Patent Grant
7294324
The present invention relates to low defect silicon carbide wafers and their use as precursors for semiconductor purposes, and to seeded sublimation growth of large, high-quality silicon carbide single crystals.
The invention is also related to the following copending and commonly assigned U.S. applications Ser. No. 10/628,189 filed Jul. 28, 2003 for Growth of Ultra-High Purity Silicon Carbide Crystals in an Ambient Containing Hydrogen; Ser. No. 10/628,188 filed Jul. 28, 2003 for Reducing Nitrogen Content in Silicon Carbide Crystals by Sublimation Growth in a Hydrogen-Containing Ambient; Ser. No. 10/707,898 filed Jan. 22, 2004 for Silicon Carbide on Diamond Substrates and Related Devices and Methods; Ser. No. 60/522,326 filed Sep. 15, 2004 for Seed Preparation for the Growth of High Quality Large Size Silicon Carbide Crystals; Ser. No. 10/915,095 filed Aug. 10, 2004 for Seed and Seedholder Combinations for High Quality Growth of Large Silicon Carbide Single Crystals; and Ser. No. 10/876,963 filed Jun. 25, 2004 for One Hundred Millimeter High Purity Semi-Insulating Single Crystal Silicon Carbide Wafer. The contents of these applications are likewise incorporated entirely herein by reference.
Silicon carbide has found use as semiconductor material for various electronic devices and purposes in recent years. Silicon carbide is especially useful due to its physical strength and high resistance to chemical attack. Silicon carbide also has excellent electronic properties, including radiation hardness, high breakdown field, a relatively wide band gap, high saturated electron drift velocity, high-temperature operation, and absorption and emission of high-energy photons in the blue, violet, and ultraviolet regions of the spectrum.
Single crystal silicon carbide is often produced by a seeded sublimation growth process. In a typical silicon carbide growth technique, the seed crystal and a source powder are both placed in a reaction crucible which is heated to the sublimation temperature of the source and in a manner that produces a thermal gradient between the source and the marginally cooler seed crystal. The thermal gradient encourages vapor phase movement of the materials from the source to the seed followed by condensation upon the seed and the resulting bulk crystal growth. The method is also referred to as physical vapor transport (PVT).
In a typical silicon carbide growth technique, the crucible is made of graphite and is heated by induction or resistance, with the relevant coils and insulation being placed to establish and control the desired thermal gradient. The source powder is silicon carbide, as is the seed. The crucible is oriented vertically, with the source powder in the lower portions and the seed positioned at the top, typically on the seed holder; see U.S. Pat. No. 4,866,005 (reissued as No. Re34,861) the contents of which are incorporated entirely herein by reference. These sources are exemplary, rather than limiting, descriptions of modern seeded sublimation growth techniques.
Although the density of structural defects in silicon carbide bulk crystals has been continually reduced in recent years, relatively high defect concentrations still appear and have been found to be difficult to eliminate, e.g. Nakamura et al., “Ultrahigh quality silicon carbide single crystals,” Nature, Vol. 430, Aug. 26, 2004, page 1009. When dislocations lying in the basal plane (c-plane) of the crystal exists on the surface of the seed crystal substrate, these dislocations may persist in the subsequent growth of the crystal. These defects can cause significant problems in limiting the performance characteristics of devices made on the substrates, or in some cases can preclude useful devices altogether.
Current seeded sublimation techniques for the production of large bulk single crystals of silicon carbide typically result in a higher than desired concentration of defects on the basal plane growing surface of the silicon carbide crystal. Higher concentrations of defects can cause significant problems in limiting the performance characteristics of devices made on the crystals, or substrates resulting from the crystals. For example, a typical micropipe defect density in the basal plane of some commercially available silicon carbide wafers can be on the order of 100 per square centimeter (cm−2). A megawatt device formed in silicon carbide, however, requires a defect free area on the order of 0.4 cm−2. Thus, obtaining large single crystals that can be used to fabricate large surface area devices for high-voltage, high current applications remain a worthwhile goal.
