JP6929933B2 - Alumina crystal - Google Patents
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- JP6929933B2 JP6929933B2 JP2019508024A JP2019508024A JP6929933B2 JP 6929933 B2 JP6929933 B2 JP 6929933B2 JP 2019508024 A JP2019508024 A JP 2019508024A JP 2019508024 A JP2019508024 A JP 2019508024A JP 6929933 B2 JP6929933 B2 JP 6929933B2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 241
- 239000013078 crystal Substances 0.000 title claims description 130
- 239000002245 particle Substances 0.000 claims description 38
- 238000005259 measurement Methods 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 description 77
- 238000001513 hot isostatic pressing Methods 0.000 description 75
- 239000011777 magnesium Substances 0.000 description 49
- 238000010304 firing Methods 0.000 description 23
- 238000000034 method Methods 0.000 description 18
- 229910052594 sapphire Inorganic materials 0.000 description 16
- 239000010980 sapphire Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000000005 dynamic secondary ion mass spectrometry Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000001887 electron backscatter diffraction Methods 0.000 description 9
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 9
- 239000000395 magnesium oxide Substances 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000011362 coarse particle Substances 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000004445 quantitative analysis Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000001133 acceleration Effects 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 230000002706 hydrostatic effect Effects 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000011002 quantification Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- 239000006061 abrasive grain Substances 0.000 description 3
- 239000006059 cover glass Substances 0.000 description 3
- 229910003460 diamond Inorganic materials 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 241000282994 Cervidae Species 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 238000003705 background correction Methods 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
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
- C30B29/20—Aluminium oxides
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
本発明は、アルミナ結晶及びその製法に関する。 The present invention relates to alumina crystals and a method for producing the same.
サファイア基板は、発光ダイオード（ＬＥＤ）等の発光素子や半導体デバイス用のエピタキシャル成長用基板や腕時計等のカバーガラス等の分野に使用されている。サファイア基板は、例えば、チョクラルスキー法（ＣＺ法）により製造された単結晶のインゴットを切り出して得られる。 Sapphire substrates are used in fields such as light emitting elements such as light emitting diodes (LEDs), epitaxial growth substrates for semiconductor devices, and cover glasses for wristwatches and the like. The sapphire substrate is obtained by cutting out, for example, a single crystal ingot produced by the Czochralski method (CZ method).
しかしながら、サファイアは、非常に硬い材料であり、加工しにくいという問題があった。 However, sapphire is a very hard material and has a problem that it is difficult to process.
本発明は、上述した課題を解決するためになされたものであり、サファイアの代替品として利用可能な単結晶様のアルミナ結晶を提供することを主目的とする。 The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a single crystal-like alumina crystal that can be used as a substitute for sapphire.
本発明のアルミナ結晶は、
単結晶様のアルミナ結晶であって、面積が２５ｍｍ2以上の結晶面を含み、前記結晶面における異物の面積比率が１０％以下であり、前記アルミナ結晶のうち前記異物を除く領域にＦを１０〜３００ａｔｐｐｍ含み、Ｍｇを１０〜２５０ａｔｐｐｍ含む、
ものである。The alumina crystal of the present invention
It is a single crystal-like alumina crystal, includes a crystal plane having an area of 25 mm 2 or more, has an area ratio of foreign matter on the crystal plane of 10% or less, and has 10 F in the region of the alumina crystal excluding the foreign matter. Contains ~ 300 atppm, contains 10 to 250 atppm of Mg,
It is a thing.
このアルミナ結晶は、微量のＦやＭｇを含むものではあるが、サファイア並みの結晶性を有するため、サファイアの代替品として利用可能である。また、このアルミナ結晶の研磨のしやすさは、サファイアと同等又はそれ以上である。 Although this alumina crystal contains a trace amount of F and Mg, it can be used as a substitute for sapphire because it has crystallinity comparable to that of sapphire. Further, the ease of polishing of the alumina crystal is equal to or higher than that of sapphire.
本発明のアルミナ結晶の製法は、
開気孔率が３％以下であり、Ｆを１０〜３００ａｔｐｐｍ含み、Ｍｇを２０〜５００ａｔｐｐｍ含むアルミナ焼結体と、Ｍｇの含有量が前記アルミナ焼結体より少なく比表面積ｂ［ｍ2／ｇ］が０．０１以上であるＡｌ含有粉末又は該Ａｌ含有粉末の圧粉成形体とを、前記アルミナ焼結体の重量をａ［ｇ］、前記Ａｌ含有粉末の比表面積をｂ［ｍ2／ｇ］、前記Ａｌ含有粉末の重量をｃ［ｇ］としたときにｂｃ／ａが０．２５以上になるように接触させた状態で、温度１８００℃以上、圧力１００ＭＰａ以上でＨＩＰ処理し、その後前記Ａｌ含有粉末の焼結物を除去することにより単結晶様のアルミナ結晶を得る、
ものである。The method for producing an alumina crystal of the present invention is
An alumina sintered body having an open pore ratio of 3% or less, containing 10 to 300 atppm of F, and containing 20 to 500 atppm of Mg, and a specific surface area b [m 2 / g] having a smaller Mg content than the alumina sintered body. The weight of the alumina sintered body is a [g], and the specific surface area of the Al-containing powder is b [m 2 / g] with the Al-containing powder or the powder compact of the Al-containing powder having a value of 0.01 or more. ], When the weight of the Al-containing powder is c [g], HIP treatment is performed at a temperature of 1800 ° C. or higher and a pressure of 100 MPa or higher in a state where the bc / a is 0.25 or higher, and then the above. A single crystal-like alumina crystal is obtained by removing the sintered product of the Al-containing powder.
It is a thing.
この製法によれば、開気孔率が３％以下であり、Ｆを１０〜３００ａｔｐｐｍ含み、Ｍｇを２０〜５００ａｔｐｐｍ含むアルミナ焼結体を用いて、サファイア並みの単結晶様のアルミナ結晶を得ることができる。そのため、単結晶様のアルミナ結晶を大量生産することができる。また、アルミナ焼結体は、種々の形状のアルミナ成形体を焼成することにより得ることができ、単結晶様のアルミナ結晶は、そのアルミナ焼結体を用いて作製することができる。そのため、単結晶様のアルミナ結晶をニアネットシェイプで作製することができ、その後の研削・研磨プロセスを簡素化できる。 According to this production method, an alumina sintered body having an open porosity of 3% or less, containing 10 to 300 atppm of F, and containing 20 to 500 atppm of Mg can be used to obtain a single crystal-like alumina crystal similar to sapphire. can. Therefore, single crystal-like alumina crystals can be mass-produced. Further, the alumina sintered body can be obtained by firing alumina molded bodies having various shapes, and a single crystal-like alumina crystal can be produced by using the alumina sintered body. Therefore, a single crystal-like alumina crystal can be produced with a near net shape, and the subsequent grinding / polishing process can be simplified.
本実施形態のアルミナ結晶は、単結晶様のアルミナ結晶であって、面積が２５ｍｍ2以上の結晶面を含み、前記結晶面における異物の面積比率が１０％以下であり、前記アルミナ結晶のうち前記異物を除く領域にＦを１０〜３００ａｔｐｐｍ含み、Ｍｇを１０〜２５０ａｔｐｐｍ含むものである。なお、結晶面とは、単結晶様のアルミナ結晶を任意の箇所で切り出したときの断面を指す。The alumina crystal of the present embodiment is a single crystal-like alumina crystal, includes a crystal plane having an area of 25 mm 2 or more, and has an area ratio of foreign matter on the crystal plane of 10% or less. The region excluding foreign matter contains 10 to 300 atppm of F and 10 to 250 atppm of Mg. The crystal plane refers to a cross section when a single crystal-like alumina crystal is cut out at an arbitrary position.
結晶面の面積は２５ｍｍ2以上が好ましく、５０ｍｍ2以上がより好ましく、８０ｍｍ2以上が更に好ましい。The area of the crystal plane is preferably 25 mm 2 or more, more preferably 50 mm 2 or more, 80 mm 2 or more is more preferable.
結晶面における異物の面積比率は、１０％以下であることが好ましく、５％以下であることがより好ましい。結晶面における異物は、通常、試料からアルミナ結晶の断面積（結晶面の断面積）が２５ｍｍ2以上となるように観察面を切り出し、鏡面研磨した後、サーマルエッチング処理を行ったときに結晶面内に現れる粒界によって区別し得るものである。異物には、例えば、気孔、異相及び結晶方位が異なる粒子が含まれる。結晶面における異物の面積比率は、以下のようにして算出することができる。The area ratio of the foreign matter on the crystal plane is preferably 10% or less, and more preferably 5% or less. For foreign matter on the crystal plane, the observation plane is usually cut out from the sample so that the cross-sectional area of the alumina crystal (cross-sectional area of the crystal plane) is 25 mm 2 or more, mirror-polished, and then the crystal plane is subjected to thermal etching treatment. It can be distinguished by the grain boundaries that appear inside. Foreign matter includes, for example, particles having different pores, different phases, and crystal orientations. The area ratio of foreign matter on the crystal plane can be calculated as follows.
まず、本実施形態のアルミナ結晶の結晶面の面積が２５ｍｍ2以上となるように試料から観察面を切り出し、ダイヤモンド砥粒を用いて鏡面研磨した後、サーマルエッチング処理を実施する。サーマルエッチング処理後の断面を走査型電子顕微鏡にて縦横が所定サイズの視野を所定倍率にて撮影し、連続的な二次電子像及び反射電子像の写真となるように並べる。こうした連続的な写真から異物を目視にて確認する。異物が存在する場合には、異物の境界を目視で容易に判別できる。なお、判別が難しい箇所については、電子線後方散乱回折法（ＥＢＳＤ）、又はＥＤＳを用いて判別してもよい。そして、画像処理ソフトＡｄｏｂｅ Ｐｈｏｔｏｓｈｏｐ（ＣＳ５）にて、結晶面の面積と、その結晶面内に存在する異物の面積を求める。まず、各二次電子像、反射電子像を上述した画像処理ソフトに取り込み、結晶面とその外部との境界、及び、結晶面とその内部に存在する異物との境界を手動で指定する。そして、結晶面のピクセル数と異物のピクセル数を算出し、以下の式を用いて結晶面における異物の面積比率を算出する。算出が難しい箇所については、高倍率で撮影した像にて判別する。
異物の面積比率（％）＝｛各異物のピクセル数の総和／結晶面のピクセル数｝×１００First, an observation surface is cut out from the sample so that the area of the crystal plane of the alumina crystal of the present embodiment is 25 mm 2 or more, mirror polishing is performed using diamond abrasive grains, and then thermal etching treatment is performed. The cross section after the thermal etching treatment is photographed with a scanning electron microscope in a field of view having a predetermined size in the vertical and horizontal directions at a predetermined magnification, and arranged so as to be a continuous secondary electron image and a backscattered electron image. Foreign matter is visually confirmed from these continuous photographs. When a foreign substance is present, the boundary of the foreign substance can be easily visually identified. For locations that are difficult to discriminate, electron backscatter diffraction (EBSD) or EDS may be used for discrimination. Then, the area of the crystal plane and the area of the foreign matter existing in the crystal plane are determined by the image processing software Adobe Photoshop (CS5). First, each secondary electron image and backscattered electron image are taken into the above-mentioned image processing software, and the boundary between the crystal plane and its outside and the boundary between the crystal plane and the foreign matter existing inside the crystal plane are manually specified. Then, the number of pixels on the crystal plane and the number of pixels of the foreign matter are calculated, and the area ratio of the foreign matter on the crystal plane is calculated using the following formula. For parts that are difficult to calculate, the image taken at high magnification is used for discrimination.
