WO2015056714A1 - n型窒化アルミニウム単結晶基板、および縦型窒化物半導体デバイス - Google Patents
n型窒化アルミニウム単結晶基板、および縦型窒化物半導体デバイス Download PDFInfo
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- WO2015056714A1 WO2015056714A1 PCT/JP2014/077442 JP2014077442W WO2015056714A1 WO 2015056714 A1 WO2015056714 A1 WO 2015056714A1 JP 2014077442 W JP2014077442 W JP 2014077442W WO 2015056714 A1 WO2015056714 A1 WO 2015056714A1
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- aluminum nitride
- single crystal
- nitride single
- layer
- type aluminum
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- 239000013078 crystal Substances 0.000 title claims abstract description 195
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 191
- 239000000758 substrate Substances 0.000 title claims abstract description 174
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 47
- 239000004065 semiconductor Substances 0.000 title claims abstract description 47
- 230000004888 barrier function Effects 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 239000010410 layer Substances 0.000 description 204
- 238000000034 method Methods 0.000 description 68
- 239000000463 material Substances 0.000 description 12
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910002601 GaN Inorganic materials 0.000 description 2
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- -1 aluminum halide Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002109 crystal growth method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- VCZQFJFZMMALHB-UHFFFAOYSA-N tetraethylsilane Chemical compound CC[Si](CC)(CC)CC VCZQFJFZMMALHB-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002017 high-resolution X-ray diffraction Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/20—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer
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- C—CHEMISTRY; METALLURGY
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/403—AIII-nitrides
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Definitions
- the present invention relates to an n-type conductive single crystal aluminum nitride substrate doped with Si (n-type aluminum nitride single crystal substrate), and a vertical nitride semiconductor device using the substrate.
- Aluminum nitride has a forbidden band width that is about twice as large as that of gallium nitride and silicon carbide known as wide band gap semiconductors (6.2 eV), high breakdown voltage (12 MV / cm), and high As a material that has excellent characteristics such as thermal conductivity (3.0 Wcm ⁇ 1 K ⁇ 1 ), and that can realize a power device having higher withstand voltage characteristics than the above-described materials. Expected.
- Patent Documents 4 and 5 since an n-type aluminum nitride single crystal layer is formed on a heterogeneous substrate such as a SiC substrate, it is difficult to produce a high-quality single crystal layer. . In particular, there is room for improvement in producing an n-type aluminum nitride single crystal layer having a high quality and a large layer thickness.
- an aluminum nitride free-standing substrate having a threading dislocation density of about 10 5 cm ⁇ 2 is manufactured by the method described in Japanese Patent Laid-Open No. 2005-2552248, and then n n is formed on the aluminum nitride free-standing substrate.
- a type aluminum nitride single crystal layer can be formed.
- an n-type aluminum nitride single crystal layer having a dislocation density of about 5 ⁇ 10 9 cm ⁇ 2 can be obtained.
- Patent Document 6 an n-type aluminum nitride single crystal layer having a small layer thickness of 10 ⁇ m or less is actually produced, and a specific example in which an electrode is formed is not shown. That is, in the prior art, a vertical semiconductor device using a high-performance aluminum nitride single crystal having a thickness that can be used as a self-supporting n-type layer and having n-type conductivity has not yet been realized. Not.
- the present invention has been made in view of the above situation, and an object of the present invention is to provide a vertical semiconductor device using an n-type aluminum nitride single crystal substrate doped with Si.
- the present inventors made an n-type single crystal aluminum nitride substrate by the method disclosed in Patent Document 6 and actually formed electrodes to confirm various characteristics. Then, in the n-type aluminum nitride single crystal substrate, the withstand voltage in the reverse direction may be remarkably lowered, and the cause was found to be the dislocation density of the n-type aluminum nitride single crystal substrate. As a result, it has been found that a high-quality n-type single crystal aluminum nitride single crystal substrate is required to produce a high-performance device, and the present invention has been completed.
- the first aspect of the present invention is An n-type aluminum nitride single crystal substrate having a Si content of 3 ⁇ 10 17 to 1 ⁇ 10 20 cm ⁇ 3 , a dislocation density of 10 6 cm ⁇ 2 or less, and a thickness of 50 to 500 ⁇ m.
- the second aspect of the present invention is a vertical nitride semiconductor device comprising electrode layers on the upper and lower main surfaces of the n-type aluminum nitride single crystal substrate.
- the electrode layer on one main surface is preferably an ohmic electrode layer.
- this vertical nitride semiconductor device is suitable as a vertical Schottky barrier diode by providing an ohmic electrode layer on one main surface of an n-type aluminum nitride single crystal substrate and a Schottky electrode layer on the other main surface. Can be used for
- Al x Ga 1-X N (Si content is 1 ⁇ 10 18 to 5 ⁇ 10 19 cm ⁇ 3) on at least one main surface of the n-type aluminum nitride single crystal substrate.
- X is a rational number satisfying 0.3 ⁇ X ⁇ 0.8).
- a vertical nitride semiconductor device comprising electrode layers on the upper and lower main surfaces of the laminate.
- the electrode layer on the layer made of Al X Ga 1-X N (where X is a rational number satisfying 0.3 ⁇ X ⁇ 0.8) is an ohmic electrode layer.
- the vertical nitride semiconductor device can be suitably used as a vertical Schottky barrier diode when the electrode layer on the n-type aluminum nitride single crystal substrate is a Schottky electrode layer.
- the fifth aspect of the present invention is characterized in that an aluminum nitride single crystal seed substrate having a dislocation density of 10 4 cm ⁇ 2 or less is used when the n-type aluminum nitride single crystal substrate is manufactured.
- a vertical nitride semiconductor device using an n-type aluminum nitride single crystal substrate which has not been realized conventionally, and the dislocation density of the n-type aluminum nitride single crystal substrate is 10 6 cm. By setting it to ⁇ 2 or less, it is possible to realize high withstand voltage characteristics.
- FIG. 6 is a current-voltage characteristic diagram of a vertical Schottky barrier diode fabricated in an example.
- the vertical nitride semiconductor device is a structure in which working electrodes are formed on the upper and lower surfaces of an n-type aluminum nitride single crystal substrate, and within the scope of the present invention, a Schottky barrier diode, a transistor It can be applied to various semiconductor devices such as light emitting diodes and laser diodes.
