JP5565680B2 - Gadolinium sulfide type structure yttrium oxide and method for producing the same - Google Patents
Gadolinium sulfide type structure yttrium oxide and method for producing the same Download PDFInfo
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- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 title claims description 40
- YIAXEFITNBBEOD-UHFFFAOYSA-N gadolinium(3+) trisulfide Chemical compound [S--].[S--].[S--].[Gd+3].[Gd+3] YIAXEFITNBBEOD-UHFFFAOYSA-N 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910003460 diamond Inorganic materials 0.000 claims description 6
- 239000010432 diamond Substances 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 description 23
- 238000002474 experimental method Methods 0.000 description 15
- 229910052761 rare earth metal Inorganic materials 0.000 description 13
- 230000007704 transition Effects 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
Description
本発明は硫化ガドリニウム（Ｇｄ２Ｓ３）型構造の酸化イットリウム（Ｙ２Ｏ３）とこの構造を有する酸化イットリウムを高温高圧処理過程により製造することに関する。 The present invention relates to producing gadolinium sulfide (Gd 2 S 3 ) type yttrium oxide (Y 2 O 3 ) and yttrium oxide having this structure by a high-temperature and high-pressure treatment process.
酸化イットリウムは耐熱セラミックに、また固体燃料電池用のイットリア安定化ジルコニアのような機能性材料の主要構成要素として広く使用されている。また、酸化イットリウムのイオン半径（Ｙ３＋＝０．９Å）はランタニド系のイオン半径（Ｌｎ３＋＝０．８６〜１．０３Å）と近いため、ランタニド系のイオンを酸化イットリウム中に取り込んでＥｕ３＋：Ｙ２Ｏ３赤色発光蛍光体やＮｄ３＋：Ｙ２Ｏ３、Ｙｂ３＋：Ｙ２Ｏ３レーザーなどの光学セラミックを製造するためにも使用されている。 Yttrium oxide is widely used in heat resistant ceramics and as a major component of functional materials such as yttria stabilized zirconia for solid fuel cells. In addition, since the ionic radius (Y 3+ = 0.9Ｙ) of yttrium oxide is close to the lanthanide-based ionic radius (Ln 3+ = 0.86 to 1.03Å), the lanthanide-based ions are incorporated into yttrium oxide and Eu 3+. : Y 2 O 3 red light-emitting phosphors and Nd 3+ : Y 2 O 3 , Yb 3+ : Y 2 O 3 lasers are also used to produce optical ceramics.
酸化イットリウムの結晶構造としては、従来、Ａ型希土類型、Ｂ型希土類型、Ｃ型希土類型、及びＣａＦ２型の４種類が知られている。室温常圧環境下では、酸化イットリウムはＬｎ２Ｏ３に見られるようなＣ型希土類型構造を取る。２．５ＧＰａ、１２７３Ｋでの高静圧実験（非特許文献１及び２）及び圧力１２ＧＰａ以上、温度６７３Ｋ以下で行われた衝撃圧縮実験（非特許文献３）でＢ型希土類型構造が得られたことが報告されている。また、高温ラマンスペクトルにより、１２ＧＰａでＣ型希土類型からＢ型希土類型へ、また１９ＧＰａでＢ型希土類型からＡ型希土類型へのステップ状の相転移が起こることが示された（非特許文献４）。これとは対照的に、高圧下のＸ線による酸化イットリウムの研究では、Ｃ型希土類型はＢ型希土類型を経ることなく１２ＧＰａにおいて直接にＡ型希土類型へ相転移し、Ｃ型希土類型⇒Ｂ型希土類型⇒Ａ型希土類型という順番の相転移はＥｕ３＋：Ｙ２Ｏ３の場合に限って見られたとされている（非特許文献５）。これに加えて、融点のわずかに下である２４９３Ｋにおいて常圧下で形成された酸化イットリウムの高温相（ＣａＦ２型）の報告もある（非特許文献６及び７）。 Conventionally, four types of crystal structures of yttrium oxide are known: A-type rare earth type, B-type rare earth type, C-type rare earth type, and CaF 2 type. Under a room temperature and atmospheric pressure environment, yttrium oxide takes a C-type rare earth structure as found in Ln 2 O 3 . A B-type rare earth structure was obtained in a high static pressure experiment at 2.5 GPa and 1273 K (Non-patent Documents 1 and 2) and an impact compression experiment (Non-patent Document 3) conducted at a pressure of 12 GPa or more and a temperature of 673 K or less. It has been reported. In addition, the high-temperature Raman spectrum shows that a step-like phase transition occurs from C-type rare earth type to B-type rare earth type at 12 GPa and from B-type rare earth type to A-type rare earth type at 19 GPa (non-patent document). 4). In contrast, in the study of yttrium oxide by X-rays under high pressure, the C-type rare earth type does not pass through the B-type rare earth type, but directly transitions to the A-type rare earth type at 12 GPa. It is said that the phase transition in the order of B-type rare earth type → A-type rare earth type was observed only in the case of Eu 3+ : Y 2 O 3 (Non-patent Document 5). In addition to this, there is also a report of a high-temperature phase (CaF 2 type) of yttrium oxide formed under normal pressure at 2493 K, which is slightly below the melting point (Non-patent Documents 6 and 7).
