JPH05201793A - Forming method for gold crystal thin film - Google Patents
Forming method for gold crystal thin filmInfo
- Publication number
- JPH05201793A JPH05201793A JP11617192A JP11617192A JPH05201793A JP H05201793 A JPH05201793 A JP H05201793A JP 11617192 A JP11617192 A JP 11617192A JP 11617192 A JP11617192 A JP 11617192A JP H05201793 A JPH05201793 A JP H05201793A
- Authority
- JP
- Japan
- Prior art keywords
- gold
- forming
- thin film
- solution
- crystal
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、金結晶膜の形成方法に
関する。特に半導体集積回路、光集積回路、磁気回路等
の電子素子、光素子、圧電素子等或は電子放出素子、記
録媒体用電極等の作製に適した金結晶薄膜の形成方法に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a gold crystal film. In particular, the present invention relates to a method for forming a gold crystal thin film suitable for producing an electronic device such as a semiconductor integrated circuit, an optical integrated circuit, a magnetic circuit, an optical device, a piezoelectric device or an electron emitting device, an electrode for a recording medium and the like.
【０００２】[0002]
【従来の技術】従来より金薄膜は、時計バンドなどのア
クセサリーの装飾用の他、リードフレームやＨＩＣ等の
厚膜分野の配線や電極、ＧａＡｓ半導体の薄膜配線など
に広く用いられてきた。最近では、Ｓｉ半導体デバイス
の高密度化から、Ａｌ配線のエレクトロ・マイグレーシ
ョンが深刻な問題となり、重金属である金が配線材料と
して有望視されている。2. Description of the Related Art Conventionally, gold thin films have been widely used not only for decoration of accessories such as watch bands but also for wiring and electrodes in the field of thick films such as lead frames and HICs, thin film wiring of GaAs semiconductors, and the like. Recently, due to high density of Si semiconductor devices, electromigration of Al wiring has become a serious problem, and gold, which is a heavy metal, is regarded as a promising wiring material.
【０００３】特に耐エレクトロ・マイグレーション、耐
腐食性、低抵抗性、耐メルト性、などで優れている大粒
径の単結晶群からなる金結晶薄膜が望まれている。In particular, a gold crystal thin film composed of a single crystal group having a large grain size, which is excellent in electromigration resistance, corrosion resistance, low resistance and melt resistance, has been desired.
【０００４】このような背景にあって、金結晶の形成方
法については、基板上への金結晶薄膜形成方法として
は、真空蒸着法、ＣＶＤ法、電解めっき法、無電解めっ
き法が知られていた。Under these circumstances, as a method of forming a gold crystal, as a method of forming a gold crystal thin film on a substrate, a vacuum deposition method, a CVD method, an electrolytic plating method, and an electroless plating method are known. It was
【０００５】真空蒸着法は、Ｓｉ、ＳｉＯ2、ＳｉＮ、
ＧａＡｓ、サファイヤ、Ｃｒ、Ｔｉ、Ｃｕなどの基板を
電子ビームや抵抗加熱により５００〜７００℃程度に加
熱したうえ、通常１０-6ｔｏｒｒ以下の真空中で金を蒸
気相で搬送して推積を行なう。真空蒸着法により、マイ
カ（雲母）上に数１０μｍに大粒径の金単結晶を形成で
きた報告がある（Ｄｅｎｎｉｓ Ｊ．Ｔｒｅｖｏｒ他
Ｐｈｙｓｉｃａｌ Ｒｅｖｉｅｗ Ｌｅｔｔｅｒｓ Ｖ
ｏ１６２ Ｎｏ８ ２０．Ｆｅｂ．１９８９）。The vacuum deposition method uses Si, SiO 2 , SiN,
Substrates made of GaAs, sapphire, Cr, Ti, Cu, etc. are heated to about 500 to 700 ° C. by electron beam or resistance heating, and gold is usually transported in a vapor phase in a vacuum of 10 −6 torr or less to obtain a deposit. To do. There is a report that a large-sized gold single crystal with a size of several tens of μm can be formed on mica by the vacuum deposition method (Dennis J. Trevor et al.
Physical Review Letters V
o162 No8 20. Feb. 1989).
【０００６】また、熱ＣＶＤ法、ＰＥＣＶＤ法により、
Ｓｉ上に金多結晶薄膜を形成した報告もある（Ｎ．Ｍｉ
ｓａｗａ他 ３７回半導体・集積回路技術シンポジウム
Ｄｅｃ．７．１９８９）。Further, by the thermal CVD method and the PECVD method,
There is also a report of forming a gold polycrystal thin film on Si (N. Mi.
Sawa et al. 37th Semiconductor / Integrated Circuit Technology Symposium Dec. 7.1989).
【０００７】そして、電解めっき、無電解めっき法は、
装飾用の金薄膜形成やリードフレームのめっきなどで古
くから利用されている方法であり、この方法は予め、基
板表面に金、銅、ニッケル面を形成した上、金薄膜を形
成するというものである。The electrolytic plating and electroless plating methods are
This is a method that has been used for a long time in the formation of gold thin films for decoration and plating of lead frames.This method involves forming gold, copper, nickel surfaces on the substrate surface in advance and then forming a gold thin film. is there.
【０００８】また、金錯体の分解による溶液内の金過飽
和現象を利用して、導電性金ペースト用の金粉末を系内
に浮遊状態で析出させる技術が特開昭５６−３８４０６
号公報、特開昭５５−５４５０９号公報に開示されてい
る。Further, there is a technique of depositing gold powder for a conductive gold paste in a system in a floating state by utilizing a gold supersaturation phenomenon in a solution due to decomposition of a gold complex.
JP-A-55-54509.
【０００９】[0009]
【発明が解決しようとする課題】真空蒸着方法やＣＶＤ
法を使用すると、マイカ（雲母）や高配向グラファイト
の不活性基板上には、大粒径単結晶群からなる金結晶薄
膜を形成できるが、Ｓｉ、ＧａＡｓなどの半導体材料上
やＳｉＯ2やＳｉＮやＡｌ2Ｏ3などのセラミック上で
は、サブミクロン径の単結晶群か多結晶膜に成ってしま
う。SUMMARY OF THE INVENTION Vacuum deposition method and CVD
By using the method, a gold crystal thin film consisting of a large grain size single crystal group can be formed on an inactive substrate of mica (mica) or highly oriented graphite. However, it can be formed on a semiconductor material such as Si or GaAs or SiO 2 or SiN. On ceramics such as Al 2 O 3 and Al 2 O 3 , a single crystal group having a submicron diameter or a polycrystalline film is formed.
【００１０】更に、真空蒸着法やＣＶＤ法では、基板温
度を高温にする必要が有るため、高温下に置くことが出
来ないデバイスには、制約を多く受ける。例えば、Ｓｉ
上に金薄膜を形成する場合メルトによってＡｕ−Ｓｉ合
金が形成されてしまう為、共晶温度３６３℃を超えるこ
とができない。Further, in the vacuum vapor deposition method and the CVD method, it is necessary to raise the substrate temperature, and therefore, there are many restrictions on devices that cannot be placed under high temperature. For example, Si
When the gold thin film is formed on the Au-Si alloy, the eutectic temperature cannot exceed 363 ° C because the Au-Si alloy is formed by the melt.
【００１１】また、電解めっき法や無電解めっき法を使
用した場合には、得られる膜は、多結晶膜となり、そも
そも単結晶は形成できない。Further, when the electrolytic plating method or the electroless plating method is used, the obtained film becomes a polycrystalline film and a single crystal cannot be formed in the first place.
【００１２】また、電解めっき法、無電解めっき法で
は、金、銅、ニッケルなどの導電性表面にデバイスを作
成する必要があった。Further, in the electrolytic plating method and the electroless plating method, it is necessary to form a device on a conductive surface of gold, copper, nickel or the like.
【００１３】更に、上述の特開昭５６−３８４０６号公
報或は特開昭５５−５４５０９号公報に開示されている
方法は、あくまで粉末状態の金を得る方法であり、所望
の基板上に膜状態の全てを得ることについての開示や示
唆は何らなされていない。こうしたことから、電子素
子、光素子等に使用し得る単結晶を含む金結晶膜を低温
で基板上に形成するについては、改善すべき余地が多く
あるのが実状である。Further, the method disclosed in the above-mentioned Japanese Patent Laid-Open No. 56-38406 or Japanese Patent Laid-Open No. 55-54509 is only a method for obtaining gold in a powder state, and a film is formed on a desired substrate. There is no disclosure or suggestion of getting all of the conditions. For this reason, there is much room for improvement in forming a gold crystal film containing a single crystal that can be used in electronic devices, optical devices, etc. on a substrate at a low temperature.
【００１４】[0014]
【課題を解決するための手段及び作用】本発明は上述し
た技術的課題に鑑みてなされたものであり、基板上に膜
状態の金結晶を低温で形成できる方法を提供することを
目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above technical problems, and an object of the present invention is to provide a method for forming a film-shaped gold crystal on a substrate at a low temperature. ..
【００１５】本発明の別の目的は、耐エレクトロ・マイ
グレーション、耐腐食性、低抵抗性、耐メルト性、など
の点で優れている大粒径の単結晶群からなる金結晶薄膜
を特別な装置を使用せずに、常圧、常温に近い低温下
で、セラミックや半導体等の基板上に形成することがで
きる金結晶の形成方法を提供することである。Another object of the present invention is to specialize a gold crystal thin film consisting of a large grain size single crystal group which is excellent in electromigration resistance, corrosion resistance, low resistance and melt resistance. It is an object of the present invention to provide a method for forming a gold crystal that can be formed on a substrate such as a ceramic or a semiconductor at a normal pressure and a low temperature near room temperature without using an apparatus.
【００１６】本発明の更に別の目的は、基板表面を構成
する材料あるいは組成の違いにより、選択的に（ｓｅｌ
ｅｃｔｉｖｅｌｙ）金結晶膜を形成し得る方法を提供す
ることにある。Still another object of the present invention is to selectively (sel) depending on the difference in the material or composition of the substrate surface.
It is to provide a method capable of forming a gold crystal film.
【００１７】本発明の金結晶膜の形成方法の第１の態様
は次のとおりのものである。The first aspect of the method for forming a gold crystal film of the present invention is as follows.
【００１８】即ち、金錯体を分解処理することで、溶液
中の金を過飽和状態に移行させ、基板表面に単結晶群か
らなる金結晶薄膜を形成することを特徴とするものであ
る。That is, the gold complex is decomposed to shift the gold in the solution to a supersaturated state to form a gold crystal thin film consisting of a single crystal group on the surface of the substrate.
【００１９】本発明の第２の態様は次のとおりのもので
ある。The second aspect of the present invention is as follows.
【００２０】即ち、核形成密度の大きい材料からなる第
１の面と、核形成密度の小さい材料からなる第２の面と
を隣接して配した基板に、金錯体溶液中の金錯体を分解
処理することで、溶液中の金を過飽和状態に移行させ、
前記核形成密度の大きい基板表面のみに単結晶群からな
る金結晶薄膜を形成することを特徴とするものである。That is, the gold complex in the gold complex solution is decomposed on the substrate on which the first surface made of a material having a high nucleation density and the second surface made of a material having a low nucleation density are arranged adjacent to each other. The treatment causes the gold in the solution to transition to a supersaturated state,
The gold crystal thin film composed of a single crystal group is formed only on the surface of the substrate having a high nucleation density.
【００２１】本発明の第３の態様は次のとおりのもので
ある。The third aspect of the present invention is as follows.
【００２２】即ち、核形成密度が大きい材料からなり単
一核が形成される程充分微細な、第１の面と、核形成密
度の小さい材料からなる第２の面とを隣接して配した基
板に、金錯体溶液中の金錯体を分解処理することで、溶
液中の金を過飽和状態に移行させ、前記単一核のみより
単結晶を成長させることを特徴とするものである。That is, a first surface made of a material having a high nucleation density and fine enough to form a single nucleus and a second surface made of a material having a low nucleation density were arranged adjacent to each other. By subjecting the substrate to decomposition treatment of the gold complex in the gold complex solution, gold in the solution is transferred to a supersaturated state, and a single crystal is grown from only the single nucleus.
【００２３】本発明の第４の態様は次のとおりのもので
ある。The fourth aspect of the present invention is as follows.
【００２４】即ち、基板材料に作用するエッチング種の
存在下で、金錯体を分解処理することで、溶液中の金を
過飽和状態に移行させ、前記、基板の表面上に単結晶群
からなる金結晶薄膜を形成することを特徴とするもので
ある。That is, by decomposing the gold complex in the presence of an etching species that acts on the substrate material, the gold in the solution is transferred to a supersaturated state, and the gold consisting of a single crystal group is formed on the surface of the substrate. It is characterized by forming a crystal thin film.
【００２５】本発明の第５の態様は次のとおりのもので
ある。The fifth aspect of the present invention is as follows.
【００２６】即ち、核形成密度の大きい材料からなる第
１の面と、核形成密度の小さい材料からなる第２の面
と、を隣接して配した基板を用意する工程と、前記核形
成密度の小さい材料に作用するエッチング種の存在下
で、金錯体溶液中の金錯体を分解処理することで、溶液
中の金を過飽和状態に移行させ、前記核形成密度の大き
い基板表面のみに単結晶群からなる金結晶薄膜を形成す
る工程と、を有することを特徴とするものである。That is, a step of preparing a substrate in which a first surface made of a material having a high nucleation density and a second surface made of a material having a low nucleation density are arranged adjacent to each other; In the presence of an etching species that acts on a small material, the gold complex in the gold complex solution is decomposed to shift the gold in the solution to a supersaturated state, and a single crystal is formed only on the substrate surface with a high nucleation density. And a step of forming a gold crystal thin film composed of a group.
【００２７】本発明の第６の態様は次のとおりのもので
ある。The sixth aspect of the present invention is as follows.
【００２８】即ち、核形成密度が大きい材料からなり単
一核が形成される程充分微細な第１の面と、核形成密度
の小さい材料からなる第２の面とを隣接して配した基板
を用意する工程と、前記核形成密度の小さい材料に作用
するエッチング種の存在下で、金錯体溶液中の金錯体を
分解処理することで溶液中の金を過飽和状態に移行さ
せ、前記核形成密度が大きい材料面より単一核からなる
単結晶を成長させる工程と、を有することを特徴とする
ものである。That is, a substrate in which a first surface made of a material having a high nucleation density and fine enough to form a single nucleus is adjacent to a second surface made of a material having a low nucleation density. In the presence of an etching species that acts on the material having a low nucleation density, the gold complex in the gold complex solution is decomposed to shift the gold in the solution to a supersaturated state, and the nucleation is performed. And a step of growing a single crystal composed of a single nucleus from a material surface having a high density.
【００２９】本発明によれば、金錯体分解処理すること
により、溶液中の金を過飽和状態に移行させることで、
特別な装置は一切必要とせず、しかも、常圧、常温に近
い温度で金結晶薄膜を形成することができる。According to the present invention, by subjecting the gold in the solution to the supersaturated state by the gold complex decomposition treatment,
No special equipment is required, and the gold crystal thin film can be formed at normal pressure and temperature close to room temperature.
【００３０】更に、本発明によれば、基板上に選択的に
金結晶を形成することができる。Further, according to the present invention, the gold crystal can be selectively formed on the substrate.
【００３１】成長系の溶液種を選択することで極めて平
滑な表面を有する単結晶からなる金結晶薄膜を得ること
ができる。A gold crystal thin film made of a single crystal having an extremely smooth surface can be obtained by selecting a growth-type solution species.
【００３２】結晶粒径は、基板の表面材料及び金錯体の
種類あるいは、基板材料に作用するエッチング種の濃度
を制御することによりコントロールすることができる。The crystal grain size can be controlled by controlling the kinds of the surface material of the substrate and the gold complex or the concentration of etching species acting on the substrate material.
【００３３】そして、本発明の方法によって得られる金
結晶薄膜は、（ｌｌｌ）に配向制御される特徴を有す
る。この為、横方向の成長レートが極めて高く、大粒径
の単結晶であっても、且つ、薄く形成することができ
る。また、得られた金結晶薄膜上に圧電体膜などを積層
させる際、（ｌｌｌ）に方位継承させることができる。The gold crystal thin film obtained by the method of the present invention has a characteristic of (lll) orientation control. Therefore, the lateral growth rate is extremely high, and even a single crystal having a large grain size can be formed thin. In addition, when a piezoelectric film or the like is laminated on the obtained gold crystal thin film, the orientation can be inherited to (111).
【００３４】本発明によって得られる金結晶膜は、耐エ
レクトロ・マイグレーション、耐腐食性、低抵抗性、耐
メルト性、などに優れた大粒径の単結晶を含むものであ
り、半導体集積回路、光集積回路、磁気回路等の電子素
子、光素子、圧電素子等或は電子放出素子、記録媒体用
電極などに利用することができる。The gold crystal film obtained by the present invention contains a large grain single crystal excellent in electromigration resistance, corrosion resistance, low resistance, melt resistance and the like. It can be used as an electronic device such as an optical integrated circuit, a magnetic circuit, an optical device, a piezoelectric device, or an electron-emitting device, an electrode for a recording medium, and the like.
【００３５】以下図面を参照しながら本発明の実施態様
例について説明する。An embodiment of the present invention will be described below with reference to the drawings.
【００３６】（実施態様例１−１）図１を参照して説明
する。(Embodiment Example 1-1) A description will be given with reference to FIG.
【００３７】金錯体として［ＡｕＩ4］-、分解処理手段
として揮発処理を用いてＳｉＯ2基板１０１上に金結晶
を形成する例について説明する。An example of forming a gold crystal on the SiO 2 substrate 101 by using [AuI 4 ] − as the gold complex and volatilization treatment as the decomposition treatment means will be described.
【００３８】まず蒸留水にヨウ化カリウム及びヨウ素を
投入してヨウ素水溶液を形成した後、これに金を投入し
攪拌溶解させ、［ＡｕＩ4］-を含有する金錯体溶液を形
成する。このとき溶液中には、金錯体［ＡｕＩ4］-の
他、First, potassium iodide and iodine are added to distilled water to form an aqueous iodine solution, and then gold is added and dissolved by stirring to form a gold complex solution containing [AuI 4 ] - . At this time, in the solution, in addition to the gold complex [AuI 4 ] - ,
【００３９】[0039]
【外１】 Ｋ+が存在するものと考えられる。[Outer 1] It is considered that K + exists.
【００４０】ヨウ素水溶液は、ヨウ化カリウム以外のヨ
ウ化化合物、例えばヨウ化アンモニウムを溶解すること
でも作成出来る。また、アルコールを溶媒として用い
た、ヨウ素アルコール溶液やアルコールと水の混合物を
溶媒として用いたヨウ素アルコール・水溶液も本発明に
用いることができる。溶液中のヨウ素、ヨウ化化合物の
濃度は、溶解することできる金の量を左右する。The iodine aqueous solution can also be prepared by dissolving an iodide compound other than potassium iodide, for example, ammonium iodide. Further, an iodine alcohol solution using alcohol as a solvent or an iodine alcohol / aqueous solution using a mixture of alcohol and water as a solvent can also be used in the present invention. The concentrations of iodine and iodide compounds in the solution influence the amount of gold that can be dissolved.
【００４１】次いで、ＳｉＯ2基板１０１の表面１０２
を溶液に接した後、溶液を３０〜１００℃に昇温し、ヨ
ウ素成分の揮発を促進させる。Next, the surface 102 of the SiO 2 substrate 101.
After contacting with the solution, the temperature of the solution is raised to 30 to 100 ° C. to promote volatilization of the iodine component.
【００４２】溶液系内では、In the solution system,
【００４３】[0043]
【外２】 の状態で存在するヨウ素成分の揮発による、溶液系内の
平衝状態の維持の為の［ＡｕＩ4］-からのＩ成分の解離
による分解、又は、［ＡｕＩ4］-の形で存在する錯体中
のヨウ素成分の直接の揮発による分解が進行すると考え
られ、結果として金が過飽和状態となる。[Outside 2] Of the iodine component existing in the state of [AuI 4 ] − for the purpose of maintaining the equilibrium state in the solution system by decomposition of the I component from the dissociation of the I component, or a complex existing in the form of [AuI 4 ] − It is thought that the decomposition of the iodine component in the inside proceeds by direct volatilization, and as a result, the gold becomes supersaturated.
【００４４】溶液中で過飽和状態となった金は、基板表
面にランダムな核１０３として析出する（図１
（Ａ））。Gold supersaturated in the solution is deposited as random nuclei 103 on the surface of the substrate (FIG. 1).
(A)).
【００４５】本発明の方法において特徴的なこととし
て、核形成密度が低い状態のまま、核が自己整合的に成
長することが挙げられる。A characteristic of the method of the present invention is that the nuclei grow in a self-aligned manner while the nucleation density is low.
【００４６】核形成密度は、基板表面材料の種類、錯体
の種類、成長条件により異なるが、特に基板表面材料の
種類には、強く存在する。The nucleation density varies depending on the type of substrate surface material, the type of complex, and the growth conditions, but is strongly present especially in the type of substrate surface material.
【００４７】成長開始から、３分程度で大きいもので３
０μｍ程度の結晶１０３に成長する（図１（Ｂ））。解
析の結果、形成された結晶は、欠陥のない単結晶であ
り、（１１１）方位を有していることが確認された。
又、成長レートについて観察した結果、縦方向：横方向
が１：１００〜２００の割合で成長することが解った。3 minutes after the start of growth
It grows to a crystal 103 of about 0 μm (FIG. 1 (B)). As a result of analysis, it was confirmed that the formed crystal was a single crystal having no defect and had a (111) orientation.
As a result of observing the growth rate, it was found that the growth was carried out at a ratio of 1: 100 to 200 in the vertical direction and the horizontal direction.
【００４８】さらに成長を続けると図１（Ｃ）及び図１
（Ｄ）の如く結晶どうしが衝突し、粒界１０４が形成さ
れ、基板を覆う。こうして平均粒径５００μｍ程度の単
結晶群からなる金結晶薄膜が形成できる。When the growth is further continued, FIG. 1 (C) and FIG.
As shown in (D), the crystals collide with each other to form grain boundaries 104 and cover the substrate. Thus, a gold crystal thin film composed of a single crystal group having an average grain size of about 500 μm can be formed.
【００４９】本実施態様例では、極めて平滑な表面を有
する金単結晶を形成できる効果がある。このことは、溶
液系に存在するヨウ素が、その金溶解作用により、成長
中の金結晶上の新たな核発生を抑制する為であると考え
られる。The present embodiment example has an effect that a gold single crystal having an extremely smooth surface can be formed. It is considered that this is because iodine existing in the solution system suppresses the generation of new nuclei on the growing gold crystal due to its gold dissolving action.
【００５０】本実施態様で作成された金薄膜を用い、レ
ジストを用いた、ウエットエッチングやドライエッチン
グにより金単結晶群からなる薄膜配線として利用でき
る。The gold thin film produced in this embodiment can be used as a thin film wiring consisting of a gold single crystal group by wet etching or dry etching using a resist.
【００５１】（実施態様例１−２）金錯体として［Ａｕ
Ｉ4］-、分解処理手段として還元剤の添加を用いてＳｉ
Ｏ2基板１０１上に金結晶を形成する例について説明す
る。(Embodiment example 1-2) [Au]
I 4 ] - , using the addition of a reducing agent as a decomposition treatment means
An example of forming a gold crystal on the O 2 substrate 101 will be described.
【００５２】実施態様例１−１と同様の方法にて、［Ａ
ｕＩ4］-を含有する金錯体溶液を形成する。次いで、還
元剤Ｎａ2ＳＯ3水溶液をゆっくり滴下させながら、溶液
を室温で放置する。In the same manner as in Example 1-1, [A
uI 4] - to form a gold complex solution containing. Then, the solution is left at room temperature while slowly adding a reducing agent Na 2 SO 3 aqueous solution.
【００５３】溶液系内では、Ｉ2の状態で存在するヨウ
素成分の２Ｉ-へのイオン化に伴い、溶液系内の平行状
態の維持の為に［ＡｕＩ4］-中のヨウ素成分の解離によ
る分解が生じると考えられ、結果として金が過飽和状態
となり、基板表面１０２上にランダムに核１０３が形成
される（図１（Ａ））。In the solution system, along with the ionization of the iodine component existing in the I 2 state to 2I − , the decomposition of the iodine component in [AuI 4 ] − by dissociation is carried out in order to maintain the parallel state in the solution system. Is considered to occur, resulting in supersaturation of gold, and nuclei 103 are randomly formed on the substrate surface 102 (FIG. 1A).
