CN103572332A - Plating solution of electroplated copper and preparation method thereof - Google Patents
Plating solution of electroplated copper and preparation method thereof Download PDFInfo
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- CN103572332A CN103572332A CN201310493581.2A CN201310493581A CN103572332A CN 103572332 A CN103572332 A CN 103572332A CN 201310493581 A CN201310493581 A CN 201310493581A CN 103572332 A CN103572332 A CN 103572332A
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Abstract
The invention belongs to the technical field of a copper interconnection structure, and particularly relates to a plating solution of electroplated copper and preparation method thereof. The plating solution of the electroplated copper comprises the compositions: 0.84-0.92mol/L of copper sulfate, 2.95-3.05mg/L of an accelerator, 195-205mg/L of polyether, 19.5-20.5mg/L of a leveling agent, 59.5-60.5mg/L of chloride ion solution. The plating solution of electroplated copper and the preparation method thereof have the advantages that the copper interconnection technology innovation is realized in an integrated circuit, good filling capability, small crystal grain size and acceptable resistivity can be effectively ensured, and a desirable electroplating realization scheme is provided for copper interconnection filling technology nodes of 90nm and below.
Description
Technical field
The invention belongs to copper interconnect structures technical field, be specifically related to plating solution of a kind of electro-coppering and preparation method thereof.
Background technology
The field of electroplating technology application is very extensive.In integrated circuit fabrication process, be mainly used in the step of copper-connection, along with the development of unicircuit, the technology of electro-coppering filling perforation is subject to people's attention day by day.In copper wiring technique, relate to a lot of relevant technology, comprise the formula of electroplate liquid, the selection of additive, electroplating device and relevant support equipment, the control of electroplating process, protection of plating piece etc.
In the copper-connection fill process of unicircuit, effectively additive component is absolutely necessary.Whether suitable additive type selecting, concentration ratio very and is each other selected proper, will produce different impacts to electroplating process.In traditional process for filling hole, we adopt be polyoxyethylene glycol PEG as inhibitor, SPS or MPS make accelerator, strong that green (JGB) does smoothing agent.This traditional additive formulations still can guarantee filling effect under large size.Along with constantly dwindling of device size, when entering the technology field of 90nm, the shortcoming of such formula aspect filling perforation just shows gradually, use the plating solution of existing electro-coppering to electroplate, in filling perforation, finedraw in various degree and little cavity have been there is, in addition, in the hole of high aspect ratio, complete the filling of copper, will seem more and more difficult.
Summary of the invention
For above-mentioned problems of the prior art, the object of the present invention is to provide a kind of plating solution of electro-coppering, to overcome above-mentioned problems of the prior art, and provide the preparation method of the plating solution of this electro-coppering.
The plating solution that the invention provides a kind of electro-coppering, comprising: the accelerator of the copper sulfate of 0.84-0.92 mol/L, 2.95-3.05 mg/litre, the polyethers of 195-205 mg/litre, the leveling agent of 19.5-20.5 mg/litre, the Chloride Solution of 59.5-60.5 mg/litre.
Further, the invention provides a kind of plating solution of electro-coppering, described polyethers is polyethers L31, polyethers L61 or polyethers L62.
Further, the invention provides a kind of plating solution of electro-coppering, described accelerator is two sulphur two propane sulfonic acid sodium SPS.
Further, the invention provides a kind of plating solution of electro-coppering, described leveling agent is strong that green JGB.
Further, the invention provides a kind of plating solution of electro-coppering, described Chloride Solution is hydrochloric acid soln.
In addition, the invention provides the preparation method of the plating solution of above-mentioned electro-coppering, concrete steps are:
Steps A. cupric sulfate pentahydrate crystal and the vitriol oil are evenly mixed as solute;
Step B. adds deionized water, is stirred to solute and dissolves completely;
Step C. adds accelerator, polyethers, leveling agent and Chloride Solution.
