WO2018059371A1 - 具有SiV发光的超小晶粒尺寸纳米金刚石薄膜及其制备 - Google Patents

具有SiV发光的超小晶粒尺寸纳米金刚石薄膜及其制备 Download PDF

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WO2018059371A1
WO2018059371A1 PCT/CN2017/103313 CN2017103313W WO2018059371A1 WO 2018059371 A1 WO2018059371 A1 WO 2018059371A1 CN 2017103313 W CN2017103313 W CN 2017103313W WO 2018059371 A1 WO2018059371 A1 WO 2018059371A1
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siv
nano
diamond film
grain size
luminescence
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胡晓君
陈成克
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浙江工业大学
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Priority to US17/072,379 priority patent/US11186923B2/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/274—Diamond only using microwave discharges
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/10—Heating of the reaction chamber or the substrate
    • C30B25/105—Heating of the reaction chamber or the substrate by irradiation or electric discharge
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/04—Diamond
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B35/00—Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
    • C30B35/007—Apparatus for preparing, pre-treating the source material to be used for crystal growth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the invention relates to an ultra-small grain size nano diamond film with SiV luminescence and a preparation method thereof.
  • the nanodiamond particles have excellent biocompatibility, easy surface modification, additional functional groups, and good optical stability. Such properties make nanodiamond particles particularly suitable for biological applications, including labeling and tracking of biological cells, extracellular drug delivery, and detection of adsorption characteristics of biological macromolecules. Therefore, the luminescent color center due to defects in diamond is extremely important (color center refers to a kind of electron or hole trapped by a point defect, a point defect pair or a point defect group in the crystal, which can cause light absorption in the visible spectral region. Defects, that is, the excitation of a certain way can make the color center emit light).
  • Nitrogen vacancies are a common defect in diamonds, and nanodiamonds containing nitrogen vacancies are readily prepared. More researchers have used biological experiments with nano-diamonds emitting nitrogen vacancies.
  • nitrogen vacancy generally has an electrically neutral nitrogen vacancy (NV 0 ) luminescence center and an electronegativity nitrogen vacancy (NV - ) luminescence center, both of which are relatively stable.
  • NV 0 electrically neutral nitrogen vacancy
  • NV - electronegativity nitrogen vacancy
  • the zero-acoustic sub-line of the SiV illuminating color center is at 738 nm and the luminescence peak is very narrow (about 5 nm), and the luminescence lifetime is extremely short, only about 1.2 ns.
  • Theoretical calculations show that the SiV luminescence center can still exist stably when the nano-diamond grain size is 1.1-1.8 nm.
  • the present invention deposits a nano-diamond film having a grain size of about 10 nm and having SiV luminescence on a single crystal silicon wafer by microwave plasma chemical vapor deposition. Oxygen plasma etches the film to reduce the diamond grain size. Finally, a nano-diamond film with a grain size of 2.5-5 nm and SiV luminescence is prepared.
  • the present invention adopts the following technical solutions:
  • An ultra-small grain size nano-diamond film with SiV luminescence is prepared as follows:
  • step (2) using an oxygen plasma (the oxygen plasma is generated by a microwave plasma chemical vapor deposition apparatus) bombardment method, in a microwave power of 600 to 1000 W, a gas pressure of 0.5 to 6 torr, and an oxygen to nitrogen volume ratio of 1:4 to 6
  • a mixed gas plasma oxygen plasma is used to etch diamonds, nitrogen acts to help oxygen become plasma and reduce partial pressure of oxygen
  • the nanodiamond film obtained in step (1) is subjected to oxygen plasma etching.
  • the etch treatment is carried out for 5 to 30 minutes to obtain the ultra-small grain size nano-diamond film having SiV luminescence.
  • the size of the nano-diamond crystal grains is 2.5 to 5 nm, and the size distribution is uniform.
  • a nano-diamond film is prepared on a single crystal silicon substrate by a microwave plasma chemical vapor deposition (MPCVD) method, which can be carried out by using a conventional microwave plasma chemical vapor deposition apparatus, and is obtained by the step (1).
  • the thickness of the nano-diamond film is usually from 1 to 3 ⁇ m, and the grain size in the film is usually from 6 to 10 nm.
