WO2008053627A1 - OHMIC ELECTRODE FOR SiC SEMICONDUCTOR, METHOD FOR MANUFACTURE OF OHMIC ELECTRODE FOR SiC SEMICONDUCTOR, SEMICONDUCTOR DEVICE, AND METHOD FOR MANUFACTURE OF SEMICONDUCTOR DEVICE - Google Patents
OHMIC ELECTRODE FOR SiC SEMICONDUCTOR, METHOD FOR MANUFACTURE OF OHMIC ELECTRODE FOR SiC SEMICONDUCTOR, SEMICONDUCTOR DEVICE, AND METHOD FOR MANUFACTURE OF SEMICONDUCTOR DEVICE Download PDFInfo
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- WO2008053627A1 WO2008053627A1 PCT/JP2007/065816 JP2007065816W WO2008053627A1 WO 2008053627 A1 WO2008053627 A1 WO 2008053627A1 JP 2007065816 W JP2007065816 W JP 2007065816W WO 2008053627 A1 WO2008053627 A1 WO 2008053627A1
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 420
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 35
- 229910052737 gold Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 171
- 239000010931 gold Substances 0.000 description 75
- 238000010438 heat treatment Methods 0.000 description 64
- 230000003746 surface roughness Effects 0.000 description 29
- 239000000758 substrate Substances 0.000 description 23
- 230000003628 erosive effect Effects 0.000 description 20
- 238000004544 sputter deposition Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 6
- 238000001771 vacuum deposition Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910021332 silicide Inorganic materials 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 4
- 229910018540 Si C Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/0445—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising crystalline silicon carbide
- H01L21/048—Making electrodes
- H01L21/0485—Ohmic electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/45—Ohmic electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to an SiC (Chemical Carbide) semiconductor ohmic electrode, a method of manufacturing an SiC semiconductor ohmic electrode, a semiconductor device, and a method of manufacturing a semiconductor device.
- SiC Chemical Carbide
- SiC semiconductors have a band gap of about 3 times, a breakdown voltage of about 10 times, an electron saturation speed of about 2 times, and a thermal conductivity of about 3 times that of Si (silicon) semiconductors.
- semiconductor devices such as electronic devices using SiC semiconductors are being developed because they have characteristics that are not found in semiconductors.
- Non-Patent Document 1 Korean 'Co-edited by Sadafumi Yoshida, “Basics and Applications of SiC Devices”, Ohmsha, March 2003, p. 116-p. 118
- An electrode made of Ni (nickel) has been disclosed as an electrode that can take the above.
- Non-Patent Document 1 describes a stacked body of a Ti (titanium) layer and an A1 (aluminum) layer as an electrode that can make ohmic contact with a p-type SiC semiconductor (the A1 layer is in contact with the p-type SiC semiconductor). ) Is disclosed. Furthermore, in Non-Patent Document 1, by using an electrode made of thin Ni as an electrode capable of making ohmic contact with both n-type SiC semiconductor and p-type SiC semiconductor, n-type SiC semiconductor and p-type SiC are used. It is disclosed that electrodes can be formed simultaneously on a semiconductor.
- Non-Patent Document 1 Kazuo Arai 'Co-edited by Sadafumi Yoshida, “Basics and Applications of SiC Devices”, Ohmsha, March 2003, p. 116—p. 118
- the object of the present invention is to make an ohmic contact with both an n-type SiC semiconductor and a p-type SiC semiconductor, and to reduce the occurrence of surface roughness of the electrode.
- An object of the present invention is to provide an SiC semiconductor ohmic electrode, a method of manufacturing an SiC semiconductor ohmic electrode, a semiconductor device using the SiC semiconductor ohmic electrode, and a method of manufacturing the semiconductor device.
- the present invention is an ohmic electrode for SiC semiconductor containing Si and Ni. With such a configuration, it is possible to make an ohmic contact with both the n-type SiC semiconductor and the p-type SiC semiconductor, reduce the occurrence of surface roughness of the electrode, and reduce the erosion of the SiC semiconductor. Power S can be.
- the ratio of the number of Si atoms to the number of Ni atoms (number of Si atoms / number of Ni atoms) in the ohmic electrode for SiC semiconductor of the present invention is preferably 0.9 or more and 1.1 or less. .
- the present invention is an ohmic electrode for a SiC semiconductor containing Si and Ni and further containing Au (gold) or Pt (platinum). Even with such a configuration, it is possible to make ohmic contact with both the n-type SiC semiconductor and the p-type SiC semiconductor, reduce the occurrence of surface roughness of the electrode, and erode the SiC semiconductor. Can be reduced.
- the ohmic electrode for SiC semiconductor of the present invention includes a mixed layer of Si and Ni formed on a SiC semiconductor, a metal layer made of Au or Pt formed on the mixed layer, and a metal layer. And a Ni layer formed on the substrate.
- the present invention also includes a step of forming S leakage on the SiC semiconductor, a step of forming a Ni layer on the Si layer, and a step of heat-treating the stacked body of the Si layer and the Ni layer.
- This is a method for producing an SiC semiconductor electrode.
- the n-type SiC semiconductor and p It is possible to produce an ohmic electrode for a SiC semiconductor that can make ohmic contact with both of the type SiC semiconductor, reduce the occurrence of surface roughness of the electrode, and reduce the erosion of the SiC semiconductor.
- the ratio between the number of Si atoms constituting the Si layer and the number of Ni atoms constituting the Ni layer (number of Si atoms)
- the number of / Ni atoms is preferably 0.9 or more and 1.1 or less.
