JPS6050172A - Method for reducing metallic ion - Google Patents

Method for reducing metallic ion

Info

Publication number
JPS6050172A
JPS6050172A JP15494483A JP15494483A JPS6050172A JP S6050172 A JPS6050172 A JP S6050172A JP 15494483 A JP15494483 A JP 15494483A JP 15494483 A JP15494483 A JP 15494483A JP S6050172 A JPS6050172 A JP S6050172A
Authority
JP
Japan
Prior art keywords
ions
metal
semiconductor material
group
pattern
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP15494483A
Other languages
Japanese (ja)
Inventor
Tomoko Sato
倫子 佐藤
Hiroshi Nakanishi
博 中西
Masayuki Suzuki
雅行 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toshiba Corp
Original Assignee
Toshiba Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toshiba Corp filed Critical Toshiba Corp
Priority to JP15494483A priority Critical patent/JPS6050172A/en
Publication of JPS6050172A publication Critical patent/JPS6050172A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
    • H05K3/185—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method by making a catalytic pattern by photo-imaging

Landscapes

  • Chemically Coating (AREA)

Abstract

PURPOSE:To reduce and deposit metallic ions on a desired pattern by forming the pattern on the surface of an electrically nonconductive substrate with a semiconductor as a catalyst for optical excitation, immersing the pattern in a soln. contg. an electron donor besides metallic ions, and irradiating light from the outside. CONSTITUTION:A desired pattern is formed on the surface of an electrically nonconductive material 4 such as a quartz plate by sputtering with metallic oxide, sulfide, phosphide, arsenide or selenide as a semiconductor substance 5. The pattern is immersed in a soln. contg. an electron donor such as ammonia, methylamine, methanol or ethanol besides metallic ions such as ions of an Fe group metal, a Pt group metal or a Cu group metal. Light from a superhigh voltage mercury lamp, a xenon short arc lamp, laser or the like is then irradiated on the semiconductor substance 5 to excite the substance 5, and the metallic ions are reduced with electrons produced by the excitation. The metallic ions are precipitated and deposited on the pattern 5 as metal 5'.

Description

【発明の詳細な説明】 〔発明の属する技術分野〕 本発明は溶液中における金属イオンの還元方法に係わり
、特に光エネルギー励起により触媒作用を発揮する光触
媒を用いた金属イオンの還元方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field to which the Invention Pertains] The present invention relates to a method for reducing metal ions in a solution, and particularly to a method for reducing metal ions using a photocatalyst that exhibits a catalytic action by excitation with light energy.

〔発明の技術的背景とその問題点〕[Technical background of the invention and its problems]

従来、溶液中の金属イオンの還元方法として、主に１外
部電流によって金属イオンを）堂元してカソード上に金
属として析出させる電気分解法と、外部電流を使わずに
溶液中の金属イオンを還元する無電解めっき法とがある
。Conventionally, the methods for reducing metal ions in a solution are mainly two methods: an electrolysis method in which metal ions are extracted using an external current and deposited as metal on the cathode, and the other is a method for reducing metal ions in a solution without using an external current. There is an electroless plating method that involves reduction.

しかしながら、前者の方法は外部電流を利用するもので
あるため、電気の良導体にしか析出させることができず
、また電流密度分布の違いにより析出膜厚に不均一さが
生じゃずいという問題点があった。また、後者の方法は
化学還元剤を利用するものであるため、絶縁体上へのメ
ッキが可能で比較的均一なメッキが得られる反面、溶液
中でメッキ反応以外の副反応も進行するため溶液の活性
が低下したり或いは活性を制御しきれずに液の分解を招
いたりす４）という問題点があった。However, since the former method uses an external current, it can only be deposited on a good electrical conductor, and there is also the problem that the difference in current density distribution causes non-uniformity in the deposited film thickness. there were. In addition, since the latter method uses a chemical reducing agent, it is possible to plate on the insulator and relatively uniform plating can be obtained, but on the other hand, side reactions other than the plating reaction also occur in the solution. There was a problem that the activity of the liquid decreased or the activity could not be fully controlled, leading to decomposition of the liquid.

