CN102533123B - Chemi-mechanical polishing fluid for polishing semiconductor wafer - Google Patents
Chemi-mechanical polishing fluid for polishing semiconductor wafer Download PDFInfo
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- CN102533123B CN102533123B CN 201010609470 CN201010609470A CN102533123B CN 102533123 B CN102533123 B CN 102533123B CN 201010609470 CN201010609470 CN 201010609470 CN 201010609470 A CN201010609470 A CN 201010609470A CN 102533123 B CN102533123 B CN 102533123B
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Abstract
The invention provides a chemi-mechanical polishing fluid for polishing a semiconductor wafer, which is prepared from the following components in percentage by weight: 0.2-5% of acidic pH regulator, 0.01-5% of piperidine nitroxide free radical, 0.1-15% of surfactant, 0.5-20% of grinding particle and the balance of water. The polishing fluid provided by the invention can obviously change the removal rate of silicon nitride under acidic conditions, can regulate the selection ratio of silicon dioxide to silicon nitride, and has the advantages of simple preparation technique, high polishing precision and the like.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid, particularly a kind ofly be applicable in the CMP technique of semiconductor shallow trench isolation (STI), to be used for polishing fluid that the silicon-dioxide on the semiconductor wafer and silicon nitride are carried out chemically machinery polished.
Background technology
Chemical Mechanical Polishing Technique (Chemical Mechanical Polishing, CMP) be the technology that chemical action and mechanical effect combine, it is by the mechanical abrasive action of superfine grinding particle in the CMP polishing fluid and the chemical corrosion effect of polishing fluid, can be on silicon wafer the height of formation even curface.The CMP technological synthesis advantage of chemical rightenning and mechanical polishing.Simple chemical rightenning, polishing speed is very fast, and surface smoothness is high, damage is low, perfection good, but its surface finish, parallelism are relatively poor, and it is also relatively poor to polish consistence; Simple mechanical polishing high conformity, surface finish is high, but poor surface smoothness, the damage layer depth.Use the CMP technology and both can obtain high polishing speed, can obtain perfect surface again, its planeness exceeds a plurality of orders of magnitude than additive method.Can really realize whole silicon wafer surface planarization in this way, and have the advantages such as working method is simple, tooling cost is low.
Shallow trench isolation technology (shallow trench isolations, STI) is a kind of widely used semiconductor fabrication, and it comprises the single-step process of series of complex.At first form Si at silicon substrate
3N
4With buffering SiO
2Figure is as the mask of guttering corrosion.Next erode away the groove with certain depth and side wall angle at the Si substrate, the skim of then growing SiO
2With the drift angle of round and smooth groove with remove the damage of introducing at silicon face in the etching process.Be trench fill and annealing after the oxidation, then use CMP technique that silicon chip surface is carried out planarization, Si
3N
4Blocking layer as CMP.If select selection than low polishing fluid, then Si at this
3N
4Removal amount larger, formed easily throwing, and caused the change of oxide regions film thickness.The selection here is than the ratio that refers to silicon-dioxide and silicon nitride removal speed.
Patent documentation CN200580009957.1 disclose a kind of for shallow trench isolation from chemical mechanical polishing liquid, this polishing fluid comprises the moisture abrasive solution that is comprised of deionized water, abrasive grains and dispersion agent and the aqueous additives solution that is comprised of carboxylic acid macromolecular compound, nitrogenous organic cyclic cpds and amino-complex.The silicon-dioxide that uses this polishing fluid is 25: 1～58: 1 with the selection ratio of silicon nitride.Used KOH as pH adjusting agent among its preferential embodiment, this has just introduced metal ion in slurries, is unfavorable for foreign ion control and rear cleaning in the polishing process.
Patent documentation US6984588 discloses a kind of chemical mechanical polishing liquid, and it is oxygenant that this polishing fluid comprises to contain ceric composite salt, and silicon-dioxide is abrasive grains, and control pH scope is 3～11.Using the silicon-dioxide of this slurry and the selection ratio of silicon nitride is 30: 1～150: 1, reached very high selection ratio, but its pH scope is too small, only reaches high selection ratio when the pH value is 4～5.
