CN111982991B - A kind of rotating electrode device with hole and electrochemical test system - Google Patents

Abstract

The invention belongs to the technical field of electrode testing, and discloses a rotating electrode device with holes and an electrochemical testing system, wherein a disc electrode and a ring electrode are arranged on the upper side of an integrated polytetrafluoroethylene supporting body, and the ring electrode is arranged on the outer side of the disc electrode; polytetrafluoroethylene layers are arranged between the disc electrode and the ring electrode and outside the ring electrode; a first noble metal platinum layer is arranged on the upper side of the disc electrode, and a polytetrafluoroethylene film with a through hole is arranged on the upper side of the first noble metal platinum layer; the upper side of the ring electrode is provided with a second noble metal platinum layer. The polytetrafluoroethylene film with the through holes is provided with a plurality of through holes; the via diameters were 10 μm and 100 μm. The height of the disc electrode is 100 mu m lower than that of the ring electrode, and the upper side of the polytetrafluoroethylene film with the through hole is flush with the ring electrode. The invention can simultaneously simulate the conditions of the bottom of the hole and the copper surface during electroplating, improve the accuracy of the test and reduce the system error.

Description

A kind of rotating electrode device with hole and electrochemical test system

technical field

The invention belongs to the technical field of electrode testing, in particular to a rotating electrode device with holes and an electrochemical testing system.

Background technique

At present, the Rotating Ring Disk Electrode (RRDE) is an ideal electrochemical test instrument, which plays an important role in the study of various mechanisms of electrochemical reactions. RRDE is a kind of electrode with controllable rotation speed. Rotating at different rotation speeds in the reaction solution can simulate the convective diffusion rate of the solute in the reaction solution, that is, RRDE makes the diffusion controllable. Therefore, in the current electrochemical research, RRDE is one of the widely used electrodes. In the electrochemical study of electroplating copper hole filling, it is necessary to measure the electrochemical behavior of the electroplating additive on the copper surface and the bottom of the hole, so as to judge whether the additive system can realize bottom-up filling of blind holes. Typically, a lower RRDE speed is used to simulate a low convection rate situation at the bottom of the hole; a higher RRDE speed is used to simulate a high convective rate situation on the copper surface. To test the electrochemical behavior of copper plating additives with traditional RRDE electrodes, when it is necessary to simulate the electrochemical behavior of additives at the bottom of blind holes, a low electrode rotation speed (eg 100rpm) is required, and when it is necessary to simulate the electrochemical behavior of additives on the copper surface When the electrochemical behavior is high, a high electrode rotation speed (eg 1000 rpm) is required. If the traditional RRDE needs to measure the electrochemical behavior of the same additive at the bottom of the blind hole and on the copper surface, two tests are required; if repeated verification experiments are required, double the test time is required. In addition, there must be systematic errors in the two tests, which will affect the accuracy of the test results. Aiming at the above shortcomings, the present invention particularly relates to a rotating ring-disc electrode device with holes, which further innovates the traditional rotating ring-disc electrode.

Through the above analysis, the problems and defects of the prior art are as follows: since the disc electrode and the ring electrode of the traditional RRDE are on the same plane, the two situations that need to be tested cannot be simulated at the same time. When the traditional RRDE is used to test the electrochemical behavior of the blind hole filling additive, it is necessary to measure the electrochemical signal of the additive before and after using two high and low rotational speeds with the same two electroplating solution systems, in order to obtain the molecular weight of the additive. Electrochemical behavior of copper surface and hole bottom. Since the experimental results are measured by two electroplating solution systems, there must be some systematic errors in the experimental data. Furthermore, performing two electrochemical tests in order to obtain suitable data adds to the time cost.

The difficulty of solving the above problems and defects is: medium. Since the existing traditional RRDE electrodes are relatively ideal for general electrochemical testing, but for the electrochemical testing of electroplated copper hole-filling additives, the traditional RRDE shows its shortcomings, so the traditional RRDE is further investigated. Innovation, so as to be more suitable for electrochemical testing of electroplating copper hole filling additives.

