JP2004300576A - Method and apparatus for substrate treatment - Google Patents

Method and apparatus for substrate treatment Download PDF

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Publication number
JP2004300576A
JP2004300576A JP2004075363A JP2004075363A JP2004300576A JP 2004300576 A JP2004300576 A JP 2004300576A JP 2004075363 A JP2004075363 A JP 2004075363A JP 2004075363 A JP2004075363 A JP 2004075363A JP 2004300576 A JP2004300576 A JP 2004300576A
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Japan
Prior art keywords
substrate
surface
plating
pretreatment
substrate processing
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JP2004075363A
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JP2004300576A5 (en
Inventor
Akira Fukunaga
Chikaaki O
Akira Owatari
Daisuke Takagi
Akihiko Tashiro
晃 尾渡
新明 王
昭彦 田代
明 福永
大輔 高木
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Ebara Corp
株式会社荏原製作所
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Application filed by Ebara Corp, 株式会社荏原製作所 filed Critical Ebara Corp
Priority to JP2004075363A priority patent/JP2004300576A/en
Publication of JP2004300576A5 publication Critical patent/JP2004300576A5/ja
Publication of JP2004300576A publication Critical patent/JP2004300576A/en
Application status is Withdrawn legal-status Critical

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Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus for substrate treatment in which initial cost and running cost can be reduced, an extensive installation space is not required, the electric characteristic of wires is not degraded, and a protective film of high quality is efficiently deposited on the surface of a metal part. <P>SOLUTION: A substrate having a metal part on the surface thereof is prepared. The surface of the substrate is brought into contact with pre-treatment solution to perform plating pre-treatment to decorate the entire surface. The pre-treatment solution remained on the surface of the substrate is removed by rinsing. The surface of the substrate is subjected to electroless plating to selectively deposit an alloy film on the surface of the metal part, and the substrate after the electroless plating is post-cleaned and dried. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a substrate processing method and a substrate processing apparatus, in particular, a bottom surface of an embedded wiring formed by embedding a conductor such as copper or silver in a fine recess for wiring provided on the surface of a substrate such as a semiconductor wafer. A conductive material having a function of preventing thermal diffusion of a wiring material into an interlayer insulating film on a side surface or an exposed surface, or a function of improving adhesion between a wiring and an interlayer insulating film or an interlayer cap layer (antioxidant film). The present invention relates to a substrate processing method and a substrate processing apparatus used for forming a film or a metal alloy film such as a magnetic film covering wiring by electroless plating.

  As a wiring forming process of a semiconductor device, a process (so-called damascene process) in which a metal (conductor) is embedded in a wiring groove and a contact hole is being used. This is because a metal such as aluminum, recently copper or silver is buried in a wiring groove or a contact hole previously formed in an interlayer insulating film, and then excess metal is removed by chemical mechanical polishing (CMP) to planarize the metal. Process technology.

  Conventionally, in the case of this type of wiring, for example, copper wiring using copper as a wiring material, in order to improve reliability, prevent thermal diffusion of wiring (copper) to an interlayer insulating film and improve electromigration resistance. A barrier film is formed on the bottom and side surfaces of the wiring to prevent the wiring (copper) from being oxidized in an oxidizing atmosphere when a semiconductor device having a multilayer wiring structure is formed by laminating an insulating film (oxide film). For example, a method such as forming an antioxidant film is employed. Conventionally, a metal such as tantalum, titanium or tungsten or a nitride thereof has been generally adopted as a barrier film of this type, and a nitride or carbide of silicon has been generally adopted as an antioxidant film.

  As an alternative to this, recently, the bottom and side surfaces of the buried wiring or the exposed surface is selectively covered with a wiring protective film made of a cobalt alloy, nickel alloy, etc. to prevent thermal diffusion, electromigration and oxidation of the wiring It is considered to be. In the case of a nonvolatile magnetic memory, when the density of the memory cells is increased and the design rule is reduced, the current density of the copper wiring increases, and the problem of electromigration occurs. Furthermore, in this writing, the writing current increases as the cell size decreases, and the cells approach each other and crosstalk becomes a problem. In order to solve this, it is considered that a yoke structure in which a magnetic film such as a cobalt alloy or a nickel alloy is provided around the copper wiring is effective. This magnetic film is obtained by, for example, electroless plating.

For example, as shown in FIG. 1, a fine concave portion 4 for wiring is formed inside an insulating film 2 made of SiO 2 or the like deposited on the surface of a substrate W such as a semiconductor wafer, and a barrier layer made of TaN or the like is formed on the surface. 6 is formed, and a copper seed film 7 is formed on the surface of the barrier layer 6 if necessary. Then, copper plating is performed, a copper film is formed on the surface of the substrate W, and copper is embedded in the recess 4. Thereafter, the surface of the substrate W is planarized by performing CMP (chemical mechanical polishing). Thus, the wiring 8 made of a copper film is formed inside the insulating film 2. Next, on the surface of the wiring (copper film) 8, a wiring protection film (cover material) 9 made of a Co-WP alloy film, which is obtained by, for example, electroless plating, is selectively formed to protect the wiring 8. I do.

A step of selectively forming the wiring protection film (cover material) 9 made of such a Co-WP alloy film on the surface of the wiring 8 by general electroless plating will be described. First, a substrate W such as a semiconductor wafer that has been subjected to a CMP process is immersed in, for example, normal temperature diluted sulfuric acid or diluted hydrochloric acid for about 1 minute to remove impurities such as a metal oxide film on the surface of the insulating film 2 and a CMP residue such as copper. I do. Then, after cleaning the surface of the substrate W with a cleaning liquid such as pure water, the substrate W is immersed in, for example, a PdCl 2 / HCl mixed solution at room temperature for about 1 minute, whereby Pd as a catalyst is deposited on the surface of the wiring 8. By adhering, the exposed surface of the wiring 8 is activated.

  Next, after cleaning (rinsing) the surface of the substrate W with pure water or the like, the activated wiring is immersed in, for example, a Co-WP plating solution having a liquid temperature of 80 ° C. for about 120 seconds to activate the wiring. The surface of the substrate 8 is selectively electrolessly plated, and then the surface of the substrate W is cleaned with a cleaning liquid such as pure water. As a result, the wiring protection film 9 made of a Co-WP alloy film is selectively formed on the exposed surface of the wiring 8 to protect the wiring 8.

By the way, when forming a wiring protective film (cover material) made of a Co-WP alloy film by electroless plating, as described above, a catalyst applying treatment for applying a catalyst such as Pd to the surface of the wiring is performed. Before performing, for example, pre-cleaning (removing a CMP residue made of copper or the like remaining on the insulating film to remove an oxide film on the wiring and to prevent an alloy film from being formed on the insulating film). A (cleaning) process is generally performed. This pre-cleaning treatment is generally performed using a pre-cleaning solution composed of an inorganic acid such as HF, H 2 SO 4 or HCl. However, such a pre-cleaning liquid has an etching power for copper, and therefore, at the same time as the pre-cleaning, a part of the copper wiring is damaged (etched), and the damage increases the wiring resistance. There is.

  In addition, when performing pre-cleaning, a small amount of copper constituting the wiring may be dissolved, and if the dissolved copper moves on the insulating film between the wirings and adheres to the insulating film, a leak current may be parsed. There is. Furthermore, after pre-cleaning, after rinsing with pure water after treatment with the pre-cleaning chemical solution, if the insulating film is exposed to the chemical solution or the rinsing solution for a long time, the insulating property of the insulating film deteriorates and the leakage current decreases. May rise. Further, if the chemical solution remains on the substrate surface after the chemical solution treatment, it also has an adverse effect on the in-plane uniformity of the film formation, and therefore it is necessary to remove the chemical solution quickly.