【００５４】本発明の方法において特徴的なこととし
て、核形成密度が低い状態のまま、核が自己整合的に成
長することが挙げられる。A characteristic of the method of the present invention is that nuclei grow in a self-aligned manner while the nucleation density is low.
【００５５】核形成密度は、基板表面材料の種類、錯体
の種類、成長条件により異なるが、特に基板表面材料の
種類には、強く存在する。本実施態様例のように基板に
分解処理手段として還元剤の添加を用いた場合、還元剤
の濃度が濃いと溶液中にて核が形成されてしまい基板上
に結晶が形成されない、又は微小な多結晶となってしま
う。The nucleation density varies depending on the type of substrate surface material, the type of complex, and the growth conditions, but is strongly present especially in the type of substrate surface material. When the addition of a reducing agent to the substrate as a decomposition treatment means is used as in the present embodiment example, when the concentration of the reducing agent is high, nuclei are formed in the solution, and crystals are not formed on the substrate, or minute particles are formed. It becomes polycrystalline.
【００５６】成長開始から、３分程度で大きいもので３
０μｍ程度の結晶１０３に成長する（図１（Ｂ））。こ
こで得られる結晶の構造、及び形状は実施態様例１−１
のものと同様なものである。3 minutes after the start of growth
It grows to a crystal 103 of about 0 μm (FIG. 1 (B)). The structure and shape of the crystal obtained here are the embodiment example 1-1.
Is similar to that of.
【００５７】さらに成長を続けると図１（Ｃ）及び図１
（Ｄ）の如く、結晶どうしが衝突し、粒界１０４が形成
され、基板を覆う。こうして平均粒径２００μｍ程度の
単結晶群からなる金結晶薄膜が形成できる。When the growth is further continued, FIG. 1 (C) and FIG.
As shown in (D), the crystals collide with each other to form grain boundaries 104 and cover the substrate. Thus, a gold crystal thin film composed of a single crystal group having an average grain size of about 200 μm can be formed.
【００５８】本実施態様例では、極めて平滑な表面を有
する金単結晶を形成できる効果がある。このことは、溶
液系に存在するヨウ素が、その金溶解作用により、成長
中の金結晶上の新たな核発生を抑制する為であると考え
られる。The present embodiment example has an effect that a gold single crystal having an extremely smooth surface can be formed. It is considered that this is because iodine existing in the solution system suppresses the generation of new nuclei on the growing gold crystal due to its gold dissolving action.
【００５９】（実施態様例１−３）Ｓｉ基板１に、金錯
体として［ＡｕＩ4］-、分解処理手段として揮発処理を
用い、Ｓｉ基板１０１上に金結晶を形成する例について
説明する。(Embodiment Example 1-3) An example of forming a gold crystal on the Si substrate 101 by using [AuI 4 ] − as the gold complex and the volatilization treatment as the decomposition treatment means on the Si substrate 1 will be described.
【００６０】実施態様例１と同様の方法にて、［ＡｕＩ
4］-を含有する金錯体溶液を形成する。次いで、Ｓｉ基
板１０１の表面１０２を溶液に接した後、溶液を３０〜
１００℃に昇温し、ヨウ素成分の揮発を促進させる。In the same manner as in Embodiment 1, [AuI
4] - to form a gold complex solution containing. Next, after the surface 102 of the Si substrate 101 is contacted with the solution, the solution is
The temperature is raised to 100 ° C. to accelerate the volatilization of the iodine component.
【００６１】溶液系内では、In the solution system,
【００６２】[0062]
【外３】 の状態で存在するヨウ素成分の揮発による、溶液系内の
平衡状態の維持の為の［ＡｕＩ4］-からのＩ成分の解離
による分解、又は［ＡｕＩ4］-の形で存在する錯体中の
ヨウ素成分の直接の揮発による分解が進行すると考えら
れ、結果として金が過飽和状態となり、基板表面上にラ
ンダムに核１０３が形成される（図１（Ａ））。[Outside 3] The due to volatilization of iodine component which is present in a state, for maintaining the equilibrium in the solution system [AuI 4] - degradation by dissociation of I component from, or [AuI 4] - in the complex present in the form of It is considered that decomposition of the iodine component by direct volatilization proceeds, and as a result, gold becomes supersaturated, and nuclei 103 are randomly formed on the substrate surface (FIG. 1A).
【００６３】成長開始から、３分程度で、大きいもので
１０μｍ程度に成長する（図１（Ｂ））。解析の結果、
形成された結晶は、欠陥のない単結晶であり、形状とし
ては三角形、六角形のものが多く、（１１１）方位を有
していることが確認された。また、成長レートについて
観察した結果、縦方向：横方向が１：１００〜２００の
割合で成長することが解った。In about 3 minutes from the start of growth, the larger one grows to about 10 μm (FIG. 1 (B)). The result of the analysis,
It was confirmed that the formed crystals were defect-free single crystals, which were mostly triangular or hexagonal in shape and had a (111) orientation. Further, as a result of observing the growth rate, it was found that the growth was performed at a ratio of 1: 100 to 200 in the vertical direction and the horizontal direction.
【００６４】さらに成長を続けると図１（Ｃ）及び図１
（Ｄ）の如く、結晶どうしが衝突し、粒界１０４が形成
され、基板を覆う。こうして平均粒径２５μｍ程度の単
結晶群からなる金結晶薄膜が形成できる。When the growth is further continued, FIG. 1C and FIG.
As shown in (D), the crystals collide with each other to form grain boundaries 104 and cover the substrate. Thus, a gold crystal thin film composed of a single crystal group having an average grain size of about 25 μm can be formed.
【００６５】本実施態様例では、極めて平滑な表面を有
する金単結晶を形成できる効果がある。このことは、溶
液系に存在するヨウ素が、その金溶解作用により、成長
中の金結晶上の新たな核発生を抑制する為であると考え
られる。The embodiment example has an effect that a gold single crystal having an extremely smooth surface can be formed. It is considered that this is because iodine existing in the solution system suppresses the generation of new nuclei on the growing gold crystal due to its gold dissolving action.
【００６６】（実施態様例１−４）金錯体として［Ａｕ
Ｃｌ4］-、分解処理手段として還元剤の添加処理を用
い、Ｓｉ基板上に金結晶を形成する例について説明す
る。(Embodiment example 1-4) [Au]
Cl 4 ] − , an example of forming a gold crystal on a Si substrate by using a reducing agent addition treatment as a decomposition treatment means will be described.
【００６７】まず塩酸と硝酸を３：１の割合で混合して
王水作成する。この溶液に金を投入し攪拌溶解させ、
［ＡｕＣｌ4］-を含有する金錯体溶液を形成する。この
とき溶液中には、金錯体［ＡｕＣｌ4］-の他、ＡｕＣｌ
3・ＮＯＣｌ，ＮＯＣｌ，Ｃｌ2が存在するものと考えら
れる。First, hydrochloric acid and nitric acid are mixed at a ratio of 3: 1 to prepare aqua regia. Add gold to this solution and stir to dissolve,
A gold complex solution containing [AuCl 4 ] − is formed. At this time, in the solution, in addition to the gold complex [AuCl 4 ] - , AuCl
It is considered that 3 · NOCl, NOCl, and Cl 2 exist.
【００６８】次いで、ＮａＯＨ水溶液をゆっくり滴下さ
せながら、溶液を室温で放置する。溶液系内では、Ｎａ
ＯＨによるＡｕ溶解物質であるＮＯＣｌの分解及び／又
は［ＡｕＣｌ4］-の直接の分解に伴い、結果として金が
過飽和状態となり、基板表面上にランダムに核１０３が
形成される（図１（Ａ））。Then, the solution is allowed to stand at room temperature while slowly adding an aqueous NaOH solution. In the solution system, Na
As a result of decomposition of NOCl, which is an Au-dissolved substance, and / or direct decomposition of [AuCl 4 ] − by OH, gold becomes supersaturated, and nuclei 103 are randomly formed on the substrate surface (see FIG. )).
【００６９】成長を続けると図１（Ｃ）及び図２（Ｄ）
の如く、結晶どうしが衝突し、粒界１０４が形成され、
基板を覆う。こうして、平均粒径４μｍ程度の単結晶群
からなる金結晶薄膜が形成できる。When the growth is continued, FIG. 1 (C) and FIG. 2 (D)
, The crystals collide with each other to form the grain boundary 104,
Cover the substrate. Thus, a gold crystal thin film composed of a single crystal group having an average grain size of about 4 μm can be formed.
【００７０】本実施態様例では、極めて平滑な表面を有
する金単結晶を形成できる効果がある。このことは、溶
液系に存在する塩化ニトロシルが、その金溶解作用によ
り、成長中の金結晶上の新たな核発生を抑制する為であ
ると考えられる。The present embodiment example has an effect that a gold single crystal having an extremely smooth surface can be formed. It is considered that this is because the nitrosyl chloride present in the solution system suppresses the generation of new nuclei on the growing gold crystal due to its gold dissolving action.
【００７１】（実施態様例１−５）金錯体として［Ａｕ
Ｉ4］-、分解処理手段として揮発処理を、Ｔｉ基板上に
金結晶を形成する例について説明する。(Embodiment example 1-5) [Au]
I 4 ] − , an example of forming a gold crystal on a Ti substrate by a volatilization treatment as a decomposition treatment means will be described.
【００７２】実施態様例１と同様の方法にて、［ＡｕＩ
4］-を含有する金錯体溶液を形成する。次いで、Ｔｉ基
板１０１の表面１０２を溶液に接した後、溶液を３０〜
１００℃に昇温し、ヨウ素成分の揮発を促進させる。In the same manner as in Embodiment 1, [AuI
4] - to form a gold complex solution containing. Next, after the surface 102 of the Ti substrate 101 is brought into contact with the solution, the solution is
The temperature is raised to 100 ° C. to accelerate the volatilization of the iodine component.
【００７３】溶液系内では、In the solution system,
【００７４】[0074]
【外４】 の状態で存在するヨウ素成分の揮発による、溶液系内の
平衡状態の維持の為の［ＡｕＩ4］-らのＩ成分の解離に
よる分解、又は［ＡｕＩ4］-の形で存在する錯体中のヨ
ウ素成分の直接の揮発による分解が進行すると考えら
れ、結果として金が過飽和状態となり、基板表面上にラ
ンダムに核１０３が形成される（図１（Ａ））。[Outside 4] Due to volatilization of iodine component which is present in a state, [AuI 4] for the maintenance of the equilibrium state of the solution system - degradation by dissociation of al of the I component, or [AuI 4] - in the complex present in the form of It is considered that decomposition of the iodine component by direct volatilization proceeds, and as a result, gold becomes supersaturated, and nuclei 103 are randomly formed on the substrate surface (FIG. 1A).
【００７５】成長を続けると図１（Ｃ）及び図２（Ｄ）
の如く、結晶どうしが衝突し、粒界１０４が形成され、
基板を覆う。こうして平均粒径２μｍ程度の単結晶群か
らなる金結晶薄膜が形成できる。When the growth is continued, FIG. 1 (C) and FIG. 2 (D)
, The crystals collide with each other to form the grain boundary 104,
Cover the substrate. Thus, a gold crystal thin film composed of a single crystal group having an average grain size of about 2 μm can be formed.
【００７６】本実施態様例では、極めて平滑な表面を有
する金単結晶を形成できる効果がある。このことは、溶
液系に存在するヨウ素が、その金溶解作用により、成長
中の金結晶上の新たな核発生を抑制する為であると考え
られる。The present embodiment example has an effect that a gold single crystal having an extremely smooth surface can be formed. It is considered that this is because iodine existing in the solution system suppresses the generation of new nuclei on the growing gold crystal due to its gold dissolving action.
【００７７】様々な基板表面、錯体の種類、形成条件に
よる、平均粒径および、１／（平均粒径の２乗）で与え
られる核形成密度の実験値を第１表に示す。Table 1 shows the experimental values of the average grain size and the nucleation density given by 1 / (square of the average grain size) depending on various substrate surfaces, kinds of complexes and formation conditions.
【００７８】同表により明らかなように、核形成密度
は、基板表面材料の種類、錯体の種類、形成条件により
異なるが、特に基板表面材料の種類には強く存在するこ
とがわかる。As is clear from the table, the nucleation density varies depending on the type of substrate surface material, the type of complex, and the forming conditions, but it is found that the nucleation density is particularly strong in the type of substrate surface material.
【００７９】（実施態様例２−１）図２を用いて説明す
る。ここで説明する方法は選択的に金結晶を形成する方
法である。(Embodiment 2-1) A description will be given with reference to FIG. The method described here is a method of selectively forming gold crystals.
【００８０】核形成密度の大きい材料からなる面として
Ｔｉからなる面、核形成密度の小さい面としてＳｉ
Ｏ2、金錯体として［ＡｕＩ4］-、分解処理手段として
揮発を用いることで本発明を実施する例について説明す
る。A surface made of Ti as a surface made of a material having a high nucleation density and Si as a surface having a low nucleation density.
An example of carrying out the present invention by using O 2 , [AuI 4 ] − as a gold complex, and volatilization as a decomposition treatment means will be described.
【００８１】まずＳｉウェハ２０１をアニール処理し、
表面にＳｉＯ2の熱酸化膜２０５を形成する。Ｔｉを全
面に蒸着したのち、レジストを用いたエッチングによ
り、図２（Ａ）の如くＳｉＯ2膜上に例えば３０×５０
μｍ角のＴｉ薄膜２０２が２００μｍ間隔でマトリクス
に形成された基板を得る。核形成面の間隔は、核形成密
度の小さい材料上の核形成を抑制する為、長距離秩序に
よって核が形成されない範囲、すなわち核形成密度の小
さい材料下で全面に薄膜形成した際の平均粒径以下の距
離が好ましい。First, the Si wafer 201 is annealed,
A thermal oxide film 205 of SiO 2 is formed on the surface. After Ti is vapor-deposited on the entire surface, etching is performed using a resist to form, for example, 30 × 50 on the SiO 2 film as shown in FIG.
A substrate is obtained in which a Ti thin film 202 of square μm is formed in a matrix at intervals of 200 μm. The interval between nucleation planes is the range in which nuclei are not formed by long-range order in order to suppress nucleation on materials with low nucleation density, that is, the average grain size when a thin film is formed on the entire surface under materials with low nucleation density. A distance less than or equal to the diameter is preferable.
【００８２】蒸留水にヨウ化カリウム及びヨウ素を投入
してヨウ素水溶液を形成した後、金を投入し撹拌溶解さ
せ、［ＡｕＩ4］-を含有する金錯体溶液を形成する。こ
のとき溶液中には、金錯体［ＡｕＩ4］-の他、After potassium iodide and iodine were added to distilled water to form an aqueous iodine solution, gold was added and dissolved by stirring to form a gold complex solution containing [AuI 4 ] - . At this time, in the solution, in addition to the gold complex [AuI 4 ] - ,
【００８３】[0083]
【外５】 Ｋ+が存在するものと考えられる。[Outside 5] It is considered that K + exists.
【００８４】ヨウ素水溶液は、ヨウ化カリウム以外のヨ
ウ化化合物、例えばヨウ化アンモニウムを溶解すること
でも作成出来る。また、アルコールを溶媒として用い
た、ヨウ素アルコール溶液やアルコールと水の混合物を
溶媒として用いたヨウ素アルコール・水溶液も本発明に
用いることができる。溶液中のヨウ素、ヨウ化化合物の
濃度は、溶解することのできる金の量を左右する。The aqueous iodine solution can also be prepared by dissolving an iodide compound other than potassium iodide, such as ammonium iodide. Further, an iodine alcohol solution using alcohol as a solvent or an iodine alcohol / aqueous solution using a mixture of alcohol and water as a solvent can also be used in the present invention. The concentrations of iodine and iodide compounds in the solution control the amount of gold that can be dissolved.
【００８５】次いで、前述の基板の表面を溶液に接した
後、溶液を３０〜１００℃に昇温し、ヨウ素成分の揮発
を促進させる。Next, after the surface of the above-mentioned substrate is brought into contact with the solution, the temperature of the solution is raised to 30 to 100 ° C. to promote volatilization of the iodine component.
【００８６】溶液系内では、In the solution system,
【００８７】[0087]
【外６】 の状態で存在するヨウ素成分の揮発による、溶液系内の
平行状態の維持の為の［ＡｕＩ4］-からのＩ成分の解離
による分解、又は［ＡｕＩ4］-の形で存在する錯体中の
ヨウ素成分の直接の揮発による分解が進行すると考えら
れ、結果として金が過飽和状態となる。[Outside 6] The due to volatilization of iodine component which is present in a state, for maintaining the parallel state within the solution system [AuI 4] - degradation by dissociation of I component from, or [AuI 4] - in the complex present in the form of It is thought that the decomposition of iodine component by direct volatilization proceeds, resulting in supersaturation of gold.
【００８８】溶液中で過飽和状態となった金は、核形成
密度の高いＴｉ膜２０２表面のみにランダムな核２０３
として析出する（図２（Ｂ））。The supersaturated gold in the solution has random nuclei 203 only on the surface of the Ti film 202 having a high nucleation density.
Precipitates as (FIG. 2 (B)).
【００８９】解析の結果、形成された結晶は、欠陥のな
い単結晶であり、（１１１）方位を有していた。又、成
長レートについて観察した結果、縦方向：横方向が１：
１００〜２００の割合で成長することが解った。As a result of the analysis, the formed crystal was a single crystal having no defect and had a (111) orientation. Moreover, as a result of observing the growth rate, the vertical direction: the horizontal direction is 1:
It was found that the growth rate was 100 to 200.
【００９０】さらに成長を続けると図２（Ｃ）の如く、
結晶どうしが衝突し、粒界２０４が形成され、核形成密
度の大きい材料からなる面を覆う。こうして、平均粒径
約２μｍ、最大粒径約５ミクロンの単結晶群からなる金
結晶薄膜が選択的に形成出来る。この場合、核形成密度
の小さい材料からなる面には、核の発生は見られない。When the growth is further continued, as shown in FIG.
Crystals collide with each other to form grain boundaries 204 and cover a surface made of a material having a high nucleation density. Thus, a gold crystal thin film composed of a single crystal group having an average grain size of about 2 μm and a maximum grain size of about 5 μm can be selectively formed. In this case, no nucleation is observed on the surface made of a material having a low nucleation density.
【００９１】本実施態様例では、極めて平滑な表面を有
する金単結晶を形成できる効果がある。このことは、溶
液系に存在するヨウ素が、その金溶解作用により、成長
中の金結晶上の新たな核発生を抑制する為であると考え
られる。The present embodiment has an effect that a gold single crystal having an extremely smooth surface can be formed. It is considered that this is because iodine existing in the solution system suppresses the generation of new nuclei on the growing gold crystal due to its gold dissolving action.
【００９２】本実施態様例においては、核形成密度が小
さい材料からなる面と核形成密度が大きい材料からなる
面は、限定されるものではなく、結局、相対的に核形成
密度の差があれば良い。In this embodiment, the surface made of a material having a low nucleation density and the surface made of a material having a high nucleation density are not limited, and in the end, there is a relative difference in nucleation density. Good.
【００９３】それぞれの核形成密度が大きい材料からな
る面の配置する最大間隔は、核形成密度が小さい材料か
らなる面に同じ条件で全面に形成した際の平均粒径以内
であることが望ましい。換言するなら、配置する最大間
隔を長くとる為には、核形成密度の特に低いＳｉＯ2，
ＳｉＮ，ＳｉＣ，Ａｌ2Ｏ3等の絶縁体材料を用いること
が好ましい。It is desirable that the maximum spacing between the surfaces made of the material having a high nucleation density is within the average grain size when they are formed on the entire surface made of the material having a low nucleation density under the same conditions. In other words, in order to increase the maximum arrangement interval, SiO 2 with a particularly low nucleation density,
It is preferable to use an insulating material such as SiN, SiC, Al 2 O 3 .
【００９４】核形成密度の大きい材料としては、Ａｕ，
Ｔｉ，Ｃｕ，Ｗ，ＷＳｉ，ＭｏＳｉ，Ｆｅ，Ｓｉ，Ｇｅ
などの導電体、半導体材料をもちいることができる。As a material having a high nucleation density, Au,
Ti, Cu, W, WSi, MoSi, Fe, Si, Ge
Conductors such as, and semiconductor materials can be used.
【００９５】金錯体は、［ＡｕＩ4］-，［ＡｕＣ
ｌ4］-，［Ａｕ（ＣＮ）2］-，［Ａｕ（ＣＮ）3］-等の
金錯体を用いることができる。The gold complexes are [AuI 4 ] - , [AuC
l 4] -, [Au ( CN) 2] -, [Au (CN) 3] - it is possible to use gold complexes such as.
【００９６】分解処理手段として、揮発や還元剤を用い
ることができる。Volatilization or a reducing agent can be used as the decomposition treatment means.
【００９７】還元剤としては、例えばハイドロキノン、
ピロガロール、パイロカテキン、グクシン、メトールハ
イドロキノン、アミドール、メトール、亜硫酸ソーダ、
チオ硫酸ナトリウムなどの他、溶液中で還元作用を有す
る物質が用いられる。Examples of the reducing agent include hydroquinone,
Pyrogallol, Pyrocatechin, Guchsin, Metol hydroquinone, Amidole, Metol, Sodium sulfite,
Other than sodium thiosulfate, a substance having a reducing action in a solution is used.
【００９８】ここで述べた材料は本発明の他の実施態様
例においても適用できるものである。The materials described here are also applicable to other embodiments of the invention.
【００９９】（実施態様例２−２）核形成密度の大きい
材料からなる面としてＳｉからなる面、核形成密度の小
さい面としてＳｉＯ2、金錯体として［ＡｕＩ4］-、分
解処理手段として揮発を用いることで本発明を実施する
例について説明する。図３を参照して説明する。(Embodiment example 2-2) A surface made of Si as a surface made of a material having a high nucleation density, SiO 2 as a surface having a low nucleation density, [AuI 4 ] − as a gold complex, and volatilization as a decomposition treatment means. An example of implementing the present invention by using is described. This will be described with reference to FIG.
【０１００】まずＳｉウェハ３０１を熱酸化処理し、表
面にＳｉＯ2の熱酸化膜３０５を形成する。次に、レジ
ストを用いたエッチングにより、図３（Ａ）の如くＳｉ
Ｏ2膜上に１００×１００μｍ角程度のＳｉ面を露出さ
せ、これを例えば３００μｍ間隔でマトリクス状に形成
した基板を得る。First, the Si wafer 301 is thermally oxidized to form a thermal oxide film 305 of SiO 2 on the surface. Next, as shown in FIG. 3A, Si is etched by etching using a resist.
A substrate in which a Si surface of about 100 × 100 μm square is exposed on the O 2 film and is formed in a matrix at intervals of 300 μm is obtained.
【０１０１】本実施態様例では、露出したＳｉウェハ表
面を核形成密度の大きい材料からなる面、熱酸化による
ＳｉＯ2表面を核形成密度の小さい材料からなる面とし
て用いている。In this embodiment, the exposed Si wafer surface is used as the surface made of a material having a high nucleation density and the SiO 2 surface formed by thermal oxidation is used as a surface made of a material having a low nucleation density.
【０１０２】次いで、基板を希フッ酸に浸漬してＳｉ上
の表面酸化膜を除去後、金錯体として［ＡｕＩ4］-、分
解処理手段として揮発処理を用いた結晶の成長を実施態
様例２−１と同様にして行なう。結晶を成長させること
により図３（Ｂ）の如く、結晶どうしが衝突し、粒界３
０４が形成される。このようにして、平均粒径約２０μ
ｍ、最大粒径約４０μｍの単結晶群からなる金結晶薄膜
が選択的に形成出来る。この場合、核形成密度の低いＳ
ｉＯ2面上には、核の発生は認められない。Then, the substrate was immersed in dilute hydrofluoric acid to remove the surface oxide film on Si, and then [AuI 4 ] − was used as a gold complex and a volatile process was used as a decomposition treatment means to grow crystals. Same as -1. By growing the crystals, the crystals collide with each other as shown in FIG.