Area ratio of foreign matter (%) = {total number of pixels of each foreign matter / number of pixels on crystal plane} x 100
本実施形態のアルミナ結晶は、異物を除く領域にＦを１０〜３００ａｔｐｐｍ、好ましくは２０〜２５０ａｔｐｐｍ含み、Ｍｇを１０〜２５０ａｔｐｐｍ、好ましくは２０〜２００ａｔｐｐｍ含むものである。ＦやＭｇはダイナミック二次イオン質量分析（Ｄ−ＳＩＭＳ）により測定することができる（詳細は後述の実験例参照）。Ｆ含有量とＭｇ含有量の比率Ｆ／Ｍｇは０．２５〜４であることが好ましく、０．３〜３．６であることがより好ましく、０．５〜２であることが更に好ましい。 The alumina crystal of the present embodiment contains F at 10 to 300 atppm, preferably 20 to 250 atppm, and Mg at 10 to 250 atppm, preferably 20 to 200 atppm in the region excluding foreign substances. F and Mg can be measured by dynamic secondary ion mass spectrometry (D-SIMS) (see the experimental examples described later for details). The ratio of F content to Mg content F / Mg is preferably 0.25 to 4, more preferably 0.3 to 3.6, and even more preferably 0.5 to 2.
本実施形態のアルミナ結晶は、（００６）面又は（１００）面のＸ線ロッキングカーブ（ＸＲＣ）測定において、半値幅（ＦＷＨＭ）が１００ａｒｃｓｅｃ以下であることが好ましく、６０ａｒｃｓｅｃ以下であることがより好ましい（測定方法の詳細は後述の実験例参照）。この半値幅は、小さいほど結晶性がよいことを示すため好ましい。 The alumina crystal of the present embodiment preferably has a half width (FWHM) of 100 arcsec or less, more preferably 60 arcsec or less, in the X-ray locking curve (XRC) measurement of the (006) plane or the (100) plane. (Refer to the experimental example described later for details of the measurement method). This half-value width is preferable because the smaller the width, the better the crystallinity.
本実施形態のアルミナ結晶は、異物を除く領域におけるＡｌ、Ｏ、Ｆ、Ｍｇ，Ｃ以外の元素（不純物元素）の含有量が１０ｐｐｍ以下であることが好ましい。こうすれば、透明性が高まるからである。不純物元素としては、Ｃ，Ｓ，Ｎ，Ｈのほか、Ｓｉ，Ｆｅ，Ｔｉ，Ｎａ，Ｃａ，Ｍｇ，Ｋ，Ｐ，Ｖ，Ｃｒ，Ｍｎ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｙ，Ｚｒ，Ｐｂ，Ｂｉ，Ｌｉ，Ｂｅ，Ｂ，Ｃｌ，Ｓｃ，Ｇａ，Ｇｅ，Ａｓ，Ｓｅ，Ｂｒ，Ｒｂ，Ｓｒ，Ｎｂ，Ｍｏ，Ｒｕ，Ｒｈ，Ｐｄ，Ａｇ，Ｃｄ，Ｉｎ，Ｓｎ，Ｓｂ，Ｔｅ，Ｃｓ，Ｂａ，Ｈｆ，Ｔａ，Ｗ，Ｉｒ，Ｐｔ，Ａｕ，Ｈｇ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｌｕ，Ｂａ，Ｓｒ，Ｐｂが挙げられる（測定方法の詳細は後述の実験例参照）。 The alumina crystal of the present embodiment preferably contains 10 ppm or less of an element (impurity element) other than Al, O, F, Mg, and C in the region excluding foreign substances. This will increase transparency. In addition to C, S, N, and H, the impurity elements include Si, Fe, Ti, Na, Ca, Mg, K, P, V, Cr, Mn, Co, Ni, Cu, Zn, Y, Zr, and Pb. , Bi, Li, Be, B, Cl, Sc, Ga, Ge, As, Se, Br, Rb, Sr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs , Ba, Hf, Ta, W, Ir, Pt, Au, Hg, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ba, Sr, Pb (For details of the measurement method, refer to the experimental example described later).
本実施形態のアルミナ結晶は、微量のＦやＭｇを含むものではあるが、サファイア並みの結晶性を有するため、サファイアの代替品として利用可能である。例えば、発光ダイオード（ＬＥＤ）等の発光素子や半導体デバイス用のエピタキシャル成長用基板や腕時計等のカバーガラスなどに利用可能である。また、このアルミナ結晶の研磨のしやすさは、サファイアと同等又はそれ以上である。 Although the alumina crystal of the present embodiment contains a trace amount of F and Mg, it can be used as a substitute for sapphire because it has crystallinity comparable to that of sapphire. For example, it can be used for a light emitting element such as a light emitting diode (LED), an epitaxial growth substrate for a semiconductor device, a cover glass for a wristwatch or the like, and the like. Further, the ease of polishing of the alumina crystal is equal to or higher than that of sapphire.
本実施形態のアルミナ結晶の製法は、開気孔率が３％以下であり、Ｆを１０〜３００ａｔｐｐｍ含み、Ｍｇを２０〜５００ａｔｐｐｍ含むアルミナ焼結体と、Ｍｇの含有量がアルミナ焼結体より少なく比表面積ｂ［ｍ2／ｇ］が０．０１以上であるＡｌ含有粉末又は該Ａｌ含有粉末の圧粉成形体とを、アルミナ焼結体の重量をａ［ｇ］、Ａｌ含有粉末の比表面積をｂ［ｍ2／ｇ］、Ａｌ含有粉末の重量をｃ［ｇ］としたときにｂｃ／ａが０．２５以上になるように接触させた状態で、温度１８００℃以上、圧力１００ＭＰａ以上でＨＩＰ処理し、その後前記Ａｌ含有粉末の焼結物を除去することにより単結晶様のアルミナ結晶を得るものである。In the method for producing an alumina crystal of the present embodiment, an alumina sintered body having an open pore ratio of 3% or less, containing 10 to 300 atppm of F, and containing 20 to 500 atppm of Mg, and an alumina sintered body having a smaller Mg content than the alumina sintered body. The specific surface area b [m 2 / g] of the Al-containing powder or the powder compact of the Al-containing powder is 0.01 or more, the weight of the alumina sintered body is a [g], and the specific surface area of the Al-containing powder. B [m 2 / g] and the weight of the Al-containing powder is c [g], the bc / a is 0.25 or more, and the temperature is 1800 ° C. or higher and the pressure is 100 MPa or higher. A single crystal-like alumina crystal is obtained by performing HIP treatment and then removing the sintered product of the Al-containing powder.
アルミナ焼結体は、どのような手法で焼成したものでもよいが、開気孔率が３％以下のものを用いる。こうすることにより、異物（気孔、異相及び結晶方位が異なる粒子）の含有率が小さく、大きな面積を有する単結晶様のアルミナ結晶を得ることができるからである。また、ＨＩＰ処理を行うことを考慮すると、アルミナ焼結体は緻密な方が好ましいからである。開気孔率は１％以下がより好ましく、０％が更に好ましい。焼成方法としては、例えば、常圧焼成、ホットプレス焼成、水素焼成などが挙げられる。 The alumina sintered body may be fired by any method, but one having an open porosity of 3% or less is used. By doing so, it is possible to obtain a single crystal-like alumina crystal having a small content of foreign substances (particles having different pores, different phases and crystal orientations) and a large area. Further, considering that the HIP treatment is performed, it is preferable that the alumina sintered body is dense. The open porosity is more preferably 1% or less, further preferably 0%. Examples of the firing method include normal pressure firing, hot press firing, hydrogen firing, and the like.
アルミナ焼結体は、Ｆを１０〜３００ａｔｐｐｍ含み、Ｍｇを２０〜５００ａｔｐｐｍ含むものである。なお、ａｔｐｐｍは原子１０6個中に含まれる特定の原子の数を表す単位である。ＦやＭｇの添加方法は特に限定されない。ＦやＭｇの含有量については、Ｄ−ＳＩＭＳを用いて測定することができる。Ｆの含有量は、２０〜２５０ａｔｐｐｍｍが好ましく、Ｍｇの含有量は３０〜３５０ａｔｐｐｍが好ましい。The alumina sintered body contains 10 to 300 atppm of F and 20 to 500 atppm of Mg. Incidentally, Atppm is a unit representing the number of specific atoms contained in 10 in six atoms. The method of adding F or Mg is not particularly limited. The contents of F and Mg can be measured using D-SIMS. The content of F is preferably 20 to 250 atppm, and the content of Mg is preferably 30 to 350 atppm.
アルミナ焼結体の粒径は、小さい方が好ましい。こうすることにより、大きな面積を有する単結晶様のアルミナ結晶を得ることができるからである。粒径は３０μｍ以下が好ましく、２０μｍ以下がより好ましく、１０μｍ以下が更に好ましく、５μｍ以下が特に好ましい。 The particle size of the alumina sintered body is preferably small. This is because a single crystal-like alumina crystal having a large area can be obtained. The particle size is preferably 30 μm or less, more preferably 20 μm or less, further preferably 10 μm or less, and particularly preferably 5 μm or less.
アルミナ焼結体の結晶配向状態は特に限定はないが、いずれかの結晶方位に配向していることが好ましい。こうすることにより、大きな面積を有する単結晶様のアルミナ結晶を得やすいからである。アルミナ焼結体中に含まれる配向している粒子の割合（配向度）はＥＢＳＤを用いて評価する。配向度の詳細な算出方法については後述する。配向度は３０％以上が好ましく、５０％以上がより好ましく、１００％が更に好ましい。また、アルミナ焼結体が配向していないものであっても、ＨＩＰ処理中の粒成長に伴って配向するものであればよい。例えば、特定の方向に配向した粗大粒子とその粗大粒子よりも細かい微細粒子とを含有するアルミナ焼結体であれば、ＨＩＰ処理中にＴＧＧ（Ｔｅｍｐｌａｔｅｄ Ｇｒａｉｎ Ｇｒｏｗｔｈ）成長して配向する。ＴＧＧ成長とは、粗大粒子が周囲の微細粒子を取り込みながら成長することをいう。ＨＩＰ処理中にＴＧＧ成長するアルミナ焼結体は、例えば、特定の方向に配向した板状アルミナ粒子とその板状アルミナ粒子よりも細かい微細粒子とを含むアルミナ成形体を温度１０００〜１８５０℃で焼成することにより得ることができる。この場合、板状アルミナ粒子としてＦ成分を含むものを用いてもよいし、成形体中にＦ成分を含むものや焼結助剤としてＭｇ成分を含むものを用いてもよい。また、焼成方法はどのような手法でもよく、常圧焼成でもよいし加圧焼成でもよい。 The crystal orientation state of the alumina sintered body is not particularly limited, but it is preferable that the alumina sintered body is oriented in any crystal orientation. This is because it is easy to obtain a single crystal-like alumina crystal having a large area. The ratio (degree of orientation) of the oriented particles contained in the alumina sintered body is evaluated using EBSD. The detailed calculation method of the degree of orientation will be described later. The degree of orientation is preferably 30% or more, more preferably 50% or more, still more preferably 100%. Further, even if the alumina sintered body is not oriented, it may be oriented as the grain grows during the HIP treatment. For example, in the case of an alumina sintered body containing coarse particles oriented in a specific direction and fine particles finer than the coarse particles, TGG (Templated Grain Growth) grows and is oriented during the HIP treatment. TGG growth means that coarse particles grow while taking in surrounding fine particles. The alumina sintered body that grows TGG during the HIP treatment is, for example, firing an alumina molded body containing plate-shaped alumina particles oriented in a specific direction and fine particles finer than the plate-shaped alumina particles at a temperature of 1000 to 1850 ° C. It can be obtained by doing. In this case, those containing the F component as the plate-shaped alumina particles may be used, those containing the F component in the molded product, and those containing the Mg component as the sintering aid may be used. Further, the firing method may be any method, and may be normal pressure firing or pressure firing.