  On the other hand, from the viewpoint of the apparatus, if each of the above-described steps is performed by a dedicated unit, not only the number of processing tanks in each step is increased, but also the reduction of the substrate transfer time by the transfer robot is limited. As a result, not only does the apparatus footprint increase and the processing throughput decrease, but also the process control between each step becomes complicated. In particular, if the substrate is left in an oxygen atmosphere for a long time between the application of the catalyst and the rinsing, or between the rinsing and the plating, the surface state of the substrate tends to change, which may adversely affect the electrical characteristics of the wiring on the processed substrate. is there.

  The present invention has been made in view of the above circumstances, can reduce the initial cost of the device, running costs, without requiring a large installation space, especially, without deteriorating the electrical characteristics such as wiring resistance and leakage current, Moreover, it is an object of the present invention to provide a substrate processing method and a substrate processing apparatus capable of efficiently forming a high-quality alloy film on the surface of a metal part.

According to the first aspect of the present invention, a substrate having a metal part on its surface is prepared, and a pretreatment is carried out to modify the entire surface by bringing a pretreatment liquid into contact with the surface of the substrate, and a pretreatment remaining on the surface of the substrate is performed. The solution is removed by a rinsing process, the surface of the substrate is subjected to electroless plating to selectively form an alloy film on the surface of the metal part, and the substrate after the electroless plating is post-washed and dried. A substrate processing method.
This greatly reduces the processing time, and when the metal part is a metal wiring such as a copper wiring, for example, minimizes the increase in wiring resistance after plating and minimizes the obtained leakage current. By lowering the thickness, an alloy film can be selectively formed on the surface of the metal. Further, the initial cost and running cost of the apparatus can be kept low, and the processing can be performed continuously without requiring a large installation space.

The invention according to claim 2 is the substrate processing method according to claim 1, wherein the metal part is an exposed surface of a buried wiring formed in an insulator.
The invention according to claim 3, wherein the metal portion is a metal film formed on a bottom surface and a side surface of a recess for a buried wiring formed on a surface of an insulator. Processing method.
The invention according to claim 4 is the substrate processing method according to claim 1, wherein the metal portion is an exposed surface of a metal wiring formed on a surface of the insulator.

The invention according to claim 5 is characterized in that the plating pretreatment is a treatment for cleaning the surface of the substrate and simultaneously activating the surface of the metal part by applying a catalyst to the metal part. A substrate processing method according to any one of claims 1 to 4.
Thus, by pre-plating treatment to modify the entire surface of the substrate, the surface of the substrate is cleaned, and at the same time, a catalyst is applied to the metal part to activate the surface of the metal part. For example, it is possible to prevent a part of a metal part such as a copper wiring from being damaged (etched) by the pretreatment liquid or dissolved in the pretreatment liquid. By cleaning the surface of the substrate, impurities such as a metal oxide film formed on the surface of the metal portion, and metals or organic substances on the substrate surface including the surface of the metal portion and impurity residues are removed.

Here, it is preferable to form a continuous pretreatment liquid film on the surface of the substrate during the progress of the plating pretreatment, whereby the substrate surface is directly exposed to the external atmosphere, and active during the treatment. The surface of the converted metal portion can be prevented from being reoxidized.
This pretreatment liquid film may be, for example, a liquid film that is generated by processing the substrate with the substrate surface facing upward and that is stationary with respect to the substrate surface or a liquid film that moves with respect to the substrate surface. Good. By using a liquid film that moves with respect to the substrate surface, the pretreatment liquid in the vicinity of the substrate surface can be constantly updated, and the plating efficiency accompanying the cleaning and the catalyst application treatment can be increased.
In addition, it is preferable that the thickness of the pretreatment liquid film be 10 mm or less, so that a small amount of the pretreatment liquid required for processing one substrate can be used. This is appropriate when the pretreatment liquid is used for single use (disposable).

The invention according to claim 6 is characterized in that the pre-plating treatment and the rinsing treatment are performed by spraying a chemical solution, pure water or the like from a nozzle toward the surface of the substrate arranged with the surface facing downward. A substrate processing method according to any one of claims 1 to 5.
As described above, by employing the spray-type pre-plating treatment or the rinsing treatment, a fresh treatment liquid can be constantly and more uniformly dispersed and supplied to the substrate surface, and the treatment time can be reduced. In addition, by adjusting the position of the injection point, the uniformity of the in-plane processing can be easily improved.
The time from completion of the plating pre-treatment to the start of the rinsing treatment is preferably within 5 seconds, whereby the continuous reaction by the residual liquid after the plating pre-treatment and the oxidation of the activated metal surface are prevented. Can be minimized.

The invention according to claim 7 is the substrate processing method according to claim 6, wherein the pre-plating process and the rinsing process are performed while rotating the substrate.
As described above, by performing the pre-plating treatment and the rinsing treatment while rotating the substrate, the uniformity of the chemical reaction or cleaning over the entire surface of the substrate is enhanced. In addition, the substrate may be rotated at different rotation speeds during the plating pretreatment and the rinsing cleaning treatment, whereby the reaction and cleaning efficiency or in-plane uniformity can be adjusted.

The substrate according to claim 6 or 7, wherein the nozzle used for the pre-plating treatment and the nozzle used for the rinsing treatment are connected to different flow path systems, respectively. Processing method.
This prevents the rinsing nozzle system from being contaminated by the pretreatment liquid, and maintains a stable rinsing liquid cleaning ability.

The invention according to claim 9 is the substrate processing method according to any one of claims 1 to 5, wherein the plating pretreatment is performed by immersing the substrate in a pretreatment liquid.
Thus, the substrate can be isolated from the external atmosphere during the substrate processing, and the surface of the activated metal portion can be prevented from being re-oxidized. Further, the amount of dissolved oxygen in the plating pretreatment liquid can be adjusted, and the reaction rate such as catalyst application in the plating pretreatment can be controlled.
The invention according to claim 10 is the substrate processing method according to any one of claims 1 to 9, wherein the substrate is rotated at a high speed after the completion of the plating pretreatment.
Accordingly, the amount of the chemical solution taken out by the substrate and the jig holding the substrate can be suppressed.

An eleventh aspect of the present invention is characterized in that the plating pretreatment is performed using a pretreatment liquid prepared by mixing at least catalytic metal ions and an acid having a function of cleaning the surface of the substrate. The substrate processing method according to any one of claims 1 to 10, wherein
This makes it possible to remove the oxide film on the surface of the metal part and remove impurities such as metal residues remaining on the interlayer insulating film at the same time as applying the catalyst to the surface of the metal part in the plating pretreatment. it can.

According to a twelfth aspect of the present invention, the rinsing process is performed by cleaning the surface of the substrate with pure water or pure water whose reducibility is enhanced by a method such as electrolysis or dissolution of hydrogen gas. Item 12. The substrate processing method according to any one of Items 1 to 11.
Thereby, for example, while preventing the metal part constituting the wiring and the like from being oxidized, the pretreatment liquid remaining on the substrate is efficiently washed, and the acidic pretreatment liquid is prevented from being mixed into the plating solution. Therefore, the plating solution can be kept stable.

The invention according to claim 13 is characterized in that the rinsing treatment is performed by cleaning the surface of the substrate with an aqueous solution prepared by mixing one or more components constituting the electroless plating solution. 13. A substrate processing method according to any one of claims 1 to 12.
This makes it possible to efficiently clean the pretreatment liquid remaining on the substrate, for example, while preventing the metal parts constituting the wiring from being oxidized.

The invention according to claim 14 is the substrate processing method according to any one of claims 1 to 13, wherein the pre-plating treatment and the rinsing treatment are performed in an atmosphere having an oxygen component smaller than that of the atmosphere.
This can prevent the oxide film from being regenerated on the surface of the metal part to which the catalyst has been applied by the plating pretreatment.

