WO2024159989A1 - 一种在固体基材表面制备无序分散微球模板的方法及应用 - Google Patents

一种在固体基材表面制备无序分散微球模板的方法及应用 Download PDF

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WO2024159989A1
WO2024159989A1 PCT/CN2023/142451 CN2023142451W WO2024159989A1 WO 2024159989 A1 WO2024159989 A1 WO 2024159989A1 CN 2023142451 W CN2023142451 W CN 2023142451W WO 2024159989 A1 WO2024159989 A1 WO 2024159989A1
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solid substrate
microsphere
microspheres
dispersed
sized
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王怀雨
吕原亮
莫师
高昂
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Shenzhen Institute of Advanced Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
    • C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
    • C12Q1/02—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving viable microorganisms
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/5005—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving human or animal cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the invention relates to the technical field of functional materials, and in particular to a method for preparing a disorderly dispersed microsphere template on the surface of a solid substrate and application thereof.
  • Constructing microstructures on the surface of solid substrates can give materials special functional properties, thus having broad application prospects in the fields of biomedical materials, chemical sensing, surface-enhanced Raman scattering, super-hydrophobic/super-hydrophobic surfaces, catalysis, etc.
  • different micro- or nanostructures on the surface of materials can activate intracellular mechanical signal transduction pathways and initiate intracellular signal cascade reactions, thereby changing cell phenotypes and functions, and thus giving medical materials certain unique biological functions.
  • This method of modifying the physical morphology of material surfaces has the characteristics of high safety, long duration, and small side effects on tissues compared to chemical methods such as grafting chemical molecules.
  • honeycomb titanium dioxide microporous structures on the surface of metal titanium can regulate macrophage polarization behavior and promote the bone integration of titanium [Zhu et al., Science Advances 2021;7:eabf6654].
  • the honeycomb microporous structure on the surface of solid catalytic materials can greatly improve the photocatalytic performance due to its larger specific surface area and reactive sites.
  • microsphere arrays on the surface of a solid substrate as a template for subsequent processing is the simplest and most effective method for constructing microstructures of different morphologies. If the microspheres can spontaneously form different structures in a self-assembled manner, the construction cost of the microstructure on the surface of the solid substrate can be further greatly reduced.
  • preparing a self-assembled microsphere template on the surface of a solid substrate is the key to constructing structures of different morphologies. Under appropriate assembly conditions, the microspheres self-assemble into a tightly arranged single-layer microsphere film under the influence of gravity, capillary force, van der Waals force, and electrostatic force.
  • the method for preparing a tightly arranged ordered microsphere template on the surface of a solid substrate is relatively mature, but the method for preparing a dispersed and disordered microsphere template is rarely reported. Therefore, how to prepare a disordered microsphere template with controllable density and uniform dispersion on the surface of a solid substrate is currently a major technical problem.
  • the present invention provides a method for preparing a disorderly dispersed microsphere template on the surface of a solid substrate and its application.
  • the first aspect of the present invention provides a method for preparing a disorderly dispersed microsphere template on the surface of a solid substrate, the method comprising: uniformly mixing large-sized microspheres and small-sized microspheres of different sizes; constructing a single-layer microsphere film on the surface of the solid substrate by self-assembly technology; removing the small-sized microspheres by etching technology, thereby obtaining a uniformly dispersed, density-controllable, and disorderly arranged large-sized microsphere template on the surface of the solid substrate.
  • the small-sized microspheres are closely arranged and the large-sized microspheres are randomly separated, so that the large-sized microspheres are dispersed and disorderly arranged on the surface of the solid substrate.
  • the step of constructing a single-layer microsphere film on the surface of a solid substrate by self-assembly technology includes: directly self-assembling the large-sized microspheres and the small-sized microspheres on the surface of the solid substrate to obtain a single-layer microsphere film on the surface of the solid substrate.
  • the step of constructing a single-layer microsphere film on the surface of a solid substrate by self-assembly technology includes: first self-assembling the large-sized microspheres and the small-sized microspheres on the surface of a solution, and then transferring the single-layer microsphere film to the surface of a solid substrate to obtain a single-layer microsphere film on the surface of the solid substrate.
  • the separation distance of the large-sized microspheres in the single-layer microsphere film is regulated by controlling the mixing ratio of the large-sized microspheres and the small-sized microspheres. That is, the density of the large-sized microspheres is controllable. For example, when the amount of large-sized microspheres added remains unchanged, the more small-sized microspheres are added, the larger the separation distance of the large-sized microspheres.
  • the self-assembly technology is one or more of dip coating, spin coating, electric field assisted self-assembly, evaporation induced self-assembly and slope induced self-assembly transfer.
  • the etching technology is plasma etching, electron beam etching or focused ion beam etching.
