CN103698384B - The measuring method of deep hole copper facing accelerator - Google Patents
The measuring method of deep hole copper facing accelerator Download PDFInfo
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- CN103698384B CN103698384B CN201310697804.7A CN201310697804A CN103698384B CN 103698384 B CN103698384 B CN 103698384B CN 201310697804 A CN201310697804 A CN 201310697804A CN 103698384 B CN103698384 B CN 103698384B
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Abstract
The present invention relates to a kind of measuring method of deep hole copper facing accelerator, comprise the steps: that step (1) selects metal electrode as working electrode, inert metal sheet is to electrode, and saturated calomel electrode is contrast electrode, and composition three-electrode system, selects copper electroplating liquid; Step (2) is measured not containing the cathodic polarization curve of the basic bath of accelerator; Step (3) adds the accelerator of variable concentrations in above-mentioned basic bath, measures corresponding cathodic polarization curve respectively; Step (4) compares the cathodic polarization curve of (2) and (3), analyzes the correlation parameter on described curve, obtains the quantitative relationship curve of relevant electrochemical parameter and accelerator concentration; Step (5) adopts same electrode system to measure actual copper electrolyte to be determined, obtains result.Present invention employs cathodic polarization curve as determination object, more closing to reality electroplating process, thus directive function is produced to copper electroplating liquid management and process quality control, promote the industrial applications of TSV copper plating process.
Description
Technical field
The invention belongs to semiconductor manufacturing, membraneous material manufacture and electrochemical techniques application, be specifically related to a kind of measuring method of deep hole copper facing accelerator.
Background technology
At present, more and more extensive in field of microelectronic fabrication application for the deep hole copper facing technology such as wiring and the vertical copper-connection of silicon through hole in chip Damascus copper-connection, pcb board, and the large absolutely degree of the copper-plated complete filling technique of these deep holes depends on the effect of adjuvant, current, different according to the effect of adjuvant, can roughly divide three kinds, respectively: accelerator, inhibitor and leveling agent, according to existing documents and materials, what play a major role in the process that deep hole copper facing is filled is accelerator and inhibitor.And mostly be organic surface active agent due to the adjuvant played a crucial role in plating solution, its concentration only has ppm magnitude, and in use also can produce the various decomposition product affecting filling effect, to the analysis of these micro constitutents and filling effect evaluation very difficult, make the plating solution maintenance of deep hole copper facing filling technique and production management very difficult, lag far behind the exploitation of adjuvant and technology.The content of inhibitor is generally a hundreds of ppm, and when reality is electroplated, its content is generally state of saturation, and the content of accelerator is generally several to dozens of ppm, and in plating, there is larger decomposition and consumption, need timing to supplement, therefore the mensuration of its content seems very important.
2003, ECITechnology company of the U.S. takes the lead in proposing three kinds of crucial adjuvant (inhibitor in copper plating bath, leveling agent and brightener) cyclic voltammetric stripping method (CyclicVoltammetryStripping, the CVS) analytical approach of concentration, and achieve United States Patent (USP).CVS method is mainly based in the galvanochemistry volt-ampere curve on platinum electrode, and in additive concentration and anodic process, the quantitative relationship of the meltage of copper, analyzes a kind of indirect measurement method of organic additive content in plating solution.However, because the method carries out measuring based on the dissolving total amount of copper in anodic process, so this analytical approach cannot evaluate affect filling effect cathodic process, judge the effect of adjuvant in electro-deposition, to the selected of technological parameter and optimization, the assessment of bath life seems helpless.Therefore need a kind of method, the action effect of adjuvant in actual electroplating process can be evaluated, thus directive function is played to the copper filling process in hole.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of measuring method of deep hole copper facing accelerator is provided, present invention employs cathodic polarization curve as research object, according to the current peak occurred on electrochemical profiles and electric current paddy, utilize the change of the difference of accelerating effect area or current/voltage peak valley, obtain the relation of accelerator content and correlation parameter, more closing to reality electroplating process, thus directive function is produced to copper electroplating process, promote the application of deep hole copper facing filling technique.
The object of the invention is to be achieved through the following technical solutions, the present invention relates to a kind of measuring method of deep hole copper facing accelerator, comprise the steps:
Step (1) selects metal electrode as working electrode, and inert metal sheet is to electrode, and saturated calomel electrode is contrast electrode, and composition three-electrode system, selects copper electroplating liquid;
Step (2) is measured not containing the cathodic polarization curve of the basic bath of accelerator;
Step (3) adds the accelerator of variable concentrations in above-mentioned basic bath, measures corresponding cathodic polarization curve respectively;
Step (4) compares the cathodic polarization curve of (2) and (3), analyzes the correlation parameter on described curve, obtains the quantitative relationship curve of relevant electrochemical parameter and accelerator concentration;
Step (5) adopts same electrode system to measure actual copper electrolyte to be determined, calculates corresponding electrochemical parameter, by with above-mentioned quantitative relationship curve comparison, obtain accelerator content in determined copper electrolyte.
