CN103698384A - Measuring method of deep-hole copper plating accelerant - Google Patents
Measuring method of deep-hole copper plating accelerant Download PDFInfo
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- CN103698384A CN103698384A CN201310697804.7A CN201310697804A CN103698384A CN 103698384 A CN103698384 A CN 103698384A CN 201310697804 A CN201310697804 A CN 201310697804A CN 103698384 A CN103698384 A CN 103698384A
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Abstract
The invention relates to a measuring method of a deep-hole copper plating accelerant. The measuring method comprises the following steps: (1) forming a three-electrode system by a metal electrode, an inert metal sheet and a saturated calomel electrode which are taken as a working electrode, a counter electrode and a reference electrode respectively, and selecting a copper electroplating solution; (2) measuring a cathodic polarization curve of an accelerant-free basic electroplating solution; (3) adding accelerants of different concentration into the basic electroplating solution, and respectively measuring corresponding cathodic polarization curves; (4) comparing the cathodic polarization curve of the step (2) with the cathodic polarization curves of the step (3), and analyzing relevant parameters of the curves so as to acquire a quantitative relation curve between relevant electrochemical parameters and the concentration of the accelerants; and (5) measuring an actual to-be-measured copper plating solution by the same electrode system so as to obtain a result. By taking the cathodic polarization curves as measuring objects, the measuring method is close to an actual electroplating process, so that the management and process quality control of the copper electroplating solution are directed, and the industrial application of a TSV copper electroplating process is promoted.
Description
Technical field
The invention belongs to semiconductor manufacture, 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 deep hole copper facing technology such as chip Damascus copper-connection, pcb board wiring and the vertical copper-connections of silicon through hole, and the absolutely large 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, known according to existing documents and materials, what in the process of filling in deep hole copper facing, play a major role is accelerator and inhibitor.And because the adjuvant playing a crucial role in plating solution mostly is organic surface active agent, its concentration only has ppm magnitude, and in use also can produce the various decomposition products that affect filling effect, very difficult to the analysis of these micro constitutents and filling effect evaluation, make plating solution maintenance and the production management of deep hole copper facing filling technique 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 regularly to supplement, so the mensuration of its content seems very important.
2003, U.S. ECI Technology company takes the lead in having proposed three kinds of crucial adjuvant (inhibitor in copper plating bath, leveling agent and brightener) cyclic voltammetric stripping method (Cyclic Voltammetry Stripping, the CVS) analytical approach of concentration, and obtained United States Patent (USP).CVS method is mainly in the galvanochemistry volt-ampere curve based on platinum electrode, and the quantitative relationship of the meltage of copper in additive concentration and anodic process is analyzed a kind of indirect measurement method of organic additive content in plating solution.However, because the method is that dissolving total amount based on copper in anodic process is measured, so cannot evaluating, this analytical approach affects the cathodic process of filling effect, the effect of judgement adjuvant in electro-deposition, to the selected and optimization of technological parameter, the assessment of bath life seems helpless.Therefore need a kind of method, can evaluate the action effect of adjuvant in actual electroplating process, thereby the copper filling process in hole is played to directive function.
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, the present invention has adopted cathodic polarization curve as research object, according to the current peak occurring on galvanochemistry curve and electric current paddy, utilize the variation of the difference of accelerating effect area or current/voltage peak valley, obtain the relation of accelerator content and correlation parameter, closing to reality electroplating process more, thereby copper electroplating process is produced to directive function, 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, forms three-electrode system, selects copper electroplating liquid;
Step (2) is measured the cathodic polarization curve that does not contain the basic plating solution of accelerator;
Step (3) adds the accelerator of variable concentrations in above-mentioned basic plating solution, measures respectively corresponding cathodic polarization curve;
Step (4) is the cathodic polarization curve of (2) and (3) relatively, analyzes the correlation parameter on described curve, obtains the quantitative relationship curve of associated electrical chemical parameters 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, and the copper ion of 0.3～100mol/L, hydrogen ion is 0.001～2mol/L.
Preferably, described basic plating solution 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, is to adopt cyclic voltammetry or linear sweep voltammetry and obtain.
Preferably, described correlation parameter comprises electric current, voltage, accelerating effect area, Δ I, Δ U.
Preferably, the assay method of described accelerator content, comprises the multiple accelerator content of linear function, polynomial expression, exponential function and the relation of accelerating effect area.
Compared with prior art, beneficial effect of the present invention is as follows: the present invention has adopted cathodic polarization curve as determination object, according to the current peak occurring on galvanochemistry curve and electric current paddy, utilize the variation of the difference of accelerating effect area or current/voltage peak valley, obtain the relation of accelerator content and correlation parameter, closing to reality electroplating process more, thus copper electroplating liquid management and procedure quality are controlled and produced directive function, promote the industrial applications of TSV copper plating process.
Accompanying drawing explanation
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is cathodic polarization curve parameter schematic diagram.
