JPH04154970A - Method for synthesizing cubic boron nitride - Google Patents
Method for synthesizing cubic boron nitrideInfo
- Publication number
- JPH04154970A JPH04154970A JP27440690A JP27440690A JPH04154970A JP H04154970 A JPH04154970 A JP H04154970A JP 27440690 A JP27440690 A JP 27440690A JP 27440690 A JP27440690 A JP 27440690A JP H04154970 A JPH04154970 A JP H04154970A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- substrate
- boron nitride
- cubic boron
- chamber
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 15
- 229910052582 BN Inorganic materials 0.000 title claims description 10
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims description 10
- 230000002194 synthesizing effect Effects 0.000 title claims description 8
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 45
- 239000002994 raw material Substances 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 5
- 229910015844 BCl3 Inorganic materials 0.000 abstract description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 description 12
- 230000005284 excitation Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000010571 fourier transform-infrared absorption spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- -1 excitation Substances 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、切削工具等の工具材料やヒートシンク等の電
子材料となる立方晶窒化硼素の合成方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for synthesizing cubic boron nitride, which is used as a tool material for cutting tools and the like, and as an electronic material for heat sinks and the like.
立方晶窒化硼素（ｃ −Ｂ Ｎ）は、ダイヤモンドに次
、゛硬さと熱伝導率を有し、鉄族合金に対して極めて化
学的に安定であり、切削工具、金型等の耐久性向上への
応用あるいは半導体素子１発光素子等への応用なと、幅
広い用途か考えられる。−般に、ｃ−ＢＮの製造には、
プラズマを用いた各種製造方法か知られている。Cubic boron nitride (c-BN) has hardness and thermal conductivity second only to diamond, and is extremely chemically stable against iron group alloys, improving the durability of cutting tools, molds, etc. A wide range of applications can be considered, such as application to semiconductor devices, light emitting devices, etc. -Generally, for the production of c-BN,
Various manufacturing methods using plasma are known.
従来、ＣＶＤ法を用いた立方晶窒化硼素（Ｃ−ＢＮ）合
成方？Ｌとしては、４￥間昭６２−２０５２７１；公ｔ
ｔＪに開小されるように、マイクロｉｌ！ｉ （二＼。Conventional method of synthesizing cubic boron nitride (C-BN) using CVD method? As L, 4 yen period 1986-205271; public t
Microil to be opened and small by tJ! i (2\.
Ｄｉ去によｌ）、硼素用（ｉ゛含灯カ′ス、窒素ＩＣ肖
“−含ｆ１ガスおよび水素ガスのｌ昆合ガスをマイクロ
波無電極放電中を通過させ、鉄分解反１２によ１）、３
００〜１３００ ’（ｊ：ｆ用執されている基板の表面
にｃ−ＢＮを析出させろ方法か知らオ］ている。For boron (light-containing gas, nitrogen IC type), a mixture of F1 gas and hydrogen gas is passed through a microwave electrodeless discharge to react with iron decomposition reactor 12. Yo1), 3
00-1300' (I know how to deposit c-BN on the surface of the substrate used for j:f).
また、特開昭６３−１３４６６２号公報には、硼素原子
含有ガスおよび窒素原子含存ガスをエキシマレーザ−Ｃ
ＶＤ法にて分解、励起状態とした後、高周波プラズマ中
を通過させ、３００〜２０００℃に加熱した基板の表面
に導入し、Ｃ−ＢＮを析出させる方法が開示されている
。Furthermore, in Japanese Patent Application Laid-Open No. 63-134662, a boron atom-containing gas and a nitrogen atom-containing gas are
A method is disclosed in which C-BN is precipitated by being decomposed and brought into an excited state by a VD method, then passed through high-frequency plasma, and introduced onto the surface of a substrate heated to 300 to 2000°C.
しかし、特開昭６２−２０５２７７号公報の従来の合成
方法においては、原料ガスをマイクロ波無電極放電中に
通過させるのみであるため、反応ガスへの投入エネルギ
ーか不足し、所望の膜質が得られにくく、再現性に乏し
いという問題点かあった。However, in the conventional synthesis method disclosed in JP-A No. 62-205277, the raw material gas is simply passed through microwave electrodeless discharge, so the energy input to the reaction gas is insufficient and the desired film quality cannot be obtained. There were problems in that it was difficult to reproduce and had poor reproducibility.
