JP2007269577A - Sapphire single crystal capable of developing color from yellow green to sky blue - Google Patents
Sapphire single crystal capable of developing color from yellow green to sky blue Download PDFInfo
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本発明はイエローグリーンからスカイブルーの発色をするサファイア単結晶に関するものである。 The present invention relates to a sapphire single crystal that develops a color from yellow green to sky blue.
サファイア単結晶は、ベルヌーイ法、ＦＺ法、ＣＺ法（チョコラルスキー法）等により育成可能であるが、ベルヌーイ法、ＦＺ法では、坩堝を使用しないので育成結晶の大きさが制約され、大型化が困難であり、生産性が悪い。さらに、非常に急峻な温度勾配から結晶育成を行うことから、出来上がった結晶に欠陥や歪みが生じやすく、良質な結晶育成は困難である。 The sapphire single crystal can be grown by Bernoulli method, FZ method, CZ method (chocolate ski method), etc. However, the Bernoulli method and FZ method do not use a crucible, so the size of the grown crystal is limited and the size is increased. It is difficult and productivity is poor. Furthermore, since crystal growth is performed from a very steep temperature gradient, defects and distortion are likely to occur in the completed crystal, and it is difficult to grow a high-quality crystal.
他方、ＣＺ法では坩堝サイズを変えることで育成結晶の大型化が可能であり、温度勾配の調整も容易であるため、高品質な結晶育成が可能である。
このＣＺ法は、坩堝内に入れた原料を溶融し、その融液にアルミナ単結晶の種子結晶をつけて回転しながら引き上げることにより単結晶を育成する方法である。坩堝にはイリジウムを用い、高周波誘導加熱により坩堝を加熱し、坩堝中の原料を溶融させる。坩堝の周囲はジルコニアからなるバブル状の保温材、その周囲をアルミナ、ジルコニア等の耐熱材で覆っている。結晶引き上げ方向は〔００１〕方向とする。育成雰囲気は、イリジウムが高温酸化により劣化するため、不活性雰囲気または不活性雰囲気に少量の（２０ｖｏｌ％未満）Ｏ２，ＣＯ２を含むような酸化雰囲気にする必要がある。
On the other hand, in the CZ method, the growth crystal can be enlarged by changing the crucible size, and the temperature gradient can be easily adjusted, so that high quality crystal growth is possible.
The CZ method is a method for growing a single crystal by melting a raw material put in a crucible, attaching a seed crystal of an alumina single crystal to the melt, and pulling it up while rotating. Iridium is used for the crucible, and the crucible is heated by high frequency induction heating to melt the raw material in the crucible. The periphery of the crucible is covered with a bubble-shaped heat insulating material made of zirconia, and the periphery thereof is covered with a heat-resistant material such as alumina or zirconia. The crystal pulling direction is the [001] direction. Since the iridium deteriorates due to high-temperature oxidation, the growing atmosphere needs to be an oxidizing atmosphere that contains a small amount (less than 20 vol%) O 2 and CO 2 in the inert atmosphere or the inert atmosphere.
従来、ＣＺ法を用いてサファイア単結晶が所定の色合いを呈するようにするために、ＣＺ法は使用坩堝内にサファイア単結晶原料と発色剤とを入れて不活性雰囲気中またはＯ２及び／又はＣＯ２を含む酸化雰囲気中で溶融させ、サファイア単結晶を育成することが行なわれてきた。 Conventionally, in order to make a sapphire single crystal exhibit a predetermined color using the CZ method, the CZ method is performed by putting a sapphire single crystal raw material and a color former in a used crucible and in an inert atmosphere or O 2 and / or It has been practiced to grow a sapphire single crystal by melting in an oxidizing atmosphere containing CO 2 .
