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WO2008117571A1 - Procédé de fabrication d'un nitrure monocristallin - Google Patents

Procédé de fabrication d'un nitrure monocristallin Download PDF

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Publication number
WO2008117571A1
WO2008117571A1 PCT/JP2008/051894 JP2008051894W WO2008117571A1 WO 2008117571 A1 WO2008117571 A1 WO 2008117571A1 JP 2008051894 W JP2008051894 W JP 2008051894W WO 2008117571 A1 WO2008117571 A1 WO 2008117571A1
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WO
WIPO (PCT)
Prior art keywords
growth
single crystal
temperature
pressure
nitrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2008/051894
Other languages
English (en)
Japanese (ja)
Inventor
Yusuke Mori
Mikiya Ichimura
Katsuhiro Imai
Takayuki Hirao
Takatomo Sasaki
Fumio Kawamura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NGK Insulators Ltd
Original Assignee
NGK Insulators Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Priority to JP2009506234A priority Critical patent/JPWO2008117571A1/ja
Publication of WO2008117571A1 publication Critical patent/WO2008117571A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C30B19/00—Liquid-phase epitaxial-layer growth
    • C30B19/02—Liquid-phase epitaxial-layer growth using molten solvents, e.g. flux
    • 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
    • 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
    • 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
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
    • C30B9/12—Salt solvents, e.g. flux growth