- the present invention is also a method for producing an ohmic electrode for SiC semiconductor, comprising a step of forming a mixed layer of Si and Ni on the SiC semiconductor and a step of thermally treating the mixed layer. Even with such a configuration, it is possible to achieve ohmic contact with both n-type and p-type SiC semiconductors, reduce the occurrence of electrode surface roughness, and reduce erosion of SiC semiconductors. It is possible to manufacture an ohmic electrode for SiC semiconductor.
- the ratio of the number of Si atoms to the number of Ni atoms in the mixed layer is 0.9 or more 1 1 or less is preferable.
- the present invention also includes a step of forming the first INi layer on the SiC semiconductor, a step of forming a metal layer composed of an Au layer or a Pt layer on the first INi layer, and a second Ni layer on the metal layer.
- a method for producing an ohmic electrode for a SiC semiconductor comprising: a step of forming; and a step of heat-treating a laminate of an INi layer, a metal layer, and a second Ni layer. Even with this configuration, it is possible to make ohmic contact with both the n-type SiC semiconductor and the p-type SiC semiconductor, reduce the occurrence of surface roughness of the electrode, and reduce the erosion of the SiC semiconductor. Can produce ohmic electrodes for SiC semiconductors.
- the present invention also includes a step of forming S leakage on the SiC semiconductor, a step of forming the INi layer on the Si layer, and a metal layer made of an Au layer or a Pt layer on the INi layer. Manufacturing a second N leakage on the metal layer, and a step of heat-treating the stacked body of the Si layer, the first N leakage, the metal layer, and the second N leakage. Is the method. Even with such a configuration, it is possible to achieve ohmic contact with both n-type and p-type SiC semiconductors, reduce the occurrence of electrode surface roughness, and reduce erosion of SiC semiconductors. It is possible to manufacture an ohmic electrode for SiC semiconductor.
- the Si of the Si layer is formed.
- the ratio of the number of atoms to the number of Ni atoms constituting the INi layer is preferably 0.9 or more and 1.1 or less.
- the present invention also includes a step of forming a mixed layer of Si and Ni on a SiC semiconductor, a step of forming a metal layer composed of an Au layer or a Pt layer on the mixed layer, and a Ni layer on the metal layer.
- a method for producing an ohmic electrode for a SiC semiconductor comprising: a step of forming a layer; and a step of heat-treating a laminate of a mixed layer, a metal layer, and a Ni layer. Even with such a configuration, it is possible to make ohmic contact with both the n-type SiC semiconductor and the p-type SiC semiconductor, reduce the occurrence of surface roughness of the electrode, and erode the SiC semiconductor.
- An ohmic electrode for SiC semiconductor can be manufactured.
- the ratio of the number of Si atoms to the number of Ni atoms in the mixed layer is 0.9 or more. 1. It is preferably 1 or less.
- the present invention is a semiconductor device having a p-type SiC semiconductor region and an n-type SiC semiconductor region, wherein the above-mentioned ohmic electrode for SiC semiconductor is formed on the p-type SiC semiconductor region, and the n-type SiC
- This is a semiconductor device in which the above-mentioned SiC semiconductor ohmic electrode is formed on a semiconductor region.
- the force S can be used to simultaneously form electrodes that make ohmic contact with each of the p-type SiC semiconductor region and the n-type SiC semiconductor region.
- the present invention performs 1S simultaneously with the formation of the above-mentioned SiC semiconductor ohmic electrode on the p-type SiC semiconductor region and the above-mentioned formation of the SiC semiconductor ohmic electrode on the n-type SiC semiconductor region.
- a method for manufacturing a semiconductor device With this configuration, it is possible to make ohmic contact with both the n-type SiC semiconductor and the p-type SiC semiconductor, reduce the occurrence of surface roughness of the electrode, and reduce the erosion of the SiC semiconductor.
- an electrode having ohmic contact with each of the p-type SiC semiconductor region and the n-type SiC semiconductor region can be formed at the same time.
- an SiC semiconductor ohmic electrode it is possible to make ohmic contact with both the n-type SiC semiconductor and the p-type SiC semiconductor, reduce the occurrence of surface roughness of the electrode, and reduce the erosion of the SiC semiconductor.
- An SiC semiconductor ohmic electrode, a method of manufacturing an SiC semiconductor ohmic electrode, a semiconductor device using the SiC semiconductor ohmic electrode, and a method of manufacturing the semiconductor device can be provided.
- FIG. 1 is a schematic cross-sectional view of a preferred example of an ohmic electrode for SiC semiconductor according to the present invention.
- FIG. 2 is a schematic cross-sectional view for illustrating a preferred example of a method for producing an SiC semiconductor ohmic electrode of the present invention.
- FIG. 3 is a schematic cross-sectional view for illustrating another preferred example of the method for producing the SiC semiconductor ohmic electrode of the present invention.
- FIG. 4 is a schematic cross-sectional view for illustrating another preferred example of the method for producing the SiC semiconductor ohmic electrode of the present invention.
- FIG. 5 is a schematic cross-sectional view for illustrating another preferred example of the method for producing the SiC semiconductor ohmic electrode of the present invention.
- FIG. 1 shows a schematic cross-sectional view of a preferred example of the SiC semiconductor ohmic electrode of the present invention.
- the SiC semiconductor ohmic electrode 2 is formed on the SiC semiconductor 1, and the SiC semiconductor ohmic electrode 2 makes ohmic contact with the SiC semiconductor 1! /.
- the conductivity type of the SiC semiconductor 1 may be either n-type or p-type.
- the Si layer 3 is formed on the SiC semiconductor 1.