04 is formed. In this way, the average particle size is about 20μ
m, and a gold crystal thin film composed of a single crystal group having a maximum grain size of about 40 μm can be selectively formed. In this case, S with low nucleation density
Nucleation is not observed on the iO 2 surface.
【０１０３】（実施態様例２−３）核形成密度の大きい
材料からなる面としてＳｉからなる面、核形成密度の小
さい面としてＳｉＯ2、金錯体として［ＡｕＩ4］-、分
解処理手段として還元剤を用いて本発明を実施する例に
ついて説明する。図４を用いて説明する。(Embodiment example 2-3) A surface made of Si as a surface made of a material having a high nucleation density, SiO 2 as a surface having a low nucleation density, [AuI 4 ] − as a gold complex, and reduction as a decomposition treatment means. An example of carrying out the present invention using an agent will be described. This will be described with reference to FIG.
【０１０４】まずＳｉウェハ４０１を熱酸化処理し、表
面にＳｉＯ2の熱酸化膜４０５を形成する。次に、例え
ば、ＬＰ−ＣＶＤ法により、ポリＳｉ（Ｐ−Ｓｉ）膜を
全面に形成する。レジストを用いたエッチングにより、
図４（Ａ）の如くＳｉＯ2膜上に１００×１００μｍ角
程度のｐ−Ｓｉ面を残し、これを例えば４００μｍ間隔
でマトリクス状に形成した基板を得る。First, the Si wafer 401 is subjected to thermal oxidation treatment to form a thermal oxide film 405 of SiO 2 on the surface. Next, a poly-Si (P-Si) film is formed on the entire surface by, for example, the LP-CVD method. By etching using a resist,
Leaving the p-Si surface of approximately 100 × 100 [mu] m square in FIG. 4 SiO 2 film as (A), to obtain a substrate formed in a matrix in this example 400μm intervals.
【０１０５】本実施態様例では、ｐ−Ｓｉ面を核形成密
度の大きい材料からなる面、熱酸化によるＳｉＯ2表面
を核形成密度の小さい材料からなる面として用いてい
る。In this embodiment, the p-Si surface is used as the surface made of a material having a high nucleation density, and the SiO 2 surface formed by thermal oxidation is used as a surface made of a material having a low nucleation density.
【０１０６】基板を希フッ酸に浸漬してｐ−Ｓｉ上の表
面酸化膜を除去後、金錯体溶液に基板を接触させる。次
いでハイドロキノン水溶液をゆっくり滴下して結晶成長
を行なう。After the substrate is immersed in dilute hydrofluoric acid to remove the surface oxide film on p-Si, the substrate is brought into contact with the gold complex solution. Then, a hydroquinone aqueous solution is slowly dropped to grow crystals.
【０１０７】結晶成長により図４（Ｂ）の如く、結晶ど
うしが衝突し、粒界４０４が形成され、核形成密度の大
きい材料からなる面を覆う。こうして平均粒径約１５μ
ｍ、最大粒径約２０μｍの単結晶群からなる金結晶薄膜
が選択的に形成出来る。この場合、核形成密度の低いＳ
ｉＯ2面上には、核の発生は認められない。As shown in FIG. 4B, due to the crystal growth, the crystals collide with each other to form grain boundaries 404 and cover the surface made of a material having a high nucleation density. Thus the average particle size is about 15μ
m, and a gold crystal thin film composed of a single crystal group having a maximum grain size of about 20 μm can be selectively formed. In this case, S with low nucleation density
Nucleation is not observed on the iO 2 surface.
【０１０８】（実施態様例２−４）図５を用いて説明す
る。(Embodiment Example 2-4) Description will be made with reference to FIG.
【０１０９】Ｓｉウェハ５０１にＴｉを全面に蒸着後、
全面にＥＣＲ−ＣＶＤ法によりＳｉＯ2膜５０５を形成
する。次にレジストを用いたエッチングにより、図５の
如く、５０×５０μｍ角のＴｉ面５０２をＳｉＯ2面中
に露出させ、これを２００μｍ間隔でマトリクス状に形
成する。本実施態様例では、露出したＴｉ表面を核形成
密度の大きい材料からなる面、ＳｉＯ2表面を核形成密
度の小さい材料からなる面として用いている。After depositing Ti on the entire surface of the Si wafer 501,
A SiO 2 film 505 is formed on the entire surface by ECR-CVD. Then, as shown in FIG. 5, a Ti surface 502 of 50 × 50 μm square is exposed in the SiO 2 surface by etching using a resist, and this is formed in a matrix at intervals of 200 μm. In this embodiment, the exposed Ti surface is used as a surface made of a material having a high nucleation density, and the SiO 2 surface is used as a surface made of a material having a low nucleation density.
【０１１０】次いで、金錯体として［ＡｕＩ4］-、分解
処理手段として揮発処理を実施態様例２−１と同様にし
て行なう。Then, [AuI 4 ] − as a gold complex and a volatilization treatment as a decomposition treatment means are performed in the same manner as in Embodiment 2-1.
【０１１１】結晶成長により図５（Ｂ）の如く、結晶ど
うしが衝突し、粒界５０４が形成される。As a result of the crystal growth, the crystals collide with each other and a grain boundary 504 is formed, as shown in FIG.
【０１１２】（実施態様例３−１）図６及び図７を参照
しながら説明する。(Embodiment 3-1) An explanation will be given with reference to FIGS. 6 and 7.
【０１１３】核形成密度の大きい材料からなる面として
Ｔｉからなる面、核形成密度の小さい面としてＳｉ
Ｏ2、金錯体として［ＡｕＩ4］-、分解処理手段として
揮発を用いることで本発明を実施する例について説明す
る。A surface made of Ti as a surface made of a material having a high nucleation density and Si as a surface having a low nucleation density.
An example of carrying out the present invention by using O 2 , [AuI 4 ] − as a gold complex, and volatilization as a decomposition treatment means will be described.
【０１１４】まずＳｉウェハ６０１を熱酸化処理し、表
面にＳｉＯ2の熱酸化膜６０５、７０５を形成する。Ｔ
ｉを全面に蒸着したのち、レジストを用いたエッチング
により、図６（Ａ）及び図７（Ａ）の如くＳｉＯ2膜上
に１×１μｍ角のＴｉ薄膜６０２、７０２が５０μｍ間
隔でマトリクスに形成された基板を得る。First, the Si wafer 601 is subjected to thermal oxidation treatment, and thermal oxide films 605 and 705 of SiO 2 are formed on the surface. T
After i is vapor-deposited on the entire surface, by etching using a resist, Ti thin films 602 and 702 of 1 × 1 μm square are formed in a matrix at intervals of 50 μm on the SiO 2 film as shown in FIGS. 6A and 7A. Obtained substrate.
【０１１５】本発明において核形成密度の大きい材料か
らなる面を充分微小な面積にすることで、単一核のみの
核発生が行なうことができる。この大きさは、好ましく
は１０μｍ以下、より好ましくは５μｍ以下である。In the present invention, when the surface made of a material having a high nucleation density has a sufficiently small area, it is possible to generate nuclei of only a single nucleus. This size is preferably 10 μm or less, more preferably 5 μm or less.
【０１１６】核形成面の間隔は、核形成密度の小さい材
料上の核形成を抑制する為、長距離秩序によって核が形
成されない範囲、すなわち核形成密度の小さい材料下で
全面に薄膜形成した際の平均粒径以下の距離が好まし
い。The distance between nucleation surfaces is such that nucleation on a material with a low nucleation density is suppressed, so that nuclei are not formed by long-range order, that is, when a thin film is formed on the entire surface under a material with a low nucleation density. A distance equal to or smaller than the average particle diameter of is preferable.
【０１１７】次いで蒸留水にヨウ化カリウム及びヨウ素
を投入してヨウ素水溶液を形成した後、金を投入し撹拌
溶解させ、［ＡｕＩ4］-を含有する金錯体溶液を形成す
る。このとき溶液中には、金錯体［ＡｕＩ4］-の他、Then, potassium iodide and iodine are added to distilled water to form an iodine aqueous solution, and then gold is added and dissolved by stirring to form a gold complex solution containing [AuI 4 ] - . At this time, in the solution, in addition to the gold complex [AuI 4 ] - ,
【０１１８】[0118]
【外７】 Ｋ+が存在するものと考えられる。[Outside 7] It is considered that K + exists.
【０１１９】ヨウ素水溶液は、ヨウ化カリウム以外のヨ
ウ化化合物、例えばヨウ化アンモニウムを溶解すること
でも作成出来る。また、アルコールを溶媒として用い
た、ヨウ素アルコール溶液やアルコールと水の混合物を
溶媒として用いたヨウ素アルコール・水溶液も本発明に
用いることができる。溶液中のヨウ素、ヨウ化化合物の
濃度は、溶解することできる金の量を左右する。The aqueous iodine solution can also be prepared by dissolving an iodide compound other than potassium iodide, such as ammonium iodide. Further, an iodine alcohol solution using alcohol as a solvent or an iodine alcohol / aqueous solution using a mixture of alcohol and water as a solvent can also be used in the present invention. The concentrations of iodine and iodide compounds in the solution influence the amount of gold that can be dissolved.
【０１２０】次いで、前述の基板の表面を溶液に接した
後、溶液を３０〜１００℃に昇温し、ヨウ素成分の揮発
を促進させる。Then, after the surface of the above-mentioned substrate is brought into contact with the solution, the temperature of the solution is raised to 30 to 100 ° C. to accelerate the volatilization of the iodine component.
【０１２１】溶液系内では、In the solution system,
【０１２２】[0122]
【外８】 の状態で存在するヨウ素成分の揮発による溶液系内の平
行状態の維持の為の［ＡｕＩ4］-からのＩ成分の解離に
よる分解、又は［ＡｕＩ4］-の形で存在する錯体中のヨ
ウ素成分の直接の揮発による分解が進行すると考えら
れ、結果として金が過飽和状態となる。[Outside 8] [AuI 4] for maintenance due to volatilization of iodine component which is present in the state of parallel state in the solution system - degradation by dissociation of I component from, or [AuI 4] - iodine in the complex present in the form of It is thought that decomposition by direct volatilization of the components proceeds, resulting in supersaturation of gold.
【０１２３】溶液中で過飽和状態となった金は、核形成
密度の高いＴｉ基板表面のみに単一核６０３、７０３と
して析出する（図６（Ｂ）及び図７（Ｂ））。この時、
核形成密度の小さい材料からなる面には、核の発生は見
られない。Gold supersaturated in the solution is deposited as single nuclei 603 and 703 only on the surface of the Ti substrate having a high nucleation density (FIGS. 6 (B) and 7 (B)). At this time,
Nucleation is not observed on the surface made of a material having a low nucleation density.
【０１２４】解析の結果、形成された結晶は、欠陥のな
い単結晶であり、（１１１）方位を有していた。又、成
長レートについて観察した結果、縦方向：横方向が１：
１００〜２００の割合で成長することが解った。As a result of the analysis, the formed crystal was a single crystal having no defect and had a (111) orientation. Moreover, as a result of observing the growth rate, the vertical direction: the horizontal direction is 1:
It was found that the growth rate was 100 to 200.
【０１２５】さらに成長を続けると図６（Ｃ）及び図７
（Ｃ）、図７（Ｄ）の如く、結晶どうしが衝突し、各々
の核形成密度の大きい材料からなる面のほぼ中間に粒界
６０４、７０３が形成され、核形成密度の小さい材料か
らなる面を覆う。こうして、粒径約５０μｍの単結晶か
らなる金結晶薄膜が形成できる。このように本発明の金
単結晶は、その形成位置（結晶の位置及び粒界位置）を
設計的に変えることができる。When the growth is further continued, FIG. 6C and FIG.
As shown in (C) and FIG. 7 (D), the crystals collide with each other, and grain boundaries 604 and 703 are formed substantially in the middle of the planes made of the materials having a high nucleation density, and the grains are made of a material having a low nucleation density. Cover the surface. Thus, a gold crystal thin film made of a single crystal having a grain size of about 50 μm can be formed. As described above, the gold single crystal of the present invention can change its formation position (the position of the crystal and the position of the grain boundary) by design.
【０１２６】本実施態様例では、極めて平滑な表面を有
する金単結晶を形成できる効果がある。このことは、溶
液系に存在するヨウ素が、その金溶解作用により、成長
中の金結晶の新たな核発生を抑制する為であると考えら
れる。The present embodiment example has an effect that a gold single crystal having an extremely smooth surface can be formed. It is considered that this is because the iodine existing in the solution system suppresses the generation of new nuclei of the growing gold crystal due to its gold dissolving action.
【０１２７】（実施態様例３−２）核形成密度の大きい
材料からなる面としてＳｉからなる面、核形成密度の小
さい面としてＳｉＯ2、金錯体として［ＡｕＩ4］-、分
解処理手段として還元剤を用いて本発明を実施した例に
ついて説明する。(Embodiment example 3-2) A surface made of Si as a surface made of a material having a high nucleation density, SiO 2 as a surface having a low nucleation density, [AuI 4 ] − as a gold complex, and reduction as a decomposition treatment means. An example of carrying out the present invention using an agent will be described.
【０１２８】まずＳｉウェハを熱酸化処理し、表面にＳ
ｉＯ2の熱酸化膜を形成する。次に、ＬＰ−ＣＶＤ法に
より、ポリＳｉ（Ｐ−Ｓｉ）膜を全面に形成する。レジ
ストを用いたエッチングにより、ＳｉＯ2膜上に例えば
５μｍ径丸のｐ−Ｓｉ面を残し、これを５０μｍ間隔で
マトリクス状に形成した基板を得る。First, the Si wafer is subjected to thermal oxidation treatment, and S is applied to the surface.
A thermal oxide film of iO 2 is formed. Next, a poly-Si (P-Si) film is formed on the entire surface by the LP-CVD method. By etching using a resist, a substrate is obtained in which a p-Si surface having a diameter of, for example, 5 μm is left on the SiO 2 film and is formed in a matrix at intervals of 50 μm.
【０１２９】次いで、基板を希フッ酸に浸漬してｐ−Ｓ
ｉの表面酸化膜を除去後、金錯体溶液に基板を接触させ
る。次にハイドロキノン水溶液をゆっく滴下して結晶成
長を行なう。Then, the substrate is dipped in dilute hydrofluoric acid to obtain p--S.
After removing the surface oxide film of i, the substrate is brought into contact with the gold complex solution. Next, a hydroquinone aqueous solution is slowly dropped to grow crystals.
【０１３０】こうすることにより結晶どうしが衝突して
粒界が形成され、核形成密度の小さい材料からなる面を
覆う。このようにして平均粒径５０μｍの単結晶が選択
的に形成出来る。As a result, the crystals collide with each other to form grain boundaries and cover the surface made of a material having a low nucleation density. Thus, a single crystal having an average grain size of 50 μm can be selectively formed.
【０１３１】（実施態様例３−３）核形成密度の大きい
材料からなる面としてＳｉからなる面、核形成密度の小
さい面としてＳｉＯ2、金錯体として［ＡｕＩ4］-、分
解処理手段として揮発を用いることで本発明を実施した
例について説明する。図８を参照して説明する。(Embodiment Example 3-3) A surface made of Si as a surface made of a material having a high nucleation density, SiO 2 as a surface having a low nucleation density, [AuI 4 ] − as a gold complex, and volatilization as a decomposition treatment means. An example in which the present invention is implemented by using will be described. This will be described with reference to FIG.
【０１３２】Ｓｉウェハ８０１を熱酸化処理し、表面に
ＳｉＯ2の熱酸化膜８０５を形成する。次に、レジスト
を用いたエッチングにより、図８（Ａ）の如くＳｉＯ2
膜上に例えば１０μｍ径のＳｉ面を露出させ、これを３
０μｍ間隔でマトリクス状に形成した基板を得る。The Si wafer 801 is thermally oxidized to form a thermal oxide film 805 of SiO 2 on the surface. Next, as shown in FIG. 8 (A), SiO 2 is removed by etching using a resist.
For example, expose a Si surface having a diameter of 10 μm on the film, and
A substrate formed in a matrix at intervals of 0 μm is obtained.
【０１３３】基板を希フッ酸に浸漬して表面酸化膜を除
去後、実施態様例３−１と同様な成長を行なう。After dipping the substrate in dilute hydrofluoric acid to remove the surface oxide film, the same growth as in Embodiment 3-1 is performed.
【０１３４】さらに、成長を続けることで、図８（Ｃ）
の如く、結晶どうしが衝突し、各々の核形成密度の大き
い材料からなる面のほぼ中間に粒界８０４が形成され
る。こうして粒径約３０μｍの単結晶からなる金結晶薄
膜が形成できる。By further continuing the growth, FIG.
As described above, the crystals collide with each other, and a grain boundary 804 is formed substantially in the middle of each surface made of a material having a high nucleation density. Thus, a gold crystal thin film made of a single crystal having a grain size of about 30 μm can be formed.
【０１３５】（実施態様例３−４）核形成密度の大きい
材料からなる面としてＴｉからなる面、核形成密度の小
さい面としてＳｉＯ2、金錯体として［ＡｕＩ4］-、分
解処理手段として揮発を用いることで本発明を実施した
例について説明する。図９を参照して説明する。(Embodiment example 3-4) A surface made of Ti as a surface made of a material having a high nucleation density, SiO 2 as a surface having a low nucleation density, [AuI 4 ] − as a gold complex, and volatilization as a decomposition treatment means. An example in which the present invention is implemented by using will be described. This will be described with reference to FIG.
【０１３６】Ｓｉウェハ９０１にＴｉを全面に蒸着後、
全面にＥＣＲ−ＣＶＤ法によりＳｉＯ2膜９０５を形成
する。次にレジストを用いたエッチングにより、図９
（Ａ）の如く、１μｍ径のＴｉ面９０２をＳｉＯ2面中
に露出させ、これを１０μｍ間隔でマトリクス状に形成
した基板を得る。After depositing Ti on the entire surface of the Si wafer 901,
A SiO 2 film 905 is formed on the entire surface by ECR-CVD. Next, as shown in FIG.
As shown in (A), a Ti surface 902 having a diameter of 1 μm is exposed in the SiO 2 surface, and a substrate is obtained by forming the Ti surface 902 in a matrix at intervals of 10 μm.
【０１３７】実施態様例３−１と同様な成長を行ったと
ころ図９（Ｂ）の如く、金単結晶９０３が凹部内を埋め
尽くす。When the same growth as in Embodiment 3-1 was carried out, as shown in FIG. 9 (B), the gold single crystal 903 completely filled the inside of the recess.
【０１３８】次に、金錯体溶液中に基板材料にエッチン
グ作用を及ぼすエッチング種を添加し、形成される核の
数及び結晶粒径の大きさを制御しながら金結晶膜の形成
を行なう本発明の態様例について説明する。Next, an etching seed having an etching action on the substrate material is added to the gold complex solution to form a gold crystal film while controlling the number of nuclei formed and the size of the crystal grain size. An example of the embodiment will be described.
【０１３９】基板材料に作用するエッチング種の混在
下、金錯体溶液中の金錯体を分解処理することで、溶液
中の金を過飽和状態に移行させ基板に金単結晶群からな
る金薄膜を形成する形成過程を説明する。By decomposing the gold complex in the gold complex solution in the presence of the etching species acting on the substrate material, the gold in the solution is transferred to a supersaturated state to form a gold thin film composed of a gold single crystal group on the substrate. The formation process of forming will be described.
【０１４０】例として、ＳｉＯ2基板に、金錯体として
［ＡｕＩ4］-、分解処理手段として揮発処理にて薄膜形
成した例を図１に添い説明する。As an example, an example in which a thin film is formed on a SiO 2 substrate by [AuI 4 ] − as a gold complex and by a volatilization process as a decomposition treatment means will be described with reference to FIG.
【０１４１】まず蒸留水にヨウ化カリウム及びヨウ素を
投入してヨウ素水溶液を作成した後、金を投入し撹拌溶
解させ、［ＡｕＩ4］-を含有する金錯体溶液を形成す
る。次にこの溶液にフッ化水素酸を滴下し混合する。こ
のとき溶液中には、金錯体［ＡｕＩ4］-の他、First, potassium iodide and iodine are added to distilled water to prepare an aqueous iodine solution, and then gold is added and dissolved by stirring to form a gold complex solution containing [AuI 4 ] - . Next, hydrofluoric acid is added dropwise to this solution and mixed. At this time, in the solution, in addition to the gold complex [AuI 4 ] - ,
【０１４２】[0142]
【外９】 Ｋ+，Ｆ-が主に存在するものと考えられる。[Outside 9] It is considered that K + and F − are mainly present.
【０１４３】次いで、ＳｉＯ2基板１０１の表面１０２
を溶液に接した後、溶液を３０〜１００℃に昇温し、ヨ
ウ素成分の揮発を促進させる。Next, the surface 102 of the SiO 2 substrate 101.
After contacting with the solution, the temperature of the solution is raised to 30 to 100 ° C. to promote volatilization of the iodine component.
【０１４４】溶液系内ではIn the solution system
【０１４５】[0145]
【外１０】 の状態で存在するヨウ素成分の揮発による、溶液系内の
平行状態の維持の為の［ＡｕＩ4］-からのＩ成分の解離
による分解、又は［ＡｕＩ4］-の形で存在する錯体中の
ヨウ素成分の直接の揮発による分解が進行すると考えら
れ、結果として金が過飽和状態となる。[Outside 10] The due to volatilization of iodine component which is present in a state, for maintaining the parallel state within the solution system [AuI 4] - degradation by dissociation of I component from, or [AuI 4] - in the complex present in the form of It is thought that the decomposition of iodine component by direct volatilization proceeds, resulting in supersaturation of gold.
【０１４６】溶液中で過飽和状態となった金は、基板表
面１０２にランダムな核１０３として析出する（図１
（Ａ））。この後、核の形成は、しばらく続くが、ある
程度の数の核が形成されると、核の増加が止まり、核が
自己整合的に単結晶成長する（図１（Ｂ））。その後、
成長を続けることで各々の単結晶同志の衝突により、粒
界が形成される（図４（Ｃ）、図５（Ｄ））。この時の
個々の単結晶の大きさは基板種、金錯体種の他、基板表
面のエッチング種量に依存する。金単結晶粒径に及ぼす
フッ化水素酸の濃度の影響の測定結果を表１に示す。基
板表面に作用するエッチング種（フッ化水素酸）の存在
により、結晶粒径の大きさは存在しない場合に比べて最
大３倍程度大きくできる。ただし、その濃度は薄過ぎる
とエッチング作用が現れず、濃過ぎると基板上に結晶核
が発生しなくなる。Gold supersaturated in the solution is deposited as random nuclei 103 on the substrate surface 102 (FIG. 1).
(A)). After that, the formation of nuclei continues for a while, but when a certain number of nuclei are formed, the number of nuclei stops increasing and the nuclei grow in a self-aligned single crystal (FIG. 1 (B)). afterwards,
As the growth continues, grain boundaries are formed by collision of the single crystals (FIG. 4 (C), FIG. 5 (D)). At this time, the size of each single crystal depends on the substrate species, the gold complex species, and the amount of etching species on the substrate surface. Table 1 shows the measurement results of the effect of the concentration of hydrofluoric acid on the gold single crystal grain size. Due to the presence of the etching species (hydrofluoric acid) that acts on the surface of the substrate, the size of the crystal grain size can be increased by a maximum of about 3 times as compared with the case where it does not exist. However, if the concentration is too low, the etching action does not appear, and if it is too high, crystal nuclei do not occur on the substrate.
【０１４７】（実施態様例４−１）図１を参照して説明
する。(Embodiment Example 4-1) Description will be made with reference to FIG.
【０１４８】金錯体として［ＡｕＩ4］-、分解処理手段
として揮発処理を用いてＳｉＯ2基板１０１上に金結晶
を形成する例について説明する。An example of forming a gold crystal on the SiO 2 substrate 101 by using [AuI 4 ] − as the gold complex and volatilization treatment as the decomposition treatment means will be described.
【０１４９】まず蒸留水にヨウ化カリウム及びヨウ素を
投入してヨウ素水溶液を作成した後、これに金を投入し
撹拌溶解させ、［ＡｕＩ4］-を含有する金錯体溶液を形
成する。次にこの溶液にフッ化水素酸を滴下し混合す
る。このとき溶液中には、金錯体［ＡｕＩ4］-の他、First, potassium iodide and iodine are added to distilled water to prepare an iodine aqueous solution, and then gold is added and stirred and dissolved to form a gold complex solution containing [AuI 4 ] - . Next, hydrofluoric acid is added dropwise to this solution and mixed. At this time, in the solution, in addition to the gold complex [AuI 4 ] - ,
【０１５０】[0150]
【外１１】 Ｋ+，Ｆ-が主に存在するものと考えられる。[Outside 11] It is considered that K + and F − are mainly present.