Definitions

  • the present invention relates to a method for producing a nitride single crystal.
  • Gallium nitride III-V nitride is attracting attention as an excellent blue light emitting device, and has been put to practical use as a material for light emitting diodes and semiconductor laser diodes.
  • a method for growing a group III nitride single crystal using 7 Lux has been reported by each organization (Japanese Patent Laid-Open No. 2000-29, 6 9-6, Japanese Patent Laid-Open No. 2000-29) No. 24 00, WO 2 0 0 5—0 9 5 6 8 2 Al, WO 2 0 0 6—0 3 0 7 1 8).
  • the temperature and pressure are classified into four regions A to D according to the growth mode of the GaN single crystal, and a plurality of regions among the four regions are used to make III
  • a method for growing a group nitride crystal is claimed [claim 9]. By growing using a plurality of regions, it is possible to grow a crystal having a plurality of forms [0068].
  • the present inventor has kept the growth temperature and pressure in the region B in Japanese Patent Laid-Open No. 2 0 0 3-2 924 00, and Japanese Patent Laid-Open No. 2 0 3-2 9 2 4 0 0
  • the generation of miscellaneous crystals was suppressed, and it was confirmed that GaN crystals grew only on the seed crystals.
  • the start of GaN crystal growth was confirmed more than 50 hours after holding the temperature and pressure in region B, and no clear growth was confirmed only by holding for 24 hours.
  • the growth of GaN crystals that do not generate miscellaneous crystals requires a long period of time, so the productivity is low.
  • Japanese Patent Laid-Open No. 2 00 3-2 924 0 0 describes that crystal growth having a plurality of forms is possible by using a plurality of regions among the four regions A to D. However, there is no description of what form of crystal can be obtained by using multiple regions. Moreover, there is no description about the growth rate in addition to the crystal form.
  • An object of the present invention is to suppress the generation of miscellaneous crystals and improve the productivity per unit time of a nitride single crystal when growing a nitride single crystal on a seed crystal substrate.
  • the present invention is a method of immersing a seed crystal substrate in a melt containing a flux and a single crystal raw material in a growth vessel, and growing a nitride single crystal on the growth surface of the seed crystal substrate,
  • the present inventor has conceived of performing the main growth process after the initial process for dissolving nitrogen.
  • the melting is performed at a higher temperature, a higher pressure, or a higher temperature and pressure than in the main growing step, and the dissolution of nitrogen into the melt is advanced.
  • the growth of GaN crystals should not start when the nitrogen concentration is saturated (see Figure 5).
  • the growth of single crystals is carried out at a temperature and pressure at which no miscellaneous crystals are generated. As a result, the production of single crystals per unit time required for growth was significantly improved while suppressing the generation of miscellaneous crystals.
  • the horizontal axis of FIG. 1 is 100 K / T, and T is the absolute temperature of the melt (unit is K).
  • the vertical axis is P / MPa, and P is the pressure of nitrogen applied to the melt (unit: MPa).
  • Equation (3) corresponds to the condition of R ⁇ l.1, where R is (Nitrogen dissolution rate in the melt in the nitrogen dissolution process) / (Nitrogen in the melt in this growth step) Dissolution rate). Specifically, R is expressed by the following formula. Also, the nitrogen dissolution rate X increases as the pressure and temperature increase.
  • Nitrogen dissolution rate X increases at high temperature and pressure ⁇
  • (T 1 ⁇ T 2) must be at least 10 ° C and (PI—P 2) must be at least 0.5 MPa, and by satisfying equation (3), It is necessary to make the nitrogen dissolution rate larger than the nitrogen dissolution rate in this growth process. As a result, the amount of nitrogen dissolved in the melting step can be increased and the productivity of single crystals can be improved. At the same time, it is necessary to set (T 1 ⁇ T 2) to 60 ° C or less and (P 1 ⁇ P 2) to 5. OMPa or less. If (T 1 – T 2) exceeds 60 ° C, a mechanism to prevent evaporation and diffusion of flux materials such as Na is required, which complicates equipment and processes. If (1? 2) exceeds 5.0 MPa, a container with high pressure resistance is required, which is a cost-up factor.
  • P1, P2, T1, and T2 satisfy the following relational expressions (4) and / or (5).
  • Figure 1 1,? 2 is a graph schematically illustrating the relationship between Ding 1 and Ding 2.
  • Figure 2 1,? 2 is a graph schematically illustrating the relationship between Ding 1 and Ding 2.
  • Figure 3 1,? 2 is a graph schematically illustrating the relationship between Ding 1 and Ding 2.
  • Fig. 4 is a diagram schematically showing the relationship between the growth time and the nitrogen dissolution amount of GaN growth in the prior art.
  • FIG. 5 is a diagram schematically showing the relationship between the growth time and the amount of growth of nitrogen dissolving gan in the present invention.
  • FIG. 6 is a schematic block diagram of a single crystal growth apparatus that can be used in the present invention.
  • FIG. 7 is a schematic diagram showing single crystal growth in a growth vessel.
  • Fig. 8 is a photograph of the growth container taken out from the atmosphere control container observed from above.
  • Fig. 9 is a photograph showing the GaN single crystal taken out from the growth vessel.
  • Figure 10 is a photograph showing the surface of a GaN single crystal observed with a microscope.
  • Figure 11 is a graph showing the relationship between the total growth time and the G a N weight.
  • FIG. 12 is a graph showing the relationship between the temperature and pressure in Examples and Comparative Examples and the regions A to D in Patent Document 2.
  • the holding time in the nitrogen dissolving step is preferably 5 hours or more and 60 hours or less. If the holding time is too short, the amount of nitrogen dissolved in the melt is small, and it becomes difficult to improve the productivity of the single crystal. On the other hand, there is no particular upper limit. However, since there is a tendency for single crystal growth to start in about 60 hours from the start of the growth process even without the nitrogen dissolution process, if the holding time in the nitrogen dissolution process exceeds 60 hours, the production according to the present invention The benefits of improved performance are reduced.
  • the growth temperature and pressure in this growth process should be determined according to the type of nitride single crystal to be grown. Should be selected.
