SILICON CARBIDE SUBSTRATE AND METHOD OF GROWING SiC SINGLE CRYSTAL BOULES
20230193508 · 2023-06-22
Inventors
- Michael Vogel (Nürnberg, DE)
- Bernhard Ecker (Nürnberg, DE)
- Ralf Müller (Zirndorf, DE)
- Matthias Stockmeier (Egloffstein, DE)
- Arnd-Dietrich Weber (Forchheim, DE)
Cpc classification
C30B23/00
CHEMISTRY; METALLURGY
Y10T428/24942
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
Abstract
The present invention relates to a silicon carbide (SiC) substrate with improved mechanical and electrical characteristics. Furthermore, the invention relates to a method for producing a bulk SiC crystal in a physical vapor transport growth system. The silicon carbide substrate comprises an inner region (102) which constitutes at least 30% of a total surface area of said substrate (100), a ring shaped peripheral region (104) radially surrounding the inner region (102), wherein a mean concentration of a dopant in the inner region (102) differs by at least 1.Math.10.sup.18 cm.sup.−3 from the mean concentration of this dopant in the peripheral region (104).
Claims
1. Method of growing at least one SiC single crystal boule (108, 109) in a physical vapor transport growth system, the method comprising the steps of: arranging an SiC powder source material (114) in a source material compartment (116), arranging at least one SiC seed crystal within a growth compartment (118, 119), wherein said source material compartment (116) is connected to said growth compartment (118, 119) for providing sublimated gaseous components to the growth compartment (118, 119), applying an elevated temperature for generating the sublimated gaseous components that generate an SiC growth phase at the SiC seed crystal, so that an SiC volume single crystal boule (108, 109) is formed at the SiC seed crystal, wherein the at least one growth compartment (118, 119) comprises a dopant source and/or a dopant sink for controlling a dopant concentration in a radial direction with reference to a longitudinal axis of the single crystal boule (108, 109) during the growth of the single crystal boule.
2. Method according to claim 1, wherein said dopant comprises nitrogen.
3. Method according to claim 2, wherein a central region of the growing boule (108,
109. is flushed with nitrogen and/or ammonia gas.
4. Method according to claim 1, wherein the SiC powder source material comprises a dopant enriched material (126) in a region opposite to a central region of the seed crystal with a concentration of the doping element in the dopant enriched material (126) of at least 1.Math.10.sup.20 cm.sup.−3 and wherein a concentration of the doping element in a lower doped outer SiC powder source material is lower than 5.Math.10.sup.17 cm.sup.−3.
5. Method according to claim 1, wherein the growth compartment is delimited by a cylindrical crucible wall and wherein an inner surface (124) of the crucible wall comprises a tantalum, tungsten, niobium, molybdenum and/or hafnium getter layer.
6. Method according to claim 5, wherein said getter layer is formed by a massive metallization layer (130) which has an inner radius which is 2 mm larger than the seed diameter, a thickness in a range from 0.5 mm to 3 mm, and a minimum length that is larger than the length of the finally grown crystal.
7. Method according to claim 5, wherein said getter layer is formed by metal particles (132, 133) as alloy or mixture of tantalum, tungsten, niobium, molybdenum and/or hafnium held in place by a porous graphite cover wall (134, 135) with a bulk density of 1.0 g.Math.cm.sup.−3 to 2.0 g.Math.cm.sup.−3, and a metal particles composition in the range of 0.01 mm to 1 mm.
8. Method according to claim 1, wherein the step of arranging the SiC powder source material in the source material compartment comprises filling in a dopant enriched SiC powder source material (126) and covering an interface between the source material compartment (116) and the growth compartment (118, 119) partly with a dopant filter (136).
9. Method according to claim 1, wherein at least one SiC seed crystal is arranged within each of two growth compartments, wherein said source material compartment is arranged symmetrically between the two growth compartments and is separated from each of the growth compartments by a gas permeable porous membrane.