一方、特開昭６３−１３４６６２号公報の従来法におい
ては、原料ガスにエキシマレーザ−光を照射した後に高
周波プラズマ中を通過させる方式をとっている。この方
式によると、基板近傍での光ＣＶＤの効果か低いため、
所望の膜質か得られにくく、光の照射位置により再現性
か乏しいという問題点かあった。On the other hand, in the conventional method disclosed in Japanese Patent Application Laid-Open No. 63-134662, a method is adopted in which a raw material gas is irradiated with excimer laser light and then passed through high-frequency plasma. According to this method, the effect of photo-CVD near the substrate is low;
There were problems in that it was difficult to obtain the desired film quality and the reproducibility was poor depending on the position of light irradiation.
本発明は、かかる従来の問題点に鑑みてなされたもので
、ＣＶＤ法において、ｃ−ＢＮ形成に有利なｃ−ＢＮの
合成方法を提供することを目的とする。The present invention was made in view of such conventional problems, and an object of the present invention is to provide a c-BN synthesis method that is advantageous for c-BN formation in the CVD method.
上記目的を達成するために、本発明は、硼素原子含有ガ
スおよび窒素原子含有ガスを原料ガスとして用い、気相
化学蒸着法により立方晶窒化硼素を合成する方法におい
て、前記原料ガスをマイクロ波無電極放電中を通過させ
ると同時に、エキシマレーサー光を光源とする紫外光を
照射し、３００〜１３００℃に加熱した基板表面にｃ−
ＢＮ膜を形成することとした。In order to achieve the above object, the present invention provides a method for synthesizing cubic boron nitride by a vapor phase chemical vapor deposition method using a boron atom-containing gas and a nitrogen atom-containing gas as raw material gases. At the same time as passing through the electrode discharge, ultraviolet light from an excimer laser light source is irradiated, and c-
It was decided to form a BN film.
また、本発明において、原料ガスに水素または不活性ガ
スの少なくともいずれか一方を混入させて導入してもよ
い。Further, in the present invention, at least one of hydrogen and an inert gas may be mixed into the raw material gas before being introduced.
さらに、マイクロ波無電極放電の下流に磁界を設けても
よい。Furthermore, a magnetic field may be provided downstream of the microwave electrodeless discharge.
すなわち、本発明においては、硼素原子含存ガス、窒素
原子含有ガスを原料ガスとして用いる。That is, in the present invention, a boron atom-containing gas and a nitrogen atom-containing gas are used as source gases.
原料ガスをマイクロ波無電極放電中を通過させると同時
に、外部に設置したエキシマレーザ−による紫外光を照
射し、原料ガスの分解、励起、反応を促し、３００〜１
３００℃に加熱した基板表面にｃ−ＢＮを析出させる。While passing the raw material gas through a microwave electrodeless discharge, it is simultaneously irradiated with ultraviolet light from an excimer laser installed outside to promote decomposition, excitation, and reaction of the raw material gas.
c-BN is deposited on the surface of the substrate heated to 300°C.
ｃ−ＢＮを生成させるための原料ガスの励起手法として
、マイクロ波プラズマのみではエネルギー的に不十分で
あり、紫外光の導入が必要となる。As a method for exciting source gas to generate c-BN, microwave plasma alone is insufficient in terms of energy, and introduction of ultraviolet light is required.
本発明の特徴は励起手段として、マイクロ波プラズマと
エキシマレーザ−を同時に用いている点である。再励起
手段を比較的近い領域で、同時に用いているのは、イオ
ンあるいはラジカル等の活性種の生成を多量に効率良く
行なうためである。A feature of the present invention is that microwave plasma and excimer laser are simultaneously used as excitation means. The reason why the re-excitation means are used simultaneously in a relatively close area is to efficiently generate a large amount of active species such as ions or radicals.
それは、原料ガスの放電位置とレーザー照射位置とに隔
たりがあると、活性種の寿命の関係で片方の励起手段を
用いている効果が抑えられてしまう場合かあるからであ
る。また、両励起方式とも空間的エネルギー密度か高く
、原料ガスの分解、励起、成膜か効率良く進み、均一で
膜質の良好なＣ−ＢＮか生成する。This is because if there is a gap between the raw material gas discharge position and the laser irradiation position, the effect of using one of the excitation means may be suppressed due to the lifetime of the active species. In addition, both excitation methods have high spatial energy densities, and the decomposition of the source gas, excitation, and film formation proceed efficiently, producing C-BN that is uniform and has good film quality.
