CN112877773B - Non-air-flow MPCVD single crystal diamond growth method using solid carbon source - Google Patents

Non-air-flow MPCVD single crystal diamond growth method using solid carbon source Download PDF

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CN112877773B
CN112877773B CN202110034019.8A CN202110034019A CN112877773B CN 112877773 B CN112877773 B CN 112877773B CN 202110034019 A CN202110034019 A CN 202110034019A CN 112877773 B CN112877773 B CN 112877773B
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carbon source
solid carbon
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crystal diamond
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CN112877773A (en
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朱嘉琦
李一村
代兵
郝晓斌
赵继文
张森
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Harbin Institute of Technology
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    • 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
    • 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

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Abstract

The invention discloses an airless MPCVD single crystal diamond growth method utilizing a solid carbon source, and aims to solve the problems that a large amount of high-purity hydrogen needs to be consumed in the existing MPCVD single crystal diamond growth process, and the utilization rate of the carbon source is low. The single crystal diamond growth method comprises the following steps: firstly, cleaning diamond seed crystals; secondly, placing single-crystal diamond seed crystals on a sample holder at the center of a sample table, and placing a solid carbon source around the single-crystal diamond seed crystals; vacuumizing the reaction cabin, introducing high-purity hydrogen, and increasing the air pressure and the microwave power; monitoring plasma in the reaction chamber by using a spectrometer in the non-air-flow stable growth process, and adjusting the temperature of the surface of the solid carbon source by adjusting the microwave power; and fifthly, ending the growth. In the non-air flow growth process, atomic hydrogen etches a solid carbon source to generate a carbon-hydrogen group, and then the carbon-hydrogen group is transported to the surface of the diamond seed crystal through thermal diffusion particles, and the process is continuously and circularly carried out, so that the rapid growth of the single crystal diamond is realized.

