CN117403321A - Tungsten nitride silicon single crystal film and preparation method thereof - Google Patents
Tungsten nitride silicon single crystal film and preparation method thereof Download PDFInfo
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- CN117403321A CN117403321A CN202311358769.6A CN202311358769A CN117403321A CN 117403321 A CN117403321 A CN 117403321A CN 202311358769 A CN202311358769 A CN 202311358769A CN 117403321 A CN117403321 A CN 117403321A
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 109
- 239000010937 tungsten Substances 0.000 title claims abstract description 109
- 239000013078 crystal Substances 0.000 title claims abstract description 59
- 239000010703 silicon Substances 0.000 title claims abstract description 47
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000011888 foil Substances 0.000 claims abstract description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 47
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 44
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910000077 silane Inorganic materials 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- -1 photoelectric device Substances 0.000 claims abstract description 5
- 238000007781 pre-processing Methods 0.000 claims abstract description 5
- 238000005019 vapor deposition process Methods 0.000 claims abstract description 5
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims abstract 18
- 239000010408 film Substances 0.000 claims description 37
- 239000010409 thin film Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000004146 energy storage Methods 0.000 abstract description 5
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012720 thermal barrier coating Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C30B29/10—Inorganic compounds or compositions
- C30B29/38—Nitrides
-
- 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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
Abstract
The invention discloses a tungsten nitride silicon single crystal film and a preparation method thereof, wherein the preparation method comprises the following steps: s1, providing a tungsten foil and cleaning the surface of the tungsten foil; s2, transferring the tungsten foil into an MOCVD growth chamber, introducing nitrogen into the MOCVD growth chamber, heating the MOCVD growth chamber, and preprocessing the surface of the tungsten foil; s3, continuously introducing hydrogen into the MOCVD growth chamber, and heating the MOCVD growth chamber to 1000-1150 ℃; and S4, continuously introducing silane and ammonia into the MOCVD growth chamber, wherein the air flow ratio of the ammonia to the silane is (2-10): 1, and growing the tungsten foil surface in a nitrogen-rich atmosphere through a metal organic vapor deposition process to obtain the tungsten nitride silicon single crystal film. The invention can efficiently and rapidly prepare the high-quality monocrystalline film with large size and controllable thickness, greatly improves the growth rate compared with a chemical vapor deposition process, and has better market application prospect in the fields of energy storage, catalyst, photoelectric device, material protection and the like.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to a tungsten nitride silicon single crystal film and a preparation method thereof.
Background
Tungsten silicon nitride (WSi) 2 N 4 ) Is a compound composed of tungsten (W), silicon (Si) and nitrogen (N), belongs to the category of silicon nitrides, and has the structural characteristics similar to Boron Nitride (BN), silicon carbide (SiC) and other compounds. WSi 2 N 4 The crystal has a layered structure similar to graphene in which silicon and nitrogen atoms constitute two-dimensional layers and tungsten atoms are sandwiched between the layers, the layered structure being such that WSi 2 N 4 Has special physical and chemical properties, and provides potential possibility for application in the fields of energy storage, catalysts, electronic devices and the like.
WSi 2 N 4 The semiconductor is a natural P-type semiconductor, the forbidden bandwidth is 3.4eV, the free electron concentration of the P-type semiconductor is low, and the free hole concentration is high, which means that a large number of positive holes exist in the P-type semiconductor, can flow under the action of an externally applied electric field or voltage, and participate in electron transport. This high free hole concentration characteristic makes P-type semiconductors more suitable for use in certain applications, such as the fabrication of P-type transistors and P-type substrates. WSi 2 N 4 The crystal has a layered structure in which silicon and nitrogen atoms constitute two-dimensional layers and tungsten atoms are intercalated between the layers, the structure being such that WSi 2 N 4 Has higher surface area and conductivity. WSi 2 N 4 Has wider energy band gap and shows certain semiconductor characteristics. The electronic structure research of the material shows that the material has good carrier migration performance and photoelectric characteristics, and shows the application potential in photoelectric devices. WSi 2 N 4 The crystal has good performance in terms of mechanical strength and hardness, and has higher elastic modulus and compressive strength, so that the crystal has potential application in the aspects of wear-resistant coating and structural materials. WSi 2 N 4 The crystal has better thermal stability and oxidation resistance under high temperature condition, which makes it have potential application in the fields of high temperature catalysis, thermal barrier coating and the like. WSi 2 N 4 The research of the crystal is still in the preliminary stage, but some important progress has been made. By means of experiments, calculation simulation and the like, related scientific researchers perform on WSi 2 N 4 The physical and chemical properties of the crystals have been studied in theory. They explore the characteristics of electronic structure, photoelectric property, mechanical property and thermal stability, etc., and provide theoretical basis for their application, and have begun to explore their application potential in the fields of energy storage, catalyst, photoelectric device and material protection, etc., and some preliminary experimental results show that WSi 2 N 4 The crystal has good performance and application prospect in the fields.