- the Si layer 3 can be formed by a conventionally known method such as a vapor deposition method or a sputtering method.
- the Ni layer 4 is formed on the Si layer 3.
- the Ni layer 4 can be formed by a conventionally known method such as vapor deposition or sputtering.
- the stacked body of the Si layer 3 and the Ni layer 4 is heat-treated by being heated.
- the stacked body of the Si layer 3 and the Ni layer 4 is silicided, and the SiC semiconductor ohmic electrode 2 shown in FIG. 2 (c) containing Si and Ni is formed.
- Silicidation means the formation of an alloy of Si and a metal other than Si!
- the ratio of the number of Si atoms constituting Si layer 3 to the number of Ni atoms constituting Ni layer 4 is 0.9 or more and 1.1 or less. It is preferable that it is 0.95 or more and 1.05 or less. If the ratio of the number of Si atoms constituting Si layer 3 to the number of Ni atoms constituting Ni layer 4 (number of Si atoms / number of Ni atoms) is less than 0.9, the above heat treatment There is a risk that the SiC semiconductor 1 may be eroded, and if it is larger than 1, a part of the Si layer 3 may remain unreacted after the heat treatment.
- the ratio of the number of Si atoms constituting the Si layer 3 to the number of Ni atoms constituting the Ni layer 4 (the number of Si atoms / the number of Ni atoms) is 0.95 or more and 1.05 or less.
- the Si C semiconductor 1 is not eroded by the heat treatment, and there is a tendency that a homogeneous Si C semiconductor ohmic electrode 2 in which Si and Ni are uniformly dispersed as a whole can be formed.
- the ratio of the number of Si atoms to the number of Ni atoms (number of Si atoms / number of Ni atoms) in the SiC semiconductor ohmic electrode 2 is preferably 0.9 or more and 1.1 or less. It is more preferably 0.95 or more and 1.0 or less 5 or less.
- the ratio of the number of Si atoms to the number of Ni atoms in the SiC semiconductor ohmic electrode 2 is less than 0.9, several types of SiC semiconductor ohmic electrodes 2 are used.
- the SiC semiconductor ohmic electrode 2 may become a heterogeneous alloy layer consisting of silicide and unreacted Si. .
- the ratio of the number of Si atoms to the number of Ni atoms in the SiC semiconductor ohmic electrode 2 (Si If the number of atoms of Ni / the number of Ni) is 0.95 or more and 1.05 or less, a homogeneous SiC semiconductor ohmic electrode 2 in which Si and Ni are uniformly dispersed as a whole can be formed. is there.
- the ratio of the number of Si atoms to the number of Ni atoms (number of Si atoms / number of Ni atoms) in the ohmic electrode 2 for SiC semiconductor is 0.9 or more and 1.1 or less, especially 0.9. If it is 1.05 or less, the surface roughness of the SiC semiconductor ohmic electrode 2 tends to decrease. Therefore, the contact resistance between the surface of the SiC semiconductor ohmic electrode 2 and the wiring metal layer formed on the surface decreases, and the adhesion strength between the SiC semiconductor ohmic electrode 2 and the wiring metal layer tends to increase. It is in.
- the total thickness of the Si layer 3 and the Ni layer 4 is preferably not less than 50 nm and not more than lOOnm. If the total thickness of the Si layer 3 and Ni layer 4 is less than 50 nm, the formed SiC semiconductor ohmic electrode 2 may not cover the entire electrode formation region. If the total thickness of the Ni layer 4 and the Ni layer 4 exceeds lOOnm, the resistance of the SiC semiconductor ohmic electrode 2 may increase.
- the heat treatment temperature of the laminate of the Si layer 3 and the Ni layer 4 is preferably 900 ° C or higher, more preferably 950 ° C or higher. If the heat treatment temperature of the laminate of Si layer 3 and N-leakage 4 is less than 900 ° C, silicidation may be insufficient during the formation of SiC semiconductor ohmic electrode 2, and Si layer 3 and Ni layer When the heat treatment temperature of the laminated body of 4 is 950 ° C. or higher, silicidation tends to be sufficiently performed during the formation of the SiC semiconductor ohmic electrode 2.
- the heat treatment temperature of the laminate of S leakage 3 and Ni layer 4 is preferably 1100 ° C or less.
- the SiC semiconductor ohmic electrode 2 may be damaged.
- the heat treatment temperature of the Si layer 3 and Ni layer 4 stack When the temperature is 1050 ° C. or lower, damage to the SiC semiconductor ohmic electrode 2 tends to be reduced.
- the heat treatment time of the laminate of the Si layer 3 and the Ni layer 4 is preferably 1 minute or more and 5 minutes or less. If the heat treatment time of the laminate of Si layer 3 and Ni layer 4 is less than 1 minute, silicidation may be insufficient during formation of the ohmic electrode 2 for SiC semiconductor. If the heat treatment time of the Ni layer 4 laminate exceeds 5 minutes, the SiC semiconductor ohmic electrode 2 may be damaged.
- the thus obtained ohmic electrode 2 for SiC semiconductor can make ohmic contact with both the n-type SiC semiconductor and the p-type SiC semiconductor, and the occurrence of surface roughness of the electrode is reduced.
- the erosion of the SiC semiconductor 1 can be reduced.
- the Si layer 3 and the Ni layer 4 are stacked and then heat-treated to form the SiC semiconductor ohmic electrode 2.
- the Si target and the Ni target are used.