Although small samples of low-defect silicon carbide have been available, a broader commercial use of silicon carbide requires larger samples, and in particular, larger wafers. By way of comparison, 100 mm (4″) silicon wafers have been commercially available since 1975 and 150 mm (6″) silicon wafers became available in 1981. Gallium arsenide (GaAs) is also commercially available in both 4″ (100 mm) and 6″ (150 mm) wafers. Thus, the commercial availability of 50 mm (2″) and 75 mm (3″) SiC wafers lags behind these other materials and to some extent limits the adoption and use of SiC in a wider range of devices and applications.
The nature and description of specific defects is generally well understood in the crystal growth art. Micropipes are common defects that can be found in SiC and can develop or propagate during the seeded sublimation production of SiC crystals. Other defects that may be present in SiC crystals include threading, edge, and screwdislocations, along with hexagonal voids, stacking faults and basal plane dislocations. If these defects remain in the SiC crystal, then resulting devices grown on the crystal may incorporate these defects.
A micropipe is a hollow core super-screw dislocation with its Burgers vector typically lying along the c-axis. A number of causes have been proposed or identified for the generation of micropipes. These include excess materials such as silicon or carbon inclusions, extrinsic impurities such as metal deposits, boundary defects, and the movement or slippage of partial dislocations. See e.g. Powell et al., Growth of Low Micropipe Density SiC Wafers, Materials Science Forum, Vols. 338-340, pp 437-440 (2000).
Hexagonal voids are flat, hexagonal platelet-shaped cavities in the crystal that often have hollow tubes trailing beneath them. Some evidence shows that micropipes are associated with hexagonal voids. A relatively recent discussion of such defects (exemplary and not limiting) is set forth in Kuhr et al., Hexagonal Voids And The Formation Of Micropipes During SiC Sublimation Growth, Journal of Applied Physics, Volume 89, No. 8, page 4625 (April 2001).
Recent research indicates that problems in the bulk crystals produced in a seeded sublimation technique can originate with the seed itself and the manner in which it is physically handled; e.g., Sanchez et al Formation Of Thermal Decomposition Cavities In Physical Vapor Transport Of Silicon Carbide, Journal of Electronic Materials, Volume 29, No. 3, page 347 (2000). Sanchez uses the term “micropipe” to describe, “approximately cylindrical voids with diameters in the range of 0.1 μm to 5 μm that form at the core of superscrew dislocations aligned parallel or nearly parallel to the [0001] axis” Id. at 347. Sanchez refers to larger voids (“diameters from 5 μm to 100 μm”) as, “thermal decomposition cavities,” and opines that micropipes and thermal decomposition cavities arise from different causes. Id.
Accordingly, producing larger high quality bulk single crystals of silicon carbide with low basal plane defect levels in crystals formed in the seeded sublimation system remains a constant technical commercial goal.
Basal plane dislocations are typically positioned within a (0001) plane either intersecting a surface or creating a closed loop. For most applications the primary concern is the number of basal plane dislocations that will intersect the wafer surface and hence propagate into the subsequently deposited epitaxial layer. When the SiC wafer is to be used as a substrate for epitaxial growth, it is critical to consider the number of dislocations that intersect the wafer surface. This number is measured by conducting a defect etch of the wafer that will reveal pits at the dislocation locations. For this measurement the number of dislocations intersecting the surface will increase as the offcut (“off-axis”) angle from the <0001> direction is increased. Most commercial SiC wafers are presently produced with an offcut angle of 4 degrees, however any other angle can be used from zero to 90 degrees. Counting the number of dislocations (observable as straight or curved lines) in a given representative area gives a representative basal plane defect density.
In the case where the substrate is used as an active device layer, the density of defects in the bulk material is also of concern and the most appropriate measurement is the total line length of basal plane dislocations in a given volume of material. This is measured by considering a small volume of material (such as that contained in a sample for X-ray topography) and measuring the total length of dislocations observed. This length is then divided by the volume of the sample to provide the total line length of basal plane dislocation per cm3.
