WO2021060369A1 - SiC基板、SiC基板の製造方法、SiC半導体装置およびSiC半導体装置の製造方法 - Google Patents
SiC基板、SiC基板の製造方法、SiC半導体装置およびSiC半導体装置の製造方法 Download PDFInfo
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Definitions
- the present invention is a SiC substrate, a method for manufacturing a SiC substrate, a SiC semiconductor device, and a method for manufacturing a SiC semiconductor device.
- SiC silicon carbide
- SiC has an insulation breakdown electric field that is an order of magnitude larger than Si (silicon), a bandgap that is three times larger, and a thermal conductivity that is about three times higher. Therefore, SiC is expected to be applied to power devices, high-frequency devices, high-temperature operation devices, and the like.
- Basal plane dislocation is known as one of the device killer defects that cause fatal defects in SiC semiconductor devices.
- Stacking Fault SF
- FIG. 17 is a cross-sectional view showing the configuration of a SiC substrate that has been subjected to a conventional treatment for suppressing stacking defects.
- the SiC substrate 100 includes an n + type SiC base substrate 101, an n-type dislocation conversion layer 102, an n + type recombination promoting layer 103, and an n-type epitaxial growth layer 104.
- Patent Document 1 describes that it is desirable that the doping concentration of the dislocation conversion layer is 1 ⁇ 10 15 cm -3 or less.
- the n + type recombination promoting layer 103 for suppressing the generation of SF is formed. Therefore, it is necessary to grow the n-type dislocation conversion layer 102, the n + -type recombination promoting layer 103, and the n-type epitaxial growth layer 104 on the n + type SiC base substrate 101, and it is necessary to set the growth conditions and the like. There was a problem that the process became complicated.
- an object to be solved by the present invention is to provide a novel technique for a SiC substrate and a SiC semiconductor having a dislocation conversion layer capable of reducing resistance.
- Another object of the present invention is to provide a novel technique for manufacturing a SiC substrate and a SiC semiconductor having a dislocation conversion layer capable of reducing resistance.
- the present invention that solves the above-mentioned problems is a SiC substrate including a dislocation conversion layer having a doping concentration of 1 ⁇ 10 15 cm -3 or more.
- a dislocation conversion layer having a doping concentration of 1 ⁇ 10 15 cm -3 or more.
- a dislocation conversion layer having a doping concentration of 1 ⁇ 10 17 cm -3 or more is provided.
- the dislocation conversion layer having such a doping concentration in addition to the function as a dislocation conversion layer that performs BPD ⁇ TED conversion, it is possible to fulfill the function as a recombination promoting layer that promotes recombination of a minority carrier.
- the dislocation conversion layer has a thickness of 1 ⁇ m or more. As described above, by forming the dislocation conversion layer thicker than that of the conventional dislocation conversion layer, the conversion rate of dislocations can be improved and the recombination of minority carriers can be promoted.
- the dislocation conversion layer has a conversion rate from basal plane dislocations to through-blade dislocations of more than 95%. Further, in a preferred embodiment of the present invention, the dislocation conversion layer has a conversion rate of 100% from basal plane dislocations to through-blade dislocations.
- a base substrate and an epitaxial growth layer are further provided, the dislocation conversion layer is provided between the base substrate and the epitaxial growth layer, and the doping concentration of the dislocation conversion layer is the epitaxial growth. Higher than the layer doping concentration.
- the present invention also relates to a method for manufacturing a SiC substrate. That is, the present invention that solves the above-mentioned problems is a method for producing a SiC substrate, which comprises a crystal growth step of growing a dislocation conversion layer having a doping concentration of 1 ⁇ 10 15 cm -3 or more under conditions where the terrace width is increased. is there.
- the crystal growth step is a step of growing in a SiC-C equilibrium vapor pressure environment.
- the crystal growth step is a step of growing crystals on a surface on which macrostep bunching is not formed.
- the present invention also relates to a SiC semiconductor device. That is, the present invention that solves the above-mentioned problems is a SiC semiconductor device including a dislocation conversion layer having a doping concentration of 1 ⁇ 10 15 cm -3 or more.
- a dislocation conversion layer having a doping concentration of 1 ⁇ 10 17 cm -3 or more is provided.
- the dislocation conversion layer has a thickness of 1 ⁇ m or more.
- the dislocation conversion layer has a conversion rate from basal plane dislocations to through-blade dislocations of more than 95%. Further, in a preferred embodiment of the present invention, the dislocation conversion layer has a conversion rate of 100% from basal plane dislocations to through-blade dislocations.
- a base substrate and an epitaxial growth layer are further provided, the dislocation conversion layer is provided between the base substrate and the epitaxial growth layer, and the doping concentration of the dislocation conversion layer is the epitaxial growth. Higher than the layer doping concentration.
- the present invention also relates to a method for manufacturing a SiC semiconductor device. That is, the present invention that solves the above-mentioned problems is a method for manufacturing a SiC semiconductor device, which comprises a crystal growth step of growing a dislocation conversion layer having a doping concentration of 1 ⁇ 10 15 cm -3 or more under the condition that the terrace width is increased. Is.
- the crystal growth step is a step of growing in a SiC-C equilibrium vapor pressure environment.
- the crystal growth step is a step of growing crystals on a surface on which macrostep bunching is not formed.
- the disclosed technique it is possible to provide a novel technique for a SiC substrate and a SiC semiconductor having a dislocation conversion layer capable of reducing resistance. Further, according to the disclosed technology, it is possible to provide a novel technology for manufacturing a SiC substrate and a SiC semiconductor having a dislocation conversion layer capable of reducing resistance.
- FIG. It is the analysis result of SIMS of the SiC substrate which concerns on Example 1. It is explanatory drawing which shows the method of obtaining the BPD ⁇ TED conversion rate. It is a graph which shows the relationship between the BPD ⁇ TED conversion rate and the terrace width increase rate. Arrhenius plot during etching and crystal growth. It is an SEM image of the surface of a SiC substrate after etching and crystal growth. It is sectional drawing which shows the structure of the SiC substrate which performed the conventional process which suppresses a stacking defect.
- FIG. 1 is a cross-sectional view showing the configuration of the SiC substrate 10 according to the embodiment.
- the SiC substrate 10 according to the embodiment includes a base substrate 11 which is an n + type substrate, a dislocation conversion layer 12 which is an n + type layer, and an epitaxial growth layer 13 which is an n type layer. ..
- the surface of the SiC substrate 10 on the side where the semiconductor device is formed (specifically, the surface on the side where the epitaxial growth layer 13 is deposited) is referred to as a main surface, and the surface facing the main surface is referred to as a back surface.
- the main surface and the back surface are collectively referred to as the front surface.
- a surface provided with an off angle of several degrees (for example, 0.4 to 8 °) from the (0001) surface or the (000-1) surface can be exemplified.
- "-" means a bar attached to the index immediately after that.
- a step-terrace structure is formed on the surface of single crystal SiC flattened at the atomic level.
- This step-terrace structure is a staircase structure in which step 14 which is a step portion having one or more molecular layers and terrace 15 which is a flat portion where the ⁇ 0001 ⁇ surface is exposed are alternately arranged.
- one molecular layer (0.25 nm) is the minimum height (minimum unit), and various step heights are formed by overlapping a plurality of the single molecular layers.
- a step 14 that is bundled (bunched) to become huge and has a height exceeding one unit cell of each polytype is called a macro step bunching (MSB).
- MSB macro step bunching
- the MSB is step 14 that bunched beyond 4 molecular layers (5 molecular layers or more) in the case of 4H-SiC, and exceeds 6 molecular layers (7 molecular layers or more) in the case of 6H-SiC. ) Bunched step 14.
- the base substrate 11 may be a single crystal SiC processed into a plate shape.
- it is a SiC wafer sliced from a SiC ingot produced by a sublimation method or the like.
- the crystal polymorphism of single crystal SiC any polymorphism can be adopted.
- the base substrate 11 that has undergone mechanical processing has a processing alteration layer 111 in which processing damage has been introduced, and a bulk layer 112 in which such processing damage has not been introduced.
- the processed alteration layer 111 includes, for example, strain 113, scratches 114, and latent scratches 115 (see FIG. 4).
- the presence or absence of the processed alteration layer 111 can be confirmed by SEM-EBSD, TEM, ⁇ XRD, or the like.
- the base substrate 11 is, for example, a nitrogen-doped SiC single crystal substrate.
- the doping concentration of the base substrate 11 is 1 ⁇ 10 17 cm -3 or more, preferably 1 ⁇ 10 18 cm -3 or more, and more preferably 1 ⁇ 10 19 cm -3 or more.
- the dislocation conversion layer 12 is, for example, a nitrogen-doped SiC layer.
- the doping concentration of the dislocation conversion layer 12 is 1 ⁇ 10 15 cm -3 or more, preferably 1 ⁇ 10 16 cm -3 or more, more preferably 1 ⁇ 10 17 cm -3 or more, and even more preferably. It is 1 ⁇ 10 18 cm -3 or more, and more preferably 1 ⁇ 10 19 cm -3 or more.
- the BPD ⁇ TED conversion rate of the dislocation conversion layer 12 is larger than 95.00%, preferably 96.00% or more, more preferably 97.00% or more, and further preferably 98.00% or more. , More preferably 99.00% or more.
- the number of BPDs existing on the main surface of the dislocation conversion layer 12 is 250 or less. Further, when the dislocation conversion layer 12 is grown on the main surface of the base substrate 11 having 10,000 BPDs, the number of BPDs existing on the main surface of the dislocation conversion layer 12 is 500 or less. Further, when the dislocation conversion layer 12 is grown on the main surface of the base substrate 11 having 20000 BPDs, the number of BPDs existing on the main surface of the dislocation conversion layer 12 is 1000 or less.
- the BPD to TED conversion rate of the dislocation conversion layer 12 is larger than 99.95%, preferably 99.96% or more, more preferably 99.97% or more, still more preferably 99.98% or more. It is more preferably 99.99% or more, still more preferably 100%.
- the BPD existing on the base substrate 11 is completely converted to TED when the dislocation conversion layer 12 is formed, and the BPD does not exist on the main surface of the dislocation conversion layer 12.
- the thickness of the dislocation conversion layer 12 is 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, still more preferably 7 ⁇ m or more, still more preferably 10 ⁇ m or more.
