WO2021109830A1 - 二维氢氧化镉材料、制备方法、生长模板及应用 - Google Patents

二维氢氧化镉材料、制备方法、生长模板及应用 Download PDF

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WO2021109830A1
WO2021109830A1 PCT/CN2020/128451 CN2020128451W WO2021109830A1 WO 2021109830 A1 WO2021109830 A1 WO 2021109830A1 CN 2020128451 W CN2020128451 W CN 2020128451W WO 2021109830 A1 WO2021109830 A1 WO 2021109830A1
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cadmium
polar solvent
layer
dimensional
fatty acid
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PCT/CN2020/128451
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French (fr)
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吴昊
张阳阳
李江宇
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中国科学院深圳先进技术研究院
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G11/00—Compounds of cadmium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the invention relates to a two-dimensional cadmium hydroxide material, in particular to a two-dimensional cadmium hydroxide material, a preparation method, a growth template and an application.
  • cadmium hydroxide As an indirect band gap semiconductor material with a wide band gap (3.2eV), cadmium hydroxide exhibits special properties in optics and electricity, so it is used in light-emitting diodes, solar cells, bioluminescent probes, and battery anode materials. There are important applications.
  • the two-dimensional material of cadmium hydroxide can be used in electronic devices such as sensors and growth templates for two-dimensional cadmium sulfide and cadmium selenide.
  • cadmium hydroxide is easily decomposed by heat, and CVD and hydrothermal methods cannot be used to prepare two-dimensional materials. Therefore, what is currently disclosed is the preparation of one-dimensional cadmium hydroxide nanomaterials.
  • Chinese invention patent CN101306833B discloses a microwave preparation method of cadmium hydroxide nanomaterials.
  • the cadmium salt is first dissolved in water, ammonia or sodium hydroxide is added to form a clear and transparent cadmium complex ion solution, and then water-insoluble fatty alcohol is added.
  • the cadmium hydroxide nanomaterial can be prepared.
  • the cadmium nanomaterials have a polycrystalline one-dimensional necklace-like structure and are assembled from the secondary structure of hollow spheres.
  • Chinese invention application CN109776831A discloses a rapid preparation method of self-supporting hydroxide film and metal-organic framework film.
  • the preparation method of self-supporting hydroxide film includes the following steps: 1) Under stirring, 1.4 The mM ethanolamine aqueous solution was injected into the same volume of 4 mM copper nitrate, zinc nitrate or cadmium nitrate aqueous solution.
  • Nanowire solution 5 ⁇ 120 mL of nanowire solution is directly suction filtered on a commercial organic phase or water phase microporous membrane to form a 150 ⁇ 800 nm thick nanowire film.
  • the organic phase or water phase microporous membrane The diameter is 10 ⁇ 47 mm, the pore diameter is 220 ⁇ 450 nm, and the porosity is 25 ⁇ 50%;
  • the first object of the present invention is to provide a two-dimensional cadmium hydroxide material, which is a two-dimensional cadmium hydroxide-fatty acid two-dimensional double-layer film.
  • the thickness of the film is only a few nanometers. It is a typical wide band gap semiconductor and can better meet the requirements of electronic devices, Sensor requirements.
  • the first objective of the present invention is achieved through the following technical solutions: a two-dimensional cadmium hydroxide material, the two-dimensional cadmium hydroxide material is a cadmium hydroxide-fatty acid two-dimensional double-layer film, and the cadmium hydroxide-fatty acid two-dimensional double-layer film The thickness of the film is less than or equal to 5 nm.
  • the thickness of the above-mentioned cadmium hydroxide-fatty acid two-dimensional double-layer film is less than 5nm, which is greatly reduced compared with the thickness of the cadmium hydroxide two-dimensional film prepared by the prior art, and an ultra-thin design is realized; the cadmium hydroxide-fatty acid two-dimensional double-layer film
  • the optical band gap of the layer film is 3.5 eV. As a typical wide band gap semiconductor, it can better meet the requirements of electronic devices and sensors, such as being suitable for use as a barrier layer in electronic devices.
  • the present invention is further configured as follows: the thickness of the cadmium hydroxide-fatty acid two-dimensional double-layer film is in the range of 1 to 4 nm;
  • the thickness of the cadmium hydroxide-fatty acid two-dimensional double-layer film is in the range of 3 to 3.4 nm.
  • the present invention is further configured as follows: the cadmium hydroxide-fatty acid two-dimensional double-layer film contains crystal grains, and the crystal phase of the crystal grains is a monoclinic crystal phase.
  • fatty acid cadmium salt is the raw material for synthesizing cadmium hydroxide-fatty acid two-dimensional double-layer membrane, the carbon chain length of the fatty acid group in the fatty acid cadmium salt is 4-30, and the number of unsaturated bonds is 0-28;
  • the fatty acid cadmium salt is cadmium oleate, cadmium eductate, cadmium stearate, cadmium palmitoleate, cadmium arachidonic acid, cadmium eicosapentaenoate, cadmium docosapentaenoate, laurel One or more of cadmium acid.
  • the second objective of the present invention is to provide a method for preparing a two-dimensional cadmium hydroxide material, which is simple, fast and efficient. It not only prepares a large-area two-dimensional cadmium hydroxide double-layer film, but also makes it more suitable Band gap; easy to large-scale industrial production.
  • the second objective of the present invention is achieved through the following technical solutions: a method for preparing a two-dimensional cadmium hydroxide material, including the following steps:
  • the upper layer of the two-phase system solvent is a non-polar solvent layer, and the lower layer is a polar solvent layer;
  • the organic cadmium salt solution gathers at the interface between the non-polar solvent and the polar solvent;
  • the alkaline polar solvent is injected into the lower polar solvent to form a two-dimensional cadmium hydroxide double-layer film; when the alkaline polar solvent is added, the temperature of the polar solvent layer is less than 150°C.
  • the organic cadmium salt at the interface of the organic cadmium salt aggregates into a film as the volume of the non-polar solvent decreases, and floats on the liquid surface of the polar solvent layer.
  • the organic cadmium salt is combined with the OH in the alkaline polar solvent.
  • the reaction produces a two-dimensional cadmium hydroxide double-layer film, which can produce a large-area nanometer-level two-dimensional cadmium hydroxide double-layer film; when alkaline polar solvents are added, the temperature of the polar solvent layer is less than 150°C, that is It is less than the decomposition temperature of cadmium hydroxide, which can ensure that the resulting film is a two-dimensional cadmium hydroxide double-layer film; the entire preparation method is simple, fast and efficient, and can better control the thickness of the film and prepare an ultra-thin large area The two-dimensional cadmium hydroxide double-layer film; the preparation cost is low, and it is easy for large-scale industrial production.
  • the present invention is further configured as follows: the thickness of the two-dimensional cadmium hydroxide double-layer film is less than or equal to 5 nm; the boiling point of the non-polar solvent layer under the air pressure at which the non-polar solvent layer located on the upper layer is evaporated is less than the boiling point of the organic cadmium salt solution, and Smaller than the non-polar solvent layer.
  • the present invention is further configured that: during the process of evaporating the non-polar solvent layer located on the upper layer, the evaporation temperature is room temperature to 80°C.
  • the low evaporation temperature helps reduce energy consumption, and the process is easier to control, less likely to cause pollution, and is more conducive to industrial production.
  • the organic cadmium salt solution includes fatty acid cadmium salt and a pre-dissolved non-polar solvent, the carbon chain length of the fatty acid group is 4-30, and the number of unsaturated bonds is 0-28.
  • fatty acid cadmium salt is more environmentally friendly and economical, and has better complete solubility with pre-dissolved non-polar solvents, so that fatty acid cadmium salts can better accumulate at the interface between non-polar solvents and polar solvents; and fatty acid-based carbon
  • the chain length can establish a larger hydrophobic group and limit the upper limit of the unsaturated bond.
  • the appropriate carbon chain length of the fatty acid group can prevent the organic cadmium salt from being evaporated during the evaporation of the non-polar solvent layer and is beneficial to the polarity of the organic cadmium salt. Orderly arrangement on the liquid surface of the solvent layer.
  • the present invention is further configured as follows: the amount of organic cadmium salt in the organic cadmium salt solution is positively correlated with the liquid surface area of the non-polar solvent layer, which conforms to: the volume of the organic cadmium salt solution is nS ⁇ 5 ⁇ 10 -10 /c 1 m 3 ;
  • the formation of the two-dimensional cadmium hydroxide double-layer film can be better ensured, and the ultra-high performance of the two-dimensional cadmium hydroxide double-layer film can be achieved. Thin design and not easy to break, higher integrity.
  • the formation of the two-dimensional cadmium hydroxide double-layer film can be better guaranteed, and the ultra-thin design of the two-dimensional cadmium hydroxide double-layer film is not easy. Fracture, higher integrity.
  • the organic cadmium salt has a hydrophobic group, which is raised on the liquid surface of the polar solvent layer after evaporating the non-polar solvent layer; or/and, the organic cadmium salt has a hydrophilic group.
  • the water group is relatively close to or sinks to the liquid surface of the polar solvent layer after evaporating the non-polar solvent layer.
  • the cadmium in the organic cadmium salt can be better placed at the interface between the non-polar solvent layer and the polar solvent layer, and it is easier to react with the OH - in the polar solvent, while ensuring two-dimensional The stability of cadmium hydroxide double-layer film.
  • the present invention is further configured to include: attaching a two-dimensional cadmium hydroxide double-layer film on the surface of the substrate.
  • the operation of attaching the two-dimensional cadmium hydroxide double-layer film to the surface of the substrate is simple and efficient, and the two-dimensional cadmium hydroxide double-layer film is not easy to break during the attaching process, and the two-dimensional cadmium hydroxide can be double-layered in a large area. Layers of film adhere to the substrate, which is convenient for post-processing and use.
  • the present invention is further configured to insert the substrate vertically below the liquid surface of the polar solvent, and then lift it obliquely to obtain a two-dimensional cadmium hydroxide double-layer film attached to the substrate.
  • the above-mentioned operation method is simple, and can better maintain the integrity of the two-dimensional cadmium hydroxide double-layer film, and does not affect the preparation of the two-dimensional cadmium hydroxide double-layer film in the early stage.
  • the organic cadmium salt is selected from the group consisting of cadmium oleate, cadmium eductate, cadmium stearate, cadmium palmitoleate, cadmium arachidonic acid, cadmium eicosapentaenoate, and cadmium eicosapentaenoate.
  • the non-polar solvent layer is selected from toluene and its homologues, acetone and its homologues, chloroform and its analogues, n-hexane, One or more of a combination of non-polar solvents having a density lower than that of the polar solvent layer; the polar solvent layer is selected from one or more of a combination of water and amides.
  • the organic cadmium salt, the non-polar solvent layer and the polar solvent layer in specific ranges, the two phases with the polar solvent layer in the lower layer and the non-polar solvent layer in the upper layer can be realized.
  • System solvent, and the specific realization that the organic cadmium salt solution can dissolve into the non-polar solvent layer is obtained.
