CN114059159A - Diamond growth method - Google Patents
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- CN114059159A CN114059159A CN202111371322.3A CN202111371322A CN114059159A CN 114059159 A CN114059159 A CN 114059159A CN 202111371322 A CN202111371322 A CN 202111371322A CN 114059159 A CN114059159 A CN 114059159A
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 69
- 239000010432 diamond Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 72
- 239000013078 crystal Substances 0.000 claims abstract description 54
- 230000006698 induction Effects 0.000 claims abstract description 30
- 230000005281 excited state Effects 0.000 claims abstract description 5
- 238000000151 deposition Methods 0.000 claims description 62
- 230000008021 deposition Effects 0.000 claims description 55
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 230000005284 excitation Effects 0.000 claims description 22
- 230000001965 increasing effect Effects 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 230000003595 spectral effect Effects 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 235000017899 Spathodea campanulata Nutrition 0.000 claims description 5
- 230000007613 environmental effect Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 34
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 229940094933 n-dodecane Drugs 0.000 description 13
- 238000005485 electric heating Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 4
- 230000001939 inductive effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001534 heteroepitaxy Methods 0.000 description 1
- 238000001657 homoepitaxy Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
Images
Classifications
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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
- 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
- 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
-
- 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
- C23C16/44—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 method of coating
- C23C16/50—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 method of coating using electric discharges
-
- 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
Abstract
The invention provides a method for growing diamond, which adopts a condensed carbon source to replace a gaseous carbon source, does not need to introduce process gas in the process of diamond growth except for providing initial conditions, and only needs to excite the condensed carbon source to form a plasma region suitable for diamond growth; the carbon source in an excited state is deposited on the induction seed crystal which is placed in advance and the diamond is grown in a homoepitaxial mode. The method expands the carbon source drawing range, saves energy, avoids waste of process gas and is convenient for continuous growth of diamond.
Description
Technical Field
The invention relates to the technical field of diamond preparation, in particular to a diamond growth method.
Background
The single crystal diamond has excellent physical and chemical properties, has important application value in the fields of machinery, electronics, jewelry and the like, and needs to be prepared into large-particle diamond in order to expand the application. Among various diamond preparation methods, Microwave Plasma Chemical Vapor Deposition (MPCVD) is the preferred method for preparing high quality diamond due to its high plasma power density, no electrode discharge contamination and stable performance. In the process of producing large-particle single-crystal diamond by using MPCVD, the diamond seed crystal is generally fixed on a deposition table, the seed crystal is subjected to temperature control by cooling the deposition table, carbon-containing gas is carried by hydrogen and sent into a deposition chamber, and then microwave is used for exciting the carbon-hydrogen mixed gas into plasma and then performing unidirectional growth on one surface of the seed crystal facing the plasma.
This method also has some disadvantages: 1. in order to maintain the air pressure and the gas concentration in the deposition chamber, the process gas is continuously introduced and simultaneously the gas is discharged in the growth process, so that a great amount of gas and energy are wasted. 2. Due to the difference of the growing environment of the side edge and the center of the crystal, the growth speed of the edge part of the upper surface of the diamond crystal is higher than that of the middle part, the energy is concentrated to cause uneven temperature, polycrystal or amorphous carbonization occurs, more and more dislocation spreads to the center of the growing surface, the growing surface of the single crystal is smaller and smaller, the crystal needs to be repeatedly cleaned and cut and then grows or is spliced and grown, and the production efficiency and the product quality are seriously influenced.
Disclosure of Invention
In order to solve the problems, the invention provides a diamond growth method, which expands the range of carbon source materials, saves energy, avoids waste of process gas and is convenient for continuous growth of diamond.
In order to achieve the purpose, the technical scheme adopted by the invention is to provide a diamond growth method, which comprises the following steps:
s100, exciting a condensed carbon source to form a plasma region suitable for diamond growth;
and S200, depositing the carbon source in the excited state on the induction seed crystal which is placed in advance to epitaxially grow the diamond.
