TW201542872A - 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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TW201542872A
TW201542872A TW104101959A TW104101959A TW201542872A TW 201542872 A TW201542872 A TW 201542872A TW 104101959 A TW104101959 A TW 104101959A TW 104101959 A TW104101959 A TW 104101959A TW 201542872 A TW201542872 A TW 201542872A
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metal
layer
electroless plating
sacrificial layer
metal layer
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TW104101959A
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TWI618815B (en
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Nobutaka Mizutani
Mitsuaki Iwashita
Takashi Tanaka
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Tokyo Electron Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C18/00—Chemical 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
    • C23C18/16—Chemical 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
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C18/00—Chemical 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
    • C23C18/16—Chemical 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
    • C23C18/1601—Process or apparatus
    • C23C18/1619—Apparatus for electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C18/00—Chemical 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
    • C23C18/16—Chemical 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C18/00—Chemical 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
    • C23C18/16—Chemical 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C18/00—Chemical 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
    • C23C18/16—Chemical 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C18/00—Chemical 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
    • C23C18/16—Chemical 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
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C18/00—Chemical 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
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating

Abstract

A multiple number of accurately-patterned metal layers can be formed on a substrate. On a substrate (11), a patterned first metal layer (12) is formed (see FIG. 1A), and then, a metal sacrificial layer (15) is formed on the first metal layer (12) (see FIG. 1B). Further, an aqueous solution containing an ionized metal allowed to be substituted with a metal of the metal sacrificial layer (15) is coated on the metal sacrificial layer (15), so that a catalyst layer (16) is formed on the metal sacrificial layer (15) (see FIG. 1E). Thereafter, a second metal layer (18) is formed on the catalyst layer (16) by performing an electroless plating process (see FIG. 1F). Furthermore, the substrate (11) is etched by using the second metal layer (18) as a mask.

Description

無電解電鍍方法、無電解電鍍裝置及記憶媒體 Electroless plating method, electroless plating device and memory medium

本發明，係有關於對基板形成無電解電鍍層之無電解電鍍方法、無電解電鍍裝置及記憶媒體。 The present invention relates to an electroless plating method, an electroless plating apparatus, and a memory medium for forming an electroless plating layer on a substrate.

在LSI之製造工程中的金屬形成，係藉由以CVD或PVD來在基板全面上成長一事而進行之。關於金屬之形狀加工，在先前技術之以藥液所進行之蝕刻、Al之配線的乾蝕刻、近年來之BEOL工程中，係藉由先對於絕緣膜進行乾蝕刻，並在所形成的溝等之內部埋入Cu等之配線用的金屬，再以CMP來進行蝕刻等的方法，而進行金屬之形狀加工(專利文獻1)。 Metal formation in the manufacturing process of LSI is carried out by CVD or PVD to grow the entire substrate. Regarding the shape processing of the metal, the etching by the chemical liquid in the prior art, the dry etching of the wiring of Al, and the BEOL engineering in recent years are performed by dry etching the insulating film first, and forming a groove or the like. The metal for wiring such as Cu is buried in the inside, and etching is performed by CMP or the like, and metal shape processing is performed (Patent Document 1).

在此種金屬之形狀加工中，係採用有下述一般之方法：亦即是，首先，係準備基板，並在此基板上藉由PVD或CVD來成膜複數層之金屬層，接著在該複數層之金屬層上設置光阻圖案，並對於複數層之金屬層進行蝕刻。 In the shape processing of such a metal, the following general method is employed: that is, first, a substrate is prepared, and a metal layer of a plurality of layers is formed on the substrate by PVD or CVD, and then A photoresist pattern is disposed on the metal layer of the plurality of layers, and the metal layer of the plurality of layers is etched.

然而，當在金屬上成膜多層之較厚的金屬層，之後對於複數層之金屬層而整批地進行乾蝕刻的情況 時，於現今的乾蝕刻中，係會耗費時間，蝕刻工程之負擔係會變大。又，依存於金屬之種類(例如Cu等)，也會有導致乾蝕刻本身成為非常困難而無法以良好精確度來進行蝕刻的情形，想要在基板上形成由被以良好精確度來作了圖案化的複數層所成之金屬層一事，係為困難。 However, when a thicker metal layer of a plurality of layers is formed on a metal, then dry etching is performed in batches for the metal layers of the plurality of layers. In the current dry etching, it takes time, and the burden of the etching process becomes large. Further, depending on the type of metal (for example, Cu, etc.), there is a case where dry etching itself becomes very difficult and it is impossible to perform etching with good precision, and it is desired to form on the substrate with good precision. The metal layer formed by the patterned plurality of layers is difficult.