  • the present invention is further configured to include the steps of: after the organic cadmium salt solution is dissolved in the non-polar solvent layer on the upper layer and before the step of evaporating the non-polar solvent layer on the upper layer, The two-phase system solvent is left standing and waiting to clearly separate the non-polar solvent layer and the polar solvent layer;
  • the step of evaporating the non-polar solvent layer on the upper layer includes completely evaporating the non-polar solvent layer
  • step of injecting the alkaline polar solvent into the lower polar solvent should be performed after the step of completely volatilizing the non-polar solvent layer;
  • the non-polar solvent layer and the polar solvent layer are clearly separated and then evaporated, which can further reduce the impact on the polar solvent layer during the evaporation process; the organic cadmium salt has a better aggregation effect after the non-polar solvent layer is completely volatilized. Injecting the alkaline polar solvent into the lower polar solvent, the reaction is more smooth and rapid, and the formed two-dimensional cadmium hydroxide double-layer film is better formed, more stable, and not easy to break.
  • the second objective of the present invention is to provide a growth template for forming a large area of two-dimensional cadmium hydroxide on a substrate, including the two-dimensional cadmium hydroxide-fatty acid two-dimensional double-layer film or the two-dimensional cadmium hydroxide double-layer film described in the above solution.
  • the growth template can be used to grow two-dimensional cadmium sulfide and cadmium selenide.
  • the third objective of the present invention is to provide the application of the two-dimensional cadmium hydroxide double-layer film prepared by the method for preparing the two-dimensional cadmium hydroxide material in the above solution in electronic devices.
  • the present invention includes at least one of the following beneficial technical effects:
  • the thickness of the cadmium hydroxide-fatty acid two-dimensional double-layer film is less than 5nm, which is greatly reduced compared with the thickness of the cadmium hydroxide two-dimensional film prepared by the prior art, and realizes an ultra-thin design.
  • the optical band gap of the cadmium hydroxide-fatty acid two-dimensional double-layer film is 3.5 eV.
  • a typical wide band gap semiconductor it can better meet the requirements of electronic devices and sensors, such as being suitable for use as a barrier layer in electronic devices.
  • the preparation method is simple, fast and efficient. It not only produces a large area of monoclinic cadmium hydroxide-fatty acid two-dimensional double-layer film; it also has a more suitable band gap; it also saves time, energy and is environmentally friendly. , Low preparation cost and easy to large-scale industrial production.
  • the non-polar solvent layer and the polar solvent layer do not participate in the reaction, and can be recycled and used repeatedly to reduce manufacturing costs, and it is more environmentally friendly and energy-saving.
  • the substrate After reacting for 1 to 36 hours, the substrate is vertically inserted into the water surface, and then lifted obliquely to obtain a two-dimensional cadmium hydroxide-fatty acid bilayer film attached to the substrate; this two-dimensional material transfer strategy ensures the liquid surface
  • the grown two-dimensional material can be transferred to any substrate for use.
  • a growth template containing cadmium hydroxide-fatty acid two-dimensional double-layer film can be prepared for the growth of two-dimensional cadmium sulfide and cadmium selenide.
  • Dissolve (1 ⁇ 1000) ⁇ nS ⁇ 5 ⁇ 10 -11kg of soluble alkali in a polar solvent to prepare an alkaline solution.
  • the alkaline is injected into the polar solvent in the lower layer; also, the concentration of the precursor is controlled to ensure that the target product is a two-dimensional material with a single layer or a few layers.
  • V is the volume of the container, a volume of polar solvent added V-pole, lower density and a volatile added over a polar solvent, a non-volume V
  • V pole ⁇ V, V non ⁇ V, V pole + V non ⁇ V not only makes the non-polar solvent easy to volatilize, but also Make the preparation process easier to implement and flexible.
  • FIG. 1 is a schematic flow diagram of a method for preparing a two-dimensional cadmium hydroxide material according to a preferred embodiment of the present invention
  • Figure 2 is an AFM image of the cadmium hydroxide/fatty acid two-dimensional double-layer film produced in Experimental Example 1 characterized by an atomic force microscope (AFM);
  • Fig. 3 is one of the results of using transmission electron microscopy (TEM) to characterize the cadmium hydroxide/fatty acid two-dimensional double-layer film prepared in Experimental Example 1.
  • Figure 3a is a transmission electron microscopy (TEM) image of a cadmium hydroxide/fatty acid two-dimensional double-layer membrane;
  • Figure 3b is a TEM image of a cadmium hydroxide/fatty acid two-dimensional double-layer membrane after tearing;
  • Figure 3c is a cadmium hydroxide/fatty acid two-dimensional double-layer membrane.
  • TEM transmission electron microscopy
  • Figure 4a is a scanning electron microscope (SEM) image of a cadmium hydroxide/fatty acid two-dimensional double-layer film prepared in Experimental Example 1;
  • 4b is a metallurgical microscope image of the cadmium hydroxide/fatty acid two-dimensional double-layer film prepared in Experimental Example 1;
  • Figure 5 is one of the results of characterizing the prepared target product using an ultraviolet-visible spectrophotometer.
  • Fig. 5a is the light absorption curve of the target product and the smoothed curve
  • Fig. 5b is calculated by using the smoothed curve to obtain the optical band gap of the target product as 3.5 eV.
  • the first embodiment of the present invention discloses a two-dimensional cadmium hydroxide material.
  • the two-dimensional cadmium hydroxide material is a cadmium hydroxide-fatty acid two-dimensional double-layer film, and the thickness of the cadmium hydroxide-fatty acid two-dimensional double-layer film is less than or equal to 5 nm.
  • the thickness of the cadmium hydroxide-fatty acid two-dimensional double-layer film is in the range of 1 to 4 nm; further, the thickness of the cadmium hydroxide-fatty acid two-dimensional double-layer film is in the range of 3 to 3.4 nm.
  • the cadmium hydroxide-fatty acid two-dimensional double-layer film contains crystal grains, and the crystal phase of the crystal grains is a monoclinic crystal phase.
  • Fatty acid cadmium salt is the raw material for the synthesis of cadmium hydroxide-fatty acid two-dimensional double-layer film.
  • the fatty acid group in the fatty acid cadmium salt has a carbon chain length of 4-30, and the number of unsaturated bonds is 0-28; in a preferred embodiment , Fatty acid cadmium salts are cadmium oleate, cadmium oleate, cadmium stearate, cadmium palmitoleate, cadmium arachidonic acid, cadmium eicosapentaenoate, cadmium docosapentaenoate, cadmium laurate One or more of.
  • the second embodiment of the present invention discloses a preparation method of a two-dimensional cadmium hydroxide material, as shown in FIG. 1, including the following steps:
  • the upper layer of the two-phase system solvent is a non-polar solvent layer, and the lower layer is a polar solvent layer;
  • the organic cadmium salt solution gathers at the interface between the non-polar solvent and the polar solvent;
  • steps S1 and S2 are not specifically limited and can be exchanged.
  • the implementation principle of this embodiment is: the organic cadmium salt at the interface of the organic cadmium salt aggregates into a film as the volume of the non-polar solvent decreases, and floats on the liquid surface of the polar solvent layer, and the organic cadmium salt is combined with the alkaline polar solvent.
  • a two-dimensional cadmium hydroxide double-layer film is formed, which can produce a large-area nanometer-level two-dimensional cadmium hydroxide double-layer film; when alkaline polar solvents are added, the temperature of the polar solvent layer is less than 150°C , which is less than the decomposition temperature of cadmium hydroxide, which can ensure that the resulting film is a two-dimensional cadmium hydroxide double-layer film.
  • the possible thickness of the two-dimensional cadmium hydroxide double-layer film is less than or equal to 5 nm.
  • the thickness of the two-dimensional cadmium hydroxide double-layer film is in the range of 1 to 4 nm; preferably, the two-dimensional cadmium hydroxide-fatty acid
  • the thickness of the double-layer film ranges from 3 to 3.4 nm.
  • the formation reaction of the two-dimensional cadmium hydroxide double-layer film is on the liquid surface of the polar solvent layer and has an ultra-thin film thickness. Therefore, the thickness of the two-dimensional cadmium hydroxide double-layer film is controlled by the interface of the two-phase system solvent. Break through the existing preparation method to generate a two-dimensional cadmium hydroxide double-layer film with nano-level film thickness.
  • the organic cadmium salt solution includes a fatty acid cadmium salt and a pre-dissolved non-polar solvent, the carbon chain length of the fatty acid group is 4-30, and the unsaturated bond is The number is 0-28.
  • the organic cadmium salt is selected from the group consisting of cadmium oleate, cadmium oleate, cadmium stearate, cadmium palmitole, One or more of cadmium arachidonic acid, cadmium eicosapentaenoate, cadmium docosapentaenoate, and cadmium laurate;
  • the non-polar solvent layer is selected from toluene and its homologs, One or more of the combination of acetone and its homologues, chloroform and its analogues, n-hexane, and non-polar solvents with a density lower than the polar solvent layer;
  • the polar solvent layer is selected from water and amides One or more of the combinations.
  • the organic cadmium salt, the non-polar solvent layer and the polar solvent layer in specific ranges, the two phases with the polar solvent layer in the lower layer and the non-polar solvent layer in the upper layer can be realized.
  • System solvent, and the specific realization that the organic cadmium salt solution can dissolve into the non-polar solvent layer is obtained.
  • the amount of organic cadmium salt in the organic cadmium salt solution is positively correlated with the liquid surface area of the non-polar solvent layer, which conforms to:
  • the two-dimensional cadmium hydroxide can be better guaranteed
  • the formation of the double-layer film realizes the ultra-thin design of the two-dimensional cadmium hydroxide double-layer film, which is not easy to break and has a higher integrity.
  • the boiling point of the non-polar solvent layer under the air pressure of the non-polar solvent layer located on the upper layer is less than the boiling point of the organic cadmium salt solution and less than the non-polar solvent layer. ⁇ solvent layer.
  • the evaporation temperature in the process of evaporating the non-polar solvent layer located on the upper layer is from room temperature to 80°C. The low evaporation temperature helps reduce energy consumption, and the process is easier to control, less likely to cause pollution, and is more conducive to industrial production.
  • the organic cadmium salt has a hydrophobic group, which is raised on the liquid surface of the polar solvent layer after evaporating the non-polar solvent layer Or/and, the organic cadmium salt has a hydrophilic group, which is relatively close to or sinks to the liquid surface of the polar solvent layer after evaporating the non-polar solvent layer. It can better let the cadmium in the organic cadmium salt be at the interface of the non-polar solvent layer and the polar solvent layer, and it is easier to react with the OH - in the polar solvent, while ensuring the two-dimensional cadmium hydroxide double-layer film stability.
  • the preparation method of the two-dimensional cadmium hydroxide material further includes S6 adhering the two-dimensional cadmium hydroxide double-layer film on the surface of the substrate.
  • the operation of attaching the two-dimensional cadmium hydroxide double-layer film to the surface of the substrate is simple and efficient, and the two-dimensional cadmium hydroxide double-layer film is not easy to break during the attaching process, and the two-dimensional cadmium hydroxide can be double-layered in a large area. Layers of film adhere to the substrate, which is convenient for post-processing and use.
