JP6169500B2 - Electroless plating method, electroless plating apparatus and storage medium - Google Patents

Electroless plating method, electroless plating apparatus and storage medium Download PDF

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JP6169500B2
JP6169500B2 JP2014017694A JP2014017694A JP6169500B2 JP 6169500 B2 JP6169500 B2 JP 6169500B2 JP 2014017694 A JP2014017694 A JP 2014017694A JP 2014017694 A JP2014017694 A JP 2014017694A JP 6169500 B2 JP6169500 B2 JP 6169500B2
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metal
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electroless plating
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JP2015145514A (en
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谷 信 崇 水
谷 信 崇 水
下 光 秋 岩
下 光 秋 岩
中 崇 田
中 崇 田
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Tokyo Electron Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1603Process or apparatus coating on selected surface areas
    • C23C18/1607Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1608Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1619Apparatus for electroless plating
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1646Characteristics of the product obtained
    • C23C18/165Multilayered product
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1646Characteristics of the product obtained
    • C23C18/165Multilayered product
    • C23C18/1651Two or more layers only obtained by electroless plating
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/1803Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • C23C18/1831Use of metal, e.g. activation, sensitisation with noble metals
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31Coating with metals
    • C23C18/32Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54Contact plating, i.e. electroless electrochemical plating

Description

本発明は基板に対して無電解めっき層を形成する無電解めっき方法、無電解めっき装置および記憶媒体に関する。   The present invention relates to an electroless plating method, an electroless plating apparatus, and a storage medium for forming an electroless plating layer on a substrate.

LSIの製造工程における金属形成は、CVDまたはPVDにより基板全面に成長することで行なわれている。金属の形状加工については、古くは薬液によるエッチングや、Alの配線のドライエッチング、昨今のBEOL工程においては絶縁膜を先にドライエッチングし、形成された溝等の内部にCuなどの配線用の金属を埋め込みCMPでエッチングする、などの方法で金属の形状加工を行なっている(特許文献1)。   Metal formation in the LSI manufacturing process is performed by growing the entire surface of the substrate by CVD or PVD. For metal shape processing, in the past, etching with chemicals, dry etching of Al wiring, and in the recent BEOL process, the insulating film is first dry etched, and the inside of the formed groove or the like is used for wiring such as Cu. Metal shape processing is performed by a method such as embedding metal and etching by CMP (Patent Document 1).

このような金属の形状加工においては、はじめに基板を準備するとともに、この基板上にPVD又はCVDにより複数層の金属層を成膜し、その複数層の金属層上にレジストパターンを設けて複数層の金属層をエッチングする方法が採用されている。   In such metal shape processing, a substrate is first prepared, a plurality of metal layers are formed on the substrate by PVD or CVD, and a resist pattern is provided on the plurality of metal layers to form a plurality of layers. A method of etching the metal layer is employed.

しかしながら、金属上に多層の厚い金属層を成膜し、その後、複数層の金属層をまとめてドライエッチングする場合、現在のドライエッチングでは時間がかかり、エッチング工程の負荷が大きくなってしまう。また、金属によって(たとえばCuなど)はドライエッチング自体が非常にむずかしく、精度良くエッチングすることができず、基板上に精度良くパターニングされた複数からなる金属層を形成することはむずかしい。   However, when a plurality of thick metal layers are formed on a metal and then a plurality of metal layers are dry etched together, the current dry etching takes time and the load of the etching process is increased. Also, depending on the metal (for example, Cu), dry etching itself is very difficult, and etching cannot be performed with high accuracy, and it is difficult to form a plurality of metal layers patterned with high accuracy on a substrate.

特開平11−297699号公報Japanese Patent Laid-Open No. 11-297699

本発明は、このような点を考慮してなされたものであり、基板上に精度良くパターニングされた金属層を確実に形成し、この金属層にドライエッチングによる形状加工が不要な金属層を形成することができる無電解めっき方法、無電解めっき装置、および記憶媒体を提供することを目的とする。   The present invention has been made in consideration of such points, and a metal layer patterned with high precision is reliably formed on a substrate, and a metal layer that does not require shape processing by dry etching is formed on the metal layer. An object of the present invention is to provide an electroless plating method, an electroless plating apparatus, and a storage medium.

