JP6806476B2 - Electrolytic treatment method and electrolytic treatment equipment - Google Patents

Description

The present invention relates to an electrolytic treatment method for performing a predetermined treatment using ions to be treated contained in a treatment liquid, and an electrolytic treatment apparatus for carrying out the electrolytic treatment method.

The electrolytic process (electrolytic treatment) is a technique used for various treatments such as plating treatment and etching treatment.

In order to perform the above-mentioned plating treatment, for example, the plating treatment described in Patent Document 1 has been proposed. In this plating process, the direct electrode and the indirect electrode are arranged in double or close to each other in the plating solution, and the counter electrode (object to be processed) is arranged so as to sandwich the plating solution with respect to the direct electrode and the indirect electrode. To do. After that, by applying a voltage to the indirect electrode to form an electric field in the plating solution, the metal ions in the plating solution are moved to the counter electrode side, and further, a voltage is applied directly between the electrode and the counter electrode. , The metal ion that has moved to the counter electrode side is reduced.

Further, as another method for performing the plating treatment, for example, the plating treatment described in Patent Document 2 has been proposed. In this plating process, the direct electrode and the indirect electrode are arranged in double or close to each other in the plating solution, and the counter electrode (object to be processed) is arranged so as to sandwich the plating solution with respect to the direct electrode and the indirect electrode. Then, for the indirect electrode, a switch for switching between the connection with the power supply and the connection with the direct electrode is arranged. After that, the indirect electrode and the power supply are connected by a switch and a voltage is applied to form an electric field in the plating solution to move the metal ions in the plating solution to the counter electrode side, and further, the indirect electrode and the power supply are connected by the switch. By disconnecting the connection and connecting the indirect electrode and the direct electrode, the metal ions that have moved to the counter electrode side are reduced.

Regardless of whether the plating treatment of Patent Document 1 or Patent Document 2 is performed, the metal ions are reduced while the metal ions are accumulated on the counter electrode side by individually moving the metal ions and reducing the metal ions. This is done to make the plating process uniform.

JP-A-2015-4124 International Publication WO2015 / 104951

As described above, in any of the plating treatments of Patent Document 1 or Patent Document 2, the movement of metal ions (hereinafter, may be referred to as “movement step”) and the reduction of metal ions (hereinafter, may be referred to as “reduction step”) may occur. However, as a result of diligent studies by the present inventor, metal ions are reduced on the counter electrode side even while the metal ions are moved to the counter electrode side and accumulated in the moving step. It turns out that there are cases. That is, it was found that the reduction step may proceed during the moving step.

The present inventor infers the cause of this as follows. In the moving step, an electric field formed in the plating solution by applying a voltage to the indirect electrode also generates an electric field between the direct electrode and the counter electrode. At that time, since both the direct electrode and the counter electrode are conductors, the charge exchange of ions between the direct electrode and the counter electrode may proceed. This charge exchange amount corresponds to the potential difference between the direct electrode and the counter electrode. On the other hand, the potential of the direct electrode is determined by the electric field distribution formed by the indirect electrode and the counter electrode, and this electric field is determined by the electric line of force distribution generated between the indirect electrode and the counter electrode. Then, the closer the arrangement of the direct electrodes is to the indirect electrodes along the lines of electric force, the higher the potential of the direct electrodes. In the plating process of Patent Document 1 or Patent Document 2, since the direct electrode is arranged close to the indirect electrode, the potential of the direct electrode becomes high, and as a result, the charge exchange of the metal ion on the counter electrode side during the moving process. Proceeds, and the metal ion is reduced.

If the electric field is increased in the plating process, that is, the amount of current is increased in order to improve the plating rate in the plating process, the movement (supply) of metal ions to the counter electrode cannot be completed in time, and water is formed on the surface of the counter electrode. Electrolysis may proceed. In such a case, the hydrogen bubbles generated by the electrolysis of water generate voids in the plating metal deposited on the object to be treated, and the desired plating film cannot be realized.

The present invention has been made in view of this point, and an object of the present invention is to perform a predetermined electrolytic treatment on a body to be treated at high speed and uniformly by using ions to be treated in a treatment liquid.

In order to achieve the above object, the present invention is an electrolytic treatment method in which a predetermined treatment is performed using ions to be treated contained in the treatment liquid, and the electrode is directly connected to the treatment liquid so as to be electrically connected to the treatment liquid. In the arrangement step of arranging the counter electrodes and indirect electrodes forming an electric field in the treatment liquid, and applying a voltage to the indirect electrodes, the ions to be processed in the treatment liquid are moved to the counter electrode side. The process includes a step of moving ions to be treated, and a step of treating ions to be treated, which connects the direct electrode and the indirect electrode to oxidize or reduce the ions to be treated that have moved to the counter electrode side. In the ion transfer step, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density , and in the arrangement step, the treatment liquid is divided into two regions and inflow / out holes of the treatment liquid are formed. A partition wall, a pore wall in which the treatment liquid is divided into two regions and a plurality of pores are formed, or a pipe which divides the treatment liquid into two regions and connects the two regions is arranged. At the same time, the direct electrode and the counter electrode are arranged so as to come into contact with the treatment liquid across the partition wall, the pore wall, or the pipe .

The critical current density is a current density at which the amount of ions to be supplied reaches the limit with respect to the amount of ions to be treated that are oxidized or reduced per unit time in the electrolytic treatment. In other words, it is the maximum value of the current density at which the supply of ions to be processed by diffusion or the like reaches the limit and the current density does not increase even if the voltage is increased. The critical current density is generally represented by the current value per unit area (for example, 100 mm ² ) of the electrode.

In this way, the critical current is the maximum current that can be plated. Then, when the current flowing directly between the electrode and the counter electrode is equal to or less than the limit current density in the ion transfer step to be processed as in the present invention, water is not electrolyzed on the surface of the counter electrode, and as a result. , No bubbles are generated. Therefore, in the process of ion transfer to be processed, the electric field formed by applying a voltage to the indirect electrode can be increased. Then, even if the charge exchange of the counter electrode is performed by the current flowing between the direct electrode and the counter electrode in the ion transfer step to be processed, the charge amount is, for example, N part of the total charge amount transferred by the electric field of the indirect electrode. It becomes 1 (1 / N). In other words, in the ion treatment step to be treated, it is possible to exchange an amount of charge N times the amount of charge exchanged in the ion transfer step to be treated, and while suppressing electrolysis of water, a large amount of ions to be treated can be oxidized or It can be reduced. Therefore, the rate of the electrolytic treatment can be improved and the electrolytic treatment can be performed at a high speed.

Further, in the state where sufficient ions to be treated are accumulated on the counter electrode side in the ion transfer step to be treated and the ions to be treated are uniformly arranged on the surface of the counter electrode, the charge exchange of the ions to be treated is performed in the ion treatment step. Is performed, and the ion to be treated is oxidized or reduced. Therefore, the electrolytic treatment can be performed uniformly.

In such a case, a switch for switching between the connection between the indirect electrode and the power supply and the connection between the indirect electrode and the direct electrode is further arranged in the arrangement step, and the indirect electrode is connected to the indirect electrode by the switch in the ion transfer step. The power supply is connected and a voltage is applied to move the ions to be processed in the treatment liquid to the counter electrode side, and in the ion treatment step, the indirect electrode and the power supply are disconnected by the switch. Then, the indirect electrode and the direct electrode may be connected to oxidize or reduce the ion to be treated that has moved to the counter electrode side.

The present invention from another viewpoint is an electrolytic treatment method in which a predetermined treatment is performed using ions to be treated contained in the treatment liquid, and the direct electrode and the counter electrode are respectively connected so as to be electrically connected to the treatment liquid. The process of arranging and arranging the indirect electrode that forms an electric field in the treatment liquid, and the treatment ion that applies a voltage to the indirect electrode to move the treatment ion in the treatment liquid to the counter electrode side. The moving step includes a moving ion treatment step of connecting the direct electrode and the indirect electrode to oxidize or reduce the treated ion that has moved to the counter electrode side, and the moving ion moving step includes a moving step. The current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density, and in the arrangement step, the direct electrode and the counter electrode are arranged so as to come into contact with the treatment liquid, and further, the indirect electrode and the power supply are provided. A first switch for switching between the connection of the indirect electrode and the connection between the indirect electrode and the direct electrode is arranged, and a second switch for switching between the connection between the direct electrode and the indirect electrode and the connection between the direct electrode and the counter electrode. In the process of moving ions to be processed, the indirect electrode and the power supply are connected by the first switch to apply a voltage, and the direct electrode and the counter electrode are connected by the second switch. By connecting, the ion to be treated in the treatment liquid is moved to the counter electrode side, and in the ion treatment step, the connection with the indirect electrode is switched from the power source to the direct electrode by the first switch. At the same time, the connection with the direct electrode is switched from the counter electrode to the indirect electrode by the second switch, the direct electrode and the indirect electrode are connected, and the ion to be processed that has moved to the counter electrode side is oxidized. Alternatively, it is characterized by reducing.

In such a case, the surface area of the direct electrode may be smaller than the surface area of the counter electrode in the arrangement step.

The present invention from another viewpoint is an electrolytic treatment method in which a predetermined treatment is performed using ions to be treated contained in the treatment liquid, and the direct electrode and the counter electrode are respectively connected so as to be electrically connected to the treatment liquid. The process of arranging and arranging the indirect electrode that forms an electric field in the treatment liquid, and the treatment ion that applies a voltage to the indirect electrode to move the treatment ion in the treatment liquid to the counter electrode side. The moving step includes a moving ion treatment step of connecting the direct electrode and the indirect electrode to oxidize or reduce the treated ion that has moved to the counter electrode side, and the moving ion moving step includes a moving step. A partition wall in which the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density, the treatment liquid is divided into two regions and an inflow / outflow hole of the treatment liquid is formed in the arrangement step. A pore wall in which the treatment liquid is divided into two regions and a plurality of pores are formed, or a pipe which divides the treatment liquid into two regions and connects the two regions is arranged, and the partition wall is provided. The direct electrode and the counter electrode are arranged so as to come into contact with the treatment liquid across the pore wall or the pipe, and further, the connection between the indirect electrode and the power supply and the connection between the indirect electrode and the direct electrode. In addition to arranging a first switch for switching between, and arranging a second switch for switching between the connection between the direct electrode and the indirect electrode and the connection between the direct electrode and the counter electrode, in the ion transfer step to be processed. The indirect electrode and the power supply are connected by the first switch to apply a voltage, and the direct electrode and the counter electrode are connected by the second switch to remove ions to be processed in the treatment liquid. It is moved to the counter electrode side, and in the ion treatment step to be processed, the connection with the indirect electrode is switched from the power source to the direct electrode by the first switch, and the connection with the direct electrode is switched by the second switch. The connection is switched from the counter electrode to the indirect electrode, the direct electrode and the indirect electrode are connected, and the ion to be processed that has moved to the counter electrode side is oxidized or reduced.

The present invention from another viewpoint is an electrolytic treatment method in which a predetermined treatment is performed using ions to be treated contained in the treatment liquid, and the direct electrode and the counter electrode are respectively connected so as to be electrically connected to the treatment liquid. The process of arranging and arranging the indirect electrode that forms an electric field in the treatment liquid, and the treatment ion that applies a voltage to the indirect electrode to move the treatment ion in the treatment liquid to the counter electrode side. The moving step includes a moving ion treatment step of connecting the direct electrode and the indirect electrode to oxidize or reduce the treated ion that has moved to the counter electrode side, and the moving ion moving step includes a moving step. The current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density, and in the arrangement step, the direct electrode and the indirect electrode are arranged alternately and the direct electrode and the indirect electrode are arranged alternately. It is arranged so as to be in contact with the treatment liquid, a partition wall is arranged between the direct electrode and the indirect electrode, and the counter electrode is extended in the direction in which the plurality of direct electrodes and the plurality of indirect electrodes are arranged. A switch for switching between the connection between the plurality of indirect electrodes and the power supply and the connection between the plurality of indirect electrodes and the plurality of direct electrodes is arranged, and in the process of ion transfer to be processed, the plurality of switches are used. The indirect electrode and the power supply are connected and a voltage is applied to move the ion to be processed in the processing liquid to the counter electrode side, and in the ion processing step to be processed, the plurality of indirect electrodes and the plurality of indirect electrodes and the said by the switch. The power supply is disconnected, the plurality of indirect electrodes and the plurality of direct electrodes are connected, and the ion to be processed that has moved to the counter electrode side is oxidized or reduced.

In such a case, in the arrangement step, a paddle of the treatment liquid is formed on the counter electrode, and the plurality of direct electrodes, the plurality of indirect electrodes, and the partition wall are arranged by being immersed in the paddle of the treatment liquid. You may. Further, in the arrangement step, an electrode holding plate is arranged below the counter electrode at a position facing each other, a paddle of the treatment liquid is formed between the electrode holding plate and the counter electrode, and the plurality of direct electrodes, The plurality of indirect electrodes and the partition wall may be arranged by being immersed in a paddle of the treatment liquid.

The present invention from another viewpoint is an electrolytic treatment method in which a predetermined treatment is performed using ions to be treated contained in the treatment liquid, and the direct electrode and the counter electrode are respectively connected so as to be electrically connected to the treatment liquid. The process of arranging and arranging the indirect electrode that forms an electric field in the treatment liquid, and the treatment ion that applies a voltage to the indirect electrode to move the treatment ion in the treatment liquid to the counter electrode side. The moving step includes a moving ion treatment step of connecting the direct electrode and the indirect electrode to oxidize or reduce the treated ion that has moved to the counter electrode side, and the moving ion moving step includes a moving step. The current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density, and in the ion transfer step to be processed, the electrical connection between the direct electrode and the treatment liquid is cut and a voltage is applied to the indirect electrode. Then, the ion to be treated in the treatment liquid was moved to the counter electrode side, and in the ion treatment step, the direct electrode and the treatment liquid were electrically connected and moved to the counter electrode side. It is characterized by oxidizing or reducing the ion to be treated.

Specifically, in the arrangement step, a partition wall is provided which divides the treatment liquid into two regions and has an opening / closing mechanism for opening and closing the inflow / outflow holes of the treatment liquid, and sandwiches the partition wall to perform the treatment. The direct electrode and the counter electrode are arranged so as to come into contact with the liquid, the inflow / outflow holes of the treated liquid are closed by the opening / closing mechanism in the ion transfer step, and the opening / closing in the ion treatment step. The inflow / outflow hole of the treatment liquid may be opened by a mechanism.

Further, in the arrangement step, a moving mechanism for moving the direct electrode with respect to the treatment liquid is arranged, and in the ion moving step to be processed, the direct electrode is moved by the moving mechanism to move the direct electrode. And the treatment liquid may be separated, and in the ion treatment step to be treated, the direct electrode may be moved by the movement mechanism to bring the direct electrode into contact with the treatment liquid.