Ａｌ含有粉末は、Ｍｇ含有量がアルミナ焼結体より少ないものを用いる。Ｍｇがアルミナ焼結体中からＡｌ含有粉末中に拡散するように移動するのに伴いアルミナ結晶が大きく成長すると考えられるからである。Ａｌ含有粉末はＭｇを含まないものが好ましい。また、透明なアルミナ結晶を得る観点では、Ａｌ、Ｏ、Ｍｇ、Ｆ以外の不純物が少ない方が好ましい。Ａｌ含有粉末は、Ａｌを含む限り化合物の材質には特に限定はないが、α−アルミナ粉末、アルミナ前駆体（例えばベーマイト）粉末、遷移アルミナ（γ−アルミナやθアルミナ）粉末などが好ましい。一方、Ａｌ含有粉末はアルミナと反応したり、焼結体に固溶するような元素を含むものは焼結体の結晶性を損なう可能性があり、その観点では好ましくない。Ａｌ含有粉末の純度は特に限定が無いが、高い方が好ましい。 As the Al-containing powder, a powder having a Mg content lower than that of the alumina sintered body is used. This is because it is considered that the alumina crystals grow significantly as Mg moves from the alumina sintered body so as to diffuse into the Al-containing powder. The Al-containing powder preferably does not contain Mg. Further, from the viewpoint of obtaining transparent alumina crystals, it is preferable that there are few impurities other than Al, O, Mg and F. The Al-containing powder is not particularly limited as long as it contains Al, but α-alumina powder, alumina precursor (for example, boehmite) powder, transition alumina (γ-alumina or θ-alumina) powder, or the like is preferable. On the other hand, the Al-containing powder containing an element that reacts with alumina or dissolves in the sintered body may impair the crystallinity of the sintered body, which is not preferable from that viewpoint. The purity of the Al-containing powder is not particularly limited, but a higher purity is preferable.
Ａｌ含有粉末は、比表面積ｂ［ｍ2／ｇ］が０．０１以上のものを用いる。こうすることにより、大きな結晶面を有する単結晶様のアルミナ結晶を得ることができるからである。このような効果が得られる理由は不明だが、Ｍｇがアルミナ焼結体中からＡｌ含有粉末中に粉末表面を拡散するように移動するのに伴いアルミナ結晶が大きく成長するからではないかと考えられる。比表面積ｂ［ｍ2／ｇ］は０．１以上が好ましく、１以上がより好ましく、３以上が更に好ましい。一方、比表面積ｂ［ｍ2／ｇ］が大きすぎるとＨＩＰ処理後にアルミナ結晶を取り出すのが難しくなるため、取り出しやすさの観点からは１５以下が好ましく、１０以下がより好ましく、５以下が更に好ましい。大面積のアルミナ結晶を得つつ、取り出しのしやすさを両立するには比表面積０．１以上１５以下が好ましく、１以上１０以下がより好ましく、３以上５以下が更に好ましい。As the Al-containing powder, a powder having a specific surface area b [m 2 / g] of 0.01 or more is used. This is because a single crystal-like alumina crystal having a large crystal plane can be obtained. The reason why such an effect can be obtained is unknown, but it is considered that the alumina crystals grow large as Mg moves from the alumina sintered body into the Al-containing powder so as to diffuse the powder surface. The specific surface area b [m 2 / g] is preferably 0.1 or more, more preferably 1 or more, and even more preferably 3 or more. On the other hand, if the specific surface area b [m 2 / g] is too large, it becomes difficult to take out the alumina crystals after the HIP treatment. Therefore, from the viewpoint of ease of taking out, 15 or less is preferable, 10 or less is more preferable, and 5 or less is further taken out. preferable. The specific surface area is preferably 0.1 or more and 15 or less, more preferably 1 or more and 10 or less, and further preferably 3 or more and 5 or less in order to obtain a large area of alumina crystals and to achieve both ease of removal.
ＨＩＰ処理を行う際、アルミナ焼結体の重量をａ［ｇ］、Ａｌ含有粉末の比表面積をｂ［ｍ2／ｇ］、Ａｌ含有粉末の重量をｃ［ｇ］としたときにｂｃ／ａが０．２５以上になるように設定する。こうすることにより、大きな面積を有する単結晶様のアルミナ結晶を得ることができるからである。ｂｃ／ａは、１以上がより好ましく、５以上がより好ましく、１０以上が更に好ましく、３０以上が特に好ましい。When the HIP treatment is performed, bc / a when the weight of the alumina sintered body is a [g], the specific surface area of the Al-containing powder is b [m 2 / g], and the weight of the Al-containing powder is c [g]. Is set to be 0.25 or more. This is because a single crystal-like alumina crystal having a large area can be obtained. As for bc / a, 1 or more is more preferable, 5 or more is more preferable, 10 or more is further preferable, and 30 or more is particularly preferable.
アルミナ焼結体とＡｌ含有粉末との接触状態としては、少なくともアルミナ焼結体の表面にＡｌ含有粉末が触れていればよいが、拡散の観点から接触面積が大きい方が好ましく、アルミナ焼結体がＡｌ含有粉末に埋設されている方がより好ましい。アルミナ焼結体とＡｌ含有粉末とを加圧して接触させてもよいが、強く接触させすぎるとＨＩＰ処理後にＡｌ含有粉末の焼結物を除去してＨＩＰ処理体（アルミナ結晶）を取り出すのが難しくなる。 As for the contact state between the alumina sintered body and the Al-containing powder, at least the surface of the alumina sintered body may be in contact with the Al-containing powder, but from the viewpoint of diffusion, it is preferable that the contact area is large, and the alumina sintered body is preferably in contact with each other. Is more preferably embedded in the Al-containing powder. The alumina sintered body and the Al-containing powder may be brought into contact with each other under pressure, but if they are brought into contact with each other too strongly, the sintered body of the Al-containing powder may be removed after the HIP treatment to take out the HIP-treated body (alumina crystal). It gets harder.
アルミナ焼結体とＡｌ含有粉末（又はＡｌ含有粉末の圧粉成形体）とを接触させた状態でＨＩＰ処理を行う場合、温度は１８００℃以上が好ましく、１８５０℃以上がより好ましい。但し、アルミナ焼結体及び埋設粉末の融点以下で実施する必要がある。例えば、埋設粉末にアルミナを用いる場合は２０５０℃以下が好ましい。圧力は、特に限定はないが、１００ＭＰａ以上が好ましく、１５０ＭＰａ以上がより好ましい。但し、一般的なＨＩＰ装置は２００ＭＰａが圧力の上限である。このようにしてＨＩＰ処理を行うことにより、ＨＩＰ処理前のアルミナ焼結体の配向状態にかかわらず、アルミナ焼結体は結晶面の大きなアルミナ結晶を有するＨＩＰ処理体になる。このようなアルミナ結晶が得られる理由は不明だが、以下のように推定している。まず、ＨＩＰ時にアルミナ焼結体がＡｌ含有粉末と接触していることで、接触点からＭｇがアルミナ焼結体中からＡｌ含有粉末中に拡散し、アルミナ焼結体中のＭｇ含有量が局所的に少ない状態、すなわちアルミナ焼結体中のＭｇ含有量に濃度勾配が生じると考えられる。このとき、Ｍｇ含有量の少ない領域で粒成長が著しく進み、周囲と比較して異常に大きな粗大粒子が生成し、その粗大粒子の周辺にＦが存在することで、他の結晶粒子が粗大粒子に容易に取り込まれ、大きなアルミナ結晶が形成されるのではないかと考えられる。 When the HIP treatment is performed in a state where the alumina sintered body and the Al-containing powder (or the powder compact of the Al-containing powder) are in contact with each other, the temperature is preferably 1800 ° C. or higher, more preferably 1850 ° C. or higher. However, it is necessary to carry out at a temperature equal to or lower than the melting point of the alumina sintered body and the buried powder. For example, when alumina is used as the buried powder, the temperature is preferably 2050 ° C. or lower. The pressure is not particularly limited, but is preferably 100 MPa or more, and more preferably 150 MPa or more. However, in a general HIP device, 200 MPa is the upper limit of the pressure. By performing the HIP treatment in this way, the alumina sintered body becomes a HIP-treated body having alumina crystals having a large crystal plane, regardless of the orientation state of the alumina sintered body before the HIP treatment. The reason why such alumina crystals are obtained is unknown, but it is estimated as follows. First, since the alumina sintered body is in contact with the Al-containing powder during HIP, Mg diffuses from the alumina sintered body into the Al-containing powder from the contact point, and the Mg content in the alumina sintered body is local. It is considered that a concentration gradient occurs in a relatively small state, that is, in the Mg content in the alumina sintered body. At this time, the grain growth progresses remarkably in the region where the Mg content is low, coarse particles that are abnormally large compared to the surroundings are generated, and F is present around the coarse particles, so that other crystal particles are coarse particles. It is considered that large alumina crystals may be formed by being easily incorporated into the particles.
ここで、アルミナ焼結体から単結晶様のアルミナ結晶が生成するときの変化の過程の一例を図１に示す。図１（ａ）はＨＩＰ処理中にＴＧＧ成長可能なアルミナ焼結体１０の断面図である。このアルミナ焼結体１０は、微細アルミナ粒子をマトリックス粒子１２とし、板状アルミナ粒子をテンプレート粒子１４として有するものである。このアルミナ焼結体１０をＡｌ含有粉末１６に埋設してＨＩＰ処理すると、アルミナ焼結体１０中でＴＧＧ成長による高配向化が起こると共に、図１（ｂ）の黒矢印のようにアルミナ焼結体中のＭｇがＡｌ含有粉末１６に拡散すると考えられ、最終的に図１（ｃ）に示す単結晶様のアルミナ結晶２０が得られる。なお、図１は本発明者の推測に基づくものであり、実際にこうした過程を辿るかどうかは不明である。
Here, FIG. 1 shows an example of the process of change when a single crystal-like alumina crystal is produced from the alumina sintered body. FIG. 1A is a cross-sectional view of the alumina sintered
本実施形態の製法によれば、開気孔率が３％以下であり、Ｆを１０〜３００ａｔｐｐｍ含み、Ｍｇを２０〜５００ａｔｐｐｍ含むアルミナ焼結体を用いて、サファイア並みの単結晶様のアルミナ結晶を得ることができる。そのため、単結晶様のアルミナ結晶を大量生産することができる。また、アルミナ焼結体は、種々の形状のアルミナ成形体を焼成することに得ることができ、単結晶様のアルミナ結晶は、そのアルミナ焼結体を用いて作製することができる。そのため、単結晶様のアルミナ結晶をニアネットシェイプで作製することができ、その後の研削・研磨プロセスを簡素化できる。また、本実施形態の製法は、上述した本実施形態のアルミナ結晶を製造するのに適している。 According to the production method of the present embodiment, an alumina sintered body having an open porosity of 3% or less, containing 10 to 300 atppm of F, and containing 20 to 500 atppm of Mg is used to obtain a single crystal-like alumina crystal similar to sapphire. Obtainable. Therefore, single crystal-like alumina crystals can be mass-produced. Further, the alumina sintered body can be obtained by firing alumina molded bodies having various shapes, and a single crystal-like alumina crystal can be produced by using the alumina sintered body. Therefore, a single crystal-like alumina crystal can be produced with a near net shape, and the subsequent grinding / polishing process can be simplified. Moreover, the production method of this embodiment is suitable for producing the alumina crystal of this embodiment described above.