- the epitaxial growth layer 13 is, for example, a nitrogen-doped SiC layer.
- the doping concentration of the epitaxial growth layer 13 is lower than the doping concentration of the dislocation conversion layer 12. In other words, the doping concentration of the dislocation conversion layer 12 is larger than the doping concentration of the epitaxial growth layer 13, and the resistance during device operation is small.
- the SiC substrate 10 according to the present invention includes a dislocation conversion layer 12 having a doping concentration of 1 ⁇ 10 15 cm -3 or more. In this way, by setting the dislocation conversion layer 12 that performs the BPD ⁇ TED conversion to a higher doping concentration than the conventional n-type dislocation conversion layer 102, the resistance of the SiC semiconductor device can be reduced.
- the SiC substrate 10 according to the present invention includes a dislocation conversion layer 12 having a doping concentration of 1 ⁇ 10 17 cm -3 or more. That is, by setting the doping concentration higher than that of the epitaxial growth layer 13 formed, the recombination of minority carriers can be promoted. As a result, the dislocation conversion layer 12 can function as a recombination promoting layer in addition to the dislocation conversion. That is, it is desirable that the doping concentration of the dislocation conversion layer 12 is higher than the doping concentration of the epitaxial growth layer 13.
- the dislocation conversion layer 12 of the SiC substrate 10 according to the present invention has a thickness of 1 ⁇ m or more.
- the BPD ⁇ TED conversion rate can be improved.
- the region where the minority carriers recombine is expanded, and the region where the frequency of recombination is high (the main surface side of the dislocation conversion layer 12) and a large number of BPDs are present.
- the distance from the region (the back surface side of the dislocation conversion layer 12) can be increased. Therefore, it is possible to suppress the energy generated by the recombination from being given to the BPD.
- the SiC substrate 10 has a three-layer structure consisting of a base substrate 11 which is an n + type substrate, a dislocation conversion layer 12 which is an n + type layer, and an epitaxial growth layer 13 which is an n type layer. ..
- the conventional SiC substrate 100 has a four-layer structure of an n + type SiC base substrate 101, an n-type dislocation conversion layer 102, an n + type recombination promoting layer 103, and an n-type epitaxial growth layer 104 (). (See FIG. 17).
- the SiC substrate 10 according to the present embodiment the number of growing layers can be reduced and the number of steps can be reduced as compared with the conventional SiC substrate 100. As a result, growth conditions can be simplified and costs can be reduced.
- FIG. 2 is a cross-sectional view showing the configuration of the SiC substrate 10 according to another embodiment.
- the SiC substrate 10 according to another embodiment is an epiready substrate including a base substrate 11 which is an n + type layer and a dislocation conversion layer 12 which is an n + type layer. In this way, the SiC substrate 10 before forming the epitaxial growth layer 13 may be manufactured.
- the dislocation conversion layer 12 is an n + type layer having a higher doping concentration than the n-type dislocation conversion layer 102 of the SiC substrate 100 that has been subjected to the conventional treatment for suppressing stacking defects.
- FIG. 3 is an explanatory diagram showing a manufacturing process of the SiC substrate according to the embodiment.
- the method for manufacturing a SiC substrate according to the present embodiment is that the processing alteration layer removing step S1 for removing the processing alteration layer 111 of the base substrate 11 and the condition that the terrace width W is increased have a doping concentration of 1 ⁇ 10 15 cm ⁇ .
- the crystal growth step S2 for growing three or more dislocation conversion layers 12 and the epitaxial growth step S3 for growing the epitaxial growth layer 13 are included.
- a bunching decomposition step S4 for removing the MSB formed on the main surface of the base substrate 11 may be included.
- a bunching decomposition step S4 for removing the MSB formed on the main surface of the dislocation conversion layer 12 may be included.
- the epitaxial growth step S3 a bunching decomposition step S4 for removing the MSB formed on the main surface of the epitaxial growth layer 13 may be included.
- the bunching disassembly step S4 can employ a common method regardless of the order in which the bunching disassembly step S4 is performed. Therefore, the bunching decomposition step S4 will be described after the processing alteration layer removing step S1, the crystal growth step S2, and the epitaxial growth step S3.
- FIG. 4 is an explanatory diagram showing the processing alteration layer removing step S1 according to the present invention.
- the processing alteration layer removing step S1 is a step of removing the processing alteration layer 111 introduced into the n + type base substrate 11.
- the processing alteration layer removing step S1 can be adopted as long as the processing alteration layer 111 can be removed.
- Si vapor pressure etching (Si-Vapor Etching: SiVE) method in which single crystal SiC is etched by heating under Si steam pressure, the hydrogen etching method using hydrogen gas as an etching gas, and chemical mechanical polishing: CMP) and the like can be exemplified.
- Si-Vapor Etching: SiVE Si-Vapor Etching: SiVE
- hydrogen etching method using hydrogen gas as an etching gas and chemical mechanical polishing: CMP
- FIG. 5 is an explanatory diagram showing the processing alteration layer removing step S1 according to the embodiment.
- the processing alteration layer removing step S1 according to the present embodiment is a step of accommodating the SiC substrate 10 in a semi-closed space including a Si element supply source and a C element supply source, and etching by heating.
- the "quasi-closed space" in the present specification means a space in which vacuuming and dopant gas can be supplied in the container, but at least a part of the vapor generated in the container can be confined.
- This semi-closed space can be formed in the main body container 30 or the melting point container 50, which will be described later.
- the SiC substrate 10 faces the SiC material body 20 in the main body container 30 in which the SiC material body 20 (Si element supply source and C element supply source) is exposed. Is a step of arranging and heating (see FIG. 5 (a)).
- an etching space X is formed between them.
- atoms are transported by using the temperature gradient formed by the heating furnace 40 as a driving force, and as a result, the SiC substrate 10 can be etched.
- heat treatment under a SiC-Si equilibrium vapor pressure environment and heat treatment under a SiC-C equilibrium vapor pressure environment can be selected. Can be done.
- SiC-Si vapor pressure environment in the present specification refers to the vapor pressure environment when SiC (solid) and Si (liquid phase) are in a phase equilibrium state via a gas phase.
- the SiC-Si equilibrium vapor pressure environment is formed by heat-treating a semi-closed space having an atomic number ratio of Si / C of more than 1.
- the main body container 30 made of SiC that satisfies the stoichiometric ratio 1: 1, the SiC substrate 10 that satisfies the stoichiometric ratio 1: 1 and the SiC material body 20 that satisfies the stoichiometric ratio 1: 1 And the Si steam supply source 35 (Si pellets or the like) are arranged, the atomic number ratio Si / C in the main body container 30 exceeds 1.
- SiC-C equilibrium vapor pressure environment in the present specification refers to the vapor pressure environment when SiC (solid phase) and C (solid phase) are in a phase equilibrium state via a gas phase. Point to.
- the SiC-C equilibrium vapor pressure environment is formed by heat-treating a semi-closed space having an atomic number ratio of Si / C of 1 or less.
- the main body container 30 made of SiC that satisfies the stoichiometric ratio 1: 1, the SiC substrate 10 that satisfies the stoichiometric ratio 1: 1 and the SiC material body 20 that satisfies the stoichiometric ratio 1: 1
- the atomic number ratio Si / C in the main body container 30 becomes 1 (see FIG. 5 (a)).
- a C steam supply source C pellet or the like
- processing alteration layer removing step S1 is a step of arranging and heating the main body container 30 described above in the high melting point container 50 in which the Si steam supply source 54 is exposed (see FIG. 5A).
- the gas phase species containing the Si element is exhausted from the main body container 30. Can be suppressed. That is, the environment inside the main body container 30 is maintained by balancing the vapor pressure of the vapor phase species containing the Si element inside the main body container 30 and the vapor pressure of the gas phase species containing the Si element outside the main body container 30. can do.
- the SiC material body 20 is composed of SiC that can receive or transfer Si element and C element to and from the SiC substrate 10 by heating the SiC material body 20 relative to the SiC substrate 10.
- a SiC container (main body container 30) or a SiC substrate (SiC material substrate) can be adopted.
- the crystal polymorph of the SiC material body 20 any polymorphic type can be adopted, and polycrystalline SiC may be adopted.
- a sintered body obtained by sintering the Si element supply source and the C element supply source may be adopted.
- the temperature gradient and the chemical potential difference between the SiC substrate 10 and the SiC material body 20 can be adopted.
- the SiC substrate 10 and the SiC material body 20 are arranged so as to face each other, and the SiC substrate 10 is on the high temperature side and the SiC material body 20 is on the low temperature side at 1400 ° C. or higher and 2300. Heat in the temperature range below ° C. As a result, it is considered that the reactions 1) to 5) below are continuously carried out, and as a result, the etching of the SiC substrate 10 proceeds. (See FIG. 5 (b)).
- the processing alteration layer removing step S1 includes a Si atom sublimation step of thermally sublimating Si atoms from the surface of the SiC substrate 10 and a quasi-closed space with the C atoms remaining on the surface of the SiC substrate 10. It includes a C atom sublimation step of sublimating from the surface of the SiC substrate 10 by reacting the Si vapor inside.
- the etching temperature according to this embodiment is preferably set in the range of 1400 to 2300 ° C.
- the etching rate according to this embodiment can be controlled by the temperature range described above, and can be selected in the range of 0.001 to 2 ⁇ m / min.
- the etching time required for this embodiment can be set to an arbitrary time so as to obtain a desired etching amount. For example, when the etching rate is 1 ⁇ m / min and the etching amount is desired to be 1 ⁇ m, the etching time is 1 minute.
- the temperature gradient according to this embodiment is set in the range of, for example, 0.1 to 5 ° C./mm. It is also possible to introduce an inert gas during etching.
- the inert gas can be selected from Ar, He, N 2, etc., and by introducing the inert gas in the range of 10-5 to 10000 Pa, the degree of vacuum of the heating furnace 40 (main heating chamber 41) is high. Can be adjusted.
- a bunching decomposition step S4 for removing the MSB formed on the surface of the base substrate 11 may be included. Further, in the processing alteration layer removing step S1, when etching is performed in a SiC-Si vapor pressure environment in which MSB is not formed on the main surface of the SiC substrate 10, the bunching decomposition step S4 may not be included. In other words, the processing alteration layer removing step S1 and the bunching decomposition step S4 may be performed at the same time.