The significance of solving the above problems and defects is: for the field of electrochemical testing, the accuracy of electrochemical testing is further improved. For the mechanism research of electroplating copper hole filling, the actual electroplating situation is more accurately and completely simulated, which improves the accuracy of the electrochemical experimental results and the fit with the actual situation.

SUMMARY OF THE INVENTION

In order to solve the problems existing in the prior art, the present invention provides a rotating electrode device with holes and an electrochemical testing system.

The present invention is achieved in that a rotating electrode device with a hole is provided with:

Integrated PTFE support;

A disc electrode and a ring electrode are arranged on the upper side of the integrated polytetrafluoroethylene support, and the ring electrode is arranged on the outside of the disc electrode; The outer sides of the electrodes are all provided with PTFE insulating layers;

A first precious metal platinum layer is arranged on the upper side of the disc electrode, and a PTFE film with through holes is arranged on the upper side of the first precious metal platinum layer; and a second precious metal platinum layer is arranged on the upper side of the ring electrode .

Further, the integrated polytetrafluoroethylene support is a hollow cylinder, and a conductor layer is provided inside the integrated polytetrafluoroethylene support;

Further, a plurality of through holes are opened on the PTFE film with through holes; the diameter of the through holes is 10 μm and the depth is 100 μm.

Another through hole on the PTFE film with through holes has a diameter of 100 μm and a depth of 100 μm.

Further, the height of the disk electrode is 100 μm lower than that of the ring electrode, and the upper side of the PTFE film with through holes is flush with the ring electrode.

Further, the axes of the integrated polytetrafluoroethylene support, the disc electrode, the ring electrode and the polytetrafluoroethylene layer are all on the same straight line.

Another object of the present invention is to provide an application method of a rotating electrode device with a hole, comprising:

The electrode simulates an actual blind hole, and the plating solution diffuses through the teflon film with through holes through convection and reaches the disc electrode for reaction.

Specifically, when BV-RRDE was used to test the electrochemical behavior of electroplating additives, the electrode surface of a rotating electrode with holes (Blind Via-Rotating Ring Disk Electrode, BV-RRDE) was first immersed in the plating solution, and the electrode rotation speed was selected. A constant value is used to simulate the air stirring speed during actual electroplating, and then the additive molecules in the plating solution interact with the electrode surface to carry out an electrochemical reaction. The additive molecules adsorbed on the ring electrode are similar to the additive molecules adsorbed on the copper surface during actual electroplating; the additive molecules adsorbed on the disk electrode through the convective diffusion through the through holes of the PTFE film with through holes are similar to the actual electroplating. At this time, the additive molecules are adsorbed to the bottom of the pores through convective diffusion. Therefore, in this electrochemical test, as long as the electrical signals of the ring electrode and the disk electrode are collected by an electrochemical workstation, the electrochemical behavior data of the additives at the bottom of the hole and the copper surface can be obtained at the same time.

Another object of the present invention is to provide an electrochemical test system for testing the electrochemical performance of the rotating electrode device with holes, the electrochemical test system is an electrochemical test system with BV-RRDE, and at the same time , the interaction between the additive molecules in the plating solution on the copper surface and the bottom of the blind hole was tested in the same plating solution system.

Another object of the present invention is to provide an electrochemical test instrument equipped with the rotating electrode device with holes.

Combined with all the above technical solutions, the advantages and positive effects of the present invention are: the present invention can simultaneously simulate the situation of the bottom of the through hole and the copper surface during electroplating, so the present invention can improve the accuracy of the test and reduce the system error.

The invention can simulate the situation of the micro-blind hole bottom and copper surface of different sizes in the actual electroplating process, so that the electrochemical behavior of additives and the deposition of copper ions measured by the electrochemical workstation are more suitable for actual electroplating, and the accuracy of experimental data is improved. Accuracy. In addition, since the electrode simulates both the hole bottom and the copper surface, it avoids the need to simulate two test conditions with different rotational speeds using traditional RRDE.

