CN104087909B - Preparation method of cubic silicon carbide film - Google Patents
Preparation method of cubic silicon carbide film Download PDFInfo
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- CN104087909B CN104087909B CN201410317559.7A CN201410317559A CN104087909B CN 104087909 B CN104087909 B CN 104087909B CN 201410317559 A CN201410317559 A CN 201410317559A CN 104087909 B CN104087909 B CN 104087909B
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Abstract
The invention discloses a preparation method of a cubic silicon carbide film, which comprises the following steps: (1) placing a monocrystalline silicon substrate on a substrate seat of a cold-wall type laser chemical vapor deposition device, vacuumizing, and raising the temperature of the substrate seat to 100-900 ℃; (2) introducing carrier gas containing HMDS into the reactor, wherein the flow rate of the HMDS is 1-20 sccm, and adjusting the vacuum degree to 10-10 kPa; (3) loading continuous laser to irradiate the surface of the silicon substrate, wherein the wavelength is 750-1150 nanometers, the power is 10-150W, and the time is 1-10 minutes; (4) and stopping introducing the current-carrying gas containing HMDS, closing the laser, stopping heating, vacuumizing and naturally cooling to room temperature to obtain the cubic silicon carbide film. The surface defects of the cubic silicon carbide film prepared by the method grow obliquely to the growth direction of the film, and the phenomenon of self-extinction can occur when adjacent defects meet, so that the crystal defects in the material are effectively reduced.
Description
Technical field
The present invention relates to a kind of preparation method of the cubic silicon carbide silicon thin film reducing crystal defect, belong to inorganic material structure
Control field.
Background technology
Carborundum has that energy gap is big, breakdown voltage is high, accommodates high temperature, high power, high frequency and extreme radiation environment
Middle application, is the ideal material developing altofrequency, high temperature resistant, radiation-resistance semiconductor microelectronic component and circuit, is important the
Three generations's semi-conducting material.
Carborundum has multiple polymorphisms, different according to atom stacking order on c-axis direction, can be by carbon
SiClx is divided into the different polytype of kind more than 200.Because cubic silicon carbide (3C-SiC) fusing point is less than silicon, (fusing point of silicon is 1420
DEG C), therefore 3C-SiC be uniquely can grow on monocrystalline silicon substrate and excellent performance carbofrax material.This means only 3C-
SiC is the crystal formation being hopeful to obtain large scale material.Additionally, (111) crystal face in 3C-SiC (is such as nitrogenized with III-V compound
Gallium) and Graphene between fabulous thermal expansion and lattice so that quasiconductor with SiC epitaxial film or wafer as substrate
Device is the device of substrate than traditional silicon or sapphire, working life improve more than 10 times and Power dissipation reductions about three/
Two, broader practice prospect is had by the semiconductor device that it derives.
But, (defect in 3C-SiC thin film crystal grain (111) face of CVD preparation is perpendicular to thin for general chemical vapor deposition
The direction of growth of film, it is impossible to eliminate, have impact on carborundum films and its popularization of related device application.Therefore, improve cube carbon
The technology of preparing of silicon nitride material is particularly important, and the technology after improvement can also control the aobvious of material while preparing material
Micro structure, and produce crystal defect in certain defect expressivity mechanism minimizing material.
Content of the invention
The technical problem to be solved is to provide a kind of cube carbon for the deficiency of above-mentioned prior art presence
The preparation method of SiClx thin film, deposition velocity is fast, and the crystal defect of gained carborundum films is few, and the crystal defect of carborundum
Increase with the deposit thickness of thin film and quickly reduce.
A kind of preparation method of cubic silicon carbide silicon thin film, comprises the steps：
(1) monocrystalline silicon substrate is put in the substrate holder of cold wall type laser chemical vapor deposition reactor, and by vacuum
It is adjusted to below 10Pa, and the heating system in reactor is set, make substrate holder temperature rise to 100～900 DEG C；
(2) hexamethyldisilane ((CH will be contained3)3-Si-Si-(CH3)3, be abbreviated as HMDS) current-carrying gas be passed through reactor
Interior, the flow of HMDS is 1～20sccm, the vacuum in regulation reactor to 10～10kPa；
(3) load continuous laser irradiate silicon substrate, 750～1150 nanometers of wavelength, adjust laser power be 10～
150W, it loads Laser Time is 1～10 minute；
(4) stop being passed through the current-carrying gas containing HMDS, close the heating system in laser and reactor, evacuation, by instead
Answer the vacuum in device to be adjusted to below 10Pa, and naturally cool to room temperature, that is, obtain cube carbon being deposited on monocrystalline silicon substrate
SiClx thin film.
