BULK GROWTH OF SILICON-CARBIDE CRYSTALS

By: Arka Majumdar Dept. of Electronics & Electrical Communication Engineering, Indian Institute of Technology, Kharagpur

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Bulk Growth of SiC crystal

OVERVIEW OF THE TALK:

Why Silicon Carbide Why Bulk Growth Different processes of bulk growth Dopant incorporation Defects associated with bulk growth Comparative study of different processes

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Bulk Growth of SiC crystal

WHY SILICON CARBIDE??

Almost all the semiconductor devices are made of Si. In room temperature and low frequency possibly no alternative of Si. Easily available , easily integrable leading to VLSI technology. But high power and high frequency operation-Si has limitations. Material scientists feel the need of another semiconductor-enter SiC.

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VIRTUE OF SiC OVER Si

Wide band-gap : SiC - 2.2-3.4eV Si - 1.1eV 1. High temperature can be reached. Si - 300 oC SiC - 1000 oC 2. SiC has optical detection capability in the UV range. But SiC is indirect band-gap Semiconductor-GaN is mainly used in commercially available LEDs. Less sensitive to high wavelength suitable for certain sensor applications.
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VIRTUE OF SiC OVER Si

High electric field advantage due to high impact ionization energy. Si 0.3MV/cm (critical field) SiC 4 MV/cm (critical field) V=EW/2; W-depletion layer width Critical electric field is obtained in depletion layer. 4. High frequency the device can be made smaller for same breakdown voltage and relative dielectric constant is lower than Si hence less parasites. Low ON-resistance in SiC. R=4V2/E3=W/qN
3.
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VIRTUE OF SiC OVER Si

5. High electron saturation drift velocity. Si 107 cm/sec SiC 2.7x107 cm/sec Smaller devices the determining factor is saturation drift velocity. 6. Si not a good thermal conductor. Hence the device gets heated fast. Si 1.3 W/cmoc SiC 5 W/cmoc
All these figures given for SiC are average values as they differ in polytype to polytepes

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Bulk Growth of SiC crystal

STILL Si!!!

At room temperature and ordinary operation Si cannot be replaced by SiC. High cut-in voltage at room-temperature (1.3 V); less mobility . SiC is 12% ionic and hence may cause problem. Applicable for certain specific applications like space where high power and high frequency is involved.

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Bulk Growth of SiC crystal

DEVICE TECHNOLOGY

Steps towards device technology : Bulk Growth Epitaxial Growth Ion implantation Metallization Device Modeling

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Bulk Growth of SiC crystal

WHY BULK GROWTH??

We require a substrate (in any semiconductor technology): To provide mechanical strength-minimum thickness is application dependent. To take contacts. Heat transfer to save the device. To form the epi-layer crystalline continuity should be maintained and matching of thermal expansion coefficient is required.

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Bulk Growth of SiC crystal

GROWTH TECHNIQUES

Bulk crystal growth is the technique for fabrication of single crystalline substrates , making the base for further device processing. To have a breakthrough in SiC technology obviously we need production of SiC substrate with a reproducible process. Today substrates up to 50 mm in diameter are commercially available and 100 mm substrate has been reported. Several methods are used for bulk growth.

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ACHESON PROCESS
Conceived by Acheson in 1891. A mixture of silica, carbon, sawdust and common salt (e.g. 50% silica, 40% coke, 7% sawdust and 3% common salt) is heated in an electric furnace .The heating is accomplished by a core of graphite and coke placed centrally in the furnace. The mixture of reactants is placed around this core. The mixture is then heated to reach a maximum temperature of approximately 2700o C, after which the temperature is gradually lowered. Sawdust makes mixture porous and NaCl is a purifier.
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ACHESON PROCESS

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LELY PROCESS
Developed in the year of 1955 by Lely. Lump of SiC are kept in the furnace. The crucible is heated to approximately 2500o C in an atmosphere of argon at atmospheric pressure. On the top and bottom of the cylinder a thick dense layer of SiC is formed. The quality of these crystals can be very high, however the yield of the process is low, the sizes irregular, the shape of the crystals is normally hexagonal and there exists no polytype control. Best crystalline quality can be very useful for further epitaxial growth.

