WO2021035706A1 - 一种含硅烯量子点的硅氧烯及其制备方法 - Google Patents

一种含硅烯量子点的硅氧烯及其制备方法 Download PDF

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WO2021035706A1
WO2021035706A1 PCT/CN2019/103779 CN2019103779W WO2021035706A1 WO 2021035706 A1 WO2021035706 A1 WO 2021035706A1 CN 2019103779 W CN2019103779 W CN 2019103779W WO 2021035706 A1 WO2021035706 A1 WO 2021035706A1
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quantum dots
siloxyene
silylene
preparing
silicene
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黄靖云
徐鑫苓
周丽萍
叶志镇
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浙江大学
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Publication of WO2021035706A1 publication Critical patent/WO2021035706A1/zh
Priority to US17/581,872 priority patent/US20220185680A1/en

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    • C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
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    • 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
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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Definitions

  • the invention belongs to the technical field of preparation of fluorescent functional nano-film materials, and specifically relates to a siloxyene containing silene quantum dots and a preparation method thereof.
  • Silylene is a 2D silicon allotrope with a unique low buckling structure. Its oxide is siloxyene. Both have unique physical and chemical properties due to their high specific surface area and quantum confinement effect. Similar to graphene, silylene also has a hexagonal honeycomb structure, and because Si and C belong to the same family in the chemical periodic table, they have similar electronic properties, but the difference is that the Si atoms in silylene are not all SP 2 heterocycles. It is between SP 2 hybridization and SP 3 hybridization, resulting in a hexagonal buckling structure and a highly chemically active surface.
  • silicene quantum dots similar to graphene quantum dots have great potential for a wide range of applications, such as biological imaging, chemical sensing, catalysis, drug delivery, light emission, and microelectronics. Therefore, research on silicene quantum dots The preparation methods, properties and potential applications are of great significance.
  • the preparation methods of silylene and siloxyene mainly include epitaxial growth method and chemical method.
  • the epitaxial growth method is mainly to use molecular beam epitaxy (MBE) method to grow single or multilayer silicene on Ag(111), Ir(111), MoS 2 and other substrates; chemical methods are mainly divided into chemical vapor deposition Method, template method and liquid phase stripping method.
  • MBE molecular beam epitaxy
  • the epitaxial growth method can control the growth of a single layer of silicene, but this method is expensive, complicated to operate, and difficult to separate the silicene from the substrate, which has caused certain limitations on the research and application of various properties of silicene, and the reported chemistry Most of the methods are tedious, the thickness of the prepared material is relatively thick, and the yield is very low.
  • the principle of the method used in the present invention is the liquid phase stripping method. After optimization, the operation is simple, the cost is low, and the raw materials used are less toxic, and are more suitable for mass preparation.
  • silylene quantum dots and siloxene are relatively few. Unlike bulk silicon with indirect band gap, silylene has a quasi-direct band gap. Therefore, studying the photoluminescence properties, energy band structure, and luminescence lifetime of silylene quantum dots and siloxene is of great significance to the future applications of this material in the fields of optoelectronics, sensors, and microelectronics.
  • the purpose of the present invention is to provide a siloxyene containing silylene quantum dots and a preparation method thereof in the technical field of nanomaterial preparation.
  • a siloxyene film containing siloxyene quantum dots is prepared from top to bottom at room temperature through a liquid-phase peeling CaSi 2 technology.
  • the method adopts transition metal chloride as a catalyst, which not only facilitates the extraction of CaSi 2 and improves the yield of the siloxyene film, but also promotes the formation of silylene quantum dots on the surface where silicon elements are enriched on the siloxyene surface.
  • the prepared siloxyene nano-film containing silicene quantum dots has strong blue fluorescence emission performance, its fluorescence lifetime is in the nanosecond level, and has broad spectrum emission tunable properties, and belongs to a quasi-direct band gap semiconductor material .
  • the invention provides a siloxyene containing silylene quantum dots and a preparation method thereof, which comprises the following steps:
  • step (2) Transfer the mixed solution obtained in step (1) to a centrifuge tube, remove the supernatant after high-speed centrifugation, and then add excess hydrochloric acid to remove metal compound impurities to obtain a mixed solution;
  • step (3) The mixture obtained in the step (2) is cleaned several times by high-speed centrifugation with anhydrous ethanol, and then anhydrous ethanol is added for ultrasonic dispersion, and then the supernatant is collected by low-speed centrifugation and vacuum dried.
