JP2001140056A - Method and system for film deposition by negative ion irradiation and multi-source evaporation - Google Patents
Method and system for film deposition by negative ion irradiation and multi-source evaporationInfo
- Publication number
- JP2001140056A JP2001140056A JP2000264418A JP2000264418A JP2001140056A JP 2001140056 A JP2001140056 A JP 2001140056A JP 2000264418 A JP2000264418 A JP 2000264418A JP 2000264418 A JP2000264418 A JP 2000264418A JP 2001140056 A JP2001140056 A JP 2001140056A
- Authority
- JP
- Japan
- Prior art keywords
- film
- substrate
- negative ions
- sample substrate
- negative
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000001704 evaporation Methods 0.000 title claims abstract description 15
- 230000008020 evaporation Effects 0.000 title abstract description 12
- 230000008021 deposition Effects 0.000 title description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 64
- 239000000758 substrate Substances 0.000 claims abstract description 49
- 239000010419 fine particle Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000011810 insulating material Substances 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 95
- 238000007740 vapor deposition Methods 0.000 claims description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 230000004907 flux Effects 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000012788 optical film Substances 0.000 claims description 2
- 101150008905 baf-1 gene Proteins 0.000 claims 1
- 238000010884 ion-beam technique Methods 0.000 description 23
- 239000010949 copper Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000012212 insulator Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 LiNbO 2 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この出願の発明は、負イオン
照射・同時蒸着による膜形成方法およびその装置に関す
るものである。さらに詳しくは、この出願の発明は、負
イオンを用いるダイナミックミキシング処理による膜形
成方法によって、非線形光学材料等の機能性膜として有
用な微粒子分散膜を形成することのできる、新しい膜形
成方法とそのための装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for forming a film by negative ion irradiation and simultaneous vapor deposition. More specifically, the invention of this application relates to a novel film forming method capable of forming a fine particle-dispersed film useful as a functional film such as a nonlinear optical material by a film forming method by a dynamic mixing process using negative ions, and Related to the device.
【０００２】[0002]
【従来の技術とその課題】真空蒸着とイオン注入を同時
に行うことによって多元の元素から成る膜を形成するダ
イナミックミキシング処理は、イオン照射によりミキシ
ングが原子レベルで行われることから、蒸気を構成する
物質とイオンビームを構成する物質とからなる膜を任意
の膜厚で緻密に形成することが可能な膜形成方法であ
る。この方法は、通常、高温の条件下でなければ形成が
不可能である膜を室温で形成することが可能であり、ま
た、基材表面の温度上昇を制御できることから、基材の
熱的変質を防止可能であるという特長も有している。2. Description of the Related Art In a dynamic mixing process for forming a film composed of multiple elements by simultaneously performing vacuum deposition and ion implantation, the mixing is performed at the atomic level by ion irradiation. This is a film forming method capable of densely forming a film including an ion beam and a substance constituting an ion beam at an arbitrary thickness. This method can form a film at room temperature, which cannot be normally formed under high-temperature conditions, and can control the temperature rise of the substrate surface. It also has the feature that it can prevent
【０００３】しかし、従来のダイナミックミキシング処
理は、正イオンを低エネルギーで照射するために、基材
が絶縁体である場合には、基材表面に蓄積された正電荷
による帯電に起因するクローン反発によりイオンビーム
が偏向するためビームの進行方向が一定とならず、さら
には、イオンビームが基材に到達しないため、継続的な
膜形成を行うことが不可能であり、また、膜を構成する
元素の密度を高密度かつ均一にすることは困難であっ
た。However, the conventional dynamic mixing treatment irradiates positive ions with low energy, so that when the base material is an insulator, clone repulsion due to charging by positive charges accumulated on the base material surface is performed. As a result, the traveling direction of the beam is not constant because the ion beam is deflected, and further, since the ion beam does not reach the base material, it is impossible to form a continuous film, and the film is formed. It was difficult to make the element density high and uniform.