【０１５１】ヨウ素水溶液は、ヨウ化カリウム以外のヨ
ウ化化合物、例えばヨウ化アンモニウムを溶解すること
でも作成出来る。また、アルコールを溶媒として用い
た、ヨウ素アルコール溶液やアルコールと水の混合物を
溶媒として用いたヨウ素アルコール・水溶液も本発明に
用いることができる。溶液中のヨウ素、ヨウ化化合物の
濃度は、溶解することのできる金の量を左右する。また
フッ化水素酸の濃度は金単結晶の大きさに影響を与え
る。The iodine aqueous solution can also be prepared by dissolving an iodide compound other than potassium iodide, such as ammonium iodide. Further, an iodine alcohol solution using alcohol as a solvent or an iodine alcohol / aqueous solution using a mixture of alcohol and water as a solvent can also be used in the present invention. The concentrations of iodine and iodide compounds in the solution control the amount of gold that can be dissolved. Further, the concentration of hydrofluoric acid affects the size of the gold single crystal.
【０１５２】次いで、ＳｉＯ2基板１０１の表面１０２
を溶液に接した後、溶液を３０〜１００℃に昇温し、ヨ
ウ素成分の揮発を促進させる。Next, the surface 102 of the SiO 2 substrate 101.
After contacting with the solution, the temperature of the solution is raised to 30 to 100 ° C. to promote volatilization of the iodine component.
【０１５３】溶液系内ではIn the solution system
【０１５４】[0154]
【外１２】 の状態で存在するヨウ素成分の揮発による、溶液系内の
平衡状態の維持の為の［ＡｕＩ4］-からのＩ成分の解離
による分解、又は［ＡｕＩ4］-の形で存在する錯体中の
ヨウ素成分の直接の揮発による分解が進行すると考えら
れ、結果として金が過飽和状態となる。[Outside 12] The due to volatilization of iodine component which is present in a state, for maintaining the equilibrium in the solution system [AuI 4] - degradation by dissociation of I component from, or [AuI 4] - in the complex present in the form of It is thought that the decomposition of iodine component by direct volatilization proceeds, resulting in supersaturation of gold.
【０１５５】溶液中で過飽和状態となった金は、基板表
面１０２にランダムな核１０３として析出する（図１
（Ａ））。Gold supersaturated in the solution is deposited as random nuclei 103 on the substrate surface 102 (FIG. 1).
(A)).
【０１５６】成長から、３分程度において大きいもので
４０μｍ程度に成長する（図１（Ｂ））。形成された結
晶は、欠陥のない単結晶であり、（１１１）方位を有し
ている。また、成長レートについては、縦方向：横方向
が１：１００〜２００の割合で成長する。In about 3 minutes from the growth, a large one grows to about 40 μm (FIG. 1 (B)). The formed crystal is a defect-free single crystal and has a (111) orientation. Regarding the growth rate, the growth rate is 1: 100 to 200 in the vertical direction and the horizontal direction.
【０１５７】さらに成長を続けると図１（Ｃ）及び
（Ｄ）の如く結晶どうしが衝突し、粒界１０４が形成さ
れ、基板を覆い、平均粒径０．５〜１．５ｍｍ程度の単
結晶群からなる金結晶薄膜が形成できる。この平均粒径
はフッ化水素酸の濃度に依存し薄過ぎるとエッチング作
用が現れず結晶を大型化できない。また濃過ぎると結晶
の核が発生しなくなる。When the growth is further continued, the crystals collide with each other as shown in FIGS. 1 (C) and 1 (D) to form grain boundaries 104, cover the substrate, and have an average grain size of 0.5 to 1.5 mm. A gold crystal thin film composed of a group can be formed. This average particle size depends on the concentration of hydrofluoric acid, and if it is too thin, the etching action does not appear and the crystal cannot be enlarged. If it is too dark, crystal nuclei will not be generated.
【０１５８】本実施態様例では、極めて大粒径の金単結
晶群が形成できるが、これは溶液中のフッ化水素酸がＳ
ｉＯ2基板１０１に作用し基板表面１０２を僅かづつエ
ッチングしていくためであると考えられる。この基板表
面のエッチング作用により、基板表面１０２における金
結晶の核発生速度が抑えられ、その結果基板表面１０２
に形成される金単結晶の結晶径は基板表面１０２をエッ
チングする作用を有しない系にくらべて大粒径の金単結
晶群薄膜になると考えられる。In this embodiment, a gold single crystal group having an extremely large grain size can be formed. This is because hydrofluoric acid in the solution contains S.
It is considered that this is because it acts on the iO 2 substrate 101 and the substrate surface 102 is etched little by little. The etching action of the substrate surface suppresses the nucleation rate of gold crystals on the substrate surface 102, and as a result, the substrate surface 102
It is considered that the crystal diameter of the gold single crystal formed in (1) becomes a gold single crystal group thin film having a large grain size as compared with a system having no action of etching the substrate surface 102.
【０１５９】さらに本実施態様例では、極めて平滑な表
面を有する金単結晶を形成できる効果がある。このこと
は、溶液系に存在するヨウ素が、その金溶解作用によ
り、成長中の金結晶上の新たな核発生を抑制する為であ
ると考えられる。Furthermore, the present embodiment example has an effect that a gold single crystal having an extremely smooth surface can be formed. It is considered that this is because iodine existing in the solution system suppresses the generation of new nuclei on the growing gold crystal due to its gold dissolving action.
【０１６０】（実施態様例４−２）金錯体として［Ａｕ
Ｉ4］-、分解処理手段として還元剤の添加を用いてＳｉ
Ｏ2基板１０１上に金結晶を形成する例について説明す
る。(Embodiment example 4-2) [Au]
I 4 ] - , using the addition of a reducing agent as a decomposition treatment means
An example of forming a gold crystal on the O 2 substrate 101 will be described.
【０１６１】実施態様例４−１と同様の方法にて、［Ａ
ｕＩ4］-及びフッ化水素酸を含有する金錯体溶液を形成
する。次いで、ＳｉＯ2基板１の表面２を溶液に接した
後、還元剤Ｎａ2ＳＯ3水溶液をゆっくり滴下させなが
ら、溶液を室温で放置する。溶液系内では、Ｉ2の状態
で存在するヨウ素成分の２Ｉ-へのイオン化に伴い、溶
液系内の平行状態の維持の為に［ＡｕＩ4］-中のヨウ素
成分の解離による分解が生じると考えられ、結果として
金が過飽和状態となり、基板表面１０２上にランダムに
核１０３が形成される（図１（Ａ））。In the same manner as in Embodiment Example 4-1, [A
uI 4] - and form a gold complex solution containing hydrofluoric acid. Next, after the surface 2 of the SiO 2 substrate 1 is brought into contact with the solution, the solution is left at room temperature while slowly adding a reducing agent Na 2 SO 3 aqueous solution. In the solution system, when the iodine component existing in the I 2 state is ionized to 2 I − , the decomposition due to the dissociation of the iodine component in [AuI 4 ] − occurs in order to maintain the parallel state in the solution system. As a result, gold is supersaturated, and nuclei 103 are randomly formed on the substrate surface 102 (FIG. 1A).
【０１６２】本実施態様例のように基板に分解処理手段
として還元剤の添加を用いた場合、還元剤の濃度が濃い
と溶液中にて核が形成されてしまい基板上に結晶が形成
されない、又は微小な多結晶となってしまう。When a reducing agent is added to the substrate as a decomposition treatment means as in this embodiment, when the concentration of the reducing agent is high, nuclei are formed in the solution and crystals are not formed on the substrate. Or, it becomes a fine polycrystal.
【０１６３】成長から、３分程度で大きいもので４０μ
ｍ程度の結晶１０３に成長する（図１（Ｂ））。さらに
成長を続けると図１（Ｃ）及び図１（Ｄ）の如く、結晶
どうしが衝突し、粒界１０４が形成され、基板を覆う。
こうして平均粒径０．２〜０．６ｍｍ程度の単結晶群か
らなる金結晶薄膜が形成できる。ここで得られる結晶の
構造及び形状は第１実施例のものと同様なものである。
平均粒径はフッ化水素酸の濃度に依存し薄過ぎるとエッ
チング作用が現れず、濃過ぎると結晶の核が発生しなく
なる。40 μ in a large one in about 3 minutes from the growth
The crystals 103 grow to about m (FIG. 1B). When the growth is further continued, as shown in FIGS. 1C and 1D, the crystals collide with each other to form grain boundaries 104 and cover the substrate.
Thus, a gold crystal thin film composed of a single crystal group having an average grain size of 0.2 to 0.6 mm can be formed. The structure and shape of the crystal obtained here are similar to those of the first embodiment.
The average particle size depends on the concentration of hydrofluoric acid, and if it is too thin, no etching action appears, and if it is too thick, crystal nuclei do not occur.
【０１６４】本実施態様例は、極めて大粒径の金単結晶
群が形成できるが、これは実施態様例４−１と同様に溶
液中のフッ化水素酸がＳｉＯ2基板１０１に作用し基板
表面２を僅かづつエッチングしていくためであると考え
られる。この基板表面のエッチング作用により、基板上
における金結晶の核発生速度が抑えられ、その結果基板
上に形成される金単結晶の粒径は基板表面２をエッチン
グする作用を有しない系にくらべて大粒径の金単結晶群
薄膜になると考えられる。さらに、本実施態様例におい
ても、極めて平滑な表面を有する金単結晶を形成できる
効果がある。このことは、溶液系に存在するヨウ素が、
その金溶解作用により、成長中の金結晶上の新たな核発
生を抑制する為であると考えられる。In this embodiment, a gold single crystal group having an extremely large grain size can be formed. This is because the hydrofluoric acid in the solution acts on the SiO 2 substrate 101 as in Embodiment 4-1. It is considered that this is because the surface 2 is etched little by little. Due to the etching action of the substrate surface, the nucleation rate of gold crystals on the substrate is suppressed, and as a result, the grain size of the gold single crystal formed on the substrate is smaller than that of the system having no action of etching the substrate surface 2. It is considered to be a large grain size single crystal gold thin film. Furthermore, the present embodiment example also has the effect of forming a gold single crystal having an extremely smooth surface. This means that the iodine present in the solution system
It is considered that the gold dissolving action suppresses the generation of new nuclei on the growing gold crystal.
【０１６５】（実施態様例４−３）図２を用いて説明す
る。(Embodiment Example 4-3) Description will be made with reference to FIG.
【０１６６】核形成密度の大きい材料からなる面として
Ｓｉからなる面、核形成密度の小さい面としてＳｉ
Ｏ2、金錯体として［ＡｕＩ4］-、エッチング種として
ＨＦ（フッ化水素酸）。分解処理手段として揮発を用い
ることで本発明を実施した例について説明する。A surface made of Si as a surface made of a material having a high nucleation density and Si as a surface having a low nucleation density
O 2 , [AuI 4 ] − as a gold complex, and HF (hydrofluoric acid) as an etching species. An example in which the present invention is carried out by using volatilization as the decomposition processing means will be described.
【０１６７】表面にＳｉＯ2の熱酸化膜を形成したＳｉ
ウェハ上に、ＬＰ−ＣＶＤ法によりポリＳｉ（Ｐ−Ｓ
ｉ）膜を全面に形成する。次に、レジストを用いたエッ
チングにより、図２（Ａ）の如くＳｉＯ2膜２０５上に
島状のｐ−Ｓｉ２０２をマトリクス状に形成し基板とす
る。Si having a thermal oxide film of SiO 2 formed on its surface
On the wafer, poly-Si (P-S
i) A film is formed on the entire surface. Next, by etching using a resist, island-like p-Si 202 is formed in a matrix on the SiO 2 film 205 as shown in FIG.
【０１６８】蒸留水にヨウ化カリウム及びヨウ素を投入
してヨウ素水溶液を形成した後、金を投入し撹拌溶解さ
せ、［ＡｕＩ4］-を含有する金錯体溶液を形成する。次
にこの溶液にフッ化水素酸を滴下し混合する。このとき
溶液中には、金錯体［ＡｕＩ4］-の他、After potassium iodide and iodine are added to distilled water to form an iodine aqueous solution, gold is added and dissolved by stirring to form a gold complex solution containing [AuI 4 ] - . Next, hydrofluoric acid is added dropwise to this solution and mixed. At this time, in the solution, in addition to the gold complex [AuI 4 ] - ,
【０１６９】[0169]
【外１３】 Ｋ+，Ｆ-が主に存在するものと考えられる。[Outside 13] It is considered that K + and F − are mainly present.
【０１７０】ヨウ素水溶液は、ヨウ化カリウム以外のヨ
ウ化化合物、例えばヨウ化アンモニウムを使用すること
でも作成出来る。また、アルコールを溶媒として用い
た、ヨウ素アルコール溶液やアルコールと水の混合物を
溶媒として用いたヨウ素アルコール水溶液も本発明に用
いることができる。溶液中のヨウ素、ヨウ化化合物の濃
度は、溶解することのできる金の量を左右する。添加し
たフッ化水素酸は核発生密度の小さい材料面であるＳｉ
Ｏ2表面を薄くエッチングするため、この表面での金の
核発生密度をフッ化水素酸が添加されていない場合に比
べてさらに小さくする。核発生密度がさらに抑制できる
ということは、即ち核発生密度の大きい材料の間隔を大
きく取れることになる。フッ化水素酸濃度は、高い程核
発生密度抑制効果が高くなるが、多過ぎるとＳｉＯ2面
を急速にエッチングしてしまうため、その濃度はＳｉＯ
2膜厚と核発生密度抑制効果の関係によって決定され
る。The aqueous iodine solution can also be prepared by using an iodide compound other than potassium iodide, for example, ammonium iodide. Also, an iodine alcohol solution using alcohol as a solvent or an iodine alcohol aqueous solution using a mixture of alcohol and water as a solvent can be used in the present invention. The concentrations of iodine and iodide compounds in the solution control the amount of gold that can be dissolved. The added hydrofluoric acid is Si, which is a material surface with a low nucleation density.
Since the O 2 surface is thinly etched, the nucleation density of gold on this surface is made smaller than that in the case where hydrofluoric acid is not added. The fact that the nucleation density can be further suppressed means that the distance between materials having a high nucleation density can be increased. The higher the concentration of hydrofluoric acid, the higher the effect of suppressing the nucleus generation density. However, if the concentration is too high, the SiO 2 surface will be rapidly etched.
2 Determined by the relationship between film thickness and nucleation density suppression effect.
【０１７１】次いで、前述の基板の表面５を溶液に接し
た後、溶液を３０〜１００℃に昇温し、ヨウ素成分の揮
発を促進させる。Then, after the surface 5 of the above-mentioned substrate is brought into contact with the solution, the temperature of the solution is raised to 30 to 100 ° C. to accelerate the volatilization of the iodine component.
【０１７２】溶液系内ではIn the solution system
【０１７３】[0173]
【外１４】 の状態で存在するヨウ素成分の揮発による、溶液系内の
平行状態の維持の為の［ＡｕＩ4］-からのＩ成分の解離
による分解、又は［ＡｕＩ4］-の形で存在する錯体中の
ヨウ素成分の直接の揮発による分解が進行すると考えら
れ、結果として金が過飽和状態となる。[Outside 14] The due to volatilization of iodine component which is present in a state, for maintaining the parallel state within the solution system [AuI 4] - degradation by dissociation of I component from, or [AuI 4] - in the complex present in the form of It is thought that the decomposition of iodine component by direct volatilization proceeds, resulting in supersaturation of gold.
【０１７４】溶液中で過飽和状態となった金は、核形成
密度の大きいＳｉ基板表面のみにランダムな核２０３と
して析出する（図２（Ｂ））。Gold supersaturated in the solution is deposited as random nuclei 203 only on the surface of the Si substrate having a high nucleation density (FIG. 2 (B)).
【０１７５】形成された結晶は、欠陥のない単結晶であ
り、（１１１）方位を有している。また、成長レートに
ついて観察した結果、縦方向：横方向が１：１００〜２
００の割合で成長する。The formed crystal is a defect-free single crystal and has a (111) orientation. Moreover, as a result of observing the growth rate, the vertical direction: the horizontal direction is 1: 100 to 2
It grows at a rate of 00.
【０１７６】さらに成長を続けると図２（Ｃ）の如く、
結晶どうしが衝突し、粒界２０４が形成され、核形成密
度の大きい材料からなる面を覆い、単結晶群からなる金
結晶薄膜を選択的に形成できる。If the growth is further continued, as shown in FIG.
Crystals collide with each other to form grain boundaries 204, cover a surface made of a material having a high nucleation density, and a gold crystal thin film made of a single crystal group can be selectively formed.
【０１７７】本実施態様例では、極めて平滑な表面を有
する金単結晶を形成できる効果がある。このことは、溶
液系に存在するヨウ素が、その金溶解作用により、成長
中の金結晶上の新たな核発生を抑制する為であると考え
られる。This embodiment example has an effect of forming a gold single crystal having an extremely smooth surface. It is considered that this is because iodine existing in the solution system suppresses the generation of new nuclei on the growing gold crystal due to its gold dissolving action.
【０１７８】（実施態様例４−４）核形成密度の大きい
材料からなる面としてＳｉからなる面、核形成密度の小
さい面としてＳｉＯ2、金錯体として［ＡｕＩ4］-、エ
ッチング種としてＨＦ（フッ化水素酸）、分解処理手段
として還元剤を用いることで本発明を実施した例につい
て説明する。図３を用いて説明する。(Embodiment Example 4-4) A surface made of Si as a surface made of a material having a high nucleation density, SiO 2 as a surface having a low nucleation density, [AuI 4 ] − as a gold complex, and HF (as an etching species). An example in which the present invention is carried out by using hydrofluoric acid) and a reducing agent as a decomposition treatment means will be described. This will be described with reference to FIG.
【０１７９】表面に熱酸化膜３０５の形成されたＳｉウ
ェハ３０１に、エッチングによって図３（Ａ）の如くホ
ールを形成し、Ｓｉ面３０２を露出させ基板とする。On the Si wafer 301 having the thermal oxide film 305 formed on the surface, holes are formed by etching as shown in FIG. 3A, and the Si surface 302 is exposed to form a substrate.
【０１８０】次に実施態様例４−３と同様に蒸留水にヨ
ウ化カリウム及びヨウ素を投入してヨウ素水溶液を形成
した後、金を投入し撹拌溶解させ、［ＡｕＩ4］-を含有
する金錯体溶液を形成した後溶液にフッ化水素酸を滴下
し混合する。Then, potassium iodide and iodine were added to distilled water to form an aqueous solution of iodine in the same manner as in Example 4-3, and then gold was added and dissolved by stirring to obtain gold containing [AuI 4 ] -. After forming the complex solution, hydrofluoric acid is added dropwise to the solution and mixed.
【０１８１】次いで、前述の基板の表面を溶液に接した
後、亜硫酸ナトリウム水溶液をゆっくり滴下して結晶成
長を行なう。Then, after the surface of the substrate is brought into contact with the solution, an aqueous solution of sodium sulfite is slowly dropped to grow crystals.
【０１８２】溶液系内では、Ｉ2・Ｉ-の状態で存在する
ヨウ素成分の３Ｉ-へのイオン化に伴い、溶液系内の平
衡状態の維持の為に［ＡｕＩ4］-中のヨウ素成分の解離
による分解が生じると考えられ、結果として金が過飽和
状態となり、核形成密度の大きい基板表面上にランダム
に核が形成される。さらに成長を続けると図３（Ｂ）の
如く、結晶どうしが衝突し、粒界３０４が形成され、核
形成密度の大きい材料からなる面を覆い、単結晶群から
なる金結晶薄膜が選択的に形成できる。核形成密度の小
さい材料からなる面には、核の発生は見られない。形成
された結晶は、欠陥のない単結晶であり、（１１１）方
位を有している。また、成長レートについて観察した結
果、縦方向：横方向が１：１００〜２００の割合で成長
する。In the solution system, with the ionization of the iodine component existing in the I 2 · I − state to 3 I − , in order to maintain the equilibrium state in the solution system, the iodine component in [AuI 4 ] − It is considered that decomposition due to dissociation occurs, resulting in supersaturation of gold and random nucleation on the surface of the substrate having a high nucleation density. When the growth is further continued, as shown in FIG. 3B, the crystals collide with each other to form grain boundaries 304 and cover the surface made of the material having a high nucleation density, and the gold crystal thin film made of the single crystal group is selectively formed. Can be formed. Nucleation is not observed on the surface made of a material having a low nucleation density. The formed crystal is a defect-free single crystal and has a (111) orientation. Moreover, as a result of observing the growth rate, the growth is performed at a ratio of 1: 100 to 200 in the vertical direction and the horizontal direction.
【０１８３】（実施態様例４−５）核形成密度の大きい
材料からなる面としてＳｉからなる面、核形成密度の小
さい面としてＳｉＯ2、金錯体として［ＡｕＩ4］-、エ
ッチング種としてフッ化水素酸、分解処理手段として揮
発を用いることで本発明を実施した例について説明す
る。図６及び図７を参照して説明する。(Embodiment Example 4-5) A surface made of Si as a surface made of a material having a high nucleation density, SiO 2 as a surface having a low nucleation density, [AuI 4 ] − as a gold complex, and fluorinated as an etching species. An example in which the present invention is carried out by using hydrogen acid and volatilization as a decomposition treatment means will be described. This will be described with reference to FIGS. 6 and 7.
【０１８４】表面にＳｉＯ2の熱酸化膜６０５、７０５
を形成したＳｉウェハ６０１上に、ＬＰ−ＣＶＤ法によ
りポリＳｉ（ｐ−Ｓｉ）膜を全面に形成する。次に、レ
ジストを用いたエッチングにより、図６（Ａ）及び図７
（Ａ）の如くＳｉＯ2膜上に１０μｍ角のｐ−Ｓｉ薄膜
６０２、７０２が１．５ｍｍ間隔でマトリクスに形成さ
れた基板を作成する。Thermal oxide films 605 and 705 of SiO 2 are formed on the surface.
A poly-Si (p-Si) film is formed on the entire surface of the formed Si wafer 601 by the LP-CVD method. Next, as shown in FIGS. 6A and 7 by etching using a resist.
As shown in (A), a substrate is prepared in which 10 μm square p-Si thin films 602 and 702 are formed in a matrix at intervals of 1.5 mm on a SiO 2 film.
【０１８５】蒸留水にヨウ化カリウム及びヨウ素を投入
してヨウ素水溶液を形成した後、金を投入し撹拌溶解さ
せ、［ＡｕＩ4］-を含有する金錯体溶液を形成する。次
に、この溶液にフッ化水素酸を滴下、混合する。このと
き溶液中には、金錯体［ＡｕＩ4］-の他、Potassium iodide and iodine are added to distilled water to form an aqueous iodine solution, and then gold is added and dissolved by stirring to form a gold complex solution containing [AuI 4 ] - . Next, hydrofluoric acid is added dropwise to this solution and mixed. At this time, in the solution, in addition to the gold complex [AuI 4 ] - ,
【０１８６】[0186]
【外１５】 Ｋ+，Ｆ-が主に存在するものと考えられる。[Outside 15] It is considered that K + and F − are mainly present.
【０１８７】次いで、 前述の基板の表面を溶液に接し
た後、溶液を３０〜１００℃に昇温し、ヨウ素成分の揮
発を促進させる。Next, after the surface of the above-mentioned substrate is brought into contact with the solution, the temperature of the solution is raised to 30 to 100 ° C. to promote volatilization of the iodine component.
【０１８８】溶液系内ではIn the solution system
【０１８９】[0189]
【外１６】 の状態で存在するヨウ素成分の揮発による溶液系内の平
衡状態の維持の為の［ＡｕＩ4］-からのＩ成分の解離に
よる分解、又は［ＡｕＩ4］-の形で存在する錯体中のヨ
ウ素成分の直接の揮発による分解が進行すると考えら
れ、結果として金が過飽和状態となる。[Outside 16] [AuI 4] for maintenance due to volatilization of iodine component which is present in a state of equilibrium in the solution system - degradation by dissociation of I component from, or [AuI 4] - iodine in the complex present in the form of It is thought that decomposition by direct volatilization of the components proceeds, resulting in supersaturation of gold.