The invention according to claim 15 is the substrate processing method according to any one of claims 1 to 14, wherein the electroless plating is performed in an atmosphere having an oxygen component less than that of the atmosphere.
Thereby, the alloy film is prevented from being oxidized during the film formation, and an alloy film having stable film quality can be formed.
The interval between the completion of the rinsing treatment of the pretreatment liquid remaining on the substrate surface and the start of the electroless plating treatment is preferably within 15 seconds, whereby the external atmosphere on the metal part surface after the plating pretreatment is reduced. Can be minimized.

16. The substrate processing apparatus according to claim 1, wherein at least one of a film thickness and a film quality of the alloy film is measured after the substrate is washed and dried. Is the way.
Thereby, for example, by measuring the thickness of the alloy film formed on the surface of the metal portion, and adjusting the processing time of the plating process on the next substrate, for example, according to the change in the film thickness, the surface of the metal portion The thickness of the alloy film formed on the substrate can be controlled.

The invention according to claim 17 is characterized in that the composition of the pretreatment solution and the rinse solution thereof, the concentration of each component, and the temperature of the pretreatment solution are maintained within predetermined ranges. Or a substrate processing method described in
Thereby, a catalyst having a stable nucleus density is applied to the surface of the metal part, and an alloy film having a stable film quality and a uniform film thickness can be formed.

The invention according to claim 18 is characterized in that the concentration of an impurity mixed in the pretreatment liquid by the plating pretreatment is measured, and the impurity is removed when the impurity reaches a predetermined concentration. Item 18. A substrate processing method according to any one of Items 1 to 17.
This makes it possible to use the pretreatment liquid stably for a long period of time while preventing a decrease in the function of the expensive pretreatment liquid.

According to a nineteenth aspect of the present invention, the electroless plating is performed by maintaining the temperature, composition, and concentration of each component of the plating solution within predetermined ranges and controlling the plating time for a predetermined film thickness. The substrate processing method according to any one of claims 1 to 18, wherein:
As described above, by controlling the plating time, the thickness of the alloy film formed on the surface of the metal part can be adjusted.

  The invention according to claim 20 is characterized in that the surface of the substrate having the metal portion is brought into contact with a pretreatment liquid to modify the entire surface and the pretreatment liquid remaining on the surface of the substrate after the plating pretreatment is treated. A pretreatment unit for performing a rinsing process for rinsing; an electroless plating unit for performing an electroless plating process on the surface of the substrate after the plating pretreatment to selectively form an alloy film on a surface of the metal part; A post-processing unit for post-cleaning and drying the substrate after the electrolytic plating process.

  As a result, compared with the case where each processing step is performed by a separate unit (processing section), the whole is compact, a large installation space is not required, the initial cost and running cost of the apparatus can be reduced, and the processing time is short. An alloy film can be formed in a short time. In particular, since the waiting time or transfer time of the substrate between each step can be adjusted to be extremely short, a high-quality alloy film can be formed without deteriorating electrical characteristics.

  The invention according to claim 21 is characterized in that the pre-plating treatment is a treatment for cleaning the surface of the substrate and simultaneously applying a catalyst to the metal part to activate the surface of the metal part. 21. A substrate processing apparatus according to claim 20, wherein:

The invention according to claim 22 is characterized in that the pretreatment unit has a function of separating a pretreatment liquid used for the plating pretreatment and a rinsing liquid used for the rinsing treatment after the substrate treatment. 22. The substrate processing apparatus according to claim 20, wherein
Thereby, the pre-plating process and the rinsing process of the substrate can be continuously performed in a single processing unit, and the processing solutions (the pre-processing solution and the rinsing solution) can be individually collected and reused. Further, the time between the pre-plating treatment and the rinsing treatment for the substrate can be adjusted to be extremely short.

In the invention according to claim 23, the pretreatment unit measures a concentration of an impurity mixed into the pretreatment liquid by the plating pretreatment, and removes the impurity when the concentration of the impurity reaches a predetermined value. 23. The substrate processing apparatus according to claim 20, further comprising a liquid purifying apparatus having a liquid purifying function for removing.
Thereby, contamination of the pretreatment liquid used for the plating pretreatment can be suppressed, and the pretreatment liquid can always have stable catalytic power and detergency.

The invention according to claim 24 has an apparatus for measuring at least one of a film thickness and a film quality of an alloy film formed on a substrate that has been dried by the post-processing unit. A substrate processing apparatus according to any one of the above.
As a result, a film with high reproducibility can be realized.

The invention according to claim 25, wherein the plating condition is changed or the quality of film formation is determined based on a measurement value of an apparatus for measuring at least one of the film thickness and the film quality. Is a substrate processing apparatus.
Thereby, at least one of the film thickness and the film quality of the alloy film formed on the surface of the metal part is measured, and according to the change of the film thickness or the film quality, for example, the processing time of the plating process for the next substrate or the composition of the plating solution By adjusting the concentration, the thickness of the alloy film formed on the surface of the metal part can be controlled with good reproducibility.

26. The invention according to claim 26, wherein the pretreatment unit and the electroless plating unit are configured to treat the surfaces of the substrates oriented in the same direction. 2. The substrate processing apparatus according to item 1.
Thus, for example, while the substrate surface is facing down (face down), the substrate is processed by the pretreatment unit and the electroless plating unit without inverting the substrate by 180 ° to shorten the moving time of the substrate, Changes in the state of the substrate can be suppressed.

The invention according to claim 27 is the substrate processing apparatus according to any one of claims 20 to 26, wherein the pretreatment unit and the electroless plating unit have a common substrate holding head.
Thereby, the interval from the completion of the rinsing treatment of the pretreatment liquid to the start of the plating treatment can be adjusted to be extremely short, and an alloy film having stable film quality can be formed. In addition, the number of times the substrate is transferred by the transfer robot hand or the like can be reduced, and contamination and damage on the back surface of the substrate can be avoided.

According to a twenty-eighth aspect of the present invention, the substrate holding head is configured so that a peripheral portion on the front surface side or a peripheral portion on the rear surface side of the substrate can be simultaneously or selectively sealed. A substrate processing apparatus according to any one of claims 20 to 27.
Thereby, for example, the pre-plating processing by the pre-processing unit is performed by sealing the peripheral portion on the front surface side of the substrate, and the rinsing process by the pre-processing unit and the plating process by the electroless plating unit are performed by sealing the peripheral portion on the back surface side of the substrate. By performing each of them, it is possible to prevent an abnormal plating film from being generated at the peripheral portion of the substrate.

The invention according to claim 29, wherein the pretreatment unit and the plating unit have an opening in a part and are disposed inside a sealable housing having a function of adjusting an internal atmosphere independently of the entire apparatus. The substrate processing apparatus according to any one of claims 20 to 28, wherein:
This allows the substrate during processing to be exposed to an atmosphere in which the substrate being processed is easily oxidized by performing the operation while transporting the substrate after rinsing of the pretreatment liquid to the plating processing unit, for example, in an atmosphere having a lower oxygen composition than the atmosphere. Is prevented, and an alloy film having a stable film quality can be obtained.

The invention according to claim 30 is the substrate processing apparatus according to any one of claims 20 to 29, wherein the substrate processing apparatus is housed in a housing that has been subjected to a light emitting process so that light does not transmit from an external environment.
Thereby, it is possible to eliminate the occurrence of electron transfer due to the light excitation effect in the elements and wirings formed on the device surface of the substrate during processing, thereby preventing the substrate device from being damaged.