しかしながら、本願発明者の知る限り、酸化イットリウムの相転移への温度の効果を入れた高圧下Ｘ線回折実験は報告されていない。 However, as far as the inventors of the present application know, no high-pressure X-ray diffraction experiments including the effect of temperature on the phase transition of yttrium oxide have been reported.
本発明の課題は、上述した既知の構造とは異なり、したがって従来にはなかった有用な特性が期待できる酸化イットリウムを得ることにある。 An object of the present invention is to obtain yttrium oxide which is different from the above-described known structure and therefore can be expected to have useful properties which have not been conventionally obtained.
本発明の一側面によれば、硫化ガドリニウム型構造を有する酸化イットリウムが与えられる。 According to one aspect of the present invention, there is provided yttrium oxide having a gadolinium sulfide type structure.
本発明の他の側面によれば、９ＧＰａ以上の圧力と８００℃以上の温度で酸化イットリウムを処理する、硫化ガドリニウム型構造を有する酸化イットリウムの製造方法が与えられる。 According to another aspect of the present invention, there is provided a method for producing yttrium oxide having a gadolinium sulfide type structure, wherein yttrium oxide is treated at a pressure of 9 GPa or more and a temperature of 800 ° C. or more.
ここにおいて、圧力は４０ＧＰａ以下とすることができる。 Here, the pressure can be 40 GPa or less.
また、圧力は１０ＧＰａ以上かつ２３ＧＰａ以下とすることができる。 The pressure can be 10 GPa or more and 23 GPa or less.
また、温度は２０００℃以下とすることができる。 Moreover, temperature can be 2000 degrees C or less.
また、レーザー照射によって昇温を行うことができる。 Further, the temperature can be raised by laser irradiation.
また、ダイヤモンドアンビルにより圧力を印加することができる。 Moreover, a pressure can be applied with a diamond anvil.
本発明は、硫化ガドリニウム型構造の酸化イットリウムという、新規な構造の酸化イットリウムを与えるものである。本構造の酸化イットリウムは常温常圧下でも準安定的に存在し、また結晶構造が密になるになるため、Ｃ型及びＢ型希土類型構造を持つＥｕ３＋：Ｙ２Ｏ３とは異なる蛍光特性が期待される。 The present invention provides a novel structure of yttrium oxide called gadolinium sulfide type yttrium oxide. The yttrium oxide of this structure exists metastable even at normal temperature and pressure, and the crystal structure becomes dense, so that the fluorescence characteristics are different from Eu 3+ : Y 2 O 3 having C-type and B-type rare earth structures. There is expected.
本発明の硫化ガドリニウム（Ｇｄ２Ｓ３）型構造の酸化イットリウム（Ｙ２Ｏ３）は高温高圧処理過程により製造した。従来の高温高圧合成法では、Ｂ型希土類構造の酸化イットリウムの合成が確認されていたが、本発明では高温下でかつ従来法より高い圧力の発生により、今まで報告されていなかった硫化ガドリニウム型構造の酸化イットリウムの製造に成功した。 The gadolinium sulfide (Gd 2 S 3 ) type yttrium oxide (Y 2 O 3 ) of the present invention was produced by a high temperature and high pressure treatment process. In the conventional high-temperature and high-pressure synthesis method, synthesis of yttrium oxide having a B-type rare earth structure has been confirmed. However, in the present invention, a gadolinium sulfide type that has not been reported so far due to generation of pressure at a high temperature and higher than that of the conventional method The structure of yttrium oxide was successfully produced.
また、本発明者の実験によれば、室温高圧下ではＡ型希土類構造ができるが、この構造は一気圧への減圧時にＢ型希土類構造へ変化することが確認された。 Further, according to the experiment by the present inventor, an A-type rare earth structure can be formed at room temperature and high pressure, but it has been confirmed that this structure changes to a B-type rare earth structure when the pressure is reduced to 1 atm.