  • Siloxyene nano-film containing silene quantum dots Siloxyene nano-film containing silene quantum dots.
  • the method for preparing siloxyene containing silylene quantum dots is characterized in that, in the step (1), the decalcification organic solvent is tetraethylorthosilicate, ethyl acetate, isopropanol, and At least one of absolute ethanol; the transition metal chloride catalyst is at least one of ferric chloride, cobalt chloride, and nickel chloride.
  • the molar ratio of CaSi 2 to the transition metal chloride catalyst is 1:1 to 1:4.
  • the reaction is to stand for 24 to 48 hours at room temperature.
  • the high-speed centrifugation in the method refers to a rotation speed of 10000 rpm or more, and a centrifugation time of 10 to 15 minutes.
  • the concentration of the hydrochloric acid is 1-4 mol/L; the reaction time is 3-7 hours, and the molar ratio of the added hydrochloric acid to all the added metal elements is greater than 2.
  • the number of times of washing with absolute ethanol is 3 to 5 times.
  • the low-speed centrifugal rotation speed is 200-500 rpm, and the centrifugal time is 3-5 min.
  • the vacuum drying temperature is 60-80° C., and the drying time is 24 hours or more.
  • the present invention prepares a siloxyene containing siloxyene quantum dots by a top-down liquid phase peeling method.
  • the siloxyene film prepared by this method has siloxyene quantum dots, and the diameter of the siloxyene quantum dots is about
  • the thickness of the siloxyene film is 2-5nm, and the thickness of the siloxyene film is 1-2.5nm. It belongs to a two-dimensional nanomaterial with a thickness of 5 atomic layers.
  • the present invention makes the self-organized growth of siloxyene quantum dots on siloxyene through transition metal chloride catalysis for the first time, has broad spectrum emission tunable properties, exhibits strong blue light emission under the excitation of ultraviolet light, and passes absorption spectrum and PL The appearance of quasi-direct band gap transitions is observed in the spectrum, which is very important for the research of silicon optoelectronics.
  • FIG. 1 is a STEM image of the siloxyene film containing siloxyene quantum dots prepared in Example 1;
  • Example 2 is an HRTEM image of the siloxyene film containing siloxyene quantum dots prepared in Example 1;
  • Fig. 3 is a selected area electron diffraction (SAED) pattern image of the corresponding area in Fig. 2;
  • Example 4 is an SEM image of a layered sample after the liquid phase peeling off CaSi 2 in Example 1;
  • Example 5 is an AFM image and thickness characterization of the siloxyene film containing siloxyene quantum dots prepared in Example 1;
  • Figure 6 is the UV-vis absorption spectrum (UV-vis) and photoluminescence spectrum (PL) images of the siloxene film containing silicene quantum dots prepared in Example 1, where the UV-vis absorption spectrum has been converted into a calculable optical band gap
  • the abscissa of the photoluminescence spectrum is converted from wavelength (nm) to photon energy (eV);
  • Example 7 is a fluorescence lifetime curve of the siloxyene film containing siloxyene quantum dots prepared in Example 1;
  • Figure 8 is an HRTEM image of a siloxyene film prepared by a traditional method
  • Figure 9 is a photoluminescence spectrum image of a siloxyene film prepared by a traditional method.
  • a method for preparing siloxyene containing silylene quantum dots includes the following steps:
  • Example 2 The same steps as in Example 1 were used to prepare siloxene containing silylene quantum dots, except that the ethyl acetate in Example 1 was replaced with 20 ml of absolute ethanol, and the other reaction conditions were not changed.
  • TEM characterization shows that the thickness and size of the silicene quantum dots are relatively large, with an average diameter of about 8nm, and its structure is closer to crystalline silicon quantum dots rather than silicene quantum dots; the sample has obvious crystals in the ultraviolet-visible absorption spectrum
  • the silicon absorption peak, and the photoluminescence spectrum results show that under the excitation of ultraviolet light, the sample has fluorescence emission in the blue wavelength band, but the intensity is not as good as that of the sample of Example 1.