本発明は、触媒性をもたない金属化合物からなるパターニングされた第1金属層と、金属犠牲層とが順次形成された基板に対して無電解めっきを施す無電解めっき方法において、前記金属犠牲層の金属と置換可能なイオン化された金属を含む水溶液を前記金属犠牲上に塗布することにより、前記金属犠牲層上に触媒層を形成する工程と、前記触媒層上に無電解めっきを施すことにより第2金属層を形成する工程を備えたことを特徴とする無電解めっき方法である。   The present invention relates to an electroless plating method for performing electroless plating on a substrate on which a patterned first metal layer made of a metal compound having no catalytic property and a metal sacrificial layer are sequentially formed. A step of forming a catalyst layer on the metal sacrificial layer by applying an aqueous solution containing an ionized metal that can replace the metal of the layer on the metal sacrificial layer, and applying electroless plating on the catalyst layer An electroless plating method characterized by comprising a step of forming a second metal layer.

本発明は、触媒性をもたない金属化合物からなるパターニングされた第1金属層と、金属犠牲層とが順次形成された基板に対して無電解めっき層を施す無電解めっき装置において、前記金属犠牲層の金属と置換可能なイオン化された金属を含む水溶液を前記金属犠牲上に塗布することにより、前記金属犠牲層上に触媒層を形成する触媒層形成部と、前記触媒層上に無電解めっきを施すことにより第2金属層を形成する第2金属層形成部を備えたことを特徴とする無電解めっき装置である。   The present invention provides an electroless plating apparatus for applying an electroless plating layer to a substrate on which a patterned first metal layer made of a metal compound having no catalytic property and a metal sacrificial layer are sequentially formed. A catalyst layer forming portion for forming a catalyst layer on the metal sacrificial layer by applying an aqueous solution containing an ionized metal that can replace the metal of the sacrificial layer on the metal sacrificial layer, and electroless on the catalyst layer An electroless plating apparatus including a second metal layer forming unit that forms a second metal layer by plating.

本発明は、コンピュータに無電解めっき方法を実行させるためのプログラムを格納した記憶媒体において、無電解めっき方法は、触媒性をもたない金属化合物からなるパターニングされた第1金属層と、金属犠牲層とが順次形成された基板に対して無電解めっきを施す無電解めっき方法であって、前記金属犠牲層の金属と置換可能なイオン化された金属を含む水溶液を前記金属犠牲上に塗布することにより、前記金属犠牲層上に触媒層を形成する工程と、前記触媒層上に無電解めっきを施すことにより第2金属層を形成する工程を備えたことを特徴とする記憶媒体である。   The present invention relates to a storage medium storing a program for causing a computer to execute an electroless plating method. The electroless plating method includes a patterned first metal layer made of a metal compound having no catalytic property, and a metal sacrificial layer. An electroless plating method for performing electroless plating on a substrate on which layers are sequentially formed, wherein an aqueous solution containing an ionized metal that can replace a metal of the metal sacrificial layer is applied onto the metal sacrificial layer Thus, there is provided a storage medium comprising a step of forming a catalyst layer on the metal sacrificial layer and a step of forming a second metal layer by performing electroless plating on the catalyst layer.

本発明によれば、基板上に精度良くパターニングされた複数の金属層を容易かつ確実に形成することができる。   According to the present invention, a plurality of metal layers patterned with high precision can be easily and reliably formed on a substrate.

図1(a)〜(f)は、本発明における無電解めっき方法を示すフローチャート。1A to 1F are flowcharts showing an electroless plating method in the present invention. 図2は、本発明における無電解めっき装置を示すブロック図。FIG. 2 is a block diagram showing an electroless plating apparatus according to the present invention. 図3(a)(b)は、比較例としての多層の金属層形成方法を示す図。FIGS. 3A and 3B are diagrams showing a multilayer metal layer forming method as a comparative example.

以下、図1および図2により本発明の実施の形態について説明する。   Hereinafter, an embodiment of the present invention will be described with reference to FIGS.