- the vertical nitride semiconductor device of the present invention is a vertical nitride semiconductor device having electrode layers on the upper and lower surfaces of an n-type aluminum nitride single crystal substrate.
- the n-type aluminum nitride single crystal substrate has a Si content, a dislocation density, and a thickness within a specific range.
- the n-type aluminum nitride single crystal substrate may be a single layer having a constant Si content or may be composed of a plurality of layers having different Si contents. Moreover, you may consist of an aluminum nitride single-crystal layer from which Si content changes in steps. Next, a specific structure will be described with reference to the drawings.
- FIG. 1 shows a vertical Schottky barrier diode structure as a typical example.
- the vertical nitride semiconductor device of the present invention has an n-type aluminum nitride single crystal substrate 1, and upper and lower surfaces ((main surface): side surfaces of the n-type aluminum nitride single crystal substrate 1
- the working electrode layers 2 and 3 are formed on the surface on which an electrode layer is formed or other layers are grown.
- the electrode on one surface is the ohmic electrode layer 3 and the electrode on the other surface is the Schottky electrode layer. 2.
- the n-type aluminum nitride single crystal substrate 1 has a dislocation density of 10 6 cm ⁇ 2 or less and contains Si in a range of 3 ⁇ 10 17 to 1 ⁇ 10 20 cm ⁇ 3 .
- This dislocation density refers to the dislocation density on the outermost surface of the n-type aluminum nitride single crystal substrate.
- Dislocations in an n-type aluminum nitride single crystal substrate become a current leakage source when a vertical device is driven, causing deterioration of initial withstand voltage characteristics, and dislocations over a long period of use. By promoting the diffusion of impurities through the device, device characteristics are gradually deteriorated. In addition, dislocations cause scattering of electrons that are n-type conductive carriers. And since there are many dislocations in the n-type aluminum nitride single crystal substrate, the mobility of electrons decreases, and as a result, the n-type conductivity tends to decrease.
- the dislocation density in the n-type aluminum nitride single crystal substrate is 10 6 cm ⁇ 2 or less, more preferably 10 4 cm ⁇ 2 or less. is there.
- a preferable lower limit of the dislocation density is 0 cm ⁇ 2 , but is 10 2 cm ⁇ 2 in view of industrial production.
- the dislocation density can be measured by observation with a transmission electron microscope (TEM) or simply by observing the etch pit density after being immersed in an alkaline solution.
- TEM transmission electron microscope
- the etch pit density is the dislocation density.
- the Si content contained in the n-type aluminum nitride single crystal substrate 1 is 3 ⁇ 10 17 to 1 ⁇ 10 20 cm ⁇ 3 .
- the Si content is less than 3 ⁇ 10 17 cm ⁇ 3 , the n-type conductive carrier concentration is lowered, so that the conductivity is lowered and the resistance value of the device is increased.
- the Si content may be included in the n-type aluminum nitride single crystal substrate within the above range.
- the Si content may be changed within the range of the upper limit and the lower limit value.
- the Si content may be appropriately determined within the above range as appropriate so that desired n-type conductivity characteristics can be exhibited.
- the Si content is preferably 1 ⁇ 10 18 to 8 ⁇ 10 19 cm ⁇ 3 , more preferably 5 ⁇ 10 18 to 5 ⁇ 10 19 cm ⁇ 3. It is.
- the concentration of the acceptor impurity (carbon) contained in the n-type aluminum nitride single crystal substrate 1 is preferably 2 ⁇ 10 17 cm ⁇ 3 or less, more preferably 1 ⁇ 10 17 cm ⁇ 3 or less.
- the lower limit of the preferable range of the acceptor impurity concentration is 0 cm ⁇ 3 , but is about 1 ⁇ 10 15 cm ⁇ 3 in consideration of the current lower limit of detection of a known analytical method described later.
- the Si content and the acceptor impurity (carbon) concentration can be measured by a known technique such as secondary ion mass spectrometry (SIMS).
- SIMS secondary ion mass spectrometry
- the n-type conductivity can be measured by known Hall effect measurement, CV measurement, or the like.
- the thickness of the n-type aluminum nitride single crystal substrate 1 is in the range of 50 to 500 ⁇ m, and may be determined in a timely manner within the above range according to the desired use and design.
- the thickness of the substrate is not more than the above lower limit value, it is difficult to ensure the self-supporting property of the substrate, and further, it becomes a cause of crack generation during the device manufacturing process, resulting in a decrease in yield.
- the thickness of the substrate exceeds the above range, in addition to the decrease in productivity due to the long manufacturing time of the n-type aluminum nitride substrate described later, the increase in the vertical resistance value in terms of device characteristics become.
- the plane orientation of the main surface of n-type aluminum nitride single crystal substrate 1 (the surface on which the electrode layer or other layer is formed on the layer, not the side surface) is the C plane (Al polar plane) and -C Plane (N-polar plane).
- the half width is 100 seconds or less in the X-ray rocking curve measurement of the (002) and (101) planes.
- the electrode layer may be appropriately determined according to the application to be used.
- a gate electrode, a source electrode layer, a drain electrode layer, etc. are formed on both main surfaces of the n-type aluminum nitride single crystal substrate. That's fine.
- an n-type ohmic electrode layer is formed on an n-type aluminum nitride single crystal substrate, and a p-type ohmic electrode layer is formed on the other surface. do it.
- the vertical nitride semiconductor device of the present invention is used for a vertical Schottky barrier diode, it is preferable to form an ohmic electrode layer and a Schottky electrode layer.
- the ohmic electrode layer 3 can use a known ohmic electrode material.
- the material is not particularly limited as long as it can reduce the contact resistance value with the n-type aluminum nitride single crystal substrate.
- Ti described in JP2011-547604A
- these electrode materials are preferably annealed in an inert gas atmosphere such as argon or nitrogen after the electrode layer is formed.
- the annealing temperature is not particularly limited, but is preferably 700 to 1100 ° C.
- the thickness of the ohmic electrode layer 3 is not particularly limited, and the layer thickness of each layer may be appropriately determined within a range in which the contact resistance value after annealing can be reduced. In consideration, the total thickness is preferably 50 to 500 nm.
