PLATING METHOD, PLATING APPARATUS AND RECORDING MEDIUM

A plating method includes preparing a substrate having a surface including an adhesive material portion made of a material to which a catalyst easily adheres and a non-adhesive material portion to which the catalyst is difficult to attach; imparting the catalyst to the substrate by supplying a catalyst solution onto the substrate; removing, by supplying a catalyst removing liquid containing a reducing agent onto the substrate, the catalyst from the non-adhesive material portion while allowing the catalyst to be left on a surface of the adhesive material portion; and forming a plating layer selectively on the adhesive material portion by supplying a plating liquid onto the substrate.

TECHNICAL FIELD

The various aspects and embodiments described herein pertain generally to a plating method, a plating apparatus and a recording medium.

BACKGROUND

Recently, as miniaturization and three-dimension of semiconductor devices are required, it is required to improve processing accuracy by etching when processing the semiconductor devices. As one way to improve the processing accuracy by etching, it is required to improve accuracy of a hard mask (HM) for dry etching which is formed on a substrate.

In general, however, there are many restrictions for a material of the hard mask. For example, the material of the hard mask needs to have high adhesivity to a substrate and a resist, needs to have high resistance against a heat treatment and an etching processing, and, also, needs to be easily removed. For the reason, only a limited material such as silicon nitride or titanium nitride has been used as the material of the hard mask.

In view of this, the present inventors have examined, on a substrate having, on a surface thereof, a portion formed of silicon oxide (hereinafter, also referred to as “SiO” for simplicity in the present specification) and a portion formed of silicon nitride (hereinafter, also referred to as “SiN” for simplicity in the present specification), applying a Pd catalyst only to a surface of the SiN portion selectively to thereby form a plating layer only on the surface of the SiN portion. The plating layer formed on the surface of the SiN portion can be used as a hard mask, and it is possible to select various kinds of materials as the plating layer depending on requirements therefor.

When performing electroless plating, a catalyst such as Pd, which acts as a nucleus of precipitation of the plating, is applied to a surface of a plating target. If the catalyst is applied to the surface of the substrate including the SiN portion and the SiO portion, the catalyst adheres to the SiO portion, on which the plating layer is not intended to be formed, as well as the SiN portion. Since adhesivity between the catalyst and the SiO is lower than adhesivity between the catalyst and the SiN, most of the catalyst adhering to the surface of the SiO portion is removed through a rinsing processing performed afterwards. However, it is difficult to remove the catalyst on the surface of the SiO portion completely through the rinsing processing. If the catalyst remains on the surface of the SiO portion, there is a concern that the plating layer may be formed as the remaining catalyst may act as the nucleus.

PRIOR ART DOCUMENT

SUMMARY

In view of foregoing, exemplary embodiments provide a technique of applying a catalyst to a surface of a substrate and efficiently removing the catalyst from a portion of the surface of the substrate which is not required to be plated.

In one exemplary embodiment, a plating method includes preparing a substrate having a surface including an adhesive material portion made of a material to which a catalyst easily adheres and a non-adhesive material portion to which the catalyst is difficult to attach; imparting the catalyst to the substrate by supplying a catalyst solution onto the substrate; removing, by supplying a catalyst removing liquid containing a reducing agent onto the substrate, the catalyst from the non-adhesive material portion while allowing the catalyst to be left on a surface of the adhesive material portion; and forming a plating layer selectively on the adhesive material portion by supplying a plating liquid onto the substrate.

In another exemplary embodiment, there is provided a computer-readable recording medium having stored thereon computer-executable instructions that, in response to execution, cause a plating apparatus to perform the plating method.

In still another exemplary embodiment, a plating apparatus includes a substrate holder configured to hold a substrate; a catalyst imparting device configured to impart a catalyst solution to the substrate; a catalyst removing liquid supply configured to supply a catalyst removing liquid onto the substrate; a plating liquid supply configured to supply a plating liquid onto the substrate; and a controller configured to control the plating apparatus to perform the plating method.