また、コランダムの発色剤としては元素（Ｃｒ,Ｆｅ，Ｔｉ，Ｍｇ，Ｍｎ，Ｎｉ，Ｖ等）が扱われており、酸化ニッケルを固溶し、Ｎｉ３＋の存在によりイエローに着色するサファイア単結晶は公知である（特許文献１）。
他方、酸化鉄および酸化チタンを含む原料を溶融させることのみで得られるサファイア単結晶がブルー色彩を呈することも知られている（特許文献２）
On the other hand, it is also known that a sapphire single crystal obtained only by melting a raw material containing iron oxide and titanium oxide exhibits a blue color (Patent Document 2).
しかしながら、高級感のあるイエローグリーンからスカイブルーにわたる発色を示したサファイア単結晶は人工的に製造することが難しいとされ、この世の中に見られていなかった。本発明では、こうした従来技術の課題を解決し、高級感のあるイエローグリーンからスカイブルーにわたる発色を示したサファイア単結晶を提供することを目的とする。 However, the sapphire single crystal showing a color from high-grade yellow green to sky blue is considered difficult to produce artificially and has not been seen in the world. The object of the present invention is to solve such problems of the prior art and to provide a sapphire single crystal exhibiting high-quality yellow green to sky blue color development.
本発明者は鋭意研究の結果、酸化ニッケルは母体に固溶してＮｉ＋２であるとブルーの着色を伴い、Ｎｉ＋３であるとイエローの着色をする働きがあるが、これに加えて酸化鉄、酸化チタンを加え、固溶した電子受容体であるＦｅ３＋と電子供与体であるＴｉ３＋が反応し、Ｆｅ２＋−Ｔｉ４＋の対が形成されると、Ｎｉ２＋とＮｉ３＋の価数が制御され、イエローグリーンからスカイブルーの発色を示したサファイア単結晶が得られることを見出した。 As a result of diligent research, the present inventor has the effect that nickel oxide is dissolved in the base and Ni +2 is accompanied by blue coloring, and Ni +3 is yellow colored. In addition to this, iron oxide is added. When titanium oxide is added and Fe 3+ which is a solid solution electron acceptor reacts with Ti 3+ which is an electron donor to form a Fe 2+ -Ti 4+ pair, the valences of Ni 2+ and Ni 3+ are It was found that a sapphire single crystal that was controlled and showed a sky blue color from yellow green was obtained.
本発明は、母体Ａｌ２Ｏ３に酸化物換算で酸化鉄と酸化チタン及び酸化ニッケルを各々０．５ｗｔ％〜５．０ｗｔ％,０．０４ｗｔ％〜３．０ｗｔ％,０．５ｗｔ％〜５．０ｗｔ％含有し、その一部がイオン化して固溶していることを特徴とするサファイア単結晶を提供するもので、酸化鉄がＦｅ２＋および／またはＦｅ３＋、酸化チタンがＴｉ３＋および／またはＴｉ４＋、酸化ニッケルがＮｉ２＋および／またはＮｉ３＋の状態で固溶しているサファイア単結晶にある。 In the present invention, the base Al 2 O 3 contains 0.5 wt% to 5.0 wt%, 0.04 wt% to 3.0 wt%, 0.5 wt% to 5 wt% of iron oxide, titanium oxide, and nickel oxide in terms of oxides. A sapphire single crystal characterized by containing 0.0 wt% and partly ionized and dissolved therein, wherein iron oxide is Fe 2+ and / or Fe 3+ , titanium oxide is Ti 3+ and / or Alternatively , Ti 4+ , nickel oxide is in a sapphire single crystal in which Ni 2+ and / or Ni 3+ are in solid solution.