  • the diameter of the large-sized microspheres is 1 ⁇ m to 10 ⁇ m
  • the diameter of the small-sized microspheres is 0.1 ⁇ m to 2 ⁇ m. It should be noted that the diameters of the large-sized microspheres and the small-sized microspheres can overlap in the range of values, but the size gap between the large-sized microspheres and the small-sized microspheres should be widened as much as possible during the selection process.
  • the second aspect of the present invention provides a uniformly dispersed, density-controllable, disorderly arranged large-sized microsphere template on the surface of a solid substrate, obtained by the method for preparing a disorderly dispersed microsphere template on the surface of a solid substrate as described above.
  • the third aspect of the present invention provides the application of the large-size microsphere template that is uniformly dispersed, density-controllable, and disorderly arranged on the surface of a solid substrate as described above in the field of surface modification of biomedical materials and in the study of the effects of porous microstructures of different densities on cell or bacterial behavior and function.
  • the technical solution provided by the present invention has at least the following advantages:
  • the method of the present invention solves the technical problem of constructing a microsphere template with controllable density and disorderly dispersion on the surface of a solid substrate;
  • the method of the present invention is based on self-assembly technology, it is possible to prepare microsphere templates on the surface of a solid substrate at low cost, over a large area and with high efficiency;
  • the method of the present invention can simply and conveniently control the density of the microsphere template
  • the technologies used in the method of the present invention are all common technologies that have been maturely applied, the process is simple and the cost is low, and it is suitable for batch and industrial production.
  • FIG. 1a is an optical microscope image of a microsphere film (Ti100) on the surface of a titanium sheet prepared by using a microsphere mixture solution in which 2 ⁇ m microspheres account for 100% in Example 2;
  • FIG1b is an optical microscope image of a microsphere film (Ti80) on the surface of a titanium sheet prepared using a microsphere mixture in which 2 ⁇ m microspheres account for 80% in Example 2;
  • FIG1c is an optical microscope image of a microsphere film (Ti50) on the surface of a titanium sheet prepared using a microsphere mixture in which 2 ⁇ m microspheres account for 50% in Example 2;
  • FIG1d is an optical microscope image of a microsphere film (Ti20) on the surface of a titanium sheet prepared using a microsphere mixture in which 2 ⁇ m microspheres account for 20% in Example 2;
  • FIG2a is a scanning electron microscope image of the Ti20 sample in Example 3 before plasma etching
  • FIG2 b is a scanning electron microscope image of the Ti20 sample in Example 3 after plasma etching
  • FIG3a is a scanning electron microscope image of the Ti100S sample in Example 5; the left side is a photo taken at low magnification, and the right side is a photo taken at high magnification;
  • FIG3 b is a scanning electron microscope image of the Ti80S sample in Example 5; the left side is a photo taken at low magnification, and the right side is a photo taken at high magnification;
  • FIG3c is a scanning electron microscope image of the Ti50S sample in Example 5; the left side is a photo taken at low magnification, and the right side is a photo taken at high magnification;
  • FIG3d is a scanning electron microscope image of the Ti20S sample in Example 5; the left side is a photo taken at low magnification, and the right side is a photo taken at high magnification;
  • FIG4 is a schematic diagram of a tightly ordered monolayer of densely packed microspheres formed by self-assembly on the surface of a solid substrate;
  • FIG5 shows that after reducing the density of microspheres, the microspheres still tend to partially aggregate together rather than being evenly dispersed on the surface of the solid substrate;
  • FIG6 is a flow chart of a method for preparing a randomly dispersed microsphere template on a solid substrate surface provided by the present invention.
  • the techniques for assembling two-dimensional monolayer microspheres on the surface of solid substrates include dip coating, spin coating, electric field-assisted self-assembly, evaporation-induced self-assembly, and inclined plane-induced self-assembly transfer. Using these techniques, a tightly ordered monolayer densely packed microsphere template can be prepared on the surface of a solid substrate, as shown in Figure 4.
  • the present invention proposes to add smaller microspheres to the self-assembled microspheres. After the two sizes of microspheres are evenly mixed, a self-assembly operation is performed, and the small-sized microspheres are closely arranged and the large-sized microspheres are randomly separated. By adjusting the addition ratio of the two different-sized microspheres, the spacing distance between the large-sized microspheres can be adjusted, that is, the density of the large-sized microspheres can be adjusted. Then, the small-sized microspheres are removed by etching technology, and a uniformly dispersed, density-controlled, and disorderly arranged microsphere template can be obtained on the surface of the solid substrate.
  • the present invention introduces a method and application for preparing a uniformly dispersed, disordered, and density-controllable microsphere template on a solid substrate surface over a large area and at a low cost.
  • the method uses two microspheres of different sizes, which are evenly mixed in different proportions, and then a single-layer microsphere film composed of a mixed arrangement of large and small microspheres of two sizes is constructed on the surface of a solid substrate by self-assembly.
  • small-sized microspheres are closely arranged, and large-sized microspheres are randomly separated from each other, so that the large-sized microspheres can be stably, disorderly, and dispersedly distributed in the film.
