SiC structure, semiconductor device having SiC structure, and process of forming the same
10283594 ยท 2019-05-07
Assignee
Inventors
- Hiroyuki Nagasawa (Sendai, JP)
- Maki Suemitsu (Sendai, JP)
- Hirokazu Fukidome (Sendai, JP)
- Yasunori Tateno (Yokohama, JP)
- Fuminori Mitsuhashi (Itami, JP)
- Masaya Okada (Itami, JP)
- Masaki Ueno (Itami, JP)
Cpc classification
H01L29/7781
ELECTRICITY
H01L29/786
ELECTRICITY
H01L29/04
ELECTRICITY
H01L21/0262
ELECTRICITY
H01L29/78684
ELECTRICITY
International classification
H01L21/02
ELECTRICITY
H01L29/04
ELECTRICITY
H01L29/786
ELECTRICITY
H01L29/778
ELECTRICITY
H01L29/66
ELECTRICITY
H01L29/06
ELECTRICITY
Abstract
A silicon carbide (SiC) structure and a method of forming the SiC structure are disclosed. The SiC structure includes an SiC substrate and a film provided on the SiC substrate. The SiC substrate contains both of a hexagonal close packed (hcp) structure and a face centered cubic (fcc) structure, and has only one of the hcp surface and the fcc surface, where the hcp surface includes atoms in the topmost layer whose rows overlap with rows of atoms in the third layer, while, the fcc surface includes atoms in the topmost layer whose rows are different from rows of atoms in the third layer.
Claims
1. A silicon carbide (SiC) structure, comprising; a SiC single crystal substrate including both of a hexagonal close packed (hcp) structure and a face centered cubic (fcc) structure; and a film provided on the SiC single crystal substrate, wherein the SiC single crystal substrate has a surface that exposes only one of an hcp surface and a fcc surface, the hcp surface having atoms in a topmost layer whose rows overlap with rows of atoms in a third layer, and the fcc surface having atoms in the topmost layer whose rows are different from rows of atoms in the third layer.
2. The SiC structure of claim 1, wherein the surface of the SiC single crystal substrate has steps on which Si atoms are exposed.
3. The SiC structure of claim 1, wherein the film is made of graphene.
4. The SiC structure of claim 1, wherein the surface of the SiC substrate has a Si-polar surface that exposes Si atoms.
5. A semiconductor device, comprising: a SiC structure including a SiC single crystal substrate having both a hexagonal close packed (hcp) structure and a face centered cubic (fcc) structure, and a surface that exposes only one of an hcp surface and an fcc surface, the hcp surface having atoms in a topmost layer whose rows overlap with of atoms in a third layer, and the fcc surface having atoms in the topmost layer whose rows are different from rows of atoms in the third layer; a film provided on the SiC single crystal substrate; ohmic electrodes provided on the film; and a gate electrode provided on the film and between the ohmic electrodes.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The foregoing and other purposes, aspects and advantages will be better understood from the following detailed description of a preferred embodiment of the invention with reference to the drawings, in which:
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DESCRIPTION OF EMBODIMENT
(16) Next, some examples according to the present invention will be described in referring to drawings. In the description of the drawings, numerals or symbols same with or similar to each other will refer to elements same with or similar to each other without overlapping explanations.
(17) The SiC single crystal alternately stacks the hexagonal close packed (hcp) structure and the face centered cubic (fcc) structure along the crystal orientation of [0001]. Depending on the combination of the stacked structures, the SiC single crystal has more than 250 poly-types. Thus, the SiC single crystal substrate exposes the hcp structure or the fcc structure in a (0001) or a (000-1) crystal plane. The specification below calls a surface that exposes the hcp structure a hcp surface, while, a surface that exposes the fcc structure is called a fcc surface. Details of the hcp surface and the fcc surface will be explained later in the specification.
(18) Many documents have been reported about a surface of the SiC single crystal substrate terminated by silicon atoms or carbon atoms. However, which structures are exposed in the surface of the SiC single crystal substrate, the fcc surface or the hcp surface, has seemed to be not reported as far as inventors know.