- FIG. 6 is an explanatory diagram showing the crystal growth step S2 according to the present invention.
- the crystal growth step S2 is a step of growing the n + type dislocation conversion layer 12 on the n + type base substrate 11 under the condition that the terrace width W is increased.
- the dislocation conversion layer 12 By growing the dislocation conversion layer 12 under the condition that the terrace width W increases in this way, it is possible to achieve both a high BPD ⁇ TED conversion rate and a high doping concentration.
- the conditions under which the terrace width W increases can be exemplified under a SiC—C equilibrium vapor pressure environment or a C-rich environment.
- the crystal growth step S2 can be adopted as long as the method allows crystal growth of the SiC substrate 10 in a SiC-C equilibrium vapor pressure environment or a C-rich environment.
- a sublimation method, a chemical vapor deposition method (CVD), and the like can be exemplified.
- CVD chemical vapor deposition method
- FIG. 7 is an explanatory diagram showing the crystal growth step S2 according to the embodiment.
- the crystal growth step S2 according to the present embodiment is a step of accommodating the SiC substrate 10 in a semi-closed space including a Si element supply source and a C element supply source and heating the SiC substrate 10 to grow crystals (FIG. 7 (a)). )reference).
- the SiC material body 20 is placed in the main body container 30 in which the SiC material body 20 (Si element supply source and C element supply source) is exposed. This is a step of arranging and heating the SiC substrate 10 so as to face the above (see FIG. 7B).
- the above-mentioned processing alteration layer removing step S1 was a step of transporting the Si element and the C element from the SiC substrate 10 to the SiC material body 20 to etch the SiC substrate 10.
- the crystal growth step S2 is a step of transporting the Si element and the C element from the SiC material body 20 to the SiC substrate 10 to grow the SiC substrate 10 as a crystal.
- a crystal growth space Y is formed between them.
- atoms are transported by using the temperature gradient formed by the heating furnace 40 as a driving force, and as a result, crystals can be grown on the SiC substrate 10.
- the crystal growth step S2 is a step of growing the dislocation conversion layer 12 in a SiC-C equilibrium vapor pressure environment. Therefore, the semi-closed space having an atomic number ratio of Si / C of 1 or less is formed by heat treatment. That is, in the crystal growth step S2, the SiC substrate 10 and the SiC material body 20 are arranged so as to face each other in a semi-closed space in which the atomic number ratio Si / C exceeds 1, and between the SiC substrate 10 and the SiC material body 20. This is a step of heating so that a temperature gradient is formed.
- the main body container 30 is placed and heated in the high melting point container 50 in which the Si steam supply source 54 is exposed, thereby heating the main body container. Maintain the environment within 30.
- the SiC substrate 10 and the SiC material body 20 are arranged so as to face each other, and the SiC substrate 10 is on the low temperature side and the SiC material body 20 is on the high temperature side at 1400 ° C. or higher and 2300 ° C. or lower. Heat in the temperature range of. As a result, it is considered that the reactions 1) to 5) below are continuously carried out, and as a result, the crystal growth of the SiC substrate 10 proceeds. (See FIG. 7 (b)).
- the dopant of the SiC material body 20 is transported together with the raw materials (Si element and C element), the doping concentration of the SiC material body 20 is attracted and the dislocation conversion layer 12 grows. Therefore, the dopant and the doping concentration of the dislocation conversion layer 12 can be controlled by selecting the type of the dopant and the doping concentration of the SiC material body 20.
- the doping concentration of nitrogen when the doping concentration of nitrogen is desired to obtain a least 1 ⁇ 10 15 cm -3 of dislocation conversion layer 12, the doping concentration of nitrogen may be used least 1 ⁇ 10 15 cm -3 of SiC material 20. Further, when the doping concentration of nitrogen is desired to obtain 1 ⁇ 10 17 cm -3 or more dislocation conversion layer 12, the doping concentration of nitrogen may be used 1 ⁇ 10 17 cm -3 or more SiC material body 20.
- the doping concentration of the SiC material body 20 is 1 ⁇ 10 15 cm -3 or more, preferably 1 ⁇ 10 16 cm -3 or more, more preferably 1 ⁇ 10 17 cm -3 or more, and further. It is preferably 1 ⁇ 10 18 cm -3 or more, and more preferably 1 ⁇ 10 19 cm -3 or more. It is also possible to dope by supplying a dopant gas during the heat treatment.
- the growth temperature according to this embodiment is preferably set in the range of 1400 to 2300 ° C.
- the growth rate according to this embodiment can be controlled by the temperature range described above, and can be selected in the range of 0.001 to 2 ⁇ m / min.
- the growth time required for this embodiment can be set to an arbitrary time so as to achieve a desired growth amount. For example, when the growth rate is 1 ⁇ m / min and the growth amount is desired to be 1 ⁇ m, the growth amount is 1 minute.
- the temperature gradient according to this embodiment is set in the range of 0.1 to 5 ° C./mm.
- a dopant gas N 2, etc.
- the crystal growth step S2 it is preferable to grow the crystal on the surface on which the MSB is not formed. Therefore, in the processing alteration layer removing step S1, it is desirable to perform etching in a SiC-Si vapor pressure environment in which MSB is not formed on the main surface of the SiC substrate 10. Further, in the processing alteration layer removing step S1, when etching is performed under the condition that the main surface of the SiC substrate 10 is formed with MSB, it is desirable to perform the bunching decomposition step S4 described later before the crystal growth step S2. ..
- a bunching decomposition step S4 for removing the MSB formed on the surface of the dislocation conversion layer 12 may be included.
- FIG. 8 is an explanatory diagram showing the epitaxial growth step S3 according to the present invention.
- the epitaxial growth step S3 is a step of growing an n-type epitaxial growth layer 13 on the dislocation conversion layer 12.
- the epitaxial growth step S3 can be adopted as long as the epitaxial growth layer 13 can be grown. Examples thereof include a chemical vapor deposition (CVD), a physical vapor deposition (PVT), a metastable solvent epitaxy (MSE), and the like. Hereinafter, preferred embodiments of this step will be described in detail.
- CVD chemical vapor deposition
- PVD physical vapor deposition
- MSE metastable solvent epitaxy
- the epitaxial growth step S3 is a step of accommodating the SiC substrate 10 in a semi-closed space including the Si element supply source and the C element supply source and heating the SiC substrate 10 to grow the crystal. Is.
- the SiC substrate 10 and the SiC material body 20 are arranged so as to face each other, and the temperature is 1400 ° C. or higher and 2300 ° C. or lower so that the SiC substrate 10 is on the low temperature side and the SiC material body 20 is on the high temperature side. Heat in the temperature range (see FIG. 7).
- This epitaxial growth step S3 is a step of crystal growth of the epitaxial growth layer 13 which is an n-type layer and has a doping concentration lower than that of the dislocation conversion layer 12 which is an n + type layer.
- the doping concentration of the SiC material body 20 used in the epitaxial growth step S3 is 1 ⁇ 10 17 cm -3 or less, preferably 1 ⁇ 10 16 cm -3 or less, and more preferably 1 ⁇ 10 15 cm -3. It is as follows.
- the growth temperature according to this embodiment is preferably set in the range of 1400 to 2300 ° C.
- the growth rate according to this embodiment can be controlled by the temperature range described above, and can be selected in the range of 0.001 to 2 ⁇ m / min.
- the growth time required for this embodiment can be set to an arbitrary time so as to achieve a desired growth amount. For example, when the growth rate is 1 ⁇ m / min and the growth amount is desired to be 1 ⁇ m, the growth amount is 1 minute.
- the temperature gradient according to this embodiment is set in the range of 0.1 to 5 ° C./mm.
- the epitaxial growth step S3 is a step of growing crystals on the surface on which the MSB is not formed. Therefore, it is desirable to perform a bunching decomposition step S4, which will be described later, before the epitaxial growth step S3.
- the epitaxial growth step S3 may include a bunching decomposition step S4 for removing the MSB formed on the surface of the epitaxial growth layer 13.
- the bunching decomposition step S4 can be adopted as long as the MSB formed on the surface of the SiC substrate 10 can be decomposed.
- a Si vapor pressure etching (Si-Vapor Etching: SiVE) method in which single crystal SiC is etched by heating under Si vapor pressure can be exemplified.
- Si-Vapor Etching: SiVE Si-Vapor Etching
- FIG. 9 is an explanatory diagram showing the bunching disassembly step S4 according to the embodiment.
- the bunching decomposition step S4 according to the present embodiment is a step of accommodating the SiC substrate 10 in a semi-closed space including a Si element supply source and a C element supply source, and etching or crystal growth in a SiC-Si equilibrium vapor pressure environment. Is.
- the bunching decomposition step S4 is carried out in the main body container 30 in which the SiC material body 20 (Si element supply source and C element supply source) is exposed, similarly to the processing alteration layer removing step S1 and the crystal growth step S2. , A step of arranging the SiC substrate 10 and the Si steam supply source 35 so as to face the SiC material body 20 and heating them (see FIG. 9).
- the main body container 30 is heated by arranging the above-mentioned main body container 30 in the high melting point container 50 in which the Si steam supply source 54 is exposed. Maintain the environment inside.
- FIG. 9A shows a form in which the MSB formed on the surface of the SiC substrate 10 is decomposed by etching in a SiC-Si equilibrium vapor pressure environment. That is, the SiC substrate 10 and the SiC material body 20 are arranged so as to face each other in a semi-closed space having an atomic number ratio of Si / C exceeding 1, so that the SiC substrate 10 is on the high temperature side and the SiC material body 20 is on the low temperature side. It is a form of heating.
- FIG. 9B shows a form in which the MSB formed on the surface of the SiC substrate 10 is decomposed by crystal growth in a SiC-Si equilibrium vapor pressure environment. That is, the SiC substrate 10 and the SiC material body 20 are arranged so as to face each other in a semi-closed space having an atomic number ratio of more than 1, so that the SiC substrate 10 is on the low temperature side and the SiC material body 20 is on the high temperature side. It is a form of heating.
- the MSB formed on the surface of the SiC substrate 10 can be decomposed by heat-treating the SiC substrate 10 in a SiC-Si equilibrium vapor pressure environment.