  • the temperature T 2 and the pressure P 2 in the main growing process satisfy the following relational expressions (6) and (7).
  • the temperature T 1 and the pressure P 1 of the nitrogen dissolving step may exist in the region C or may exist in the region B. But especially preferred is 1 chopstick 1 also satisfies the following equations (8) and (9). That is, it exists in area B.
  • a plurality of heating elements 6 ⁇ , 6 ⁇ , and 6 C are installed in the vertical direction, and the heating value is controlled independently for each heating element.
  • multi-zone control is performed in the vertical direction.
  • the material of the heating element is not particularly limited, but alloy heating elements such as iron-chromium-aluminum and nickel-chromium, refractory metal heating elements such as platinum, molybdenum, tantalum and tandastain, silicon carbide, molybdenum silicate Non-metallic heating elements such as carbon can be exemplified.
  • an apparatus for heating the raw material mixture to generate a melt is not particularly limited.
  • This device is a hot isostatic press
  • other atmospheric pressure heating furnaces may be used.
  • the flux for producing the melt is not particularly limited, but one or more metals selected from the group consisting of Al-rich metal and Al-rich earth metal or alloys thereof are preferable.
  • the metal include lithium, sodium, potassium, norevidium, cesium, beryllium, magnesium, calcium, strontium, and palium, and lithium, sodium, and calcium are particularly preferable. Sodium is most preferred.
  • the material of the growth vessel for carrying out the reaction is not particularly limited as long as it is a material that is durable under the intended heating and pressurizing conditions.
  • These materials include high melting point metals such as metal tantalum, tungsten, and molybdenum, oxides such as alumina, sapphire, and yttrium, nitride ceramics such as aluminum nitride, titanium nitride, zirconium nitride, and boron nitride, Examples include carbides of refractory metals such as tungsten carbide and tantanore carbide, and pyrolysis products such as p-BN (pyrolytic BN) and p-Gr (pyrolytic graphite).
  • a single crystal of gallium nitride can be grown using a flux containing at least sodium metal. This flux dissolves the gallium source material.
  • gallium simple metal, gallium alloy and gallium compound can be applied, but gallium simple metal is also preferable in terms of handling.
  • This flux can contain metals other than sodium, such as lithium.
  • the usage ratio of the raw material of the gallium and the flux raw material such as sodium may be appropriate, but in general, the use of an excess amount of sodium is considered. Of course, this is not limiting.
  • Gas other than nitrogen in the atmosphere is not limited, but inert gas is preferable, Argon, helium and neon are particularly preferred.
  • the material of the growth substrate for epitaxial growth of gallium nitride crystal is not limited, but sapphire, A 1 N template, GaN template, silicon single crystal, SiC single crystal, MgO single Perovsky such as crystals, spinel (Mg A l 2 0 4 ), L i A 1 0 2 , L i G a 0 2 , L a A 1 O 3 , L a G a O 3, N d G a 0 3 Can be exemplified.
  • Perovskite structure complex oxides can also be used. Further, SCAM (ScAlMg0 4) can also be used.
  • GaN single crystals were grown according to the method described with reference to Figs. 1, 2, and 5.
  • a growth vessel 7 As shown in FIG.
  • the seed crystal 9 was a gallium nitride single crystal thin film epitaxially grown on sapphire.
  • This growth vessel 7 was placed and sealed in an atmosphere control vessel 4 having a gas inlet. A series of operations were performed in an inert gas atmosphere to prevent oxidation of raw materials and flux. 5 is a melt.
  • the gas tank 1 was connected to the gas inlet through the pressure controller 2.
  • GaN single crystals were grown at the main growth process temperature of 890 ° C.
  • the nitrogen gas pressure was kept constant at 3 ⁇ 9 MPa.
  • the total training time (initial process 20 hours + main training process time) was 150 hours.
  • the growth container was taken out of the cooled atmosphere control container, and the flux was reacted with ethanol to remove the GaN single crystal grown on the seed crystal.
  • Figure 8 shows the observation of the growth container taken out from the atmosphere control container from above.
  • Figure 9 shows the GaN single crystal taken out from the growth vessel.
  • Fig. 10 shows the surface of a GaN single crystal observed with a microscope. There were no miscellaneous crystals at the gas-liquid interface, and no miscellaneous crystals adhered to the GaN single crystal. The crystal surface was smooth. The weight of the grown GaN single crystal was 1.08 g.
  • the training preparation was performed in the same manner as in Example 1. After maintaining the initial process pressure at 4.3 MPa for 20 hours, GaN single crystals were grown at the main growth process pressure of 3.9 MPa. The temperature was kept constant at 890 ° C. The total training time (initial process 20 hours + main training process time) was 150 hours. After the growth process was completed, GaN single crystals were collected. The GaN single crystal weight was 0.98 g.
  • the training preparation was performed in the same manner as in Example 1.
  • a GaN single crystal was grown at a constant temperature of 890 ° C and a pressure of 3.9 MPa.
  • the training time was 150 hours.
  • GaN single crystals were collected.
  • the GaN single crystal weight was 0.54 g.
  • Example 2 Under the same conditions as in Example 1, only the total growth time (initial process 20 hours + main growth process time) was changed, and a GaN single crystal was grown.
  • the weight of the grown GaN single crystal grown at the total growth time of 50, 75, 100, 125 hours is They were 0.11, 0.28, 0.55, and 0.73 g, respectively.
  • a GaN single crystal was grown under the same conditions as in Comparative Example 1 while changing only the growth time.
  • the weight of the grown GaN single crystal grown at the growth time of 25, 50, 75, 100, and 125 hours is 0.0C! 0.00, 0.02, 0.10, 0.30g
  • FIG. 12 is a graph showing the relationship between the temperature and pressure in each example and the regions A to D in Patent Document 2.
  • the temperature and pressure conditions in the examples and comparative examples are all within the region B.
  • Table 1 shows the range where R (nitrogen dissolution rate in the melt in the nitrogen dissolution process) / (nitrogen dissolution rate in the melt in the main growth process) is 1.1 or more.
  • the activation energy E of nitrogen dissociation and dissolution was used after calculating a value of 2.8 eV by cluster model simulation. As a result, it can be seen that R is 1.1 or more within the range of Eq. (3).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

