CN117418309A - Preparation method of 3C-SiC monocrystal - Google Patents
Preparation method of 3C-SiC monocrystal Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 96
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 32
- 230000008719 thickening Effects 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims description 172
- 239000002131 composite material Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 28
- 230000003746 surface roughness Effects 0.000 claims description 21
- 238000005520 cutting process Methods 0.000 claims description 18
- 238000003486 chemical etching Methods 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims 1
- 230000008018 melting Effects 0.000 abstract description 11
- 238000002844 melting Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 228
- 239000007789 gas Substances 0.000 description 26
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 18
- 229910003460 diamond Inorganic materials 0.000 description 16
- 239000010432 diamond Substances 0.000 description 16
- 238000005498 polishing Methods 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 238000000227 grinding Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 9
- 239000003085 diluting agent Substances 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 244000137852 Petrea volubilis Species 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
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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
- C30B29/10—Inorganic compounds or compositions
- C30B29/36—Carbides
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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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a preparation method of a 3C-SiC monocrystal, which relates to the technical field of semiconductor material preparation, and comprises the steps of firstly growing a 3C-SiC monocrystal initial layer on a Si monocrystal substrate by adopting chemical vapor deposition at a certain temperature lower than the melting point of Si, then contacting the 3C-SiC monocrystal initial layer with a 4H-SiC monocrystal substrate for bonding, removing the Si monocrystal substrate, and further rapidly growing a 3C-SiC monocrystal thickening layer on the 3C-SiC monocrystal initial layer by adopting chemical vapor deposition at a certain temperature higher than the melting point of Si. The preparation method solves the problems that the 3C-SiC monocrystal grows slowly and is difficult to grow thick on the Si monocrystal substrate, the growth speed of the 3C-SiC monocrystal can reach 200 mu m/h, the thickness of the prepared 3C-SiC monocrystal is more than or equal to 1mm, and the half width of a (111) peak is less than 50arcsec.
Description
Technical Field
The invention relates to the technical field of semiconductor material preparation, in particular to a preparation method of a 3C-SiC monocrystal.
Background
The silicon carbide material has the advantages of high temperature resistance, high pressure resistance, radiation resistance, chemical corrosion resistance, high hardness, high thermal conductivity and the like. Compared with the hexagonal single crystal 4H-SiC which has been widely used in industry, the cubic single crystal 3C-SiC has higher electron mobility, saturated electron velocity and heat conductivity, and is more suitable for preparing devices such as MOSFETs and the like.
Currently, 4H-SiC single crystals have been widely used in the manufacture of IGBT, MOSFET and other devices. In industrial production, the first step in producing a 4H-SiC single crystal substrate is to grow a single crystal having a thickness of 10mm or more, followed by cutting, grinding and polishing steps to produce a substrate having a thickness of 350 μm. However, for 3C-SiC single crystals, preparing single crystals with a large thickness (> 1 mm) remains a challenge. CN115692181a discloses a method specifically comprising growing a 3C-SiC single crystal on a positive axis 4H-SiC single crystal substrate, but cannot be applied because of the easy formation of double stacked grain boundary defects. The prior art also discloses another method, specifically comprising growing a 3C-SiC single crystal on a Si single crystal substrate by chemical vapor deposition, but since the melting point of Si is 1414 ℃, the growth temperature cannot be higher or close to this temperature, otherwise the melted or softened Si substrate cannot be used as a growth substrate. Due to the low growth temperature, the growth rate of the 3C-SiC single crystal is slow, and it is difficult to grow a large-thickness 3C-SiC single crystal. For example, journal articles corresponding to Materials Science Forum Vols 457-460 (2004) pp 285-288 disclose the use of chemical vapor deposition methods for growing 3C-SiC single crystals on Si single crystal substrates at 1300℃, at a growth rate of 0.4-1.5 μm/h, and at a growth thickness of 2-6 μm.
In view of the foregoing, there is a need to develop a new preparation method of 3C-SiC single crystals to increase the growth rate and obtain large-thickness 3C-SiC single crystals.