Further, in the arrangement step, the direct electrode is arranged outside the treatment liquid, and a flow path for moving the treatment liquid by Coulomb force is arranged, and in the ion transfer step to be processed, the flow path is passed through the flow path. The treatment liquid is moved to separate the treatment liquid from the direct electrode, and in the ion treatment step, the treatment liquid is moved through the flow path to bring the treatment liquid into contact with the direct electrode. You may let me.

Further, in the arrangement step, the direct electrode is arranged outside the treatment liquid, and a liquid supply mechanism for supplying charged droplets in contact with the direct electrode is arranged, and in the ion transfer step to be processed. The supply of the charged droplets by the liquid supply mechanism may be stopped, and the charged droplets may be supplied to the treatment liquid by the liquid supply mechanism in the ion treatment step.

An electric field may be formed in the treatment liquid in the arrangement step.

In the process of moving ions to be treated, a voltage is applied to the indirect electrode, and at least the applied voltage or capacitance of the indirect electrode is controlled to move a plurality of ions to be treated in the treatment liquid to the counter electrode side. Then, in the charge arrangement step, at least the applied voltage or capacitance of the indirect electrode is controlled in the counter electrode so as to correspond to the amount of ions to be treated that is equal to or less than the amount transferred in the ion transfer step. The electric charge is arranged at a predetermined charge arrangement position, and then, in the ion treatment step to be processed, a current is passed through the direct electrode to move the electric charge to the counter electrode side. The ion to be treated at the position corresponding to the position may be oxidized or reduced, and the charge arrangement step and the ion treatment step to be treated may be repeated in this order.

In such a case, the capacitance of the indirect electrode may be controlled by dividing the indirect electrode into a plurality of parts and forming an electric field in the treatment liquid for each of the divided indirect electrodes.

Further, in the ion transfer step, the plurality of ions to be processed are moved to the counter electrode side, and charges are arranged at positions corresponding to the plurality of ions to be processed on the counter electrode, and the charge arrangement step. The thinning ratio, which is the ratio of the amount of electric charge arranged on the counter electrode in the process of moving ions to be processed to the amount of electric charge arranged on the counter electrode, may be a power of 2.

Further, in the charge arrangement step, the thinning ratio of the region far from the region near the counter electrode is increased, and in the ion treatment step, the ions to be treated are reduced to form crystals, and the charge arrangement is performed. After repeating the step and the ion treatment step to be treated, the particle size of the crystal formed in the region far from the region near the counter electrode may be increased.

Further, in the ion treatment step, the ions to be treated are reduced to form crystals, and in the charge arrangement step, the distance between adjacent charges among the plurality of charges arranged at the predetermined charge arrangement positions. May be an integral multiple of the size of the crystal lattice.

From another point of view, the present invention is an electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid, and is a direct electrode arranged so as to be electrically connected to the treatment liquid and a counter electrode. An electrode, an indirect electrode that forms an electric field in the treatment liquid, a partition wall in which the treatment liquid is divided into two regions and an inflow / outflow hole of the treatment liquid is formed, and the treatment liquid is divided into two regions. The indirect electrode has a pore wall in which a plurality of pores are formed, or a pipe that divides the treatment liquid into two regions and connects the two regions, and a voltage is applied to the indirect electrode. Then, the ion to be treated in the treatment liquid was moved to the counter electrode side, and the direct electrode and the indirect electrode were moved to the counter electrode side by connecting the direct electrode and the indirect electrode. Oxidizes or reduces treated ions,
When the ion to be processed is moved to the counter electrode side, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density , and the direct electrode and the counter electrode are the partition wall and the pore size. It is characterized in that it is arranged so as to come into contact with the treatment liquid across the wall or the pipe .

In such a case, the electrolytic treatment apparatus further has a switch for switching between the connection between the indirect electrode and the power supply and the connection between the indirect electrode and the direct electrode, and when the ion to be processed is moved to the counter electrode side, When the switch connects the indirect electrode and the power supply and oxidizes or reduces the ion to be processed that has moved to the counter electrode side, the switch disconnects the indirect electrode and the power supply and the indirect. The electrode and the direct electrode may be connected.

From another point of view, the present invention is an electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid, and is a direct electrode arranged so as to be electrically connected to the treatment liquid and a counter electrode. An electrode, an indirect electrode that forms an electric field in the treatment liquid, a first switch that switches between the connection between the indirect electrode and the power supply, and the connection between the indirect electrode and the direct electrode, and the direct electrode and the indirect electrode. The indirect electrode has a connection and a second switch for switching between the direct electrode and the connection of the counter electrode, and the indirect electrode is subjected to a voltage to transfer ions to be processed in the treatment liquid to the counter electrode. The direct electrode and the indirect electrode are moved to the side, and by connecting the direct electrode and the indirect electrode, the processed ion that has moved to the counter electrode side is oxidized or reduced, and the processed ion is converted to the above-mentioned. When moving to the counter electrode side, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density, and the direct electrode and the counter electrode are arranged so as to be in contact with the treatment liquid, and the subject is covered. When the processed ion is moved to the counter electrode side, the first switch connects the indirect electrode and the power supply, and the second switch connects the direct electrode and the counter electrode to the counter electrode. When oxidizing or reducing the ion to be processed that has moved to the side, the first switch switches the connection with the indirect electrode from the power source to the direct electrode, and the second switch is connected to the direct electrode. The connection is switched from the counter electrode to the indirect electrode, and the direct electrode and the indirect electrode are connected.

In such a case, the surface area of the direct electrode may be smaller than the surface area of the counter electrode.

From another point of view, the present invention is an electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid, and is a direct electrode arranged so as to be electrically connected to the treatment liquid and a counter electrode. An electrode, an indirect electrode that forms an electric field in the treatment liquid, a partition wall in which the treatment liquid is divided into two regions and an inflow / outflow hole of the treatment liquid is formed, and the treatment liquid is divided into two regions. A pore wall in which a plurality of pores are formed, a pipe that divides the treatment liquid into two regions and connects the two regions, a connection between the indirect electrode and a power source, and the indirect electrode and the direct The indirect electrode has a first switch for switching the connection of the electrodes, a second switch for switching the connection between the direct electrode and the indirect electrode, and the connection between the direct electrode and the counter electrode. When a voltage is applied, the ion to be treated in the treatment liquid is moved to the counter electrode side, and the direct electrode and the indirect electrode are connected to the direct electrode and the indirect electrode, whereby the counter electrode is connected. When the ion to be treated that has moved to the side is oxidized or reduced and the ion to be treated is moved to the counter electrode side, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density, and the direct The electrode and the counter electrode are arranged so as to come into contact with the treatment liquid across the partition wall, the pore wall or the pipe, and when the ion to be treated is moved to the counter electrode side, the first The switch connects the indirect electrode and the power supply, and the second switch connects the direct electrode and the counter electrode, and when oxidizing or reducing the processed ion that has moved to the counter electrode side, the switch The first switch switches the connection with the indirect electrode from the power source to the direct electrode, and the second switch switches the connection with the direct electrode from the counter electrode to the indirect electrode, and the direct electrode. It is characterized in that the indirect electrode is connected to the indirect electrode.

From another point of view, the present invention is an electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid, and is a direct electrode arranged so as to be electrically connected to the treatment liquid and a counter electrode. The electrodes, the indirect electrodes that form an electric field in the treatment liquid, the plurality of direct electrodes and the plurality of indirect electrodes arranged so that the direct electrodes and the indirect electrodes are alternately arranged and in contact with the treatment liquid. It has a partition wall provided between the direct electrode and the indirect electrode, a switch for switching between the connection between the plurality of indirect electrodes and a power source, and the connection between the plurality of indirect electrodes and the plurality of direct electrodes. When a voltage is applied to the indirect electrode, ions to be processed in the treatment liquid are moved to the counter electrode side, and the direct electrode and the indirect electrode are connected to the direct electrode and the indirect electrode. As a result, when the ion to be treated that has moved to the counter electrode side is oxidized or reduced and the ion to be treated is moved to the counter electrode side, the current flowing between the direct electrode and the counter electrode is the limit current density. The counter electrode is arranged so as to extend in the direction in which the plurality of direct electrodes and the plurality of indirect electrodes are arranged, and when the ion to be processed is moved to the counter electrode side, the switch is used. When the plurality of indirect electrodes are connected to the power source and the ion to be processed that has moved to the counter electrode side is oxidized or reduced, the switch disconnects the plurality of indirect electrodes and the power source, and the switch is used. It is characterized in that a plurality of indirect electrodes and the plurality of direct electrodes are connected.

In such a case, a paddle of the treatment liquid is formed on the counter electrode, and the plurality of direct electrodes, the plurality of indirect electrodes, and the partition wall may be arranged by being immersed in the paddle of the treatment liquid. Further, the electrolytic treatment apparatus further has an electrode holding plate provided at a position facing the opposite electrode below the counter electrode, and a paddle of the treatment liquid is formed between the electrode holding plate and the counter electrode. The plurality of direct electrodes, the plurality of indirect electrodes, and the partition wall may be arranged by being immersed in a paddle of the treatment liquid.

From another point of view, the present invention is an electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid, and is a direct electrode arranged so as to be electrically connected to the treatment liquid and a counter electrode. It has an electrode, an indirect electrode that forms an electric field in the treatment liquid, and a partition wall that divides the treatment liquid into two regions and has an opening / closing mechanism for opening and closing the inflow / outflow holes of the treatment liquid. When a voltage is applied to the indirect electrode, the ion to be treated in the treatment liquid is moved to the counter electrode side, and the direct electrode and the indirect electrode are connected to the direct electrode and the indirect electrode. When the ion to be treated that has moved to the counter electrode side is oxidized or reduced and the ion to be treated is moved to the counter electrode side, the current flowing between the direct electrode and the counter electrode is below the limit current density. The direct electrode and the counter electrode are arranged so as to come into contact with the treatment liquid with the partition wall interposed therebetween, and when the ion to be treated is moved to the counter electrode side, the opening / closing mechanism is the treatment liquid. When the inflow / out holes are closed, the electrical connection between the direct electrode and the treatment liquid is cut, and the ion to be treated that has moved to the counter electrode side is oxidized or reduced, the opening / closing mechanism is used for the treatment liquid. It is characterized in that the inflow / out holes of the above are opened to electrically connect the direct electrode and the treatment liquid.

From another point of view, the present invention is an electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid, and is a direct electrode arranged so as to be electrically connected to the treatment liquid and a counter electrode. The indirect electrode has an electrode, an indirect electrode that forms an electric field in the treatment liquid, and a moving mechanism that allows the direct electrode to move back and forth with respect to the treatment liquid. The indirect electrode is subjected to a voltage to be applied. The ion to be treated in the treatment liquid is moved to the counter electrode side, and the direct electrode and the indirect electrode are moved to the counter electrode side by connecting the direct electrode and the indirect electrode. When the ion to be treated is moved to the counter electrode side by oxidizing or reducing, the current flowing between the direct electrode and the counter electrode is equal to or less than the critical current density, and the ion to be treated is moved to the counter electrode side. When moving, the moving mechanism moves the direct electrode to separate the direct electrode from the processing liquid, and when oxidizing or reducing the ion to be treated that has moved to the counter electrode side, the moving mechanism moves. The direct electrode is moved so that the direct electrode and the treatment liquid are brought into contact with each other.

From another point of view, the present invention is an electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid, and is a direct electrode arranged so as to be electrically connected to the treatment liquid and a counter electrode. The indirect electrode has an electrode, an indirect electrode that forms an electric field in the treatment liquid, and a flow path that moves the treatment liquid by a Coulomb force, and the indirect electrode is in the treatment liquid when a voltage is applied. The ion to be treated is moved to the counter electrode side, and the direct electrode and the indirect electrode are connected to the direct electrode and the indirect electrode to oxidize or reduce the ion to be treated that has moved to the counter electrode side. When the ion to be treated is moved to the counter electrode side, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density, and the direct electrode is arranged outside the treatment liquid to be treated. When the treated ion is moved to the counter electrode side, the flow path moves the treated liquid to separate the treated liquid from the direct electrode, and oxidizes or oxidizes the processed ion moved to the counter electrode side. At the time of reduction, the flow path is characterized in that the treatment liquid is moved to bring the treatment liquid into direct contact with the electrode.

From another point of view, the present invention is an electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid, and is a direct electrode arranged so as to be electrically connected to the treatment liquid and a counter electrode. The indirect electrode has an electrode, an indirect electrode that forms an electric field in the treatment liquid, and a liquid supply mechanism that supplies charged droplets in contact with the direct electrode, and the indirect electrode is subjected to a voltage. The ion to be treated in the treatment liquid is moved to the counter electrode side, and the direct electrode and the indirect electrode are moved to the counter electrode side by connecting the direct electrode and the indirect electrode. When the ions are oxidized or reduced and the ions to be treated are moved to the counter electrode side, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density, and the direct electrode is outside the treatment liquid. When the ion to be treated is moved to the counter electrode side, the liquid supply mechanism stops the supply of the charged droplets and disconnects the electrical connection between the direct electrode and the treatment liquid. Then, when oxidizing or reducing the ion to be treated that has moved to the counter electrode side, the liquid supply mechanism supplies the charged droplets to the treatment liquid and electrically supplies the direct electrode and the treatment liquid. It is characterized by connecting to.

According to the present invention, a predetermined electrolytic treatment on a body to be treated can be performed at high speed and uniformly by using the ions to be treated in the treatment liquid.

