CN102533125A - Chemically mechanical polishing solution - Google Patents
Chemically mechanical polishing solution Download PDFInfo
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- CN102533125A CN102533125A CN2010106201523A CN201010620152A CN102533125A CN 102533125 A CN102533125 A CN 102533125A CN 2010106201523 A CN2010106201523 A CN 2010106201523A CN 201010620152 A CN201010620152 A CN 201010620152A CN 102533125 A CN102533125 A CN 102533125A
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- triazole
- tetrazole
- mechanical polishing
- chemical mechanical
- polishing liquid
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Abstract
The invention discloses a novel chemically mechanical polishing solution for polycrystal silicon. The novel chemically mechanical polishing solution comprises grinding particles, at least one azoles compound and at least one polyalcohol nonionic surfactant. The novel chemically mechanical polishing solution can be used for adjusting the selection rate between the polycrystal silicon and silicon dioxide and remarkably improving the polarization efficiency of the polycrystal silicon.
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 to have the saucerization of polysilicon unavoidably when last polishing process stops on the silicon dioxide layer than too high because of the polishing speed of polycrystalline silicon/silicon dioxide.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 saucerization, causes in the polishing process after subsequent step covers polysilicon layer residual polysilicon in the silicon-dioxide saucerization.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 surperficial saucerization defective in the polysilicon polishing process, and to remove the problem of polysilicon residual in the silicon-dioxide saucerization 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), the compound of-NH2 (OH) 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 silica sphere saucerization 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 polishing fluid 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 above-mentioned 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 polyol-based non-ionic surfactant 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 polyol-based non-ionic surfactant is esters surface active agent and/or the polyglycol surfactants that polyvalent alcohol and lipid acid generate through esterification.
Described esters surface active agent is polyhydric alcohol fatty acid ester R
1O
mH
M-n(OCR
2)
n, cithrol R
2COO (CH
2CH
2O)
pH or R
2COO (CH
2CH
2O)
pOCR
2, polyoxyethylene polyols fatty ester R
1O
mH
M-n(CH
2CH
2O)
p(OCR
2)
n, wherein, R
1(OH)
mBe the polyvalent alcohol of 2≤m≤8,4≤p≤120, R
2COOH is that carbonatoms is 8～22 lipid acid, n=1～4 and m>=n
Described polyvalent alcohol is terepthaloyl moietie, glycol ether, Tri Ethyleneglycol, Ucar 35, glycerine, poly-glycerol, T 46155 glycerine, tetramethylolmethane, dehydration Xylitol, T 46155 dehydration Xylitol, sorbyl alcohol, polyoxyethylene sorbitol, anhydrous sorbitol, polyoxyethylene sorbitan, sucrose or polyoxyethylene glycol.
Described polyglycol surfactants is that molecular weight is 200～20000 polyoxyethylene glycol.
The content of described polyol-based non-ionic surfactant is preferably 0.0001～5wt%, is more preferred from 0.001～1wt%.
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.
The pH value of polishing fluid of the present invention is preferably 7～12.
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.
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, polyol-based non-ionic surfactant 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 regulating the amount of azole compounds and polyol-based non-ionic surfactant, 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 problem of the generation of polysilicon saucerization defective and the residual polycrystalline silicon in the silicon-dioxide saucerization between the silicon-dioxide raceway groove.Can realize high planarization degree through step polishing, no residual polycrystalline silicon can obtain chip architecture as shown in Figure 3 after the polishing.Polishing fluid 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 Chemico-mechanical polishing slurry for polysilicon 1～35 of the present invention; Mix by each composition and the content thereof given in the table; Water is supplied weight percent to 100%, adopts Pottasium Hydroxide and nitric acid etc. to be adjusted to the polishing fluid that suitable pH value can make each embodiment afterwards, and water is surplus.
The chemical mechanical polishing liquid 1～35 of table 1 polysilicon
Effect embodiment
Table 2 has provided the prescription of contrast polishing fluid 1～2 and polishing fluid 36～41 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 and silicon-dioxide, 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 36～41
Visible by table 2 data; Compare with contrast polishing fluid 1, polishing fluid 36～41 of the present invention all has lower removal rate of polysilicon, and the removal speed of silicon-dioxide slightly improves; Thereby reduced the selection ratio of polysilicon, improved planarization efficiency with silicon-dioxide.
