WO2022045160A1 - ワイドギャップ半導体装置 - Google Patents

ワイドギャップ半導体装置 Download PDF

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Publication number
WO2022045160A1
WO2022045160A1 PCT/JP2021/031066 JP2021031066W WO2022045160A1 WO 2022045160 A1 WO2022045160 A1 WO 2022045160A1 JP 2021031066 W JP2021031066 W JP 2021031066W WO 2022045160 A1 WO2022045160 A1 WO 2022045160A1
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Prior art keywords
gap semiconductor
wide
metal electrode
element content
designated element
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English (en)
French (fr)
Japanese (ja)
Inventor
雄介 前山
俊一 中村
仁 大貫
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Shindengen Electric Manufacturing Co Ltd
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Shindengen Electric Manufacturing Co Ltd
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Priority to US18/008,657 priority Critical patent/US12363927B2/en
Priority to EP21861584.7A priority patent/EP4207308A4/en
Priority to CN202180052727.2A priority patent/CN115989584B/zh
Priority to JP2022545650A priority patent/JP7369302B2/ja
Publication of WO2022045160A1 publication Critical patent/WO2022045160A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10DINORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D62/00Semiconductor bodies, or regions thereof, of devices having potential barriers
    • H10D62/80Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials
    • H10D62/83Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials being Group IV materials, e.g. B-doped Si or undoped Ge
    • H10D62/832Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials being Group IV materials, e.g. B-doped Si or undoped Ge being Group IV materials comprising two or more elements, e.g. SiGe
    • H10D62/8325Silicon carbide
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10DINORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D64/00Electrodes of devices having potential barriers
    • H10D64/01Manufacture or treatment
    • H10D64/012Manufacture or treatment of electrodes comprising a Schottky barrier to a semiconductor
    • H10D64/0121Manufacture or treatment of electrodes comprising a Schottky barrier to a semiconductor to Group IV semiconductors
    • H10D64/0123Manufacture or treatment of electrodes comprising a Schottky barrier to a semiconductor to Group IV semiconductors to silicon carbide
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10DINORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D64/00Electrodes of devices having potential barriers
    • H10D64/60Electrodes characterised by their materials
    • H10D64/64Electrodes comprising a Schottky barrier to a semiconductor
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10DINORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00Field-effect transistors [FET]
    • H10D30/60Insulated-gate field-effect transistors [IGFET]
    • H10D30/67Thin-film transistors [TFT]
    • H10D30/6729Thin-film transistors [TFT] characterised by the electrodes
    • H10D30/6737Thin-film transistors [TFT] characterised by the electrodes characterised by the electrode materials
    • H10D30/6738Schottky barrier electrodes
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10DINORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00Field-effect transistors [FET]
    • H10D30/60Insulated-gate field-effect transistors [IGFET]
    • H10D30/67Thin-film transistors [TFT]
    • H10D30/674Thin-film transistors [TFT] characterised by the active materials
    • H10D30/675Group III-V materials, Group II-VI materials, Group IV-VI materials, selenium or tellurium
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10DINORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D8/00Diodes
    • H10D8/60Schottky-barrier diodes 