In one aspect, the present invention is a high quality single crystal wafer of SiC having a diameter of at least about 3 inches (75 mm) and at least one continuous square inch (6.25 cm2) of surface area having a basal plane dislocation density of less than about 200 cm−2.
In another aspect, the invention is a SiC semiconductor precursor wafer having a diameter of at least about 3 inches (75 mm) and at least one continuous square inch (6.25 cm2) of surface area having a basal plane dislocation density of less than about 100 cm−2.
In another aspect, the invention is a method of using a high quality single crystal wafer of SiC having a diameter of at least about 3 inches (75 mm) and at least one continuous square inch (6.25 cm2) of surface area having a basal plane dislocation density of less than about 100 cm−2 in a seeded sublimation growth system.
In yet another aspect, the invention is a plurality of power devices built on a single crystal seed of SiC having a diameter of at least about 3 inches (75 mm) and at least one continuous square inch (6.25 cm2) of surface area having a basal plane dislocation density of less than about 100 cm−2.
The present invention relates to high quality silicon carbide wafers. In particular, the present invention incorporates several techniques for improving the growth of such wafers using seeded sublimation.
In the following description basal plane dislocation densities will be specified as the area density for a 4 degree off-axis wafer. There is, however, an explicit assumption that a direct relationship exists between this area measurement and the total basal plane line length in the material.
In one aspect, the present invention is a high quality single crystal wafer of SiC having a diameter of at least about 3 inches (75 mm) and at least one continuous square inch (6.25 cm2) of surface area having a basal plane dislocation density of less than about 500 cm−2, more preferably less than about 75 cm−2, and most preferably less than about 50 cm−2. The polytype of the single crystal SiC is preferably 3C, 4H, 6H, 2H, or 15R.
In considering the proportional dimensions of the diameter and thickness of the seed crystal, whether expressed as a percentage, a fraction, or a ratio, it will be understood that in the context of the improvements provided by the invention, these proportions have their inventive meaning in the context of the larger-diameter seed crystals that are described herein.
Accordingly, in certain embodiments the invention is described and claimed herein in the relevant embodiments in a manner that includes the absolute dimensions of the crystal, usually in terms of a diameter, of which 2 inch (50 mm), 3 inch (75 mm), and 100 mm diameter single crystals are preferred. More precisely of course, one inch is equal to 25.4 mm, meaning that three inches are equal to 76.2 mm. As is sometimes common in the wafer art, however, terms such as “three inches” and “75 mm” are used interchangeably. Those of ordinary skill in the art will recognize this common practice, along with the substitution of “50 mm” for “two inches,” “100 mm” for “four inches,” etc. These substitutions are not intended to limit the conversion of English to metric units, but are, instead, intended to represent common usage in the art.
The 4 degree offcut sample shown in
In yet another aspect, the invention is a high quality semiconductor precursor wafer of silicon carbide having a 4H polytype, a diameter of at least about 3 inches (75 mm), and having at least one continuous square inch (6.25 cm2) of surface area having between about 2,000 and 20,000 dislocations intersecting the surface of the wafer (for a 4 degree off-axis wafer).
In another aspect as schematically depicted in
The growth and electronic characteristics of Group III nitrides are generally well-understood in this art. Group III nitride layers on silicon carbide substrates are a basic feature of certain types of light emitting diodes (LEDs). Among other desirable factors, the atomic fraction of the Group III element (e.g. InxGayN1-x-y) tailors the bandgap of the composition (within limits) to likewise tailor the resulting emission frequency and thus the color of the LED.
In another aspect, the invention is a method of producing a high quality bulk single crystal of silicon carbide in a seeded sublimation system. In this aspect, the invention includes growing a SiC boule having a diameter of at least about 3 inches (75 mm) and having at least one continuous square inch (6.25 cm2) of surface area with a basal plane dislocation density of less than about 500 cm−2, thereafter slicing the SiC boule, preferably mechanically, into wafers, wherein each wafer has a basal plane dislocation density of less than about 500 cm−2 on at least one continuous square inch (6.25 cm2) of the surface. The wafers are preferably about 0.5 mm thick.