［実験例１］
１．アルミナ結晶の作製
（１）板状アルミナ粉末の作製
高純度γ−アルミナ粉末（ＴＭ−３００Ｄ、大明化学製）９６質量部と、高純度ＡｌＦ3粉末（関東化学製、鹿特級）４質量部と、種結晶として高純度α−アルミナ粉末（ＴＭ−ＤＡＲ、大明化学製、Ｄ５０＝１μｍ）０．１７質量部とを、溶媒をＩＰＡ（イソプロピルアルコール）としてφ２ｍｍのアルミナボールを用いて５時間ポットミルで混合した。ポットミル混合した後、ＩＰＡをエバポレータにて乾燥し、混合粉末を得た。得られた混合粉末３００ｇを純度９９．５質量％の高純度アルミナ製のさや（容積７５０ｃｍ3）に入れ、純度９９．５質量％の高純度アルミナ製の蓋をして電気炉内でエアフロー中、９００℃、３時間熱処理した。エアーの流量は２５０００ｃｃ／ｍｉｎとした。熱処理後の粉末を大気中、１１５０℃で４２．５時間アニール処理した後、φ２ｍｍのアルミナボールを用いて４時間粉砕して平均粒径２μｍ、厚み０．３μｍ、アスペクト比約７の板状アルミナ粉末を得た。粒子の平均粒径、平均厚み、アスペクト比は、走査型電子顕微鏡（ＳＥＭ）で板状アルミナ粉末中の任意の粒子１００個を観察して決定した。平均粒径は、粒子板面の長軸長の平均値、平均厚みは、粒子の短軸長（厚み）の平均値、アスペクト比は、平均粒径／平均厚みである。図２は、板状アルミナ粒子の模式図であり、（ａ）は平面図、（ｂ）は正面図である。板状アルミナ粒子は、平面視したときの形状が略六角形状であり、その粒径は図２（ａ）に示したとおりであり、厚みは図２（ｂ）に示したとおりである。[Experimental Example 1]
1. 1. Preparation of alumina crystals (1) Preparation of plate-shaped alumina powder 96 parts by mass of high-purity γ-alumina powder (TM-300D, manufactured by Daimei Chemical Co., Ltd.) and 4 parts by mass of high-purity AlF 3 powder (manufactured by Kanto Chemical Co., Inc., special grade deer) , 0.17 parts by mass of high-purity α-alumina powder (TM-DAR, manufactured by Daimei Chemical Co., Ltd., D50 = 1 μm) as seed crystals, using a φ2 mm alumina ball with IPA (isopropyl alcohol) as the solvent, in a pot mill for 5 hours. Mixed. After mixing in a pot mill, IPA was dried on an evaporator to obtain a mixed powder. 300 g of the obtained mixed powder is placed in a pod (volume 750 cm 3 ) made of high-purity alumina having a purity of 99.5% by mass, covered with a lid made of high-purity alumina having a purity of 99.5% by mass, and air-flowing in an electric furnace. , 900 ° C. for 3 hours. The air flow rate was 25000 cc / min. The heat-treated powder is annealed in the air at 1150 ° C. for 42.5 hours and then pulverized for 4 hours using a φ2 mm alumina ball to have an average particle size of 2 μm, a thickness of 0.3 μm, and an aspect ratio of about 7. Obtained powder. The average particle size, average thickness, and aspect ratio of the particles were determined by observing 100 arbitrary particles in the plate-shaped alumina powder with a scanning electron microscope (SEM). The average particle size is the average value of the major axis length of the particle plate surface, the average thickness is the average value of the minor axis length (thickness) of the particles, and the aspect ratio is the average particle size / average thickness. 2A and 2B are schematic views of plate-shaped alumina particles, where FIG. 2A is a plan view and FIG. 2B is a front view. The plate-shaped alumina particles have a substantially hexagonal shape when viewed in a plan view, the particle size thereof is as shown in FIG. 2A, and the thickness is as shown in FIG. 2B.
（２）テープ成形
上記（１）で作製した板状アルミナ粉末２．０質量部と、平均粒径がこの板状アルミナ粉末の厚みより小さい微細アルミナ粉末（ＡＫＰ−２０、住友化学製）９８．０質量部とを混合した。この混合アルミナ粉末１００質量部に対し、酸化マグネシウム（５００Ａ、宇部マテリアルズ製）０．０２５質量部と、バインダーとしてポリビニルブチラール（品番ＢＭ−２、積水化学工業製）７．８質量部と、可塑剤としてジ（２−エチルヘキシル）フタレート（黒金化成製）３．９質量部と、分散剤としてトリオレイン酸ソルビタン（レオドールＳＰ−Ｏ３０、花王製）２質量部と、分散媒として２−エチルヘキサノールとを加えて混合した。分散媒の量は、スラリー粘度が２００００ｃＰとなるように調整した。このようにして調製されたスラリーを、ドクターブレード法によってＰＥＴフィルムの上に乾燥後の厚さが４０μｍとなるようにシート状に成形した。得られたテープを３０ｍｍ四方の正方形に切断した後、３０枚積層し、厚さ１０ｍｍのＡｌ板の上に載置した後、パッケージに入れて内部を真空にすることで真空パックとした。この真空パックを８５℃の温水中で２００ｋｇｆ／ｃｍ2の圧力にて静水圧プレスを行い、成形体を得た。(2) Tape molding 2.0 parts by mass of the plate-shaped alumina powder produced in (1) above and a fine alumina powder (AKP-20, manufactured by Sumitomo Chemical Co., Ltd.) whose average particle size is smaller than the thickness of the plate-shaped alumina powder 98. 0 parts by mass was mixed. With respect to 100 parts by mass of this mixed alumina powder, 0.025 parts by mass of magnesium oxide (500A, manufactured by Ube Materials) and 7.8 parts by mass of polyvinyl butyral (product number BM-2, manufactured by Sekisui Chemical Co., Ltd.) as a binder, and plasticizer. 3.9 parts by mass of di (2-ethylhexyl) phthalate (manufactured by Kurogane Kasei) as an agent, 2 parts by mass of sorbitan trioleate (Leodor SP-O30, manufactured by Kao) as a dispersant, and 2-ethylhexanol as a dispersion medium. And were added and mixed. The amount of the dispersion medium was adjusted so that the slurry viscosity was 20000 cP. The slurry thus prepared was formed into a sheet on a PET film by a doctor blade method so that the thickness after drying was 40 μm. The obtained tape was cut into a 30 mm square, 30 sheets were laminated, placed on an Al plate having a thickness of 10 mm, and then placed in a package to evacuate the inside to form a vacuum pack. This vacuum pack was hydrostatically pressed at a pressure of 200 kgf / cm 2 in warm water at 85 ° C. to obtain a molded product.
（３）アルミナ焼結体の作製
得られた成形体を脱脂炉中に配置し、６００℃で１０時間の条件で脱脂を行った。得られた脱脂体を９０ｍｍ角のアルミナ製の鞘に入れ、大気中、１５５０℃で４時間の条件で常圧焼成し、アルミナ焼結体を作製した。(3) Preparation of Alumina Sintered Body The obtained molded product was placed in a degreasing furnace and degreased at 600 ° C. for 10 hours. The obtained degreased material was placed in a 90 mm square alumina sheath and fired in the air at 1550 ° C. for 4 hours under normal pressure to prepare an alumina sintered body.
（４）ＨＩＰ処理体（アルミナ結晶）の作製
作製したアルミナ焼結体から質量が１．５ｇ（＝質量ａ）のサンプルを切り出し、そのサンプルを内径５０ｍｍ、高さ４０ｍｍの蓋付きのアルミナ製の坩堝の中に高純度α−アルミナ粉末（ＡＫＰ−２０、住友化学製、比表面積ｂは４．３ｍ2／ｇ）１２ｇ（＝質量ｃ）に埋設して入れ、更にその坩堝を内径７４ｍｍ、高さ６０ｍｍの蓋付きのアルミナ製の坩堝に入れた。その蓋付きの坩堝を、８００℃で４時間熱処理した高純度α−アルミナ粉末（ＡＫＰ−２０、住友化学製）１７ｇに埋設し、熱間等方圧加圧法（ＨＩＰ）処理をＡｒガス、圧力１８５ＭＰａ、１９７０℃で２時間の条件で行った。その後、アルミナ粉末の焼結物を除去することにより、ＨＩＰ処理体（アルミナ焼結体がＨＩＰ処理された固形物）を得た。なお、実験例１では、図１の変化の過程を通ってＨＩＰ処理体が得られたと推察している。(4) Preparation of HIP-treated body (alumina crystal) A sample having a mass of 1.5 g (= mass a) was cut out from the produced alumina sintered body, and the sample was made of alumina having an inner diameter of 50 mm and a height of 40 mm and a lid. High-purity α-alumina powder (AKP-20, manufactured by Sumitomo Chemical Co., Ltd., specific surface area b is 4.3 m 2 / g) 12 g (= mass c) is embedded in the crucible, and the crucible is placed with an inner diameter of 74 mm and a high height. It was placed in an alumina crucible with a 60 mm lid. The crucible with a lid was embedded in 17 g of high-purity α-alumina powder (AKP-20, manufactured by Sumitomo Chemical Co., Ltd.) heat-treated at 800 ° C. for 4 hours, and hot isostatic pressing (HIP) treatment was performed with Ar gas and pressure. The operation was carried out at 185 MPa and 1970 ° C. for 2 hours. Then, the sintered product of the alumina powder was removed to obtain a HIP-treated product (a solid product in which the alumina sintered body was HIP-treated). In Experimental Example 1, it is presumed that the HIP-treated product was obtained through the process of change in FIG.
２．アルミナ焼結体の特性
ＨＩＰ処理前のアルミナ焼結体について、以下の特性を測定した。
（１）Ｆ含有量について
アルミナ焼結体の板面を鏡面研磨し、その研磨面に対してダイナミック二次イオン質量分析（Ｄ−ＳＩＭＳ）を行った。測定装置は、Ｃａｍｅｃａ社製ＩＭＳ−７ｆを用いた。測定条件は下記のとおり。
・一次イオン種：Ｃｓ+
・一次イオン加速エネルギー：１４．５ｋｅＶ
・二次イオン極性：Ｎｅｇａｔｉｖｅ
・電荷補償：Ｅ−ｇｕｎ，Ｍｅｔａｌ ｃｏａｔ
・スパッタサイクル：０〜６０サイクル
０〜６０スパッタサイクル間の平均値をＦ含有量として用いた。定量分析の際は濃度既知の標準試料（Ａｌ2Ｏ3）を分析試料と同条件で測定し、相対感度係数を求めて定量を行った。実験例１のアルミナ焼結体中のＦ含有量は７６（ａｔｐｐｍ）であった。2. Characteristics of Alumina Sintered Alumina sintered body before HIP treatment was measured with the following characteristics.