Disclosure of Invention
In view of the problems existing in the prior art, the invention provides a preparation method of a 3C-SiC monocrystal, which comprises the steps of firstly growing a 3C-SiC monocrystal initial layer on a Si monocrystal substrate by adopting chemical vapor deposition at a certain temperature lower than the melting point of Si, then contacting the 3C-SiC monocrystal initial layer with a 4H-SiC monocrystal substrate for bonding, removing the Si monocrystal substrate, and further rapidly growing a 3C-SiC monocrystal thickening layer on the 3C-SiC monocrystal initial layer by adopting chemical vapor deposition at a certain temperature higher than the melting point of Si. The preparation method solves the problems that the 3C-SiC monocrystal grows slowly and is difficult to grow thick on the Si monocrystal substrate, the growth speed of the 3C-SiC monocrystal can reach 200 mu m/h, the thickness of the prepared 3C-SiC monocrystal is more than or equal to 1mm, and the half width of a (111) peak is less than 50arcsec.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a 3C-SiC monocrystal, which comprises the following steps:
(1) Growing a 3C-SiC single crystal initial layer on a Si single crystal substrate by adopting chemical vapor deposition to obtain a Si/3C-SiC composite;
(2) Cutting the side surface of the Si/3C-SiC composite body in the step (1), removing the 3C-SiC single crystal initial layer positioned on the side surface, and respectively contacting and bonding the outer surfaces of the 3C-SiC single crystal initial layers on the upper side surface and the lower side surface with the outer surfaces of two 4H-SiC single crystal substrates to obtain the Si/3C-SiC/4H-SiC composite body;
(3) Removing the Si single crystal substrate from the Si/3C-SiC/4H-SiC composite in the step (2) to obtain two 4H-SiC/3C-SiC composites;
(4) Growing a 3C-SiC single crystal thickening layer on the 3C-SiC single crystal initial layer of the 4H-SiC/3C-SiC composite body in the step (3) by adopting chemical vapor deposition to obtain the 4H-SiC/3C-SiC thickening composite body;
(5) And (3) removing the 4H-SiC monocrystalline substrate from the 4H-SiC/3C-SiC thickened complex in the step (4), and performing circular cutting to obtain the 3C-SiC monocrystal.
The preparation method comprises the steps of firstly growing a 3C-SiC single crystal initial layer on a Si single crystal substrate by adopting chemical vapor deposition at a certain temperature lower than the melting point of Si, then contacting the 3C-SiC single crystal initial layer with a 4H-SiC single crystal substrate for bonding, removing the Si single crystal substrate, and further rapidly growing a 3C-SiC single crystal thickening layer on the 3C-SiC single crystal initial layer by adopting chemical vapor deposition at a certain temperature higher than the melting point of Si. The preparation method solves the problems that the 3C-SiC monocrystal grows slowly and is difficult to grow thick on the Si monocrystal substrate, the growth speed of the 3C-SiC monocrystal can reach 200 mu m/h, the thickness of the prepared 3C-SiC monocrystal is more than or equal to 1mm, and the half width of a (111) peak is less than 50arcsec.
In the present invention, the chemical vapor deposition in the step (1) and the step (4) may be horizontal air intake or vertical air intake, preferably vertical air intake, and the chemical vapor deposition device used may be hot wall type or cold wall type, preferably hot wall type. The substrate is fixed in the cavity and can be fixed by suspension wires or by other connecting pieces. The suspension wire may be a graphite rope or a molybdenum wire, preferably a molybdenum wire. The gaseous starting material used to form SiC via chemical reaction may be trichloromethylsilane (CH 3 SiCl 3 ) The trichloromethylsilane which is in liquid state at normal temperature is converted into gas state by adopting a bubbling method, and carrier gas which is introduced during bubbling is hydrogen (H) 2 ) The diluent gas introduced into the chamber is hydrogen or argon (Ar), preferably hydrogen. When the growth starts, the cavity is heated to the growth temperature and maintained at a certain pressure, and then the gas raw material and the diluent gas are introduced for growth. The raw material gas is trichloromethylsilane and hydrogen, and the flow ratio of the trichloromethylsilane to the hydrogen is 1:20.
In the preferred embodiment of the present invention, in the step (1), the surface roughness of the Si single crystal substrate is less than 0.5nm, the growth direction of the growth is that the surface normal of the Si single crystal substrate is 2-4 degrees, for example, 2 degrees, 2.2 degrees, 2.5 degrees, 2.8 degrees, 3 degrees, 3.1 degrees, 3.3 degrees, 3.5 degrees, 3.7 degrees or 4 degrees, which are the (111) plane deviation [001] direction, but the present invention is not limited to the listed values, and other non-listed values within the above-mentioned values are equally applicable.
In the invention, the surface roughness of the Si single crystal substrate is required to be smaller than 0.5nm, and excessive surface roughness can lead to epitaxial growth of the SiC single crystal on the surface other than the (111) surface of Si, so that additional defects are introduced; in addition, the growth direction is that the surface normal of the Si single crystal substrate is 2-4 degrees in the [001] direction of the (111) plane, if the off-axis angle in the [001] direction is too small, double-stacked grain boundary defects are introduced when the 3C-SiC single crystal is grown, and if the off-axis angle in the [001] direction is too large, the produced 3C-SiC single crystal is not suitable for epitaxial growth.