Definitions

  • the present invention relates to a wide-gap semiconductor device having a wide-gap semiconductor layer and a metal electrode provided on the wide-gap semiconductor layer.
  • SiC which is a type of wide-gap semiconductor device
  • ⁇ B of N-type SiC-SBD Schottky barrier diode
  • N-type SiC- Ti, Ni, Pt and the like are used as the Schottky electrodes of the SBD.
  • Ti has the smallest ⁇ B
  • most of the commercially available N-type SiC-SBDs use Ti as a Schottky electrode.
  • the inventors of the present application refer to the non-patent document (Extended Abstracts of the 2013 International Conference on Solid State Devices and Materials, Fukuoka, 2013, pp468-469) and have a configuration having two layers of TiO at the interface as a method for lowering ⁇ B.
  • the non-patent document Extended Abstracts of the 2013 International Conference on Solid State Devices and Materials, Fukuoka, 2013, pp468-469) and have a configuration having two layers of TiO at the interface as a method for lowering ⁇ B.
  • the present invention provides a wide-gap semiconductor device capable of lowering ⁇ B without causing an abnormal leak.
  • the wide-gap semiconductor device is Wide-gap semiconductor layer and
  • the metal electrode provided on the wide-gap semiconductor layer and Equipped with The metal electrode has a single crystal layer having a hexagonal close-packed structure (HCP) in the interface region on the metal electrode side with the wide-gap semiconductor layer.
  • the single crystal layer may have a designated element content range containing O, S, P or Se.
  • the metal electrode is made of Ti, Cd, Hf, Mg, Zr or Sc.
  • the designated element content range contains O, S, P or Se.
  • the metal electrode is made of Cd, Hf, Mg, Zr or Sc, the designated element content range may contain O.
  • the total atomic concentration of O, S, P and Se in the designated element content range may be 7% to 33%.
  • the designated element content range may exist between the interface of the metal electrode with the wide-gap semiconductor layer and the distance from the interface to a distance of 11 nm to 37 nm in the thickness direction.
  • the designated element content range may be scattered in an island shape in the in-plane direction.
  • the designated element content range consists of a high concentration designated element content range.
  • the metal electrode is provided on the side of the high concentration designated element content region opposite to the wide gap semiconductor layer side, and has a low concentration designated element content having an oxygen concentration lower than the oxygen concentration contained in the interface region. It may have a region.
  • the metal electrode may have a polycrystalline layer on the side opposite to the wide-gap semiconductor layer side.
  • the metal electrode may have a hydrogen content range containing hydrogen on the side opposite to the wide-gap semiconductor layer side.
  • the metal electrode has a single crystal layer having a hexagonal close-packed structure (HCP) in the interface region on the metal electrode side with the wide gap semiconductor layer, and the single crystal layer contains O, S, P or Se.
  • HCP hexagonal close-packed structure
  • the vertical sectional view which showed the wide-gap semiconductor apparatus by 1st Embodiment of this invention.
  • the graph which showed the relationship between VF (V) and IF (A) in Example 1, Comparative Example 1 and Comparative Example 2.
  • the graph which showed the relationship between the C-axis lattice constant (nm) and Fermi energy (eV / atm).
  • An image of the metal electrode in the embodiment of the present invention taken by STEM (scanning equivalent electron microscope).
  • An image of the metal electrode in Comparative Example 1 taken by STEM (scanning equivalent electron microscope).
  • FIG. 7A is a diagram following FIG. 7A, showing an example of a method for manufacturing a wide-gap semiconductor device according to the first embodiment of the present invention.
  • the vertical sectional view which showed the wide gap semiconductor apparatus by the 2nd Embodiment of this invention.
  • the wide-gap semiconductor device of the present embodiment has a wide-gap semiconductor layer 10 and a metal electrode 20 provided on the wide-gap semiconductor layer 10.
  • the metal electrode 20 may have a single crystal layer 21 having a hexagonal close-packed structure (HCP) in the interface region on the metal electrode 20 side (back surface side) with the wide-gap semiconductor layer 10.
  • the single crystal layer 21 has a designated element content range 22 containing O (oxygen), S (sulfur), P (phosphorus) or Se (selenium) in the interface region on the metal electrode 20 side with the wide-gap semiconductor layer 10. You may have.