  • the smaller-sized microspheres are removed by etching technology, and the remaining larger-sized microspheres form a disordered and dispersed microsphere template on the surface of the solid substrate.
  • the separation density of the large-sized microspheres can be controlled by adjusting the addition ratio of the large and small microspheres.
  • the first aspect of the present invention provides a method for preparing a disorderly dispersed microsphere template on the surface of a solid substrate, the method comprising: uniformly mixing large-sized microspheres and small-sized microspheres of different sizes; constructing a single-layer microsphere film on the surface of the solid substrate by self-assembly technology; and removing the small-sized microspheres by etching technology, thereby obtaining a uniformly dispersed, density-controllable, and disorderly arranged large-sized microsphere template on the surface of the solid substrate.
  • the second aspect of the present invention provides a large-sized microsphere template uniformly dispersed on the surface of a solid substrate with controllable density and disordered arrangement, obtained by the method for preparing a disorderly dispersed microsphere template on the surface of a solid substrate as described above.
  • the third aspect of the present invention provides the application of the large-size microsphere template as described above, which is uniformly dispersed, density-controllable, and disorderly arranged on the surface of a solid substrate, in the field of surface modification of biomedical materials and in the study of the effects of porous microstructures of different densities on cell or bacterial behavior and function.
  • large and small microspheres are selected from polystyrene (PS) microspheres of two sizes, 2 ⁇ m and 0.1 ⁇ m, respectively, and the solid substrate is selected from pure titanium sheet.
  • the construction technology of the microsphere film is to transfer it to the surface of the solid substrate by using the immersion pulling method after liquid surface self-assembly, and the etching technology is to use plasma etching, thereby proving the feasibility of the method described in the present invention.
  • this example will further process the prepared microsphere template to confirm the feasibility of using the microsphere template to construct different microstructures on the surface of the solid substrate.
  • a titanium sheet with a diameter of 10 mm and a thickness of 2 mm was polished with 800 mesh, 1200 mesh, 2000 mesh and 4000 mesh sandpaper in sequence. Then, acetone, alcohol and deionized water were ultrasonically cleaned for 10 minutes in sequence.
  • the titanium sheet obtained after the pretreatment was used as the solid substrate in this embodiment.
  • a plasma cleaning machine can also be used to treat the titanium sheet to improve the hydrophilicity of the titanium sheet, so as to facilitate the subsequent transfer of microspheres on the surface of the titanium sheet.
  • Aqueous suspensions containing 10 wt% of 0.1 ⁇ m and 2 ⁇ m PS microspheres were mixed with an equal volume of ethanol. Then, ultrasonic dispersion was performed using an ultrasonic cleaner for 30 min. The ultrasonically dispersed 0.1 ⁇ m and 2 ⁇ m PS microspheres were mixed in different volume ratios of 0:1, 1:4, 1:1, and 4:1, and then vortexed and ultrasonically dispersed again for 30 min to make them uniformly mixed. The proportion of 2 ⁇ m microspheres in the microsphere mixture was recorded as 100%, 80%, 50%, and 20%.
  • the obtained titanium sheet samples are named Ti100, Ti80, Ti50 and Ti20 according to the proportion of 2 ⁇ m microspheres in the microsphere mixture.
  • microspheres on the surface of the titanium sheet was observed using an optical microscope (the optical microscope can only see large-sized microspheres with a diameter of 2 ⁇ m, but cannot see small-sized microspheres with a diameter of 0.1 ⁇ m).
  • the optical microscope can only see large-sized microspheres with a diameter of 2 ⁇ m, but cannot see small-sized microspheres with a diameter of 0.1 ⁇ m.
  • the density of large-sized microspheres on the surface of the titanium sheet gradually decreases, and its distribution state gradually evolves from a highly ordered distribution (Ti100) to a disordered dispersed distribution (Ti80, Ti50, and Ti20).
  • the small-sized microspheres in the microsphere film constructed on the surface of the titanium sheet in Example 2 were removed using plasma etching technology.
  • the sample was placed in the sample chamber of the plasma etcher and evacuated.
  • the RF power was then set to 100 W, and the pressure in the sample chamber reached about 0.4 mbar after oxygen was introduced.
  • the plasma etching treatment was activated for 5-10 min to remove 0.1 ⁇ m PS microspheres and retain 2 ⁇ m PS microspheres.
  • the samples Ti100, Ti80, Ti50 and Ti20 obtained after plasma etching were marked as Ti100P, Ti80P, Ti50P and Ti20P, respectively.
  • Figure 2a shows the morphology of the microsphere film on the surface of the Ti20 sample before plasma etching, taken by a scanning electron microscope. It can be seen from the figure that large-sized microspheres are randomly and disorderly distributed on the surface, while small-sized microspheres are closely arranged between large-sized microspheres.