特に、原料ガスに水素または不活性ガスの少なくともい
ずれか一方を混入させて導入すれば、ｃ−ＢＮ構造以外
のＢＮ構造を選択的にエツチング除去することができ、
ｃ−ＢＮ形成に有利である。In particular, if at least one of hydrogen and inert gas is introduced into the raw material gas, BN structures other than the c-BN structure can be selectively etched away.
It is advantageous for c-BN formation.
また、マイクロ波無電極放電の下流に磁界を設けること
により、イオンを加速し、基板表面付近で均一に反応を
行うことができ、ｃ−ＢＮ形成に有利である。Further, by providing a magnetic field downstream of the microwave electrodeless discharge, ions can be accelerated and reactions can be uniformly performed near the substrate surface, which is advantageous for c-BN formation.
（第１実施例）
第１図に示す合成装置を用いて、ｃ−ＢＮ膜の形成を行
った。原料ガスとしてＮ２ガス１．ＢＣｌ３ガス２を用
い、基板３としてＳｉウェハを用いた。基板３をサセプ
ター４の上に設置し、排気系５によりチャンバー６内を
減圧にした。(First Example) A c-BN film was formed using the synthesis apparatus shown in FIG. N2 gas as raw material gas 1. BCl3 gas 2 was used, and a Si wafer was used as the substrate 3. The substrate 3 was placed on the susceptor 4, and the pressure inside the chamber 6 was reduced by the exhaust system 5.
あらかじめＮ、ガスＩ、ＢＣ１ｓガス２をそれぞれｌ
Ｏｃｃ／ｍｉｎ、 ｌｃｃ／ｍｉｎの流速で混合し、チ
ャンバー６内に導入し、２４５０ＭＨｚのマイクロ波発
振器７により基板３の外周を囲繞するマイクロ波キャビ
ティ８内に無電極放電を発生させた。これと同時に、チ
ャンバー６の外部に設けたエキシマレーザ−９により石
英窓ｌＯを介してレーザー光を照射した。チャンバー６
内の圧力はＩ Ｔｏｒｒて、基板３の温度は９００’Ｃ
とした。In advance, add l each of N, gas I, and BC1s gas 2.
The mixture was mixed at a flow rate of occ/min and lcc/min, introduced into the chamber 6, and a 2450 MHz microwave oscillator 7 generated an electrodeless discharge in the microwave cavity 8 surrounding the outer periphery of the substrate 3. At the same time, a laser beam was irradiated from an excimer laser 9 provided outside the chamber 6 through the quartz window IO. chamber 6
The internal pressure is I Torr, and the temperature of the substrate 3 is 900'C.
And so.
１時間反応させ、基板３表面に１μｍの厚さの膜を成膜
した。The reaction was allowed to proceed for 1 hour, and a film having a thickness of 1 μm was formed on the surface of the substrate 3.
この膜をＦＴ−ＩＲ（フーリエ変換赤外線吸収スペクト
ル）で調べたところ、１０５０ａｎ−’に顕著な吸収を
示した。これにより、ｃ−ＢＮ膜の形成を確認すること
ができた。When this film was examined by FT-IR (Fourier transform infrared absorption spectrum), it showed remarkable absorption at 1050an-'. Thereby, formation of the c-BN film could be confirmed.
（第２実施例）
第２図に示す合成装置を用いて、第１実施例と同様にｃ
−ＢＮ膜の成膜を行った。基板３としてＳｉウェハを用
い、原料ガスとしてＢ、Ｈ，ガス１１、ＮＮ２ガス１２
、アシストガスとしてＨ，ガス１３を用いた。基板３を
サセプター４の上に設置し、排気系５によりチャンバー
６内を減圧にした。(Second Example) Using the synthesis apparatus shown in FIG. 2, c
- A BN film was formed. A Si wafer is used as the substrate 3, and B, H, gas 11, and NN2 gas 12 are used as the raw material gases.
, H gas 13 was used as an assist gas. The substrate 3 was placed on the susceptor 4, and the pressure inside the chamber 6 was reduced by the exhaust system 5.