製造された硫化ガドリニウム型構造の酸化イットリウムはＢ型希土類構造に比べ８％高密度である。 The produced gadolinium sulfide type yttrium oxide is 8% denser than the B type rare earth structure.
以下、本発明を温度、圧力などを変化させて行った実施例に基づいて更に詳細に説明する。 Hereinafter, the present invention will be described in more detail based on examples carried out by changing temperature, pressure and the like.
微量の金粉末（０．１重量％未満）を混入した粉末のＹ２Ｏ３(Aldrich P/N 204927、純度９９．９９９％）を８７３Ｋで３時間乾燥させたものを高圧実験用の試料として準備した。なお、ここで金粉末を混入するのは、加熱及び圧力測定のためであり、結晶の構造には何の影響も与えない。すなわち、加熱は以下で説明するようにレーザー光（Ｎｄ：ＹＬＦレーザー）の吸収により行われる。しかし、酸化イットリウムは当該レーザー波長（１０５３ｎｍ）に対し透明であるため、微量の金粉末を試料に分散することによりレーザー吸収を可能にする。また、高圧下で金の格子定数をX線回折データから計算することにより、圧力測定をおこなうことも可能となる。 A sample of Y 2 O 3 (Aldrich P / N 204927, purity 99.999%) mixed with a small amount of gold powder (less than 0.1% by weight) dried at 873 K for 3 hours was used as a sample for high-pressure experiments. Got ready. Note that the gold powder is mixed here for heating and pressure measurement, and has no effect on the crystal structure. That is, heating is performed by absorption of laser light (Nd: YLF laser) as described below. However, since yttrium oxide is transparent to the laser wavelength (1053 nm), laser absorption is enabled by dispersing a small amount of gold powder in the sample. It is also possible to measure pressure by calculating the lattice constant of gold from X-ray diffraction data under high pressure.
試料に圧力をかけるため、図１に示す、上下に設けられた一対のダイヤモンドアンビル３でその間に存在する試料２を挟んで加圧する対称型のダイヤモンドアンビルセル（ＤＡＣ）を使用した。図１において、５０〜７０μｍの厚さのレニウム製のガスケット１に開設された直径１００〜１５０μｍの孔に試料２を装填した。室温での加圧の際には液圧媒体（hydrostatic medium）（ここではメタノール：エタノール：水＝１６：３：１）を使用したが、高温での加圧の際には液圧媒体は使用しなかった。室温及び高温でのその場高圧力Ｘ線回折実験は、夫々ＢＬ０４Ｂ２及びＳＰｒｉｎｇ８（財団法人高輝度光科学研究センター（ＪＡＳＲＩ））で行った。３０または３８ｋｅＶに調節された単色シンクロトロンＸ線（monochromatic synchrotron X-ray）を、ＤＡＣ中の試料上で直径が約５０μｍのスポットに収束させた。回折されたＸ線はイメージ板（ＩＰ）とＣＣＤを使用して検出した。検出器に記録したデバイ（Debye）リングはＦＩＴ２Ｄプログラム（非特許文献８）を使用して図２に示す強度対２θのデータに変換した。レーザービーム４による加熱はＮｄ：ＹＬＦレーザー（図示せず）を使用し、レーザービーム４をＤＡＣ中の試料２上で直径２０μｍのスポットに収束させた。試料の温度は、試料からの灰色放射（gray body radiation）を測定することによってモニタした。圧力は金の格子定数から判定した（非特許文献９）。 In order to apply pressure to the sample, a symmetrical diamond anvil cell (DAC) shown in FIG. 1 is used in which a pair of diamond anvils 3 provided on the upper and lower sides are pressed between the sample 2 existing therebetween. In FIG. 1, a sample 2 was loaded into a hole having a diameter of 100 to 150 μm opened in a rhenium gasket 1 having a thickness of 50 to 70 μm. Hydrostatic medium (in this case methanol: ethanol: water = 16: 3: 1) was used for pressurization at room temperature, but hydraulic medium was used for pressurization at high temperature. I did not. In-situ high pressure X-ray diffraction experiments at room temperature and high temperature were performed at BL04B2 and SPring8 (High Intensity Photoscience Research Center (JASRI)), respectively. Monochromatic synchrotron X-rays adjusted to 30 or 38 keV were focused on a spot of about 50 μm in diameter on the sample in the DAC. Diffracted X-rays were detected using an image plate (IP) and a CCD. The Debye ring recorded in the detector was converted into the intensity versus 2θ data shown in FIG. 2 using the FIT2D program (Non-Patent Document 8). For the heating by the laser beam 4, an Nd: YLF laser (not shown) was used, and the laser beam 4 was focused on a spot having a diameter of 20 μm on the sample 2 in the DAC. The temperature of the sample was monitored by measuring the gray body radiation from the sample. The pressure was determined from the lattice constant of gold (Non-Patent Document 9).