- the plane orientation of the surface of the n-type aluminum nitride single crystal substrate on which the ohmic electrode layer is formed is not particularly limited, and may be appropriately determined depending on the device structure. Among these, when applied to a vertical Schottky barrier diode as described in the first embodiment, the C plane (Al polar plane) is preferable.
- the Schottky electrode layer 2 is preferably formed on the n-type aluminum nitride single crystal substrate 1.
- the material of the Schottky electrode layer 2 is not particularly limited as long as it is a material that forms a Schottky barrier with the n-type aluminum nitride single crystal substrate.
- the work function of Ni, Pt, Pd, Au, or the like A relatively large material can be used.
- the monolayer which consists of these materials may be sufficient, and it may consist of multiple layers.
- the thickness is not particularly limited, but is generally in the range of 10 to 500 nm.
- the plane orientation of the surface of the n-type aluminum nitride single crystal substrate forming the Schottky electrode layer 2 is opposite to the plane orientation forming the ohmic electrode layer 3 described above, that is, the ⁇ C plane (N polar plane). preferable.
- FIG. 2 that is, a stacked body of the present invention and a vertical nitride semiconductor device in which an electrode layer is formed on the stacked body will be described.
- n-type Al X Ga 1-X N layer 4 is formed on an n-type aluminum nitride single crystal substrate.
- the n-type Al X Ga 1-X N layer is not particularly limited, but contains Si between the n-type aluminum nitride single crystal substrate 1 and the ohmic electrode layer 3 as shown in FIG. That is, it is preferable that the n-type Al X Ga 1-X N layer 4 is formed.
- the n-type aluminum nitride single crystal substrate 1, the ohmic electrode layer 3, and the Schottky electrode layer 2 are the same as the substrates and layers described in the first embodiment.
- the laminate is a laminate in which an n-type Al X Ga 1-X N layer is laminated on at least one main surface of the n-type aluminum nitride single crystal substrate.
- the n-type Al X Ga 1-X N layer is preferably formed on the Al polar face 1b side of the n-type aluminum nitride single crystal substrate.
- the Si content in the n-type Al X Ga 1-X N layer is preferably 1 ⁇ 10 18 to 5 ⁇ 10 19 cm ⁇ 3 .
- the Si content is not particularly limited as long as it is within the above range, but preferably 5 ⁇ 10 18 to 4 ⁇ 10 19 cm ⁇ 3 in order to further reduce the contact resistance value. More preferably, it is 8 ⁇ 10 18 to 3 ⁇ 10 19 cm ⁇ 3 .
- the Al composition X of the n-type Al X Ga 1-X N layer 4 may be appropriately determined according to the type and purpose of the semiconductor device, but is preferably 0.3 ⁇ X ⁇ 0.8.
- the optimum composition may be determined in view of the contact resistance and the withstand voltage characteristics of the element, but preferably 0.4 ⁇ X ⁇ 0.75. Yes, and more preferably 0.5 ⁇ X ⁇ 0.7.
- the thickness of the n - type Al X Ga 1-X N layer is not particularly limited as in the case of the n-type aluminum nitride single crystal substrate, and may be appropriately determined according to the desired application and design.
- the thickness is preferably 20 to 500 nm.
- Such a laminated body in which the n-type Al X Ga 1-X N layer 4 is laminated on the n-type aluminum nitride single crystal substrate 1 has an n-type Al X Ga 1-X N layer depending on its use.
- An electrode layer may be formed on the surface and the surface of the n-type aluminum nitride single crystal substrate.
- an ohmic electrode is formed on the n-type Al X Ga 1-X N layer 4, preferably on the Al polar face of the n-type Al X Ga 1-X N layer 4.
- the layer 3 is formed, and the Schottky electrode layer 2 is preferably formed on the surface of the n-type aluminum nitride single crystal substrate, preferably on the N-polar surface 1a of the n-type aluminum nitride single crystal substrate 1.
- the ohmic electrode layer 3 and the crystal layer are further included in the first embodiment.
- the contact resistance value can be reduced.
- the ohmic electrode layer 3 and the Schottky electrode layer 2 can be the same as those described in the first embodiment.
- the method for manufacturing the vertical nitride semiconductor device of the first and second embodiments is not particularly limited. Among them, an n-type aluminum nitride single crystal layer having a Si content of 3 ⁇ 10 17 to 1 ⁇ 10 20 cm ⁇ 3 is grown on an aluminum nitride single crystal seed substrate having a dislocation density of 10 4 cm ⁇ 2 or less, and It is preferable to adopt a method of separating the n-type aluminum nitride single crystal layer and using it as an n-type aluminum nitride single crystal substrate.
- the Si content is 3 ⁇ 10 17 to 1 ⁇ 10 20 cm ⁇ 3 .
- An n-type aluminum nitride single crystal substrate having a dislocation density of 10 6 cm ⁇ 2 or less can be easily obtained.
- an aluminum nitride single crystal seed substrate of about 10 5 cm ⁇ 2 is used and an n-type aluminum nitride single crystal layer is grown thereon.
- an n-type aluminum nitride single crystal layer having a dislocation density of about 5 ⁇ 10 9 cm ⁇ 2 could be obtained.
- an n-type aluminum nitride single crystal substrate having a higher quality than the conventional one is used.
- a seed substrate for producing an n-type aluminum nitride single crystal layer (substrate) is important. It is preferable to manufacture by the following method. I will explain in order.
- An example of the manufacturing method of the vertical nitride semiconductor device of the first embodiment will be described with reference to FIG. First, an aluminum nitride single crystal seed substrate 5 used for manufacturing an n-type aluminum nitride single crystal substrate is prepared. First, the aluminum nitride single crystal seed substrate will be described.
- the n-type aluminum nitride single crystal substrate is formed by forming an n-type aluminum nitride single crystal layer 1 ′ on an aluminum nitride single crystal seed substrate 5 and then separating the seed substrate 5 and the n-type aluminum nitride single crystal layer 1 ′.
- An n-type aluminum nitride single crystal substrate 1 is used.