- the etching conditions and the growth conditions the conditions described in the processing alteration layer removing step S1 or the crystal growth step S2 can be adopted.
- a temperature gradient is formed between the main body container 30 capable of accommodating the SiC substrate 10 and the SiC substrate 10 and the SiC material body 20.
- a heating furnace 40 capable of heating is provided.
- the main body container 30 is a fitting container including an upper container 31 and a lower container 32 that can be fitted to each other.
- a minute gap 33 is formed in the fitting portion between the upper container 31 and the lower container 32, and the inside of the main body container 30 can be exhausted (evacuated) from the gap 33.
- the upper container 31 and the lower container 32 according to the present embodiment are made of polycrystalline SiC. Therefore, the main body container 30 itself may be the SiC material body 20. Further, only the portion of the main body container 30 facing the SiC substrate 10 may be composed of the SiC material body 20. In that case, a high melting point material (a material similar to the high melting point container 50 described later) can be used for the portion other than the SiC material body 20.
- a configuration may be adopted in which the substrate-shaped SiC material body 20 is separately housed.
- a spacer (a substrate holder 34 or the like) may be arranged between the substrate-shaped SiC material body 20 and the SiC substrate 10 to form an etching space X or a crystal growth space Y. It is desirable that the substrate holder 34 is made of the same high melting point material as the high melting point container 50.
- the main body container 30 is configured to generate an atmosphere containing Si element and C element in the internal space when heated while accommodating the SiC substrate 10.
- the SiC material body 20 composed of polycrystalline SiC is heated to form an atmosphere containing Si element and C element in the internal space.
- the space in the heated main body container 30 becomes a vapor pressure environment of a mixed system of a gas phase species containing a Si element and a gas phase species containing a C element.
- the vapor phase species containing the Si element include Si, Si 2 , Si 3 , Si 2 C, SiC 2 , and SiC.
- the gas phase species containing the C element include Si 2 C, SiC 2 , SiC and C. That is, it is preferable that the SiC gas is present in the semi-closed space.
- the etching space X or the crystal growth space Y is a space for transporting raw materials from the SiC substrate 10 to the SiC material body 20 by using a temperature gradient provided between the SiC substrate 10 and the SiC material body 20 as a driving force. This is a space for transporting raw materials from the SiC material body 20 to the SiC substrate 10.
- the temperature on the SiC substrate 10 side is high and the temperature of the SiC material body 20 is low.
- the SiC substrate 10 is arranged (see FIG. 9A).
- the SiC substrate 10 and the SiC material body 20 are arranged so as to face each other and heated so that the SiC substrate 10 is on the high temperature side and the SiC material body 20 is on the low temperature side, the SiC substrate 10 to the SiC material body are heated.
- the raw material is transported to 20 and the SiC substrate 10 is etched. That is, an etching space X is formed between the SiC material body 20 and the SiC substrate 10.
- the temperature of the surface of the SiC substrate 10 and the temperature of the SiC material body 20 facing the surface are compared, the temperature of the SiC substrate 10 side is low and the temperature of the SiC material body 20 is high.
- the substrate 10 is arranged (see FIG. 9B).
- the SiC substrate 10 and the SiC material body 20 are arranged so as to face each other and heated so that the SiC substrate 10 is on the low temperature side and the SiC material body 20 is on the high temperature side, the SiC material body 20 to the SiC substrate are heated.
- the raw material is transported to No. 10, and single crystal SiC grows on the SiC substrate 10. That is, a crystal growth space Y is formed between the SiC material body 20 and the SiC substrate 10.
- the heating furnace 40 includes a main heating chamber 41 capable of heating an object to be processed (SiC substrate 10 or the like) to a temperature of 1000 ° C. or higher and 2300 ° C. or lower, and an object to be processed at 500 ° C. or higher.
- a preheating chamber 42 capable of preheating to the same temperature
- a refractory container 50 capable of accommodating the main body container 30, and a moving means 43 (moving) capable of moving the refractory container 50 from the preheating chamber 42 to the main heating chamber 41. It is equipped with a stand).
- the heating chamber 41 is formed in a regular hexagonal shape in a plan sectional view, and the melting point container 50 is arranged inside the heating chamber 41.
- a heating heater 44 (mesh heater) is provided inside the heating chamber 41.
- a multilayer heat-reflecting metal plate is fixed to the side wall and ceiling of the main heating chamber 41 (not shown). The multilayer heat-reflecting metal plate is configured to reflect the heat of the heating heater 44 toward the substantially central portion of the main heating chamber 41.
- the heating heater 44 is arranged so as to surround the melting point container 50 in which the object to be processed is housed, and further, the multilayer heat-reflecting metal plate is arranged outside the heating heater 44, whereby the temperature is 1000 ° C.
- the temperature can be raised to 2300 ° C. or lower.
- a resistance heating type heater or a high frequency induction heating type heater can be used as the heating heater 44.
- the heating heater 44 may adopt a configuration capable of forming a temperature gradient in the melting point container 50.
- the heating heater 44 may be configured so that many heaters are arranged on the upper side. Further, the heating heater 44 may be configured so that the width increases toward the upper side. Alternatively, the heating heater 44 may be configured so that the electric power supplied can be increased toward the upper side.
- a vacuum forming valve 45 for exhausting the inside of the main heating chamber 41, an inert gas injection valve 46 for introducing an inert gas into the main heating chamber 41, and the main heating chamber 41.
- a vacuum gauge 47 for measuring the degree of vacuum inside is connected.
- the vacuum forming valve 45 is connected to a vacuum drawing pump that exhausts the inside of the main heating chamber 41 to create a vacuum (not shown). With the vacuum forming valve 45 and the vacuum pulling pump, the degree of vacuum in the main heating chamber 41 can be adjusted to , for example, 10 Pa or less, more preferably 1 Pa or less, still more preferably 10 -3 Pa or less. As this evacuation pump, a turbo molecular pump can be exemplified.
- the Inert gas injection valve 46 is connected to the Inactive gas supply source (not shown). With the inert gas injection valve 46 and the inert gas supply source, the inert gas can be introduced into the heating chamber 41 in the range of 10-5 to 10000 Pa. As the inert gas, Ar, He, N 2, or the like can be selected.
- the inert gas injection valve 46 is a dopant gas supply means capable of supplying the dopant gas into the main body container 30. That is, the doping concentration of the growth layer can be adjusted by selecting a dopant gas (for example, N 2 or the like) as the inert gas.
- a dopant gas for example, N 2 or the like
- the preheating chamber 42 is connected to the main heating chamber 41, and the high melting point container 50 can be moved by the moving means 43.
- the preheating chamber 42 of the present embodiment is configured so that the temperature can be raised by the residual heat of the heating heater 44 of the main heating chamber 41. For example, when the temperature of the main heating chamber 41 is raised to 2000 ° C., the temperature of the preheating chamber 42 is raised to about 1000 ° C., and the object to be treated (SiC substrate 10, main body container 30, high melting point container 50, etc.) is removed. Gas treatment can be performed.
- the moving means 43 is configured so that the high melting point container 50 is placed on the moving means 43 so that the main heating chamber 41 and the preheating chamber 42 can be moved. Since the transfer between the main heating chamber 41 and the preheating chamber 42 by the moving means 43 is completed in about 1 minute at the shortest, the temperature can be raised or lowered at 1 to 1000 ° C./min. Since the rapid temperature rise and the rapid temperature decrease can be performed in this way, it is possible to observe a surface shape having no history of low temperature growth during temperature rise and temperature reduction, which was difficult with conventional devices. Further, in FIG. 10, the preheating chamber 42 is arranged below the main heating chamber 41, but the present invention is not limited to this, and the preheating chamber 42 may be arranged in any direction.
- the moving means 43 is a moving table on which the melting point container 50 is placed. A small amount of heat is released from the contact portion between the moving table and the melting point container 50. Thereby, a temperature gradient can be formed in the high melting point container 50 (and in the main body container 30). That is, in the heating furnace 40 of the present embodiment, since the bottom of the melting point container 50 is in contact with the moving table, the temperature gradient is such that the temperature decreases from the upper container 51 to the lower container 52 of the melting point container 50. Is provided. It is desirable that this temperature gradient is formed along the front and back directions of the SiC substrate 10. Further, as described above, a temperature gradient may be formed by the configuration of the heater 44. Further, the heating heater 44 may be configured so that the temperature gradient can be reversed.
- the heating furnace 40 forms an atmosphere containing a Si element, and the main body container 30 can be heated in this atmosphere.
- the atmosphere containing the Si element in the heating furnace 40 according to the present embodiment is formed by using the high melting point container 50 and the Si steam supply source 54. As long as the method can form an atmosphere containing Si element around the main body container 30, it can be naturally adopted.
- the high melting point container 50 is configured to contain a high melting point material.
- a general purpose heat-resistant member C, W is a refractory metal, Re, Os, Ta, Mo , Ta 9 C 8 is a carbide, HfC, TaC, NbC, ZrC , Ta 2 C, TiC, WC, MoC, a nitride HfN, TaN, BN, Ta 2 N, ZrN, TiN, HfB 2, TaB 2, ZrB 2, NB 2, TiB 2 is a boride, it can be exemplified polycrystalline SiC.
- the high melting point container 50 is a fitting container including an upper container 51 and a lower container 52 that can be fitted to each other, and is configured to be able to accommodate the main body container 30.
- a minute gap 53 is formed in the fitting portion between the upper container 51 and the lower container 52, and the inside of the high melting point container 50 can be exhausted (evacuated) from the gap 53.
- the high melting point container 50 preferably has a Si steam supply source 55 capable of supplying the vapor pressure of a vapor phase species containing a Si element in the high melting point container 50.
- the Si vapor supply source 55 may have a configuration in which Si vapor is generated in the melting point container 50 at the time of heating, and examples thereof include solid Si (Si pellets such as single crystal Si pieces and Si powder) and Si compounds. be able to.
- the SiC substrate manufacturing apparatus employs TaC as the material of the melting point container 50 and tantalum Silicide as the Si vapor supply source 55. That is, as shown in FIGS. 5, 7, and 9, a tantalum Silicide layer is formed inside the melting point container 50, and Si vapor is supplied from the tantalum Silicide layer to the inside of the container during heating, whereby Si It is configured to form a vapor pressure environment. In addition to this, any configuration can be adopted as long as the vapor pressure of the vapor phase species containing the Si element is formed in the melting point container 50 during heating.