【０１９０】溶液中で過飽和状態となった金は、核形成
密度の高いＳｉ基板表面のみに単一核６０３、７０３と
して析出する（図６（Ｂ）及び図７（Ｂ））。Gold supersaturated in the solution is deposited as single nuclei 603 and 703 only on the surface of the Si substrate having a high nucleation density (FIGS. 6 (B) and 7 (B)).
【０１９１】形成された結晶は、欠陥のない単結晶であ
り、（１１１）方位を有している。また、成長レート
は、縦方向：横方向が１：１００〜２００の割合で成長
する。The formed crystal is a defect-free single crystal and has a (111) orientation. In addition, the growth rate is such that the vertical direction and the horizontal direction grow at a ratio of 1: 100 to 200.
【０１９２】さらに成長を続けると図６（Ｃ）及び図７
（Ｃ）、（Ｄ）の如く、結晶どうしが衝突し、各々の核
形成密度の大きい材料からなる面のほぼ中間に粒界６０
４、７０４が形成され、核形成密度の小さい材料からな
る面を覆い、単結晶からなる金結晶薄膜６０３、７０３
が形成できる。このように本発明の金単結晶は、その形
成位置（結晶の位置及び粒界位置）を設計的に知ること
ができる。本発明で作成された金単結晶群からなる金薄
膜を用い、半導体集積回路などに用いる薄膜配線として
利用できる。Continuing to grow, FIG. 6C and FIG.
As in (C) and (D), the crystals collide with each other, and the grain boundaries 60 are formed almost in the middle of the planes of the materials each having a high nucleation density.
4, 704 are formed and cover the surface made of a material having a low nucleation density, and are gold crystal thin films 603 and 703 made of a single crystal.
Can be formed. As described above, the gold single crystal of the present invention can know the formation position (crystal position and grain boundary position) by design. The gold thin film composed of the gold single crystal group produced by the present invention can be used as a thin film wiring used in a semiconductor integrated circuit or the like.
【０１９３】本発明において核形成密度の大きい材料か
らなる面を充分微小な面積にすることで、単一核のみの
核発生が行なうことができる。この大きさは、好ましく
は１０μｍ以下、より好ましくは５μｍ以下である。In the present invention, when the surface made of a material having a high nucleation density has a sufficiently small area, it is possible to generate nuclei of only a single nucleus. This size is preferably 10 μm or less, more preferably 5 μm or less.
【０１９４】また、ヨウ素水溶液はヨウ化カリウム以外
のヨウ化化合物、例えばヨウ化アンモニウムを使用する
ことでも作成出来る。また、アルコールを溶媒として用
いた、ヨウ素アルコール溶液やアルコールと水の混合物
を溶媒として用いたヨウ素アルコール・水溶液も本発明
に用いることができる。溶液中のヨウ素、ヨウ化化合物
の濃度は、溶解することのできる金の量を左右する。添
加したフッ化水素酸は核発生密度の小さい材料面である
ＳｉＯ2表面を薄くエッチングするため、この表面での
金の核発生密度をフッ化水素酸が添加されていない場合
に比べてさらに小さくする。核発生密度がさらに抑制で
きるということは、即ち核発生密度の大きい材料の相互
の間隔を大きく取れることになる。フッ化水素酸濃度
は、高い程核発生密度抑制効果が高くなるが、高過ぎる
とＳｉＯ2表面を急速にエッチングしてしまうため、そ
の濃度はＳｉＯ2膜厚と核発生密度抑制効果の関係によ
って決定される。The iodine aqueous solution can also be prepared by using an iodide compound other than potassium iodide, such as ammonium iodide. Further, an iodine alcohol solution using alcohol as a solvent or an iodine alcohol / aqueous solution using a mixture of alcohol and water as a solvent can also be used in the present invention. The concentrations of iodine and iodide compounds in the solution control the amount of gold that can be dissolved. Since the added hydrofluoric acid thinly etches the SiO 2 surface, which is a material surface with a low nucleation density, the nucleation density of gold on this surface is made smaller than in the case where hydrofluoric acid is not added. To do. The fact that the nucleation density can be further suppressed means that the distance between materials having a high nucleation density can be increased. The higher the concentration of hydrofluoric acid, the higher the effect of suppressing the nucleus generation density, but if it is too high, the SiO 2 surface will be etched rapidly. Therefore, the concentration depends on the relationship between the SiO 2 film thickness and the effect of suppressing the nucleus generation density. It is determined.
【０１９５】（実施態様例４−６）核形成密度の大きい
材料からなる面としてＳｉからなる面、核形成密度の小
さい面としてＳｉＯ2、金錯体として［ＡｕＩ4］-、エ
ッチング種としてフッ化水素酸、分解処理手段として還
元剤を用いて本発明を実施した例について説明する。(Embodiment 4-6) A surface made of Si as a surface made of a material having a high nucleation density, SiO 2 as a surface having a low nucleation density, [AuI 4 ] − as a gold complex, and fluorinated as an etching species. An example in which the present invention is carried out by using a reducing agent as a hydrolytic acid and a decomposition treatment means will be described.
【０１９６】表面に熱酸化膜の形成されたＳｉウェハ
に、エッチングにより、ホールを形成し、Ｓｉ面を露出
させ基板とする。A hole is formed in a Si wafer having a thermal oxide film formed on the surface by etching, and the Si surface is exposed to form a substrate.
【０１９７】次に実施態様例４−５と同様に蒸留水にヨ
ウ化カリウム及びヨウ素を投入してヨウ素水溶液を形成
し、金を投入し撹拌溶解させ、［ＡｕＩ4］-を含有する
金錯体溶液を形成した後、溶液にフッ化水素酸を滴下し
混合する。Then, potassium iodide and iodine were added to distilled water to form an aqueous iodine solution in the same manner as in Example 4-5, and gold was added and dissolved by stirring to give a gold complex containing [AuI 4 ] -. After forming the solution, hydrofluoric acid is added dropwise to the solution and mixed.
【０１９８】次いで、前述の基板の表面を溶液に接した
後、ハイドロキノン水溶液を徐々に滴下して結晶成長を
行う。Then, after the surface of the above-mentioned substrate is brought into contact with the solution, an aqueous solution of hydroquinone is gradually dropped to grow crystals.
【０１９９】溶液系内ではＩ2Ｉ-の状態で存在するヨウ
素成分の３Ｉ-へのイオン化に伴い、溶液系内の平衡状
態の維持の為に［ＡｕＩ4］-中のヨウ素成分の解離によ
る分解が生じると考えられ、結果として金が過飽和状態
となる。[0199] In the solution-based I 2 I - due to the ionization of the, for the maintenance of the equilibrium in the solution system [AuI 4] - - 3I iodine component which is present in the state by dissociation of the iodine components of the medium Decomposition is believed to occur, resulting in supersaturation of gold.
【０２００】溶液中で過飽和状態となった金は、核形成
密度の高いＳｉ基板表面のみに単一核３として析出する
形成された結晶は、欠陥のない単結晶であり、（１１
１）方位を有している。また、成長レートは、縦方向：
横方向が１：１００〜２００の割合で成長する。さらに
成長を続けると、結晶がホール内を埋め尽くす。Gold supersaturated in the solution is deposited as a single nucleus 3 only on the surface of the Si substrate having a high nucleation density. The formed crystal is a defect-free single crystal.
1) It has an azimuth. The growth rate is vertical:
The lateral direction grows at a ratio of 1: 100 to 200. When the growth is further continued, the crystal fills the hole.
【０２０１】本発明は、前述した実施態様例以外にも様
々な態様にて実施可能である。The present invention can be implemented in various modes other than the above-described embodiment modes.
【０２０２】本発明において核形成密度が小さい材料か
らなる面と核形成密度が大きい材料からなる面は、限定
されるものではなく、結局、相対的に核形成密度の差が
あり且つ核形成密度が大きい材料が単一核が形成される
程充分微細な面であり、しかも核形成密度が小さい材料
に作用し得るエッチング種が溶液系内に存在していれば
良い。In the present invention, the surface made of a material having a low nucleation density and the surface made of a material having a high nucleation density are not limited, and as a result, there is a relative difference in the nucleation density and the nucleation density. It is sufficient if the material having a large n is a surface fine enough to form a single nucleus, and an etching species capable of acting on the material having a small nucleation density is present in the solution system.
【０２０３】それぞれの核形成密度が大きい材料からな
る面の配置する最大間隔は、核形成密度が小さい材料か
らなる面のみに同一条件で全面に形成した際の平均粒径
以内であることが望ましい。換言するなら、配置する最
大間隔を長くとる為には、核形成密度が小さい材料に核
形成密度の特に低いＳｉＯ2，ＳｉＮ，ＳｉＣ，Ａｌ2Ｏ
3等の絶縁性材料を用いることが好ましい。It is desirable that the maximum spacing between the surfaces made of the material having a high nucleation density is within the average grain size when formed on the entire surface under the same conditions only on the surface made of the material having a low nucleation density. .. In other words, in order to make the maximum interval of arrangement long, a material with a low nucleation density is formed of SiO 2 , SiN, SiC, Al 2 O having a particularly low nucleation density.
It is preferable to use an insulating material such as 3 .
【０２０４】核形成密度が大きい材料としては、Ａｕ，
Ａｇ，Ｃｕ，Ｗ，ＷＳｉ，ＭｏＳｉ，Ｆｅ，Ｓｉ，Ｇｅ
などの導電性材料、半導体材料を用いることができる。As a material having a high nucleation density, Au,
Ag, Cu, W, WSi, MoSi, Fe, Si, Ge
A conductive material such as, or a semiconductor material can be used.
【０２０５】金錯体は、［ＡｕＩ4］-，［ＡｕＣ
ｌ4］-，［Ａｕ（ＣＮ）2］-，［Ａｕ（ＣＮ）3］-，
［ＡｕＢｒ3］等の金錯体を用いることができる。The gold complexes are [AuI 4 ] - , [AuC
l 4 ] − , [Au (CN) 2 ] − , [Au (CN) 3 ] − ,
A gold complex such as [AuBr 3 ] can be used.
【０２０６】エッチング種としては、フッ化水素酸、塩
酸、硝酸、硫酸などの酸性溶液が好ましく用いられる。As the etching species, an acidic solution of hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid or the like is preferably used.
【０２０７】分解処理手段として、加熱による揮発や還
元剤を用いることができる。Volatilization by heating or a reducing agent can be used as the decomposition treatment means.
【０２０８】還元剤としては、例えばハイドロキノン、
ピロガノール、パイロカキテン、グクシン、メトールハ
イドロキノン、アミドール、メトール、亜硫酸ソーダ、
チオ硫酸ナトリウムなどの他、溶液中で還元作用を有す
る物質が用いられる。Examples of the reducing agent include hydroquinone,
Pyroganol, Pyrocachytene, Guchcine, Metolhydroquinone, Amidole, Metol, Sodium sulfite,
Other than sodium thiosulfate, a substance having a reducing action in a solution is used.
【０２０９】ここで説明した溶液、材料等は本発明の他
の実施態様例においても使用できることはいうまでもな
い。It goes without saying that the solutions, materials, etc. described here can be used in other embodiments of the present invention.
【０２１０】[0210]
【実施例】以下、具体的な実施例を挙げて本発明を説明
するが、本発明はこれら実施例に限定されるものではな
い。EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.
【０２１１】（実施例１）蒸留水５００ｍｌにヨウ化カ
リウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器にいれ、
ここにさらに蒸留水を５００ｍｌ加えて撹拌した。熱酸
化膜０．５μｍ厚が形成されたＳｉウエハ基板の表面を
溶液に接し、次いで、溶液を８０℃に加熱して放置し
た。１時間後基板を取り出し観察したところ、熱酸化膜
上に（１１１）面を有した単結晶群が形成されていた。
各単結晶間には粒界が形成されており、平均粒径は５６
０μｍで約２μｍの膜厚を有していた。ＳＴＭ（走査型
トンネル顕微鏡）で観察した結果、個々の単結晶表面の
凹凸は、１μｍ□内で５Åであった。Example 1 40 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, take 100 ml of this solution and put in a reaction vessel.
Further, 500 ml of distilled water was added to this and the mixture was stirred. The surface of the Si wafer substrate having a thermal oxide film of 0.5 μm thickness was brought into contact with the solution, and then the solution was heated to 80 ° C. and left to stand. When the substrate was taken out and observed after 1 hour, a single crystal group having a (111) plane was formed on the thermal oxide film.
Grain boundaries are formed between the single crystals, and the average grain size is 56.
It had a film thickness of about 2 μm at 0 μm. As a result of observation with an STM (scanning tunneling microscope), the unevenness of the surface of each single crystal was 5Å within 1 μm □.
【０２１２】（実施例２）蒸留水５００ｍｌにヨウ化カ
リウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金３ｇを投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器に入れ、
ここにさらに蒸留水５００ｍｌを加えながら、撹拌し
た。次いで、この溶液中にハイドロキノン１００ｍｇが
溶解した水溶液５０ｍｌを徐々加えた。希フッ酸で表面
酸化膜を除去したＳｉ基板の表面を溶液に接し、室温の
まま放置した。３時間後基板を取り出し観察したとこ
ろ、Ｓｉ基板上に（１１１）面を有した単結晶群が形成
されていた。平均粒径は１５μｍであり、膜厚は約０．
２μｍであった。Example 2 To 500 ml of distilled water, 40 g of potassium iodide and 6 g of iodine were added and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, 100 ml of this solution was taken and placed in a reaction container.
The mixture was stirred while further adding 500 ml of distilled water. Then, 50 ml of an aqueous solution in which 100 mg of hydroquinone was dissolved was gradually added to this solution. The surface of the Si substrate from which the surface oxide film was removed with dilute hydrofluoric acid was brought into contact with the solution and left at room temperature. When the substrate was taken out and observed after 3 hours, a single crystal group having a (111) plane was formed on the Si substrate. The average particle size is 15 μm, and the film thickness is about 0.
It was 2 μm.
【０２１３】（実施例３）蒸留水５００ｍｌにヨウ化カ
リウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を２ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器にいれ、
ここにさらに蒸留水を３００ｍｌ加えて撹拌した。次
に、希フッ酸で表面酸化膜を除去したＳｉ基板の表面を
溶液に接し８０℃に加熱した。１時間後基板を取り出し
観察したところ、Ｓｉ基板上に（１１１）面を有した単
結晶群が形成されていた。平均粒径は２０μｍであり、
膜厚は約０．３μｍであった。Example 3 40 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 2 g of gold was added to this solution and dissolved by stirring. After dissolution, take 100 ml of this solution and put in a reaction vessel.
Then, 300 ml of distilled water was further added and stirred. Next, the surface of the Si substrate from which the surface oxide film was removed with dilute hydrofluoric acid was brought into contact with the solution and heated to 80 ° C. After 1 hour, the substrate was taken out and observed. As a result, a single crystal group having a (111) plane was formed on the Si substrate. The average particle size is 20 μm,
The film thickness was about 0.3 μm.
【０２１４】（実施例４）蒸留水５００ｍｌにヨウ化カ
リウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器にいれ、
ここにされに蒸留水を５００ｍｌ加えて撹拌した。熱酸
化膜０．５μｍ厚が形成されたＳｉウエハ基板の表面を
溶液に接し、次いで、溶液を８０℃に加熱して放置し
た。１時間後基板を取り出し観察したところ、熱酸化膜
上に（１１１）面を有した単結晶群が形成されていた。
各単結晶間には粒界が形成されており、平均粒径は５６
０μｍで約２μｍの膜厚を有していた。Example 4 40 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, take 100 ml of this solution and put in a reaction vessel.
500 ml of distilled water was added to this and stirred. The surface of the Si wafer substrate having a thermal oxide film of 0.5 μm thickness was brought into contact with the solution, and then the solution was heated to 80 ° C. and left to stand. When the substrate was taken out and observed after 1 hour, a single crystal group having a (111) plane was formed on the thermal oxide film.
Grain boundaries are formed between the single crystals, and the average grain size is 56.
It had a film thickness of about 2 μm at 0 μm.
【０２１５】次に、単結晶群上にレジストパターン形成
を形成し、Ａｒガスを用いたイオンエッチングにより、
３μｍ幅の金単結晶群配線をうず巻き状に形成した。Next, a resist pattern is formed on the single crystal group, and ion etching using Ar gas is performed to form a resist pattern.
A gold single crystal group wiring having a width of 3 μm was formed in a spiral shape.
【０２１６】この金単結晶群からなる薄膜配線は、平均
５６０μｍ間隔で粒界が形成されていた。この金結晶配
線の電気抵抗を測定したところ、２．３×１０-6ｃｍ・
Ωという十分に低い値が得られた。In the thin film wiring made of this gold single crystal group, grain boundaries were formed at an average interval of 560 μm. When the electric resistance of this gold crystal wiring was measured, it was 2.3 × 10 −6 cm ·
A sufficiently low value of Ω was obtained.
【０２１７】（実施例５）塩酸３０ｍｌと硝酸１０ｍｌ
を混合して王水を作成した後、この溶液に金を２ｇ投入
して撹拌溶解させた。溶解後、この溶液から１０ｍｌ分
取して反応容器にいれ、ここにさらに蒸留水を１００ｍ
ｌ加えて撹拌した。次に、この溶液中に水酸化ナトリウ
ム（ＮａＯＨ）を１０ｇを溶解した水溶液を徐々に加え
た。この溶液中に窒化Ｓｉ膜で被覆されたＳｉ基板を投
入して、溶液を４０℃で放置した。１時間後基板を取出
し観察したところ、窒化Ｓｉ基板上に（１１１）面を有
する単結晶群が形成されていた。単結晶の平均粒径は約
２２０μｍであった。(Example 5) 30 ml of hydrochloric acid and 10 ml of nitric acid
Was mixed to prepare aqua regia, and 2 g of gold was added to this solution and dissolved by stirring. After dissolution, 10 ml of this solution was sampled and placed in a reaction vessel.
1 and stirred. Next, an aqueous solution in which 10 g of sodium hydroxide (NaOH) was dissolved was gradually added to this solution. A Si substrate coated with a Si nitride film was put into this solution, and the solution was allowed to stand at 40 ° C. When the substrate was taken out and observed after 1 hour, a single crystal group having a (111) plane was formed on the Si nitride substrate. The average grain size of the single crystal was about 220 μm.
【０２１８】（実施例６）蒸留水５００ｍｌにヨウ化カ
リウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器にいれ、
ここにさらに蒸留水を５００ｍｌ加えて撹拌した。次
に、Ｔｉ基板の表面を溶液に接し、次いで、溶液を８０
℃に加熱して放置した。３０分後基板を取り出し観察し
たところ、Ｔｉ基板上に（１１１）面を有する単結晶群
が形成されていた。各単結晶間には粒界が形成されてい
た。平均粒径は、２μｍで、膜の厚さは約０．１μｍで
あった。Example 6 To 500 ml of distilled water, 40 g of potassium iodide and 6 g of iodine were added and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, take 100 ml of this solution and put in a reaction vessel.
Further, 500 ml of distilled water was added to this and the mixture was stirred. Next, the surface of the Ti substrate is contacted with the solution, and then the solution is
It was heated to ℃ and left to stand. After 30 minutes, the substrate was taken out and observed. As a result, a single crystal group having a (111) plane was formed on the Ti substrate. Grain boundaries were formed between the single crystals. The average particle size was 2 μm and the film thickness was about 0.1 μm.
【０２１９】（実施例７）蒸留水５００ｍｌにヨウ化カ
リウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器にいれ、
ここにさらに蒸留水を５００ｍｌ加えて撹拌し結晶成長
用溶液とした。Example 7 40 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, take 100 ml of this solution and put in a reaction vessel.
Distilled water (500 ml) was further added and stirred to obtain a crystal growth solution.
【０２２０】熱酸化膜０．５μｍ厚が形成されたＳｉウ
エハ上にＥＢ蒸着法によりＴｉ膜０．１μｍ厚を形成し
た。このＴｉ上にレジスト層を形成、露光、現像を行い
パターニングを行った。このレジストパターンをマスク
として、ＣＦ4 ガスを用いたリアクティブイオンエッチ
ング（ＲＩＥ）を行いＴｉをパターニングし、レジスト
層を剥離した。パターンは、３０×５０μｍ角で、２０
０μｍ間隔のマトリックス状とした。A Ti film having a thickness of 0.1 μm was formed by an EB vapor deposition method on a Si wafer having a thermal oxide film having a thickness of 0.5 μm. A resist layer was formed on this Ti, exposed, and developed to perform patterning. Using this resist pattern as a mask, reactive ion etching (RIE) using CF 4 gas was performed to pattern Ti, and the resist layer was peeled off. The pattern is 30 × 50 μm square and 20
It was in a matrix shape with 0 μm intervals.
【０２２１】作成した基板の方面を結晶成長用溶液に接
し、次いで、溶液を８０℃に加熱して放置した。１時間
後基板を取り出し観察したところ、Ｔｉ上に（１１１）
面を有する単結晶群が形成されていた。各単結晶間には
粒界が形成されていた。単結晶の平均粒径は約２μｍで
あった。膜の厚さは約１００ｎｍであった。ＳＴＭで観
察した結果、個々の単結晶表面の凹凸は、１μｍ角内で
５Åであった。核形成密度の低いＳｉＯ2 面上には、核
の発生は認められなかった。The surface of the prepared substrate was brought into contact with the crystal growth solution, and then the solution was heated to 80 ° C. and left to stand. After 1 hour, the substrate was taken out and observed.
A single crystal group having a face was formed. Grain boundaries were formed between the single crystals. The average grain size of the single crystal was about 2 μm. The film thickness was about 100 nm. As a result of STM observation, the unevenness of the surface of each single crystal was 5Å within 1 μm square. No nucleation was observed on the SiO 2 surface having a low nucleation density.
【０２２２】（実施例８）蒸留水５００ｍｌにヨウ化ア
ンモニウム４０ｇ及びヨウ素１０ｇを投入して撹拌溶解
させた。この溶液に金を３ｇ投入して撹拌溶解させた。
溶解後、この溶液から１００ｍｌ分取して反応容器にい
れ、ここにさらに蒸留水を５００ｍｌ加えて撹拌し結晶
成長用溶液とした。熱酸化膜０．３μｍ厚が形成された
Ｓｉウエハ上にレジスト層を形成、露光、現像を行いパ
ターニングを行った。このレジストパターンをマスクと
して、ＣＦ4 ガスを用いたＲＩＥを行い熱酸化膜をエッ
チング除去しＳｉ面を露出させ、レジスト層を剥離し
た。パターンは、１００×１００μｍ角で、３００μｍ
間隔のマトリックス状とした。Example 8 40 g of ammonium iodide and 10 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring.
After dissolution, 100 ml of this solution was sampled and placed in a reaction vessel, and 500 ml of distilled water was further added thereto and stirred to obtain a crystal growth solution. A resist layer was formed on a Si wafer having a thermal oxide film thickness of 0.3 μm, exposed, and developed for patterning. Using this resist pattern as a mask, RIE using CF 4 gas was performed to remove the thermal oxide film by etching to expose the Si surface, and the resist layer was peeled off. The pattern is 100 × 100μm square, 300μm
A matrix of intervals is used.
【０２２３】作成した基板を希フッ酸に浸漬して表面酸
化膜を除去した後、基板表面を結晶成長用溶液に接し、
次いで、溶液を８０℃に加熱して放置した。１．５時間
後基板を取り出し観察したところ、Ｓｉ上に（１１１）
面を有する単結晶群が形成されていた。各単結晶間には
粒界が形成されていた。単結晶の平均粒径は約２０μｍ
であった。膜の厚さは約３００ｎｍであった。ＳＴＭで
観察した結果、個々の単結晶表面の凹凸は、１μｍ角内
で５Åであった。核形成密度の低いＳｉＯ2 面上には、
核の発生は認められなかった。The prepared substrate was dipped in dilute hydrofluoric acid to remove the surface oxide film, and then the substrate surface was contacted with a crystal growth solution,
The solution was then heated to 80 ° C and left to stand. After 1.5 hours, the substrate was taken out and observed. As a result, (111)
A single crystal group having a face was formed. Grain boundaries were formed between the single crystals. Average grain size of single crystal is about 20μm
Met. The film thickness was about 300 nm. As a result of STM observation, the unevenness of the surface of each single crystal was 5Å within 1 μm square. On the SiO 2 surface with low nucleation density,
Nucleation was not observed.