【０００４】一方、イオン蒸着の分野においては、絶縁
性基板への成膜にともなう前記のような帯電、つまりチ
ャージアップを防止するために負イオンを利用しようと
の試みがなされてもいる。On the other hand, in the field of ion deposition, attempts have been made to use negative ions in order to prevent the above-mentioned charge, that is, charge-up caused by film formation on an insulating substrate.
【０００５】しかし、これまでの負イオンの利用につい
ては、金属負イオンによる金属皮膜の形成や、酸素、窒
素等のガス元素の負イオンを利用した反応性膜の形成が
報告されているものの、負イオンによる新しい膜構造
や、新しい機能性膜の製造についてはほとんど検討され
ていないのが実情である。However, regarding the use of negative ions so far, although formation of a metal film using metal negative ions and formation of a reactive film using negative ions of gas elements such as oxygen and nitrogen have been reported, In fact, little has been studied about the production of new membrane structures or new functional membranes using negative ions.
【０００６】このため、たとえば、イオン照射の非平衡
性を利用して新しい非線形光学材料を製造するとのこと
も試みられていない。For this reason, for example, no attempt has been made to produce a new nonlinear optical material by utilizing the non-equilibrium of ion irradiation.
【０００７】そこで、この出願の発明は、以上の通りの
事情に鑑みてなされたものであり、負イオンによるダイ
ナミックミキシング処理により、絶縁体物質を膜基材と
して、新しい膜構造や、新しい機能性膜を任意の膜厚で
製造することのできる膜形成方法とそのための装置を提
供することを課題としている。Therefore, the invention of this application has been made in view of the above circumstances, and a new film structure and new functionality are obtained by using an insulating substance as a film substrate by dynamic mixing processing using negative ions. An object of the present invention is to provide a film forming method capable of manufacturing a film with an arbitrary film thickness and an apparatus therefor.
【０００８】[0008]
【課題を解決するための手段】この出願の発明は、上記
の課題を解決するものとして、第１には、真空容器内部
において、イオン源から試料基板表面へのイオン照射
と、膜基材の試料基板表面への蒸着とを同時に行うダイ
ナミックミキシング処理による膜形成方法であって、イ
オン源から照射されるイオンが負イオンで、試料基板に
同時蒸着する膜基材が絶縁体物質であり、微粒子が分散
されている微粒子分散膜を形成することを特徴とする負
イオン照射・同時蒸着による膜形成方法を提供する。Means for Solving the Problems The invention of the present application solves the above-mentioned problems. First, in a vacuum vessel, ion irradiation from an ion source to the surface of a sample substrate is performed, A method for forming a film by a dynamic mixing process that simultaneously performs vapor deposition on a sample substrate surface, wherein ions irradiated from an ion source are negative ions, the film base material that is simultaneously vapor-deposited on the sample substrate is an insulating material, and fine particles are formed. The present invention provides a method for forming a film by negative ion irradiation and simultaneous vapor deposition, which comprises forming a fine particle dispersion film in which is dispersed.
【０００９】また、この出願の発明は、上記方法につい
て、第２には、膜基材が、ＳｉＯ2，Ａｌ2Ｏ3，Ｍｇ
Ｏ，ＭｇＯ−Ａｌ2Ｏ3，ＬｉＮｂＯ2およびＢａＦ2のう
ちの１種または２種以上である膜形成方法を提供し、第
３には、負イオンが、金属元素の負イオンである膜形成
方法を、第４には、微粒子は、その径が１〜２０ｎｍで
ある膜形成方法を、第５には、微粒子が単結晶である膜
形成方法を提供する。Further, the invention of this application relates to the above method, in the second aspect, when the film substrate is made of SiO 2 , Al 2 O 3 , Mg
O, MgO—Al 2 O 3 , LiNbO 2, and BaF 2 are provided. The third aspect of the invention provides a method for forming a film, wherein the negative ions are negative ions of a metal element. The fourth method provides a film forming method in which the fine particles have a diameter of 1 to 20 nm, and the fifth method provides a film forming method in which the fine particles are a single crystal.