本発明によれば、固溶した電子受容体であるＦｅ３＋と電子供与体であるＴｉ３＋が反応し、Ｆｅ２＋−Ｔｉ４＋の対が形成されると、Ｎｉ２＋とＮｉ３＋の価数が制御され、イエローグリーンからスカイブルーの発色を示し、着色の制御が容易である。
本発明によれば、酸化鉄及び酸化ニッケルの各組成比は酸化チタンよりも多いことにより、サファイア単結晶はイエローグリーンからスカイブルーまで多色化が与えられる。
かかる本発明の効果はチョコラルスキー法で引き上げられるサファイア単結晶において顕著に示される。
According to the present invention, when Fe 3+ which is a solid solution electron acceptor and Ti 3+ which is an electron donor react to form a Fe 2+ -Ti 4+ pair, the valences of Ni 2+ and Ni 3+ are increased. Controlled, showing yellow-green to sky-blue coloration, and easy to control coloring.
According to the present invention, since each composition ratio of iron oxide and nickel oxide is higher than that of titanium oxide, the sapphire single crystal is provided with multiple colors from yellow green to sky blue.
Such an effect of the present invention is remarkably exhibited in a sapphire single crystal pulled by the chocolate ski method.
本発明は、母体Ａｌ２Ｏ３に酸化物換算で酸化鉄と酸化チタン及び酸化ニッケルを各々０．５ｗｔ％〜５ｗｔ％,０．０４ｗｔ％〜５ｗｔ％,０．５ｗｔ％〜５ｗｔ％含有し、その一部がイオン化して固溶していることを特徴とするサファイア単結晶ものであるが、通常、以下のようにして製造される。 The present invention is an oxide and titanium oxide iron oxide translation and nickel oxide in the base Al 2 O 3, respectively 0.5wt% ~5wt%, 0.04wt% ~5wt %, containing 0.5 wt% to 5 wt%, The sapphire single crystal is characterized in that a part of the sapphire is ionized and dissolved, and is usually produced as follows.
（１）主成分の酸化アルミニウムに発色剤として酸化鉄を育成原料全量に対して１ｗｔ％なるように添加し、十分混合する。また、同様に酸化アルミニウムに酸化チタンを育成原料全量に対して０．０４ｗｔ％〜２．２５ｗｔ％になるように添加し、十分混合する。また、同様に酸化アルミニウムに酸化ニッケルを育成原料全量に対して１．０ｗｔ％になるように添加し、均一になるように十分混合する。 (1) Iron oxide as a color former is added to the main component aluminum oxide so as to be 1 wt% with respect to the total amount of the growth raw material, and sufficiently mixed. Similarly, titanium oxide is added to aluminum oxide so as to be 0.04 wt% to 2.25 wt% with respect to the total amount of the growth raw material, and sufficiently mixed. Similarly, nickel oxide is added to aluminum oxide so as to be 1.0 wt% with respect to the total amount of the growth raw material, and sufficiently mixed so as to be uniform.
（２）上記育成原料に用いる酸化鉄、酸化ニッケルは酸化アルミニウムに添加混合後、大気雰囲気で焼成したものを用いる。また、酸化チタンは酸化アルミニウムに添加混合後、還元雰囲気で焼成したものを用いる。焼成後、両者を十分混合して育成原料とする。このとき酸化チタンが０.０４ｗｔ％より少ない場合、黄色の発色を示してしまい、また０．２２５ｗｔ％より多い場合、青色の発色を示してしまうことがある。 (2) The iron oxide and nickel oxide used for the growth raw material are those added and mixed with aluminum oxide and then fired in an air atmosphere. Further, titanium oxide is used after being added and mixed with aluminum oxide and then fired in a reducing atmosphere. After firing, the two are mixed thoroughly to obtain a growth raw material. At this time, if the titanium oxide is less than 0.04 wt%, a yellow color may be exhibited, and if it is greater than 0.225 wt%, a blue color may be exhibited.