It is a vertical cross-sectional view which shows the outline of the structure of the plating processing apparatus which concerns on 1st Embodiment. It is explanatory drawing which shows the state which connected the indirect electrode and the DC power source in 1st Embodiment. It is explanatory drawing which shows typically the arrangement of electric charge and ion at the time of charging in 1st Embodiment. It is explanatory drawing which shows the state which connected the indirect electrode and the direct electrode in 1st Embodiment. It is explanatory drawing which shows typically the arrangement of charge and ion at the time of discharge in 1st Embodiment. It is explanatory drawing which shows the mode that the indirect electrode and the DC power source were reconnected in the 1st Embodiment. It is explanatory drawing which shows the appearance that the predetermined copper plating was formed on the counter electrode in the 1st Embodiment. It is a vertical cross-sectional view which shows the outline of the structure of the plating processing apparatus which concerns on other embodiment of 1st Embodiment. It is a vertical cross-sectional view which shows the outline of the structure of the plating processing apparatus which concerns on other embodiment of 1st Embodiment. It is a vertical cross-sectional view which shows the outline of the structure of the plating processing apparatus which concerns on 2nd Embodiment. It is explanatory drawing which shows the mode which connected the indirect electrode and the DC power source in the 2nd Embodiment, and connected the direct electrode and the counter electrode. It is explanatory drawing which shows typically the arrangement of electric charge and ion at the time of charge in 2nd Embodiment. It is explanatory drawing which shows the state which the direct electrode and the indirect electrode were connected in the 2nd Embodiment. It is explanatory drawing which shows typically the arrangement of charge and ion at the time of discharge in 2nd Embodiment. It is a vertical cross-sectional view which shows the outline of the structure of the plating processing apparatus which concerns on 3rd Embodiment. It is explanatory drawing which shows the mode which connected the indirect electrode and the DC power source in the 3rd Embodiment, and connected the direct electrode and the counter electrode. It is explanatory drawing which shows the state which the direct electrode and the indirect electrode were connected in the 3rd Embodiment. It is a vertical cross-sectional view which shows the outline of the structure of the plating processing apparatus which concerns on 4th Embodiment. It is explanatory drawing which shows the state which connected the indirect electrode and the DC power source in 4th Embodiment. It is explanatory drawing which shows the state which connected the indirect electrode and the direct electrode in 4th Embodiment. It is a vertical cross-sectional view which shows the outline of the structure of the plating processing apparatus which concerns on other embodiment of 4th Embodiment. It is explanatory drawing which shows the appearance of connecting a plurality of indirect electrodes and a DC power source in another embodiment of 4th Embodiment. It is explanatory drawing which shows the mode that the plurality of indirect electrodes and the plurality of direct electrodes are connected in another embodiment of the fourth embodiment. It is a vertical cross-sectional view which shows the outline of the structure of the plating processing apparatus which concerns on other embodiment of 4th Embodiment. It is a vertical cross-sectional view which shows the outline of the structure of the plating processing apparatus which concerns on other embodiment of 4th Embodiment. It is explanatory drawing which shows the state that the inflow / out hole was closed by the opening / closing mechanism in the 1st 5th Embodiment. It is explanatory drawing which shows the state that the inflow / out hole was opened by the opening / closing mechanism in the 1st 5th Embodiment. It is explanatory drawing which shows the state which directly separated the electrode and the plating solution in the 2nd 5th Embodiment. It is explanatory drawing which shows the state that the electrode and the plating solution were brought into direct contact with each other in the 2nd 5th Embodiment. It is explanatory drawing which shows the state that the electrode and the plating solution were separated directly in the 3rd 5th Embodiment. It is explanatory drawing which shows the state that the electrode and the plating solution were brought into direct contact with each other in the 3rd 5th Embodiment. It is explanatory drawing which shows the state which stopped the supply of the charged droplet by the liquid supply mechanism in the 4th 5th Embodiment. It is explanatory drawing which shows the state which the droplet charged by the liquid supply mechanism was supplied in the 4th 5th Embodiment. It is explanatory drawing which shows the potential of an indirect electrode and the on / off state of a switch in each step of a plating process. It is explanatory drawing which shows the state which connected the indirect electrode and the DC power source. It is explanatory drawing which shows typically the charge of the counter electrode and the state of a copper ion in step S1. It is explanatory drawing which shows typically the charge of the counter electrode and the state of a copper ion in step S2. It is explanatory drawing which shows the appearance of connecting the indirect electrode and the direct electrode. It is explanatory drawing which shows typically the charge of the counter electrode and the state of a copper ion in step S3. It is explanatory drawing which shows typically the charge of the counter electrode and the state of a copper ion in step S4. It is explanatory drawing which shows typically the charge of the counter electrode and the state of a copper ion in step S5. It is explanatory drawing which shows typically the charge of the counter electrode and the state of a copper ion after performing step S9. It is explanatory drawing which shows typically the charge of the counter electrode and the state of a copper ion in the 2nd step S1. It is explanatory drawing which shows the state that the predetermined copper plating was formed on the counter electrode. It is a vertical cross-sectional view which shows the outline of the structure of the plating processing apparatus which concerns on other embodiment. It is explanatory drawing which shows typically the crystal structure of copper plating. It is explanatory drawing of the vertical cross section which shows the state that the via hole and the wiring groove were plated. It is explanatory drawing of the plane which shows the state that the wiring groove was plated.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the present specification and the drawings, components having substantially the same functional configuration are designated by the same reference numerals, so that duplicate description will be omitted. In the present embodiment, a case where a plating treatment is performed as the electrolytic treatment according to the present invention will be described.

<1. Plating processing apparatus according to the first embodiment>
FIG. 1 is a vertical cross-sectional view showing an outline of the configuration of a plating processing apparatus 1 as an electrolytic processing apparatus according to the first embodiment. In the drawings used in the following description, the dimensions of each component do not necessarily correspond to the actual dimensions in order to prioritize the ease of understanding the technology.

The plating processing apparatus 1 has a plating tank 10 that stores a plating solution M as a processing liquid inside. The plating tank 10 is provided with a partition wall 11 for partitioning the inside (plating liquid M) into two regions T1 and T2. The partition wall 11 is formed with inflow / out holes 12 for flowing the plating solution M between the two regions T1 and T2. As the plating solution M, for example, a solution in which copper sulfate is dissolved is used. That is, the plating solution M contains copper ions as ions to be treated.

Inside the plating tank 10, the direct electrode 20, the indirect electrode 21, and the counter electrode 22 are each immersed in the plating solution M. The direct electrode 20 is arranged in the region T1. The indirect electrode 21 and the counter electrode 22 are respectively arranged in the region T2, the indirect electrode 21 is arranged apart from the partition wall 11, and the counter electrode 22 is arranged close to the partition wall 11. That is, the direct electrode 20 is provided close to the indirect electrode 21, and is arranged apart from the counter electrode 22 with the partition wall 11 interposed therebetween.

The indirect electrode 21 is provided with an insulating material 23 so as to cover the indirect electrode 21. Further, the counter electrode 22 is an object to be plated.

A DC power supply 30 is connected to the indirect electrode 21 and the counter electrode 22. The indirect electrode 21 is connected to the positive electrode side of the DC power supply 30. The counter electrode 22 is connected to the negative electrode side of the DC power supply 30.

The indirect electrode 21 is provided with a switch 31. The switch 31 switches between the connection between the indirect electrode 21 and the DC power supply 30 and the connection between the indirect electrode 21 and the direct electrode 20. The switching of the switch 31 is controlled by the control unit 40.

Next, the plating process using the plating process device 1 configured as described above will be described.

As shown in FIG. 2, the indirect electrode 21 and the DC power supply 30 (counter electrode 22) are connected by a switch 31. Then, a DC voltage is applied by using the indirect electrode 21 as an anode and the counter electrode 22 as a cathode to form an electric field (electrostatic field). Then, as shown in FIG. 3, a positive charge is accumulated on the indirect electrode 21, and anions A, which are negatively charged particles, are collected on the indirect electrode 21 side. On the other hand, a negative charge is accumulated in the counter electrode 22, and copper ions C, which are positively charged particles, move to the counter electrode 22 side. In the following description, such a state in which electric charges are accumulated in the electrodes may be referred to as "charging".

Here, since the direct electrode 20 and the indirect electrode 21 are not connected during charging, the potential of the direct electrode 20 is determined by the electric field distribution formed by the indirect electrode 21 and the counter electrode 22, and this electric field faces the indirect electrode 21. It is determined by the distribution of electric potential lines generated between the electrodes 22. Then, the farther the arrangement of the direct electrode 20 is from the indirect electrode 21 along the electric line of force, the lower the potential of the direct electrode 20. In the present embodiment, since the direct electrode 20 is arranged close to the counter electrode 22 and away from the indirect electrode 21, the potential of the direct electrode 20 is close to zero. Since the potential of the direct electrode 20 is not completely zero, copper ions C corresponding to the potential move to the direct electrode 20. Then, even during charging, charge exchange (oxidation-reduction) proceeds between the direct electrode 20 and the counter electrode 22.

Further, since the partition wall 11 is provided between the direct electrode 20 and the indirect electrode 21, the partition wall 11 becomes a physical and electrical resistance, and the amount of electric charge of the direct electrode 20 is reduced. Therefore, the amount of charge exchanged (oxidation-reduction) between the direct electrode 20 and the counter electrode 22 can be reduced.

Further, the direct electrode 20 and the counter electrode 22 are arranged so that the current flowing between the direct electrode 20 and the counter electrode 22 at the time of charging is equal to or less than the limit current density. The critical current density is the current density at which the amount of copper ions C supplied reaches the limit with respect to the amount of copper ions C reduced per unit time in the plating process, that is, the critical current is the maximum that can be plated. It is an electric current. Then, the movement (supply) of the copper ion C does not become insufficient on the surface of the counter electrode 22 during charging, and it is possible to suppress the electrolysis of water. As a result, the generation of bubbles can be suppressed, and the generation of voids in the copper plating 50, which will be described later, can also be suppressed.

Further, in order to prevent the direct electrode 20 from becoming a cathode, the direct electrode 20 is not directly connected to the ground and is electrically floated.

Then, the indirect electrode 21 and the DC power supply 30 are connected by the switch 31 until a sufficient charge is accumulated in the indirect electrode 21 and the counter electrode 22, that is, until the indirect electrode 21 is fully charged. The charges of the indirect electrode 21 and the counter electrode 22 in this full charge are equivalent. Then, as described above, during charging, the charge exchange in the counter electrode 22 is performed at high speed while suppressing the electrolysis of water, so that the copper ions C are uniformly arranged on the surface of the counter electrode 22. Further, since the electrolysis of water is suppressed on the surface of the counter electrode 22, the electric field when applying a voltage between the indirect electrode 21 and the counter electrode 22 can be increased. This high electric field can speed up the movement of copper ions C. Further, by arbitrarily controlling this electric field, the copper ions C arranged on the surface of the counter electrode 22 are also arbitrarily controlled.

After that, as shown in FIG. 4, the switch 31 is switched, the connection between the indirect electrode 21 and the DC power supply 30 is cut off, and the indirect electrode 21 and the direct electrode 20 are connected. Then, as shown in FIG. 5, the positive charge accumulated in the indirect electrode 21 moves directly to the electrode 20, the charge of the anion A collected on the direct electrode 20 side is exchanged, and the anion A is oxidized. .. Along with this, the charges of the copper ions C arranged on the surface of the counter electrode 22 are exchanged, and the copper ions C are reduced. Then, as shown in FIG. 4, the copper plating 50 is deposited on the surface of the counter electrode 22. In the following description, such a state in which electric charges move between electrodes may be referred to as “discharge”.

Here, assuming that the amount of charge exchanged between the direct electrode 20 and the counter electrode 22 during charging is 1/N (1 / N) of the total amount of electric charge moved by the electric field, the amount of charge during charging during discharging It is possible to exchange N times the amount of electric charge. That is, a large amount of copper ions C can be reduced while suppressing the electrolysis of water. Therefore, the plating rate can be improved and the plating process can be performed at high speed.

Since the charges of the indirect electrode 21 and the counter electrode 22 are equivalent during charging, the amounts of charge exchanged during discharging are also equivalent.

Then, since sufficient copper ions C are accumulated on the surface of the counter electrode 22 and reduced in a uniformly arranged state, the copper plating 50 can be uniformly deposited on the surface of the counter electrode 22. As a result, the density of crystals in the copper plating 50 is increased, and a high quality copper plating 50 can be formed.

After that, as shown in FIG. 6, the switch 31 is switched to connect the indirect electrode 21 and the DC power supply 30, and the copper ions C are moved and integrated on the counter electrode 22 side. Then, when the copper ions C are uniformly arranged on the surface of the counter electrode 22, the switch 31 is switched to connect the indirect electrode 21 and the direct electrode 20 to reduce the copper ions C.

By repeatedly moving and accumulating the copper ions C during charging and reducing the copper ions C during discharging in this way, the copper plating 50 grows to a predetermined film thickness as shown in FIG. In this way, a series of plating processes in the plating processing apparatus 1 is completed.

According to the above embodiment, when the copper ion C is moved during charging, the current flowing directly between the electrode 20 and the counter electrode 22 is equal to or less than the limit current density, so that water is electrolyzed on the surface of the counter electrode 22. As a result, the generation of air bubbles can be suppressed, and the generation of voids in the copper plating 50 can also be suppressed. Therefore, the electric field formed by the indirect electrode 21 and the counter electrode 22 during charging can be increased. Then, at the time of discharging, it is possible to exchange an amount of electric charge that is several times the amount of electric charge exchanged at the time of charging, and it is possible to reduce a large amount of copper ions C while suppressing electrolysis of water. Therefore, the rate of the plating process can be improved and the plating process can be performed at a high speed.

Further, since the direct electrode 20 is arranged close to the counter electrode 22 and separated from the indirect electrode 21, the potential of the direct electrode 20 is low and close to zero. Moreover, the partition wall 11 between the direct electrode 20 and the indirect electrode 21 serves as a resistor. Therefore, although charge exchange (oxidation-reduction) proceeds directly between the electrode 20 and the counter electrode 22 during charging, the amount of electric charge can be reduced. Then, at the time of charging, the copper ions C are reduced in a state where the copper ions C are uniformly arranged on the surface of the counter electrode 22. Therefore, the plating process can be performed uniformly, and the film thickness of the copper plating 50 can be made uniform. Moreover, since the copper ions C are uniformly arranged, the crystals in the copper plating 50 can be densely arranged. Therefore, the quality of the copper plating 50 after the plating treatment can be improved.

Further, since sufficient charge is accumulated in the indirect electrode 21 and copper ions C are uniformly arranged on the surface of the counter electrode 22, the switch 31 switches from charging to discharging, so that sufficient copper is provided on the counter electrode 22 side. Copper ion C can be reduced in a state where ions C are accumulated. Therefore, it is not necessary to pass a current consumed for electrolysis of water between the anode and the cathode, and the copper ion C can be efficiently reduced.

Further, the electric field when applying a voltage to the indirect electrode 21 at the time of charging can be increased, the movement of the copper ion C can be accelerated, and the rate of the plating process can be improved. Moreover, a large-scale mechanism is not required to improve the plating processing rate, and the device configuration can be simplified.

In the plating processing apparatus 1 of the present embodiment, the partition wall 11 is provided in order to increase the resistance between the direct electrode 20 and the indirect electrode 21, but a pore wall or piping may be provided instead. ..

As shown in FIG. 8, instead of the partition wall 11, the plating tank 10 is provided with a pore wall 60 that divides the inside into two regions T1 and T2. A plurality of pores are formed in the pore wall 60, and the plating solution M can flow through the plurality of pores. Even in such a case, the pore wall 60 becomes a physical and electrical resistance, and the amount of charge exchange (oxidation-reduction) between the direct electrode 20 and the counter electrode 22 can be reduced.

Further, as shown in FIG. 9, the plating tank 10 is divided into a plating tank 10a (region T1) and a plating tank 10b (region T2). A pipe 70 for connecting these plating tanks 10a and 10b is provided between the plating tanks 10a and 10b. Even in such a case, the pipe 70 becomes a physical and electrical resistance, and the amount of electric charge exchanged (oxidation-reduction) between the direct electrode 20 and the counter electrode 22 can be reduced.

<2. Plating processing apparatus according to the second embodiment>
Next, a second embodiment of the plating processing apparatus will be described. FIG. 10 is a vertical cross-sectional view showing an outline of the configuration of the plating processing apparatus 100 according to the second embodiment.