〔先行技術文獻〕 [prior technical literature] 〔專利文獻〕 [Patent Document]

[專利文獻1]日本特開平11-297699號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 11-297699

本發明，係為有鑑於此問題而進行者，其目的，係在於提供一種能夠在基板上確實地形成以良好精確度來作了圖案化的金屬層並且能夠在此金屬層上形成不需要進行由乾蝕刻所致之形狀加工的金屬層之無電解電鍍方法、無電解電鍍裝置、以及記憶媒體。 The present invention has been made in view of the above problems, and an object thereof is to provide a metal layer which can be patterned on a substrate with good precision and can be formed on the metal layer without being formed. An electroless plating method of a metal layer processed by dry etching, an electroless plating apparatus, and a memory medium.

本發明，係為一種無電解電鍍方法，其係對於依序被形成有由並不具備觸媒性之金屬化合物所成並被作了圖案化的第1金屬層和金屬犧牲層之基板，而施加無電解電鍍，該無電解電鍍方法，其特徵為，係具備有：將包含有能夠與前述金屬犧牲層之金屬作置換的被作了離子 化之金屬之水溶液，塗佈在前述金屬犧牲層上，藉此來在前述金屬犧牲層上形成觸媒層之工程；和藉由在前述觸媒層上施加無電解電鍍，而形成第2金屬層之工程。 The present invention is an electroless plating method for sequentially forming a substrate of a first metal layer and a metal sacrificial layer which are formed of a metal compound which is not provided with a catalytic property and which is patterned. Applying electroless plating, the electroless plating method, characterized in that the ion-containing plating method comprises: disposing an ion containing a metal capable of being replaced with the metal sacrificial layer An aqueous solution of a metal, coated on the metal sacrificial layer, thereby forming a catalyst layer on the metal sacrificial layer; and forming a second metal by applying electroless plating on the catalyst layer Layer engineering.

本發明，係為一種無電解電鍍裝置，其係對於依序被形成有由並不具備觸媒性之金屬化合物所成並被作了圖案化的第1金屬層和金屬犧牲層之基板，而施與無電解電鍍層，該無電解電鍍裝置，其特徵為，係具備有：觸媒層形成部，係藉由將包含有能夠與前述金屬犧牲層之金屬作置換的被作了離子化之金屬之水溶液，塗佈在前述金屬犧牲層上，來在前述金屬犧牲層上形成觸媒層；和第2金屬層形成部，係藉由在前述觸媒層上施加無電解電鍍，而形成第2金屬層。 The present invention is an electroless plating apparatus which is formed by sequentially forming a substrate of a first metal layer and a metal sacrificial layer which are formed of a metal compound which is not provided with a catalytic property and which is patterned. The electroless plating apparatus is characterized in that the electroless plating apparatus is characterized in that the catalyst layer forming portion is ionized by including a metal capable of being replaced with the metal sacrificial layer. a metal aqueous solution coated on the metal sacrificial layer to form a catalyst layer on the metal sacrificial layer; and a second metal layer forming portion formed by electroless plating on the catalyst layer 2 metal layers.

本發明，係為一種記憶媒體，其係儲存有用以使電腦實行無電解電鍍方法之程式，其特徵為：無電解電鍍方法，係對於依序被形成有由並不具備觸媒性之金屬化合物所成並被作了圖案化的第1金屬層和金屬犧牲層之基板，而施加無電解電鍍，並具備有：將包含有能夠與前述金屬犧牲層之金屬作置換的被作了離子化之金屬之水溶液，塗佈在前述金屬犧牲層上，藉此來在前述金屬犧牲層上形成觸媒層之工程；和藉由在前述觸媒層上施加無電解電鍍，而形成第2金屬層之工程。 The present invention relates to a memory medium for storing a program for causing a computer to perform an electroless plating method, characterized in that an electroless plating method is formed by sequentially forming a metal compound which does not have catalytic properties. Electrolytic plating is applied to the substrate of the first metal layer and the metal sacrificial layer which are patterned and patterned, and the ionized metal is replaced by a metal capable of being replaced with the metal sacrificial layer. a metal aqueous solution coated on the metal sacrificial layer to form a catalyst layer on the metal sacrificial layer; and a second metal layer formed by applying electroless plating on the catalyst layer engineering.

若依據本發明，則係能夠在基板上容易且確 實地形成被以良好精確度而作了圖案化的複數之金屬層。 According to the present invention, it is easy and accurate on the substrate A plurality of metal layers patterned in good precision are formed in the field.

