CN102559059A - Chemical-mechanical polishing liquid - Google Patents
Chemical-mechanical polishing liquid Download PDFInfo
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- CN102559059A CN102559059A CN2010106040220A CN201010604022A CN102559059A CN 102559059 A CN102559059 A CN 102559059A CN 2010106040220 A CN2010106040220 A CN 2010106040220A CN 201010604022 A CN201010604022 A CN 201010604022A CN 102559059 A CN102559059 A CN 102559059A
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- triazole
- tetrazole
- mechanical polishing
- chemical mechanical
- sulfydryl
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- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention discloses novel chemical-mechanical polishing liquid, which is used for polycrystalline silicon. The polishing liquid comprises grinding particles, at least one kind of azole compound and at least one kind of phosphate ester surfactant. According to the polishing liquid, the selection ratio of polycrystalline silicon to silicon dioxide can be regulated, and the flattening efficiency of the polycrystalline silicon is obviously enhanced.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid, relate in particular to a kind of chemical mechanical polishing liquid that is used for polishing polycrystalline silicon.
Background technology
In unicircuit was made, the standard of interconnection technique deposited one deck again improving above one deck, make to have formed irregular pattern at substrate surface.A kind of flattening method that uses in the prior art is exactly chemically machinery polished (CMP), and CMP technology just is to use a kind of mixture and polishing pad that contains abrasive material to remove to polish a silicon chip surface.In typical cmp method, substrate is directly contacted with rotating polishing pad, exert pressure at substrate back.During polishing; Pad and operator's console rotation; The power that keeps down at substrate back simultaneously is applied to abrasive material and chemically reactive solution (being commonly referred to polishing fluid or polishing slurries) on the pad, and this polishing fluid begins to carry out polishing process with the film generation chemical reaction that is polishing.
In the polishing process of polysilicon, can there be following two problems usually: 1. select to make when last polishing process stops on the silicon dioxide layer because of the polishing speed of polycrystalline silicon/silicon dioxide, have the dish-shaped recessed damage of polysilicon unavoidably than too high.As shown in Figure 1, a, b are respectively before the polishing and the structure after the polishing among the figure.And this problem can increase the weight of along with the increase of the groove width between the silicon-dioxide.This can cause the performance of device and have a strong impact on.2. in shallow trench isolation (STI) chemical mechanical planarization process, silica sphere forms dish-shaped recessed damage, causes in the polishing process after subsequent step covers polysilicon layer residual polysilicon in the recessed damage of silicon-dioxide dish.As shown in Figure 2, a, b are respectively before the polishing and the structure after the polishing among the figure.This can cause the performance of device equally and have a strong impact on.
Therefore, solve the dish-shaped recessed damage defective in surface in the polysilicon polishing process, and the problem of the recessed damage of silicon-dioxide dish of removing polysilicon residual most important.US2003/0153189A1 discloses a kind of chemical mechanical polishing liquid and method that is used for the polysilicon polishing; This polishing fluid comprises a kind of polymeric surfactant and a kind of abrasive grains that is selected from aluminum oxide and cerium oxide; This polymeric surfactant is the polycarboxylate tensio-active agent; Can make the polishing speed in polysilicon surface bulk zone be much higher than the polishing speed in the groove with this slurry, thereby reduce depression.US2003/0216003A1 and US2004/0163324A1 disclose the method for a kind of Flash of manufacturing.Comprising a kind of polishing fluid of polishing polycrystalline silicon, comprise at least a containing-N (OH) in this polishing fluid ,-NH (OH) ,-NH
2(OH) compound of group, the polishing selection ratio of polysilicon and silicon-dioxide of using this slurry is greater than 50.US2004/0123528A1 discloses a kind of acid polishing slurry that comprises abrasive grains and anionic compound, and this anionic compound can reduce the removal speed of resist film, improves the removal rate selection ratio of polysilicon and resist film.US2005/0130428A1 and CN 1637102A disclose a kind of slurry that is used for multi crystal silicon chemical mechanical polishing, and this paste composition comprises that one or more form passivation layer on polysilicon layer nonionogenic tenside and a kind of can form that second passivation layer can reduce silicon nitride or silicon oxide is removed the second surface promoting agent of speed.Patent documentation US6191039 has disclosed a kind of cmp method, can reduce the time and the cost of chemical rightenning, and good planarization effect is arranged.Though above technology has reached certain planarization effect to a certain extent; Polishing time and cost have been shortened; But or operation in two steps, perhaps just suppressed the polishing speed of polysilicon, be unfavorable for the removal of polysilicon in the silicon-dioxide butterfly depression; And complicated operation, polishing effect is limited.