The plating processing apparatus 100 has a plating tank 110 that stores the plating solution M inside. Inside the plating tank 110, the direct electrode 120, the indirect electrode 121, and the counter electrode 122 are each immersed in the plating solution M. The direct electrode 120 is arranged close to the counter electrode 122. The indirect electrode 121 is arranged apart from the direct electrode 120 and the counter electrode 122.

The indirect electrode 121 is provided with an insulating material 123 so as to cover the indirect electrode 121. Further, the counter electrode 122 is an object to be plated.

A DC power supply 130 is connected to the indirect electrode 121 and the counter electrode 122. The indirect electrode 121 is connected to the positive electrode side of the DC power supply 130. The counter electrode 122 is connected to the negative electrode side of the DC power supply 130.

The indirect electrode 121 is provided with a first switch 131. The first switch 131 switches between the connection between the indirect electrode 121 and the DC power supply 130 and the connection between the indirect electrode 121 and the direct electrode 120.

The direct electrode 120 is provided with a second switch 132. The second switch 132 switches between the connection between the direct electrode 120 and the indirect electrode 121 and the connection between the direct electrode 120 and the counter electrode 122.

Next, a plating process using the plating processing apparatus 100 configured as described above will be described.

First, at the time of charging, as shown in FIG. 11, the indirect electrode 121 and the DC power supply 130 are connected by the first switch 131, and the direct electrode 120 and the counter electrode 122 are connected by the second switch 132. Then, an electric field (electrostatic field) is formed by applying a DC voltage using the indirect electrode 121 as an anode and the counter electrode 122 as a cathode. Then, as shown in FIG. 12, positive charges are accumulated in the indirect electrode 121, and anions A, which are negatively charged particles, are collected on the indirect electrode 121 side. On the other hand, negative charges are accumulated in the counter electrode 122 and the direct electrode 120, respectively, and copper ions C, which are positively charged particles, move to the counter electrode 122 side.

At the time of this charging, since the direct electrode 120 and the counter electrode 122 are connected, the direct electrode 120 and the counter electrode 122 have equal potentials. Therefore, charge exchange (oxidation-reduction) between the direct electrode 120 and the counter electrode 122 can be suppressed.

Then, in the connection between the indirect electrode 121 and the DC power supply 130 by the first switch 131 and the connection between the direct electrode 120 and the counter electrode 122 by the second switch 132, sufficient charges are accumulated in the indirect electrode 121 and the counter electrode 122. Until it is fully charged, that is, until it is fully charged. As described above, since the charge exchange in the counter electrode 122 is suppressed during charging, the copper ions C are uniformly arranged on the surface of the counter electrode 122. Further, since the charge exchange of copper ions C is not performed on the surface of the counter electrode 122 and the electrolysis of water is suppressed, the electric field when applying a voltage between the indirect electrode 121 and the counter electrode 122 is increased. Can be done. This high electric field can speed up the movement of copper ions C. Further, by arbitrarily controlling this electric field, the copper ions C arranged on the surface of the counter electrode 122 are also arbitrarily controlled.

After that, at the time of discharge, as shown in FIG. 13, the connection with the indirect electrode 121 is switched from the DC power supply 130 to the direct electrode 120 by the first switch 131, and the connection with the direct electrode 120 is opposed by the second switch 132. The direct electrode 120 and the indirect electrode 121 are connected by switching from the electrode 122 to the indirect electrode 121. Then, as shown in FIG. 14, the positive charge accumulated in the indirect electrode 121 moves directly to the electrode 120, the charge of the anion A collected on the direct electrode 120 side is exchanged, and the anion A is oxidized. .. Along with this, the charges of the copper ions C arranged on the surface of the counter electrode 122 are exchanged, and the copper ions C are reduced. Then, as shown in FIG. 13, the copper plating 150 is deposited on the surface of the counter electrode 122.

Then, since sufficient copper ions C are accumulated on the surface of the counter electrode 122 and reduced in a uniformly arranged state, the copper plating 150 can be uniformly deposited on the surface of the counter electrode 122. As a result, the density of crystals in the copper plating 150 is increased, and a high quality copper plating 150 can be formed.

Here, since the direct electrode 120 and the counter electrode 122 are connected during charging, when the surface area of the direct electrode 120 and the surface area of the counter electrode 122 are equal, the charge amounts of the direct electrode 120 and the counter electrode 122 are equivalent, and further, the indirect electrode The charge amount of 121 is the sum of the charge amounts of the direct electrode 120 and the counter electrode 122. That is, a negative charge having an electric charge Q is accumulated in the direct electrode 120 and the counter electrode 122, respectively, and a positive electric charge having an electric charge 2Q is accumulated in the indirect electrode 121. Then, at the time of discharge, a positive charge having a charge amount of 2Q moves from the indirect electrode 121 to the direct electrode 120, and the positive charge of the transferred charge amount Q is neutralized by a negative charge of the charge amount Q of the direct electrode 120. , A positive charge having an electric charge Q remains on the direct electrode 120. Further, the positive charge of the amount of charge Q remaining on the direct electrode 120 completes the charge exchange at the time of discharge, and no charge remains on the direct electrode 120. Therefore, wasteful electricity is consumed by this neutralization, and in order to reduce this, the surface area of the direct electrode 120 may be reduced, or as described above, the partition wall 11, the pore wall 60, and the pipe 70 may be reduced. May be provided.

Then, the copper plating 150 grows to a predetermined film thickness by repeatedly moving and accumulating the copper ions C during charging and reducing the copper ions C during discharging. In this way, a series of plating processes in the plating processing apparatus 100 is completed.

According to the present embodiment, when the copper ion C is moved during charging, since the direct electrode 120 and the counter electrode 122 are connected, the charge exchange between the direct electrode 120 and the counter electrode 122 can be suppressed, and copper can be suppressed. The reduction of ion C can be suppressed. Then, at the time of charging, the copper ions C are reduced in a state where the copper ions C are uniformly arranged on the surface of the counter electrode 122. Therefore, the plating process can be performed uniformly.

The surface area of the direct electrode 120 is preferably smaller than the surface area of the counter electrode 122. In such a case, the capacitance (C) of the direct electrode 120 can be reduced to reduce the amount of charge (Q = CV), and wasteful power consumption due to charge neutralization during discharge can be suppressed.

<3. Plating processing apparatus according to the third embodiment>
Next, a third embodiment of the plating processing apparatus will be described. FIG. 15 is a vertical cross-sectional view showing an outline of the configuration of the plating processing apparatus 200 according to the third embodiment.

The plating processing device 200 of the third embodiment has a configuration in which the plating processing device 1 of the first embodiment and the plating processing device 100 of the second embodiment are combined. That is, the plating processing device 200 replaces the configuration of the switch 31 in the plating processing device 1 with the configuration of the first switch 131 and the second switch 132 of the plating processing device 100.

In the plating processing apparatus 200, the plating tank 210, the partition wall 211, the inflow / out hole 212, the direct electrode 220, the indirect electrode 221, the counter electrode 222, and the insulating material 223 are the plating tank 10, the partition wall 11, and the inflow / outflow in the plating processing apparatus 1, respectively. It corresponds to the hole 12, the direct electrode 20, the indirect electrode 21, the counter electrode 22, and the insulating material 23.

Further, in the plating processing apparatus 200, the DC power supply 230, the first switch 231 and the second switch 232 correspond to the DC power supply 130, the first switch 131, and the second switch 132 in the plating processing apparatus 100, respectively. doing.

Since the configuration of each member of the plating processing apparatus 200 is the same as the configuration of the corresponding member, the description thereof will be omitted.

Next, the plating process using the plating process device 200 configured as described above will be described.

First, at the time of charging, as shown in FIG. 16, the indirect electrode 221 and the DC power supply 230 are connected by the first switch 231 and the direct electrode 220 and the counter electrode 222 are connected by the second switch 232. Then, a DC voltage is applied by using the indirect electrode 221 as an anode and the counter electrode 222 as a cathode to form an electric field (electrostatic field). Then, a positive charge is accumulated on the indirect electrode 221 and anions A, which are negatively charged particles, are collected on the indirect electrode 221 side. On the other hand, negative charges are accumulated in the counter electrode 222 and the direct electrode 220, respectively, and copper ions C, which are positively charged particles, move to the counter electrode 222 side.

At the time of this charging, since the direct electrode 220 and the counter electrode 222 are connected, the direct electrode 220 and the counter electrode 222 have equal potentials. Therefore, charge exchange (oxidation-reduction) between the direct electrode 220 and the counter electrode 222 can be suppressed. Moreover, since the partition wall 211 is provided between the direct electrode 220 and the indirect electrode 221, the partition wall 211 becomes a physical and electrical resistance, and the amount of electric charge of the direct electrode 220 is reduced. Therefore, wasteful power consumption due to charge neutralization during discharge can be suppressed. As in the first embodiment, in order to increase the resistance between the direct electrode 220 and the indirect electrode 221, a pore wall or piping may be provided instead of the partition wall 211.

Then, in the connection between the indirect electrode 221 and the DC power supply 230 by the first switch 231 and the connection between the direct electrode 220 and the counter electrode 222 by the second switch 232, sufficient charges are accumulated in the indirect electrode 221 and the counter electrode 222. Until it is fully charged, that is, until it is fully charged. As described above, since the charge exchange in the counter electrode 222 is suppressed during charging, the copper ions C are uniformly arranged on the surface of the counter electrode 222. Further, since the charge exchange of copper ions C is not performed on the surface of the counter electrode 222 and the electrolysis of water is suppressed, the electric field when applying a voltage between the indirect electrode 221 and the counter electrode 222 should be increased. Can be done. This high electric field can speed up the movement of copper ions C. Further, by arbitrarily controlling this electric field, the copper ions C arranged on the surface of the counter electrode 222 are also arbitrarily controlled.

After that, at the time of discharge, as shown in FIG. 17, the connection with the indirect electrode 221 is switched from the DC power supply 230 to the direct electrode 220 by the first switch 231 and the connection with the direct electrode 220 is opposed by the second switch 232. The direct electrode 220 and the indirect electrode 221 are connected by switching from the electrode 222 to the indirect electrode 221. Then, the positive charge accumulated in the indirect electrode 221 moves directly to the electrode 220, the charge of the anion A collected on the indirect electrode 221 side is exchanged, and the anion A is oxidized. Along with this, the charges of the copper ions C arranged on the surface of the counter electrode 222 are exchanged, and the copper ions C are reduced. Then, the copper plating 250 is deposited on the surface of the counter electrode 222.

Then, since sufficient copper ions C are accumulated on the surface of the counter electrode 222 and reduced in a uniformly arranged state, the copper plating 250 can be uniformly deposited on the surface of the counter electrode 222. As a result, the density of crystals in the copper plating 250 is increased, and a high quality copper plating 250 can be formed.

Then, the copper plating 250 grows to a predetermined film thickness by repeatedly moving and accumulating the copper ions C during charging and reducing the copper ions C during discharging. In this way, a series of plating processes in the plating processing apparatus 200 is completed.

In the third embodiment, the same effect as that of the second embodiment can be enjoyed. That is, since the direct electrode 220 and the counter electrode 222 are connected when the copper ion C is moved during charging, the charge exchange between the direct electrode 220 and the counter electrode 222 can be suppressed, and the reduction of the copper ion C is suppressed. can do. Moreover, since the partition wall 211 is provided between the direct electrode 220 and the indirect electrode 221, the amount of electric charge of the direct electrode 220 is reduced, and wasteful power consumption due to charge neutralization during discharge can be suppressed. Then, at the time of charging, the copper ions C are reduced in a state where the copper ions C are uniformly arranged on the surface of the counter electrode 222. Therefore, the plating process can be performed uniformly.

<4. Plating processing apparatus according to the fourth embodiment>
Next, a fourth embodiment of the plating processing apparatus will be described. FIG. 18 is a vertical cross-sectional view showing an outline of the configuration of the plating processing apparatus 300 according to the fourth embodiment.

The plating processing apparatus 300 has a plating tank 310 inside which stores the plating liquid M as the processing liquid. The plating tank 310 is provided with a partition wall 311 that divides the inside into two regions T1 and T2. The partition wall 311 is formed with inflow / out holes 312 for flowing the plating solution M between the two regions T1 and T2. Further, a space for providing the counter electrode 322, which will be described later, is formed in the lower portion of the partition wall 311. As in the first embodiment, in order to increase the resistance between the direct electrode 320 and the indirect electrode 321, a pore wall or piping may be provided instead of the partition wall 311.

Inside the plating tank 310, a direct electrode 320, an indirect electrode 321 and a counter electrode 322 are each immersed in the plating solution M. The direct electrode 320 is arranged in the region T1. The indirect electrode 321 is arranged apart from the partition wall 311 in the region T2. The counter electrode 322 is provided so as to extend between the regions T1 and T2 in the lower part of the partition wall 311. That is, the direct electrode 320 and the indirect electrode 321 are respectively stretched in the vertical direction, and the counter electrode 322 is stretched in the horizontal direction.

The indirect electrode 321 is provided with an insulating material 323 so as to cover the indirect electrode 321. Further, the counter electrode 322 is an object to be plated.

A DC power supply 330 is connected to the indirect electrode 321 and the counter electrode 322. The indirect electrode 321 is connected to the positive electrode side of the DC power supply 330. The counter electrode 322 is connected to the negative electrode side of the DC power supply 330.

The indirect electrode 321 is provided with a switch 331. The switch 331 switches between the connection between the indirect electrode 321 and the DC power supply 330 and the connection between the indirect electrode 321 and the direct electrode 320.

Next, the plating process using the plating process device 300 configured as described above will be described.

First, at the time of charging, the indirect electrode 321 and the DC power supply 330 (opposite electrode 322) are connected by the switch 331 as shown in FIG. Then, a DC voltage is applied by using the indirect electrode 321 as an anode and the counter electrode 322 as a cathode to form an electric field (electrostatic field). Then, a positive charge is accumulated on the indirect electrode 321 and anions A, which are negatively charged particles, are collected on the indirect electrode 321 side. On the other hand, a negative charge is accumulated in the counter electrode 322, and copper ions C, which are positively charged particles, move to the counter electrode 322 side.

At this time, as in the first embodiment, the partition wall 311 becomes a physical and electrical resistance, and the amount of charge exchange (oxidation-reduction) between the direct electrode 320 and the counter electrode 322 can be reduced. Further, the direct electrode 320 and the counter electrode 322 are arranged so that the current flowing between the direct electrode 320 and the counter electrode 322 during charging is equal to or less than the limit current density. Therefore, the movement (supply) of copper ions C is not insufficient on the surface of the counter electrode 322 during charging, and it is possible to suppress the electrolysis of water. As a result, the generation of bubbles can be suppressed, and the generation of voids in the copper plating 350, which will be described later, can also be suppressed.