- SiC semiconductor device and manufacturing method of SiC semiconductor device A case where a pin diode is manufactured from the SiC substrate 10 according to the embodiment will be described as an example.
- the SiC substrate 10 according to the embodiment is n-type and an n-channel type pin diode is manufactured.
- the base substrate 11 becomes a cathode region
- the dislocation conversion layer 12 functions as a buffer layer
- the epitaxial growth layer 13 functions as an intrinsic semiconductor layer (i layer).
- a p + type anode region is formed by injecting a p-type impurity, for example, aluminum (Al), into the surface layer on the main surface side of the epitaxial growth layer 13 by an ion implantation method.
- a p-type impurity for example, aluminum (Al)
- Al aluminum
- an anode electrode is formed on the upper surface of the anode region by forming a film of nickel (Ni) or the like and heat-treating it, and a cathode electrode is formed on the upper surface of the cathode region.
- the SiC substrate of the present invention includes a piper element, an IGBT (Insulated Gate Bipolar Transistor) element, and a MOS (Metal Oxized Semiconductor). ) It can also be applied to parasitic diodes with structures.
- IGBT Insulated Gate Bipolar Transistor
- MOS Metal Oxized Semiconductor
- dislocation conversion layer 12 of the n + type layer and the epitaxial growth layer 13 of the n type layer are laminated on the main surface of the n + type SiC substrate 10
- the main surface of the p + type SiC substrate is shown.
- the dislocation conversion layer 12 of the p + type layer and the epitaxial growth layer 13 of the p type layer may be laminated on the surface.
- the SiC substrate 10 after removing the work-altered layer 111 was housed in the main body container 30 and the melting point container 50 (see FIG. 11), and heat-treated under the following heat treatment conditions.
- the main body container 30 is formed of polycrystalline SiC so that the main body container 30 itself functions as a SiC material body 20 (Si element supply source and C element supply source). ..
- the presence / absence and depth of the processed alteration layer 111 were confirmed by the SEM-EBSD method.
- the presence / absence and depth of the processed alteration layer 111 can also be confirmed by TEM, ⁇ XRD, or Raman spectroscopy.
- the presence or absence of MSB was confirmed by the method for evaluating SEM image contrast described in AFM and Japanese Patent Application Laid-Open No. 2015-179882.
- the dislocation conversion layer 12 was grown on the SiC substrate 10 by heating under the heat treatment conditions described above (crystal growth step S2).
- the dislocation conversion layer 12 was grown by 0.5 ⁇ m, but it is possible to grow it by 1 ⁇ m or more by lengthening the heating time.
- FIG. 12 is an analysis result of SIMS of the SiC substrate according to the first embodiment. As shown in FIG. 12, the doping concentration of the dislocation conversion layer 12 according to Example 1 was 3 ⁇ 10 17 cm -3 , and the doping concentration of the base substrate 11 was 6 ⁇ 10 18 cm -3 .
- the dislocation conversion layer 12 grown in the crystal growth step S2 according to Example 1 is as follows.
- FIG. 13 is an explanatory diagram of a method for obtaining a conversion rate obtained by converting BPD into other defects / dislocations (TED or the like) during the crystal growth step S2.
- FIG. 13A shows the base substrate 11 having the processed alteration layer 111. At this stage, BPDs are present from the bulk layer 112 to the processed alteration layer 111.
- FIG. 13B shows the base substrate 11 from which the processed alteration layer 111 has been removed by the processing alteration layer removing step S1. At this stage, the BPD is present on the base substrate 11 (bulk layer 112).
- FIG. 13C shows the SiC substrate 10 in which the dislocation conversion layer 12 is grown by the crystal growth step S2.
- FIG. 13D shows a state in which defects in the dislocation conversion layer 12 were confirmed on the SiC substrate 10 after the crystal growth step S2 by using the KOH dissolution etching method.
- KOH dissolution etching method a SiC substrate is immersed in a molten salt (KOH, etc.) heated to about 500 ° C. to form etch pits in dislocations and defective parts, and the type of dislocation is determined by the size and shape of the etch pits. It is a method to do.
- FIG. 13E shows how the dislocation conversion layer 12 is removed after the KOH dissolution etching method.
- the dislocation conversion layer 12 is removed by the SiVE method or the like to expose the base substrate 11 (bulk layer 112).
- FIG. 13 (f) shows a state in which defects in the base substrate 11 are confirmed by using the KOH dissolution etching method on the base substrate 11 from which the dislocation conversion layer 12 has been removed.
- the number of BPDs propagating in the dislocation conversion layer 12 in FIG. 13 (d) is compared with the number of BPDs present on the surface of the base substrate 11 in FIG. 13 (f) according to the sequence shown in FIG. By doing so, the BPD ⁇ TED conversion rate converted from BPD to other defects / dislocations can be obtained during the crystal growth step S2.
- the dislocation conversion layer 12 is grown on the surface on which the MSB is not formed in a SiC-C equilibrium vapor pressure environment, so that the doping concentration is 1 ⁇ 10 17 cm -3 or more.
- a SiC substrate including the dislocation conversion layer 12 having a high BPD ⁇ TED conversion rate can be manufactured.
- a dislocation conversion layer 12 having a doping concentration of 1 ⁇ 10 17 cm -3 or more was used using a SiC material body 20 having a doping concentration of 5 ⁇ 10 17 cm -3 to 5 ⁇ 10 18 cm -3.
- Example 2 and Example 3 Next, the heat treatment conditions for improving the BPD ⁇ TED conversion rate will be described in detail with reference to Example 2, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3.
- the SiC semiconductor substrates of Example 2, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3 were manufactured under the conditions shown in Table 1.
- the depth of the processed alteration layer 111 of the SiC substrate 10 used in these Examples and Comparative Examples was confirmed by SEM-EBSD to be about 5 ⁇ m.
- the size of the melting point container 50 used is 160 mm in diameter ⁇ 60 mm in height, and the size of the main body container 30 is 60 mm in diameter ⁇ 4 mm in height.
- Example 2 the processed alteration layer 111 was removed using the Si vapor pressure etching method under the condition that MSB was not formed (processed alteration layer removal step S1), and the process was grown in a SiC-C equilibrium vapor pressure environment using the sublimation method. (Crystal growth step S2).
- the BPD ⁇ TED conversion rate of the dislocation conversion layer 12 was 100%.
- the terrace width W1 before the crystal growth step S2 was 14 nm
- MSB is formed by introducing 10000 Pa of Ar gas, whereas in the processed altered layer removing step S1 of Comparative Example 2, TaSi 2 is formed on the tantalum ⁇ layer.
- the MSB is formed by adopting.
- the processed altered layer 111 was removed under the condition that MSB was not formed (processed altered layer removing step S1) as in Example 2, and the mixture was grown in a SiC-Si equilibrium vapor pressure environment using a sublimation method. (Crystal growth step S2).
- the SiC-Si equilibrium vapor pressure environment is formed by arranging a Si substrate in the main body container 30.
- the BPD ⁇ TED conversion rate of the dislocation conversion layer 12 was 93.24%.
- the present inventors diligently examined and experimented whether there was a rule in the BPD ⁇ TED conversion rate, and as shown in FIG. 14, the BPD ⁇ TED conversion rate increased or decreased the terrace width W before and after the epitaxial growth. It was found that it is greatly related to the rate (terrace width increase rate).
- FIG. 14 is a graph in which the terrace width increase rate ((terrace width W2-before growth W2-terrace width W1 after growth) / terrace width W1 after growth) is plotted on the horizontal axis and the BPD ⁇ TED conversion rate is plotted on the vertical axis. is there.
- the plot shown in FIG. 14 shows the growth temperature of 1700 ° C., 1800 ° C., or 1900 ° C. for a plurality of SiC substrates 10 having different terrace widths W1 from which the processed alteration layer 111 has been removed, and SiC-.
- the results of a plurality of experiments in which 3 ⁇ m was grown under a Si equilibrium vapor pressure environment or a SiC-C equilibrium vapor pressure environment are shown.
- step S2 the BPD ⁇ TED conversion rate in the dislocation conversion layer 12 can be improved.
- the dislocation conversion layer 12 is grown on the SiC substrate 10 on which the MSB is not formed, thereby causing the BPD in the dislocation conversion layer 12 to grow.
- the TED conversion rate can be set to approximately 100%.
- FIG. 15A is a graph showing the relationship between the heating temperature and the etching rate in the etching process of the present invention.
- the horizontal axis of this graph is the reciprocal of temperature, and the vertical axis of this graph shows the etching rate logarithmically.
- FIG. 15B is a graph showing the relationship between the heating temperature and the growth rate in the crystal growth step of the present invention.
- the horizontal axis of this graph is the reciprocal of temperature, and the vertical axis of this graph is the logarithmic growth rate.
- the result of heat-treating the SiC substrate 10 by arranging the SiC substrate 10 in a space where the atomic number ratio Si / C exceeds 1 (inside the main body container 30) is indicated by ⁇ . Further, the result of heat-treating the SiC substrate 10 by arranging the SiC substrate 10 in a space (inside the main body container 30) in which the atomic number ratio Si / C is 1 or less is indicated by a cross.
- MSB was formed on the surface of the SiC substrate 10 marked with a circle, and the height of step 14 was the height of one unit cell.
- MSBs were formed on the surfaces of the SiC substrates 10 marked with x.
- thermodynamic calculation in the SiC-Si equilibrium vapor pressure environment is shown by a broken line (Arenius plot), and the result of the thermodynamic calculation in the SiC-C equilibrium vapor pressure environment is shown by a two-dot chain line (Arenius plot). It is shown in.
- Renius plot the result of the thermodynamic calculation in the SiC-C equilibrium vapor pressure environment is shown by a two-dot chain line (Arenius plot).
- thermodynamic calculation of the etching process the amount of vapor (gas phase species containing Si element and vapor phase species containing C element) generated from the SiC substrate 10 when the main body container 30 is heated can be converted into the etching amount.
- the etching rate of the SiC substrate 10 is obtained by the following equation 1.
- T is the temperature of the SiC substrate 10
- k is Boltzmann's constant.