Effect of the present invention
According to plating solution of electro-coppering provided by the invention and preparation method thereof, because adopt polyethers to replace traditional polyoxyethylene glycol PEG as inhibitor, the electroplate liquid preparing can obtain the copper coating that purity is high and crystalline size is little, so this electroplate liquid is realized copper wiring technique and is brought innovation in unicircuit, the filling capacity that can effectively guarantee, less grain-size and acceptable resistivity, for 90 nm and following copper-connection fill process technology node thereof provide a kind of desirable plating implementation.
Accompanying drawing explanation
Fig. 1 is that the plating solution of electro-coppering provided by the invention is electroplated the X-ray diffraction result figure that obtains sample.
Fig. 2 is for being used polyoxyethylene glycol PEG to electroplate the X-ray diffraction result figure that obtains sample as the plating solution of inhibitor.
Fig. 3 is that the plating solution of electro-coppering provided by the invention is electroplated the surface topography map that obtains sample.
Fig. 4 is that the plating solution of electro-coppering provided by the invention is electroplated the cross section filling condition diagram that obtains sample.
Fig. 5 is for being used polyoxyethylene glycol PEG to electroplate the cross section filling condition diagram that obtains sample as the plating solution of inhibitor.
Fig. 6 is that the plating solution of electro-coppering provided by the invention is electroplated the energy spectrum analysis figure that obtains sample.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Embodiment 1
The preparation method of the plating solution of electro-coppering is as follows:
Steps A:
Utilize the cupric sulfate pentahydrate crystal of the electronic balance weighing 210g that precision is 0.001g;
Utilize glue head dropper, the concentration that measures 50g on electronic balance is about 98% vitriol oil;
By claim cupric sulfate pentahydrate crystal and the vitriol oil be blended in sufficiently uniformly a 2000ml standard beaker in;
Step B:
In standard beaker, add the solute mixing in 750ml deionized water dissolving steps A;
Under normal temperature, stir 10-20 minute, until that copper sulfate crystal fully dissolves is complete, do not have crystal to separate out;
Step C:
In solution, add the two sulphur two propane sulfonic acid sodium SPS of 2.95 milligrams;
Add again the polyethers L31 of 195 milligrams;
Add again strong that green JGB of 19.5 milligrams;
Add the hydrochloric acid soln that contains 59.5 milligrams of chlorions is provided again;
Finally add deionized water and solution is modulated into the solution of 1000ml.
The final plating solution that obtains electro-coppering contains:
The copper sulfate of 0.84 mol/L, accelerator are that two sulphur two propane sulfonic acid sodium SPS, the polyethers L31 of 195 mg/litre, the leveling agent of 2.95 mg/litre is strong that green JGB of 19.5 mg/litre, the Chloride Solution of 59.5 mg/litre.
The preparation method of the plating solution of electro-coppering is as follows:
Steps A:
Utilize the cupric sulfate pentahydrate crystal of the electronic balance weighing 220g that precision is 0.001g;
Utilize glue head dropper, the concentration that measures 55g on electronic balance is about 98% vitriol oil;
By claim cupric sulfate pentahydrate crystal and the vitriol oil be blended in sufficiently uniformly a 2000ml standard beaker in;
Step B:
In standard beaker, add the solute mixing in 800ml deionized water dissolving steps A;
Under normal temperature, stir 10-20 minute, until that copper sulfate crystal fully dissolves is complete, do not have crystal to separate out;
Step C:
In solution, add the two sulphur two propane sulfonic acid sodium SPS of 3 milligrams;
Add again the polyethers L61 of 200 milligrams;
Add again strong that green JGB of 20 milligrams;
Add the hydrochloric acid soln that contains 60 milligrams of chlorions is provided again;
Finally add deionized water and solution is modulated into the solution of 1000ml.
The final plating solution that obtains electro-coppering contains:
The copper sulfate of 0.88 mol/L, accelerator are that two sulphur two propane sulfonic acid sodium SPS, the polyethers L61 of 200 mg/litre, the leveling agent of 3 mg/litre is strong that green JGB of 20 mg/litre, the Chloride Solution of 60 mg/litre.