Description of drawings

In order to explain the technical solutions of the embodiments of the present application more clearly, the following will briefly introduce the drawings that need to be used in the embodiments of the present application. Obviously, the drawings described below are only some embodiments of the present application. For those of ordinary skill in the art, other drawings can also be obtained from these drawings without creative effort.

1 is a schematic structural diagram of a rotating electrode device with holes provided by an embodiment of the present invention;

2 is a schematic cross-sectional structure diagram of a rotating electrode device with holes provided by an embodiment of the present invention;

In the figure: 1. Integrated PTFE support; 2. Second precious metal platinum layer; 3. PTFE film with through holes; 4. First precious metal platinum layer; 5. Ring electrode; 6. Through hole; 7. Conductor layer (internal conductor of BV-RRDE); 8. Disk electrode; 9. Simulated blind hole.

FIG. 3 is a comparison diagram of simulating actual blind holes of the rotating electrode device with holes provided by the embodiment of the present invention.

Detailed ways

In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

In view of the problems existing in the prior art, the present invention provides a rotating electrode device with holes and an electrochemical test system. The present invention will be described in detail below with reference to the accompanying drawings.

As shown in FIG. 1 to FIG. 2 , the rotating electrode device with holes provided by the present invention includes: an integrated polytetrafluoroethylene support 1, a second precious metal platinum layer 2, a polytetrafluoroethylene film with through holes 3, First precious metal platinum layer 4, ring electrode ((ring electrode and its platinum-coated surface)) 5, through hole 6, conductor layer 7, disc electrode ((indented disc electrode and its platinum-coated surface)) 8.

A polytetrafluoroethylene insulating layer is spaced between the ring electrode 5 and the disk electrode 8 .

The integrated polytetrafluoroethylene support 1 in this embodiment is made of polytetrafluoroethylene or other acid-resistant materials. The inner side of the integrated polytetrafluoroethylene support 1 is provided with a disc electrode 8 and a ring electrode 5, and the ring electrode 5 is provided with On the outside of the disk electrode 8; between the disk electrode 8 and the ring electrode 5 and on the outside of the ring electrode 5, a polytetrafluoroethylene insulating layer is provided; the integrated polytetrafluoroethylene support 1, the disk electrode 8, the The axes of the ring electrode 5 and the Teflon layer are on the same straight line.

The upper side of the disc electrode 8 is provided with a first precious metal platinum layer 4, the upper side of the first precious metal platinum layer 5 is provided with a PTFE film 3 with through holes; the upper side of the circular electrode 5 is provided with a second precious metal platinum layer 2 .

In this embodiment, the integrated polytetrafluoroethylene support body 1 is a hollow cylinder inside, and a conductor layer 7 is provided inside the integrated polytetrafluoroethylene support body 1 .

In this embodiment, a plurality of through holes 6 are opened on the PTFE film 3 with through holes; the diameter of the through holes 6 is 10 μm and the depth is 100 μm.

Another through hole on the PTFE film with through holes has a diameter of 100 μm and a depth of 100 μm.

Among them, the 10μm through hole diameter simulates the through-silicon via (TSV) used in the field of advanced packaging technology,

The 100 μm through hole diameter simulates a blind hole 9 in a high-density printed circuit board (PCB);

Two through holes with different apertures are respectively on the two electrodes, that is, the Teflon film 3 of one rotating electrode only contains through holes with one aperture.

In this embodiment, the height of the disk electrode 8 is 100 μm lower than that of the ring electrode 5 , and the upper side of the PTFE film 3 with through holes is flush with the ring electrode 5 .

The working principle of the present invention is as follows: as shown in FIG. 3 , the second noble metal platinum layer 2 under the ring electrode 5 is equivalent to the actual copper surface area, and the disc electrode 8 above the PTFE film 3 with through holes is equivalent to the actual copper surface area. The first precious metal platinum layer 5 corresponds to the actual hole bottom area.