  • Example 2 The same steps as in Example 1 were used to prepare siloxyene containing silylene quantum dots, except that the ferric trichloride hexahydrate in Example 1 was replaced with 0.48 g cobalt chloride hexahydrate, and the other reaction conditions were not changed. .
  • TEM characterization shows that the thickness of the siloxyene film is thicker, but the yield of siloxyene quantum dots is low, with an average diameter of about 3nm, and its crystallization degree is lower, which is closer to the concentration area of silicon-rich atoms; the sample is in the ultraviolet -Visible absorption spectrum has a weak absorption peak of crystalline silicon, and the results of photoluminescence spectroscopy show that under the excitation of ultraviolet light, the sample has fluorescence emission in the blue-green light band, which belongs to the joint effect of silylene quantum dots and siloxyene film result.
  • FIG. 1 is a scanning transmission electron microscope (STEM) image of the sample, showing that the siloxyene film has an extremely thin thickness, a certain degree of flexibility, and a large size.
  • Figure 2 is a high-resolution transmission electron microscopy (HRTEM) image of a siloxyene film containing siloxyene quantum dots. It shows that the siloxyene quantum dots are uniformly distributed on the siloxyene film, with a size of about 2-5 nm, which is similar to the nature of blue light emission. correspond.
  • Figure 3 is an image of the selected area electron diffraction pattern corresponding to the area in Figure 2, showing that the prepared silicene quantum dots belong to a kind of polycrystalline. After calibration, the crystal structure corresponding to the diffraction pattern corresponds to the silicene, and the lattice fringe spacing is It is proved that the prepared quantum dots are different from silicon crystal quantum dots.
  • Figure 4 is the SEM image of the layered sample after the liquid phase peeling off the CaSi 2. It shows that the CaSi 2 has obvious delamination and peeling phenomenon after the reaction, indicating that under the combined action of the decalcification solvent and the transition metal chloride catalyst, the CaSi 2 is The calcium metal ions of the ions are extracted, leaving silicon atoms to form a siloxyene film, and self-organizing silicene quantum dots are grown on it.
  • FIG. 5 is the AFM image of the sample dispersed on the mica sheet. The measurement shows that the thickness of the siloxyene film is within 2nm, and the surface is distributed with uneven silylene quantum dots. The calculation shows that the siloxyene and silylene quantum dots The number of atomic layers is within 5 layers.
  • UV-vis Ultraviolet-visible spectroscopy
  • the optical band gap of the sample is about 3.01eV, excluding the interference of instrument error and the test environment, the optical band gap corresponds to the sample's fluorescence emission peak at 435nm (325nm excitation), and the UV-visible absorption spectrum data processing
  • the coefficient indicates that the sample belongs to a direct band gap semiconductor at this time, so the sample undergoes a quasi-direct band gap transition at 435 nm, which is due to the change of the silicon material band gap caused by the quantum confinement effect.
  • the photoluminescence spectrum image in Figure 6 shows that under the excitation of 325nm ultraviolet light, the sample has obvious blue emission peaks at 435nm and 465nm, and the emission peak at 435nm is caused by the band edge transition of silylene quantum dots.
  • the emission peak at 465 nm also has luminescence centers such as the oxygen-deficiency composite luminescence and surface state luminescence of the siloxyene film itself.
  • Figure 7 is the fluorescence lifetime curve of the siloxyene film containing silylene quantum dots at the emission peak of 435nm.
  • the excitation light wavelength used in the test is 375nm.
  • the fitting calculation shows that the fluorescence lifetime of the sample is about 1.098ns, which corresponds to the silylene quantum dots.
  • the fluorescence lifetime of the point band edge transition also indirectly proves that the sample belongs to a quasi-direct band gap semiconductor.
  • the siloxyene film prepared by the improved liquid phase peeling method in the present invention uses organic solvents and transition metal chlorides as catalysts so that the prepared siloxyene film has silylene quantum dots, which can adjust its luminescence performance, so that It exhibits strong blue emission (435nm) under the excitation of ultraviolet light (325nm). This is quite different from the siloxyene film prepared by the traditional method.
  • the present invention adopts the same method as in Example 1, except that step (1) is omitted and the mixed solution in step (2) is replaced with hydrochloric acid.