  • the substrate is vertically inserted below the surface of the polar solvent, and then lifted obliquely to obtain a two-dimensional cadmium hydroxide double-layer film attached to the substrate, which can better maintain the two-dimensional cadmium hydroxide double-layer film.
  • the integrity of the film does not affect the preparation of the two-dimensional cadmium hydroxide double-layer film in the early stage.
  • the forming method further includes the following steps: after step S3, before step S4, the two-phase system solvent is left to stand and wait , In order to clearly separate the non-polar solvent layer and the polar solvent layer; in step S4, after the step of completely volatilizing the non-polar solvent layer, step S5 is performed to inject the alkaline polar solvent into the lower layer In the polar solvent; and in step S5, after the alkaline polar solvent is injected into the lower polar solvent, the two-dimensional cadmium hydroxide double-layer film floating on the surface of the polar solvent is transferred after standing for 1 to 36 hours.
  • the non-polar solvent layer and the polar solvent layer are clearly separated and then evaporated, which can further reduce the impact on the polar solvent layer during the evaporation process; the organic cadmium salt has a better aggregation effect after the non-polar solvent layer is completely volatilized. Injecting the alkaline polar solvent into the lower polar solvent, the reaction is more smooth and rapid, and the formed two-dimensional cadmium hydroxide double-layer film is better formed, more stable, and not easy to break.
  • the third embodiment of the present invention discloses a growth template for forming two-dimensional cadmium hydroxide on a large area on a substrate, including the two-dimensional cadmium hydroxide-fatty acid two-dimensional bilayer film or the two-dimensional cadmium hydroxide bilayer described in the above solution. membrane.
  • the growth template can be used to grow two-dimensional cadmium sulfide and cadmium selenide.
  • the fourth embodiment of the present invention discloses the application of the two-dimensional cadmium hydroxide double-layer film prepared by the preparation method of the two-dimensional cadmium hydroxide material in the above scheme in electronic devices.
  • the fifth embodiment of the present invention provides a low-cost preparation method of a monoclinic cadmium hydroxide-fatty acid two-dimensional double-layer film on any substrate, including a wet chemical method, in particular, the main steps are as follows:
  • Step 1 cadmium fatty acid salt is dissolved in a nonpolar solvent, to give the concentration of cadmium salt of a fatty acid solution c 1.
  • concentration of cadmium salt of a fatty acid solution c 1 3 ⁇ 40 ⁇ 10 -8kg /m 3
  • the carbon chain length of fatty acid cadmium is 4-30
  • the number of unsaturated bonds is 0-28.
  • Step 2 the area S (unit is m 2), V is the volume of a container, the polar solvent is added to the volume V of electrode. Over a lower density and a polar solvent volatile, non-polar solvent volume of Non-V. A two-phase system in which the upper layer is a non-polar solvent and the lower layer is a polar solvent is obtained. Wherein, V polar ⁇ V, V non ⁇ V, V + V non-polar ⁇ V.
  • Step 4 Dissolve (1 ⁇ 1000) ⁇ nS ⁇ 5 ⁇ 10 -11kg of soluble alkali in a polar solvent to prepare an alkaline solution. After the non-polar solvent in the upper layer of the two-phase solution system in step 3 is completely volatilized, the alkaline polar solvent is injected into the polar solvent in the lower layer.
  • Step 5 After 1 to 36 hours, the substrate is vertically inserted into the water surface, and then lifted obliquely to obtain a two-dimensional cadmium hydroxide-fatty acid double-layer film attached to the substrate.
  • the number of saturated bonds is 0-28; the concentration of the precursor is controlled to ensure that the target product is a two-dimensional material with a single layer or a few layers.
  • V the volume of the container, the volume of a polar solvent is added V-pole, was added over a smaller density and a volatile polar solvent, a volume V of a non-non-polar solvent ,
  • V pole ⁇ V, V non ⁇ V, V pole + V non ⁇ V the upper layer is a non-polar solvent and the lower layer is a polar solvent, where V pole ⁇ V, V non ⁇ V, V pole + V non ⁇ V; not only makes the non-polar solvent easy to volatilize, but also makes the preparation The process is easier to implement and flexible.
  • the substrate After 1 to 36 hours, the substrate is vertically inserted into the water surface, and then lifted obliquely to obtain a two-dimensional cadmium hydroxide-fatty acid two-dimensional double-layer film attached to the substrate; this two-dimensional material transfer strategy ensures that the two layers grow on the liquid surface.
  • the dimensional material can be transferred to any substrate for use.
  • the prepared target products were characterized by atomic force microscope, transmission electron microscope scanning electron microscope, and metallographic microscope. The results show that the target product is large area, good uniformity, and thickness of 3.0-3.4nm. Cadmium hydroxide-fatty acid two-dimensional double-layer film, the crystal phase is monoclinic.
  • the prepared target product was characterized by an ultraviolet-visible spectrophotometer. From the results, it can be seen that the optical band gap of the target product is 3.5 eV, which is a typical wide band gap semiconductor and is suitable for use as a barrier layer in electronic devices. .
  • the preparation method is simple, fast, and efficient. It not only prepares a large area of monoclinic cadmium hydroxide-fatty acid two-dimensional double-layer film; it also has a relatively suitable band gap; it also saves time, energy and is green.
  • 1-5 grams of industrial grade fatty acid cadmium can prepare more than 100 square meters of cadmium hydroxide-fatty acid two Dimensional double-layer membrane has huge economic benefits.
  • Volatile non-polar solvent as the target substrate after the two-dimensional material is transferred from the liquid surface, it is purchased from the market or prepared by conventional methods.
  • Test Example 1 The specific steps for the preparation of Test Example 1 are:
  • Step 1 cadmium fatty acid salt is dissolved in a nonpolar solvent, to give the concentration of cadmium salt of a fatty acid solution c 1.
  • c 1 16 ⁇ 10 -8kg /m 3
  • the fatty acid cadmium is cadmium oleate
  • the non-polar solvent is toluene.
  • Step 4 Dissolve (1 ⁇ 1000) ⁇ nS ⁇ 5 ⁇ 10 -11kg of soluble alkali in a polar solvent to prepare an alkaline solution.
  • the alkaline polar solvent is injected into the polar solvent in the lower layer.
  • the polar solvent is water
  • the non-polar solvent is toluene
  • the soluble base is sodium hydroxide
  • Step 5 After 1 to 36 hours, the substrate is vertically inserted into the water surface, and then lifted obliquely to obtain a two-dimensional cadmium hydroxide-fatty acid double-layer film attached to the substrate. Among them, 1 to 36 hours is 30 hours. A large area of cadmium hydroxide-fatty acid two-dimensional double-layer film with monoclinic cadmium hydroxide crystal grains is prepared.
  • the target product obtained by the above preparation method is a uniform two-dimensional material with a thickness of 3.2 nm.
  • the target product obtained by the above preparation method is a stable film-like structure.
  • the TEM image of Figure 3b an obvious two-dimensional cadmium hydroxide/fatty acid double-layer membrane structure can be observed.
  • the layer shown in Figure 3a is an inorganic layer formed by cadmium hydroxide, and an organic layer formed by fatty acids can be seen after tearing.
  • the present invention also performs EDS analysis on the target product, and the specific analysis location is the part of the frame in Figure 3b.
  • the test results are shown in the following table:
  • Si originates from the TEM probe
  • Cu originates from the sample copper carrier net
  • N originates from nitrogen in the air
  • C, H, O which proves that the transparent film is an organic fatty acid film, thus confirming that the product is Cadmium hydroxide/fatty acid two-dimensional double-layer membrane.
  • Figure 3c is a high-resolution transmission electron microscope image of the target product, combined with the electron diffraction spot pattern of the target product in Figure 3d, which is consistent with the standard electron diffraction spot of monoclinic cadmium hydroxide in Figure 3e, which proves that the target product is monoclinic hydrogen.
  • Cadmium oxide is a high-resolution transmission electron microscope image of the target product, combined with the electron diffraction spot pattern of the target product in Figure 3d, which is consistent with the standard electron diffraction spot of monoclinic cadmium hydroxide in Figure 3e, which proves that the target product is monoclinic hydrogen.
  • Cadmium oxide Cadmium oxide.
  • the lighter part in the upper left of the TEM image of Fig. 4a is a two-dimensional cadmium hydroxide/fatty acid two-dimensional double-layer film, and the darker part on the lower right is a silica substrate; the metallographic microscope photo of Fig. 4b, the lower part is darker It is a cadmium hydroxide/fatty acid two-dimensional double-layer film, and the upper part with a lighter color is a silica substrate.
  • Figure 4 shows that the target product is a uniform two-dimensional material with a large area.
  • Figure 5 is one of the results of characterizing the prepared target product using an ultraviolet-visible spectrophotometer.
  • Figure 5 shows that the optical band gap of the target product is 3.5 eV, indicating that the target product is a wide band gap semiconductor, and its band gap is suitable for use as an insulating layer in an electronic device.
  • Test Example 2 The specific steps for the preparation of Test Example 2 are:
  • Step 1 cadmium fatty acid salt is dissolved in a nonpolar solvent, to give the concentration of cadmium salt of a fatty acid solution c 1.
  • concentration of cadmium salt of a fatty acid solution c 1 32 ⁇ 10 -8kg /m 3
  • the fatty acid cadmium is cadmium oleate
  • the non-polar solvent is toluene.
  • Step 4 Dissolve (1 ⁇ 1000) ⁇ nS ⁇ 5 ⁇ 10 -11kg of soluble alkali in a polar solvent to prepare an alkaline solution.
  • the alkaline polar solvent is injected into the polar solvent in the lower layer.
  • the polar solvent is water
  • the non-polar solvent is toluene
  • the soluble base is sodium hydroxide
  • Step 5 After 1 to 36 hours, the substrate is vertically inserted into the water surface, and then lifted obliquely to obtain a two-dimensional cadmium hydroxide-fatty acid double-layer film attached to the substrate. Among them, 1 to 36 hours is 6 hours. A large-area cadmium hydroxide-fatty acid two-dimensional double-layer film with monoclinic cadmium hydroxide crystal grains similar to those shown in Figs. 2, 3, and 4 and whose properties are shown in Fig. 5 was prepared.
  • Test Example 3 The specific steps for the preparation of Test Example 3 are:
  • Step 1 cadmium fatty acid salt is dissolved in a nonpolar solvent, to give the concentration of cadmium salt of a fatty acid solution c 1.
  • concentration of cadmium salt of a fatty acid solution c 1 20 ⁇ 10 -8kg /m 3
  • the fatty acid cadmium is cadmium stearate
  • the non-polar solvent is chloroform.
  • Step 4 Dissolve (1 ⁇ 1000) ⁇ nS ⁇ 5 ⁇ 10 -11kg of soluble alkali in a polar solvent to prepare an alkaline solution. After the non-polar solvent in the upper layer of the two-phase solution system in step 3 is completely volatilized, the alkaline polar solvent is injected into the polar solvent in the lower layer.
  • the polar solvent is water, and the soluble base is potassium hydroxide.
