JPH0158267B2 - - Google Patents
Info
- Publication number
- JPH0158267B2 JPH0158267B2 JP62250298A JP25029887A JPH0158267B2 JP H0158267 B2 JPH0158267 B2 JP H0158267B2 JP 62250298 A JP62250298 A JP 62250298A JP 25029887 A JP25029887 A JP 25029887A JP H0158267 B2 JPH0158267 B2 JP H0158267B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- cerium oxide
- sputtering
- cerium
- deposition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 21
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 9
- 239000008188 pellet Substances 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 238000001771 vacuum deposition Methods 0.000 claims description 7
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 6
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 6
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 5
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 10
- 238000000151 deposition Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000007740 vapor deposition Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
Description
【発明の詳細な説明】
本発明は、真空蒸着用及びスパツタ用酸化セリ
ウム組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cerium oxide composition for vacuum deposition and sputtering.
光学、オプトエレクトロニクス等の分野で、化
学的に安定で可視域及び近赤外域で透明な高屈折
率多層膜材料には酸化ジルコニウム、酸化チタ
ン、酸化タンタル、硫化亜鉛等が使用されてき
た。酸化セリウムの屈折率ｎは2.1〜2.3（基板300
℃）と高いにもかかわらず、真空蒸着の際にガス
化するとき強い昇華性のため蒸着が不安定になつ
たり、蒸着用ペレツトが割れたりして高品質膜が
得にくかつた。近年になつて従来から多く行なわ
れて来たガラス基板への蒸着に加え、各種プラス
チツクへの真空蒸着が行なわれるに至つた。各種
プラスチツクへ光学多層膜を蒸着する場合、その
構成膜に酸化セリウムを用いるのは高い屈折率
と、蒸着時の加熱電力が少なくて、蒸発物からの
輻射熱が小さい等の利点があるため等の理由によ
るものである。しかし酸化セリウム単成分の蒸着
用ペレツトやグラニユーを用いて真空蒸着を行な
う場合、突沸現象が生じる等蒸発ガスが不安定で
再現性も乏しいため良好な膜を得にくかつた。 In fields such as optics and optoelectronics, zirconium oxide, titanium oxide, tantalum oxide, zinc sulfide, etc. have been used as high refractive index multilayer film materials that are chemically stable and transparent in the visible and near-infrared regions. The refractive index n of cerium oxide is 2.1 to 2.3 (substrate 300
Despite the high temperature (°C), it was difficult to obtain high-quality films because of the strong sublimation during gasification during vacuum deposition, which resulted in unstable deposition and cracked deposition pellets. In recent years, in addition to vapor deposition on glass substrates, which has traditionally been widely used, vacuum vapor deposition on various plastics has come into use. When depositing optical multilayer films on various plastics, cerium oxide is used as the constituent film because it has the advantages of a high refractive index, low heating power during vapor deposition, and low radiant heat from evaporated materials. This is due to a reason. However, when vacuum deposition is performed using pellets or granules for deposition containing cerium oxide as a single component, it is difficult to obtain a good film because the evaporated gas is unstable, such as bumping phenomenon, and the reproducibility is poor.
又スパツタターゲツトに酸化セリウムを用いる
場合には、酸化セリウムが熱衝撃に弱いため割れ
たり、ひびが入つたりすることがあり、ターゲツ
ト作成に特別の配慮が必要であつた。 Furthermore, when cerium oxide is used as a sputter target, special consideration has been required in the preparation of the target because cerium oxide is susceptible to thermal shock and may break or crack.
本発明の目的は、これらの欠点を改善した真空
蒸着用又はスパツタ用酸化セリウム組成物を提供
することである。 An object of the present invention is to provide a cerium oxide composition for vacuum deposition or sputtering that has improved these drawbacks.
本発明の特徴は酸化セリウムに含有する各種の
蒸発物質にある。そして酸化セリウムに酸化チタ
ン、酸化イツトリウム、酸化アルミニウム、酸化
タンタル、酸化アンチモン、酸化ジルコニウム、
酸化ビスマスの一種類或いは二種類以上を混合し
たペレツト又はスパツタターゲツトを用い、薄膜
を形成することにある。 The feature of the present invention lies in the various evaporative substances contained in cerium oxide. Cerium oxide, titanium oxide, yttrium oxide, aluminum oxide, tantalum oxide, antimony oxide, zirconium oxide,
The purpose of this method is to form a thin film using pellets or sputter targets containing one or more types of bismuth oxide.