  • the prepared siloxyene film does not contain silylene quantum dots (as shown in Figure 8), and has a thickness of 1 to 2.5 nm, and its emission peak is located at 485 nm under the excitation of ultraviolet light (325 nm) (as shown in Figure 9) .

Abstract

提供了一种含硅烯量子点的硅氧烯薄膜及其制备方法，属于荧光功能纳米材料领域。将CaSi 2与脱钙有机溶剂、过渡金属氯化物催化剂按比例混合均匀，酸洗后超声分散制备获得了镶嵌硅烯量子点的硅氧烯薄膜，这种硅氧烯薄膜厚度在1～2.5nm以下，硅烯量子点尺寸在2～5nm，并且在蓝光区域有很强的荧光发射性能，具有准直接带隙，显示了其在光电等领域良好的应用前景。

Description

一种含硅烯量子点的硅氧烯及其制备方法 技术领域
本发明属于荧光功能纳米薄膜材料制备技术领域，具体涉及一种含硅烯量子点的硅氧烯及其制备方法。
背景技术
二维硅基材料由于高比表面积和量子限域效应而具有独特的物理和化学性质。硅烯是一种具有独特低屈曲结构的2D硅同素异形体，其氧化物为硅氧烯，两者因为高比表面积和量子限域效应而具有独特的物理和化学性质。与石墨烯类似，硅烯也具有六角蜂窝状结构，并且由于Si与C在化学周期表中属于同族，他们具有相似的电子特性，但不同的是，硅烯中的Si原子并非全部SP 2杂化，而是介于SP 2杂化与SP 3杂化之间，导致其六边形具有屈曲结构，并具有高化学活性的表面。这使得调控带隙、实现硅烯的化学官能团功能化成为了可能，因此对纳米硅烯及其氧化物的研究越来越受到重视。值得注意的是，类似石墨烯量子点的硅烯量子点具有广泛应用的巨大潜力，例如生物成像、化学传感、催化、药物输送、光发射和微电子领域等，因此研究硅烯量子点的制备方法、性质与潜在应用极具意义。
目前，硅烯与硅氧烯的制备方法主要有外延生长法和化学方法。其中，外延生长法主要是在Ag(111)、Ir(111)、MoS 2等衬底上采用分子束外延(MBE)方法生长单层或多层硅烯；化学方法则主要分为化学气相沉积法、模板法和液相剥离法。外延生长法能够可控生长单层硅烯，但是该方法成本高昂，操作复杂，并且难以将硅烯与衬底分离，对硅烯的各种性质研究及应用造成一定局限，而已经报道的化学方法大多过程冗杂，制备出的材料厚度较厚，产率很低。本发明使用的方法原理是液相剥离法，经过优化后操作简便，成本低廉，所用原料毒害性较低，更适用于大批量制备。
目前，对硅烯量子点及硅氧烯的光致发光特性研究还较少，而与间接带隙的块体硅不同，硅烯具有准直接带隙。因此，研究硅烯量子点及硅氧烯的光致发光性质、能带结构和发光寿命对未来该材料应用于光电、传感器、微电子等 领域具有重要意义。
发明内容
本发明目的是在纳米材料制备技术领域提供一种含硅烯量子点的硅氧烯及其制备方法。该方法通过液相剥离CaSi 2技术在室温下自上而下制备一种含硅烯量子点的硅氧烯薄膜。该方法采用过渡金属氯化物作为催化剂，不仅有利于CaSi 2的抽层剥离，提高硅氧烯薄膜的产率，还可以促使在硅氧烯表面硅元素富集处形成硅烯量子点。所制备获得的含硅烯量子点的硅氧烯纳米薄膜具有较强的蓝色荧光发射性能，其荧光寿命在纳秒级别，具有宽光谱发射可调谐性质，属于一种准直接带隙半导体材料。
本发明提供一种含硅烯量子点的硅氧烯及其制备方法，包括以下步骤：
(1)将CaSi 2、脱钙有机溶剂和过渡金属氯化物催化剂混合均匀，待充分反应脱钙后得到混合溶液；