According to the exemplary embodiments, after the catalyst is applied to the surface of the substrate, it is possible to remove the catalyst efficiently from the portion of the surface of the substrate which is not required to be plated. Thus, it is possible to suppress the plating layer from being formed on the portion which is not required to be plated.

DETAILED DESCRIPTION

Hereinafter, exemplary embodiments will be described with reference to the accompanying drawings.

Referring toFIG. 1, a configuration of a plating apparatus according to an exemplary embodiment will be explained.FIG. 1is a schematic diagram illustrating the configuration of the plating apparatus according to the exemplary embodiment.

As depicted inFIG. 1, a plating apparatus2according to the present exemplary embodiment is equipped with a controller3configured to control an operation of the plating apparatus2.

The plating apparatus2is configured to perform various processings on a substrate. The various processings performed by the plating apparatus2will be discussed later.

The controller3is implemented by, for example, a computer, and includes an operation controller and a storage unit. The operation controller is implemented by, for example, a CPU (Central Processing Unit) and is configured to control an operation of the plating apparatus2by reading and executing the programs stored in the storage unit. The storage unit is implemented by a memory device such as, but not limited to, a RAM (Random Access Memory), a ROM (Read Only Memory) or a hard disk, and stores thereon programs for controlling various processings performed in the plating apparatus2. Further, the programs may be recorded in a computer-readable recording medium, or may be installed from the recording medium to the storage unit. The computer-readable recording medium may be, for example, a hard disc (HD), a flexible disc (FD), a compact disc (CD), a magnet optical disc (MO), or a memory card. Stored in the recording medium is a program which, when executed by a computer for controlling an operation of the plating apparatus2, allows the computer to control the plating apparatus2to perform a plating method to be described later.

Referring toFIG. 1, a configuration of the plating apparatus2will be discussed.FIG. 1is a schematic plan view illustrating the configuration of the plating unit2.

The plating apparatus2includes a carry-in/out station21and a processing station22which is provided adjacent to the carry-in/out station21.

The carry-in/out station21is equipped with a placing section211and a transfer section212which is provided adjacent to the placing section211.

In the placing section211, transfer containers (hereinafter, referred to as “carriers C”) for accommodating therein a plurality of substrates W horizontally are placed.

The transfer section212is equipped with a transfer device213and a delivery unit214. The transfer device213is provided with a holding mechanism configured to hold a substrate W and is configured to be movable horizontally and vertically and pivotable around a vertical axis.

The processing station22includes plating units5. In the present exemplary embodiment, the number of the plating units5belonging to the processing station22is two or more. However, only one plating unit5may be provided. The plating units5are arranged at both sides of a transfer path221which extends in a preset direction.

A transfer device222is provided in the transfer path221. The transfer device222is equipped with a holding mechanism configured to hold the substrate W and is configured to be movable horizontally and vertically and pivotable around a vertical axis.

In the plating apparatus2, the transfer device213of the carry-in/out station21is configured to transfer the substrate W between the carrier C and the delivery unit214. To elaborate, the transfer device213takes out the substrate W from the carrier C which is placed in the placing section211, and places the substrate W in the delivery unit214. Further, the transfer device213takes out the substrate W which is placed in the delivery unit214by the transfer device222of the processing station22, and accommodates the substrate W back into the carrier C on the placing section211.

In the plating apparatus2, the transfer device222of the processing station22is configured to transfer the substrate W between the delivery unit214and the plating unit5and between the plating unit5and the delivery unit214. To elaborate, the transfer device222takes out the substrate W which is placed in the delivery unit214and then carries the substrate W into the plating unit5. Further, the transfer device222takes out the substrate W from the plating unit5and places the substrate W in the delivery unit214.

Now, referring toFIG. 2, a configuration of the plating unit5will be explained.FIG. 2is a schematic cross sectional view illustrating the configuration of the plating unit5.