It may be preferable to thin the SiC wafers to highlight defects for x-ray topography. A preferred thickness for counting purposes is about 80 μm. The thinning of the wafer is carried out in order to highlight the defects on the surface, and is unnecessary as a precursor step to seeded sublimation. Thus, sublimation growth is typically carried out on a polished seed that has not been thinned.
As is known in the art, the SiC boule is preferably grown in a seeded sublimation system. After the boule is sliced into wafers, the wafers may then, in turn, be used as the seed in a seeded sublimation growth of a single crystal of silicon carbide.
As noted in the background portion of the specification, the general aspects of seeded sublimation growth of silicon carbide have been generally well established for a number of years. Furthermore, those familiar with the growth of crystals, particularly in difficult material systems such as silicon carbide, will recognize that the details of a given technique can and will vary, usually purposefully, depending upon the relevant circumstances. Accordingly, the descriptions given herein are most appropriately given in a general and schematic sense with the recognition that those persons of skill in this art will be able to carry out the improvements of the invention based on the disclosures herein without undue experimentation.
In describing the invention, it will be understood that a number of techniques are disclosed. Each of these has individual benefit, and each can also be used in conjunction with one or more, or in some cases all, of the other disclosed techniques. Accordingly, for the sake of clarity, this description will refrain from repeating every possible combination of the individual steps in an unnecessary fashion. Nevertheless, the specification and claims should be read with the understanding that such combinations are entirely within the scope of the invention and the claims.
The susceptor 14 is typically surrounded by insulation 18, several portions of which are illustrated in
For purposes of clarity, the singular term, “thermal gradient,” will be used herein, but it will be understood by those of skill in this art that several gradients can desirably co-exist in the susceptor 14 and can be subcategorized as axial and radial gradients, or as a plurality of isotherms.
The susceptor 14 includes one or more portions for containing a silicon carbide powder source 20. Such a powder source 20 is most commonly—although not exclusively—used in seeded sublimation growth techniques for silicon carbide.
A silicon carbide seed is designated at 22, and is typically placed in upper portions of the susceptor 14. The seed 22 is preferably a monocrystalline SiC seed having a diameter of at least about 3 inches (75 mm). A growing crystal 26 is deposited on the seed 22 during the seeded sublimation growth.
A seed holder 28 typically holds the seed 22 in place with the seed holder 28 being attached to the susceptor 14 in an appropriate fashion. This can include various arrangements known in the art. In the orientation illustrated in
In some embodiments, it may be preferred to include dopant atoms in the sublimation system 12. Introducing dopant gases to the seeded sublimation system 12 incorporates dopant atoms in a growing crystal. Dopants are selected for their acceptor or donor capabilities. In a given semiconductor, donor dopants produce n-type conductivity and acceptor dopants produce p-type conductivity. Preferred dopant atoms include n-type and p-type dopant atoms. Especially preferred n-type dopants include N, P, As, Sb, Bi, and mixtures thereof. Especially preferred p-type dopants include B, Al, Ga, In, Tl, and mixtures thereof.
In a typical sublimation growth technique, an electric current, having a frequency to which the susceptor 14 responds, is passed through the induction coils 16 to heat the graphite susceptor 14. The amount and placement of the insulation 18 are selected to create a thermal gradient between the powder source 20 and the growing crystal 26 when the susceptor 14 heats the powder source 20 to sublimation temperatures, which are typically above about 2000° C., preferably between about 2100° C. and about 2500° C. The thermal gradient is established to maintain the temperature of the seed 22 and thereafter a growing crystal near, but below, the temperature of the silicon carbide source to thereby thermodynamically encourage the vaporized species that are generated when silicon carbide sublimes (Si, Si2C, and SiC2) to condense first upon the seed crystal and thereafter upon the growing crystal; e.g., U.S. Pat. No. 4,866,005.