本発明による金属層形成方法は、図1(a)(b)(c)(d)(e)(f)に示すように、半導体ウエハ等からなるシリコン基板(以下、基板ともいう)11に対して第1金属層12と、金属犠牲層15と、触媒層16と、無電解めっき層18とを順次形成するものである。なお、第1金属層12と、金属犠牲擬制層15と、触媒層16と、無電解めっき層18とを順次形成し得られた金属層の全体の厚さは、後述する比較例の図3の第1金属層12および第2金属層18を形成し得られた金属層の全体の厚さと同じ金属層を形成する。   As shown in FIGS. 1A, 1B, 1C, 1D, 1E, and 1F, a metal layer forming method according to the present invention is applied to a silicon substrate 11 (hereinafter also referred to as a substrate) 11 made of a semiconductor wafer or the like. On the other hand, the 1st metal layer 12, the metal sacrificial layer 15, the catalyst layer 16, and the electroless-plating layer 18 are formed in order. Note that the total thickness of the metal layer obtained by sequentially forming the first metal layer 12, the metal sacrificial pseudo control layer 15, the catalyst layer 16, and the electroless plating layer 18 is shown in FIG. A metal layer having the same thickness as the entire metal layer obtained by forming the first metal layer 12 and the second metal layer 18 is formed.

この場合、基板11としてはSiからなる基板本体を用いることができ、あるいは基板11として、Siからなる基板本体と、基板本体上に設けられたTEOS層とを有するものを用いてもよい。   In this case, a substrate body made of Si can be used as the substrate 11, or a substrate having a substrate body made of Si and a TEOS layer provided on the substrate body may be used.

次に基板11に対して第1金属層12と、金属犠牲層15と、触媒層16と、無電解めっき層18とを順次形成する無電解めっき装置30について、図2により説明する。   Next, an electroless plating apparatus 30 that sequentially forms the first metal layer 12, the metal sacrificial layer 15, the catalyst layer 16, and the electroless plating layer 18 on the substrate 11 will be described with reference to FIG.

このような無電解めっき装置30は、基板上11に触媒性をもたない金属化合物からなる第1金属層12を形成する第1金属層形成部31と、第1金属層12上に金属犠牲層15を形成する金属犠牲層形成部32と、金属犠牲層15の金属と置換可能なイオン化された金属を含む水溶液を前記金属犠牲層15上に塗布することにより、前記金属犠牲層15上に触媒層16を形成する触媒層形成部33と、触媒層16上に無電解めっきを施すことにより第2金属層18を形成する第2金属層形成部34とを備えている。   Such an electroless plating apparatus 30 includes a first metal layer forming portion 31 for forming a first metal layer 12 made of a metal compound having no catalytic property on the substrate 11, and a metal sacrifice on the first metal layer 12. A metal sacrificial layer forming portion 32 for forming the layer 15 and an aqueous solution containing an ionized metal that can replace the metal of the metal sacrificial layer 15 are applied onto the metal sacrificial layer 15, thereby forming a metal sacrificial layer 15 on the metal sacrificial layer 15. A catalyst layer forming portion 33 for forming the catalyst layer 16 and a second metal layer forming portion 34 for forming the second metal layer 18 by performing electroless plating on the catalyst layer 16 are provided.

また触媒層形成部33および第2金属層形成部34の後段に、第2金属層18をマスクトとして基板11にエッチングを施し、基板11に対してパターニングを施すエッチング部35が設けられている。   Further, an etching unit 35 that etches the substrate 11 using the second metal layer 18 as a mask and performs patterning on the substrate 11 is provided after the catalyst layer forming unit 33 and the second metal layer forming unit 34.