- this mixed layer is heat-treated to silicidize the mixed layer to form an ohmic electrode 2 for SiC semiconductor containing Si and Ni You can also
- the thickness of the mixed layer is preferably 50 nm or more and lOOnm or less. If the thickness of the mixed layer is less than 50 nm, the formed SiC semiconductor ohmic electrode 2 may not cover the entire electrode formation region. If the thickness exceeds lOOnm, the SiC semiconductor ohmic electrode 2 Resistance may increase.
- the ratio of the number of Si atoms to the number of Ni atoms (number of Si atoms / number of Ni atoms) in the mixed layer is preferably 0.9 or more and 1.1 or less. It is more preferably 0.95 or more and 1.05 or less.
- the ratio of the number of Si atoms to the number of Ni atoms in the above mixed layer is less than 0.9, several SiC ohmic electrodes 2 are used.
- the SiC semiconductor ohmic electrode 2 may become an inhomogeneous alloy layer consisting of silicide and unreacted Si. There is.
- the ratio of the number of Si atoms to the number of Ni atoms (number of Si atoms / number of Ni atoms) in the above mixed layer is 0.9 or more and 1.1 or less, especially 0.9 or more and 1 If it is less than 05, the surface roughness of the SiC semiconductor ohmic electrode 2 tends to decrease. Therefore, the contact resistance between the surface of the SiC semiconductor ohmic electrode 2 and the wiring metal layer formed on the surface is small. At the same time, the adhesive strength between the SiC semiconductor ohmic electrode 2 and the wiring metal layer tends to increase.
- the heat treatment temperature of the mixed layer is preferably 900 ° C or higher, more preferably 950 ° C or higher. If the heat treatment temperature of the mixed layer is less than 900 ° C, silicidation may be insufficient during the formation of the SiC semiconductor ohmic electrode 2, and the heat treatment temperature of the mixed layer is 950 ° C or higher. In this case, silicidation tends to be sufficiently performed during the formation of the SiC semiconductor ohmic electrode 2.
- the heat treatment temperature of the mixed layer is preferably 1100 ° C or lower, more preferably 1050 ° C or lower! /. If the heat treatment temperature of the above mixed layer is higher than 1100 ° C !, the SiC semiconductor ohmic electrode 2 may be damaged, and the heat treatment temperature of the above mixed layer is 1050 ° C or less There is a tendency that damage to the ohmic electrode 2 for SiC semiconductor can be reduced.
- the heat treatment time of the mixed layer is preferably 1 minute or more and 5 minutes or less. If the heat treatment time of the mixed layer is less than 1 minute, silicidation may be insufficient during the formation of the SiC semiconductor ohmic electrode 2, and the heat treatment time of the mixed layer exceeds 5 minutes. In some cases, the SiC semiconductor ohmic electrode 2 may be damaged.
- an INi layer 4 a is formed on the SiC semiconductor 1.
- the first Ni layer 4a can be formed by a conventionally known method such as vapor deposition or sputtering.
- the Au layer 5 is formed on the INi layer 4a.
- the Au layer 5 can be formed by a conventionally known method such as vapor deposition or sputtering.
- a second Ni layer 4b is formed on the Au layer 5.
- the second Ni layer 4b can be formed by a conventionally known method such as vapor deposition or sputtering.
- the laminated body of the INi layer 4a, the Au layer 5, and the second Ni layer 4b is heat-treated by being heated.
- the SiC semiconductor ohmic electrode 2 shown in FIG. 3 (d) containing Si and Ni and further containing Au is formed.
- the thickness of the second Ni layer 4b is preferably not less than 50 nm and not more than lOOnm. If the thickness of the second Ni layer 4b is less than 50 nm, the formed SiC semiconductor ohmic electrode 2 may not cover the entire electrode forming region, and if it exceeds lOOnm, the resistance of the SiC semiconductor ohmic electrode 2 is reduced. May grow.
- the thickness of the Au layer 5 is preferably 20 nm or more and 30 nm or less. If the thickness force of the Au layer 5 is less than 3 ⁇ 4 Onm, Si may diffuse into the second Ni layer 4b through the Au layer 5 and the second Ni layer 4b may be silicided. The resistance of the SiC semiconductor ohmic electrode 2 may increase.
- the heat treatment temperature of the laminate of the INi layer 4a, the Au layer 5 and the second Ni layer 4b is preferably 900 ° C or higher, more preferably 950 ° C or higher. If the heat treatment temperature of the 1N leakage 4a, Au layer 5 and 2Ni layer 4b stack is less than 900 ° C, silicidation may be insufficient during the formation of the SiC semiconductor ohmic electrode 2, When the heat treatment temperature of the laminated body of the INi layer 4a, the Au layer 5 and the second Ni layer 4b is 950 ° C. or higher, silicidation tends to be sufficiently performed when the SiC semiconductor ohmic electrode 2 is formed.
- the heat treatment temperature of the laminate of the INi layer 4a, the Au layer 5 and the second Ni layer 4b is preferably 1100 ° C or less, and more preferably 1050 ° C or less. If the heat treatment temperature of the laminated body of the INi layer 4a, Au layer 5 and 2Ni layer 4b is higher than 1100 ° C, the SiC semiconductor ohmic electrode 2 may be damaged, and the INi layer 4a and Au When the heat treatment temperature of the laminate of the layer 5 and the second Ni layer 4b is 1050 ° C. or lower, damage to the SiC semiconductor ohmic electrode 2 tends to be reduced.