(1) F content The plate surface of the alumina sintered body was mirror-polished, and dynamic secondary ion mass spectrometry (D-SIMS) was performed on the polished surface. As the measuring device, IMS-7f manufactured by Cameca was used. The measurement conditions are as follows.
・ Primary ion species: Cs +
・ Primary ion acceleration energy: 14.5 keV
-Secondary ion polarity: Negative
-Charge compensation: E-gun, Metal coat
-Spatter cycle: 0 to 60 cycles The average value between 0 to 60 spatter cycles was used as the F content. In the quantitative analysis, a standard sample (Al 2 O 3 ) having a known concentration was measured under the same conditions as the analysis sample, and the relative sensitivity coefficient was obtained for quantification. The F content in the alumina sintered body of Experimental Example 1 was 76 (atppm).
（２）Ｍｇ含有量について
Ｆ含有量測定と同様にして得た研磨面に対してダイナミック二次イオン質量分析（Ｄ−ＳＩＭＳ）を行った。測定装置は、ＦＥＩ社製ＳＩＭＳ４５５０を用いた。測定条件は下記のとおりとした。
・一次イオン種：Ｏ2+
・一次イオン加速エネルギー：３ｋｅＶ
・二次イオン極性：Ｐｏｓｉｔｉｖｅ
・電荷補償：Ｅ−ｇｕｎ
・スパッタサイクル：０〜２００サイクル
０〜２００スパッタサイクル間の平均値をＭｇ含有量として用いた。定量分析の際は濃度既知の標準試料（Ｓｉ）を分析試料と同条件で測定し、相対感度係数を求めて定量を行った。実験例１のアルミナ焼結体中のＭｇ含有量は１２８（ａｔｐｐｍ）であった。(2) Mg content Dynamic secondary ion mass spectrometry (D-SIMS) was performed on the polished surface obtained in the same manner as in the F content measurement. As the measuring device, SIMS4550 manufactured by FEI was used. The measurement conditions were as follows.
・ Primary ion species: O 2+
・ Primary ion acceleration energy: 3 keV
-Secondary ion polarity: Positive
・ Charge compensation: E-gun
-Spatter cycle: 0 to 200 cycles The average value between 0 to 200 spatter cycles was used as the Mg content. In the quantitative analysis, a standard sample (Si) having a known concentration was measured under the same conditions as the analysis sample, and the relative sensitivity coefficient was obtained for quantification. The Mg content in the alumina sintered body of Experimental Example 1 was 128 (atppm).
（３）開気孔率について
得られたアルミナ焼結体の開気孔率をアルキメデス法により求めた。実験例１のアルミナ焼結体の開気孔率は０．２％であった。(3) Open Porosity The open porosity of the obtained alumina sintered body was determined by the Archimedes method. The open porosity of the alumina sintered body of Experimental Example 1 was 0.2%.
（４）配向度について
アルミナ焼結体の配向度を以下の方法で測定した。アルミナ焼結体を任意の断面にて切断し、ダイヤモンド砥粒を用いて予備研磨した後、クロスセクションポリッシャ（ＣＰ）（日本電子製、ＩＢ−０９０１０ＣＰ）で研磨した。得られた研磨面をカーボン蒸着し、ＥＢＳＤ（オックスフォード・インストゥルメンツ株式会社製、Ｎｏｒｄｌｙｓ Ｎａｎｏ）を組み合わせた走査型電子顕微鏡（日立ハイテクノロジーズ製、ＳＵ−５０００）を用いて、ＥＢＳＤ測定を行った。ＥＢＳＤの測定範囲はアルミナ粒子が２０〜５０個含む範囲とした。得られた結果から結晶方位マップを作成し、観察領域の全てのアルミナ粒子の結晶方位を調べ、最大頻度となる結晶方位を求めた。最大頻度結晶方位から±１０°以内の角度差に含まれる粒子の頻度（％）を算出し、配向度とした。実験例１のアルミナ焼結体の配向度は＜５％であった。なお、ＥＢＳＤ測定の諸条件、及び結晶方位マップの作成条件は以下のとおり。
＜ＥＢＳＤ測定条件＞
測定プログラム：Aｚｔｅｃ（ｖｅｒｓｉｏｎ３．３）
・加速電圧：１５ｋｖ
・スポット強度：７０
・ワーキングディスタンス：２２．５mm
・ステップサイズ：０．５μm
・試料傾斜角：７０°
・ＥＢＳＤカメラピニングモード：１×１
・フレーム平均：５フレーム
・静的バックグラウンド補正：オン
・自動バックグラウンド補正：オン
・Ｚ軸の規定：サンプル台座表面に対し法線方向をＺとする
＜結晶方位マップ作成＞
解析プログラム：ＯＸＦＯＲＤ ＨＫＬ ＣＨＡＮＮＥＬ５（ｖｅｒｓｉｏｎ５．１２．５７．０）
・ソフト内のアプリケーション「Ｔａｎｇｏ」を使用し、Ｔｅｘｔｕｒｅｃｏｍｐｏｎｅｎｔマップ（結晶方位マップ）を作成。
・Ｄｅｓｃｉｐｔｉｏｎ ｍｅｔｈｏｄはＦｉｂｒｅ ｔｅｘｔｕｒｅとし、Ｚ方向を基軸として、任意の結晶方位からの傾きを０〜９０℃の範囲をマッピング(4) Orientation degree The orientation degree of the alumina sintered body was measured by the following method. The alumina sintered body was cut at an arbitrary cross section, pre-polished using diamond abrasive grains, and then polished with a cross section polisher (CP) (IB-09010CP, manufactured by JEOL Ltd.). The obtained polished surface was carbon-deposited, and EBSD measurement was performed using a scanning electron microscope (SU-5000, manufactured by Hitachi High-Technologies Corporation) combined with EBSD (Nordlys Nano, manufactured by Oxford Instruments Co., Ltd.). .. The measurement range of EBSD was a range containing 20 to 50 alumina particles. A crystal orientation map was created from the obtained results, the crystal orientations of all the alumina particles in the observation region were examined, and the crystal orientation with the maximum frequency was determined. The frequency (%) of the particles contained in the angle difference within ± 10 ° from the maximum frequency crystal orientation was calculated and used as the degree of orientation. The degree of orientation of the alumina sintered body of Experimental Example 1 was <5%. The conditions for EBSD measurement and the conditions for creating a crystal orientation map are as follows.
<EBSD measurement conditions>
Measurement program: Aztec (version 3.3)
・ Acceleration voltage: 15kv
・ Spot intensity: 70
・ Working distance: 22.5mm
・ Step size: 0.5 μm
-Sample tilt angle: 70 °
・ EBSD camera pinning mode: 1 × 1
-Frame average: 5 frames-Static background correction: On-Automatic background correction: On-Z-axis specification: Normal direction is Z with respect to the sample pedestal surface <Crystal orientation map creation>
Analysis program: OXFORD HKL CHANNEL5 (version 5.12.57.0)
-Create a Texture component map (crystal orientation map) using the application "Tango" in the software.
-The Specification method is Fiber texture, and the inclination from an arbitrary crystal orientation is mapped in the range of 0 to 90 ° C. with the Z direction as the base axis.
３．ＨＩＰ処理体（アルミナ結晶）の特性
得られたＨＩＰ処理体について、以下の特性を測定した。
（１）Ｆ含有量について
ＨＩＰ処理体からアルミナ結晶を含むように切り出した面を鏡面研磨し、その研磨面に対してダイナミック二次イオン質量分析（Ｄ−ＳＩＭＳ）を行った。測定装置及び測定条件は上記２．（１）と同じとした。０〜６０スパッタサイクル間の平均値をＦ含有量として用いた。定量分析の際は濃度既知の標準試料（Ａｌ2Ｏ3）を分析試料と同条件で測定し、相対感度係数を求めて定量を行った。実験例１のアルミナ結晶中のＦ含有量は７５（ａｔｐｐｍ）であった。3. 3. Characteristics of HIP-treated product (alumina crystal) The following characteristics were measured for the obtained HIP-treated product.
(1) F content The surface cut out from the HIP-treated body so as to contain alumina crystals was mirror-polished, and dynamic secondary ion mass spectrometry (D-SIMS) was performed on the polished surface. The measuring device and measuring conditions are as described in 2. above. Same as (1). The average value between 0 to 60 spatter cycles was used as the F content. In the quantitative analysis, a standard sample (Al 2 O 3 ) having a known concentration was measured under the same conditions as the analysis sample, and the relative sensitivity coefficient was obtained for quantification. The F content in the alumina crystal of Experimental Example 1 was 75 (atppm).
（２）Ｍｇ含有量について
Ｆ含有量測定と同様にして得た研磨面に対して、ダイナミック二次イオン質量分析（Ｄ−ＳＩＭＳ）を行った。測定装置及び測定条件は上記２．（２）と同じとした。０〜２００スパッタサイクル間の平均値をＭｇ含有量として用いた。定量分析の際は濃度既知の標準試料（Ｓｉ）を分析試料と同条件で測定し、相対感度係数を求めて定量を行った。実験例１のアルミナ結晶中のＭｇ含有量は７０（ａｔｐｐｍ）であった。(2) Mg content Dynamic secondary ion mass spectrometry (D-SIMS) was performed on the polished surface obtained in the same manner as in the F content measurement. The measuring device and measuring conditions are as described in 2. above. Same as (2). The average value between 0 to 200 spatter cycles was used as the Mg content. In the quantitative analysis, a standard sample (Si) having a known concentration was measured under the same conditions as the analysis sample, and the relative sensitivity coefficient was obtained for quantification. The Mg content in the alumina crystal of Experimental Example 1 was 70 (atppm).
（３）Ｍｇ／Ｆについて
上記３．（１）及び（２）で求めたＦ含有量，Ｍｇ含有量（ａｔｐｐｍ）より、Ｆ／Ｍｇの値を求めた。実験例１のＦ／Ｍｇの値は１．１であった。(3) About Mg / F 3. The value of F / Mg was determined from the F content and Mg content (atppm) obtained in (1) and (2). The value of F / Mg in Experimental Example 1 was 1.1.