Description of drawings
Fig. 1 is in the conventional polysilicon polishing process, the chip architecture figure of (a) and polishing back (b) before the polishing;
Fig. 2 is the recessed damage of silica sphere dish that causes in shallow trench isolation (STI) chemical mechanical planarization process, the synoptic diagram of (a) back (b) before the polysilicon polishing process;
Fig. 3 is for using new purposes of the present invention obtainable chip architecture figure after polishing.
Summary of the invention
The objective of the invention is to select than too high in order to solve in the above-mentioned prior art polycrystalline silicon/silicon dioxide; Residual polysilicon is removed difficult problem in the silicon-dioxide butterfly depression, and a kind of chemical mechanical polishing liquid that the suitable polycrystalline silicon/silicon dioxide of having of polishing polycrystalline silicon is selected ratio that is used for is provided.
Polishing fluid of the present invention contains abrasive grains, at least a azole compounds, at least a phosphoric acid ester tensio-active agent and water.
Among the present invention, described azole compounds is preferable is in triazole and verivate and salt and tetrazole and verivate and the salt one or more.What described triazole and verivate thereof were preferable is 1,2,3-triazole, 5-sulfydryl-1,2,3-triazole, benzotriazole, 5-chloro benzo triazole, 5-carboxy benzotriazole, 5-methyl benzotriazazole, 1,2; 4-triazole, 1,2,4-triazole-3-methane amide, 1,2,4-triazole-3-carboxylic acid, 3-sulfydryl-1,2; 4-triazole, 3-amino-1,2,4-triazole, 3-amino-1,2,4-triazole-5-carboxylic acid, 3-amino-5-sulfydryl-1; 2,4-triazole, 3-nitro-1,2,4-triazole, 4-amino-1,2; 4-triazole, 3-sulfydryl-4-methyl isophthalic acid, 2,4-triazole, 3,5-diaminostilbene, 2; 4-triazole, 1,2,4-triazole-3-carboxylate methyl ester and 5-amino-1,2, one or more in 4-triazole-3-carboxylate methyl ester.Described tetrazole and verivate thereof are the 1H-tetrazole; 1H-tetrazole-5-ethyl formate; 5-phenyl-tetrazole; 5-methyl-tetrazole; 1-methyl-5-sulfydryl-1H-tetrazole; 5-chloromethyl-1H-tetrazole; 5-benzyl tetrazole; 5-benzylthio-tetrazole; The amino tetrazole of 5-; 2-methyl-5-amino-2H-tetrazole; 5-methylthio group tetrazole; 5-ethylmercapto group tetrazole; 1-hydroxyethyl-5-sulfydryl-tetrazole; 1-phenyl-5-sulfydryl-tetrazole; Tetrazoleacetic acid; In 1-ethyl-5-sulfydryl-tetrazole and the 4-hydroxy phenyl-5-sulfydryl-tetrazole one or more.Described salt is sodium salt, sylvite or ammonium salt.
The content of described azole compounds in polishing fluid is preferably 0.0001～10wt%, is more preferred from 0.001～3wt%.
Among the present invention, described phosphoric acid ester tensio-active agent has following structure:
Or
Or contain the PAPE of two above structural formulas (1), and wherein, X=RO, RO-(CH
2CH
2O)
n, RCOO-(CH
2CH
2O)
nR is the alkyl of C8～C22, korenyl and/or glyceryl (C
3H
5O
3-); The value of n is selected from 3～30, and M is H, K, NH
4, (CH
2CH
2O)
1～3NH
3～1And/or Na.
The content of described phosphoric acid ester tensio-active agent is 0.0005～1wt%, is preferably 0.001～0.5wt%.
Among the present invention, said abrasive grains is that this area abrasive grains commonly used is one or more in silicon-dioxide, cerium dioxide, titanium oxide and the polymer abrasive grains of silicon-dioxide, aluminium coating of silicon-dioxide, aluminium sesquioxide, adulterated al.
The content of described abrasive grains is 0.1～30wt%.Be more preferred from 0.5～20wt%.
The particle diameter of described abrasive grains is preferably 20～150nm, is more preferred from 30～120nm.
What the pH value of polishing fluid of the present invention was preferable is 2～12, is 7～12 more.
Can also contain pH regulator agent commonly used in the polishing fluid of the present invention, viscosity modifier and/or skimmer etc. are controlled the characteristic such as pH and viscosity of polishing fluid through them.
Polishing fluid of the present invention is simply mixed promptly by mentioned component and gets.
Polishing fluid of the present invention can concentrate preparation, adds deionized water during use and is diluted to concentration range of the present invention, mixes to get final product.
In the present invention, polishing fluid is used to relate to the polishing of silicon single crystal and polysilicon.