Patent documentation WO2007135794A1 discloses a kind of chemical mechanical polishing liquid, and this polishing fluid comprises composite particles and a kind of planarization agent that forms with cerium oxide and PMMA.Using the silicon-dioxide of this polishing fluid and the selection ratio of silicon nitride is 20: 1～60: 1, selects highlyer, but its polishing precision is inadequate, easily produces to scratch.
As seen from the above, be used at present the chemical mechanical polishing liquid in the CMP technique of semiconductor shallow trench isolation (STI), exist easy introducing metal ion, narrow application range is polished the shortcomings such as precision is low.Therefore, need to develop a kind of high selectivity that possesses simultaneously, metal ion is not applied widely, the new chemical mechanical polishing liquid of polishing precision advantages of higher.
Summary of the invention
The object of the present invention is to provide a kind of chemical mechanical polishing liquid for polishing of semiconductor wafers, the defects that exists to overcome prior art, satisfy shallow trench isolation that semi-conductor makes from the requirement of CMP technique increasingly stringent.
Chemical mechanical polishing liquid of the present invention is comprised of the component of following weight percent:
Acid pH modulator 0.2-5%, piperidine nitroxide free-radical 0.01-5%, tensio-active agent 0.1-15%, the water of abrasive grains 0.5-20% and surplus;
The pH value is 2～5;
The meta particle diameter of abrasive grains is 100～400nm;
Corresponding particle diameter when the cumulative particle size distribution percentage ratio that meta particle diameter of the present invention is abrasive grains reaches 50%.
Described acid pH modulator is selected from one or more in nitric acid, sulfuric acid, hydrochloric acid, ammonium nitrate or the propionic acid, preferred ammonium nitrate;
Described piperidine nitroxide free-radical is selected from 2,2,6,6-tetramethyl piperidine-1-oxyradical, 4-hydroxy piperidine alcohol oxyradical or 4-oxygen-2,2,6, one or more in 6-tetramethyl piperidine-1-oxyradical; Preferred 2,2,6,6-tetramethyl piperidine-1-oxyradical.Piperidine nitroxide free-radical can produce synergy with tensio-active agent in polishing fluid of the present invention, significantly reduce the removal speed of silicon nitride, and do not reduce the removal speed of silicon-dioxide, improves optionally purpose thereby reach.
Described tensio-active agent is selected from that the lipid acid sorb is smooth, in stearic acid, Cetyltrimethylammonium bromide or the trimethyl-glycine one or more; Preferred Cetyltrimethylammonium bromide.
Described abrasive grains is selected from cerium oxide, the cerium oxide of adulterated al or silicon-dioxide, preferential oxidation cerium.
Among the present invention, all reagent and raw material be commercially available getting all.
The preparation method of the chemical mechanical polishing liquid for polishing of semiconductor wafers of the present invention is the physical mixed method of routine.
Positive progressive effect of the present invention is: polishing fluid of the present invention can significantly change the removal speed of silicon nitride under acidic conditions, regulates the selection ratio of silicon-dioxide and silicon nitride, and has that blending process is simple, polishing precision advantages of higher.
Description of drawings
Fig. 1～Fig. 5 is the size-grade distribution of embodiment 1 prescription 1～5 polishing fluid.
Embodiment
Mode below by embodiment further specifies the present invention, does not therefore limit the present invention among the described scope of embodiments.
Embodiment 1
Table 1 has provided the prescription of chemical mechanical polishing liquid 1～5 of the present invention, mixes by each composition and the content thereof given in the table and gets final product to get the polishing fluid of each embodiment, and water is surplus.
Use LS-POP (VI) the type laser particle analyzer of Zhuhai American-European gram company respectively the abrasive grains in the polishing fluid 1～5 to be carried out testing graininess, the gained particle size distribution figure is seen Fig. 1～5, and the testing graininess result is CeO in the polishing fluid 1
2The meta particle diameter of particle is 103nm, the CeO of adulterated al in the polishing fluid 2
2The meta particle diameter of particle is 392nm, SiO in the polishing 3
2The meta particle diameter of particle is 334nm, CeO in the polishing fluid 4
2The meta particle diameter of particle is 215nm, SiO in the polishing fluid 5
2The meta particle diameter of particle is 146nm.
Table 1 chemical mechanical polishing liquid 1～5 of the present invention
Effect embodiment 1
Table 2 has provided prescription and the polishing effect data of contrast polishing fluid 1 and polishing fluid of the present invention 6～10, mixes by each composition and the content thereof given in the table and gets final product to get the polishing fluid of each embodiment, and water is surplus.