（４）異物のアルミナ結晶に対する面積比率について
ＨＩＰ処理体からアルミナ結晶の断面積が２５ｍｍ2以上となるように観察面を切り出し、ダイヤモンド砥粒を用いて鏡面研磨した後、純度９９．５質量％の高純度アルミナ製のさや（容積７５０ｃｍ3）に入れ、大気中で１５５０℃で４５分間、サーマルエッチング処理を実施した。サーマルエッチング処理を行うことにより、粒内部と粒界部にてエッチンングレートが異なるために粒界を鮮明に観察できるようになった。得られた断面を走査型電子顕微鏡（日本電子製、ＪＳＭ−６３９０）にて縦１９２０μｍ×横２５６０μｍの視野を加速電圧１０ｋＶ、スポットサイズ６０、ワーキングディスタンス１０ｍｍ、倍率５０倍にて撮影し、連続的な二次電子像及び反射電子像の写真（縦５枚、横４枚分：縦９６００μｍ×横１０２４０μｍ）となるように並べた。異物（気孔、異相、結晶方位が異なる粒子など）が存在する場合には、粒界が生じるため異物を容易に判別することができた。判別が難しい箇所については、ＥＢＳＤ（オックスフォード・インストゥルメンツ製、Ｎｏｒｄｌｙｓ Ｎａｎｏ）又はＥＤＳ（日本電子製、ＪＳＭ−６３９０）を用いて判別した。画像処理ソフトＡｄｏｂｅ Ｐｈｏｔｏｓｈｏｐ（ＣＳ５）に各写真を取り込み、アルミナ結晶の結晶面とその外部との境界、及び、結晶面とその内部に存在する異物との境界を手動で指定した。そして、結晶面のピクセル数及び結晶面内部に存在する異物のピクセル数を求め、以下の式を用いて、アルミナ結晶の結晶面における異物の面積比率を算出した。算出が難しい箇所については、更に高倍率で撮影した写真にて判別した。実験例１のアルミナ結晶の結晶面の面積は８５（ｍｍ2）であり、異物の面積比率は３（％）であった。
異物の面積比率（％）＝｛各異物のピクセル数の総和／結晶面のピクセル数｝×１００(4) Area ratio of foreign matter to alumina crystals An observation surface was cut out from the HIP-treated body so that the cross-sectional area of the alumina crystals was 25 mm 2 or more, mirror-polished using diamond abrasive grains, and then the purity was 99.5% by mass. It was placed in a pod made of high-purity alumina (volume 750 cm 3 ) and subjected to thermal etching treatment at 1550 ° C. for 45 minutes in the air. By performing the thermal etching treatment, the grain boundaries can be clearly observed because the etching rates differ between the inside of the grains and the grain boundaries. The obtained cross section was photographed with a scanning electron microscope (JSM-6390 manufactured by JEOL Ltd.) in a field of 1920 μm in length × 2560 μm in width at an acceleration voltage of 10 kV, a spot size of 60, a working distance of 10 mm, and a magnification of 50 times, and continuously. The secondary electron images and backscattered electron images were arranged so as to be photographs (5 vertical, 4 horizontal: 9600 μm in length × 10240 μm in width). When foreign matter (pores, different phases, particles having different crystal orientations, etc.) is present, grain boundaries are generated, so that the foreign matter can be easily identified. The parts that were difficult to discriminate were discriminated using EBSD (Oxford Instruments, Nordlys Nano) or EDS (JEOL, JSM-6390). Each photograph was taken into the image processing software Adobe Photoshop (CS5), and the boundary between the crystal plane of the alumina crystal and the outside thereof and the boundary between the crystal plane and the foreign matter existing inside the crystal plane were manually specified. Then, the number of pixels on the crystal plane and the number of pixels of the foreign matter existing inside the crystal plane were obtained, and the area ratio of the foreign matter on the crystal plane of the alumina crystal was calculated using the following formula. The parts that were difficult to calculate were identified by photographs taken at a higher magnification. The area of the crystal plane of the alumina crystal of Experimental Example 1 was 85 (mm 2 ), and the area ratio of the foreign matter was 3 (%).
Area ratio of foreign matter (%) = {total number of pixels of each foreign matter / number of pixels on crystal plane} x 100
（５）結晶性について
鏡面研磨後のＨＩＰ処理体のＸ線ロッキングカーブ（ＸＲＣ）半値幅（ＦＷＨＭ）を測定した。測定装置は、Ｂｒｕｋｅｒ−ＡＸＳ製、Ｄ８−ＤＩＳＣＯＶＥＲを用いた。測定条件は下記のとおりであり、ＨＩＰ処理体の結晶面の高さに合わせてＺ軸を調整した後、板面（（００６）面、又は（１００）面）に対して、ＣｈｉとＰｈｉを調整して軸立てを行い、図３のようにＸ線源に対して試料と検出器を連動させてスキャンし、得られたカーブの半値幅を測定した。検出器と結晶面とのなす角度を固定し、ω（結晶面と入射Ｘ線とのなす角度）のみ操作する測定方法をロッキングカーブ測定と呼ぶ。実験例１の半値幅の値は３２（ａｒｃｓｅｃ）であった。
＜ＸＲＣ測定条件＞
・コリメータ径０．５ｍｍ
・アンチスキャッタリングスリット３ｍｍ
・Ｇｅ（０２２）非対称反射モノクロメーターにて平行単色光化（半値幅２８秒）したＣｕＫα線
・電圧４０ｋＶ
・電流４０ｍＡ
・走査範囲を３．８°〜３８．８°（ωスキャン速度０．０１°／Ｓｔｅｐ、１秒／Ｓｔｅｐ）(5) Crystallinity The X-ray locking curve (XRC) full width at half maximum (FWHM) of the HIP-treated body after mirror polishing was measured. As a measuring device, D8-DISCOVER manufactured by Bruker-AXS was used. The measurement conditions are as follows. After adjusting the Z-axis according to the height of the crystal plane of the HIP-treated product, Chi and Ph are applied to the plate surface ((006) surface or (100) surface). After adjusting and setting the shaft, the sample and the detector were interlocked with the X-ray source and scanned as shown in FIG. 3, and the half width of the obtained curve was measured. A measurement method in which the angle between the detector and the crystal plane is fixed and only ω (the angle between the crystal plane and the incident X-ray) is operated is called locking curve measurement. The value of the half width of Experimental Example 1 was 32 (arcsec).
<XRC measurement conditions>
・ Collimator diameter 0.5mm
・ Anti-scattering slit 3mm
・ CuKα line with parallel monochromatic light (half width 28 seconds) with Ge (022) asymmetric reflection monochromator ・ Voltage 40 kV
・ Current 40mA
-Scanning range is 3.8 ° to 38.8 ° (ω scan speed 0.01 ° / Step, 1 second / Step)
（６）純度について
ＨＩＰ処理体を純度９９．９％のアルミナ乳鉢で粉砕した後、Ａｌ，Ｏ，Ｆ，Ｍｇ以外の元素について、下記方法により定量分析を行った。実験例１のアルミナ焼結体のＡｌ，Ｏ，Ｆ，Ｍｇ以外の元素は、Ｃが４０ｐｐｍ検出され、それ以外の元素は検出されなかった。
Ｃ，Ｓ：炭素・硫黄分析装置（ＬＥＣＯ製ＣＳ８４４）を用いて燃焼（高周波加熱）−赤外線吸収法にて分析した。検出下限は１０ｐｐｍである。
Ｎ：酸素・窒素分析装置（堀場製作所製ＥＭＧＡ−６５０Ｗ）を用いて不活性ガス融解−熱伝導度法にて分析した。検出下限は１０ｐｐｍである。
Ｈ：水素分析装置（堀場製作所製ＥＭＧＡ−９２１）を用いて不活性ガス融解−非分散型赤外線吸収法にて分析した。検出下限は１０ｐｐｍである。
上記以外の元素（主にＳｉ，Ｆｅ，Ｔｉ，Ｎａ，Ｃａ，Ｍｇ，Ｋ，Ｐ，Ｖ，Ｃｒ，Ｍｎ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｙ，Ｚｒ，Ｐｂ，Ｂｉ，Ｌｉ，Ｂｅ，Ｂ，Ｃｌ，Ｓｃ，Ｇａ，Ｇｅ，Ａｓ，Ｓｅ，Ｂｒ，Ｒｂ，Ｓｒ，Ｎｂ，Ｍｏ，Ｒｕ，Ｒｈ，Ｐｄ，Ａｇ，Ｃｄ，Ｉｎ，Ｓｎ，Ｓｂ，Ｔｅ，Ｃｓ，Ｂａ，Ｈｆ，Ｔａ，Ｗ，Ｉｒ，Ｐｔ，Ａｕ，Ｈｇ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｌｕ，）：ＪＩＳＲ１６４９に準拠した加圧硫酸分解法にてアルミナ粉末を溶解し、ＩＣＰ（誘導結合プラズマ）発光分析装置（日立ハイテクサイエンス製ＰＳ３５２０ＵＶ−ＤＤ）にて分析した。検出下限は１０ｐｐｍである。
Ｂａ，Ｓｒ，Ｐｂ：炭酸ナトリウム融液にてアルミナ粉末を融解し、ＩＣＰ（誘導結合プラズマ）質量分析装置（サーモフィッシャーサイエンス製ｉＣＡＰＱＣ）にて分析した。(6) Purity After pulverizing the HIP-treated product in an alumina mortar having a purity of 99.9%, quantitative analysis was performed on elements other than Al, O, F and Mg by the following method. As for the elements other than Al, O, F, and Mg of the alumina sintered body of Experimental Example 1, 40 ppm of C was detected, and no other elements were detected.
C, S: Analysis was performed by a combustion (high frequency heating) -infrared absorption method using a carbon / sulfur analyzer (CS844 manufactured by LECO). The lower limit of detection is 10 ppm.
N: Analysis was performed by the inert gas melting-thermal conductivity method using an oxygen / nitrogen analyzer (EMGA-650W manufactured by Horiba Seisakusho). The lower limit of detection is 10 ppm.
H: Analysis was performed by an inert gas melting-non-dispersion infrared absorption method using a hydrogen analyzer (EMGA-921 manufactured by HORIBA, Ltd.). The lower limit of detection is 10 ppm.
Elements other than the above (mainly Si, Fe, Ti, Na, Ca, Mg, K, P, V, Cr, Mn, Co, Ni, Cu, Zn, Y, Zr, Pb, Bi, Li, Be, B , Cl, Sc, Ga, Ge, As, Se, Br, Rb, Sr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, Hf, Ta, W , Ir, Pt, Au, Hg, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; Alumina powder was dissolved and analyzed with an ICP (inductively coupled plasma) emission spectrometer (PS3520UV-DD manufactured by Hitachi High-Tech Science). The lower limit of detection is 10 ppm.
Ba, Sr, Pb: Alumina powder was melted in a sodium carbonate melt and analyzed by an ICP (inductively coupled plasma) mass spectrometer (iCAPQC manufactured by Thermo Fisher Scientific).
［実験例２］
上記１．（２）のテープ成形において酸化マグネシウム（５００Ａ、宇部マテリアルズ製）を０．０６５質量部使用したこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 2]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that 0.065 parts by mass of magnesium oxide (500 A, manufactured by Ube Material Industries Ltd.) was used in the tape molding of (2). The characteristics were measured. The results are shown in Table 1.
［実験例３］
上記１．（２）のテープ成形において酸化マグネシウム（５００Ａ、宇部マテリアルズ製）を０．００７５質量部使用したこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 3]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that 0.0075 parts by mass of magnesium oxide (500 A, manufactured by Ube Material Industries Ltd.) was used in the tape molding of (2). The characteristics were measured. The results are shown in Table 1.
［実験例４］
上記１．（１）の板状アルミナ作製時にアニール処理を温度を１２５０℃にしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 4]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the temperature of the annealing treatment was set to 1250 ° C. at the time of producing the plate-shaped alumina of (1), and their characteristics were measured. The results are shown in Table 1.
［実験例５］
上記１．（３）の脱脂体の焼成温度を１５００℃にしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 5]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the firing temperature of the degreased body in (3) was set to 1500 ° C., and their characteristics were measured. The results are shown in Table 1.