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LELY PROCESS

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MODIFIED LELY PROCESS

Developed by Tairov and Tsvetkov in 1978. Also known as seeded sublimation method. SiC powder or lumps of SiC are placed inside a cylindrical graphite crucible. The crucible is heated to approximately 2200o C normally in an Ar atmosphere at a pressure below atmospheric pressure. A temperature gradient (typically 20-40o C/cm) is applied over the length of the crucible in such a way that the SiC powder at the bottom of the crucible is at a higher temperature than the seed crystal. The growth rate is largely governed by the temperature, the quality of the seed, the pressure and the temperature gradient . Easily controllable , high yield and definite size.
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MODIFIED LELY PROCESS

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MODIFIED LELY PROCESS

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MODIFIED LELY PROCESS

This method is today used for fabrication of most SiC substrates. The technique has been employed by other groups. In 1987 Cree Research Inc. was founded and substrates made by the seeded sublimation growth technique became commercially available in 1991. Reactions: SiC2 (g) + Si2C (g) 3SiC (s) SiC2 (g) + 3Si (g) 2 Si2C (g) Si2C (g) C (s) + 2 Si (g) Si (g) Si (l)

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COMPARISON
The width of the rocking curve is a direct measure of the range of orientation present in the irradiated area of the crystal, as each sub grain of the crystal will come into orientation as the crystal is rotated.

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LIQUID PHASE EPITAXY

SiC can be grown by dissolving C in liquid Si. Difficult to melt Si (100000 bar & 3200oC ). Solubility of C in Si is 15% at 2800oC. By adding rare earth metal (Sc, Tb, Pr) the solubility becomes 50%. High Si vapor pressure(0.25 bar at 2300oC) can be combated by applying high pressure of an inert gas (e.g. Ar). The furnace is resistively heated and thermally insulated by graphite. Rotation of the melt is applied to ensure radial homogeneity of growth. The driving force for crystal growth is a slow cooling , leading to a continuously reduced solubility of C in Si and a following nucleation of a solid SiC phase on the seed crystal. Growth rate is low (0.5 m/h). Polytype stability & low density of micro-pipes.

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LIQUID PHASE EPITAXY

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HIGH TEMPERATURE CHEMICAL VAPOR DEPOSITION (HTCVD)

Growth takes place in a vertical reactor made of graphite. Seed is placed in the top and instead of a solid source the growth species consist of a stagnant supply of Si and C containing precursors (silane and propane) diluted in a carrier gas. By letting the precursors pass into a cracking zone , preferably heated by walls of reactor enclosure, reactive radicals are formed before reaching the seed. The temperature in the cracking zone - slightly higher than that of the seed in order to maintain a supersaturation in the gas phase at the surface of the seed.
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HIGH TEMPERATURE CHEMICAL VAPOR DEPOSITION (HTCVD)

Reactor walls are coated with SiC , not graphite to avoid graphite evaporation and to avoid the release of the impurities bound to graphite. He a carrier gas high thermal conductivity and low density. Growth rate obtained 0.5-0.8 mm/h at a sufficiently high precursor concentration, reactor pressure of 200800 mbar and a seed temperature 2000-2300oC. Growth temperature , carrier gas , super-saturation, precursor purity , C:Si ratio can be chosen independently.
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HIGH TEMPERATURE CHEMICAL VAPOR DEPOSITION (HTCVD)

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DOPANT INCORPORATION:
Can be doped during Bulk Growth. Nitrogen n type; Aluminum p type. N2 incorporation is independent of growth rate and proportional to square root of vapor pressure.(1017 1021 cm-3). The N incorporation is 2-3 times higher for growth on the C face than Si face but at 2300oc but this difference decreases with temperature. Al incorporation is higher in Si face(5-10 times). But that difference also decreases with temperature. Doping incorporation is also sensitive to small variation in crystallographic orientation.
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CHALLENGES OF SiC GROWTH

Several polytypes. Impurities. Defects: Micro-pipe Formation Dislocation

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POLYTYPES
A special form of polymorphism. The occurrence of a given compound in more than one crystal structure is known as polymorphism. Polytypes differ in stacking. In 2-D within the sheet there is no difference between the different polytypes. Not all polytypes are stable. The stability of different polytypes can be explained in two ways kinetics and thermodynamics. There are meta-stable polytypes also.

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POLYTYPES
As the electronic, chemical as well as mechanical properties of different SiC polytypes are totally different hence single polytype growth is required. During growth a mixture of polytypes is produced. Some important polytypes are discussed in next slide. C-cubic H-Hexagonal R-Rhombohedral

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SOME POLYTYPES

3C-SiC (Zincblende): Low-temperature stable. Transforms to 6H-SiC (or sometimes 15R-SiC) at a high temperature (above 2000 o C). 2H-SiC (Wurtzite): Low-temperature stable. Rarely obtained because of less thermal stability than even 3C-SiC at a high temperature. 4H-SiC, 6H-SiC: High-temperature stable. Bulk crystal is obtainable by sublimation method, which has promoted researches of these polytypes. 8H, 15R, 21R, ... more than 200 polytypes are reported. 4-D representation.
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SOME POLYTYPES
Stacking Order of 6H-SiC Stacking Order of 4H-SiC