If the temperature gradients and other conditions (pressure, carrier gases, etc.) are properly maintained, the overall thermodynamics will encourage the vaporized species to condense first on the seed 22 and then on the growing crystal 26 in the same polytype as the seed 22.
After reaching the desired crystal size, growth is terminated by reducing the temperature of the system to below about 1900° C. and raising the pressure to above about 400 torr.
It may be further desirable to anneal the crystal after completion of the sublimation growth process. The crystal may be annealed at temperatures at or above the growth temperature for a period greater than about 30 minutes.
As generally noted in the Background, the performance properties of electronic devices will typically improve as the crystal quality of the various device portions improves. Thus, the reduced-defect characteristics of wafers of the present invention similarly provide improved devices. In particular, higher power higher current devices become increasingly available as the basal plane dislocation density on at least one continuous square inch (6.25 cm2) of surface area drops to about 500 cm−2 or below.
Thus, in another aspect, the invention is a plurality of field-effect transistors formed on a low-defect 3 inch (75 mm) silicon carbide wafer having at least one continuous square inch (6.25 cm2) of surface area with a basal plane dislocation density of between about 50 and 500 cm−2.
In another aspect and as schematically illustrated in
With reference to
As is known in the art, more than one type of device may be situated on a silicon carbide wafer in accordance with the present invention. Additional devices that may be included are junction-field effect transistors, hetero field effect transistors, diodes, and other devices known in the art. The structure and operation of these (and other) devices are well-understood in this art and can be practiced using the substrates described and claimed herein without undue experimentation.
In the specification and the drawings, typical embodiments of the invention have been disclosed. Specific terms have been used only in a generic and descriptive sense, and not for purposes of limitation. The scope of the invention is set forth in the following claims.
This application claims benefit of 60/522,366 Sep. 21, 2004.
This invention was developed under Office of Naval Research/DARPA Contract No. N00014-02-C-0302. The government may have certain rights in this invention.
| Number | Name | Date | Kind |
|---|---|---|---|
| 2938136 | Fischer | May 1960 | A |
| 4865685 | Palmour | Sep 1989 | A |
| 4866005 | Davis et al. | Sep 1989 | A |
| 5006914 | Beetz, Jr. | Apr 1991 | A |
| 5030583 | Beetz, Jr. | Jul 1991 | A |
| 5119540 | Kong et al. | Jun 1992 | A |
| 5151384 | Williams | Sep 1992 | A |
| 5210051 | Carter, Jr. | May 1993 | A |
| 5311055 | Goodman et al. | May 1994 | A |
| 5373171 | Imai et al. | Dec 1994 | A |
| 5382822 | Stein | Jan 1995 | A |
| RE34861 | Davis et al. | Feb 1995 | E |
| 5393993 | Edmond et al. | Feb 1995 | A |
| 5422901 | Lebby et al. | Jun 1995 | A |
| 5523589 | Edmond et al. | Jun 1996 | A |
| 5611955 | Barrett et al. | Mar 1997 | A |