As a preferable scheme, the step S100 includes the steps of:
s101, placing an induction seed crystal in a deposition cavity;
s102, vacuumizing the deposition cavity, introducing high-purity hydrogen, starting a microwave source after the initial air pressure is reached, and exciting the hydrogen to glow;
s103, continuously introducing hydrogen, synchronously increasing the microwave power, and stopping introducing the hydrogen when the air pressure in the deposition cavity reaches a specific air pressure;
and S104, increasing the temperature of the induction seed crystal by increasing the microwave power or heating through other auxiliary means, and adding the condensed carbon source into the deposition cavity after the induction seed crystal reaches the set temperature.
Preferably, in step S104, the spectral intensity of the characteristic spectrum of the plasma is detected by a spectrometer, and the feeding amount of the condensed carbon source is controlled by comparing the ratio of the spectral intensity of the characteristic spectrum to the process set value.
As a preferable scheme, in step S104, the concentration of the excited-state carbon source during the growth process is controlled by adjusting the position, surface area or temperature of the condensed-state carbon source exposed to the excited region.
As a preferable scheme, the step S200 includes the steps of:
s201, continuously adding a condensed carbon source into a deposition cavity, so that a fireball of a plasma just covers an induction seed crystal, and continuously depositing carbon-containing active groups in the plasma on the surface of the induction seed crystal;
s202, stopping introducing the condensed carbon source until the carbon source grows to a set time, reducing the microwave power and the air pressure in the deposition cavity, and turning off the microwave power supply until the microwave power is reduced to a set value;
s203, vacuumizing the deposition cavity, and stopping vacuumizing when the vacuum degree reaches the lower limit of the display of the instrument;
and S204, introducing air until the air pressure in the deposition cavity is recovered to the environmental pressure, and taking out the diamond finished product.
Preferably, in step S201, the inducing seed crystal is fixed, flipped or rotated by alternately clamping different contact points of the inducing seed crystal, so that each growth surface of the inducing seed crystal can contact with the plasma containing the excited carbon source during the deposition growth process, thereby realizing the multi-directional growth.
Preferably, the condensed carbon source is one of a liquid carbon source, a glassy carbon source and a solid carbon source.
Preferably, the condensed carbon source has the formula CmHn、CmHnOx、CmHnNx、CmHnOxNyWherein C represents carbon, H represents hydrogen, O represents oxygen, N represents nitrogen, and m, N, x, and y are natural numbers.
Preferably, the condensed carbon source is excited by one or more of heating excitation, optical excitation, electromagnetic wave excitation, ultrasonic excitation, acoustic wave excitation, mechanical friction and mechanical impact excitation.
Preferably, the induction seed crystal is one of diamond, crystalline silicon or other heterogeneous materials.
The invention has the beneficial effects that:
the invention adopts the condensed carbon source to replace the gaseous carbon source, and does not need to introduce process gas in the diamond growth process except that auxiliary gas is required to be introduced when initial conditions are provided, so that the discharged gas is greatly reduced, the waste of the gas is reduced, and the waste of energy is also reduced. In addition, the growth method of the invention expands the material selection range of the carbon source, is beneficial to improving the growth quality of the crystal and reducing the cost of raw materials, and is convenient for the continuous growth of the diamond.
Drawings
Fig. 1 is a block flow diagram of a diamond growth method of the present invention.
Fig. 2 is a schematic structural view of the diamond growth apparatus of the present invention.
The reference numbers illustrate: 1-a microwave source; 2-auxiliary gas inlet pipe; 3-a deposition chamber; 4-plasma; 5-inducing seed crystals; 6-sample holder; 7-auxiliary electric heating; 8-an exhaust pipe; 9-a filling device; 10-a first conduit; 11-a second conduit; 12-a spectrometer; 13-optical thermometer.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Referring to fig. 1, the present invention relates to a method for growing diamond, comprising the following steps:
s100, exciting a condensed carbon source to form a plasma region suitable for diamond growth;
and S200, depositing the carbon source in the excited state on the induction seed crystal which is placed in advance to epitaxially grow the diamond.