The preparation method of the plating solution of electro-coppering is as follows:
Steps A:
Utilize the cupric sulfate pentahydrate crystal of the electronic balance weighing 230g that precision is 0.001g;
Utilize glue head dropper, the concentration that measures 55g on electronic balance is about 98% vitriol oil;
By claim cupric sulfate pentahydrate crystal and the vitriol oil be blended in sufficiently uniformly a 2000ml standard beaker in;
Step B:
In standard beaker, add the solute mixing in 800ml deionized water dissolving steps A;
Under normal temperature, stir 10-20 minute, until that copper sulfate crystal fully dissolves is complete, do not have crystal to separate out;
Step C:
In solution, add the accelerator MPS of 3.05 milligrams;
Add again the polyethers L62 of 205 milligrams;
Add again the leveling agent BAT of 20.5 milligrams;
Finally add the hydrochloric acid soln that contains 60.5 milligrams of chlorions is provided.
The final plating solution that obtains electro-coppering contains:
The copper sulfate of 0.92 mol/L, accelerator are the MPS of 3.05 mg/litre, the polyethers L62 of 205 mg/litre, leveling agent are the BAT of 20.5 mg/litre, the Chloride Solution of 60.5 mg/litre.
experiment test
Use the plating solution of electro-coppering provided by the invention to test as follows:
1, the preparation of electroplate liquid and aging
According to the preparation method in embodiment, prepare the plating solution of required electro-coppering, and carry out 6-8 hour aging.
2, electroplate experiment
As requested, select different current densities to electroplate experiment, can select 0.1,0.2,0.4, 0.8(unit: ASD) these 4 groups experiments.Every group of sample will comprise a plane mating plate and a sample that has figure.
3, every group two samples, before electroplating, be fixed on same negative electrode copper sheet, once immerse in plating solution.To guarantee the plating term harmonization of 2 samples of same group.
4, the test of sample.
Test one: X-ray diffraction test
K α 1 ray that adopts Cu, sweep limit is set as 20 ~ 65 °.The sample of testing must be planar sample.
Fig. 1 is that the plating solution of electro-coppering provided by the invention is electroplated the X-ray diffraction result figure that obtains sample.
Fig. 2 is for being used polyoxyethylene glycol PEG to electroplate the X-ray diffraction result figure that obtains sample as the plating solution of inhibitor.
As depicted in figs. 1 and 2, the Cu(111 of electroplated sample of the present invention) grain-size is between 24nm-28nm, and polyoxyethylene glycol PEG is as the Cu(111 of the electroplated sample of the plating solution of inhibitor) grain-size is between 26nm ~ 30nm.As can be seen here, polyethers is electroplated the Cu(111 obtaining as the plating solution of inhibitor) grain-size has certain reducing, and contributes to the copper that improves small size device to electroplate performance.
Test two: scanning electron microscope sem test
1. the surface topography of viewing plane sample
Fig. 3 is that the plating solution of electro-coppering provided by the invention is electroplated the surface topography map that obtains sample.
As shown in Figure 3, the surface appearance feature of sample shows uniform particles, and surfacing, without defects such as cavities.
2. observe the cross section of figure sample and fill situation
Fig. 4 is that the plating solution of electro-coppering provided by the invention is electroplated the cross section filling condition diagram that obtains sample.
Fig. 5 is for being used polyoxyethylene glycol PEG to electroplate the cross section filling condition diagram that obtains sample as the plating solution of inhibitor.
As shown in Figure 4 and Figure 5, the plating solution of electro-coppering provided by the invention is electroplated the cross section of acquisition sample and is filled without finedraw, and the cross section of using polyoxyethylene glycol PEG to electroplate acquisition sample as the plating solution of inhibitor is filled with obvious finedraw.As can be seen here, in filling process, use polyethers to substitute the plating solution of polyoxyethylene glycol PEG, can avoid the generation of finedraw, so the inhibition ability of polyethers is better, help the performance after the electro-coppering that improves device.
Test three: energy spectrum analysis EDXS
Be to utilize scanning electron microscope equally, effects on surface sample carries out an energy spectrum analysis, to determine dopant species and content wherein, whether purer characterizes electroplated copper film by this kind of mode.
Fig. 6 is that the plating solution of electro-coppering provided by the invention is electroplated the energy spectrum analysis figure that obtains sample.