Perio dicity is the main differ ence here

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IMPURITY
Impurity depends on the source of SiC used. No process has inherent mechanisms to remove impurities. Generally heavy metals (like Sc) may be there as impurity. They form deep layer and the mobility is affected. Sometimes deliberately impurities are introduced to change the property. Like vanadium produces deep level in the band-gap acting as trap for holes. Hence intentional doping of V is done to make a semiinsulating material.
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DEFECTS: MICROPIPE FORMATION

Hollow core defects with a typical diameter of 1-10m. Micro-pipe density is reduced now from more than 1000 cm-2 to less than 1 cm-2. Micro-pipe reduces the effective area for usage. Theories for micro-pipe production: Incorporation of an inclusion (graphite particle or a Si droplet). It hinders the surface mobility of growth process. Center of a screw dislocation with a large Burgers vector- the diameter of micro-pipe is dependent on the magnitude of the Burgers vector.

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DEFECTS: MICROPIPE FORMATION

Optical micrographs taken from a SiC layer grown by LPE with filled micropipes:transmission light focused below the layer surface.

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DEFECTS: MICROPIPE CLOSING

Appropriate way to reduce micro-pipes in the growing crystal is through accurate control of the growth parameters, keeping the conditions for nucleation stable at the growing surface and hence avoiding deposition of liquid or solid phases. 1995 micro-pipe existing in the substrates can be closed during LPE. The actual internal chemical process is not yet been known. The micro-pipe closing process is stable and irreversible under thermal treatment.

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DEFECTS: MICROPIPE CLOSING

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DEFECTS: MICROPIPE CLOSING

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DEFECTS:DISLOCATION
Line discontinuity in the regular crystal structure . Two basic types: Edge dislocations, and Screw dislocations. Edge dislocation : insertion (or removal) of an extra half plane of atoms in the crystal structure. Screw Dislocation : changes the character of the atom planes. The atom planes no longer exist separately from each other. They form a single surface, like a screw thread, which "spirals" from one end of the crystal to the other.

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DEFECTS:DISLOCATION
In the average crystal structure, there are ~1012 m of dislocation lines per m3 of crystal. Combinations of edge and screw dislocations are often formed as edge dislocations can be formed by branching off a screw dislocation. Cannot end inside crystal has to end in a close line or in the surface. Magnitude of Burgers vector is a measure of dislocation energy. Burgers vector can be found out be Transmission Electron Microscope. Defects in bulk can propagate in epi-layer.
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DEFECTS:DISLOCATION

Screw Dislocation
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Edge Dislocation

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EDGE & SCREW DISLOCATION:PROPERTIES

Burgers Vector in an Edge Dislocation is Perpendicular to dislocation line Burgers Vector in a Screw Dislocation is Parallel to dislocation line. Edge Dislocation moves in a direction perpendicular to the dislocation line. Screw dislocation moves in a direction perpendicular to dislocation line. Slip Step in an edge dislocation occurs in the direction of dislocation motion. Slip Step in a screw dislocation occurs perpendicular to dislocation motion.
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DEFECTS: MICROPIPE & DISLOCATION

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DEFECTS: MICROPIPE & DISLOCATION

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COMPARISON OF DIFFERENT PROCESSES:

Technique and Parameter Growth Rate Boule Diameter Boule Length Defect Control Impurities Stability/Control Equipment Cost Process Cost Maturity Potential
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Seeded Sublimation Medium Good Good Medium Medium Medium Medium Good Very Good Good

LPE Bad Medium Bad Very Good Medium Medium Very Bad Good Very Bad Medium

HTCVD Bad Medium Medium Medium Very Good Good Bad Bad Bad Good
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Bulk Growth of SiC crystal

SUMMARY
A new way to combat high frequency and high power requirement. But Si is still indispensable. Seeded sublimation growth is the best technique. LPE and HTCVD have lots of potential for defect minimization and in near future can be a good competitor of Seeded sublimation growth. But only good bulk growth does not guarantee device fabrication. Epitaxial growth and ion-implantation is also important.

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REFERENCES:
Process Technology for Silicon Carbide Devices; edited by Carl-Mikael Zetterling www.ndt-ed.org www.ecn.purdue.edu www.ifn.liu.se Naval Research Reviews, Vol. 51, No. 1 Silicon Carbide Electronic Devices P. G. Neudeck High growth rate epitaxy of SiC: growth process and structural quality; Mikael Syvjrvi

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