［実験例６］
上記１．（３）の脱脂体の焼成温度を１４８０℃にしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 6]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the firing temperature of the degreased body in (3) was set to 1480 ° C., and their characteristics were measured. The results are shown in Table 1.
［実験例７］
上記１．（４）のＨＩＰ処理する際のアルミナ焼結体を埋設するα−アルミナ粉末の質量ｃを０．１ｇにしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 7]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the mass c of the α-alumina powder in which the alumina sintered body was embedded during the HIP treatment in (4) was 0.1 g. And these characteristics were measured. The results are shown in Table 1.
［実験例８］
上記１．（４）のＨＩＰ処理する際のアルミナ焼結体を埋設するα−アルミナ粉末の質量ｃを０．５ｇにしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 8]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the mass c of the α-alumina powder in which the alumina sintered body was embedded during the HIP treatment in (4) was 0.5 g. And these characteristics were measured. The results are shown in Table 1.
［実験例９］
上記１．（４）のＨＩＰ処理する際のアルミナ焼結体を埋設するα−アルミナ粉末の質量ｃを３ｇにしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 9]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the mass c of the α-alumina powder in which the alumina sintered body was embedded during the HIP treatment in (4) was set to 3 g. These characteristics were measured. The results are shown in Table 1.
［実験例１０］
上記１．（４）のＨＩＰ処理する際のアルミナ焼結体を埋設するα−アルミナ粉末の質量ｃを５ｇにしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 10]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the mass c of the α-alumina powder in which the alumina sintered body was embedded during the HIP treatment in (4) was set to 5 g. These characteristics were measured. The results are shown in Table 1.
［実験例１１］
上記１．（４）のＨＩＰ処理の焼成温度を１８５０℃にしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 11]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the firing temperature of the HIP treatment in (4) was set to 1850 ° C., and their characteristics were measured. The results are shown in Table 1.
［実験例１２］
上記１．（４）のＨＩＰ処理の圧力を１００ＭＰａ、焼成温度を１８５０℃にしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 12]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the pressure of the HIP treatment in (4) was 100 MPa and the firing temperature was 1850 ° C., and their characteristics were measured. The results are shown in Table 1.
［実験例１３］
上記１．（４）のＨＩＰ処理の焼成温度を１９８０℃にしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 13]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the firing temperature of the HIP treatment in (4) was set to 1980 ° C., and their characteristics were measured. The results are shown in Table 1.
［実験例１４］
上記１．（４）のＨＩＰ処理する際のアルミナ焼結体を埋設する粉末種をα−アルミナ粉末（ＡＫＰ−５０、住友化学製）５ｇにしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 14]
Above 1. Alumina sintered body in the same manner as in Experimental Example 1 except that the powder type for embedding the alumina sintered body in the HIP treatment of (4) was 5 g of α-alumina powder (AKP-50, manufactured by Sumitomo Chemical Co., Ltd.). And HIP-treated products were prepared and these characteristics were measured. The results are shown in Table 1.
［実験例１５］
上記１．（１）において、板状アルミナ作製時にアニール処理を実施しなかったことと、上記１．（２）のテープ成形において、板状アルミナ粉末２．５質量部と、平均粒径がこの板状アルミナ粉末の厚みより小さい微細アルミナ粉末（ＴＭ−ＤＡＲ、平均粒径０．１μｍ、大明化学製）９７．５質量部とし、酸化マグネシウム（５００Ａ、宇部マテリアルズ製）を０．０５質量部使用したこと、得られたテープを直径５０．８ｍｍ（２インチ）の円形に切断した後１５０枚積層し、厚さ１０ｍｍのＡｌ板の上に載置した後、パッケージに入れて内部を真空にすることで真空パックし、８５℃の温水中で１００ｋｇｆ／ｃｍ2の圧力にて静水圧プレスを行い、円板状の成形体を得たことと、上記１．（３）の焼成において、得られた脱脂体を黒鉛製の型を用い、ホットプレスにて窒素中１８００℃で４時間、面圧２００ｋｇｆ／ｃｍ2の条件で焼成し、その後降温し、１２００℃になった時点で面圧を開放し、直径５０．８ｍｍのアルミナ焼結体を得たこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 15]
Above 1. In (1), the annealing treatment was not performed when the plate-shaped alumina was produced, and the above 1. In the tape molding of (2), 2.5 parts by mass of the plate-shaped alumina powder and a fine alumina powder having an average particle size smaller than the thickness of the plate-shaped alumina powder (TM-DAR, average particle size 0.1 μm, manufactured by Daimei Chemicals Co., Ltd.) ) 97.5 parts by mass, 0.05 parts by mass of magnesium oxide (500A, manufactured by Ube Materials) was used, and the obtained tape was cut into a circle with a diameter of 50.8 mm (2 inches) and then 150 sheets were laminated. Then, after placing it on an Al plate with a thickness of 10 mm, it is put in a package and vacuum-packed by vacuuming the inside, and hydrostatic press is performed at a pressure of 100 kgf / cm 2 in warm water at 85 ° C. , Obtaining a disk-shaped molded body and the above 1. In the firing of (3), the obtained degreased body was calcined in nitrogen at 1800 ° C. for 4 hours under the condition of a surface pressure of 200 kgf / cm 2 using a graphite mold, and then the temperature was lowered to 1200 ° C. Alumina sintered body and HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the surface pressure was released to obtain an alumina sintered body having a diameter of 50.8 mm. It was measured. The results are shown in Table 1.
［実験例１６］
上記１．（２）のテープ成形において、酸化マグネシウム（５００Ａ、宇部マテリアルズ製）を０．０３５質量部使用したこと、得られたテープを直径５０．８ｍｍ（２インチ）の円形に切断した後１５０枚積層し、厚さ１０ｍｍのＡｌ板の上に載置した後、パッケージに入れて内部を真空にすることで真空パックし、８５℃の温水中で１００ｋｇｆ／ｃｍ2の圧力にて静水圧プレスを行い、円板状の成形体を得たことと、上記１．（３）の焼成において、得られた脱脂体を黒鉛製の型を用い、ホットプレスにて窒素中１８００℃で４時間、面圧２００ｋｇｆ／ｃｍ2の条件で焼成し、その後降温し、１２００℃になった時点で面圧を開放し、直径５０．８ｍｍのアルミナ焼結体を得たこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 16]
Above 1. In the tape molding of (2), 0.035 parts by mass of magnesium oxide (500A, manufactured by Ube Material Industries Ltd.) was used, and the obtained tape was cut into a circle with a diameter of 50.8 mm (2 inches) and then 150 sheets were laminated. Then, after placing it on an Al plate with a thickness of 10 mm, put it in a package and evacuate the inside to vacuum pack it, and then perform a hydrostatic pressure press at a pressure of 100 kgf / cm 2 in warm water at 85 ° C. , Obtaining a disk-shaped molded body and the above 1. In the firing of (3), the obtained degreased body was calcined in nitrogen at 1800 ° C. for 4 hours under the condition of a surface pressure of 200 kgf / cm 2 using a graphite mold, and then the temperature was lowered to 1200 ° C. Alumina sintered body and HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the surface pressure was released to obtain an alumina sintered body having a diameter of 50.8 mm. It was measured. The results are shown in Table 1.
［実験例１７］
上記実験例１６のホットプレスにて窒素中１７００℃で１時間、面圧１７０ｋｇｆ／ｃｍ2の条件で焼成し、その後降温し、１２００℃になった時点で面圧を開放し、直径５０．８ｍｍのアルミナ焼結体を得たこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 17]
The hot press of Experimental Example 16 was fired in nitrogen at 1700 ° C. for 1 hour under the condition of a surface pressure of 170 kgf / cm 2 , then the temperature was lowered, and when the temperature reached 1200 ° C., the surface pressure was released and the diameter was 50.8 mm. Alumina sintered body and HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the alumina sintered body was obtained, and their characteristics were measured. The results are shown in Table 1.
［実験例１８］
上記実験例１６のホットプレスにて窒素中１５００℃で１時間、面圧１７０ｋｇｆ／ｃｍ2の条件で焼成し、その後降温し、１２００℃になった時点で面圧を開放し、直径５０．８ｍｍのアルミナ焼結体を得たこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 18]
The hot press of Experimental Example 16 was fired in nitrogen at 1500 ° C. for 1 hour under the condition of a surface pressure of 170 kgf / cm 2 , then the temperature was lowered, and when the temperature reached 1200 ° C., the surface pressure was released and the diameter was 50.8 mm. Alumina sintered body and HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the alumina sintered body was obtained, and their characteristics were measured. The results are shown in Table 1.
［実験例１９］
上記１．（２）のテープ成形において、作製した板状アルミナ粉末を用いず、微細アルミナ粉末（ＡＫＰ−２０、住友化学製）１００．０質量部とし、このアルミナ粉末１００質量部に対し、酸化マグネシウム（５００Ａ、宇部マテリアルズ製）を０．０３５質量部とし、高純度ＡｌＦ3粉末（関東化学製、鹿特級）を０．０１３質量部使用したこと、得られたテープを直径５０．８ｍｍ（２インチ）の円形に切断した後１５０枚積層し、厚さ１０ｍｍのＡｌ板の上に載置した後、パッケージに入れて内部を真空にすることで真空パックし、８５℃の温水中で１００ｋｇｆ／ｃｍ2の圧力にて静水圧プレスを行い、円板状の成形体を得たことと、上記１．（３）の焼成において、得られた脱脂体を黒鉛製の型を用い、ホットプレスにて窒素中１８００℃で４時間、面圧２００ｋｇｆ／ｃｍ2の条件で焼成し、その後降温し、１２００℃になった時点で面圧を開放し、直径５０．８ｍｍのアルミナ焼結体を得たこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 19]
Above 1. In the tape molding of (2), the prepared plate-shaped alumina powder was not used, but fine alumina powder (AKP-20, manufactured by Sumitomo Chemical Co., Ltd.) was made into 100.0 parts by mass, and magnesium oxide (500A) was made with respect to 100 parts by mass of this alumina powder. , Ube Materials) was 0.035 parts by mass, and 0.013 parts by mass of high-purity AlF 3 powder (Kanto Chemical Co., Ltd., special grade deer) was used, and the obtained tape was 50.8 mm (2 inches) in diameter. After cutting into a circle, 150 sheets are laminated, placed on an Al plate with a thickness of 10 mm, placed in a package and vacuum packed by vacuuming the inside, and 100 kgf / cm 2 in warm water at 85 ° C. A hydrostatic press was performed at the same pressure as described in 1. to obtain a disk-shaped molded body. In the firing of (3), the obtained degreased body was calcined in nitrogen at 1800 ° C. for 4 hours under the condition of a surface pressure of 200 kgf / cm 2 using a graphite mold, and then the temperature was lowered to 1200 ° C. Alumina sintered body and HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the surface pressure was released to obtain an alumina sintered body having a diameter of 50.8 mm. It was measured. The results are shown in Table 1.
［実験例２０］
上記１．（２）のテープ成形において酸化マグネシウム（５００Ａ、宇部マテリアルズ製）を０．１質量部使用したこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 20]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that 0.1 part by mass of magnesium oxide (500 A, manufactured by Ube Material Industries Ltd.) was used in the tape molding of (2). The characteristics were measured. The results are shown in Table 1.