  • the operation method of the step (1) is:
  • the concentration of the Ti powder is 0.001 to 0.005 g/mL, and the concentration of the diamond fine powder is 0.001 to 0.005 g/mL.
  • step (b) depositing a thin film: the single crystal silicon substrate pretreated by the step (a) is placed in a microwave plasma chemical vapor deposition apparatus, and a mixed gas of methane and argon volume ratio of 1 to 2:49 is used as a reaction gas.
  • the reaction was carried out at 400 to 500 ° C for 1 h, that is, a nano-diamond film having a thickness of 1 to 3 ⁇ m and a grain size of 6 to 10 nm was deposited on the surface of the single crystal silicon substrate.
  • the method is simple and easy to operate, and the process of film growth and ion bombardment to reduce crystal grains can be completed in one device;
  • the diamond grain size is small (2.5 ⁇ 5nm), which is of great scientific significance and value for the application of nanodiamond in biological experiments (biomarker tracking, drug delivery, etc.).
  • Figure 1 Raman spectrum of the sample treated with oxygen plasma for 10 min in Example 1;
  • FIG. 1 Photoluminescence spectrum of the sample treated by oxygen plasma treatment for 10 minutes in Example 1;
  • FIG. 3 Transmission electron micrograph of the sample treated by oxygen plasma in Example 1 for 10 minutes;
  • Figure 4 Raman spectrum of the oxygen plasma treatment 20 min sample in Example 2;
  • FIG. 1 Photoluminescence spectrum of the sample treated with oxygen plasma for 20 min in Example 2;
  • Figure 6 Transmission electron micrograph of the oxygen plasma treated 20 min sample in Example 2.
  • the single crystal silicon substrate was first placed in a mixture of Ti powder (0.1 g), diamond micropowder (0.1 g) and acetone (50 mL), ultrasonically (ultrasound power 200 W), shaken for 45 min, and then placed in freshly taken acetone. The mixture was shaken for 1 min, taken out and dried, and then placed in freshly taken acetone for 1 min, then removed and dried to serve as a substrate for nanodiamond film growth.
  • the above-mentioned pretreated single crystal silicon substrate is placed in a microwave plasma chemical vapor deposition apparatus (the equipment is Taiwan Shuojie Enterprise Co., Ltd.
  • the nano-diamond film has a grain size of about 10 nm.
  • the grown nano-diamond film is subjected to an oxygen plasma treatment, and the oxygen plasma can be produced by a microwave plasma chemical vapor deposition apparatus.
  • the gas source is 20 sccm of oxygen and 80 sccm of nitrogen
  • the microwave power is 900 W
  • the chamber pressure is 5 torr.
  • the film was treated for 10 minutes to obtain the diamond film of the ultra-small size nanodiamond crystal grain having the SiV illuminating color center.
  • the composition of the film was analyzed by Raman spectroscopy with a laser wavelength of 532 nm, as shown in Fig. 1. It can be seen that characteristic peaks such as 1140, 1332, 1350, 1470 and 1560 cm -1 appear in the spectrum, and 1332 cm -1 is a characteristic peak of diamond, but it is not obvious in the spectrum, which is due to the grain size being too small. of. 1560cm -1 disordered graphite sp 2 bonds characteristic peaks, 1140 and 1470cm -1 as a characteristic peak trans-polyacetylene chains, 1350cm -1 of sp 3 bonding characteristic peaks of carbon clusters. It is indicated that the film is mainly composed of a diamond phase and a disordered graphite phase, but a small amount of other phases are contained in the grain boundary, which is consistent with the visible Raman characteristic spectrum of the conventional nanodiamond film.
  • the luminescence properties of the film were analyzed by PL spectrum with a laser wavelength of 532 nm, as shown in Fig. 2. It can be seen that the SiV luminescence peak appears at the 738 nm position in the PL spectrum, and there is a nitrogen vacancy luminescence peak at 637 nm, but as mentioned before, the peak width of the nitrogen vacancy luminescence peak is too wide to be suitable for use in living organisms. label. This shows that we have prepared a nano-diamond film with a SiV luminescence center.