Overall, WSi 2 N 4 The crystal is used as a novel material and has unique structure and excellent physical and chemical properties. Although still in the research primary stage at present, the research on the synthesis method and application prospect of the compound has demonstrated wide application potential. With further research and exploration, WSi 2 N 4 The crystal is expected to show important application value in a plurality of fields.
Preparation of WSi by chemical vapor deposition in the prior art 2 N 4 However, the rate of preparation is too slow, and only WSi with a single lateral dimension within 5 microns grows in 5 hours 2 N 4 The coverage of the triangular single crystal film is lower than 10 percent.
Accordingly, in view of the above-described problems, there is a need for a tungsten nitride silicon single crystal thin film and a method for producing the same.
Disclosure of Invention
In view of the above, the present invention aims to provide a tungsten nitride silicon single crystal thin film and a method for producing the same.
In order to achieve the above object, an embodiment of the present invention provides the following technical solution:
a method for preparing a tungsten nitride silicon single crystal film, comprising the following steps:
s1, providing a tungsten foil and cleaning the surface of the tungsten foil;
s2, transferring the tungsten foil into an MOCVD growth chamber, introducing nitrogen into the MOCVD growth chamber, heating the MOCVD growth chamber, and preprocessing the surface of the tungsten foil;
s3, continuously introducing hydrogen into the MOCVD growth chamber, and heating the MOCVD growth chamber to 1000-1150 ℃;
and S4, continuously introducing silane and ammonia into the MOCVD growth chamber, wherein the air flow ratio of the ammonia to the silane is (2-10): 1, and growing the tungsten foil surface in a nitrogen-rich atmosphere through a metal organic vapor deposition process to obtain the tungsten nitride silicon single crystal film.
In one embodiment, the step S1 includes:
carrying out ultrasonic treatment on the tungsten foil in an ethanol solution to remove residual impurities and organic matters on the surface of the tungsten foil;
carrying out ultrasonic treatment on the tungsten foil in deionized water to remove the residual organic solvent on the surface of the tungsten foil;
and (3) purging the tungsten foil by adopting nitrogen to remove water vapor on the surface of the tungsten foil.
In one embodiment, the MOCVD growth chamber in the step S2 is an atmospheric pressure environment, and the flow rate of nitrogen is 20 slm-1000 slm.
In one embodiment, in the step S2, "heating the MOCVD growth chamber and pretreating the surface of the tungsten foil" specifically includes:
heating the MOCVD growth chamber to 50-70 ℃ at a speed of 5-20 ℃/min, and keeping for 10-30 min to remove organic matters on the surface of the tungsten foil;
heating the MOCVD growth chamber to 80-100 ℃ at a speed of 5-20 ℃/min, and keeping for 10-30 min to remove water vapor on the surface of the tungsten foil;
heating the MOCVD growth chamber to 110-130 ℃ at 5-20 ℃/min, and maintaining for 20-40 min to remove carbon deposition on the surface of the tungsten foil.
In one embodiment, the flow rate of the hydrogen gas in the step S3 is 1slm to 20slm.
In one embodiment, the temperature rising rate of the MOCVD growth chamber in the step S3 is 20 ℃/min-50 ℃/min; and/or the number of the groups of groups,
in the step S4, the air flow rate of the ammonia gas is 100 sccm-1000 sccm, and the air flow rate of the silane is 50 sccm-500 sccm.
In one embodiment, the growth rate of the tungsten nitride silicon single crystal film in the step S4 is
In an embodiment, the step S4 further includes:
and stopping introducing silane and ammonia after the growth of the tungsten nitride silicon single crystal film is completed, and continuing introducing nitrogen and hydrogen to perform high-temperature annealing on the tungsten nitride silicon single crystal film.
In one embodiment, the purity of the tungsten foil is not lower than 99.99%, and the roughness of the surface of the tungsten foil is less than 10nm; and/or the number of the groups of groups,
the purity of the ammonia gas is not lower than 99.99 percent, and the purity of the silane is not lower than 99.99 percent.
The technical scheme provided by the embodiment of the invention is as follows:
a tungsten nitride silicon single crystal thin film produced by the above production method.