本発明において、真空蒸着用又はスパツタ用酸
化セリウム組成物の酸化チタン、酸化イツトリウ
ム、酸化アルミニウム、酸化タンタル、酸化アン
チモン、酸化ジルコニウム、酸化ビスマスの一種
類又は二種類以上を混合して用いる量は10重量％
〜50重量％が最も良好である。この範囲では真空
蒸着用電子銃の加熱電力も少なくすみ、良好な膜
が得られる。 In the present invention, the cerium oxide composition for vacuum evaporation or sputtering uses one or more of titanium oxide, yttrium oxide, aluminum oxide, tantalum oxide, antimony oxide, zirconium oxide, and bismuth oxide in a mixed amount of 10 weight%
~50% by weight is best. In this range, the heating power of the electron gun for vacuum evaporation can be reduced, and a good film can be obtained.
又混合して用いる量が0.5重量％〜10重量％の
範囲でもほぼ同様の効果が認められる。 Moreover, almost the same effect is observed even when the amount used in the mixture is in the range of 0.5% to 10% by weight.
本発明により酸化セリウムの持つ高い屈折率を
損なうことなく、より安定な再現性のある蒸着が
可能になる。 The present invention enables more stable and reproducible vapor deposition without impairing the high refractive index of cerium oxide.
又本発明の酸化セリウム組成物を用いてスパツ
タを行なうことによりスパツタターゲツトは割れ
たり、ひびが入ることなく安定した条件で高い屈
折率の高品質の膜を形成できる。 Furthermore, by performing sputtering using the cerium oxide composition of the present invention, a high quality film with a high refractive index can be formed under stable conditions without the sputtering target breaking or cracking.
実施例 １
酸化セリウム（CeO2）に酸化チタンを25重量
％添加し、充分混合して200Kg/cm2の圧力でプレス
成形した後約1300℃で２時間焼結を行なつて蒸着
用ペレツトを得た。電子銃加熱蒸着装置に装填し
て真空蒸着を行なつた。真空度1.5×10-5torrにな
るまで排気後青板ガラス（屈折率ｎ＝1.51）基板
上に（基板温度が300℃）酸素を注入しながら真
空度８×10-5torrで光学的膜厚nd（ｎ＝屈折率、
ｄ＝膜厚）がλ/4（λ＝520nm）となるまで蒸着
した。このとき加熱されたペレツトは割れず、突
沸現象を生じなかつた。又電子銃加熱出力電流も
小さく、ガラス基板上に蒸着された蒸着膜の屈折
率ｎ＝2.25で吸収もなく基板に対する付着力も大
きかつた。そして化学的に安定で良好な蒸着膜が
得られた。Example 1 25% by weight of titanium oxide was added to cerium oxide (CeO 2 ), thoroughly mixed and press-molded at a pressure of 200 kg/cm 2 , followed by sintering at about 1300°C for 2 hours to form pellets for deposition. Obtained. It was loaded into an electron gun heating evaporation apparatus and vacuum evaporation was performed. After evacuation to a vacuum level of 1.5×10 -5 torr, the optical film thickness was measured at a vacuum level of 8×10 -5 torr while injecting oxygen onto a blue plate glass (refractive index n=1.51) substrate (substrate temperature 300°C). nd (n=refractive index,
Vapor deposition was performed until d=film thickness) became λ/4 (λ=520 nm). The pellets heated at this time did not crack and no bumping phenomenon occurred. In addition, the electron gun heating output current was small, and the refractive index of the vapor deposited film on the glass substrate was n=2.25, with no absorption and strong adhesion to the substrate. A chemically stable and good vapor deposited film was obtained.
実施例 ２
酸化セリウム（CeO2）に酸化タンタルを40重
量％添加し、前記実施例と同様な方法で直径100
mm、厚みが６mmのスパツタターゲツトを得た。そ
してRFマグネトロンスパツタ装置を用いてスパ
ツタを行なつた。真空度が１×10-6torrまで排気
後、10分間のプレスパツタを行なつた。そして青
板ガラス基板上に、Arガスを25m／分及びO2
ガスを2.5m／分の速度で注入しながら真空度
が１×10-2torrでスパツタを行なつた。RF出力
が200Wで30分間スパツタを行なつたところ、タ
ーゲツトは割れたりひびを生ずることがなく、放
電も安定しており、良好な薄膜を形成した。膜の
屈折率は2.10で膜の強度も大きい高品質のスパツ
タ膜ができた。Example 2 40% by weight of tantalum oxide was added to cerium oxide (CeO 2 ), and the diameter was 100% by the same method as in the previous example.
A sputter target with a thickness of 6 mm was obtained. Then, sputtering was performed using an RF magnetron sputtering device. After evacuation to a degree of vacuum of 1×10 −6 torr, press spattering was performed for 10 minutes. Then, on the blue plate glass substrate, Ar gas was applied at 25 m/min and O 2
Sputtering was performed at a vacuum level of 1×10 −2 torr while injecting gas at a rate of 2.5 m/min. When sputtering was performed for 30 minutes at an RF output of 200 W, the target did not break or crack, the discharge was stable, and a good thin film was formed. A high-quality sputtered film with a refractive index of 2.10 and high film strength was created.
