TW202014557A - Electroless plating method, electroless plating apparatus, and program product - Google Patents

Electroless plating method, electroless plating apparatus, and program product Download PDF

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TW202014557A
TW202014557A TW108119401A TW108119401A TW202014557A TW 202014557 A TW202014557 A TW 202014557A TW 108119401 A TW108119401 A TW 108119401A TW 108119401 A TW108119401 A TW 108119401A TW 202014557 A TW202014557 A TW 202014557A
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plating
liquid
main surface
liquid layer
substrate
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TW108119401A
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Chinese (zh)
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TWI720503B (en
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梅田栄次
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日商斯庫林集團股份有限公司
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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
    • 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
    • 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
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents

Abstract

In an electroless plating, a step of forming a liquid layer of a plating liquid which covers an upper surface (91) of a substrate (9) in horizontal state is performed by ejecting the plating liquid toward the upper surface (91) from a mixing nozzle (31). Subsequently, a step of promoting an electroless plating reaction on the upper surface (91) is performed by starting to heat the liquid layer with a heater (41) in a state where the mixing nozzle (31) stops ejecting the plating liquid to the upper surface (91) and the liquid layer is held on the upper surface (91). It is therefore possible to improve a uniformity of thickness of the plating layer.

Description

無電解鍍覆方法、無電解鍍覆裝置以及程式產品Electroless plating method, electroless plating device and program product

本發明係有關於一種無電解鍍覆方法、無電解鍍覆裝置以及程式產品。The invention relates to an electroless plating method, an electroless plating device and a formula product.

近年來，在半導體器件(semiconductor device)的製造中嘗試對半導體基板(以下簡稱為「基板」)施予無電解鍍覆。例如，在日本特開2006-111938號公報(文獻1)的無電解鍍覆裝置中，將無電解鍍覆液預先區分成包含有金屬鹽之第一藥液以及包含有還原劑之第二藥液，並在開始一個基板的處理後在移行至下一個基板的處理之期間混合兩種藥液。接著，在下一個基板的處理中使用該混合的混合液(無電解鍍覆液)，藉此可進行穩定的鍍覆處理。In recent years, in the manufacture of semiconductor devices (semiconductor devices), attempts have been made to apply electroless plating to semiconductor substrates (hereinafter simply referred to as "substrates"). For example, in the electroless plating apparatus of Japanese Unexamined Patent Publication No. 2006-111938 (Document 1), the electroless plating solution is preliminarily divided into a first chemical solution containing a metal salt and a second drug containing a reducing agent After the treatment of one substrate is started, the two chemical solutions are mixed during the process of moving to the next substrate. Next, the mixed liquid mixture (electroless plating liquid) is used in the processing of the next substrate, whereby stable plating processing can be performed.

然而，在文獻1的裝置中，即將供給至基板之鍍覆液係被加熱而成為活性的狀態。在從噴嘴將此種鍍覆液連續性地噴出至基板上之情形中，由於在基板上的噴出位置中接觸至基板表面之鍍覆液被瞬間置換，亦即由於基板表面中的鍍覆液的流速變大，因此難以局部性地進行無電解鍍覆反應。結果，在基板表面中，鍍覆層的厚度在噴出位置與其他的區域中有差異，鍍覆層的厚度的均一性變低。However, in the device of Document 1, the plating solution to be supplied to the substrate is heated to become active. In the case where such plating liquid is continuously ejected from the nozzle onto the substrate, the plating liquid contacting the surface of the substrate in the ejection position on the substrate is instantly replaced, that is, due to the plating liquid in the surface of the substrate The flow rate of becomes larger, so it is difficult to locally perform the electroless plating reaction. As a result, on the surface of the substrate, the thickness of the plating layer differs from the other regions in the ejection position, and the uniformity of the thickness of the plating layer becomes low.

[發明所欲解決之課題][Problems to be solved by the invention]

本發明係著眼於無電解鍍覆方法，目的在於提升鍍覆層的厚度的均一性。The present invention focuses on the electroless plating method, and aims to improve the uniformity of the thickness of the plating layer.

本發明的無電解鍍覆方法係具備有：工序(a)，係從噴嘴朝水平狀態的基板的一個主表面噴出鍍覆液，藉此形成覆蓋前述一個主表面之前述鍍覆液的液層；以及工序(b)，係在停止從前述噴嘴朝前述一個主表面噴出前述鍍覆液且在前述一個主表面上保持前述液層的狀態下開始前述液層的加熱或者前述液層的搖動，藉此促進前述一個主表面中的無電解鍍覆反應。The electroless plating method of the present invention includes the step (a) of spraying a plating solution from a nozzle toward one main surface of a horizontal substrate to form a liquid layer of the plating solution covering the one main surface And step (b), starting the heating of the liquid layer or the shaking of the liquid layer while stopping the spraying of the plating liquid from the nozzle toward the one main surface and maintaining the liquid layer on the one main surface; Thereby, the electroless plating reaction in the aforementioned one main surface is promoted.

依據本發明，能提升鍍覆層的厚度均一性。According to the present invention, the thickness uniformity of the plating layer can be improved.

在本發明的一個較佳形態中，前述鍍覆液係包含有鍍覆金屬的金屬鹽以及用以使前述鍍覆金屬的離子還原析出之還原劑，且不包含有用以防止鍍覆液的分解之穩定劑或者不包含有錯化劑。In a preferred embodiment of the present invention, the plating solution contains a metal salt of the plating metal and a reducing agent for reducing and depositing ions of the plating metal, and does not contain a useful agent to prevent decomposition of the plating solution The stabilizing agent may not contain a misalignment agent.

在此情形中，較佳為在前述工序(a)中，在即將從前述噴嘴噴出前述鍍覆液之前，混合包含有前述金屬鹽之第一藥液以及包含有前述還原劑之第二藥液，藉此生成前述鍍覆液。In this case, it is preferable that in the step (a), immediately before the plating solution is ejected from the nozzle, a first chemical solution containing the metal salt and a second chemical solution containing the reducing agent are mixed , Thereby generating the aforementioned plating solution.

在本發明的其他的較佳形態中，在前述工序(a)中，在即將從前述噴嘴噴出前述鍍覆液之前，混合包含有鍍覆金屬的金屬鹽之第一藥液與包含有用以使前述鍍覆金屬的離子還原析出的還原劑之第二藥液，藉此生成前述鍍覆液。In another preferred embodiment of the present invention, in the step (a), immediately before the plating solution is ejected from the nozzle, the first chemical solution containing the metal salt of the plating metal is mixed with The second chemical solution of the reducing agent of the plating metal ions is reduced to generate the plating solution.

在本發明的一個態樣中，前述第一藥液與前述第二藥液係在前述噴嘴內被混合。In one aspect of the present invention, the first chemical solution and the second chemical solution are mixed in the nozzle.

在本發明的其他的態樣中，前述第一藥液與前述第二藥液係在連接至前述噴嘴的混合閥中被混合。In another aspect of the present invention, the first chemical solution and the second chemical solution are mixed in a mixing valve connected to the nozzle.

在本發明的其他的態樣中，無電解鍍覆方法係進一步具備有下述工序：在前述工序(b)之後，從前述噴嘴朝前述一個主表面噴出清洗液；在噴出前述清洗液之前，前述清洗液係通過從前述第一藥液與前述第二藥液的混合位置至前述噴嘴的噴出口之流路。In another aspect of the present invention, the electroless plating method further includes the following steps: after the step (b), the cleaning liquid is sprayed from the nozzle toward the one main surface; before the cleaning liquid is sprayed, The cleaning liquid passes through a flow path from the mixing position of the first chemical liquid and the second chemical liquid to the discharge port of the nozzle.

在本發明的其他的較佳形態中，無電解鍍覆方法係進一步包含有：工序(c)，係在前述工序(b)之後，從前述噴嘴朝前述一個主表面上的前述鍍覆液的前述液層噴出新的鍍覆液，藉此形成用以覆蓋前述一個主表面之前述新的鍍覆液的液層；以及工序(d)，係在停止從前述噴嘴朝前述一個主表面噴出前述新的鍍覆液且在前述一個主表面上保持前述新的鍍覆液的前述液層之狀態下進行前述液層的加熱或者前述液層的搖動，藉此促進前述一個主表面中的無電解鍍覆反應。In another preferred embodiment of the present invention, the electroless plating method further includes a step (c) after the step (b), from the nozzle toward the plating solution on the main surface Spraying a new plating liquid on the liquid layer, thereby forming a liquid layer of the new plating liquid to cover the one main surface; and step (d), stopping spraying the aforesaid one from the nozzle toward the one main surface New plating liquid and heating of the liquid layer or shaking of the liquid layer while maintaining the liquid layer of the new plating liquid on the main surface, thereby promoting electrolessness in the main surface Plating reaction.

在本發明的其他的較佳形態中，無電解鍍覆方法係進一步包含有：工序(c)，係在前述工序(b)之後，旋轉前述基板藉此去除前述鍍覆液的前述液層，接著從前述噴嘴朝前述一個主表面噴出新的鍍覆液，藉此形成用以覆蓋前述一個主表面之前述新的鍍覆液的液層；以及工序(d)，係在停止從前述噴嘴朝前述一個主表面噴出前述新的鍍覆液且在前述一個主表面上保持前述新的鍍覆液的前述液層之狀態下進行前述液層的加熱或者前述液層的搖動，藉此促進前述一個主表面中的無電解鍍覆反應。In another preferred embodiment of the present invention, the electroless plating method further includes: step (c), after the step (b), rotating the substrate to remove the liquid layer of the plating solution, Next, a new plating solution is sprayed from the nozzle toward the one main surface, thereby forming a liquid layer of the new plating solution to cover the one main surface; and step (d) is to stop the direction from the nozzle The new plating solution is ejected from the one main surface and the liquid layer is heated or the liquid layer is shaken while the liquid layer of the new plating liquid is held on the main surface, thereby promoting the aforementioned one Electroless plating reaction in the main surface.

無電解鍍覆方法亦可進一步具備有用以重複前述工序(c)以及前述工序(d)之工序。The electroless plating method may further include a step useful to repeat the step (c) and the step (d).

在本發明的其他的較佳形態中，在前述工序(a)中將加熱器所為之前述液層的加熱設定成非作動(OFF)狀態，在前述工序(b)中將前述加熱器所為之前述液層的加熱設定成作動(ON)狀態。In another preferred embodiment of the present invention, in the step (a), the heating of the liquid layer by the heater is set to an inactive (OFF) state, and in the step (b), the heater is the same The heating of the aforementioned liquid layer is set to the ON state.

較佳為，在前述工序(a)以及前述工序(c)中將加熱器所為之前述液層的加熱設定成非作動狀態，在前述工序(b)以及前述工序(d)中將前述加熱器所為之前述液層的加熱設定成作動狀態。Preferably, in the step (a) and the step (c), the heating of the liquid layer to which the heater is set is set to an inactive state, and the heater is set in the step (b) and the step (d). The heating of the aforementioned liquid layer is set to the actuated state.

例如，前述加熱器係與前述基板的另一個主表面對向；在前述作動狀態下，前述加熱器係配置於接近或者接觸至前述另一個主表面之位置；在前述非作動狀態下，前述加熱器係配置於已從前述另一個主表面離開之位置。For example, the heater is opposed to the other main surface of the substrate; in the actuated state, the heater is disposed close to or in contact with the other main surface; in the non-activated state, the heating The device is disposed at a position away from the other main surface.

在本發明的其他的較佳形態中，在前述工序(b)中，在加熱前述鍍覆液的前述液層並在前述一個主表面上保持前述液層的狀態下旋轉前述基板。In another preferred embodiment of the present invention, in the step (b), the substrate is rotated while the liquid layer of the plating solution is heated and the liquid layer is held on the one main surface.

在本發明的其他的較佳形態中，在前述工序(b)中，在前述一個主表面上保持前述鍍覆液的前述液層的狀態下，旋轉前述基板或者對前述基板賦予振動。In another preferred embodiment of the present invention, in the step (b), the substrate is rotated or vibration is applied to the substrate while the liquid layer of the plating solution is held on the one main surface.

本發明亦著眼於無電解鍍覆裝置。本發明的無電解鍍覆裝置係具備有：基板保持部，係以水平狀態保持基板；鍍覆液供給部，係從噴嘴朝前述基板的一個主表面噴出鍍覆液，藉此形成用以覆蓋前述一個主表面之前述鍍覆液的液層；鍍覆反應促進部，係進行前述液層的加熱或者前述液層的搖動；以及控制部，係在停止從前述噴嘴朝前述一個主表面噴出前述鍍覆液且在前述一個主表面上保持前述液層之狀態下開始前述鍍覆反應促進部所為之前述液層的加熱或者前述液層的搖動，藉此促進前述一個主表面中的無電解鍍覆反應。The invention also focuses on electroless plating devices. The electroless plating apparatus of the present invention includes: a substrate holding portion that holds the substrate in a horizontal state; a plating liquid supply portion that ejects the plating liquid from a nozzle toward one main surface of the substrate, thereby forming a cover A liquid layer of the plating liquid on the one main surface; a plating reaction promoting portion that heats the liquid layer or shakes the liquid layer; and a control portion that stops spraying the aforesaid nozzle from the nozzle toward the one main surface Plating liquid and starting the heating of the liquid layer or the shaking of the liquid layer by the plating reaction promoting portion while maintaining the liquid layer on the one main surface, thereby promoting electroless plating on the one main surface Cover reaction.

本發明亦著眼於程式產品，係使電腦進行無電解鍍覆裝置的控制，前述無電解鍍覆裝置係具備有基板保持部、鍍覆液供給部以及鍍覆反應促進部。The present invention also focuses on a program product, which causes a computer to control an electroless plating device, which is provided with a substrate holding part, a plating liquid supply part, and a plating reaction promoting part.

上述目的以及其他的目的、特徵、態樣以及優點係藉由參照隨附的圖式以及以下所進行的本發明的詳細的說明而明瞭。The above object and other objects, features, aspects, and advantages are made clear by referring to the accompanying drawings and the following detailed description of the present invention.

圖1係顯示本發明實施形態之一的無電解鍍覆裝置1的構成之圖。無電解鍍覆裝置1係葉片式的裝置，用以逐片地處理圓板狀的基板9。無電解鍍覆裝置1係具備有基板保持部21、基板旋轉機構22、罩部(cup)23、鍍覆液供給部3、鍍覆反應促進部4以及電腦11。FIG. 1 is a diagram showing the configuration of an electroless plating apparatus 1 according to an embodiment of the present invention. The electroless plating apparatus 1 is a blade-type apparatus for processing the disk-shaped substrate 9 piece by piece. The electroless plating apparatus 1 is provided with a substrate holding part 21, a substrate rotating mechanism 22, a cup 23, a plating liquid supply part 3, a plating reaction promoting part 4, and a computer 11.