あらかじめＢ ２ Ｈ−ガス＋ ＋、ＮＨ３ガス１２お
よびＮ２ガス１３をそれぞれｌｃｃ／ｍｉｎ、５ｃｃ／
ｍｉｎおよび２０ ｃｃ／ｍｉｎの流速で混合し、チャ
ンバー６内に導入し、２４５０ＭＨｚのマイクロ波発振
器７により基板３の外周を囲繞するマイクロ波キャビテ
ィ８内に無電極放電を発生させた。これと同時に、チャ
ンバー６の外部に設けたエキシマレーザ−９により石英
窓ＩＯを介してレーザー光を照射した。チャンバー６内
の圧力はＩ Ｔｏｒｒて、基板３の温度は９５０℃とし
た。B 2 H-gas ++, NH3 gas 12 and N2 gas 13 were supplied in advance at lcc/min and 5cc/min, respectively.
The mixture was mixed at a flow rate of 20 cc/min and 20 cc/min, introduced into the chamber 6, and a 2450 MHz microwave oscillator 7 generated an electrodeless discharge in the microwave cavity 8 surrounding the outer periphery of the substrate 3. At the same time, an excimer laser 9 provided outside the chamber 6 irradiated laser light through the quartz window IO. The pressure inside the chamber 6 was I Torr, and the temperature of the substrate 3 was 950°C.
２時間反応させ、基板３表面に１μｍの厚さの膜を成膜
した。The reaction was carried out for 2 hours, and a film with a thickness of 1 μm was formed on the surface of the substrate 3.
この膜をＦＴ−ＩＲて調べたところ、１０５０の−１に
顕著な吸収を示し、ｃ−ＢＮ膜の形成を確認できた。When this film was examined by FT-IR, it showed remarkable absorption at -1 of 1050, confirming the formation of a c-BN film.
（第３実施例）
第３図に示す合成装置を用いて、第１実施例と同様にｃ
−ＢＮ膜の成膜を行った。基板３としてＳｉウェハを用
い、原料ガスとしてＢＣｚ、ガス２、ＮＨ３ガス１２お
よびＡｒガス１４をそれぞれＩ ｃｃ／ｍｉｎ、 ｌ
Ｏｃｃ／ｍｉｎおよび３０ ｃｃ／ｍｉｎの流速で混
合した後、チャンバー６内に導入し、２４５０ＭＨｚの
マイクロ波発振器７により無電極放電を発生させた。こ
れと同時に、外部より石英窓ｌＯを介し、エキシマレー
ザ−光を基板３に照射した。(Third Example) Using the synthesis apparatus shown in FIG. 3, c
- A BN film was formed. A Si wafer was used as the substrate 3, and BCz, gas 2, NH3 gas 12, and Ar gas 14 were used as source gases at I cc/min, l, respectively.
After mixing at flow rates of Occ/min and 30 cc/min, the mixture was introduced into the chamber 6 and a 2450 MHz microwave oscillator 7 generated an electrodeless discharge. At the same time, excimer laser light was irradiated onto the substrate 3 from the outside through the quartz window IO.
本実施例では、基板３の近傍でマイクロ波キャビティ８
のすぐ下（下流）の位置にコイル！５を □配置し、８
７５ガウスの磁場を設けた。チャンバー６内の圧力は２
Ｔｏｒｒで、基板３の温度は９２０℃とした。In this embodiment, a microwave cavity 8 is provided near the substrate 3.
Coil located just below (downstream)! Place 5 □ and place 8
A magnetic field of 75 Gauss was set up. The pressure inside chamber 6 is 2
Torr, and the temperature of the substrate 3 was 920°C.
１時間反応させ、基板３表面にｌａｍの厚さの膜を成膜
した。The reaction was allowed to proceed for 1 hour, and a film having a thickness of 1 lam was formed on the surface of the substrate 3.
この膜をＦＴ−ＩＲで調べたところ、１０５１０５Ｏ’
に顕著な吸収を示し、ｃ−ＢＮ膜の形成を確認できた。When this film was examined by FT-IR, it was found that 105105O'
It was confirmed that a c-BN film was formed.