11‧‧‧基板 11‧‧‧Substrate

12‧‧‧第1金屬層 12‧‧‧1st metal layer

13‧‧‧光阻圖案 13‧‧‧resist pattern

15‧‧‧金屬犧牲層 15‧‧‧metal sacrificial layer

16‧‧‧觸媒層 16‧‧‧ catalyst layer

18‧‧‧第2金屬層 18‧‧‧2nd metal layer

23‧‧‧光阻圖案 23‧‧‧resist pattern

30‧‧‧無電解電鍍裝置 30‧‧‧Electroless plating equipment

31‧‧‧第1金屬層形成部 31‧‧‧1st metal layer forming part

32‧‧‧金屬犧牲層形成部 32‧‧‧Metal sacrificial layer formation

33‧‧‧觸媒層形成部 33‧‧‧catalyst layer formation

34‧‧‧第2金屬層形成部 34‧‧‧2nd metal layer forming part

35‧‧‧蝕刻部 35‧‧‧Erosion Department

40‧‧‧控制裝置 40‧‧‧Control device

41‧‧‧記憶媒體 41‧‧‧Memory Media

[圖1]圖1(a)~(g)，係為對於本發明之無電解電鍍方法作展示的流程圖。 Fig. 1 (a) to (g) are flowcharts showing the electroless plating method of the present invention.

[圖2]圖2，係為對於本發明之無電解電鍍裝置作展示的區塊圖。 Fig. 2 is a block diagram showing the electroless plating apparatus of the present invention.

[圖3]圖3(a)、(b)，係為對於作為比較例的多層之金屬層形成方法作展示之圖。 Fig. 3 (a) and (b) are views showing a method of forming a metal layer of a plurality of layers as a comparative example.

以下，使用圖1以及圖2，針對本發明之實施形態作說明。 Hereinafter, an embodiment of the present invention will be described with reference to Figs. 1 and 2 .

由本發明所致之金屬層形成方法，係如同在圖1(a)、(b)、(c)、(d)、(e)、(f)中所示一般，為對於由半導體晶圓等所成之矽基板(以下，亦稱作基板)11而依序形成第1金屬層12、金屬犧牲層15、觸媒層16、無電解電鍍層18者。另外，關於依序形成第1金屬層12、金屬犧牲層15、觸媒層16、無電解電鍍層18所得到的金屬層之全體的厚度，係形成與後述之比較例的圖3之形成第1金屬層12以及第2金屬層18所得到的金屬層全體之厚度相同厚度的金屬層。 The metal layer forming method by the present invention is as shown in FIGS. 1(a), (b), (c), (d), (e), (f), and is generally used for semiconductor wafers or the like. The first metal layer 12, the metal sacrificial layer 15, the catalyst layer 16, and the electroless plating layer 18 are sequentially formed on the formed substrate (hereinafter also referred to as substrate) 11. In addition, the thickness of the entire metal layer obtained by sequentially forming the first metal layer 12, the metal sacrificial layer 15, the catalyst layer 16, and the electroless plating layer 18 is formed in the form of FIG. 3 of a comparative example to be described later. A metal layer having the same thickness as the entire metal layer obtained by the metal layer 12 and the second metal layer 18.

於此情況，作為基板11，係可使用由Si所成 之基板本體，或者是，作為基板11，係亦可使用具備有由Si所成之基板本體和被設置在基板本體上之TEOS層者。 In this case, as the substrate 11, it can be made of Si. As the substrate body, or as the substrate 11, a substrate body made of Si and a TEOS layer provided on the substrate body may be used.

接著，參照圖2，針對對於基板11而依序形成第1金屬層12、金屬犧牲層15、觸媒層16、無電解電鍍層18之無電解電鍍裝置30作說明。 Next, an electroless plating apparatus 30 in which the first metal layer 12, the metal sacrificial layer 15, the catalyst layer 16, and the electroless plating layer 18 are sequentially formed on the substrate 11 will be described with reference to FIG.

此種無電解電鍍裝置30，係具備有在基板11上形成由並不具備觸媒性之金屬化合物所成的第1金屬層12之第1金屬層形成部31、和在第1金屬層12上形成金屬犧牲層15之金屬犧牲層形成部32、和藉由將包含有能夠與金屬犧牲層15之金屬作置換的被作了離子化之金屬之水溶液，塗佈在前述金屬犧牲層15上，來在前述金屬犧牲層15上形成觸媒層16之觸媒層形成部33、以及藉由在觸媒層16上施加無電解電鍍，而形成第2金屬層18之第2金屬層形成部34。 The electroless plating apparatus 30 includes a first metal layer forming portion 31 in which a first metal layer 12 made of a metal compound which does not have catalytic properties is formed on the substrate 11, and a first metal layer 12 is provided. The metal sacrificial layer forming portion 32 on which the metal sacrificial layer 15 is formed, and the aqueous solution containing the ionized metal including the metal capable of being replaced with the metal sacrificial layer 15 are coated on the metal sacrificial layer 15 a catalyst layer forming portion 33 in which the catalyst layer 16 is formed on the metal sacrificial layer 15, and a second metal layer forming portion in which the second metal layer 18 is formed by applying electroless plating on the catalyst layer 16. 34.