  • Figure 2b shows the morphology of the microsphere film on the surface of the Ti20 sample after plasma etching, taken by a scanning electron microscope.
  • small-sized microspheres are basically not visible on the surface of the titanium sheet, and the diameter of large-sized microspheres has basically not changed significantly after the treatment. Therefore, through the above treatment, a microsphere template with controllable density and disordered dispersion was successfully prepared on the surface of the titanium sheet.
  • microsphere template prepared in the above example is further processed to construct disordered microstructures with different densities on the surface of the titanium sheet.
  • Ti(SO 4 ) 2 0.5 wt% titanium sulfate
  • TTIP titanium isopropoxide
  • the titanium sheet to which the Ti(SO 4 ) 2 solution or the hydrosol precursor solution was added was dried and placed in an oven at 50°C for 2 h.
  • the sample was then placed in a muffle furnace and heated to 400°C ⁇ 500°C and kept for 2 ⁇ 3 hours.
  • the high temperature treatment here can generate a titanium dioxide film layer from the Ti(SO 4 ) 2 or the hydrosol precursor on the sample surface, and on the other hand, remove the 2 ⁇ m PS microsphere template by high temperature.
  • the sample was cooled to room temperature with the furnace, and a uniformly distributed disordered TiO 2 porous structure with different densities was obtained.
  • the porous samples obtained after the above treatment of the samples Ti100P, Ti80P, Ti50P and Ti20P were marked as Ti100S, Ti80S, Ti50S and Ti20S, respectively.
  • the surface morphology of the obtained structure was observed using a scanning electron microscope.
  • Figure X a porous microstructure with different pore densities was successfully constructed on the surface of the titanium sheet.
  • the pores in the microstructure are left after removing the microsphere template, so the density and distribution of the microspheres in the microsphere template determine the density and distribution of the pores in the microstructure.
