WO2014189010A1

WO2014189010A1 - Single-crystal silicon carbide and process for producing same

Info

Publication number: WO2014189010A1
Application number: PCT/JP2014/063230
Authority: WO
Inventors: 藤井　邦治; 武井　康一; 蔵重　和央; ナチムス　セングットバン; 長井　一郎; 智久加藤; 武志三谷; 直佳小松; 高橋　徹夫
Original assignee: 日立化成株式会社; 独立行政法人産業技術総合研究所
Priority date: 2013-05-20
Filing date: 2014-05-19
Publication date: 2014-11-27
Also published as: JPWO2014189010A1; JP6230031B2

Abstract

The present invention provides single-crystal silicon carbide which contains Ti in a concentration of 1.0×10¹⁶ (cm^-3) or higher and has an n-type carrier density of 3.0×10¹⁸ (cm^-3) or less.

Description

Silicon carbide single crystal and method for producing the same

The present invention relates to a silicon carbide single crystal and a method for producing the same.

In recent years, silicon carbide (SiC) has attracted attention as a material constituting semiconductor devices. A semiconductor substrate made of SiC is superior to a semiconductor substrate made of silicon (Si) in that it has a wide band gap, a high thermal conductivity, and a large dielectric breakdown electric field. Therefore, a semiconductor substrate made of SiC can be advantageously applied to applications such as power devices. Since SiC is a compound semiconductor that does not coincide with melting (a phenomenon in which a solid dissolves into a solution having the same composition), a SiC single crystal is generally formed by a method called a sublimation method.

In addition, as a technique for growing a crystal having a higher quality than that of the sublimation method (for example, the proportion of polycrystal contained in the crystal is small), a method of forming a SiC single crystal by a liquid phase growth method has been studied (for example, Patent Document 1).

JP 2009-91222 A

In the liquid phase growth method, a transition metal element such as Ti is generally added to the Si melt in order to improve the crystal growth rate. In this case, the added transition metal element is taken into the obtained SiC single crystal. Furthermore, by adding a transition metal, the incorporation of residual nitrogen in the atmospheric gas into the SiC crystal is promoted, and as a result, the n-type carrier density in the SiC single crystal is increased, which greatly affects the performance as a semiconductor. There is a risk of giving.

Therefore, an object of the present invention is to provide a SiC single crystal having a reduced n-type carrier density while containing a transition metal element such as Ti, and a method for producing the same.

The present invention provides a silicon carbide single crystal containing Ti at a concentration of 1.0 × 10 ¹⁶ (cm ⁻³ ) or more and having an n-type carrier density of 3.0 × 10 ¹⁸ (cm ⁻³ ) or less. provide.

Further, the present invention uses a raw material solution in which at least one transition metal element is dissolved in a Si melt and a carbon source, and heats the raw material solution in a state where the silicon carbide seed crystal is in contact with the raw material solution, Provided is a method for producing a silicon carbide single crystal, in which a temperature gradient of 1.0 to 2.0 ° C./cm is generated in the vicinity of a silicon carbide seed crystal and crystal growth is performed at a growth temperature of 2050 ° C. or higher.

According to the present invention, it is possible to provide a SiC single crystal having a reduced n-type carrier density while containing a transition metal element such as Ti, and a method for producing the same.

It is principal part sectional drawing which shows the whole structure of the crystal growth apparatus used with the manufacturing method of the SiC single crystal which concerns on this embodiment. It is principal part sectional drawing which shows the whole structure of the crystal growth apparatus used with the manufacturing method of the SiC single crystal which concerns on this embodiment. It is a figure which shows the relationship between the growth temperature and n-type carrier density of the SiC crystal obtained by the Example, the comparative example, and the reference example.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Moreover, the pressure unit in this embodiment is a gauge pressure.

[Production of SiC single crystal]
The SiC single crystal manufacturing method according to the present embodiment includes a preparatory step for preparing crystal growth, a meltback step for removing a work-affected layer remaining on the surface of the polished SiC seed crystal, and growing the SiC single crystal. The growth process is provided. In manufacturing the SiC single crystal, for example, an SiC crystal growth apparatus shown in FIGS. 1 and 2 is used.