- the heat treatment time of the laminate of the INi layer 4a, the Au layer 5 and the second Ni layer 4b is 1 minute or more and 5 minutes or less. Preferably it is below. If the heat treatment time of the laminate of the INi layer 4a, the Au layer 5 and the second Ni layer 4b is less than ⁇ minutes, silicidation may be insufficient during the formation of the SiC semiconductor ohmic electrode 2, and the INi layer 4a and the Au layer 5 in the case where the heat treatment time of the stack of the 2Ni layer 4b exceeds 5 minutes is a fear force s SiC semiconductor for Omikku electrode 2 may be damaged.
- the thus obtained ohmic electrode 2 for SiC semiconductor is composed of an n-type SiC semiconductor and a p-type
- a Pt layer may be formed. This is because the Pt layer is not silicided like the Au layer 5. At this time, the thickness of the Pt layer is preferably 20 nm or more and 30 nm or less for the same reason as in the case where the Au layer 5 is used.
- S leakage 3 is formed on SiC semiconductor 1.
- the first INi layer 4 a is formed on the S leakage 3.
- a second Ni layer 4b is formed on the Au layer 5.
- the stacked body of the Si layer 3, the INi layer 4a, the Au layer 5, and the second Ni layer 4b is heat-treated by being heated.
- the SiC semiconductor ohmic electrode 2 shown in FIG. 4 (e) containing Si and Ni and further containing Au is formed.
- the thus obtained ohmic electrode 2 for SiC semiconductor comprises an n-type SiC semiconductor and a p-type
- Si diffuses from the Si layer 3 in contact with the SiC semiconductor 1 by the heat treatment.
- Si layer 3 and INi layer 4a are silicided.
- Au layer 5 is not silicided. Therefore,
- the heat treatment temperature of the laminated body of the Si layer 3, the INi layer 4a, the Au layer 5, and the second Ni layer 4b is preferably 900 ° C or higher, more preferably 950 ° C or higher.
- the heat treatment temperature of the laminate of Si layer 3, INi layer 4a, Au layer 5, and second Ni layer 4b is less than 900 ° C, silicidation at the time of forming the ohmic electrode 2 for SiC semiconductor is insufficient. If the heat treatment temperature of the stack of Si layer 3, INi layer 4a, Au layer 5, and second Ni layer 4b is 950 ° C or higher, silicidation during formation of ohmic electrode 2 for SiC semiconductors Tend to be fully implemented.
- the heat treatment temperature of the laminate of the Si layer 3, the INi layer 4a, the Au layer 5, and the second Ni layer 4b is preferably 1100 ° C or less, more preferably 1050 ° C or less. . If the heat treatment temperature of the stack of Si layer 3, INi layer 4a, Au layer 5, and second Ni layer 4b is higher than 1100 ° C, the ohmic electrode 2 for Si C semiconductor may be damaged. If the heat treatment temperature of the laminate of the INi layer 4a, the Au layer 5 and the second Ni layer 4b is 1050 ° C. or less, the damage to the SiC semiconductor ohmic electrode 2 tends to be reduced.
- the heat treatment time of the laminated body of the Si layer 3, the INi layer 4a, the Au layer 5, and the second Ni layer 4b is preferably 1 minute or more and 5 minutes or less. If the heat treatment time of the stack of Si layer 3, INi layer 4a, Au layer 5, and 2Ni layer 4b is less than 1 minute, silicidation may be insufficient during formation of SiC semiconductor ohmic electrode 2 If the heat treatment time of the laminate of the Si layer 3, the INi layer 4a, the Au layer 5, and the second Ni layer 4b exceeds 5 minutes, the SiC semiconductor ohmic electrode 2 may be damaged.
- a mixed layer 6 of Si and Ni is formed on SiC semiconductor 1 by, for example, simultaneously sputtering a Si target and a Ni target.
- the ratio of the number of Si atoms to the number of Ni atoms in the mixed layer 6 (the number of Si atoms / The number of Ni atoms is preferably 0.9 or more and 1.1 or less for the same reason as described in Embodiment 1 above, but is 0.9 or more and 1.05 or less. Is more preferred.
- the Au layer 5 is formed on the mixed layer 6.
- the Ni layer 4 is formed on the Au layer 5.
- the laminated body of the mixed layer 6, the Au layer 5, and the Ni layer 4 is heat-treated by being heated.
- the mixed layer of Si and Ni is silicided to form the SiC semiconductor ohmic electrode 2 shown in FIG. 5 (d) including the mixed layer of Si and Ni, the Au layer, and the Ni layer.
- the heat treatment temperature of the laminate of the mixed layer 6, the Au layer 5 and the Ni layer 4 is preferably 900 ° C or higher, more preferably 950 ° C or higher. If the heat treatment temperature of the laminate of mixed layer 6, Au layer 5 and Ni layer 4 is less than 900 ° C, silicidation may be insufficient during formation of SiC semiconductor ohmic electrode 2, and the mixed layer When the heat treatment temperature of the laminated body of 6, Au layer 5 and N leakage 4 is 950 ° C or higher, silicidation tends to be sufficiently performed during the formation of the SiC semiconductor ohmic electrode 2.
- the heat treatment temperature of the laminate of the mixed layer 6, the Au layer 5, and the Ni layer 4 is preferably 1100 ° C or lower, more preferably 1050 ° C or lower. If the heat treatment temperature of the laminate of mixed layer 6, Au layer 5 and Ni layer 4 is higher than 1100 ° C, ohmic electrode 2 for SiC semiconductors may be damaged, and mixed layer 6, Au layer 5 and Ni layer When the heat treatment temperature of the laminate 4 is 1050 ° C or lower, damage to the SiC semiconductor ohmic electrode 2 tends to be reduced.