Description
[0041] The accompanying drawings are incorporated into and form a part of the specification to illustrate several embodiments of the present invention. These drawings together with the description serve to explain the principles of the invention. The drawings are merely for the purpose of illustrating the preferred and alternative examples of how the invention can be made and used and are not to be construed as limiting the invention to only the illustrated and described embodiments. Furthermore, several aspects of the embodiments may form—individually or in different combinations—solutions according to the present invention. Further features and advantages will become apparent from the following more particular description of the various embodiments of the invention, as illustrated in the accompanying drawings, in which like references refer to like elements, and wherein:
[0042]
[0043]
[0044]
[0045]
[0046]
[0047]
[0048]
[0049]
[0050]
[0051] The present invention will now be described in more detail with reference to the
[0052] Figures. Turning first to
[0053] According to the present invention, the circular inner region 102 takes up at least 45%±15% of the total wafer surface. Accordingly, the ring shaped outer region 104 of course also takes up at least 45%±15% of the total wafer surface. As a result, it can be avoided that a tensile ring shaped stress is generated in the peripheral region 104. Rather, in the peripheral region 104, a compressive stress prevails which results in a tensile, radially acting stress in the first region 102. This tensile stress in the first region 102 counteracts a preset deflection due to the growth of convex crystals (or at least reduces this effect).
[0054] By introducing impurity atoms with different mean concentrations in the different first and second regions, mechanical stress can selectively be generated inside the silicon carbide substrate in a way that the thermal tension which is generated during the growth procedure is compensated. As a result, the SiC substrate 100 according to the present invention is low strain or ideally strainless after removal of all near surface disturbing layers by applying the final polishing steps. Consequently, the SiC substrate 100 does not have stress induced geometric errors and therefore has low bow and warp values. This advantageous geometry allows for an excellent thermal coupling of such substrates in an epitaxial reactor, the thermal coupling being decisive for homogeneous high-quality epitaxial layer growth. Furthermore, high-quality electronic components can be fabricated on a substrate according to the present invention. Moreover, also the material loss can be reduced during machining because due to the compensation of stress no distortion is occurring and therefore the material removal is decreased significantly. As already mentioned above, known thick substrates exhibit even with the thermal or mechanical stress low bow and warp values. However, the SiC substrates according to the present invention may have much lower thicknesses and still exhibit excellent geometric characteristics. For instance, ratios of the thickness and the diameter in a range between 0.002 and 0.004 can be achieved.
[0055] The SiC substrate 100 according to the present invention may be distinguished by the following features when providing a nitrogen dopant concentration which is about 5.Math.10.sup.18 cm.sup.−3 higher in the first (inner) region 102 than in the second (outer) region 104: The dimensions may be chosen so that the diameter is 100 mm or even 150 mm or even 200 mm with a wafer thickness of less than 1000 μm and more than 200 μm, for example 350 μm±25 μm. The overall dislocation density as indicated by the etch pit density (EPD) may amount to 50 000 cm.sup.−2, preferably stay below 10 000 cm.sup.−2. The electrical resistivity may be in a range between 12 mΩcm and 26 mΩcm, preferably between 18 mΩcm and 22 mΩcm.
[0056] It could be shown that these SiC substrates have a bow of less than 25 μm, even below 15 μm, and a warp of less than 40 μm, even below 30 μm.
[0057] Depending on the intended subsequent epitaxial layers and on the required optical and semiconductor material properties, the SiC substrate may have one of the more than 200 possible SiC polytypes that have been found up to date. As this known in the art, the most common polytypes include 3C, 2H, 4H, 6H, 8H, 9R, 10H, 14H, 15R, 19R, 20H, 21 H, and 24R, where (C), (H) and (R) are the three basic cubic, hexagonal and rhombohedral crystallographic categories. In the cubic zinc-blende structure, labelled as 3C-SiC or β-SiC, Si and C occupy ordered sites in a diamond framework. In hexagonal polytypes nH-SiC and rhombohedral polytypes nR-SiC, generally referred to as α-SiC, nSi—C bilayers consisting of C and Si layers stack in the primitive unit cell. Preferably, the substrate according to the present invention is of the 4H polytype. Moreover, the orientation of the substrate is between 0° and 8°, preferably 4° off-axis. Polytype and orientation is usually controlled by the orientation of the seed crystal or by tilting during the crystal preparation.