【００１０】そして、この出願の発明は、第６には、非
線形光学膜を形成する前記のいずれかの膜形成方法を提
供する。[0010] Sixth, the invention of this application provides any one of the above film forming methods for forming a nonlinear optical film.
【００１１】さらに、この出願の発明は、第７には、前
記いずれかの方法のための装置として、真空容器内部
に、試料基板表面に負イオンを照射するイオン源と、膜
基材を加熱蒸発し試料基板表面に膜基材蒸気を蒸着させ
るための蒸着源とを具備し、負イオンと膜基材蒸発粒子
の各々の粒子束の制御手段を備えており、膜の形成をダ
イナミックミキシング処理により実施することを特徴と
する負イオン照射・同時蒸着による膜形成装置を提供す
る。Furthermore, the invention of this application is, in a seventh aspect, an ion source for irradiating negative ions to the surface of a sample substrate inside a vacuum vessel and heating a film substrate as an apparatus for any of the above methods. It has an evaporation source for evaporating and vapor-depositing the film substrate vapor on the surface of the sample substrate, and has a control means for each particle flux of negative ions and film substrate vaporized particles. A film forming apparatus by negative ion irradiation and simultaneous vapor deposition.
【００１２】[0012]
【発明の実施の形態】この出願の発明は上記のとおりの
特徴をもつものであるが、以下に、この出願の発明の負
イオン照射・同時蒸着による膜形成方法に関する実施の
形態を説明する。BEST MODE FOR CARRYING OUT THE INVENTION The invention of this application has the features as described above. Hereinafter, an embodiment relating to a film forming method by negative ion irradiation and simultaneous vapor deposition of the invention of this application will be described.
【００１３】この出願の発明の負イオン照射・同時蒸着
による膜形成方法は、真空容器内部にて実施される。真
空容器内部には、試料基板表面に対して負イオンビーム
を照射するためのイオン源と、るつぼ内部に収容された
膜基材を加熱し蒸発させ、試料基板表面への蒸着を行う
ための蒸着源とを具備する。蒸発源には、電子ビーム蒸
着源や高周波加熱蒸着源などが用いられる。真空容器内
部にいおては、膜基材の真空蒸着と負イオンビーム照射
とが同時に行われ、多元の元素から成る膜が、ダイナミ
ックミキシング処理により形成される。The method of forming a film by negative ion irradiation and simultaneous vapor deposition of the invention of this application is carried out inside a vacuum vessel. Inside the vacuum vessel, an ion source for irradiating the sample substrate surface with a negative ion beam, and evaporation for heating and evaporating the film base material housed inside the crucible to perform evaporation on the sample substrate surface A source. As the evaporation source, an electron beam evaporation source, a high-frequency heating evaporation source, or the like is used. Inside the vacuum vessel, vacuum deposition of the film substrate and negative ion beam irradiation are performed simultaneously, and a film composed of multiple elements is formed by dynamic mixing.
【００１４】この出願の発明の膜形成方法においては、
前記のイオン源や蒸着源の個数は限定されるものではな
く、形成される膜の構成、機能に応じて、適宜最適な個
数が設定される。In the film forming method of the present invention,
The number of the above-mentioned ion sources and vapor deposition sources is not limited, and an optimal number is appropriately set according to the configuration and function of the film to be formed.