以上のように、本発明のｃ−ＢＮの合成方法によれば、
マイクロ波プラズマとエキシマレーザ−を同時に用いる
こととしたので、原料ガスの分解、励起、成膜か効率良
く進行し、ｃ−ＢＮの形成に有利である。As described above, according to the c-BN synthesis method of the present invention,
Since microwave plasma and excimer laser are used simultaneously, the decomposition, excitation, and film formation of the source gas proceed efficiently, which is advantageous for the formation of c-BN.
特に、原料ガスに水素または不活性ガスの少なくともい
ずれか一方を混入させて導入したり、マイクロ波無電極
放電の下流に磁界を設けることにより、ｃ−ＢＮをさら
に有利に形成できる。In particular, c-BN can be formed more advantageously by introducing at least one of hydrogen or an inert gas into the raw material gas or by providing a magnetic field downstream of the microwave electrodeless discharge.
第１図、第２図および第３図はそれぞれ本発明の第１、
第２および第３実施例で用いた合成装置の概略構成図で
ある。
ｌ・・・Ｎ２ガス
２・・・ＢＣ１ｓガス
３・・・基板
６・・・チャンバー
７・・・マイクロ波発信器
８・・・マイクロ波キャビティ
９・・・エキシマレーザ−
ＩＩ・・・Ｂ２Ｈ，ガス
１２・・・ＮＨ，ガス
１３・・・Ｎ２ガス
１４・・・Ａｒガス
１５・・・コイルFIG. 1, FIG. 2, and FIG. 3 are the first and second embodiments of the present invention, respectively.
FIG. 2 is a schematic configuration diagram of a synthesis apparatus used in the second and third examples. l...N2 gas 2...BC1s gas 3...Substrate 6...Chamber 7...Microwave transmitter 8...Microwave cavity 9...Excimer laser II...B2H, Gas 12...NH, Gas 13...N2 gas 14...Ar gas 15...Coil
Claims (3)
ガスとして用い、気相化学蒸着法により立方晶窒化硼素
を合成する方法において、前記原料ガスをマイクロ波無
電極放電中を通過させると同時に、エキシマレーザー光
を光源とする紫外光を照射し、３００〜１３００℃に加
熱した基板表面に立方晶窒化硼素膜を形成することを特
徴とする立方晶窒化硼素の合成方法。(1) In a method of synthesizing cubic boron nitride by a vapor phase chemical vapor deposition method using a boron atom-containing gas and a nitrogen atom-containing gas as raw material gases, at the same time passing the raw material gases through a microwave electrodeless discharge, A method for synthesizing cubic boron nitride, which comprises forming a cubic boron nitride film on the surface of a substrate heated to 300 to 1300° C. by irradiating ultraviolet light using excimer laser light as a light source.
ずれか一方を混入させて、導入することを特徴とする請
求項１記載の立方晶窒化硼素の合成方法。(2) The method for synthesizing cubic boron nitride according to claim 1, characterized in that the raw material gas is mixed with at least one of hydrogen and an inert gas before being introduced.
を特徴する請求項１又は２記載の立方晶窒化硼素の合成
方法。(3) The method for synthesizing cubic boron nitride according to claim 1 or 2, characterized in that a magnetic field is provided downstream of the microwave electrodeless discharge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27440690A JPH04154970A (en) | 1990-10-12 | 1990-10-12 | Method for synthesizing cubic boron nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27440690A JPH04154970A (en) | 1990-10-12 | 1990-10-12 | Method for synthesizing cubic boron nitride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04154970A true JPH04154970A (en) | 1992-05-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27440690A Pending JPH04154970A (en) | 1990-10-12 | 1990-10-12 | Method for synthesizing cubic boron nitride |
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| Country | Link |
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| JP (1) | JPH04154970A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009238504A (en) * | 2008-03-26 | 2009-10-15 | National Institute For Materials Science | Method for forming cone emitter |
| JP2011060796A (en) * | 2009-09-07 | 2011-03-24 | Hitachi Zosen Corp | Thin film depositing method and apparatus therefor |
-
1990
- 1990-10-12 JP JP27440690A patent/JPH04154970A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009238504A (en) * | 2008-03-26 | 2009-10-15 | National Institute For Materials Science | Method for forming cone emitter |
| JP2011060796A (en) * | 2009-09-07 | 2011-03-24 | Hitachi Zosen Corp | Thin film depositing method and apparatus therefor |
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