The invention has the following beneficial effects:
the invention can efficiently and rapidly prepare the high-quality monocrystalline film with large size and controllable thickness, greatly improves the growth rate compared with a chemical vapor deposition process, and has better market application prospect in the fields of energy storage, catalyst, photoelectric device, material protection and the like.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for preparing a tungsten nitride silicon single crystal film according to the present invention;
FIGS. 2a and 2b are optical microscopic views of a tungsten nitride silicon single crystal thin film of example 1 of the present invention at 200 times and 500 times, respectively;
FIG. 3 is an EDS diagram of the elemental analysis of the film of example 1 of the present invention;
FIG. 4 is an electron diffraction pattern of the thin film of example 1 of the present invention;
FIG. 5 is an optical microscopic image of a tungsten nitride silicon single crystal thin film at a magnification of 50 in example 2 of the present invention.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Referring to FIG. 1, the invention discloses a preparation method of a tungsten nitride silicon single crystal film, which comprises the following steps:
s1, providing a tungsten foil and cleaning the surface of the tungsten foil;
s2, transferring the tungsten foil into an MOCVD growth chamber, introducing nitrogen into the MOCVD growth chamber, heating the MOCVD growth chamber, and preprocessing the surface of the tungsten foil;
s3, continuously introducing hydrogen into the MOCVD growth chamber, and heating the MOCVD growth chamber to 1000-1150 ℃;
and S4, continuously introducing silane and ammonia into the MOCVD growth chamber, wherein the air flow ratio of the ammonia to the silane is (2-10): 1, and growing the tungsten foil surface in a nitrogen-rich atmosphere through a metal organic vapor deposition process to obtain the tungsten nitride silicon single crystal film.
Further, after the growth of the tungsten nitride silicon single crystal film is completed, stopping the introduction of silane and ammonia, continuously introducing nitrogen and hydrogen, and carrying out high-temperature annealing on the tungsten nitride silicon single crystal film.
By the method of the inventionHigh-quality WSi with large size and controllable thickness is prepared efficiently and quickly 2 N 4 A single crystal thin film.
The invention is further illustrated below with reference to specific examples.
Example 1:
in this embodiment, tungsten silicon nitride (WSi) 2 N 4 ) The preparation method of the monocrystalline film comprises the following steps:
1. a tungsten foil is provided and the surface of the tungsten foil is cleaned.
In this embodiment, the purity of the tungsten foil is not less than 99.99%, and the roughness of the surface of the tungsten foil is less than 10nm.
The cleaning of the surface of the tungsten foil is carried out in a beaker, and the specific steps are as follows:
1.1, cleaning the beaker.
In this example, the beaker was sonicated with deionized water for 5min,30mL acetone for 5min, and repeated multiple times.
1.2, carrying out ultrasonic treatment on the tungsten foil in ethanol solution to remove residual impurities and organic matters on the surface of the tungsten foil.
In this example, the sheared tungsten foil was placed in a cleaned beaker, 30mL of ethanol solution was added, and the ultrasonic treatment was repeated twice for 10 min.
And 1.3, carrying out ultrasonic treatment on the tungsten foil in deionized water to remove the residual organic solvent on the surface of the tungsten foil.
In this example, a suitable amount of deionized water was added to the beaker and the same sonicated for 10min, repeated twice.
And 1.4, purging the tungsten foil by adopting nitrogen to remove water vapor on the surface of the tungsten foil.
2. Transferring the tungsten foil into an MOCVD growth chamber, introducing nitrogen into the MOCVD growth chamber, heating the MOCVD growth chamber, and preprocessing the surface of the tungsten foil.
In this example, the tungsten foil cleaned in step 1 was placed on a quartz substrate and transferred from an MOCVD (metal organic vapor deposition) sample introduction chamber into an MOCVD growth chamber.
The MOCVD growth chamber is in a normal pressure environment, the carrier gas maintaining the pressure of the growth chamber is nitrogen, the flow rate of the nitrogen is 20 slm-1000 slm, and in the embodiment, the flow rate of the nitrogen is 20slm.
After the tungsten foil is transferred to the MOCVD growth chamber, preliminary treatment of the tungsten foil is realized by step-by-step heating, specifically:
heating the MOCVD growth chamber to 50-70 ℃ at a speed of 5-20 ℃/min, and keeping for 10-30 min to remove organic matters on the surface of the tungsten foil; preferably, the temperature rise rate in this embodiment is 20 ℃/min, the temperature is raised to 60 ℃, and the holding time is 20min;
heating the MOCVD growth chamber to 90 ℃ at a speed of 5-20 ℃/min, and keeping for 10-30 min to remove water vapor on the surface of the tungsten foil; preferably, the temperature rise rate in this embodiment is 20 ℃/min, the temperature is raised to 60 ℃, and the holding time is 20min;
heating the MOCVD growth chamber to 110-130 ℃ at 5-20 ℃/min, and maintaining for 20-40 min to remove carbon deposition on the surface of the tungsten foil; preferably, the temperature rise rate in this embodiment is 20 ℃/min, the temperature is raised to 120 ℃, and the holding time is 30min.