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(20) Details of the h-sites and the c-sites will be further specifically described. Referring to
(21) The h-sites, that is, a site sandwiched by two sites having the same type, are called as the hexagonal close packed (hcp) stack 32. On the other hand, the c-site accompanied with two sites sandwiching the c-site and having the types different from each other and also different from the c-site, for example, the first A-row sandwiched by the C-row in the upper side and the B-row in the lower side, or the second appearing A-site sandwiched by the B-row in the upper side and the C-row in the lower side thereof, are collectively called as the face centered cubic (fcc) stack 34.
(22) In the hcp surface 12, the topmost Si atom 18 in the row thereof overlaps with the row of the Si atom 18 in the third topmost layer. For instance, the Si atoms 18 in the topmost layer in the hcp surface 12 position in the A-row, the Si atoms 18 in the second one position in the B-row, and the Si atoms 18 in the third one also exist in the A-row. On the other hand, in the fcc surface 14, the topmost Si atoms in the rows thereof are different from the rows of the Si atoms 18 in the third topmost layer. For instance, in the fcc surface 14, the topmost Si atoms 18 exist in the C-row, the Si atoms 18 in the second topmost layer exist in the A-row, and the Si atoms 18 in the third topmost layer exist in the B-row. When atoms existing in the topmost layer are carbon (C), that is, when the surface is the C-polar surface, the positional relations of the C atoms 16 show the relationship same with those for the Si atoms 18. The hcp surface 12 and the fcc surface 14 both become the closest packed surface. It is hard or almost impossible for the whole surface of the SiC substrate 10 to be flat within a range of one atom. The surface of the SiC substrate 10 inevitably shows steps accompanied with the hcp surfaces 12 and the fcc surfaces. The film 20 provided on the surface of the SiC substrate 10 is in contact with both of the hcp surface 12 and the fcc surface 14.
(23) Because the fcc stack 34 shows an inversion symmetry, while, the hcp stack 32 shows no inversion symmetry; the hcp stack 32 causes a spontaneous polarization but the fcc stack 34 causes no spontaneous polarization. This means that charge density on the hcp surface 12 becomes different from the charge density on the fcc surface 14. Inhomogeneous charge density results in non-uniform distribution in electric fields, which causes a non-uniform Schottky barrier height, local variation in the threshold voltage of a MOSFET, and/or reduction of carrier mobility because of increased scattering of the carrier in the channel of the MOS FET or in an active layer grown on the SiC substrate.
(24) One of types of the SiC single crystal often denoted as 3C-SiC type may realize a structure where the film 20 is in contact with only the fcc surface 14.
(25) Another type denoted as the 2H-SiC provides only the hcp surface 12 shown in
(26) However, the former type, 3C-SiC, shows relatively smaller bandgap energy, accordingly, it is inadequate for forming a device with a high breakdown voltage and also for an application where a substrate with high resistivity is required. Also, the latter type, 2H-SiC, is hard to produce with enough reproducibility. A SiC substrate with types of 4H-SiC and 6H-SiC are preferably available in the field; but these types stack the h-sites and the c-sites by a predetermined order. In such types, it is hard or impossible to get the topmost surface flat enough within one atomic range and have only one type.
(27) The present invention provides an SiC substrate with a film provided thereon, where the SiC substrate has only one type, the fcc surface or the hcp surface, but has substantial steps.
(28) Next, embodiment of the present invention will be described.
(29) First Embodiment
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(35) As shown in
(36) The first embodiment provides the SiC single crustal substrate that includes both the fcc stack 32 and the hcp stack 34, like the 4H-SiC substrate and/or 6H-SiC substrate, and the film 20 made of material except for SiC. The surface of the SiC single crystal substrate 10, with which the film is in contact, exposes only one of the hcp surface 12 and the fcc surface 14. Accordingly, the SiC substrate 10 may make the surface electrical potential uniform. For instance, when a MOSFET is formed with a gate insulating layer made of film 20, such a surface with a uniform electrical potential distribution may suppress localized variation in a threshold voltage of the MOSFET. When the film 20 is a Schottky metal, Schottky barrier height may be controlled. Also, carrier scattering due to the electrical potential distribution in the channel of a MOSFET or in the film 20 on the SiC substrate 10, for instance, a graphene layer, may be suppressed, which means the carrier mobility increases.