  • the technical solution of the present invention is mainly divided into two parts: 1. Mixing microspheres of different sizes (theoretically, the diameter difference should be large, such as 0.1 ⁇ m and 2 ⁇ m) evenly; 2. Constructing a single-layer microsphere film on the surface of a solid substrate by self-assembly. It can be directly self-assembled on the surface of a solid substrate, such as using spin coating, evaporation-induced self-assembly, etc.; it can also be self-assembled on the surface of a solution first, and then the single-layer microsphere film is transferred to the surface of a solid substrate.
  • microsphere film small-sized microspheres are closely arranged, and large-sized microspheres are randomly separated from each other, so that large-sized microspheres are dispersed and arranged disorderly on the surface of a solid substrate.
  • the separation spacing of large-sized microspheres can be adjusted by adjusting the mixing ratio of large and small microspheres. 3.
  • the present invention provides a method for constructing a density-controllable and disorderly dispersed microsphere template on the surface of a solid substrate over a large area and at a low cost.
  • the small-sized microspheres randomly separate the large-sized microspheres during the self-assembly process, and then removing the small-sized microspheres by etching, a uniformly dispersed, density-controllable, and disorderly arranged large-sized microsphere template is obtained on the surface of the solid substrate.
  • the template preparation method provided by the present invention can also be applied to industrial manufacturing, such as the production of photolithography templates.

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Abstract

一种在固体基材表面制备无序分散微球模板的方法及应用，该方法包括：将尺寸不同的大尺寸微球和小尺寸微球混合均匀，通过自组装技术在固体基材表面构建得到单层微球薄膜，利用刻蚀技术去除所述小尺寸微球，从而在固体基材表面得到均匀分散且无序排列的大尺寸微球模板。模板的密度可以通过改变大、小尺寸微球的混合比例来进行调控。本方法能够低成本、大面积、高效地在固体基材表面制备微球模板，工艺过程简单且成本低廉，适用于批量及工业化生产。

Description

一种在固体基材表面制备无序分散微球模板的方法及应用 技术领域
本发明涉及功能材料技术领域，具体涉及一种在固体基材表面制备无序分散微球模板的方法及应用。
 背景技术
在固体基材表面构建微结构能够赋予材料特殊的功能特性，从而在生物医用材料、化学传感、表面增强拉曼散射、超亲/超疏水表面、催化等领域有广阔的应用前景。例如，在生物医用材料领域，材料表面不同的微米或纳米结构可以激活细胞内力学信号转导通路并启动细胞内信号级联反应，从而改变细胞表型与功能，进而赋予医用材料某些独特的生物学功能。这种材料表面物理形貌改性方法相对于接枝化学分子等化学方法来说具有安全性高、持续性长、对组织副作用小等特点。有研究表明在金属钛表面构建蜂窝状二氧化钛微孔结构可以调控巨噬细胞极化行为并促进钛的骨整合性能[Zhu et al., Science Advances 2021;7:eabf6654]。在工业光催化领域，固体催化材料表面的蜂窝状微孔结构由于更大的比表面积和反应活性位点能够大大提高光催化性能。