実施例 ３
酸化セリウムに酸化アルミニウムを25重量％添
加し、前記実施例と同様な方法で蒸着用ペレツト
を得た。約１ミクロンSiO2薄膜コート済みのア
クリル基板に、基板温度を60℃に加熱しながら実
施例１と同様の方法で蒸着を行なつた。加熱され
たペレツトは蒸着中に割れず、突沸現象も生じな
かつた。膜の屈折率ｎ＝1.95で、基板に対する付
着力の大きな良好な薄膜ができた。Example 3 25% by weight of aluminum oxide was added to cerium oxide, and pellets for deposition were obtained in the same manner as in the previous example. Vapor deposition was performed on an acrylic substrate coated with a SiO 2 thin film of approximately 1 micron in the same manner as in Example 1 while heating the substrate temperature to 60°C. The heated pellets did not crack during deposition and no bumping phenomenon occurred. A good thin film with a refractive index n=1.95 and strong adhesion to the substrate was formed.
また、酸化セリウムに酸化チタン、酸化ビスマ
スの二種類をそれぞれ15重量％づつ混合して実施
例１と同様の方法で作成した蒸着用ペレツト又は
これを砕いて１〜３mmのグラニユー状にしたもの
を用いて蒸着したところ、実施例１と同様な屈折
率ｎ＝2.20の良好な蒸着膜が得られた。 In addition, deposition pellets prepared in the same manner as in Example 1 by mixing cerium oxide with 15% by weight of titanium oxide and bismuth oxide, or crushed into granules of 1 to 3 mm in size, were used. As a result, a good vapor-deposited film with a refractive index n=2.20 similar to that of Example 1 was obtained.
さらに、酸化セリウムに特許請求の範囲１項記
載の組成物を混合する方法は、粉体同志を乾式又
は湿式混合する方法と、粉体を生成する前に液状
で混合してから粉体をつくる共沈法とを比較した
がいづれも良好な結果が得られた。 Furthermore, the method of mixing the composition according to claim 1 with cerium oxide includes a method of dry or wet mixing of powders together, and a method of mixing powders in a liquid state before producing powder. When compared with the coprecipitation method, good results were obtained in both cases.
Claims (1)
ム、酸化アルミニウム、酸化タンタル、酸化アン
チモン、酸化ジルコニウム、酸化ビスマスを含有
することを特徴とする真空蒸着又はスパツタ用酸
化セリウム組成物。 ２ 酸化セリウムに酸化チタン、酸化イツトリウ
ム、酸化アルミニウム、酸化タンタル、酸化アン
チモン、酸化ジルコニウム、酸化ビスマスを一種
類或いは二種類以上を混合してその含有量が0.5
重量％−50重量％である特許請求の範囲１項記載
の真空蒸着用又はスパツタ用酸化セリウム組成
物。 ３ 特許請求の範囲２項記載の組成物を混合或い
は共沈法で得た粉体を成形し、焼結して真空蒸着
用ペレツト又はスパツタターゲツトを製造する方
法。[Scope of Claims] 1. A cerium oxide composition for vacuum deposition or sputtering, characterized in that it contains titanium oxide, yttrium oxide, aluminum oxide, tantalum oxide, antimony oxide, zirconium oxide, and bismuth oxide in cerium oxide. 2 One or more types of titanium oxide, yttrium oxide, aluminum oxide, tantalum oxide, antimony oxide, zirconium oxide, and bismuth oxide are mixed with cerium oxide so that the content is 0.5
%-50% by weight of the cerium oxide composition for vacuum deposition or sputtering according to claim 1. 3. A method for producing pellets or sputter targets for vacuum deposition by molding the powder obtained by mixing or co-precipitating the composition according to claim 2 and sintering the powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25029887A JPH0192365A (en) | 1987-10-02 | 1987-10-02 | Cerium oxide composition for vacuum metallizing or sputtering |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25029887A JPH0192365A (en) | 1987-10-02 | 1987-10-02 | Cerium oxide composition for vacuum metallizing or sputtering |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0192365A JPH0192365A (en) | 1989-04-11 |
| JPH0158267B2 true JPH0158267B2 (en) | 1989-12-11 |
Family
ID=17205824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25029887A Granted JPH0192365A (en) | 1987-10-02 | 1987-10-02 | Cerium oxide composition for vacuum metallizing or sputtering |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0192365A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0339467A (en) * | 1989-07-06 | 1991-02-20 | Matsushita Electric Ind Co Ltd | Production of sputtering target |
| TWI249164B (en) | 2001-11-22 | 2006-02-11 | Tdk Corp | Optical recording medium |
-
1987
- 1987-10-02 JP JP25029887A patent/JPH0192365A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0192365A (en) | 1989-04-11 |
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