Description

Non-air-flow MPCVD single crystal diamond growth method using solid carbon source
Technical Field
The invention belongs to the field of diamond material preparation, and particularly relates to a preparation method of an airless MPCVD single crystal diamond by using a solid carbon source as a precursor.
Background
The technology of synthetic diamond has developed very rapidly over the last decades, with high temperature and pressure (HPHT) and Chemical Vapor Deposition (CVD) being the most widely used. Microwave Plasma Chemical Vapor Deposition (MPCVD) adopts microwaves as an energy source, has no electrode pollution, generates plasma with higher stability and energy density, and is one of the most promising methods for preparing large-size and high-quality single crystal diamond materials. In the conventional MPCVD method single crystal diamond growth process, the method is generally adoptedGaseous carbon sources such as methane and carbon dioxide are used as growth precursors, solid carbon sources such as graphite flakes and graphite powder are also used as precursors, but no matter which carbon source is selected, a large amount of hydrogen or mixed gas such as hydrogen and methane needs to be continuously introduced and discharged in the growth process, so that the utilization rate of the carbon source is low, and a large amount of high-purity hydrogen is wasted. In the CVD diamond growth mechanism, atomic hydrogen generated by hydrogen dissociation acts like a catalyst, which suppresses sp2The phase is generated, and the combination of the carbon dangling bond and the carbon-containing group on the surface of the substrate is promoted, and the phase is not consumed.
Disclosure of Invention
The invention aims to solve the problems that a large amount of high-purity hydrogen needs to be consumed and the utilization rate of a carbon source is low in the existing MPCVD method single-crystal diamond growth process, and provides a non-air-flow MPCVD method for growing single-crystal diamond by utilizing a solid carbon source.
The method for growing the non-air-flow MPCVD single crystal diamond by utilizing the solid carbon source is realized according to the following steps:
firstly, ultrasonically cleaning diamond seed crystals sequentially through acetone, deionized water and absolute ethyl alcohol to obtain cleaned single crystal diamond seed crystals;
secondly, placing the cleaned monocrystalline diamond seed crystal on a sample holder at the center of a sample table, placing a solid carbon source around the monocrystalline diamond seed crystal, and controlling the total area of the upper surface of the solid carbon source (namely the area contacted with the plasma) to be 10-25 times of the area of the upper surface of the monocrystalline diamond seed crystal;
thirdly, vacuumizing the CVD reaction chamber to 5 x 10-3Introducing high-purity hydrogen (9N) below Pa, raising the air pressure and the microwave power until the temperature of the single crystal diamond seed crystal reaches 900-1000 ℃, closing an air inlet valve and an air exhaust valve when the temperature of the solid carbon source is 650-800 ℃, and forming a closed environment in the CVD reaction chamber;
fourthly, monitoring the plasma in the CVD reaction chamber by a spectrometer in the non-air-flow stable growth process, and calculating C in the emission spectrum obtained by testing2(514nm) and Hα(656nm) the relative intensity ratio of the spectral lines,the temperature of the surface of the solid carbon source is adjusted by adjusting the microwave power, so that the etching rate of atomic hydrogen to the solid carbon source is adjusted, and C is controlled2(514nm) and Hα(656nm) the relative intensity ratio of the spectral lines is between 0.25 and 0.55;
and fifthly, finishing the growth after no time is needed by the air flow growth, and obtaining a monocrystalline diamond epitaxial growth layer with a certain thickness on the surface of the monocrystalline diamond seed crystal.
The method is based on the process mechanism of the MPCVD diamond growth, namely atomic hydrogen generated by hydrogen dissociation is in dynamic circulation and is not consumed, so that gas is not required to be introduced into and extracted from the reaction cavity in the stable growth process by using a solid carbon source. In the non-air flow growth process, atomic hydrogen etches a solid carbon source to generate a carbon-hydrogen group, then the carbon-hydrogen group is transported to the surface of the diamond seed crystal through thermal diffusion particles, atomic hydrogen is removed after deposition growth, the process is continuously and circularly carried out, and the rapid growth of the single crystal diamond is realized.
Drawings
FIG. 1 is a schematic diagram showing the arrangement of single crystal diamond seed crystals and solid carbon sources in the example, wherein the crystal is a water cooling table, the diamond seed crystals, graphite flakes and molybdenum support;
FIG. 2 is a graph showing a plasma emission spectrum test during the growth without a gas flow in the example;
FIG. 3 is an optical photograph of a sample of a single crystal diamond epitaxial growth layer obtained after growth in the example;
fig. 4 is a raman spectrum test chart of a sample of the single crystal diamond epitaxial growth layer obtained after growth in example.
Detailed Description
The first embodiment is as follows: the method for growing the non-air-flow MPCVD single-crystal diamond by utilizing the solid carbon source is implemented according to the following steps:
firstly, ultrasonically cleaning diamond seed crystals sequentially through acetone, deionized water and absolute ethyl alcohol to obtain cleaned single crystal diamond seed crystals;
secondly, placing the cleaned monocrystalline diamond seed crystal on a sample holder at the center of a sample table, placing a solid carbon source around the monocrystalline diamond seed crystal, controlling the total area of the upper surface of the solid carbon source (namely the area contacted with the plasma) to be 10-25 times of the area of the upper surface of the monocrystalline diamond seed crystal,