- the dislocation density of the aluminum nitride single crystal seed substrate 5 is preferably 10 4 cm ⁇ 2 or less, more preferably 10 3 cm ⁇ 2 or less.
- the dislocation density exceeds 10 4 cm ⁇ 2 , stress is accumulated in the n-type aluminum nitride single crystal layer when the n-type aluminum nitride single crystal layer 1 ′ is formed on the aluminum nitride single crystal seed substrate 5.
- the resulting n-type aluminum nitride single crystal layer 1 ′ (n-type aluminum nitride single crystal substrate 1) has a dislocation density of 10 6 cm ⁇ 2 or less. It becomes difficult.
- the lower limit of the dislocation density of the aluminum nitride single crystal seed substrate is 0 cm ⁇ 2 , but is 10 2 cm ⁇ 2 in consideration of industrial production.
- the dislocation density can be measured by observation with a transmission electron microscope (TEM) or simply by observing the etch pit density after being immersed in an alkaline solution.
- TEM transmission electron microscope
- the etch pit density is the dislocation density.
- Such a low dislocation density aluminum nitride single crystal seed substrate 5 can be manufactured by a known method. As long as the above characteristics are obtained, the method is not particularly limited, but may be proposed in the sublimation method (for example, described in Journal of Crystal Growth 312.2519) or Japanese Patent Application Laid-Open No. 2010-89971. Can be used.
- the main surface on which the n-type aluminum nitride single crystal layer 1 'is formed is preferably a C plane (Al polar plane).
- the surface roughness of the main surface is preferably smooth at the atomic layer level so as not to deteriorate the crystal quality of the n-type aluminum nitride single crystal layer.
- the mean square roughness (RMS) is preferably 0.2 nm or less over the entire main surface of the seed substrate. If the surface roughness exceeds the above range, or if the main surface of the seed substrate has scratches due to polishing, cracks are generated in the n-type aluminum nitride single crystal layer 1 ′ as in the case where the dislocation density is high. It becomes easy to do.
- the plane orientation of the main surface on which the n-type aluminum nitride single crystal layer 1 ′ is grown is preferably the C plane, and the inclination (off angle) from the C plane is not particularly limited, but is 0 to 3 °. It is preferable that it is a grade.
- the thickness of the aluminum nitride single crystal seed substrate 5 is not particularly limited, but is usually about 0.3 to 1.0 mm. By preparing such a seed substrate, it is possible to form a high crystal quality n-type aluminum nitride single crystal layer 1 '.
- the n-type aluminum nitride single crystal layer 1 ′ is manufactured by a known crystal growth method such as HVPE method, MOVPE method, molecular beam epitaxy (MBE) method or the like.
- HVPE method in consideration of productivity such as obtaining a relatively high crystal growth rate, the HVPE method or the MOVPE method is preferable, and the HVPE method capable of obtaining the highest growth rate is most preferable.
- the temperature of the seed substrate 5 when growing the n-type aluminum nitride single crystal layer 1 ′ is preferably 1100 to 1800 ° C., more preferably 1250 to 1600 ° C., and most preferably 1400 to 1550 ° C. is there.
- an n-type aluminum nitride single crystal layer having a layer thickness of 50 ⁇ m or more is grown by growing an n-type aluminum nitride single crystal layer at a high temperature of 1100 ° C. or more, preferably 1250 ° C. or more, particularly preferably 1400 ° C. or more as described above. Even in the case of forming a crystal layer, it is possible to significantly reduce the occurrence of new dislocations and cracks during growth. Further, the supply molar ratio (V / III ratio) between nitrogen atoms and aluminum atoms depends on the structure of the crystal growth apparatus to be used, but is preferably 0.5 to 100, and more preferably 2 to 20. It is preferable.
- the Si doping method for growing the n-type aluminum nitride single crystal layer 1 ′ is, for example, SiH ⁇ Cl 4- ⁇ ( ⁇ is an integer of 0 to 3) as a Si source as described in Japanese Patent No. 5234968. It is preferable to use a method of doping with When the Si concentration in the layer thickness direction is made constant, the SiH ⁇ Cl 4- ⁇ flow rate during the growth of n-type aluminum nitride may be kept constant.
- Si source materials containing Si such as quartz and Si
- Si are installed around the susceptor for heating the aluminum nitride single crystal seed substrate, and desorbed Si from these materials
- a method of doping using can be used.
- the Si content may be appropriately determined by adjusting the supply amount of the SiH ⁇ Cl 4- ⁇ gas described above, the number of Si supply source materials, and the like.
- trimethylaluminum and ammonia may be used as the raw material for the aluminum nitride single crystal layer.
- a known material such as tetraethylsilane can be used as the Si raw material.
- the growth temperature may be determined as appropriate by evaluating the characteristics of the n-type aluminum nitride single crystal layer after growth using an X-ray rocking curve or the like and appropriately determining a range in which high crystal quality can be obtained. It is.
- the n-type aluminum nitride single crystal layer 1 ′ having a Si content of 3 ⁇ 10 17 to 1 ⁇ 10 20 cm ⁇ 3 and a dislocation density of 10 6 cm ⁇ 2 or less. can be grown on the aluminum nitride single crystal seed substrate 5.
- the dislocation density is particularly low, specifically, the aluminum nitride single crystal seed substrate 5 having a dislocation density of 10 4 cm ⁇ 2 or less is used, the Si content is high and the dislocation density is low.
- a low n-type aluminum nitride single crystal layer 1 ′ can be easily grown.
- the thickness of the n-type aluminum nitride single crystal layer 1 ′ is not particularly limited, but is set larger than the desired n-type aluminum nitride single crystal substrate 1. Therefore, the n-type aluminum nitride single crystal layer 1 ′ is preferably 50 to 600 ⁇ m.
- the n-type aluminum nitride single crystal layer 1 ′ and the aluminum nitride single crystal seed substrate 5 grown as described above are separated into the n-type aluminum nitride single crystal substrate 1. This method will be described.
- the separation method is not particularly limited, and a known technique exemplified below can be used.
- a method of mechanically polishing a seed substrate portion after preparing a laminated substrate a method of dissolving only the seed substrate portion by dipping in an alkali solution such as potassium hydroxide, a laser beam proposed in Japanese Patent Application Laid-Open No. 2003-168820 And the like.