The copper plating solution directly reacts with the second precious metal platinum layer 2 of the ring electrode 5, that is, the copper plating solution directly contacts and reacts with the actual copper surface, and the copper plating solution needs to be convectively diffused through the PTFE film 3 with through holes to reach The first precious metal platinum layer 4 of the disk electrode 8 reacts, that is, the copper plating solution needs to diffuse through the actual blind hole 9 to reach the bottom of the actual blind hole for reaction.

On the surfaces of the first noble metal platinum layer 4 and the second noble metal platinum layer 2, copper ions are obtained from the electrodes, and electrons are reduced to copper element and deposited on the surface of the electrodes. The circular electrodes 5 are collected separately using an electrochemical test system with BV-RRDE. And the electrochemical signal of the disk electrode 8, the interaction effect of the additive molecules in the copper plating solution on the actual copper surface and the actual bottom of the through hole can be tested in the same copper plating solution system at the same time, avoiding the traditional The RRDE can only simulate the situation of the actual blind hole bottom and the actual copper surface through different rotational speeds.

In the description of the present invention, unless otherwise stated, "plurality" means two or more; the terms "upper", "lower", "left", "right", "inner", "outer" The orientation or positional relationship indicated by , "front end", "rear end", "head", "tail", etc. are based on the orientation or positional relationship shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, not An indication or implication that the referred device or element must have a particular orientation, be constructed and operate in a particular orientation, is not to be construed as a limitation of the invention. Furthermore, the terms "first," "second," "third," etc. are used for descriptive purposes only and should not be construed to indicate or imply relative importance.

The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited to this. Any person skilled in the art is within the technical scope disclosed by the present invention, and all within the spirit and principle of the present invention Any modifications, equivalent replacements and improvements made within the scope of the present invention should be included within the protection scope of the present invention.

Claims (9)

1. A rotary electrode device with a hole, characterized in that it is provided with:

an integral polytetrafluoroethylene support;

a disc electrode and a ring electrode are arranged on the upper side of the integrated polytetrafluoroethylene supporting body, and the ring electrode is arranged on the outer side of the disc electrode; polytetrafluoroethylene layers are arranged between the disc electrode and the ring electrode and outside the ring electrode;

a first noble metal platinum layer is arranged on the upper side of the disc electrode, and a polytetrafluoroethylene film with a through hole is arranged on the upper side of the first noble metal platinum layer; and a second noble metal platinum layer is arranged on the upper side of the circular ring electrode.

2. The rotatable electrode assembly with holes of claim 1, wherein the integrated teflon support is a cylinder with a hollow interior and a conductive layer is disposed inside the integrated teflon support.

3. The rotatable electrode assembly with hole of claim 1, wherein the polytetrafluoroethylene membrane with through holes has a plurality of through holes; the diameter of the through hole is 10 mu m, and the depth of the through hole is 100 mu m;

the other through hole on the polytetrafluoroethylene film with the through hole has the diameter of 100 mu m and the depth of 100 mu m.

4. The rotatable electrode assembly with the aperture of claim 1, wherein the disk electrode height is 100 μm lower than the ring electrode.

5. The rotatable electrode assembly with an orifice of claim 1 wherein the upper side of the ptfe membrane with the through-hole is flush with the annular electrode.

6. The rotatable electrode assembly with holes of claim 1, wherein the axes of the integrated ptfe support, the disk electrode, the ring electrode, and the ptfe layer are all collinear.

7. A method of using a rotating electrode assembly having a hole, the method comprising:

the electrode simulates an actual blind hole, and plating solution passes through a polytetrafluoroethylene film with a through hole through convection diffusion and reaches the disc electrode for reaction.

8. An electrochemical test system for testing the electrochemical performance of the rotating electrode device with the hole according to any one of claims 1 to 6, wherein the electrochemical test system is an electrochemical test system of the rotating electrode with the hole, and the interaction condition of additive molecules in the plating solution with the bottom of the hole on the copper surface is tested in the same plating solution system at the same time.

9. An electrochemical test apparatus equipped with the rotary electrode device with a hole according to any one of claims 1 to 6.

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