（３）黄緑色の発色を示したサファイアは、ベルヌーイ法、ＦＺ法、ＣＺ法等により育成可能であるが、ベルヌーイ法、ＦＺ法では、坩堝を使用しないために育成結晶の大きさが制約されるため、大型化が困難であり生産性が悪い。さらに、非常に急峻な温度勾配から結晶育成を行うことから、出来上がった結晶に欠陥や歪みが生じやすく、良質な結晶育成は困難である。ＣＺ法では坩堝サイズを変えることで育成結晶の大型化が可能であり、温度勾配の調整も容易であるため、高品質な結晶育成が可能である。 (3) Sapphire showing yellow-green color can be grown by Bernoulli method, FZ method, CZ method, etc. However, Bernoulli method and FZ method do not use a crucible, so the size of the grown crystal is limited. Therefore, the enlargement is difficult and the productivity is poor. Furthermore, since crystal growth is performed from a very steep temperature gradient, defects and distortions are likely to occur in the completed crystal, and it is difficult to grow a high-quality crystal. In the CZ method, the growth crystal can be enlarged by changing the crucible size, and the temperature gradient can be easily adjusted, so that high quality crystal growth is possible.
（４）ＣＺ法は、坩堝内に入れた原料を溶融し、その融液にコランダム単結晶の種子結晶をつけて回転しながら引き上げることにより単結晶を育成する方法である。
坩堝にはイリジウムを用い、高周波誘導加熱により坩堝を加熱し、坩堝中の原料を溶融させる。坩堝の周囲はジルコニアからなるバブル状の保温材、その周囲をアルミナ、ジルコニア等の耐熱材で覆っている。結晶引き上げ方向は〔００１〕方向とし、育成雰囲気は不活性雰囲気あるいは酸化雰囲気とする。ただし、イリジウムは高温酸化により劣化するため、育成雰囲気を酸化雰囲気とする場合は濃度が薄い方が望ましい。また、引き上げ速度は２ｍｍ／Ｈ以下とする。２ｍｍ／Ｈより速いと偏析が生じやすく不適である。
(4) The CZ method is a method for growing a single crystal by melting a raw material put in a crucible, attaching a seed crystal of a corundum single crystal to the melt and pulling it up while rotating.
Iridium is used for the crucible, and the crucible is heated by high frequency induction heating to melt the raw material in the crucible. The periphery of the crucible is covered with a bubble-shaped heat insulating material made of zirconia, and the periphery thereof is covered with a heat-resistant material such as alumina or zirconia. The crystal pulling direction is the [001] direction, and the growing atmosphere is an inert atmosphere or an oxidizing atmosphere. However, since iridium deteriorates due to high-temperature oxidation, it is desirable that the concentration be low when the growing atmosphere is an oxidizing atmosphere. The pulling speed is 2 mm / H or less. If it is faster than 2 mm / H, segregation is likely to occur, which is inappropriate.
（５）本発明においては、酸化鉄、酸化チタン、酸化ニッケルをサファイアに固溶させるに、育成中の雰囲気ガスと使用する原料の前処理を工夫するのがよい。すなわち、育成雰囲気は不活性雰囲気あるいは、酸化雰囲気が好ましい。原料の前処理は、酸化鉄と酸化ニッケルについては酸化アルミニウムに酸化鉄、酸化ニッケルをそれぞれ添加したものを混合後、大気雰囲気にて焼成したものを育成原料として使用するのがよい。
また、酸化チタンは、酸化アルミニウムに酸化チタンを添加したものを混合後、還元雰囲気にて焼成したものを育成原料として使用するのがよい。
(5) In the present invention, in order to solidify iron oxide, titanium oxide, and nickel oxide in sapphire, it is preferable to devise pretreatment of the atmosphere gas being grown and the raw material to be used. That is, the growing atmosphere is preferably an inert atmosphere or an oxidizing atmosphere. In the pretreatment of the raw materials, it is preferable to use iron oxide and nickel oxide, which are prepared by mixing iron oxide and nickel oxide added to aluminum oxide and then firing in an air atmosphere as a growth raw material.
In addition, it is preferable to use titanium oxide obtained by mixing titanium oxide added with titanium oxide and firing it in a reducing atmosphere as a growth raw material.