Then, the indirect electrode 321 and the DC power supply 330 are connected by the switch 331 until sufficient charges are accumulated in the indirect electrode 321 and the counter electrode 322, that is, until they are fully charged. The charges of the indirect electrode 321 and the counter electrode 322 in this full charge are equivalent. Then, as described above, during charging, the charge exchange in the counter electrode 322 is performed at high speed while suppressing the electrolysis of water, so that the copper ions C are uniformly arranged on the surface of the counter electrode 322. Further, since the electrolysis of water is suppressed on the surface of the counter electrode 322, the electric field when applying a voltage between the indirect electrode 321 and the counter electrode 322 can be increased. This high electric field can speed up the movement of copper ions C. Further, by arbitrarily controlling this electric field, the copper ions C arranged on the surface of the counter electrode 322 are also arbitrarily controlled.

After that, at the time of discharging, the switch 331 is switched as shown in FIG. 20, the connection between the indirect electrode 321 and the DC power supply 330 is disconnected, and the indirect electrode 321 and the direct electrode 320 are connected. Then, the positive charge accumulated in the indirect electrode 321 moves directly to the electrode 320, the charge of the anion A collected directly on the electrode 320 side is exchanged, and the anion A is oxidized. Along with this, the charges of the copper ions C arranged on the surface of the counter electrode 322 are exchanged, and the copper ions C are reduced. Then, the copper plating 350 is deposited on the surface of the counter electrode 322.

At this time, as in the first embodiment, it is possible to exchange a larger amount of electric charge than during charging, and it is possible to reduce a large amount of copper ions C while suppressing electrolysis of water. Therefore, the plating rate can be improved and the plating process can be performed at high speed.

Then, since sufficient copper ions C are accumulated on the surface of the counter electrode 322 and reduced in a uniformly arranged state, the copper plating 350 can be uniformly deposited on the surface of the counter electrode 322. As a result, the density of crystals in the copper plating 350 is increased, and a high quality copper plating 350 can be formed.

Then, the copper plating 350 grows to a predetermined film thickness by repeatedly moving and accumulating the copper ions C during charging and reducing the copper ions C during discharging. In this way, a series of plating processes in the plating processing apparatus 1 is completed.

Also in the fourth embodiment, the same effect as that of the first embodiment can be enjoyed.

In the plating processing apparatus 300 of the present embodiment, as shown in FIG. 21, a plurality of direct electrodes 320 and a plurality of indirect electrodes 321 may be provided. The direct electrode 320 and the indirect electrode 321 are arranged so as to be arranged alternately in the horizontal direction.

The partition wall 311 is provided between the direct electrode 320 and the indirect electrode 321 in contact with the direct electrode 320. That is, a pair of partition walls 311 and 311 are provided facing each other on both side surfaces of the direct electrode 320. The inflow / outflow holes 312 are formed by opening at the lower ends of these pair of partition walls 311 and 311.

The counter electrode 322 is provided so as to cover the plurality of direct electrodes 320 and the plurality of indirect electrodes 321 in the direction (horizontal direction) in which the plurality of direct electrodes 320 and the plurality of indirect electrodes 321 are arranged. That is, the plurality of direct electrodes 320 and the plurality of indirect electrodes 321 are respectively stretched in the vertical direction, and the counter electrode 322 is stretched in the horizontal direction.

The plating process in the plating processing apparatus 300 shown in FIG. 21 is the same as the plating processing performed in the plating processing apparatus 300 shown in FIG. That is, first, at the time of charging, as shown in FIG. 22, a plurality of indirect electrodes 321 and a DC power supply 330 (opposite electrode 322) are connected by a switch 331. Then, a DC voltage is applied using the plurality of indirect electrodes 321 as the anode and the counter electrode 322 as the cathode to form an electric field (electrostatic field). Then, positive charges are accumulated in the plurality of indirect electrodes 321 and negative ion A, which is a negatively charged particle, is collected on the side of the plurality of indirect electrodes 321. On the other hand, a negative charge is accumulated in the counter electrode 322, and copper ions C, which are positively charged particles, move to the counter electrode 322 side.

After that, at the time of discharging, the switch 331 is switched as shown in FIG. 23, the connection between the indirect electrode 321 and the DC power supply 330 is disconnected, and the indirect electrode 321 and the direct electrode 320 are connected. Then, the positive charge accumulated in the indirect electrode 321 moves directly to the electrode 320, the charge of the anion A collected directly on the electrode 320 side is exchanged, and the anion A is oxidized. Along with this, the charges of the copper ions C arranged on the surface of the counter electrode 322 are exchanged, and the copper ions C are reduced. Then, the copper plating 350 is deposited on the surface of the counter electrode 322.

At the time of this discharge, since a plurality of direct electrodes 320 are arranged side by side in the horizontal direction with respect to one counter electrode 322, the electric fields in the plurality of direct electrodes 320 become uniform, and charge exchange can be performed uniformly. .. Therefore, it is possible to form a copper plating 350 having higher uniformity.

In the plating processing apparatus 300 shown in FIG. 21, the plating solution M was stored in the plating tank 310, but as shown in FIGS. 24 and 25, the plating tank 310 was omitted and the paddle of the plating solution M was used. It may be formed.

In the plating processing apparatus 300 shown in FIG. 24, a paddle of the plating solution M is formed on the counter electrode 322. The method of forming the paddle of the plating solution M is arbitrary, but the paddle is formed by supplying the plating solution M onto the counter electrode 322 via, for example, a pipe (not shown). After that, a plurality of direct electrodes 320, a plurality of indirect electrodes 321 and a plurality of partition walls 311 are arranged on the paddle of the plating solution M.

Further, in the plating processing apparatus 300 shown in FIG. 25, the electrode holding plate 360 is arranged below the counter electrode 322 so as to face the counter electrode 322. After that, a paddle of the plating solution M is formed between the electrode holding plate 360 and the counter electrode 322. After that, a plurality of direct electrodes 320, a plurality of indirect electrodes 321 and a plurality of partition walls 311 are arranged on the paddle of the plating solution M.

In any of the plating processing devices 300 shown in FIGS. 24 and 25, the same effect as that of the plating processing device 300 shown in FIG. 21 can be enjoyed.

<5. Plating processing apparatus according to the fifth embodiment>
Next, a fifth embodiment of the plating processing apparatus will be described. In the plating processing apparatus of the fifth embodiment, the electrical connection between the electrode and the plating solution is directly disconnected during charging, and the electrode and the plating solution are electrically connected during discharging. Various configurations of the plating processing apparatus that realizes such a plating treatment can be considered, and four plating processing apparatus will be described below by way of exemplification based on FIGS. 26 to 33.

The first plating processing apparatus will be described. 26 and 27 are vertical cross-sectional views showing an outline of the configuration of the first plating processing apparatus 400 according to the fifth embodiment.

The first plating processing apparatus 400 has a plating tank 410 that stores the plating solution M inside. The plating tank 410 is provided with a partition wall 411 that divides the inside into two regions T1 and T2. The partition wall 411 is provided with an opening / closing mechanism 412 that opens / closes an inflow / out hole for flowing the plating solution M between the two regions T1 and T2. The configuration of the opening / closing mechanism 412 is not particularly limited, but for example, a solenoid valve is used.

Inside the plating tank 10, a direct electrode 420, an indirect electrode 421, and a counter electrode 422 are each immersed in the plating solution M. The direct electrode 420 is located in region T1. The indirect electrode 421 and the counter electrode 422 are respectively arranged in the region T2, the indirect electrode 421 is arranged apart from the partition wall 411, and the counter electrode 422 is arranged close to the partition wall 411. The direct electrode 420 is provided close to the indirect electrode 421, and is arranged apart from the counter electrode 422 with the partition wall 411 interposed therebetween.

The indirect electrode 421 is provided with an insulating material 423 so as to cover the indirect electrode 421. Further, the counter electrode 422 is an object to be plated.

A DC power supply 430 is connected to the direct electrode 420, the indirect electrode 421, and the counter electrode 422. The direct electrode 420 and the indirect electrode 421 are each connected to the positive electrode side of the DC power supply 430. The counter electrode 422 is connected to the negative electrode side of the DC power supply 430.

The indirect electrode 421 is provided with a switch 431. The switch 431 switches between the connection between the indirect electrode 421 and the DC power supply 430 and the connection between the indirect electrode 421 and the direct electrode 420.

Next, a plating process using the first plating processing apparatus 400 configured as described above will be described.

First, at the time of charging, the indirect electrode 421 and the DC power supply 430 (opposite electrode 422) are connected by the switch 431 as shown in FIG. Then, a DC voltage is applied by using the indirect electrode 421 as an anode and the counter electrode 422 as a cathode to form an electric field (electrostatic field). Then, a positive charge is accumulated on the indirect electrode 421, and anions A, which are negatively charged particles, are collected on the indirect electrode 421 side. On the other hand, a negative charge is accumulated in the counter electrode 422, and copper ions C, which are positively charged particles, move to the counter electrode 422 side.

At the time of this charging, the opening / closing mechanism 412 closes the inflow / outflow holes of the plating solution M between the regions T1 and T2. That is, the regions T1 and T2 are separated. Then, no current flows between the direct electrode 420 and the counter electrode 422, and charge exchange (oxidation reduction) between the direct electrode 420 and the counter electrode 422 can be suppressed.

Then, copper ions C are uniformly arranged on the surface of the counter electrode 422. Since the charge exchange of copper ions C is not performed on the surface of the counter electrode 422 and the electrolysis of water is suppressed, the electric field when applying a voltage between the indirect electrode 421 and the counter electrode 422 can be increased. .. This high electric field can speed up the movement of copper ions C. Further, by arbitrarily controlling this electric field, the copper ions C arranged on the surface of the counter electrode 422 are also arbitrarily controlled.

After that, when sufficient copper ions C move to the counter electrode 422 side and accumulate, the switch 431 is switched as shown in FIG. 27 at the time of discharge, the connection between the indirect electrode 421 and the DC power supply 430 is disconnected, and the indirect electrode 421 and the indirect electrode 421 are connected. The electrode 420 is directly connected. Further, the opening / closing mechanism 412 opens the inflow / outflow holes of the plating solution M between the regions T1 and T2. That is, the areas T1 and T2 are connected. Then, the positive charge accumulated in the indirect electrode 421 is directly transferred to the electrode 420, the charge of the anion A collected on the indirect electrode 421 side is exchanged, and the anion A is oxidized. Along with this, the charges of the copper ions C arranged on the surface of the counter electrode 422 are exchanged, and the copper ions C are reduced. Then, the copper plating 450 is deposited on the surface of the counter electrode 422.

Since sufficient copper ions C are accumulated on the surface of the counter electrode 422 and reduced in a uniformly arranged state, the copper plating 450 can be uniformly deposited on the surface of the counter electrode 422. As a result, the crystal density in the copper plating 450 is increased, and a high quality copper plating 450 can be formed.

Then, the copper plating 450 grows to a predetermined film thickness by repeatedly moving and accumulating the copper ions C during charging and reducing the copper ions C during discharging. In this way, a series of plating processes in the plating processing apparatus 1 is completed.

Next, the second plating processing apparatus will be described. 28 and 29 are vertical cross-sectional views showing an outline of the configuration of the second plating processing apparatus 400 according to the fifth embodiment.

The second plating processing device 400 is the first plating processing device 400 described above, in which the partition wall 411 and the opening / closing mechanism 412 are omitted, and the configuration of the direct electrode 420 is changed.

The second plating processing apparatus 400 has a moving mechanism 460 that directly moves the electrode 420 back and forth with respect to the plating solution M. That is, the moving mechanism 460 directly raises and lowers the electrode 420 to separate it from the plating solution M or bring it into contact with the plating solution M. The other configuration of the second plating processing apparatus 400 is the same as the other configuration of the first plating processing apparatus 400.

Then, at the time of charging, as shown in FIG. 28, the indirect electrode 421 and the DC power supply 430 (counter electrode 422) are connected by the switch 431, and a DC voltage is applied between the indirect electrode 421 and the counter electrode 422 to generate an electric field (counter electrode 422). An electrostatic field) is formed, and copper ions C, which are positively charged particles, are moved to the counter electrode 422 side. At the time of this charging, the moving mechanism 460 raises the direct electrode 420 to the outside of the plating solution M to separate the direct electrode 420 and the plating solution M. Then, no current flows between the direct electrode 420 and the counter electrode 422, and charge exchange (oxidation reduction) between the direct electrode 420 and the counter electrode 422 can be suppressed.

After that, at the time of discharging, the switch 431 is switched as shown in FIG. 29, the connection between the indirect electrode 421 and the DC power supply 430 is disconnected, and the indirect electrode 421 and the direct electrode 420 are connected. Further, the direct electrode 420 is lowered into the plating solution M by the moving mechanism 460, and the direct electrode 420 and the plating solution M are brought into contact with each other. Then, the charges of the copper ions C arranged on the surface of the counter electrode 422 are exchanged, and the copper ions C are reduced. Then, the copper plating 450 is deposited on the surface of the counter electrode 422.

Next, the third plating processing apparatus will be described. 30 and 31 are vertical cross-sectional views showing an outline of the configuration of the fifth plating processing apparatus 400 according to the fifth embodiment.

The third plating processing device 400 is the first plating processing device 400 described above, in which the partition wall 411 and the opening / closing mechanism 412 are omitted, and the configuration of the direct electrode 420 is changed.

In the third plating processing apparatus 400, the direct electrode 420 is arranged outside the plating solution M. Further, the third plating processing apparatus 400 has a flow path 470 that moves (elevates) the plating solution M by Coulomb force (electrostatic force). The Coulomb force is generated by forming an electric field in the plating solution M from the outside of the plating solution M, for example. One end portion 470a of the flow path 470 is positioned so as to be immersed in the plating solution M. The other end 470b of the flow path 470 is positioned so as to come into direct contact with the electrode 420 when the plating solution M moves up and down. The other configuration of the third plating processing apparatus 400 is the same as the other configuration of the first plating processing apparatus 400.

Then, at the time of charging, as shown in FIG. 30, the indirect electrode 421 and the DC power supply 430 (counter electrode 422) are connected by the switch 431, and a DC voltage is applied between the indirect electrode 421 and the counter electrode 422 to generate an electric field (counter electrode 422). An electrostatic field) is formed, and copper ions C, which are positively charged particles, are moved to the counter electrode 422 side. At the time of this charging, the plating solution M stored in the plating tank 410 is not raised through the flow path 470 and is not brought into direct contact with the electrode 420. Then, the electrode 420 and the plating solution M are directly separated. Then, no current flows between the direct electrode 420 and the counter electrode 422, and charge exchange (oxidation reduction) between the direct electrode 420 and the counter electrode 422 can be suppressed.

After that, at the time of discharging, the switch 431 is switched as shown in FIG. 31, the connection between the indirect electrode 421 and the DC power supply 430 is cut off, and the indirect electrode 421 and the direct electrode 420 are connected. Further, the plating solution M stored in the plating tank 410 is raised through the flow path 470 by Coulomb force and is brought into direct contact with the electrode 420. Then, the electrode 420 and the plating solution M are brought into direct contact with each other. Then, the charges of the copper ions C arranged on the surface of the counter electrode 422 are exchanged, and the copper ions C are reduced. Then, the copper plating 450 is deposited on the surface of the counter electrode 422.