(Outline of crystal growth equipment)
FIG. 1 and FIG. 2 are main part sectional views showing the overall structure of the crystal growth apparatus used in the method for producing an SiC single crystal according to the present embodiment, and show the state of the crystal growth apparatus in the growth process and the preparation process, respectively. Yes.

The SiC crystal growth apparatus shown in FIG. 1 includes a graphite raw material container 1 (carbon source) filled with a raw material solution 2 and a graphite container support 8 that supports the graphite raw material container 1, and a lower end face of the graphite seed crystal support 4. The SiC seed crystal 3 held in is immersed in the raw material solution 2 and heated by the graphite heater 6 to form the SiC growth crystal 5. These are covered with a heat insulating structural member 7 for heat insulation, and the whole is housed in a sealed container body 11 having an inert gas inlet 9 and a gas exhaust 10. Furthermore, a radiation thermometer 12 for measuring the temperature of the graphite raw material container 1 and the like, and a DC voltage application power source 14 and an ammeter 13 connected to the electrode 15 are provided outside the sealed container body 11. Yes.

In the present embodiment, the graphite raw material container 1 is used as the carbon source, but a container made of another material may be used. The other material is not particularly limited as long as it is a non-consumable material that can withstand the heating in the growth process, and may be a material other than graphite that can supply carbon to the raw material solution 2, and a material that does not supply carbon to the raw material solution 2 It may be. When a container made of a material that does not supply carbon is used as the raw material solution 2, a solid carbon source is put into the container, or a gaseous carbon source is blown into the raw material solution 2 or mixed with an atmospheric gas, thereby Carbon can be supplied to the solution 2. As the solid carbon source, graphite such as block, rod, granule and powder, metal carbide, SiC and the like can be used. As the carbon source gas can be a hydrocarbon gas such as CH _4.

As the raw material solution 2, a solution in which a transition metal element such as Ti, Cr, Ni or the like is dissolved in Si melt (that is, Si—Ti solution, Si—Cr solution, Si—Ni solution, etc.) is used. Among these, the raw material solution 2 is preferably a Si—Ti solution or a Si—Cr solution. In the raw material solution 2, for example, alkali metal elements; alkaline earth metals; rare earth elements such as Sc and Y may be dissolved.

Examples of the Si source contained in the raw material solution 2 include Si, SiC, titanium silicide, chromium silicide, and aluminum silicide. Further, examples of the Ti source and the Cr source in the case where the raw material solution 2 contains Ti and Cr include the following.
Ti source: metal Ti, titanium carbide, titanium silicide.
Cr source: metal Cr, chromium carbide, chromium silicide.

In the case of Ti, the content of the transition metal element in the raw material solution 2 is preferably 10 to 25 at%, more preferably 15 to 23 at%, based on the total amount of the raw material solution 2, and 20 to More preferably, it is 23 at%. In the case of Cr, it is preferably 20 to 60 at%, more preferably 30 to 50 at%, further preferably 35 to 45 at%, based on the total amount of the raw material solution 2. The content of each atom in the raw material solution 2 can be calculated as follows. For example, when the composition of the raw material solution 2 is Si _x Ti _y , consider the case where Si and metal Ti are used as raw materials as the Si source and the Ti source, respectively. At this time, the number of moles of Si and Ti which is calculated from the weight of each raw material and M _Si and M _Ti respectively, by dividing these respective number of moles in the total number of moles of M _Si and M _Ti, x and y are respectively Calculated.

As the SiC seed crystal 3, for example, a wafer that is manufactured by a sublimation method and whose surface is polished can be used. The shape of the SiC seed crystal 3 may be a plate shape such as a disc shape, a hexagonal flat plate shape, a rectangular flat plate or the like, or a cubic shape, but a plate shape is preferable. Moreover, if the magnitude | size is disk shape, for example, a diameter of 0.1 cm or more is preferable, 0.5 cm or more is more preferable, and 1 cm or more is still more preferable. A preferable upper limit of the diameter is not particularly limited, and may be adjusted according to the capacity of the crystal growth apparatus, and may be, for example, 10 cm.