(2)将所述步骤(1)得到的混合溶液转移至离心管中，高速离心后去除上清液，然后加入过量盐酸去除金属化合物杂质，获得混合液；
(3)将所述步骤(2)得到的混合液使用无水乙醇进行高速离心反复清洗数次后，再加入无水乙醇进行超声分散，之后低速离心收集上清液，真空干燥后即可得到含硅烯量子点的硅氧烯纳米薄膜。
所述的含硅烯量子点的硅氧烯的制备方法，其特征在于，所述步骤(1)中，所述脱钙有机溶剂为正硅酸四乙酯、乙酸乙酯、异丙醇以及无水乙醇中的至少一种；所述过渡金属氯化物催化剂为氯化铁、氯化钴、氯化镍中的至少一种。
所述的含步骤(1)中，CaSi 2、过渡金属氯化物催化剂两者的摩尔比为1:1～1:4。
所述的步骤(1)中，所述的反应为在室温下静置反应24～48h。
所述方法中所述的高速离心是指转速为10000rpm以上，离心时间为10～15min。
所述的步骤(2)中，所述盐酸浓度为1-4mol/L；所述反应时间为3-7h，所加入的盐酸与所加入的所有金属元素的摩尔比大于2。
所述的步骤(3)中，无水乙醇清洗次数为3～5次。
所述的步骤(3)中，所述低速离心转速为200～500rpm，离心时间为3～5min。
所述的步骤(3)中，所述真空干燥温度为60～80℃，干燥时间为24h以上。
本发明通过自上而下的液相剥离法制备一种含硅烯量子点的硅氧烯，这种方法所制得的硅氧烯薄膜上具有硅烯量子点，且硅烯量子点直径约为2～5nm，硅氧烯薄膜厚度为1～2.5nm，属于一种二维纳米材料，具有5个原子层内的厚度。本发明首次通过过渡金属氯化物催化使得在硅氧烯上自组织生长形成硅烯量子点，具有宽光谱发射可调谐性质，在紫外光激发下显示出强的蓝光发射，并且通过吸收光谱和PL光谱观察到准直接带隙跃迁的出现，这对硅光电子学的研究十分重要。
附图说明
图1是实施例1制备的含硅烯量子点的硅氧烯薄膜的STEM图像；
图2是实施例1制备的含硅烯量子点的硅氧烯薄膜的HRTEM图像；
图3是图2对应区域的选区电子衍射(SAED)花样图像；
图4是实施例1中液相剥离CaSi 2后分层样品的SEM图像；
图5是实施例1制备的含硅烯量子点的硅氧烯薄膜的AFM图像及厚度表征；
图6是实施例1制备的含硅烯量子点的硅氧烯薄膜的紫外可见吸收光谱(UV-vis)和光致发光光谱(PL)图像，其中紫外可见吸收光谱已转化为可计算光学带隙的数据图，光致发光图谱的横坐标由波长(nm)换算为光子能量(eV)；
图7是实施例1制备的含硅烯量子点的硅氧烯薄膜的荧光寿命曲线；
图8是采用传统方法制备的硅氧烯薄膜的HRTEM图像；
图9是采用传统方法制备的硅氧烯薄膜的光致发光光谱图像。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步的详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1：
一种含硅烯量子点的硅氧烯制备方法，包括以下步骤：
(1)称取0.54g六水合三氯化铁，加入20ml乙酸乙酯充分搅拌溶解。
(2)称取0.2gCaSi 2加入(1)中的混合溶液中，于通风橱中静置24h使其充分反应。
(3)将反应后的混合溶液转移至离心管中，设置离心转速为10000rpm，离心时间为10min。
(4)完成离心后取下层沉淀，加入25ml浓度为2mol/L的盐酸，搅拌混合均匀后于通风橱中静置3h以溶解反应产物中残留的金属氧化物等杂质。
(5)将反应后的混合溶液转移至离心管中，设置离心转速为10000rpm，离心时间为10min，完成离心后吸取上清液倒弃，加入20ml无水乙醇搅拌清洗下层沉淀，再以相同参数离心并弃去上清液，反复3次后加入20ml无水乙醇分散下层沉淀。