  According to the present invention, by performing a series of processes for selectively forming an alloy film by electroless plating on the surface of the metal portion on the substrate surface, each processing step is performed in a separate unit (processing unit). As compared with the case where the method is performed, the whole is compact, a large installation space is not required, the initial cost and running cost of the apparatus can be reduced, and the alloy film can be formed in a short processing time. In particular, the waiting time or transport time of the substrate between each step can be adjusted to be extremely short, or the series of processes of surface cleaning, catalyst application, rinsing and plating are continuously performed in an atmosphere that is not easily oxidized, so that the electric power of the metal part is reduced. It is possible to form a high quality alloy film while preventing performance deterioration.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 2 is a plan layout view of the substrate processing apparatus according to the embodiment of the present invention. As shown in FIG. 2, the substrate processing apparatus includes a substrate cassette 10 containing a substrate W (see FIG. 1, the same applies hereinafter) in which a wiring 8 made of copper or the like is formed in a wiring recess 4 formed on the surface. And a loading / unloading unit 12 for placing and housing the. Although only one cassette 10 is accommodated in the load / unload unit 12 shown in FIG. 2, a plurality of cassettes may be accommodated.

  The pre-processing unit 18 is located inside the rectangular housing 16 provided with the exhaust system, and performs the pre-plating processing of the substrate W, for example, the cleaning processing and the catalyst application processing simultaneously using the same pre-processing liquid. An electroless plating unit 20 for performing electroless plating on the surface (substrate to be processed) of the substrate W, a protective film (alloy film) 9 formed on the surface of the wiring 8 by the electroless plating (see FIG. 3) a film thickness / film quality measuring unit 22 for measuring at least one of the film thickness and the film quality, and a post-cleaning unit (post-processing unit) 24 for post-cleaning and drying the substrate W after the plating process. Further, the first transfer robot 26 is positioned between the load / unload unit 12 and the film thickness / film quality measuring unit 22 by the pre-processing unit 18, the electroless plating unit 20, the film thickness / film quality measuring unit 22, and The second transfer robots 28 are arranged at positions between the cleaning units 24.

  In this example, as a pre-plating process, an example is shown in which a substrate surface cleaning process and a catalyst applying process for a wiring, which is a metal part, are simultaneously performed using the same pre-treatment liquid. This pre-plating treatment is a treatment in which a chemical solution is brought into contact with the surface of the substrate and the entire surface is modified with the chemical solution. What is necessary is just to perform simultaneously with the same chemical | medical solution.

  A turning shaft 30 that can move up and down and can turn freely is provided upright on the side of the pretreatment unit 18 and the electroless plating unit 20, and a swing arm 32 is fixed to an upper end of the turning shaft 30. A motor 34 is attached to a free end of the swing arm 32 in a downward direction, and a substrate holding head 38 for detachably holding a substrate W is attached to a lower end of an output shaft 36 of the motor 34 so as to face downward. ing. Accordingly, the swing arm 32 swings in the horizontal direction in accordance with the swing of the swing shaft 30, and the swing of the swing arm 32 causes the substrate holding head 38 to move to the position immediately above the pre-processing unit 18 and the electroless plating. The pretreatment unit 18 and the electroless plating unit 20 are configured to have a common substrate holding head 38 by moving between a position immediately above the unit 20 and the unit 20. The substrate holding head 38 rotates with the driving of the motor 34.

  As shown in FIG. 6, the pre-processing unit 18 and the electroless plating unit 20, the revolving shaft 30, the swing arm 32 and the substrate holding head 38 are provided with a supply / exhaust system 40 and can be hermetically sealed during substrate processing. It is arranged inside a housing 42 whose atmosphere can be independently controlled.

  The pre-processing unit 18 performs a pre-plating process on the substrate W, that is, a cleaning process for cleaning the surface of the embedded wiring 8 formed on the surface of the substrate W and the surface of the insulating film 2, and the wiring 8 after the cleaning process. This is for performing a catalyst applying treatment for applying and activating a catalyst to the surface to be treated, and performing a rinsing treatment for rinsing the pretreatment liquid (chemical solution) used for the catalyst addition with a rinsing liquid. , Are performed by a single pre-processing unit 18.

  The pretreatment unit 18 employs a two-liquid separation method for preventing mixing of different liquids. As shown in FIGS. 3 to 5, the pretreatment unit 18 has an upward opening having an inner diameter slightly larger than the outer diameter of the substrate holding head 38. A processing tank 100 (see FIG. 6) having an inner tank 100a and an outer tank 100b is provided. A pair of legs 104 attached to the lid 102 is rotatably supported on the outer peripheral portion of the inner tank 100a. Further, a crank 106 is integrally connected to the leg 104, and a free end of the crank 106 is rotatably connected to a rod 110 of a cylinder 108 for moving the lid.

  Thus, with the operation of the lid moving cylinder 108, the lid 102 is configured to move between the processing position covering the upper end opening of the inner tank 100a and the side retract position. . On the surface (upper surface) of the lid 102, as described below, pure water, electrolytic ionic water having a reducing power, or an aqueous solution prepared by mixing one or more components constituting an electroless plating solution is used. A nozzle plate 112 having a number of spray nozzles 112a for spraying the rinsing liquid outward (upward) is provided.

  As shown in FIG. 6, inside the processing tank 100, a plurality of spray nozzles 124a for injecting the pretreatment liquid supplied from the pretreatment liquid tank 120 by driving the pretreatment liquid supply pump 122 upward are sprayed. Is disposed in a state where the spray nozzles 124 a are more evenly distributed over the entire cross section of the processing tank 100. A drain pipe 126 for discharging a pretreatment liquid (drained liquid) to the outside is connected to the inner tank 100a of the processing tank 100. A three-way valve 128 is interposed in the middle of the drain pipe 126, and the pre-treatment liquid (drain liquid) is provided as necessary via a return pipe 130 connected to one outlet port of the three-way valve 128. Is returned to the pretreatment liquid tank 120 and can be reused.

  Here, the plating pretreatment liquid removes catalytic metal ions and impurities including metal residues and the like remaining on the surface of the metal oxide film on the surface of the metal part or the surface of the metal part and other insulating films on the substrate. The pretreatment liquid is prepared by mixing an acid having a cleaning function to contact the surface of the substrate, thereby applying a catalyst to the wiring surface and simultaneously removing an oxide film of the wiring metal or an interlayer insulating film. The upper metal residue can be removed. Specifically, as the plating pretreatment liquid, at least one kind of palladium hydrochloride, palladium sulfate and palladium acetate was mixed with at least one kind of hydrochloric acid, sulfuric acid, hydrofluoric acid, acetic acid, oxalic acid, formic acid, citric acid and tartaric acid. Aqueous solution.

  Further, in this example, the nozzle plate 112 provided on the surface (upper surface) of the lid 102 is connected to the rinsing liquid supply source 132, and the rinsing processing of the pretreatment liquid remaining on the substrate surface after the plating pretreatment ( The cleaning process is performed using the rinse solution, for example, pure water. A drain pipe 127 for discharging a rinsing liquid (waste liquid) to the outside is connected to an outer tank 100b of the processing tank 100.

  In this example, pure water is used as the rinsing liquid of the pretreatment liquid, for example, but electrolytic ionic water having reducing power or reducing water ionized by an arbitrary method is used. Alternatively, the pretreatment liquid remaining on the substrate may be efficiently rinsed (washed) while preventing the wiring from being oxidized. Further, the rinsing treatment of the pretreatment liquid may be performed by cleaning the surface of the substrate with an aqueous solution in which one component or a large number of components constituting the electroless plating solution is mixed, whereby the wiring is also oxidized. The pretreatment liquid remaining on the substrate can be efficiently cleaned while preventing the above.