As a preferred embodiment of the present invention, in the step (1), the chemical vapor deposition is performed at a growth temperature of 1000 to 1300 ℃, for example 1000 ℃, 1030 ℃, 1050 ℃, 1070 ℃, 1100 ℃, 1120 ℃, 1150 ℃, 1180 ℃, 1200 ℃, 1220 ℃, 1250 ℃, 1270 ℃, 1300 ℃, etc., at a growth pressure of 100 to 500Pa, for example 100Pa, 200Pa, 300Pa, 400Pa, 500Pa, etc., at a growth rate of 0.5 to 2 μm/h, for example 0.5 μm/h, 0.7 μm/h, 1 μm/h, 1.1 μm/h, 1.3 μm/h, 1.5 μm/h, 1.8 μm/h, 2 μm/h, etc., but the present invention is not limited to the recited values, and other values not recited in the above-mentioned value ranges are equally applicable.
In the invention, for growing the 3C-SiC single crystal initial layer on the Si single crystal substrate, the growth temperature is in the range of 1000-1300 ℃, the growth temperature is too low to form a 3C-SiC single crystal structure, the growth temperature is too high, the Si single crystal substrate is softened, and the 3C-SiC single crystal layer with a flat surface can not be grown; the growth pressure is in the range of 100-500Pa, the growth pressure is too low, the growth speed is slow, the growth pressure is too high, and SiC polycrystal is easy to grow; suitable growth rates are controlled in the range of 0.5-2 μm/h.
In the preferred embodiment of the present invention, in the step (1), the thickness of the 3C-SiC single crystal starting layer is 1 to 5. Mu.m, for example, 1. Mu.m, 1.5. Mu.m, 2. Mu.m, 2.5. Mu.m, 3. Mu.m, 3.5. Mu.m, 4. Mu.m, 4.5. Mu.m, 5. Mu.m, etc., but not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are similarly applicable.
In the present invention, the thickness of the initial layer of 3C-SiC single crystal grown on the Si single crystal substrate is 1-5 μm, if the thickness is too thin, chipping may occur during the subsequent polishing process, and if the thickness is too thick, the process time is consumed because the growth rate is too slow.
In the step (2), the surface roughness of the outer surface of the 3C-SiC single crystal initial layer for bonding is less than 2nm, and the surface roughness of the outer surface of the 4H-SiC single crystal substrate for bonding is less than 2nm.
In the invention, the diamond wire is adopted for cutting in the step (2) to form a round shape, then the outer surfaces of the 3C-SiC single crystal initial layers on the upper side and the lower side are sequentially ground and polished, and the diamond grinding wheel is adopted for grinding and the chemical mechanical polishing method is adopted for polishing; if the surface roughness of the outer surface of the 3C-SiC single crystal initial layer for bonding is too large, the contact of the subsequent bonding surface is poor, the bonding effect is affected, and similarly, the surface roughness of the outer surface of the 4H-SiC single crystal substrate for bonding of the support layer is too large, the contact of the subsequent bonding surface is poor, and the bonding effect is affected.
As a preferred embodiment of the present invention, the bonding in step (2) is performed at a temperature of 20 to 40℃such as 20℃23℃25℃27℃30℃33℃35℃38℃or 40℃under vacuum, and the absolute vacuum is controlled to be 10 or less -3 Pa; the bonding time is 5 to 30s, for example, 5s, 7s, 10s, 13s, 15s, 18s, 20s, 23s, 25s, 28s or 30s, etc., but is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
In the invention, the bonding method adopts a surface activation bonding mode, specifically, the bonding of atomic level is realized after the outer surface of the 3C-SiC single crystal initial layer is contacted with the outer surface of the 4H-SiC single crystal substrate.
In the step (3), the Si single crystal substrate is removed by chemical etching, for example, HF acid solution is used as chemical raw material.
In the invention, the surface of the 3C-SiC single crystal initial layer adopts a chemical etching method, and grinding and polishing steps are not needed after the Si single crystal substrate is removed.
As a preferred embodiment of the present invention, in the step (4), the chemical vapor deposition has a growth temperature of 1500 to 1600 ℃, for example 1500 ℃, 1510 ℃, 1520 ℃, 1530 ℃, 1540 ℃, 1550 ℃, 1560 ℃, 1570 ℃, 1580 ℃, 1590 ℃, 1600 ℃, etc., a growth pressure of 500 to 2000Pa, for example 500Pa, 800Pa, 1000Pa, 1300Pa, 1500Pa, 1700Pa, 1800Pa, 2000Pa, etc., a growth rate of 50 to 200 μm/h, for example 50 μm/h, 80 μm/h, 100 μm/h, 120 μm/h, 150 μm/h, 160 μm/h, 180 μm/h, 200 μm/h, etc., but the present invention is not limited to the above-mentioned values, and other non-mentioned values within the above-mentioned value ranges are equally applicable.