  • Step 5 After 1 to 36 hours, the substrate is vertically inserted into the water surface, and then lifted obliquely to obtain a two-dimensional cadmium hydroxide-fatty acid double-layer film attached to the substrate. Among them, 1 to 36 hours is 3 hours. A large-area cadmium hydroxide-fatty acid two-dimensional double-layer film with monoclinic cadmium hydroxide crystal grains similar to those shown in Figs. 2, 3, and 4 and whose properties are shown in Fig. 5 was prepared.
  • Test Example 4 The specific steps for the preparation of Test Example 4 are:
  • Step 1 cadmium fatty acid salt is dissolved in a nonpolar solvent, to give the concentration of cadmium salt of a fatty acid solution c 1.
  • concentration of cadmium salt of a fatty acid solution c 1 40 ⁇ 10 -8kg /m 3
  • the fatty acid cadmium is cadmium palmitoleate
  • the non-polar solvent is acetone.
  • Step 4 Dissolve (1 ⁇ 1000) ⁇ nS ⁇ 5 ⁇ 10 -11kg of soluble alkali in a polar solvent to prepare an alkaline solution.
  • the alkaline polar solvent is injected into the polar solvent in the lower layer.
  • Step 5 After 1 to 36 hours, the substrate is vertically inserted into the water surface, and then lifted obliquely to obtain a two-dimensional cadmium hydroxide-fatty acid double-layer film attached to the substrate. Among them, 1 to 36 hours is 8 hours. A large-area cadmium hydroxide-fatty acid two-dimensional double-layer film with monoclinic cadmium hydroxide crystal grains similar to those shown in Figs. 2, 3, and 4 and whose properties are shown in Fig. 5 was prepared.
  • Test Example 5 The specific steps for the preparation of Test Example 5 are:
  • Step 1 to obtain fatty acid cadmium salt is dissolved in a nonpolar solvent in a concentration of c 1 fatty acid cadmium salt solution.
  • c 1 10 ⁇ 10 -8kg /m 3
  • the fatty acid cadmium is cadmium arachidonic acid
  • the non-polar solvent is n-hexane.
  • Step 2 the area S (unit is m 2), V is the volume of a container, the polar solvent is added to the volume V of electrode. Over a lower density and a polar solvent volatile, non-polar solvent volume of Non-V. A two-phase system in which the upper layer is a non-polar solvent and the lower layer is a polar solvent is obtained.
  • Step 4 Dissolve (1 ⁇ 1000) ⁇ nS ⁇ 5 ⁇ 10 -11kg of soluble alkali in a polar solvent to prepare an alkaline solution.
  • the alkaline polar solvent is injected into the polar solvent in the lower layer.
  • the polar solvent is formamide
  • the soluble base is ammonia
  • (1 ⁇ 1000) is 1000
  • Step 5 After 1 to 36 hours, the substrate is vertically inserted into the water surface, and then lifted obliquely to obtain a two-dimensional cadmium hydroxide-fatty acid double-layer film attached to the substrate. Among them, 1 to 36 hours is 2 hours. A large-area cadmium hydroxide-fatty acid two-dimensional double-layer film with monoclinic cadmium hydroxide crystal grains similar to those shown in Figs. 2, 3, and 4 and whose properties are shown in Fig. 5 was prepared.
  • fatty acid cadmium with a carbon chain length of 4-30 and the number of unsaturated bonds 0-28, such as cadmium eicosapentaenoate, cadmium docosapentaenoate or cadmium laurate as the source of cadmium.
  • Fatty acid cadmium concentration c 1 select 12 ⁇ 10 -8kg /m 3 , 25 ⁇ 10 -8kg /m 3 or 30 ⁇ 10 -8kg /m 3 , choose formamide as polar solvent, choose n-hexane as non-polar solvent, soluble Sodium hydroxide, potassium hydroxide or ammonia water is selected for alkali, S, V pole , V non , n, T, (1 ⁇ 1000) and 1 ⁇ 36 hours to take any value that meets the actual production and the requirements of this patent, repeat the above implementation In Examples 1 to 5, large-area monoclinic phase two-dimensional cadmium hydroxide with properties as shown in or similar to those shown in Figure 2, Figure 3 and Figure 4 and the properties of Figure 5 were also prepared.

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Abstract

一种二维氢氧化镉材料、制备方法、生长模板及应用。二维氢氧化镉材料是氢氧化镉-脂肪酸二维双层膜，膜的厚度小于等于5nm。制备方法包括如下步骤：制备有机镉盐溶液；提供两相体系溶剂，两相体系溶剂的上层为非极性溶剂层，下层为极性溶剂层；有机镉盐溶液聚集于非极性溶剂与极性溶剂的界面处；蒸发位于上层的所述非极性溶剂层，使有机镉盐随非极性溶剂体积减小而聚集成膜，漂浮于极性溶剂层的液面；将碱性极性溶剂注入下层的温度小于150℃的极性溶剂中，生成二维氢氧化镉双层膜。氢氧化镉-脂肪酸二维双层膜能用于生长二维硫化镉和硒化镉的生长模板以及电子器件的应用；制备方法简便、高效，易于工业化生产。

Description

二维氢氧化镉材料、制备方法、生长模板及应用 技术领域
本发明涉及一种二维氢氧化镉材料，尤其是二维氢氧化镉材料、制备方法、生长模板及应用。
 背景技术
自发现石墨烯以来，二维材料因其独特的电学、光学、磁学和机械性能及其在纳米器件构造中的潜在应用而备受关注，探索大面积、单层或少层的二维材料一直是研究的热点。相关科研人员和技术人员在二维材料的制备方面已经做了很多的尝试，其中化学气相沉积（CVD）、机械剥离、水热法等是普遍采用的二维材料制备方法。然而，机械剥离和水热法无法制备出大面积的二维材料；而化学气相沉积虽然在近期发展迅速，已经可以制备出大面积、高质量的二维材料，但其高昂的成本是其产业化的巨大障碍。