【００１５】この発明においては、従来の正イオン照射
による膜形成方法では問題となっていたイオン粒子衝撃
によって発生する２次電子放出と、負イオン照射による
負電荷の流入との均整がなされ、絶縁体膜基材とイオン
として導入される元素から構成される膜の成長におい
て、無帯電状態が継続し、すなわち、継続的な膜形成に
よる膜の厚膜化が可能となり、また、膜を構成する元素
の密度の高密度化および均一化が実現される。In the present invention, the secondary electron emission generated by ion particle bombardment, which has been a problem in the conventional film formation method by positive ion irradiation, and the inflow of negative charges due to negative ion irradiation are balanced. In the growth of the film composed of the body film substrate and the element introduced as ions, the uncharged state continues, that is, the film can be made thicker by continuous film formation, and the film is formed. The density and uniformity of the element density are realized.
【００１６】注入イオンとしての負イオンは、絶縁体中
で固溶度のほとんどない金属元素として、例えば、Ｃｕ
の他に、Ｃｏ、Ｎｉ、Ｚｎ、Ｍｏ、Ｐｄ、Ａｇ、Ｃｄ、
Ｈｆ、Ｔａ、Ｗ、Ｒｅ、Ｉｒ、Ｐｔ、Ａｕ、Ｈｇ等の負
イオンが例示される。また、固溶限よりも過飽和にする
ことができるという利点に着目すれば、Ｂ、Ｃ、Ｓｉ、
Ｐ、Ｇｅ、Ａｓ、Ｓｅ、Ｓｂ等の非金属元素の負イオン
も例示される。一方、蒸着される膜基材としては、絶縁
体物質の各種のものであってよく、たとえば、光学用途
に限れば、透明基材として、たとえば、溶融石英あるい
は結晶石英ＳｉＯ２ の他に、ソーダガラス、Ａｌ2Ｏ3
、サファイアＡｌ2Ｏ3、ＭｇＯ、スピネルＭｇＯ・ｎ
（Ａｌ2Ｏ3）、ＬｉＮｂＯ2、ＢａＦ2等が例示される。Negative ions as implanted ions are metal elements having almost no solid solubility in the insulator, such as Cu
Besides, Co, Ni, Zn, Mo, Pd, Ag, Cd,
Examples include negative ions such as Hf, Ta, W, Re, Ir, Pt, Au, and Hg. Further, if attention is paid to the advantage that supersaturation can be made higher than the solid solubility limit, B, C, Si,
Negative ions of nonmetallic elements such as P, Ge, As, Se, and Sb are also exemplified. On the other hand, the film substrate to be deposited may be any of various insulating materials. For example, in the case of optical applications only, as a transparent substrate, for example, in addition to fused quartz or crystalline quartz SiO2, soda glass , Al 2 O 3
, Sapphire Al 2 O 3 , MgO, spinel MgOn
(Al 2 O 3 ), LiNbO 2 , BaF 2 and the like.
【００１７】この出願の発明の膜形成方法においては、
微粒子が分散された膜が形成されることになる。形成さ
れた膜は、母相材とその中に分散分布している微粒子と
によって構成されている。In the film forming method of the present invention,
A film in which fine particles are dispersed is formed. The formed film is composed of a matrix material and fine particles dispersed and distributed therein.
【００１８】微粒子は、負イオンの注入による拡散の促
進で母相材中に凝集して形成されたものであって、たと
えば膜基材にほとんど固溶しない金属元素の負イオンの
注入による金属の微粒子がその代表的なものである。こ
の場合には、母相材は膜基材の蒸着によって形成され
る。The fine particles are formed by agglomeration in the matrix material by promoting diffusion by injecting negative ions. For example, fine particles are formed by injecting negative ions of a metal element which hardly forms a solid solution in the film substrate. Fine particles are typical. In this case, the matrix material is formed by vapor deposition of a film substrate.
【００１９】形成される微粒子は、その径として各種の
ものとすることができるが、一般的には１００ｎｍ以下
のものが例示される。そして、微粒子としては単結晶で
あるものとすることができる。The fine particles to be formed may be of various diameters, but generally those having a diameter of 100 nm or less are exemplified. The fine particles may be single crystals.