(37) The SiC single crystal layer may be the SiC single crystal substrate 10 itself or a SiC layer grown on the substrate 10. The film 20 may be a film such as those made of silicon oxide (SiO), silicon nitride (SiN), and silicon oxy-nitride (SiON), or a film primarily made of carbon or silicon, or a metal film. The film 20 also may be made of two-dimensional material such as graphene film.
(38) As
(39) A surface at least 90% thereof preferably shows the fcc surface 14 or the hcp surface 12 in order to show the function according to the present invention. A surface at least 95% thereof is one of the fcc surface 14 and the hcp surface 12 is further preferable.
(40) Second Embodiment
(41) The second embodiment according to the present invention relates to a process of forming the SiC structure; specifically, the process of forming the fcc surface 14 of the SiC substrate by etching.
(42) Because the SiC substrate 10 in surface thereof is not completely flat; steps appear in the surface thereof. Sides of the steps expose carbon atoms 16 or silicon atoms 18. In
(43) It is known in the field that surface energy Ec of the C-step is higher than surface energy E.sub.Si of the Si-step. For instance, Journal of Crystal Growth published in 1984 in pages 30 to 40 of volume 70 has reported this fact. Accordingly, etching the SiC substrate 10, or exposing the surface thereof in an oxidizing atmosphere, the C-steps are primarily etched or oxidized as shown in arrows indicated in
(44) The velocity v.sub.Si, or the etching rate, of the Si-step and that of the C-step are denoted as v.sub.Si=Aexp(E.sub.Si/k/T) and v.sub.C=Bexp(E.sub.C/k/T), respectively where A and B are constants, k is a Boltzmann constant, and T is an absolute temperature. In order to get the fcc surface 14, a ratio of the velocity vc against the velocity v.sub.Si is preferably larger; that is, v.sub.C/v.sub.Si=A/Bexp((E.sub.SiE.sub.C)/k/T) becomes larger. Accordingly, the temperature T of the process is preferably set lower. However, a lower temperature T decreases absolutes of the velocities, vc and vsi. Thus, the temperature of the process is necessary to be determined taking a process time, namely, etching time of the process.
(45) An example to obtain the fcc surface of the SiC substrate 10 will be explained by exposing the SiC substrate 10 in hydrogen (H.sub.2) atmosphere. When the temperature of the exposure exceeds 1500 C., the etching velocity vc of the C-step and that v.sub.Si becomes comparable. The process first prepares a 4H-SiC substrate with (0001) crystal surface as the topmost surface. This SiC substrate 10 is exposed in H.sub.2 atmosphere at a temperature of 500 C. Under such a temperature, the C-step is promptly etched compared with the Si-step as shown in
(46) The process described above may be similarly applicable to another SiC substrate with the 6H-SiC type. Also, the temperature for exposing H.sub.2 atmosphere is preferably lower than 600 C. Oppositely, in order to shorten the process time with securing substantial etching, the process temperature is preferably higher than 300 C. The H.sub.2 atmosphere may contain inactive gases of, for instance, nitrogen (N.sub.2), helium (He), argon (Ar), neon (Ne), xenon (Xe), and mixtures of those gases. The H.sub.2 atmosphere in a pressure thereof is not restricted to an atmospheric pressure.
(47) Third Embodiment
(48) The third embodiment of the present invention relates to a process of forming the fcc surface 14 on the SiC substrate by growing the SiC.
(49) The growth velocity r.sub.Si of the Si-step is denoted as r.sub.Si=exp (E.sub.Si/k/T), while, that r.sub.C of the C-step is denoted as r.sub.C=exp (E.sub.C/k/T), where and are constants, k is the Boltzmann constant, and T is an absolute temperature. In order to obtain the fcc surface 14, a ratio of the former velocity r.sub.C against the latter one r.sub.Si is preferably larger, that is, r.sub.C/r.sub.Si=/exp(E.sub.SiE.sub.C)/k/T) becomes larger. Similar to the aforementioned embodiment, the process temperature is preferably lowered to enhance the ratio. However, a lower process temperature T results in reduction of the absolute growth rate of the C-step and the Si-step. Also, a lower growth temperature causes inferior quality of grown layers. Accordingly, the growth temperature of the C-step is necessary to be determined taking those effects into account.
