CN104479560A - Integrated circuit copper polishing solution used at low down pressure - Google Patents
Integrated circuit copper polishing solution used at low down pressure Download PDFInfo
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- CN104479560A CN104479560A CN201410849637.8A CN201410849637A CN104479560A CN 104479560 A CN104479560 A CN 104479560A CN 201410849637 A CN201410849637 A CN 201410849637A CN 104479560 A CN104479560 A CN 104479560A
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- acid
- polishing fluid
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- triazole
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- Organic Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention relates to an integrated circuit copper polishing solution used as low down pressure and belongs to the technical field of micro-electronic auxiliary materials and ultra-precision machining technologies. The polishing solution provided by the invention comprises abrasive particles, an oxidizing agent, deionized water, a compound inhibitor, a compound complexing agent and a silica sol bridging agent. The polishing solution can realize high removal rate and high surface evenness of copper polishing under the low down pressure (below 1 psi) condition.
Description
Technical field
The invention belongs to microelectronics subsidiary material and Ultra-precision Turning Technology field, particularly a kind ofly remove the copper polishing fluid that speed is high and surface evenness is high.
Background technology
Chemically machinery polished (CMP) is the most effectual way realizing material local and global planarizartion of generally acknowledging at present, is widely used in the flattening surface process of IC processing procedure.Copper goes between as the middle layer of IC unicircuit, and the CMP of copper is as the main process of microdevice, and various countries are all stepping up tackling key problem research.The key factor affecting copper CMP global planarizartion is polishing fluid, it determine whole glossing and polish results whether desirable.In addition, along with the development of microelectronics, unicircuit is to highly integrated, characteristic dimension miniaturization future development.In order to reduce the serious interconnect delay produced because characteristic dimension constantly reduces as far as possible, in integrated circuit fabrication process, tend to gradually apply the dielectric substance of more low-k and there is the copper interconnecting line replacement aluminium interconnection line of more low-resistivity, more excellent anti-electronic migration performance.But, have the dielectric substance of more low-k, be easy to cause because stress is excessive copper interconnecting line major injury under traditional chemically machinery polished condition, make ic failure.Therefore, the copper polishing fluid that exploitation is applicable to low overdraft becomes the gordian technique in the integrated circuit fabrication process of application low-dielectric constant dielectric medium material and copper interconnecting line.Generally, reduce overdraft to have a negative impact to the CMP overall performance comprising polishing speed.Such as, adopt ripe commercial copper polishing composition to carry out copper polishing, when pressure is 5.0psi, polishing speed is 333.3nm/min, and when pressure is reduced to about 0.5psi, polishing speed is decreased to 101.9nm/min, differs about 3 times.Therefore, what reduction press polish can be serious affects throughput.Generally speaking, uniformity coefficient will be unfavorable for later process and operation lower than 5%, and along with polish pressure reduces, after polishing, the uniformity controlling on copper surface becomes more difficult.Therefore, a kind of task of removing the copper polishing fluid that speed is high, surface evenness is good is developed not only urgent but also necessary.
Summary of the invention
The present invention is directed to the defect that present technology also exists, propose a kind of copper polishing fluid being applicable to low overdraft.The height that the present invention can realize copper polishing under low overdraft (below 1psi) condition removes speed and high surface homogenity.
A kind of integrated circuit copper polishing fluid being applicable to low overdraft, this polishing fluid comprises abrasive particle, oxygenant and deionized water, it is characterized in that, this polishing fluid also comprises abrasive particle, oxygenant and deionized water, containing composite inhibitor, compound complex agent and silicon sol bridging agent.
Component proportion of the present invention is:
Described low overdraft is below 1psi.
Described abrasive particle is acidic oxidation silicon abrasive particle, and particle diameter is within the scope of 1 ~ 100nm, and pH is less than 4.
Described composite inhibitor is the mixture of azole compounds and self-assembly corrosion inhibition agent.