［実験例２１］
上記１．（２）のテープ成形において酸化マグネシウム（５００Ａ、宇部マテリアルズ製）を０．００１質量部使用したこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 21]
Above 1. Alumina sintered body and HIP-treated body were prepared in the same manner as in Experimental Example 1 except that 0.001 part by mass of magnesium oxide (500A, manufactured by Ube Material Industries Ltd.) was used in the tape molding of (2). The characteristics were measured. The results are shown in Table 1.
［実験例２２］
上記１．（１）の板状アルミナ作製時にアニール処理を温度を１３５０℃にしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 22]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the temperature of the annealing treatment was set to 1350 ° C. at the time of producing the plate-shaped alumina of (1), and their characteristics were measured. The results are shown in Table 1.
［実験例２３］
上記１．（３）の脱脂体の焼成温度を１４５０℃にしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 23]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the firing temperature of the degreased body in (3) was set to 1450 ° C., and their characteristics were measured. The results are shown in Table 1.
［実験例２４］
上記１．（４）の焼成体をＨＩＰ処理の焼成温度を１７５０℃にしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 24]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the firing temperature of the fired body of (4) was HIP-treated at 1750 ° C., and their characteristics were measured. The results are shown in Table 1.
［実験例２５］
上記１．（４）の焼成体をＨＩＰ処理の圧力を８０ＭＰａ、焼成温度を１８５０℃にしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 25]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the HIP-treated pressure of the fired body (4) was 80 MPa and the firing temperature was 1850 ° C., and their characteristics were measured. .. The results are shown in Table 1.
［実験例２６］
上記１．（４）の焼成体をＨＩＰ処理する際の焼成体を埋設する粉末の量を０．０５ｇにしたこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 26]
Above 1. An alumina sintered body and a HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the amount of powder for embedding the fired body when the fired body of (4) was HIP-treated was 0.05 g. The characteristics of were measured. The results are shown in Table 1.
［実験例２７］
上記１．（１）において、板状アルミナ作製時にアニール処理を実施しなかったことと、上記１．（２）のテープ成形において、板状アルミナ粉末３．５質量部と、平均粒径がこの板状アルミナ粉末の厚みより小さい微細アルミナ粉末（ＴＭ−ＤＡＲ、平均粒径０．１μｍ、大明化学製）９６．５質量部としたこと、得られたテープを直径５０．８ｍｍ（２インチ）の円形に切断した後１５０枚積層し、厚さ１０ｍｍのＡｌ板の上に載置した後、パッケージに入れて内部を真空にすることで真空パックし、８５℃の温水中で１００ｋｇｆ／ｃｍ2の圧力にて静水圧プレスを行い、円板状の成形体を得たことと、上記１．（３）の焼成において、得られた脱脂体を黒鉛製の型を用い、ホットプレスにて窒素中１８００℃で４時間、面圧２００ｋｇｆ／ｃｍ2の条件で焼成し、その後降温し、１２００℃になった時点で面圧を開放し、直径５０．８ｍｍのアルミナ焼結体を得たこと以外は、実験例１と同様にしてアルミナ焼結体とＨＩＰ処理体を作製し、これらの特性を測定した。その結果を表１に示す。[Experimental Example 27]
Above 1. In (1), the annealing treatment was not performed when the plate-shaped alumina was produced, and the above 1. In the tape molding of (2), 3.5 parts by mass of the plate-shaped alumina powder and a fine alumina powder (TM-DAR, average particle size 0.1 μm, manufactured by Daimei Chemicals Co., Ltd.) whose average particle size is smaller than the thickness of the plate-shaped alumina powder. ) 96.5 parts by mass, the obtained tape was cut into a circle with a diameter of 50.8 mm (2 inches), 150 sheets were laminated, placed on an Al plate with a thickness of 10 mm, and then put into a package. The inside was vacuum-packed by putting it in and vacuum-packed, and hydrostatic press was performed at a pressure of 100 kgf / cm 2 in warm water at 85 ° C. to obtain a disk-shaped molded body. In the firing of (3), the obtained degreased body was calcined in nitrogen at 1800 ° C. for 4 hours under the condition of a surface pressure of 200 kgf / cm 2 using a graphite mold, and then the temperature was lowered to 1200 ° C. Alumina sintered body and HIP-treated body were prepared in the same manner as in Experimental Example 1 except that the surface pressure was released to obtain an alumina sintered body having a diameter of 50.8 mm. It was measured. The results are shown in Table 1.
［実験例２８］
実験例１のアルミナ結晶と同様にサファイアの特性を測定した。その結果を表１に示す。[Experimental Example 28]
The characteristics of sapphire were measured in the same manner as the alumina crystal of Experimental Example 1. The results are shown in Table 1.
［評価］
実験例１〜１９のＨＩＰ処理体は、面積が２５ｍｍ2以上の結晶面を含み、その結晶面における異物の面積比率が１０％以下であり、Ｆを１０〜３００ａｔｐｐｍ含み、Ｍｇを１０〜２５０ａｔｐｐｍ含むアルミナ結晶を有していた。これら試料のＸＲＣの半値幅はいずれも１００ａｒｃｓｅｃ未満であり、サファイア（２５ａｒｃｓｅｃ）に近い値であった。このように、実験例１〜１９では、サファイア並みの単結晶様のアルミナ結晶を得ることができた。[evaluation]
The HIP-treated bodies of Experimental Examples 1 to 19 include a crystal plane having an area of 25 mm 2 or more, an area ratio of foreign matter on the crystal plane is 10% or less, F is contained in an amount of 10 to 300 atppm, and Mg is contained in an amount of 10 to 250 atppm. It had alumina crystals. The full width at half maximum of XRC of these samples was less than 100 arcsec, which was close to sapphire (25 arcsec). As described above, in Experimental Examples 1 to 19, single crystal-like alumina crystals comparable to sapphire could be obtained.
実験例２０〜実験例２７では、いずれもサファイア並みの単結晶様のアルミナ結晶を得ることができなかった。実験例２０では、アルミナ焼結体のＭｇ含有量が多すぎたため、ＨＩＰ処理体のＭｇ含有量も多くなりすぎたことが原因と考えられる。実験例２１では、アルミナ焼結体のＭｇ含有量が少なすぎたため、ＨＩＰ処理体のＭｇ含有量も少なくなりすぎたことが原因と考えられる。実験例２２では、アルミナ焼結体のＦ含有量が少なすぎたため、ＨＩＰ処理体のＦ含有量も少なくなりすぎたことが原因と考えられる。実験例２３では、アルミナ焼結体の開気孔率が３％を超えたことが原因と考えられる。実験例２４では、ＨＩＰ処理時の焼成温度が低すぎたことが原因と考えられる。実験例２５では、ＨＩＰ処理時の圧力が低すぎたことが原因と考えられる。実験例２６では、アルミナ焼結体を埋設するα−アルミナ粉末の量が少なすぎてｂｃ／ａが小さくなりすぎたことが原因と考えられる。実験例２７では、テープ成形時に板状アルミナが多すぎてアルミナ焼結体、ひいてはＨＩＰ処理体のＦ含有量が多くなりすぎたことが原因と考えられる。 In Experimental Examples 20 to 27, it was not possible to obtain single crystal-like alumina crystals comparable to sapphire. In Experimental Example 20, since the Mg content of the alumina sintered body was too high, it is considered that the cause was that the Mg content of the HIP-treated body was also too high. In Experimental Example 21, since the Mg content of the alumina sintered body was too low, it is considered that the cause was that the Mg content of the HIP-treated body was also too low. In Experimental Example 22, since the F content of the alumina sintered body was too low, it is considered that the cause was that the F content of the HIP-treated body was also too low. In Experimental Example 23, it is considered that the cause is that the open porosity of the alumina sintered body exceeds 3%. In Experimental Example 24, it is considered that the cause is that the firing temperature during the HIP treatment was too low. In Experimental Example 25, it is considered that the cause was that the pressure during the HIP treatment was too low. In Experimental Example 26, it is considered that the cause is that the amount of α-alumina powder in which the alumina sintered body is embedded is too small and the bc / a becomes too small. In Experimental Example 27, it is considered that the cause was that the amount of plate-like alumina was too large during tape molding, and the F content of the alumina sintered body and, by extension, the HIP-treated body was too large.
上述した実験例１〜２８のうち実験例１〜１９が本発明の実施例に相当し、実験例２０〜２８が比較例に相当する。なお、上述した実施例は本発明を何ら限定するものでないことは言うまでもない。 Of the above-mentioned Experimental Examples 1 to 28, Experimental Examples 1 to 19 correspond to Examples of the present invention, and Experimental Examples 20 to 28 correspond to Comparative Examples. Needless to say, the above-mentioned examples do not limit the present invention in any way.
本発明のアルミナ結晶は、発光ダイオード（ＬＥＤ）等の発光素子や半導体デバイス用のエピタキシャル成長用基板や腕時計等のカバーガラス等の分野で利用可能である。 The alumina crystal of the present invention can be used in the fields of light emitting elements such as light emitting diodes (LEDs), epitaxial growth substrates for semiconductor devices, and cover glasses for watches and the like.
１０ アルミナ焼結体、１２ マトリックス粒子、１４ テンプレート粒子、１６ Ａｌ含有粉末、２０ 単結晶様のアルミナ結晶。 10 Alumina sintered body, 12 Matrix particles, 14 Template particles, 16 Al-containing powder, 20 Single crystal-like alumina crystals.
Claims (6)
面積が２５ｍｍ2以上の、前記アルミナ結晶を任意の箇所で切り出したときの断面である結晶面を含み、前記結晶面における異物の面積比率が１０％以下であり、前記アルミナ結晶のうち前記異物を除く領域にＦを１０〜３００ａｔｐｐｍ含み、Ｍｇを１０〜２５０ａｔｐｐｍ含み、
（００６）面又は（１００）面のＸ線ロッキングカーブ（ＸＲＣ）測定において、半値幅が３２ａｒｃｓｅｃ以上１００ａｒｃｓｅｃ以下である、
アルミナ結晶。 It is a single crystal-like alumina crystal.
It includes a crystal plane having an area of 25 mm 2 or more, which is a cross section when the alumina crystal is cut out at an arbitrary position, and the area ratio of foreign matter on the crystal plane is 10% or less. The area to be excluded contains 10 to 300 atppm of F and 10 to 250 atppm of Mg.
In the X-ray locking curve (XRC) measurement of the (006) plane or the (100) plane, the half width is 32 arcsec or more and 100 arcsec or less.
Alumina crystal.
請求項１に記載のアルミナ結晶。 The ratio of F content to Mg content F / Mg is 0.25-4.
The alumina crystal according to claim 1.
請求項１又は２に記載のアルミナ結晶。 The area of the crystal plane is 50 mm 2 or more.
The alumina crystal according to claim 1 or 2.
請求項１〜３のいずれか１項に記載のアルミナ結晶。 The area of the crystal plane is 80 mm 2 or more.
The alumina crystal according to any one of claims 1 to 3.
請求項１〜４のいずれか１項に記載のアルミナ結晶。 The content of elements other than Al, O, F, Mg, and C in the region of the alumina crystal excluding foreign matter is 10 ppm or less.
The alumina crystal according to any one of claims 1 to 4.
請求項１〜５のいずれか１項に記載のアルミナ結晶。 The foreign matter is at least one of particles having different pores, different phases and crystal orientations.
The alumina crystal according to any one of claims 1 to 5.
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