【００２０】以上のような微粒子分散膜によって、非線
形光学材料を提供することが可能ともなる。With the above-described fine particle dispersed film, a nonlinear optical material can be provided.
【００２１】この出願の発明の膜形成方法においては、
イオン源から試料基板表面へ照射される負イオンビーム
と蒸着源より試料基板表面へ蒸着される膜基材に関し
て、それぞれの粒子束を制御可能とする。これにより、
形成される膜の組成、構造、機能が制御され、さらに
は、イオンによる非平衡効果も制御される。具体的に
は、試料基板の直前位置に、例えばビームプロフィルモ
ニターと水冷式ファラデーカップが設置され、それぞ
れ、負イオンビームの空間分布および負イオンビームの
電流密度が定量的に測定され、イオン源からのイオンビ
ームの照射量の制御がなされる。また、蒸着源には、蒸
着源を覆うようにシールドが設置され、基材蒸気を試料
基板へ蒸着するための射出孔と基材蒸気の蒸着速度を定
量的に測定するための射出孔が設けられている。基材蒸
気の蒸着速度を定量的に測定するための射出孔から射出
する蒸気によって形成される膜を、例えば水晶発振型膜
厚計によって測定し、これを参照しつつ蒸着源の出力の
制御がなされる。In the film forming method of the present invention,
It is possible to control the respective particle fluxes of the negative ion beam irradiated from the ion source to the sample substrate surface and the film base material deposited on the sample substrate surface from the deposition source. This allows
The composition, structure, and function of the film to be formed are controlled, and the non-equilibrium effect due to ions is also controlled. Specifically, for example, a beam profile monitor and a water-cooled Faraday cup are installed immediately before the sample substrate, and the spatial distribution of the negative ion beam and the current density of the negative ion beam are quantitatively measured, respectively. Of the ion beam is controlled. In addition, a shield is installed on the evaporation source to cover the evaporation source, and an injection hole for depositing the base material vapor on the sample substrate and an injection hole for quantitatively measuring the deposition rate of the base material vapor are provided. Have been. The film formed by the vapor ejected from the injection hole for quantitatively measuring the vapor deposition rate of the substrate vapor is measured by, for example, a quartz oscillation type film thickness meter, and the output of the vapor deposition source can be controlled while referring to this. Done.
【００２２】粒子束の制御ファクターとしては、前記の
とおり、膜基材の蒸着速度と、負イオンの注入密度（線
量）、すなわち電流密度（μＡ／ｃｍ2）が考慮される
ことになる。このファクターを可変とすることで、微粒
子の膜中への含有量と粒径を変化させることが可能とな
る。As described above, the control factors of the particle flux take into account the deposition rate of the film substrate and the implantation density (dose) of negative ions, that is, the current density (μA / cm 2 ). By making this factor variable, it is possible to change the content and particle size of the fine particles in the film.
【００２３】微粒子の含有量は主として膜基材の蒸着速
度で、粒径は負イオンの注入密度により規定されること
になる。The content of the fine particles is mainly determined by the deposition rate of the film substrate, and the particle size is determined by the density of the injected negative ions.
【００２４】この出願の発明は、以上の特徴を持つもの
であるが、以下に実施例を示し、さらに具体的に説明す
る。The invention of this application has the above-mentioned features. Examples will be shown below and will be described more specifically.
【００２５】[0025]
【実施例】この出願の発明の実施例として、溶融石英基
板に対して絶縁体物質の膜基材としてのＳｉＯ2の真空
蒸着とＣｕ負イオンビームの照射を同時に行い、ダイナ
ミックミキシング処理によりＣｕ−ＳｉＯ2膜を形成し
た。As an example of EXAMPLES of the claimed invention performs irradiation of SiO 2 vacuum deposition and Cu negative ion beam as membrane base of the insulator material to the molten quartz substrate simultaneously by the dynamic mixing process Cu- An SiO 2 film was formed.