另外，对于大量的高温不稳定材料，如受热易分解的材料以及各种亚稳相等，都不能采用CVD和水热法制备二维材料。
氢氧化镉作为一种宽禁带（3.2eV）的间接带隙半导体材料，在光学和电学中表现出特殊的性能，因此使其在发光二极管、太阳能电池、生物荧光探针和电池负极材料中有重要的应用。氢氧化镉的二维材料更是可以用于传感器等电子器件以及二维硫化镉和硒化镉的生长模板等。但是氢氧化镉受热易分解，不能采用CVD和水热法制备二维材料。因此目前公开的都是制备一维的氢氧化镉纳米材料。
中国发明专利CN1297483C公开了一种氢氧化镉单晶纳米线的合成方法，按如下步骤进行：a.先将可溶性镉盐溶解在去离子水中，再缓慢加入碱溶液至pH值为10～14，搅拌下生成白色Cd(OH) 2沉淀；b.将白色Cd(OH) 2沉淀离心洗涤至pH值为中性；c.将洗涤后的白色Cd(OH) 2沉淀重新分散在去离子水中，按可溶性镉盐∶无机盐矿化剂＝0.001mol∶0.3克的比例加入无机盐矿化剂；d、放入密闭容器中于200～250℃下水热反应10～15小时，得氢氧化镉单晶纳米线。
中国发明专利CN101306833B公开了一种氢氧化镉纳米材料的微波制备方法，先将镉盐溶解于水中，加入氨水或氢氧化钠形成澄清透明的镉络合离子溶液，然后加入不溶于水的脂肪醇，以脂肪醇—水界面体系为反应介质，采用微波辐照技术，控制微波功率和反应时间，并加入表面活性剂改变产物的尺寸和形貌，即可制备出氢氧化镉纳米材料，氢氧化镉纳米材料呈多晶一维项链状结构，且由空心球的次级结构组装而成。
上述技术方案都是得到了氢氧化镉的一维结构，未得到氢氧化镉的二维材料。还有一些虽然能够能到氢氧化镉的薄膜，但是薄膜的厚度很厚，无法满足电子器件、传感器的要求。
中国发明申请CN109776831A公开了一种自支撑氢氧化物薄膜和金属有机骨架薄膜的快速制备方法，自支撑氢氧化物薄膜的制备方法包括如下步骤：1）在搅拌下，将1.4 mM乙醇胺水溶液注入到同体积的4 mM硝酸铜、硝酸锌或者硝酸镉水溶液中，1分钟后，将反应容器密封置于60℃烘箱中1小时，获得氢氧化铜、氢氧化锌或者氢氧化镉纳米线溶液，将纳米线溶液5∼120 mL直接抽滤在商用有机相或者水相微孔滤膜上形成一层150∼800 nm厚的纳米线薄膜，有机相或者水相微孔滤膜的直径为10∼47 mm，孔径为220∼450 nm，孔隙率25∼50%；
2）将负载氢氧化物纳米线薄膜的微孔滤膜在60∼120℃环境下烘烤5∼20分钟，而后迅速在水、乙醇、丙酮、N,N-二甲基甲酰胺中的一种或多种混合的溶液的表面冷却下层微孔滤膜致使上层材料薄膜自动脱离下层微孔滤膜，最终得到自支撑氢氧化物薄膜。上述方案的制得的自支撑氢氧化物薄膜为150∼800nm，无法满足电子器件、传感器的要求。
 技术问题
本发明的目的一是提供一种二维氢氧化镉材料，是氢氧化镉-脂肪酸二维双层膜，膜的厚度只有几纳米，是典型的宽带隙半导体，能够更好的满足电子器件、传感器的要求。
 技术解决方案
本发明的目的一是通过以下技术方案得以实现的：一种二维氢氧化镉材料，二维氢氧化镉材料是氢氧化镉-脂肪酸二维双层膜，氢氧化镉-脂肪酸二维双层膜的厚度小于等于5nm。
上述氢氧化镉-脂肪酸二维双层膜的厚度在5nm以下，相对于现有技术制得的氢氧化镉二维膜的厚度大大降低，实现了超薄设计；氢氧化镉-脂肪酸二维双层膜光学带隙为3.5eV，作为典型的宽带隙半导体，能够更好的满足电子器件、传感器的要求，如适用于作为电子器件中的阻挡层。
本发明进一步设置为：氢氧化镉-脂肪酸二维双层膜的厚度范围为1～4nm；
优选的，氢氧化镉-脂肪酸二维双层膜的厚度范围为3～3.4nm。
本发明进一步设置为：氢氧化镉-脂肪酸二维双层膜中含有晶粒，晶粒的晶相为单斜晶相。
本发明进一步设置为：脂肪酸镉盐是合成氢氧化镉-脂肪酸二维双层膜的原料，脂肪酸镉盐中脂肪酸基的碳链长度为4～30，不饱和键数量为0～28；
优选的，脂肪酸镉盐为油酸镉、反油酸镉、硬脂酸镉、棕榈油酸镉、花生四烯酸镉、二十碳五烯酸镉、二十二碳五烯酸镉、月桂酸镉中的一种或多种。
本发明的目的二是提供一种二维氢氧化镉材料的制备方法，制备方法简便、快速、高效，不仅制得了大面积的二维氢氧化镉双层膜；也使其具有了较为合适的带隙；易于大规模工业化生产。
本发明的目的二是通过以下技术方案得以实现的：一种二维氢氧化镉材料的制备方法，包括如下步骤：
制备有机镉盐溶液；
提供两相体系溶剂，所述两相体系溶剂的上层为非极性溶剂层，下层为极性溶剂层；
所述有机镉盐溶液聚集于非极性溶剂与极性溶剂的界面处；
蒸发位于上层的所述非极性溶剂层，使界面处的有机镉盐随非极性溶剂体积减小而聚集成膜，漂浮于所述极性溶剂层的液面；
将碱性极性溶剂注入下层的极性溶剂中，生成二维氢氧化镉双层膜；其中加入碱性极性溶剂时，极性溶剂层温度小于150℃。
通过上述技术方案，有机镉盐界面处的有机镉盐随非极性溶剂体积减小而聚集成膜，漂浮于极性溶剂层的液面，有机镉盐再与碱性极性溶剂中的OH -反应，生成二维氢氧化镉双层膜，能够制得大面积纳米等级厚度的二维氢氧化镉双层膜；加入碱性极性溶剂时，极性溶剂层温度小于150℃，也就是小于氢氧化镉的分解温度，能够很好的保证生成的膜是二维氢氧化镉双层膜；整个制备方法简便、快速、高效，能够更好的控制膜的厚度，制备超薄的大面积的二维氢氧化镉双层膜；制备成本低，易于大规模工业化生产。
本发明进一步设置为：二维氢氧化镉双层膜的厚度小于等于5nm；蒸发位于上层的所述非极性溶剂层的气压下非极性溶剂层的沸点小于有机镉盐溶液的沸点，且小于非极性溶剂层。
利用极性溶剂和非极性溶剂的沸点不同，能够更好的控制更多的蒸发非极性溶剂，对极性溶剂层影响更小，更符合工业低成本大规模生产的要求。
本发明进一步设置为：蒸发位于上层的所述非极性溶剂层的过程中蒸发温度为室温～80℃。
蒸发的温度低，利于减少能耗，过程也更容易控制，不容易造成污染，更利于工业化生产。
本发明进一步设置为：有机镉盐溶液包括脂肪酸镉盐与预溶非极性溶剂，脂肪酸基的碳链长度为4~30，且不饱和键的数量为0~28。
选用脂肪酸镉盐更加环保、经济，而且与预溶非极性溶剂完全溶解性能更好，使脂肪酸镉盐能够更好的聚集于非极性溶剂与极性溶剂的界面处；并且脂肪酸基的碳链长度能建立较大的疏水基团并限制不饱和键的上限，脂肪酸基的适当碳链长度可以避免在蒸发非极性溶剂层过程中有机镉盐被蒸发并有利于有机镉盐在极性溶剂层液面上的有序排列。
本发明进一步设置为：有机镉盐溶液中有机镉盐用量与非极性溶剂层的液面面积为正相关，符合：有机镉盐溶液的体积为nS×5×10 -10/c 1m 3；
其中n=0.1～10，为常数；S为所述非极性溶剂层的液面面积；c1=3～40×10 -8kg/m 3，为有机镉盐溶液的浓度。
通过限定有机镉盐溶液的浓度、体积与非极性溶剂层的液面面积的关系，能够更好的保证二维氢氧化镉双层膜的生成，实现二维氢氧化镉双层膜的超薄设计且不容易破裂，完整度更高。
本发明进一步设置为：碱性极性溶剂中可溶性碱的量与极性溶剂层的液面面积为正相关，符合：可溶性碱的量为(1～1000)×nS×5×10 -11kg；其中n=0.1～10，为常数；S为所述极性溶剂层的液面面积。
通过限定可溶性碱的量与极性溶剂层的液面面积的关系，能够更好的保证二维氢氧化镉双层膜的生成，实现二维氢氧化镉双层膜的超薄设计且不容易破裂，完整度更高。
本发明进一步设置为：所述有机镉盐具有疏水基团，在蒸发所述非极性溶剂层后浮凸于所述极性溶剂层的液面；或者/以及，所述有机镉盐具有亲水基团，在蒸发所述非极性溶剂层后相对接近或下沉于所述极性溶剂层的液面。
通过采用上述优选技术方案，能够更好的让有机镉盐中的镉处于非极性溶剂层和极性溶剂层的界面处，更容易与极性溶剂中的OH -发生反应，同时保证二维氢氧化镉双层膜的稳定性。
本发明进一步设置为：还包括将二维氢氧化镉双层膜沾附于基底的表面上。
将二维氢氧化镉双层膜沾附于基底的表面上操作简单、高效，而且沾附的过程中二维氢氧化镉双层膜不容易破裂，能够大面积的将二维氢氧化镉双层膜沾附在基底上，便于后期处理和使用。
本发明进一步设置为：将基底竖直插入极性溶剂液面以下，再倾斜抬起，得到附着于基底上的二维氢氧化镉双层膜。
上述操作方法简单，而且能够更好的保持二维氢氧化镉双层膜的完整，也不影响前期二维氢氧化镉双层膜的制备。
本发明进一步设置为：所述有机镉盐选自于油酸镉、反油酸镉、硬脂酸镉、棕榈油酸镉、花生四烯酸镉、二十碳五烯酸镉、二十二碳五烯酸镉与月桂酸镉的组合的其中一种或多种；所述非极性溶剂层选自于甲苯及其同系物、丙酮及其同系物、氯仿及其类似物、正己烷、密度小于所述极性溶剂层的非极性溶剂的组合的其中一种或多种；所述极性溶剂层选自于水、酰胺类的组合的其中一种或多种。
通过具体范围限定所述有机镉盐、所述非极性溶剂层与所述极性溶剂层，能够实现所述极性溶剂层在下层、所述非极性溶剂层在上层的所述两相体系溶剂，并且得到所述有机镉盐溶液能够溶入所述非极性溶剂层的具体实现。
本发明进一步设置为：还包括的步骤有：在所述有机镉盐溶液溶入位于上层的所述非极性溶剂层之后与蒸发位于上层的所述非极性溶剂层的步骤之前，对所述两相体系溶剂静置等待，以清楚分离所述非极性溶剂层与所述极性溶剂层；
以及蒸发位于上层的所述非极性溶剂层的步骤中包括完全挥发所述非极性溶剂层；
以及将碱性极性溶剂注入下层的极性溶剂中的步骤要在完全挥发所述非极性溶剂层的步骤之后执行；
以及将碱性极性溶剂注入下层的极性溶剂中的步骤之后静置1~36小时后，再转移漂浮在极性溶剂表面的二维氢氧化镉双层膜。
非极性溶剂层与极性溶剂层清楚分离后再进行蒸发，能够进一步减小蒸发过程中对极性溶剂层的影响；非极性溶剂层完全挥发后有机镉盐的聚集效果更好，再将碱性极性溶剂注入下层的极性溶剂中，反应更加顺利，快速，生成的二维氢氧化镉双层膜成型更好，也更加稳定，不容易破裂。
本发明的目的二是提供一种基底上大面积形成二维氢氧化镉的生长模板，包括上述方案中所述的氢氧化镉-脂肪酸二维双层膜或二维氢氧化镉双层膜。生长模板能够用于生长二维硫化镉和硒化镉。
本发明的目的三是提供上述方案中所述的二维氢氧化镉材料的制备方法制得的二维氢氧化镉双层膜在电子器件中的应用。
 有益效果
综上所述，本发明包括以下至少一个有益技术效果：
1. 氢氧化镉-脂肪酸二维双层膜的厚度在5nm以下，相对于现有技术制得的氢氧化镉二维膜的厚度大大降低，实现了超薄设计。
2. 氢氧化镉-脂肪酸二维双层膜光学带隙为3.5eV，作为典型的宽带隙半导体，能够更好的满足电子器件、传感器的要求，如适用于作为电子器件中的阻挡层。