- P i is that value obtained by adding the vapor pressure generated in the container body 30 by the SiC substrate 10 is heated.
- vapor-phase species of P i SiC, Si 2 C , SiC 2 and the like is contemplated.
- the broken line in FIG. 15A shows the heat generated when single crystal SiC is etched in a vapor pressure environment when SiC (solid) and Si (liquid phase) are in a phase equilibrium state via a gas phase. It is the result of mechanical calculation. Specifically, the thermodynamic calculation was performed under the following conditions (i) to (iv) using Equation 1. (I) it is a constant volume of SiC-Si equilibrium vapor pressure environment, (ii) etching the driving force, it is the temperature gradient in the main container 30, (iii) a raw material gas, SiC, Si 2 C, SiC 2. (iv) The desorption coefficient at which the raw material sublimates from step 14 is 0.001.
- the two-point chain line of FIG. 15 (a) is obtained by etching single crystal SiC in a vapor pressure environment when SiC (solid phase) and C (solid phase) are in a phase equilibrium state via a gas phase.
- This is the result of the thermodynamic calculation.
- the thermodynamic calculation was performed under the following conditions (i) to (iv) using Equation 1.
- (I) it is a constant volume of SiC-C equilibrium vapor pressure environment, (ii) etching the driving force, it is the temperature gradient in the main container 30,
- the raw material gas is SiC, Si 2 C, SiC 2
- the desorption coefficient at which the raw material sublimates from step 14 is 0.001.
- the values in the JANAF thermochemistry table were used for the data of each chemical species used in the thermodynamic calculation.
- the result of etching the SiC substrate 10 by arranging the SiC substrate 10 in a space where the atomic number ratio Si / C exceeds 1 (inside the main body container 30) is (marked with ⁇ ).
- the tendency is in agreement with the result of thermodynamic calculation of single crystal SiC etching in the SiC-Si equilibrium vapor pressure environment.
- the result of etching the SiC substrate 10 by arranging the SiC substrate 10 in a space where the atomic number ratio Si / C is 1 or less (inside the main body container 30) (x mark) is the result in the SiC-C equilibrium vapor pressure environment. It can be seen that the tendency is in agreement with the result of thermodynamic calculation of single crystal SiC etching.
- step 14 having a height of 1 nm (1 unit cell) was formed on the surface of the SiC substrate 10. It was lined up.
- the MSB was formed under the condition of the x-marked portion etched in the SiC-C equilibrium vapor pressure environment.
- thermodynamic calculation of crystal growth process the partial pressure difference between the SiC raw material and the steam generated from the SiC substrate when the inside of the main body container 30 is heated can be converted into the growth amount.
- the chemical potential difference and the temperature gradient can be assumed as the growth driving force.
- T is the temperature of the SiC raw material side
- k is Boltzmann's constant.
- P raw i -P substrate i is the raw material gas becomes a supersaturated state, a growth amount deposited as SiC, as a raw material gas SiC, Si 2 C, SiC 2 is assumed.
- the broken line in FIG. 15B shows a single crystal using polycrystalline SiC as a raw material in a vapor pressure environment when SiC (solid) and Si (liquid phase) are in a phase equilibrium state via a gas phase. This is the result of thermodynamic calculation when SiC is grown.
- thermodynamic calculation was performed under the following conditions (i) to (iv) using Equation 2.
- (I) It is a SiC-Si equilibrium vapor pressure environment with a constant volume, and (ii) the growth driving force is the temperature gradient in the main body container 30 and the vapor pressure difference (chemical potential difference) between the polycrystalline SiC and the single crystal SiC. That is, (iii) the raw material gas is SiC, SiC 2 C, SiC 2 , and (iv) the adsorption coefficient at which the raw material is adsorbed on the step of the SiC substrate 10 is 0.001.
- the two-point chain line in FIG. 15B uses polycrystalline SiC as a raw material in a vapor pressure environment when SiC (solid phase) and C (solid phase) are in a phase equilibrium state via a gas phase. It is the result of the thermodynamic calculation when the single crystal SiC was grown.
- thermodynamic calculation was performed under the following conditions (i) to (iv) using Equation 2.
- (I) It is a SiC-C equilibrium vapor pressure environment with a constant volume, and (ii) the growth driving force is the temperature gradient in the main body container 30 and the vapor pressure difference (chemical potential difference) between the polycrystalline SiC and the single crystal SiC. That is, (iii) the raw material gas is SiC, SiC 2 C, SiC 2 , and (iv) the adsorption coefficient at which the raw material is adsorbed on the step of the SiC substrate 10 is 0.001.
- the values in the JANAF thermochemistry table were used for the data of each chemical species used in the thermodynamic calculation.
- the result of arranging the SiC substrate 10 in a space where the atomic number ratio Si / C exceeds 1 (inside the main body container 30) and growing a growth layer on the SiC substrate 10 ( It can be seen that the values marked with ⁇ ) are in agreement with the results of the thermodynamic calculation of SiC growth in the SiC-Si equilibrium vapor pressure environment.
- the result (x mark) of arranging the SiC substrate 10 in a space (inside the main body container 30) in which the atomic number ratio Si / C is 1 or less and growing the growth layer on the SiC substrate 10 is the SiC-C equilibrium. It can be seen that the tendency is in agreement with the result of the thermodynamic calculation of SiC growth in the vapor pressure environment.