The plating unit5is configured to perform a plating processing on a substrate W having a surface including a non-adhesive material portion31and an adhesive material portion32, and configured to form a plating layer35selectively on the adhesive material portion32(details of this plating processing will be described later). The adhesive material portion32refers to a portion made of a material to which a catalyst is difficult to attach. The non-adhesive material portion31refers to a portion made of a material to which the catalyst easily adheres. A substrate processing performed by the plating unit5includes a catalyst imparting processing and an electroless plating processing at least. However, the substrate processing may include other processings besides the catalyst imparting processing and the plating processing.

The plating unit5includes a chamber51; a substrate holder52provided within the chamber51and configured to hold the substrate W; and a plating liquid supply53configured to supply a plating liquid M1to the substrate W held by the substrate holder52.

The substrate holder52includes a rotation shaft521extending in a vertical direction within the chamber51; a turntable522provided at an upper end portion of the rotation shaft521; a chuck523provided on an outer peripheral portion of a top surface of the turntable522and configured to support an edge portion of the substrate W; and a driving unit524configured to rotate the rotation shaft521.

The substrate W is supported by the chuck523to be horizontally held by the turntable522while being slightly spaced apart from the top surface of the turntable522. In the present exemplary embodiment, a mechanism of holding the substrate W by the substrate holder52is of a so-called mechanical chuck type in which the edge portion of the substrate W is held by the chuck523which is configured to be movable. However, a so-called vacuum chuck type in which a rear surface of the substrate W is vacuum-attracted may be used instead.

A base end portion of the rotation shaft521is rotatably supported by the driving unit524, and a leading end portion of the rotation shaft521sustains the turntable522horizontally. If the rotation shaft521is rotated, the turntable522placed on the upper end portion of the rotation shaft521is rotated, and, as a result, the substrate W which is held by the turntable522with the chuck523is also rotated.

The plating liquid supply53is equipped with a nozzle531configured to discharge the plating liquid M1onto the substrate W held by the substrate holder52; and a plating liquid source532configured to supply the plating liquid M1to the nozzle531. The plating liquid M1is stored in a tank of the plating liquid source532, and the plating liquid M1is supplied into the nozzle531from the plating liquid source532through a supply passageway534which is equipped with a flow rate controller such as a valve533.

The plating liquid M1is a plating liquid for an autocatalytic (reduction) electroless plating. The plating liquid M1contains a metal ion such as a cobalt (Co) ion, a nickel (Ni) ion, or a tungsten (W) ion; and a reducing agent such as hypophosphorous acid or dimethylamineborane. Further, in the autocatalytic (reduction) electroless plating, the metal ion in the plating liquid M1is reduced by electrons emitted in an oxidation reaction of the reducing agent in the plating liquid M1to be precipitated as a metal, so that a metal film (plating film) is formed. The plating liquid M1may further contain an additive or the like. The metal film (plating film) formed by the plating processing with the plating liquid M1may be, by way of non-limiting example, CoB, CoP, CoWP, CoWB, CoWBP, NiWB, NiB, NiWP, NiWBP, or the like. P (phosphorus) in the metal film (plating film) is originated from the reducing agent (e.g., hypophosphorous acid) containing P, and B (boron) in the plating film is originated from the reducing agent (e.g., dimethylamineborane) containing B.

The nozzle531is connected to a nozzle moving device54. The nozzle moving device54is configured to drive the nozzle531. The nozzle moving device54includes an arm541, a moving body542which is configured to be movable along the arm541and has a driving mechanism embedded therein; and a rotating/elevating device543configured to rotate and move the arm541up and down. The nozzle531is provided at the moving body542. The nozzle moving device54is capable of moving the nozzle531between a position above a center of the substrate W held by the substrate holder52and a position above a periphery of the substrate W, and is also capable of moving the nozzle531up to a stand-by position outside a cup57to be described later when viewed from the top.