| 5661312 | Weitzel et al. | Aug 1997 | A |
| 5667586 | Ek et al. | Sep 1997 | A |
| 5709745 | Larkin et al. | Jan 1998 | A |
| 5718760 | Carter et al. | Feb 1998 | A |
| 5872415 | Dreifus et al. | Feb 1999 | A |
| 5964944 | Sugiyama et al. | Oct 1999 | A |
| 6025289 | Carter, Jr. et al. | Feb 2000 | A |
| 6113451 | Hobart et al. | Sep 2000 | A |
| 6150239 | Goesele et al. | Nov 2000 | A |
| 6156581 | Vaudo et al. | Dec 2000 | A |
| 6196901 | Minami | Mar 2001 | B1 |
| 6200917 | Carter et al. | Mar 2001 | B1 |
| 6201342 | Hobart et al. | Mar 2001 | B1 |
| 6218680 | Carter, Jr. et al. | Apr 2001 | B1 |
| 6316793 | Sheppard et al. | Nov 2001 | B1 |
| 6316826 | Yamamoto et al. | Nov 2001 | B1 |
| 6329088 | Landini et al. | Dec 2001 | B1 |
| 6396080 | Carter, Jr. et al. | May 2002 | B2 |
| 6396864 | O'Brien et al. | May 2002 | B1 |
| 6403982 | Carter, Jr. et al. | Jun 2002 | B2 |
| 6497763 | Kub et al. | Dec 2002 | B2 |
| 6497764 | Kuhn et al. | Dec 2002 | B2 |
| 6507046 | Mueller | Jan 2003 | B2 |
| 6533874 | Vaudo et al. | Mar 2003 | B1 |
| 6548333 | Smith | Apr 2003 | B2 |
| 6568384 | Onizaki | May 2003 | B1 |
| 6583454 | Sheppard et al. | Jun 2003 | B2 |
| 6586781 | Wu et al. | Jul 2003 | B2 |
| 6599815 | Yang | Jul 2003 | B1 |
| 6634770 | Cao | Oct 2003 | B2 |
| 6639247 | Carter, Jr. et al. | Oct 2003 | B2 |
| 6670693 | Quick | Dec 2003 | B1 |
| 6686676 | McNulty et al. | Feb 2004 | B2 |
| 6692568 | Cuomo et al. | Feb 2004 | B2 |
| 6706114 | Mueller | Mar 2004 | B2 |
| 6757314 | Kneissl et al. | Jun 2004 | B2 |
| 6814801 | Jenny et al. | Nov 2004 | B2 |
| 6849874 | Sumakeris et al. | Feb 2005 | B2 |
| 20010017374 | Tsvetkov | Aug 2001 | A1 |
| 20020078881 | Cuomo et al. | Jun 2002 | A1 |
| 20020086534 | Cuomo et al. | Jul 2002 | A1 |
| 20020096104 | Yagi et al. | Jul 2002 | A1 |
| 20020117695 | Borges et al. | Aug 2002 | A1 |
| 20020123204 | Torvik | Sep 2002 | A1 |
| 20020167023 | Chavarkar et al. | Nov 2002 | A1 |
| 20020180351 | McNulty et al. | Dec 2002 | A1 |
| 20020182779 | Bewley et al. | Dec 2002 | A1 |
| 20030096507 | Baker et al. | May 2003 | A1 |
| 20030102482 | Saxler | Jun 2003 | A1 |
| 20030107045 | Eisert et al. | Jun 2003 | A1 |
| 20030127654 | Eisert et al. | Jul 2003 | A1 |
| 20030219959 | Ghyselen et al. | Nov 2003 | A1 |
| 20030233975 | Jenny et al. | Dec 2003 | A1 |
| 20040023468 | Ghyselen et al. | Feb 2004 | A1 |
| 20040051141 | Udrea | Mar 2004 | A1 |
| 20040201024 | Tsvetkov et al. | Oct 2004 | A1 |
| 20040206298 | Jenny et al. | Oct 2004 | A1 |
| 20050022724 | Malta et al. | Feb 2005 | A1 |
| 20050022727 | Fechko et al. | Feb 2005 | A1 |
| 20060011128 | Ellison et al. | Jan 2006 | A1 |
| 20060073707 | Powell et al. | Apr 2006 | A1 |
| Number | Date | Country |
|---|---|---|
| 0 561 462 | Sep 1993 | EP |
| 772 691 | Apr 1957 | GB |
| 3295267 | Dec 1991 | JP |
| 11233391 | Feb 1998 | JP |
| 2002265296 | Sep 2002 | JP |
| 2003037074 | Feb 2003 | JP |
| 2004 099340 | Sep 2005 | JP |
| WO 9000817 | Jan 1990 | WO |
| WO 9728297 | Aug 1997 | WO |
| WO 2006041660 | Apr 2006 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20060075958 A1 | Apr 2006 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60522366 | Sep 2004 | US |