The crystal structure of the SiC seed crystal 3 can be appropriately selected according to the type of the target SiC growth crystal, and for example, 2H type, 3C type, 4H type, 6H type and the like can be used. For example, in order to obtain a 2H type SiC grown crystal, it is preferable to use a 2H type SiC seed crystal 3. In the present embodiment, it is preferable to use 4H-type SiC seed crystal 3 (4H—SiC single crystal wafer) manufactured by a vapor phase method or the like as SiC seed crystal 3.

Since the SiC single crystal has a structure in which Si and C are laminated in layers, the SiC seed crystal 3 has an exposed C surface where C is aligned on the crystal surface and an Si surface where Si is aligned. There is a surface that is. In the present embodiment, either plane in the SiC seed crystal 3 can be used, but a crystal having a better surface morphology can be produced by starting crystal growth from the C plane.

In the present embodiment, the growth surface of the SiC seed crystal 3 may be either a {0001} plane (on-axis plane) or a plane inclined from the {0001} plane (off-axis plane).

As the graphite heater 6, a resistance heating type heating device can be used. As another embodiment of the method of heating the graphite raw material container 1 by the resistance heating method, the graphite raw material container 1 and the DC voltage application power source 14 are electrically connected, and a current is directly supplied to the graphite raw material container 1. (Current path 16 in FIG. 2), a method of generating resistance heat is conceivable. However, in this case, there is a concern that a large current flows through the raw material solution 2 through the graphite raw material container 1, and the convection of the raw material solution 2 is hindered by the current. Therefore, as shown in FIGS. 1 and 2, it is preferable to heat by a graphite heater 6 disposed around the graphite raw material container 1.

Further, the graphite seed crystal support 4 is excessively heated by the heat of the graphite heater 6, and the surface of the graphite seed crystal support 4 holding the SiC seed crystal 3 and the temperature of the SiC seed crystal 3 are From the viewpoint of suppressing the temperature from becoming higher than the temperature of the raw material solution 2, as shown in FIGS. 1 and 2, in the region where the inner surface of the graphite heater 6 and the graphite seed crystal support 4 are opposed, It is preferable to interpose a graphite raw material container 1.

Next, a method for manufacturing the SiC single crystal according to the present embodiment will be described with reference to FIGS. 1 and 2 as appropriate.

(Preparation process)
First, the raw material of the raw material solution 2 is filled in the graphite raw material container 1, and the SiC seed crystal 3 held on the lower end face of the graphite seed crystal support 4 is disposed away from the liquid surface of the raw material solution 2. . Next, after the inside of the sealed container body 11 is evacuated, the temperature is raised while continuing the vacuum evacuation.

Thereafter, a growth atmosphere gas is introduced. The growth atmosphere gas is not particularly limited, but is preferably an inert gas such as He, Ne, or Ar in order to prevent oxidation of the SiC crystal and the solution. Alternatively, a gas such as N ₂ , H ₂ , or CH ₄ mixed with the inert gas may be used as the growth atmosphere gas.

(Meltback process)
Subsequent to the above preparation step, the pressure in the sealed container body 11 is increased to the growth pressure, for example, to about 1950 ° C. Note that any atmosphere of a pressurized atmosphere and a decompressed atmosphere may be used as long as it is an inert gas atmosphere. From the viewpoint of suppressing evaporation of the raw material solution 2, the pressure is preferably 0.1 MPa or more, and more preferably, for example, about 0.8 MPa.

Next, the graphite seed crystal support 4 and the SiC seed crystal 3 are slowly lowered toward the surface of the raw material solution 2, and the descent is stopped when the lower surface of the SiC seed crystal 3 comes into contact with the raw material solution 2. From the position, only the SiC seed crystal 3 comes into contact with the raw material solution 2, and the graphite seed crystal support 4 is held at a position not in contact with the raw material solution 2.

If the graphite seed crystal support 4 is in contact with the raw material solution 2, the following adverse effects may occur. That is, during crystal growth, the raw material solution 2 rises to the side surface of the graphite seed crystal support 4 due to surface tension and forms a meniscus. And in the area | region in which the meniscus was formed, since the volume of the raw material solution 2 becomes small, the temperature of the raw material solution 2 is rapidly cooled locally and a crystal | crystallization is formed. When a crystal is formed on the side surface of the graphite seed crystal support 4, it moves forward in the growth direction of the SiC growth crystal 5 and inhibits crystal growth. Further, the crystal formed by this phenomenon is not preferable because it may become polycrystalline.