Within the chamber51, there are arranged a catalyst solution supply (catalyst imparting device)55a, a cleaning liquid supply55b, and a rinse liquid supply55cconfigured to supply a catalyst solution N1, a cleaning liquid N2, and a rinse liquid N3onto the substrate W held by the substrate holder52, respectively. Further, a catalyst removing liquid supply55dis also provided within the chamber51.

The catalyst solution supply (catalyst imparting device)55aincludes a nozzle551aconfigured to discharge the catalyst solution N1onto the substrate W held by the substrate holder52; and a catalyst solution source552aconfigured to supply the catalyst solution N1to the nozzle551a. The catalyst solution N1is stored in a tank of the catalyst solution source552a, and the catalyst solution N1is supplied to the nozzle551afrom the catalyst solution source552athrough a supply passageway554awhich is provided with a flow rate controller such as a valve553a.

The cleaning liquid supply55bincludes a nozzle551bconfigured to discharge the cleaning liquid N2onto the substrate W held by the substrate holder52; and a cleaning liquid source552bconfigured to supply the cleaning liquid N2to the nozzle551b. The cleaning liquid N2is stored in a tank of the cleaning liquid source552b, and the cleaning liquid N2is supplied to the nozzle551bfrom the cleaning liquid source552bthrough a supply passageway554bwhich is provided with a flow rate controller such as a valve553b.

The rinse liquid supply55cincludes a nozzle551cconfigured to discharge the rinse liquid N3onto the substrate W held by the substrate holder52; and a rinse liquid source552cconfigured to supply the rinse liquid N3to the nozzle551c. The rinse liquid N3is stored in a tank of the rinse liquid source552c, and the rinse liquid N3is supplied to the nozzle551cfrom the rinse liquid source552cthrough a supply passageway554cwhich is provided with a flow rate controller such as a valve553c.

The catalyst removing liquid supply55dis equipped with a nozzle551dconfigured to discharge the catalyst removing liquid N4onto the substrate W held by the substrate holder52; and a catalyst removing liquid source552dconfigured to supply the catalyst removing liquid N4to the nozzle551d. The catalyst removing liquid N4is stored in a tank of the catalyst removing liquid source552d, and the catalyst removing liquid N4is supplied to the nozzle551dfrom the catalyst removing liquid source552dthrough a supply passageway554dwhich is provided with a flow rate controller such as a valve553d.

The catalyst solution N1contains a metal catalyst in the form of particles, more particularly, nanoparticles. To elaborate, the catalyst solution N1includes a metal catalyst in the form of nanoparticles, a dispersant, and water as a dispersion medium. This metal catalyst in the form of nanoparticles may be, by way of non-limiting example, palladium (Pd) in the form of nanoparticles. The dispersant serves to allow the metal catalyst in the form of nanoparticles to be easily dispersed in the catalyst solution N1. The dispersant may be, by way of non-limiting example, polyvinylpyrrolidone (PVP). The metal catalyst needs to have sufficient catalytic activity to the oxidation reaction of the reducing agent contained in the plating liquid M1. By way of non-limiting example, such a metal catalyst may include, besides the aforementioned Pd, iron group elements (Fe, Co, Ni), platinum group elements (Ru, Rh, Os, Ir, Pt), Cu, Ag or Au. The catalyst solution N1may further include an adsorption accelerator configured to accelerate adsorption of the catalyst to a surface of a material to which the catalyst is imparted.

As an example of the cleaning liquid N2, an organic acid such as a formic acid, malic acid, a succinic acid, a citric acid or a malonic acid, or hydrofluoric acid (DHF) (aqueous solution of hydrogen fluoride) diluted to the extent that it does not corrode the plating target surface of the substrate may be used.

As an example of the rinse liquid N3, pure water may be used.

As an example of the catalyst removing liquid N4, a reducing agent, desirably, the same reducing agent as the reducing agent contained in the plating liquid M1may be used. Such a reducing agent may be, by way of example, but not limitation, the aforementioned dimethylamineborane (DMAB). The DMAB is used as the catalyst removing liquid N4after being diluted to about 100 times to about 1000 times with, for example, DIW (pure water).