Positive progressive effect of the present invention is: polishing fluid of the present invention can polish silicon single crystal and polysilicon membrane preferably under alkaline condition.Wherein, the phosphoric acid ester tensio-active agent can significantly reduce removal rate of polysilicon, and does not significantly reduce the removal speed of silicon-dioxide, thereby significantly reduces the selection ratio of polysilicon and silicon-dioxide; Azole compounds can dissolve polysilicon, will polish resistates and take away, and avoids being adsorbed on again on wafer or the polishing pad.Through the amount of azole compounds and phosphoric acid ester tensio-active agent, can obtain to have the polishing fluid that suitable polycrystalline silicon/silicon dioxide is selected ratio.This polishing fluid has compared with prior art better solved in the existing polysilicon polishing process generation of the recessed damage defective of polysilicon dish in the silicon-dioxide raceway groove and the problem of the residual polycrystalline silicon in the silicon-dioxide saucerization.Can realize high planarization degree through step polishing, no residual polycrystalline silicon can obtain the chip architecture shown in accompanying drawing 3 after the polishing.New purposes of the present invention also has the wide characteristics of process window, and productivity is improved greatly, and production cost reduces greatly.
Embodiment
Mode through embodiment further specifies the present invention below, does not therefore limit the present invention among the described scope of embodiments.
The chemical mechanical polishing liquid of embodiment 1 polysilicon
Table 1 has provided the prescription of polysilicon 2 chemical mechanical polishing liquids 1～36 of the present invention; Mix by each composition and the content thereof given in the table; Water is supplied weight percent to 100%; Adopt Pottasium Hydroxide and nitric acid etc. to be adjusted to the polishing fluid that suitable pH value can make each embodiment afterwards, water is surplus.Mentioned all commercially available the getting of compound among the present invention.
The chemical mechanical polishing liquid 1～36 of table 1 polysilicon
Effect embodiment
Table 2 has provided the prescription of contrast polishing fluid 1 and polishing fluid 37～42 of the present invention, by table 2 each component is mixed, and water is supplied weight percent to 100%, adopts Pottasium Hydroxide and nitric acid to be adjusted to suitable pH value afterwards and can make each polishing fluid.
Above-mentioned each polishing fluid is used for polishing polycrystalline silicon 2 and silica 1, and the processing parameter of polishing is: overdraft 3psi, the rotating speed 70rpm of polishing disk (14 inches of diameters); Rubbing head rotating speed 80rpm; Polishing slurries flow velocity 100ml/min, polishing pad are politex, and polishing machine is Logitech LP50.The result is as shown in table 2.
The compositing formula and the polishing speed of table 2 contrast polishing fluid 1～2 and polishing fluid 37～42
Visible by table 2 data; Compare with contrast polishing fluid 1, polishing fluid 37～42 of the present invention all has the removal speed of lower polysilicon 2, and the removal speed of silica 1 slightly improves; Thereby reduced the selection ratio of polysilicon 2, improved planarization efficiency with silica 1.
Data by contrast polishing fluid 2 and polishing fluid 37～42 in the table 2 are visible, under all identical situation of other compositions and content thereof, added azole compounds after, the polishing speed of polysilicon 2 can raise thereupon slightly.But its to the influence degree of polishing speed much smaller than the phosphoric acid ester tensio-active agent.Therefore, can regulate the polysilicon 2/ silica 1 selection ratio of polishing fluid through the content of regulating two kinds of compounds.Compare with contrast polishing fluid 2, added azole compounds in the polishing fluid of the present invention, make polishing fluid of the present invention excessively not suppress the removal speed of polysilicon 2, the polysilicon 2 that helps to remove in the silica 1 butterfly depression is residual.Azole compounds also helps the polishing resistates after the polishing is taken away.
In the accompanying drawings, mark 1 is a silicon-dioxide, and mark 2 is a polysilicon, and mark 3 is substrate.
Claims (12)
1. chemical mechanical polishing liquid, it comprises:
(a) abrasive grains,
(b) azole compounds,
(c) phosphoric acid ester tensio-active agent,
(d) water.
2. chemical mechanical polishing liquid as claimed in claim 1 is characterized in that: said azole compounds is one or more in triazole and verivate and salt and tetrazole and verivate and the salt.