In the invention, for growing a 3C-SiC single crystal thickening layer on a 3C-SiC single crystal initial layer, the growth temperature is in the range of 1500-1600 ℃, if the growth temperature is too low, the growth speed is too low, and if the growth temperature is too high, the defect of a 4H-SiC crystal form is easy to introduce; the growth pressure is in the range of 500-2000Pa, if the growth pressure is too low, the growth speed is slow, and if the growth pressure is too high, yi Shengchang SiC polycrystal is produced; suitable growth rates are controlled in the range of 50-200 μm/h.
In the preferred embodiment of the present invention, in the step (4), the thickness of the 3C-SiC single crystal thickening layer is 1 to 5mm, for example, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm or 5mm, etc., but the thickness is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are equally applicable.
In the step (5), the 4H-SiC single crystal substrate is cut by diamond wires, and the circular 3C-SiC single crystal is obtained by cutting by diamond wires.
As a preferable technical scheme of the invention, in the step (5), the thickness of the 3C-SiC monocrystal is more than or equal to 1mm, and the half width of the (111) peak is less than 50arcsec.
Compared with the prior art, the invention has at least the following beneficial effects:
the preparation method comprises the steps of firstly growing a 3C-SiC single crystal initial layer on a Si single crystal substrate by adopting chemical vapor deposition at a certain temperature lower than the melting point of Si, then contacting the 3C-SiC single crystal initial layer with a 4H-SiC single crystal substrate for bonding, removing the Si single crystal substrate, and further rapidly growing a 3C-SiC single crystal thickening layer on the 3C-SiC single crystal initial layer by adopting chemical vapor deposition at a certain temperature higher than the melting point of Si. The preparation method solves the problems that the 3C-SiC monocrystal grows slowly and is difficult to grow thick on the Si monocrystal substrate, the growth speed of the 3C-SiC monocrystal can reach 200 mu m/h, the thickness of the prepared 3C-SiC monocrystal is more than or equal to 1mm, and the half width of a (111) peak is less than 50arcsec.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a 3C-SiC monocrystal according to the invention;
FIG. 2 is a graph showing the XRD rocking curve of the 3C-SiC single crystal according to example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
the flow chart of the preparation method of the 3C-SiC monocrystal is shown in figure 1, and the preparation method comprises the following steps:
(1) Growing a 3C-SiC single crystal initial layer on a Si single crystal substrate by adopting chemical vapor deposition to obtain a Si/3C-SiC composite;
(2) Cutting the side surface of the Si/3C-SiC composite body in the step (1), removing the 3C-SiC single crystal initial layer positioned on the side surface, and respectively contacting and bonding the outer surfaces of the 3C-SiC single crystal initial layers on the upper side surface and the lower side surface with the outer surfaces of two 4H-SiC single crystal substrates to obtain the Si/3C-SiC/4H-SiC composite body;
(3) Removing the Si single crystal substrate from the Si/3C-SiC/4H-SiC composite of step (2) to obtain two 4H-SiC/3C-SiC composites (only one 4H-SiC/3C-SiC composite is shown in FIG. 1);
(4) Growing a 3C-SiC single crystal thickening layer on the 3C-SiC single crystal initial layer of the 4H-SiC/3C-SiC composite body in the step (3) by adopting chemical vapor deposition to obtain the 4H-SiC/3C-SiC thickening composite body;
(5) And (3) removing the 4H-SiC monocrystalline substrate from the 4H-SiC/3C-SiC thickened complex in the step (4), and performing circular cutting to obtain the 3C-SiC monocrystal.
