CN111982991B - Rotary electrode device with hole and electrochemical test system - Google Patents
Rotary electrode device with hole and electrochemical test system Download PDFInfo
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- CN111982991B CN111982991B CN202010872044.9A CN202010872044A CN111982991B CN 111982991 B CN111982991 B CN 111982991B CN 202010872044 A CN202010872044 A CN 202010872044A CN 111982991 B CN111982991 B CN 111982991B
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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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
Technical Field
The invention belongs to the technical field of electrode testing, and particularly relates to a rotary electrode device with holes and an electrochemical testing system.
Background
At present, a Rotating Ring Disk Electrode (RRDE) is an ideal electrochemical testing instrument and plays an important role in researching various mechanisms of electrochemical reactions. RRDE is an electrode with controllable rotation speed, and the rotation speed in the reaction solution can simulate the convective diffusion rate of solute in the reaction solution, namely RRDE changes the diffusion into controllable. Therefore, in the current electrochemical research, RRDE is one of the more widely used electrodes. In the electrochemical research of filling holes with electroplated copper, the electrochemical behaviors of the electroplating additive on the copper surface and the hole bottom need to be respectively measured, so that whether the additive system can realize the bottom-up filling of the blind holes is judged. Under the normal condition, the low convection rate condition of the hole bottom is simulated by using the low rotation speed of RRDE; the high convection rate condition of the copper surface is simulated by the higher rotation speed of RRDE. If conventional RRDE electrodes are to be used to test the electrochemical behavior of the copper plating additive, a low electrode speed (e.g., 100rpm) is required when it is desired to simulate the electrochemical behavior of the additive at the bottom of the blind via, and a high electrode speed (e.g., 1000rpm) is required when it is desired to simulate the electrochemical behavior of the additive on the copper surface. If the traditional RRDE needs to measure the electrochemical behaviors of the same additive on the bottom of a blind hole and the copper surface, two times of tests are needed; if repeated verification experiments are also required, double the test time is also required. In addition, the two tests must have system errors, which affects the accuracy of the test result. The present invention addresses the above deficiencies and, in particular, relates to a rotating ring-disk electrode assembly with holes that further improves upon conventional rotating ring-disk electrodes.
Through the above analysis, the problems and defects of the prior art are as follows: because the disc electrode and the ring electrode of the traditional RRDE are on the same plane, two conditions needing to be tested can not be simulated and tested at the same time. When the traditional RRDE is used for testing the electrochemical behavior of the blind hole filling additive, the electrochemical behavior of the molecules of the additive on the copper surface and the hole bottom can be obtained only by measuring the electrochemical signal of the additive under the action of the additive before and after matching two electroplating liquid systems with the same rotating speed at high and low speeds. As the experimental results are measured by two electroplating liquid systems, certain system errors necessarily exist in the experimental data. Furthermore, performing two electrochemical tests in order to obtain suitable data increases the time cost.
The difficulty in solving the above problems and defects is: medium, etc. Since the conventional RRDE electrodes are relatively ideal for general electrochemical testing, but exhibit their shortcomings for electrochemical testing of electroplated copper fill additives, further innovations have been made in conventional RRDE to better suit electrochemical testing of electroplated copper fill additives.
The significance of solving the problems and the defects is as follows: for the field of electrochemical testing, the accuracy of electrochemical testing is further improved. For the mechanism research of the electro-coppering hole filling, the actual electro-coppering situation is simulated more accurately and more completely, and the accuracy of the electrochemical experimental result and the fitting degree with the actual situation are improved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a rotary electrode device with holes and an electrochemical testing system.
The present invention is achieved by a rotary electrode apparatus with a hole 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 insulating 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.
Further, the integrated polytetrafluoroethylene supporting body is a cylinder with a hollow inner part, and a conductor layer is arranged inside the integrated polytetrafluoroethylene supporting body;
furthermore, a plurality of through holes are formed in the polytetrafluoroethylene film with the 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.
Further, the height of the disc electrode is lower than that of the ring electrode by 100 microns, and the upper side of the polytetrafluoroethylene film with the through hole 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 a method for applying a rotating electrode device with a hole, 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.