Next, the fourth plating processing apparatus will be described. 32 and 33 are vertical cross-sectional views showing an outline of the configuration of the fourth plating processing apparatus 400 according to the fifth embodiment.

The fourth plating treatment device 400 is the first plating treatment device 400 described above, in which the partition wall 411 and the opening / closing mechanism 412 are omitted, and the configuration of the direct electrode 420 is changed.

In the fourth plating processing apparatus 400, the direct electrode 420 is arranged outside the plating solution M. Further, the fourth plating processing apparatus 400 has a liquid supply mechanism 480 that directly contacts the electrode 420 and supplies the charged droplet D. The liquid supply mechanism 480 has, for example, a nozzle (not shown), and the droplet D is supplied from the nozzle. The droplet D supplied from the liquid supply mechanism 480 has the same components as the plating solution M. The other configuration of the fourth plating processing device 400 is the same as the other configuration of the first plating processing device 1.

Then, at the time of charging, as shown in FIG. 32, the indirect electrode 421 and the DC power supply 430 (counter electrode 422) are connected by the switch 431, and a DC voltage is applied between the indirect electrode 421 and the counter electrode 422 to generate an electric field (counter electrode 422). An electrostatic field) is formed, and copper ions C, which are positively charged particles, are moved to the counter electrode 422 side. At the time of this charging, the supply of the droplet D from the liquid supply mechanism 480 is stopped. Then, the electrode 420 and the plating solution M are directly separated. Then, no current flows between the direct electrode 420 and the counter electrode 422, and charge exchange (oxidation reduction) between the direct electrode 420 and the counter electrode 422 can be suppressed.

After that, at the time of discharging, the switch 431 is switched as shown in FIG. 33, the connection between the indirect electrode 421 and the DC power supply 430 is cut off, and the indirect electrode 421 and the direct electrode 420 are connected. In addition, the liquid supply mechanism 480 directly contacts the electrode 420 to supply the charged droplet D to the plating solution M. Then, the electrode 420 and the plating solution M are brought into direct contact with each other. Then, the charges of the copper ions C arranged on the surface of the counter electrode 422 are exchanged, and the copper ions C are reduced. Then, the copper plating 450 is deposited on the surface of the counter electrode 422.

When any of the first plating processing apparatus 400 to the fourth plating processing apparatus 400 of the fifth embodiment is used, the same effect as that of the first embodiment can be enjoyed. That is, when the copper ion C is moved during charging, the electrical connection between the direct electrode 420 and the plating solution M is cut off, so that charge exchange between the direct electrode 420 and the counter electrode 422 can be suppressed, and the copper ion The reduction of C can be suppressed. Then, at the time of charging, the copper ions C are reduced in a state where the copper ions C are uniformly arranged on the surface of the counter electrode 422. Therefore, the plating process can be performed uniformly.

In the fifth embodiment, the configuration of the plating processing apparatus 400 is not limited to the above four examples. The plating processing apparatus 400 may have any configuration as long as it has a configuration in which the electrical connection between the electrode 420 and the plating solution M is directly disconnected during charging and the electrode 420 and the plating solution M are electrically connected during discharging. ..

<6. Prevention of peeling of plating base film>
In the above plating processing apparatus, a predetermined base film may be formed on the surface of the counter electrode before forming copper plating on the counter electrode as the object to be processed. For example, in a semiconductor device, when forming a wiring made of copper plating, a barrier film (base film) made of, for example, cobalt plating is formed on the surface of a semiconductor substrate (counter electrode). If the ionization tendency of the metal of the base film is smaller than the ionization tendency of copper in the plating solution, electroless substitution plating may be performed and the base film may be peeled off.

On the other hand, in order to prevent this replacement plating, it is necessary to apply an appropriate voltage, but this voltage may cause electrolytic plating to proceed and the electrolytic plating process may not be performed uniformly. That is, in the above-mentioned plating processing apparatus, for example, when the counter electrode is arranged in the plating solution, the copper ions of the plating solution accumulated on the counter electrode are unevenly distributed or the electric field is unstable. When electrolytic plating is performed, the plated metal is unevenly deposited, and the plating process is not performed uniformly. Therefore, when arranging the counter electrode in the plating solution, it is necessary to prevent electroless replacement plating and prevent electrolytic plating from proceeding.

Therefore, for example, in the plating processing apparatus 1 of the first embodiment, when the counter electrode 22 is arranged in the plating solution M, the indirect electrode 21 and the DC power supply 30 are connected by the switch 31 as shown in FIG. .. Then, a DC voltage is applied using the indirect electrode 21 as an anode and the counter electrode 22 as a cathode to form an electric field in the plating solution M. As a result, for example, even when a base film is formed on the surface of the counter electrode 22, electroless replacement plating can be prevented and peeling of the base film can be suppressed, and electrolytic plating with the plating solution M does not proceed. As a result, the plating process can be performed uniformly.

It should be noted that suppressing the peeling of the base film by forming an electric field in the plating solution M in this way is applied to any of the plating treatment devices of the other second embodiment to the fifth embodiment. it can.

<7. Crystal structure>
The present inventor has diligently studied the copper plating crystals formed by using the above plating treatment apparatus, and has come up with a method for further improving the crystallinity. Hereinafter, this method will be described using the plating processing apparatus 1 of the first embodiment, but the plating processing apparatus of any of the other second embodiment to the fifth embodiment will be used. Applicable.

<7-1. Crystal grain size control and plating rate improvement>
FIG. 34 is an explanation showing the potential of the indirect electrode 21 and the switching state of the switch 31, that is, the connection between the indirect electrode 21 and the DC power supply 30, and the connection between the indirect electrode 21 and the direct electrode 20 in each step of the plating process. It is a figure.

First, in step S1, as shown in FIG. 35, the indirect electrode 21 and the DC power supply 30 (counter electrode 22) are connected by a switch 31, and a DC voltage is applied by using the indirect electrode 21 as an anode and the counter electrode 22 as a cathode. To form an electric field (electrostatic field). Then, as shown in FIG. 36, a positive charge is accumulated on the indirect electrode 21, and anions A, which are negatively charged particles, are collected on the indirect electrode 21 side. On the other hand, a negative charge is accumulated in the counter electrode 22, and copper ions C, which are positively charged particles, move to the counter electrode 22 side. FIG. 36 shows how copper ions C are arranged on the surface of the counter electrode 22. The copper ions C are arranged corresponding to the charges E stored in the counter electrode 22.

In step S1, the charge exchange of copper ions C is not performed on the surface of the counter electrode 22, and the electrolysis of water can be suppressed, so that a high voltage can be applied between the indirect electrode 21 and the counter electrode 22. By applying such a high voltage, it is possible to improve the movement rate of a large amount of copper ions C to the counter electrode 22 side, and a plurality of copper ions C are densely and uniformly arranged on the surface of the counter electrode 22. be able to.

The amount of copper ions C moving to the counter electrode 22 side can be controlled by the voltage between the indirect electrode 21 and the counter electrode 22 as described above, or is controlled by the capacitance of the indirect electrode 21 as described later. You can also do it. Alternatively, it may be controlled by both these voltages and capacitances.

After that, in step S2, the voltage applied between the indirect electrode 21 and the counter electrode 22 is lowered. For example, the voltage V in step S1 is reduced to 1/4. Then, as shown in FIG. 37, the electric charge E accumulated in the counter electrode 22 is also thinned out to 1/4 and arranged sparsely. In other words, the amount of charge E remaining on the counter electrode 22 is equal to or less than the amount of copper ions C transferred in step S1. Then, the position of the remaining charge E becomes the predetermined charge arrangement position P in the present invention. In the illustrated example, only one charge arrangement position P is shown, but in reality, a plurality of charge arrangement positions P are arranged at equal intervals on the counter electrode 22.

In step S2, the copper ions C arranged on the surface of the counter electrode 22 remain due to the presence of the plating solution M and remain densely arranged.

In the following description, the ratio of the amount of charge E arranged on the counter electrode 22 in step S1 to the amount of charge E remaining on the counter electrode 22 in step S2 is referred to as a thinning rate. The thinning rate is set according to the particle size of the crystals formed on the surface of the counter electrode 22 as described later. That is, if the thinning rate is increased, the crystal grain size is increased, and if the thinning rate is decreased, the crystal grain size is decreased.

The thinning rate is set so that the distance between adjacent charge array positions P and P is an integral multiple of the size of the crystal lattice. For example, if the distance between the charge array positions P and P is equal to the size of the crystal lattice, it becomes a single crystal, and if it is an integral multiple of 2 times or more, it is advantageous to join adjacent crystals. In such a case, the crystallinity can be improved. Moreover, since the crystallinity is improved in this way, the crystal surface can be flattened.

The thinning rate (the amount of charge E remaining on the counter electrode 22) can be controlled by the voltage between the indirect electrode 21 and the counter electrode 22 as described above, and the capacitance of the indirect electrode 21 as described later. It can also be controlled by capacity. Alternatively, it may be controlled by both these voltages and capacitances.

Then, in step S3, the switch 31 is switched as shown in FIG. 38 to connect the indirect electrode 21 and the direct electrode 20. Then, as shown in FIG. 39, at the charge arrangement position P, the copper ion C is charged-exchanged with the charge E and oxidized, and the crystal G of the copper ion C is precipitated. Of the copper ions C arranged on the surface of the counter electrode 22, the copper ions C located at positions other than the charge arrangement position P are not charged-exchanged and remain as ions. At this time, the anion A is oxidized on the indirect electrode 21 side.

After that, in step S4, the switch 31 is switched, the indirect electrode 21 and the DC power supply 30 are connected, and the charge E is arranged again at the charge arrangement position P of the counter electrode 22 as shown in FIG. 40. When the counter electrode 22 is charged with the electric charge E in this way, the voltage applied between the indirect electrode 21 and the counter electrode 22 is the same as the voltage (V / 4) in step S2. Further, at this time, the copper ion C whose charge has not been exchanged in step S3 moves to the charge arrangement position P.

After that, in step S5, the switch 31 is switched to connect the indirect electrode 21 and the direct electrode 20. Then, as shown in FIG. 41, at the charge arrangement position P, the copper ion C is charged-exchanged with the charge E and oxidized, and the crystal G of the copper ion C is precipitated. Although two crystals G are shown in FIG. 41 for ease of explanation, they actually grow as one crystal G.

After that, the same processing as in steps S4 and S5 is repeated in this order. That is, the arrangement of the charge E and the copper ion C at the charge arrangement position P in step S6, the reduction of the copper ion C in step S7, the arrangement of the charge E and the copper ion C at the charge arrangement position P in step S8, in step S9. Copper ion C is reduced in sequence. Then, as shown in FIG. 42, the crystal G grows at the charge arrangement position P.

After that, steps S1 to S9 are repeated to grow the crystal G at the charge arrangement position P. FIG. 43 shows how the second step S1 was performed. Then, the crystal G formed at one charge arrangement position P grows until it comes into contact with the crystal G formed at the adjacent charge arrangement position P. In other words, the particle size of the crystal G depends on the distance between the adjacent charge arrangement positions P and P, and depends on the thinning rate of the charge E of the counter electrode 22 in step S2 as described above. When increasing the particle size of the crystal G, the thinning rate may be increased to increase the distance between adjacent charge array positions P and P. Further, when the particle size of the crystal G is reduced, the thinning rate may be reduced to reduce the distance between the adjacent charge arrangement positions P and P.

In this way, as shown in FIG. 44, the copper plating 50 is formed on the surface of the counter electrode 22 with a predetermined film thickness, and a series of plating treatments in the plating treatment apparatus 1 is completed.

According to the present embodiment, the particle size of the crystal G in the copper plating 50 can be controlled by controlling the thinning rate of the charge E of the counter electrode 22 in step S2. Then, for example, when the particle size of the crystal G is increased, electromigration at the time of wiring formation can be suppressed, electron scattering can be suppressed, and the resistance of the wiring can be reduced.

Here, conventionally, in order to grow crystals of the plating metal after the plating treatment and remove impurities such as voids generated by electrolysis of water, there is a case where the thermal annealing treatment is performed after the plating treatment. In this respect, since the particle size of the crystal G can be controlled as described above, the conventional crystal growth treatment by thermal annealing becomes unnecessary. Further, since a solution in which copper sulfate is dissolved is used as the plating solution M, conventional voids caused by hydrogen or the like can be removed. From this point of view, the thermal annealing treatment becomes unnecessary, and stress migration during wiring formation can be suppressed.

Further, in step S1, since the copper ion C moves in the plating solution M, the moving distance is long, whereas in steps S4, S6, and S8, the copper ion C arranged on the surface of the counter electrode 22 is concerned. Since it only moves to the charge arrangement position P along the surface of the counter electrode 22, the moving distance is short. Then, in order to form the crystal G having a large particle size, according to the present embodiment, the copper ions C are compared with the case where the copper ions are repeatedly moved in the plating solution having a long moving distance as in the conventional case. The moving distance can be shortened. Therefore, the plating process can be performed in a short time, and the rate of the plating process can be improved.

<7-2. Control of charge amount of counter electrode>
In the above embodiment, the amount of movement of the copper ion C in step S1 (charge E of the counter electrode 22) and the thinning ratio of the charge E of the counter electrode 22 in step S2 are between the indirect electrode 21 and the counter electrode 22, respectively. Although it was controlled by the voltage, it may be controlled by the capacitance of the indirect electrode 21.

The capacitance C can be expressed by C = εA / d (ε: dielectric constant of the dielectric between the electrodes, A: area of the electrodes, d: distance between the electrodes). In order to control the capacitance C, any of these parameters of the permittivity ε, the area A, and the distance d may be controlled, but it is actually difficult to control the permittivity ε and the distance d. In the present embodiment, a case where the area A is controlled will be described.

For example, the indirect electrode 21 is divided into a plurality of parts in order to control the capacitance. As shown in FIG. 45, in the plating processing apparatus 1, two indirect electrodes 21a and 21b are provided in the plating tank 10. Further, with the division of the indirect electrode 21, the direct electrode 20 is also divided into the direct electrodes 20a and 20b.

The indirect electrodes 21a and 21b are provided with switches 31a and 31b, respectively. These switches 31a and 31b each perform the same functions as the switch 31 of the first embodiment.

In such a case, when the copper ion C is moved to the counter electrode 22 side in step S1, the indirect electrodes 21a and 21b and the DC power supply 30 are connected by switches 31a and 31b, respectively. Then, since the capacitance becomes large, the amount of movement of the copper ion C can be increased, and the amount of the electric charge E accumulated in the counter electrode 22 can also be increased.

After that, in step S2, when thinning out the charge E of the counter electrode 22, for example, the switch 31a is switched and the switch 31b is not switched. Then, since the capacitance becomes small, the charge E accumulated in the counter electrode 22 also becomes small. The number of the indirect electrode 21 and the direct electrode 20 to be divided is not limited to the present embodiment, and is set according to the thinning rate. For example, in order to reduce the thinning rate to 1/4, the indirect electrode 21 and the direct electrode 20 may be divided into four parts each.