又，在觸媒層形成部33以及第2金屬層形成部34之後段處，係被設置有將第2金屬層18作為遮罩並對於基板11施加蝕刻以對於基板11施加圖案化之蝕刻部35。 Further, in the subsequent stage of the catalyst layer forming portion 33 and the second metal layer forming portion 34, an etching portion that applies the etching to the substrate 11 by applying the second metal layer 18 as a mask and applying a pattern to the substrate 11 is provided. 35.

又，上述之無電解電鍍裝置10之各構成構件、例如第1金屬層形成部31、金屬犧牲層形成部32、觸媒層形成部33、第2金屬層形成部34、蝕刻部35，係均為藉由控制裝置40來依據被記錄在設置於控制裝置40處之記憶媒體41中的各種之程式而作驅動控制，並藉由 此來對於基板11進行各種的處理。於此，記憶媒體41，係儲存有各種的設定資料和後述之金屬層形成程式等的各種之程式。作為記憶媒體41，係可使用電腦可讀取之ROM或RAM等之記憶體，或是硬碟、CD-ROM、DVD-ROM或軟碟等之碟片狀記憶媒體等的周知之物。 Further, each of the constituent members of the electroless plating apparatus 10 described above, for example, the first metal layer forming portion 31, the metal sacrificial layer forming portion 32, the catalyst layer forming portion 33, the second metal layer forming portion 34, and the etching portion 35 are The driving control is performed by the control device 40 according to various programs recorded in the memory medium 41 disposed at the control device 40, and by Thus, various processes are performed on the substrate 11. Here, the memory medium 41 stores various programs such as various setting data and a metal layer forming program to be described later. As the memory medium 41, a memory such as a computer-readable ROM or RAM, or a disk-shaped memory medium such as a hard disk, a CD-ROM, a DVD-ROM, or a floppy disk can be used.

接下來，參照圖1，針對由此種構成所成之本實施形態的作用作說明。 Next, the operation of this embodiment formed by such a configuration will be described with reference to Fig. 1 .

首先，由半導體晶圓等所成之基板11，係被搬運至無電解電鍍裝置30處。 First, the substrate 11 made of a semiconductor wafer or the like is transported to the electroless plating apparatus 30.

於此情況，基板11之表面係可為平坦化(參考圖1(a))，亦可在基板11之表面上形成凹部。 In this case, the surface of the substrate 11 may be planarized (refer to FIG. 1(a)), and a recess may be formed on the surface of the substrate 11.

於此，作為在基板11處形成凹部之方法，係可適宜採用先前技術所周知之方法。具體而言，例如，作為乾蝕刻技術，係可適用使用有氟系或氯系氣體等之汎用性的技術，但是，特別是為了形成縱橫比(孔之深度/孔徑)為大的孔，係以採用能夠進行高速之深度挖掘蝕刻的ICP-RIE(Inductively Coupled Plasma Reactive Ion Etching：感應耦合電漿反應性離子蝕刻)之技術的方法為更理想，特別是可適當採用將使用有六氟化硫(SF6)之蝕刻步驟和使用有C4F8等之TEFLON(註冊商標)系氣體之保護步驟作反覆進行的被稱為波希法(BOSCH Process)之方法。 Here, as a method of forming the concave portion at the substrate 11, a method well known in the prior art can be suitably employed. Specifically, for example, as a dry etching technique, a technique using a general-purpose property such as a fluorine-based or chlorine-based gas can be applied, but in particular, in order to form a hole having a large aspect ratio (depth of pores/pore diameter), It is more preferable to adopt a technique of ICP-RIE (Inductively Coupled Plasma Reactive Ion Etching) capable of high-speed deep excavation etching, and in particular, sulfur hexafluoride may be suitably used. The etching step (SF 6 ) and the method of performing the protection step using a TEFLON (registered trademark) gas having a C 4 F 8 or the like are referred to as a BOSCH process.

接著，在無電解電鍍裝置30中，基板11係被送至第1金屬層形成部31處。之後，在此第1金屬層 形成部31處，於基板11上係被形成有被作了圖案化之第1金屬層12。 Next, in the electroless plating apparatus 30, the substrate 11 is sent to the first metal layer forming portion 31. After this, the first metal layer At the forming portion 31, a patterned first metal layer 12 is formed on the substrate 11.

具體而言，如同圖1(a)中所示一般，在基板11上，係藉由CVD或PVD而被形成有由TiN或TaN所成之第1金屬層12。此些之TiN或TaN，係成為後述之相對於藉由無電解電鍍所形成的第2金屬層18而並不具備觸媒性的金屬化合物。 Specifically, as shown in FIG. 1(a), on the substrate 11, a first metal layer 12 made of TiN or TaN is formed by CVD or PVD. Such TiN or TaN is a metal compound which does not have catalytic properties with respect to the second metal layer 18 formed by electroless plating to be described later.