以上の、育成方法によれば、サファイア単結晶が透明感のある安定的な着色を呈した高品質なコランダム単結晶を提供することが可能になる。本発明の効果をより一層はっきりさせるために、以下に実施例を述べる。 According to the above growth method, it becomes possible to provide a high-quality corundum single crystal in which the sapphire single crystal exhibits a transparent and stable coloring. In order to further clarify the effects of the present invention, examples will be described below.
サファイア単結晶原料としての酸化アルミニウムにＮｉの価数を制御するものとしての酸化鉄を育成原料全量に対して１．０ｗｔ％なるように添加し、十分混合する。また、同様に酸化アルミニウムにＮｉの価数を制御するものとしての酸化チタンを育成原料全量に対して０．０７ｗｔ％になるように添加し、均一になるように十分混合する。また、同様に酸化アルミニウムに発色剤として酸化ニッケルを育成原料全量に対して１．０ｗｔ％になるように添加し、均一になるように十分混合する。上記育成原料に用いる酸化鉄、酸化ニッケルは酸化アルミニウムに添加混合後、大気雰囲気で焼成したものを用いる。また、酸化チタンは酸化アルミニウムに添加混合後、還元雰囲気で焼成したものを用いる。焼成後、両者を十分混合して育成原料とする。イリジウム製の坩堝に原料を充填し、ＣＺ装置を用いて下記の条件により結晶を育成する。 Iron oxide as a material for controlling the valence of Ni is added to aluminum oxide as a sapphire single crystal raw material so as to be 1.0 wt% with respect to the total amount of the growth raw material, and sufficiently mixed. Similarly, titanium oxide as a material for controlling the valence of Ni is added to aluminum oxide so as to be 0.07 wt% with respect to the total amount of the growth raw material, and sufficiently mixed so as to be uniform. Similarly, nickel oxide as a color former is added to aluminum oxide so as to be 1.0 wt% with respect to the total amount of the growth raw material, and sufficiently mixed so as to be uniform. The iron oxide and nickel oxide used for the growth material are those that are added to and mixed with aluminum oxide and then fired in an air atmosphere. Further, titanium oxide is used after being added and mixed with aluminum oxide and then fired in a reducing atmosphere. After firing, the two are mixed thoroughly to obtain a growth raw material. A raw material is filled in an iridium crucible, and a crystal is grown under the following conditions using a CZ apparatus.
種結晶 コランダム単結晶
引き上げ方向 〔００１〕
引き上げ速度 ０．６ｍｍ／Ｈ
結晶回転数 ２．５ｒｐｍ
育成雰囲気 酸化雰囲気
Seed crystal Corundum single crystal pulling direction [001]
Lifting speed 0.6mm / H
Crystal rotation speed 2.5rpm
Growing atmosphere Oxidizing atmosphere
上記条件で育成した結晶は結晶全体にイエローグリーンの発色をするサファイア単結晶が得られた。かかる単結晶中の酸化鉄、酸化チタンおよび酸化ニッケルの添加量と固溶量とは以下の通りである。 A crystal grown under the above conditions yielded a sapphire single crystal that colored yellow-green throughout the crystal. The addition amount and solid solution amount of iron oxide, titanium oxide and nickel oxide in the single crystal are as follows.