  • the microstructure was analyzed by high resolution transmission electron microscopy, as shown in Figure 3. It can be observed that the grain size of the sample is about 4-5 nm in the oxygen plasma treatment for 10 minutes, and the grain size distribution is uniform, and the corresponding selected area electron diffraction patterns indicate that the crystal grains are diamond grains. This shows that when treated by oxygen plasma for 10 minutes, we prepared a nano-diamond film having a SiV luminescence center with a grain size of 4-5 nm.
  • the single crystal silicon substrate was first placed in a mixture of Ti powder (0.1 g), diamond micropowder (0.1 g) and acetone (50 mL), ultrasonically (ultrasound power 200 W), shaken for 45 min, and then placed in freshly taken acetone. The mixture was shaken for 1 min, taken out and dried, and then placed in freshly taken acetone for 1 min, then removed and dried to serve as a substrate for nanodiamond film growth.
  • the above-prepared single crystal silicon substrate was placed in a microwave plasma chemical vapor deposition apparatus (the equipment was manufactured by Taiwan Shuojie Enterprise Co., Ltd., cavity 6 inches, model IPLAS-CYRANNUS), with methane and argon gas.
  • a gas source As a gas source, a gas volume ratio of 4:196, a growth power of 1200 W, a growth pressure of 150 torr, and a growth time of 1 h, a nano-diamond film having a thickness of about 1 ⁇ m was prepared, and the grain size was about 10 nm.
  • the grown nano-diamond film is subjected to an oxygen plasma treatment, and the oxygen plasma can be produced by a microwave plasma chemical vapor deposition apparatus.
  • the gas source is 20 sccm of oxygen and 80 sccm of nitrogen
  • the microwave power is 900 W
  • the chamber pressure is 5 torr.
  • the film was treated for 20 minutes to obtain the diamond film of the ultra-small size nanodiamond crystal grain having the SiV illuminating color center.
  • the composition of the film was analyzed by Raman spectroscopy with a laser wavelength of 532 nm, as shown in FIG. It can be seen that characteristic peaks such as 1140, 1332, 1350, 1470 and 1560 cm -1 appear in the spectrum, and 1332 cm -1 is a characteristic peak of diamond, but it is not obvious in the spectrum, which is due to the grain size being too small. of. 1560cm -1 disordered graphite sp 2 bonds characteristic peaks, 1140 and 1470cm -1 as a characteristic peak trans-polyacetylene chains, 1350cm -1 of sp 3 bonding characteristic peaks of carbon clusters. It is indicated that the film is mainly composed of a diamond phase and a disordered graphite phase, but a small amount of other phases are contained in the grain boundary, which is consistent with the visible Raman characteristic spectrum of the conventional nanodiamond film.
  • the luminescence properties of the film were analyzed using a PL spectrum with a laser wavelength of 532 nm, as shown in FIG. It can be seen that the SiV luminescence peak appears at the 738 nm position in the PL spectrum, which indicates that we have prepared a nano-diamond film having a SiV luminescence center.
  • the microstructure was analyzed by high resolution transmission electron microscopy, as shown in Figure 6. It can be observed that the grain size of the sample in the oxygen plasma treatment for 20 minutes is about 2.5-4 nm, and the grain size distribution is uniform, and the corresponding selected area electron diffraction pattern is illustrated. These grains are diamond grains. This shows that when treated by oxygen plasma for 20 minutes, we prepared nanodiamond crystallites having a SiV luminescence center with a grain size of 2.5-4 nm.
  • the microstructure of the film was characterized by high-resolution transmission electron microscopy.
  • the sample did contain 2-5 nm particles, but the grain distribution was concentrated and uneven. The uniformity of the film could not be proven.
  • the sample was tested by Raman spectroscopy with a laser wavelength of 488 nm. Compared with the microcrystalline diamond film, it is found that the nano-diamond film has a strong diamond peak, which also indicates that there are large-sized nano-diamond particles in the sample, that is, the grain size distribution in the film is not uniform.