また上述した無電解めっき装置10の各構成部材、例えば第1金属層形成部31、金属犠牲層形成部32,触媒層形成部33、第2金属層形成部34、エッチング部35は、いずれも制御装置40に設けられた記憶媒体41に記録された各種のプログラムに従って制御装置40で駆動制御され、これによって基板11に対する様々な処理が行われる。ここで、記憶媒体41は、各種の設定データや後述する金属層形成プログラム等の各種のプログラムを格納している。記憶媒体41としては、コンピューターで読み取り可能なROMやRAMなどのメモリーや、ハードディスク、CD−ROM、DVD−ROMやフレキシブルディスクなどのディスク状記憶媒体などの公知のものが使用されうる。   Further, each component of the electroless plating apparatus 10 described above, for example, the first metal layer forming part 31, the metal sacrificial layer forming part 32, the catalyst layer forming part 33, the second metal layer forming part 34, and the etching part 35 are all included. Drive control is performed by the control device 40 in accordance with various programs recorded in the storage medium 41 provided in the control device 40, whereby various processes are performed on the substrate 11. Here, the storage medium 41 stores various setting data and various programs such as a metal layer forming program described later. As the storage medium 41, a known medium such as a computer-readable memory such as ROM or RAM, or a disk-shaped storage medium such as a hard disk, CD-ROM, DVD-ROM, or flexible disk can be used.

次にこのような構成からなる本実施の形態の作用について、図1により説明する。   Next, the operation of the present embodiment having such a configuration will be described with reference to FIG.

まず、半導体ウエハ等からなる基板11が無電解めっき装置30に搬送される。   First, the substrate 11 made of a semiconductor wafer or the like is transferred to the electroless plating apparatus 30.

この場合、基板11の表面は平坦状であってもよく(図1(a)参照)、基板11の表面に凹部を形成してもよい。   In this case, the surface of the substrate 11 may be flat (see FIG. 1A), or a recess may be formed on the surface of the substrate 11.

ここで基板11に凹部を形成する方法としては、従来公知の方法から適宜採用することができる。具体的には、例えば、ドライエッチング技術として、弗素系又は塩素系ガス等を用いた汎用的技術を適用できるが、特にアスペクト比(孔の深さ/孔の径)の大きな孔を形成するには、高速な深掘エッチングが可能なICP−RIE(Inductively Coupled Plasma Reactive Ion Etching:誘導結合プラズマ−反応性イオンエッチング)の技術の採用した方法をより好適に採用でき、特に、六フッ化硫黄(SF6)を用いたエッチングステップとC4F8などのテフロン(登録商標)系ガスを用いた保護ステップとを繰り返しながら行うボッシュプロセスと称される方法を好適に採用できる。   Here, as a method of forming the concave portion in the substrate 11, a conventionally known method can be appropriately employed. Specifically, for example, as a dry etching technique, a general-purpose technique using a fluorine-based or chlorine-based gas or the like can be applied. In particular, a hole having a large aspect ratio (hole depth / hole diameter) is formed. Can adopt the method which adopted the technique of ICP-RIE (Inductively Coupled Plasma Reactive Ion Etching: Inductively Coupled Plasma-Reactive Ion Etching) capable of high-speed deep etching, more particularly, sulfur hexafluoride ( A method called a Bosch process in which an etching step using SF6) and a protection step using a Teflon-based gas such as C4F8 are repeated can be suitably employed.

次に無電解めっき装置30において、基板11が第1金属層形成部31へ送られる。そしてこの第1金属層形成部31において、基板11上にパターン化された第1金属層12が形成されている。   Next, in the electroless plating apparatus 30, the substrate 11 is sent to the first metal layer forming unit 31. In the first metal layer forming portion 31, the patterned first metal layer 12 is formed on the substrate 11.

具体的には、図1(a)に示すように、基板11上にCVD又はPVDによりTiN又はTaNからなる第1金属層12が形成される。これらのTiN又はTaNは、後述する無電解めっきにより形成された第2金属層18に対して触媒性をもたない金属化合物となっている。   Specifically, as shown in FIG. 1A, a first metal layer 12 made of TiN or TaN is formed on a substrate 11 by CVD or PVD. These TiN or TaN is a metal compound that does not have catalytic properties for the second metal layer 18 formed by electroless plating described later.

次に第1金属層12が形成された基板11は金属犠牲層形成部32へ送られ、この金属犠牲層形成部32において、第1金属層12上に金属犠牲層15が形成される(図1(b)参照)。   Next, the substrate 11 on which the first metal layer 12 is formed is sent to the metal sacrificial layer forming portion 32, and the metal sacrificial layer 15 is formed on the first metal layer 12 in the metal sacrificial layer forming portion 32 (FIG. 1 (b)).