  • the designated element content range 22 can contain any one or more of O, S, P and Se, but the typical element is O.
  • the wide-gap semiconductor include SiC, GaN and the like.
  • the upper part of FIG. 1 is the front surface side of the wide-gap semiconductor device, and the lower part is the back surface side of the wide-gap semiconductor device.
  • the metal electrode 20 of the present embodiment constitutes a Schottky electrode.
  • the single crystal layer 21 may be made of Ti (titanium), Cd (cadmium), Hf (hafnium), Mg (magnesium), Zr (zirconium) or Sc (scandium), or two or more of these metals. It may consist of a contained embodiment. Of these, the typical metal is Ti, and the following description will be made mainly using an embodiment using Ti. Since Cd, Hf, Mg, Zr and Sc have a hexagonal close-packed structure (HCP) and a lattice constant close to SiC, they are the same as when Ti is used. You will be able to draw conclusions.
  • HCP hexagonal close-packed structure
  • the designated element content range 22 of the single crystal layer 21 may contain O, S, P or Se.
  • the single crystal layer 21 is composed of Cd, Hf, Mg, Zr and Sc, the designated element content range 22 of the single crystal layer 21 may contain O.
  • the total atomic concentration of O, S, P and Se in the designated element content range 22 may be 7% to 33%. Since it is a "total amount", when any two or more of O, S, P and Se are included, the total of them is 7% to 33%. On the other hand, when only one of O, S, P and Se is contained, the atomic concentration of one element contained is 7% to 33%. Of O, S, P and Se, it is typically O, and in the following, O will be mainly used for description. Since the theoretical upper limit of the atomic concentration at which atoms such as O, S, P, and Se can be inserted while maintaining the HCP structure is 33%, an upper limit of 33% is set. If the HCP structure is maintained, no abnormal leak will occur. On the contrary, when the impurity concentration is 33% or more like TiO 2 in the above non-patent document, an abnormal leak occurs because the crystal structure of the single crystal layer 21 cannot maintain the original hexagonal close-packed structure (HCP). It ends up.
  • HCP hexagon
  • any of S, P, and Se can be chemically bonded to Ti, etc., and when they have the same structure, the number of valence electrons is relative. It is thought that the Fermi energy rises when the amount increases. Therefore, in any of S, P and Se, the same conclusion as in the case of using O can be drawn. For example, comparing Ti 6 O and Ti 2 S, assuming that they have the same structure, it is considered that the Fermi energy increases because the number of valence electrons in Ti 2 S is relatively large. Even if they do not have the same structure, the same effect can be obtained if a structure close to it can exist stably.
  • the designated element content region 22 may exist between the interface of the metal electrode 20 with the wide-gap semiconductor layer 10 and the distance from the interface to a distance of 11 nm to 37 nm in the thickness direction.
  • the thickness of the designated element content region 22 from the interface of the metal electrode 20 with the wide-gap semiconductor layer 10 may be 11 nm to 37 nm.
  • the designated element content range 22 is a region in which any of O, S, P, and Se exists in a significant amount in the atomic state, and typically exists at an atomic concentration of 5% or more. This is the area where you are doing.
  • the designated element content range 22 may be provided over one surface in the in-plane direction.
  • the metal electrode 20 may have a polycrystalline layer 29 on the side opposite to the wide-gap semiconductor layer 10 side (front surface side).
  • a single crystal main body layer 25 may be provided between the designated element content range 22 and the polycrystalline layer 29, which does not contain the designated element or contains a smaller amount than the designated element content range 22.
  • the single crystal layer 21 may be formed by the single crystal main body layer 25 and the designated element content range 22.
  • the designated element content range 22 may consist of a high concentration designated element content range.
  • the metal electrode 20 is provided on the side opposite to the wide-gap semiconductor layer 10 side (upper side in FIG. 1) in the high concentration designated element content range, and has a low oxygen concentration lower than the oxygen concentration contained in the interface region. It may have a concentration-designated element content range.
  • the single crystal main body layer 25 has a low concentration designated element content range.