【０２２４】（実施例９）蒸留水５００ｍｌにヨウ化カ
リウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器に入れ、
ここにさらに蒸留水を５００ｍｌ加えて撹拌し結晶成長
用溶液とした。Example 9 40 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved with stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, 100 ml of this solution was taken and placed in a reaction container.
Distilled water (500 ml) was further added and stirred to obtain a crystal growth solution.
【０２２５】熱酸化膜０．５μｍ厚が形成されたＳｉウ
エハ上にＬＰ−ＣＶＤ法によりポリＳｉ膜（ｐ−Ｓｉ）
０．１μｍ厚を形成した。このｐ−Ｓｉ上にレジスト層
を形成、露光、現像を行いパターニングを行った。この
レジストパターンをマスクとして、ＳＦ6 ガスを用いた
リアクティブイオンエッチング（ＲＩＥ）を行いｐ−Ｓ
ｉをパターニングし、レジスト層を剥離した。パターン
は、１００×１００μｍ角で、４００μｍ間隔のマトリ
ックス状とした。A poly-Si film (p-Si) is formed by LP-CVD on a Si wafer having a thermal oxide film of 0.5 μm thick.
A thickness of 0.1 μm was formed. A resist layer was formed on this p-Si, exposed, and developed to perform patterning. Using this resist pattern as a mask, reactive ion etching (RIE) using SF 6 gas is performed and p-S
i was patterned and the resist layer was peeled off. The pattern was a matrix with 100 × 100 μm square and 400 μm intervals.
【０２２６】作成した基板を希フッ酸に浸漬してｐ−Ｓ
ｉ上の表面酸化膜を除去した後、基板表面を結晶成長用
溶液に接し、溶液中にハイドロキノン１００ｍｇを溶解
した水溶液３０ｍｌをゆっくり加え放置した。３時間後
基板を取り出し観察したところ、ｐ−Ｓｉ上に（１１
１）面を有する単結晶群が形成されていた。各単結晶間
には粒界が形成されていた。単結晶の平均粒径は約１５
μｍであった。膜の厚さは約１５０ｎｍであった。ＳＴ
Ｍで観察した結果、個々の単結晶表面の凹凸は、１μｍ
角内で５Åであった。核形成密度の低いＳｉＯ2 面上に
は、核の発生は、認められなかった。The prepared substrate was dipped in dilute hydrofluoric acid to obtain pS.
After removing the surface oxide film on i, the substrate surface was brought into contact with the crystal growth solution, and 30 ml of an aqueous solution in which 100 mg of hydroquinone was dissolved was slowly added and left to stand. After 3 hours, the substrate was taken out and observed.
1) A single crystal group having a face was formed. Grain boundaries were formed between the single crystals. Average grain size of single crystal is about 15
was μm. The film thickness was about 150 nm. ST
As a result of observation with M, the unevenness on the surface of each single crystal is 1 μm.
It was 5Å within the corner. Nucleation was not observed on the SiO 2 surface having a low nucleation density.
【０２２７】（実施例１０）蒸留水５００ｍｌにヨウ化
カリウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器にいれ、
ここにさらに蒸留水を５００ｍｌ加えて撹拌し結晶成長
用溶液とした。Example 10 40 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, take 100 ml of this solution and put in a reaction vessel.
Distilled water (500 ml) was further added and stirred to obtain a crystal growth solution.
【０２２８】熱酸化膜０．５μｍ厚が形成されたＳｉウ
エハ上にＥＢ蒸着法によりＴｉ膜０．２μｍ厚を形成し
た。次に、ＥＣＲ−ＣＶＤ法によりＳｉ酸化膜０．３μ
ｍ厚を形成した。このＳｉ酸化膜上にレジスト層を形
成、露光、現像を行い、パターニングを行った。このレ
ジストパターンをマスクとして、ＣＦ4 ガスを用いたＲ
ＩＥを行いＳｉ酸化膜を除去、Ｔｉ面を露出させ、レジ
スト層を剥離した。パターンは、５０×５０μｍ角で、
２００μｍ間隔のマトリックス状とした。A Ti film having a thickness of 0.2 μm was formed by an EB vapor deposition method on a Si wafer having a thermal oxide film having a thickness of 0.5 μm. Next, a Si oxide film 0.3 μm is formed by ECR-CVD
m thickness was formed. A resist layer was formed on this Si oxide film, exposed and developed, and patterned. R using CF 4 gas with this resist pattern as a mask
IE was performed to remove the Si oxide film, expose the Ti surface, and peel the resist layer. The pattern is 50 x 50 μm square,
It was in a matrix shape with 200 μm intervals.
【０２２９】作成した基板の表面を結晶成長用溶液に接
し、次いで、溶液を６０℃に加熱して放置した。１時間
後基板を取り出し観察したところ、Ｔｉ上に（１１１）
面を有する単結晶群が形成されていた。各単結晶間には
粒界が形成されていた。単結晶の平均粒径は約２μｍで
あった。膜の厚さは約１００ｎｍであった。ＳＴＭで観
察した結果、個々の単結晶表面の凹凸は、１μｍ角内で
５Åであった。核形成密度の低いＳｉ酸化膜面上には、
核の発生は認められなかった。The surface of the prepared substrate was brought into contact with the crystal growth solution, and then the solution was heated to 60 ° C. and left to stand. After 1 hour, the substrate was taken out and observed.
A single crystal group having a face was formed. Grain boundaries were formed between the single crystals. The average grain size of the single crystal was about 2 μm. The film thickness was about 100 nm. As a result of STM observation, the unevenness of the surface of each single crystal was 5Å within 1 μm square. On the Si oxide film surface with low nucleation density,
Nucleation was not observed.
【０２３０】（実施例１１）塩酸６０ｍｌと硝酸２０ｍ
ｌを混合して王水を作成した後、この溶液に金を４ｇ投
入して撹拌溶解させた。溶解後、この溶液から３０ｍｌ
分取して反応容器に入れ、ここにさらに蒸留水を３００
ｍｌ加えて撹拌し、結晶成長用溶液とした。Example 11 60 ml of hydrochloric acid and 20 m of nitric acid
l was mixed to prepare aqua regia, and 4 g of gold was added to this solution and dissolved by stirring. 30 ml from this solution after dissolution
Collect it and put it in a reaction vessel.
ml was added and stirred to obtain a crystal growth solution.
【０２３１】窒化Ｓｉ膜０．３μｍ厚で全面被覆された
Ｓｉウエハ上にレジスト層を形成、露光、現像を行いパ
ターニングを行った。このレジストパターンをマスクと
して、ＣＦ4 ガスを用いたＲＩＥを行い窒化Ｓｉ膜をエ
ッチング除去しＳｉ面を露出させ、レジスト層を剥離し
た。パターンは、５０×５０μｍ角で、２００μｍ間隔
のマトリックス状とした。A resist layer was formed, exposed and developed on the Si wafer entirely covered with the Si nitride film having a thickness of 0.3 μm to perform patterning. Using this resist pattern as a mask, RIE using CF 4 gas was carried out to remove the Si nitride film by etching to expose the Si surface, and the resist layer was peeled off. The pattern was a 50 × 50 μm square matrix with 200 μm intervals.
【０２３２】作成した基板を希フッ酸に浸漬して表面酸
化膜を除去した後、基板表面を結晶成長用溶液に接し、
次いで、溶液を４０℃に加熱した後水酸化カリウム３０
ｇを溶解した水溶液を徐々に加え、放置した。１．５時
間後基板を取り出し観察したところ、Ｓｉ上に（１１
１）面を有する単結晶群が形成されていた。各単結晶間
には粒界が形成されていた。単結晶の平均粒径は約６μ
ｍであった。膜の厚さは約２００ｎｍであった。ＳＴＭ
で観察した結果、個々の単結晶表面の凹凸は、１μｍ角
内で５Åであった。核形成密度の低い窒化Ｓｉ面上に
は、核の発生は、認められなかった。The prepared substrate was immersed in dilute hydrofluoric acid to remove the surface oxide film, and then the substrate surface was contacted with a crystal growth solution,
Then the solution is heated to 40 ° C. and then potassium hydroxide 30
An aqueous solution in which g was dissolved was gradually added and left to stand. After 1.5 hours, the substrate was taken out and observed.
1) A single crystal group having a face was formed. Grain boundaries were formed between the single crystals. Average grain size of single crystal is about 6μ
It was m. The film thickness was about 200 nm. STM
As a result of observation, the unevenness on the surface of each single crystal was 5Å within 1 μm square. No nucleation was observed on the Si-nitride surface having a low nucleation density.
【０２３３】（実施例１２）蒸留水５００ｍｌにヨウ化
カリウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器に入れ、
ここにさらに蒸留水を５００ｍｌ加えて撹拌し結晶成長
用溶液とした。(Example 12) 40 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, 100 ml of this solution was taken and placed in a reaction container.
Distilled water (500 ml) was further added and stirred to obtain a crystal growth solution.
【０２３４】熱酸化膜０．５μｍ厚が形成されたＳｉウ
エハ上にＥＢ蒸着法によりＴｉ膜５０ｎｍ厚を形成し
た。このＴｉ上にレジスト層を形成、露光、現像を行い
パターニングを行った。このレジストパターンをマスク
として、ＣＦ4 ガスを用いたリアクティブイオンエッチ
ング（ＲＩＥ）を行いＴｉをパターニングし、レジスト
層を剥離した。パターンは、１×１μｍ角で、５０μｍ
間隔のマトリックス状とした。A Ti film having a thickness of 50 nm was formed on the Si wafer having a thermal oxide film having a thickness of 0.5 μm by the EB vapor deposition method. A resist layer was formed on this Ti, exposed, and developed to perform patterning. Using this resist pattern as a mask, reactive ion etching (RIE) using CF 4 gas was performed to pattern Ti, and the resist layer was peeled off. The pattern is 1 × 1μm square and 50μm
A matrix of intervals is used.
【０２３５】作成した基板の表面を結晶成長用溶液に接
し、次いで、溶液を８０℃に加熱して放置した。５０分
後基板を取り出し観察したところ、Ｔｉ上にほぼ中心を
有する（１１１）面を有した粒径約５０μｍの単結晶か
らなる金結晶薄膜が形成出来た。各単結晶間には粒界が
形成されていた。膜の厚さは約２００ｎｍであった。Ｓ
ＴＭで観察した結果、個々の単結晶表面の凹凸は、１μ
ｍ角内で５Åであった。The surface of the prepared substrate was brought into contact with the crystal growth solution, and then the solution was heated to 80 ° C. and left to stand. After 50 minutes, the substrate was taken out and observed. As a result, a gold crystal thin film composed of a single crystal having a (111) plane having the center substantially on the Ti and a grain size of about 50 μm could be formed. Grain boundaries were formed between the single crystals. The film thickness was about 200 nm. S
As a result of observing with TM, the unevenness on the surface of each single crystal is 1 μm.
It was 5Å within m square.
【０２３６】（実施例１３）蒸留水５００ｍｌにヨウ化
カリウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器にいれ、
ここにさらに蒸留水を５００ｍｌ加えて撹拌し結晶成長
用溶液とした。Example 13 40 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved with stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, take 100 ml of this solution and put in a reaction vessel.
Distilled water (500 ml) was further added and stirred to obtain a crystal growth solution.
【０２３７】熱酸化膜０．５μｍ厚が形成されたＳｉウ
エハ上にＬＰ−ＣＶＤ法によりポリＳｉ膜（ｐ−Ｓｉ）
５０ｎｍ厚を形成した。このｐ−Ｓｉ上にレジスト層を
形成、露光、現像を行いパターニングを行った。このレ
ジストパターンをマスクとして、ＳＦ6 ガスを用いたリ
アクティブイオンエッチング（ＲＩＥ）を行いｐ−Ｓｉ
をパターニングし、レジスト層を剥離した。パターン
は、５μｍ径で、５０μｍ間隔のマトリックス状とし
た。[0237] A poly-Si film (p-Si) is formed on the Si wafer on which a thermal oxide film having a thickness of 0.5 µm is formed by LP-CVD
A thickness of 50 nm was formed. A resist layer was formed on this p-Si, exposed, and developed to perform patterning. Using this resist pattern as a mask, reactive ion etching (RIE) using SF 6 gas is performed to p-Si.
Was patterned and the resist layer was peeled off. The pattern was a matrix with a diameter of 5 μm and an interval of 50 μm.
【０２３８】作成した基板を希フッ酸に浸漬してｐ−Ｓ
ｉ上の表面酸化膜を除去した後、基板表面を結晶成長用
溶液に接し、溶液中にハイドロキノン１００ｍｇを溶解
した水溶液３０ｍｌをゆっくり加え放置した。４時間基
板を取り出し観察したところ、ｐ−Ｓｉ上にほぼ中心を
有する（１１１）面を有した粒径約５０μｍの単結晶が
形成されていた。各単結晶間には粒界が形成されてい
た。膜の厚さは約１５０ｎｍであった。ＳＴＭで観察し
た結果、個々の単結晶表面の凹凸は、１μｍ角内で５Å
であった。The prepared substrate was dipped in dilute hydrofluoric acid to obtain pS.
After removing the surface oxide film on i, the substrate surface was brought into contact with the crystal growth solution, and 30 ml of an aqueous solution in which 100 mg of hydroquinone was dissolved was slowly added and left to stand. When the substrate was taken out and observed for 4 hours, a single crystal having a (111) plane having a substantially center and a grain size of about 50 μm was formed on p-Si. Grain boundaries were formed between the single crystals. The film thickness was about 150 nm. As a result of STM observation, the unevenness of the surface of each single crystal is 5Å within 1 μm square.
Met.
【０２３９】（実施例１４）蒸留水５００ｍｌにヨウ化
アンモニウム４０ｇ及びヨウ素１０ｇを投入して撹拌溶
解させた。この溶液に金を３ｇ投入して撹拌溶解させ
た。溶解後、この溶液から１００ｍｌ分取して反応容器
にいれ、ここにさらに蒸留水を５００ｍｌ加えて撹拌し
結晶成長用溶液とした。熱酸化膜０．３μｍ厚が形成さ
れたＳｉウエハ上にレジスト層を形成、露光、現像を行
いパターニングを行った。このレジストパターンをマス
クして、ＣＦ4 ガスを用いたＲＩＥを行い熱酸化膜をエ
ッチング除去しＳｉ面を露出させ、レジスト層を剥離し
た。パターンは、５μｍ径で、１００μｍ間隔のマトリ
ックス状とした。Example 14 40 g of ammonium iodide and 10 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, 100 ml of this solution was sampled and placed in a reaction vessel, and 500 ml of distilled water was further added thereto and stirred to obtain a crystal growth solution. A resist layer was formed on a Si wafer having a thermal oxide film thickness of 0.3 μm, exposed, and developed for patterning. Using this resist pattern as a mask, RIE using CF 4 gas was performed to remove the thermal oxide film by etching to expose the Si surface, and the resist layer was peeled off. The pattern was a matrix with a diameter of 5 μm and an interval of 100 μm.
【０２４０】作成した基板を希フッ酸に浸漬して表面酸
化膜を除去した後、基板表面を結晶成長用溶液に接し、
次いで、溶液を８０℃に加熱して放置した。１時間後基
板を取り出し観察したところ、Ｓｉ径内は（１１１）面
を有した単結晶によって埋め尽くされていた。The formed substrate was immersed in dilute hydrofluoric acid to remove the surface oxide film, and then the substrate surface was contacted with a crystal growth solution,
The solution was then heated to 80 ° C and left to stand. When the substrate was taken out and observed after 1 hour, the inside of the Si diameter was found to be filled with a single crystal having a (111) plane.
【０２４１】さらに成長を続けたところ、金単結晶どう
しが衝突し、各々のＳｉ面のほぼ中間に粒界が形成され
た。膜の厚さは約０．４μｍであった。When the growth was further continued, the gold single crystals collided with each other, and a grain boundary was formed almost in the middle of each Si surface. The thickness of the film was about 0.4 μm.
【０２４２】（実施例１５）蒸留水５００ｍｌにヨウ化
カリウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器にいれ、
ここにさらに蒸留水を５００ｍｌ加えて撹拌し結晶成長
用溶液とした。Example 15 To 500 ml of distilled water, 40 g of potassium iodide and 6 g of iodine were added and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, take 100 ml of this solution and put in a reaction vessel.
Distilled water (500 ml) was further added and stirred to obtain a crystal growth solution.
【０２４３】熱酸化膜０．５μｍ厚が形成されたＳｉウ
エハ上にＥＢ蒸着法によりＴｉ膜０．２μｍ厚を形成し
た。次に、ＥＣＲ−ＣＶＤ法によりＳｉ酸化膜０．３μ
ｍ厚を形成した。このＳｉ酸化膜上にレジスト層を形
成、露光、現像を行い、パターニングを行った。このレ
ジストパターンをマスクとして、ＣＦ4 ガスを用いたＲ
ＩＥを行いＳｉ酸化膜を除去、Ｔｉ面を露出させ、レジ
スト層を剥離した。パターンは、１μｍ径で、５０μｍ
間隔のマトリックス状とした。A Ti film having a thickness of 0.2 μm was formed on the Si wafer having a thermal oxide film having a thickness of 0.5 μm by the EB vapor deposition method. Next, the Si oxide film 0.3 μm is formed by the ECR-CVD method.
m thickness was formed. A resist layer was formed on this Si oxide film, exposed and developed, and patterned. R using CF 4 gas with this resist pattern as a mask
IE was performed to remove the Si oxide film, expose the Ti surface, and peel the resist layer. The pattern is 1 μm diameter and 50 μm
A matrix of intervals is used.
【０２４４】作成した基板の表面を結晶成長用溶液に接
し、次いで、溶液を６０℃に加熱して放置した。１時間
後基板を取り出し観察したところ、Ｔｉ径内は（１１
１）面を有した単結晶によって埋め尽くされていた。膜
の厚さは約１００ｎｍであった。Ｓｉ酸化膜面上には、
核の発生は、認められなかった。The surface of the prepared substrate was brought into contact with the crystal growth solution, and then the solution was heated to 60 ° C. and left to stand. After 1 hour, the substrate was taken out and observed.
1) It was completely filled with a single crystal having a face. The film thickness was about 100 nm. On the Si oxide film surface,
Nucleation was not observed.
【０２４５】（実施例１６）蒸留水５００ｍｌにヨウ化
カリウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器にいれ、
ここにさらに蒸留水を５００ｍｌ加えて撹拌し結晶成長
用溶液とした。(Example 16) 40 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, take 100 ml of this solution and put in a reaction vessel.
Distilled water (500 ml) was further added and stirred to obtain a crystal growth solution.
【０２４６】次に、この溶液をホットプレートにより加
熱し８０℃にした。溶液色が褐色から淡黄色に変化した
ところで、基板を溶液に接触させた。基板は厚さ５００
０Åの熱酸化膜によって被覆されたシリコーンウエハ中
に、イオン注入法により金元素を直径０．５μｍ程度の
スポツトを３０μｍ間隔でマトリックス状に形成したも
のを用いた。イオン注入はＦＩＢ装置（ＪＩＢＬ−１０
０Ａ：ＪＥＯＬ製）でイオン電流値：３０ｐＡ、イオン
注入量：５Ｘ１０１５ｉｏｎｓ／ｃｍ２の条件で行っ
た。１時間後、基板板を取り出し観察したところ、Ａｕ
を注入した点をほぼ中心とした（１１１）面を有する粒
径約３０μｍの単結晶からなる金結晶が形成出来た。各
単結晶間には粒界が形成されていた。膜の厚さは約２０
０ｎｍであった。ＳＴＭで観察した結果、個々の単結晶
表面の凹凸は、１μｍ角内で５Åであった。Next, this solution was heated to 80 ° C. by a hot plate. When the solution color changed from brown to pale yellow, the substrate was brought into contact with the solution. The thickness of the substrate is 500
A silicon wafer covered with a 0Å thermal oxide film was used in which spots having a diameter of about 0.5 μm were formed in a matrix form at intervals of 30 μm by an ion implantation method. Ion implantation is performed by a FIB device (JIBL-10
OA: manufactured by JEOL) under the conditions of ion current value: 30 pA and ion implantation amount: 5 × 1015 ions / cm2. After 1 hour, the substrate plate was taken out and observed.
A gold crystal consisting of a single crystal having a (111) plane centered on the point where was implanted and having a grain size of about 30 μm could be formed. Grain boundaries were formed between the single crystals. The thickness of the film is about 20
It was 0 nm. As a result of STM observation, the unevenness of the surface of each single crystal was 5Å within 1 μm square.
【０２４７】（実施例１７）蒸留水５００ｍｌにヨウ化
カリウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器にいれ、
ここにさらに蒸留水を５００ｍｌ加えて撹拌し結晶成長
用溶液とした。(Example 17) 40 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, take 100 ml of this solution and put in a reaction vessel.
Distilled water (500 ml) was further added and stirred to obtain a crystal growth solution.
【０２４８】次に、この溶液をホットプレートにより加
熱し８０℃にした。溶液色が褐色から淡黄色に変化した
ところで、基板を溶液に接触させた。基板はＳｉウエハ
上に、走査型トンネル顕微鏡（ＳＴＭ）によりＡｕ元素
を直径２０ｎｍ程度、厚さ８ｎｍ程度のスポットとして
５μｍ間隔でマトリックス状に形成したものを用いた。Next, this solution was heated to 80 ° C. by a hot plate. When the solution color changed from brown to pale yellow, the substrate was brought into contact with the solution. The substrate used was a Si wafer on which an Au element was formed in a matrix at intervals of 5 μm as spots having a diameter of about 20 nm and a thickness of about 8 nm by a scanning tunneling microscope (STM).
【０２４９】ＳＴＭによるＡｕパターン形成は、十分導
電性を有するＳｉウエハを希フッ酸に浸漬して表面酸化
膜を除去した後、パルス印加電圧３．５Ｖ、パルスタイ
ム１μｓｅｃの条件で行った。次に、作成して基板を大
気中３日間放置してＳｉ上に表面酸化膜を形成させて結
晶成長用基板とした。The Au pattern formation by STM was performed under the conditions of a pulse applied voltage of 3.5 V and a pulse time of 1 μsec after a Si wafer having sufficient conductivity was immersed in dilute hydrofluoric acid to remove the surface oxide film. Next, the created substrate was left in the atmosphere for 3 days to form a surface oxide film on Si, and used as a substrate for crystal growth.
【０２５０】１時間後、基板板を取り出し観察したとこ
ろ、Ａｕを注入した点をほぼ中心とした（１１１）面を
有する粒径約５μｍの単結晶からなる金結晶が形成出来
た。各単結晶間には粒界が形成されていた。膜の厚さは
約１００ｎｍであった。ＳＴＭで観察した結果、個々の
単結晶表面の凹凸は、１μｍ角内で５Åであった。After 1 hour, the substrate plate was taken out and observed. As a result, a gold crystal composed of a single crystal having a (111) plane with the center of the point where Au was injected and having a grain size of about 5 μm was formed. Grain boundaries were formed between the single crystals. The film thickness was about 100 nm. As a result of STM observation, the unevenness of the surface of each single crystal was 5Å within 1 μm square.
【０２５１】（実施例１８）塩酸６０ｍｌと硝酸２０ｍ
ｌを混合して王水を作成した後、この溶液に金を４ｇ投
入して撹拌溶解した。溶解後、この溶液から３０ｍｌ分
取して反応容器にいれ、ここにさらに蒸留水を３００ｍ
ｌ加えて撹拌し、結晶成長用溶液とした。(Example 18) 60 ml of hydrochloric acid and 20 m of nitric acid
l was mixed to prepare aqua regia, and 4 g of gold was added to this solution and dissolved by stirring. After dissolution, a 30 ml aliquot of this solution was placed in a reaction vessel, and distilled water was further added thereto in an amount of 300 m.
1 and then stirred to obtain a crystal growth solution.