Example 1
The embodiment provides a preparation method of a 3C-SiC monocrystal, which comprises the following steps:
(1) A vertical air inlet hot wall type chemical vapor deposition device is adopted to grow a 3C-SiC single crystal initial layer on a Si single crystal substrate, the Si single crystal substrate is fixed in a cavity through molybdenum wires, the surface roughness of the Si single crystal substrate is 0.25nm, the growth direction of the Si single crystal substrate is that the surface normal direction of the Si single crystal substrate is the (111) plane is 4 degrees in the [001] direction, the cavity is firstly heated to a growth temperature and maintained at a certain pressure when the growth starts, the growth temperature is 1300 ℃, the growth pressure is 500Pa, then raw material gas and diluent gas are introduced for growth, the raw material gas is trichloromethylsilane and hydrogen, and the flow ratio of the trichloromethylsilane to the hydrogen is 1:20. The growth speed is 2 mu m/h, the growth time is 2.5h, and a 3C-SiC single crystal initial layer with the thickness of 5 mu m is grown to obtain a Si/3C-SiC composite;
(2) Cutting the side surface of the Si/3C-SiC composite body in the step (1), removing the 3C-SiC single crystal initial layer positioned on the side surface, cutting a diamond wire into a round shape, respectively grinding and polishing the outer surfaces of the 3C-SiC single crystal initial layers on the upper side surface and the lower side surface, specifically grinding by using diamond sand paper, polishing by using a chemical mechanical polishing method, wherein the surface roughness of the outer surface of the 3C-SiC single crystal initial layer for bonding after polishing is 1.6nm, the surface roughness of the outer surface of the 4H-SiC single crystal substrate for bonding is 1nm, and respectively contacting the outer surfaces of the 3C-SiC single crystal initial layers on the upper side surface and the lower side surface with the outer surfaces of the two 4H-SiC single crystal substrates for bonding to realize atomic-level bonding to obtain the Si/3C-SiC/4H-SiC composite body;
(3) Etching the Si/3C-SiC/4H-SiC composite body in the step (2) by adopting an HF acid solution to remove the Si single crystal substrate, so as to obtain two 4H-SiC/3C-SiC composite bodies;
(4) And (3) growing a 3C-SiC monocrystal thickening layer on the 3C-SiC monocrystal initial layer of the 4H-SiC/3C-SiC composite body in the step (3) by adopting a hot wall type chemical vapor deposition device with vertical air inlet, wherein the 4H-SiC/3C-SiC composite body is fixed in the cavity through molybdenum wires. When the growth starts, the cavity is heated to the growth temperature and maintained at a certain pressure, the growth temperature is 1600 ℃, and the growth pressure is 2000Pa. Then, introducing raw material gas and diluent gas for growth, wherein the raw material gas is trichloromethylsilane and hydrogen, the flow ratio of the trichloromethylsilane to the hydrogen is 1:20, the growth speed is 200 mu m/H, the growth time is 25H, and a 3C-SiC monocrystal thickening layer with the thickness of 5mm is grown to obtain a 4H-SiC/3C-SiC thickening complex;
(5) And (3) cutting the 4H-SiC/3C-SiC thickened complex in the step (4) by adopting diamond wire to remove a 4H-SiC single crystal substrate, and adopting diamond wire to cut to obtain a round 3C-SiC single crystal, wherein the thickness of the single crystal is 4.5mm, and the half width of the (111) peak of the 3C-SiC single crystal is 32arcsec through XRD rocking curve detection, as shown in figure 2.
Example 2
The embodiment provides a preparation method of a 3C-SiC monocrystal, which comprises the following steps:
(1) A vertical air inlet hot wall type chemical vapor deposition device is adopted to grow a 3C-SiC single crystal initial layer on a Si single crystal substrate, the Si single crystal substrate is fixed in a cavity through molybdenum wires, the surface roughness of the Si single crystal substrate is 0.35nm, the growth direction of the Si single crystal substrate is that the surface normal direction of the Si single crystal substrate is the (111) plane is 3 degrees in the [001] direction, the cavity is firstly heated to a growth temperature and maintained at a certain pressure when the growth starts, the growth temperature is 1200 ℃, the growth pressure is 300Pa, then raw material gas and diluent gas are introduced for growth, the raw material gas is trichloromethylsilane and hydrogen, and the flow ratio of the trichloromethylsilane to the hydrogen is 1:20. The growth speed is 1 mu m/h, the growth time is 5h, and a 3C-SiC single crystal initial layer with the thickness of 5 mu m is grown to obtain a Si/3C-SiC complex;
(2) Cutting the side surface of the Si/3C-SiC composite body in the step (1), removing the 3C-SiC single crystal initial layer positioned on the side surface, cutting a diamond wire into a round shape, respectively grinding and polishing the outer surfaces of the 3C-SiC single crystal initial layers on the upper side surface and the lower side surface, specifically grinding by using diamond sand paper, polishing by using a chemical mechanical polishing method, wherein the surface roughness of the outer surface of the 3C-SiC single crystal initial layer for bonding after polishing is 1.6nm, the surface roughness of the outer surface of the 4H-SiC single crystal substrate for bonding is 1nm, and respectively contacting the outer surfaces of the 3C-SiC single crystal initial layers on the upper side surface and the lower side surface with the outer surfaces of the two 4H-SiC single crystal substrates for bonding to realize atomic-level bonding to obtain the Si/3C-SiC/4H-SiC composite body;
