WO2007052632A1 - PROCEDE DE PRODUCTION DE MONOCRISTAL DE RUTILE (TiO2), MONOCRISTAL DE RUTILE (TiO2) ET ISOLANT OPTIQUE LE COMPRENANT - Google Patents

PROCEDE DE PRODUCTION DE MONOCRISTAL DE RUTILE (TiO2), MONOCRISTAL DE RUTILE (TiO2) ET ISOLANT OPTIQUE LE COMPRENANT Download PDF

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Publication number
WO2007052632A1
WO2007052632A1 PCT/JP2006/321705 JP2006321705W WO2007052632A1 WO 2007052632 A1 WO2007052632 A1 WO 2007052632A1 JP 2006321705 W JP2006321705 W JP 2006321705W WO 2007052632 A1 WO2007052632 A1 WO 2007052632A1
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WO
WIPO (PCT)
Prior art keywords
rutile
single crystal
tio
producing
metal element
Prior art date
Application number
PCT/JP2006/321705
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English (en)
Japanese (ja)
Inventor
Isao Tanaka
Satoshi Watauchi
Shinsuke Morimoto
Jongkwan Pak
Original Assignee
University Of Yamanashi
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 University Of Yamanashi filed Critical University Of Yamanashi
Priority to JP2007542744A priority Critical patent/JP4882075B2/ja
Publication of WO2007052632A1 publication Critical patent/WO2007052632A1/fr

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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
    • 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
    • C30B29/16—Oxides
    • 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
    • C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
    • C30B13/08—Single-crystal growth by zone-melting; Refining by zone-melting adding crystallising materials or reactants forming it in situ to the molten zone