- the heat treatment time of the laminate of the mixed layer 6, the Au layer 5 and the Ni layer 4 is preferably 1 minute or more and 5 minutes or less. If the laminated body of Au 6, Au 5 and Ni 4 is less than the heat treatment time, the silicidation may be insufficient during the formation of the SiC semiconductor ohmic electrode 2. In addition, if the heat treatment time of the laminate of Au layer 5 and Ni layer 4 exceeds 5 minutes, the SiC semiconductor ohmic electrode 2 may be damaged.
- the thus obtained ohmic electrode 2 for SiC semiconductor can make ohmic contact with both the n-type SiC semiconductor and the p-type SiC semiconductor, and the generation of surface roughness of the electrode is reduced.
- the erosion of the SiC semiconductor 1 can be reduced.
- the SiC semiconductor ohmic electrode of the present invention obtained as described above can be suitably used for a semiconductor device having a p-type SiC semiconductor region and an n-type SiC semiconductor region.
- the SiC semiconductor ohmic electrode of the present invention makes ohmic contact with each of the p-type SiC semiconductor region and the n-type SiC semiconductor region. Therefore, in the manufacturing process of the semiconductor device described above, after exposing the p-type SiC semiconductor region and the n-type SiC semiconductor region, respectively, the P-type SiC semiconductor region and the n-type SiC semiconductor region are exposed. By simultaneously forming the ohmic electrodes for SiC semiconductor of the present invention in each case, the electrode forming process can be simplified.
- a semiconductor device of the present invention for example, a junction field effect transistor, a MOS field effect transistor or a bipolar transistor can be cited.
- an n-type 4H—SiC semiconductor layer is epitaxially grown on a 2 inch diameter 4H—SiC semiconductor substrate with a thickness of 2 am and a p-type 4H—SiC semiconductor layer with a thickness of 2 ⁇ m.
- the n- type 4H—SiC semiconductor layer was doped with nitrogen as an n-type impurity, and the n-type impurity concentration in the n-type 4H—SiC semiconductor layer was 1.4 ⁇ 10 19 cm ⁇ 3 .
- the p-type 4H—SiC semiconductor layer was doped with aluminum as a p-type impurity, and the p-type impurity concentration in the p-type 4H—SiC semiconductor layer was 5.0 ⁇ 10 18 cm ⁇ 3 .
- a Si layer was formed to a thickness of 48 nm on the surface of each of the n-type 4H—SiC semiconductor layer and the p-type 4H—SiC semiconductor layer by a sputtering method.
- a Ni layer having a thickness of 26 nm was formed on the Si layer by sputtering.
- the number of Si atoms constituting the Si layer and Ni constituting the Ni layer The ratio of this to the number of atoms was measured by Auger electron spectroscopy.
- the resist pattern is removed by lift-off, and the n-type 4H—SiC semiconductor layer and the p-type are removed.
- a stack of patterned Si and Ni layers was formed on each surface of the 4H—SiC semiconductor layer.
- a 4H- SiC semiconductor substrate having an n-type 4H- SiC semiconductor layer formed with a Si layer and Ni layer stack, and a p-type 4H- SiC semiconductor formed with a Si layer and Ni layer stack Each 4H—SiC semiconductor substrate having a layer was placed in a chamber and heat-treated by heating at 1000 ° C. for 2 minutes in an argon atmosphere. As a result, the electrode of Example 1 containing Si and Ni was formed on the surface of each of the n-type 4H—SiC semiconductor layer and the p-type 4H—SiC semiconductor layer.
- Si and Ni targets are simultaneously sputtered on the surface of each of the n-type 4H—SiC semiconductor layer and the p-type 4H—SiC semiconductor layer, thereby simultaneously forming Si and Ni.
- the mixed layer was formed with a thickness of 80 nm.
- the ratio of the number of Si atoms and the number of Ni atoms constituting the mixed layer separately formed under the same method and under the same conditions as this mixed layer was measured by the Auger electron spectroscopy.
- the Si atoms constituting the mixed layer The ratio of the number of atoms to the number of Ni atoms (number of Si atoms / number of Ni atoms) was confirmed to be 1.03.
- the resist pattern is removed by lift-off, and the n-type 4H—SiC semiconductor layer and the p-type
- a mixed layer containing Si and Ni patterned on each surface of the 4H—SiC semiconductor layer was formed.
- a 4H- SiC semiconductor substrate having an n-type 4H- SiC semiconductor layer formed with a mixed layer containing Si and Ni and a 4H- SiC semiconductor substrate having a p-type 4H- SiC semiconductor layer respectively in the chamber Then, heat treatment was performed by heating at 1000 ° C for 2 minutes in an argon atmosphere. As a result, the electrodes of Example 2 containing Si and Ni were formed on the surfaces of the n-type 4H—SiC semiconductor layer and the p-type 4H—SiC semiconductor layer, respectively.
- Example 2 formed on the surface of the n-type 4H-SiC semiconductor layer was obtained.
- the current voltage of the electrode of Example 2 formed on the surfaces of the n-type 4H-SiC semiconductor layer and the p-type 4H-SiC semiconductor layer by passing a current between the electrodes of Example 2 adjacent to each other Special Sex was measured respectively.
- the displacement of the electrode of Example 2 formed on the surface of the n-type 4H-SiC semiconductor layer and the electrode of Example 2 formed on the surface of the p-type 4H-SiC semiconductor layer was reduced! / Even though it was confirmed to show ohmic characteristics.
- an INi layer having a thickness of 50 nm was formed on the surface of each of the n-type 4H—SiC semiconductor layer and the p-type 4H—SiC semiconductor layer by vacuum evaporation.