3. And continuously introducing hydrogen into the MOCVD growth chamber, and heating the MOCVD growth chamber to 1000-1150 ℃.
Wherein the air flow of the hydrogen is 1 slm-20 slm, and the heating rate of the MOCVD growth chamber is 20 ℃/min-50 ℃/min. Preferably, the flow rate of hydrogen in this embodiment is 20slm, the heating rate of the MOCVD growth chamber is 50 ℃/min, and the final heating temperature is 1080 ℃.
4. And continuing to introduce silane and ammonia gas into the MOCVD growth chamber, wherein the gas flow rate of the ammonia gas and the silane is (2-10): 1, and growing the tungsten foil surface in a nitrogen-rich atmosphere through a metal organic vapor deposition process to obtain the tungsten nitride silicon single crystal film.
Wherein the purity of the ammonia gas is not lower than 99.99%, the purity of the silane is not lower than 99.99%, the air flow of the ammonia gas is 100 sccm-1000 sccm, the air flow of the silane is 50 sccm-500 sccm, and the growth rate of the tungsten nitride silicon single crystal film is
The higher the temperature in the temperature range of 1000-1150 ℃, the larger the flow of ammonia and silane, the faster the growth rate, but the too fast growth rate can cause the degradation of crystal quality, preferably, the film growth rate is finally controlled by controlling the temperature of the growth chamber and the flow of ammonia and silane in the invention
In the embodiment, silane is firstly introduced, then ammonia gas is introduced, the gas flow of the ammonia gas and the silane is 2:1, the gas flow of the ammonia gas is 100sccm, the gas flow of the silane is 50sccm, the MOCVD growth chamber always maintains a nitrogen-rich atmosphere, and the growth time is 5min.
5. And stopping introducing silane and ammonia after the growth of the tungsten nitride silicon single crystal film is completed, and continuing introducing nitrogen and hydrogen to perform high-temperature annealing on the tungsten nitride silicon single crystal film.
The atoms can be relaxed by high-temperature annealing, so that the atoms can be rearranged, and the crystal quality of the tungsten nitride silicon single crystal film is improved.
Referring to FIGS. 2a and 2b, there are shown optical microscopic diagrams of the tungsten nitride silicon single crystal thin film of the present example at different magnifications (200 times and 500 times), the flow rate of ammonia gas was 100sccm, the flow rate of silane gas was 50sccm, and the growth time was 5min.
Referring to FIG. 3, which shows an EDS (energy spectrometer, energy Dispersive Spectrometer) chart of elemental analysis of the film in this example, it can be confirmed that the obtained film is WSi 2 N 4 A film.
Referring to FIG. 4, which shows an electron diffraction pattern of the film in this example, it can be seen that the film prepared was a single crystal film.
Example 2:
the preparation method in this example was substantially the same as in example 1, except that the flow rate of ammonia gas in this example was 400sccm, the flow rate of silane was 200sccm, the growth time was 1min, and the film after growth was transferred to SiO 2 On the substrate.
Referring to FIG. 5, there is shown an optical microscopic image (magnification: 50 times) of a tungsten nitride silicon single crystal thin film of the present example, in which the size of the tungsten nitride silicon single crystal thin film prepared in the present example was about 54.98. Mu.m.
It should be understood that the above embodiments are described by taking a specific growth temperature (1080 ℃) and a specific ammonia gas to silane gas flow ratio (2:1) as examples, and that in other embodiments, the growth temperature may be any temperature in the interval of 1000 ℃ to 1150 ℃, and the gas flow ratio may be greater than 2:1.
specifically, the gas flow of ammonia is 100 sccm-1000 sccm, the gas flow of silane is 50 sccm-500 sccm, and the growth rate of the film is controlledThus realizing the preparation of the high-quality tungsten nitride silicon single crystal film.
The technical scheme shows that the invention has the following beneficial effects:
the invention can efficiently and rapidly prepare the high-quality monocrystalline film with large size and controllable thickness, greatly improves the growth rate compared with a chemical vapor deposition process, and has better market application prospect in the fields of energy storage, catalyst, photoelectric device, material protection and the like.