Specifically, when BV-RRDE is used for testing the electrochemical behavior of the electroplating additive, the Electrode surface of a Rotating Electrode (BV-RRDE) with holes is immersed into the electroplating solution, the Rotating speed of the Electrode is selected to be a constant value to simulate the air stirring speed in actual electroplating, and then additive molecules in the electroplating solution interact with the Electrode surface to perform electrochemical reaction. Additive molecules adsorbed on the circular ring electrode are like additive molecules adsorbed on the copper surface during actual electroplating; the additive molecules adsorbed to the disk electrode by convection diffusion through the through-holes of the through-hole polytetrafluoroethylene film are adsorbed to the bottom of the holes by convection diffusion as in the case of actual plating. Therefore, the electrochemical test can simultaneously obtain the electrochemical behavior data of the additives on the bottom and the copper surface of the hole by only collecting the electric signals of the ring electrode and the disc electrode by using an electrochemical workstation.
The invention also aims to provide an electrochemical testing system for testing the electrochemical performance of the rotary electrode device with the hole, wherein the electrochemical testing system is an electrochemical testing system with BV-RRDE, and the interaction condition of additive molecules in the plating solution and the bottom of the blind hole on the copper surface is tested in the same plating solution system at the same time.
Another object of the present invention is to provide an electrochemical test apparatus carrying the rotary electrode device with holes.
By combining all the technical schemes, the invention has the advantages and positive effects that: the invention can simultaneously simulate the conditions of the bottom of the through hole and the copper surface during electroplating, thereby improving the test accuracy and reducing the system error.
The invention can simulate the conditions of the bottom and the copper surface of the micro blind hole with different sizes in the actual electroplating process, so that the electrochemical behavior of the additive and the deposition condition of copper ions measured by an electrochemical workstation are more fit for the actual electroplating, and the accuracy of experimental data is improved. In addition, because the electrode simulates the conditions of the hole bottom and the copper surface at the same time, the situation that the traditional RRDE needs to simulate two test conditions by different rotating speeds is avoided.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained from the drawings without creative efforts.
FIG. 1 is a schematic diagram of a rotary electrode assembly with holes according to an embodiment of the present invention;
FIG. 2 is a schematic cross-sectional view of a rotatable electrode assembly with holes according to an embodiment of the present invention;
in the figure: 1. an integral polytetrafluoroethylene support; 2. a second noble metal platinum layer; 3. a polytetrafluoroethylene film with through holes; 4. a first noble metal platinum layer; 5. a ring electrode; 6. a through hole; 7. a conductor layer (inner conductor of BV-RRDE); 8. a disk electrode; 9. simulating a blind hole.
FIG. 3 is a comparison diagram of a rotary electrode device with holes simulating actual blind holes, provided by an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In view of the problems of the prior art, the present invention provides a rotary electrode device with holes and an electrochemical testing system, and the present invention will be described in detail with reference to the accompanying drawings.
As shown in fig. 1 to 2, the present invention provides a rotary electrode device with holes, comprising: an integrated polytetrafluoroethylene support 1, a second noble metal platinum layer 2, a polytetrafluoroethylene film 3 with a through hole, a first noble metal platinum layer 4, a ring electrode ((ring electrode and platinum-coated surface thereof)) 5, a through hole 6, a conductor layer 7, and a disc electrode ((retracted disc electrode and platinum-coated surface thereof)) 8.
A polytetrafluoroethylene insulating layer is arranged between the circular ring electrode 5 and the disc electrode 8 at intervals.
The integrated polytetrafluoroethylene support 1 of the embodiment is made of polytetrafluoroethylene or other acid-resistant materials, a disc electrode 8 and a ring electrode 5 are arranged on the inner side of the integrated polytetrafluoroethylene support 1, and the ring electrode 5 is arranged on the outer side of the disc electrode 8; polytetrafluoroethylene insulating layers are arranged between the disc electrode 8 and the ring electrode 5 and outside the ring electrode 5; the axes of the integrated polytetrafluoroethylene supporting body 1, the disc electrode 8, the ring electrode 5 and the polytetrafluoroethylene layer are all on the same straight line.
A first noble metal platinum layer 4 is arranged on the upper side of the disc electrode 8, and a polytetrafluoroethylene film 3 with a through hole is arranged on the upper side of the first noble metal platinum layer 5; the upper side of the ring electrode 5 is provided with a second noble metal platinum layer 2.
In this embodiment, the integrated polytetrafluoroethylene support 1 is a hollow cylinder, and the conductor layer 7 is provided inside the integrated polytetrafluoroethylene support 1.
In the embodiment, the polytetrafluoroethylene film 3 with the through holes is provided with a plurality of through holes 6; the through-holes 6 have a diameter of 10 μm and a depth of 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.