The plating unit5includes a nozzle moving device56configured to move the nozzles551ato551c. The nozzle moving device56is equipped with an arm561; a moving body562which is configured to be movable along the arm561and has a moving mechanism embedded therein; and a rotating/elevating device563configured to rotate and move the arm561up and down. The nozzles551ato551care provided at the moving body562. The nozzle moving device56is capable of moving the nozzles551ato551cbetween a position above the central portion of the substrate W held by the substrate holder52and a position above the peripheral portion of the substrate W, and also capable of moving the nozzles551ato551cup to a stand-by position outside the cup57to be described later when viewed from the top. In the present exemplary embodiment, though the nozzles551ato551care held by the common arm, they may be configured to be held by different arms and moved independently.

The cup57is disposed around the substrate holder52. The cup57is configured to receive various kinds of processing liquids (e.g., the catalyst solution, the plating liquid, the cleaning liquid, the rinse liquid, the catalyst removing liquid, etc.) scattered from the substrate W and drain the received processing liquids to the outside of the chamber51. The cup57is equipped with an elevating device58configured to move the cup57up and down.

Now, a structure of the substrate on which the plating layer is to be formed by the plating method according to the present exemplary embodiment will be explained.

As depicted inFIG. 3, the surface of the substrate W on which the plating layer35is to be formed includes the non-adhesive material portion31made of the material to which the catalyst is difficult to attach and the adhesive material portion32made of the material to which the catalyst easily adheres. There is no specific limitation in the structure of the non-adhesive material portion31and the adhesive material portion32as long as they are exposed at the surface of the substrate W. In the present exemplary embodiment, the substrate W includes a base member42made of the adhesive material portion32and a core member41which is protruded from the base member42and is made of the non-adhesive material portion31having a pattern shape.

For example, the non-adhesive material portion31is made of a material containing SiO2as a main component, and the adhesive material portion32is made of a material containing SiN as a main component. Mostly, the catalyst does not adhere to a surface of the SiO2portion. However, there is still a chance for the catalyst to adhere to the surface of the SiO2portion slightly. Since the catalyst (herein, Pd) is attracted to N atoms contained in the SiN, the catalyst easily adheres to a surface of the SiN portion.

Now, a method of producing the substrate W shown inFIG. 3will be explained with reference toFIG. 4AtoFIG. 4E. To produce the substrate W shown inFIG. 3, the base member42made of the adhesive material portion32is first prepared, as illustrated inFIG. 4A.

Thereafter, as depicted inFIG. 4B, a film of a material31a, which forms the non-adhesive material portion31, is formed on the entire surface of the base member42made of the adhesive material portion32by a CVD method, a PVD method or the like. The material31ais composed of, for example, the material containing SiO2as the main component.

Subsequently, as illustrated inFIG. 4C, a photosensitive resist33ais coated on the entire surface of the material31aforming the non-adhesive material portion31and then is dried. Then, by exposing the photosensitive resist33athrough a photo mask and developing it, a resist film33having a required pattern is formed, as shown inFIG. 4D.

Afterwards, as depicted inFIG. 4E, the material31ais dry-etched by using the resist film33as a mask. As a result, the core member41made of the non-adhesive material portion31is patterned to have substantially the same shape as the pattern shape of the resist film33. Then, by removing the resist film33, there is obtained the substrate W having the non-adhesive material portion31and the adhesive material portion32formed on the surface thereof.

Now, the plating method using the plating apparatus1will be discussed. The plating method performed by plating apparatus1includes a plating processing upon the aforementioned substrate W. The plating processing is performed by the plating unit5. An operation of the plating unit5is controlled by the controller3.

First, the substrate W having the non-adhesive material portion31and the adhesive material portion32formed on the surface thereof is prepared by performing the above-described method ofFIG. 4AtoFIG. 4E(preparation process: process S1ofFIG. 5) (seeFIG. 6A).