基板保持部21係具有將朝向上下方向的中心軸J1作為中心之圓板狀的基座部211。於基座部211的上表面設置有複數個夾具銷(chuck pin)212。複數個夾具銷212係等間隔地配置於將中心軸J1作為中心之圓周上的周方向。各個夾具銷212係可藉由銷驅動機構(未圖示)將與中心軸J1平行的軸作為中心轉動。於夾具銷212的前端設置有把持部213。在基板保持部21保持基板9時，各個夾具銷212轉動。藉此，複數個把持部213被按壓至基板9的外周緣，基板9係以水平狀態被保持於基座部211的上方。被基板保持部21保持的基板9的中心係位於中心軸J1上。基座部211的上表面係與基板9中之朝向下方的主表面92(以下稱為「下表面92」)平行，且兩者隔著間隙彼此對向。The substrate holding portion 21 has a disk-shaped base portion 211 having a center axis J1 oriented in the vertical direction as a center. A plurality of chuck pins 212 are provided on the upper surface of the base portion 211. The plurality of jig pins 212 are arranged at equal intervals in the circumferential direction on the circumference centered on the center axis J1. Each clamp pin 212 can be rotated by a pin drive mechanism (not shown) about an axis parallel to the central axis J1 as a center. A grip portion 213 is provided at the front end of the jig pin 212. When the substrate holding portion 21 holds the substrate 9, each jig pin 212 rotates. Thereby, the plurality of gripping portions 213 are pressed against the outer periphery of the substrate 9, and the substrate 9 is held above the base portion 211 in a horizontal state. The center of the substrate 9 held by the substrate holding portion 21 is located on the central axis J1. The upper surface of the base portion 211 is parallel to the downwardly facing main surface 92 (hereinafter referred to as "lower surface 92") of the substrate 9, and the two face each other with a gap therebetween.

於基座部211的下表面的中央固定有將中心軸J1作為中心之軸部221的上端。具有馬達之基板旋轉機構22係旋轉軸部221的下端部，藉此基板保持部21係與基板9一起將中心軸J1作為中心旋轉。罩部23係略筒狀，圍繞基座部211的周圍。在後述的基板9的處理中，從旋轉中的基板9的外周緣飛散的各種處理液係被罩部23的內周面接住並被回收。在無電解鍍覆裝置1中，罩部23的上部係可藉由未圖示的罩部升降機構於上下方向升降。於無電解鍍覆裝置1中的基板9的搬入以及搬出時，罩部23的上部下降，防止罩部23與外部的搬運機構干擾。An upper end of the shaft portion 221 centered on the center axis J1 is fixed to the center of the lower surface of the base portion 211. The substrate rotating mechanism 22 having a motor rotates the lower end portion of the shaft portion 221, whereby the substrate holding portion 21 rotates together with the substrate 9 about the central axis J1 as the center. The cover portion 23 is slightly cylindrical and surrounds the base portion 211. In the processing of the substrate 9 described later, various processing liquids scattered from the outer peripheral edge of the rotating substrate 9 are caught by the inner peripheral surface of the cover portion 23 and collected. In the electroless plating apparatus 1, the upper portion of the cover portion 23 can be raised and lowered in the vertical direction by a cover portion lifting mechanism (not shown). During the loading and unloading of the substrate 9 in the electroless plating apparatus 1, the upper portion of the cover portion 23 is lowered to prevent the cover portion 23 from interfering with an external transport mechanism.

鍍覆反應促進部4係具備有加熱器41以及加熱器升降機構42。加熱器41係將中心軸J1作為中心之圓板狀，配置於被基板保持部21保持的基板9與基座部211之間。加熱器41係位於基板9的下表面92之一側。加熱器41係例如為具有鎳鉻線等電阻發熱體之加熱板(hot plate)。加熱器41亦可利用電阻發熱體以外的熱源。加熱器41的上表面係遍及基板9的下表面92的大致整體，並直接地與下表面92對向。加熱器41的上表面係大致與基板9的下表面92平行。The plating reaction promotion unit 4 is provided with a heater 41 and a heater elevating mechanism 42. The heater 41 is in the form of a disk with the center axis J1 as the center, and is disposed between the substrate 9 held by the substrate holding portion 21 and the base portion 211. The heater 41 is located on one side of the lower surface 92 of the substrate 9. The heater 41 is, for example, a hot plate having a resistance heating element such as nickel-chromium wire. The heater 41 may use a heat source other than the resistance heating element. The upper surface of the heater 41 extends over substantially the entire lower surface 92 of the substrate 9 and directly faces the lower surface 92. The upper surface of the heater 41 is substantially parallel to the lower surface 92 of the substrate 9.

於加熱器41的下表面的中央固定有將中心軸J1作為中心之升降軸421的上端。於基座部211以及軸部221的中心軸J1上設置有於上下方向延伸之中空部，且於該中空部內配置有升降軸421。升降軸421係延伸至比軸部221的下端還下方。在軸部221的下方中，升降軸421的下端部係連接至加熱器升降機構42。At the center of the lower surface of the heater 41, the upper end of the lifting shaft 421 centering on the central axis J1 is fixed. A hollow portion extending in the up-down direction is provided on the center axis J1 of the base portion 211 and the shaft portion 221, and the lifting shaft 421 is disposed in the hollow portion. The lifting shaft 421 extends below the lower end of the shaft portion 221. Below the shaft portion 221, the lower end of the lifting shaft 421 is connected to the heater lifting mechanism 42.

加熱器升降機構42係經由升降軸421支撐加熱器41。例如，加熱器升降機構42係包含有滾珠螺桿機構以及馬達，並藉由馬達的驅動將升降軸421於上下方向移動。藉此，加熱器41係選擇性地配置於上位置與下位置，該上位置係加熱器41的上表面接近至基板9的下表面92之位置，該下位置係加熱器41的上表面已從基板9的下表面92離開之位置。在圖1的例子中，在下位置中，加熱器41的下表面係接近或者接觸至基座部211的上表面。加熱器41亦可配置於上位置與下位置之間的任意的位置。在本實施形態中，加熱器41係以固定溫度恆常地被加熱，藉由將加熱器41配置於上位置，能將基板9的下表面92大致均一地加熱。另一方面，在已將加熱器41配置於下位置的狀態下，基板9係幾乎不會被加熱。在基板9的加熱時不旋轉基板9之情形中，在上位置中加熱器41的上表面亦可接觸至基板9的下表面92。The heater lifting mechanism 42 supports the heater 41 via the lifting shaft 421. For example, the heater lifting mechanism 42 includes a ball screw mechanism and a motor, and the lifting shaft 421 is moved in the up-down direction by driving of the motor. As a result, the heater 41 is selectively disposed at the upper position and the lower position. The upper position is the position where the upper surface of the heater 41 approaches the lower surface 92 of the substrate 9. The lower position is the upper surface of the heater 41 The position away from the lower surface 92 of the substrate 9. In the example of FIG. 1, in the lower position, the lower surface of the heater 41 is close to or in contact with the upper surface of the base portion 211. The heater 41 may be arranged at any position between the upper position and the lower position. In this embodiment, the heater 41 is constantly heated at a fixed temperature, and by arranging the heater 41 at the upper position, the lower surface 92 of the substrate 9 can be heated substantially uniformly. On the other hand, in the state where the heater 41 has been arranged at the lower position, the substrate 9 system is hardly heated. In the case where the substrate 9 is not rotated during the heating of the substrate 9, the upper surface of the heater 41 in the upper position may also contact the lower surface 92 of the substrate 9.

鍍覆液供給部3係具備有混合噴嘴31、第一藥液供給源33、第二藥液供給源34以及清洗液供給源35。混合噴嘴31係與基板9中之朝向上方的主表面91(以下稱為「上表面91」)對向。詳細而言，混合噴嘴31係配置於上表面91的中央部的上方，混合噴嘴31的噴出口312係直接地與上表面91對向。混合噴嘴31係具有混合室311以及上述噴出口312。於混合室311經由第一藥液供給管331連接有第一藥液供給源33，並經由第二藥液供給管341連接有第二藥液供給源34。此外，於混合室311經由清洗液供給管351連接有清洗液供給源35。於第一藥液供給管331從第一藥液供給源33之側朝向混合噴嘴31依序設置有流量調整閥332以及開閉閥333。於第二藥液供給管341從第二藥液供給源34之側朝向混合噴嘴31依序設置有流量調整閥342以及開閉閥343。於清洗液供給管351設置有開閉閥353。The plating solution supply unit 3 includes a mixing nozzle 31, a first chemical solution supply source 33, a second chemical solution supply source 34, and a cleaning solution supply source 35. The mixing nozzle 31 is opposed to the main surface 91 (hereinafter referred to as "upper surface 91") facing upward in the substrate 9. In detail, the mixing nozzle 31 is arranged above the center of the upper surface 91, and the ejection port 312 of the mixing nozzle 31 directly faces the upper surface 91. The mixing nozzle 31 has a mixing chamber 311 and the above-mentioned discharge port 312. The first chemical liquid supply source 33 is connected to the mixing chamber 311 via the first chemical liquid supply tube 331, and the second chemical liquid supply source 34 is connected to the second chemical liquid supply tube 341. In addition, a washing liquid supply source 35 is connected to the mixing chamber 311 via a washing liquid supply pipe 351. The first chemical solution supply pipe 331 is provided with a flow rate adjustment valve 332 and an on-off valve 333 in order from the side of the first chemical solution supply source 33 toward the mixing nozzle 31. A flow rate adjustment valve 342 and an on-off valve 343 are provided in order from the side of the second chemical solution supply source 34 toward the mixing nozzle 31 in the second chemical solution supply tube 341. The cleaning liquid supply pipe 351 is provided with an on-off valve 353.

如後所述，在鍍覆液供給部3中，同時進行從第一藥液供給源33朝混合室311內供給第一藥液以及從第二藥液供給源34朝混合室311內供給第二藥液。第一藥液係包含有無電解鍍覆中的鍍覆金屬的金屬鹽。鍍覆金屬係例如為鎳(Ni)、銅(Cu)、鈷(Co)、鈷鎢硼(CoWB)、金(Au)或者銀(Ag)等。第二藥液係包含有用以使鍍覆金屬的離子還原析出之還原劑。還原劑係例如為DMAB(硼化合物)等。在混合室311中混合第一藥液與第二藥液，藉此生成包含有上述金屬鹽以及還原劑之鍍覆液。As will be described later, in the plating solution supply unit 3, the first chemical solution supply from the first chemical solution supply source 33 into the mixing chamber 311 and the second chemical solution supply source 34 into the mixing chamber 311 are simultaneously performed. Two medicine liquid. The first chemical solution contains the metal salt of the metal plating in electroless plating. The plating metal system is, for example, nickel (Ni), copper (Cu), cobalt (Co), cobalt tungsten boron (CoWB), gold (Au), silver (Ag), or the like. The second chemical solution contains a reducing agent useful for reducing and depositing ions of the metal plating. The reducing agent system is, for example, DMAB (boron compound). The first chemical solution and the second chemical solution are mixed in the mixing chamber 311, thereby generating a plating solution containing the metal salt and the reducing agent.

鍍覆液係從連續至混合室311之噴出口312朝基板9的上表面91的中央部例如柱狀地被噴出。鍍覆液中的第一藥液與第二藥液的混合比係藉由控制流量調整閥332、342的開放度而被調製。較佳為，第一藥液以及第二藥液雙方係未包含有用以防止鍍覆液的分解之穩定劑(例如於羧酸添加有烷基醇之混合液等)或者未包含有錯化劑(例如包含有乙二胺之混合液等)。在此情形中，在混合噴嘴31內生成的鍍覆液亦未包含有穩定劑或者錯化劑。更佳為，鍍覆液係未包含有穩定劑以及錯化劑雙方。鍍覆液亦可包含有用以調製鍍覆液的ph(power of hydrogen；酸鹼值)之ph調整劑(例如氨等)以及用以抑制ph的變動之緩衝劑(例如氨等)。The plating liquid is ejected from the ejection port 312 continuous to the mixing chamber 311 toward the center of the upper surface 91 of the substrate 9, for example, in a column shape. The mixing ratio of the first chemical solution and the second chemical solution in the plating solution is adjusted by controlling the opening degrees of the flow rate adjustment valves 332 and 342. Preferably, both the first chemical solution and the second chemical solution do not contain a stabilizer that is useful to prevent the decomposition of the plating solution (for example, a mixed solution in which an alkyl alcohol is added to the carboxylic acid) or do not contain a misalignment agent (For example, a mixed solution containing ethylenediamine, etc.). In this case, the plating solution generated in the mixing nozzle 31 also does not contain a stabilizer or a distorting agent. More preferably, the plating liquid system does not include both the stabilizer and the distorting agent. The plating solution may also contain a pH adjuster (for example, ammonia, etc.) useful for adjusting the pH (power of hydrogen; pH value) of the plating solution, and a buffering agent (for example, ammonia, etc.) for suppressing changes in ph.

在本實施形態中，在第一藥液供給源33以及第一藥液供給管331中未設置有用以加熱第一藥液之加熱器。此外，在第二藥液供給源34以及第二藥液供給管341中未設置有用以加熱第二藥液之加熱器。再者，亦未於混合噴嘴31設置加熱器。因此，大致常溫的鍍覆液係從混合噴嘴31朝基板9的上表面91噴出。從混合噴嘴31噴出的鍍覆液的溫度係例如為23℃至40℃。In the present embodiment, the first chemical solution supply source 33 and the first chemical solution supply pipe 331 are not provided with a heater for heating the first chemical solution. In addition, the second chemical solution supply source 34 and the second chemical solution supply pipe 341 are not provided with a heater for heating the second chemical solution. Furthermore, no heater is provided in the mixing nozzle 31. Therefore, the plating solution at approximately normal temperature is ejected from the mixing nozzle 31 toward the upper surface 91 of the substrate 9. The temperature of the plating liquid discharged from the mixing nozzle 31 is, for example, 23°C to 40°C.