The invention adopts the condensed carbon source to replace the gaseous carbon source, and does not need to introduce process gas in the diamond growth process except that auxiliary gas is required to be introduced when initial conditions are provided, so that the discharged gas is greatly reduced, the waste of the gas is reduced, and the waste of energy is also reduced. In addition, the growth method of the invention expands the material selection range of the carbon source, is beneficial to improving the growth quality of the crystal and reducing the cost of raw materials, and is convenient for the continuous growth of the diamond.
Referring to fig. 2, the diamond growth apparatus is a 5kw2.45ghz microwave-enhanced plasma chemical vapor deposition apparatus, and the specific steps of step S100 and step S200 are as follows:
s101, cleaning the induction seed crystal 5 and placing the cleaned induction seed crystal on a sample holder 6 in a deposition cavity 3;
s102, after the deposition cavity 3 is vacuumized by using the exhaust pipe 8, high-purity hydrogen is introduced through the auxiliary gas inlet pipe 2, the microwave source 1 is started after the initial gas pressure is reached, and the hydrogen is excited to glow;
s103, continuously introducing hydrogen, synchronously increasing microwave power through the microwave source 1, closing the auxiliary gas inlet pipe 2 after the gas pressure in the deposition cavity 3 reaches a specific gas pressure, and stopping introducing the hydrogen;
after the valve on the auxiliary gas inlet pipe 2 is closed, the gas pressure in the deposition chamber is adjusted by controlling the opening degree of the valve on the exhaust pipe 8;
s104, increasing the temperature of the induction seed crystal 5 by increasing the microwave power, detecting the temperature of the induction seed crystal 5 in real time by using an optical thermometer, and adding the condensed carbon source into the deposition cavity 3 by using the first conduit 10 or/and the second conduit 11 by using the filling device 9 after the induction seed crystal 5 reaches the set temperature;
detecting the spectral intensity of the characteristic spectral line of the plasma 4 through a spectrometer 12, and regulating and controlling the feeding amount of the condensed carbon source by comparing the spectral intensity with a process set value; the feeding amount is realized by adjusting the power of the auxiliary electric heating 7 outside the first conduit 10 and the second conduit 11;
controlling the concentration of the excited carbon source in the growth process by adjusting the position, the surface area or the temperature of the condensed carbon source exposed in the excited region;
s201, continuously adding a condensed carbon source into the deposition cavity 3, so that the fireball of the plasma 4 just covers the induction seed crystal 5, and continuously depositing carbon-containing active groups in the plasma 4 on the surface of the induction seed crystal 5;
in the process, the induction seed crystal is fixed, turned over or rotated by using a non-fixed technology through alternately clamping different contact points of the induction seed crystal, so that each growth surface of the induction seed crystal 5 can contact with the plasma 4 containing the excited carbon source in the deposition growth process, and multi-directional growth is realized;
s202, after the growth reaches the set time, closing the auxiliary electric heating 7, pumping out the condensed carbon source by utilizing the first conduit 10 or/and the second conduit 11, reducing the microwave power and the air pressure in the deposition cavity 3, and turning off the microwave power supply 1 until the microwave power is reduced to 600W;
s203, vacuumizing the deposition cavity 3 by using the exhaust tube 8, and stopping vacuumizing when the vacuum degree reaches the lower limit of the display of the instrument;
and S204, introducing nitrogen through the auxiliary gas inlet pipe 2 until the pressure in the deposition chamber is recovered to the environmental pressure, and taking out the diamond finished product grown on the induction seed crystal 5.
The first conduit 10 and the second conduit 11 of the apparatus have a trumpet-shaped opening, and the electrical heating 7 is provided outside the conduits, and in step S104, the condensed carbon source is maintained not to exceed the openings of the conduits.