According to the present embodiment, even if the voltage between the indirect electrode 21 and the counter electrode 22 is constant, the amount of charge E of the counter electrode 22 can be controlled by controlling the capacitance, and the crystal G The particle size of the can be controlled.

<7-3. Plating flattening>
In the above embodiment, the thinning rate of the charge E of the counter electrode 22 in step S2 is preferably a power of 2 from the viewpoint of flattening the copper plating 50. In such a case, the particle size of the crystal G precipitated on the counter electrode 22 is the product of the size of the atomic lattice and the number of precipitations (power of 2). Then, as shown in FIG. 46, when the crystals G1 and G2 are sequentially formed and laminated toward the side away from the counter electrode 22, the crystals G2 are filled between the adjacent crystals G1 and G1 without any gap. Similarly, by sequentially forming the crystals G3 to G5 toward the side away from the counter electrode 22, these crystals G1 to G5 can be filled without gaps. As a result, the surface of the copper plating 50 made of crystals G1 to G5 can be flattened.

Although the shapes of the crystals G1 to G5 are shown in triangles in FIG. 46 for the sake of simplicity, the surface of the copper plating 50 can be flattened by the same method even if the crystals are hemispherical, for example. ..

Further, as shown in FIG. 46, when the crystals G1 to G5 are formed on the counter electrode 22, the thinning ratio of step S2 is directed toward the side away from the counter electrode 22 (toward the region far from the region near the counter electrode 22). To increase. In such a case, the thinning rate when forming the crystal G2 is larger than the thinning rate when forming the crystal G1, so that the particle size of the crystal G2 is larger than the particle size of the crystal G1. Then, the particle sizes of the crystals G1 to G5 increase in this order.

In such a case, by reducing the particle size of the crystal G1, the number of bonding points between the surface of the counter electrode 22 and the crystal G1 increases. Therefore, the adhesion of the copper plating 50 to the surface of the counter electrode 22 can be improved. Then, in the present embodiment, a crystal G1 having a small particle size can be formed and flattened in a region near the counter electrode 22, and a crystal G5 having a large particle size can be formed in a region far from the counter electrode 22.

Here, when the particle size of the crystal is increased, unevenness proportional to the particle size is generated on the film-forming surface, and the polishing load for flattening the film-forming surface increases in the subsequent steps. In this respect, since the particle size of the crystal G5 can be increased while flattening, there is also an effect that the polishing load can be reduced.

<7-4. Application to damascene process>
Next, an example in which the plating treatment method shown in FIG. 46 is applied to the damascene process will be described. In FIGS. 47 and 48, the via hole 500 and the wiring groove 501 are plated. In the following description, crystals G1 to G6 may be collectively referred to as crystal G.

In the via hole 500, the above-mentioned crystals G1 to G5 are formed on the bottom surface and the side surface thereof. Then, a crystal G6 having a particle size larger than that of the crystal G5 is formed so as to further fill the inside of the crystal G5. In this way, the via hole 500 is plated to form a via.

Also in the wiring groove 501, the above-mentioned crystals G1 to G5 are formed on the bottom surface and the side surface thereof. Then, a crystal G6 having a particle size larger than that of the crystal G5 is formed so as to further fill the inside of the crystal G5. As shown in the figure, the crystals G1 to G6 are arranged side by side in the wiring direction (longitudinal direction).

After that, a current is passed in the wiring direction of the wiring groove 501. Then, since electromigration occurs between the adjacent crystals G and G, electron scattering and cavities (voids) at the grain boundaries between the crystals G and G can be suppressed and compensated. Further, the crystals G and G are also bonded by an intermolecular force, but the crystals G and G can be firmly bonded by passing a current in the wiring direction. In this way, the wiring groove 501 is plated to form the wiring.

If the wiring width is smaller than the particle size of the crystal G, the plating method shown in FIG. 46 may not be able to increase the particle size of the crystal G. In such a case, the resistivity of the wiring can be reduced by forming the crystal G into flat grains having a long crystal length in the wiring direction. That is, in the triangle of crystal G shown in FIG. 46, the ratio of the height to the base may be reduced.

In order to realize flat grains of crystal G, the following two conditions are required. The first condition is to increase the surface energy of the interface where the crystal G is precipitated. The factor that reduces the surface energy of the precipitation interface is the hydrogen termination. In this regard, as described above, since a solution in which copper sulfate is dissolved is used as the plating solution M, hydrogen is not generated by electrolysis of water. Therefore, hydrogen termination is not performed at the precipitation interface, and the surface energy of the precipitation interface can be increased.

The second condition is to flatten the interface where the crystal G is deposited. In order to stack flat grains having a long crystal length without gaps, it is necessary that the precipitation interface is flat. In this regard, flattening of the precipitation interface can be realized by executing the plating treatment method shown in FIG. 46, that is, by setting the thinning rate of the charge E of the counter electrode 22 to the power of 2 in step S2.

From the above, it is possible to form crystals G having a small particle size in a region close to the bottom surface and the side surface of the wiring groove 501 to achieve flattening, and to achieve flat crystal growth (planar growth) in a region far away. G can be a flat grain. Therefore, low resistance wiring can be formed.

<8. Other embodiments>
In the above embodiments, the case where the plating treatment is performed as the electrolytic treatment has been described, but the present invention can be applied to various electrolytic treatments such as an etching treatment.

Further, in the above embodiment, the case where the copper ion C is reduced on the counter electrode 22 side has been described, but the present invention can also be applied to the case where the ion to be treated is oxidized on the counter electrode 22 side.

In such a case, the ion to be treated is an anion, and the same electrolytic treatment may be performed with the anode and cathode reversed in the above embodiment. That is, a voltage is applied between the indirect electrode and the counter electrode to form an electric field, and the ion to be processed is moved to the counter electrode side. After that, a current is passed between the direct electrode and the indirect electrode. Then, the electric charge of the ion to be processed that has moved to the counter electrode side is exchanged, and the ion to be processed is oxidized.

Also in this embodiment, the same effect as that of the above-described embodiment can be enjoyed, although there is a difference between oxidation and reduction of the ion to be treated.

Although preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to such examples. It is clear that a person skilled in the art can come up with various modifications or modifications within the scope of the ideas described in the claims, which naturally belong to the technical scope of the present invention. It is understood as a thing. The present invention is not limited to this example, and various aspects can be adopted.

1, 100, 200, 300, 400 Plating apparatus 10 (10a, 10b), 110, 210, 310, 410 Plating tank 11, 211, 311, 411 Bulk partition 12, 212, 312 Inflow / out holes 20, 120, 220, 320, 420 Direct electrode 21, 121, 221, 321, 421 Indirect electrode 22, 122, 222, 322, 422 Counter electrode 23, 123, 223, 323, 423 Insulation material 30, 130, 230, 330, 430 DC power supply 31 , 331, 431 Switch 40 Control unit 50, 150, 250, 350, 450 Copper plating 60 Porous wall 70 Piping 131, 231 First switch 132, 232 Second switch 360 Electrode holding plate 412 Opening and closing mechanism 460 Moving mechanism 470 Flow path 480 Liquid supply mechanism 500 Via hole 501 Wiring groove A Anion C Copper ion D Droplet E Charge G (G1 to G6) Crystal M Plating liquid T1, T2 region

Claims (31)