在鍍覆液供給部3中，從清洗液供給源35對混合噴嘴31的混合室311內供給清洗液，藉此從噴出口312朝基板9的上表面91的中央部噴出清洗液。在朝混合噴嘴31供給清洗液時，不進行對混合室311內供給第一藥液以及第二藥液。清洗液係例如為純水。亦可使用純水以外的清洗液。In the plating solution supply unit 3, the cleaning solution is supplied from the cleaning solution supply source 35 into the mixing chamber 311 of the mixing nozzle 31, whereby the cleaning solution is discharged from the discharge port 312 toward the center of the upper surface 91 of the substrate 9. When the cleaning liquid is supplied to the mixing nozzle 31, the first chemical liquid and the second chemical liquid are not supplied into the mixing chamber 311. The cleaning liquid system is, for example, pure water. You can also use a cleaning solution other than pure water.

無電解鍍覆裝置1係進一步具備有處理液供給部5。處理液供給部5係具備有輔助噴嘴51、觸媒溶液供給源52、洗淨液供給源53以及清洗液供給源54。輔助噴嘴51係配置於基板9的上方。於輔助噴嘴51經由閥分別連接有觸媒溶液供給源52、洗淨液供給源53以及清洗液供給源54。從觸媒溶液供給源52對輔助噴嘴51供給觸媒溶液，藉此從輔助噴嘴51朝基板9的上表面91的中央部噴出觸媒溶液。觸媒溶液係包含有利用於無電解鍍覆的觸媒(例如鈀(Pd)等金屬的離子)之溶液。The electroless plating apparatus 1 further includes a processing liquid supply unit 5. The processing liquid supply unit 5 includes an auxiliary nozzle 51, a catalyst solution supply source 52, a cleaning solution supply source 53, and a cleaning solution supply source 54. The auxiliary nozzle 51 is arranged above the substrate 9. The auxiliary nozzle 51 is connected to the catalyst solution supply source 52, the cleaning solution supply source 53, and the cleaning solution supply source 54 via valves, respectively. The catalyst solution is supplied from the catalyst solution supply source 52 to the auxiliary nozzle 51, whereby the catalyst solution is discharged from the auxiliary nozzle 51 toward the center of the upper surface 91 of the substrate 9. The catalyst solution is a solution containing a catalyst (such as ions of metal such as palladium (Pd)) which is advantageous for electroless plating.

此外，從洗淨液供給源53朝輔助噴嘴51供給洗淨液，藉此從輔助噴嘴51朝基板9的上表面91的中央部噴出洗淨液。洗淨液係例如為DHF(dilute hydrofluoric acid；稀釋氫氟酸)。從清洗液供給源54朝輔助噴嘴51供給清洗液，藉此從輔助噴嘴51朝基板9的上表面91的中央部噴出清洗液。清洗液係例如為純水。在處理液供給部5中，亦可使用蝕刻液等其他的處理液。觸媒溶液供給源52、洗淨液供給源53以及清洗液供給源54亦可分別連接至不同的噴嘴。此外，鍍覆液供給部3的清洗液供給源35亦可兼作為清洗液供給源54。In addition, the cleaning liquid is supplied from the cleaning liquid supply source 53 to the auxiliary nozzle 51, whereby the cleaning liquid is discharged from the auxiliary nozzle 51 toward the center of the upper surface 91 of the substrate 9. The washing liquid system is, for example, DHF (dilute hydrofluoric acid; diluted hydrofluoric acid). The cleaning liquid is supplied from the cleaning liquid supply source 54 to the auxiliary nozzle 51, whereby the cleaning liquid is discharged from the auxiliary nozzle 51 toward the center of the upper surface 91 of the substrate 9. The cleaning liquid system is, for example, pure water. In the processing liquid supply part 5, other processing liquids, such as an etching liquid, can also be used. The catalyst solution supply source 52, the cleaning solution supply source 53, and the cleaning solution supply source 54 may also be connected to different nozzles, respectively. In addition, the cleaning solution supply source 35 of the plating solution supply unit 3 may also serve as the cleaning solution supply source 54.

在無電解鍍覆裝置1中，亦可設置有用以移動混合噴嘴31以及輔助噴嘴51之噴嘴移動機構。噴嘴移動機構係將混合噴嘴31以及輔助噴嘴51選擇性地配置於對向位置與待機位置，該對向位置係與基板9的上表面91對向之位置，該待機位置係已從基板9朝水平方向離開之位置。噴嘴移動機構亦可個別地移動混合噴嘴31以及輔助噴嘴51。The electroless plating apparatus 1 may be provided with a nozzle moving mechanism that moves the mixing nozzle 31 and the auxiliary nozzle 51. The nozzle moving mechanism selectively arranges the mixing nozzle 31 and the auxiliary nozzle 51 at a facing position opposed to the upper surface 91 of the substrate 9, which has been facing away from the substrate 9 The position to leave in the horizontal direction. The nozzle moving mechanism may move the mixing nozzle 31 and the auxiliary nozzle 51 individually.

圖2係顯示電腦11的構成之圖。電腦11係成為一般的電腦系統的構成，並包含有：CPU(Central Processing Unit；中央處理器)111，係進行各種運算處理；ROM(Read Only Memory；唯讀記憶體)112，係記憶基本程式；以及RAM(Random Access Memory；隨機存取記憶體)113，係記憶各種資訊。電腦11係進一步包含有：固定硬碟114，係進行資訊記憶；顯示部115，係進行各種資訊的顯示；鍵盤116a以及滑鼠116b，係作為輸入部116，接收來自操作者的輸入；讀取寫入裝置118，係從光碟、磁碟、光磁碟等電腦可讀取的記錄媒體81進行資訊的讀取，並對記錄媒體81進行資訊的寫入；以及通訊部119，係與無電解鍍覆裝置1的各構成進行通訊。FIG. 2 is a diagram showing the configuration of the computer 11. The computer 11 is the structure of a general computer system and includes: CPU (Central Processing Unit; central processing unit) 111, which performs various arithmetic processing; ROM (Read Only Memory; read only memory) 112, which is the basic program of memory ; And RAM (Random Access Memory) 113, which stores various information. The computer 11 further includes: a fixed hard disk 114 for information storage; a display 115 for displaying various kinds of information; a keyboard 116a and a mouse 116b for inputting 116 to receive input from the operator; reading The writing device 118 reads information from a computer-readable recording medium 81 such as an optical disc, a magnetic disk, an optical disk, etc., and writes information to the recording medium 81; Each configuration of the plating apparatus 1 communicates.

在電腦11中，事前經由讀取寫入裝置118從屬於程式產品的記錄媒體81讀出程式810並記憶至固定硬碟114。接著，CPU111係利用RAM113以及固定硬碟114依循程式810執行運算處理(亦即電腦執行程式)，藉此電腦11係作為圖1的無電解鍍覆裝置1中的控制部110而發揮作用。在無電解鍍覆裝置1中，控制部110係負責整體控制。控制部110亦可由專用的電性電路來構築，亦可局部性地利用專用的電性電路。In the computer 11, the program 810 is read out from the recording medium 81 belonging to the program product via the reading and writing device 118 in advance and stored in the fixed hard disk 114. Next, the CPU 111 uses the RAM 113 and the fixed hard disk 114 to perform calculation processing according to the program 810 (that is, the computer executes the program), whereby the computer 11 functions as the control unit 110 in the electroless plating apparatus 1 of FIG. 1. In the electroless plating apparatus 1, the control unit 110 is responsible for overall control. The control unit 110 may be constructed by a dedicated electrical circuit, or a dedicated electrical circuit may be used locally.

圖3係顯示無電解鍍覆裝置1中的無電解鍍覆處理的流程之圖。在無電解鍍覆處理中，藉由圖1的控制部110進行無電解鍍覆裝置1的控制(除了控制部110之外，進行無電解鍍覆裝置1的各構成的控制)。FIG. 3 is a diagram showing the flow of the electroless plating process in the electroless plating apparatus 1. In the electroless plating process, the control unit 110 of FIG. 1 performs control of the electroless plating device 1 (in addition to the control unit 110, control of each configuration of the electroless plating device 1).

在無電解鍍覆裝置1中，事前藉由外部的搬運機構搬入處理對象的基板9並藉由基板保持部21保持基板9。在無電解鍍覆處理中，首先，藉由基板旋轉機構22開始旋轉基板9。基板9係在水平狀態下與基板保持部21一起旋轉。此外，從洗淨液供給源53經由配置於對向位置的輔助噴嘴51對基板9的上表面91的中央部供給洗淨液(步驟S11)。In the electroless plating apparatus 1, the substrate 9 to be processed is carried in by an external conveyance mechanism in advance, and the substrate 9 is held by the substrate holding portion 21. In the electroless plating process, first, the substrate 9 is rotated by the substrate rotating mechanism 22. The substrate 9 rotates together with the substrate holding portion 21 in a horizontal state. In addition, the cleaning liquid is supplied from the cleaning liquid supply source 53 to the central portion of the upper surface 91 of the substrate 9 via the auxiliary nozzle 51 disposed at the opposed position (step S11).

在上表面91中，洗淨液係藉由基板9的旋轉所致使之離心力朝基板9的外周緣擴展，且洗淨液係被供給至上表面91的整體。從基板9的外周緣飛散的洗淨液係被罩部23的內周面接住並被回收(在後述的清洗液、觸媒溶液以及鍍覆液的供給時亦同樣)。藉由洗淨液的供給，去除上表面91上的異物以及自然氧化膜等。洗淨液的噴出係持續預定時間。In the upper surface 91, the washing liquid is centrifugal force caused by the rotation of the substrate 9 to expand toward the outer periphery of the substrate 9, and the washing liquid is supplied to the entire upper surface 91. The cleaning liquid scattered from the outer peripheral edge of the substrate 9 is caught by the inner circumferential surface of the cover portion 23 and recovered (the same applies to the supply of cleaning liquid, catalyst solution, and plating liquid described later). By the supply of the cleaning liquid, the foreign matter and the natural oxide film on the upper surface 91 are removed. The spraying of the cleaning liquid lasts for a predetermined time.

當停止噴出洗淨液時，從清洗液供給源54經由輔助噴嘴51對上表面91的中央部供給清洗液(步驟S12)。在上表面91中，清洗液係藉由基板9的旋轉朝基板9的外周緣擴展，且清洗液係被供給至上表面91的整體。藉由清洗液的供給，去除附著至上表面91的洗淨液。清洗液係持續噴出預定時間後，停止噴出清洗液。When the discharge of the cleaning liquid is stopped, the cleaning liquid is supplied from the cleaning liquid supply source 54 to the central portion of the upper surface 91 via the auxiliary nozzle 51 (step S12). In the upper surface 91, the cleaning liquid spreads toward the outer periphery of the substrate 9 by the rotation of the substrate 9, and the cleaning liquid is supplied to the entire upper surface 91. By the supply of the cleaning liquid, the cleaning liquid adhering to the upper surface 91 is removed. After the cleaning liquid system continues to spray for a predetermined time, the spray of cleaning liquid is stopped.

接著，從觸媒溶液供給源52經由輔助噴嘴51對上表面91的中央部供給觸媒溶液(步驟S13)。在上表面91中，觸媒溶液係藉由基板9的旋轉朝基板9的外周緣擴展，且觸媒溶液係被供給至上表面91的整體。藉此，觸媒(例如鈀)係吸附至上表面91並形成觸媒層。觸媒溶液的噴出係持續預定時間。Next, the catalyst solution is supplied from the catalyst solution supply source 52 to the central portion of the upper surface 91 via the auxiliary nozzle 51 (step S13). In the upper surface 91, the catalyst solution spreads toward the outer periphery of the substrate 9 by the rotation of the substrate 9, and the catalyst solution is supplied to the entire upper surface 91. Thereby, the catalyst (for example, palladium) is adsorbed on the upper surface 91 and forms a catalyst layer. The spraying of the catalyst solution lasts for a predetermined time.

當停止噴出觸媒溶液時，從清洗液供給源54經由輔助噴嘴51對上表面91的中央部供給清洗液(步驟S14)。在上表面91中，清洗液係藉由基板9的旋轉朝基板9的外周緣擴展，且清洗液係被供給至上表面91的整體。藉由清洗液的供給，去除附著至上表面91的觸媒溶液。此外，維持形成於上表面91的觸媒層。清洗液係持續噴出預定時間後，停止噴出清洗液。When the discharge of the catalyst solution is stopped, the cleaning liquid is supplied from the cleaning liquid supply source 54 to the central portion of the upper surface 91 via the auxiliary nozzle 51 (step S14). In the upper surface 91, the cleaning liquid spreads toward the outer periphery of the substrate 9 by the rotation of the substrate 9, and the cleaning liquid is supplied to the entire upper surface 91. By the supply of the cleaning liquid, the catalyst solution adhering to the upper surface 91 is removed. In addition, the catalyst layer formed on the upper surface 91 is maintained. After the cleaning liquid system continues to spray for a predetermined time, the spray of cleaning liquid is stopped.

接著，開始從第一藥液供給源33朝混合噴嘴31的混合室311內供給第一藥液，且開始從第二藥液供給源34朝混合室311內供給第二藥液。第一藥液以及第二藥液係在混合室311中被混合並生成鍍覆液。混合噴嘴31係配置於對向位置，從混合噴嘴31的噴出口312朝基板9的上表面91的中央部連續性地噴出鍍覆液。在上表面91中，鍍覆液係藉由基板9的旋轉朝基板9的外周緣擴展，且鍍覆液係被供給至上表面91的整體。Next, the supply of the first chemical liquid from the first chemical liquid supply source 33 into the mixing chamber 311 of the mixing nozzle 31 is started, and the supply of the second chemical liquid from the second chemical liquid supply source 34 into the mixing chamber 311 is started. The first chemical solution and the second chemical solution are mixed in the mixing chamber 311 to generate a plating solution. The mixing nozzle 31 is arranged at the facing position, and the plating liquid is continuously discharged from the discharge port 312 of the mixing nozzle 31 toward the center of the upper surface 91 of the substrate 9. In the upper surface 91, the plating solution spreads toward the outer periphery of the substrate 9 by the rotation of the substrate 9, and the plating solution is supplied to the entire upper surface 91.