- FIG. 16A is an SEM image of the 4H-SiC (0001) plane side arranged so that the atomic number ratio Si / C in the main container 30 is 1 or less and crystal-grown at 1800 ° C. That is, it is an example of the part marked with x in FIG. 15B, and is an example of the surface where the SiC substrate 10 is crystal-grown in a SiC-C equilibrium vapor pressure environment.
- the surface shape obtained under these conditions is, for example, a step-terrace structure having a terrace width W of 40 to 200 nm and a step 14 height of 3 to 14 nm, and an MSB having a zigzag shape at the step end is formed. You can see that.
- FIG. 16B is an SEM image on the 4H-SiC (0001) plane side in which the atomic number ratio Si / C in the main container 30 is arranged so as to exceed 1, and the crystal is grown at 1800 ° C. That is, it is an example of the portion marked with a circle in FIG. 15 (b), and is an example of a surface in which crystals are grown under a SiC-Si equilibrium vapor pressure environment. It can be seen that in the surface shape obtained under these conditions, a step-terrace structure having a terrace width of 14 nm and a step height of 1.0 nm (full unit cell) is formed, and no MSB is formed.
- the step height and terrace width can be confirmed by the method for evaluating the SEM image contrast described in AFM and Japanese Patent Application Laid-Open No. 2015-179802.
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Abstract
Description
また、抵抗を低減可能な転位変換層を有するSiC基板およびSiC半導体を製造するための新規の技術を提供することにある。
このようなドーピング濃度の転位変換層を備えることにより、転位変換層における抵抗を低減することができる。
このようなドーピング濃度の転位変換層を備えることにより、BPD→TED変換を行う転位変換層としての機能に加え、少数キャリアの再結合を促進させる再結合促進層としての機能を果たすことができる。
このように、従来の転位変換層と比較して厚く形成することにより、転位の変換率を向上させるとともに、少数キャリアの再結合を促進させることができる。
また、本発明の好ましい形態では、前記転位変換層は、基底面転位から貫通刃状転位への変換率が100%である。
このように、高い変換率と高いドーピング濃度を両立することにより、従来法と比較して、下地基板上に成長させる層を削減することができる。これにより、SiC基板の製造手順の削減やコストを低減することができる。
また、本発明の好ましい形態では、前記転位変換層は、基底面転位から貫通刃状転位への変換率が100%である。
また、開示した技術によれば、抵抗を低減可能な転位変換層を有するSiC基板およびSiC半導体を製造するための新規の技術を提供することができる。
図1は、実施の形態にかかるSiC基板10の構成を示す断面図である。図1に示すように、実施の形態にかかるSiC基板10は、n+型基板である下地基板11と、n+型層である転位変換層12と、n型層であるエピタキシャル成長層13と、を備える。
また、20000個のBPDが存在する下地基板11の主面上に転位変換層12を成長させる場合には、転位変換層12の主面に存在するBPDは1000個以下となる。
そのため、エピタキシャル成長層13の主面は、MSBが形成されていないことが望ましい。また、エピタキシャル成長層13の主面は、1ユニットセル高さのステップ14が配列していることが望ましい。このステップ14高さやテラス幅Wは、AFMや特開2015-179082号公報に記載のSEM像コントラストを評価する手法により確認することができる。
すなわち、転位変換層12のドーピング濃度は、エピタキシャル成長層13のドーピング濃度よりも高いことが望ましい。
さらに、このように1μm以上の厚みを設けることにより、少数キャリアが再結合する領域を拡大するとともに、再結合の頻度が高い領域(転位変換層12の主面側)と、BPDが多く存在する領域(転位変換層12の裏面側)と、の距離を大きくすることができる。そのため、再結合により発生するエネルギーがBPDに与えられることを抑制することができる。
このように、エピタキシャル成長層13形成前のSiC基板10を製造しても良い。
そのため、転位変換層12の主面は、MSBが形成されていないことが望ましい。また、転位変換層12の主面は、1ユニットセル高さのステップ14が配列していることが望ましい。
次に、実施の形態にかかるSiC基板の製造方法について詳細に説明する。図3は、実施の形態にかかるSiC基板の製造工程を示す説明図である。
なお、バンチング分解工程S4は、何れの順序で実施する場合でも、共通の手法を採用することができる。そのため、バンチング分解工程S4については、加工変質層除去工程S1,結晶成長工程S2,エピタキシャル成長工程S3の後に説明する。
図4は、本発明にかかる加工変質層除去工程S1を示す説明図である。加工変質層除去工程S1は、n+型の下地基板11に導入された加工変質層111を除去する工程である。
以下、本工程の好ましい実施の形態について、詳細に説明する。
本実施の形態にかかる加工変質層除去工程S1は、Si元素供給源およびC元素供給源を含む準閉鎖空間内にSiC基板10を収容し、加熱することでエッチングする工程である。
このエッチング空間Xでは、加熱炉40が形成する温度勾配を駆動力として原子の輸送が起こり、結果として、SiC基板10をエッチングすることができる。
SiC-Si平衡蒸気圧環境は、原子数比Si/Cが1を超える準閉鎖空間が熱処理されることで形成される。具体的には、化学量論比1:1を満たすSiC製の本体容器30内に、化学量論比1:1を満たすSiC基板10と、化学量論比1:1を満たすSiC材料体20と、Si蒸気供給源35(Siペレット等)と、を配置した場合には、本体容器30内の原子数比Si/Cは1を超える。
SiC-C平衡蒸気圧環境は、原子数比Si/Cが1以下である準閉鎖空間が熱処理されることで形成される。具体的には、化学量論比1:1を満たすSiC製の本体容器30内に、化学量論比1:1を満たすSiC基板10と、化学量論比1:1を満たすSiC材料体20と、を配置した場合には、本体容器30内の原子数比Si/Cは1となる(図5(a)参照)。また、C蒸気供給源(Cペレット等)を配置して原子数比Si/Cを1以下としても良い。
また、SiC材料体20として、Si元素供給源およびC元素供給源を焼結させた焼結体を採用しても良い。
これにより、以下1)~5)の反応が持続的に行われ、結果としてSiC基板10のエッチングが進行すると考えられる。(図5(b)参照)。
2) 2C(s)+Si(v)→SiC2(v)
3) C(s)+2Si(v)→Si2C(v)
4) Si(v)+SiC2(v)→2SiC(s)
5) Si2C(v)→Si(v)+SiC(s)
2)および3)の説明:Si原子(Si(v))が脱離することで、SiC基板10表面に残存したC原子(C(s))は、準閉鎖空間内のSi蒸気(Si(v))と反応する。その結果、C原子(C(s))は、Si2CまたはSiC2等となってSiC基板10表面から昇華する(C原子昇華工程)。
4)および5)の説明:昇華したSi2CまたはSiC2等が、温度勾配によって準閉鎖空間内のSiC材料体20に到達し、結晶成長する。
本実施の形態にかかるエッチング速度は、上述した温度領域によって制御することができ、0.001~2μm/minの範囲で選択することが可能である。
本実施の形態にかかるエッチング時間は、所望のエッチング量となるよう任意の時間に設定することができる。例えば、エッチング速度が1μm/minの時に、エッチング量を1μmとしたい場合には、エッチング時間は1分間となる。
本実施の形態にかかる温度勾配は、例えば、0.1~5℃/mmの範囲に設定される。
なお、エッチング中に不活性ガスを導入することも可能である。この不活性ガスは、ArやHe、N2等を選択することができ、この不活性ガスを10-5~10000Paの範囲で導入することによって、加熱炉40(本加熱室41)の真空度を調整することができる。
また、加工変質層除去工程S1において、SiC基板10の主面にMSBが形成されないSiC-Si蒸気圧環境下でエッチングを施した場合には、バンチング分解工程S4を含まなくても良い。言い換えれば、加工変質層除去工程S1とバンチング分解工程S4とを同時に行ってもよい。
図6は、本発明にかかる結晶成長工程S2を示す説明図である。結晶成長工程S2は、n+型の下地基板11の上に、n+型の転位変換層12をテラス幅Wが増大する条件で成長させる工程である。
以下、本工程の好ましい実施の形態について、詳細に説明する。
本実施の形態にかかる結晶成長工程S2は、Si元素供給源およびC元素供給源を含む準閉鎖空間内にSiC基板10を収容し、加熱することで結晶成長させる工程である(図7(a)参照)。
これとは逆に、結晶成長工程S2は、SiC材料体20からSiC基板10にSi元素およびC元素を輸送してSiC基板10を結晶成長させる工程である。
この結晶成長空間Yでは、加熱炉40が形成する温度勾配を駆動力として原子の輸送が起こり、結果として、SiC基板10の上に結晶成長させることができる。
すなわち、結晶成長工程S2は、原子数比Si/Cが1を超える準閉鎖空間内にSiC基板10とSiC材料体20を相対させて配置し、SiC基板10とSiC材料体20との間に温度勾配が形成されるよう加熱する工程である。
これにより、以下1)~5)の反応が持続的に行われ、結果としてSiC基板10の結晶成長が進行すると考えられる。(図7(b)参照)。
2) 2C(s)+Si(v)→SiC2(v)
3) C(s)+2Si(v)→Si2C(v)
4) Si(v)+SiC2(v)→2SiC(s)
5) Si2C(v)→Si(v)+SiC(s)
2)および3)の説明:Si原子(Si(v))が脱離することで残存したC原子(C(s))は、準閉鎖空間内のSi蒸気(Si(v))と反応する。その結果、C原子(C(s))は、Si2CまたはSiC2等となって準閉鎖空間内に昇華する。
4)および5)の説明:昇華したSi2CまたはSiC2等が、温度勾配(または化学ポテンシャル差)によってSiC基板10のテラスに到達・拡散しステップに到達することで、下地のSiC基板10の多型を引き継いで成長する(ステップフロー成長)。
そのため、SiC材料体20のドーパントの種類やドーピング濃度を選択することにより、転位変換層12のドーパントおよびドーピング濃度を制御することができる。
また、加熱処理中にドーパントガスを供給することにより、ドーピングすることも可能である。
本実施の形態にかかる成長速度は、上述した温度領域によって制御することができ、0.001~2μm/minの範囲で選択することが可能である。
本実施の形態にかかる成長時間は、所望の成長量となるよう任意の時間に設定することができる。例えば、成長速度が1μm/minの時に、成長量を1μmとしたい場合には、成長量は1分間となる。
本実施の形態にかかる温度勾配は、0.1~5℃/mmの範囲で設定される。
本手法においては、ドーパントガス(N2等)を供給することができ、本加熱室41に10-5~10000Paの範囲で導入することができる。
また、加工変質層除去工程S1において、SiC基板10の主面にMSBが形成される条件でエッチングを施した場合には、結晶成長工程S2の前段に後述するバンチング分解工程S4を施すことが望ましい。
図8は、本発明にかかるエピタキシャル成長工程S3を示す説明図である。エピタキシャル成長工程S3は、転位変換層12上に、n型のエピタキシャル成長層13を成長させる工程である。
以下、本工程の好ましい実施の形態について、詳細に説明する。
本実施の形態にかかる成長速度は、上述した温度領域によって制御することができ、0.001~2μm/minの範囲で選択することが可能である。
本実施の形態にかかる成長時間は、所望の成長量となるよう任意の時間に設定することができる。例えば、成長速度が1μm/minの時に、成長量を1μmとしたい場合には、成長量は1分間となる。
本実施の形態にかかる温度勾配は、0.1~5℃/mmの範囲で設定される
バンチング分解工程S4は、SiC基板10の表面に形成されたMSBを分解可能な手法であれば採用することができる。例えば、Si蒸気圧下で加熱することで単結晶SiCをエッチングするSi蒸気圧エッチング(Si-Vapor Etching:SiVE)法等を例示できる。
以下、本工程の好ましい実施の形態について、詳細に説明する。