By such scheme, described monocrystalline silicon substrate may be pretreated makes its clean surface, and monocrystal silicon is fully exposed.Institute
The method stating pretreatment is：Substrate is initially positioned at supersound process 15 minutes in ethanol, is then placed in ammonia, hydrogen peroxide and water
Heating in water bath 10 minutes in mixed solution, are subsequently placed in Fluohydric acid. and the mixed solution of water and soak 1 minute, finally use deionization
Water washing is totally.Wherein, the volume ratio of ammonia, hydrogen peroxide and water is 1:1:5, the bath temperature of this mixed solution is set to
80℃；The volume ratio of Fluohydric acid. and water is 1:50.In this technique, ammonia used is to analyze pure ammonia, NH3Mass fraction is
28%；Hydrogen peroxide is to analyze pure hydrogen peroxide, H2O2＞ 30%；Fluohydric acid. is to analyze pure Fluohydric acid., and HF is more than 40%.
By such scheme, described current-carrying gas is argon, hydrogen etc..
The present invention transports the current-carrying throughput of hexamethyldisilane, is passed through depositing silicon after hexamethyldisilane by adjusting
During silicon, the temperature of substrate surface, the laser power loading and time, to control the thickness of cubic silicon carbide silicon thin film and the knot of deposition
Structure.
Compared with prior art, the invention has the beneficial effects as follows：
First, the planar defect of the cubic silicon carbide silicon thin film of present invention preparation favours the growth of the thin film direction of growth, adjacent scarce
Fall into and " from withering away " phenomenon can occur when meeting, thus effectively reducing the crystal defect in material, and the crystal of carborundum
Defect increases with the deposit thickness of thin film and quickly reduces；
Second, when the present invention prepares cubic silicon carbide silicon thin film, the sedimentation rate of cubic silicon carbide silicon thin film is fast, deposition velocity energy
Reach 50 μm/min；
3rd, the method for the invention very energy-conservation, laser direct irradiation silicon substrate, mainly give substrate surface localized heat
Can, other positions of reactor are heated less, reduce energy consumption.
Brief description
Fig. 1 is the process chart of the present invention.
Fig. 2 is the XRD spectrum of the cubic silicon carbide silicon thin film of the embodiment of the present invention 1 preparation.
Fig. 3 be the embodiment of the present invention 1 preparation cubic silicon carbide silicon thin film cross section transmission electron microscope (TEM) as.
Fig. 4 (a) is the transmission electron microscope (TEM) of the cubic silicon carbide silicon thin film cross section of the embodiment of the present invention 1 preparation
Picture, (b) is the TEM picture of the carborundum films of traditional CVD method preparation.
When in Fig. 5, (b) and (d) is to prepare cubic silicon carbide silicon thin film, (111) face that the carborundum films direction of growth is at an angle of
Defect disappearance schematic diagram.B () and (d) represent respectively to have in carborundum films in the present invention and favour the anti-phase of the thin film direction of growth
Domain boundary (APB) and twin boundary (TB).In figure five, (a) and (c) is illustrated respectively in the carborundum films of general CVD method preparation,
APB (APB) and twin boundary (TB) are perpendicular to the direction of growth of thin film；
Specific embodiment
For a better understanding of the present invention, it is further elucidated with present disclosure with reference to embodiment, but the present invention is not
It is limited only to the following examples.
Monocrystalline silicon substrate described in following embodiments may be pretreated makes its clean surface, the method for described pretreatment
It is：It is 1cm × 2cm that monocrystalline silicon substrate is cut into size, is cleaned by ultrasonic 15 minutes in ethanol first, then is 80 DEG C in temperature
Clean in the mixed solution of ammonia, hydrogen peroxide and water 10 minutes, then clean 1 minute in hydrofluoric acid aqueous solution, finally spend
Ionized water is rinsed well.Wherein in the mixed solution of ammonia, hydrogen peroxide and water, the specific volume ratio of ammonia, hydrogen peroxide and water is
1:1:5, in hydrofluoric acid aqueous solution, the volume ratio of Fluohydric acid. and water is 1:50.The ammonia being used is to analyze pure ammonia, NH3Quality
Fraction is 28%；Hydrogen peroxide is to analyze pure hydrogen peroxide, H2O2＞ 30%；Fluohydric acid. is to analyze pure Fluohydric acid., and HF is more than 40%.