【００２６】この実施例で用いた膜形成装置の概略図を
図１に示す。FIG. 1 is a schematic view of a film forming apparatus used in this embodiment.
【００２７】負イオン源として、プラズマ・スパッター
型負重イオン源を用いた。このイオン源は、ＢからＡｕ
までの元素を対象として負イオンを生成し、６０ｋｅＶ
まで加速するものである。この実施例においては、Ｃｕ
負イオンビームを６０ｋｅＶ、電流密度５〜５０μＡ／
ｃｍ2でイオンビームの粒子束を制御しながら照射を行
った。As the negative ion source, a plasma sputter type negative heavy ion source was used. The ion source is B to Au
Negative ions are generated for the elements up to 60 keV
It accelerates up to. In this example, Cu
A negative ion beam of 60 keV and a current density of 5 to 50 μA /
Irradiation was performed while controlling the particle flux of the ion beam in cm 2 .
【００２８】負イオン源より発射された負イオンビーム
（１）は、真空ダクトを通過し、高真空チャンバーに入
射される。高真空チャンバー入口において、負イオンビ
ーム（１）は、四重極トリプレットレンズにより、直径
４０ｍｍの円形ビームに整形され、試料基板へ照射され
る。試料基板の直前位置には、負イオンビーム（１）の
空間分布を測定するためのビームプロフィルモニター
と、負イオンビームの電流密度を測定するための水冷式
ファラデーカップを設置した。The negative ion beam (1) emitted from the negative ion source passes through a vacuum duct and enters a high vacuum chamber. At the entrance of the high vacuum chamber, the negative ion beam (1) is shaped into a circular beam having a diameter of 40 mm by a quadrupole triplet lens, and is applied to the sample substrate. A beam profile monitor for measuring the spatial distribution of the negative ion beam (1) and a water-cooled Faraday cup for measuring the current density of the negative ion beam were installed immediately before the sample substrate.
【００２９】一方、高真空チャンバーの底部には、電子
ビーム蒸着源を設置し、蒸着源を構成するるつぼ（２）
内部のＳｉＯ2を、試料基板へ蒸着した。この際、蒸着
速度は０．２〜０．４ｎｍ／ｓで設定し、形成される膜
の組成に関して制御を行った。On the other hand, an electron beam evaporation source is provided at the bottom of the high vacuum chamber, and a crucible (2) constituting the evaporation source is provided.
The internal SiO 2 was deposited on the sample substrate. At this time, the deposition rate was set at 0.2 to 0.4 nm / s, and the composition of the formed film was controlled.
【００３０】蒸着源の電子ビーム（３）の加速電圧は３
ｋｅＶ、最大定格電流は７００ｍＡであった。進行方向
が試料基板方向へと向かわないＳｉＯ2蒸気（４）は不
要であり、負イオンビームの照射の妨げとなることか
ら、ＳｉＯ2蒸気（４）が負イオンビームの照射経路に
侵入しないように、シールドを設置することが有効であ
ることから、蒸着源を覆うようにステンレス製シールド
（５）を設置した。ステンレス製シールド（５）には、
ＳｉＯ2蒸気を試料基板へ蒸着するための射出孔（６）
を設けた。さらに、ステンレス製シールドには、ＳｉＯ
2蒸気の蒸着速度を定量的に測定するための射出孔を設
けた。The accelerating voltage of the electron beam (3) of the evaporation source is 3
KeV and the maximum rated current were 700 mA. Since the SiO 2 vapor (4) whose traveling direction does not go toward the sample substrate is unnecessary and hinders the irradiation of the negative ion beam, the SiO 2 vapor (4) does not enter the irradiation path of the negative ion beam. Since it is effective to install a shield, a stainless steel shield (5) was installed to cover the evaporation source. The stainless steel shield (5)
Injection hole for depositing SiO 2 vapor on sample substrate (6)
Was provided. Further, the stainless steel shield is made of SiO
(2) An injection hole for quantitatively measuring the vapor deposition rate of vapor was provided.