接著，被形成有第1金屬層12之基板11，係被送至金屬犧牲層形成部32處，並在此金屬犧牲層形成部32處，於第1金屬層12上被形成有金屬犧牲層15(參考圖1(b))。 Next, the substrate 11 on which the first metal layer 12 is formed is sent to the metal sacrificial layer forming portion 32, and at the metal sacrificial layer forming portion 32, a metal sacrificial layer is formed on the first metal layer 12. 15 (refer to Figure 1 (b)).

此金屬犧牲層15，係包含有能夠與構成後述之觸媒層16的金屬作置換之金屬，並在金屬犧牲層形成部32處，藉由CVD或PVD而被形成於第1金屬層12上。 The metal sacrificial layer 15 includes a metal which can be substituted with a metal constituting the catalyst layer 16 to be described later, and is formed on the first metal layer 12 by CVD or PVD at the metal sacrificial layer forming portion 32. .

另外，此金屬犧牲層15，係亦可作為在第1金屬層12上而連續性地相連接之較第1金屬層12而更薄之膜來形成之。又，亦可在第1金屬層12上而作為不連續之膜來形成之，亦可形成為粒狀。另外，由第1金屬層12和金屬犧牲層15所成的金屬層之厚度，係被形成為較先前技術的圖3之由第1金屬層12以及第2金屬層18所成的金屬層而更薄。 Further, the metal sacrificial layer 15 may be formed as a thinner film which is continuously connected to the first metal layer 12 on the first metal layer 12. Further, it may be formed as a discontinuous film on the first metal layer 12, or may be formed into a granular shape. Further, the thickness of the metal layer formed by the first metal layer 12 and the metal sacrificial layer 15 is formed as a metal layer formed by the first metal layer 12 and the second metal layer 18 of FIG. 3 of the prior art. Thinner.

接著，在此第1金屬層12以及金屬犧牲層15上，設置光阻圖案13，並藉由對於被設置有光阻圖案13 之第1金屬層12以及金屬犧牲層15施加蝕刻，來得到被作了圖案化的第1金屬層12以及金屬犧牲層15(參考圖1(c))。之後，光阻圖案13係被從第1金屬層12上以及金屬犧牲層15除去(參考圖1(d))。 Next, on the first metal layer 12 and the metal sacrificial layer 15, a photoresist pattern 13 is provided, and by being provided with a photoresist pattern 13 The first metal layer 12 and the metal sacrificial layer 15 are etched to obtain the patterned first metal layer 12 and the metal sacrificial layer 15 (see FIG. 1(c)). Thereafter, the photoresist pattern 13 is removed from the first metal layer 12 and the metal sacrificial layer 15 (refer to FIG. 1(d)).

作為構成此種金屬犧牲層15之金屬，係可使用Ti、W、Cu、Ni或Co之任一者。 As the metal constituting the metal sacrificial layer 15, any of Ti, W, Cu, Ni or Co can be used.

接著，在第1金屬層12上被形成有金屬犧牲層15之基板11，之後係被送至觸媒層形成部33處。接著，在觸媒層形成部33處，對於基板11上之金屬犧牲層15，塗佈包含有能夠與金屬犧牲層15之金屬作置換的被作了離子化之金屬之水溶液，藉由此，在金屬犧牲層15上係被形成有觸媒層16(參考圖1(e))。 Next, the substrate 11 on which the metal sacrificial layer 15 is formed is formed on the first metal layer 12, and then sent to the catalyst layer forming portion 33. Next, at the catalyst layer forming portion 33, an aqueous solution containing the ionized metal which can be substituted with the metal of the metal sacrificial layer 15 is applied to the metal sacrificial layer 15 on the substrate 11, whereby A catalyst layer 16 is formed on the metal sacrificial layer 15 (refer to FIG. 1(e)).

具體而言，當金屬犧牲層15為由Ti或W所成的情況時，係對於金屬犧牲層15而塗佈氯化鈀液或硫酸鈀液等之水溶液。於此情況，水溶液中之鈀離子和金屬犧牲層15之Ti或W係相互置換，在金屬犧牲層15上係析出有鈀離子。 Specifically, when the metal sacrificial layer 15 is made of Ti or W, an aqueous solution of a palladium chloride solution or a palladium sulfate solution or the like is applied to the metal sacrificial layer 15 . In this case, the palladium ions in the aqueous solution and the Ti or W of the metal sacrificial layer 15 are replaced with each other, and palladium ions are deposited on the metal sacrificial layer 15.