この金属犠牲層15は、後述する触媒層16を構成する金属と置換可能な金属を含んでおり、金属犠牲層形成部32において、第1金属層12上にCVD又はPVDにより形成される。   The metal sacrificial layer 15 includes a metal that can replace the metal constituting the catalyst layer 16 described later, and is formed on the first metal layer 12 by CVD or PVD in the metal sacrificial layer forming portion 32.

なお、この金属犠牲層15は、第1金属層12上に連続的につながった第1金属層12より薄い膜として形成されてもよく。また、第1金属層12上に不連続の膜として形成されていてもよく、粒状で形成されていてもよい。なお、第1金属層12と金属犠牲層15からなる金属層の厚さは従来技術の図3の第1金属層12および第2金属層18からなる金属層よりも薄く形成される。   The metal sacrificial layer 15 may be formed as a film thinner than the first metal layer 12 continuously connected to the first metal layer 12. Further, it may be formed as a discontinuous film on the first metal layer 12 or may be formed in a granular form. The thickness of the metal layer composed of the first metal layer 12 and the metal sacrificial layer 15 is made thinner than the metal layer composed of the first metal layer 12 and the second metal layer 18 of FIG.

次にこの第1金属層12および金属犠牲層15上にレジストパターン13が設けられ、レジストパターン13が設けられた第1金属層12および金属犠牲層15に対してエッチングを施すことにより、パターニングされた第1金属層12および金属犠牲層15が得られる(図1(c)参照)。その後第1金属層12上および金属犠牲層15からレジストパターン13が除去される(図1(d)参照)。   Next, a resist pattern 13 is provided on the first metal layer 12 and the metal sacrificial layer 15, and patterning is performed by etching the first metal layer 12 and the metal sacrificial layer 15 provided with the resist pattern 13. Thus, the first metal layer 12 and the metal sacrificial layer 15 are obtained (see FIG. 1C). Thereafter, the resist pattern 13 is removed from the first metal layer 12 and from the metal sacrificial layer 15 (see FIG. 1D).

このような金属犠牲層15を構成する金属としては、Ti、W、Cu、Ni又はCoのいずれかを用いることができる。   Any of Ti, W, Cu, Ni, and Co can be used as the metal constituting the metal sacrificial layer 15.

次に第1金属層12上に金属犠牲層15が形成された基板11は、その後触媒層形成部33に送られる。次に触媒層形成部33において、基板11上の金属犠牲層15に対して、金属犠牲層15の金属と置換可能なイオン化された金属を含む水溶液が塗布され、このことにより金属犠牲層15上に触媒層16が形成される(図1(e)参照)。   Next, the substrate 11 on which the metal sacrificial layer 15 is formed on the first metal layer 12 is then sent to the catalyst layer forming unit 33. Next, in the catalyst layer forming unit 33, an aqueous solution containing ionized metal that can replace the metal of the metal sacrificial layer 15 is applied to the metal sacrificial layer 15 on the substrate 11, thereby Thus, the catalyst layer 16 is formed (see FIG. 1E).

具体的には金属犠牲層15がTi又はWからなる場合、金属犠牲層15に対して塩化Pd液または硫酸Pd液等の水溶液が塗布される。この場合、水溶液中のPdイオンと、金属犠牲層15のTi又はWとが置換し、金属犠牲層15上にPdイオンが折出する。   Specifically, when the metal sacrificial layer 15 is made of Ti or W, an aqueous solution such as a Pd chloride solution or a Pd sulfate solution is applied to the metal sacrificial layer 15. In this case, Pd ions in the aqueous solution are replaced with Ti or W of the metal sacrificial layer 15, and Pd ions break out on the metal sacrificial layer 15.

このようにして金属犠牲層15上にPd、Au、Ptのいずれかの金属からなる触媒層16を形成することができる。   In this way, the catalyst layer 16 made of any one of Pd, Au, and Pt can be formed on the metal sacrificial layer 15.

次に表面触媒層16が形成された基板11は、第2金属層形成部34へ送られ、この第2金属層形成部34において基板11に対して無電解めっきが施されて第2金属層18が形成される。   Next, the substrate 11 on which the surface catalyst layer 16 is formed is sent to the second metal layer forming unit 34, and the second metal layer forming unit 34 performs electroless plating on the substrate 11 to form the second metal layer. 18 is formed.