3. 制备方法简便、快速、高效，不仅制得了大面积的单斜相氢氧化镉-脂肪酸二维双层膜；也使其具有了较为合适的带隙；还有着省时、节能，绿色环保、制备成本低和易于大规模工业化生产的特点。
4. 极少量的工业级原料可以获得大量利润，以工业生产一般标准，1-5克工业级脂肪酸镉可以制备100平方米以上的氢氧化镉-脂肪酸二维双层膜，具有巨大的经济效益。
5. 制备过程中无需高温加热，尤其是反应成为氢氧化镉的过程中无需加热，能够保证氢氧化镉的稳定存在。将得到的两相溶液体系置于温度为T的烘箱中蒸发，其中T=室温～80℃；增加温度有利于缩短制备时间，适于工业化生产。
6. 生产过程中，非极性溶剂层与极性溶剂层皆不参与反应，可重复回收使用，以降低制造成本，也更加环保，节能。
7. 反应1～36小时后，将基底竖直插入水面，再倾斜抬起，得到附着于基底上的氢氧化镉-脂肪酸二维双层膜；这种二维材料转移策略确保了液面上生长的二维材料可以被转移到任意衬底上使用。能够制备包含氢氧化镉-脂肪酸二维双层膜的生长模板，用于生长二维硫化镉和硒化镉。
8. 将脂肪酸镉盐溶解在非极性溶剂中，得到浓度为c 1的脂肪酸镉盐溶液，其中c 1=3～40×10 -8kg/m 3，脂肪酸镉的碳链长度为4～30，不饱和键的数量为0～28；控制了前驱体的浓度，确保了目标产物是单层或少层的二维材料。将(1～1000) ×nS×5×10 -11kg可溶性碱溶解于极性溶剂中，配制碱性溶液，待步骤3中两相溶液体系上层的非极性溶剂完全挥发后，将碱性极性溶剂注入下层的极性溶剂中；同样，控制了前驱体的浓度，确保了目标产物是单层或少层的二维材料。
9. 在面积为S（单位是m 2），容积为V的容器中，加入体积为V 极的极性溶剂，在极性溶剂上方加入密度较小且易挥发，体积为V 非的非极性溶剂，得到上层是非极性溶剂，下层是极性溶剂的两相体系，其中，V 极＜V，V 非＜V，V 极+V 非≤V；不仅使得非极性溶剂易于挥发，还使制备工艺更易实施且灵活。
10. 两相上方体系的非极性溶剂中，加入体积为nS×5×10 -10/c 1（单位是m 3）已配制好的脂肪酸镉溶液，其中n=0.1～10；控制了前驱体的量，确保了目标产物是单层或少层的二维材料。
附图说明
图1为本发明一较佳实施例的二维氢氧化镉材料的制备方法的流程示意图；
图2是试验实施例1制得的氢氧化镉/脂肪酸二维双层膜使用原子力显微镜（AFM）进行表征的AFM图；
图3是对试验实施例1制得的氢氧化镉/脂肪酸二维双层膜使用透射电镜（TEM）进行表征的结果之一。其中图3a是氢氧化镉/脂肪酸二维双层膜的透射电镜（TEM）图；图3b是氢氧化镉/脂肪酸二维双层膜的膜撕裂后的TEM图像；图3c为氢氧化镉/脂肪酸二维双层膜的高分辨透射电镜（TEM）图；图3d为氢氧化镉/脂肪酸二维双层膜的TEM电子衍射图；图3e是单斜相氢氧化镉的标准TEM电子衍射图；
图4a是试验实施例1制得的氢氧化镉/脂肪酸二维双层膜的扫描电镜（SEM）图;
图4b是试验实施例1制得的氢氧化镉/脂肪酸二维双层膜的金相显微镜图；
图5是对制得的目标产物使用紫外-可见光分光光度计进行表征的结果之一。其中，图5a为目标产物的光吸收曲线及其平滑后的曲线；图5b为利用平滑后曲线进行计算得到目标产物光学带隙为3.5eV。
 本发明的实施方式
为了更方便理解本发明的技术方案，以下将本发明的二维氢氧化镉做进一步详细描述，但不作为本发明限定的保护范围。
本发明实施例一公开二维氢氧化镉材料，二维氢氧化镉材料是氢氧化镉-脂肪酸二维双层膜，氢氧化镉-脂肪酸二维双层膜的厚度小于等于5nm。在一较佳的实施例中，氢氧化镉-脂肪酸二维双层膜的厚度范围为1～4nm；进一步的，氢氧化镉-脂肪酸二维双层膜的厚度范围为3～3.4nm。
氢氧化镉-脂肪酸二维双层膜中含有晶粒，晶粒的晶相为单斜晶相。脂肪酸镉盐是合成氢氧化镉-脂肪酸二维双层膜的原料，脂肪酸镉盐中脂肪酸基的碳链长度为4～30，不饱和键数量为0～28；在一较佳的实施例中，脂肪酸镉盐为油酸镉、反油酸镉、硬脂酸镉、棕榈油酸镉、花生四烯酸镉、二十碳五烯酸镉、二十二碳五烯酸镉、月桂酸镉中的一种或多种。
本发明实施例二公开一种二维氢氧化镉材料的制备方法，如图1所示，包括如下步骤：
S1. 制备有机镉盐溶液；
S2.提供两相体系溶剂，所述两相体系溶剂的上层为非极性溶剂层，下层为极性溶剂层；
S3.所述有机镉盐溶液聚集于非极性溶剂与极性溶剂的界面处；
S4.蒸发位于上层的所述非极性溶剂层，使界面处的有机镉盐随非极性溶剂体积减小而聚集成膜，漂浮于所述极性溶剂层的液面；
S5.将碱性极性溶剂注入下层的极性溶剂中，生成二维氢氧化镉双层膜；其中加入碱性极性溶剂时，极性溶剂层温度小于150℃。
其中步骤S1和S2的顺序不做具体限定，可以调换。
本实施例的实施原理为：有机镉盐界面处的有机镉盐随非极性溶剂体积减小而聚集成膜，漂浮于极性溶剂层的液面，有机镉盐再与碱性极性溶剂中的OH -反应，生成二维氢氧化镉双层膜，能够制得大面积纳米等级厚度的二维氢氧化镉双层膜；加入碱性极性溶剂时，极性溶剂层温度小于150℃，也就是小于氢氧化镉的分解温度，能够很好的保证生成的膜是二维氢氧化镉双层膜。
关于步骤S5中，二维氢氧化镉双层膜的可能厚度小于等于5nm，优选的，二维氢氧化镉双层膜的厚度厚度范围为1～4nm；优选的，氢氧化镉-脂肪酸二维双层膜的厚度范围为3～3.4nm。二维氢氧化镉双层膜的生成反应是在所述极性溶剂层的液面，具有超薄膜厚度，因此，二维氢氧化镉双层膜的厚度由两相体系溶剂的界面控制，能够突破现有的制备方法，生成纳米级膜厚的二维氢氧化镉双层膜。
关于步骤S1中有机镉盐溶液的制备，在一较佳示例中，有机镉盐溶液包括脂肪酸镉盐与预溶非极性溶剂，脂肪酸基的碳链长度为4~30，且不饱和键的数量为0~28。
关于步骤S1中预溶非极性溶剂与两相体系溶剂的非极性溶剂的具体溶剂选择，有机镉盐选自于油酸镉、反油酸镉、硬脂酸镉、棕榈油酸镉、花生四烯酸镉、二十碳五烯酸镉、二十二碳五烯酸镉与月桂酸镉的组合的其中一种或多种；非极性溶剂层选自于甲苯及其同系物、丙酮及其同系物、氯仿及其类似物、正己烷、密度小于所述极性溶剂层的非极性溶剂的组合的其中一种或多种；极性溶剂层选自于水、酰胺类的组合的其中一种或多种。通过具体范围限定所述有机镉盐、所述非极性溶剂层与所述极性溶剂层，能够实现所述极性溶剂层在下层、所述非极性溶剂层在上层的所述两相体系溶剂，并且得到所述有机镉盐溶液能够溶入所述非极性溶剂层的具体实现。
关于步骤S3中有机镉盐溶液的可能添加量，在一较佳示例中，有机镉盐溶液中有机镉盐用量与非极性溶剂层的液面面积为正相关，符合：有机镉盐溶液的体积为nS×5×10 -10/c 1m 3；其中n=0.1～10，为常数；S为所述非极性溶剂层的液面面积；c 1=3～40×10 -8kg/m 3，为有机镉盐溶液的浓度。
关于步骤S5中碱性极性溶剂的可能添加量，在一较佳示例中，碱性极性溶剂中可溶性碱的量与极性溶剂层的液面面积为正相关，符合：可溶性碱的量为(1～1000)×nS×5×10 -11kg；其中n=0.1～10，为常数；S为所述极性溶剂层的液面面积。
通过限定有机镉盐溶液的浓度、体积与非极性溶剂层的液面面积的关系，以及可溶性碱的量与极性溶剂层的液面面积的关系，能够更好的保证二维氢氧化镉双层膜的生成，实现二维氢氧化镉双层膜的超薄设计且不容易破裂，完整度更高。
关于步骤S4的一种可行蒸发条件，在一较佳示例中，蒸发位于上层的所述非极性溶剂层的气压下非极性溶剂层的沸点小于有机镉盐溶液的沸点，且小于非极性溶剂层。利用极性溶剂和非极性溶剂的沸点不同，能够更好的控制更多的蒸发非极性溶剂，对极性溶剂层影响更小，更符合工业低成本大规模生产的要求。进一步的，蒸发位于上层的所述非极性溶剂层的过程中蒸发温度为室温～80℃。蒸发的温度低，利于减少能耗，过程也更容易控制，不容易造成污染，更利于工业化生产。
关于步骤S3的有机镉盐漂浮的可能样态，在一较佳示例中，有机镉盐具有疏水基团，在蒸发所述非极性溶剂层后浮凸于所述极性溶剂层的液面；或者/以及，所述有机镉盐具有亲水基团，在蒸发所述非极性溶剂层后相对接近或下沉于所述极性溶剂层的液面。能够更好的让有机镉盐中的镉处于非极性溶剂层和极性溶剂层的界面处，更容易与极性溶剂中的OH - 发生反应，同时保证二维氢氧化镉双层膜的稳定性。
二维氢氧化镉材料的制备方法，还包括S6将二维氢氧化镉双层膜沾附于基底的表面上。将二维氢氧化镉双层膜沾附于基底的表面上操作简单、高效，而且沾附的过程中二维氢氧化镉双层膜不容易破裂，能够大面积的将二维氢氧化镉双层膜沾附在基底上，便于后期处理和使用。在一较佳示例中，将基底竖直插入极性溶剂液面以下，再倾斜抬起，得到附着于基底上的二维氢氧化镉双层膜，能够更好的保持二维氢氧化镉双层膜的完整，也不影响前期二维氢氧化镉双层膜的制备。
关于本发明的附加步骤与主要步骤的可能顺序，在一具体较佳示例中，所述形成方法还包括的步骤有：在步骤S3之后，步骤S4之前，对所述两相体系溶剂静置等待，以清楚分离所述非极性溶剂层与所述极性溶剂层；步骤S4中要在完全挥发所述非极性溶剂层的步骤之后再执行步骤S5，将碱性极性溶剂注入下层的极性溶剂中；并且在步骤S5将碱性极性溶剂注入下层的极性溶剂中之后静置1~36小时后，再转移漂浮在极性溶剂表面的二维氢氧化镉双层膜。非极性溶剂层与极性溶剂层清楚分离后再进行蒸发，能够进一步减小蒸发过程中对极性溶剂层的影响；非极性溶剂层完全挥发后有机镉盐的聚集效果更好，再将碱性极性溶剂注入下层的极性溶剂中，反应更加顺利，快速，生成的二维氢氧化镉双层膜成型更好，也更加稳定，不容易破裂。
此外，本发明第三实施例公开一种基底上大面积形成二维氢氧化镉的生长模板，包括上述方案中所述的氢氧化镉-脂肪酸二维双层膜或二维氢氧化镉双层膜。生长模板能够用于生长二维硫化镉和硒化镉。
本发明第四实施例公开上述方案中二维氢氧化镉材料的制备方法制得的二维氢氧化镉双层膜在电子器件中的应用。
本发明第五实施例提出一种任意基底上单斜相氢氧化镉-脂肪酸二维双层膜的低成本制备方法，包括湿化学法，特别是主要步骤如下：
步骤1，将脂肪酸镉盐溶解在非极性溶剂中，得到浓度为c 1的脂肪酸镉盐溶液。其中c 1=3～40×10 -8kg/m 3，脂肪酸镉的碳链长度为4～30，不饱和键的数量为0～28。
步骤2，在面积为S（单位是m 2），容积为V的容器中，加入体积为V 极的极性溶剂。在极性溶剂上方加入密度较小且易挥发，体积为V 非的非极性溶剂。得到上层是非极性溶剂，下层是极性溶剂的两相体系。其中，V 极＜V，V 非＜V，V 极+V 非≤V。
