terpineol binder, showing good flexibility.
  • a curved ceramic tube is used to pick up the CuO nano-array, and the CuO nano-array is spontaneously attached to the curved ceramic tube. Finally, the curved ceramic tube is heat-treated at 400°C to realize the transfer of the large-area CuO nano-array to the curved ceramic tube.
  • a layer of NiO film was prepared by spin coating-annealing method on the surface of Si substrate with an area of 4 cm 2 by spin coating and annealing 3 times. Prepare 0.15 mol/L Ni(NO 3 ) 2 and 90 ml of HMTA aqueous solution, and mix these two solutions to obtain a hydrothermal precursor solution.
  • the Si substrate spin-coated with NiO film was immersed in the hydrothermal precursor solution and kept at 90°C for 4 hours. After the hydrothermal reaction solution is naturally cooled to room temperature, the Si substrate is taken out, washed with deionized water, and dried.
  • NiO nanoarray By visually observing the dried Si substrate, it was found that part of the NiO nanoarray was separated from the Si substrate.
  • the phase and morphology of the NiO nanoarray can be known through XRD patterns and FESEM images.
  • the Si substrate on which the NiO nanoarray was grown was annealed at 500°C for 10 minutes. After the temperature dropped to room temperature, it was found that the area of the NiO nanoarray separated from the Si substrate increased significantly, reaching 1cm 2 .
  • the separated NiO nano-array is peeled from the Si substrate into the nickel acetate sol.
  • the NiO nano-array can be bent freely in the nickel acetate sol and exhibits good flexibility. Then, the NiO nano-array is picked up by the flexible polytetrafluoroethylene substrate with interdigital electrodes, and the NiO nano-array is spontaneously attached to the flexible polytetrafluoroethylene substrate.
  • the PTFE flexible substrate is heat-treated at 350°C to realize the transfer of the large-area NiO nano-array to the PTFE flexible substrate.
  • the FESEM image showed that the structure of the NiO nanoarray transferred to the flexible PTFE substrate was not damaged.
  • the spin coating-annealing method was used to spin-coat and anneal 3 times on the surface of a Si substrate with an area of 4 cm 2 to prepare a Co 3 O 4 film.
  • the Si substrate spin-coated with the Co 3 O 4 film was immersed in the hydrothermal precursor solution and kept at 95° C. for 6 hours. After the hydrothermal reaction solution is naturally cooled to room temperature, the Si substrate is taken out, washed with deionized water, and dried.
  • phase and morphology of the Co 3 O 4 nano-array can be known through XRD patterns and FESEM images.
  • the Si substrate on which the Co 3 O 4 nano-array was grown was annealed at 500° C. for 10 minutes. After the temperature dropped to room temperature, it was found that the area of the Co 3 O 4 nano-array separated from the Si substrate was significantly increased, reaching 1 cm 2 .
  • the separated Co 3 O 4 nano-array is peeled from the Si substrate into the cobalt acetate sol.
  • the Co 3 O 4 nano-array can be bent freely in the cobalt acetate sol and exhibits good flexibility.
  • a flexible polytetrafluoroethylene substrate with interdigital electrodes is used to harvest the Co 3 O 4 nano-array, and the Co 3 O 4 nano-array is spontaneously attached to the flexible polytetrafluoroethylene substrate.
  • the flexible polytetrafluoroethylene substrate is heat-treated at 300°C to realize the transfer of the large-area Co 3 O 4 nano-array to the flexible polytetrafluoroethylene substrate.
  • the FESEM image showed that the structure of the Co 3 O 4 nano-array transferred to the flexible polytetrafluoroethylene substrate was not damaged.
  • the beneficial effect of the present invention is that the present invention can realize the simple and rapid peeling and transfer of metal oxide nano-arrays with an area of 1 cm 2 without the aid of organic resins and special instruments and equipment, and can be transferred to curved substrates and flexible substrates. on.
  • This method is simpler than previously reported methods, making it more suitable for the preparation of large-scale, low-cost nanodevices, and is conducive to expanding the assembly form of nanodevices.

Abstract

La présente invention concerne un procédé de transfert de décapage pour un nanoréseau d'oxyde métallique de grande surface comprenant les étapes consistant à : (1) sélectionner un matériau de substrat ayant un taux de désadaptation de constante de maille cristalline supérieur à 5 % et une différence de coefficient de dilatation thermique supérieure à 5*10 -6K par rapport à l'oxyde métallique ; (2) pré-préparer un film de couche de germe d'oxyde métallique sur la surface du matériau de substrat, la température de recuit étant régulée à 200-500 °C ; (3) immerger dans la solution de précurseur hydrothermique le matériau de substrat ayant le film de couche de germe d'oxyde métallique préparé sur sa surface pour effectuer une réaction hydrothermique pour faire croître une couche de nanoréseau d'oxyde métallique sur la surface ; (4) réaliser un traitement thermique sur le nanoréseau d'oxyde métallique préparé à 200-500 °C pour obtenir une séparation du matériau de substrat ; et (5) décaper le nanoréseau d'oxyde métallique dans un liant organique ou un sol, sélectionner un substrat cible, retirer le nanoréseau d'oxyde métallique séparé et fixer celui-ci à la surface du substrat cible, puis réaliser un traitement thermique à 200-500 °C dans une atmosphère d'air pour éliminer les matières organiques résiduelles, de manière à réaliser le transfert du nanoréseau d'oxyde métallique.
PCT/CN2020/123985 2019-12-12 2020-10-27 Procédé de transfert de décapage pour nanoréseau d'oxyde métallique de grande surface WO2021114910A1 (fr)

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CN111056527A (zh) * 2019-12-12 2020-04-24 深圳瀚光科技有限公司 一种大面积金属氧化物纳米阵列的剥离转移方法
CN114369252A (zh) * 2020-10-14 2022-04-19 中国科学院福建物质结构研究所 一种基于自牺牲金属氧化物薄膜模板制备金属-有机框架薄膜的方法

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