[0058]
[0059] Importantly, it has to be noted that
[0060]
[0061] Physical vapor transport (PVT), also known as seeded sublimation growth, has been the most popular and successful method to grow large sized SiC single crystals. U.S. Pat. No. 8,747,982 B2 describes an advantageous fabrication method that can be used and modified to fabricate SiC substrates according to the present invention.
[0062] A first example of generating a dopant profile in a radial direction during growth of an SiC single crystal 108 will be explained with reference to
[0063]
[0064] The sublimation source 114 is usually a polycrystalline SiC grain or powder synthesized in a separate process. The loaded crucible 112 is placed inside a growth chamber where it is surrounded by the thermal insulation (not shown in the Figures).
[0065] Inductive or resistive heating (not shown in the Figures) is used to bring the crucible 112 to a suitable temperature, generally between 2000° C. and 2400° C. for the PVT growth of a SiC single crystal on the SiC single crystal seed. The growth chamber may for instance be made of fused silica, and an RF coil is positioned with respect to the crucible 112 such that during growth of the single crystal the temperature of the sublimation source 114 is maintained higher than the temperature of the seed crystal (typically with a difference of 10 to 200K).
[0066] Upon reaching a suitably high temperature, the sublimation source 114 vaporizes and fills a growth compartment 118 of the crucible 112 with a vapor of silicon, Si.sub.2C and SiC.sub.2 molecules. The temperature difference between the sublimation source 114 and the seed crystal forces the vapor to migrate and to condense on the seed crystal, thereby forming a growing single crystal boule 108. In order to control the growth rate, PVT growth is typically carried out in the presence of a small pressure of inert gas, usually between 0.1 mbar and 100 mbar.
[0067] In addition to known arrangements as the ones shown in U.S. Pat. No. 8,747,982 B2, the present invention provides a gas inlet 120 which is arranged centrally within the growth compartment 118 in order to provide a directed gas stream 122 that is directed towards a central region of the growing crystal 108. Thereby, a dopant concentration difference occurs between those regions of the growth compartment 118 which are close to an inner wall 124 of the crucible 112 and the central region. By providing a higher dopant concentration close to the center of the growing crystal 108, a higher dopant concentration is built into the growing crystal lattice in the center compared to the concentration that is built in in the peripheral regions. Depending on the particular parameters of the gas stream 122, a concentration profile as shown in
[0068] In the shown embodiment, the gas stream 122 contains nitrogen as a dopant. However, of course, also other suitable gases, e.g. ammonia, can be introduced into the growth compartment 118 via the inlet 120.
[0069]
[0070] The advantage of this embodiment compared to the embodiment shown in
[0071]
[0072] As shown in
[0073] For instance, when using nitrogen as a dopant, the solid getter material 130 may comprise a metal such as tantalum, tungsten, niobium, molybdenum or hafnium or alloys thereof. These elements bind nitrogen irreversibly by forming nitride bonds. Other suitable getter materials may of course also be used. The design of the getter is such that it is in cylindrical shape with a diameter slightly larger than the seed diameter, with a radial gap of 2 mm, preferably with a gap of 1 mm, to be close enough for effective gettering, with a thickness in the range of 0.5 mm to 3 mm, and a minimum length larger than the crystal length maintaining absorption of nitrogen at the crystal rim during the complete crystal growth process.