具体的には基板11に対してNi金属の無電解めっきを施すことにより、基板11上に触媒層16のPd金属を触媒とするめっきが施されて、触媒層16上にNi金属により第2金属層18が形成される(図1(f)参照)。   Specifically, by performing electroless plating of Ni metal on the substrate 11, plating using the Pd metal of the catalyst layer 16 as a catalyst is performed on the substrate 11, and second plating is performed on the catalyst layer 16 with Ni metal. A metal layer 18 is formed (see FIG. 1 (f)).

このとき、無電解めっきが施されて形成された第2金属層18は、比較例を示す図3の第1金属層12および第2金属層18からなる金属層の厚さと同等の厚さになるよう形成する。本発明により形成された第2金属層18は、パターニングされた金属層のみに選択的に形成される。   At this time, the second metal layer 18 formed by electroless plating has a thickness equivalent to the thickness of the metal layer formed of the first metal layer 12 and the second metal layer 18 in FIG. To form. The second metal layer 18 formed according to the present invention is selectively formed only on the patterned metal layer.

なお、第2金属層形成部34において、Ni金属を用いることなく、Cu金属を用いて無電解めっきを施し、触媒層16上にCu金属による第2金属層18を形成してもよい。   Note that the second metal layer forming unit 34 may form the second metal layer 18 made of Cu metal on the catalyst layer 16 by performing electroless plating using Cu metal without using Ni metal.

次に表面に第2金属層18が形成された基板11は、エッチング部35に送られ、このエッチング部35において、第2金属層18をマスクとして基板11に対してエッチングが施される(図1(g)参照)。   Next, the substrate 11 on which the second metal layer 18 is formed is sent to the etching unit 35, and the etching is performed on the substrate 11 using the second metal layer 18 as a mask (see FIG. 5). 1 (g)).

このように本実施の形態によれば、基板11上に第1金属層12および金属犠牲層15を形成した後、この第1金属層12および金属犠牲層15にレジストパターン13を用いてエッチングを施し、パターニングされた第1金属層12および金属犠牲層15上に触媒層16を設け、その後触媒層16を用いて無電解めっきにより第2金属層18を設けることができる。このように第1金属層12および金属犠牲層15の薄い金属層にレジストパターン13を用いたドライエッチングを施すことができ、エッチング工程の負荷を軽減して、精度良くパターニングされた第1金属層12および第2金属層18を形成することができる。また、基板11上の全面にCVD又はPVDにより金属層を形成するのに比べ、パターニングされた第1金属層12および金属犠牲層15のみに触媒層16を介して選択的に第2金属層18を形成することができる。   As described above, according to the present embodiment, after the first metal layer 12 and the metal sacrificial layer 15 are formed on the substrate 11, the first metal layer 12 and the metal sacrificial layer 15 are etched using the resist pattern 13. The catalyst layer 16 can be provided on the first metal layer 12 and the metal sacrificial layer 15 that have been applied and patterned, and then the second metal layer 18 can be provided by electroless plating using the catalyst layer 16. Thus, dry etching using the resist pattern 13 can be performed on the thin metal layers of the first metal layer 12 and the metal sacrificial layer 15, reducing the load of the etching process, and accurately patterning the first metal layer. 12 and the second metal layer 18 can be formed. Further, as compared with the case where a metal layer is formed on the entire surface of the substrate 11 by CVD or PVD, the second metal layer 18 is selectively selectively formed only on the patterned first metal layer 12 and metal sacrificial layer 15 via the catalyst layer 16. Can be formed.

次に本発明に対する比較例を図3(a)(b)により述べる。図3(a)(b)に示すように、基板11上に多層の金属層を設ける場合、基板11上にCVD又はPVDによりTiN又はTaNからなる第1金属層12およびNiからなる第2金属層18を形成しておき、次に第2金属層18上にレジストパターン23を設けてエッチングすることにより、パターニングされた第1金属層12および第2金属層18を形成することも可能である。   Next, a comparative example for the present invention will be described with reference to FIGS. As shown in FIGS. 3A and 3B, when a multilayer metal layer is provided on the substrate 11, the first metal layer 12 made of TiN or TaN and the second metal made of Ni are formed on the substrate 11 by CVD or PVD. It is also possible to form the patterned first metal layer 12 and second metal layer 18 by forming the layer 18 and then providing the resist pattern 23 on the second metal layer 18 and etching. .