Wherein, the simulation of the through hole diameter of 10 μm is a silicon through hole (TSV) used in the advanced packaging technology field,
a 100 μm through hole diameter simulates a blind hole 9 in a high density Printed Circuit Board (PCB);
the two through holes with different apertures are respectively arranged on the two electrodes, namely the polytetrafluoroethylene film 3 of one rotating electrode only contains the through hole with one aperture.
In this embodiment, the height of the disc electrode 8 is lower than the ring electrode 5100 μm, and the upper side of the polytetrafluoroethylene film 3 with the through hole is flush with the ring electrode 5.
The working principle of the invention is as follows: as shown in FIG. 3, the second noble metal platinum layer 2 under the ring electrode 5 corresponds to the actual copper surface area, and the first noble metal platinum layer 5 of the disk electrode 8 over the through-hole polytetrafluoroethylene film 3 corresponds to the actual hole bottom area.
The copper plating solution directly contacts with the second noble metal platinum layer 2 of the ring electrode 5 for reaction, namely the copper plating solution directly contacts with the actual copper surface for reaction, the copper plating solution can reach the first noble metal platinum layer 4 of the disc electrode 8 for reaction only by convection diffusion through the polytetrafluoroethylene film 3 with the through hole, namely the copper plating solution can reach the bottom of the actual blind hole for reaction only by diffusion through the actual blind hole 9.
The copper ions on the surfaces of the first noble metal platinum layer 4 and the second noble metal platinum layer 2 are reduced into copper simple substances from the electrodes and deposited on the surfaces of the electrodes, electrochemical testing systems with BV-RRDE are used for collecting electrochemical signals of the ring electrode 5 and the disc electrode 8 respectively, and the interaction effect of additive molecules in 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, so that the condition that the actual bottom of the blind hole and the actual copper surface can only be simulated by the traditional RRDE at different rotating speeds is avoided.
In the description of the present invention, "a plurality" means two or more unless otherwise specified; the terms "upper", "lower", "left", "right", "inner", "outer", "front", "rear", "head", "tail", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, should not be construed as limiting the invention. Furthermore, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010872044.9A CN111982991B (en) | 2020-08-26 | 2020-08-26 | Rotary electrode device with hole and electrochemical test system |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010872044.9A CN111982991B (en) | 2020-08-26 | 2020-08-26 | Rotary electrode device with hole and electrochemical test system |
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| Publication Number | Publication Date |
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| CN111982991A CN111982991A (en) | 2020-11-24 |
| CN111982991B true CN111982991B (en) | 2022-04-29 |
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| Application Number | Title | Priority Date | Filing Date |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2746391Y (en) * | 2004-11-19 | 2005-12-14 | 江苏江分电分析仪器有限公司 | Ring-disk electrode body |
| JP2008184681A (en) * | 2007-01-31 | 2008-08-14 | Osaka Prefecture Univ | Method of monitoring electrolytic copper plating solution of wiring board or semiconductor circuit |
| EP2019308A2 (en) * | 2007-07-14 | 2009-01-28 | DECHEMA Gesellschaft für Chemische Technik und Biotechnologie e.V. | Device for spectroscopic characterisation of electrochemical reactive products fixed to an electrode |
| CN104422721A (en) * | 2013-09-06 | 2015-03-18 | 波音公司 | Device and method for determining fluid streaming potential |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8535504B2 (en) * | 2010-05-03 | 2013-09-17 | Eci Technology, Inc. | Analysis of an auxiliary leveler additive in an acid copper plating bath |
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2020
- 2020-08-26 CN CN202010872044.9A patent/CN111982991B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2746391Y (en) * | 2004-11-19 | 2005-12-14 | 江苏江分电分析仪器有限公司 | Ring-disk electrode body |
| JP2008184681A (en) * | 2007-01-31 | 2008-08-14 | Osaka Prefecture Univ | Method of monitoring electrolytic copper plating solution of wiring board or semiconductor circuit |
| EP2019308A2 (en) * | 2007-07-14 | 2009-01-28 | DECHEMA Gesellschaft für Chemische Technik und Biotechnologie e.V. | Device for spectroscopic characterisation of electrochemical reactive products fixed to an electrode |
| CN104422721A (en) * | 2013-09-06 | 2015-03-18 | 波音公司 | Device and method for determining fluid streaming potential |
Non-Patent Citations (1)
| Title |
|---|
| Experimental and Simulation Investigations of Copper Reduction Mechanism with and without Addition of SPS;Litao Yin 等;《Journal of The Electrochemical Society》;20180918;第D604-D611页 * |
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| CN111982991A (en) | 2020-11-24 |
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