  • the metal electrode 20 may have a hydrogen content range containing hydrogen on the side opposite to the wide-gap semiconductor layer 10 side.
  • the above-mentioned polycrystalline layer 29 may have a hydrogen content range, and in this case, a hydrogen content range is provided in the polycrystalline layer 29. At this time, the entire polycrystalline layer 29 may be in the hydrogen content range, or a part of the polycrystalline layer 29 may be in the hydrogen content range.
  • the metal electrode 20 is made of Ti, Ti is easily oxidized, so that a layer made of TiO 2 is provided on the surface of the metal electrode 20 (see FIG. 7B).
  • FIG. 2 shows an embodiment in which the wide-gap semiconductor layer 10 is made of SiC, the metal electrode 20 is made of Ti, and the designated element content range 22 contains O atoms, and SiC-SBD (Schottky barrier) is used.
  • the IV waveform of the diode) is shown.
  • the embodiment of Comparative Example 1 is an embodiment in which the designated element content region 22 does not contain a significant amount of O atoms
  • Comparative Example 2 contains TiO 2 in the designated element content region 22, and Example 1 is an embodiment.
  • the designated element content range 22 contains a significant amount of O atoms.
  • the rising voltage is high.
  • Comparative Example 2 it can be confirmed that an abnormal leak occurs at 0 to 0.2 V.
  • the abnormal leakage as in the comparative example 2 does not occur, and the rising voltage can be reduced.
  • FIG. 3 shows that the wide-gap semiconductor layer 10 is made of SiC, the metal electrode 20 is made of Ti, and the designated element content range 22 contains O atoms. It is the result of the first-principles calculation showing the relationship between the length of the lattice constant C axis and the Fermi energy when the content of the contained O atom is increased. It can be confirmed that as the concentration of O atoms present in the interface region between Ti and SiC increases, the Fermi energy increases and ⁇ B (Schottky barrier height) decreases.
  • FIG. 4A and 4B show an embodiment in which the wide-gap semiconductor layer 10 is made of SiC, the metal electrode 20 is made of Ti, and the designated element content range 22 contains O atoms, and Ti and O are used.
  • EDX energy dispersive X-ray spectroscopy
  • STEM scan equivalent electron microscope
  • H glow discharge emission analyzer
  • the energy dispersive X-ray spectroscopy (EDX) cut line is shown by straight lines IV-IV in FIG. 4A.
  • the depth of 0 ⁇ m in FIG. 4B is the interface on the front surface side of the metal electrode 20, and the depth of 0.15 ⁇ m is the interface between Ti and SiC.
  • Table 1 below shows the site, crystal structure, composition and crystal orientation in FIG. 4B.
  • the designated element content region 22 exists between the interface of the metal electrode 20 with the wide-gap semiconductor layer 10 and the distance from the interface to 30 nm in the thickness direction.
  • the hydrogen content region is in a region separated from the interface of the metal electrode 20 with the wide-gap semiconductor layer 10 by 80 nm or more in the thickness direction.
  • 5A and 5B show an embodiment in which the wide-gap semiconductor layer 10 is made of SiC and the metal electrode 20 is made of Ti, but the designated element content range 22 does not exist (Comparative Example 1).
  • 5A corresponds to FIG. 4A
  • FIG. 5B corresponds to FIG. 4B.
  • the cut line of energy dispersive X-ray spectroscopy (EDX) is shown by a straight line VV in FIG. 5A.
  • no “hump” of oxygen concentration corresponding to the Ti—O layer was not detected at the interface between the SiC layer and the Ti layer.
  • the oxygen concentration near the interface between the SiC layer and the Ti layer was 6.6%, which was below the lower limit of detection of about 10%.
  • the EELS signal waveform of Ti in the Ti—O layer having the designated element content range 22 is the EELS signal waveform of the single crystal Ti in Comparative Example 1 epigrown on SiC. It is similar to. From this, it can be confirmed that in the Ti—O layer in the designated element content range 22, the O atom exists between the lattices of Ti and is not covalently bonded to Ti and O. In Example 1, the oxygen concentration on the front surface side is as high as 40%, and Ti and O are covalently bonded, so that the EELS signal waveform is shifted. From this, it can be confirmed that in the Ti—O layer in the designated element content range 22, the O atom exists between the lattices of Ti and is not covalently bonded to Ti and O.
  • a metal electrode 20 made of Ti is provided on the wide-gap semiconductor layer 10 made of SiC (see FIG. 7A). At this time, since Ti is easily oxidized, the surface (Hyomen) of the metal electrode 20 made of Ti is exposed to oxygen to form a layer (TIO 2 layer) 30 made of TIO 2 .