【００３１】試料基板である溶融石英基板（７）は銅製
のステージ（８）上に設置され、基板平面の法線方向と
Ｃｕ負イオンビームの照射方向のなす角度および基板平
面の法線方向とＳｉＯ2蒸気の射出方向のなす角度は、
それぞれ約２０°、約１５°に設定された。A fused quartz substrate (7), which is a sample substrate, is placed on a copper stage (8), and the angle between the normal direction of the substrate plane and the irradiation direction of the Cu negative ion beam and the normal direction of the substrate plane are determined. The angle between the injection direction of SiO 2 vapor is
They were set to about 20 ° and about 15 °, respectively.
【００３２】以上の膜形成装置を用いて膜形成を行うこ
とにより、粒径が３〜１０ｎｍのＣｕ微粒子が分散した
Ｃｕ−ＳｉＯ2膜が得られる。By performing film formation using the above film forming apparatus, a Cu—SiO 2 film in which fine Cu particles having a particle size of 3 to 10 nm are dispersed can be obtained.
【００３３】Ｃｕ微粒子は、膜中に均等に分散分布して
いる。しかもこれらのＣｕ微粒子は単結晶であることが
透過電子顕微鏡観察により確認されている。The Cu fine particles are uniformly distributed in the film. Moreover, it has been confirmed by transmission electron microscope observation that these Cu fine particles are single crystals.
【００３４】図２は、ＳｉＯ2蒸着速度０．４ｎｍ／
ｓ、Ｃｕ負イオンビームの電流密度２０μＡ／ｃｍ2で
成膜したＣｕ−ＳｉＯ2膜（膜厚５００ｎｍ）の透過電
子顕微鏡による断面観察写真を例示したものである。FIG. 2 shows the SiO 2 deposition rate of 0.4 nm /
FIG. 3 illustrates a cross-sectional observation photograph by a transmission electron microscope of a Cu—SiO 2 film (thickness: 500 nm) formed at a current density of 20 μA / cm 2 of s, Cu negative ion beam.
【００３５】また、形成条件をＣｕ負イオンビームの電
流密度を５０μＡ／ｃｍ2、ＳｉＯ 2蒸気の蒸着速度を
０．４ｎｍ／ｓに設定して形成した、５００ｎｍＣｕ微
粒子が分散分布したＣｕ−ＳｉＯ2膜について、非線形
光学特性評価法（縮退４波混合法）を適用し、非線形性
に関する検討を行った。その結果を図３に示した。非線
形反射率が、ポンプ光強度の２乗に比例することから、
この厚膜は３次の非線形性を持つことが確認された。In addition, the forming conditions were changed to the electric power of the Cu negative ion beam.
Flow density of 50 μA / cmTwo, SiO TwoVapor deposition rate
500 nm Cu fine formed at 0.4 nm / s
Cu-SiO with dispersed particlesTwoAbout the membrane, non-linear
Applying the optical property evaluation method (degenerate four-wave mixing method)
Was examined. The result is shown in FIG. Non-linear
Since the shape reflectance is proportional to the square of the pump light intensity,
It was confirmed that this thick film had a third-order nonlinearity.
【００３６】[0036]
【発明の効果】この出願の負イオン照射・同時蒸着によ
る膜形成方法とその装置によって、絶縁体を基材とする
膜を安定して形成することが可能とされ、非線形光学特
性を持つ新たな厚膜材料等の機能性材料の創製が可能と
なる。According to the method and the apparatus for forming a film by negative ion irradiation and simultaneous vapor deposition of the present application, it is possible to stably form a film having an insulator as a base material, and to obtain a new film having nonlinear optical characteristics. Functional materials such as thick film materials can be created.