しかしながら図3(a)(b)において、基板11上の第1金属層12および第2金属層18の厚い金属層をまとめてエッチングする必要があり、現在のドライエッチングでは時間がかかるなどエッチング工程の負荷が大きくなるため、精度良くパターニングされた第1金属層12および第2金属18を形成することはむずかしい。   However, in FIGS. 3A and 3B, the thick metal layers of the first metal layer 12 and the second metal layer 18 on the substrate 11 need to be etched together, and the current dry etching takes time, etc. Therefore, it is difficult to form the first metal layer 12 and the second metal 18 patterned with high accuracy.

これに対して本実施の形態によれば、エッチング工程の負荷を軽減して、精度良くパターニングされた第1金属層12および第2金属層18を得ることができる。   On the other hand, according to the present embodiment, it is possible to reduce the load of the etching process and obtain the first metal layer 12 and the second metal layer 18 that are accurately patterned.

なお、本実施の形態では第2金属層18をマスクとして基板11に対してエッチングを施すために用いたが、これに限ることはなく、第2金属層18を必要な厚さに調整してデバイスの配線として使用することができる。   In the present embodiment, the second metal layer 18 is used as a mask for etching the substrate 11. However, the present invention is not limited to this, and the second metal layer 18 is adjusted to a necessary thickness. Can be used as device wiring.

11 基板
12 第1金属層
13 レジストパターン
15 金属犠牲層
16 触媒層
18 第2金属層
23 レジストパターン
30 無電解めっき装置
31 第1金属層形成部
32 金属犠牲層形成部
33 触媒層形成部
34 第2金属層形成部
35 エッチング部
40 制御装置
41 記憶媒体
11 substrate 12 first metal layer 13 resist pattern 15 metal sacrificial layer 16 catalyst layer 18 second metal layer 23 resist pattern 30 electroless plating apparatus 31 first metal layer forming part 32 metal sacrificial layer forming part 33 catalyst layer forming part 34 Two metal layer forming part 35 Etching part 40 Control device 41 Storage medium

Claims (6)