(6)将混合液超声分散2h，其中超声功率为100％，以分散剥离更多纳米薄膜样品。
(7)完成超声分散后将混合溶液转移至离心管中，设置离心转速为300rpm，离心时间为3min，离心结束后吸取上层液体，于60℃真空干燥24h以获得含硅烯量子点的硅氧烯薄膜粉末样品，同时保留一部分上层液体样品用于后续分析测试，除去上层液体后的下层沉淀用于后续的液相剥离CaSi 2形貌研究。
实施例2：
采取与实施例1相同的步骤制备含硅烯量子点的硅氧烯，区别在于：将实例1中的乙酸乙酯更换为20ml的无水乙醇，其他反应条件均不作改变。
经过TEM表征，显示硅烯量子点的厚度与尺寸较大，平均直径在8nm左右，其结构更接近于晶体硅量子点而非硅烯量子点；样品在紫外-可见吸收光谱中具有明显的晶体硅吸收峰，且光致发光谱结果表明在紫外光激发下，样品在蓝光波段具有荧光发射，但是强度不如实施例1的样品。
实施例3：
采取与实施例1相同的步骤制备含硅烯量子点的硅氧烯，区别在于：将实例1中的六水合三氯化铁更换为0.48g的六水合氯化钴，其他反应条件均不作改变。
经过TEM表征，显示硅氧烯薄膜的厚度较厚，但硅烯量子点的产率较低，平均直径在3nm左右，其晶体化程度较低，更接近于富硅原子聚集区；样品在紫外-可见吸收光谱中具有较弱的晶体硅吸收峰，且光致发光谱结果表明在紫外光激发下，样品在蓝绿光波段具有荧光发射，属于硅烯量子点与硅氧烯薄膜共同作用的结果。
实施例4：
透射电子显微镜(TEM)的表征和分析
使用透射电子显微镜来确定含硅烯量子点的硅氧烯薄膜尺寸、量子点分布以及结晶度。图1为样品的扫描透射电镜(STEM)图像，显示出硅氧烯薄膜具有极薄的厚度，有一定柔性，并且具有较大的尺寸。图2为含硅烯量子点的硅氧烯薄膜的高分辨透射电镜(HRTEM)图像，显示硅烯量子点在硅氧烯薄膜上分布均匀，尺寸在2～5nm左右，与其蓝光发射的性质相对应。图3为图2中区域对应的选区电子衍射花样图像，显示出制备的硅烯量子点属于一种多晶体，标定后其衍射花样对应的晶体结构与硅烯对应，其晶格条纹间距为
Figure PCTCN2019103779-appb-000001
证明制备出的量子点是与硅晶体量子点有别的硅烯量子点。
实施例5：
扫描电子显微镜(SEM)的表征和分析
使用扫描电子显微镜来观察制备样品后下层沉淀中CaSi 2的形貌变化。图4为液相剥离CaSi 2后分层样品的SEM图像，显示出反应后CaSi 2出现了明显的分层剥离现象，说明在脱钙溶剂与过渡金属氯化物催化剂的共同作用下，CaSi 2中的钙金属离子被抽离，剩下硅原子形成硅氧烯薄膜，并且在之上自组织生长硅烯量子点。
实施例6：
原子力显微镜(AFM)的表征和分析
使用原子力显微镜来确定含硅烯量子点的硅氧烯薄膜厚度。图5为样品在云母片上分散后的AFM图像，经过测定表明硅氧烯薄膜的厚度在2nm以内，且其表面分布着凹凸不平的硅烯量子点，计算表明硅氧烯及硅烯量子点的原子层数在5层以内。
实施例7：
紫外-可见光谱(UV-vis)分析
使用紫外-可见分光光度计分析含硅烯量子点的硅氧烯薄膜的光吸收能力，得到吸收光谱图后经数据处理计算其光学带隙。由图6可知样品的光学带隙约为3.01eV，排除仪器误差与测试环境的干扰，该光学带隙对应于样品在435nm的荧光发射峰(325nm激发)，而紫外-可见吸收光谱数据处理的系数表明此时样品属于直接带隙半导体，因此样品在435nm处发生的是准直接带隙跃迁，这是 由于量子限域效应引起的硅材料带隙变化。
实施例8：
光致发光(PL)光谱及荧光寿命分析