  As a result, the substrate holding head 38 holding the substrate W is lowered, and the substrate holding head 38 is positioned inside the inner tank 100a of the processing tank 100. In this state, the nozzle plate 124 disposed inside the inner tank 100a By spraying the pretreatment liquid toward the substrate W from the spray nozzle 124a, the pretreatment liquid is uniformly sprayed over the entire lower surface (processing surface) of the substrate W, and the pretreatment liquid is scattered outside. The pretreatment liquid can be discharged to the outside from the drain pipe 126 while preventing the occurrence of the pretreatment liquid.

  Further, the substrate holding head 38 is raised, and the upper end opening of the inner tank 100a of the processing tank 100 is closed with the cover 102, and the upper surface of the cover 102 is moved toward the substrate W held by the substrate holding head 38. By spraying a rinsing liquid such as pure water or electrolytic ionic water having a reducing power, or an aqueous solution prepared by mixing one or more components constituting an electroless plating solution, from a spray nozzle 112a of the arranged nozzle plate 112. Then, a rinsing process (cleaning process) of the pretreatment liquid remaining on the substrate surface after the application of the catalyst is performed. The rinse liquid (waste liquid) after the treatment is collected in the outer tank 100b of the processing tank 100, and is discarded through the drain pipe 127. As described above, the rinsing liquid such as electrolytic ion water having the reducing power is prevented from flowing into the inside of the processing tank 100, so that the two liquids are not mixed.

  According to the pretreatment unit 18, as shown in FIG. 3, the substrate W is inserted and held inside the substrate holding head 38 in a state where the substrate holding head 38 is raised, and thereafter, as shown in FIG. The holding head 38 is lowered to be positioned in the inner tank 100a (see FIG. 6) of the processing tank 100. Then, while rotating the substrate holding head 38 and rotating the substrate W held by the substrate holding head 38, the pretreatment liquid is directed toward the substrate W from the spray nozzle 124 a of the nozzle plate 124 disposed inside the processing bath 100. By jetting, the pretreatment liquid is jetted uniformly over the entire surface of the substrate W. Further, the substrate holding head 38 is raised and stopped at a predetermined position, and the lid 102 at the retreat position is moved to a position covering the upper end opening of the inner tank 100a of the processing tank 100 as shown in FIG.

  In this state, pure water or electrolytic ionized water having a reducing power is sprayed from the spray nozzle 112a of the nozzle plate 112 disposed on the upper surface of the lid 102 toward the substrate W held and rotated by the substrate holding head 38, Alternatively, a rinsing liquid such as an aqueous solution prepared by mixing one or more components constituting the electroless plating solution is sprayed. Thereby, an aqueous solution prepared by mixing the cleaning treatment and the catalyst application treatment with the pretreatment liquid for the substrate W and one or more components constituting the pure water or electrolytic ionic water having a reducing power, or the electroless plating solution. A rinsing process using a rinsing liquid, such as spraying, can be performed while the two liquids are not mixed.

  Further, in the pretreatment liquid tank 120, the concentration of impurities such as copper mixed in the pretreatment liquid by the plating pretreatment is measured, and when the concentration of the impurities reaches a predetermined value, the concentration of the impurities before removal is measured. A processing liquid purifying device 140 is provided. Thereby, contamination of the pretreatment liquid used for the plating pretreatment can be suppressed, and the pretreatment liquid can always have stable catalytic power and detergency. In addition, it is preferable to maintain the temperature, composition, and concentration of each component of the pretreatment solution within predetermined ranges, whereby a catalyst having a stable nucleus density is provided on the wiring surface, and the film quality is stable and the film thickness is uniform It is possible to form a suitable alloy film.

  In addition, by adjusting the lowering position of the substrate holding head 38 and adjusting the distance between the substrate W held by the substrate holding head 38 and the nozzle plate 124, the pre-processing sprayed from the spray nozzle 124 a of the nozzle plate 124 is performed. It is possible to arbitrarily adjust the region where the liquid contacts the substrate W and the injection pressure.

  The above example corresponds to the case where one type of processing solution is used for the plating pretreatment. When a plurality of types, for example, two types of processing solutions are used for the plating pre-processing, three independent systems can be provided in the pre-processing unit so that three types of chemicals (including pure water) can be used. it can. In other words, the first system dedicated to the first plating pretreatment liquid, the second system dedicated to the second plating pretreatment liquid, and the third system dedicated to the rinsing liquid are individually connected to the same unit.

  As shown in FIG. 6, the electroless plating unit 20 is provided with a plating tank 200 for storing therein a plating solution controlled at a predetermined temperature (for example, 80 ° C.). The plating tank 200 extends from a plating solution supply tank 202 at the bottom, is connected to a plating solution supply pipe 208 provided with a plating solution supply pump 204 and a three-way valve 206 on the way, and has a plating solution recovery groove 210 Is provided. Thereby, during the plating process, the plating solution is supplied into the plating tank 200 from the bottom thereof, and the overflowing plating solution is collected from the plating solution collecting groove 210 to the plating solution supply tank 202, whereby the plating solution is supplied. Can be circulated.

  In the vicinity of the bottom of the plating tank 200, the temperature of a plating solution introduced into the plating tank 200 is measured, and based on the measurement result, a temperature measuring device 214 for controlling a heater 216 and a flow meter 218 described below. Is installed.

  Further, in this example, the heat exchanger 220 is installed in the plating solution in the plating solution supply tank 202 by using water that has been heated using a separate heater 216 and passed through the flow meter 218 as a heat medium. A heating device 222 for indirectly heating the plating solution and a stirring pump 224 for circulating and stirring the plating solution in the plating solution supply tank 202 are provided. This is because the plating solution may be used at a high temperature (approximately 80 ° C.) in plating, which is used to cope with this. According to this method, the plating solution is much more expensive than the in-line heating method. It is possible to prevent unwanted substances and the like from being mixed into the delicate plating solution.

  In the electroless plating unit 20, the substrate W held by the substrate holding head 38 is lowered while rotating the plating solution in the plating tank 200, and the substrate W is lowered. Immerse in the plating solution inside. At this time, the temperature of the plating solution, the composition of the plating solution, and the concentration of each component are maintained within predetermined ranges by the plating solution management device 240 and the heating device 222 attached to the plating tank 200. Then, after immersing the substrate W in the plating solution for a predetermined time, the substrate W is pulled up to a position above the plating tank 200, the rotation of the substrate holding head 38 is stopped, and the plating process is completed. As described above, by controlling the processing time, the thickness of the alloy film formed on the base surface of the substrate to be processed is adjusted.

  As shown in detail in FIGS. 7 to 9, the substrate holding head 38 has a suction head 234 and a substrate receiver 236 surrounding the periphery of the suction head 234. The suction head 234 and the substrate receiver 236 rotate integrally with the driving of the motor 34 via a spline structure, but relatively move up and down with the operation of a cylinder (not shown). It is configured.

At the periphery of the lower surface of the suction head 234, a suction ring 250 that suctions and holds the substrate W with a lower surface as a sealing surface is attached via a press ring 251 and is provided on the lower surface of the suction ring 250 so as to be continuous in the circumferential direction. The concave portion 250a and the vacuum line 252 extending inside the suction head 234 communicate with each other via a communication hole 250b provided in the suction ring 250. Thus, the substrate W is sucked and held by evacuating the concave portion 250a. In this manner, the substrate W is held by being evacuated to a small width (in the radial direction) in a circular shape. Influences (such as bending) on the substrate W due to the vacuum can be minimized. The release of the substrate W is performed by supplying N 2 and / or pure water to the vacuum line 252.