- an Au layer with a thickness of 30 nm was formed on the INi layer by vacuum deposition.
- a second Ni layer having a thickness of 50 nm was formed on the Au layer by vacuum deposition.
- the resist pattern is removed by lift-off, and the n-type 4H—SiC semiconductor layer and the p-type are removed.
- a 4H— SiC semiconductor substrate having an n-type 4H—SiC semiconductor layer and a 4H—having a p-type 4H—SiC semiconductor layer on which a laminate composed of an INi layer, an Au layer, and a second Ni layer is formed.
- Each SiC semiconductor substrate was placed in a chamber and heat-treated by heating at 1000 ° C for 2 minutes in an argon atmosphere.
- the electrode of Example 3 containing Si and Ni and further containing Au was formed on the surface of each of the n-type 4H—SiC semiconductor layer and the p-type 4H—SiC semiconductor layer.
- Example 3 formed on the surface of the n-type 4H—SiC semiconductor layer was obtained.
- a Si layer having a thickness of 48 nm was formed on the surface of each of the n-type 4H—SiC semiconductor layer and the p-type 4H—SiC semiconductor layer by a sputtering method.
- an INi layer having a thickness of 26 nm was formed on the Si layer by sputtering.
- the number of Si atoms constituting the Si layer and the Ni content constituting the INi layer are The ratio to the number of atoms was measured by Auger electron spectroscopy.
- both the Si layer and the INi layer formed on the surface of the n-type 4H-SiC semiconductor layer and the Si layer and the INi layer formed on the surface of the p-type 4H-SiC semiconductor layer It was confirmed that the ratio of the number of Si atoms constituting the Si layer to the number of Ni atoms constituting the INi layer (number of Si atoms / number of Ni atoms) was 1.02.
- the resist pattern is removed by lift-off, and the n-type 4H—SiC semiconductor layer and the p-type
- a layered body consisting of a patterned Si layer, INi layer, Au layer, and 2Ni layer was formed.
- a 4H- SiC semiconductor substrate having an n-type 4H-SiC semiconductor layer and a p-type 4H- SiC semiconductor layer on which a laminate composed of a Si layer, a first N leakage, an Au layer, and a second Ni layer is formed.
- Each 4H—SiC semiconductor substrate is placed in a chamber and placed in an argon atmosphere at 1000 ° C for 2 minutes. Heat treatment was performed with heating in between.
- the electrode of Example 4 containing Si and Ni and further containing Au was formed on the surface of each of the n-type 4H—SiC semiconductor layer and the p-type 4H—SiC semiconductor layer.
- Example 4 formed on the surface of the n-type 4H-SiC semiconductor layer was obtained.
- Si and Ni targets are simultaneously sputtered on the surface of each of the n-type 4H—SiC semiconductor layer and the p-type 4H—SiC semiconductor layer, thereby simultaneously forming Si and Ni.
- the mixed layer was formed with a thickness of 80 nm.
- the ratio of the number of Si atoms and the number of Ni atoms constituting the mixed layer separately formed under the same method and under the same conditions as this mixed layer was measured by the Auger electron spectroscopy.
- the Si atoms constituting the mixed layer The ratio of the number of atoms to the number of Ni atoms (number of Si atoms / number of Ni atoms) was confirmed to be 1.03.
- Ni layer having a thickness of 50 nm was formed on the Au layer by vacuum deposition.
- the resist pattern was removed by lift-off, and the n-type 4H—SiC semiconductor layer and p-type On each surface of the 4H—SiC semiconductor layer, a layered product composed of the above mixed layer, Au layer and Ni layer was formed.
- a 4H-SiC semiconductor substrate having an n-type 4H-SiC semiconductor layer on which a laminate composed of the mixed layer, Au layer and Ni layer is formed, the mixed layer, the Au layer and the Ni layer is used.
- a 4H—SiC semiconductor substrate having a P-type 4H—SiC semiconductor layer on which the laminate was formed was placed in a chamber, and heat-treated by heating at 1000 ° C. for 2 minutes in an argon atmosphere.
- the electrode of Example 5 containing Si and Ni and further containing Au was formed on the surface of each of the n-type 4H—SiC semiconductor layer and the p-type 4H—SiC semiconductor layer.
- Example 5 formed on the surface of the n-type 4H-SiC semiconductor layer was obtained.
- a Ni layer having a thickness of lOOnm was formed on the surface of each of the n-type 4H—SiC semiconductor layer and the p-type 4H—SiC semiconductor layer by vacuum evaporation.
- the resist pattern was removed by lift-off, and the n-type 4H—SiC semiconductor layer and p-type
- a patterned Ni layer was formed on each surface of the 4H—SiC semiconductor layer.
- the n-type 4H-SiC semiconductor layer and the p-type 4H-SiC semiconductor layer on which the Ni layer was formed were placed in a chamber, and heated at 1000 ° C for 2 minutes in an argon atmosphere. The Heat treatment was performed. Thus, the electrode of Comparative Example 1 containing Ni was formed on the surface of each of the n-type 4H—SiC semiconductor layer and the p-type 4H—SiC semiconductor layer.
- the electrodes of Examples;! To 5 are ohmic electrodes with respect to the SiC semiconductor.
- the present invention it is possible to make ohmic contact with both the n-type SiC semiconductor and the p-type SiC semiconductor, reduce the occurrence of surface roughness of the electrode, and reduce the erosion of the SiC semiconductor.