〔発明の目的〕[Purpose of the invention]

本発明の目的は、上記した問題点の解消にあり、更に詳
しくは、非導電性物質への析出が可能で、かつ、金属イ
オンの析出反応を外部から制御できる溶液中の金属イオ
ンの還元方法を提供するものである。The purpose of the present invention is to solve the above-mentioned problems, and more specifically, a method for reducing metal ions in a solution that allows precipitation on a non-conductive substance and that allows external control of the metal ion precipitation reaction. It provides:

〔発明の概要〕[Summary of the invention]

本発明の金属イオンの還元方法は、金属イオンを含む液
中に、可視および／または紫外光により励起される触媒
としての半導体物質を少なくともその表面の一部に担持
させた非導電性物質を浸漬し、該半導体物質の光励起状
態下で該半導体物質に電子を注入できろ電子エネルギー
配置をもつ水溶性電子供与体を共存させ、該半導体物質
の励起エネルギー以」−のエネルギーをもつ光を該半導
体物質に１！（１躬することを特徴とするものである。The method for reducing metal ions of the present invention involves immersing a non-conductive material on at least a portion of its surface carrying a semiconductor material as a catalyst that is excited by visible and/or ultraviolet light, in a solution containing metal ions. A water-soluble electron donor having an electron energy configuration capable of injecting electrons into the semiconductor material under the photoexcitation state of the semiconductor material is present, and light with an energy higher than the excitation energy of the semiconductor material is injected into the semiconductor material. 1 for matter! (It is characterized by 1.

本発明の方法において使用される金属イオンは、用いる
半導体物質の光励起により還元ｉＪ　Ｑｌなものならい
かなるものであってもよい。この金属イオンとしては、
例えば鉄族イオン、白金族イオンまたは銅族イオン端が
好ましいものとし、て挙げられる。なお、金属イオンレ
′、■、溶液中において、錯化剤により金属イオンが錯
イオンを形成していてもよい。The metal ion used in the method of the invention may be any metal ion that can be reduced by photoexcitation of the semiconductor material used. This metal ion is
For example, preferred examples include iron group ions, platinum group ions, and copper group ion ends. Note that metal ions may form complex ions using a complexing agent in the metal ion solution.

本発明の方法において使用される電子供与体は、半導体
物質に電子を注入できる電子エネルギー配置をもつもの
であればいかなるものであってもよく、例えばアンモニ
ア、アミン類、アルコ−／Ｉ／類、アルデヒド類、ケト
ン類、エーテル類、スルホキシド類およびアミド類から
なる群より選ばれる少なくとも１種のものが挙げられる
。好ましくは、アンモニア、メチルアミン、メタノール
、エタノール等である。The electron donor used in the method of the present invention may be anything that has an electron energy configuration capable of injecting electrons into a semiconductor material, such as ammonia, amines, alcohol/I/s, At least one selected from the group consisting of aldehydes, ketones, ethers, sulfoxides, and amides can be mentioned. Preferred are ammonia, methylamine, methanol, ethanol and the like.

本発明の方法において使用される溶液は、常用の混合方
法により上記した金属イオンを生成する塩を上記した水
溶性電子供与体に混合して得られる。The solution used in the process of the invention is obtained by mixing the metal ion-producing salt described above with the water-soluble electron donor described above by conventional mixing methods.

本発明の方法において使用される半導体物質は、可視お
よび／または紫外領域の光により励起された光酸化還元
作用を有するものであればいかなるものであってもよい
。この？１５１体物質としては、通常、金属酸化物、金
属硫化物、金属リン化物、全屈砒化物、金属セレン化物
および金属テルル化物からなる群より選ばれる少なくと
も１種以上のものが挙げられ、例えばＴ　１０２　＊　
Ｓ　ｒ　’ｌ　ｓ　Ｏｚ　ｔ　Ｚ　ｎ　Ｏ、Ｆ　ｅ　ｚ
　０３９　Ｃｄ　Ｓ　ｐ　Ｃｄ　Ｓ　ｅ　ｔＣｄＴｅ、
　Ｇａｐ、　ＧａＡｓ、　Ｉｎｋ、　ＺｎＳ、　Ｚｎ５
ｅからなる群より選ばれる少なくとも１種以上のものが
挙げられる。The semiconductor material used in the method of the present invention may be any material as long as it has a photooxidation-reduction action excited by light in the visible and/or ultraviolet region. this? The 151-body substance usually includes at least one selected from the group consisting of metal oxides, metal sulfides, metal phosphides, total arsenides, metal selenides, and metal tellurides, such as T 102 *
S r 'l s Oz t Z n O, F e z
039 Cd S p Cd S e tCdTe,
Gap, GaAs, Ink, ZnS, Zn5
Examples include at least one kind selected from the group consisting of e.

本発明の方法において使用される：Ｊｌ’導？ｌモ性物
質は、通常に用いられる絶縁体および半導体であれば格
別に限定されるものではない。Used in the method of the invention: Jl'guide? The l-molar substance is not particularly limited as long as it is a commonly used insulator or semiconductor.

本発明に係る非導電性物質への半導体物質の担持方法と
しては、例えば真空蒸着法、スパッタリング法、含浸法
、沈着法等による固定のはか、半導体物質を非導電性物
質に分Ｉｆｆさせて圧縮形成する方法等が挙げられる。The method of supporting a semiconductor substance on a non-conductive substance according to the present invention includes fixing by vacuum evaporation, sputtering, impregnation, deposition, etc., and separating the semiconductor substance into a non-conductive substance. Examples include a compression forming method.