  On the other hand, the substrate receiver 236 is formed in a cylindrical shape with a bottom and opened downward, a peripheral wall of which is provided with a substrate insertion window 236a for inserting the substrate W therein, and a disk protruding inward at a lower end. A substrate guide portion 254 is provided, and a seal ring 254a is provided at an inner peripheral end of the substrate guide portion 254 so as to protrude slightly upward. Further, a protrusion 256 having a tapered surface 256a on the inner peripheral surface serving as a guide for the substrate W is provided on the upper portion of the substrate guide portion 254.

  Thus, as shown in FIG. 7, the substrate W is inserted into the substrate receiver 236 from the substrate insertion window 236a with the substrate receiver 236 lowered. Then, the substrate W is guided by the tapered surface 256a of the protruding piece 256, positioned and held at a predetermined position on the upper surface of the substrate guide portion 254. In this state, the relative positions of the substrate receiver 236 and the suction head 234 are approached, and as shown in FIG. 8, the upper surface of the substrate W placed and held on the substrate guide portion 254 of the substrate receiver 236 is The seal ring 254a of the substrate guide 254 is pressed against the lower surface of the peripheral portion of the substrate W by bringing the substrate W into contact with the suction ring 250 and further bringing the relative position closer. As a result, the lower surface of the peripheral portion of the substrate W is sealed with the seal ring 254a to hold the substrate W.

  Then, for example, when performing the pre-processing of the substrate W, as described above, the concave portion 250a of the suction ring 250 is evacuated through the vacuum line 252 so that the peripheral portion of the upper surface of the substrate W is held at the lower surface of the suction ring 250. The substrate W is suction-held while being sealed. In this state, the pretreatment of the substrate is performed by spraying the pretreatment liquid toward the surface (lower surface) of the substrate W. This can prevent the catalyst from being applied to the peripheral portion of the substrate W. Also, at the time of rinsing and plating, as shown in FIG. 9, the relative position between the substrate receiver 236 and the suction head 234 is separated by, for example, several mm to several tens mm, and the substrate W is moved from the substrate guide portion 254. Then, only the suction ring 250 is used to hold the device. Thereby, the peripheral portion of the surface (lower surface) of the substrate W is purified by the rinsing liquid. Furthermore, even when the peripheral portions of the front and rear surfaces of the substrate are not sealed during the plating process, the catalyst is not attached to the peripheral portions, so that contamination of the peripheral portion of the substrate due to plating can be prevented.

  In this example, as shown in FIG. 10A, the seal ring 254a of the substrate guide portion 254 is pressed against the lower surface of the peripheral edge of the substrate W, and the lower surface of the peripheral edge of the substrate W is sealed by the seal ring 254a. As described above, the pre-treatment liquid is sprayed toward the substrate W from the spray nozzle 124a of the nozzle plate 124 to the region (lower surface) sealed by the seal ring 254a to perform the pre-treatment of the substrate W, that is, the cleaning treatment. And a catalyst application treatment.

  Further, as shown in FIG. 10B, the substrate W is sucked and held while the peripheral edge of the upper surface of the substrate W is sealed with the lower surface of the suction ring 250, and the substrate W is further separated from the substrate guide portion 254. A rinsing liquid such as pure water or electrolytic ionic water having reducing power, or an aqueous solution prepared by mixing one or more components constituting an electroless plating solution is directed to the substrate W from the spray nozzle 112a of the nozzle plate 112. To perform a rinsing process for rinsing the pretreatment liquid attached to the substrate W. At that time, the seal ring 254a of the substrate guide portion 254 and the outer peripheral portion of the substrate surface are cleaned by spraying a rinsing liquid from a dedicated nozzle (not shown).

  Further, as shown in FIG. 10C, the substrate W is sucked and held while the periphery of the upper surface of the substrate W is sealed with the lower surface of the suction ring 250, and further, the substrate W is separated from the substrate guide portion 254. Then, the substrate W is immersed in a plating solution in the plating tank 200 to perform a plating process on the substrate surface.

The time from completion of the plating pre-treatment to the start of the rinsing treatment is preferably within 5 seconds, whereby the continuous reaction by the residual liquid after the plating pre-treatment and the oxidation of the activated metal surface are prevented. Can be minimized.
The interval between the completion of the rinsing treatment of the pretreatment liquid remaining on the substrate surface and the start of the electroless plating treatment is preferably within 15 seconds, whereby the surface of the metal part after the plating pretreatment is removed. Reoxidation due to the influence of the external atmosphere can be minimized.

  Although not shown in FIG. 6, the plating tank 200 may have a double structure substantially similar to that of the pretreatment tank 100. Thus, by making the plating tank 200 have a double structure, the substrate can be transferred from the inner tank to the outer tank immediately after the plating treatment, and the primary rinse can be immediately performed. In this example, an electroless plating unit 20 having no rinsing function is used. Immediately after the plating process, the substrate is transferred from the plating tank 200 to the plating pretreatment unit 18, The primary rinsing is performed in the outer tank 100b.

  The post-cleaning unit 24 removes the plating solution remaining on the surface of the substrate W plated by the electroless plating unit 20 or unnecessary deposits on the insulating film by secondary cleaning, and simultaneously cleans the back surface of the substrate W. Furthermore, the substrate W is configured to be rotated at a high speed and spin-dried.

  In other words, the post-cleaning unit 24 includes a substrate stage that detachably holds the substrate W via a clamp mechanism and rotates the substrate W at a high speed, and pure water or pure water on both the front and back surfaces of the substrate held by the substrate stage. A cleaning liquid supply nozzle for supplying a cleaning liquid such as a chemical liquid is provided. A cleaning liquid such as pure water or a chemical solution is supplied to the front and back surfaces of the substrate W while rotating the substrate held on the substrate stage, so that the plating solution remaining on the surface of the substrate W or unnecessary deposition on the insulating film is removed. The substrate W is spin-dried by removing the object, cleaning the back surface of the substrate at the same time, and rotating the substrate W at a high speed via a substrate stage.

  Next, a series of electroless plating processes performed by the substrate processing apparatus will be described with reference to FIG. In this example, as shown in FIG. 1, a case will be described in which an alloy film (wiring protection film) 9 made of a Co-WP alloy is selectively formed to protect the wiring 8.

  First, a substrate cassette 10 mounted on a load / unload unit 12 with a substrate W (see FIG. 1, the same applies hereinafter) having the wiring 8 formed on the surface thereof is loaded with the surface of the substrate W facing up (face-up). The first substrate W is taken out by the first transport robot 26 and transported to the film thickness / film quality measurement unit 22. Then, the substrate W placed on the film thickness / film quality measurement unit 22 is received by the second transfer robot 28, turned 180 °, and then transferred to the substrate holding head 38. That is, as described above, with the substrate receiver 236 lowered, the substrate W is inserted into the substrate receiver 236 from the substrate insertion window 236a, the substrate receiver 236 is raised, and the seal ring 254a of the substrate guide portion 254 is attached to the substrate. The substrate W is held by being pressed against the lower surface of the peripheral portion of the W.

Next, the swing arm 32 is swung to move the substrate holding head 38 to a position immediately above the pre-processing unit 18. Next, with the lid 102 moved from the position covering the upper end opening of the processing tank 100 to the retracted position, the substrate holding head 38 is lowered to be positioned inside the inner tank 100a of the processing tank 100, The pretreatment liquid is sprayed toward the substrate W from the spray nozzle 124a of the nozzle plate 124 disposed inside the inner tank 100a toward the substrate W held and rotated by the head 38. Is pre-processed. Examples of the pretreatment liquid include a mixture of 0.005 g / L of PdCl 2 and 0.2 ml / L of HCl or a mixture of 0.04 g / L of PdSO 4 and 20 ml / L at a liquid temperature of 25 ° C. A mixed solution of H 2 SO 4 can be used.