The detailed description set forth above in connection with the appended drawings describes exemplary embodiments, but does not represent all embodiments that may be implemented or fall within the scope of the claims. The term "exemplary" used throughout this specification means "serving as an example, instance, or illustration," and does not mean "preferred" or "advantageous over other embodiments. The detailed description includes specific details for the purpose of providing an understanding of the described technology. However, the techniques may be practiced without these specific details. In some instances, well-known structures and devices are shown in block diagram form in order to avoid obscuring the concepts of the described embodiments.
The previous description of the disclosure is provided to enable any person skilled in the art to make or use the disclosure. Various modifications to the disclosure will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other variations without departing from the scope of the disclosure. Thus, the disclosure is not limited to the examples and designs described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for preparing a tungsten nitride silicon single crystal film, which is characterized by comprising the following steps:
s1, providing a tungsten foil and cleaning the surface of the tungsten foil;
s2, transferring the tungsten foil into an MOCVD growth chamber, introducing nitrogen into the MOCVD growth chamber, heating the MOCVD growth chamber, and preprocessing the surface of the tungsten foil;
s3, continuously introducing hydrogen into the MOCVD growth chamber, and heating the MOCVD growth chamber to 1000-1150 ℃;
and S4, continuously introducing silane and ammonia into the MOCVD growth chamber, wherein the air flow ratio of the ammonia to the silane is (2-10): 1, and growing the tungsten foil surface in a nitrogen-rich atmosphere through a metal organic vapor deposition process to obtain the tungsten nitride silicon single crystal film.
2. The method for producing a tungsten nitride silicon single crystal thin film according to claim 1, wherein the step S1 comprises:
carrying out ultrasonic treatment on the tungsten foil in an ethanol solution to remove residual impurities and organic matters on the surface of the tungsten foil;
carrying out ultrasonic treatment on the tungsten foil in deionized water to remove the residual organic solvent on the surface of the tungsten foil;
and (3) purging the tungsten foil by adopting nitrogen to remove water vapor on the surface of the tungsten foil.
3. The method for preparing a silicon tungsten nitride single crystal film according to claim 1, wherein the MOCVD growth chamber in step S2 is an atmospheric pressure environment, and the flow rate of nitrogen is 20 slm-1000 slm.
4. The method for preparing a tungsten nitride silicon single crystal thin film according to claim 3, wherein in the step S2, "heating the MOCVD growth chamber and pretreating the surface of the tungsten foil" specifically comprises:
heating the MOCVD growth chamber to 50-70 ℃ at a speed of 5-20 ℃/min, and keeping for 10-30 min to remove organic matters on the surface of the tungsten foil;
heating the MOCVD growth chamber to 80-100 ℃ at a speed of 5-20 ℃/min, and keeping for 10-30 min to remove water vapor on the surface of the tungsten foil;
heating the MOCVD growth chamber to 110-130 ℃ at 5-20 ℃/min, and maintaining for 20-40 min to remove carbon deposition on the surface of the tungsten foil.
5. The method for producing a tungsten nitride silicon single crystal thin film according to claim 1, wherein the flow rate of hydrogen gas in step S3 is 1slm to 20slm.
6. The method for producing a tungsten nitride silicon single crystal thin film according to claim 1, wherein the temperature rising rate of the MOCVD growth chamber in step S3 is 20 ℃/min to 50 ℃/min; and/or the number of the groups of groups,
in the step S4, the air flow rate of the ammonia gas is 100 sccm-1000 sccm, and the air flow rate of the silane is 50 sccm-500 sccm.
7. The method for producing a tungsten nitride silicon single crystal thin film according to claim 1, wherein the growth rate of the tungsten nitride silicon single crystal thin film in step S4 is
8. The method for preparing a tungsten nitride silicon single crystal thin film according to claim 1, wherein the step S4 further comprises:
and stopping introducing silane and ammonia after the growth of the tungsten nitride silicon single crystal film is completed, and continuing introducing nitrogen and hydrogen to perform high-temperature annealing on the tungsten nitride silicon single crystal film.
9. The method for producing a tungsten nitride silicon single crystal thin film according to claim 1, wherein the purity of the tungsten foil is not less than 99.99%, and the roughness of the surface of the tungsten foil is less than 10nm; and/or the number of the groups of groups,
the purity of the ammonia gas is not lower than 99.99 percent, and the purity of the silane is not lower than 99.99 percent.
10. A tungsten nitride silicon single crystal thin film, characterized in that the tungsten nitride silicon single crystal thin film is produced by the production method according to any one of claims 1 to 9.
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