Described azole compounds is nitrogenous azole compounds, there are a nitrogen azoles, ribavirin or triazole, one nitrogen azoles, 1,3-benzene a pair of horses going side by side ribavirin, 1,3-ribavirin, 1,2-ribavirin, benzotriazole, imidazoles, 1-hydroxy benzo triazole, 2-mercaptobenzimidazole, 1,2,4-triazole, 5-tolyltriazole, 1,2, one or more in 3-triazole, 3-amino triazole-5-carboxylic acid, amino-1,2, the 4-triazole of 3-, 5-carboxy benzotriazole, 5-methyl tetrazole, 5-phenyl tetrazole, 5-aminotetrazole, 1-phenyl-5-mercapto tetrazole;
Described self-assembly corrosion inhibition agent is main chain is polyether structure, end active functional group is the polymkeric substance of amido, comprise difunctionality, trifunctional, molecular weight is from 230 to 5000, as two functional groups (D-230, D-400, D-2000, D-4000), (T-403, T-5000) of trifunctional;
Described compound complex agent is phosphonic acid based and amino acid whose mixture.
Described phosphonic acids is Amino Trimethylene Phosphonic Acid, hydroxy ethylene diphosphonic acid, 2-HPAA, two hexene triamine pentamethylene phosphonic acids, 2-phosphono-1,2,4-butane tricarboxylic acid, 2-phosphonobutane-1, one or more in 2,4-tricarboxylic acid four sodium and two hexene triamine pentamethylene Alendronates;
Described amino acid is one or more in glycine, aspartic acid, Serine, Threonine, halfcystine, proline(Pro), L-glutamic acid, Histidine, arginine;
Described silicon sol bridging agent is the polymkeric substance of poly-hydroxy or polyether base, is selected from one or more in polyvinyl alcohol, polyvinyl alcohol and polystyrene block copolymer, polyoxyethylene glycol, polyoxyethylene, polyoxyethylene and ethylene oxide-propylene oxide block copolymer, polyoxyethylene nonylphenol ether.
Described oxygenant is one or more in hydrogen peroxide (HPO) and derivative, urea peroxide (UHPO), peroxyformic acid (FPOA), Peracetic Acid (EPOA), SPC-D (SPC), persulfuric acid (PSA) and salt thereof, Periodic acid (PIA) and salt, perchloric acid (PCA) and salt thereof, chloric acid (CA) and salt, hypochlorous acid (HCA) and salt thereof, molybdic acid (MA) and salt, nitric acid (NA) and salt thereof.
For ensureing oxidizing effect, oxygenant described in the present invention can add before polishing temporarily.
The copper polishing fluid being applicable to low overdraft (below 1psi) of the present invention, the method preparation that this area can be adopted conventional, such as, adds deionized water for stirring evenly by each composition by proportioning.
The copper polishing fluid being applicable to low overdraft (below 1psi) of the present invention, tool has the following advantages:
1. the inhibitor in copper polishing fluid of the present invention, can form more loose passive film on copper surface, remain high and remove speed while protection copper surface;
2. the complexing agent in copper polishing fluid of the present invention, can under low overdraft (below 1psi) condition, effectively copper surface uniformity after raising polishing, and surperficial non-uniformity is less than 5%;
3. copper polishing fluid of the present invention also has that technique is simple, low price, low cost and other advantages
Accompanying drawing explanation
Fig. 1 is the homogeneity schematic diagram on copper surface after this employing inventive embodiments and comparative example polishing.
Embodiment
Below by specific embodiment, the invention will be further elaborated, certainly in no case should be construed as limiting the scope of the invention.
Specific embodiment:
Polishing fluid after configuration is used for polishing experiments, and polishing experiments parameter is as follows:
Polishing machine: 12 inches of chemical-mechanical polishing mathings (Strasbaugh 6EG type), is furnished with 1 rubbing head, can throw 1 12 inches of electroless copper plating film (from magnificent power semi-conductor customization, thickness of coated copper layer is 2 microns);
Polishing rotary speed: 100 turns/min;
Rubbing head rotating speed: 95 turns/min;
Polishing electroless copper plating film specification: diameter 300mm;
Polishing time: 1min;
Polishing pad: IC 1000-XY/SUBA IV20 type composite polishing pad;
Polishing fluid flow: 80ml/min;
Polish pressure: 0.5-1psi;
Polish temperature: 25 DEG C
Polishing speed: adopt electroless copper plating film thickness before and after ResMap-273 type four-point probe measurment instrument test polishing, calculate and remove speed;
After polishing, copper sheet surface uniformity detects: adopt ResMap-273 type four-point probe measurment instrument in wafer diameter, to test 81 points continuously, carry out successive mining, non-uniformity=(thickness standard deviation/thickness average value) × 100%.