(3) Etching the Si/3C-SiC/4H-SiC composite body in the step (2) by adopting an HF acid solution to remove the Si single crystal substrate, so as to obtain two 4H-SiC/3C-SiC composite bodies;
(4) And (3) growing a 3C-SiC monocrystal thickening layer on the 3C-SiC monocrystal initial layer of the 4H-SiC/3C-SiC composite body in the step (3) by adopting a hot wall type chemical vapor deposition device with vertical air inlet, wherein the 4H-SiC/3C-SiC composite body is fixed in the cavity through molybdenum wires. When the growth starts, the cavity is heated to the growth temperature and maintained at a certain pressure, the growth temperature is 1550 ℃ and the growth pressure is 1000Pa. Then, introducing raw material gas and diluent gas for growth, wherein the raw material gas is trichloromethylsilane and hydrogen, the flow ratio of the trichloromethylsilane to the hydrogen is 1:20, the growth speed is 100 mu m/H, the growth time is 50H, and a 3C-SiC monocrystal thickening layer with the thickness of 5mm is grown to obtain a 4H-SiC/3C-SiC thickening complex;
(5) And (3) cutting the 4H-SiC/3C-SiC thickened complex in the step (4) by adopting diamond wire to remove a 4H-SiC single crystal substrate, and adopting diamond wire to cut to obtain a round 3C-SiC single crystal, wherein the thickness of the single crystal is 4.5mm, and the half width of the (111) peak of the 3C-SiC single crystal is 45arcsec through XRD rocking curve detection.
Example 3
The embodiment provides a preparation method of a 3C-SiC monocrystal, which comprises the following steps:
(1) A vertical air inlet hot wall type chemical vapor deposition device is adopted to grow a 3C-SiC single crystal initial layer on a Si single crystal substrate, the Si single crystal substrate is fixed in a cavity through molybdenum wires, the surface roughness of the Si single crystal substrate is 0.45nm, the growth direction of the Si single crystal substrate is that the surface normal direction of the Si single crystal substrate is 2 degrees in the (111) plane direction, at the beginning of growth, the cavity is heated to a growth temperature and maintained at a certain pressure, the growth temperature is 1000 ℃, the growth pressure is 100Pa, then raw material gas and diluent gas are introduced for growth, the raw material gas is trichloromethylsilane and hydrogen, and the flow ratio of the trichloromethylsilane to the hydrogen is 1:20. The growth speed is 0.5 mu m/h, the growth time is 10h, and a 3C-SiC single crystal initial layer with the thickness of 5 mu m is grown to obtain a Si/3C-SiC composite;
(2) Cutting the side surface of the Si/3C-SiC composite body in the step (1), removing the 3C-SiC single crystal initial layer positioned on the side surface, cutting a diamond wire into a round shape, respectively grinding and polishing the outer surfaces of the 3C-SiC single crystal initial layers on the upper side surface and the lower side surface, specifically grinding by using diamond sand paper, polishing by using a chemical mechanical polishing method, wherein the surface roughness of the outer surface of the 3C-SiC single crystal initial layer for bonding after polishing is 1.6nm, the surface roughness of the outer surface of the 4H-SiC single crystal substrate for bonding is 1nm, and respectively contacting the outer surfaces of the 3C-SiC single crystal initial layers on the upper side surface and the lower side surface with the outer surfaces of the two 4H-SiC single crystal substrates for bonding to realize atomic-level bonding to obtain the Si/3C-SiC/4H-SiC composite body;
(3) Etching the Si/3C-SiC/4H-SiC composite body in the step (2) by adopting an HF acid solution to remove the Si single crystal substrate, so as to obtain two 4H-SiC/3C-SiC composite bodies;
(4) And (3) growing a 3C-SiC monocrystal thickening layer on the 3C-SiC monocrystal initial layer of the 4H-SiC/3C-SiC composite body in the step (3) by adopting a hot wall type chemical vapor deposition device with vertical air inlet, wherein the 4H-SiC/3C-SiC composite body is fixed in the cavity through molybdenum wires. When the growth starts, the cavity is heated to the growth temperature and maintained at a certain pressure, the growth temperature is 1500 ℃, and the growth pressure is 500Pa. Then, introducing raw material gas and diluent gas for growth, wherein the raw material gas is trichloromethylsilane and hydrogen, the flow ratio of the trichloromethylsilane to the hydrogen is 1:20, the growth speed is 50 mu m/H, the growth time is 100H, and a 3C-SiC monocrystal thickening layer with the thickness of 5mm is grown to obtain a 4H-SiC/3C-SiC thickening complex;
(5) And (3) cutting the 4H-SiC/3C-SiC thickened complex in the step (4) by adopting diamond wire to remove a 4H-SiC single crystal substrate, and adopting diamond wire to cut to obtain a round 3C-SiC single crystal, wherein the thickness of the single crystal is 4.5mm, and the half width of the (111) peak of the 3C-SiC single crystal is 40arcsec through XRD rocking curve detection.