The prepared substrate W is then carried into the plating unit5and is held by the substrate holder52(seeFIG. 2). In the meanwhile, the controller3controls the elevating device58to move the cup57down to a preset position. Then, the controller3controls the transfer device222to place the substrate W on the substrate holder52. The substrate W is horizontally placed on the turntable522while its periphery portion is held by the chuck523.

Then, the substrate W held by the substrate holder52is cleaned (pre-cleaning process: process S2ofFIG. 5). At this time, while controlling the driving unit524to rotate the substrate W held by the substrate holder52at a preset speed, the controller3controls the cleaning liquid supply55bto locate the nozzle551bat a position above the substrate W and to supply the cleaning liquid N2onto the substrate W from the nozzle551b. The cleaning liquid N2supplied onto the substrate W is diffused on the surface of the substrate W by a centrifugal force which is caused by the rotation of the substrate W. As a result, a deposit or the like adhering to the substrate W is removed from the substrate W. The cleaning liquid N2scattered from the substrate W is drained through the cup57.

Subsequently, the substrate W after being cleaned is rinsed (rinsing process: process S3ofFIG. 5). At this time, while controlling the driving unit524to rotate the substrate W held by the substrate holder52at a preset speed, the controller3controls the rinse liquid supply55cto locate the nozzle551cat a position above the substrate W and to supply the rinse liquid N3onto the substrate W from the nozzle551c. The rinse liquid N3supplied onto the substrate W is diffused on the surface of the substrate W by the centrifugal force which is caused by the rotation of the substrate W. As a result, the cleaning liquid N2remaining on the substrate W is washed away. The rinse liquid N3scattered from the substrate W is drained through the cup57.

Thereafter, a catalyst imparting processing is performed on the substrate W (catalyst imparting process: process S4ofFIG. 5). At this time, while controlling the driving unit524to rotate the substrate W held by the substrate holder52at a preset speed, the controller3controls the catalyst solution supply55ato locate the nozzle551aat a position above the substrate W and to supply the catalyst solution N1onto the substrate W from the nozzle551a. The catalyst solution N1supplied onto the substrate W is diffused on the surface of the substrate W by the centrifugal force which is caused by the rotation of the substrate W. The catalyst solution N1scattered from the substrate W is drained through the cup57.

Through the catalyst imparting processing, the catalyst adheres to the entire surface of the substrate W (both the non-adhesive material portion31and the adhesive material portion32) (though adhesion strengths are different) (seeFIG. 8A). The catalyst (e.g., Pd) contained in the catalyst solution N1has high adsorption property with respect to the material (e.g., SiN) forming the adhesive material portion32, whereas the catalyst is difficult to adsorb to the material (e.g., SiO2) forming the non-adhesive material portion31.

Thereafter, a rinsing processing is performed on the substrate W after being cleaned (rinsing process: process S5ofFIG. 5). This rinsing processing is performed in the same way as the aforementioned process S3. Through this rinsing processing, most of the catalyst attached to the surface of the non-adhesive material portion31is washed away. Even if the adhesivity (adsorption property) of the catalyst to the non-adhesive material portion31is low, however, a small amount of the catalyst may remain on (still adheres to) the surface of the non-adhesive material portion31(seeFIG. 8B). This remaining catalyst may act as a nucleus of precipitation in a plating process. That is, in the plating process, an undesirable (unintended) plating may be precipitated on the surface of the non-adhesive material portion31.