As shown in Figure 6, the surface of sample only has micro-C and Si element, according to chart, can draw, the purity that the plating solution of electro-coppering provided by the invention is electroplated acquisition sample surfaces Cu is very high.
Claims (6)
1. a plating solution for electro-coppering, is characterized in that, composition is:
The copper sulfate of 0.84-0.92 mol/L, the accelerator of 2.95-3.05 mg/litre, the polyethers of 195-205 mg/litre, the leveling agent of 19.5-20.5 mg/litre, the Chloride Solution of 59.5-60.5 mg/litre.
2. the plating solution of electro-coppering according to claim 1, is characterized in that: polyethers is polyethers L31, polyethers L61 or polyethers L62.
3. the plating solution of electro-coppering according to claim 1, is characterized in that: described accelerator is two sulphur two propane sulfonic acid sodium SPS.
4. the plating solution of electro-coppering according to claim 1, is characterized in that: described leveling agent is strong that green JGB.
5. the plating solution of electro-coppering according to claim 1, is characterized in that: described Chloride Solution is hydrochloric acid soln.
6. a preparation method for the plating solution of the electro-coppering as described in one of claim 1 to 5, is characterized in that concrete steps are:
Steps A. cupric sulfate pentahydrate crystal and the vitriol oil are evenly mixed, as solute;
Step B. adds deionized water, is stirred to described solute and dissolves completely;
Step C. adds described accelerator, described polyethers, described leveling agent and described Chloride Solution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104313553A (en) * | 2014-09-26 | 2015-01-28 | 丽水学院 | An electroless copper plating liquid used for surface copper plating of polyimide film, and a preparing method and a using method thereof |
| CN107326408A (en) * | 2017-08-04 | 2017-11-07 | 台湾先进系统股份有限公司 | Copper electroplating liquid, the method for electro-coppering and the method for forming copper post |
| CN111155153A (en) * | 2020-02-19 | 2020-05-15 | 广州三孚新材料科技股份有限公司 | Copper electroplating solution and copper electroplating method |
Citations (4)
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|---|---|---|---|---|
| US5174886A (en) * | 1991-02-22 | 1992-12-29 | Mcgean-Rohco, Inc. | High-throw acid copper plating using inert electrolyte |
| CN101481812A (en) * | 2008-12-31 | 2009-07-15 | 清华大学 | Electrolytic solution for integrated circuit copper wire laying electrodeposition |
| CN103103586A (en) * | 2013-02-22 | 2013-05-15 | 陕西师范大学 | Thiazole compound-containing copper electroplating solution |
| CN103103587A (en) * | 2013-02-22 | 2013-05-15 | 陕西师范大学 | Copper electroplating solution containing mercapto heterocyclic compound |
-
2013
- 2013-10-21 CN CN201310493581.2A patent/CN103572332A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5174886A (en) * | 1991-02-22 | 1992-12-29 | Mcgean-Rohco, Inc. | High-throw acid copper plating using inert electrolyte |
| CN101481812A (en) * | 2008-12-31 | 2009-07-15 | 清华大学 | Electrolytic solution for integrated circuit copper wire laying electrodeposition |
| CN103103586A (en) * | 2013-02-22 | 2013-05-15 | 陕西师范大学 | Thiazole compound-containing copper electroplating solution |
| CN103103587A (en) * | 2013-02-22 | 2013-05-15 | 陕西师范大学 | Copper electroplating solution containing mercapto heterocyclic compound |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104313553A (en) * | 2014-09-26 | 2015-01-28 | 丽水学院 | An electroless copper plating liquid used for surface copper plating of polyimide film, and a preparing method and a using method thereof |
| CN104313553B (en) * | 2014-09-26 | 2016-07-06 | 丽水学院 | Chemical bronze plating liquid of copper coating for Kapton and preparation method thereof, using method |
| CN107326408A (en) * | 2017-08-04 | 2017-11-07 | 台湾先进系统股份有限公司 | Copper electroplating liquid, the method for electro-coppering and the method for forming copper post |
| CN111155153A (en) * | 2020-02-19 | 2020-05-15 | 广州三孚新材料科技股份有限公司 | Copper electroplating solution and copper electroplating method |
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Application publication date: 20140212 |