Selon l'invention, un substrat de cristal d'ensemencement est immergé dans une masse fondue contenant un fondant et une matière première monocristalline dans un récipient de croissance, et un nitrure monocristallin est amené à croître sur la surface de croissance du substrat de cristal d'ensemencement. Le procédé comprend l'étape préparatoire consistant à dissoudre de l'azote dans la masse fondue ci-dessus à la température T1 (K) sous pression P1 (MPa) et l'étape de croissance principale consistant à faire croître un nitrure monocristallin sur la surface de croissance du substrat de cristal d'ensemencement à la température T2 (K) sous pression P2 (MPa). Ces P1, P2, T1 et T2 satisfont les formules : T2-10 ≤ T1 ≤ T2+60 (1) P2-0,5 ≤ P1 ≤ P2+5,0 (2), et P1 ≥ 1,1 x P2 x (T1/T2)0.5exp[(E/k)•[(1/T1)-(1/T2)]] (3).
PCT/JP2008/051894 2007-03-26 2008-01-30 Procédé de fabrication d'un nitrure monocristallin Ceased WO2008117571A1 (fr)

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JP2009506234A JPWO2008117571A1 (ja) 2007-03-26 2008-01-30 窒化物単結晶の製造方法

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003292400A (ja) * 2002-01-29 2003-10-15 Ricoh Co Ltd Ｉｉｉ族窒化物結晶成長方法およびｉｉｉ族窒化物結晶成長装置およびｉｉｉ族窒化物結晶および半導体デバイス
JP2004231447A (ja) * 2003-01-29 2004-08-19 Ricoh Co Ltd Ｉｉｉ族窒化物結晶成長方法およびｉｉｉ族窒化物結晶および半導体デバイス
JP2005154254A (ja) * 2003-10-31 2005-06-16 Sumitomo Electric Ind Ltd Ｉｉｉ族窒化物結晶およびその製造方法、ならびにｉｉｉ族窒化物結晶の製造装置
WO2005095681A1 (fr) * 2004-03-31 2005-10-13 Matsushita Electric Industrial Co., Ltd. Procédé de fabrication de cristal de nitrure d’élément du groupe iii, appareil de fabrication pour utilisation dans ce contexte, et élément semi-conducteur ainsi produit

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003292400A (ja) * 2002-01-29 2003-10-15 Ricoh Co Ltd Ｉｉｉ族窒化物結晶成長方法およびｉｉｉ族窒化物結晶成長装置およびｉｉｉ族窒化物結晶および半導体デバイス
JP2004231447A (ja) * 2003-01-29 2004-08-19 Ricoh Co Ltd Ｉｉｉ族窒化物結晶成長方法およびｉｉｉ族窒化物結晶および半導体デバイス
JP2005154254A (ja) * 2003-10-31 2005-06-16 Sumitomo Electric Ind Ltd Ｉｉｉ族窒化物結晶およびその製造方法、ならびにｉｉｉ族窒化物結晶の製造装置
WO2005095681A1 (fr) * 2004-03-31 2005-10-13 Matsushita Electric Industrial Co., Ltd. Procédé de fabrication de cristal de nitrure d’élément du groupe iii, appareil de fabrication pour utilisation dans ce contexte, et élément semi-conducteur ainsi produit

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