【図１】この出願の発明の膜形成方法に関する実施例に
用いた膜形成装置の概略図である。FIG. 1 is a schematic view of a film forming apparatus used in an embodiment relating to a film forming method of the present invention.
【図２】この出願の発明の膜形成方法によって形成され
たＣｕ−ＳｉＯ2膜の断面を例示した、図面に代わる透
過電子顕微鏡写真である。FIG. 2 is a transmission electron micrograph instead of a drawing, illustrating a cross section of a Cu—SiO 2 film formed by the film forming method of the present invention.
【図３】Ｃｕ−ＳｉＯ2厚膜の非線形光学特性を示す図
である。FIG. 3 is a diagram showing nonlinear optical characteristics of a Cu—SiO 2 thick film.
１ 負イオンビーム ２ るつぼ ３ 電子ビーム ４ ＳｉＯ2蒸気 ５ ステンレス製シールド ６ 射出孔 ７ 溶融石英基板 ８ 銅製のステージ1 Negative ion beam 2 crucible three electron beams 4 SiO 2 vapor 5 stainless steel shield 6 injection holes 7 fused quartz substrate 8 copper stage
Claims (7)
料基板表面へのイオン照射と、膜基材の試料基板表面へ
の蒸着とを同時に行うダイナミックミキシング処理によ
る膜形成方法であって、イオン源から照射されるイオン
が負イオンで、試料基板に同時蒸着する膜基材が絶縁体
物質であり、微粒子が分散されている微粒子分散膜を形
成することを特徴とする負イオン照射・同時蒸着による
膜形成方法。1. A method for forming a film by a dynamic mixing process in which ion irradiation from the ion source to the surface of the sample substrate and vapor deposition of the film base material on the surface of the sample substrate are simultaneously performed inside the vacuum vessel. The film is a negative ion irradiation / simultaneous vapor deposition film characterized in that the ion to be irradiated is negative ions and the film substrate to be co-deposited on the sample substrate is an insulating material, and forms a fine particle dispersion film in which fine particles are dispersed. Forming method.
Ｏ，ＭｇＯ−Ａｌ2Ｏ3，ＬｉＮｂＯ2およびＢａＦ2のう
ちの１種または２種以上である請求項１の膜形成方法。2. The method according to claim 1, wherein the film substrate is made of SiO 2 , Al 2 O 3 , Mg.
O, MgO-Al 2 O 3 , LiNbO 2 and BaF 1 or two or more in film forming method according to claim 1 which is of the two.
請求項１または２の膜形成方法。3. The film forming method according to claim 1, wherein the negative ions are negative ions of a metal element.
請求項１ないし３のいずれかの膜形成方法。4. The film forming method according to claim 1, wherein the fine particles have a diameter of 1 to 20 nm.
のいずれかの膜形成方法。5. The fine particle is a single crystal.
Any one of the film forming methods.
５のいずれかの膜形成方法。6. The film forming method according to claim 1, wherein the non-linear optical film is formed.
めの装置であって、真空容器内部に、試料基板表面に負
イオンを照射するイオン源と、膜基材を加熱蒸発し試料
基板表面に膜基材蒸気を蒸着させるための蒸着源とを具
備し、負イオンと膜基材蒸発粒子の各々の粒子束の制御
手段を備えており、膜の形成をダイナミックミキシング
処理により実施することを特徴とする負イオン照射・同
時蒸着による膜形成装置。7. An apparatus for the method according to claim 1, wherein an ion source for irradiating the surface of the sample substrate with negative ions and a sample substrate for heating and evaporating the film base material are provided inside the vacuum vessel. A vapor deposition source for vapor-depositing the film substrate vapor on the surface; and a means for controlling each particle flux of the negative ions and the film substrate vaporized particles, and forming the film by a dynamic mixing process. A film forming apparatus using negative ion irradiation and simultaneous vapor deposition.
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| JP11-245934 | 1999-08-31 | ||
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