原料 添加量 固溶量
酸化鉄 １ｗｔ％ ０．０４６ｗｔ％
酸化チタン ０．０７ｗｔ％ ０．０１９ｗｔ％
酸化ニッケル １ｗｔ％ ０．０３８ｗｔ％
着色 イエローグリーン
Raw material Addition amount Solid solution amount Iron oxide 1wt% 0.046wt%
Titanium oxide 0.07wt% 0.019wt%
Nickel oxide 1wt% 0.038wt%
Yellow-green
コランダム単結晶原料としての酸化アルミニウムにＮｉの価数を制御するものとしての酸化鉄を育成原料全量に対して３．３３ｗｔ％なるように添加し、十分混合する。また、同様に酸化アルミニウムにＮｉの価数を制御するものとしての酸化チタンを育成原料全量に対して０．２２５ｗｔ％になるように添加し、均一になるように十分混合する。また、同様に酸化アルミニウムに発色剤として酸化ニッケルを育成原料全量に対して１．０ｗｔ％になるように添加し、均一になるように十分混合する。上記育成原料に用いる酸化鉄、酸化ニッケルは酸化アルミニウムに添加混合後、大気雰囲気で焼成したものを用いる。また、酸化チタンは酸化アルミニウムに添加混合後、還元雰囲気で焼成したものを用いる。焼成後、両者を十分混合して育成原料とする。イリジウム製の坩堝に原料を充填し、ＣＺ装置を用いて下記の条件により結晶を育成する。 Iron oxide as a material for controlling the valence of Ni is added to aluminum oxide as a corundum single crystal raw material so as to be 3.33 wt% with respect to the total amount of the growth raw material, and sufficiently mixed. Similarly, titanium oxide as a material for controlling the valence of Ni is added to aluminum oxide so as to be 0.225 wt% with respect to the total amount of the growth raw material, and sufficiently mixed so as to be uniform. Similarly, nickel oxide as a color former is added to aluminum oxide so as to be 1.0 wt% with respect to the total amount of the growth raw material, and sufficiently mixed so as to be uniform. The iron oxide and nickel oxide used for the growth material are those that are added to and mixed with aluminum oxide and then fired in an air atmosphere. Further, titanium oxide is used after being added and mixed with aluminum oxide and then fired in a reducing atmosphere. After firing, the two are mixed thoroughly to obtain a growth raw material. A raw material is filled in an iridium crucible, and a crystal is grown under the following conditions using a CZ apparatus.
種結晶 コランダム単結晶
引き上げ方向 〔００１〕
引き上げ速度 ０．８ｍｍ／Ｈ
結晶回転数 ２．５ｒｐｍ
育成雰囲気 不活性雰囲気
上記条件で育成した結晶は結晶全体からブルーの発色をするサファイア単結晶が得られた。
Seed crystal Corundum single crystal pulling direction [001]
Lifting speed 0.8mm / H
Crystal rotation speed 2.5rpm
Growing atmosphere Inert atmosphere A crystal grown under the above conditions yielded a sapphire single crystal that developed blue color from the entire crystal.
コランダム単結晶原料としての酸化アルミニウムにＮｉの価数を制御するものとしての酸化鉄を育成原料全量に対して１．０ｗｔ％なるように添加し、十分混合する。また、同様に酸化アルミニウムにＮｉの価数を制御するものとしての酸化チタンを育成原料全量に対して０．１ｗｔ％になるように添加し、均一になるように十分混合する。また、同様に酸化アルミニウムに発色剤として酸化ニッケルを育成原料全量に対して１．０ｗｔ％になるように添加し、均一になるように十分混合する。上記育成原料に用いる酸化鉄、酸化ニッケルは酸化アルミニウムに添加混合後、大気雰囲気で焼成したものを用いる。また、酸化チタンは酸化アルミニウムに添加混合後、還元雰囲気で焼成したものを用いる。焼成後、両者を十分混合して育成原料とする。イリジウム製の坩堝に原料を充填し、ＣＺ装置を用いて下記の条件により結晶を育成する。 Iron oxide as a material for controlling the valence of Ni is added to aluminum oxide as a corundum single crystal raw material so as to be 1.0 wt% with respect to the total amount of the growth raw material, and sufficiently mixed. Similarly, titanium oxide as a material for controlling the valence of Ni is added to aluminum oxide so as to be 0.1 wt% with respect to the total amount of the growth raw material, and sufficiently mixed so as to be uniform. Similarly, nickel oxide as a color former is added to aluminum oxide so as to be 1.0 wt% with respect to the total amount of the growth raw material, and sufficiently mixed so as to be uniform. The iron oxide and nickel oxide used for the growth material are those that are added to and mixed with aluminum oxide and then fired in an air atmosphere. Further, titanium oxide is used after being added and mixed with aluminum oxide and then fired in a reducing atmosphere. After firing, the two are mixed thoroughly to obtain a growth raw material. A raw material is filled in an iridium crucible, and a crystal is grown under the following conditions using a CZ apparatus.