Thereby, Pd as a catalyst is attached to the surface of the wiring 8 at the same time as removing the metal oxide film on the surface of the wiring 8 and the CMP residue remaining on the surfaces of the wiring 8 and the insulating film 2. That is, a Pd nucleus as a catalyst nucleus (seed) is formed on the surface of the wiring 8 and the exposed surface of the wiring 8 is activated. As described above, the concentration of impurities such as copper mixed into the pretreatment liquid by the catalyst application treatment is measured, and when the concentration of the impurities reaches a predetermined value, the pretreatment liquid purifying apparatus for removing the impurities is used. By providing 140, the used pretreatment liquid can be circulated and reused.
It is preferable that the substrate W be rotated during the plating pretreatment, whereby the uniformity of the chemical solution reaction over the entire surface of the substrate can be improved.

Then, the substrate holding head 38 is once raised, and if necessary, the substrate W is rotated at a high speed to shake off the pretreatment liquid. Then, as described above, the peripheral portion of the upper surface of the substrate W is The substrate W is sucked and held while being sealed on the lower surface, and the substrate W is further separated from the substrate guide portion 254. Thereafter, the lid 102 is positioned at a position covering the upper end opening of the processing tank 100, and a rinsing liquid such as pure water or electrolytic ion water having reducing power is sprayed from the spray nozzle 112 a of the nozzle plate 112 toward the substrate W. Then, a rinsing process for rinsing the pretreatment liquid attached to the substrate is performed.
It is preferable to rotate the substrate W also during the rinsing process, whereby the uniformity of cleaning over the entire surface of the substrate can be improved.

  Next, the substrate holding head 38 is moved to a position immediately above the electroless plating unit 20 while holding the substrate W with the substrate holding head 38 as described above. Then, in a state where the plating solution in the plating tank 200 is circulated, the surface of the substrate W is subjected to electroless plating. That is, for example, the substrate W is immersed in, for example, about 120 seconds in a Co-WP plating solution having a liquid temperature of 80 ° C., and selectively electroless plating (electroless Co -WP lid plating), and thereafter, the substrate holding head 38 is raised to perform primary rinsing after plating. As a result, an alloy film (wiring protection film) 9 made of a Co-WP alloy is selectively formed on the surface of the wiring 8 to protect the wiring 8. Examples of the composition of the plating solution include the following.

Plating solution composition CoSO 4 · 7H 2 O: 14g / L
· Na 3 C 6 H 5 O 7 · 2H 2 O: 70g / L
・ H 3 BO 3 : 40 g / L
· Na 2 WO 4 · 2H 2 O: 12g / L
· NaH 2 PO 2 · H 2 O: 21g / L
-PH: 9.5 (adjusted with NaOH)
The plating solution capacity, temperature, and each composition component are maintained within predetermined ranges by the plating solution management device 240.

  Here, the inside of the housing 42 is filled or circulated with an inert gas or a reducing gas to make the inside of the housing 42 at least an atmosphere having an oxygen component smaller than that of the atmosphere. And a plating treatment. As a result, it is possible to prevent the oxide film from being regenerated on the surface of the wiring 8 to which the catalyst has been applied, or to prevent the protective film from being oxidized during the film formation, thereby forming a stable alloy film. can do.

  The substrate after the plating is received from the substrate holding head 38 by the second transfer robot 28, turned 180 °, and then transferred to the post-cleaning unit 24. Thereafter, the cleaning unit 24 supplies a cleaning liquid such as pure water to both the front and back surfaces of the substrate W while holding and rotating the substrate W on the substrate stage to clean the front and back surfaces of the substrate W, and further passes through the substrate stage. The substrate W after the post-cleaning is spin-dried by rotating the substrate W at a high speed.

  Next, the substrate W after the spin drying is transported to the film thickness / film quality measuring unit 22 by the second transport robot 28, and is formed on the surface of the wiring 8 as required by the film thickness / film quality measuring unit 22. At least one of the film thickness and the film quality of the alloy film 9 is measured, and the substrate W after measuring the film thickness or the film quality is returned to the substrate cassette 10 mounted on the load / unload unit 12 by the first transfer robot 26.

  Then, a measurement result obtained by measuring the film thickness or the film quality of the protective film 9 formed on the exposed surface of the wiring 8 is fed back before the next substrate is subjected to the electroless plating treatment, whereby the film thickness or the film quality is changed. Accordingly, the thickness and quality of the alloy film formed on the base surface of the substrate to be processed are controlled, for example, by adjusting the processing time of the plating process on the next substrate or the components of the plating solution.

According to this example, any liquid such as pure water can be used as a rinsing liquid for rinsing the pretreatment liquid remaining on the substrate after the plating pretreatment.
In the above example, an example in which a Co-WP alloy film is used as the alloy film (wiring protection film) 9 is shown, but Co-P, Co-WB, Co-B, and Ni- A wiring protection film made of WP, Ni-P, Ni-WB or Ni-B may be used. Although an example using copper as the wiring material is shown, a copper alloy, silver, a silver alloy, gold, a gold alloy, or the like may be used in addition to copper.

  Further, in this example, an example is shown in which an alloy film is formed on the exposed surface of the embedded wiring formed in the insulator. An alloy film may be formed on the surface of the metal film formed on the bottom surface and the side surface of the recess for embedded wiring formed on the surface of the insulator, or the exposed surface of the metal wiring formed on the surface of the insulator, that is, the upper surface and An alloy film may be formed on the side surface.

  The plating pretreatment may be performed by immersing the substrate in a pretreatment liquid as in the case of the electroless plating treatment. Thus, the substrate can be isolated from the external atmosphere during the substrate processing, and the surface of the activated metal portion can be prevented from being re-oxidized. Further, the amount of dissolved oxygen in the plating pretreatment liquid can be adjusted, and the reaction rate such as catalyst application in the plating pretreatment can be controlled.

It is sectional drawing which shows the state which formed the wiring protective film by electroless plating. 1 is a plan layout view of a substrate processing apparatus according to an embodiment of the present invention. It is a front view at the time of substrate delivery of the pre-processing unit. It is a front view at the time of the catalyst provision process of a pretreatment unit. It is a front view at the time of the cleaning process of the pre-processing unit, and at the time of the rinsing process of a catalyst solution. It is a system diagram of a pretreatment unit and an electroless plating unit. FIG. 5 is an enlarged sectional view of a main part when the substrate holding head transfers the substrate. FIG. 11 is an enlarged sectional view of a main part in a state where the substrate holder of the substrate holding head is raised and the seal ring of the substrate guide portion is pressed against the lower surface of the peripheral portion of the substrate to hold the substrate. FIG. 4 is an enlarged cross-sectional view of a main part of the substrate holding head in a state where a peripheral portion of an upper surface of a substrate is sealed with a lower surface of a suction ring to suck and hold the substrate and further separate the substrate from a substrate guide portion. (A) shows a state in which a pretreatment (cleaning treatment and catalyst application treatment) of the substrate is performed, (b) shows a state in which a rinsing treatment for rinsing a chemical solution attached to the substrate is performed, (c) FIG. 3 is a schematic view showing a state where a plating process is being performed on the substrate surface. FIG. 3 is a process flow chart in the substrate processing apparatus shown in FIG. 2.