[0074]
[0075] According to the present invention, the getter particles 132 may comprise one or more nitrogen binding metals such as tantalum, tungsten, niobium, molybdenum or hafnium as alloy or mixture, in a granulated or powdered form. Nitrogen which is present as a dopant in the growth compartment 118 diffuses through the porous graphite wall 134 and irreversibly forms nitride bonds with the getter particles 132. Thereby the lateral nitrogen distribution close to the growth front of the crystal 108 is influenced in a way that less nitrogen is available for being built into the crystal at the margin than within the center of the crystal 108. To balance the getter functionality over the whole time of the crystal growth process, the composition of grain and powder sizes has to be adjusted in the range of 0.01 mm to 1 mm, preferably in the range of 0.05 mm to 0.5 mm, in order to offer an optimized free surface of the getter.
[0076] A concentration profile according to the present invention as shown in
[0077]
[0078] As shown in
[0079] Of course, the ideas according to the embodiments shown in
[0080] As already mentioned above, the production times for growing SiC single crystals may be significantly reduced by simultaneously growing two crystals instead of one. In order to achieve such a simultaneous growth, the principles of European patent EP 2 664 695 B1 may be adapted to the ideas according to the present invention.
[0081] As shown in
[0082] In each of the growth compartments 118, 119 a dopant inlet 121, 123 is arranged in a way that the respective central region of the growth compartments 118, 119 are supplied with a higher concentration of dopant than the peripheral regions.
[0083] In an analogous way as explained with reference to
[0084] By binding a certain amount of the dopant atoms from the peripheral regions of the growth compartments 118, 119, the getter particles 132, 133 generate a concentration gradient of the dopant inside the growth compartments 118, 119. In particular, the dopant concentration, e.g. nitrogen, in the center of the growth compartments 118, 119 is higher than in the peripheral region in order to lead to a higher dopant concentration being built into the growing crystals 108, 109 in their central regions.
[0085] Instead of providing getter particles 134, 133, also a solid getter material as shown in
[0086] According to the present invention, the mean concentration of a dopant in the inner region 102 differs by an absolute value of at least 1.Math.10.sup.18 cm.sup.−3 from the mean concentration of this dopant in the peripheral region 104. When assuming for instance that the mean concentration in the inner region 102 is in a range between 3.Math.10.sup.18 cm.sup.−3 and 3.Math.10.sup.19 cm.sup.−3 and that the mean concentration of the dopant in the peripheral region 104 is lower than in the inner region 102, this would mean that the absolute difference of at least 1.Math.10.sup.18 cm.sup.−3 would correspond to relative differences between 3% and 50% in relation to the mean concentration of the dopant in the peripheral region 104. This relationship can be derived from the following calculation.
[0087] For a mean concentration of the dopant in the inner region of 3.Math.10.sup.19 cm.sup.−3, the mean concentration in the peripheral region is calculated as 3.Math.10.sup.19 cm.sup.−3−1.Math.10.sup.18 cm.sup.−3=2.9 10.sup.19 cm.sup.−3, so that the value of 1.Math.10.sup.18 cm.sup.−3 corresponds to 3%.
[0088] On the other hand, for a mean concentration of the dopant in the inner region of 3.Math.10.sup.18 cm.sup.−3, the mean concentration in the peripheral region is calculated as 3.Math.10.sup.18 cm.sup.−3−1.Math.10.sup.18 cm.sup.−3=2.Math.10.sup.18 cm.sup.−3, so that the absolute value of 1.Math.10.sup.18 cm.sup.−3 corresponds to 50%.
TABLE-US-00001 Reference Numerals: Reference Numeral Description 100 SiC substrate 102 Inner region 104 Outer region 106 Transitional region 108, 109 SiC single crystal boule 110, 210 Growth cell 112 Crucible 114 Sublimation source material 116 Source material compartment 118, 119 Growth compartment 120, 121, 123 Gas inlet 122 Gas stream 124 Inner wall of crucible 126 Dopant enriched source material 128 Stream of dopant 130 Solid getter material 132, 133 Getter particles 134, 135 Porous cover wall 136 Dopant filter