Furthermore, the condensed carbon source is one of a liquid carbon source, a glassy carbon source or a solid carbon source, the glassy carbon source can be paraffin or vaseline, the solid carbon source can be carbon black or graphite, and the like; accordingly, the epitaxial growth method may be a homoepitaxy technique or a heteroepitaxy technique, which is not described herein again.
In addition, the condensed carbon source has the molecular formula of CmHn、CmHnOx、CmHnNx、CmHnOxNyWherein C represents carbon, H represents hydrogen, O represents oxygen, N represents nitrogen, and m, N, x, and y are natural numbers.
Further, the excitation mode of the condensed carbon source is one or more of heating excitation, light excitation, electromagnetic wave excitation, ultrasonic wave excitation, sound wave excitation, mechanical friction and mechanical impact excitation.
Further, the induction seed is one of diamond seed, crystalline silicon or other heterogeneous materials, preferably spherical diamond seed, which is kept rotating during the deposition growth process.
The invention is further illustrated by the following specific examples.
Example one
In the method for growing diamond according to the embodiment, n-dodecane and ethanol are used as a condensed carbon source, the n-dodecane is communicated with the deposition cavity through a first conduit, and the ethanol is communicated with the deposition cavity through a second conduit; the induction seed crystal adopts a cubic diamond seed crystal.
The diamond growth method comprises the following steps:
s100, exciting a condensed carbon source to form a plasma region suitable for diamond growth
Placing diamond seed crystals with smooth and clean surfaces on a molybdenum sample holder in a deposition chamber;
after the deposition chamber is vacuumized, high-purity hydrogen is slowly introduced through an auxiliary gas inlet pipe, after the initial pressure of 5 torr is reached, a microwave source is started, and the hydrogen is excited to glow with 600W power;
continuously introducing hydrogen, synchronously increasing the microwave power, closing a valve on an auxiliary gas inlet pipe after the air pressure in the deposition cavity reaches 120 torr, and stopping introducing the hydrogen;
after a valve on the auxiliary gas inlet pipe is closed, the gas pressure in the deposition chamber is adjusted by controlling the opening degree of the valve on the exhaust pipe 8 (increasing the opening degree of the valve reduces the gas pressure in the deposition chamber, reducing the opening degree of the valve increases the gas pressure in the deposition chamber); the pressure is preferably 150 torr;
increasing the temperature of the diamond seed crystal by increasing microwave power, and slowly pressing n-dodecane and ethanol into the first conduit and the second conduit respectively by using a filling device after the temperature of the diamond seed crystal 5 reaches a set temperature (preferably 1000 ℃), so as to keep the liquid levels of the n-dodecane and the ethanol not to exceed the opening of the conduits;
detection of C in plasma by spectrometer2Characteristic lines for radicals, hydrogen ions and OH groups [ C2(516.08nm), H α (656.30nm) and OH (309.30nm)]By comparing the ratio of the spectral intensities with a process set point (preferably I)C2/IHα＝0.6，IOH/IHα0.3) to regulate the feeding amount of dodecane and ethanol;
the method specifically comprises the following steps: when I isC2/IHαWhen the flow rate is less than the set value, the power of the auxiliary electric heating outside the first conduit is increased, so that the n-dodecane is excited at a higher speed; when I isOH/IHαWhen the temperature is lower than the set value, the power of the auxiliary electric heating outside the second conduit is increased, so that the ethanol is excited at a higher speed.
On the contrary, when IC2/IHαWhen the flow rate is larger than the set value, reducing the power of auxiliary electric heating outside the first conduit and slowing down the excitation rate of the n-dodecane; when I isOH/IHαAbove the set point, the power of the auxiliary electrical heating outside the second conduit is reduced, allowing the ethanol to be excited at a slower rate.