第1金属層と、置換可能金属層とが順次形成され、前記第1金属層と前記置可能金属層がパターニングされた基板に対して無電解めっきを施す無電解めっき方法において、
前記基板上に前記第1金属層を形成する工程と、
前記第1金属層上に前記置換可能金属層を形成する工程と、
前記置換可能金属層上にレジストパターンを形成する工程と、
前記第1金属層と前記置換可能金属層をレジストパターンを介してエッチングする工程と、
前記置換可能金属層上からレジストパターンを除去する工程と、
前記置換可能金属層の金属と置換可能なイオン化された金属を含む水溶液を前記置換可能金属層上に塗布することにより、パターニングされた前記第1金属層および前記置換可能金属層上のみに触媒層を形成する工程と、
前記触媒層上に無電解めっきを施すことにより第2金属層を形成する工程を備え、
前記第1金属層は、前記第2金属層に対して触媒性をもたない金属化合物であり、
前記置換可能金属層は、前記水溶液中のイオン化された金属と置換反応し、前記置換可能金属層上に前記イオン化された金属を折出させるための金属層であり、かつ、前記第1金属層より薄く形成され、
前記触媒層は、前記水溶液中のイオン化された金属が折出した金属である、ことを特徴とする無電解めっき方法。
In an electroless plating method in which a first metal layer and a replaceable metal layer are sequentially formed, and electroless plating is performed on a substrate on which the first metal layer and the replaceable metal layer are patterned,
Forming the first metal layer on the substrate;
Forming the replaceable metal layer on the first metal layer;
Forming a resist pattern on the replaceable metal layer;
Etching the first metal layer and the replaceable metal layer through a resist pattern;
Removing a resist pattern from the replaceable metal layer;
A catalyst layer is formed only on the patterned first metal layer and the replaceable metal layer by applying an aqueous solution containing an ionized metal replaceable with the metal of the replaceable metal layer onto the replaceable metal layer. Forming a step;
A step of forming a second metal layer by performing electroless plating on the catalyst layer;
The first metal layer is a metal compound having no catalytic property with respect to the second metal layer,
The substitutable metal layer is a metal layer for causing a substitution reaction with the ionized metal in the aqueous solution and folding out the ionized metal on the substitutable metal layer, and the first metal layer Formed thinner,
The electroless plating method, wherein the catalyst layer is a metal formed by folding an ionized metal in the aqueous solution.
前記第1金属層の金属化合物は、TiN又はTaNからなることを特徴とする請求項1記載の無電解めっき方法。   The electroless plating method according to claim 1, wherein the metal compound of the first metal layer is made of TiN or TaN. 前記置換可能金属層の金属はTi、W、Cu、Ni、又はCoからなることを特徴とする請求項1または2記載の無電解めっき方法。   3. The electroless plating method according to claim 1, wherein the metal of the replaceable metal layer is made of Ti, W, Cu, Ni, or Co. 前記触媒層の金属はPd、Au、Ptからなることを特徴とする請求項1乃至3のいずれか記載の無電解めっき方法。   The electroless plating method according to any one of claims 1 to 3, wherein the metal of the catalyst layer is made of Pd, Au, or Pt. 前記第2金属層はNiの無電解めっき層からなることを特徴とする請求項1乃至4のいずれか記載の無電解めっき方法。   The electroless plating method according to claim 1, wherein the second metal layer is made of an electroless plating layer of Ni. コンピュータに無電解めっき方法を実行させるためのプログラムを格納した記憶媒体において、
無電解めっき方法は、第1金属層と、置換可能金属層とが順次形成され、前記第1金属層と前記置換可能金属層がパターニングされた基板に対して無電解めっきを施す無電解めっき方法において、
前記基板上に前記第1金属層を形成する工程と、
前記第1金属層上に前記置換可能金属層を形成する工程と、
前記置換可能金属層上にレジストパターンを形成する工程と、
前記第1金属層と前記置換可能金属層をレジストパターンを介してエッチングする工程と、
前記置換可能金属層上からレジストパターンを除去する工程と、
前記置換可能金属層の金属と置換可能なイオン化された金属を含む水溶液を前記置換可能金属層上に塗布することにより、パターニングされた前記第1金属層および前記置換可能金属層上のみに触媒層を形成する工程と、
前記触媒層上に無電解めっきを施すことにより第2金属層を形成する工程を備え、
前記第1金属層は、前記第2金属層に触媒性をもたない金属化合物であり、
前記置換可能金属層は、前記水溶液中のイオン化された金属と置換反応し、前記置換可能金属層上に前記イオン化された金属を折出させるための金属であり、かつ、前記第1金属層より薄く形成され、
前記触媒層は、前前記水溶液中のイオン化された金属が折出した金属である、ことを特徴とする記憶媒体。
In a storage medium storing a program for causing a computer to execute an electroless plating method,
The electroless plating method is an electroless plating method in which a first metal layer and a replaceable metal layer are sequentially formed, and electroless plating is performed on a substrate on which the first metal layer and the replaceable metal layer are patterned. In
Forming the first metal layer on the substrate;
Forming the replaceable metal layer on the first metal layer;
Forming a resist pattern on the replaceable metal layer;
Etching the first metal layer and the replaceable metal layer through a resist pattern;
Removing a resist pattern from the replaceable metal layer;
A catalyst layer is formed only on the patterned first metal layer and the replaceable metal layer by applying an aqueous solution containing an ionized metal replaceable with the metal of the replaceable metal layer onto the replaceable metal layer. Forming a step;
A step of forming a second metal layer by performing electroless plating on the catalyst layer;
The first metal layer is a metal compound having no catalytic property to the second metal layer,
The substitutable metal layer is a metal for causing a substitution reaction with the ionized metal in the aqueous solution and folding the ionized metal on the substitutable metal layer, and from the first metal layer Thinly formed,
The storage medium according to claim 1, wherein the catalyst layer is a metal obtained by folding an ionized metal in the aqueous solution.
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