Embodiment 1
A kind of preparation method of cubic silicon carbide silicon thin film, comprises the steps：
(1) monocrystalline silicon substrate is put in the substrate holder of cold wall type laser chemical vapor deposition reactor, and by vacuum
It is adjusted to below 10Pa, and the heating system in reactor is set, make substrate holder temperature rise to 300 DEG C；
(2) the current-carrying gas Ar gas containing hexamethyldisilane (HMDS) is passed through in reactor, the flow of HMDS is 3sccm,
It is 10000Pa by adjust vacuum pump extraction valve making the vacuum in reactor；
(3) load continuous laser and irradiate silicon substrate, 808 nanometers of wavelength, regulation laser power is 80W, loads laser
Time is 10 minutes；
(4) stop being passed through the Ar gas containing HMDS, close the heating system in laser and reactor, evacuation, will react
Vacuum in device is adjusted to below 10Pa, and naturally cools to room temperature, that is, obtain the cubic silicon carbide being deposited on monocrystalline silicon substrate
Silicon thin film.
As shown in Figure 2, cubic silicon carbide silicon thin film manufactured in the present embodiment carries out XRD test.As can be seen that only having from figure
Cubic silicon carbide (111) and the diffraction maximum of (222), without the diffraction maximum of carborundum other crystal face, result shows thin film composition
It is 3C-SiC, its (111) crystal face is parallel to substrate.
Fig. 3 is deposited on the transmission electron microscope (TEM) of the cubic silicon carbide silicon thin film on monocrystalline silicon substrate for the present embodiment
Picture.According to Fig. 3, on the in-plane parallel to substrate surface, the average cross sectional diameter d of carborundum grain and its distance
Silicon substrate apart from h, meet formula d=hv, v is 0.7, much larger than the cubic silicon carbide silicon thin film (v of conventional CVD method preparation
Value is about 0.517).This show the present invention prepare gained carborundum growth during crystal defect in the increase with thickness
And quick disappearance.
Fig. 4 (a) is deposited on the TEM picture of the cubic silicon carbide silicon thin film on monocrystalline silicon substrate, wherein, carborundum for the present embodiment
Planar defect favours the direction of growth of thin film, and (b) is the TEM picture of the carborundum films of traditional CVD method preparation, its silicon carbide surface
Defect is parallel to substrate surface.
In the carborundum films of traditional CVD method preparation, APB (APB) and twin boundary (TB) are perpendicular to thin film
Shown in the direction of growth, such as Fig. 5 (a) and (c), APB or TB that it is parallel to each other is difficult to meet and disappears.On the contrary, in the present invention
In, have the APB favouring the thin film direction of growth in thin film, shown in such as Fig. 5 (b), this APB can with the growth of thin film and
Adjacent APB meets, and finally mutually buries in oblivion；TB also has similar situation, such as shown in Fig. 5 (d).
Embodiment 2
A kind of preparation method of cubic silicon carbide silicon thin film, comprises the steps：
(1) monocrystalline silicon substrate is put in the substrate holder of cold wall type laser chemical vapor deposition reactor, and by vacuum
It is adjusted to below 10Pa, and the heating system in reactor is set, make substrate holder temperature rise to 600 DEG C；
(2) the current-carrying gas Ar gas containing hexamethyldisilane (HMDS) is passed through in reactor, the flow of HMDS is 10sccm,
Adjusting the vacuum in reactor is 1000Pa；
(3) load continuous laser and irradiate silicon substrate, 1080 nanometers of wavelength, regulation laser power is 20W, loads laser
Time is 3 minutes；
(4) stop being passed through the H containing HMDS2, close the heating system in laser and reactor, evacuation, by reactor
Interior vacuum is adjusted to below 10Pa, and naturally cools to room temperature, that is, obtain the cubic silicon carbide being deposited on monocrystalline silicon substrate
Thin film.
Cubic silicon carbide thin film composition manufactured in the present embodiment is 3C-SiC, and its (111) crystal face is parallel to substrate.
Embodiment 3
A kind of preparation method of cubic silicon carbide silicon thin film, comprises the steps：
(1) monocrystalline silicon substrate is put in the substrate holder of cold wall type laser chemical vapor deposition reactor, and by vacuum
It is adjusted to below 10Pa, and the heating system in reactor is set, make substrate holder temperature rise to 900 DEG C；
(2) the current-carrying gas H of hexamethyldisilane (HMDS) will be contained2It is passed through in reactor, the flow of HMDS is 18sccm, adjusts
Vacuum in section reactor is 100Pa；
(3) load continuous laser and irradiate silicon substrate, optical maser wavelength is 1080 nanometers, regulation laser power is 150W,
Loading Laser Time is 1 minute；
(4) stop being passed through the current-carrying gas H containing HMDS2, close the heating system in laser and reactor, evacuation, incite somebody to action
Vacuum in reactor is adjusted to below 10Pa, and naturally cools to room temperature, that is, obtain being deposited on monocrystalline silicon substrate cube
Carborundum films.