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Abstract

一种具有SiV发光的超小晶粒尺寸纳米金刚石薄膜，按如下方法制备得到：（1）采用微波等离子体化学气相沉积方法，在单晶硅衬底上制备具有SiV发光的纳米金刚石薄膜；（2）采用氧等离子体轰击方法，在微波功率600～1000W，气压0.5～6torr，氧气氮气体积比1：4～6的混合气体等离子体中，对步骤（1）得到的纳米金刚石薄膜进行氧等离子体刻蚀处理5～30min，即得具有SiV发光的超小晶粒尺寸纳米金刚石薄膜。

Description

具有SiV发光的超小晶粒尺寸纳米金刚石薄膜及其制备 (一)技术领域
本发明涉及一种具有SiV发光的超小晶粒尺寸纳米金刚石薄膜及其制备方法。
(二)背景技术
纳米金刚石颗粒具有极好的生物相容性，容易进行表面修饰、附加官能团，以及很好的光学稳定性。这样的特性使纳米金刚石颗粒特别适合于生物学上的应用，包括生物细胞的标记和追踪，细胞外药物传输和生物大分子的吸附特性检测。因此金刚石中由于缺陷造成的发光色心显得极其重要(色心是指晶体中由点缺陷、点缺陷对或点缺陷群捕获电子或空穴而构成的一种可导致可见光谱区的光吸收的缺陷，即通过一定方式激发可以使色心发光)。结构越稳定、发光效率越高、空间相干性越好、发光寿命越短的色心越有利于生物标签的应用。相比于其他空位色心，SiV发光色心在这些方面具有更好的性能。同时，越小尺寸的纳米金刚石颗粒越有利于金刚石颗粒进入细胞内部，并且对于细胞内的定位追踪更加准确。因此成功制备具有SiV发光色心的尺寸超小的纳米金刚石晶粒对于纳米金刚石在生物实验中的应用有极大的帮助。
氮空位属于金刚石中一种常见的缺陷，并且含氮空位的纳米金刚石容易制备。已经有较多研究者使用氮空位发光的纳米金刚石进行生物实验研究。在金刚石中，氮空位发光一般有电中性氮空位(NV0)发光中心和电负性氮空位(NV-)发光中心，这两种结构都比较稳定。前者的零声子线发光在575nm处，并且在580～650nm左右有一个较宽的伴随峰。后者的零声子线发光在637nm处，并且在800nm左右有一个伴随峰。这么宽的激发范围导致氮空位发光色心的发光效率低，空间相干性差。另外，有研究者的理论计算结果发现，氮在金刚石中能够稳定存在的最小晶粒尺寸为2nm左右。实验中很难制得该尺寸的氮空位发光缺陷纳米金刚石。目前在生物实验中使用的氮空位发光纳米金刚石颗粒一般在5～10nm。同时氮空位的发光寿命长达25ns。这都限制了氮空位发光纳米金刚石颗粒在生物实验中的应用。SiV发光色心的零声子线在738nm且发光峰很窄(约5nm)，发光寿命极短，只有约1.2ns。理论计算表明，纳米金刚石晶粒尺寸为1.1～1.8nm时，SiV发光中心仍然可以稳定存在。2013年在陨石中发现，具有SiV发光中心的晶粒尺寸2nm左右的纳米金刚石晶粒，但还未能在实验上制备晶粒尺寸达到2nm且尺寸均匀的纳米金刚石晶粒。因此，制备具有SiV发光中心的超小尺寸纳米金刚石晶粒是具有可行性的。
(三)发明内容
本发明的目的是提供一种具有SiV发光色心的超小晶粒尺寸纳米金刚石薄膜及其制备方法。
为了制备得到具有SiV发光色心的超小晶粒尺寸纳米金刚石薄膜，本发明使用微波等离子体化学气相沉积在单晶硅片上沉积晶粒尺寸约10nm并且具有SiV发光的纳米金刚石薄膜，再通过氧等离子对薄膜进行刻蚀处理，使金刚石晶粒尺寸逐渐减小，最后制备得到了晶粒尺寸为2.5～5nm，并且具有SiV发光的纳米金刚石薄膜。
为实现上述目的，本发明采用如下技术方案：
一种具有SiV发光的超小晶粒尺寸纳米金刚石薄膜，按如下方法制备得到：
(1)采用微波等离子体化学气相沉积方法，在单晶硅衬底上制备具有SiV发光的纳米金 刚石薄膜；