- an alkali solution such as potassium hydroxide
- a laser beam proposed in Japanese Patent Application Laid-Open No. 2003-168820 And the like.
- a self-supporting n-type aluminum nitride single crystal substrate 1 can be obtained.
- the surface on which the aluminum nitride single crystal seed substrate 5 is separated by the above-described method and the opposite surface (growth surface) are subjected to chemical mechanical (CMP) polishing, and are damaged by mechanical polishing and surface oxidation after growth.
- CMP chemical mechanical
- the order of performing CMP polishing on the growth surface is not limited after the separation, and may be determined as appropriate. For example, it may be performed after the growth of the n-type aluminum nitride single crystal layer 1 ′.
- the growth surface of the aluminum nitride single crystal seed substrate 5 is a C plane
- the surface on the side separated from the aluminum nitride single crystal seed substrate 5 is the N-polar surface 1a, and the opposite surface (growth surface) ) Becomes the Al polar face 1b.
- the Al polar surface 1b of the n-type aluminum nitride single crystal substrate 1 is formed by a known film forming technique such as a vacuum deposition method or a sputtering method.
- the ohmic electrode layer 3 is preferably formed.
- the n-type ohmic electrode layer 3 is formed of a metal such as Ti or Al in a predetermined thickness and stacking order. After forming the ohmic electrode, it is preferable to anneal in an inert gas atmosphere such as nitrogen or argon.
- each layer is the same as those described for the ohmic electrode layer in the first embodiment.
- a Schottky electrode layer 4 made of Ni, Pt, Pd, Au or the like is formed on the N-polar surface 1a by the same method as that for the ohmic electrode layer 3.
- the thickness and layer structure of each layer in the Schottky electrode layer are the same as those described in the Schottky electrode layer layer in the first embodiment.
- the first vertical nitride semiconductor device can be manufactured by the above method.
- FIG. 4 shows a method of forming the n-type Al X Ga 1-X N layer 4 on the N-polar face of the n-type aluminum nitride single crystal layer 1. In this case, until the n-type nitride single crystal substrate 1 is manufactured, the manufacturing method of the vertical nitride semiconductor device of the first embodiment is the same.
- an n-type Al X Ga 1-X N layer 4 is grown on the N-polar face 1 a of the obtained n-type nitride single crystal substrate 1.
- the n-type Al X Ga 1-X N layer can be formed by a known crystal growth method such as the HVPE method, the MOVPE method, or the MBE method, but the MOVPE method is most preferable in consideration of the ease of control of the composition and the layer thickness. .
- An n-type aluminum nitride single crystal substrate 1 is placed in a reaction apparatus, and an n-type Al X Ga 1-X N layer 4 is formed under the growth conditions exemplified below.
- the plane orientation of the main surface of the n-type aluminum nitride single crystal substrate 1 forming the n - type Al X Ga 1-X N layer 4 is an N-polar plane. Further, the polarity of the growth surface of the n-type Al X Ga 1-X N layer 4 after the growth may be the same as that of the substrate, or the polarity may be reversed.
- the polarity of the n-type Al X Ga 1-X N layer 4 is reversed, the growth surface
- the polarity of (the outermost surface of the n-type Al X Ga 1-X N layer 4) is preferably Al polarity.
- the n-type Al X Ga 1-X N layer 4 is produced by the MOCVD method, for example, Applied Physics Letters. As described in 81.1038, the n-type Al X Ga 1-X N layer 4 can be formed using trimethylaluminum, trimethylgallium, ammonia, and silane as raw materials. In addition to the silane gas described in the above document, a known material such as tetraethylsilane can be used as the Si raw material.
- the growth temperature may be appropriately determined within a range in which the desired conductivity characteristic of the n-type Al X Ga 1-X N layer 4 can be obtained, but is usually about 1050 to 1100 ° C.
- the ohmic electrode layer 3 is formed on the n-type Al x Ga 1-x N layer 4 (preferably on the Al polar face), and the n-type Al x Ga 1-x N layer 4 is formed.
- Schottky electrode layer 2 is formed on the surface of aluminum nitride single crystal substrate 1 (preferably on the N polar surface). As a method for forming these electrode layers, a method similar to the method described in the section of the method for forming the ohmic electrode layer and the Schottky electrode layer can be employed.
- FIG. 5 shows a method of growing the n-type Al x Ga 1-x N layer 4 on the growth surface (on the Al polar face 1b) of the n-type aluminum nitride single crystal layer 1 ′.
- separation of the n-type aluminum nitride single crystal substrate 1, growth method of the n-type Al x Ga 1-x N layer 4, ohmic electrode layer 3, and formation method of the Schottky electrode layer 2 are the methods described above. The same method can be adopted.
- the n-type Al x Ga 1-x N layer 4 is grown before the separation of the n-type aluminum nitride single crystal substrate, but it can also be performed after the separation.
- the manufacturing method of the vertical Schottky barrier diode has been described based on FIGS. 3, 4, and 5.
- the present invention is not limited to the vertical Schottky barrier diode, and does not depart from the present invention. Therefore, it can be applied to various devices such as vertical light emitting diodes, bipolar transistors, and unipolar transistors.
- an n-type and p-type Al Y Ga 1-Y N layer (where Y is After being stacked, a source electrode, a gate electrode, and the like can be formed.
- the n-type and p-type Al Y Ga 1-Y N layers are preferably grown by the MOVPE method, and the composition, layer thickness, and the like may be appropriately determined according to the design of the transistor. In this case, it is preferable to form an ohmic electrode (drain electrode) on the N polar face side of the n-type aluminum nitride single crystal substrate.
- Example 1 As the aluminum nitride single crystal seed substrate for producing the n-type aluminum nitride single crystal substrate of the present invention, a C-plane aluminum nitride single crystal seed substrate ( ⁇ 15 mm ⁇ thickness 500 ⁇ m) was used. The dislocation density (etch pit density) of this aluminum nitride single crystal seed substrate was 1 ⁇ 10 4 cm ⁇ 2 . This dislocation density was determined by the same method as the method for measuring the dislocation density of the n-type aluminum nitride single crystal substrate described below.