Therefore, as described above, it is preferable to raise the SiC seed crystal 3 after contacting the raw material solution 2 so that the graphite seed crystal support 4 does not contact the raw material solution 2. Sometimes the distance between the meniscus formed on the SiC seed crystal 3 and the SiC growth crystal 5 is preferably 5 mm or less, more preferably 3 mm or less, and more preferably 1 mm or less. More preferably, the distance is such that When the distance to be raised is within the above range, the above-described adverse effects can be easily prevented.

Thereafter, by raising the temperature to the growth temperature, a part including the surface of the SiC seed crystal 3 is melted. The growth temperature is set at a temperature at which the liquidus line in the phase diagram is the boundary between the liquid phase and the liquid + SiC phase, but is 2050 ° C. or higher from the viewpoint of reducing n-type carriers derived from nitrogen in the SiC single crystal. . From the same viewpoint, the growth temperature is preferably 2100 ° C. or higher. On the other hand, the upper limit of the growth temperature is not particularly limited, but is, for example, 2300 ° C. or lower. The growth temperature in this embodiment means the temperature of the lower surface of the bottom of the graphite raw material container 1 and is measured by the radiation thermometer 12.

It should be noted that it is preferable to provide an etch back step after the SiC seed crystal 3 is brought into contact with the raw material solution 2 and before crystal growth is started. This is because if the growth surface of the seed crystal is contaminated at the start of crystal growth, the quality of the grown crystal is significantly reduced. Thereby, the work-affected layer remaining on the surface of the surface-polished SiC seed crystal 3 can be removed.

(Growth process)
In the solution growth method, a method of forming a supersaturated state by forming a temperature gradient so that the temperature in the vicinity of the seed crystal is lower than that of the raw material solution (temperature gradient method) allows stable crystal growth for a long time. Because it is general. Also in this embodiment, it is preferable to implement by the temperature gradient method. In addition, as another method, a method (supercooling method) in which a supersaturated state is formed by lowering the temperature of the entire solution in which the seed crystal is immersed is performed. In the slow cooling method, crystals are grown by repeatedly performing heating and cooling. However, since the temperature changes during growth and the growth conditions are not stable, it is not preferable for the production of high quality crystals.

In this embodiment, the mechanism of crystal growth is described as follows. That is, since the heat of the raw material solution 2 in the vicinity of the SiC seed crystal 3 is transferred to the outside through the SiC seed crystal 3 and the graphite seed crystal support 4, the temperature of the raw material solution 2 in the vicinity of the SiC seed crystal 3 decreases. To do. For this reason, a temperature gradient is generated in the raw material solution 2 in the vicinity of the SiC seed crystal 3. In the region where the temperature is low, the carbon in the raw material solution 2 is supersaturated, so that the SiC growth crystal 5 is deposited on the surface of the SiC seed crystal 3.

Here, the temperature gradient in this embodiment is more specifically the temperature at the lower surface (referred to as “point A”) at the bottom of the graphite raw material container 1 as T _A (° C.), the melt surface (“point”). The temperature at ( _B ) is defined as T _B (° C.) as follows.
Temperature gradient (° C./cm)=(T _A −T _B ) / (Distance between points A and B (cm))
Incidentally, the T _A and T _B can be measured by a radiation thermometer and a thermocouple (measuring perform another experiment not during the growth was measured).

The temperature gradient is preferably 1.0 to 10 ° C./cm, more preferably 1.0 to 5.0 ° C./cm, and further preferably 1.0 to 3.0 ° C./cm. It is preferably 1.0 to 2.0 ° C./cm. By setting the temperature gradient within the above range, it is possible to perform crystal growth for a long time while maintaining a relatively high quality crystal growth surface. The temperature gradient can be controlled, for example, by changing the upper / lower output ratio of the heater.

While the SiC seed crystal 3 immersed in the raw material solution 2 is pulled upward at a rate similar to the growth rate, the SiC grown crystal 5 is formed on the SiC seed crystal 3 for a time corresponding to the required thickness of the SiC grown crystal 5. Then, the SiC seed crystal 3 is separated from the raw material solution 2. Thus, a SiC single crystal is obtained. The solution growth method is generally performed while rotating the seed crystal and the crucible during crystal growth. The rotation axis of this rotation is a rotation axis parallel to the seed crystal holding axis and the crucible holding axis parallel thereto. The rotation direction of the seed crystal and the crucible may be the same or reversed. Further, the rotational speed may be constant, for example, in the range of about 2 to 70 rpm, or may be changed periodically.