種結晶 コランダム単結晶
引き上げ方向 〔００１〕
引き上げ速度 ０．８ｍｍ／Ｈ
結晶回転数 ２．５ｒｐｍ
育成雰囲気 不活性雰囲気
Seed crystal Corundum single crystal pulling direction [001]
Lifting speed 0.8mm / H
Crystal rotation speed 2.5rpm
Growing atmosphere Inert atmosphere
上記条件で育成した結晶は結晶全体にイエローグリーンからスカイブルーの発色をするサファイア単結晶が得られた。
以上のように本発明によれば、黄色、黄緑色、青色の発色を示したサファイアを得ることができる。この代表的結果を下記表１〜表３に示す。
A crystal grown under the above conditions yielded a sapphire single crystal that developed yellow-green to sky-blue color throughout the crystal.
As described above, according to the present invention, it is possible to obtain sapphire exhibiting yellow, yellow-green, and blue coloring. The representative results are shown in Tables 1 to 3 below.
本発明では発色源であるＦｅ２＋−Ｔｉ４＋、Ｎｉ２＋およびＮｉ３＋の比率により発色が変化するが、一般に酸化鉄／酸化ニッケル比の１／１以上ではブルーサファイア色が強くなる傾向にあり、１／１以下ではイエローサファイア色が強くなる傾向にある。 In the present invention, the color development changes depending on the ratio of Fe 2+ -Ti 4+ , Ni 2+ and Ni 3+ which are color developing sources, but generally the blue sapphire color tends to become stronger at an iron oxide / nickel oxide ratio of 1/1 or more. Below 1/1, the yellow sapphire tends to be strong.
比較例 １
コランダム単結晶原料としての酸化アルミニウムに発色剤としての酸化鉄を育成原料全量に対して１．５ｗｔ％なるように添加し、十分混合する。また、同様に酸化アルミニウムに発色剤として酸化チタンを育成原料全量に対して０．５ｗｔ％になるように添加し、均一になるように十分混合する。上記育成原料に用いる酸化鉄は酸化アルミニウムに添加混合後、大気雰囲気で焼成したものを用いる。また、酸化チタンは酸化アルミニウムに添加混合後、還元雰囲気で焼成したものを用いる。焼成後、両者を十分混合して育成原料とする。イリジウム製の坩堝に原料を充填し、ＣＺ装置を用いて下記の条件により結晶を育成する。
Comparative Example 1
Iron oxide as a color former is added to aluminum oxide as a corundum single crystal raw material so as to be 1.5 wt% with respect to the total amount of the growth raw material, and sufficiently mixed. Similarly, titanium oxide as a color former is added to aluminum oxide so as to be 0.5 wt% with respect to the total amount of the growth raw material, and sufficiently mixed so as to be uniform. The iron oxide used for the growing material is one that is added to and mixed with aluminum oxide and then baked in an air atmosphere. Further, titanium oxide is used after being added and mixed with aluminum oxide and then fired in a reducing atmosphere. After firing, the two are mixed thoroughly to obtain a growth raw material. A raw material is filled in an iridium crucible, and a crystal is grown under the following conditions using a CZ apparatus.