如此這般，係可在金屬犧牲層15上，形成由Pd、Au、Pt之任一者之金屬所成的觸媒層16。 In this manner, the catalyst layer 16 made of a metal of any one of Pd, Au, and Pt can be formed on the metal sacrificial layer 15.

接著，被形成有表面觸媒層16之基板11，係被送至第2金屬層形成部34處，並在此第2金屬層形成部34處，對於基板11施加無電解電鍍，而被形成有第2金屬層18。 Then, the substrate 11 on which the surface catalyst layer 16 is formed is sent to the second metal layer forming portion 34, and at the second metal layer forming portion 34, electroless plating is applied to the substrate 11 to be formed. There is a second metal layer 18.

具體而言，藉由對於基板11施加Ni金屬之 無電解電鍍，在基板11上係被施加有以觸媒層16之Pd金屬作為觸媒的電鍍，在觸媒層16上係藉由Ni金屬而被形成有第2金屬層18(參考圖1(f))。 Specifically, by applying Ni metal to the substrate 11 Electroless plating is performed by plating a Pd metal having a catalyst layer 16 as a catalyst on the substrate 11, and a second metal layer 18 is formed on the catalyst layer 16 by Ni metal (refer to FIG. 1). (f)).

此時，被施加無電解電鍍所形成的第2金屬層18，係被形成為與在比較例中所示之圖3之由第1金屬層12以及第2金屬層18所成的金屬層之厚度同等的厚度。藉由本發明所形成之第2金屬層18，係僅在被作了圖案化的金屬層上而被選擇性地形成。 At this time, the second metal layer 18 formed by electroless plating is formed into a metal layer formed of the first metal layer 12 and the second metal layer 18 of FIG. 3 shown in the comparative example. The thickness is the same thickness. The second metal layer 18 formed by the present invention is selectively formed only on the patterned metal layer.

另外，在第2金屬層形成部34處，係亦可並不使用Ni金屬，而是使用Cu金屬來施加無電解電鍍，並在觸媒層16上形成由Cu金屬所成之第2金屬層18。 Further, in the second metal layer forming portion 34, electroless plating may be applied using Cu metal instead of Ni metal, and a second metal layer made of Cu metal may be formed on the catalyst layer 16. 18.

接著，於表面上被形成有第2金屬層18之基板11，係被送至蝕刻部35處，並在此蝕刻部35處，以第2金屬層18作為遮罩而對於基板11施加蝕刻(參考圖1(g))。 Next, the substrate 11 on which the second metal layer 18 is formed is sent to the etching portion 35, and at the etching portion 35, etching is applied to the substrate 11 with the second metal layer 18 as a mask ( Refer to Figure 1 (g)).

如此這般，若依據本實施形態，則當在基板11上形成了第1金屬層12以及金屬犧牲層15之後，係使用光阻圖案13來對於此第1金屬層12以及金屬犧牲層15施加蝕刻，並在被作了圖案化的第1金屬層12以及金屬犧牲層15上設置觸媒層16，之後，係能夠使用觸媒層16來藉由無電解電鍍而設置第2金屬層18。如此這般，係能夠對於第1金屬層12以及金屬犧牲層15之薄的金屬層而使用光阻圖案13來施加乾蝕刻，而能夠將蝕刻工程之負擔減輕，並能夠形成以良好精確度來作了圖案化的第 1金屬層12以及第2金屬層18。又，相較於在基板11之全面上而藉由CVD或PVD來形成金屬層的情形，係能夠僅對於被作了圖案化的第1金屬層12以及金屬犧牲層15而經由觸媒層16來選擇性地形成第2金屬層18。 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 photoresist pattern 13 is used to apply the first metal layer 12 and the metal sacrificial layer 15 to the first metal layer 12 and the metal sacrificial layer 15. The catalyst layer 16 is provided on the patterned first metal layer 12 and the metal sacrificial layer 15 by etching, and then the second metal layer 18 can be provided by electroless plating using the catalyst layer 16. In this manner, the dry etching can be applied to the thin metal layer of the first metal layer 12 and the metal sacrificial layer 15 by using the photoresist pattern 13, and the burden of the etching process can be reduced, and the formation can be performed with good precision. Patterned 1 metal layer 12 and second metal layer 18. Further, the case where the metal layer is formed by CVD or PVD over the entire surface of the substrate 11 can pass through the catalyst layer 16 only for the patterned first metal layer 12 and the metal sacrificial layer 15 The second metal layer 18 is selectively formed.