To remove the catalyst from the surface of the non-adhesive material portion31, a catalyst removing processing is performed on the substrate W after being rinsed (catalyst removing process: process S6ofFIG. 5). At this time, while controlling the driving unit524to rotate the substrate W held by the substrate holder52at a preset speed, the controller3controls the catalyst removing liquid supply55dto locate the nozzle551dat a position above the substrate W and to supply the catalyst removing liquid N4onto the substrate W from the nozzle551d. The catalyst removing liquid N4supplied onto the substrate W is diffused on the surface of the substrate W by the centrifugal force which is caused by the rotation of the substrate W. Accordingly, all or most of the catalyst having adhered to the non-adhesive material portion31is washed away (that is, to the extent that the plating is not formed in the subsequent plating processing). The catalyst removing liquid N4scattered from the substrate W is drained through the cup57. Meanwhile, though the catalyst is also removed from the surface of the adhesive material portion32to some degree, the amount of the catalyst remaining on the adhesive material portion32is enough not to cause any failure in the formation of the plating in the subsequent plating processing (seeFIG. 8C).

In case of using the DMAB diluted to about 100 times to about 1000 times with DIW (pure water) as the catalyst removing liquid N4, a time during which the catalyst removing liquid N4is supplied onto the substrate W from the nozzle551donly needs to be a short time of, e.g., 10 seconds.

Further, after performing the catalyst imparting processing by using the Pd catalyst in the form of nanoparticles, the dispersant composed of the polyvinylpyrrolidone (PVP) and the catalyst solution N1containing pure water, as a result of performing the catalyst removing processing for about 10 seconds by using the DMAB diluted to about 100 times to 1000 times with the pure water as the catalyst removing liquid N4, it is found out that the Pd nanoparticles adhering to the non-adhesive material portion31made of SiO2can be removed and the amount of the Pd nanoparticles remaining on the surface of the adhesive material portion32made of SiN is enough not to cause any problem in the plating processing.

A mechanism by which the Pd catalyst in the form of nanoparticles can be removed with the aforementioned catalyst removing liquid N4is not clearly investigated. However, the present inventors have made conjectures as follows.

(1) Surfaces of the Pd nanoparticles in an oxidation state are reduced by an action of the reducing agent, and sizes of the nanoparticles are reduced to be lifted off the substrate W.

(2) A hydrogen gas is generated by a decomposition reaction of the reducing agent on the surfaces of the Pd nanoparticles, and the catalyst nanoparticles are lifted off while being surrounded by air bubbles (by buoyancy).

(3) The aforementioned phenomena (1) and (2) both take place.

After the completion of the above-stated catalyst removing processing and before the plating processing to be described below, a rinsing processing may be performed on the substrate W. If, however, the component of the catalyst removing liquid used in the catalyst removing processing does not have an adverse influence on the plating liquid, this rinsing processing can be omitted. By way of example, when the DMAB diluted to about 100 time to about 1000 times with the DIW (pure water) is used as the catalyst removing liquid N4and the DMAB is included in the plating liquid M1as the reducing agent, the rinsing processing can be omitted.

After the catalyst is removed from the non-adhesive material portion31, the plating processing is performed on the substrate W (plating process: process S7ofFIG. 5). At this time, while controlling the driving unit524to rotate the substrate W held by the substrate holder52at a preset speed or while maintaining the substrate W held by the substrate holder52stopped, the controller3controls the plating liquid supply53to locate the nozzle531at a position above the substrate W and to supply the plating liquid M1onto the substrate W from the nozzle531. As a result, the plating metal is selectively precipitated on the adhesive material portion32of the substrate W (specifically, on the catalyst adhering to the surface of the adhesive material portion32), so that the plating layer35is formed. Meanwhile, since the catalyst does not substantially exist on the non-adhesive material portion31of the substrate W, no plating metal is precipitated on the non-adhesive material portion31, so that no plating layer35is formed on the non-adhesive material portion31(seeFIG. 6B).

After the plating processing as described above is completed, the substrate W held by the substrate holder52is cleaned (post-cleaning process: process S8ofFIG. 5). At this time, while controlling the driving unit524to rotate the substrate W held by the substrate holder52at a preset speed, the controller3controls the cleaning liquid supply55bto locate the nozzle551bat the position above the substrate W and to supply the cleaning liquid N2onto the substrate W from the nozzle551b. The cleaning liquid N2supplied onto the substrate W is diffused on the surface of the substrate W by the centrifugal force which is caused by the rotation of the substrate W. Accordingly, the abnormal plating film or the reaction by-product adhering to the substrate W is removed from the substrate W. The cleaning liquid N2scattered from the substrate W is drained through the cup57.