The glossing parameter is: polishing machine is that Buehler Phoenix Beta, polishing pad are IC1000/SUBAIV, overdraft 2psi, load plate speed 100rpm, a speed 100rpm, polishing slurries flow velocity 200ml/min.The result is as shown in table 2.
Compositing formula and the polishing effect of table 2 contrast polishing fluid 1 and polishing fluid of the present invention 6～10
By table 2 data as seen, compare with contrast polishing fluid 1, polishing fluid 6～10 of the present invention removal speed of silicon-dioxide that is significantly increased, and reduced the removal speed of silicon nitride, thus improved the selection ratio of silicon-dioxide with silicon nitride.
Table 3 has provided prescription and the polishing effect data of contrast polishing fluid 2～4 and polishing fluid 11, mixes by each composition and the content thereof given in the table and gets final product to get the polishing fluid of each embodiment, and water is surplus.
The glossing parameter is: polishing machine is that Buehler Phoenix Beta, polishing pad are politex, overdraft 1psi, load plate speed 100rpm, a speed 100rpm, polishing slurries flow velocity 200ml/min.The result is as shown in table 3.
Compositing formula and the polishing effect of table 3 contrast polishing fluid 2～4 and polishing fluid of the present invention 11
By the data that contrast polishing fluid 2～4 in the table 3 as seen, add surfactivity and can significantly improve silicon-dioxide removal speed, reduce silicon nitride and remove speed, thereby reach higher selection ratio, polishing effect is affected little and add separately piperidine NO free radical.By the data that contrast polishing fluid 4 and polishing fluid 11 in the table 3 as seen, after having added piperidine NO free radical, because the synergy between itself and the tensio-active agent, significantly reduce the removal speed of silicon nitride, and do not reduce the removal speed of silicon-dioxide, select ratio thereby improved.
Claims (5)
1. the chemical mechanical polishing liquid that is used for polishing of semiconductor wafers, it is characterized in that, formed by the component of following weight percent: acid pH modulator 0.2-5%, piperidine nitroxide free-radical 0.01-5%, tensio-active agent 0.1-15%, the water of abrasive grains 0.5-20% and surplus;
Described piperidine nitroxide free-radical is selected from 2,2,6,6-tetramethyl piperidine-1-oxyradical, 4-hydroxy piperidine alcohol oxyradical or 4-oxygen-2,2,6, one or more in 6-tetramethyl piperidine-1-oxyradical;
Described tensio-active agent is selected from that the lipid acid sorb is smooth, in stearic acid, Cetyltrimethylammonium bromide or the trimethyl-glycine one or more.
2. the chemical mechanical polishing liquid for polishing of semiconductor wafers according to claim 1 is characterized in that, the pH value is 2～5.
3. the chemical mechanical polishing liquid for polishing of semiconductor wafers according to claim 1 is characterized in that, the meta particle diameter of abrasive grains is 100～400nm.
4. each described chemical mechanical polishing liquid for polishing of semiconductor wafers is characterized in that according to claim 1～3, and described acid pH modulator is selected from one or more in nitric acid, sulfuric acid, hydrochloric acid, ammonium nitrate or the propionic acid.
5. each described chemical mechanical polishing liquid for polishing of semiconductor wafers is characterized in that described abrasive grains is selected from cerium oxide, the cerium oxide of adulterated al or silicon-dioxide according to claim 1～3.
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| CN102533123B true CN102533123B (en) | 2013-10-30 |
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| CN107365997A (en) * | 2017-07-13 | 2017-11-21 | 温州万众表面处理技术有限公司 | A kind of polishing agent and preparation method thereof |
| WO2020245904A1 (en) * | 2019-06-04 | 2020-12-10 | 昭和電工マテリアルズ株式会社 | Polishing solution, dispersion, polishing solution production method, and polishing method |
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| CN101437912A (en) * | 2006-03-20 | 2009-05-20 | 卡伯特微电子公司 | Oxidation-stabilized cmp compositions and methods |
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| CN101437912A (en) * | 2006-03-20 | 2009-05-20 | 卡伯特微电子公司 | Oxidation-stabilized cmp compositions and methods |
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