An electrolytic treatment method in which a predetermined treatment is performed using ions to be treated contained in the treatment liquid.
An arrangement step of arranging a direct electrode and a counter electrode so as to be electrically connected to the treatment liquid, and arranging an indirect electrode that forms an electric field in the treatment liquid, respectively.
A process of moving ions to be treated by applying a voltage to the indirect electrode to move the ions to be treated in the treatment liquid to the counter electrode side.
It has a process ion treatment step of connecting the direct electrode and the indirect electrode and oxidizing or reducing the ion to be processed that has moved to the counter electrode side.
In the ion transfer step to be processed, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density .
In the arrangement step, a partition wall in which the treatment liquid is divided into two regions and inflow / out holes of the treatment liquid are formed, and pores in which the treatment liquid is divided into two regions and a plurality of pores are formed. The quality wall or the treatment liquid is divided into two regions and a pipe connecting the two regions is arranged, and the partition wall, the pore quality wall or the pipe is sandwiched so as to come into contact with the treatment liquid. An electrolytic treatment method comprising arranging the direct electrode and the counter electrode . In the arrangement step, a switch for switching between the connection between the indirect electrode and the power supply and the connection between the indirect electrode and the direct electrode is further arranged.
In the ion transfer step, the indirect electrode and the power supply are connected by the switch and a voltage is applied to move the ions to be processed in the treatment liquid to the counter electrode side.
In the ion treatment step, the switch disconnects the indirect electrode from the power supply, connects the indirect electrode to the direct electrode, and oxidizes or reduces the ion to be treated that has moved to the counter electrode side. The electrolytic treatment method according to claim 1 , wherein the method is characterized by the above. An electrolytic treatment method in which a predetermined treatment is performed using ions to be treated contained in the treatment liquid.
An arrangement step of arranging a direct electrode and a counter electrode so as to be electrically connected to the treatment liquid, and arranging an indirect electrode that forms an electric field in the treatment liquid, respectively.
A process of moving ions to be treated by applying a voltage to the indirect electrode to move the ions to be treated in the treatment liquid to the counter electrode side.
It has a process ion treatment step of connecting the direct electrode and the indirect electrode and oxidizing or reducing the ion to be processed that has moved to the counter electrode side.
In the ion transfer step to be processed, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density .
In the arrangement step, the first switch arranges the direct electrode and the counter electrode so as to come into contact with the treatment liquid, and further switches between the connection between the indirect electrode and the power supply and the connection between the indirect electrode and the direct electrode. A second switch for switching between the connection between the direct electrode and the indirect electrode and the connection between the direct electrode and the counter electrode is arranged.
In the ion transfer step to be processed, the indirect electrode and the power supply are connected by the first switch to apply a voltage, and the direct electrode and the counter electrode are connected by the second switch to perform the processing. The ions to be treated in the liquid are moved to the counter electrode side to move them.
In the ion treatment step, the connection with the indirect electrode is switched from the power source to the direct electrode by the first switch, and the connection with the direct electrode is made from the counter electrode by the second switch. An electrolytic treatment method comprising switching to an electrode, connecting the direct electrode and the indirect electrode, and oxidizing or reducing the ion to be treated that has moved to the counter electrode side . The electrolysis treatment method according to claim 3 , wherein the surface area of the direct electrode is smaller than the surface area of the counter electrode in the arrangement step. An electrolytic treatment method in which a predetermined treatment is performed using ions to be treated contained in the treatment liquid.
An arrangement step of arranging a direct electrode and a counter electrode so as to be electrically connected to the treatment liquid and arranging an indirect electrode that forms an electric field in the treatment liquid.
A process of moving ions to be treated by applying a voltage to the indirect electrode to move the ions to be treated in the treatment liquid to the counter electrode side.
It has a process ion treatment step of connecting the direct electrode and the indirect electrode and oxidizing or reducing the ion to be processed that has moved to the counter electrode side.
In the ion transfer step to be processed, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density .
In the arrangement step, a partition wall in which the treatment liquid is divided into two regions and inflow / out holes of the treatment liquid are formed, and a pore in which the treatment liquid is divided into two regions and a plurality of pores are formed. The quality wall or the treatment liquid is divided into two regions and a pipe connecting the two regions is arranged so as to be in contact with the treatment liquid across the partition wall, the pore quality wall or the pipe. The direct electrode and the counter electrode are arranged, and a first switch for switching between the connection between the indirect electrode and the power supply and the connection between the indirect electrode and the direct electrode is arranged, and the direct electrode and the indirect electrode are arranged. A second switch for switching the connection and the connection between the direct electrode and the counter electrode is arranged.
In the ion transfer step to be processed, the indirect electrode and the power supply are connected by the first switch to apply a voltage, and the direct electrode and the counter electrode are connected by the second switch to perform the processing. The ions to be treated in the liquid are moved to the counter electrode side to move them.
In the ion treatment step, the connection with the indirect electrode is switched from the power source to the direct electrode by the first switch, and the connection with the direct electrode is made from the counter electrode by the second switch. An electrolytic treatment method comprising switching to an electrode, connecting the direct electrode and the indirect electrode, and oxidizing or reducing the ion to be treated that has moved to the counter electrode side . An electrolytic treatment method in which a predetermined treatment is performed using ions to be treated contained in the treatment liquid.
An arrangement step of arranging a direct electrode and a counter electrode so as to be electrically connected to the treatment liquid, and arranging an indirect electrode that forms an electric field in the treatment liquid, respectively.
A process of moving ions to be treated by applying a voltage to the indirect electrode to move the ions to be treated in the treatment liquid to the counter electrode side.
It has a process ion treatment step of connecting the direct electrode and the indirect electrode and oxidizing or reducing the ion to be processed that has moved to the counter electrode side.
In the ion transfer step to be processed, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density .
In the placement process
The plurality of the direct electrodes and the plurality of the indirect electrodes are arranged so that the direct electrodes and the indirect electrodes are alternately arranged and in contact with the treatment liquid.
A partition wall is placed between the direct electrode and the indirect electrode,
The counter electrode is arranged so as to extend in the direction in which the plurality of direct electrodes and the plurality of indirect electrodes are arranged.
A switch for switching between the connection between the plurality of indirect electrodes and the power supply and the connection between the plurality of indirect electrodes and the plurality of direct electrodes is arranged.
In the ion transfer step to be processed, the switch connects the plurality of indirect electrodes and the power source and applies a voltage to move the ions to be processed in the processing liquid to the counter electrode side.
In the ion treatment step to be processed, the switch disconnects the connection between the plurality of indirect electrodes and the power supply, connects the plurality of indirect electrodes and the plurality of direct electrodes, and moves the subject to the counter electrode side. An electrolytic treatment method characterized by oxidizing or reducing treated ions . In the arrangement step, a paddle of the treatment liquid is formed on the counter electrode, and the plurality of direct electrodes, the plurality of indirect electrodes, and the partition wall are arranged by being immersed in the paddle of the treatment liquid. The electrolytic treatment method according to claim 6 , which is characterized. In the arrangement step, an electrode holding plate is arranged below the counter electrode at a position facing each other, a paddle of the treatment liquid is formed between the electrode holding plate and the counter electrode, and the plurality of direct electrodes, the plurality of direct electrodes. The electrolytic treatment method according to claim 6 , wherein the indirect electrode and the partition wall of the above are arranged by being immersed in a paddle of the treatment liquid. An electrolytic treatment method in which a predetermined treatment is performed using ions to be treated contained in the treatment liquid.
An arrangement step of arranging a direct electrode and a counter electrode so as to be electrically connected to the treatment liquid, and arranging an indirect electrode that forms an electric field in the treatment liquid, respectively.
A process of moving ions to be treated by applying a voltage to the indirect electrode to move the ions to be treated in the treatment liquid to the counter electrode side.
It has a process ion treatment step of connecting the direct electrode and the indirect electrode and oxidizing or reducing the ion to be processed that has moved to the counter electrode side.
In the ion transfer step to be processed, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density .
In the ion transfer step to be processed, the electrical connection between the direct electrode and the treatment liquid is cut and a voltage is applied to the indirect electrode to move the ions to be processed in the treatment liquid to the counter electrode side.
An electrolytic treatment method, characterized in that, in the ion treatment step, the direct electrode and the treatment liquid are electrically connected to oxidize or reduce the ions to be treated that have moved to the counter electrode side . In the arrangement step, a partition wall is arranged in which the treatment liquid is divided into two regions and an opening / closing mechanism for opening / closing the inflow / outflow hole of the treatment liquid is provided, and the partition wall is sandwiched so as to come into contact with the treatment liquid. The direct electrode and the counter electrode are arranged in the
In the ion transfer step to be processed, the inflow / outflow holes of the treatment liquid are closed by the opening / closing mechanism.
The electrolytic treatment method according to claim 9 , wherein in the ion treatment step to be treated, the inflow / outflow holes of the treatment liquid are opened by the opening / closing mechanism. In the arrangement step, a movement mechanism for moving the direct electrode directly with respect to the treatment liquid is arranged.
In the ion transfer step to be processed, the direct electrode is moved by the transfer mechanism to separate the direct electrode and the treatment liquid.
The electrolytic treatment method according to claim 9 , wherein in the ion treatment step to be treated, the direct electrode is moved by the moving mechanism to bring the direct electrode into contact with the treatment liquid. In the arrangement step, the direct electrode is arranged outside the treatment liquid, and a flow path for moving the treatment liquid by Coulomb force is arranged.
In the ion transfer step to be processed, the treatment liquid is moved through the flow path to separate the treatment liquid from the direct electrode.
The electrolytic treatment method according to claim 9 , wherein in the ion treatment step to be treated, the treatment liquid is moved through the flow path to bring the treatment liquid into direct contact with the electrode. In the arrangement step, the direct electrode is arranged outside the treatment liquid, and a liquid supply mechanism that contacts the direct electrode and supplies charged droplets is arranged.
In the ion transfer step to be processed, the supply of the charged droplets by the liquid supply mechanism is stopped.
The electrolytic treatment method according to claim 9 , wherein in the ion treatment step to be treated, the charged droplets are supplied to the treatment liquid by the liquid supply mechanism. The electrolytic treatment method according to any one of claims 1 to 13 , wherein an electric field is formed in the treatment liquid in the arrangement step. In the ion transfer step, a voltage is applied to the indirect electrode, and at least the applied voltage or capacitance of the indirect electrode is controlled to move a plurality of ions to be processed in the treatment liquid to the counter electrode side. Let me
After that, in the charge arrangement step, at least the applied voltage or capacitance of the indirect electrode is controlled, and the counter electrode is predetermined so as to correspond to the amount of ions to be treated that is equal to or less than the amount transferred in the ion transfer step. Arrange the charge at the charge arrangement position,
After that, in the ion treatment step, a current is passed through the direct electrode to oxidize the ion to be treated at a position corresponding to the predetermined charge arrangement position among the plurality of ions to be treated that have moved to the counter electrode side. Or reduce
The electrolysis treatment method according to any one of claims 1 to 14 , wherein the charge arrangement step and the ion treatment step to be treated are repeated in this order. The 15th aspect of the present invention, wherein the capacitance of the indirect electrode is controlled by dividing the indirect electrode into a plurality of parts and forming an electric field in the treatment liquid for each of the divided indirect electrodes. Electrolytic treatment method. In the ion transfer step, the plurality of ions to be processed are moved to the counter electrode side, and charges are arranged at positions corresponding to the plurality of ions to be processed on the counter electrode.
The thinning ratio, which is the ratio of the amount of charges arranged on the counter electrode in the ion transfer step to be processed, to the amount of charges arranged on the counter electrode in the charge arrangement step is a power of 2. The electrolytic treatment method according to claim 15 or 16 . In the charge arrangement step, the thinning rate in the region far from the counter electrode is increased as compared with the region near the counter electrode.
In the ion treatment step, the ions to be treated are reduced to form crystals.
17. The invention according to claim 17 , wherein after repeating the charge arrangement step and the ion treatment step to be treated, the particle size of the crystal formed in the region far from the counter electrode is increased as compared with the region near the counter electrode. Electrolytic treatment method. In the ion treatment step, the ions to be treated are reduced to form crystals.
Claims 15 to 18 are characterized in that, in the charge arrangement step, the distance between adjacent charges among the plurality of charges arranged at the predetermined charge arrangement position is an integral multiple of the size of the crystal lattice. The electrolytic treatment method according to any one of the above. An electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid.
A direct electrode and a counter electrode arranged so as to be electrically connected to the treatment liquid,
And indirect electrodes forming an electric field in the treatment liquid,
A partition wall in which the treatment liquid is divided into two regions and inflow / out holes of the treatment liquid are formed, a pore wall in which the treatment liquid is divided into two regions and a plurality of pores are formed, or the above. It has a pipe that divides the treatment liquid into two regions and connects the two regions .
When a voltage is applied to the indirect electrode, ions to be processed in the treatment liquid are moved to the counter electrode side.
The direct electrode and the indirect electrode are connected to the direct electrode and the indirect electrode to oxidize or reduce the ion to be processed that has moved to the counter electrode side.
When the ion to be processed is moved to the counter electrode side, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density .
An electrolytic treatment apparatus, characterized in that the direct electrode and the counter electrode are arranged so as to be in contact with the treatment liquid with the partition wall, the pore wall or the pipe sandwiched therein . Further having a switch for switching between the connection between the indirect electrode and the power supply and the connection between the indirect electrode and the direct electrode.
When moving the ion to be processed to the counter electrode side, the switch connects the indirect electrode and the power supply.
When oxidizing or reducing the ion to be processed that has moved to the counter electrode side, the switch is characterized in that the connection between the indirect electrode and the power supply is cut off and the indirect electrode and the direct electrode are connected. The electrolytic treatment apparatus according to claim 20 . An electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid.
A direct electrode and a counter electrode arranged so as to be electrically connected to the treatment liquid,
And indirect electrodes forming an electric field in the treatment liquid,
A first switch that switches between the connection between the indirect electrode and the power supply and the connection between the indirect electrode and the direct electrode.
It has a second switch for switching between the connection between the direct electrode and the indirect electrode and the connection between the direct electrode and the counter electrode .
When a voltage is applied to the indirect electrode, ions to be processed in the treatment liquid are moved to the counter electrode side.
The direct electrode and the indirect electrode are connected to the direct electrode and the indirect electrode to oxidize or reduce the ion to be processed that has moved to the counter electrode side.
When the ion to be processed is moved to the counter electrode side, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density .
The direct electrode and the counter electrode are arranged so as to be in contact with the treatment liquid.
When the ion to be processed is moved to the counter electrode side, the first switch connects the indirect electrode and the power supply, and the second switch connects the direct electrode and the counter electrode.
When oxidizing or reducing the ion to be processed that has moved to the counter electrode side, the first switch switches the connection with the indirect electrode from the power supply to the direct electrode, and the second switch is the direct. An electrolytic treatment apparatus, characterized in that the connection with the electrode is switched from the counter electrode to the indirect electrode, and the direct electrode and the indirect electrode are connected . The electrolysis treatment apparatus according to claim 22 , wherein the surface area of the direct electrode is smaller than the surface area of the counter electrode. An electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid.
A direct electrode and a counter electrode arranged so as to be electrically connected to the treatment liquid,
And indirect electrodes forming an electric field in the treatment liquid,
A partition wall in which the treatment liquid is divided into two regions and inflow / out holes of the treatment liquid are formed, a pore wall in which the treatment liquid is divided into two regions and a plurality of pores are formed, or the above. A pipe that divides the treatment liquid into two areas and connects the two areas,
A first switch that switches between the connection between the indirect electrode and the power supply and the connection between the indirect electrode and the direct electrode.
It has a second switch for switching between the connection between the direct electrode and the indirect electrode and the connection between the direct electrode and the counter electrode .
When a voltage is applied to the indirect electrode, ions to be processed in the treatment liquid are moved to the counter electrode side.
The direct electrode and the indirect electrode are connected to the direct electrode and the indirect electrode to oxidize or reduce the ion to be processed that has moved to the counter electrode side.
When the ion to be processed is moved to the counter electrode side, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density .
The direct electrode and the counter electrode are arranged so as to come into contact with the treatment liquid across the partition wall, the pore wall or the pipe.
When the ion to be processed is moved to the counter electrode side, the first switch connects the indirect electrode and the power supply, and the second switch connects the direct electrode and the counter electrode.
When oxidizing or reducing the ion to be processed that has moved to the counter electrode side, the first switch switches the connection with the indirect electrode from the power supply to the direct electrode, and the second switch is the direct. An electrolytic treatment apparatus, characterized in that the connection with the electrode is switched from the counter electrode to the indirect electrode, and the direct electrode and the indirect electrode are connected . An electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid.
A direct electrode and a counter electrode arranged so as to be electrically connected to the treatment liquid,
And indirect electrodes forming an electric field in the treatment liquid,
A plurality of the direct electrodes and a plurality of the indirect electrodes arranged so that the direct electrodes and the indirect electrodes are alternately arranged and in contact with the treatment liquid.
A partition wall provided between the direct electrode and the indirect electrode,
It has a switch for switching between the connection between the plurality of indirect electrodes and a power source and the connection between the plurality of indirect electrodes and the plurality of direct electrodes .
When a voltage is applied to the indirect electrode, ions to be processed in the treatment liquid are moved to the counter electrode side.
The direct electrode and the indirect electrode are connected to the direct electrode and the indirect electrode to oxidize or reduce the ion to be processed that has moved to the counter electrode side.
When the ion to be processed is moved to the counter electrode side, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density .
The counter electrode is arranged so as to extend in the direction in which the plurality of direct electrodes and the plurality of indirect electrodes are arranged.
When moving the ion to be processed to the counter electrode side, the switch connects the plurality of indirect electrodes and the power supply.
When oxidizing or reducing the ion to be processed that has moved to the counter electrode side, the switch disconnects the plurality of indirect electrodes and the power supply, and connects the plurality of indirect electrodes and the plurality of direct electrodes. An electrolytic processing apparatus characterized in that. A paddle of the treatment liquid is formed on the counter electrode.
The electrolytic treatment apparatus according to claim 25 , wherein the plurality of direct electrodes, the plurality of indirect electrodes, and the partition wall are arranged by being immersed in a paddle of the treatment liquid. Further having an electrode holding plate provided below the counter electrode at a position facing each other,
A paddle of the treatment liquid is formed between the electrode holding plate and the counter electrode.
The electrolytic treatment apparatus according to claim 25 , wherein the plurality of direct electrodes, the plurality of indirect electrodes, and the partition wall are arranged by being immersed in a paddle of the treatment liquid. An electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid.
A direct electrode and a counter electrode arranged so as to be electrically connected to the treatment liquid,
And indirect electrodes forming an electric field in the treatment liquid,
It has a partition wall that divides the treatment liquid into two regions and is provided with an opening / closing mechanism for opening and closing the inflow / outflow holes of the treatment liquid .
When a voltage is applied to the indirect electrode, ions to be processed in the treatment liquid are moved to the counter electrode side.
The direct electrode and the indirect electrode are connected to the direct electrode and the indirect electrode to oxidize or reduce the ion to be processed that has moved to the counter electrode side.
When the ion to be processed is moved to the counter electrode side, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density .
The direct electrode and the counter electrode are arranged so as to be in contact with the treatment liquid with the partition wall interposed therebetween.
When the ion to be processed is moved to the counter electrode side, the opening / closing mechanism closes the inflow / outflow hole of the processing liquid and disconnects the electrical connection between the direct electrode and the processing liquid.
When oxidizing or reducing the ion to be treated that has moved to the counter electrode side, the opening / closing mechanism opens an inflow / out hole of the treatment liquid to electrically connect the direct electrode and the treatment liquid. A featured electrolytic processing device. An electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid.
A direct electrode and a counter electrode arranged so as to be electrically connected to the treatment liquid,
And indirect electrodes forming an electric field in the treatment liquid,
It has a moving mechanism for freely moving the direct electrode with respect to the treatment liquid .
When a voltage is applied to the indirect electrode, ions to be processed in the treatment liquid are moved to the counter electrode side.
The direct electrode and the indirect electrode are connected to the direct electrode and the indirect electrode to oxidize or reduce the ion to be processed that has moved to the counter electrode side.
When the ion to be processed is moved to the counter electrode side, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density .
When the ion to be processed is moved to the counter electrode side, the moving mechanism moves the direct electrode to separate the direct electrode and the treatment liquid.
When oxidizing or reducing the ion to be treated that has moved to the counter electrode side, the moving mechanism moves the direct electrode so that the direct electrode and the treatment liquid are brought into contact with each other. .. An electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid.
A direct electrode and a counter electrode arranged so as to be electrically connected to the treatment liquid,
And indirect electrodes forming an electric field in the treatment liquid,
It has a flow path for moving the treatment liquid by Coulomb force .
When a voltage is applied to the indirect electrode, ions to be processed in the treatment liquid are moved to the counter electrode side.
The direct electrode and the indirect electrode are connected to the direct electrode and the indirect electrode to oxidize or reduce the ion to be processed that has moved to the counter electrode side.
When the ion to be processed is moved to the counter electrode side, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density .
The direct electrode is arranged outside the treatment liquid and
When the ion to be treated is moved to the counter electrode side, the flow path moves the treatment liquid to separate the treatment liquid from the direct electrode.
When oxidizing or reducing the ion to be treated that has moved to the counter electrode side, the flow path moves the treatment liquid so that the treatment liquid and the direct electrode are brought into contact with each other. .. An electrolytic treatment apparatus that performs a predetermined treatment using ions to be treated contained in the treatment liquid.
A direct electrode and a counter electrode arranged so as to be electrically connected to the treatment liquid,
And indirect electrodes forming an electric field in the treatment liquid,
It has a liquid supply mechanism that directly contacts the electrode and supplies charged droplets .
When a voltage is applied to the indirect electrode, ions to be processed in the treatment liquid are moved to the counter electrode side.
The direct electrode and the indirect electrode are connected to the direct electrode and the indirect electrode to oxidize or reduce the ion to be processed that has moved to the counter electrode side.
When the ion to be processed is moved to the counter electrode side, the current flowing between the direct electrode and the counter electrode is equal to or less than the limit current density .
The direct electrode is arranged outside the treatment liquid and
When the ion to be processed is moved to the counter electrode side, the liquid supply mechanism stops the supply of the charged droplet and disconnects the direct electrode and the treatment liquid.
When oxidizing or reducing the ion to be treated that has moved to the counter electrode side, the liquid supply mechanism supplies the charged droplets to the treatment liquid and electrically connects the direct electrode and the treatment liquid. An electrolytic treatment apparatus characterized in that it is used.

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