- An SiC semiconductor ohmic electrode, a method of manufacturing an SiC semiconductor ohmic electrode, a semiconductor device using the SiC semiconductor ohmic electrode, and a method of manufacturing the semiconductor device can be provided.
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Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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CN2007800407529A CN101536152B (zh) | 2006-11-02 | 2007-08-13 | SiC半导体用欧姆电极、半导体装置及其制造方法 |
KR1020097007415A KR101283774B1 (ko) | 2006-11-02 | 2007-08-13 | SiC 반도체용 오믹 전극, SiC 반도체용 오믹 전극의 제조 방법, 반도체 장치 및 반도체 장치의 제조 방법 |
CA002667648A CA2667648A1 (en) | 2006-11-02 | 2007-08-13 | Ohmic electrode for sic semiconductor, method of manufacturing ohmic electrode for sic semiconductor, semiconductor device, and method of manufacturing semiconductor device |
US12/444,537 US8623752B2 (en) | 2006-11-02 | 2007-08-13 | Ohmic electrode for SiC semiconductor, method of manufacturing ohmic electrode for SiC semiconductor, semiconductor device, and method of manufacturing semiconductor device |
EP07792459A EP2079101B1 (en) | 2006-11-02 | 2007-08-13 | OHMIC ELECTRODE FOR SiC SEMICONDUCTOR, METHOD FOR MANUFACTURE OF OHMIC ELECTRODE FOR SiC SEMICONDUCTOR, SEMICONDUCTOR DEVICE, AND METHOD FOR MANUFACTURE OF SEMICONDUCTOR DEVICE |
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JP2006-299349 | 2006-11-02 | ||
JP2006299349A JP4140648B2 (ja) | 2006-11-02 | 2006-11-02 | SiC半導体用オーミック電極、SiC半導体用オーミック電極の製造方法、半導体装置および半導体装置の製造方法 |
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WO2008053627A1 true WO2008053627A1 (en) | 2008-05-08 |
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PCT/JP2007/065816 WO2008053627A1 (en) | 2006-11-02 | 2007-08-13 | OHMIC ELECTRODE FOR SiC SEMICONDUCTOR, METHOD FOR MANUFACTURE OF OHMIC ELECTRODE FOR SiC SEMICONDUCTOR, SEMICONDUCTOR DEVICE, AND METHOD FOR MANUFACTURE OF SEMICONDUCTOR DEVICE |
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US (1) | US8623752B2 (ja) |
EP (1) | EP2079101B1 (ja) |
JP (1) | JP4140648B2 (ja) |
KR (1) | KR101283774B1 (ja) |
CN (1) | CN101536152B (ja) |
CA (1) | CA2667648A1 (ja) |
TW (1) | TW200832525A (ja) |
WO (1) | WO2008053627A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010062513A (ja) * | 2008-08-05 | 2010-03-18 | Toyota Motor Corp | 半導体装置及びその製造方法 |
CN103779419B (zh) * | 2008-12-25 | 2017-01-04 | 罗姆股份有限公司 | 半导体装置 |
Families Citing this family (10)
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JP5446148B2 (ja) * | 2008-07-02 | 2014-03-19 | 富士電機株式会社 | 炭化珪素半導体装置の製造方法 |
JP5391643B2 (ja) * | 2008-10-22 | 2014-01-15 | 住友電気工業株式会社 | 炭化珪素半導体装置およびその製造方法 |
US8188484B2 (en) | 2008-12-25 | 2012-05-29 | Rohm Co., Ltd. | Semiconductor device |
JP5369762B2 (ja) * | 2009-03-02 | 2013-12-18 | 株式会社デンソー | 炭化珪素半導体装置の製造方法 |
JP2011134910A (ja) | 2009-12-24 | 2011-07-07 | Rohm Co Ltd | SiC電界効果トランジスタ |
EP2560194A4 (en) | 2010-04-14 | 2013-11-20 | Sumitomo Electric Industries | SEMICONDUCTOR DEVICE OF SILICON CARBIDE AND METHOD FOR MANUFACTURING THE SAME |
JP5636752B2 (ja) * | 2010-06-15 | 2014-12-10 | 日産自動車株式会社 | 半導体装置及びその製造方法 |
JP5418466B2 (ja) * | 2010-11-01 | 2014-02-19 | 住友電気工業株式会社 | 半導体装置およびその製造方法 |
US9917171B2 (en) * | 2016-07-21 | 2018-03-13 | International Business Machines Corporation | Low-resistive, CMOS-compatible, Au-free ohmic contact to N—InP |
US10629686B2 (en) | 2018-08-02 | 2020-04-21 | Semiconductor Components Industries, Llc | Carbon-controlled ohmic contact layer for backside ohmic contact on a silicon carbide power semiconductor device |
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- 2007-08-13 EP EP07792459A patent/EP2079101B1/en not_active Not-in-force
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- 2007-08-13 CA CA002667648A patent/CA2667648A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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EP2079101A1 (en) | 2009-07-15 |
US8623752B2 (en) | 2014-01-07 |
KR20090088354A (ko) | 2009-08-19 |
EP2079101B1 (en) | 2012-07-18 |
TW200832525A (en) | 2008-08-01 |
JP2008117923A (ja) | 2008-05-22 |
KR101283774B1 (ko) | 2013-07-08 |
JP4140648B2 (ja) | 2008-08-27 |
EP2079101A4 (en) | 2011-03-30 |
CA2667648A1 (en) | 2008-05-08 |
US20100102331A1 (en) | 2010-04-29 |
CN101536152B (zh) | 2010-12-01 |
CN101536152A (zh) | 2009-09-16 |
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