種結晶 コランダム単結晶
引き上げ方向 〔００１〕
引き上げ速度 ０．６ｍｍ／Ｈ
結晶回転数 ２．５ｒｐｍ
育成雰囲気 酸化雰囲気
Seed crystal Corundum single crystal pulling direction [001]
Lifting speed 0.6mm / H
Crystal rotation speed 2.5rpm
Growing atmosphere Oxidizing atmosphere
比較例 ２
コランダム単結晶原料としての酸化アルミニウムに発色剤としての酸化鉄を育成原料全量に対して１．５ｗｔ％なるように添加し、十分混合する。また、同様に酸化アルミニウムに発色剤として酸化チタンを育成原料全量に対して０．１ｗｔ％になるように添加し、均一になるように十分混合する。上記育成原料に用いる酸化鉄は酸化アルミニウムに添加混合後、大気雰囲気で焼成したものを用いる。また、酸化チタンは酸化アルミニウムに添加混合後、還元雰囲気で焼成したものを用いる。焼成後、両者を十分混合して育成原料とする。イリジウム製の坩堝に原料を充填し、ＣＺ装置を用いて下記の条件により結晶を育成する。
Comparative Example 2
Iron oxide as a color former is added to aluminum oxide as a corundum single crystal raw material so as to be 1.5 wt% with respect to the total amount of the growth raw material, and sufficiently mixed. Similarly, titanium oxide as a color former is added to aluminum oxide so as to be 0.1 wt% with respect to the total amount of the growth raw material, and sufficiently mixed so as to be uniform. The iron oxide used for the growing material is one that is added to and mixed with aluminum oxide and then baked in an air atmosphere. Further, titanium oxide is used after being added and mixed with aluminum oxide and then fired in a reducing atmosphere. After firing, the two are mixed thoroughly to obtain a growth raw material. A raw material is filled in an iridium crucible, and a crystal is grown under the following conditions using a CZ apparatus.
種結晶 コランダム単結晶
引き上げ方向 〔００１〕
引き上げ速度 ０．６ｍｍ／Ｈ
結晶回転数 ２．５ｒｐｍ
育成雰囲気 酸化雰囲気
Seed crystal Corundum single crystal pulling direction [001]
Lifting speed 0.6mm / H
Crystal rotation speed 2.5rpm
Growing atmosphere Oxidizing atmosphere
比較例では、青みが強いのに対して、本発明の実施例２、３ではスカイブルーとなった。
ここで、実施例２、３と比較例１、２とのブルーカラーの違いを示すため、Ｌａｂ表色およびマンセル色票にて測色を行った。
In the comparative example, the bluish color was strong, whereas in Examples 2 and 3 of the present invention, the color was sky blue.
Here, in order to show the difference in blue color between Examples 2 and 3 and Comparative Examples 1 and 2, color measurement was performed using the Lab color and Munsell color chart.
実際には得られた結晶のＣ面がテーブルとなるように１０ｍｍ×１０ｍｍ×３ｍｍのサイズの試料を作製し計測を行った。得られた結果が下記となる。 Actually, a sample having a size of 10 mm × 10 mm × 3 mm was prepared and measured so that the C-plane of the obtained crystal was a table. The results obtained are as follows.
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| US9225056B2 (en) | 2014-02-12 | 2015-12-29 | Apple Inc. | Antenna on sapphire structure |
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| US9632537B2 (en) | 2013-09-23 | 2017-04-25 | Apple Inc. | Electronic component embedded in ceramic material |
| US9678540B2 (en) | 2013-09-23 | 2017-06-13 | Apple Inc. | Electronic component embedded in ceramic material |
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| US10052848B2 (en) | 2012-03-06 | 2018-08-21 | Apple Inc. | Sapphire laminates |
| US9221289B2 (en) | 2012-07-27 | 2015-12-29 | Apple Inc. | Sapphire window |
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| KR20160066111A (en) * | 2014-12-01 | 2016-06-10 | 서울시립대학교 산학협력단 | Method of enhancing qualities of sapphires |
| US10406634B2 (en) | 2015-07-01 | 2019-09-10 | Apple Inc. | Enhancing strength in laser cutting of ceramic components |
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