Data by contrast polishing fluid 2 and polishing fluid 36～41 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 can rise thereupon slightly.Therefore, can regulate the polycrystalline silicon/silicon dioxide 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 removal rate of polysilicon, help to remove the residual polycrystalline silicon in the silicon-dioxide butterfly depression.Azole compounds also helps the polishing resistates after the polishing is taken away.
Mentioned all commercially available the getting of compound among the present invention.
Claims (13)
1. a chemical mechanical polishing liquid comprises abrasive grains, at least a azole compounds and at least a polyol-based non-ionic surfactant.
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 each described chemical mechanical polishing liquid of claim 1-3, it is characterized in that: the concentration of said azole compounds is 0.0001～10wt%.
5. chemical mechanical polishing liquid as claimed in claim 1 is characterized in that, described polyol-based non-ionic surfactant is esters surface active agent and/or the polyglycol surfactants that polyvalent alcohol and lipid acid generate through esterification.
6. chemical mechanical polishing liquid as claimed in claim 5 is characterized in that: described esters surface active agent is polyhydric alcohol fatty acid ester R
1O
mH
M-n(OCR
2)
n, cithrol R
2COO (CH
2CH
2O)
pH or R
2COO (CH
2CH
2O)
pOCR
2, polyoxyethylene polyols fatty ester R
1O
mH
M-n(CH
2CH
2O)
p(OCR
2)
n, wherein, R
1(OH)
mBe the polyvalent alcohol of 2≤m≤8,4≤p≤120, R
2COOH is that carbonatoms is 8～22 lipid acid, n=1～4 and m>=n.
7. chemical mechanical polishing liquid as claimed in claim 6 is characterized in that: described polyvalent alcohol is terepthaloyl moietie, glycol ether, Tri Ethyleneglycol, Ucar 35, glycerine, poly-glycerol, T 46155 glycerine, tetramethylolmethane, dehydration Xylitol, T 46155 dehydration Xylitol, sorbyl alcohol, polyoxyethylene sorbitol, anhydrous sorbitol, polyoxyethylene sorbitan, sucrose or polyoxyethylene glycol.
8. chemical mechanical polishing liquid as claimed in claim 5 is characterized in that: described polyglycol surfactants is that molecular weight is 200～20000 polyoxyethylene glycol.
9. chemical mechanical polishing liquid as claimed in claim 1 is characterized in that, the concentration of described polyol-based non-ionic surfactant is 0.0001～5wt%.
10. 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.
11. like claim 1 or 10 described chemical mechanical polishing liquids, it is characterized in that: the concentration of said abrasive grains is 0.1～30wt%.
12. like claim 1 or 10 described chemical mechanical polishing liquids, it is characterized in that: the particle diameter of said abrasive grains is 20～150nm.
13. 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.
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|---|---|---|---|
| CN2010106201523A CN102533125A (en) | 2010-12-30 | 2010-12-30 | Chemically mechanical polishing solution |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104745086A (en) * | 2013-12-25 | 2015-07-01 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution for barrier layer planarization, and use method thereof |
| CN106567122A (en) * | 2017-02-17 | 2017-04-19 | 大博医疗科技股份有限公司 | Electrochemical polishing electrolyte and polishing method for titanium and titanium alloy |
| CN108026434A (en) * | 2015-09-25 | 2018-05-11 | 荣昌化学制品株式会社 | CMP paste compounds and the polishing method using said composition |
| CN113308696A (en) * | 2021-05-28 | 2021-08-27 | 昆山市韩铝化学表面材料有限公司 | Chemical polishing bright additive for chemical polishing of aluminum alloy two acids and polishing process |
-
2010
- 2010-12-30 CN CN2010106201523A patent/CN102533125A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104745086A (en) * | 2013-12-25 | 2015-07-01 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution for barrier layer planarization, and use method thereof |
| CN108026434A (en) * | 2015-09-25 | 2018-05-11 | 荣昌化学制品株式会社 | CMP paste compounds and the polishing method using said composition |
| CN106567122A (en) * | 2017-02-17 | 2017-04-19 | 大博医疗科技股份有限公司 | Electrochemical polishing electrolyte and polishing method for titanium and titanium alloy |
| CN113308696A (en) * | 2021-05-28 | 2021-08-27 | 昆山市韩铝化学表面材料有限公司 | Chemical polishing bright additive for chemical polishing of aluminum alloy two acids and polishing process |
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Application publication date: 20120704 |