From embodiment, in best polishing combination liquid under polishing technological conditions of the present invention, each component concentration is (embodiment 4): the pH containing median size 50nm is the colloid silica abrasive particle 2wt% of 2.6, containing HPO 2wt% and 0.5wt%UHPO oxygenant, containing composite inhibitor 0.05%5-carboxy benzotriazole+0.05% benzotriazole and 0.02%D2000, containing compound complex agent 0.2%2-HPAA and 2% glycine, containing 0.1% polyoxyethylene nonylphenol ether, the electroless copper plating film surface non-uniformity of polishing combination liquid under 0.8PSI pressure after polishing is low to moderate 1.76%, remove rate 6261.78 dusts/min.
The above is only the preferred embodiment of the present invention; it should be noted that the those skilled in the art for the art; under the prerequisite not departing from the technology of the present invention principle, can also make corresponding adjustment and improve, these adjustment and improvement also should be considered as protection scope of the present invention.
Claims (10)
1. one kind is applicable to the integrated circuit copper polishing fluid of low overdraft, this polishing fluid comprises abrasive particle, oxygenant and deionized water, it is characterized in that, this polishing fluid also comprises abrasive particle, oxygenant and deionized water, containing composite inhibitor, compound complex agent and silicon sol bridging agent.
2. polishing fluid according to claim 1, is characterized in that described component proportion is:
3. polishing fluid according to claim 1 and 2, is characterized in that, described low overdraft is below 1psi.
4. polishing fluid according to claim 3, is characterized in that, described abrasive particle is acidic oxidation silicon abrasive particle, and particle diameter is within the scope of 1 ~ 100nm, and pH is less than 4.
5. polishing fluid according to claim 3, is characterized in that, described composite inhibitor is the mixture of azole compounds and self-assembly corrosion inhibition agent.
6. polishing fluid according to claim 5, it is characterized in that, described azole compounds is nitrogenous azole compounds, there is a nitrogen azoles, ribavirin or triazole, one nitrogen azoles, 1, 3-benzene a pair of horses going side by side ribavirin, 1, 3-ribavirin, 1, 2-ribavirin, benzotriazole, imidazoles, 1-hydroxy benzo triazole, 2-mercaptobenzimidazole, 1, 2, 4-triazole, 5-tolyltriazole, 1, 2, 3-triazole, 3-amino triazole-5-carboxylic acid, 3-amino-1, 2, 4-triazole, 5-carboxy benzotriazole, 5-methyl tetrazole, 5-phenyl tetrazole, 5-aminotetrazole, one or more in 1-phenyl-5-mercapto tetrazole,
Described self-assembly corrosion inhibition agent is main chain is polyether structure, end active functional group is the polymkeric substance of amido, comprise difunctionality, trifunctional, molecular weight is from 230 to 5000, as two functional groups (D-230, D-400, D-2000, D-4000), (T-403, T-5000) of trifunctional.
7. polishing fluid according to claim 3, is characterized in that, described compound complex agent is phosphonic acid based and amino acid whose mixture.
8. polishing fluid according to claim 7, it is characterized in that, described phosphonic acids is Amino Trimethylene Phosphonic Acid, hydroxy ethylene diphosphonic acid, 2-HPAA, two hexene triamine pentamethylene phosphonic acids, 2-phosphono-1,2,4-butane tricarboxylic acid, 2-phosphonobutane-1, one or more in 2,4-tricarboxylic acid four sodium and two hexene triamine pentamethylene Alendronates; Described amino acid is one or more in glycine, aspartic acid, Serine, Threonine, halfcystine, proline(Pro), L-glutamic acid, Histidine, arginine.