步骤3，在两相上方体系的非极性溶剂中，加入体积为nS×5×10 -10/c 1（单位是m 3）已配制好的脂肪酸镉溶液，其中n=0.1～10。将得到的两相溶液体系置于温度为T的烘箱中蒸发，其中T=室温～80℃。
步骤4，将(1～1000) ×nS×5×10 -11kg可溶性碱溶解于极性溶剂中，配制碱性溶液。待步骤3中两相溶液体系上层的非极性溶剂完全挥发后，将碱性极性溶剂注入下层的极性溶剂中。
步骤5，1～36小时后，将基底竖直插入水面，再倾斜抬起，得到附着于基底上的氢氧化镉-脂肪酸二维双层膜。
作为一种新方法，其独特性在于：
将脂肪酸镉盐溶解在非极性溶剂中，得到浓度为c 1的脂肪酸镉盐溶液，其中c 1=3～40×10 -8kg/m 3，脂肪酸镉的碳链长度为4～30，不饱和键的数量为0～28；控制了前驱体的浓度，确保了目标产物是单层或少层的二维材料。
在面积为S（单位是m 2），容积为V的容器中，加入体积为V 极的极性溶剂，在极性溶剂上方加入密度较小且易挥发，体积为V 非的非极性溶剂，得到上层是非极性溶剂，下层是极性溶剂的两相体系，其中，V 极＜V，V 非＜V，V 极+V 非≤V；不仅使得非极性溶剂易于挥发，还使制备工艺更易实施且灵活。
两相上方体系的非极性溶剂中，加入体积为nS×5×10 -10/c 1（单位是m 3）已配制好的脂肪酸镉溶液，其中n=0.1～10；控制了前驱体的量，确保了目标产物是单层或少层的二维材料。
将得到的两相溶液体系置于温度为T的烘箱中蒸发，其中T=室温～80℃；增加温度有利于缩短制备时间，适于工业化生产。
将(1～1000)×nS×5×10 -11kg可溶性碱溶解于极性溶剂中，配制碱性溶液，待步骤3中两相溶液体系上层的非极性溶剂完全挥发后，将碱性极性溶剂注入下层的极性溶剂中；同样，控制了前驱体的浓度，确保了目标产物是单层或少层的二维材料。
1～36小时后，将基底竖直插入水面，再倾斜抬起，得到附着于基底上的氢氧化镉-脂肪酸二维双层膜；这种二维材料转移策略确保了液面上生长的二维材料可以被转移到任意衬底上使用。
通过这种新的制备方法，达到的独特效果是：
其一，对制得的目标产物分别使用原子力显微镜、透射电镜扫描电子显微镜、金相显微镜进行表征，由其结果可知，目标产物为大面积的、均匀性好的、厚度为3.0-3.4nm的氢氧化镉-脂肪酸二维双层膜，晶相为单斜相。
其二，对制得的目标产物使用紫外-可见光分光光度计进行表征，由其结果可知，目标产物的光学带隙为3.5eV，是典型的宽带隙半导体，适用于作为电子器件中的阻挡层。
其三，制备方法简便、快速、高效，不仅制得了大面积的单斜相氢氧化镉-脂肪酸二维双层膜；也使其具有了较为合适的带隙；还有着省时、节能，绿色环保、制备成本低和易于大规模工业化生产的特点：所需原料均为普通的工业生产用原材料，即作为原料的脂肪酸镉和可溶性碱均为工业级，所用极性溶剂和非极性溶剂也为工业级，并均易于获得且价格便宜；极少量的工业级原料可以获得大量利润，以工业生产一般标准，1-5克工业级脂肪酸镉可以制备100平方米以上的氢氧化镉-脂肪酸二维双层膜，具有巨大的经济效益。
以下以五个试验实施例结合附图作具体说明
作为镉源的碳链长度为4～30，不饱和键的数量为0～28的脂肪酸镉；作为反应物的可溶性碱；用于提供反应界面的极性溶剂以及密度较极性溶剂小且易挥发的非极性溶剂；作为二维材料从液面转移后的目标基底，均由市场购得或用常规方法制得。
试验实施例1制备的具体步骤为：
步骤1，将脂肪酸镉盐溶解在非极性溶剂中，得到浓度为c 1的脂肪酸镉盐溶液。其中c 1=16×10 -8kg/m 3，脂肪酸镉为油酸镉，非极性溶剂为甲苯。
步骤2，在面积为S（单位是m 2），容积为V的容器中，加入体积为V 极的极性溶剂。在极性溶剂上方加入密度较小且易挥发，体积为V 非的非极性溶剂。得到上层是非极性溶剂，下层是极性溶剂的两相体系。其中，极性溶剂为水，非极性溶剂为甲苯，S=1m 2，V 极=50%V，V 非=20%V。
步骤3，在两相上方体系的非极性溶剂中，加入体积为nS×5×10 -10/c 1（单位是m 3）已配制好的脂肪酸镉溶液，n=1，S=1m 2，c 1=16×10 -8kg/m 3。将得到的两相溶液体系置于温度为T的烘箱中蒸发，其中T=室温。
步骤4，将(1～1000) ×nS×5×10 -11kg可溶性碱溶解于极性溶剂中，配制碱性溶液。待步骤3中两相溶液体系上层的非极性溶剂完全挥发后，将碱性极性溶剂注入下层的极性溶剂中。其中极性溶剂为水，非极性溶剂为甲苯，可溶性碱为氢氧化钠，(1～1000)取10，n=1，S=1m 2。
步骤5，1～36小时后，将基底竖直插入水面，再倾斜抬起，得到附着于基底上的氢氧化镉-脂肪酸二维双层膜。其中1～36小时为30小时。制得大面积的具有单斜相氢氧化镉晶粒的氢氧化镉-脂肪酸二维双层膜。
性能测试
从图2的AFM图中可以清楚的看出，上述制备方法得到的目标产物是厚度3.2nm的均匀二维材料。
从图3a的TEM图像可以清楚的看出，上述制备方法得到的目标产物是稳定的膜状结构，结合图3b的TEM图像，可以观察到明显的氢氧化镉/脂肪酸二维双层膜结构，图3a显示的层是氢氧化镉形成的无机层，撕裂后可以看到脂肪酸形成的有机层。
本发明还对目标产物进行了EDS分析，具体分析部位为图3b中画框的部分，测试结果见下表：
元素 质量百分比% 原子百分比%
C 87.22 95.73
N 1.53 1.44
O 0.76 0.62
Si 0.12 0.05
Cu 10.38 2.15
上表中Si源于透射电镜探头，Cu源于样品铜载网，N源于空气中氮气，剩下绝大部分为C、H、O，证明透明膜为有机脂肪酸膜，从而证实了产物为氢氧化镉/脂肪酸二维双层膜。
图3c为目标产物的高分辨透射电镜图，再结合图3d中目标产物的电子衍射斑点图，与图3e中单斜相氢氧化镉的标准电子衍射斑点一致,证明目标产物是单斜相氢氧化镉。
图4a的TEM图中左上方颜色较浅部分为氢氧化镉/脂肪酸二维双层膜，右下方颜色较深部分为二氧化硅衬底；图4b的金相显微镜照片，下方颜色较深部分为氢氧化镉/脂肪酸二维双层膜，上方颜色较浅部分为二氧化硅衬底。图4表明了目标产物为大面积的均匀二维材料。
图5是对制得的目标产物使用紫外-可见光分光光度计进行表征的结果之一。图5中可以得出目标产物的光学带隙为3.5eV，表明目标产物是宽带隙半导体，其带隙适于用作电子器件中的绝缘层。
试验实施例2制备的具体步骤为：
步骤1，将脂肪酸镉盐溶解在非极性溶剂中，得到浓度为c 1的脂肪酸镉盐溶液。其中c 1=32×10 -8kg/m 3，脂肪酸镉为油酸镉，非极性溶剂为甲苯。
步骤2，在面积为S（单位是m 2），容积为V的容器中，加入体积为V 极的极性溶剂。在极性溶剂上方加入密度较小且易挥发，体积为V 非的非极性溶剂。得到上层是非极性溶剂，下层是极性溶剂的两相体系。其中，极性溶剂为水，非极性溶剂为甲苯，S=2m 2，V 极=40%V，V 非=40%V。
步骤3，在两相上方体系的非极性溶剂中，加入体积为nS×5×10 -10/c 1（单位是m 3）已配制好的脂肪酸镉溶液，其中n=3，S=2m 2，c 1=32×10 -8kg/m 3。。将得到的两相溶液体系置于温度为T的烘箱中蒸发，其中T=60℃。
步骤4，将(1～1000) ×nS×5×10 -11kg可溶性碱溶解于极性溶剂中，配制碱性溶液。待步骤3中两相溶液体系上层的非极性溶剂完全挥发后，将碱性极性溶剂注入下层的极性溶剂中。其中极性溶剂为水，非极性溶剂为甲苯，可溶性碱为氢氧化钠，(1～1000)取100，n=3，S=2m 2。
步骤5，1～36小时后，将基底竖直插入水面，再倾斜抬起，得到附着于基底上的氢氧化镉-脂肪酸二维双层膜。其中1～36小时为6小时。制得近似于图2、图3和图4所示，以及性质如图5的大面积的具有单斜相氢氧化镉晶粒的氢氧化镉-脂肪酸二维双层膜。
试验实施例3制备的具体步骤为：
步骤1，将脂肪酸镉盐溶解在非极性溶剂中，得到浓度为c 1的脂肪酸镉盐溶液。其中c 1=20×10 -8kg/m 3，脂肪酸镉为硬脂酸镉，非极性溶剂为氯仿。
步骤2，在面积为S（单位是m 2），容积为V的容器中，加入体积为V 极的极性溶剂。在极性溶剂上方加入密度较小且易挥发，体积为V 非的非极性溶剂。得到上层是非极性溶剂，下层是极性溶剂的两相体系。其中，S=1m 2，V 极=60%V，V 非=30%V，极性溶剂为水，非极性溶剂为氯仿。
步骤3，在两相上方体系的非极性溶剂中，加入体积为nS×5×10 -10/c 1（单位是m 3）已配制好的脂肪酸镉溶液，其中n=0.5，S=1m 2，c 1=20×10 -8kg/m 3。将得到的两相溶液体系置于温度为T的烘箱中蒸发，其中T=50℃。
步骤4，将(1～1000) ×nS×5×10 -11kg可溶性碱溶解于极性溶剂中，配制碱性溶液。待步骤3中两相溶液体系上层的非极性溶剂完全挥发后，将碱性极性溶剂注入下层的极性溶剂中。其中极性溶剂为水，可溶性碱为氢氧化钾，(1～1000)取1000，n=0.5，S=1m 2。
步骤5，1～36小时后，将基底竖直插入水面，再倾斜抬起，得到附着于基底上的氢氧化镉-脂肪酸二维双层膜。其中1～36小时为3小时。制得近似于图2、图3和图4所示，以及性质如图5的大面积的具有单斜相氢氧化镉晶粒的氢氧化镉-脂肪酸二维双层膜。
试验实施例4制备的具体步骤为：
步骤1，将脂肪酸镉盐溶解在非极性溶剂中，得到浓度为c 1的脂肪酸镉盐溶液。其中c 1=40×10 -8kg/m 3，脂肪酸镉为棕榈油酸镉，非极性溶剂为丙酮。
步骤2，在面积为S（单位是m 2），容积为V的容器中，加入体积为V 极的极性溶剂。在极性溶剂上方加入密度较小且易挥发，体积为V 非的非极性溶剂。得到上层是非极性溶剂，下层是极性溶剂的两相体系。其中，极性溶剂为水，非极性溶剂为丙酮，S=3m 2，V 极=50%V，V 非=10%V。
步骤3，在两相上方体系的非极性溶剂中，加入体积为nS×5×10 -10/c 1（单位是m 3）已配制好的脂肪酸镉溶液，其中n=5，S=3m 2，c 1=40×10 -8kg/m 3。。将得到的两相溶液体系置于温度为T的烘箱中蒸发，其中T=40℃。
步骤4，将(1～1000) ×nS×5×10 -11kg可溶性碱溶解于极性溶剂中，配制碱性溶液。待步骤3中两相溶液体系上层的非极性溶剂完全挥发后，将碱性极性溶剂注入下层的极性溶剂中。其中极性溶剂为水，可溶性碱为氨水，(1～1000)取1000，n=5，S=3m 2。