(50) An example will be described. The process first prepares a 4H-SiC substrate whose topmost surface is inclined to the [11-20] crystal orientation from (0001) surface. Such an inclined surface causes steps in the topmost surface. Growing SiC layer on such a surface at a temperature of 1650 C. by the aforementioned step controlling epitaxy and flowing silane (SiH.sub.4), propane (C.sub.3H.sub.8), and hydrogen (H.sub.2) by respective flow rates of 20 sccm, 13 sccm, and 2 slm, the SiC layer is epitaxially grown on the SiC substrate 10. Because the C-step promptly grows laterally on the surface compared with the Si-step, and the lateral growth of the C-step effectively stops when it is aligned with the Si-step, the SiC substrate 10 shows the fcc surface 14 on the topmost thereof, as shown in
(51) In an alternative, the process prepares a SiC substrate with a topmost surface thereof inclined by 4 toward [11-20] crystal orientation from (0001) surface thereof. Similar to the process above described, the step controlling epitaxy may grow the SiC layer so as to form the fcc surface 14 in the topmost thereof. Covering the topmost surface of the SiC substrate with the film 20, the SiC structure shown in
(52) The growth temperature for the SiC layer is preferably lower than 1700 C. to enhance the ratio r.sub.C/r.sub.Si of the growth rates for the C-step and the Si-step, respectively. Also, from absolute growth rates thereof, the growth temperature is preferably higher than 1450 C. Flow rates of the source gases of silane (SiH.sub.4) and propane (C.sub.3H.sub.8), and that of the carrier gas of hydrogen (H.sub.2) may be optional.
(53) Thus, the second embodiment and the third embodiment may form the topmost surface of the SiC single crystal substrate 10, which contains both the hexagonal close packed cells and the face centered cubic unit cells, having only one of the hcp surface 12 and the fcc surface 14. The topmost surface of the substrate 10 thus formed may appear the fcc surface 14. The topmost surface of the SiC substrate 10 becomes the Si-polar surface because of lowered surface energy of silicon (Si) compared with carbon (C). Covering this topmost surface by the film 20 so as to be in direct contact therewith, the SiC structure of the first embodiment may be obtained. The topmost surface of the film 20 becomes parallel to the topmost surface of the SiC substrate 10.
(54) The process has an etching condition where one of the C-step and the Si-step may be promptly etched compared with the other of the C-step and the Si-step. Thus, the process may form the topmost surface of the SiC substrate 10 exposing only one of the hcp surface 12 and the fcc surface 14. The etching temperature for the SiC substrate 10 is preferably between 300 to 600 C. Also, the process has a growth condition where one of the C-step and the Si-step promptly grows compared with the other of the C-step and the Si-step, which may also form the topmost surface of the SiC substrate having only one of the hcp surface and the fcc surface.
(55) Fourth Embodiment
(56) The fourth embodiment according to the present invention relates to a process of forming a graphene layer on a SiC substrate. Sublimating Si on the topmost of the SiC substrate by a process disclosed in the first non-patent document, a graphene layer may be formed on the SiC substrate. Forming an odd number of graphene layers on the 4H-SiC substrate 10 whose topmost surface is the fcc surface 14, the topmost surface of the SiC substrate 10 becomes the hcp surface 12. Also, forming an even number of graphene layers on the 4H-SiC substrate 10 whose topmost surface is the fcc surface 14, the topmost surface of the SiC substrate 10 becomes the fcc surface 14. Thus, a graphene layer 20 may be formed on the SiC substrate 10 with the fcc surface 14.