- the pressure in the HVPE apparatus was 750 Torr, and the seed substrate was heated to 1450 ° C. in a mixed carrier gas atmosphere of hydrogen and nitrogen. .
- ammonia gas was supplied so as to be 0.5% by volume with respect to the total carrier gas flow rate (10 slm).
- aluminum chloride gas obtained by reacting metal Al heated to 450 ° C. with hydrogen chloride gas is supplied so as to be 0.05% by volume with respect to the total carrier gas supply amount, and n-type is formed on the seed substrate.
- An aluminum nitride single crystal layer was formed to 300 ⁇ m.
- a quartz piece ( ⁇ 3 mm ⁇ thickness 1 mm) was placed on the susceptor, and Si was doped into the aluminum nitride single crystal layer by utilizing the natural detachment phenomenon of quartz that occurred during growth.
- the conditions for an acceleration voltage of 45 kV and an acceleration current of 40 mA are obtained using a high-resolution X-ray diffraction apparatus (X'Pert manufactured by Spectris Corp. Then, X-ray rocking curve measurement of the (002) and (101) planes of the n-type aluminum nitride single crystal layer was performed. The half widths of the X-ray rocking curves were 22 and 15 arcsec, respectively.
- the aluminum nitride single crystal seed substrate portion was removed by mechanical polishing to expose the N-polar face of the HVPE method: n-type aluminum nitride single crystal layer.
- the growth surface Al polar surface
- CMP chemical mechanical
- n-type aluminum nitride single crystal substrate was cut into a square shape of about 5 mm square (four square-shaped n-type aluminum nitride single crystal substrates of about 5 mm square).
- One of the cut substrates was subjected to quantitative analysis of Si and carbon from both sides of the Al polar face and the N polar face by SIMS using cesium ions as primary ions.
- the concentration was quantified based on the nitrogen secondary ion intensity of the aluminum nitride standard sample.
- the Si concentration was 3 ⁇ 10 17 cm ⁇ 3 on both sides of the Al polar face and the N polar face.
- the carbon concentration was also 1 ⁇ 10 17 cm ⁇ 3 (the lower limit of detection in this measurement). Further, after immersing the same substrate in a mixed solution of potassium hydroxide and sodium hydroxide heated to 300 ° C.
- etch pit density was 2 ⁇ 10 5 cm ⁇ 2 .
- the other three substrates were cleaned in hydrochloric acid heated to 40 ° C.
- a Ti (20 nm) / Al (100 nm) / Ti (20 nm) / Au (50 nm) electrode is formed as an ohmic electrode layer on the entire surface of the Al polar surface by vacuum deposition.
- heat treatment was performed at 1000 ° C. in a nitrogen atmosphere.
- a resist was applied to the electrode formation surface to form a protective film, and the surface was washed again in hydrochloric acid heated to 40 ° C.
- a 300 ⁇ m-square Ni (20 nm) / Au (50 nm) electrode was formed as a Schottky electrode layer on the N polar face side of the obtained substrate.
- the substrate on which the electrode layer was formed was immersed in acetone to remove the resist, and a vertical Schottky barrier diode using an n-type aluminum nitride single crystal substrate was completed.
- FIG. 6 shows current-voltage characteristics between the Schottky electrode layer and the ohmic electrode layer of the obtained vertical Schottky barrier diode.
- a Schottky diode characteristic with a rising voltage of 3 V was confirmed.
- the current density was 5 ⁇ 10 ⁇ 7 Acm ⁇ 2 when the reverse voltage value was 100 V.
- Example 2 In Example 1, except that an ohmic electrode layer was formed on the N polar face side and a Schottky electrode layer was formed on the Al polar face side using one of the other substrates whose surface was washed in hydrochloric acid heated to 40 ° C. Produced a vertical Schottky barrier diode under the same conditions as in Example 1, and performed the same evaluation. The current-voltage characteristics are shown in FIG. A Schottky diode characteristic with a rising voltage of about 10 V was confirmed. When the reverse voltage value was 100 V, the current density was 5 ⁇ 10 ⁇ 7 Acm ⁇ 2 as in Example 1.
- Example 3 In Example 1, using one of the other substrates whose surface was cleaned in hydrochloric acid heated to 40 ° C., an n-type Al 0.7 Ga 0.3 N layer was formed on the Al polar face side of the substrate by MOVPE. Except that an ohmic electrode layer is formed on the Al polar face side of the n-type Al 0.7 Ga 0.3 N layer and a Schottky electrode layer is formed on the N polar face side of the substrate. A vertical Schottky barrier diode was fabricated under the same conditions as in Example 1, and the same evaluation was performed. The Si concentration in the n-type Al 0.7 Ga 0.3 N layer obtained by SIMS analysis was 1 ⁇ 10 19 cm ⁇ 3 . The current-voltage characteristics are shown in FIG. A Schottky barrier diode characteristic with a rising voltage of 3 V was confirmed. The current density was 5 ⁇ 10 ⁇ 7 Acm ⁇ 2 when the reverse voltage value was 100 V.
- Comparative Example 1 An aluminum nitride free-standing substrate serving as a seed substrate was produced by the method described in Example 3 of Patent Document 6. The obtained free-standing substrate had an etch pit density (dislocation density) of 2 ⁇ 10 6 cm ⁇ 2 .
- An n-type aluminum nitride single crystal layer was formed to a thickness of 300 ⁇ m in the same manner as in Example 1 except that this free-standing substrate was used as a seed substrate and grown at 1300 ° C. Cracks occurred in the n-type aluminum nitride single crystal layer taken out from the reaction furnace, and it was impossible to form a Schottky barrier diode.