本発明の方法において使用される光ΔＩＮは、可視およ
び／または紫外領域の波長の光を発し、触媒物質を励起
するに足るものであればいかなるものであってもよい。The light ΔIN used in the method of the present invention may be any light that emits light with a wavelength in the visible and/or ultraviolet region and is sufficient to excite the catalyst substance.

この光源としては、例えば超高圧水銀ランプ、キセノン
ショートアークランプ、各種レーザー等が挙げられる。Examples of this light source include an ultra-high pressure mercury lamp, a xenon short arc lamp, and various lasers.

１（・″）対時間は目的に応じて適宜選択ずればよい。1(.'') versus time may be selected as appropriate depending on the purpose.

次に第１図を参照して不発１！ＩＪによる金１・１４イ
オンの還元方法の原理を説明する。第１図で２は非導電
性物質、３は非導電性物質２に担持した半導体物質であ
る。半導体物質３に光１もしくは光１′を照射すると半
導体物質３は励起されて電子ｅ−と正孔ｈ＋が生成する
。生成した電子ｅ−は溶液中の金属イオンを還元し、一
方正孔ｈ＋には溶液中の電子供与体りが作用することに
より電子が注入される。なお、「励起」とは半導体物質
が光１照射によりエネルギーを吸収し、その価電子帯も
しくは基底状態の電子が伝導帯もしくは励起状態に遷移
することをいう。Next, refer to Figure 1 and see ``Unexploded 1!'' The principle of the method for reducing gold 1.14 ions using IJ will be explained. In FIG. 1, 2 is a non-conductive material, and 3 is a semiconductor material supported on the non-conductive material 2. In FIG. When the semiconductor material 3 is irradiated with the light 1 or the light 1', the semiconductor material 3 is excited and generates electrons e- and holes h+. The generated electrons e- reduce metal ions in the solution, while electrons are injected into holes h+ by the action of electron donors in the solution. Note that "excitation" refers to a semiconductor substance absorbing energy by irradiation with light 1, and electrons in the valence band or ground state transition to the conduction band or excited state.

なお、本発明方法の応用可能例として、回路基板（マス
クレスパターン）もしくは半導体集積回路形成方法への
応用等の金属導電膜（層）の形成、種々の表示もしくは
情報記憶的な応用、金属イオンの回収（貴金属）もしく
は重金属イオンの除去、または、金属磁性体膜の形成等
が挙げられる。Examples of possible applications of the method of the present invention include the formation of metal conductive films (layers) such as application to circuit boards (maskless patterns) or semiconductor integrated circuit formation methods, various display or information storage applications, and metal ion (noble metals), removal of heavy metal ions, or formation of a metal magnetic film.

以下において、本発明の実施例を掲げ、更に詳しく説明
する。EXAMPLES Below, examples of the present invention will be given and explained in more detail.

〔発明の実施例〕[Embodiments of the invention]

実施例は第２図に基づいて説明する。４０−ｒｒｒｍ四
方の石英基板から成る非導電性物質４０表面に半導体物
質５を第２図ａに示すようにスパッタリング（厚さ８１
μｍ）した。全体を電子供与体を含む金属塩溶液中に浸
漬して光を照射した。The embodiment will be explained based on FIG. As shown in FIG.
μm). The whole was immersed in a metal salt solution containing an electron donor and irradiated with light.

その結果、第２図すに示すように石英基板上の半導体物
質のパターン上に金属５′の析出が認められた。As a result, as shown in FIG. 2, metal 5' was observed to be deposited on the pattern of the semiconductor material on the quartz substrate.

なお、各実施例における半導体物質、金属塩溶液、電子
供与体、光源および析出金属の膜厚は一括して表に示す
。Note that the film thicknesses of the semiconductor material, metal salt solution, electron donor, light source, and deposited metal in each example are collectively shown in the table.

〔発明の効果〕〔Effect of the invention〕

以上詳述したように、本発明の金属イオンの還元方法は
非導電性物質への析出が可能で、かつ、金属イオンの還
元反応の制御が外部から容易になし得るものであり、そ
の工業的価値は大である。As detailed above, the method for reducing metal ions of the present invention allows deposition on non-conductive substances, and the reduction reaction of metal ions can be easily controlled from the outside, making it suitable for industrial use. The value is great.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は本発明方法により溶液中の金属イオンを非導電
性物質上へ還元析出させる原理を示した説明図、第２図
は本発明の実施例に係わるもので、ａは半導体物質を担
持した非導電性物質、ｂは光照射後のａの外観図である
。Fig. 1 is an explanatory diagram showing the principle of reducing and precipitating metal ions in a solution onto a non-conductive substance by the method of the present invention, and Fig. 2 is related to an embodiment of the present invention, where a is a support for a semiconductor substance. b is an external view of a after irradiation with light.