Explanation of reference numerals

Reference Signs List 8 Wiring 9 Protective film 10 Substrate cassette 12 Load / unload unit 18 Pretreatment unit 20 Electroless plating unit 22 Film thickness measurement unit 24 Post-cleaning unit 30 Rotating shaft 32 Swing arm 38 Substrate holding head 40 Housing 100 Processing tank 102 Lid Body 104 Leg 106 Crank 108 Lid moving cylinder 112, 124 Nozzle plate 112a, 124a Spray nozzle 120 Pretreatment liquid tank 126 Drainage pipe 132 Rinse liquid supply source 140 Pretreatment liquid purification device 200 Plating tank 202 Plating liquid supply tank 210 Plating solution recovery groove 216 Heater 218 Flow meter 220 Heat exchanger 222 Heating device 224 Stirring pump 234 Suction head 236 Substrate receiver 240 Plating solution management device 250 Suction ring 252 Vacuum line 254 Substrate guide 254a Seal ring

Claims (30)

  1. Prepare a substrate with a metal part on the surface,
    Perform a plating pre-treatment to modify the entire surface by contacting the pre-treatment liquid to the surface of the substrate,
    Pretreatment liquid remaining on the surface of the substrate is removed by rinsing,
    Performing an electroless plating process on the surface of the substrate to selectively form an alloy film on the surface of the metal part,
    A substrate processing method, wherein the substrate after the electroless plating is post-washed and dried.
  2.   2. The substrate processing method according to claim 1, wherein the metal part is an exposed surface of a buried wiring formed in an insulator.
  3.   2. The substrate processing method according to claim 1, wherein the metal part is a metal film formed on a bottom surface and a side surface of a recess for a buried wiring formed on a surface of the insulator.
  4.   2. The substrate processing method according to claim 1, wherein the metal part is an exposed surface of a metal wiring formed on a surface of the insulator.
  5.   5. The plating pretreatment according to claim 1, wherein the surface of the substrate is cleaned, and at the same time, a catalyst is applied to the metal part to activate the surface of the metal part. 3. The substrate processing method according to 1.
  6.   The method according to claim 1, wherein the pre-plating treatment and the rinsing treatment are performed by spraying a chemical solution, pure water, or the like from a nozzle toward the surface of the substrate arranged with the surface facing downward. 3. The substrate processing method according to 1.
  7.   7. The substrate processing method according to claim 6, wherein the pre-plating process and the rinsing process are performed while rotating the substrate.
  8.   8. The substrate processing method according to claim 6, wherein a nozzle used for the plating pretreatment and a nozzle used for the rinsing treatment are connected to different flow path systems, respectively.
  9.   The substrate processing method according to claim 1, wherein the plating pretreatment is performed by immersing the substrate in a pretreatment liquid.
  10.   10. The substrate processing method according to claim 1, wherein the substrate is rotated at a high speed after the completion of the plating pretreatment.
  11.   The plating pre-treatment is performed using a pre-treatment liquid prepared by mixing at least a catalytic metal ion and an acid having a function of cleaning the surface of the substrate. A substrate processing method according to any one of the above.
  12.   12. The substrate according to claim 1, wherein the rinsing treatment is performed by cleaning the surface of the substrate with pure water or pure water whose reducibility is increased by a method such as electrolysis or dissolution of hydrogen gas. Substrate processing method.
  13.   The substrate according to any one of claims 1 to 12, wherein the rinsing process is performed by cleaning a surface of the substrate with an aqueous solution prepared by mixing one or more components constituting an electroless plating solution. Processing method.
  14.   14. The substrate processing method according to claim 1, wherein the pre-plating process and the rinsing process are performed in an atmosphere having an oxygen component smaller than that of the atmosphere.
  15.   The substrate processing method according to any one of claims 1 to 14, wherein the electroless plating is performed in an atmosphere having an oxygen component less than that of the atmosphere.
  16.   16. The substrate processing method according to claim 1, wherein at least one of a film thickness and a film quality of the alloy film is measured after post-washing and drying the substrate.
  17.   17. The substrate processing method according to claim 1, wherein the composition of the pretreatment liquid and the rinse liquid, the concentration of each component, and the temperature of the pretreatment liquid are maintained within predetermined ranges.
  18.   18. The method according to claim 1, wherein a concentration of an impurity mixed in the pretreatment liquid by the plating pretreatment is measured, and the impurity is removed when the impurity reaches a predetermined concentration. Substrate processing method.
  19.   4. The electroless plating process according to claim 1, wherein the temperature, composition, and concentration of each component of the plating solution are maintained within predetermined ranges, and the plating time is controlled for a predetermined film thickness. 19. The substrate processing method according to any one of 18.
  20. A pretreatment unit that performs plating pretreatment for bringing the surface of a substrate having a metal part into contact with a pretreatment liquid to modify the entire surface, and rinsing treatment for rinsing the pretreatment liquid remaining on the surface of the substrate after the plating pretreatment. When,
    An electroless plating unit that performs an electroless plating process on the surface of the substrate after the plating pretreatment and selectively forms an alloy film on the surface of the metal part.
    And a post-processing unit for post-cleaning and drying the substrate after the electroless plating.
  21.   21. The substrate processing apparatus according to claim 20, wherein the pre-plating process is a process of cleaning a surface of the substrate and simultaneously activating a surface of the metal part by applying a catalyst to the metal part. .
  22.   22. The pretreatment unit according to claim 20, wherein the pretreatment unit has a function of separating a pretreatment liquid used for the plating pretreatment and a rinsing liquid used for the rinsing treatment after the substrate treatment. Substrate processing equipment.
  23.   The pretreatment unit measures a concentration of an impurity mixed into the pretreatment solution by the plating pretreatment, and has a liquid purification function of removing the impurity when the concentration of the impurity reaches a predetermined value. 23. The substrate processing apparatus according to claim 20, further comprising an apparatus.
  24.   24. The substrate processing apparatus according to claim 20, further comprising an apparatus for measuring at least one of a film thickness and a film quality of an alloy film formed on the substrate that has been dried by the post-processing unit. .
  25.   25. The substrate processing apparatus according to claim 24, wherein a plating condition is changed or a quality of a film is determined based on a measurement value of an apparatus that measures at least one of the film thickness and the film quality.
  26.   The substrate processing apparatus according to any one of claims 20 to 25, wherein the pretreatment unit and the electroless plating unit are configured to treat the surfaces of the substrates having the same orientation.
  27.   27. The substrate processing apparatus according to claim 20, wherein the pretreatment unit and the electroless plating unit have a common substrate holding head.
  28.   28. The substrate holding head according to claim 20, wherein the substrate holding head is configured to be able to simultaneously or selectively seal a peripheral edge on the front surface side or a peripheral edge on the back surface side of the substrate. The substrate processing apparatus according to any one of the preceding claims.
  29.   The said pre-processing unit and the said plating processing unit have an opening in a part, and are arrange | positioned inside the sealable housing | casing which has the function which can adjust the inside atmosphere independently of the whole apparatus. Item 29. The substrate processing apparatus according to any one of Items 20 to 28.
  30.   The substrate processing apparatus according to any one of claims 20 to 29, wherein the substrate processing apparatus is housed in a housing that has been subjected to a light emitting process so that light does not transmit from an external environment.
JP2004075363A 2003-03-20 2004-03-16 Method and apparatus for substrate treatment Withdrawn JP2004300576A (en)

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WO2005105322A1 (en) * 2004-04-28 2005-11-10 Ebara Corporation Substrate processing unit and substrate processing apparatus
WO2006095881A1 (en) * 2005-03-07 2006-09-14 Ebara Corporation Substrate processing method and substrate processing apparatus
WO2007111127A1 (en) * 2006-03-27 2007-10-04 Tokyo Electron Limited Method of substrate treatment, process for producing semiconductor device, substrate treating apparatus, and recording medium
JP2008038215A (en) * 2006-08-08 2008-02-21 Ebara Corp Substrate-treating method and substrate-treating apparatus
JP2011519393A (en) * 2008-03-28 2011-07-07 ラム リサーチ コーポレーションLam Research Corporation Substrate cleaning and electroless deposition processes and solutions
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