Example 4
The present example provides a method for preparing a 3C-SiC single crystal, which differs from example 1 only in that: the surface roughness of the Si single crystal substrate in the step (1) is 0.6nm.
Example 5
The present example provides a method for preparing a 3C-SiC single crystal, which differs from example 1 only in that: the growth direction of the growth in the step (1) is that the surface normal of the Si single crystal substrate is 1 degree from the (111) plane to the [001] direction.
Example 6
The present example provides a method for preparing a 3C-SiC single crystal, which differs from example 1 only in that: the growth direction of the growth in the step (1) is that the surface normal of the Si single crystal substrate is 5 degrees from the (111) plane to the [001] direction.
Example 7
The present example provides a method for preparing a 3C-SiC single crystal, which differs from example 1 only in that: the growth temperature in the step (4) is 1400 ℃.
Example 8
The present example provides a method for preparing a 3C-SiC single crystal, which differs from example 1 only in that: the growth temperature in the step (4) is 1700 ℃.
Comparative example 1
This comparative example provides a method for preparing a 3C-SiC single crystal, differing from example 1 only in that: the whole process adopts chemical vapor deposition to grow 3C-SiC monocrystal on the Si monocrystal substrate, and 4H-SiC monocrystal substrate is not adopted any more; the specific contents are as follows:
A3C-SiC monocrystalline layer grows on a Si monocrystalline substrate by adopting a hot wall type chemical vapor deposition device with vertical air inlet, the Si monocrystalline substrate is fixed in a cavity through molybdenum wires, the surface roughness of the Si monocrystalline substrate is 0.25nm, the growth direction of the Si monocrystalline substrate is that the surface normal direction of the Si monocrystalline substrate is the (111) plane is 4 degrees in the [001] direction, the cavity is firstly heated to a growth temperature and maintained at a certain pressure when the growth starts, the growth temperature is 1300 ℃, the growth pressure is 500Pa, then raw material gas and diluent gas are introduced for growth, the raw material gas is trichloromethylsilane and hydrogen, and the flow ratio of the trichloromethylsilane to the hydrogen is 1:20. The growth rate was 2 μm/h and the growth time was 100h, and a 3C-SiC single crystal layer of 200 μm was grown in total.
The results of the above examples with respect to the 3C-SiC single crystals obtained in the comparative examples are summarized in Table 1.
TABLE 1
Note that: "-" means uncharacterized.
Since comparative example 1 took 100 hours to grow only a 3C-SiC single crystal layer having a thickness of 200 μm, i.e., a 3C-SiC single crystal layer having a thickness of 0.2mm on a Si single crystal substrate, it was not advantageous to remove the Si single crystal substrate to obtain a 3C-SiC single crystal, and therefore XRD rocking curve characterization was not performed.
In summary, the preparation method of the invention comprises the steps of growing a 3C-SiC single crystal initial layer on a Si single crystal substrate by chemical vapor deposition at a certain temperature lower than the Si melting point, then contacting the 3C-SiC single crystal initial layer with a 4H-SiC single crystal substrate for bonding, removing the Si single crystal substrate, and further rapidly growing a 3C-SiC single crystal thickening layer on the 3C-SiC single crystal initial layer by chemical vapor deposition at a certain temperature higher than the Si melting point. The preparation method solves the problems that the 3C-SiC monocrystal grows slowly and is difficult to grow thick on the Si monocrystal substrate, the growth speed of the 3C-SiC monocrystal can reach 200 mu m/h, the thickness of the prepared 3C-SiC monocrystal is more than or equal to 1mm, and the half width of a (111) peak is less than 50arcsec.