Preferably, described metal electrode, comprises carbon electrode and silver, gold, ruthenium, rhodium, palladium, osmium, iridium or platinum or its alloy.
Preferably, described inert electrode, comprises carbon electrode, gold or platinum group metal.
Preferably, described copper electroplating liquid, comprises the negative ion of sulfate, pyrophosphate, sulfamate or alkyl sulfonate, 0 ~ 100ppm chlorion, the copper ion of 0.3 ~ 100mol/L, and hydrogen ion is 0.001 ~ 2mol/L.
Preferably, described basic bath comprises inhibitor, leveling agent.
Preferably, described accelerator is for containing sulfenyl and sulfonic short chain compound.
Preferably, described accelerator concentration is 0.5 ~ 100ppm.
Preferably, described cathodic polarization curve adopts cyclic voltammetry or linear sweep voltammetry and obtains.
Preferably, described correlation parameter comprises electric current, voltage, accelerating effect area, Δ I, Δ U.
Preferably, the assay method of described accelerator content, comprises linear function, polynomial expression, the multiple accelerator content of exponential function and the relation of accelerating effect area.
Compared with prior art, beneficial effect of the present invention is as follows: present invention employs cathodic polarization curve as determination object, according to the current peak occurred on electrochemical profiles and electric current paddy, utilize the change of the difference of accelerating effect area or current/voltage peak valley, obtain the relation of accelerator content and correlation parameter, more closing to reality electroplating process, thus directive function is produced to copper electroplating liquid management and process quality control, promote the industrial applications of TSV copper plating process.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is cathodic polarization curve parameter schematic diagram.
Fig. 2 is 40g/LCu
2+, 50ppmCl
-, 300ppmPEG, pH value be 1 plating solution add the cathodic polarization curve of different content SPS.
Fig. 3 is 40g/LCu
2+, 50ppmCl
-, 300ppmPEG, pH value be 1 plating solution add the change curve of the accelerating effect area of different content SPS.
Fig. 4 is 40g/LCu
2+, 50ppmCl
-, 300ppmPEG, pH value be 1 plating solution add the change curve of the Δ I of different content SPS.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
embodiment 1
The present embodiment relates to the assay method of a kind of copper-connection plating accelerator content, and concrete steps are as follows:
(1) adopt Au electrode as working electrode, TSV copper electroplate liquid is electrolytic solution, and saturated calomel electrode is contrast electrode, and platinized platinum is to electrode composition three-electrode system,
(2) cathodic polarization curve of Fundamentals of Measurement plating solution, basic bath forms: copper ion concentration is 40g/L, and chlorine ion concentration is 50ppm, and pH value is 1;
(3) in basic bath, add the polyglycol (PEG) of 300ppm, measure its cathodic polarization curve, as shown in Fig. 2 (0), can be observed the inhibiting effect of PEG.
(4) in basic bath, add the PEG of 300ppm, and keep concentration constant, and then in plating solution, add the sodium polydithio-dipropyl sulfonate (SPS) of variable concentrations, concentration range is 0 ~ 6ppm, measures its cathodic polarization curve respectively; Fig. 1 is the signal of cathodic polarization curve parameter.And compared with the LSV curve adding 300ppmPEG single in basic bath, as shown in Figure 2.As seen from the figure, after adding the SPS of 1ppm, there is above-mentioned current peak.Continue add SPS, when SPS content arrive 2ppm time, current peak and electric current paddy fairly obvious.This is due to the suction-operated at low-voltage region mainly SPS, SPS dosage is larger more in the amount of electrode surface at this stage adsorption, current peak is larger, and replace SPS gradually at high-voltage region PEG and be adsorbed on electrode surface, at low ebb place, PEG instead of most SPS, inhibiting effect is maximum, reaches electric current valley.
(5) calculate the accelerating effect area of the cathodic polarization curve of the SPS of variable concentrations respectively, obtain along with SPS content, the change curve of accelerating effect area.As shown in Figure 3, when SPS content is less than 2, the change of accelerating effect area almost point-blank, illustrate when SPS content is less, area is directly proportional to SPS content, we can obtain the relational expression of SPS content and accelerating effect area thus, thus this relational expression can be utilized to carry out corresponding with the corresponding parameter of the cathodic polarization curve of actual electroplate liquid, obtain the content of SPS.