使用荧光光谱对样品进行光致发光测试与荧光寿命分析。图6中的光致发光光谱图像表明在325nm的紫外光激发下，样品于435nm和465nm处具有明显的蓝光发射峰，其中，435nm处的发光峰是由于硅烯量子点的带边跃迁引起的，而465nm处的发光峰除了包含不同尺寸硅烯量子点的带边发光外，还存在硅氧烯薄膜本身的氧缺陷复合发光与表面态发光等发光中心。图7为含硅烯量子点的硅氧烯薄膜在435nm发射峰处的荧光寿命曲线，测试所用激发光波长375nm，经拟合计算表明样品的荧光寿命约为1.098ns，这对应于硅烯量子点带边跃迁的荧光寿命，也间接证明了样品属于一种准直接带隙半导体。
本发明采用改进的液相剥离法制备的硅氧烯薄膜，由于使用有机溶剂、及使用过渡金属氯化物作为催化剂使得制备获得的硅氧烯薄膜具有硅烯量子点，可调节其发光性能，使其在紫外光激发下(325nm)显示出强的蓝光发射(435nm)。这与传统方法制得的硅氧烯薄膜具有较大区别，本发明采用实施例1相同的方法，区别仅在于：省去步骤(1)且将步骤(2)中的混合溶液替换为盐酸，制得的硅氧烯薄膜中不含有硅烯量子点(如图8所示)，厚度为1～2.5nm，且在紫外光激发下(325nm)其发射峰位于485nm(如图9所示)。

Claims (10)

  1. 一种含硅烯量子点的硅氧烯的制备方法，其特征在于，该方法包括下述步骤：
    (1)将CaSi 2、脱钙有机溶剂和过渡金属氯化物催化剂混合均匀，待充分反应、脱钙后得到混合溶液；
    (2)将所述步骤(1)得到的混合溶液转移至离心管中，高速离心后去除上清液，然后加入过量盐酸去除金属化合物杂质，获得混合液；
    (3)将所述步骤(2)得到的混合液使用无水乙醇进行高速离心反复清洗数次后，再加入无水乙醇进行超声分散，之后低速离心收集上清液，真空干燥后即可得到含硅烯量子点的硅氧烯纳米薄膜。
  2. 如权利要求1所述的含硅烯量子点的硅氧烯的制备方法，其特征在于，所述步骤(1)中，所述脱钙有机溶剂为正硅酸四乙酯、乙酸乙酯、异丙醇以及无水乙醇中的至少一种；所述过渡金属氯化物催化剂为氯化铁、氯化钴、氯化镍中的至少一种。
  3. 如权利要求1所述的含硅烯量子点的硅氧烯的制备方法，其特征在于，所述步骤(1)中，CaSi 2、过渡金属氯化物催化剂两者的摩尔比为1:1～1:4。
  4. 如权利要求1所述的含硅烯量子点的硅氧烯的制备方法，其特征在于，所述步骤(1)中，所述的反应为在室温下静置反应24～48h。
  5. 如权利要求1所述的含硅烯量子点的硅氧烯的制备方法，其特征在于，所述方法中所述的高速离心是指转速为10000rpm以上，离心时间为10～15min。
  6. 如权利要求1所述的含硅烯量子点的硅氧烯的制备方法，其特征在于，所述步骤(2)中，所述盐酸浓度为1-4mol/L；所述反应时间为3-7h，所加入的盐酸与所加入的所有金属元素的摩尔比大于2。
  7. 如权利要求1所述的含硅烯量子点的硅氧烯的制备方法，其特征在于，所述步骤(3)中，无水乙醇清洗次数为3～5次。
  8. 如权利要求1所述的含硅烯量子点的硅氧烯的制备方法，其特征在于，所述步骤(3)中，所述低速离心转速为200～500rpm，离心时间为3～5min。
  9. 如权利要求1所述的含硅烯量子点的硅氧烯的制备方法，其特征在于，所述步骤(3)中，所述真空干燥温度为60～80℃，干燥时间为24h以上。
  10. 一种含硅烯量子点的硅氧烯薄膜，其特征在于，采用如权利要求1-9 任一项所述的方法制得，所述的硅氧烯薄膜上具有硅烯量子点，所述的硅烯量子点尺寸为2～5nm，硅氧烯薄膜厚度为1～2.5nm，所述的薄膜在紫外光源激发下可发出蓝色荧光。
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