表１に本願発明者が行った代表的な実験の結果をまとめた。なお、表１には圧力と温度を維持した時間は記載していないが、これは、相転移は加熱時間には敏感でないからである。表１で「高圧状態の構造」の列が「硫化ガドリニウム型」となっている圧力・温度条件下では数秒から数１０秒程度の加熱・加圧時間でも十分に相転移する。余裕を見ても、おおむね１分以上の加熱・加圧を行えば十分である。 Table 1 summarizes the results of representative experiments conducted by the inventors. In Table 1, the time for maintaining the pressure and temperature is not described, because the phase transition is not sensitive to the heating time. In Table 1, under the pressure and temperature conditions in which the column of “high-pressure structure” is “gadolinium sulfide type”, a sufficient phase transition can be achieved even with a heating and pressurizing time of several seconds to several tens of seconds. Even if there is a margin, it is sufficient to perform heating and pressurizing for approximately 1 minute or more.
表１に示す実験結果において、実験Ｎｏ．１、５及び９の場合に硫化ガドリニウム型への相転移が観察された。一旦高温状態で硫化ガドリニウム型に相転移すると、実験Ｎｏ．１及び９の「減圧試料の構造」（ＤＡＣによる加圧をやめて常圧に戻した状態での試料の構造）カラムに示すように、常圧に戻しても硫化ガドリニウム型構造を維持した。 In the experimental results shown in Table 1, Experiment No. In cases 1, 5, and 9, a phase transition to the gadolinium sulfide type was observed. Once the phase transition to the gadolinium sulfide type at high temperature, the experiment No. As shown in the column “Structure of the reduced pressure sample” 1 and 9 (the structure of the sample in a state where the pressure applied by the DAC was stopped and returned to the normal pressure), the gadolinium sulfide structure was maintained even when the pressure was returned to the normal pressure.
なお、実験Ｎｏ．５の「減圧試料の構造」カラムには「（回収せず）」と記載されている。これは、実験Ｎｏ．１及び９において、硫化ガドリニウム型が常圧でも構造が維持されていることを確認できているので、ここでは常圧下で試料をＤＡＣから回収して構造を確認することを省略したことを意味する。 Experiment No. In the column “Structure of the reduced pressure sample” 5, “(not recovered)” is written. This is the result of Experiment No. In 1 and 9, since it has been confirmed that the structure of the gadolinium sulfide type is maintained even under normal pressure, it means that the structure is not confirmed by collecting the sample from the DAC under normal pressure. .
また、「減圧試料の構造」カラムには他のいくつかの実験でも「（回収せず）」との記載があるが、上の場合と同様に、敢えて確認するまでもないなどの理由で常圧下での試料構造の確認を省略したことを意味する。 In addition, in the “reduced pressure sample structure” column, “(not recovered)” is also described in some other experiments. However, as in the above case, it is always necessary to confirm it. This means that the confirmation of the sample structure under pressure was omitted.
ここで行った実験で硫化ガドリニウム型の酸化イットリウムができたことを確認するため、図２に示すＸ線解析の強度対２θのデータを検討した。本データは実験Ｎｏ．１の試料から得られたものである。 In order to confirm that gadolinium sulfide type yttrium oxide was formed in the experiment conducted here, the data of the intensity versus 2θ of the X-ray analysis shown in FIG. 2 was examined. This data is from Experiment No. It was obtained from one sample.
図２のグラフにおいて、実測データ点は小さな十字マークで表す。また、これらの実測データ点に当てはめたところの、硫化ガドリニウム構造から観測されるはずの理論的な曲線は細い実線で示す。また、実測データ点と理論的なデータとの差を、図２のグラフ領域の下端近くに細い点線で示す。なお、実測データと重なった理論的な曲線がほぼ垂直方向を向いている箇所（そのような箇所はかなり多い）では、実測データ点の十字マークの縦方向の線は理論的なデータの曲線と重なって判別できず、実測テータ点のマークは短い横方向の細線のように見えることに注意されたい。 In the graph of FIG. 2, the measured data points are represented by small cross marks. The theoretical curve that should be observed from the gadolinium sulfide structure, applied to these measured data points, is indicated by a thin solid line. Further, the difference between the actually measured data point and the theoretical data is indicated by a thin dotted line near the lower end of the graph area of FIG. Note that in the places where the theoretical curve that overlaps the actual measurement data is almost vertical (there are many such places), the vertical line of the cross mark of the actual measurement data points is the curve of the theoretical data. Note that the mark of the measured data point looks like a short horizontal thin line because it cannot be distinguished by overlapping.