步骤5，1～36小时后，将基底竖直插入水面，再倾斜抬起，得到附着于基底上的氢氧化镉-脂肪酸二维双层膜。其中1～36小时为8小时。制得近似于图2、图3和图4所示，以及性质如图5的大面积的具有单斜相氢氧化镉晶粒的氢氧化镉-脂肪酸二维双层膜。
试验实施例5制备的具体步骤为：
步骤1，将脂肪酸镉盐溶解在非极性溶剂中得到浓度为c 1的脂肪酸镉盐溶液。c 1=10×10 -8kg/m 3，脂肪酸镉为花生四烯酸镉，非极性溶剂为正己烷。
步骤2，在面积为S（单位是m 2），容积为V的容器中，加入体积为V 极的极性溶剂。在极性溶剂上方加入密度较小且易挥发，体积为V 非的非极性溶剂。得到上层是非极性溶剂，下层是极性溶剂的两相体系。其中，极性溶剂为甲酰胺，非极性溶剂为正己烷，S=3m 2，V 极=70%V，V 非=20%V。
步骤3，在两相上方体系的非极性溶剂中，加入体积为nS×5×10 -10/c 1（单位是m 3）已配制好的脂肪酸镉溶液，其中n=2，S=10m 2，c 1=10×10 -8kg/m 3。。将得到的两相溶液体系置于温度为T的烘箱中蒸发，其中T=60℃。
步骤4，将(1～1000) ×nS×5×10 -11kg可溶性碱溶解于极性溶剂中，配制碱性溶液。待步骤3中两相溶液体系上层的非极性溶剂完全挥发后，将碱性极性溶剂注入下层的极性溶剂中。其中极性溶剂为甲酰胺，可溶性碱为氨水，(1～1000)取1000，n=2，S=10m 2。
步骤5，1～36小时后，将基底竖直插入水面，再倾斜抬起，得到附着于基底上的氢氧化镉-脂肪酸二维双层膜。其中1～36小时为2小时。制得近似于图2、图3和图4所示，以及性质如图5的大面积的具有单斜相氢氧化镉晶粒的氢氧化镉-脂肪酸二维双层膜。
再分别选用作为碳链长度为4～30，不饱和键的数量为0～28的脂肪酸镉，如二十碳五烯酸镉、二十二碳五烯酸镉或月桂酸镉等作为镉源，脂肪酸镉浓度c 1选取12×10 -8kg/m 3、25×10 -8kg/m 3或30×10 -8kg/m 3，极性溶剂选甲酰胺，非极性溶剂选正己烷，可溶性碱选氢氧化钠、氢氧化钾或氨水等，S、V 极、V 非、n、T、(1～1000)以及1～36小时取符合实际生产和本专利要求的任意值，重复上述实施例1～5，同样制得了如或近似于图2、图3和图4所示，以及性质如图5的大面积单斜相二维氢氧化镉。
显然，本领域的技术人员可以对本发明的任意基底上大面积氢氧化镉-脂肪酸二维双层膜的低成本制备方法进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若对本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内，则本这些改动和变型均应涵盖于本发明的保护范围之内。

Claims (17)

  1. 一种二维氢氧化镉材料，其特征是，二维氢氧化镉材料是氢氧化镉-脂肪酸二维双层膜，氢氧化镉-脂肪酸二维双层膜的厚度小于等于5nm。
  2. 根据权利要求1所述的二维氢氧化镉材料，其特征是，氢氧化镉-脂肪酸二维双层膜的厚度范围为1～4nm；
    优选的，氢氧化镉-脂肪酸二维双层膜的厚度范围为3～3.4nm。
  3. 根据权利要求1所述的二维氢氧化镉材料，其特征是，氢氧化镉-脂肪酸二维双层膜中含有晶粒，晶粒的晶相为单斜晶相。
  4. 根据权利要求1所述的二维氢氧化镉材料，其特征是，脂肪酸镉盐是合成氢氧化镉-脂肪酸二维双层膜的原料，脂肪酸镉盐中脂肪酸基的碳链长度为4～30，不饱和键数量为0～28；
    优选的，脂肪酸镉盐为油酸镉、反油酸镉、硬脂酸镉、棕榈油酸镉、花生四烯酸镉、二十碳五烯酸镉、二十二碳五烯酸镉、月桂酸镉中的一种或多种。
  5. 一种二维氢氧化镉材料的制备方法，其特征是，包括如下步骤：
    制备有机镉盐溶液；
    提供两相体系溶剂，所述两相体系溶剂的上层为非极性溶剂层，下层为极性溶剂层；
    所述有机镉盐溶液聚集于非极性溶剂与极性溶剂的界面处；
    蒸发位于上层的所述非极性溶剂层，使界面处的有机镉盐随非极性溶剂体积减小而聚集成膜，漂浮于所述极性溶剂层的液面；
    将碱性极性溶剂注入下层的极性溶剂中，生成二维氢氧化镉双层膜；其中加入碱性极性溶剂时，极性溶剂层温度小于150℃。
  6. 根据权利要求5所述的二维氢氧化镉材料的制备方法，其特征是，二维氢氧化镉双层膜的厚度小于等于5nm；蒸发位于上层的所述非极性溶剂层的气压下非极性溶剂层的沸点小于有机镉盐溶液的沸点，且小于非极性溶剂层。
  7. 根据权利要求5所述的二维氢氧化镉材料的制备方法，其特征是，蒸发位于上层的所述非极性溶剂层的过程中蒸发温度为室温～80℃。
  8. 根据权利要求5所述的二维氢氧化镉材料的制备方法，其特征是，有机镉盐溶液包括脂肪酸镉盐与预溶非极性溶剂，脂肪酸基的碳链长度为4~30，且不饱和键的数量为0~28。
  9. 根据权利要求8所述的二维氢氧化镉材料的制备方法，其特征是，有机镉盐溶液中有机镉盐用量与非极性溶剂层的液面面积为正相关，符合：有机镉盐溶液的体积为nS×5×10 -10/c 1m 3；
    其中n=0.1～10，为常数；S为所述非极性溶剂层的液面面积；c 1=3～40×10 -8kg/m 3，为有机镉盐溶液的浓度。
  10. 根据权利要求9所述的二维氢氧化镉材料的制备方法，其特征是，碱性极性溶剂中可溶性碱的量与极性溶剂层的液面面积为正相关，符合：可溶性碱的量为(1～1000)×nS×5×10 -11kg；其中n=0.1～10，为常数；S为所述极性溶剂层的液面面积。
  11. 根据权利要求5所述的二维氢氧化镉材料的制备方法，其特征是，所述有机镉盐具有疏水基团，在蒸发所述非极性溶剂层后浮凸于所述极性溶剂层的液面；或者/以及，所述有机镉盐具有亲水基团，在蒸发所述非极性溶剂层后相对接近或下沉于所述极性溶剂层的液面。
  12. 根据权利要求5所述的二维氢氧化镉材料的制备方法，其特征是，还包括将二维氢氧化镉双层膜沾附于基底的表面上。
  13. 根据权利要求12所述的二维氢氧化镉材料的制备方法，其特征是，将基底竖直插入极性溶剂液面以下，再倾斜抬起，得到附着于基底上的二维氢氧化镉双层膜。
  14. 根据权利要求5所述的二维氢氧化镉材料的制备方法，其特征是，所述有机镉盐选自于油酸镉、反油酸镉、硬脂酸镉、棕榈油酸镉、花生四烯酸镉、二十碳五烯酸镉、二十二碳五烯酸镉与月桂酸镉的组合的其中一种或多种；所述非极性溶剂层选自于甲苯及其同系物、丙酮及其同系物、氯仿及其类似物、正己烷、密度小于所述极性溶剂层的非极性溶剂的组合的其中一种或多种；所述极性溶剂层选自于水、酰胺类的组合的其中一种或多种。
  15. 根据权利要求5-14任意一项所述的二维氢氧化镉材料的制备方法，其特征是，还包括的步骤有：在所述有机镉盐溶液溶入位于上层的所述非极性溶剂层之后与蒸发位于上层的所述非极性溶剂层的步骤之前，对所述两相体系溶剂静置等待，以清楚分离所述非极性溶剂层与所述极性溶剂层；
    以及蒸发位于上层的所述非极性溶剂层的步骤中包括完全挥发所述非极性溶剂层；
    以及将碱性极性溶剂注入下层的极性溶剂中的步骤要在完全挥发所述非极性溶剂层的步骤之后执行；
    以及将碱性极性溶剂注入下层的极性溶剂中的步骤之后静置1~36小时后，再转移漂浮在极性溶剂表面的二维氢氧化镉双层膜。
  16. 一种基底上大面积形成二维氢氧化镉的生长模板，其特征是，包括权利要求1-4任意一项所述的氢氧化镉-脂肪酸二维双层膜
    或包括权利要求5-15任意一项所述的二维氢氧化镉材料的制备方法制得的二维氢氧化镉双层膜。
  17. 权利要求5-15任意一项所述的二维氢氧化镉材料的制备方法制得的二维氢氧化镉双层膜在电子器件中的应用。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020071952A1 (en) * 2000-12-08 2002-06-13 Moungi Bawendi Preparation of nanocrystallites
CN101045552A (zh) * 2007-04-02 2007-10-03 沈阳工业大学 硫化镉半导体纳米粒子的界面化学制备方法
CN102947218A (zh) * 2010-04-23 2013-02-27 皮瑟莱根特科技有限责任公司 纳米晶体的合成、盖帽和分散
CN108114612A (zh) * 2016-11-26 2018-06-05 中国科学院大连化学物理研究所 层状mof纳米片复合膜
CN109776831A (zh) * 2019-03-20 2019-05-21 福州大学 一种自支撑氢氧化物薄膜和金属有机骨架薄膜的快速制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101306833B (zh) * 2008-07-03 2011-04-13 上海交通大学 氢氧化镉纳米材料的微波制备方法
CN103482684B (zh) * 2013-09-23 2014-11-05 哈尔滨工程大学 一种对dna有吸附提取能力的氢氧化镉纳米阵列的制备方法
CN106698365A (zh) * 2015-11-16 2017-05-24 天津大学 过渡金属硫属化合物中空多孔纳米片的制备方法及其应用
CN107051548B (zh) * 2017-04-18 2019-11-05 曲阜师范大学 一种简易制备六边形CdO/CdS异质结纳米复合材料的方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020071952A1 (en) * 2000-12-08 2002-06-13 Moungi Bawendi Preparation of nanocrystallites
CN101045552A (zh) * 2007-04-02 2007-10-03 沈阳工业大学 硫化镉半导体纳米粒子的界面化学制备方法
CN102947218A (zh) * 2010-04-23 2013-02-27 皮瑟莱根特科技有限责任公司 纳米晶体的合成、盖帽和分散
CN108114612A (zh) * 2016-11-26 2018-06-05 中国科学院大连化学物理研究所 层状mof纳米片复合膜
CN109776831A (zh) * 2019-03-20 2019-05-21 福州大学 一种自支撑氢氧化物薄膜和金属有机骨架薄膜的快速制备方法

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