Definitions

  • the present invention relates to a floaty using a rutile (TiO 2) single crystal, for example, using an infrared concentration heating furnace.
  • rutile (TiO) single crystal having a light transmittance of 60% or more in a wavelength region of 420 nm or longer without the treatment of oxygen annealing or the like is manufactured. It is about how to do.
  • Rutile (TiO) single crystal is an indispensable optical material as a component of optical isolators.
  • rutile (TiO) single crystals are generally used in the floating zone method.
  • the former causes a decrease in light transmittance and the latter causes a change in refractive index, both of which are rutile (TiO 2) single crystals.
  • Patent Document 1 As a method for suppressing the generation of low-angle grain boundaries, the growth atmosphere is grown under low oxygen partial pressure or high pressure oxygen pressurization in carbon dioxide gas or the like in crystal growth by the FZ method (Patent Document 1), or A method of adding metal ions such as Al 3+ and Sc 3+ to raw materials has been reported (Patent Document 2).
  • Patent Document 2 as a method for producing a high-quality rutile single crystal having a large diameter and few lattice defects, a rutile (Ti 0) single crystal is grown using a sintered raw material rod containing an aluminum raw material.
  • Patent Document 1 JP-A-61-101495
  • Patent Document 2 Japanese Patent Laid-Open No. 6-48894
  • a single crystal causes a decrease in light transmittance and a change in refractive index, and it is difficult to grow a single crystal having a large diameter. For this reason, it is necessary to grow single crystals under high-pressure oxygen pressurization as described above, or to perform oxygen heat treatment at 1000 ° C or higher for several tens of hours or more, which causes high costs. Yes.
  • an object of the present invention is to bring a rutile (Ti 0) solvent or rutile melt (TiO 2) seed crystal containing a small amount of different metal elements into contact with a high-purity rutile raw material, Ti ⁇
  • a rutile raw material rod and a rutile seed crystal are melted to form a molten zone, and while the molten zone is moved, a rutile (TiO) unit is formed.
  • a heterogeneous metal element having a valence lower than 4 is added, and oxygen vacancies in the grown rutile (TiO) single crystal are suppressed by the dissimilar metal element contained in the melting zone.
  • the different metal element contained in the molten zone is one metal element selected from the group consisting of aluminum (A1), iron (Fe), calcium (Ca), and nickel (Ni). Also It is preferable that the growing atmosphere is oxygen 0. IMPa or more.
  • the rutile (TiO) single crystal produced according to the present invention is in the wavelength region of 420 nm or more.
  • the light transmittance of the rutile (TiO) single crystal is 1 mm or more in the light transmission direction.
  • the concentration of the dissimilar metal element contained in the single crystal is 30 ppm or less. This indicates that the foreign element contained in the liquid phase is not taken into the growing crystal, or that the proportion of the foreign element contained in the growing crystal is small.
  • the concentration of the foreign element in the liquid phase is CL, and the concentration contained in the growing crystal is CS. This means that CS / CL is very small compared to 1.
  • a single crystal having low oxygen vacancies or small tilt grain boundaries and a norretyl (TiO 2) single crystal can be obtained.
  • FIG. 1 is an explanatory diagram of a four-elliptic infrared intensive heating furnace used in a method for producing a rutile single crystal.
  • FIG. 2 is a diagram showing a bonding method (solvent attachment) between a solvent raw material and a rutile raw material and a method for growing a rutile single crystal.
  • FIG. 3 is a photograph of the color shape of the obtained grown crystal.
  • FIG. 4 is a graph showing the results of measuring light transmittance.
  • FIG. 1 is an explanatory view of a four-elliptic infrared central heating apparatus 1 used in the method for producing a rutile single crystal of the present invention.
  • a melting zone 19 formed between the raw material rod 18 and the seed crystal 20 rotating in opposite directions is disposed. These are located in an infrared-transmitting cylindrical body 13 made of quartz glass or the like, and the raw material rod 18 and the seed crystal 20 are respectively coupled to an upper rotating shaft 14 and a lower rotating shaft 15 driven by a rotation driving mechanism. .
  • the raw material rod 18 is a cold isostatic press (CI) packed with TiO powder in a rubber tube.
  • CI cold isostatic press
  • a gas exhaust port 16 is communicated with the upper portion of the cylindrical body 13 and a gas inlet port 17 is communicated with the lower portion thereof, and oxygen is introduced from the gas inlet port 17 as a growing atmosphere in the cylindrical body 13. A constant oxygen pressure is maintained in the cylindrical body 13.
  • the melting zone 19 is moved by relatively moving the seed crystal 20 and the heating position at a speed of 3 mm / hour or more to cause rutile to crystallize in the seed crystal 20 to form a single crystal. obtain.
  • a rutile raw material rod 18 was produced by the following procedure. Rutile raw material: Ti ⁇ (99.9%) (Toho Chitani)
  • each additive was wet mixed in an alumina mortar, placed in an alumina crucible, baked in air at 1000 ° C for 12 hours in a cantal furnace, and solvent powder. The powder was made.
  • the solvent powder is packed into a long and narrow rubber tube, molded into a rod shape, vacuumed for 30 minutes with an aspirator, and the air in the tube is evacuated, and a hydrostatic pressure of 300 MPa is applied by a cold isostatic press (CIP). After molding with a press, it was taken out from the rubber tube, drilled on one side, passed through a white wire, and sintered in air in a super cantal furnace at 1200 ° C for 12 hours to produce a sintered body of solvent raw material .
  • CIP cold isostatic press
  • a rutile single crystal growth apparatus was used for joining (solvent attachment) of the solvent raw material and the rutile raw material.
  • This device is a four elliptical mirror type infrared condensing heating device 1 (FZ-T-4000-H manufactured by Crystal System Co., Ltd.) using four l.OkW halogen lamps as light sources.
  • the quartz tube of this equipment was 2 mm thick when the growth atmosphere was oxygen O. lMPa, and 5 mm thick when oxygen was 0.5 MPa.
  • the raw material rod is fixed to the alumina tube with a platinum wire, 0.3 g of the solvent raw material is placed on the tip of the raw material rod (setting), and the atmosphere takes about 1.5 hours in the air.
  • the lamp voltage was adjusted to melt the solvent and attach the solvent raw material to the tip of the raw material rod (melting / solidification).
  • the growth conditions for the rutile single crystal were 5 mm / h at 1 atmosphere or 5 atmospheres of oxygen, and the rutile seed crystal 20 was a rutile single crystal grown in CO with an orientation ⁇ 001> and a diameter of 3 mm.
  • Figure 2 The growth conditions for the rutile single crystal were 5 mm / h at 1 atmosphere or 5 atmospheres of oxygen, and the rutile seed crystal 20 was a rutile single crystal grown in CO with an orientation ⁇ 001> and a diameter of 3 mm.
  • the solvent-adhered material rod was hooked on the hook of the upper shaft with a platinum wire, and the rutile seed crystal 20 was installed on the lower shaft.
  • pressurize the oxygen pressure to an arbitrary value, increase the lamp output to 3.17 to 3.44 kW over about 1.5 hours, and rotate the upper and lower shafts in opposite directions at lOrpm (up) and 30 rpm (down) I let you.
  • the tip of the raw material rod 18 was melted to form the melting zone 19 (FIG. 2 (b) melting).
  • the seed crystal 20 was raised to the heating zone and the seed crystal 20 was heated, and then joined to the raw material rod 18 to form a melting zone 19 (see FIG. 2 (b) seeding).
  • the heating zone was moved relatively upward at 5 mm / h to grow the rutile seed crystal 20 in the direction ⁇ 001>.
  • the relative movement of the heating zone includes a method in which the heating furnace is moved upward and a method in which the raw material rod 18 and the seed crystal 20 are simultaneously moved downward, either of which may be used.
  • the lamp voltage was adjusted by looking at the situation in the melting zone 19 (Fig. 2 (b)).
  • the ramp voltage was gradually decreased, and the grown crystal and the material rod 18 were separated in about 20 minutes (Fig. 2 (b) Melting zone separation).
  • the lamp output was set to 0 W over about 1 hour.
  • the oxygen pressure was maintained until the lamp output was 0 W and the grown crystal was removed from the furnace.
  • a halogen lamp is placed at one focal point of a spheroid coated with an aluminum film or a gold film, and a seed crystal fixed to the tip of the raw material rod suspended on the upper shaft and the lower shaft at the other focal point. Arrange so that the top of 20 comes.
  • the infrared light emitted from the halogen lamp at one focal point is condensed at the other focal point, melting part of the raw material rod 18 and seed crystal 20 and joining them together.
  • a melting zone 19 is formed, and the melting zone 19 is sequentially moved upward to grow a single crystal.
  • the stable melting zone 19 is maintained by adjusting the lamp voltage and the position of the upper and lower shafts while observing the melting zone.
  • the crystal growth section is shielded from the atmosphere by a transparent quartz tube, it is possible to grow crystals in any atmospheric gas.
  • a container such as a crucible is not required for forming the molten zone, there is no problem such as chemical reaction between the crucible and the raw material due to contamination from the crucible.
  • the shape of the grown crystal was a quadrangular prism because four facets appeared in parallel with the c-axis direction. There was a difference in the color of the grown crystal depending on the additive to the rutile solvent. As shown in Fig. 3, Al, Fe, and Ca were rutile's original pale yellow color regardless of the oxygen pressure in the growth atmosphere, but Ni is a neutral color between yellow and blue, and Y and Ga are slightly yellower than blue. It had a different color.
  • FIG. 4 is a graph showing the results of measuring the light transmittance.
  • the sample used here is l-2mm thick and polished Mirror-polished with lxm agent, unheat-treated.
  • the UV_Spectrophotometer was used to measure the light transmittance in the 200 to 900 nm wavelength range at room temperature, and as shown in FIG. 4, the rutile (TiO) single crystal grown at an oxygen pressure of 0.5 MPa was 420 nm or more.
  • Solvent composition A11 350ppm, oxygen pressure O. lMPa grown rutile (TiO) crystal
  • Each sample was cut out with a sample, 0.1 g of a sample obtained by treating the tip of the grown crystal (0.252 g) and the latter half (0.208 g) in sulfuric acid at 90 ° C for 3.5 hours, weighed with alkali, and the molten salt was dissolved in hydrochloric acid. Dissolved in.
  • Aluminum (A1) contained in this solution was measured by inductively coupled plasma optical emission spectrometry (device used: SPS-1700HVR type). As shown in Table 2, both Al and Fe were below the detection limit of the measuring device. .
  • the manufactured rutile (TiO) single crystal has an initial part and an end part.