- n-type aluminum nitride single crystal substrate 1a N polar face 1b Al polar face 2 Schottky electrode layer (electrode layer) 3 Ohmic electrode layer (electrode layer) 4 n-type Al X Ga 1-X N layer 5 aluminum nitride single crystal seed substrate 1 ′ n-type aluminum nitride single crystal layer
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Abstract
Description
Si含有量が3×1017~1×1020cm-3であり、転位密度が106cm-2以下であり、かつ厚みが50~500μmであるn型窒化アルミニウム単結晶基板である。
先ず、初めに、Si含有量が一定である単層、またはSi含有量が段階的に変化する窒化アルミニウム単結晶層からなる場合について説明する。図1に、典型例として、縦型ショットキーバリアダイオード構造を示した。
(n型窒化アルミニウム単結晶基板)
n型窒化アルミニウム単結晶基板1は、転位密度が106cm-2以下であり、Siを3×1017~1×1020cm-3の範囲で含んでいる。なお、この転位密度は、n型窒化アルミニウム単結晶基板の最表面の転位密度を指す。
本発明において、電極層は、使用する用途に応じて適宜決定すればよい。例えば、縦型のトランジスタに本発明の縦型窒化物半導体デバイスを使用する場合には、ゲート電極、ソース電極層、ドレイン電極層などを前記n型窒化アルミニウム単結晶基板の両主表面に形成すればよい。また、発光ダイオードに本発明の縦型窒化物半導体デバイスを適用する場合には、n型窒化アルミニウム単結晶基板にn型オーミック電極層を形成し、他方の面にはp型オーミック電極層を形成すればよい。中でも、本発明の縦型窒化物半導体デバイスを縦型ショットキーバリアダイオードに使用する場合には、オーミック電極層とショットキー電極層を形成することが好ましい。
次に、オーミック電極層3について説明する。このオーミック電極層3は、公知のオーミック電極材料を使用することができる。具体的には、n型窒化アルミニウム単結晶基板との接触抵抗値を低減可能な材料であれば、特に限定されるものではないが、例えば、特開2011-547604に記載されているTi、およびAlを含む電極材料を使用することが好ましい。これらの電極材料は、接触抵抗値を低減させるため、電極層を形成した後に、アルゴン、窒素などの不活性ガス雰囲気中でアニールすることが好ましい。アニール温度は特に制限されるものではないが、700~1100℃であることが好ましい。また、オーミック電極層3の厚みは、特に限定されるものではなく、アニール後の接触抵抗値の低減が可能な範囲で各層の層厚みを適宜決定すればよいが、電極層の生産性などを考慮すると、総厚を50~500nmにすることが好ましい。
本発明の縦型窒化物半導体デバイスは、n型窒化アルミニウム単結晶基板1上に、ショットキー電極層2が形成されることが好ましい。
第二態様例としては、n型窒化アルミニウム単結晶基板上に、Siを含む、即ち、n型AlXGa1-XN層4が形成されている積層体を使用するものである。このn型AlXGa1-XN層は、特に制限されるものではないが、図2に示す通り、n型窒化アルミニウム単結晶基板1とオーミック電極層3との間に、Siを含む、即ち、n型AlXGa1-XN層4が形成されていることが好ましい。なお、第二態様例において、n型窒化アルミニウム単結晶基板1、オーミック電極層3、ショットキー電極層2は、第一態様例で説明した基板、層と同様のものである。
本発明において、積層体は、前記n型窒化アルミニウム単結晶基板の少なくとも一方の主面に、n型AlXGa1-XN層が積層されたものである。中でも、n型AlXGa1-XN層は、前記n型窒化アルミニウム単結晶基板のAl極性面1b側に形成されることが好ましい。
次に、本発明の縦型窒化物半導体デバイスの製造方法について説明する。上記第一、二態様例の縦型窒化物半導体デバイスの製造方法は、特に制限されるものではない。中でも、転位密度が104cm-2以下の窒化アルミニウム単結晶種基板上に、Si含有量が3×1017~1×1020cm-3のn型窒化アルミニウム単結晶層を成長させ、そして、このn型窒化アルミニウム単結晶層を分離して、n型窒化アルミニウム単結晶基板として使用する方法を採用することが好ましい。つまり、転位密度が極めて低い(転位密度が104cm-2以下)の窒化アルミニウム単結晶種基板を使用することにより、Si含有量が3×1017~1×1020cm-3であり、転位密度が106cm-2以下であるn型窒化アルミニム単結晶基板を容易に得ることができる。
第一態様例の縦型窒化物半導体デバイスの製造方法の一例を、図3を用いて説明する。
先ず、n型窒化アルミニウム単結晶基板を製造するために使用する、窒化アルミニウム単結晶種基板5を準備する。先ず、この窒化アルミニウム単結晶種基板について説明する。
n型窒化アルミニウム単結晶基板は、窒化アルミニウム単結晶種基板5上に、n型窒化アルミニウム単結晶層1’を形成した後、種基板5とn型窒化アルミニウム単結晶層1’を分離して、n型窒化アルミニウム単結晶基板1とする。
上記窒化アルミニウム単結晶種基板5上に、n型窒化アルミニウム単結晶層1’を形成する方法について説明する。n型窒化アルミニウム単結晶層1’は、HVPE法、MOVPE法、分子線エピタキシー(MBE:Molecule Beam Epitaxy)法など、公知の結晶成長法によって製造される。中でも、比較的高い結晶成長速度が得られるなどの生産性を考慮すると、HVPE法もしくはMOVPE法が好ましく、最も高い成長速度が得られるHVPE法が最も好ましい。
次に、上述の方法により窒化アルミニウム単結晶種基板5上にn型窒化アルミニウム単結晶層1’が形成された積層基板を作製した後、種基板5とn型窒化アルミニウム単結晶層1’とを分離する方法について説明する。
n型窒化アルミニウム単結晶基板を使用したショットキーバリアダイオードを作製する場合は、n型窒化アルミニウム単結晶基板1のAl極性面1b上に、真空蒸着法、スパッタリング法などの公知の製膜技術によって、オーミック電極層3を形成することが好ましい。n型オーミック電極層3は、Ti、Alなどの金属を所定の厚み、積層順で形成する。オーミック電極を形成した後、窒素、アルゴンなどの不活性ガス雰囲気下でアニールすることが好ましい。これによって、オーミック電極層とn型窒化アルミニウム単結晶(基板)との接触抵抗値を低減することができる。各層の厚み、層構成は、第一態様例におけるオーミック電極層で説明したものと同じである。