虽然使用压印、光刻、聚焦离子束刻蚀、电子束刻蚀等先进的加工技术可以在固体基材表面加工出高精度的微结构，但是这些加工技术的广泛应用都受到了加工面积、加工效率、工艺成本、基材选择性等方面的严重限制。在固体基材表面构建微球阵列作为后续处理的模板，是构建不同形貌的微结构最为简单有效的方法。而微球若能够以自组装的方式自发形成不同的结构，则能够进一步大大降低固体基材表面微结构的构建成本。因此，在固体基材表面制备自组装的微球模板是构建不同形貌结构的关键。在合适的组装条件下，微球在重力、毛细作用力、范德华力及静电作用力等的影响下，自组装成为一层紧密排列的单层微球薄膜。目前，在固体基材表面制备紧密排列的有序微球模板的方法已比较成熟，然而分散无序排列的微球模板的制备方法却鲜有报道。因此，如何在固体基材表面制备密度可控且均匀分散的无序微球模板是目前的一大技术难题。
发明内容
为解决上述技术问题，本发明提供一种在固体基材表面制备无序分散微球模板的方法及应用。
为实现上述目的，本发明采用的技术方案如下：
本发明第一方面提供一种在固体基材表面制备无序分散微球模板的方法，该方法包括：将尺寸不同的大尺寸微球和小尺寸微球混合均匀；通过自组装技术在固体基材表面构建得到单层微球薄膜；利用刻蚀技术去除所述小尺寸微球，从而在固体基材表面得到均匀分散的、密度可控的、无序排列的大尺寸微球模板。在本发明提供的方法中，通过自组装技术构建的单层微球薄膜中，小尺寸微球紧密排列并将大尺寸微球随机分隔开，从而使大尺寸微球分散、无序地排布在固体基材表面。
进一步的，在所述通过自组装技术在固体基材表面构建得到单层微球薄膜的步骤中，包括：直接将所述大尺寸微球和小尺寸微球在所述固体基材表面进行自组装，得到在固体基材表面的单层微球薄膜。
进一步的，在所述通过自组装技术在固体基材表面构建得到单层微球薄膜的步骤中，包括：先将所述大尺寸微球和小尺寸微球在溶液表面进行自组装，然后将单层微球薄膜转移至固体基材表面，得到在固体基材表面的单层微球薄膜。
进一步的，在所述将尺寸不同的大尺寸微球和小尺寸微球混合均匀的步骤中，包括：通过控制大尺寸微球和小尺寸微球的混合比例，来调控所述单层微球薄膜中大尺寸微球的分隔距离。即大尺寸微球的密度可控。例如，在大尺寸微球添加量不变的情况下，小尺寸微球添加越多，大尺寸微球分隔距离越大。
进一步的，所述自组装技术为浸涂法、旋涂法、电场辅助自组装方式、蒸发诱导自组装方式和斜面诱导自组装转移方式中的一种或多种。
进一步的，所述刻蚀技术为等离子体刻蚀、电子束刻蚀或聚焦离子束刻蚀。
进一步的，所述大尺寸微球的直径为1 μm~10 μm，所述小尺寸微球的直径为0.1 μm~2 μm。需要说明的是，大尺寸微球和小尺寸微球的直径尺寸在取值范围上可以重叠，但是在选取过程中需尽量拉开大尺寸微球和小尺寸微球的尺寸差距。
本发明第二方面提供如上述的在固体基材表面制备无序分散微球模板的方法所制得的在固体基材表面的均匀分散的、密度可控的、无序排列的大尺寸微球模板。
本发明第三方面提供如上述的在固体基材表面的均匀分散的、密度可控的、无序排列的大尺寸微球模板在生物医用材料的表面改性领域、不同密度的多孔微结构对于细胞或者细菌行为及功能的影响研究领域中的应用。
相较于现有技术，本发明提供的技术方案至少具有以下优点：
1.本发明所述方法解决了在固体基材表面构建密度可控且无序分散的微球模板这一技术难题；
2.由于本发明所述方法基于自组装技术，所以能够低成本、大面积、高效地在固体基材表面制备微球模板；
3.本发明所述方法能够简单、方便地对微球模板的密度进行调控；
4.本发明所述方法中使用的技术都是已经成熟应用的常见技术，工艺过程简单且成本低廉，适用于批量及工业化生产。
 附图说明
一个或多个实施例通过与之对应的附图中的图片进行示例性说明，这些示例性说明并不构成对实施例的限定，除非有特别申明，附图中的图不构成比例限制。
图1a是实施例2中利用2 μm微球所占比例为100%的微球混合液制备的钛片表面的微球薄膜（Ti100）的光学显微镜图片；
图1b是实施例2中利用2 μm微球所占比例为80%的微球混合液制备的钛片表面的微球薄膜（Ti80）的光学显微镜图片；
图1c是实施例2中利用2 μm微球所占比例为50%的微球混合液制备的钛片表面的微球薄膜（Ti50）的光学显微镜图片；
图1d是实施例2中利用2 μm微球所占比例为20%的微球混合液制备的钛片表面的微球薄膜（Ti20）的光学显微镜图片；
图2a是实施例3中Ti20样品在进行等离子体刻蚀处理之前的扫描电子显微镜图片；
图2b是实施例3中Ti20样品在进行等离子体刻蚀处理之后的扫描电子显微镜图片；
图3a是实施例5中Ti100S样品的扫描电子显微镜图片；左侧为低倍下所拍摄照片，右侧为高倍下所拍摄照片；
图3b是实施例5中Ti80S样品的扫描电子显微镜图片；左侧为低倍下所拍摄照片，右侧为高倍下所拍摄照片；
图3c是实施例5中Ti50S样品的扫描电子显微镜图片；左侧为低倍下所拍摄照片，右侧为高倍下所拍摄照片；
图3d是实施例5中Ti20S样品的扫描电子显微镜图片；左侧为低倍下所拍摄照片，右侧为高倍下所拍摄照片；
图4是固体基材表面自组装形成的紧密有序排列的单层密堆积微球示意图；
图5是降低微球密度后，微球仍倾向于部分聚集在一起而非均匀分散于固体基材表面；
图6是本发明提供的一种在固体基材表面制备无序分散微球模板的方法流程图。
具体实施方式
发明人发现，固体基材表面微结构制备的关键在于模板的设计与构建，而目前大多数微结构的制备都以自组装微球为模板。因此微球的组装方法、有序度等参数是决定所获得微结构的形貌和有序度的关键因素。在固体基材表面组装二维单层微球的技术包括浸涂、旋涂、电场辅助自组装、蒸发诱导自组装和斜面诱导自组装转移等。利用这些技术可在固体基材表面制备出紧密有序排列的单层密堆积的微球模板，如图4所示。然而想要利用这些技术制备均匀分散的、密度可控的、无序排列的单层微球模板时却难以获得理想的效果。因为当降低微球的密度想要使微球随机分散于固体基材表面时，由于液体表面张力以及微球之间电荷作用力的存在，微球仍然倾向于聚集在一起，如图5所示。因此很难通过自组装的方式使微球自发地在固体基材表面形成均匀分散的、密度可控的、无序排列的单层微球模板。