thirdly, vacuumizing the CVD reaction chamber to 5 x 10-3Introducing high-purity hydrogen (9N) below Pa, raising the air pressure and the microwave power until the temperature of the single crystal diamond seed crystal reaches 900-1000 ℃, closing an air inlet valve and an air exhaust valve when the temperature of the solid carbon source is 650-800 ℃, and forming a closed environment in the CVD reaction chamber;
fourthly, monitoring the plasma in the CVD reaction chamber by a spectrometer in the non-air-flow stable growth process, and calculating C in the emission spectrum obtained by testing2(514nm) and Hα(656nm), and adjusting the surface temperature of the solid carbon source by adjusting the microwave power, thereby adjusting the etching rate of atomic hydrogen on the solid carbon source and controlling C2(514nm) and Hα(656nm) the relative intensity ratio of the spectral lines is between 0.25 and 0.55;
and fifthly, finishing the growth after no time is needed by the air flow growth, and obtaining a monocrystalline diamond epitaxial growth layer with a certain thickness on the surface of the monocrystalline diamond seed crystal.
In the non-air-flow MPCVD single crystal diamond growth process utilizing the solid carbon source, except for the hydrogen introduced in the process of initiating the plasma glow at the initial stage and boosting the pressure to the preparation conditions, the hydrogen does not need to be introduced and extracted in the long-term stable growth process, so that the consumption of high-purity hydrogen is obviously reduced, the atomic hydrogen dissociated by the hydrogen is utilized to etch the solid carbon source and deposit the diamond in the circulating process, the utilization rate of the carbon source is improved, and the high-efficiency utilization of the carbon source and the rapid growth of the single crystal diamond are realized.
The second embodiment is as follows: the difference between the present embodiment and the first embodiment is that the material of the sample holder in the second step is molybdenum.
The third concrete implementation mode: the difference between this embodiment and either embodiment is that the purity of the solid carbon source is greater than 99.9%.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is that the solid carbon source is graphite flakes, graphite particles, or graphene powder.
The fifth concrete implementation mode is as follows: the difference between the first embodiment and the fourth embodiment is that when the solid carbon source is in the form of particles or powder, the solid carbon source is placed in the grooves of the sample stage and filled to be flush with the surface of the water-cooling stage.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is that the spacing between the solid carbon source and the single crystal diamond seed crystal in step two is 1-40 mm.
The seventh embodiment: the present embodiment is different from one of the first to the sixth embodiments in that in the third step, when the temperature of the solid carbon source is 700 to 750 ℃, the air intake valve and the air exhaust valve are closed.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is the control C in step four2(514nm) and HαThe relative intensity ratio of the (656nm) spectral line is between 0.35 and 0.45.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is that the growth without air flow is controlled in the fourth step for 2 to 100 hours.
The specific implementation mode is ten: the present embodiment is different from one of the first to ninth embodiments in that the thickness of the step five single crystal diamond epitaxial growth layer is 0.02 to 2 mm.
Example (b): the method for growing the non-air-flow MPCVD single-crystal diamond by using the solid carbon source is implemented according to the following steps:
firstly, ultrasonically cleaning diamond seed crystals sequentially through acetone, deionized water and absolute ethyl alcohol, wherein each cleaning step is 15min, and obtaining cleaned single crystal diamond seed crystals, wherein the size of the diamond seed crystals is 5mm multiplied by 5 mm;
secondly, placing the cleaned single-crystal diamond seed crystals on a molybdenum support at the center of a sample table, taking graphite sheets (with the purity of 99.99%) as a solid carbon source, wherein the size of a single graphite sheet is 10mm multiplied by 10mm, and all four graphite sheets are symmetrically placed around the diamond seed crystals;
thirdly, vacuumizing the CVD reaction chamber to 5 x 10-3Pa, then onIntroducing high-purity hydrogen (9N) of 200sccm, increasing the air pressure and the microwave power until the temperature of the monocrystalline diamond seed crystal reaches 980 ℃, closing an air inlet valve and an air exhaust valve when the temperature of the solid carbon source is 720 ℃, and forming a closed environment in the CVD reaction chamber;
fourthly, starting to grow in an airless mode, monitoring plasma in the CVD reaction chamber by adopting a spectrometer in the stable growth process of the airless mode, and calculating C in the emission spectrum obtained by testing2(514nm) and Hα(656nm), and adjusting the surface temperature of the solid carbon source by adjusting the microwave power, thereby adjusting the etching rate of atomic hydrogen on the solid carbon source and controlling C2(514nm) and Hα(656nm) the relative intensity ratio of the spectral lines is 0.42;
fifthly, stopping the machine for sampling after 20 hours of non-air flow growth, and obtaining a 0.36mm monocrystalline diamond epitaxial growth layer on the surface of the monocrystalline diamond seed crystal.
FIG. 2 shows the result of plasma emission spectroscopy in the airless growth process of this embodiment, in which a strong C is present2Spectral line and HαLine indicating atomic hydrogen generated by dissociation of hydrogen gas etches graphite into carbon-containing groups, where C2Spectral line and HαThe relative intensity ratio of the spectral lines was 0.42.
FIG. 4 shows the results of Raman spectroscopy on the growth sample, high intensity sharp 1332.5cm-1The first-order Raman peak of the diamond shows that the prepared diamond sample has higher quality.