此時，由於基板9的旋轉數較低，因此如圖4A所示形成有用以覆蓋上表面91的整體之鍍覆液的液層93(亦稱為覆液(paddle))(步驟S15)。亦即，於上表面91盛液有鍍覆液。在圖4A中，藉由箭頭A1顯示基板9的旋轉(後述的圖4C、圖4E、圖4F、圖5A以及圖5B中亦同樣)。如上述般，鍍覆液係大致常溫。此外，加熱器41係配置於已從基板9的下表面92離開之下位置。因此，液層93所含有之鍍覆液的溫度被維持在大致常溫，且上表面91中的無電解鍍覆反應變成被抑制的狀態，亦即變成反應速度低的狀態(惰性的狀態)。如後述般，加熱器41係配置於已接近下表面92之上位置，藉此加熱器41對於液層93的加熱係變成作動狀態，因此在加熱器41配置於已從下表面92離開之下位置的步驟S15中加熱器41對於液層93的加熱為非作動狀態。At this time, since the rotation number of the substrate 9 is low, as shown in FIG. 4A, a liquid layer 93 (also referred to as a paddle) with a plating liquid covering the entire upper surface 91 is formed (step S15). That is, the upper surface 91 contains the plating solution. In FIG. 4A, the rotation of the substrate 9 is indicated by the arrow A1 (the same applies to FIGS. 4C, 4E, 4F, 5A, and 5B described later). As mentioned above, the plating solution is approximately normal temperature. In addition, the heater 41 is arranged at a lower position away from the lower surface 92 of the substrate 9. Therefore, the temperature of the plating solution contained in the liquid layer 93 is maintained at approximately normal temperature, and the electroless plating reaction in the upper surface 91 becomes a suppressed state, that is, a state where the reaction rate is low (inert state). As will be described later, the heater 41 is arranged close to the position above the lower surface 92, whereby the heating system of the heater 41 with respect to the liquid layer 93 becomes actuated, so the heater 41 is arranged below the lower surface 92 In step S15 of the position, the heating of the liquid layer 93 by the heater 41 is inactive.

在鍍覆液供給部3中，於從混合噴嘴31連續性地噴出鍍覆液之期間(步驟S15的處理期間)，在混合室311所生成的鍍覆液的總量(體積)係遠大於混合室311的容積。因此，在上述期間中藉由第一藥液以及第二藥液的混合所生成的鍍覆液的大部分係在上述期間中朝基板9噴出。換言之，在無電解鍍覆裝置1中，在即將從混合噴嘴31噴出鍍覆液之前，混合第一藥液與第二藥液並生成鍍覆液。In the plating solution supply unit 3, while the plating solution is continuously ejected from the mixing nozzle 31 (the processing period of step S15), the total amount (volume) of the plating solution generated in the mixing chamber 311 is much larger than The volume of the mixing chamber 311. Therefore, most of the plating solution generated by the mixing of the first chemical solution and the second chemical solution during the above period is ejected toward the substrate 9 during the above period. In other words, in the electroless plating apparatus 1, immediately before the plating liquid is ejected from the mixing nozzle 31, the first chemical liquid and the second chemical liquid are mixed to generate a plating liquid.

在基板9的直徑為300mm且以每分鐘0.05L(公升)至0.3L的流量從混合噴嘴31噴出鍍覆液之情形中，從適當地形成某種程度的厚度的鍍覆液的液層93之觀點而言，基板9的旋轉數較佳為300rpm以下。在無電解鍍覆裝置1中，可在已停止基板9的旋轉之狀態下形成鍍覆液的液層93。在此情形中，連續性地供給至上表面91的中央部之鍍覆液係逐漸地朝基板9的外周緣擴展，且於上表面91的整體形成有鍍覆液的液層93。如上所述，形成鍍覆液的液層93時之基板9的旋轉數(以下稱為「液層形成旋轉數」)較佳為0rpm至300rpm。液層形成旋轉數較佳為0rpm至50rpm，更佳為0rpm至10rpm。此外，鍍覆液的流量較佳為每分鐘0.05L至0.3L。在以下的說明中，基板9以液層形成旋轉數旋轉係包含有基板9的旋轉數為0之情形，亦即包含有停止基板9的旋轉之情形。In the case where the diameter of the substrate 9 is 300 mm and the plating liquid is ejected from the mixing nozzle 31 at a flow rate of 0.05 L (liter) to 0.3 L per minute, a liquid layer 93 of the plating liquid of a certain thickness is appropriately formed From a viewpoint, the rotation number of the substrate 9 is preferably 300 rpm or less. In the electroless plating apparatus 1, the liquid layer 93 of the plating liquid can be formed in a state where the rotation of the substrate 9 has been stopped. In this case, the plating solution continuously supplied to the central portion of the upper surface 91 gradually spreads toward the outer periphery of the substrate 9, and a liquid layer 93 of the plating solution is formed on the entire upper surface 91. As described above, the number of rotations of the substrate 9 when forming the liquid layer 93 of the plating liquid (hereinafter referred to as "liquid layer formation rotation number") is preferably 0 rpm to 300 rpm. The rotation number of the liquid layer formation is preferably 0 rpm to 50 rpm, more preferably 0 rpm to 10 rpm. In addition, the flow rate of the plating solution is preferably 0.05 L to 0.3 L per minute. In the following description, the number of rotations of the substrate 9 with the formation of the liquid layer rotation includes the case where the rotation number of the substrate 9 is 0, that is, the case where the rotation of the substrate 9 is stopped.

當持續預定時間噴出鍍覆液並形成有鍍覆液的液層93時，停止從混合噴嘴31噴出鍍覆液。在上表面91中，藉由鍍覆液的表面張力保持液層93。接著，加熱器41係藉由加熱器升降機構42上升，且如圖4B所示般配置於已接近基板9的下表面92之上位置。藉此，加熱器41開始對基板9加熱。藉由基板9的加熱，液層93亦被加熱。如此，將加熱器41配置於上位置，藉此加熱器41對於液層93的加熱係變成作動狀態。When the plating liquid is ejected for a predetermined time and the liquid layer 93 with the plating liquid is formed, the ejection of the plating liquid from the mixing nozzle 31 is stopped. On the upper surface 91, the liquid layer 93 is maintained by the surface tension of the plating liquid. Next, the heater 41 is raised by the heater elevating mechanism 42 and is arranged at a position close to the lower surface 92 of the substrate 9 as shown in FIG. 4B. With this, the heater 41 starts heating the substrate 9. The liquid layer 93 is also heated by the heating of the substrate 9. In this way, the heater 41 is arranged at the upper position, whereby the heating system of the heater 41 with respect to the liquid layer 93 becomes an actuated state.

液層93所含有之鍍覆液的溫度上升，藉此該鍍覆液變成活性的狀態(反應速度高的狀態)，並促進上表面91的整體中的無電解鍍覆反應(步驟S16)。例如，液層93所含有之鍍覆液係被加熱至40℃至60℃。在無電解鍍覆反應中，藉由形成於上表面91上之觸媒層的觸媒作用，鍍覆液所含有之還原劑係被氧化，且鍍覆液所含有之鍍覆金屬的離子係藉由來自還原劑的電子而被還原，並於觸媒層上析出鍍覆金屬。此外，藉由所析出的鍍覆金屬自身的觸媒作用，還原劑係被氧化，進一步還原析出鍍覆金屬的離子。在無電解鍍覆裝置1中，基板9的下表面92係被均一地加熱，在上表面91的整體中同時地促進無電解鍍覆反應。藉此，在上表面91的整體中均一地成長鍍覆金屬並形成有一樣的鍍覆層94(參照後述的圖4C)。步驟S16中的成膜速率係步驟S15中的成膜速率(反應被抑制的狀態中的成膜速率)的例如5倍以上(相當於整個膜)。The temperature of the plating solution contained in the liquid layer 93 rises, whereby the plating solution becomes active (state with a high reaction rate), and promotes the electroless plating reaction in the entire upper surface 91 (step S16). For example, the plating solution contained in the liquid layer 93 is heated to 40°C to 60°C. In the electroless plating reaction, the reducing agent contained in the plating solution is oxidized by the catalyst action of the catalyst layer formed on the upper surface 91, and the ion system of the plating metal contained in the plating solution It is reduced by the electrons from the reducing agent, and the plated metal is deposited on the catalyst layer. In addition, due to the catalytic action of the deposited plating metal itself, the reducing agent system is oxidized to further reduce the ions of the deposited plating metal. In the electroless plating apparatus 1, the lower surface 92 of the substrate 9 is uniformly heated, and the electroless plating reaction is simultaneously promoted in the entire upper surface 91. With this, the metal plating is uniformly grown on the entire upper surface 91 and the same plating layer 94 is formed (see FIG. 4C described later). The film formation rate in step S16 is, for example, 5 times or more (corresponding to the entire film) the film formation rate in step S15 (the film formation rate in a state where the reaction is suppressed).

在基板9的一例中，在上表面91上形成有直立的多個圖案要素，且於該圖案要素的表面形成有鍍覆層94。此時，當著眼於彼此鄰接的圖案要素間的微小的間隙時，當存在於該間隙的鍍覆液的鍍覆金屬以及還原劑被消耗時，在該間隙中變成無法進行無電解鍍覆反應。因此，較佳為在無電解鍍覆裝置1中以可保持上表面91上的鍍覆液的液層93之旋轉數(例如300rpm以下的旋轉數)旋轉基板9，藉此將存在於該間隙的鍍覆液緩緩地與周圍的鍍覆液置換。如此，在加熱鍍覆液的液層93並在上表面91上保持液層93的狀態下旋轉基板9，藉此可進一步地促進無電解鍍覆反應，並可效率佳地(減少無必要的耗費)利用鍍覆液。另一方面，從在促進上表面91中的無電解鍍覆反應時在上表面91上更確實地保持液層93之觀點而言，亦可停止旋轉基板9。步驟S16中的基板9的旋轉數係例如為0rpm至300rpm，較佳為0rpm至50rpm，更佳為0rpm至10rpm。In an example of the substrate 9, a plurality of upright pattern elements are formed on the upper surface 91, and a plating layer 94 is formed on the surface of the pattern elements. At this time, when focusing on a small gap between pattern elements adjacent to each other, when the plating metal and the reducing agent of the plating solution existing in the gap are consumed, the electroless plating reaction becomes impossible in the gap . Therefore, it is preferable to rotate the substrate 9 in the electroless plating apparatus 1 by the number of rotations (for example, the number of rotations of 300 rpm or less) of the liquid layer 93 that can hold the plating solution on the upper surface 91, thereby existing in the gap The plating solution is gradually replaced with the surrounding plating solution. In this way, the substrate 9 is rotated while the liquid layer 93 of the plating liquid is heated and the liquid layer 93 is held on the upper surface 91, whereby the electroless plating reaction can be further promoted and can be efficiently (reduced unnecessary) (Consumption) Use plating solution. On the other hand, from the viewpoint of more reliably holding the liquid layer 93 on the upper surface 91 when promoting the electroless plating reaction in the upper surface 91, the rotation of the substrate 9 may also be stopped. The rotation number of the substrate 9 in step S16 is, for example, 0 rpm to 300 rpm, preferably 0 rpm to 50 rpm, and more preferably 0 rpm to 10 rpm.

當加熱器41開始加熱液層93經過預定時間時，加熱器41係藉由加熱器升降機構42下降並配置於已從基板9的下表面92離開之下位置(參照後述的圖4C)。藉此，實質性地停止加熱器41對於基板9的加熱。換言之，加熱器41對於液層93的加熱係變成非作動狀態。接著，確認是否重複上述步驟S15、S16的處理。在控制部110中，預先輸入步驟S15、S16的重複次數的設定值，並確認實際的重複次數是否已到達設定值。在實際的重複次數未到達設定值之情形中(步驟S17)，一邊以液層形成旋轉數旋轉基板9，一邊如圖4C所示般從混合噴嘴31朝上表面91上的鍍覆液的液層93噴出新的鍍覆液。在圖4C中，將對液層93附上之平行斜線的寬度縮小成比圖4A以及圖4B還窄，並顯示使用完畢的液層93。藉由從混合噴嘴31噴出新的鍍覆液，形成有用以覆蓋上表面91之新的鍍覆液的液層93a(參照後述的圖4D)(步驟S15)。如上所述，由於加熱器41對於液層93a的加熱為非作動狀態，因此上表面91中的無電解鍍覆反應係被抑制。When the heater 41 starts heating the liquid layer 93 for a predetermined period of time, the heater 41 is lowered by the heater elevating mechanism 42 and arranged at a lower position away from the lower surface 92 of the substrate 9 (refer to FIG. 4C described later). As a result, the heating of the substrate 9 by the heater 41 is substantially stopped. In other words, the heating system of the liquid layer 93 by the heater 41 becomes inactive. Next, it is confirmed whether the processes of steps S15 and S16 described above are repeated. The control unit 110 inputs the set value of the number of repetitions of steps S15 and S16 in advance, and confirms whether the actual number of repetitions has reached the set value. In the case where the actual number of repetitions does not reach the set value (step S17), while rotating the substrate 9 with the number of revolutions of the liquid layer, as shown in FIG. 4C, the liquid of the plating solution on the upper surface 91 from the mixing nozzle 31 Layer 93 sprays a new plating solution. In FIG. 4C, the width of the parallel diagonal line attached to the liquid layer 93 is reduced to be narrower than that of FIGS. 4A and 4B, and the used liquid layer 93 is shown. By ejecting a new plating solution from the mixing nozzle 31, a liquid layer 93a (see FIG. 4D described later) with a new plating solution covering the upper surface 91 is formed (step S15). As described above, since the heating of the liquid layer 93a by the heater 41 is in an inactive state, the electroless plating reaction system in the upper surface 91 is suppressed.

此時，新的鍍覆液亦可包含有在先前的步驟S15的處理期間(最初的鍍覆液的液層93的形成時)在混合室311所生成的鍍覆液的一部分。在無電解鍍覆處理中，在藉由各個步驟S15的處理期間中藉由第一藥液以及第二藥液的混合而生成的鍍覆液的至少一部分在該處理期間中朝基板9噴出之情形中，能在即將從混合噴嘴31噴出之前生成鍍覆液。At this time, the new plating solution may include a part of the plating solution generated in the mixing chamber 311 during the process of the previous step S15 (when the liquid layer 93 of the initial plating solution was formed). In the electroless plating process, at least a part of the plating solution generated by the mixing of the first chemical solution and the second chemical solution in the processing period of each step S15 is ejected toward the substrate 9 during the processing period In this case, the plating liquid can be generated immediately before being ejected from the mixing nozzle 31.