(6) calculate the Δ I of the cathodic polarization curve of the SPS of variable concentrations respectively, obtain along with SPS content, the change curve of Δ I.As shown in Figure 4, when SPS content is less than 2, the change of Δ I almost point-blank, illustrate when SPS content is less, Δ I is directly proportional to SPS content, we can obtain the relational expression of SPS content and Δ I thus, thus this relational expression can be utilized to carry out corresponding with the corresponding parameter of the cathodic polarization curve of actual electroplate liquid, obtain the content of SPS.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (9)
1. a measuring method for deep hole copper facing accelerator, is characterized in that, comprises the steps:
Step (1) selects metal electrode as working electrode, and inert metal sheet is to electrode, and saturated calomel electrode is contrast electrode, and composition three-electrode system, selects copper electroplating liquid;
Step (2) is measured not containing the cathodic polarization curve of the basic bath of accelerator;
Step (3) adds the accelerator of variable concentrations in above-mentioned basic bath, measures corresponding cathodic polarization curve respectively;
Step (4) compares the cathodic polarization curve of (2) and (3), analyzes the correlation parameter on described curve, and described correlation parameter comprises electric current, voltage, accelerating effect area, Δ I, Δ U; Obtain the quantitative relationship curve of accelerating effect area, Δ I and accelerator concentration;
Step (5) adopts same electrode system to measure actual copper electrolyte to be determined, calculates corresponding electrochemical parameter, by with above-mentioned quantitative relationship curve comparison, obtain accelerator content in determined copper electrolyte.
2. the measuring method of deep hole copper facing accelerator according to claim 1, it is characterized in that, described metal electrode, comprises silver, gold, ruthenium, rhodium, palladium, osmium, iridium or platinum or its alloy.
3. the measuring method of deep hole copper facing accelerator according to claim 1, is characterized in that described inert electrode comprises carbon electrode, gold or platinum group metal.
4. the measuring method of deep hole copper facing accelerator according to claim 1, it is characterized in that, described copper electroplating liquid, comprise the negative ion of sulfate, pyrophosphate, sulfamate or alkyl sulfonate, 0 ~ 100ppm chlorion, the copper ion of 0.3 ~ 100mol/L, hydrogen ion is 0.001 ~ 2mol/L.
5. the measuring method of deep hole copper facing accelerator according to claim 1, it is characterized in that, described basic bath comprises inhibitor, leveling agent.
6. the measuring method of deep hole copper facing accelerator according to claim 1, is characterized in that, described accelerator is for containing sulfenyl and sulfonic short chain compound.
7. the measuring method of deep hole copper facing accelerator according to claim 6, is characterized in that, described accelerator concentration is 0.5 ~ 100ppm.
8. the measuring method of deep hole copper facing accelerator according to claim 1, is characterized in that, described cathodic polarization curve, is adopt cyclic voltammetry or linear sweep voltammetry and obtain.
9. the measuring method of deep hole copper facing accelerator according to claim 1, is characterized in that, the assay method of described accelerator content, comprises linear function, polynomial expression, the multiple accelerator content of exponential function and the relation of accelerating effect area.
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| CN108760821B (en) * | 2018-06-04 | 2020-09-25 | 电子科技大学 | Qualitative and quantitative analysis method for electroplating additive |
| CN112986369B (en) * | 2021-02-05 | 2022-05-17 | 深圳日山科技有限公司 | Method for measuring concentration of brightener in electroplating solution |
| CN113430595A (en) * | 2021-06-24 | 2021-09-24 | 惠州市安泰普表面处理科技有限公司 | Method for plating copper on surface of brass casting |
Citations (3)
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| CN1550578A (en) * | 2003-04-25 | 2004-12-01 | ��ķ��˹���Ӳ����������ι�˾ | Analysis method |
| CN1564941A (en) * | 2001-10-01 | 2005-01-12 | G·恰雷特 | Improved method for analysis of three organic additives in an acid copper plating bath |
| CN101004401A (en) * | 2006-01-17 | 2007-07-25 | 伊希特化股份有限公司 | Method for analyzing accelerating agent of electro coppering, and deposited electrolyte |
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| US6875474B2 (en) * | 2001-11-06 | 2005-04-05 | Georgia Tech Research Corporation | Electroless copper plating solutions and methods of use thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1564941A (en) * | 2001-10-01 | 2005-01-12 | G·恰雷特 | Improved method for analysis of three organic additives in an acid copper plating bath |
| CN1550578A (en) * | 2003-04-25 | 2004-12-01 | ��ķ��˹���Ӳ����������ι�˾ | Analysis method |
| CN101004401A (en) * | 2006-01-17 | 2007-07-25 | 伊希特化股份有限公司 | Method for analyzing accelerating agent of electro coppering, and deposited electrolyte |
Non-Patent Citations (2)
| Title |
|---|
| Sensitivity Enhancement for Quantitative Electrochemical Determination of a Trace Amount of Accelerator in Copper Plating Solutions;Yong-Da Chiu等;《The Electrochemical Society》;20110328;第158卷(第5期);第D290-D297页 * |
| 有机添加剂对铜互连线脉冲电镀的影响;陈敏娜等;《半导体技术》;20070531;第32卷(第5期);第387-390页 * |
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