また、図２において、上述の細い点線と実測データ点及び理論的なデータの曲線との間に見える目盛マーク（tick mark）は、計算により夫々当該角度位置に硫化ガリウム型構造のピークが出現する位置を示し、目盛マークの下側にある上向きの細い８本の矢印は、夫々金粉からの回折の位置を示す。 In addition, in FIG. 2, a tick mark that appears between the above-mentioned thin dotted line, the measured data point, and the theoretical data curve has a peak of a gallium sulfide type structure at the angular position by calculation. The eight thin arrows pointing up and below the scale mark indicate the positions of diffraction from the gold powder.
図２に示されるように、実験Ｎｏ．１の処理を行った試料から得られたＸ線回折データと硫化ガドリニウム構造から得られるはずの理論データは非常によく一致しているため、ここで得られた酸化イットリウムは硫化ガドリニウム型の構造を有していることが確認できた。図示しないが、他の条件で処理した試料についても同様な方法で夫々の構造を同定した。 As shown in FIG. Since the X-ray diffraction data obtained from the sample treated in 1 and the theoretical data that should be obtained from the gadolinium sulfide structure are in good agreement, the obtained yttrium oxide has a gadolinium sulfide type structure. It was confirmed that it had. Although not shown, the structures of the samples treated under other conditions were identified by the same method.
また、得られた硫化ガドリニウム型構造を有する酸化イットリウムの密度を測定したところ、Ｂ型希土類型構造の酸化イットリウムに比べて８％の密度上昇が見られた。なお、１気圧における密度（ｇ／ｃｍ３）は、Ｃ型希土類型構造は５．０３、Ｂ型希土類型構造は４．６３、硫化ガドリニウム型構造の場合は４．２７であった。 Further, when the density of the obtained yttrium oxide having a gadolinium sulfide type structure was measured, an increase in density of 8% was observed as compared with the yttrium oxide having a B type rare earth type structure. The density (g / cm 3 ) at 1 atm was 5.03 for the C-type rare earth structure, 4.63 for the B-type rare earth structure, and 4.27 for the gadolinium sulfide structure.
なお、上の表には示さないが、３０ＧＰａ以上の圧力を印加した場合でも硫化ガドリニウム型への相転移が起こることがわかった。また、圧力の下限については実験的にほぼ９ＧＰａであることがわかった。したがって、硫化ガドリニウム型構造への相転移を起こすための圧力範囲は９ＧＰａ以上、好ましくは９ＧＰａから４０Ｐａ、より好ましくは１０ＧＰａから２３ＧＰａの範囲である。 Although not shown in the above table, it was found that even when a pressure of 30 GPa or more was applied, a phase transition to the gadolinium sulfide type occurred. The lower limit of the pressure was experimentally found to be about 9 GPa. Therefore, the pressure range for causing the phase transition to the gadolinium sulfide type structure is 9 GPa or more, preferably 9 GPa to 40 Pa, more preferably 10 GPa to 23 GPa.
また、この相転移を起こすための温度範囲は８００℃以上で酸化イットリウムの融点未満、好ましくは８００℃から２０００℃の範囲である。 The temperature range for causing this phase transition is 800 ° C. or more and less than the melting point of yttrium oxide, preferably 800 ° C. to 2000 ° C.
図３に、上記実験の結果判明した酸化イットリウムの相転移を図式的に表す。同図からわかるように、従来試みられたことがなかった圧力及び温度の条件下で、硫化ガドリニウム型構造という新規な構造を有する酸化イットリウムが得られる。 FIG. 3 schematically shows the phase transition of yttrium oxide which has been found as a result of the above experiment. As can be seen from the figure, yttrium oxide having a novel structure called gadolinium sulfide type structure can be obtained under conditions of pressure and temperature that have not been attempted in the past.
以上詳細に説明したように、結晶構造が密になるため、Ｃ型およびＢ型希土類構造をもつＥｕ３＋：Ｙ２Ｏ３とは違う蛍光特性が期待される。 As described above in detail, since the crystal structure becomes dense, fluorescence characteristics different from Eu 3+ : Y 2 O 3 having C-type and B-type rare earth structures are expected.
１ ガスケット
２ 試料
３ ダイヤモンドアンビル
４ レーザービーム
1 Gasket 2 Sample 3 Diamond anvil 4 Laser beam
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