從混合噴嘴31朝上表面91持續預定時間噴出新的鍍覆液後，停止噴出新的鍍覆液。接著，加熱器41係藉由加熱器升降機構42上升並如圖4D所示般配置於已接近基板9的下表面92之上位置。藉此，在上表面91中已保持液層93a之狀態下開始加熱液層93a(亦即加熱器41對於液層93a的加熱被設定成作動狀態)，並促進上表面91中的無電解鍍覆反應(步驟S16)。藉由使用了針對上表面91之液層93a的無電解鍍覆，上表面91中的鍍覆層94的厚度係均一地增大。當從開始加熱液層93a經過預定時間時，加熱器41下降，停止加熱液層93a。在無電解鍍覆裝置1中，重複上述步驟S15、S16的處理直至步驟S15、S16的實際的重複次數到達設定值為止(步驟S17)。藉此，鍍覆層94的厚度進一步地增大。After spraying a new plating liquid from the mixing nozzle 31 toward the upper surface 91 for a predetermined time, the spray of the new plating liquid is stopped. Next, the heater 41 is raised by the heater elevating mechanism 42 and arranged at a position close to the lower surface 92 of the substrate 9 as shown in FIG. 4D. Thereby, the heating of the liquid layer 93a is started with the liquid layer 93a held in the upper surface 91 (that is, the heating of the liquid layer 93a by the heater 41 is set to the active state), and the electroless plating on the upper surface 91 is promoted Coverage reaction (step S16). By using electroless plating for the liquid layer 93a of the upper surface 91, the thickness of the plating layer 94 in the upper surface 91 is uniformly increased. When a predetermined time elapses from the start of heating the liquid layer 93a, the heater 41 descends, and the heating of the liquid layer 93a is stopped. In the electroless plating apparatus 1, the processes of steps S15 and S16 described above are repeated until the actual number of repetitions of steps S15 and S16 reaches the set value (step S17). With this, the thickness of the plating layer 94 is further increased.

當步驟S15、S16的實際的重複次數到達設定值時(步驟S17)，從清洗液供給源35對混合噴嘴31供給清洗液。藉此，如圖4E所示，從混合噴嘴31朝上表面91的中央部噴出清洗液(步驟S18)。在上表面91中，清洗液係藉由基板9的旋轉朝基板9的外周緣擴展，且清洗液係被供給至上表面91的整體。藉由清洗液的供給，去除附著於上表面91的鍍覆液。此時，在圖1的混合噴嘴31中，清洗液被填充至混合室311內後從噴出口312噴出。因此，殘留於混合室311內的鍍覆液係藉由通過混合室311的清洗液而被去除。持續預定時間噴出清洗液後，停止噴出清洗液。When the actual number of repetitions of steps S15 and S16 reaches the set value (step S17), the cleaning liquid is supplied from the cleaning liquid supply source 35 to the mixing nozzle 31. Thereby, as shown in FIG. 4E, the cleaning liquid is discharged from the mixing nozzle 31 toward the center of the upper surface 91 (step S18). In the upper surface 91, the cleaning liquid spreads toward the outer periphery of the substrate 9 by the rotation of the substrate 9, and the cleaning liquid is supplied to the entire upper surface 91. By the supply of the cleaning liquid, the plating liquid adhering to the upper surface 91 is removed. At this time, in the mixing nozzle 31 of FIG. 1, the cleaning liquid is filled into the mixing chamber 311 and is discharged from the discharge port 312. Therefore, the plating liquid remaining in the mixing chamber 311 is removed by the cleaning liquid passing through the mixing chamber 311. After spraying the cleaning liquid for a predetermined time, the spray of the cleaning liquid is stopped.

接著，基板旋轉機構22係將基板9的旋轉數設定成比供給清洗液時還高，藉此如圖4F所示開始基板9的乾燥處理(旋乾(spin drying))(步驟S19)。藉由乾燥處理去除附著於上表面91的清洗液。當結束乾燥處理時，停止旋轉基板9。之後，基板9係被外部的搬運機構從無電解鍍覆裝置1搬出。藉此，完成無電解鍍覆裝置1中的基板9的處理。Next, the substrate rotating mechanism 22 sets the number of rotations of the substrate 9 to be higher than when the cleaning liquid is supplied, thereby starting the drying process (spin drying) of the substrate 9 as shown in FIG. 4F (step S19). The cleaning solution adhering to the upper surface 91 is removed by the drying process. When the drying process is ended, the rotation of the substrate 9 is stopped. Thereafter, the substrate 9 is carried out of the electroless plating apparatus 1 by an external conveying mechanism. With this, the processing of the substrate 9 in the electroless plating apparatus 1 is completed.

在此，說明比較例的無電解鍍覆裝置，比較例的無電解鍍覆裝置係從噴嘴朝基板9的上表面91噴出經過加熱的鍍覆液。在比較例的無電解鍍覆裝置中，由於鍍覆液在藉由加熱而成為活性的狀態下從噴嘴噴出，因此在上表面91中藉由擴展的鍍覆液進行無電解鍍覆反應。另一方面，在從噴嘴噴出的鍍覆液所碰撞的上表面91上的位置(噴出位置)中，接觸至上表面91的鍍覆液係被瞬間置換，亦即上表面91中的鍍覆液的流速變大。結果，在上表面91上的噴出位置中，變得難以局部性地進行無電解鍍覆反應(鍍覆金屬變得難以成長)，且鍍覆層的厚度的均一性變低。Here, the electroless plating apparatus of the comparative example will be described. The electroless plating apparatus of the comparative example ejects the heated plating liquid from the nozzle toward the upper surface 91 of the substrate 9. In the electroless plating apparatus of the comparative example, since the plating liquid is ejected from the nozzle while being activated by heating, the electroless plating reaction is performed on the upper surface 91 with the expanded plating liquid. On the other hand, at a position on the upper surface 91 where the plating liquid ejected from the nozzle collides (ejection position), the plating liquid system contacting the upper surface 91 is instantly replaced, that is, the plating liquid in the upper surface 91 The flow rate becomes larger. As a result, in the ejection position on the upper surface 91, it becomes difficult to locally perform the electroless plating reaction (the plating metal becomes difficult to grow), and the uniformity of the thickness of the plating layer becomes low.

相對於此，在無電解鍍覆裝置1的處理中進行下述工序：從混合噴嘴31噴出常溫的鍍覆液，藉此形成用以覆蓋上表面91之鍍覆液的液層。接著，進行下述工序：在停止從混合噴嘴31朝上表面91噴出鍍覆液且在上表面91上保持該液層的狀態下開始加熱該液層，藉此促進上表面91中的無電解鍍覆反應。如此，從混合噴嘴31噴出鍍覆液時，在上表面91的整體中抑制無電解鍍覆反應，並在形成鍍覆液的液層後藉由基板9的加熱在上表面91的整體中促進無電解鍍覆反應，藉此抑制噴出位置與其他的區域之間的鍍覆金屬的成長差異，並能提升鍍覆層的厚度的均一性。On the other hand, in the process of the electroless plating apparatus 1, the following process is performed: The plating liquid of normal temperature is sprayed from the mixing nozzle 31, thereby forming a liquid layer of the plating liquid for covering the upper surface 91. Next, the following process is performed: heating of the liquid layer is started in a state where the spraying of the plating liquid from the mixing nozzle 31 toward the upper surface 91 is stopped and the liquid layer is maintained on the upper surface 91, thereby promoting electrolessness in the upper surface 91 Plating reaction. In this way, when the plating liquid is ejected from the mixing nozzle 31, the electroless plating reaction is suppressed in the entire upper surface 91, and after the formation of the liquid layer of the plating liquid, the entire upper surface 91 is promoted by the heating of the substrate 9 The electroless plating reaction suppresses the difference in the growth of the plating metal between the ejection position and other areas, and improves the thickness uniformity of the plating layer.

此外，在上述工序後進行下述工序：從混合噴嘴31朝上表面91上的上述液層噴出新的鍍覆液，藉此形成用以覆蓋上表面91之新的鍍覆液的液層。接著，進行下述工序：在停止從混合噴嘴31朝上表面91噴出新的鍍覆液且在上表面91上保持該液層的狀態下開始加熱該液層，藉此促進上表面91中的無電解鍍覆反應。藉此，能形成均一且厚的鍍覆層。In addition, after the above process, a process is performed in which a new plating liquid is sprayed from the mixing nozzle 31 toward the liquid layer on the upper surface 91, thereby forming a new liquid layer for covering the upper surface 91 with the new plating liquid. Next, the following process is performed: heating of the liquid layer is started while the spraying of a new plating liquid from the mixing nozzle 31 toward the upper surface 91 is stopped and the liquid layer is maintained on the upper surface 91, thereby promoting the Electroless plating reaction. Thereby, a uniform and thick plating layer can be formed.

此外，在鍍覆液包含有穩定劑或者錯化劑之情形中，會有穩定劑或者錯化劑係吸附至形成於上表面91上的觸媒層並阻礙觸媒層的觸媒作用所致使之還原劑的氧化之情形，亦即會有穩定劑或者錯化劑作為觸媒毒素而發揮作用之情形。在此情形中，變得無法適當地形成鍍覆層。In addition, in the case where the plating solution contains a stabilizer or a distorting agent, the stabilizer or the distorting agent is adsorbed to the catalyst layer formed on the upper surface 91 and hinders the catalyst function of the catalyst layer. In the case of the oxidation of the reducing agent, that is, a stabilizer or a disintegrant may act as a catalyst toxin. In this case, it becomes impossible to form the plating layer properly.

相對於此，在較佳的無電解鍍覆處理中，能使用未包含有穩定劑或者錯化劑之鍍覆液。藉此，能抑制阻礙還原劑的氧化，而能適當地形成鍍覆層。在更佳的無電解鍍覆處理中鍍覆液未包含有穩定劑以及錯化劑雙方，藉此能更進一步地抑制阻礙還原劑的氧化。此外，省略穩定劑或者錯化劑，藉此能減少鍍覆液的生成所需的成本。根據鍍覆液的種類等，鍍覆液亦可包含有穩定劑或者錯化劑。On the other hand, in a preferred electroless plating process, a plating solution that does not contain a stabilizer or a distorting agent can be used. Thereby, the inhibition of oxidation of the reducing agent can be suppressed, and the plating layer can be appropriately formed. In a better electroless plating process, the plating solution does not contain both the stabilizer and the distorting agent, thereby further suppressing the inhibition of oxidation of the reducing agent. In addition, omitting the stabilizer or the distorting agent can reduce the cost required for the generation of the plating solution. Depending on the type of plating solution, etc., the plating solution may also contain stabilizers or distorting agents.

在假設採用用以儲留鍍覆液之槽(tank)之情形中，為了將槽內的鍍覆液的濃度保持成一定，變得需要濃度監視器以及／或者液體補充系統等。此外，為了使槽內的鍍覆液的性狀穩定，因此亦需要添加穩定劑或者錯化劑。再者，亦存在將槽與噴嘴之間連接的管的內部被鍍覆之可能性。In the case where it is assumed that a tank for storing the plating liquid is used, in order to keep the concentration of the plating liquid in the tank constant, a concentration monitor and/or a liquid replenishment system and the like are required. In addition, in order to stabilize the properties of the plating solution in the tank, it is also necessary to add a stabilizer or a distorting agent. Furthermore, there is a possibility that the inside of the tube connecting the groove and the nozzle is plated.

相對於此，在圖1的無電解鍍覆裝置1中，在即將從混合噴嘴31噴出鍍覆液之前，在混合噴嘴31內混合第一藥液與第二藥液並生成鍍覆液。藉此，能防止將第一藥液供給源33與混合噴嘴31連接之第一藥液供給管331以及將第二藥液供給源34與混合噴嘴31連接之第二藥液供給管341的內部被鍍覆。此外，無須設置濃度監視器以及液體補充系統等，即能將已均一地混合金屬鹽與還原劑的鍍覆液容易地以需要的量供給至基板9上。結果，能實現無電解鍍覆裝置1的製造成本的降低以及鍍覆液的節省所致使之運轉成本(running cost)的降低。再者，亦能抑制因為鍍覆液中未存在有穩定劑或者錯化劑產生的不良影響(例如鍍覆液的劣化等)。On the other hand, in the electroless plating apparatus 1 of FIG. 1, immediately before the plating liquid is ejected from the mixing nozzle 31, the first chemical liquid and the second chemical liquid are mixed in the mixing nozzle 31 to generate a plating liquid. By this, the inside of the first chemical liquid supply pipe 331 connecting the first chemical liquid supply source 33 to the mixing nozzle 31 and the second chemical liquid supply tube 341 connecting the second chemical liquid supply source 34 to the mixing nozzle 31 can be prevented Be plated. In addition, it is possible to easily supply the plating liquid in which the metal salt and the reducing agent are uniformly supplied to the substrate 9 in a required amount without providing a concentration monitor, a liquid replenishment system, and the like. As a result, it is possible to reduce the manufacturing cost of the electroless plating apparatus 1 and the running cost due to the saving of the plating liquid. In addition, it is also possible to suppress the adverse effects (for example, deterioration of the plating liquid, etc.) due to the absence of stabilizers or distorting agents in the plating liquid.

此外，從混合噴嘴31噴出清洗液時，清洗液係通過從第一藥液與第二藥液的混合位置(在圖1中為混合室311)至混合噴嘴31的噴出口312之流路。藉此，能藉由清洗液去除殘留於從混合位置至噴出口312之路徑的鍍覆液，而能防止該流路被鍍覆。當然，亦可根據無電解鍍覆裝置1的設計而採用用以儲留鍍覆液之槽。In addition, when the cleaning liquid is discharged from the mixing nozzle 31, the cleaning liquid passes through a flow path from the mixing position of the first chemical liquid and the second chemical liquid (the mixing chamber 311 in FIG. 1) to the discharge port 312 of the mixing nozzle 31. Thereby, the plating liquid remaining on the path from the mixing position to the ejection port 312 can be removed by the cleaning liquid, and the flow path can be prevented from being plated. Of course, according to the design of the electroless plating apparatus 1, a tank for storing a plating solution may also be used.

在無電解鍍覆裝置1中，在液層的加熱的作動狀態中，加熱器41係配置於接近或者接觸基板9的下表面92之位置；在液層的加熱的非作動狀態中，加熱器41係配置於已從下表面92離開之位置。藉此，使用難以使溫度急遽地上升下降之加熱器41，從而能適當地進行液層的加熱的作動狀態以及非作動狀態的切換。In the electroless plating apparatus 1, in the active state of heating of the liquid layer, the heater 41 is disposed close to or in contact with the lower surface 92 of the substrate 9; in the non-active state of heating of the liquid layer, the heater 41 is arranged at a position that has left from the lower surface 92. With this, the heater 41 that makes it difficult to rapidly increase and decrease the temperature is used, so that the operating state and the non-operating state of the heating of the liquid layer can be appropriately switched.