【０２５２】０．５μｍ厚の窒化Ｓｉ膜で被覆されたＳ
ｉウエハ上にレジスト層を形成、露光、現像を行いパタ
ーニングを行った。このレジストパターンをマスクとし
て、ＣＦ4 ガスを用いたＲＩＥを行い窒化Ｓｉ膜をエッ
チング除去しＳｉ面を露出させ、レジスト層を剥離し
た。パターンは、３μｍ径で、１００μｍ間隔のマトリ
ックス状とした。S coated with 0.5 μm thick Si nitride film
A resist layer was formed on the i-wafer, exposed, and developed to perform patterning. Using this resist pattern as a mask, RIE using CF 4 gas was carried out to remove the Si nitride film by etching to expose the Si surface, and the resist layer was peeled off. The pattern was a matrix having a diameter of 3 μm and spaced at 100 μm intervals.
【０２５３】次に、この基板を結晶成長用溶液と接触さ
せた後、水酸化ナトリウム（ＮａＯＨ）を３０ｇを溶解
した水溶液を徐々に加え、溶液を４０℃で放置した。１
時間後基板を取り出し観察したところ、Ｓｉ径内は（１
１１）面を有する単結晶によって埋め尽くされていた。
核形成密度の低い窒化Ｓｉ膜面上には、核の発生は認め
られなかった。Next, after the substrate was brought into contact with the crystal growth solution, an aqueous solution in which 30 g of sodium hydroxide (NaOH) was dissolved was gradually added, and the solution was allowed to stand at 40 ° C. 1
After a lapse of time, the substrate was taken out and observed.
11) It was completely filled with a single crystal having a face.
Nucleation was not observed on the surface of the silicon nitride film having a low nucleation density.
【０２５４】（実施例１９）蒸留水５００ｍｌにヨウ化
カリウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を２．５ｇ投入して撹拌溶解させた。
溶解後、この溶液から１００ｍｌ分取して反応容器にい
れ、ここにさらに蒸留水を５００ｍｌ及びフッ化水素酸
０．５ｍｌを加えて撹拌した。熱酸化膜１μｍ厚が形成
されたＳｉウエハ基板の表面を溶液に接し、次いで、溶
液を８０℃に加熱して放置した。２時間後基板を取り出
し観察したところ、熱酸化膜上に金単結晶群が形成され
ていた。各単結晶間には粒界が形成されており、平均粒
径は１．５６ｍｍで約２０μｍの膜厚を有していた。電
子線チャネリングコントラスト、電子線チャネリングパ
ターン及びＸ線回折分析の結果、この単結晶群は（１１
１）面を有すると共に、個々の単結晶はほぼ無欠陥であ
ることがわかった。また走査型トンネル顕微鏡で結晶表
面を観察した結果、個々の単結晶表面の凹凸は、５μｍ
□内で５Åであった。Example 19 40 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 2.5 g of gold was added to this solution and dissolved by stirring.
After dissolution, 100 ml of this solution was sampled and placed in a reaction vessel, to which 500 ml of distilled water and 0.5 ml of hydrofluoric acid were added and stirred. The surface of the Si wafer substrate having a thermal oxide film of 1 μm thickness was brought into contact with the solution, and then the solution was heated to 80 ° C. and left to stand. When the substrate was taken out and observed after 2 hours, a gold single crystal group was formed on the thermal oxide film. Grain boundaries were formed between the single crystals, the average grain size was 1.56 mm, and the film thickness was about 20 μm. As a result of electron beam channeling contrast, electron beam channeling pattern and X-ray diffraction analysis, this single crystal group was (11
It was found that each single crystal has a 1) plane and is almost defect-free. Moreover, as a result of observing the crystal surface with a scanning tunneling microscope, the unevenness on the surface of each single crystal is 5 μm.
It was 5Å in □.
【０２５５】（実施例２０）蒸留水５００ｍｌにヨウ化
カリウム４ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器に入れ、
ここにさらに蒸留水を５００ｍｌ及びフッ化水素酸０．
３ｍｌを加えて撹拌した。次いで、熱酸化膜１μｍ厚が
形成されたＳｉウエハ基板の表面を溶液に接しこの溶液
中にハイドロキノン１００ｍｇが溶解した水溶液５０ｍ
ｌを徐々に加え、室温のまま放置した。３時間後基板を
取り出し観察したところ、熱酸化膜上に平均粒径は６５
０μｍであり、膜厚は約６μｍの金単結晶群薄膜が形成
されていた。電子線チャネリングコントラスト、電子線
チャネリングパターン及びＸ線回折分析の結果、この単
結晶群は（１１１）面を有すると共に、個々の単結晶は
ほぼ無欠陥であることがわかった。また走査型トンネル
顕微鏡で結晶表面を観察した結果、個々の単結晶表面の
凹凸は、５μｍ□内で５Åであった。Example 20 4 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, 100 ml of this solution was taken and placed in a reaction container.
500 ml of distilled water and hydrofluoric acid of 0.1.
3 ml was added and stirred. Then, the surface of the Si wafer substrate on which the thermal oxide film having a thickness of 1 μm was formed was brought into contact with a solution, and 50 m of an aqueous solution in which 100 mg of hydroquinone was dissolved in the solution.
1 was gradually added, and the mixture was left at room temperature. After 3 hours, the substrate was taken out and observed, and it was found that the average grain size was 65 on the thermal oxide film.
A gold single crystal group thin film having a thickness of 0 μm and a thickness of about 6 μm was formed. As a result of electron beam channeling contrast, electron beam channeling pattern and X-ray diffraction analysis, it was found that this single crystal group has a (111) plane and each single crystal is almost defect-free. As a result of observing the crystal surface with a scanning tunneling microscope, the irregularities on the surface of each single crystal were 5Å within 5 μm □.
【０２５６】（実施例２１）蒸留水５００ｍｌにヨウ化
カリウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を２．５ｇ投入して撹拌溶解させた。
溶解後、この溶液から１００ｍｌ分取して反応容器にい
れ、ここにさらに蒸留水を５００ｍｌ及びフッ化水素酸
１ｍｌを加えて撹拌した。シリコン窒化膜０．５μｍ厚
が形成されたＳｉウエハ基板の表面を溶液に接し、次い
で、溶液を７０℃に加熱して放置した。２時間後基板を
取り出し観察したところ、シリコン窒化膜上に金単結晶
群が形成されていた。各単結晶間には粒界が形成されて
おり、平均粒径は８００μｍで約１０μｍの膜厚を有し
ていた。電子線チャネリングコントラスト、電子線チャ
ネリングパターン及びＸ線回折分析の結果、この単結晶
群は（１１１）面を有すると共に、個々の単結晶はほぼ
無欠陥であることがわかった。また走査型トンネル顕微
鏡で結晶表面を観察した結果、個々の単結晶表面の凹凸
は、５μｍ□内で５Åであった。Example 21 40 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 2.5 g of gold was added to this solution and dissolved by stirring.
After dissolution, 100 ml of this solution was sampled and placed in a reaction vessel, to which 500 ml of distilled water and 1 ml of hydrofluoric acid were added and stirred. The surface of a Si wafer substrate having a silicon nitride film of 0.5 μm thickness was brought into contact with the solution, and then the solution was heated to 70 ° C. and left to stand. After 2 hours, the substrate was taken out and observed, whereupon a gold single crystal group was formed on the silicon nitride film. Grain boundaries were formed between the single crystals, the average grain size was 800 μm, and the film thickness was about 10 μm. As a result of electron beam channeling contrast, electron beam channeling pattern and X-ray diffraction analysis, it was found that this single crystal group has a (111) plane and each single crystal is almost defect-free. As a result of observing the crystal surface with a scanning tunneling microscope, the irregularities on the surface of each single crystal were 5Å within 5 μm □.
【０２５７】次に、単結晶群上にレジストパターン形成
を形成し、Ａｒガスを用いたイオンエッチングにより、
３μｍ幅の金単結晶群配線をうず巻き状に形成した。Next, a resist pattern is formed on the single crystal group, and ion etching is carried out using Ar gas.
A gold single crystal group wiring having a width of 3 μm was formed in a spiral shape.
【０２５８】この金結晶配線の電気抵抗を測定したとこ
ろ、２．３×１０-6ｃｍ・Ωという十分に低い値が得ら
れた。When the electric resistance of this gold crystal wiring was measured, a sufficiently low value of 2.3 × 10 −6 cm · Ω was obtained.
【０２５９】（実施例２２）蒸留水５００ｍｌにヨウ化
カリウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器にいれ、
ここにさらに蒸留水を５００ｍｌ及びフッ化水素酸（４
６％）０．５ｍｌを加えて撹拌し結晶成長用溶液とし
た。Example 22 40 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, take 100 ml of this solution and put in a reaction vessel.
500 ml of distilled water and hydrofluoric acid (4
6%) 0.5 ml was added and stirred to obtain a crystal growth solution.
【０２６０】Ｓｉウエハを熱酸化処理し、表面にＳｉＯ
2 の熱酸化膜を形成した。次に、ＬＰ−ＣＶＤ法によ
り、ポリＳｉ（Ｐ−Ｓｉ）膜を全面に０．１μｍ厚形成
した。このｐ−Ｓｉ上にレジスト層を形成、露光、現像
を行いパターニングを行った。このレジストパターンを
マスクとして、ＳＦ6 ガスを用いたリアクティブイオン
エッチング（ＲＩＥ）を行いｐ−Ｓｉをパターニング
し、レジスト層を剥離した。パターンは、５０μｍ丸
で、１．５ｍｍ間隔のマトリックス状とした。[0260] The Si wafer is subjected to thermal oxidation treatment, and SiO
A thermal oxide film of 2 was formed. Next, a poly-Si (P-Si) film was formed over the entire surface to a thickness of 0.1 μm by the LP-CVD method. A resist layer was formed on this p-Si, exposed, and developed to perform patterning. Using this resist pattern as a mask, reactive ion etching (RIE) using SF 6 gas was performed to pattern p-Si, and the resist layer was peeled off. The pattern was a matrix of 50 μm circles with 1.5 mm intervals.
【０２６１】作成した基板の表面を結晶成長用溶液に接
し、次いで、溶液を６０℃に加熱して放置した。１時間
後基板を取り出し観察したところ、ｐ−Ｓｉ上に単結晶
群が形成されていた。各単結晶間には粒界が形成されて
いた。単結晶の平均粒径は約２５μｍ、膜の厚さは約１
００ｎｍであった。電子線チャネリングコントラスト、
電子線チャネリングパターン及びＸ線回折分析の結果、
この単結晶群は（１１１）面を有すると共に、個々の単
結晶はほぼ無欠陥であることがわかった。また走査型ト
ンネル顕微鏡で結晶表面を観察した結果、個々の単結晶
表面の凹凸は、５μｍ角内で５Åであった。核形成密度
の小さいＳｉＯ2 面上には、核の発生は認められなかっ
た。The surface of the prepared substrate was brought into contact with the crystal growth solution, and then the solution was heated to 60 ° C. and left to stand. When the substrate was taken out and observed after 1 hour, a single crystal group was formed on p-Si. Grain boundaries were formed between the single crystals. The average grain size of the single crystal is about 25 μm, and the thickness of the film is about 1
It was 00 nm. Electron beam channeling contrast,
As a result of electron beam channeling pattern and X-ray diffraction analysis,
It was found that this single crystal group has a (111) plane and that each single crystal is almost defect-free. As a result of observing the crystal surface with a scanning tunneling microscope, the unevenness of the surface of each single crystal was 5Å within a square of 5 μm. Nucleation was not observed on the SiO 2 surface having a low nucleation density.
【０２６２】蒸留水５００ｍｌにヨウ化カリウム４０ｇ
及びヨウ素６ｇを投入して撹拌溶解させた。この溶液に
金を３ｇ投入して撹拌溶解させた。溶解後、この溶液か
ら１００ｍｌ分取して反応容器にいれ、ここにさらに蒸
留水５００ｍｌ及びフッ化水素酸（４６％）０．５ｍｌ
を加えて撹拌し結晶成長用溶液とした。40 g of potassium iodide in 500 ml of distilled water
And 6 g of iodine were added and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, 100 ml of this solution was taken and placed in a reaction vessel, and 500 ml of distilled water and 0.5 ml of hydrofluoric acid (46%) were added to the reaction vessel.
Was added and stirred to obtain a crystal growth solution.
【０２６３】熱酸化膜１μｍ厚が形成されたＳｉウエハ
の熱酸化膜上にレジスト層を形成、露光、現像を行いパ
ターニングを行った。このレジストパターンをマスクと
して、ＣＦ4 ガスを用いたリアクティブイオンエッチン
グ（ＲＩＥ）を行い熱酸化膜をパターニングし、レジス
ト層を剥離した。パターンは、１００μｍ角で、１．２
ｍｍ間隔のマトリックス状とした。A resist layer was formed on the thermal oxide film of the Si wafer on which the thermal oxide film 1 μm thick was formed, and exposure and development were performed for patterning. Using this resist pattern as a mask, reactive ion etching (RIE) using CF 4 gas was performed to pattern the thermal oxide film, and the resist layer was peeled off. The pattern is 100 μm square and 1.2
It was in a matrix shape with mm intervals.
【０２６４】作成した基板の表面を結晶成長用溶液に接
し、溶液中にハイドロキノン１００ｍｇを溶解した水溶
液３０ｍｌをゆっくり加え放置した。３時間後基板を取
り出し観察したところ、Ｓｉホール内に単結晶群が形成
されていた。各単結晶間には粒界が形成されていた。単
結晶の平均粒径は約１５μｍであった。膜の厚さは約３
００ｎｍであった。電子線チャネリングコントラスト、
電子線チャネリングパターン及びＸ線回折分析の結果、
この単結晶群は（１１１）面を有すると共に、個々の単
結晶はほぼ無欠陥であることがわかった。また走査型ト
ンネル顕微鏡で結晶表面を観察した結果、個々の単結晶
表面の凹凸は、５μｍ角内で５Åであった。核形成密度
の低いＳｉＯ2 面上には、核の発生は認められなかっ
た。The surface of the prepared substrate was brought into contact with the crystal growth solution, and 30 ml of an aqueous solution in which 100 mg of hydroquinone was dissolved was slowly added to the solution and allowed to stand. When the substrate was taken out and observed after 3 hours, a single crystal group was formed in the Si hole. Grain boundaries were formed between the single crystals. The average grain size of the single crystal was about 15 μm. The thickness of the film is about 3
It was 00 nm. Electron beam channeling contrast,
As a result of electron beam channeling pattern and X-ray diffraction analysis,
It was found that this single crystal group has a (111) plane and that each single crystal is almost defect-free. As a result of observing the crystal surface with a scanning tunneling microscope, the unevenness of the surface of each single crystal was 5Å within a square of 5 μm. No nucleation was observed on the SiO 2 surface having a low nucleation density.
【０２６５】（実施例２３）蒸留水５００ｍｌにヨウ化
カリウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器にいれ、
ここにさらに蒸留水を５００ｍｌ及びフッ化水素酸（４
６％）０．５ｍｌを加えて撹拌し結晶成長用溶液とし
た。Example 23 To 500 ml of distilled water, 40 g of potassium iodide and 6 g of iodine were put and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, take 100 ml of this solution and put in a reaction vessel.
500 ml of distilled water and hydrofluoric acid (4
6%) 0.5 ml was added and stirred to obtain a crystal growth solution.
【０２６６】ＬＰ−ＣＶＤ法によりＳｉウエハ上に窒化
Ｓｉ膜を全面に１μｍ厚形成した。この窒化Ｓｉ上にレ
ジスト層を形成、露光、現像を行いパターニングを行っ
た。このレジストパターンをマスクとして、ＳＦ6 ガス
を用いたリアクティブイオンエッチング（ＲＩＥ）を行
い窒化ＳｉをパターニングしてＳｉ面を露出させた。次
いでレジスト層を剥離した。パターンは、１００μｍ丸
で、１．７ｍｍ間隔のマトリックス状とした。A 1-μm thick Si nitride film was formed on the entire surface of the Si wafer by the LP-CVD method. A resist layer was formed on this Si nitride, exposed, and developed to perform patterning. Using this resist pattern as a mask, reactive ion etching (RIE) using SF 6 gas was performed to pattern Si nitride to expose the Si surface. Then, the resist layer was peeled off. The pattern was 100 μm round and was in a matrix shape with 1.7 mm intervals.
【０２６７】作成した基板の表面を結晶成長用溶液に接
し、次いで、溶液を８０℃に加熱して放置した。２時間
後基板を取り出し観察したところ、Ｓｉ上に単結晶群が
形成されていた。各単結晶間には粒界が形成されてい
た。単結晶の平均粒径は約２０μｍ、膜の厚さは約１０
０ｎｍであった。電子線チャネリングコントラスト、電
子線チャネリングパターン及びＸ線回折分析の結果、こ
の単結晶群は（１１１）面を有すると共に、個々の単結
晶はほぼ無欠陥であることがわかった。また走査型トン
ネル顕微鏡で結晶表面を観察した結果、個々の単結晶表
面の凹凸は、５μｍ角内で５Åであった。核形成密度の
低い窒化Ｓｉ面上には、核の発生は認められなかった。The surface of the prepared substrate was brought into contact with the crystal growth solution, and then the solution was heated to 80 ° C. and left to stand. After 2 hours, the substrate was taken out and observed, whereupon a single crystal group was formed on Si. Grain boundaries were formed between the single crystals. The average grain size of the single crystal is about 20 μm, and the film thickness is about 10
It was 0 nm. As a result of electron beam channeling contrast, electron beam channeling pattern and X-ray diffraction analysis, it was found that this single crystal group has a (111) plane and each single crystal is almost defect-free. As a result of observing the crystal surface with a scanning tunneling microscope, the unevenness of the surface of each single crystal was 5Å within a square of 5 μm. No nucleation was observed on the Si-nitride surface having a low nucleation density.
【０２６８】（実施例２４）蒸留水５００ｍｌにヨウ化
カリウム４０ｇ及びヨウ素６ｇを投入して撹拌溶解させ
た。この溶液に金２．４ｇを投入して撹拌溶解させた。
溶解後、この溶液から１００ｍｌ分取して反応容器に入
れ、ここにさらに蒸留水を５００ｍｌ及びフッ化水素酸
（４６％）を０．３ｍｌを加えて撹拌し結晶成長用溶液
とした。(Example 24) 40 g of potassium iodide and 6 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 2.4 g of gold was added to this solution and dissolved by stirring.
After dissolution, 100 ml of this solution was sampled and placed in a reaction vessel, to which 500 ml of distilled water and 0.3 ml of hydrofluoric acid (46%) were further added and stirred to obtain a crystal growth solution.
【０２６９】Ｓｉウエハを熱酸化処理し、表面にＳｉＯ
2 の熱酸化膜を形成した。次にＬＰ−ＣＶＤ法により、
ポリＳｉ（ｐ−Ｓｉ）膜を熱酸化膜上に１μｍ厚形成し
た。このｐ−Ｓｉ上にレジスト層を形成、露光、現像を
行いレジストパターンを形成した。このレジストパター
ンをマスクとしてＳＦ6 ガスを用いたリアクティブイオ
ンエッチング（ＲＩＥ）を行いｐ−Ｓｉをパターニング
し、レジスト層を剥離した。パターンは、８μｍｍ丸
で、１．０ｍｍ間隔のマトリックス状とした。A Si wafer is subjected to thermal oxidation treatment, and SiO 2 is formed on the surface.
A thermal oxide film of 2 was formed. Next, by the LP-CVD method,
A poly Si (p-Si) film was formed on the thermal oxide film to a thickness of 1 μm. A resist layer was formed on this p-Si, exposed and developed to form a resist pattern. Using this resist pattern as a mask, reactive ion etching (RIE) using SF 6 gas was performed to pattern p-Si, and the resist layer was peeled off. The pattern was a 8 μm circle and was in the form of a matrix with 1.0 mm intervals.
【０２７０】作成した基板の表面を結晶成長用溶液に接
し、次いで、溶液を８０℃に加熱して放置した。２時間
後基板を取り出し観察したところ、ｐ−Ｓｉ上にほぼ中
心を有する粒径約１ｍｍの単結晶からなる金結晶薄膜が
形成できた。各単結晶間には粒界が形成されていた。膜
の厚さは約２０μｍであった。電子線チャネリングコン
トラスト、電子線チャネリングパターン及びＸ線回折分
析の結果、この単結晶群は（１１１）面を有すると共に
個々の単結晶はほぼ無欠陥であることがわかった。ま
た、走査型トンネル顕微鏡で結晶表面を観察した結果、
個々の単結晶表面の凹凸は、５μｍ角内で５Åであっ
た。核形成密度の小さいＳｉＯ2 面上には核の発生は認
められなかった。The surface of the prepared substrate was brought into contact with the crystal growth solution, and then the solution was heated to 80 ° C. and left to stand. After 2 hours, the substrate was taken out and observed. As a result, a gold crystal thin film composed of a single crystal having a grain size of about 1 mm and having a substantially center was formed on p-Si. Grain boundaries were formed between the single crystals. The thickness of the film was about 20 μm. As a result of electron beam channeling contrast, electron beam channeling pattern and X-ray diffraction analysis, it was found that this single crystal group has a (111) plane and each single crystal is almost defect-free. In addition, as a result of observing the crystal surface with a scanning tunneling microscope,
The unevenness on the surface of each single crystal was 5Å within a 5 μm square. No nucleation was observed on the SiO 2 surface having a low nucleation density.
【０２７１】（実施例２５）蒸留水５００ｍｌにヨウ化
カリウム５０ｇ及びヨウ素７ｇを投入して撹拌溶解させ
た。この溶液に金を３ｇ投入して撹拌溶解させた。溶解
後、この溶液から１００ｍｌ分取して反応容器にいれ、
ここにさらに蒸留水を５００ｍｌ及びフッ化水素酸（４
６％）を０．４ｍｌを加えて撹拌し結晶成長用溶液とし
た。(Example 25) 50 g of potassium iodide and 7 g of iodine were put into 500 ml of distilled water and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, take 100 ml of this solution and put in a reaction vessel.
500 ml of distilled water and hydrofluoric acid (4
0.4% of 6%) was added and stirred to obtain a crystal growth solution.
【０２７２】熱酸化膜５０ｎｍ厚が形成されたＳｉウエ
ハの熱酸化膜上にレジスト層を形成、露光、現像を行い
レジストパターンを形成した。このレジストパターンを
マスクとして、ＳＦ6 ガスを用いたリアクティブイオン
エッチング（ＲＩＥ）を行い熱酸化膜をパターニング
し、レジスト層を剥離した。パターンは、５μｍ径のＳ
ｉ面を、０．５ｍｍ間隔のマトリックス状に配した。A resist layer was formed on the thermal oxide film of the Si wafer having a thickness of 50 nm, and exposed and developed to form a resist pattern. Using this resist pattern as a mask, reactive ion etching (RIE) using SF 6 gas was performed to pattern the thermal oxide film, and the resist layer was peeled off. The pattern is 5 μm diameter S
The i-plane was arranged in a matrix with 0.5 mm intervals.
【０２７３】作成した基板の表面を結晶成長用溶液に接
し、溶液中に亜硫酸ソーダ１０ｍｇを溶解した水溶液３
０ｍｌをゆっくり加え放置した。４時間後基板を取り出
し観察したところ、Ｓｉ上にほぼ中心を有した０．５ｍ
ｍ径の単結晶群が形成されていた。各単結晶間には粒界
が形成されていた。膜の厚さは約１０μｍであった。電
子線チャネリングコントラスト、電子線チャネリングパ
ターン及びＸ線回折分析の結果、この単結晶群は（１１
１）面を有すると共に個々の単結晶はほぼ無欠陥である
ことがわかった。また、走査型トンネル顕微鏡で結晶表
面を観察した結果、個々の単結晶表面の凹凸は、５μｍ
角内で５Åであった。核形成密度の小さいＳｉＯ2 面上
には核の発生は認められなかった。The surface of the prepared substrate was brought into contact with a crystal growth solution, and an aqueous solution 3 in which 10 mg of sodium sulfite was dissolved in the solution.
0 ml was slowly added and left to stand. After 4 hours, the substrate was taken out and observed. As a result, it was found that 0.5 m
A single crystal group of m diameter was formed. Grain boundaries were formed between the single crystals. The thickness of the film was about 10 μm. As a result of electron beam channeling contrast, electron beam channeling pattern and X-ray diffraction analysis, this single crystal group was (11
It was found that each single crystal had a 1) plane and was almost defect-free. In addition, as a result of observing the crystal surface with a scanning tunneling microscope, unevenness on the surface of each single crystal is 5 μm
It was 5Å within the corner. No nucleation was observed on the SiO 2 surface having a low nucleation density.