S200, carrying out homoepitaxial growth on diamond on a diamond seed crystal interface preset in a plasma region by using an excited carbon source
Maintaining the deposition growth process, enabling the fireball of the plasma to just cover the diamond seed crystal, and continuously depositing the carbon-containing active groups in the plasma on the surface of the diamond seed crystal under the set process condition;
wherein, the set process conditions are preferably as follows: the surface temperature of the diamond seed crystal is detected to be 1000 ℃ by an optical thermodetector, and the C in the plasma is detected by a spectrometer2Characteristic lines for radicals, hydrogen ions and OH groups [ C2(516.08nm), H α (656.30nm) and OH (309.30nm)]Ratio of spectral intensities of IC2/IHα＝0.6，IOH/IHα＝0.3)；
After the growth reaches the set time, all auxiliary electric heating is closed, n-dodecane and ethanol are pumped out through the first guide pipe and the second guide pipe, the power of the microwave source and the air pressure in the deposition cavity are reduced, and the microwave power supply is turned off until the microwave power is reduced to 600W;
and continuously vacuumizing, introducing nitrogen through another auxiliary gas inlet pipe to break vacuum when the vacuum degree reaches the lower limit displayed by the instrument, and taking out the grown diamond finished product to finish a process flow after the air pressure in the deposition cavity is restored to the environmental pressure.
Example two
Example two differs from example one in that n-dodecane was used as the condensed carbon source, diamond seeds were not used for the induction seeds, and instead a 100-orientation case-carburized single crystal silicon substrate was used.
S100, exciting a condensed carbon source to form a plasma region suitable for diamond growth
Placing the carburized surface of the monocrystalline silicon substrate upwards on a molybdenum sample holder in a deposition chamber;
after the deposition cavity is vacuumized, high-purity hydrogen is slowly introduced through an auxiliary gas inlet pipe, after the initial pressure reaches 5 torr, a microwave source is started, and the hydrogen is excited to glow with 600W power;
continuously introducing hydrogen, synchronously increasing the microwave power, closing a valve on an auxiliary gas inlet pipe after the air pressure in the deposition cavity reaches 40 torr, and stopping introducing the hydrogen;
increasing the temperature of the monocrystalline silicon substrate by increasing the power of a microwave source, slowly pressing the n-dodecane into the first conduit through a filling device after the surface temperature of the monocrystalline silicon substrate reaches a set temperature (preferably 650 ℃), and keeping the liquid level of the n-dodecane not to exceed the opening of the first conduit;
detection of C in plasma by spectrometer2Radical and characteristic lines of hydrogen ions [ C ]2(516.08nm)，Hα(656.30nm)]Of (2) a lightSpectral intensity by comparing the measured value with the process set point (preferably I)C2/IHα0.5) to regulate the feeding amount of dodecane;
the method specifically comprises the following steps: when I isC2/IHαWhen the flow rate is less than the set value, the power of the auxiliary electric heating outside the first conduit is increased, so that the n-dodecane is excited at a higher speed. On the contrary, when IC2/IHαAnd when the value is larger than the set value, reducing the power of the auxiliary electric heating outside the first conduit and slowing down the excitation rate of the n-dodecane.
S200, epitaxially growing diamond on the carburized interface of the silicon substrate by using an excited carbon source
Maintaining the deposition and nucleation process conditions, enabling the fireball of the plasma to just cover the monocrystalline silicon substrate, and performing deposition growth for 20 minutes under the set process conditions; wherein the process conditions at this time are preferably: the pressure in the deposition chamber is 40 torr, the surface temperature of the monocrystalline silicon substrate is 650 ℃, IC2/IHα＝0.5；
Then increasing the air pressure and the microwave power in the deposition chamber until the process conditions are set, and stopping increasing the air pressure and the microwave power in the deposition chamber; wherein the process conditions at this time are preferably: the surface temperature of the monocrystalline silicon substrate is 950 ℃, IC2/IHα＝0.4；
Until the diamond grows to the set time (if the set time is 100 hours, the thickness of the diamond can reach 0.2mm at the moment), closing the auxiliary electric heating outside the first conduit, extracting the n-dodecane in the first conduit, reducing the power of the microwave source and the air pressure in the deposition cavity, and turning off the microwave power supply until the microwave power is reduced to 600W;
and continuously vacuumizing, introducing air through another auxiliary gas inlet pipe to break vacuum when the vacuum degree reaches the lower limit displayed by the instrument, and taking out the diamond finished product grown on the monocrystalline silicon substrate to finish a process flow after the air pressure in the deposition cavity is restored to the environmental pressure.