The detailed structural features of the present invention are described in the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. The preparation method of the 3C-SiC monocrystal is characterized by comprising the following steps of:
(1) Growing a 3C-SiC single crystal initial layer on a Si single crystal substrate by adopting chemical vapor deposition to obtain a Si/3C-SiC composite;
(2) Cutting the side surface of the Si/3C-SiC composite body in the step (1), removing the 3C-SiC single crystal initial layer positioned on the side surface, and respectively contacting and bonding the outer surfaces of the 3C-SiC single crystal initial layers on the upper side surface and the lower side surface with the outer surfaces of two 4H-SiC single crystal substrates to obtain the Si/3C-SiC/4H-SiC composite body;
(3) Removing the Si single crystal substrate from the Si/3C-SiC/4H-SiC composite in the step (2) to obtain two 4H-SiC/3C-SiC composites;
(4) Growing a 3C-SiC single crystal thickening layer on the 3C-SiC single crystal initial layer of the 4H-SiC/3C-SiC composite body in the step (3) by adopting chemical vapor deposition to obtain the 4H-SiC/3C-SiC thickening composite body;
(5) And (3) removing the 4H-SiC monocrystalline substrate from the 4H-SiC/3C-SiC thickened complex in the step (4), and performing circular cutting to obtain the 3C-SiC monocrystal.
2. The method according to claim 1, wherein in the step (1), the surface roughness of the Si single crystal substrate is less than 0.5nm, and the growth direction of the Si single crystal substrate is 2-4 degrees from the (111) plane to the [001] direction.
3. The method according to claim 1, wherein in the step (1), the chemical vapor deposition is performed at a growth temperature of 1000 to 1300 ℃, a growth pressure of 100 to 500Pa, and a growth rate of 0.5 to 2 μm/h.
4. The method according to claim 1, wherein in the step (1), the thickness of the 3C-SiC single crystal starting layer is 1 to 5 μm.
5. The method according to claim 1, wherein in the step (2), the surface roughness of the outer surface of the 3C-SiC single crystal initiation layer for bonding is < 2nm, and the surface roughness of the outer surface of the 4H-SiC single crystal substrate for bonding is < 2nm.
6. The method of claim 1 or 5, wherein the bonding temperature in step (2) is 20-40 ℃; the bonding is performed under vacuum, and the absolute vacuum degree is controlled to be less than or equal to 10 -3 Pa; the bonding time is 5-30s.
7. The method of claim 1, wherein in step (3), the Si single crystal substrate is removed by chemical etching.
8. The method according to claim 1, wherein in the step (4), the chemical vapor deposition is performed at a growth temperature of 1500-1600 ℃, a growth pressure of 500-2000Pa, and a growth rate of 50-200 μm/h.
9. The method of claim 1, wherein in step (4), the thickness of the 3C-SiC single crystal thickening layer is 1 to 5mm.
10. The method according to claim 1, wherein in the step (5), the thickness of the 3C-SiC single crystal is not less than 1mm, and the half width of the (111) peak is less than 50arcsec.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108140540A (en) * | 2015-09-11 | 2018-06-08 | 信越化学工业株式会社 | The manufacturing method of SiC composite substrates and the manufacturing method of semiconductor substrate |
| CN113668052A (en) * | 2021-08-13 | 2021-11-19 | 厦门大学 | SiC step flow rapid growth method for chemical potential regulation growth monomer under non-equilibrium condition |
| CN115023802A (en) * | 2020-03-27 | 2022-09-06 | 索泰克公司 | Method for producing a composite structure comprising a thin layer of monocrystalline SiC on a carrier substrate made of SiC |
| CN115088063A (en) * | 2020-03-27 | 2022-09-20 | Soitec公司 | Method for producing a composite structure comprising a thin layer made of single crystal SiC on a carrier substrate made of SiC |
| CN115961342A (en) * | 2022-12-12 | 2023-04-14 | 青禾晶元(天津)半导体材料有限公司 | Composite silicon carbide substrate and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108140540A (en) * | 2015-09-11 | 2018-06-08 | 信越化学工业株式会社 | The manufacturing method of SiC composite substrates and the manufacturing method of semiconductor substrate |
| CN115023802A (en) * | 2020-03-27 | 2022-09-06 | 索泰克公司 | Method for producing a composite structure comprising a thin layer of monocrystalline SiC on a carrier substrate made of SiC |
| CN115088063A (en) * | 2020-03-27 | 2022-09-20 | Soitec公司 | Method for producing a composite structure comprising a thin layer made of single crystal SiC on a carrier substrate made of SiC |
| CN113668052A (en) * | 2021-08-13 | 2021-11-19 | 厦门大学 | SiC step flow rapid growth method for chemical potential regulation growth monomer under non-equilibrium condition |
| CN115961342A (en) * | 2022-12-12 | 2023-04-14 | 青禾晶元(天津)半导体材料有限公司 | Composite silicon carbide substrate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李斌等: ""利用侧向生长机制在偏向4H-SiC衬底上生长3C-SiC"", 《电子工艺技术》, vol. 38, no. 1, 31 January 2017 (2017-01-31), pages 41 - 44 * |
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