Fig. 2 is 40g/L Cu
2+, 50ppm Cl
-, 300ppm PEG, the pH value plating solution that is 1 adds the cathodic polarization curve of different content SPS.
Fig. 3 is 40g/L Cu
2+, 50ppm Cl
-, 300ppm PEG, the pH value plating solution that is 1 adds the change curve of the accelerating effect area of different content SPS.
Fig. 4 is 40g/L Cu
2+, 50ppm Cl
-, 300ppm PEG, the pH value plating solution that is 1 adds 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 further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
The present embodiment relates to the assay method that a kind of copper-connection is electroplated accelerator content, and concrete steps are as follows:
(1) adopt Au electrode as working electrode, TSV copper electroplating liquid is electrolytic solution, and saturated calomel electrode is contrast electrode, and platinized platinum is that electrode is formed to three-electrode system,
(2) cathodic polarization curve of Fundamentals of Measurement plating solution, basic plating solution forms: copper ion concentration is 40g/L, and chlorine ion concentration is 50ppm, and pH value is 1;
(3) in basic plating solution, 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 plating solution, add the PEG of 300ppm, and keep concentration constant, and then to the sodium polydithio-dipropyl sulfonate (SPS) that adds variable concentrations in plating solution, concentration range is 0～6ppm, measures respectively its cathodic polarization curve; Fig. 1 is the signal of cathodic polarization curve parameter.And compare with the LSV curve of the single 300ppmPEG of adding in basic plating solution, as shown in Figure 2.As seen from the figure, add after the SPS of 1ppm, occur above-mentioned current peak.Continue to add SPS, when SPS content arrives 2ppm, current peak and electric current paddy are fairly obvious.This is owing to being mainly the suction-operated of SPS at low-voltage region, SPS dosage is larger, and in this stage, to be adsorbed on the amount of electrode surface just more, current peak is larger, and replace gradually SPS at high-voltage region PEG, be adsorbed on electrode surface, at low ebb place, PEG has replaced most SPS, inhibiting effect is maximum, reaches electric current valley.
(5) calculate respectively the accelerating effect area of cathodic polarization curve of the SPS of variable concentrations, obtain the content along with SPS, the change curve of accelerating effect area.As shown in Figure 3, SPS content is less than at 2 o'clock, the variation of accelerating effect area almost point-blank, explanation is 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, thereby it is corresponding to utilize this relational expression and the corresponding parameter of the cathodic polarization curve of actual electroplate liquid to carry out, and obtain the content of SPS.
(6) calculate respectively the Δ I of cathodic polarization curve of the SPS of variable concentrations, obtain the content along with SPS, the change curve of Δ I.As shown in Figure 4, SPS content is less than at 2 o'clock, the variation of Δ I almost point-blank, explanation is 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, thereby it is corresponding to utilize this relational expression and the corresponding parameter of the cathodic polarization curve of actual electroplate liquid to carry out, and obtain the content of SPS.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (10)
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, forms three-electrode system, selects copper electroplating liquid;
Step (2) is measured the cathodic polarization curve that does not contain the basic plating solution of accelerator;
Step (3) adds the accelerator of variable concentrations in above-mentioned basic plating solution, measures respectively corresponding cathodic polarization curve;
Step (4) is the cathodic polarization curve of (2) and (3) relatively, analyzes the correlation parameter on described curve, obtains the quantitative relationship curve of associated electrical chemical parameters 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, is characterized in that, described metal electrode comprises carbon electrode and 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, the negative ion that comprises 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, is characterized in that, described basic plating solution 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 to 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, described correlation parameter comprises electric current, voltage, accelerating effect area, Δ I, Δ U.
10. 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 the multiple accelerator content of linear function, polynomial expression, exponential function and the relation of accelerating effect area.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108760821A (en) * | 2018-06-04 | 2018-11-06 | 电子科技大学 | A kind of qualitative and quantitative analysis method of electroplating additive |
| CN112986369A (en) * | 2021-02-05 | 2021-06-18 | 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 |
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| US20040086656A1 (en) * | 2001-11-06 | 2004-05-06 | Kohl Paul A. | Electroless copper plating solutions and methods of use thereof |
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| 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 |
| US20040086656A1 (en) * | 2001-11-06 | 2004-05-06 | Kohl Paul A. | Electroless copper plating solutions and methods of use thereof |
| CN1550578A (en) * | 2003-04-25 | 2004-12-01 | ��ķ��˹���Ӳ����������ι�˾ | Analysis method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108760821A (en) * | 2018-06-04 | 2018-11-06 | 电子科技大学 | A kind of qualitative and quantitative analysis method of electroplating additive |
| CN108760821B (en) * | 2018-06-04 | 2020-09-25 | 电子科技大学 | Qualitative and quantitative analysis method for electroplating additive |
| CN112986369A (en) * | 2021-02-05 | 2021-06-18 | 深圳日山科技有限公司 | Method for measuring concentration of brightener in electroplating solution |
| 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 |
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