  • H 2 gas or H 2 gas diluted with Ar (H 2 gas having a flow rate ratio of 1 to 20%) is supplied and annealed at 300 to 600 degrees.
  • the provided H 2 gas causes a Ti-H layer to be formed on the front surface side.
  • the metal electrode 20 originally made of Ti is formed. It is considered that the contained oxygen is pushed toward the Ti / SiC interface side to form a Ti—O layer having a designated element content range 22. It is considered that the H atom of the provided H 2 gas penetrates into Ti through a defect or the like in the TiO 2 layer.
  • the surface of Ti is oxidized by the residual oxygen and water in the chamber.
  • a part of O atoms derived from oxygen and water in the chamber also penetrates into the inside through the grain boundaries of Ti which is polycrystalline on the front surface side, and the Ti-O layer which is the designated element content range 22. Is thought to increase. More specifically, the oxygen remaining in the chamber is separated into O atoms, penetrates into the metal electrode 20 made of Ti, oxidizes the surface of the metal electrode 20 or moves to the Ti / SiC interface, and increases the Ti—O layer. (The layer indicated by reference numeral 79 in FIG. 7B).
  • the water (H 2 O) remaining in the chamber is separated into H and OH, and the OH penetrates into the metal electrode 20 made of Ti, and the surface is oxidized or moved to the Ti / SiC interface to form the Ti—O layer. It is believed to increase 22.
  • Example 1 is the result of annealing at 350 ° C. or higher in the presence of H2 gas.
  • the metal electrode 20 has a single crystal layer 21 having a hexagonal close-packed structure (HCP) in the interface region on the metal electrode 20 side with the wide gap semiconductor layer 10, and is a single crystal.
  • HCP hexagonal close-packed structure
  • the layer 21 has an embodiment having a designated element content range 22 containing O, S, P or Se, ⁇ B can be lowered without causing an abnormal leak (see FIG. 2).
  • the metal electrode 20 is made of Ti and the designated element content range 22 is O, S, P or Se, or the metal electrode 20 is made of Cd, Hf, Mg, Zr or Sc, the designated element content range.
  • the designated element content range When 22 contains O, ⁇ B can be lowered more reliably without causing an abnormal leak.
  • the total atomic concentration of O, S, P and Se in the designated element content range 22 is 7% to 33%. Is beneficial. This is because if more than 33% of O, S, and P are introduced, the metal electrode 20 cannot maintain the hexagonal close-packed structure (HCP) and an abnormal leak occurs.
  • HCP hexagonal close-packed structure
  • the designated element content region 22 is provided over one surface in the in-plane direction, but is not limited to this.
  • the designated element content regions 22 are scattered in an island shape in the in-plane direction.
  • FIG. 9 is a plan view showing only the designated element content region 22 inside the metal electrode 20 in order to show the designated element content region 22 arranged in an island shape.
  • Such an island-shaped designated element content range 22 can be formed when annealed using H 2 gas diluted with Ar. When diluted with Ar, the push of oxygen or the like by H 2 is not so strong, so that an island-shaped designated element content range 22 may be formed.
  • the same effect as that realized by the first embodiment can be obtained by the present embodiment as well. That is, even in the embodiment in which the designated element content range 22 containing O, S, P or Se is provided in an island shape in the in-plane direction as in the present embodiment, the total atomic concentration is 7%. If it is ⁇ 33%, ⁇ B can be lowered without causing an abnormal leak.

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PCT/JP2021/031066 2020-08-27 2021-08-25 ワイドギャップ半導体装置 Ceased WO2022045160A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US18/008,657 US12363927B2 (en) 2020-08-27 2021-08-25 Wide gap semiconductor device
EP21861584.7A EP4207308A4 (en) 2020-08-27 2021-08-25 WIDE BAND GAP SEMICONDUCTOR DEVICE
CN202180052727.2A CN115989584B (zh) 2020-08-27 2021-08-25 宽带隙半导体装置
JP2022545650A JP7369302B2 (ja) 2020-08-27 2021-08-25 ワイドギャップ半導体装置

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JP2020143284 2020-08-27

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US (1) US12363927B2 (https=)
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WO2022215471A1 (ja) * 2021-04-05 2022-10-13 ローム株式会社 半導体装置および半導体装置の製造方法

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EP4207308A4 (en) 2024-09-04
US20230246111A1 (en) 2023-08-03
JP7369302B2 (ja) 2023-10-25
US12363927B2 (en) 2025-07-15
CN115989584A (zh) 2023-04-18

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