Cubic silicon carbide thin film composition manufactured in the present embodiment is 3C-SiC, and its (111) crystal face is parallel to substrate.
Particular embodiments described above, has been carried out further to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail.For a person skilled in the art, the present invention can have various modifications and variations, all spirit in the present invention
With any modification made in principle, equivalent, improvement etc., all should be within the scope of the present invention.
Claims (4)
1. a kind of preparation method of cubic silicon carbide silicon thin film is it is characterised in that comprise the steps：
（1）Monocrystalline silicon substrate is put in the substrate holder of cold wall type laser chemical vapor deposition reactor, and vacuum is adjusted to
Below 10Pa, and the heating system in reactor is set, make substrate holder temperature rise to 100 ~ 900 DEG C；
（2）Current-carrying gas containing hexamethyldisilane is passed through in reactor, the flow of hexamethyldisilane is 1 ~ 20sccm, adjusts
Vacuum in reactor is to 10 ~ 10kPa；
（3）Load continuous laser and irradiate silicon substrate, 1080 ~ 1150 nanometers of wavelength, regulation laser power is 10 ~ 150W, its
Loading Laser Time is 1 ~ 10 minute；
（4）Stop being passed through the current-carrying gas containing hexamethyldisilane, close the heating system in laser and reactor, by reactor
Interior vacuum is adjusted to below 10Pa, and is cooled to room temperature, that is, obtain the cubic silicon carbide silicon thin film being deposited on monocrystalline silicon substrate.
2. a kind of preparation method of cubic silicon carbide silicon thin film according to claim 1 is it is characterised in that described monocrystalline silicon substrate
Plate makes its clean surface through pretreatment.
3. a kind of preparation method of cubic silicon carbide silicon thin film according to claim 2 is it is characterised in that described pretreatment
Method is：Substrate is initially positioned at supersound process in ethanol, is then placed in cleaning in ammonia and the mixed solution of hydrogen peroxide, then
After being placed in cleaning in hydrofluoric acid aqueous solution, it is washed with deionized clean.
4. a kind of preparation method of cubic silicon carbide silicon thin film according to claim 1 is it is characterised in that described hexamethyl two
The current-carrying solid/liquid/gas reactions device of silane is argon or hydrogen.
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| CN104498897B (en) * | 2014-12-12 | 2017-08-25 | 武汉理工大学 | A kind of preparation method of carborundum films |
| JP6622912B2 (en) * | 2015-10-29 | 2019-12-18 | イビデン株式会社 | CVD-SiC film and composite material |
| CN105671628B (en) * | 2016-02-01 | 2018-04-20 | 昝涵今 | A kind of laser heats the device and its growing method of the big thin slice of growing by zone melting or Special-shaped warp monocrystalline |
| CN105803422B (en) * | 2016-05-27 | 2019-05-03 | 洛阳理工学院 | A kind of SiC film preparation device and the method that SiC film is prepared under rough vacuum |
| CN106044774B (en) * | 2016-05-31 | 2018-02-27 | 上海纳晶科技有限公司 | A kind of preparation method of low temperature low cost high-purity silicon carbide ultrafine dust |
| CN106835071A (en) * | 2017-01-23 | 2017-06-13 | 武汉理工大学 | A kind of preparation method of CVD silicon carbide material |
| CN107513698B (en) * | 2017-09-08 | 2019-03-08 | 武汉理工大学 | A kind of preparation method of cubic silicon carbide silicon coating |
| CN107881489B (en) * | 2017-10-31 | 2019-12-24 | 浙江大学 | Laser-assisted heating chemical vapor deposition coating device and method |
| JP7146946B2 (en) * | 2018-05-31 | 2022-10-04 | イビデン株式会社 | Process for preparing 3C-SiC films |
| CN110323126B (en) * | 2019-04-15 | 2021-09-14 | 武汉理工大学 | Preparation method of Si/SiC/graphene material |
| CN110534348A (en) * | 2019-07-31 | 2019-12-03 | 气相科技(武汉)有限公司 | A kind of electrode material and preparation method thereof based on 3C-SiC film |
| CN114150292B (en) * | 2021-12-14 | 2023-03-10 | 武汉理工大学 | Thermal shock resistant silicon carbide nano porous coating material and preparation method and application thereof |
| CN115959669A (en) * | 2023-01-30 | 2023-04-14 | 武汉理工大学 | Preparation method of SiC nano powder |
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