在上述處理例中，在重複步驟S15、S16的處理時，雖然從混合噴嘴31朝上表面91上的鍍覆液的液層93噴出新的鍍覆液，但亦可在噴出新的鍍覆液之前去除上表面91上的液層93。在此情形中，在藉由步驟S17而重複的步驟S15中，以比液層形成旋轉數還高的旋轉數旋轉基板9，藉此如圖5A所示般去除上表面91上的液層93。此時，加熱器41係配置於下位置。接著，一邊以液層形成旋轉數旋轉基板9，一邊從混合噴嘴31朝上表面91噴出新的鍍覆液，藉此如圖5B所示般形成有用以覆蓋上表面91之新的鍍覆液的液層93a。In the above processing example, when the processing of steps S15 and S16 is repeated, although a new plating liquid is ejected from the mixing nozzle 31 toward the liquid layer 93 of the plating liquid on the upper surface 91, a new plating may also be ejected The liquid layer 93 on the upper surface 91 is removed before the liquid. In this case, in step S15 repeated by step S17, the substrate 9 is rotated at a rotation number higher than the liquid layer formation rotation number, thereby removing the liquid layer 93 on the upper surface 91 as shown in FIG. 5A . At this time, the heater 41 is arranged at the lower position. Next, while rotating the substrate 9 with the number of revolutions in the liquid layer, a new plating liquid is ejected from the mixing nozzle 31 toward the upper surface 91, thereby forming a new plating liquid to cover the upper surface 91 as shown in FIG. 5B的液层93a。 The liquid layer 93a.

在步驟S16中，如圖5C所示，在停止從混合噴嘴31朝上表面91噴出新的鍍覆液且在上表面91上保持新的鍍覆液的液層93a之狀態下，加熱器41係配置於上位置。藉此，加熱器41對於液層93a的加熱係被設定成作動狀態，並促進上表面91中的無電解鍍覆反應。結果，增大上表面91中的鍍覆層94的厚度。上述步驟S15、S16的處理係因應需要進一步地重複。In step S16, as shown in FIG. 5C, in a state where the spraying of the new plating liquid from the mixing nozzle 31 toward the upper surface 91 is stopped and the liquid layer 93a of the new plating liquid is held on the upper surface 91, the heater 41 It is placed in the upper position. With this, the heating system of the heater 41 with respect to the liquid layer 93a is set to an actuated state, and the electroless plating reaction in the upper surface 91 is promoted. As a result, the thickness of the plating layer 94 in the upper surface 91 is increased. The processing of the above steps S15 and S16 is further repeated as necessary.

在上述步驟S15、S16的處理中，在噴出新的鍍覆液之前以高的旋轉數旋轉基板9，藉此能去除使用完畢的鍍覆液的液層93並降低基板9的溫度。藉此，在形成新的鍍覆液的液層93a時，能將基板9以及鍍覆液的溫度保持成較低，並更確實地抑制上表面91中的無電解鍍覆反應。結果，能進一步地提升鍍覆層的厚度的均一性。此外，能減少形成液層93a(使用完畢的鍍覆液與新的鍍覆液的置換)所需的新的鍍覆液的量。In the processes of steps S15 and S16 described above, the substrate 9 is rotated at a high number of revolutions before the new plating solution is discharged, whereby the liquid layer 93 of the used plating solution can be removed and the temperature of the substrate 9 can be lowered. Thereby, when the liquid layer 93a of the new plating liquid is formed, the temperature of the substrate 9 and the plating liquid can be kept low, and the electroless plating reaction in the upper surface 91 can be more reliably suppressed. As a result, the thickness uniformity of the plating layer can be further improved. In addition, the amount of new plating liquid required to form the liquid layer 93a (replacement of the used plating liquid with a new plating liquid) can be reduced.

圖6係顯示鍍覆液供給部的其他的例子之圖。圖6的鍍覆液供給部3a係具備有噴嘴31a、混合閥32、第一藥液供給源33、第二藥液供給源34以及清洗液供給源35。噴嘴31a係例如為直式噴嘴(straight nozzle)，且配置於基板9的上表面91的中央部的上方。混合閥32係具備有混合室320、第一閥321、第二閥322、第三閥323以及第四閥324。第一閥321、第二閥322、第三閥323以及第四閥324係連接至混合室320。於第一閥321經由第一藥液供給管331連接有第一藥液供給源33，於第二閥322經由第二藥液供給管341連接有第二藥液供給源34。此外，於第三閥323經由清洗液供給管351連接有清洗液供給源35，於第四閥324連接有噴嘴31a。於第一藥液供給管331設置有流量調整閥332，於第二藥液供給管341設置有流量調整閥342。FIG. 6 is a diagram showing another example of the plating solution supply unit. The plating solution supply unit 3a of FIG. 6 includes a nozzle 31a, a mixing valve 32, a first chemical solution supply source 33, a second chemical solution supply source 34, and a cleaning solution supply source 35. The nozzle 31 a is, for example, a straight nozzle, and is arranged above the central portion of the upper surface 91 of the substrate 9. The mixing valve 32 includes a mixing chamber 320, a first valve 321, a second valve 322, a third valve 323, and a fourth valve 324. The first valve 321, the second valve 322, the third valve 323, and the fourth valve 324 are connected to the mixing chamber 320. The first chemical liquid supply source 33 is connected to the first valve 321 via the first chemical liquid supply pipe 331, and the second chemical liquid supply source 34 is connected to the second valve 322 via the second chemical liquid supply pipe 341. In addition, a cleaning liquid supply source 35 is connected to the third valve 323 via a cleaning liquid supply pipe 351, and a nozzle 31a is connected to the fourth valve 324. The first chemical liquid supply pipe 331 is provided with a flow rate adjustment valve 332, and the second chemical liquid supply pipe 341 is provided with a flow rate adjustment valve 342.

在形成鍍覆液的液層時，開啟第一閥321、第二閥322以及第四閥324，藉此來自第一藥液供給源33的第一藥液以及來自第二藥液供給源34的第二藥液係在混合閥32的混合室320內被混合並作為鍍覆液被供給至噴嘴31a。如上所述，第一藥液係包含有鍍覆金屬的金屬鹽，第二藥液係包含有還原劑。鍍覆液中的第一藥液與第二藥液的混合比係被流量調整閥332、342調整。較佳為於鍍覆液中未包含有穩定劑或者錯化劑，更佳為於鍍覆液中未包含有穩定劑以及錯化劑雙方。此外，在藉由清洗液去除上表面91上的鍍覆液時，關閉第一閥321以及第二閥322並開啟第三閥323以及第四閥324，藉此將來自清洗液供給源35的清洗液經由混合室320供給至噴嘴31a。When the liquid layer of the plating liquid is formed, the first valve 321, the second valve 322, and the fourth valve 324 are opened, whereby the first chemical liquid from the first chemical liquid supply source 33 and the second chemical liquid supply source 34 The second chemical liquid system is mixed in the mixing chamber 320 of the mixing valve 32 and supplied to the nozzle 31a as a plating liquid. As described above, the first chemical liquid system includes a metal-plated metal salt, and the second chemical liquid system includes a reducing agent. The mixing ratio of the first chemical solution and the second chemical solution in the plating solution is adjusted by the flow rate adjustment valves 332 and 342. Preferably, the plating solution does not contain a stabilizer or a distorting agent, and more preferably, the plating solution does not contain both a stabilizer and a distorting agent. In addition, when the plating liquid on the upper surface 91 is removed by the cleaning liquid, the first valve 321 and the second valve 322 are closed and the third valve 323 and the fourth valve 324 are opened, whereby the cleaning liquid supply source 35 The cleaning liquid is supplied to the nozzle 31a via the mixing chamber 320.

在鍍覆液供給部3a中，由於在連接至噴嘴31a的混合閥32中混合第一藥液與第二藥液，因此能防止第一藥液供給管331以及第二藥液供給管341的內部被鍍覆。此外，能容易地將已均一地混合金屬鹽與還原劑的鍍覆液供給至基板9上。再者，由於在剛生成鍍覆液後從噴嘴31a噴出該鍍覆液，因此亦能抑制因為於鍍覆液中未存在有穩定劑或者錯化劑所產生的不良影響(例如鍍覆液的劣化等)。在噴出清洗液時，清洗液係從第一藥液與第二藥液的混合位置(在圖6中為混合室320)至噴嘴31a的噴出口之流路。藉此，能藉由清洗液去除殘留於該流路的鍍覆液，並能防止該流路被鍍覆。In the plating solution supply part 3a, since the first chemical solution and the second chemical solution are mixed in the mixing valve 32 connected to the nozzle 31a, the first chemical solution supply pipe 331 and the second chemical solution supply pipe 341 can be prevented The interior is plated. In addition, the plating solution in which the metal salt and the reducing agent have been uniformly mixed can be easily supplied to the substrate 9. Furthermore, since the plating liquid is ejected from the nozzle 31a immediately after the plating liquid is generated, the adverse effects caused by the absence of the stabilizer or the distorting agent in the plating liquid can also be suppressed (for example, the plating liquid Deterioration, etc.). When the cleaning liquid is discharged, the cleaning liquid is a flow path from the mixing position of the first chemical liquid and the second chemical liquid (the mixing chamber 320 in FIG. 6) to the discharge port of the nozzle 31a. Thereby, the plating solution remaining in the flow path can be removed by the cleaning liquid, and the flow path can be prevented from being plated.

在上述無電解鍍覆處理以及無電解鍍覆裝置1中可進行各種變化。Various changes can be made in the above-mentioned electroless plating process and the electroless plating apparatus 1.

在上述實施形態中，雖然藉由開始加熱鍍覆液的液層來促進上表面91中的無電解鍍覆反應，但亦可藉由開始搖動液層來促進上表面91中的無電解鍍覆反應。例如，在圖7的鍍覆反應促進部4a中設置有振動器(vibrator)43以取代圖1的加熱器41。振動器43係藉由未圖示的升降機構選擇性地配置於上位置與下位置，該上位置係與基板9的下表面92接觸之位置，該下位置係已從下表面92離開之位置。在圖3的處理中的步驟S16中，在停止從混合噴嘴31朝上表面91噴出鍍覆液且在上表面91上保持鍍覆液的液層93的狀態下，振動器43係配置於上位置。此時，停止旋轉基板9。接著，開始驅動振動器43，藉此對基板9賦予振動從而搖動液層93。藉此，緩緩地攪拌液層93中的鍍覆液，從而促進上表面91中的無電解鍍覆反應。在鍍覆反應促進部4a中，亦可對基板9賦予超音波振動。In the above-mentioned embodiment, although the electroless plating reaction in the upper surface 91 is promoted by starting to heat the liquid layer of the plating solution, the electroless plating in the upper surface 91 may also be promoted by starting to shake the liquid layer reaction. For example, a vibrator 43 is provided in the plating reaction promotion part 4a of FIG. 7 instead of the heater 41 of FIG. The vibrator 43 is selectively arranged at an upper position and a lower position by a lifting mechanism (not shown), the upper position is a position in contact with the lower surface 92 of the substrate 9, and the lower position is a position away from the lower surface 92 . In step S16 in the process of FIG. 3, the vibrator 43 is disposed on the top in a state where the spraying of the plating liquid from the mixing nozzle 31 toward the upper surface 91 is stopped and the liquid layer 93 of the plating liquid is held on the upper surface 91. position. At this time, the rotation of the substrate 9 is stopped. Next, the driving of the vibrator 43 is started, whereby the substrate 9 is vibrated to shake the liquid layer 93. Thereby, the plating liquid in the liquid layer 93 is gradually stirred, thereby promoting the electroless plating reaction in the upper surface 91. In the plating reaction promotion portion 4a, the substrate 9 may be given ultrasonic vibration.

此外，亦可在上表面91上保持鍍覆液的液層93之狀態下旋轉基板9，藉此搖動液層93。再者，亦可於加熱器41附加振動器，並進行加熱器41對於液層93的加熱以及振動器對於液層93的搖動雙方。如上所述，在無電解鍍覆處理中，在停止從噴嘴朝上表面91噴出鍍覆液且在上表面91上保持液層的狀態下開始液層的加熱以及／或者液層的搖動，藉此可促進上表面91中的無電解鍍覆反應。此外，在藉由基板9的旋轉促進無電解鍍覆反應之情形中，較佳為於形成液層時停止旋轉基板9。In addition, the substrate 9 may be rotated while the liquid layer 93 of the plating liquid is held on the upper surface 91, thereby shaking the liquid layer 93. Furthermore, a vibrator may be added to the heater 41 to perform both the heating of the liquid layer 93 by the heater 41 and the shaking of the liquid layer 93 by the vibrator. As described above, in the electroless plating process, the heating of the liquid layer and/or the shaking of the liquid layer are started in a state where the spraying of the plating liquid from the nozzle toward the upper surface 91 is stopped and the liquid layer is held on the upper surface 91. This can promote the electroless plating reaction in the upper surface 91. In addition, in the case where the electroless plating reaction is promoted by the rotation of the substrate 9, it is preferable to stop the rotation of the substrate 9 when the liquid layer is formed.

在無電解鍍覆裝置1中，亦可利用用以圍繞基板9的外周緣之構件在上表面91保持鍍覆液的液層93。在圖8的無電解鍍覆裝置1a中，基板保持部21a係具有將中心軸J1作為中心之環狀的保持構件214。保持構件214的內周面215的直徑係愈隨著朝向上方則愈增大。亦即，內周面215係圓錐台狀的面。內周面215的下部中的直徑係比基板9的外徑還小，且內周面215的上部中的直徑係比基板9的外徑還大。於保持構件214的下方設置有用以使基板9升降之基板升降機構216。In the electroless plating apparatus 1, a liquid layer 93 for holding the plating liquid on the upper surface 91 may also be used by a member surrounding the outer periphery of the substrate 9. In the electroless plating apparatus 1 a of FIG. 8, the substrate holding portion 21 a has an annular holding member 214 centered on the center axis J1. The diameter of the inner peripheral surface 215 of the holding member 214 increases as it faces upward. That is, the inner peripheral surface 215 is a truncated cone-shaped surface. The diameter in the lower portion of the inner peripheral surface 215 is smaller than the outer diameter of the substrate 9, and the diameter in the upper portion of the inner peripheral surface 215 is larger than the outer diameter of the substrate 9. A substrate raising and lowering mechanism 216 for raising and lowering the substrate 9 is provided below the holding member 214.