[SiC single crystal]
The SiC single crystal of the present embodiment contains Ti at a concentration of 1.0 × 10 ¹⁶ (cm ⁻³ ) or more. The upper limit of the Ti concentration is not particularly limited, but is, for example, 5.0 × 10 ¹⁶ (cm ⁻³ ) or less. Here, “Ti” may be either a Ti atom or a Ti ion. In addition, the n-type carrier density in the SiC crystal of the present embodiment is 3.0 × 10 ¹⁸ (cm ⁻³ ) or less, preferably 2.0 × 10 ¹⁸ (cm ⁻³ ) or less. More preferably, it is 0.0 × 10 ¹⁸ (cm ⁻³ ) or less. The lower limit of the n-type carrier density is not particularly limited, but can be, for example, 5.0 × 10 ¹⁷ (cm ⁻³ ) or more.

The Ti concentration can be measured, for example, by SIMS analysis of the obtained single crystal. The n-type carrier density can be measured, for example, by performing Raman analysis on the obtained crystal. As the measurement conditions for Raman analysis, for example, the measurement surface: the surface of the obtained crystal ((000-1) plane), the measurement laser wavelength: 514.5 nm, and the backscattering conditions of normal incidence and vertical scattering. it can.

The SiC single crystal of the present embodiment is an ingot-shaped or wafer-shaped SiC single crystal. The ingot-shaped SiC single crystal can be obtained by separating the cylindrical SiC growth crystal 5 obtained by the above-described manufacturing method from the SiC seed crystal 3. When separating the SiC growth crystal 5 from the SiC seed crystal 3, for example, the SiC growth crystal 5 can be separated from the interface between the SiC seed crystal 3 and the SiC growth crystal 5 at a position of about 0.3 mm toward the SiC growth crystal 5. The wafer-like SiC single crystal can be obtained by slicing the resulting ingot-like SiC single crystal to a desired thickness.

The diameter of the SiC single crystal of this embodiment is preferably 0.1 cm or more, more preferably 0.5 cm or more, and still more preferably 1 cm or more. The preferable upper limit of the diameter is not particularly limited, and can be, for example, 10 cm.

(Example 1)
[Preparation of SiC single crystal]
A SiC single crystal was grown using the SiC crystal growth apparatus shown in FIG.

<Preparation process>
Each raw material was filled in a graphite raw material container (cylindrical crucible, inner diameter 50 mm, outer diameter 70 mm, height 100 mm) so that the initial composition of the raw material solution was Si / Ti = 85/15 (unit: at%). . C was supplied from the graphite raw material container into the solution during crystal growth. This graphite raw material container was placed in a crystal growth apparatus, and a SiC seed crystal (disk shape, diameter 22 mm, thickness 0.5 mm, growth surface: {0001} surface (existing) on the lower end face of the graphite seed crystal support. The on-axis surface)) was held 14.5 cm above the solution liquid level. In this state, the temperature was raised to a predetermined temperature while evacuating the inside of the apparatus.

Thereafter, He gas was introduced into the apparatus as a growth atmosphere gas. At this time, the solution raw material in the graphite raw material container was melted to form a solution.

<Meltback process>
After this, the pressure is increased to 800 kPa, which is the growth pressure, and the temperature is raised to a temperature lower by 50 ° C. than the growth temperature. Immediately, the seed crystal was moved 1 mm upward from the position of the seed crystal. By raising the temperature to 2050 ° C., which is the growth temperature, at this seed crystal position, a part of the seed crystal including the seed crystal surface was melted. In consideration of the thermal expansion of the graphite seed crystal support accompanying the temperature rise to 2050 ° C., the distance between the seed crystal surface and the liquid surface at the growth temperature of 2050 ° C. is estimated to be about 0.5 mm (meniscus height: 0.5 mm).