Then, while controlling the driving unit524to rotate the substrate W held by the substrate holder52at a preset speed, the controller3controls the rinse liquid supply55cto locate the nozzle551cat the position above the substrate W and to supply the rinse liquid N3onto the substrate W from the nozzle551c(rinsing process: process S9ofFIG. 5). Accordingly, the plating liquid M1, the cleaning liquid N2and the rinse liquid N3on the substrate W are scattered from the substrate W by the centrifugal force which is caused by the rotation of the substrate W, and are drained through the cup57.

Thereafter, the substrate W on which the plating layer35is formed is carried out of the plating unit5. At this time, the controller3controls the transfer device222to take out the substrate W from the plating unit5and place the taken-out substrate W in the delivery unit214. Then, the controller3controls the transfer device213to take out the substrate W placed in the delivery unit214and to carry the substrate W into the carrier C in the placing section211.

Then, the substrate W is etched by using the plating layer35as a hard mask.

In this case, the non-adhesive material portion31is first removed selectively from the substrate W which is taken out of the plating unit5(FIG. 7A). Meanwhile, the plating layer35formed on the adhesive material portion32remains without being removed.

Subsequently, as shown inFIG. 7B, the base member42made of the adhesive material portion32is dry-etched by using the plating layer35as a hard mask. Accordingly, the portion of the base member42which is not covered with the plating layer35is etched to a preset depth, and recesses having a pattern shape are formed.

Afterwards, by removing the plating layer35through a wet cleaning method, the base member42provided with the recesses having the pattern shape is obtained, as illustrated inFIG. 7C. Since the plating layer35can be removed by the wet cleaning method, it is easy to remove the plating layer35. An acidic solvent is employed as a chemical liquid used in this wet cleaning method.

Although the various exemplary embodiments have been described so far, those exemplary embodiments are not limiting and can be modified in various ways without departing from the technical conception and essence of the present disclosure. Further, the constituent components described in the above exemplary embodiments may be combined appropriately to produce various other embodiments, and may be partially deleted in various ways. Further, the constituent components in the different exemplary embodiments may be appropriately combined.

A pH adjuster such as, but not limited to, PMA (polymethylacrylate) may be added into the catalyst removing liquid N4, so the catalyst removing liquid N4may be adjusted to be alkaline. Since surfaces of various members tend to be negatively charged in the alkaline cleaning liquid, re-adhesion of once removed materials in the form of particles (Pd particles, etc.) to the substrate can be suppressed.

In the above-described exemplary embodiments, the liquid contained in the catalyst removing liquid N4is the DMAB. However, this liquid is not limited thereto. By way of example, if a reducing agent including P (phosphorous), e.g., hypophosphorous acid, is contained in the plating liquid M1, the hypophosphorous acid diluted with pure water may be used as the catalyst removing liquid N4. In such a case, the rinsing processing need not be performed between the catalyst removing processing and the plating processing.

In the above-described exemplary embodiments, the adhesive material portion32is made of silicon nitride, and the non-adhesive material portion31is made of silicon oxide. However, the exemplary embodiments are not limited thereto. The adhesive material portion32may be made of any one of (1) a material containing at least one of a OCHxgroup or a NHxgroup; (2) a metal material containing a Si-based material as a main component; (3) a material containing a catalyst metal material as a main component; and (4) a material containing carbon as a main component. The material (1) may be a material containing a Si—OCHxgroup or a Si—NHxgroup such as SiOCH or SiN. The material (2) may be, by way of non-limiting example, B-doped or P-doped poly-Si, poly-Si, or Si.

EXPLANATION OF CODES