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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

La présente invention concerne un monocristal de rutile (TiO2) ayant une transmittance élevée, lequel est produit sans la nécessité d’effectuer la croissance du monocristal sous une atmosphère d’oxygène à haute pression ou sous un traitement thermique. Le procédé de production d’un monocristal de rutile (TiO2) comprend la fusion d’un joint entre une tige de rutile brut et un germe de cristal de rutile pour former une zone de fusion et la croissance d’un monocristal de rutile (TiO2) tout en déplaçant la zone de fusion. Dans le procédé, un élément de métal différent ayant une valence inférieure à celle du titane, à savoir, +4, est ajouté dans la zone de fusion, moyennant quoi on empêche le monocristal de rutile (TiO2) en croissance d’avoir une insuffisance d’oxygène grâce à l'élément de métal différent. On produit ainsi un monocristal de rutile (TiO2) dans lequel la concentration en métal différent est inférieure ou égale à 30 ppm.
PCT/JP2006/321705 2005-11-01 2006-10-31 PROCEDE DE PRODUCTION DE MONOCRISTAL DE RUTILE (TiO2), MONOCRISTAL DE RUTILE (TiO2) ET ISOLANT OPTIQUE LE COMPRENANT WO2007052632A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007542744A JP4882075B2 (ja) 2005-11-01 2006-10-31 ルチル（ＴｉＯ２）単結晶の製造方法及びルチル（ＴｉＯ２）単結晶、並びにこれを用いた光アイソレータ

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-318706 2005-11-01
JP2005318706 2005-11-01

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WO2007052632A1 true WO2007052632A1 (fr) 2007-05-10

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PCT/JP2006/321705 WO2007052632A1 (fr) 2005-11-01 2006-10-31 PROCEDE DE PRODUCTION DE MONOCRISTAL DE RUTILE (TiO2), MONOCRISTAL DE RUTILE (TiO2) ET ISOLANT OPTIQUE LE COMPRENANT

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JP (1) JP4882075B2 (fr)
WO (1) WO2007052632A1 (fr)

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HATTA K. ET AL: "Floating zone growth and characterization of aluminum-doped rutile single crystals", JOURNAL OF CRYSTAL GROWTH, vol. 163, 1996, pages 279 - 284, XP003012605 *
PARK J.K. ET AL: "Characteristics of rutile single crystals grown under two different oxygen partial pressures", JOURNAL OF CRYSTAL GROWTH, vol. 268, 2004, pages 103 - 107, XP003012606 *

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JPWO2007052632A1 (ja) 2009-04-30
JP4882075B2 (ja) 2012-02-22

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