本実施の形態にかかるバンチング分解工程S4は、Si元素供給源およびC元素供給源を含む準閉鎖空間内にSiC基板10を収容し、SiC-Si平衡蒸気圧環境下でエッチング若しくは結晶成長させる工程である。
すなわち、原子数比Si/Cが1を超える準閉鎖空間内に、SiC基板10とSiC材料体20を相対させて配置し、SiC基板10が高温側、SiC材料体20が低温側となるよう加熱する形態である。
すなわち、原子数比Si/Cが1を超える準閉鎖空間内に、SiC基板10とSiC材料体20を相対させて配置し、SiC基板10が低温側、SiC材料体20が高温側となるよう加熱する形態である。
なお、エッチング条件および成長条件は、加工変質層除去工程S1または結晶成長工程S2で説明した条件を採用することができる。
次に、上述したSiC基板の製造方法を実現する製造装置について詳細に説明する。
本実施の形態にかかるSiC基板の製造装置は、図10に示すように、SiC基板10を収容可能な本体容器30と、SiC基板10とSiC材料体20との間に温度勾配が形成されるよう加熱可能な加熱炉40と、を備える。
本体容器30は、互いに嵌合可能な上容器31および下容器32と、を備える嵌合容器である。上容器31と下容器32の嵌合部には、微小な間隙33が形成されており、この間隙33から本体容器30内の排気(真空引き)が可能なよう構成されている。
加熱炉40は、図10に示すように、被処理物(SiC基板10等)を1000℃以上2300℃以下の温度に加熱することが可能な本加熱室41と、被処理物を500℃以上の温度に予備加熱可能な予備加熱室42と、本体容器30を収容可能な高融点容器50と、この高融点容器50を予備加熱室42から本加熱室41へ移動可能な移動手段43(移動台)と、を備えている。
本加熱室41の内部には、加熱ヒータ44(メッシュヒーター)が備えられている。また、本加熱室41の側壁や天井には多層熱反射金属板が固定されている(図示せず。)。この多層熱反射金属板は、加熱ヒータ44の熱を本加熱室41の略中央部に向けて反射させるように構成されている。
なお、加熱ヒータ44としては、例えば、抵抗加熱式のヒータや高周波誘導加熱式のヒータを用いることができる。
このように急速昇温および急速降温が行えるため、従来の装置では困難であった、昇温中および降温中の低温成長履歴を持たない表面形状を観察することが可能である。
また、図10においては、本加熱室41の下方に予備加熱室42を配置しているが、これに限られず、何れの方向に配置しても良い。
すなわち、本実施の形態の加熱炉40は、高融点容器50の底部が移動台と接触しているため、高融点容器50の上容器51から下容器52に向かって温度が下がるように温度勾配が設けられる。この温度勾配は、SiC基板10の表裏方向に沿って形成されていることが望ましい。
また、上述したように、加熱ヒータ44の構成により、温度勾配を形成してもよい。また、この加熱ヒータ44により、温度勾配を逆転可能に構成しても良い。
加熱炉40は、Si元素を含む雰囲気を形成し、この雰囲気内で本体容器30を加熱可能であることが好ましい。本実施の形態にかかる加熱炉40内のSi元素を含む雰囲気は、高融点容器50およびSi蒸気供給源54を用いて形成している。
なお、本体容器30の周囲にSi元素を含む雰囲気を形成可能な方法であれば、当然に採用することができる。
この他にも、加熱時に高融点容器50内にSi元素を含む気相種の蒸気圧が形成される構成であれば採用することができる。
実施の形態にかかるSiC基板10から、pinダイオードを製造する場合を例に説明する。例えば、実施の形態にかかるSiC基板10をn型とし、nチャネル型pinダイオードを製造する場合を考える。この時、下地基板11はカソード領域となり、転位変換層12はバッファ層として機能し、エピタキシャル成長層13は真性半導体層(i層)として機能する。
次に、アノード領域の上面に、ニッケル(Ni)等を成膜し熱処理する等してアノード電極を形成し、カソード領域の上面にカソード電極を形成する。これにより、nチャネル型pinダイオードが製造できる。
加工変質層111除去後のSiC基板10を、本体容器30および高融点容器50に収容し(図11参照)、以下の熱処理条件で熱処理した。なお、この実施例1においては、本体容器30を多結晶SiCで形成することにより、本体容器30自体がSiC材料体20(Si元素供給源およびC元素供給源)として機能するよう構成されている。
多型:4H-SiC
基板サイズ:横幅10mm×縦幅10mm×厚み0.45mm
オフ方向およびオフ角:<11-20>方向4°オフ
成長面:(0001)面
加工変質層111の有無:無し
MSBの有無:無し
ステップ14高さ:1.0nm
テラス幅W1:14nm
また、MSBの有無は、AFMおよび特開2015-179082号公報に記載のSEM像コントラストを評価する手法により確認した。
また、ステップ14高さは、AFMにより測定した。
また、テラス幅W(テラス幅W1およびテラス幅W2含む)の値としては、撮影したSEM像のステップ14に対して垂直なラインを引き、このライン上に存在するステップ14数をカウントすることで、テラス幅の平均値を採用した(テラス幅W=ライン長さ/ライン上のステップ数)。
材料:多結晶SiC
容器サイズ:直径60mm×高さ4mm
SiC基板10と本体容器30天面との距離:2mm
容器内の原子数比Si/C:1以下
ドーパント:N
ドーピング濃度:5×1017cm-3~5×1018cm-3
材料:TaC
容器サイズ:直径160mm×高さ60mm
Si蒸気供給源54(Si化合物):TaSi2
上述した条件で配置したSiC基板10を、以下の条件で熱処理した。
加熱温度:1800℃
加熱時間:8min
成長量:0.5μm
温度勾配:1℃/mm
図12は、実施例1にかかるSiC基板のSIMSの分析結果である。この図12に示すように、実施例1にかかる転位変換層12のドーピング濃度は3×1017cm-3であり、下地基板11のドーピング濃度は6×1018cm-3であった。
実施例1にかかる結晶成長工程S2にて成長した転位変換層12は、以下の通りである。
ドーパント:N
ドーピング濃度:3×1017cm-3
MSBの有無:有り
ステップ14高さ:>1.0nm
ステップ端形状:ジグザグ形状
テラス幅W2:55nm
BPD→TED変換率:100%
図13(a)は、加工変質層111を有した下地基板11を示している。この段階ではバルク層112から加工変質層111まで、BPDが存在している。
図13(b)は、加工変質層除去工程S1により加工変質層111を除去した下地基板11を示している。この段階では、下地基板11(バルク層112)にBPDが存在している。
図13(c)は、結晶成長工程S2により転位変換層12を成長させたSiC基板10を示している。この工程でバルク層112に存在していたBPDが、ある確率でTEDに変換される。ここで転位変換層12の表面には、100%変換されない限り、TEDとBPDが混在していることとなる。
図13(d)は、結晶成長工程S2後のSiC基板10に対し、KOH溶解エッチング法を用いて転位変換層12中の欠陥を確認した様子を示している。このKOH溶解エッチング法は、約500℃に加熱した溶解塩(KOH等)にSiC基板を浸し、転位や欠陥部分にエッチピットを形成し、そのエッチピットの大きさ・形状により転位の種類を判別する手法である。この手法により、結晶成長工程S2後の転位変換層12中を伝播したBPDの数を得る。
図13(e)は、KOH溶解エッチング法後に転位変換層12を除去する様子を示している。本手法では、エッチピット深さまで機械研磨やCMP等により平坦化した後、SiVE法等により転位変換層12を除去し、下地基板11(バルク層112)を表出させている。
図13(f)は、転位変換層12を除去した下地基板11に対し、KOH溶解エッチング法を用いて下地基板11中の欠陥を確認した様子を示している。この手法により、転位変換層12直下の下地基板11に存在しているBPDの数を得る。
また、実施例1においては、ドーピング濃度が5×1017cm-3~5×1018cm-3のSiC材料体20を用いて、ドーピング濃度1×1017cm-3以上の転位変換層12を形成したが、ドーパントガスを導入してドーピング濃度を高めることも可能である。
次に、実施例2,実施例3,比較例1,比較例2,比較例3を参照して、BPD→TED変換率が向上する熱処理条件について詳細に説明する。
図15(a)は、本発明のエッチング工程における、加熱温度とエッチング速度の関係を示すグラフである。このグラフの横軸は温度の逆数であり、このグラフの縦軸はエッチング速度を対数で表示している。
以下、エッチング工程の熱力学計算と、結晶成長工程の熱力学計算と、に分けて詳細に説明する。
エッチング工程の熱力学計算においては、本体容器30を加熱した際に、SiC基板10から発生する蒸気量(Si元素を含む気相種およびC元素を含む気相種)をエッチング量に換算できる。その場合、SiC基板10のエッチング速度は以下の数1で求められる。
また、Piは、SiC基板10が加熱されることで本体容器30内に発生する蒸気圧を足し合わせた値のことである。なお、Piの気相種としては、SiC,Si2C,SiC2等が想定される。
なお、熱力学計算に用いた各化学種のデータはJANAF熱化学表の値を採用した。
一方で、SiC-C平衡蒸気圧環境下でエッチングされた×印箇所の条件においては、MSBが形成されていた。
次に、結晶成長工程の熱力学計算においては、本体容器30内の加熱した際に、SiC原料とSiC基板から発生する蒸気の分圧差を成長量に換算できる。この時の、成長駆動力としては、化学ポテンシャル差や温度勾配を想定できる。なお、この化学ポテンシャル差は、多結晶SiC(SiC材料体20)と単結晶SiC(SiC基板10)の表面で発生する気相種の分圧差を想定できる。その場合、SiCの成長速度は以下の数2で求められる。
また、P原料i-P基板iは、原料ガスが過飽和な状態となって、SiCとして析出した成長量であり、原料ガスとしてはSiC,Si2C,SiC2が想定される。
なお、熱力学計算に用いた各化学種のデータはJANAF熱化学表の値を採用した。
11 下地基板
111 加工変質層
112 バルク層
113 歪み
114 傷
115 潜傷
12 転位変換層
13 エピタキシャル成長層
14 ステップ
15 テラス
20 SiC材料体
30 本体容器
31 上容器
32 下容器
33 間隙
34 基板保持具
35 Si蒸気供給源
40 加熱炉
41 本加熱室
42 予備加熱室
43 移動手段
44 加熱ヒータ
45 真空形成用バルブ
46 不活性ガス注入用バルブ
47 真空計
50 高融点容器
51 上容器
52 下容器
53 間隙
54 Si蒸気供給源
X エッチング空間
Y 結晶成長空間
S1 加工変質層除去工程
S2 結晶成長工程
S3 エピタキシャル成長工程
S4 バンチング分解工程
Claims (18)
- ドーピング濃度が1×1015cm-3以上である転位変換層を備える、SiC基板。
- ドーピング濃度が1×1017cm-3以上である転位変換層を備える、請求項1に記載のSiC基板。
- 前記転位変換層は、1μm以上の厚みを有する、請求項1又は請求項2に記載のSiC基板。
- 前記転位変換層は、基底面転位から貫通刃状転位への変換率が95%より大きい、請求項1~3の何れか一項に記載のSiC基板。
- 前記転位変換層は、基底面転位から貫通刃状転位への変換率が100%である、請求項1~4の何れか一項に記載のSiC基板。
- 下地基板と、エピタキシャル成長層と、をさらに備え、
前記転位変換層は、前記下地基板と前記エピタキシャル成長層との間に設けられ、
前記転位変換層のドーピング濃度は、前記エピタキシャル成長層のドーピング濃度よりも高い、請求項1~5の何れか一項に記載のSiC基板。 - ドーピング濃度が1×1015cm-3以上の転位変換層を、テラス幅が増大する条件で成長させる結晶成長工程を含む、SiC基板の製造方法。
- 前記結晶成長工程は、SiC-C平衡蒸気圧環境下で成長させる工程である、請求項7に記載のSiC基板の製造方法。
- 前記結晶成長工程は、マクロステップバンチングが形成されていない表面に対して結晶成長させる工程である、請求項7又は請求項8に記載のSiC基板の製造方法。
- ドーピング濃度が1×1015cm-3以上である転位変換層を備える、SiC半導体装置。
- ドーピング濃度が1×1017cm-3以上である転位変換層を備える、請求項10に記載のSiC半導体装置。
- 前記転位変換層は、1μm以上の厚みを有する、請求項10又は請求項11に記載のSiC半導体装置。
- 前記転位変換層は、基底面転位から貫通刃状転位への変換率が95%より大きい、請求項10~12の何れか一項に記載のSiC半導体装置。
- 前記転位変換層は、基底面転位から貫通刃状転位への変換率が100%である、請求項10~13の何れか一項に記載のSiC半導体装置。
- 下地基板と、エピタキシャル成長層と、をさらに備え、
前記転位変換層は、前記下地基板と前記エピタキシャル成長層との間に設けられ、
前記転位変換層のドーピング濃度は、前記エピタキシャル成長層のドーピング濃度よりも高い、請求項10~14の何れか一項に記載のSiC半導体装置。 - ドーピング濃度が1×1015cm-3以上の転位変換層を、テラス幅が増大する条件で成長させる結晶成長工程を含む、SiC半導体装置の製造方法。
- 前記結晶成長工程は、SiC-C平衡蒸気圧環境下で成長させる工程である、請求項16に記載のSiC半導体装置の製造方法。
- 前記結晶成長工程は、マクロステップバンチングが形成されていない表面に対して結晶成長させる工程である、請求項16又は請求項17に記載のSiC半導体装置の製造方法。
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