Claims (8)

1. The method for growing the non-air-flow MPCVD single crystal diamond by utilizing the solid carbon source is characterized by being realized according to the following steps:
firstly, ultrasonically cleaning diamond seed crystals sequentially through acetone, deionized water and absolute ethyl alcohol to obtain cleaned single crystal diamond seed crystals;
secondly, placing the cleaned monocrystalline diamond seed crystal on a sample holder at the center of a sample table, placing a solid carbon source around the monocrystalline diamond seed crystal, and controlling the total area of the upper surface of the solid carbon source to be 10-25 times of the area of the upper surface of the monocrystalline diamond seed crystal;
thirdly, vacuumizing the CVD reaction chamber to 5 x 10-3Introducing high-purity hydrogen below Pa, raising the air pressure and the microwave power until the temperature of the single crystal diamond seed crystal reaches 900-1000 ℃, closing an air inlet valve and an air exhaust valve when the temperature of the solid carbon source is 650-800 ℃, and forming a closed environment in the CVD reaction chamber;
fourthly, monitoring the plasma in the CVD reaction chamber by a spectrometer in the non-air-flow stable growth process, and calculating C in the emission spectrum obtained by testing2And HαThe relative intensity ratio of the spectral line is adjusted by adjusting the microwave power to adjust the temperature of the surface of the solid carbon source, thereby adjusting the etching rate of atomic hydrogen to the solid carbon source and controlling C2And HαThe relative intensity ratio of the spectral lines is between 0.25 and 0.55;
fifthly, after the time required by the air flow-free growth is not needed, the growth is finished, and a single crystal diamond epitaxial growth layer with a certain thickness is obtained on the surface of the single crystal diamond seed crystal;
wherein the solid carbon source is graphite flake.
2. The method for growing MPCVD single crystal diamond using solid carbon source without flow according to claim 1, wherein the material of the sample holder in the second step is molybdenum.
3. The airless MPCVD single crystal diamond growth method using a solid carbon source of claim 1, wherein the purity of the solid carbon source is greater than 99.9%.
4. The airless MPCVD single crystal diamond growth method using a solid carbon source as in claim 1, wherein the spacing between the solid carbon source and the single crystal diamond seed in step two is 1-40 mm.
5. The airless MPCVD single crystal diamond growth method using a solid carbon source of claim 1, wherein in the third step, the air inlet valve and the air outlet valve are closed when the temperature of the solid carbon source is 700-750 ℃.
6. The method for non-flow MPCVD single crystal diamond growth using a solid carbon source according to claim 1, wherein C is controlled in step four2And HαThe relative intensity ratio of the spectral lines is between 0.35 and 0.45.
7. The method for growing the MPCVD single-crystal diamond by using the solid carbon source according to claim 1, wherein the growth in the fourth step is controlled to be carried out for 2-100 h without air flow.
8. The airless MPCVD single crystal diamond growth method using a solid carbon source according to claim 1, wherein the thickness of the step five single crystal diamond epitaxial growth layer is 0.02-2 mm.
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JP7033824B1 (en) * 2021-06-28 2022-03-11 株式会社ディスコ Manufacturing method of single crystal diamond and single crystal diamond
CN113652746B (en) * 2021-10-21 2022-01-25 天津本钻科技有限公司 Method for improving quality of single crystal diamond
CN114032526A (en) * 2021-11-10 2022-02-11 哈尔滨工业大学 Integrated high-quality diamond MPCVD growth equipment without external raw material gas and growth method
CN114059159A (en) * 2021-11-18 2022-02-18 北京大学东莞光电研究院 Diamond growth method
CN114481310B (en) * 2022-02-25 2023-09-08 北京北方华创微电子装备有限公司 Diamond growth equipment and method
CN115125614A (en) * 2022-07-21 2022-09-30 生命珍宝有限公司 Technology for recycling carbon source gasified by hairs in process of growing diamond by MPCVD method
CN115198359A (en) * 2022-07-21 2022-10-18 生命珍宝有限公司 Method for cultivating hair carbon source into diamond by MPCVD device

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