在無電解鍍覆裝置1a中，基板9在保持構件214的上方中從外部的搬運機構被授受至基板升降機構216後，基板升降機構216係將基板9朝下方移動。藉此，基板9的外周緣係遍及全周地與保持構件214的內周面215接觸，且基板9係被基板保持部21a水平狀態地保持。在無電解鍍覆處理中，從混合噴嘴31朝基板9的上表面91噴出鍍覆液。鍍覆液係被儲留於被基板9的上表面91與保持構件214的內周面215圍繞的儲留空間。換言之，在上表面91上保持鍍覆液的液層93。停止從混合噴嘴31朝上表面91噴出鍍覆液後，藉由未圖示的加熱器移動機構將加熱器41a配置於液層93的上方。藉此，開始加熱液層93並促進上表面91中的無電解鍍覆反應。In the electroless plating apparatus 1a, after the substrate 9 is transferred to the substrate lifting mechanism 216 from the external transport mechanism above the holding member 214, the substrate lifting mechanism 216 moves the substrate 9 downward. Thereby, the outer peripheral edge of the substrate 9 is in contact with the inner peripheral surface 215 of the holding member 214 over the entire circumference, and the substrate 9 is held horizontally by the substrate holding portion 21a. In the electroless plating process, the plating liquid is ejected from the mixing nozzle 31 toward the upper surface 91 of the substrate 9. The plating solution is stored in the storage space surrounded by the upper surface 91 of the substrate 9 and the inner peripheral surface 215 of the holding member 214. In other words, the liquid layer 93 of the plating liquid is held on the upper surface 91. After stopping the spraying of the plating liquid from the mixing nozzle 31 toward the upper surface 91, the heater 41a is arranged above the liquid layer 93 by a heater moving mechanism (not shown). With this, the heating of the liquid layer 93 is started and the electroless plating reaction in the upper surface 91 is promoted.

藉由無電解鍍覆裝置1a中的上述處理，亦能提升鍍覆層的厚度的均一性。此外，在去除上表面91上的鍍覆液時，基板升降機構216係將基板9上升，藉此於基板9的外周緣與保持構件214的內周面215之間形成有間隙，鍍覆液係經由該間隙朝下方排出。在無電解鍍覆裝置1a中亦可使用振動器。By the above-mentioned processing in the electroless plating apparatus 1a, the thickness uniformity of the plating layer can also be improved. In addition, when the plating solution on the upper surface 91 is removed, the substrate lifting mechanism 216 raises the substrate 9, thereby forming a gap between the outer peripheral edge of the substrate 9 and the inner peripheral surface 215 of the holding member 214, the plating solution It is discharged downward through this gap. A vibrator can also be used in the electroless plating apparatus 1a.

鍍覆液的液層的加熱亦可藉由各種構成來實現。例如如圖9所示，亦可將已配置於基板9的上方之加熱器41b沿著上表面91移動(掃描)，藉此加熱鍍覆液的液層93。此外，亦可設置使用了燈的加熱器等。亦可根據加熱器的構造，藉由加熱器本體的作動以及非作動來切換液層的加熱的作動狀態與非作動狀態。The heating of the liquid layer of the plating solution can also be achieved by various configurations. For example, as shown in FIG. 9, the heater 41b disposed above the substrate 9 may be moved (scanned) along the upper surface 91 to thereby heat the liquid layer 93 of the plating solution. In addition, a heater using a lamp or the like may be provided. According to the structure of the heater, the operation state and the non-operation state of the heating of the liquid layer can be switched by the operation and non-operation of the heater body.

混合噴嘴31以及噴嘴31a只要能對基板9的上表面91的整體供給鍍覆液，則亦可朝上表面91中從中央部偏離的位置噴出鍍覆液。As long as the mixing nozzle 31 and the nozzle 31 a can supply the plating liquid to the entire upper surface 91 of the substrate 9, the plating liquid may be ejected toward the position of the upper surface 91 that deviates from the center.

藉由其他的裝置進行基板9的上表面91中的觸媒層的形成。此外，在無須形成觸媒層即可於上表面91形成鍍覆層之情形中，亦可省略朝上表面91供給觸媒溶液。The formation of the catalyst layer on the upper surface 91 of the substrate 9 is performed by another device. In addition, in the case where the plating layer can be formed on the upper surface 91 without forming a catalyst layer, the supply of the catalyst solution to the upper surface 91 can also be omitted.

根據鍍覆反應促進部4、4a的構造等，亦可使用用以吸附並保持基板9的下表面92之基板保持部。Depending on the structure of the plating reaction promoting portions 4 and 4a and the like, a substrate holding portion for sucking and holding the lower surface 92 of the substrate 9 may also be used.

在無電解鍍覆裝置1、1a中進行處理的基板係未限定於半導體基板，亦可為其他的基板。The substrate processed in the electroless plating apparatuses 1 and 1a is not limited to a semiconductor substrate, and may be other substrates.

上述實施形態以及各個變化例中的構成只要相互無矛盾即可適當地組合。The configurations in the above-described embodiments and various modifications may be combined as appropriate as long as there is no contradiction.

雖然已詳細地描述並說明本發明，但上述說明僅為例示性而非是限定性。因此，只要未逸離本發明的範圍即能有各種的變化以及態樣。Although the present invention has been described and illustrated in detail, the above description is only illustrative rather than limiting. Therefore, as long as it does not deviate from the scope of the present invention, there can be various changes and aspects.

1、1a:無電解鍍覆裝置 3、3a:鍍覆液供給部 4、4a:鍍覆反應促進部 5:處理液供給部 9:基板 11:電腦 21、21a:基板保持部 22:基板旋轉機構 23:罩部 31:混合噴嘴 31a:噴嘴 32混合閥 33:第一藥液供給源 34:第二藥液供給源 35:清洗液供給源 41、41a、41b:加熱器 42:加熱器升降機構 43:振動器 51:輔助噴嘴 52:觸媒溶液供給源 53:洗淨液供給源 54:清洗液供給源 81:記錄媒體 91:(基板的)上表面 92:(基板的)下表面 93、93a:(鍍覆液的)液層 94:鍍覆層 110:控制部 111:CPU 112:ROM 113:RAM 114:固定硬碟 115:顯示部 116:輸入部 116a:鍵盤 116b:滑鼠 118:讀取寫入裝置 119:通訊部 211:基座部 212:夾具銷 213:把持部 214:保持構件 215:內周面 216:基板升降機構 221:軸部 110:控制部 311、320:混合室 312:噴出口 321:第一閥 322:第二閥 323:第三閥 324:第四閥 331:第一藥液供給管 332、342:流量調整閥 333、343、353:開閉閥 341:第二藥液供給管 351:清洗液供給管 421:升降軸 810:程式 J1:中心軸 1. 1a: Electroless plating device 3. 3a: Plating solution supply section 4, 4a: Plating reaction promotion section 5: Processing liquid supply unit 9: substrate 11: Computer 21, 21a: substrate holding section 22: substrate rotation mechanism 23: Hood 31: mixing nozzle 31a: Nozzle 32 mixing valve 33: The first chemical liquid supply source 34: Second medical fluid supply source 35: Cleaning fluid supply source 41, 41a, 41b: heater 42: Heater lifting mechanism 43: Vibrator 51: auxiliary nozzle 52: Catalyst solution supply source 53: source of cleaning solution 54: Cleaning fluid supply source 81: Recording media 91: upper surface (of the substrate) 92: lower surface (of the substrate) 93, 93a: (plating liquid) liquid layer 94: plating layer 110: Control Department 111: CPU 112:ROM 113: RAM 114: fixed hard drive 115: Display 116: Input section 116a: keyboard 116b: mouse 118: Reading and writing device 119: Ministry of Communications 211: Base part 212: Fixture pin 213: Control Department 214: Holding member 215: Inner peripheral surface 216: substrate lifting mechanism 221: Shaft 110: Control Department 311, 320: mixing room 312: spout 321: the first valve 322: Second valve 323: Third valve 324: Fourth valve 331: First chemical liquid supply tube 332, 342: flow adjustment valve 333, 343, 353: On-off valve 341: Second chemical liquid supply tube 351: Cleaning fluid supply pipe 421: Lifting shaft 810: Program J1: Central axis

圖1係顯示無電解鍍覆裝置的構成之圖。 圖2係顯示電腦的構成之圖。 圖3係顯示無電解鍍覆處理的流程之圖。 圖4A係用以說明無電解鍍覆處理之圖。 圖4B係用以說明無電解鍍覆處理之圖。 圖4C係用以說明無電解鍍覆處理之圖。 圖4D係用以說明無電解鍍覆處理之圖。 圖4E係用以說明無電解鍍覆處理之圖。 圖4F係用以說明無電解鍍覆處理之圖。 圖5A係用以說明無電解鍍覆處理的其他的例子之圖。 圖5B係用以說明無電解鍍覆處理的其他的例子之圖。 圖5C係用以說明無電解鍍覆處理的其他的例子之圖。 圖6係顯示鍍覆液供給部的其他的例子之圖。 圖7係顯示鍍覆反應促進部的其他的例子之圖。 圖8係顯示無電解鍍覆裝置的其他的例子之圖。 圖9係顯示加熱器的其他的例子之圖。FIG. 1 is a diagram showing the structure of an electroless plating apparatus. Figure 2 is a diagram showing the structure of a computer. FIG. 3 is a diagram showing the flow of electroless plating treatment. FIG. 4A is a diagram for explaining the electroless plating process. 4B is a diagram for explaining the electroless plating process. 4C is a diagram for explaining the electroless plating process. 4D is a diagram for explaining the electroless plating process. FIG. 4E is a diagram for explaining the electroless plating process. FIG. 4F is a diagram for explaining the electroless plating process. FIG. 5A is a diagram for explaining another example of electroless plating treatment. 5B is a diagram for explaining another example of electroless plating treatment. 5C is a diagram for explaining another example of electroless plating treatment. FIG. 6 is a diagram showing another example of the plating solution supply unit. FIG. 7 is a diagram showing another example of the plating reaction promotion section. 8 is a diagram showing another example of the electroless plating apparatus. 9 is a diagram showing another example of the heater.

1:無電解鍍覆裝置 1: Electroless plating device

3:鍍覆液供給部 3: Plating solution supply section

4:鍍覆反應促進部 4: Plating reaction promotion department

5:處理液供給部 5: Processing liquid supply unit

9:基板 9: substrate

11:電腦 11: Computer

21:基板保持部 21: substrate holding section

22:基板旋轉機構 22: substrate rotation mechanism

23:罩部 23: Hood

31:混合噴嘴 31: mixing nozzle

33:第一藥液供給源 33: The first chemical liquid supply source

34:第二藥液供給源 34: Second medical fluid supply source

35:清洗液供給源 35: Cleaning fluid supply source

41:加熱器 41: Heater

42:加熱器升降機構 42: Heater lifting mechanism

51:輔助噴嘴 51: auxiliary nozzle

52:觸媒溶液供給源 52: Catalyst solution supply source

53:洗淨液供給源 53: source of cleaning solution

54:清洗液供給源 54: Cleaning fluid supply source

91:(基板的)上表面 91: upper surface (of the substrate)

92:(基板的)下表面 92: lower surface (of the substrate)

110:控制部 110: Control Department

211:基座部 211: Base part

212:夾具銷 212: Fixture pin

213:把持部 213: Control Department

221:軸部 221: Shaft

311:混合室 311: Mixing room

312:噴出口 312: spout

331:第一藥液供給管 331: First chemical liquid supply tube

332、342:流量調整閥 332, 342: flow adjustment valve

333、343、353:開閉閥 333, 343, 353: On-off valve

341:第二藥液供給管 341: Second chemical liquid supply tube

351:清洗液供給管 351: Cleaning fluid supply pipe

421:升降軸 421: Lifting shaft

J1:中心軸 J1: Central axis

Claims (27)