为了解决这个问题，本发明提出在自组装的微球中添加尺寸更小的微球。两种尺寸的微球混合均匀后进行自组装操作，小尺寸微球紧密排列并将大尺寸微球随机分隔开来。通过调控两种不同尺寸微球的添加比例，可以调控大尺寸微球之间的间隔距离，也即调控大尺寸微球的密度。然后利用刻蚀技术去除小尺寸微球，即可在固体基材表面获得均匀分散的、密度可控的、无序排列的微球模板。
本发明介绍了一种在固体基材表面大面积、低成本地制备均匀分散的、无序的、密度可控的微球模板的方法及应用。该方法使用两种不同尺寸的微球，按不同比例混合均匀后，通过自组装的方式在固体基材表面构建由两种尺寸的大小微球混合排列的单层微球薄膜。微球薄膜里小尺寸微球紧密排列，并将大尺寸微球相互随机分隔开来，使大尺寸微球能够稳定地、无序地、分散地分布于薄膜中。随后利用刻蚀技术去除尺寸较小的微球，剩余尺寸较大的微球在固体基材表面形成无序且分散的微球模板。通过调控大小微球的添加比例可以控制大尺寸微球的分隔密度。
本发明第一方面提供一种在固体基材表面制备无序分散微球模板的方法，该方法包括：将尺寸不同的大尺寸微球和小尺寸微球混合均匀；通过自组装技术在固体基材表面构建得到单层微球薄膜；利用刻蚀技术去除所述小尺寸微球，从而在固体基材表面得到均匀分散的、密度可控的、无序排列的大尺寸微球模板。
本发明第二方面提供如上述的在固体基材表面制备无序分散微球模板的方法所制得的在固体基材表面得均匀分散的、密度可控的、无序排列的大尺寸微球模板。
本发明第三方面提供如上述的在固体基材表面得均匀分散的、密度可控的、无序排列的大尺寸微球模板在生物医用材料的表面改性领域、不同密度的多孔微结构对于细胞或者细菌行为及功能的影响研究领域中的应用。
下面结合具体实施方式对本发明进行详细说明。
以下实施例中的大、小微球分别选用2 μm和0.1 μm两种尺寸的聚苯乙烯（Polystyrene，PS）微球，固体基材选用纯钛片，微球薄膜的构建技术使用液面自组装后使用浸渍提拉法转移至固体基材表面，刻蚀技术选用等离子体刻蚀，从而证明本发明所述方法的可行性。另外，本实施例也将对所制备的微球模板进一步处理，从而证实利用微球模板在固体基材表面构建不同微结构的可行性。
实施例1
将直径10 mm，厚2 mm的钛片依次使用800目、1200目、2000目和4000目的砂纸打磨。然后依次用丙酮、酒精、去离子水超声清洗10分钟。由此预处理后所得钛片作为本实施例中的固体基材。另外，亦可使用等离子体清洗机对钛片进行处理提高钛片的亲水性，以利于后续微球在钛片表面的转移。
实施例2
取含有10 wt%的0.1 μm和2 μm的PS微球的水悬浊液分别与等体积的乙醇混合。然后使用超声清洗机超声分散30 min。将超声分散后的0.1 μm和2 μm的PS微球按体积比0:1、1:4、1:1、4:1不同比例混合，涡旋震荡后再次超声分散30 min使其均匀混合。微球混合液中2 μm微球所占比例记为100%、80%、50%和20%。
取一片清洗干净的载玻片，将一侧浸入盛有蒸馏水的培养皿中，支撑另一侧使其倾角为50度左右。随后将不同比例的PS微球混合液缓慢滴加在倾斜的载玻片上，微球混合液接触蒸馏水面后，在布朗运动和表面张力等的作用下，在水面均匀地自组装成单层微球膜。然后将培养皿底部没入超声清洗机超声5 min，使大小微球分散地更为均匀。最后使用镊子将实施案例1中所得的钛片沿培养皿侧边浸入水面以下。将钛片转移至单层微球薄膜下方后，垂直向上提拉钛片，从而通过这种浸渍-提拉的方法将液面上的微球薄膜转移至钛片表面。然后将钛片平放并在室温下干燥。以微球混合液中2 μm微球所占比例命名所得钛片样品为Ti100、Ti80、Ti50和Ti20。
使用光学显微镜观察钛片表面微球的分布情况（光学显微镜只能看到直径2 μm的大尺寸微球，无法看到直径0.1 μm的小尺寸微球）。如图1a-d所示，随着微球混合液中大尺寸（2 μm）微球所占比例的减小，钛片表面的大尺寸微球的密度也逐渐降低，并且其分布状态从高度有序分布（Ti100）逐步演变成为无序分散分布（Ti80、Ti50和Ti20）。
实施例3
使用等离子体刻蚀技术去除实施例2中在钛片表面构建的微球薄膜中的小尺寸微球。将样品放入等离子体刻蚀机的样品室内，抽真空。随后将射频电源功率设置为100 W，通入氧气后使样品室内压力达到约为0.4 mbar，稳定后激活等离子体刻蚀处理5-10 min，去除0.1 μm的PS微球，而保留2 μm的PS微球。样品Ti100、Ti80、Ti50和Ti20经等离子体刻蚀处理后所得样品分别标记为Ti100P、Ti80P、Ti50P和Ti20P。图2a所示为扫描电子显微镜拍摄的Ti20样品在等离子体刻蚀前表面微球薄膜的形貌。由图可见大尺寸微球随机无序分布于表面，而小尺寸微球紧密排列于大尺寸微球之间。图2b所示为扫描电子显微镜拍摄的Ti20样品在等离子体刻蚀后表面的微球薄膜的形貌。由图可见刻蚀处理后，钛片表面基本看不到小尺寸微球，并且处理以后大尺寸微球的直径基本没有显著变化。因此，通过上述处理，成功在钛片表面制备了密度可控且无序分散的微球模板。
实施例4
对上述实施例中所制备的微球模板进一步处理，从而在钛片表面构建出不同密度的无序微结构。