(2)采用氧等离子体(所述的氧等离子体采用微波等离子体化学气相沉积设备来产生)轰击方法，在微波功率600～1000W，气压0.5～6torr，氧气氮气体积比1：4～6的混合气体等离子体中(对金刚石有刻蚀作用的是氧等离子体，氮气的作用是帮助氧气成为等离子体以及减少氧的分压)，对步骤(1)得到的纳米金刚石薄膜进行氧等离子体刻蚀处理5～30min，即得所述具有SiV发光的超小晶粒尺寸纳米金刚石薄膜。
按照本发明方法制得的具有SiV发光的超小晶粒尺寸纳米金刚石薄膜中，纳米金刚石晶粒的尺寸在2.5～5nm，并且尺寸分布均匀。
所述步骤(1)中，采用微波等离子体化学气相沉积(MPCVD)法在单晶硅衬底上制备纳米金刚石薄膜，可采用常规微波等离子体化学气相沉积设备进行，步骤(1)制得的纳米金刚石薄膜厚度通常在1～3μm，薄膜中的晶粒尺寸通常为6～10nm。
进一步，所述步骤(1)的操作方法为：
(a)预处理：将单晶硅衬底先置于Ti粉、金刚石微粉和丙酮的混合液中超声震荡45min，然后再置于新取的丙酮中超声震荡1min，取出吹干后，再次置于新取的丙酮中超声震荡1min，之后取出干燥，作为纳米金刚石薄膜生长的衬底；
所述Ti粉、金刚石微粉和丙酮的混合液中，Ti粉的浓度为0.001～0.005g/mL，金刚石微粉的浓度为0.001～0.005g/mL。
(b)沉积薄膜：将经过步骤(a)预处理的单晶硅衬底放入微波等离子体化学气相沉积设备中，以甲烷和氩气体积比1～2：49的混合气体为反应气体，在400～500℃下反应1h，即在单晶硅衬底表面沉积得到厚度为1～3μm，晶粒尺寸为6～10nm的纳米金刚石薄膜。
本发明的有益效果主要体现在：
(1)方法简单、易于操作，可在一台设备中完成薄膜生长和离子轰击减小晶粒的过程；
(2)制备得到的超小尺寸金刚石晶粒粒径分布均匀；
(3)金刚石晶粒尺寸小(2.5～5nm)，对纳米金刚石在生物实验(生物标签追踪，药物传输等)方面的应用具有十分重要的科学意义和价值。
(四)附图说明
图1：实施例1中氧等离子体处理10min样品的拉曼谱图；
图2：实施例1中氧等离子体处理10min样品的光致发光谱图；
图3：实施例1中氧等离子体处理10min样品的透射电镜图；
图4：实施例2中氧等离子体处理20min样品的拉曼谱图；
图5：实施例2中氧等离子体处理20min样品的光致发光谱图；
图6：实施例2中氧等离子体处理20min样品的透射电镜图。
(五)具体实施方式
下面结合具体实施例对本发明进行进一步描述，但本发明的保护范围并不仅限于此。
实施例1：
将单晶硅衬底先置于Ti粉(0.1g)、金刚石微粉(0.1g)和丙酮(50mL)的混合液中超声(超声机功率200W)震荡45min，然后再置于新取的丙酮中超声震荡1min，取出吹干后，再次置于新取的丙酮中超声震荡1min，之后取出干燥，作为纳米金刚石薄膜生长的衬底。将经过以上预处理的单晶硅衬底放入微波等离子体化学气相沉积设备(设备为台湾硕傑企业股份 有限公司生产，腔体6英寸，型号为IPLAS-CYRANNUS)中，以甲烷和氩气为气源，气体体积比4：196，生长功率1200W，生长气压150torr，生长时间1h，制备出厚度约1μm的纳米金刚石薄膜，晶粒尺寸约10nm。
对生长好的纳米金刚石薄膜进行氧等离子体处理，氧等离子体可用微波等离子体化学气相沉积设备产生。气源为20sccm的氧气和80sccm的氮气，微波功率900W，腔体气压5torr。对薄膜处理10分钟，即得所述具备SiV发光色心的超小尺寸纳米金刚石晶粒的金刚石薄膜。
采用激光波长为532nm的Raman光谱对薄膜成分进行分析，如图1所示。可以看出，谱图中出现了1140,1332,1350,1470和1560cm-1等特征峰，1332cm-1为金刚石特征峰，但在谱图中并不明显，这是由于晶粒尺寸过于细小导致的。1560cm-1为无序sp2键石墨的特征峰，1140和1470cm-1为反式聚乙炔链的特征峰，1350cm-1为sp3键碳团簇的特征峰。说明薄膜主要由金刚石相和无序石墨相组成，但晶界中包含少量其他相，这与通常的纳米金刚石薄膜的可见光Raman特征谱图一致。