接著，根據圖3(a)、(b)，針對相對於本發明之比較例作敘述。如同圖3(a)、(b)中所示一般，當在基板11上設置多層之金屬層的情況時，係預先在基板11上藉由CVD或PVD來形成由TiN或TaN所成之第1金屬層12以及由Ni所成之第2金屬層18，接著，在第2金屬層18上設置光阻圖案23，並進行蝕刻，藉由此，亦能夠形成被作了圖案化的第1金屬層12以及第2金屬層18。 Next, a comparative example with respect to the present invention will be described with reference to Figs. 3(a) and 3(b). As shown in FIGS. 3(a) and (b), when a plurality of metal layers are provided on the substrate 11, the first layer formed of TiN or TaN is formed on the substrate 11 by CVD or PVD. 1 metal layer 12 and second metal layer 18 made of Ni, and then a photoresist pattern 23 is provided on the second metal layer 18 and etched, whereby the patterned first layer can be formed. The metal layer 12 and the second metal layer 18.

然而，在圖3(a)、(b)中，係有必要對於基板11上之第1金屬層12以及第2金屬層18之較厚的金屬層而整批地進行蝕刻，在現今的乾蝕刻中，係會耗費時間，並起因於此而導致蝕刻工程之負擔變大，因此，係難以形成以良好精確度來作了圖案化的第1金屬層12以及第2金屬層18。 However, in FIGS. 3(a) and 3(b), it is necessary to etch the entire metal layer 12 on the substrate 11 and the thick metal layer of the second metal layer 18 in a batch, and dry it today. In the etching, it takes time, and the burden of the etching process is increased because of this. Therefore, it is difficult to form the first metal layer 12 and the second metal layer 18 which are patterned with good precision.

相對於此，若依據本實施形態，則係能夠將蝕刻工程之負擔減輕，並能夠得到以良好精確度來作了圖案化的第1金屬層12以及第2金屬層18。 On the other hand, according to the present embodiment, the burden of the etching process can be reduced, and the first metal layer 12 and the second metal layer 18 patterned with good precision can be obtained.

另外，在本實施形態中，雖係將第2金屬層18作為遮罩而用來對於基板11施加蝕刻，但是，係並不被限定於此，亦可將第2金屬層18調整為所需要之厚度 並作為裝置之配線來使用。 Further, in the present embodiment, the second metal layer 18 is used as a mask for etching the substrate 11, but the second metal layer 18 is not limited thereto, and the second metal layer 18 may be adjusted as needed. Thickness It is used as wiring for the device.

11‧‧‧基板 11‧‧‧Substrate

12‧‧‧第1金屬層 12‧‧‧1st metal layer

13‧‧‧光阻圖案 13‧‧‧resist pattern

15‧‧‧金屬犧牲層 15‧‧‧metal sacrificial layer

16‧‧‧觸媒層 16‧‧‧ catalyst layer

18‧‧‧第2金屬層 18‧‧‧2nd metal layer

Claims (13)