Claims (1)

【特許請求の範囲】 １、　金属イオンを含む液中に、可視および／または紫
外光に励起される触媒として半導体物質を少なくともそ
の表面の一部に担持させた非導電性物質を浸漬し、該半
導体物質の光励起状態下で該半導体物質に電子を注入で
きる電子エネルギー配置をもつ水溶性電子供与体＼を共
存させ、該半導体物質の励起エネルギー以上のエネルギ
ーをもつ光を該半導体物質に照射することを特徴とする
金属イオンの還元方法。 ２、金属イオンが、鉄族イオン、白金族イオンおよび銅
族イオンからなる群より選ばれる少なくとも１種のもの
である特許請求の範囲第１項記載の金属イオンの還元方
法。 ３　半導体物質が、金属酸化物、金属硫化物、金属リン
化物、全屈砒化物、金属セレン化物および金属テルル化
物がら成る群より選ばれる少なくとも１種のものである
特許請求の範囲第１項記載の金属イオンの還元方法。 ４、　電子供与体が、アンモニア、アミン類、アルコー
ル類、アルデヒド類、ケトン類、エーテル類、スルホキ
シド類およびアミド類からなる群より選ばれる少なくと
も１種のものである特許請求の範囲第１項記載の金属イ
オンの還元方法。[Claims] 1. A non-conductive material having a semiconductor material supported on at least a part of its surface as a catalyst excited by visible and/or ultraviolet light is immersed in a liquid containing metal ions, and A water-soluble electron donor with an electron energy configuration capable of injecting electrons into the semiconductor material under the photoexcitation state of the semiconductor material coexists with the semiconductor material, and the semiconductor material is irradiated with light having an energy higher than the excitation energy of the semiconductor material. A method for reducing metal ions characterized by: 2. The method for reducing metal ions according to claim 1, wherein the metal ions are at least one selected from the group consisting of iron group ions, platinum group ions, and copper group ions. 3. Claim 1, wherein the semiconductor substance is at least one selected from the group consisting of metal oxides, metal sulfides, metal phosphides, total arsenides, metal selenides, and metal tellurides. method for reducing metal ions. 4. Claim 1, wherein the electron donor is at least one member selected from the group consisting of ammonia, amines, alcohols, aldehydes, ketones, ethers, sulfoxides, and amides. method for reducing metal ions.
JP15494483A 1983-08-26 1983-08-26 Method for reducing metallic ion Pending JPS6050172A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP15494483A JPS6050172A (en) 1983-08-26 1983-08-26 Method for reducing metallic ion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP15494483A JPS6050172A (en) 1983-08-26 1983-08-26 Method for reducing metallic ion

Publications (1)

Publication Number Publication Date
JPS6050172A true JPS6050172A (en) 1985-03-19

Family

ID=15595337

Family Applications (1)

Application Number Title Priority Date Filing Date
JP15494483A Pending JPS6050172A (en) 1983-08-26 1983-08-26 Method for reducing metallic ion

Country Status (1)

Country Link
JP (1) JPS6050172A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4774026A (en) * 1986-01-22 1988-09-27 Hitachi, Ltd. Process and apparatus for oxidizing or reducing dissolved substance
WO2007034583A1 (en) * 2005-09-20 2007-03-29 Japan Science And Technology Agency Process for producing metal covering-type organic crystal
JP2009001897A (en) * 2007-05-08 2009-01-08 Interuniv Micro Electronica Centrum Vzw Bipolar electroless processing method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51126931A (en) * 1975-04-29 1976-11-05 Matsushita Electric Works Ltd Method of surface metallizing
JPS586982A (en) * 1981-07-02 1983-01-14 Toshiba Corp Decomposing method for water
JPS58125601A (en) * 1982-01-20 1983-07-26 Toshiba Corp Decomposition method of water

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51126931A (en) * 1975-04-29 1976-11-05 Matsushita Electric Works Ltd Method of surface metallizing
JPS586982A (en) * 1981-07-02 1983-01-14 Toshiba Corp Decomposing method for water
JPS58125601A (en) * 1982-01-20 1983-07-26 Toshiba Corp Decomposition method of water

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4774026A (en) * 1986-01-22 1988-09-27 Hitachi, Ltd. Process and apparatus for oxidizing or reducing dissolved substance
WO2007034583A1 (en) * 2005-09-20 2007-03-29 Japan Science And Technology Agency Process for producing metal covering-type organic crystal
US8025930B2 (en) 2005-09-20 2011-09-27 Japan Science And Technology Agency Method for fabricating metal-coated organic crystal
JP2009001897A (en) * 2007-05-08 2009-01-08 Interuniv Micro Electronica Centrum Vzw Bipolar electroless processing method

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