对氧等离子体处理后的样品，采用激光波长为532nm的PL光谱对薄膜发光性能进行分析，如图2所示。可以看出，在PL谱图中的738nm位置出现了SiV发光峰，并且在637nm处有氮空位发光峰，但是如之前提到的，氮空位发光峰的峰宽太宽，不适合用于生物标签。这说明我们已经制备得到了具有SiV发光中心得纳米金刚石薄膜。
采用高分辨透射电镜对样品进行微结构分析，如图3所示。可以观察到，氧等离子体处理10分钟样品晶粒大小在4-5nm左右，且晶粒大小分布均匀，对应的选区电子衍射图说明这些晶粒为金刚石晶粒。这说明通过氧等离子体处理10分钟时，我们制备得到了晶粒尺寸在4-5nm的具有SiV发光中心的纳米金刚石薄膜。
实施例2：
将单晶硅衬底先置于Ti粉(0.1g)、金刚石微粉(0.1g)和丙酮(50mL)的混合液中超声(超声机功率200W)震荡45min，然后再置于新取的丙酮中超声震荡1min，取出吹干后，再次置于新取的丙酮中超声震荡1min，之后取出干燥，作为纳米金刚石薄膜生长的衬底。将经过以上预处理的单晶硅衬底放入微波等离子体化学气相沉积设备(设备为台湾硕傑企业股份有限公司生产，腔体6英寸，型号为IPLAS-CYRANNUS)中，以甲烷和氩气为气源，气体体积比4：196，生长功率1200W，生长气压150torr，生长时间1h，制备出厚度约1μm的纳米金刚石薄膜，晶粒尺寸约10nm。
对生长好的纳米金刚石薄膜进行氧等离子体处理，氧等离子体可用微波等离子体化学气相沉积设备产生。气源为20sccm的氧气和80sccm的氮气，微波功率900W，腔体气压5torr。对薄膜处理20分钟，即得所述具备SiV发光色心的超小尺寸纳米金刚石晶粒的金刚石薄膜。
采用激光波长为532nm的Raman光谱对薄膜成分进行分析，如图4所示。可以看出，谱图中出现了1140,1332,1350,1470和1560cm-1等特征峰，1332cm-1为金刚石特征峰，但在谱图中并不明显，这是由于晶粒尺寸过于细小导致的。1560cm-1为无序sp2键石墨的特征峰，1140和1470cm-1为反式聚乙炔链的特征峰，1350cm-1为sp3键碳团簇的特征峰。说明薄膜主要由金刚石相和无序石墨相组成，但晶界中包含少量其他相，这与通常的纳米金刚石薄膜的可见光Raman特征谱图一致。
对氧等离子体处理后的样品，采用激光波长为532nm的PL光谱对薄膜发光性能进行分析，如图5所示。可以看出，在PL谱图中的738nm位置出现了SiV发光峰，这说明我们已经制备得到了具有SiV发光中心得纳米金刚石薄膜。
采用高分辨透射电镜对样品进行微结构分析，如图6所示。可以观察到，氧等离子体处理20分钟样品晶粒大小在2.5-4nm左右，且晶粒大小分布均匀，对应的选区电子衍射图说明 这些晶粒为金刚石晶粒。这说明通过氧等离子体处理20分钟时，我们制备得到了晶粒尺寸在2.5-4nm的具有SiV发光中心的纳米金刚石晶粒。
对比例1：
Igor I.Vlasov等人，在10mm*10mm*0.5mm的硅片上，采用微波等离子体化学气相沉积法直接制备小晶粒尺寸纳米金刚石薄膜。气体比例93％Ar/5％H2/2％CH4，生长气压1.2*104Pa，微波功率2.4kW，薄膜厚度1微米。可参考文献Vlasov II,Barnard AS,Ralchenko VG,Lebedev OI,Kanzyuba MV,Saveliev AV,et al.Nanodiamond Photoemitters Based on Strong Narrow-Band Luminescence from Silicon-Vacancy Defects.Advanced materials.2009；21(7):808-12.