一種無電解鍍覆方法，係具備有： 工序(a)，係從噴嘴朝水平狀態的基板的一個主表面噴出鍍覆液，藉此形成覆蓋前述一個主表面之前述鍍覆液的液層；以及 工序(b)，係在停止從前述噴嘴朝前述一個主表面噴出前述鍍覆液且在前述一個主表面上保持前述液層的狀態下開始前述液層的加熱或者前述液層的搖動，藉此促進前述一個主表面中的無電解鍍覆反應。An electroless plating method, with: Step (a) is to spray a plating solution from a nozzle toward one main surface of the substrate in a horizontal state, thereby forming a liquid layer of the plating solution covering the one main surface; and Step (b) is to start the heating of the liquid layer or the shaking of the liquid layer while stopping the spraying of the plating liquid from the nozzle toward the one main surface and maintaining the liquid layer on the one main surface Promote the electroless plating reaction in the aforementioned one main surface. 如請求項1所記載之無電解鍍覆方法，其中前述鍍覆液係包含有鍍覆金屬的金屬鹽以及用以使前述鍍覆金屬的離子還原析出之還原劑，且不包含有用以防止鍍覆液的分解之穩定劑或者不包含有錯化劑。The electroless plating method as described in claim 1, wherein the plating solution contains a metal salt of the plating metal and a reducing agent for reducing and depositing ions of the plating metal, and does not include a useful agent to prevent plating The decomposed stabilizer of the coating liquid may not contain a misalignment agent. 如請求項2所記載之無電解鍍覆方法，其中在前述工序(a)中，在即將從前述噴嘴噴出前述鍍覆液之前，混合包含有前述金屬鹽之第一藥液以及包含有前述還原劑之第二藥液，藉此生成前述鍍覆液。The electroless plating method according to claim 2, wherein in the step (a), immediately before the plating solution is sprayed from the nozzle, the first chemical solution containing the metal salt and the reducing solution are mixed The second chemical solution of the agent, thereby generating the aforementioned plating solution. 如請求項1所記載之無電解鍍覆方法，其中在前述工序(a)中，在即將從前述噴嘴噴出前述鍍覆液之前，混合包含有鍍覆金屬的金屬鹽之第一藥液與包含有用以使前述鍍覆金屬的離子還原析出的還原劑之第二藥液，藉此生成前述鍍覆液。The electroless plating method according to claim 1, wherein in the step (a), immediately before the plating solution is sprayed from the nozzle, the first chemical solution containing the metal salt of the plating metal is mixed with There is a second chemical solution of a reducing agent for reducing and depositing the ions of the plating metal, thereby generating the plating solution. 如請求項3所記載之無電解鍍覆方法，其中前述第一藥液與前述第二藥液係在前述噴嘴內被混合。The electroless plating method according to claim 3, wherein the first chemical solution and the second chemical solution are mixed in the nozzle. 如請求項3所記載之無電解鍍覆方法，其中前述第一藥液與前述第二藥液係在連接至前述噴嘴的混合閥中被混合。The electroless plating method according to claim 3, wherein the first chemical solution and the second chemical solution are mixed in a mixing valve connected to the nozzle. 如請求項3所記載之無電解鍍覆方法，其中進一步具備有下述工序：在前述工序(b)之後，從前述噴嘴朝前述一個主表面噴出清洗液； 在噴出前述清洗液之前，前述清洗液係通過從前述第一藥液與前述第二藥液的混合位置至前述噴嘴的噴出口之流路。The electroless plating method according to claim 3, further comprising the step of: after the step (b), the cleaning liquid is sprayed from the nozzle toward the one main surface; Before the cleaning liquid is discharged, the cleaning liquid passes through a flow path from the mixing position of the first chemical liquid and the second chemical liquid to the discharge port of the nozzle. 如請求項1所記載之無電解鍍覆方法，其中進一步包含有： 工序(c)，係在前述工序(b)之後，從前述噴嘴朝前述一個主表面上的前述鍍覆液的前述液層噴出新的鍍覆液，藉此形成用以覆蓋前述一個主表面之前述新的鍍覆液的液層；以及 工序(d)，係在停止從前述噴嘴朝前述一個主表面噴出前述新的鍍覆液且在前述一個主表面上保持前述新的鍍覆液的前述液層之狀態下進行前述液層的加熱或者前述液層的搖動，藉此促進前述一個主表面中的無電解鍍覆反應。The electroless plating method as described in claim 1, which further includes: Step (c) is that after the step (b), a new plating liquid is sprayed from the nozzle toward the liquid layer of the plating liquid on the one main surface, thereby forming a layer for covering the one main surface The liquid layer of the aforementioned new plating solution; and Step (d) is to perform heating of the liquid layer in a state where the spraying of the new plating liquid from the nozzle toward the one main surface is stopped and the liquid layer of the new plating liquid is held on the one main surface Or the shaking of the aforementioned liquid layer, thereby promoting the electroless plating reaction in the aforementioned one main surface. 如請求項1所記載之無電解鍍覆方法，其中進一步包含有： 工序(c)，係在前述工序(b)之後，旋轉前述基板藉此去除前述鍍覆液的前述液層，接著從前述噴嘴朝前述一個主表面噴出新的鍍覆液，藉此形成用以覆蓋前述一個主表面之前述新的鍍覆液的液層；以及 工序(d)，係在停止從前述噴嘴朝前述一個主表面噴出前述新的鍍覆液且在前述一個主表面上保持前述新的鍍覆液的前述液層之狀態下進行前述液層的加熱或者前述液層的搖動，藉此促進前述一個主表面中的無電解鍍覆反應。The electroless plating method as described in claim 1, which further includes: Step (c), after the step (b), rotating the substrate to remove the liquid layer of the plating liquid, and then spraying a new plating liquid from the nozzle toward the one main surface, thereby forming a A liquid layer of the aforementioned new plating liquid covering the aforementioned main surface; and Step (d) is to perform heating of the liquid layer in a state where the spraying of the new plating liquid from the nozzle toward the one main surface is stopped and the liquid layer of the new plating liquid is held on the one main surface Or the shaking of the aforementioned liquid layer, thereby promoting the electroless plating reaction in the aforementioned one main surface. 如請求項8所記載之無電解鍍覆方法，其中進一步具備有用以重複前述工序(c)以及前述工序(d)之工序。The electroless plating method according to claim 8, further comprising a step useful to repeat the step (c) and the step (d). 如請求項1所記載之無電解鍍覆方法，其中在前述工序(a)中，將加熱器所為之前述液層的加熱設定成非作動狀態； 在前述工序(b)中，將前述加熱器所為之前述液層的加熱設定成作動狀態。The electroless plating method according to claim 1, wherein in the step (a), the heating of the liquid layer by the heater is set to an inactive state; In the step (b), the heating of the liquid layer by the heater is set to an actuated state. 如請求項8所記載之無電解鍍覆方法，其中在前述工序(a)以及前述工序(c)中將加熱器所為之前述液層的加熱設定成非作動狀態； 在前述工序(b)以及前述工序(d)中將前述加熱器所為之前述液層的加熱設定成作動狀態。The electroless plating method according to claim 8, wherein in the step (a) and the step (c), the heating of the liquid layer by the heater is set to an inactive state; In the step (b) and the step (d), the heating of the liquid layer by the heater is set to an actuated state. 如請求項11所記載之無電解鍍覆方法，其中前述加熱器係與前述基板的另一個主表面對向； 在前述作動狀態下，前述加熱器係配置於接近或者接觸至前述另一個主表面之位置； 在前述非作動狀態下，前述加熱器係配置於已從前述另一個主表面離開之位置。The electroless plating method as recited in claim 11, wherein the heater is opposed to the other main surface of the substrate; In the actuated state, the heater is disposed close to or in contact with the other main surface; In the inactive state, the heater is arranged at a position away from the other main surface. 如請求項1至13中任一項所記載之無電解鍍覆方法，其中在前述工序(b)中，在加熱前述鍍覆液的前述液層並在前述一個主表面上保持前述液層的狀態下旋轉前述基板。The electroless plating method according to any one of claims 1 to 13, wherein in the step (b), the liquid layer of the plating solution is heated and the liquid layer is held on the one main surface The aforementioned substrate is rotated in a state. 如請求項1至13中任一項所記載之無電解鍍覆方法，其中在前述工序(b)中，在前述一個主表面上保持前述鍍覆液的前述液層的狀態下，旋轉前述基板或者對前述基板賦予振動。The electroless plating method according to any one of claims 1 to 13, wherein in the step (b), the substrate is rotated while the liquid layer of the plating solution is held on the one main surface Alternatively, vibration may be applied to the aforementioned substrate. 一種無電解鍍覆裝置，係具備有： 基板保持部，係以水平狀態保持基板； 鍍覆液供給部，係從噴嘴朝前述基板的一個主表面噴出鍍覆液，藉此形成用以覆蓋前述一個主表面之前述鍍覆液的液層； 鍍覆反應促進部，係進行前述液層的加熱或者前述液層的搖動；以及 控制部，係在停止從前述噴嘴朝前述一個主表面噴出前述鍍覆液且在前述一個主表面上保持前述液層之狀態下開始前述鍍覆反應促進部所為之前述液層的加熱或者前述液層的搖動，藉此促進前述一個主表面中的無電解鍍覆反應。An electroless plating device is equipped with: The substrate holding part holds the substrate in a horizontal state; The plating solution supplying part ejects the plating solution from the nozzle toward one main surface of the substrate, thereby forming a liquid layer of the plating solution to cover the one main surface; The plating reaction promotion part performs heating of the liquid layer or shaking of the liquid layer; and The control unit starts the heating of the liquid layer or the liquid by the plating reaction promotion unit while stopping the spraying of the plating liquid from the nozzle toward the one main surface and maintaining the liquid layer on the one main surface The shaking of the layer thereby promotes the electroless plating reaction in the aforementioned one main surface. 如請求項16所記載之無電解鍍覆裝置，其中前述鍍覆液係包含有鍍覆金屬的金屬鹽以及用以使前述鍍覆金屬的離子還原析出之還原劑，且不包含有用以防止鍍覆液的分解之穩定劑或者不包含有錯化劑。The electroless plating apparatus as described in claim 16, wherein the plating solution contains a metal salt of a plating metal and a reducing agent for reducing and depositing ions of the plating metal, and does not include a useful agent to prevent plating The decomposed stabilizer of the coating liquid may not contain a misalignment agent. 如請求項16所記載之無電解鍍覆裝置，其中前述鍍覆液供給部係在即將從前述噴嘴噴出前述鍍覆液之前混合包含有鍍覆金屬的金屬鹽之第一藥液以及包含有用以使前述鍍覆金屬的離子還原析出的還原劑之第二藥液，藉此生成前述鍍覆液。The electroless plating apparatus as recited in claim 16, wherein the plating solution supply unit mixes the first chemical solution containing a metal salt of the plating metal immediately before the plating solution is ejected from the nozzle and contains The second chemical solution of the reducing agent that precipitates the ions of the plating metal is reduced, thereby generating the plating solution. 如請求項18所記載之無電解鍍覆裝置，其中在使用了前述液層之無電解鍍覆之後，前述鍍覆液供給部係從前述噴嘴朝前述一個主表面噴出清洗液； 在噴出前述清洗液時，前述清洗液係通過從前述第一藥液與前述第二藥液的混合位置至前述噴嘴的噴出口之流路。The electroless plating apparatus according to claim 18, wherein after the electroless plating using the liquid layer, the plating liquid supply unit sprays the cleaning liquid from the nozzle toward the one main surface; When the cleaning liquid is discharged, the cleaning liquid passes through a flow path from the mixing position of the first chemical liquid and the second chemical liquid to the discharge port of the nozzle. 如請求項16至19中任一項所記載之無電解鍍覆裝置，其中前述鍍覆反應促進部係進一步具備有：加熱器，係進行前述液層的加熱； 在形成前述液層時，將前述加熱器所為之前述液層的加熱設定成非作動狀態； 在促進前述無電解鍍覆反應時，將前述加熱器所為之前述液層的加熱設定成作動狀態。The electroless plating apparatus according to any one of claims 16 to 19, wherein the plating reaction promotion section is further provided with: a heater for heating the liquid layer; When forming the liquid layer, the heating of the liquid layer by the heater is set to an inactive state; When accelerating the electroless plating reaction, the heating of the liquid layer by the heater is set to an actuated state. 如請求項20所記載之無電解鍍覆裝置，其中前述加熱器係與前述基板的另一個主表面對向； 在前述作動狀態下，前述加熱器係配置於接近或者接觸至前述另一個主表面之位置； 在前述非作動狀態下，前述加熱器係配置於已從前述另一個主表面離開之位置。The electroless plating apparatus as recited in claim 20, wherein the heater is opposed to the other main surface of the substrate; In the actuated state, the heater is disposed close to or in contact with the other main surface; In the inactive state, the heater is arranged at a position away from the other main surface. 一種程式產品，係使電腦進行具備有基板保持部、鍍覆液供給部以及鍍覆反應促進部之無電解鍍覆裝置的控制； 前述電腦係執行前述程式產品所顯示的程式，藉此使前述電腦執行： 工序(a)，係從前述鍍覆液供給部的噴嘴朝被前述基板保持部以水平狀態保持的基板的一個主表面噴出鍍覆液，藉此形成覆蓋前述一個主表面之前述鍍覆液的液層；以及 工序(b)，係在停止從前述噴嘴朝前述一個主表面噴出前述鍍覆液且在前述一個主表面上保持前述液層的狀態下開始前述鍍覆反應促進部所為之前述液層的加熱或者前述液層的搖動，藉此促進前述一個主表面中的無電解鍍覆反應。A program product that enables a computer to control an electroless plating device equipped with a substrate holding part, a plating liquid supply part, and a plating reaction promoting part; The aforementioned computer executes the program displayed by the aforementioned program product, thereby causing the aforementioned computer to execute: Step (a) is to spray the plating liquid from the nozzle of the plating liquid supply part toward one main surface of the substrate held horizontally by the substrate holding part, thereby forming the plating liquid covering the one main surface Liquid layer; and The step (b) is to start the heating of the liquid layer by the plating reaction promotion section while stopping the spraying of the plating liquid from the nozzle toward the one main surface and maintaining the liquid layer on the one main surface or The shaking of the aforementioned liquid layer thereby promotes the electroless plating reaction in the aforementioned one main surface. 如請求項22所記載之程式產品，其中前述鍍覆液係包含有鍍覆金屬的金屬鹽以及用以使前述鍍覆金屬的離子還原析出之還原劑，且不包含有用以防止鍍覆液的分解之穩定劑或者不包含有錯化劑。The program product as recited in claim 22, wherein the plating solution contains a metal salt of the plating metal and a reducing agent for reducing and depositing ions of the plating metal, and does not contain any useful substance to prevent the plating solution The decomposed stabilizer may not contain the wrong stabilizer. 如請求項22所記載之程式產品，其中在前述工序(a)中，在即將從前述噴嘴噴出前述鍍覆液之前，混合包含有鍍覆金屬的金屬鹽之第一藥液以及包含有用以使前述鍍覆金屬的離子還原析出的還原劑之第二藥液，藉此生成前述鍍覆液。The program product as recited in claim 22, wherein in the aforementioned step (a), immediately before the plating solution is ejected from the nozzle, the first chemical solution containing the metal salt of the plating metal is mixed with The second chemical solution of the reducing agent of the plating metal ions is reduced to generate the plating solution. 如請求項24所記載之程式產品，其中進一步執行下述工序：在前述工序(b)之後，從前述噴嘴朝前述一個主表面噴出清洗液； 在噴出前述清洗液時，前述清洗液係通過從前述第一藥液與前述第二藥液的混合位置至前述噴嘴的噴出口之流路。The program product as recited in claim 24, wherein the following process is further performed: after the foregoing process (b), the cleaning liquid is sprayed from the nozzle toward the one main surface; When the cleaning liquid is discharged, the cleaning liquid passes through a flow path from the mixing position of the first chemical liquid and the second chemical liquid to the discharge port of the nozzle. 如請求項22至25中任一項所記載之程式產品，其中前述鍍覆反應促進部係進一步具備有：加熱器，係進行前述液層的加熱； 在前述工序(a)中，將前述加熱器所為之前述液層的加熱設定成非作動狀態； 在前述工序(b)中，將前述加熱器所為之前述液層的加熱設定成作動狀態。The program product as recited in any one of claims 22 to 25, wherein the plating reaction promotion section is further provided with: a heater for heating the liquid layer; In the step (a), the heating of the liquid layer by the heater is set to an inactive state; In the step (b), the heating of the liquid layer by the heater is set to an actuated state. 如請求項26所記載之程式產品，其中前述加熱器係與前述基板的另一個主表面對向； 在前述作動狀態下，前述加熱器係配置於接近或者接觸至前述另一個主表面之位置； 在前述非作動狀態下，前述加熱器係配置於已從前述另一個主表面離開之位置。The program product as recited in claim 26, wherein the heater is opposed to the other main surface of the substrate; In the actuated state, the heater is disposed close to or in contact with the other main surface; In the inactive state, the heater is arranged at a position away from the other main surface.
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