(57) The number of graphene layers depends on the sublimation of Si atoms from the SiC surface. The sublimation of Si atoms may be suppressed as the temperature becomes lower and the vapor pressure of Si becomes lower. Accordingly, precisely controlled temperature and the Si vapor pressure in atmosphere may form a mono layer or double layers of the graphene on the SiC substrate 10. Forming the mono layer of the graphene on the 4H-SiC substrate 10 with the fcc surface 14, the graphene in contact with the hcp surface 12 may be obtained; while, forming the double layer of the graphene on the 4H-SiC substrate 10 with the fcc surface 14, the graphene in contact with the fcc surface 14 may be obtained. Thus, the carrier mobility within the graphene increases because of a uniform distribution of the electrical field within the SiC substrate 10. Also, the graphene may enhance the quality thereof.
(58) Such a graphene may be obtained by exposing the SiC substrate 10 at a temperature of 1600 C. within argon (Ar) atmosphere; that is, the sublimation of Si atoms may be carried out at the temperature of 1600 C. Temperatures from 1600 to 1800 C. may be applicable for forming the graphene. Also, the sublimation may be carried out within an atmosphere of, not only Ar, but nitrogen (N.sub.2), and other noble and inactive gases, or within a vacuum.
(59) A graphene formed by the sublimation of Si atoms may enhance the layer quality, or may reduce defected induced within the formed graphene. Also, the formed graphene is in contact with only one of the hcp surface 12 and the fcc surface 14 of the SiC substrate 10, which makes the surface distribution of the electrical field homogeneous in the SiC substrate 10 and enhances the carrier mobility in the graphene.
(60) Fifth Embodiment
(61) The fifth embodiment according to the present invention relates to a process of forming a film on the hcp surface of the SiC substrate 10.
(62) Sixth Embodiment
(63) The sixth embodiment according to the present invention relates to a semiconductor device.
(64) The topmost layer of the SiC substrate that is in direct contact with the graphene layer 20a is formed by only one of the hcp surface 12 and the fcc surface 14. Thus, the carrier mobility of electrons and/or holes within the graphene layer 20a may be enhanced.
(65) In an alternative, an electronic device implementing the SiC substrate 10 may be a type of MOSFET having a gate insulating film made of film 20 on the SiC substrate 10, which involves the SiC structure of the first embodiment of the present invention. When the film 20 plays a role of the gate insulating film, the channel formed beneath the film 20 may enhance the carrier mobility thereof and the MOSFET with the film 20 as the gate insulating film may suppress local variations in the threshold voltage thereof. On the other hand, when the film 20 is a type of Schottky metal, the barrier height of the Schottky metal may be uniform.
EXAMPLE
(66) An example of obtaining an SiC substrate having only one type, the fcc surface or the hcp surface, but accompanied with substantial steps will be described. An SiC substrate with the 4H-SiC type, where the SiC substrate had the Si-polar surface, was first treated in hydrogen (H.sub.2) under conditions of: within a pure hydrogen (H.sub.2) without any noble or inert gases at an atmospheric pressure, a temperature of 500 C., and a period of 300 minutes. A surface of the sample was compared before and after the hydrogen (H.sub.2) treatment by the atomic force microscope (AFM).
(67) Although the surface after the treatment, as shown in
(68) Next, a graphene was formed on the SiC substrates one of which was not treated in hydrogen (H.sub.2), while, the other was treated in hydrogen (H.sub.2). The graphene was formed by exposing the SiC substrates in conditions of: argon (Ar) atmosphere in an atmospheric pressure, a temperature of 1600 C., and a period of 10 minutes. The Raman spectroscopy took two peeks, one of which was the G-band around 1590 cm.sup.1, while, the other was the D-band around 1350 cm.sup.1, where the former peak is due to the sp2 bond of carbon (C) atoms forming the six-membered ring, while, the latter corresponds to a case when the six-membered ring forms a dangling bond, namely, the imperfect six-membered ring. When a ratio of the latter peak against the former peak D/G increases, defects involved in the graphene become larger.
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(70) While particular embodiments of the present invention have been described herein for purposes of illustration, many modifications and changes will become apparent to those skilled in the art. Accordingly, the appended claims are intended to encompass all such modifications and changes as fall within the true spirit and scope of this invention.
(71) The present application claims the benefit of priority of Japanese Patent Application 2016-172296, filed on Sep. 2, 2016, which is incorporated herein by reference.