<Growth process>
Then, the growth was started by pulling the seed crystal upward at a speed of 50 μm / h. During the growth, the temperature gradient was 1.5 ° C./cm and the gas flow rate was 0.5 L / min. Further, the seed crystal and the raw material container were rotated in opposite directions, and the rotational speed of the seed crystal was 50 rpm, and the rotational speed of the raw material container was 10 rpm. The seed crystal was immersed in the raw material solution for 24 hours and then pulled up from the raw material solution to obtain a single crystal A. The thickness of the obtained single crystal A was 290 μm.

[Measurement of Ti concentration]
The Ti concentration was measured by SIMS analysis of the crystal surface after growth. The Ti concentration in the single crystal A was 3.0 × 10 ¹⁶ (cm ⁻³ ).

[Measurement of n-type carrier density]
After the raw material solution solidified material adhering to the crystal surface after growth was removed with an acid, Raman spectroscopic measurement was performed from the crystal surface side. Specifically, the measurement was carried out under the conditions of measurement of the measurement surface: the surface of the obtained crystal ((000-1) plane), the measurement laser wavelength: 514.5 nm, and normal incidence and backscattering conditions of vertical scattering. The n-type carrier density was calculated by performing fitting calculation on the longitudinal optical phonon mode of the measured Raman spectrum. The n-type carrier density in the single crystal A was 2.3 × 10 ¹⁸ (cm ⁻³ ).

(Example 2)
A SiC single crystal B was produced in the same manner as in Example 1 except that the growth temperature was changed to 2100 ° C. The meniscus height at the growth temperature was 0.5 mm, the temperature gradient was 1.9 ° C./cm, and the thickness of the obtained single crystal B was 320 μm. The Ti concentration in the single crystal B was 3.2 × 10 ¹⁶ (cm ⁻³ ), and the n-type carrier density was 1.7 × 10 ¹⁸ (cm ⁻³ ).

(Comparative example)
A SiC single crystal C was produced in the same manner as in Example 1 except that the growth temperature was changed to 2000 ° C. The meniscus height at the growth temperature was 0.5 mm, the temperature gradient was 1.4 ° C./cm, and the thickness of the obtained single crystal B was 655 μm. Further, the Ti concentration in the single crystal C was 2.0 × 10 ¹⁶ (cm ⁻³ ), and the n-type carrier density was 3.8 × 10 ¹⁸ (cm ⁻³ ).

(Reference example)
A SiC single crystal D was produced in the same manner as in the comparative example except that the initial composition of the raw material solution was changed to only Si. The meniscus height at the growth temperature was 0.5 mm, the temperature gradient was 6.7 ° C./cm, and the thickness of the obtained single crystal D was 400 μm. Further, the Ti concentration in the single crystal D was below the detection limit, and the n-type carrier density was 9.8 × 10 ¹⁷ (cm ⁻³ ).

FIG. 3 shows the relationship between the growth temperature and the n-type carrier density for the single crystals A, B, C and D. As shown in FIG. 3, the n-type carrier density is increased by adding Ti to the raw material solution, but it can be seen that the n-type carrier density can be reduced by increasing the growth temperature.

DESCRIPTION OF SYMBOLS 1 ... Graphite raw material container, 2 ... Raw material solution, 3 ... SiC seed crystal, 4 ... Graphite seed crystal support body, 5 ... SiC growth crystal, 6 ... Graphite heater, 7 ... Thermal insulation structural material, 8 ... Graphite container Support: 9 ... Inert gas introduction port, 10 ... Gas exhaust port, 11 ... Sealed container body, 12 ... Radiation thermometer, 13 ... Ammeter, 14 ... DC voltage application power source, 15 ... Electrode, 16 ... Current path.

Claims

A silicon carbide single crystal containing Ti at a concentration of 1.0 × 10 16 (cm −3 ) or more and having an n-type carrier density of 3.0 × 10 18 (cm −3 ) or less.
Using a raw material solution in which at least one transition metal element is dissolved in a Si melt and a carbon source, the raw material solution is heated in a state where the silicon carbide seed crystal is in contact with the raw material solution, and the silicon carbide species A method for producing a silicon carbide single crystal, wherein a temperature gradient of 1.0 to 2.0 ° C./cm is generated in the vicinity of a crystal, and crystal growth is performed at a growth temperature of 2050 ° C. or higher.