使用0.05 M H 2SO 4溶液配制0.5 wt%硫酸钛（Ti(SO 4) 2）溶液；将120 μL异丙醇钛（TTIP）加入到10 mL无水乙醇中，吹打混匀并震荡30 min，接着滴加100 μL纯水和2 mL异丙醇的混合液，继续震荡混匀30 min，用数滴浓盐酸调节pH至3~4，混匀即制得二氧化钛水溶胶前驱体。取20 μL制备的Ti(SO 4) 2溶液或二氧化钛水溶胶前驱体滴加在实施例3中制备的不同密度的微球模板上，室温下晾干。
实施例5
将滴加了Ti(SO 4) 2溶液或水溶胶前驱体溶液的钛片晾干后放入烘箱50℃加热2 h，然后将样品放入马弗炉中，加热至400℃~500℃后保持2~3小时。此处的高温处理一方面可以使样品表面的Ti(SO 4) 2或水溶胶前驱体生成二氧化钛膜层，另一方面可以通过高温去除2 μm的PS微球模板。随后随炉降温冷却至室温，即可得到分布均匀的不同密度的无序TiO 2多孔结构。样品Ti100P、Ti80P、Ti50P和Ti20P经上述处理后所得多孔样品分别标记为Ti100S、Ti80S、Ti50S和Ti20S。使用扫描电子显微镜观察所得结构的表面形貌。如图X所示，成功在钛片表面构建了多孔且孔洞密度不同的微结构。微结构中的孔是去除微球模板以后留下的，所以微球模板中微球的密度和分布决定了微结构中孔的密度和分布。由图3a至图3d可知，随着2 μm微球添加比例的减小，所制得微结构中孔洞的密度也逐渐降低，并且微结构从高度有序（Ti100S）逐渐演变成为随机无序状态（Ti80S、TI50S和TI20S）。
可以看出，本发明技术方案主要分为两个部分：1、将尺寸不同的大小微球（理论上直径差距应较大，如0.1 μm和2 μm）混合均匀；2、通过自组装的方式在固体基材表面构建单层微球薄膜。既可以在固体基材表面直接自组装，如使用旋涂法、蒸发诱导自组装等；也可以先在溶液表面进行自组装，然后将单层微球薄膜转移至固体基材表面。该微球薄膜里小尺寸微球紧密排列，并将大尺寸微球相互随机分隔开来，从而使大尺寸微球分散、无序地排布在固体基材表面。通过调控大小微球的混合比例可以调控大尺寸微球的分隔间距。3、利用刻蚀技术去除小尺寸微球，留下均匀分散的、密度可控的、无序排列的大尺寸微球模板。该方法的流程图如图6所示。
综上所述，本发明提供了一种固体基材表面大面积、低成本地构建密度可控且无序分散的微球模板的方法。通过在以往自组装微球中添加尺寸更小的微球，使小尺寸微球在自组装过程中将大尺寸微球随机分隔开来，然后通过刻蚀的方法去除小尺寸微球，从而在固体基材表面获得均匀分散的、密度可控的、无序排列的大尺寸微球模板。既可以用于生物医用材料的表面改性以改善材料服役效果，或者应用于一些基础研究，例如不同密度的多孔微结构对于细胞或者细菌行为及功能的影响研究。本发明提供的模板制备方法同样可以应用于工业制造中，例如应用于光刻模板的制作。
本领域的普通技术人员可以理解，上述各实施方式是实现本申请的具体实施例，而在实际应用中，可以在形式上和细节上对其作各种改变，而不偏离本申请的精神和范围。任何本领域技术人员，在不脱离本申请的精神和范围内，均可作各自更动与修改，因此本申请的保护范围应当以权利要求限定的范围为准。

Claims (9)

  1. 一种在固体基材表面制备无序分散微球模板的方法，其特征在于，该方法包括：将尺寸不同的大尺寸微球和小尺寸微球混合均匀；通过自组装技术在固体基材表面构建得到单层微球薄膜；利用刻蚀技术去除所述小尺寸微球，从而在固体基材表面得到均匀分散的、密度可控的、无序排列的大尺寸微球模板。
  2. 根据权利要求1所述的在固体基材表面制备无序分散微球模板的方法，其特征在于，在所述通过自组装技术在固体基材表面构建得到单层微球薄膜的步骤中，包括：直接将所述大尺寸微球和小尺寸微球在所述固体基材表面进行自组装，得到在固体基材表面的单层微球薄膜。
  3. 根据权利要求1所述的在固体基材表面制备无序分散微球模板的方法，其特征在于，在所述通过自组装技术在固体基材表面构建得到单层微球薄膜的步骤中，包括：先将所述大尺寸微球和小尺寸微球在溶液表面进行自组装，然后将单层微球薄膜转移至固体基材表面，得到在固体基材表面的单层微球薄膜。
  4. 根据权利要求1所述的在固体基材表面制备无序分散微球模板的方法，其特征在于，在所述将尺寸不同的大尺寸微球和小尺寸微球混合均匀的步骤中，包括：通过控制大尺寸微球和小尺寸微球的混合比例，来调控所述单层微球薄膜中大尺寸微球的分隔距离。
  5. 根据权利要求1所述的在固体基材表面制备无序分散微球模板的方法，其特征在于，所述自组装技术为浸涂法、旋涂法、电场辅助自组装方式、蒸发诱导自组装方式和斜面诱导自组装转移方式中的一种或多种。
  6. 根据权利要求1所述的在固体基材表面制备无序分散微球模板的方法，其特征在于，所述刻蚀技术为等离子体刻蚀、电子束刻蚀或聚焦离子束刻蚀。
  7. 根据权利要求1所述的在固体基材表面制备无序分散微球模板的方法，其特征在于，所述大尺寸微球的直径为1 μm~10 μm，所述小尺寸微球的直径为0.1 μm~2 μm。
  8. 如权利要求1至7中任一项所述的在固体基材表面制备无序分散微球模板的方法所制得的在固体基材表面的均匀分散的、密度可控的、无序排列的大尺寸微球模板。
  9. 如权利要求8所述的在固体基材表面的均匀分散的、密度可控的、无序排列的大尺寸微球模板在生物医用材料的表面改性领域、不同密度的多孔微结构对于细胞或者细菌行为及功能的影响研究领域中的应用。
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