図4では、n型窒化アルミニウム単結晶層1のN極性面上にn型AlXGa1-XN層4を形成する方法を示している。この場合、n型窒化物単結晶基板1を製造するまでは、第一態様例の縦型窒化半導体デバイスの製造方法と同じである。
n型AlXGa1-XN層は、HVPE法、MOVPE法、MBE法など、公知の結晶成長法によって形成できるが、組成や層厚みの制御の容易さを考慮すると、MOVPE法が最も好ましい。
以上、図3、図4、図5に基づいて、縦型ショットキーバリアダイオードの製法について説明したが、本発明は縦型ショットキーバリアダイオードに制限されるものではなく、本発明を逸脱しない範囲で、縦型発光ダイオード、バイポーラトランジスタ、ユニポーラトランジスタなどの様々なデバイスに応用することができる。例えば、縦型のトランジスタを作製する場合は、n型窒化アルミニウム単結晶基板のAl極性面1b側に、必要に応じてn型、p型AlYGa1-YN層(但し、Yは、0.0≦Y≦1.0を満足する有理数である。)を積層した後、ソース電極、ゲート電極などを形成することができる。n型、p型AlYGa1-YN層はMOVPE法で成長することが好ましく、組成および層厚みなどはトランジスタの設計に応じて適宜決定すればよい。また、この場合はn型窒化アルミニウム単結晶基板のN極性面側にオーミック電極(ドレイン電極)を形成することが好ましい。
本発明のn型窒化アルミニウム単結晶基板を作製するための窒化アルミニウム単結晶種基板にはC面窒化アルミニウム単結晶種基板(□15mm×厚み500μm)を用いた。この窒化アルミニウム単結晶種基板の転位密度(エッチピット密度)は、1×104cm-2であった。なお、この転位密度は、下記に記述するn型窒化アルミニウム単結晶基板の転位密度の測定方法と同じ方法で求めた。
実施例1において、40℃に加熱した塩酸中で表面を洗浄したその他の基板の1つを使用して、N極性面側にオーッミック電極層、Al極性面側にショットキー電極層を形成した以外は、実施例1と同様の条件で縦型ショットキーバリアダイオードを作製し、同じ評価を行った。電流―電圧特性を図6に示す。立ち上がり電圧10V程度のショットキーダイオード特性が確認された。また、逆方向電圧値を100Vとしたときの、電流密度は実施例1と同様に5×10-7Acm-2であった。
実施例1において、40℃に加熱した塩酸中で表面を洗浄したその他の基板の1つを使用して、該基板のAl極性面側にn型Al0.7Ga0.3N層をMOVPE法により、1080℃で30nm成長させて、n型Al0.7Ga0.3N層のAl極性面側にオーミック電極層、該基板のN極性面側にショットキー電極層を形成した以外は、実施例1と同様の条件で縦型ショットキーバリアダイオードを作製し、同じ評価を行った。なお、SIMS分析により求めたn型Al0.7Ga0.3N層中のSi濃度は1×1019cm-3であった。電流―電圧特性を図6に示す。立ち上がり電圧3Vのショットキーバリアダイオード特性が確認された。また、逆方向電圧値を100Vとしたときの、電流密度は5×10-7Acm-2であった。
特許文献6の実施例3に記載されている方法により種基板となる窒化アルミニウム自立基板を作製した。得られた自立基板のエッチピット密度(転位密度)は2×106cm-2であった。この自立基板を種基板として使用し、1300℃で成長した以外は、実施例1と同様にしてn型窒化アルミニウム単結晶層を300μm形成した。反応炉から取り出したn型窒化アルミニウム単結晶層にはクラックが発生しており、ショットキーバリアダイオードを形成することは不可能であった。
1a N極性面
1b Al極性面
2 ショットキー電極層(電極層)
3 オーミック電極層(電極層)
4 n型AlXGa1-XN層
5 窒化アルミニウム単結晶種基板
1’ n型窒化アルミニウム単結晶層
Claims (9)
- Si含有量が3×1017~1×1020cm-3であり、転位密度が106cm-2以下であり、かつ厚みが50~500μmであるn型窒化アルミニウム単結晶基板。
- 請求項1に記載のn型窒化アルミニウム単結晶基板の上下の主面に電極層を備えた縦型窒化物半導体デバイス。
- 請求項2に記載の縦型窒化物半導体デバイスにおいて、一方の主面側にオーミック電極層を有し、他方の主面にショットキー電極層を有する縦型ショットキーバリアダイオード。
- 請求項1に記載のn型窒化アルミニウム単結晶基板の少なくとも一方の主面上に、Si含有量が1×1018~5×1019cm-3であるAlXGa1-XN(但し、Xは、0.3≦X≦0.8を満足する有理数である。)からなる層が積層された積層体。
- 請求項4に記載の積層体の上下の主面に電極層を備えた縦型窒化物半導体デバイス。
- AlXGa1-XN(但し、Xは、0.3≦X≦0.8を満足する有理数である。)からなる層上の電極層がオーミック電極層である請求項5に記載の縦型窒化物半導体デバイス。
- 請求項6に記載の縦型窒化物半導体デバイスにおいて、n型窒化アルミニウム単結晶基板上の電極層がショットキー電極層である縦型ショットキーバリアダイオード。
- 逆方向電圧値を100Vとしたとき、電流密度が10-6Acm-2以下となる請求項3または7に記載の縦型ショットキーバリアダイオード。
- 転位密度が104cm-2以下の窒化アルミニウム単結晶種基板上に、Si含有量が1×1017~1×1020cm-3であり、転位密度が106cm-2以下であるn型窒化アルミニム単結晶層を形成する工程と、前記窒化アルミニウム単結晶種基板と前記n型窒化アルミニウム単結晶層を分離することにより、前記n型窒化アルミニウム単結晶層をn型窒化アルミニウム単結晶基板とする工程と、を含むことを特徴とする請求項1に記載のn型窒化アルミニウム単結晶基板の製造方法。
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CN105658848B (zh) | 2018-03-09 |
US20160254391A1 (en) | 2016-09-01 |
KR102171509B1 (ko) | 2020-10-29 |
US9748410B2 (en) | 2017-08-29 |
DE112014004744B4 (de) | 2020-05-07 |
DE112014004744T5 (de) | 2016-10-27 |
JP5818853B2 (ja) | 2015-11-18 |
JP2015078076A (ja) | 2015-04-23 |
CN105658848A (zh) | 2016-06-08 |
KR20160070743A (ko) | 2016-06-20 |
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