采用高分辨透射电镜对薄膜进行微结构表征，样品中确实包含2-5nm大小颗粒，但是晶粒分布集中，不均匀。未能证明薄膜的均匀性。同时，对样品采用激光波长为488nm的Raman光谱测试。对比微晶金刚石薄膜，会发现纳米金刚石薄膜有较强的金刚石峰，这也说明样品中存在尺寸较大的纳米金刚石颗粒，即薄膜中晶粒尺寸分布不均匀。
这说明我们通过先制备5-8nm的均匀纳米金刚石薄膜，然后通过微波等离子体处理减小金刚石颗粒的方法，可以制备超小晶粒尺寸，且晶粒尺寸分布均匀的纳米金刚石薄膜。

Claims (5)

  1. 一种具有SiV发光的超小晶粒尺寸纳米金刚石薄膜，其特征在于，所述的具有SiV发光的超小晶粒尺寸纳米金刚石薄膜按如下方法制备得到：
    (1)采用微波等离子体化学气相沉积方法，在单晶硅衬底上制备具有SiV发光的纳米金刚石薄膜；
    (2)采用氧等离子体轰击方法，在微波功率600～1000W，气压0.5～6torr，氧气氮气体积比1：4～6的混合气体等离子体中，对步骤(1)得到的纳米金刚石薄膜进行氧等离子体刻蚀处理5～30min，即得所述具有SiV发光的超小晶粒尺寸纳米金刚石薄膜。
  2. 如权利要求1所述的具有SiV发光的超小晶粒尺寸纳米金刚石薄膜，其特征在于，所述的具有SiV发光的超小晶粒尺寸纳米金刚石薄膜中，纳米金刚石晶粒的尺寸在2.5～5nm，并且尺寸分布均匀。
  3. 如权利要求1所述的具有SiV发光的超小晶粒尺寸纳米金刚石薄膜，其特征在于，步骤(1)制得的纳米金刚石薄膜的厚度在1～3μm，薄膜中的晶粒尺寸为6～10nm。
  4. 如权利要求1所述的具有SiV发光的超小晶粒尺寸纳米金刚石薄膜，其特征在于，所述步骤(1)的操作方法为：
    (a)预处理：将单晶硅衬底先置于Ti粉、金刚石微粉和丙酮的混合液中超声震荡45min，然后再置于新取的丙酮中超声震荡1min，取出吹干后，再次置于新取的丙酮中超声震荡1min，之后取出干燥，作为纳米金刚石薄膜生长的衬底；
    (b)沉积薄膜：将经过步骤(a)预处理的单晶硅衬底放入微波等离子体化学气相沉积设备中，以甲烷和氩气体积比1～2：49的混合气体为反应气体，在400～500℃下反应1h，即在单晶硅衬底表面沉积得到厚度为1～3μm，晶粒尺寸为6～10nm的纳米金刚石薄膜。
  5. 如权利要求4所述的具有SiV发光的超小晶粒尺寸纳米金刚石薄膜，其特征在于，步骤(a)中，所述Ti粉、金刚石微粉和丙酮的混合液中，Ti粉的浓度为0.001～0.005g/mL，金刚石微粉的浓度为0.001～0.005g/mL。
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WANG JUNFENG: "Preparation, Coherence and Temperature detection of Diamond NV color center", CHINA DOCTORAL DISSERTATIONS, no. 9, 15 September 2016 (2016-09-15), pages 46 - 55, ISSN: 1674-022 *

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