一種無電解電鍍方法，係對於依序被形成有由並不具備觸媒性之金屬化合物所成並被作了圖案化的第1金屬層和金屬犧牲層之基板，而施加無電解電鍍，該無電解電鍍方法，其特徵為，係具備有：將包含有能夠與前述金屬犧牲層之金屬作置換的被作了離子化之金屬之水溶液，塗佈在前述金屬犧牲層上，藉此來在前述金屬犧牲層上形成觸媒層之工程；和藉由在前述觸媒層上施加無電解電鍍，而形成第2金屬層之工程。 An electroless plating method for applying electroless plating to a substrate on which a first metal layer and a metal sacrificial layer which are formed of a metal compound which is not provided with a catalytic property and which are patterned, are sequentially formed. An electroless plating method, comprising: coating an aqueous solution containing a metal capable of being replaced with a metal of the metal sacrificial layer, and coating the metal sacrificial layer on the metal sacrificial layer; A process of forming a catalyst layer on the metal sacrificial layer; and a process of forming a second metal layer by applying electroless plating on the catalyst layer. 如申請專利範圍第1項所記載之無電解電鍍方法，其中，係更進而具備有：在形成前述觸媒層之前，在前述基板上形成由並不具備觸媒性之金屬化合物所成並被作了圖案化的第1金屬層之工程；和在前述第1金屬層上形成前述金屬犧牲層之工程。 The electroless plating method according to the first aspect of the invention, further comprising: forming a metal compound which does not have catalytic properties on the substrate before forming the catalyst layer A process of patterning the first metal layer; and a process of forming the metal sacrificial layer on the first metal layer. 如申請專利範圍第1項或第2項所記載之無電解電鍍方法，其中，前述第1金屬層之金屬化合物，係由TiN或TaN所成。 The electroless plating method according to the first or second aspect of the invention, wherein the metal compound of the first metal layer is made of TiN or TaN. 如申請專利範圍第1項或第2項所記載之無電解電鍍方法，其中，前述金屬犧牲層之金屬，係由Ti、W、Cu、Ni或Co所成。 The electroless plating method according to the first or second aspect of the invention, wherein the metal of the metal sacrificial layer is made of Ti, W, Cu, Ni or Co. 如申請專利範圍第1項或第2項所記載之無電解 電鍍方法，其中，前述觸媒層之金屬，係由Pd、Au、Pt所成。 No electrolysis as described in item 1 or 2 of the patent application scope In the electroplating method, the metal of the catalyst layer is made of Pd, Au, and Pt. 如申請專利範圍第1項或第2項所記載之無電解電鍍方法，其中，前述第2金屬層，係由Ni之無電解電鍍層所成。 The electroless plating method according to the first or second aspect of the invention, wherein the second metal layer is made of an electroless plating layer of Ni. 一種無電解電鍍裝置，係對於依序被形成有由並不具備觸媒性之金屬化合物所成並被作了圖案化的第1金屬層和金屬犧牲層之基板，而施與無電解電鍍層，該無電解電鍍裝置，其特徵為，係具備有：觸媒層形成部，係藉由將包含有能夠與前述金屬犧牲層之金屬作置換的被作了離子化之金屬之水溶液，塗佈在前述金屬犧牲層上，來在前述金屬犧牲層上形成觸媒層；和第2金屬層形成部，係藉由在前述觸媒層上施加無電解電鍍，而形成第2金屬層。 An electroless plating apparatus for applying an electroless plating layer to a substrate in which a first metal layer and a metal sacrificial layer which are formed of a metal compound which is not provided with a catalytic property and which are patterned, are sequentially formed. The electroless plating apparatus is characterized in that the catalyst layer forming portion is provided by coating an aqueous solution containing a metal which can be ionized with a metal of the metal sacrificial layer. A catalyst layer is formed on the metal sacrificial layer on the metal sacrificial layer; and a second metal layer forming portion is formed by applying electroless plating to the catalyst layer to form a second metal layer. 如申請專利範圍第7項所記載之無電解電鍍裝置，其中，係更進而具備有：第1金屬層形成部，係在形成前述觸媒層之前，在前述基板上形成由並不具備觸媒性之金屬化合物所成並被作了圖案化的第1金屬層；和金屬犧牲層形成部，係在前述第1金屬層上形成前述金屬犧牲層。 The electroless plating apparatus according to claim 7, wherein the first metal layer forming portion is formed on the substrate before the formation of the catalyst layer, and the catalyst is not provided with a catalyst. The first metal layer formed by the metal compound and patterned, and the metal sacrificial layer forming portion are formed on the first metal layer to form the metal sacrificial layer. 如申請專利範圍第7項或第8項所記載之無電解 電鍍裝置，其中，前述第1金屬層之金屬化合物，係由TiN或TaN所成。 No electrolysis as stated in item 7 or item 8 of the patent application In the electroplating apparatus, the metal compound of the first metal layer is made of TiN or TaN. 如申請專利範圍第7項或第8項所記載之無電解電鍍裝置，其中，前述金屬犧牲層之金屬，係由Ti、W、Cu、Ni或Co所成。 The electroless plating apparatus according to claim 7 or 8, wherein the metal of the metal sacrificial layer is made of Ti, W, Cu, Ni or Co. 如申請專利範圍第7項或第8項所記載之無電解電鍍裝置，其中，前述觸媒層之金屬，係由Pd、Au、Pt所成。 The electroless plating apparatus according to claim 7 or 8, wherein the metal of the catalyst layer is made of Pd, Au or Pt. 如申請專利範圍第7項或第8項所記載之無電解電鍍裝置，其中，前述第2金屬層，係由Ni之無電解電鍍層所成。 The electroless plating apparatus according to claim 7 or 8, wherein the second metal layer is made of an electroless plating layer of Ni. 一種記憶媒體，係儲存有用以使電腦實行無電解電鍍方法之程式，其特徵為：無電解電鍍方法，係對於依序被形成有由並不具備觸媒性之金屬化合物所成並被作了圖案化的第1金屬層和金屬犧牲層之基板，而施加無電解電鍍，並具備有：將包含有能夠與前述金屬犧牲層之金屬作置換的被作了離子化之金屬之水溶液，塗佈在前述金屬犧牲層上，藉此來在前述金屬犧牲層上形成觸媒層之工程；和藉由在前述觸媒層上施加無電解電鍍，而形成第2金屬層之工程。 A memory medium is a program for storing a method for electroless plating of a computer, characterized in that an electroless plating method is formed by sequentially forming a metal compound which does not have catalytic properties and is formed. An electroless plating is applied to the patterned first metal layer and the metal sacrificial layer substrate, and an aqueous solution containing the ionized metal capable of being replaced with the metal sacrificial layer is coated. On the metal sacrificial layer, a process of forming a catalyst layer on the metal sacrificial layer; and a process of forming a second metal layer by applying electroless plating on the catalyst layer.
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