【０２７４】（実施例２６）蒸留水５００ｍｌにヨウ化
アンモニウム４０ｇ及びヨウ素１０ｇを投入して撹拌溶
解させた。この溶液に金を３ｇ投入して撹拌溶解させ
た。溶解後、この溶液から１００ｍｌ分取して反応容器
にいれ、ここにさらに蒸留水を５００ｍｌ及びフッ化水
素酸（４６％）を０．５ｍｌ加えて撹拌し結晶成長用溶
液とした。Example 26 To 500 ml of distilled water, 40 g of ammonium iodide and 10 g of iodine were added and dissolved by stirring. 3 g of gold was added to this solution and dissolved by stirring. After dissolution, 100 ml of this solution was taken and placed in a reaction vessel, and 500 ml of distilled water and 0.5 ml of hydrofluoric acid (46%) were further added and stirred to obtain a crystal growth solution.
【０２７５】ＬＰ−ＣＶＤ法によりＳｉウエハ上に窒化
Ｓｉ膜を全面に１μｍ厚形成した。この窒化Ｓｉ上にレ
ジスト層を形成、露光、現像を行いレジストパターンを
形成した。このレジストパターンをマスクとして、ＳＦ
6 ガスを用いたＲＩＥを行い窒化Ｓｉ膜をエッチング除
去しＳｉ面を露出させ、レジスト層を剥離した。パター
ンは、１０μｍ径で、１．５ｍｍ間隔のマトリックス状
とした。A 1-μm thick Si nitride film was formed on the entire surface of the Si wafer by the LP-CVD method. A resist layer was formed on the silicon nitride, exposed and developed to form a resist pattern. SF using this resist pattern as a mask
RIE using 6 gas was performed to remove the Si nitride film by etching to expose the Si surface, and the resist layer was peeled off. The pattern was a matrix with a diameter of 10 μm and a space of 1.5 mm.
【０２７６】作成した基板の表面を結晶成長用溶液に接
し、次いで、溶液を８０℃に加熱して放置した。３０分
後基板を取り出し観察したところ、Ｓｉ径内は（１１
１）面を有した単結晶によって埋め尽くされていた。膜
の厚さは約１μｍであった。窒化Ｓｉ面上には、核の発
生は、認められなかった。The surface of the formed substrate was brought into contact with the crystal growth solution, and then the solution was heated to 80 ° C. and left to stand. After 30 minutes, the substrate was taken out and observed.
1) It was completely filled with a single crystal having a face. The thickness of the film was about 1 μm. No nucleation was observed on the Si nitride surface.
【０２７７】電子線チャネリングコントラスト、電子線
チャネリングパターン及びＸ線回折分析の結果、この単
結晶群は（１１１）面を有すると共に個々の単結晶はほ
ぼ無欠陥であることがわかった。また、走査型トンネル
顕微鏡で結晶表面を観察した結果、個々の単結晶表面の
凹凸は、５μｍ角内で５Åであった。As a result of electron beam channeling contrast, electron beam channeling pattern and X-ray diffraction analysis, it was found that this single crystal group has a (111) plane and each single crystal is almost defect-free. As a result of observing the crystal surface with a scanning tunneling microscope, the irregularities on the surface of each single crystal were 5Å within a 5 μm square.
【０２７８】[0278]
【表１】 [Table 1]
【０２７９】[0279]
【表２】 [Table 2]
【０２８０】[0280]
【発明の効果】本発明によれば、金錯体分解処理するこ
とにより、溶液中の金を過飽和状態に移行させること
で、特別な装置は一切必要とせず、しかも、常圧、常温
に近い温度で金結晶薄膜を形成することができる。EFFECTS OF THE INVENTION According to the present invention, a gold complex is decomposed to bring gold in a solution into a supersaturated state, so that no special device is required, and the atmospheric pressure and the temperature close to room temperature are used. Thus, a gold crystal thin film can be formed.
【０２８１】さらに、本発明によれば、基板上に選択的
に金結晶を形成することができる。Further, according to the present invention, the gold crystal can be selectively formed on the substrate.
【０２８２】成長系の溶液種を選択することで極めて平
滑な表面を有する単結晶からなる金結晶薄膜を得ること
ができる。A gold crystal thin film made of a single crystal having an extremely smooth surface can be obtained by selecting the growth type solution species.
【０２８３】結晶粒径は、基板の表面材料及び金錯体の
種類あるいは、基板材料に作用するエッチング種の濃度
を制御することによりコントロールすることができる。The crystal grain size can be controlled by controlling the types of the surface material of the substrate and the gold complex, or the concentrations of the etching species that act on the substrate material.
【０２８４】そして、本発明の方法によって得られる金
結晶薄膜は、（１１１）に配向制御される特徴を有す
る。この為、横方向の成長レートが極めて高く、大粒径
の単結晶であっても、且つ、薄く形成することができ
る。また、得られた金結晶薄膜上に圧電体膜などを積層
させる際、（１１１）に方位継承させることができる。The gold crystal thin film obtained by the method of the present invention has a feature of (111) orientation control. Therefore, the lateral growth rate is extremely high, and even a single crystal having a large grain size can be formed thin. Further, when a piezoelectric film or the like is laminated on the obtained gold crystal thin film, the (111) orientation can be inherited.
【０２８５】本発明によって得られる金結晶膜は、耐エ
レクトロ・マイグレーション、耐腐食性、低抵抗性、耐
メルト性、などに優れた大粒径の単結晶を含むものであ
り、半導体集積回路、光集積回路、磁気回路等の電子素
子、光素子、圧電素子等或は電子放出素子、記録媒体用
電極などに利用することができる。The gold crystal film obtained by the present invention contains a single crystal having a large grain size, which is excellent in electromigration resistance, corrosion resistance, low resistance, melt resistance, and the like. It can be used as an electronic device such as an optical integrated circuit, a magnetic circuit, an optical device, a piezoelectric device, or an electron-emitting device, an electrode for a recording medium, and the like.
【図１】本発明の金結晶膜の形成方法の１例を示す模式
図である。FIG. 1 is a schematic view showing an example of a method for forming a gold crystal film of the present invention.
【図２】本発明の金結晶膜の形成方法の１例を示す模式
図である。FIG. 2 is a schematic view showing an example of a method for forming a gold crystal film of the present invention.
【図３】本発明の金結晶膜の形成方法の１例を示す模式
図である。FIG. 3 is a schematic diagram showing an example of a method for forming a gold crystal film of the present invention.
【図４】本発明の金結晶膜の形成方法の１例を示す模式
図である。FIG. 4 is a schematic view showing an example of a method for forming a gold crystal film of the present invention.
【図５】本発明の金結晶膜の形成方法の１例を示す模式
図である。FIG. 5 is a schematic view showing an example of a method for forming a gold crystal film of the present invention.
【図６】本発明の金結晶膜の形成方法の１例を示す模式
図である。FIG. 6 is a schematic view showing an example of a method for forming a gold crystal film of the present invention.
【図７】本発明の金結晶膜の形成方法の１例を示す模式
図である。FIG. 7 is a schematic view showing an example of a method for forming a gold crystal film of the present invention.
【図８】本発明の金結晶膜の形成方法の１例を示す模式
図である。FIG. 8 is a schematic view showing an example of a method for forming a gold crystal film of the present invention.
【図９】本発明の金結晶膜の形成方法の１例を示す模式
図である。FIG. 9 is a schematic view showing an example of a method for forming a gold crystal film of the present invention.
───────────────────────────────────────────────────── フロントページの続き (31)優先権主張番号 特願平3−312546 (32)優先日 平３(1991)11月27日 (33)優先権主張国 日本（ＪＰ） (72)発明者 宮本 雅彦 東京都大田区下丸子３丁目30番２号キヤノ ン株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese patent application No. 3-312546 (32) Priority date Hei 3 (1991) November 27 (33) Priority claim country Japan (JP) (72) Inventor Masahiko Miyamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.
Claims (59)
金を過飽和状態に移行させ、基板表面に単結晶群からな
る金結晶薄膜を形成することを特徴とする金薄膜の形成
方法。1. A method for forming a gold thin film, which comprises decomposing a gold complex to transfer gold in a solution to a supersaturated state to form a gold crystal thin film consisting of a single crystal group on the surface of a substrate.
する請求項１記載の金薄膜の形成方法。2. The method for forming a gold thin film according to claim 1, wherein the single crystal group has a grain size of 1 μm or more.
い単結晶の群からなる請求項１記載の金薄膜の形成方
法。3. The method for forming a gold thin film according to claim 1, wherein the gold crystal thin film comprises a group of single crystals having a high (111) orientation.
項１記載の金薄膜の形成方法。4. The method for forming a gold thin film according to claim 1, wherein the gold complex is [AuI 4 ] − .
求項１記載の金薄膜の形成方法。5. The method of forming a gold thin film according to claim 1, wherein the gold complex is [AuCl 4 ] − .
成分の溶液系からの揮発により行なわれる請求項１記載
の金結晶薄膜の形成方法。6. The method for forming a gold crystal thin film according to claim 1, wherein the decomposition treatment is performed by volatilization of components constituting the gold complex from a solution system.
加によって、分解処理を行なわれる請求項１記載の金結
晶薄膜の形成方法。7. The method for forming a gold crystal thin film according to claim 1, wherein the decomposition treatment is performed by adding a reducing agent to a solution system.
求項１記載の金結晶薄膜の形成方法。8. The method for forming a gold crystal thin film according to claim 1, wherein the substrate surface is made of an insulating material.
求項１記載の金結晶薄膜の形成方法。9. The method for forming a gold crystal thin film according to claim 1, wherein the substrate surface is made of a semiconductor material.
ことを特徴とする請求項１記載の金結晶薄膜の形成方
法。10. The method for forming a gold crystal thin film according to claim 1, wherein the surface of the substrate is made of a conductive material.
の面と、核形成密度の小さい材料からなる第２の面とを
隣接して配した基板に、金錯体溶液中の金錯体を分解処
理することで、溶液中の金を過飽和状態に移行させ、前
記核形成密度の大きい基板表面のみに単結晶群からなる
金結晶薄膜を形成することを特徴とする金薄膜の選択形
成方法。11. A first material made of a material having a high nucleation density.
And a second surface made of a material having a low nucleation density are arranged adjacent to each other on the substrate to decompose the gold complex in the gold complex solution to shift the gold in the solution to a supersaturated state. A method for selectively forming a gold thin film, comprising forming a gold crystal thin film consisting of a single crystal group only on the surface of the substrate having a high nucleation density.
高い単結晶の群からなる請求項１１記載の金薄膜の選択
形成方法。12. The method for selectively forming a gold thin film according to claim 11, wherein the gold crystal thin film comprises a group of single crystals having a high (111) orientation.
求項１１記載の金薄膜の選択形成方法。13. The method for selectively forming a gold thin film according to claim 11, wherein the gold complex is [AuI 4 ] − .
請求項１１記載の金薄膜の選択形成方法。14. The method for selectively forming a gold thin film according to claim 11, wherein the gold complex is [AuCl 4 ] − .
る物質の溶液系からの揮発により行なわれる請求項１１
記載の金結晶薄膜の選択形成方法。15. The decomposition treatment is performed by volatilization of a substance forming the gold complex from a solution system.
A method for selectively forming a gold crystal thin film as described.
る物質の溶液系への還元剤の添加によって行なわれる請
求項１１記載の金結晶薄膜の選択形成方法。16. The method for selectively forming a gold crystal thin film according to claim 11, wherein the decomposition treatment is performed by adding a reducing agent to a solution system of a substance forming the gold complex.
導体材料である請求項１１記載の金結晶薄膜の選択形成
方法。17. The method for selectively forming a gold crystal thin film according to claim 11, wherein the material having a high nucleation areal density is a semiconductor material.
電体材料である請求項１１記載の金結晶薄膜の選択形成
方法。18. The method for selectively forming a gold crystal thin film according to claim 11, wherein the material having a high nucleation areal density is a conductor material.
縁体材料である請求項１１記載の金結晶薄膜の選択形成
方法。19. The method for selectively forming a gold crystal thin film according to claim 11, wherein the material having a low nucleation areal density is an insulator material.
核が形成される程充分微細な第１の面と、核形成密度の
小さい材料からなる第２の面とを隣接して配した基板
に、金錯体溶液中の金錯体を分解処理することで、溶液
中の金を過飽和状態に移行させ、前記単一核のみより単
結晶を成長させることを特徴とする金単結晶の形成方
法。20. A substrate in which a first surface made of a material having a high nucleation density and fine enough to form a single nucleus is disposed adjacent to a second surface made of a material having a low nucleation density. In the method for forming a gold single crystal, the gold complex in the gold complex solution is decomposed to shift the gold in the solution to a supersaturated state, and the single crystal is grown from only the single nucleus.
単結晶である請求項２０記載の金単結晶の形成方法。21. The method for forming a gold single crystal according to claim 20, wherein the single crystal is a single crystal having a high (111) orientation.
求項２０記載の金単結晶の形成方法。22. The method for forming a gold single crystal according to claim 20, wherein the gold complex is [AuI 4 ] - .
請求項２０記載の金単結晶の形成方法。23. The method for forming a gold single crystal according to claim 20, wherein the gold complex is [AuCl 4 ] − .
る物質の溶液系からの揮発により行なわれる請求項２０
記載の金単結晶の形成方法。24. The decomposition treatment is carried out by volatilization of a substance forming the gold complex from a solution system.
A method for forming a gold single crystal as described.
る物質の溶液系への還元剤の添加によって行なわれる請
求項２０記載の金単結晶の形成方法。25. The method for forming a gold single crystal according to claim 20, wherein the decomposition treatment is performed by adding a reducing agent to a solution system of a substance forming the gold complex.
導体材料である請求項２０記載の金結晶の形成方法。26. The method for forming a gold crystal according to claim 20, wherein the material having a high nucleation areal density is a semiconductor material.
電性材料である請求項２０記載の金結晶の形成方法。27. The method for forming a gold crystal according to claim 20, wherein the material having a high nucleation areal density is a conductive material.
縁性材料である請求項２０記載の金結晶の形成方法。28. The method for forming a gold crystal according to claim 20, wherein the material having a low nucleation areal density is an insulating material.
在下で、金錯体を分解処理することで溶液中の金を過飽
和状態に移行させ、前記基板の表面上に単結晶群からな
る金結晶薄膜を形成することを特徴とする金薄膜の形成
方法。29. A gold crystal thin film comprising a single crystal group on the surface of the substrate, which is obtained by decomposing a gold complex in the presence of an etching species that acts on a substrate material to transfer gold in a solution to a supersaturated state. Forming a gold thin film.
有する単結晶よりなる請求項２９記載の金薄膜の形成方
法。30. The method for forming a gold thin film according to claim 29, wherein the single crystal group is made of a single crystal having a grain size of 3 μm or more.
単結晶の群からなる請求項２９記載の金薄膜の形成方
法。31. The method for forming a gold thin film according to claim 29, wherein the gold crystal thin film comprises a group of single crystals having a (111) orientation.
酸）である請求項２９記載の金薄膜の形成方法。32. The method of forming a gold thin film according to claim 29, wherein the etching species is HF (hydrofluoric acid).
求項２９記載の金薄膜の形成方法。33. The method of forming a gold thin film according to claim 29, wherein the gold complex is [AuI 4 ] − .
る成分の溶液系からの揮発により行なわれる請求項２９
記載の金結晶薄膜の形成方法。34. The decomposition treatment is performed by volatilization of a component of the gold complex from a solution system.
A method for forming a gold crystal thin film as described above.
添加によって、分解処理を行なわれる請求項２９記載の
金結晶薄膜の形成方法。35. The method for forming a gold crystal thin film according to claim 29, wherein the decomposition treatment is performed by adding a reducing agent to a solution system.
請求項２９記載の金結晶薄膜の形成方法。36. The method for forming a gold crystal thin film according to claim 29, wherein the substrate surface is made of an insulating material.
請求項２９記載の金結晶薄膜の形成方法。37. The method for forming a gold crystal thin film according to claim 29, wherein the substrate surface is made of a semiconductor material.
なる請求項２９記載の金結晶薄膜の形成方法。38. The method for forming a gold crystal thin film according to claim 29, wherein the substrate surface is made of a silicon compound.
の面と、核形成密度の小さい材料からなる第２の面とを
隣接して配した基板を用意する工程と、前記核形成密度
の小さい材料に作用するエッチング種の存在下で金錯体
溶液中の金錯体を分解処理することで、溶液中の金を過
飽和状態に移行させ、前記核形成密度の大きい基板表面
のみに単結晶群からなる金結晶薄膜を形成する工程と、
を有することを特徴とする金薄膜の選択形成方法。39. A first material made of a material having a high nucleation density
And a second surface made of a material having a low nucleation density are arranged adjacent to each other in a gold complex solution in the presence of an etching species that acts on the material having a low nucleation density. By decomposing the gold complex of, the gold in the solution is transferred to a supersaturated state, and a step of forming a gold crystal thin film consisting of a single crystal group only on the substrate surface of the large nucleation density,
A method for selectively forming a gold thin film, comprising:
有する単結晶からなる請求項３９記載の金薄膜の選択形
成方法。40. The method for selectively forming a gold thin film according to claim 39, wherein the single crystal group comprises a single crystal having a grain size of 3 μm or more.
単結晶の群からなる請求項３９記載の金薄膜の選択形成
方法。41. The method for selectively forming a gold thin film according to claim 39, wherein the gold crystal thin film comprises a group of single crystals having a (111) orientation.
酸）である請求項３９記載の金薄膜の選択形成方法。42. The method for selectively forming a gold thin film according to claim 39, wherein the etching species is HF (hydrofluoric acid).
求項３９記載の金薄膜の選択形成方法。43. The method for selectively forming a gold thin film according to claim 39, wherein the gold complex is [AuI 4 ] − .
る物質の溶液系からの揮発により行なわれる請求項３９
記載の金結晶薄膜の選択形成方法。44. The decomposition treatment is performed by volatilization of a substance forming the gold complex from a solution system.
A method for selectively forming a gold crystal thin film as described.
る物質の溶液系への還元剤の添加によって行なわれる請
求項３９記載の金結晶薄膜の選択形成方法。45. The method for selectively forming a gold crystal thin film according to claim 39, wherein the decomposition treatment is performed by adding a reducing agent to a solution system of a substance forming the gold complex.
は、半導体材料である請求項３９記載の金結晶薄膜の選
択形成方法。46. The method for selectively forming a gold crystal thin film according to claim 39, wherein the substrate material having a high nucleation areal density is a semiconductor material.
は、導電体材料である請求項３９記載の金結晶薄膜の選
択形成方法。47. The method for selectively forming a gold crystal thin film according to claim 39, wherein the substrate material having a high nucleation surface density is a conductor material.
は、絶縁体材料である請求項３９記載の金結晶薄膜の選
択形成方法。48. The method for selectively forming a gold crystal thin film according to claim 39, wherein the substrate material having a low nucleation areal density is an insulator material.
シリコン化合物である請求項３９記載の金薄膜の選択形
成方法。49. The substrate material having a low nucleation density is
The method for selectively forming a gold thin film according to claim 39, which is a silicon compound.
核が形成される程充分微細な第１の面と、核形成密度の
小さい材料からなる第２の面とを隣接して配した基板を
用意する工程と、前記核形成密度の小さい材料に作用す
るエッチング種の存在下で、金錯体溶液中の金錯体を分
解処理することで、溶液中の金を過飽和状態に移行さ
せ、前記核形成密度が大きい材料面より単一核からなる
単結晶を成長させる工程と、を有することを特徴とする
金単結晶の形成方法。50. A substrate in which a first surface made of a material having a high nucleation density and fine enough to form a single nucleus is adjacent to a second surface made of a material having a low nucleation density. And in the presence of an etching species that acts on the material having a low nucleation density, the gold complex in the gold complex solution is decomposed to shift the gold in the solution to a supersaturated state, And a step of growing a single crystal composed of a single nucleus from a material surface having a high formation density, the method for forming a gold single crystal.
晶である請求項５０記載の金単結晶の形成方法。51. The method for forming a gold single crystal according to claim 50, wherein the single crystal is a (111) -oriented single crystal.
求項５０記載の金単結晶の形成方法。52. The method for forming a gold single crystal according to claim 50, wherein the gold complex is [AuI 4 ] − .
素酸）である請求項５０記載の金単結晶の形成方法。53. The method for forming a gold single crystal according to claim 50, wherein the etching species is HF (hydrofluoric acid).
る物質の溶液系からの揮発により行なわれる請求項５０
記載の金単結晶の形成方法。54. The decomposition treatment is performed by volatilization of a substance forming the gold complex from a solution system.
A method for forming a gold single crystal as described.
る物質の溶液系への還元剤の添加によって行なわれるこ
とを特徴とする請求項５０記載の金単結晶の形成方法。55. The method for forming a gold single crystal according to claim 50, wherein the decomposition treatment is performed by adding a reducing agent to a solution system of a substance forming the gold complex.
導体材料である請求項５０記載の金結晶の形成方法。56. The method for forming a gold crystal according to claim 50, wherein the material having a high nucleation areal density is a semiconductor material.
電性材料である請求項５０記載の金結晶の形成方法。57. The method of forming a gold crystal according to claim 50, wherein the material having a high nucleation areal density is a conductive material.
縁体材料である請求項５０記載の金結晶の形成方法。58. The method for forming a gold crystal according to claim 50, wherein the material having a low nucleation areal density is an insulator material.
コン化合物である請求項５０記載の金結晶の形成方法。59. The method for forming a gold crystal according to claim 50, wherein the material having a low nucleation density is a silicon compound.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT92107818T ATE204099T1 (en) | 1991-05-09 | 1992-05-08 | METHOD FOR PRODUCING A CRYSTALLINE GOLD FILM |
| EP92107818A EP0513693B1 (en) | 1991-05-09 | 1992-05-08 | Process for forming gold crystal film |
| US07/880,233 US5320703A (en) | 1991-05-09 | 1992-05-08 | Process for forming gold crystal film |
| JP11617192A JP3192472B2 (en) | 1991-05-09 | 1992-05-08 | Method of forming gold crystal thin film |
| DE69231985T DE69231985T2 (en) | 1991-05-09 | 1992-05-08 | Process for the production of a crystalline gold film |
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13217691 | 1991-05-09 | ||
| JP30923891 | 1991-11-25 | ||
| JP31082991 | 1991-11-26 | ||
| JP3-310829 | 1991-11-27 | ||
| JP3-132176 | 1991-11-27 | ||
| JP3-309238 | 1991-11-27 | ||
| JP3-312546 | 1991-11-27 | ||
| JP31254691 | 1991-11-27 | ||
| JP11617192A JP3192472B2 (en) | 1991-05-09 | 1992-05-08 | Method of forming gold crystal thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05201793A true JPH05201793A (en) | 1993-08-10 |
| JP3192472B2 JP3192472B2 (en) | 2001-07-30 |
Family
ID=27526716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11617192A Expired - Fee Related JP3192472B2 (en) | 1991-05-09 | 1992-05-08 | Method of forming gold crystal thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3192472B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06302600A (en) * | 1993-04-14 | 1994-10-28 | Nec Corp | Semiconductor device |
| US6110579A (en) * | 1996-12-17 | 2000-08-29 | Canon Kabushiki Kaisha | Recording medium used in information processing apparatus using probe |
| JP2009228103A (en) * | 2008-03-25 | 2009-10-08 | Sekisui Chem Co Ltd | Plating structure, and method for manufacturing plating structure |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101943062B1 (en) * | 2018-08-30 | 2019-01-28 | 주식회사 조조인터네셔널 | Assembling apparatus of solid tire for fork lift |
-
1992
- 1992-05-08 JP JP11617192A patent/JP3192472B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06302600A (en) * | 1993-04-14 | 1994-10-28 | Nec Corp | Semiconductor device |
| US6110579A (en) * | 1996-12-17 | 2000-08-29 | Canon Kabushiki Kaisha | Recording medium used in information processing apparatus using probe |
| JP2009228103A (en) * | 2008-03-25 | 2009-10-08 | Sekisui Chem Co Ltd | Plating structure, and method for manufacturing plating structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3192472B2 (en) | 2001-07-30 |
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