3. chemical mechanical polishing liquid as claimed in claim 2 is characterized in that: said triazole and verivate thereof are selected from 1,2,3-triazole, 5-sulfydryl-1,2,3-triazole, benzotriazole, 5-chloro benzo triazole, 5-carboxy benzotriazole, 5-methyl benzotriazazole, 1; 2,4-triazole, 1,2,4-triazole-3-methane amide, 1,2,4-triazole-3-carboxylic acid, 3-sulfydryl-1; 2,4-triazole, 3-amino-1,2,4-triazole, 3-amino-1,2,4-triazole-5-carboxylic acid, 3-amino-5-sulfydryl-1; 2,4-triazole, 3-nitro-1,2,4-triazole, 4-amino-1,2; 4-triazole, 3-sulfydryl-4-methyl isophthalic acid, 2,4-triazole, 3,5-diaminostilbene, 2; 4-triazole, 1,2,4-triazole-3-carboxylate methyl ester and 5-amino-1,2, one or more in 4-triazole-3-carboxylate methyl ester; Said tetrazole and verivate thereof are the 1H-tetrazole; 1H-tetrazole-5-ethyl formate; 5-phenyl-tetrazole; 5-methyl-tetrazole; 1-methyl-5-sulfydryl-1H-tetrazole; 5-chloromethyl-1H-tetrazole; 5-benzyl tetrazole; 5-benzylthio-tetrazole; The amino tetrazole of 5-; 2-methyl-5-amino-2H-tetrazole; 5-methylthio group tetrazole; 5-ethylmercapto group tetrazole; 1-hydroxyethyl-5-sulfydryl-tetrazole; 1-phenyl-5-sulfydryl-tetrazole; Tetrazoleacetic acid; In 1-ethyl-5-sulfydryl-tetrazole and the 4-hydroxy phenyl-5-sulfydryl-tetrazole one or more; Said salt is sodium salt, sylvite or ammonium salt.
4. like the described chemical mechanical polishing liquid of claim 1-3, it is characterized in that: the concentration of said azole compounds is for being 0.0001～10wt%.
5. chemical mechanical polishing liquid as claimed in claim 1 is characterized in that: said phosphoric acid ester tensio-active agent has following structure:
6. like claim 1 or 5 described chemical mechanical polishing liquids, it is characterized in that: said phosphoric acid ester surfactant concentrations is 0.0005～1wt%.
7. chemical mechanical polishing liquid as claimed in claim 6 is characterized in that: said phosphoric acid ester surfactant concentration is 0.001～0.5wt%.
8. chemical mechanical polishing liquid as claimed in claim 1 is characterized in that: said abrasive grains is selected from one or more in silicon-dioxide, cerium dioxide, titanium oxide and the polymer abrasive grains of silicon-dioxide, aluminium coating of silicon-dioxide, aluminium sesquioxide, adulterated al.
9. like claim 1 or 8 described chemical mechanical polishing liquids, it is characterized in that: the concentration of said abrasive grains is 0.1～30wt%.
10. like claim 1 or 8 described chemical mechanical polishing liquids, it is characterized in that: the particle diameter of said abrasive grains is 20～150nm.
11. chemical mechanical polishing liquid as claimed in claim 1 is characterized in that: the pH value of said chemical mechanical polishing liquid is 7～12.
12. polishing fluid as claimed in claim 1 is characterized in that, said polishing fluid is used to relate to the polishing of silicon single crystal and polysilicon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106040220A CN102559059A (en) | 2010-12-21 | 2010-12-21 | Chemical-mechanical polishing liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106040220A CN102559059A (en) | 2010-12-21 | 2010-12-21 | Chemical-mechanical polishing liquid |
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|---|---|
| CN102559059A true CN102559059A (en) | 2012-07-11 |
Family
ID=46405721
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|---|---|---|---|
| CN2010106040220A Pending CN102559059A (en) | 2010-12-21 | 2010-12-21 | Chemical-mechanical polishing liquid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014089906A1 (en) * | 2012-12-10 | 2014-06-19 | 安集微电子（上海）有限公司 | Application of phosphate ester surfactant in self-stopping polishing |
| CN109971359A (en) * | 2017-12-27 | 2019-07-05 | 安集微电子（上海）有限公司 | A kind of chemical mechanical polishing liquid |
| CN111378367A (en) * | 2018-12-27 | 2020-07-07 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| WO2023103853A1 (en) * | 2021-12-09 | 2023-06-15 | 安集微电子科技（上海）股份有限公司 | Cleaning fluid and use thereof |
-
2010
- 2010-12-21 CN CN2010106040220A patent/CN102559059A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014089906A1 (en) * | 2012-12-10 | 2014-06-19 | 安集微电子（上海）有限公司 | Application of phosphate ester surfactant in self-stopping polishing |
| CN109971359A (en) * | 2017-12-27 | 2019-07-05 | 安集微电子（上海）有限公司 | A kind of chemical mechanical polishing liquid |
| CN109971359B (en) * | 2017-12-27 | 2021-12-07 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| CN111378367A (en) * | 2018-12-27 | 2020-07-07 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| WO2023103853A1 (en) * | 2021-12-09 | 2023-06-15 | 安集微电子科技（上海）股份有限公司 | Cleaning fluid and use thereof |
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Application publication date: 20120711 |