9. polishing fluid according to claim 3, it is characterized in that, described silicon sol bridging agent is the polymkeric substance of poly-hydroxy or polyether base, is selected from one or more in polyvinyl alcohol, polyvinyl alcohol and polystyrene block copolymer, polyoxyethylene glycol, polyoxyethylene, polyoxyethylene and ethylene oxide-propylene oxide block copolymer, polyoxyethylene nonylphenol ether.
10. polishing fluid according to claim 3, it is characterized in that, described oxygenant is one or more in hydrogen peroxide (HPO) and derivative, urea peroxide (UHPO), peroxyformic acid (FPOA), Peracetic Acid (EPOA), SPC-D (SPC), persulfuric acid (PSA) and salt thereof, Periodic acid (PIA) and salt, perchloric acid (PCA) and salt thereof, chloric acid (CA) and salt, hypochlorous acid (HCA) and salt thereof, molybdic acid (MA) and salt, nitric acid (NA) and salt thereof.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410849637.8A CN104479560B (en) | 2014-12-30 | 2014-12-30 | Integrated circuit copper polishing solution used at low down pressure |
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| CN201410849637.8A CN104479560B (en) | 2014-12-30 | 2014-12-30 | Integrated circuit copper polishing solution used at low down pressure |
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| CN104479560A true CN104479560A (en) | 2015-04-01 |
| CN104479560B CN104479560B (en) | 2017-04-12 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774467A (en) * | 2018-06-29 | 2018-11-09 | 东莞市硕丰研磨科技有限公司 | Glass polishing composition |
| CN110997856A (en) * | 2017-08-09 | 2020-04-10 | 日立化成株式会社 | Polishing liquid and polishing method |
| CN113122145A (en) * | 2019-12-31 | 2021-07-16 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
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| US6197703B1 (en) * | 1998-08-17 | 2001-03-06 | Advanced Micro Devices, Inc. | Apparatus and method for manufacturing semiconductors using low dielectric constant materials |
| CN101302404A (en) * | 2008-07-01 | 2008-11-12 | 上海大学 | Preparation of nano-cerium oxide composite abrasive grain polishing solution |
| CN101671527A (en) * | 2009-09-27 | 2010-03-17 | 大连三达奥克化学股份有限公司 | Copper chemical mechanical polishing solution with high removing rate and low damage, and preparation method thereof |
| WO2010063165A1 (en) * | 2008-12-05 | 2010-06-10 | Song Peter Weihong | Chmical-mechanical polishing liquid |
| CN102477262A (en) * | 2010-11-30 | 2012-05-30 | 安集微电子（上海）有限公司 | Chemically mechanical polishing slurry |
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2014
- 2014-12-30 CN CN201410849637.8A patent/CN104479560B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6197703B1 (en) * | 1998-08-17 | 2001-03-06 | Advanced Micro Devices, Inc. | Apparatus and method for manufacturing semiconductors using low dielectric constant materials |
| CN101302404A (en) * | 2008-07-01 | 2008-11-12 | 上海大学 | Preparation of nano-cerium oxide composite abrasive grain polishing solution |
| WO2010063165A1 (en) * | 2008-12-05 | 2010-06-10 | Song Peter Weihong | Chmical-mechanical polishing liquid |
| CN101671527A (en) * | 2009-09-27 | 2010-03-17 | 大连三达奥克化学股份有限公司 | Copper chemical mechanical polishing solution with high removing rate and low damage, and preparation method thereof |
| CN102477262A (en) * | 2010-11-30 | 2012-05-30 | 安集微电子（上海）有限公司 | Chemically mechanical polishing slurry |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110997856A (en) * | 2017-08-09 | 2020-04-10 | 日立化成株式会社 | Polishing liquid and polishing method |
| CN110997856B (en) * | 2017-08-09 | 2021-10-29 | 昭和电工材料株式会社 | Polishing liquid and polishing method |
| CN108774467A (en) * | 2018-06-29 | 2018-11-09 | 东莞市硕丰研磨科技有限公司 | Glass polishing composition |
| CN113122145A (en) * | 2019-12-31 | 2021-07-16 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
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Granted publication date: 20170412 Termination date: 20191230 |