The above embodiments are merely illustrative of the preferred embodiments of the present invention, and not restrictive, and various changes and modifications to the technical solutions of the present invention may be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are intended to fall within the scope of the present invention defined by the appended claims.
Claims (10)
1. A method of diamond growth comprising the steps of:
s100, exciting a condensed carbon source to form a plasma region suitable for diamond growth;
and S200, depositing the carbon source in the excited state on the induction seed crystal which is placed in advance to epitaxially grow the diamond.
2. The diamond growth method according to claim 1, wherein the step S100 comprises the steps of:
s101, placing an induction seed crystal in a deposition cavity;
s102, vacuumizing the deposition cavity, introducing high-purity hydrogen, starting a microwave source after the initial air pressure is reached, and exciting the hydrogen to glow;
s103, continuously introducing hydrogen, synchronously increasing the microwave power, and stopping introducing the hydrogen when the air pressure in the deposition cavity reaches a specific air pressure;
and S104, increasing the temperature of the induction seed crystal by increasing the microwave power or heating through other auxiliary means, and adding the condensed carbon source into the deposition cavity after the induction seed crystal reaches the set temperature.
3. The diamond growth method according to claim 2, wherein: in step S104, the spectral intensity of the characteristic spectral line of the plasma is detected by the spectrometer, and the feeding amount of the condensed carbon source is regulated and controlled by comparing the spectral intensity of the characteristic spectral line with a process set value.
4. The diamond growth method of claim 3, wherein: in step S104, the concentration of the excited carbon source during growth is controlled by adjusting the position, surface area or temperature of the condensed carbon source exposed to the excited region.
5. The diamond growth method according to any one of claims 2 to 4, wherein the step S200 comprises the steps of:
s201, continuously adding a condensed carbon source into a deposition cavity, so that a fireball of a plasma just covers an induction seed crystal, and continuously depositing carbon-containing active groups in the plasma on the surface of the induction seed crystal;
s202, stopping introducing the condensed carbon source until the carbon source grows to a set time, reducing the microwave power and the air pressure in the deposition cavity, and turning off the microwave power supply until the microwave power is reduced to a set value;
s203, vacuumizing the deposition cavity, and stopping vacuumizing when the vacuum degree reaches the lower limit of the display of the instrument;
and S204, introducing air until the air pressure in the deposition cavity is recovered to the environmental pressure, and taking out the diamond finished product.
6. The diamond growth method of claim 5, wherein: in step S201, the induced seed crystal is fixed, turned over or rotated by alternately clamping different contact points of the induced seed crystal, so that each growth surface of the induced seed crystal can contact plasma containing an excited carbon source during the deposition growth process, thereby realizing multidirectional growth.
7. The diamond growth method of claim 1, wherein: the condensed carbon source is one of a liquid carbon source, a glassy carbon source or a solid carbon source.
8. The diamond growth method of claim 1, wherein: the molecular formula of the condensed carbon source is CmHn、CmHnOx、CmHnNx、CmHnOxNyWherein C represents carbon, H represents hydrogen, O represents oxygen, N represents nitrogen, and m, N, x, and y are natural numbers.
9. The diamond growth method of claim 1, wherein: the excitation mode of the condensed carbon source is one or more of heating excitation, light excitation, electromagnetic wave excitation, ultrasonic wave excitation, sound wave excitation, mechanical friction and mechanical impact excitation.
10. The diamond growth method of claim 1, wherein: the induction seed crystal is one of diamond, crystalline silicon or other heterogeneous materials.
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