CN101906272A - Solution for polishing and cleaning silicon - Google Patents
Solution for polishing and cleaning silicon Download PDFInfo
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- CN101906272A CN101906272A CN2009100526618A CN200910052661A CN101906272A CN 101906272 A CN101906272 A CN 101906272A CN 2009100526618 A CN2009100526618 A CN 2009100526618A CN 200910052661 A CN200910052661 A CN 200910052661A CN 101906272 A CN101906272 A CN 101906272A
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Abstract
The invention relates to solution for chemically mechanical polishing or surface cleaning for silicon. The aqueous solution consists of water and at least one compound. The solution does not contain abrasive particles. The compound in the solution can be guanidine or guanidyl-containing compound, amide or acylamino-containing compound, imidazole or imidazolyl-containing compound, urea or carbamido-containing compound, compound of molecules simultaneously containing at least two of guanidine functional group, imidazole functional group, urea functional group and amide functional group, or mixture of the compounds. The solution also can comprise silicon inhibitor and/or metal ion complexing agent compound. When the solution is used for chemically mechanical polishing or cleaning for the silicon, the silicon surface can obtain extremely low surface roughness, extremely low surface heavy metal ion content and extremely low surface granule residue.
Description
Technical field
The present invention relates to a kind of solution that is used for the chemically machinery polished and the cleaning of silicon chip or silicon film.
Background technology
Silicon film refers generally to polysilicon membrane and monocrystalline silicon sheet surface.Up to the present, for the chemically machinery polished of the silicon chemical mechanical polishing liquids that contain abrasive grains that adopt more.And the chemically machinery polished for silicon in early days is many based on mechanical effect mechanism.Thereby in corresponding chemical mechanical polishing liquid, contain a large amount of abrasive grains.The use of a large amount of abrasive grains, the level that one side makes the roughness of surface of polished to reach is limited, and on the other hand, the particle residue on surface is more, also makes the yield of producing descend in the burden that has strengthened back cleaning.At present, the chemical mechanical polishing liquid that comprehensively works with mechanical effect and chemical action has also appearred.This is improved above-mentioned problem relatively.But silicon face roughness after polishing, surface particles is residual, and there is certain limit in the stable aspect of polishing fluid.Simultaneously, owing to contain more metal ion in the abrasive grains colloidal sol, this is at silicon polishing and desiredly in cleaning definitely avoid.EP 1072662 has disclosed a kind of chemical mechanical polishing liquid that is used for film such as silicon, and it is by water-soluble medium, and polishing accelerator and abrasive grains are formed.Wherein polish accelerator and comprised guanidine.This polishing fluid can improve the polishing speed of silicon, but the speed that is improved is limited.Because have abrasive grains in the polishing fluid, easily cause machinery to scratch surface irregularity, problems such as particle residue simultaneously.US6852009 has also disclosed a kind of chemical mechanical polishing liquid that is used for film such as silicon, and it is by water, the silicon-dioxide abrasive grains, and alkaline matter, and prevent the chemical combination additive that transition metal stains.Although it can make moderate progress aspect the metal contamination preventing, still there is above-mentioned deficiency.Therefore people wish to have a kind of polishing fluid or scavenging solution can make silicon face realize extremely low surfaceness, and extremely low surperficial heavy metal ion content and extremely low surface particles are residual.
Summary of the invention
The technical problem to be solved in the present invention is to overcome existing polishing fluid to cause the silicon face roughness bigger after polishing, exists surface particles residual, the defective that stability is not good; A kind of abrasive grains that do not contain is provided, can makes silicon face realize extremely low surfaceness, the silicon polishing and the scavenging solution of extremely low surperficial heavy metal ion content and extremely low surface particles residual effect.
The present invention disclosed a kind of for silicon carry out chemically machinery polished with or the aqueous solution used of surface cleaning.This aqueous solution is made up of water and at least a compound.Do not contain abrasive grains in the solution.Compound in the solution can or contain the compound of guanidine radicals for the guanidine class, amides or contain the compound of amide group, azole or contain the compound of azoles base, ureas or contain in the compound of urea groups one or more.Wherein guanidine class or the compound that contains guanidine radicals can be single guanidine, biguanides and polyguanidine compounds, guanidine for example, N1,N1-Dimethylbiguanide, phenformin, Moroxydine, 1, one or more in the acid salt of one or more in 1 '-hexyl two [5-(rubigan) biguanides] and the poly hexamethylene biguanide and above-claimed cpd.Amides or the compound that contains amide group can be Cellmic C 121
1, the 6-hexanolactam
N, N '-methylene-bisacrylamide
Deng.Described azole or the compound that contains the azoles base are one or more in triazole and tetrazole and the derivative thereof, benzotriazole (BTA) for example, 1,2,4-triazole (TAZ), 3-amino-1,2,4-triazole, 5-carboxyl-3-amino 1,2, one or more in the amino tetrazole of 4-triazole and 5-.Ureas or contain the compound such as the biuret of urea groups
Methylolurea
L-urea groups Beta Alanine
Deng.
Compound in the described solution also can be to contain the compound of at least two kinds of functional groups in guanidine functional group, azoles functional group, urea functional group and the amide functional group or the mixture of compound in the molecule simultaneously.As, (E)-1-(2-chloro-1,3-thiazoles-5-ylmethyl)-3-methyl-2-nitroguanidine (thiophene worm amine),
N '-methyl-N " (2-(((5-methyl isophthalic acid H-imidazol-4 yl) methyl) sulfo-) ethyl)-N-dicyanodiamide hydrochloric acid (cimetidine hydrochloride),
Benzophenone guanidine methyl esters (mebendazole),
2,4-diamino-6-methyl isophthalic acid, 3,5-triazine (methyl 4 guanamines),
Deng.
The removal speed or the cleaning efficiency that mainly act as raising silicon of above compound.Its total content in solution is: 0.001～30wt% or on be limited to the maxima solubility of each chemical combination in the aqueous solution.
Except above-mentioned compound.The complexing agent that can also further contain metal ion in the solution is as ethylenediamine tetraacetic acid (EDTA) (EDTA), oxalic acid, citric acid, Succinic Acid etc.
The inhibitor that can also further contain silicon in the solution as, polyoxyethylene glycol, tween, quaternary amine etc.
The pH value of this solution can be used inorganic or organic acid or alkali are regulated.
Positive progressive effect of the present invention is:
Make after the polishing and obtain extremely low surperficial heavy metal ion content and the extremely low residual effect of surface particles on the silicon materials with low surfaceness.
Because do not use abrasive grains, thereby avoided polishing fluid particle suspension stability problem.
Can realize that thereby higher concentration ratio reduces production greatly, transportation, costs such as use.
Embodiment
Further specify the present invention below by embodiment.Further specify the present invention with embodiment below.Among the following embodiment, per-cent is mass percent.
Table 1 has provided the prescription of solution embodiment 1～17 of the present invention, presses listed component and content thereof in the table 1, simply mixes, and promptly makes each solution.
Table 1 embodiments of the invention 1～17
Effect embodiment 18～22
Further set forth advantage of the present invention below by effect embodiment, press listed component and content thereof in the table 2, simply mix, promptly make each solution.
Adopt 12 " the politex polishing pad, the rotating speed of polishing disk is 70rpm, the rotating speed of rubbing head is 120rpm.The overdraft of rubbing head is 3psi.Solution polishes the polysilicon membrane of silicon chip surface deposit in the employing table 2 respectively.Polishing time is 1min.The flow velocity of solution is 100ml/min.The polishing back has been carried out calculating to removal rate of polysilicon and has been listed in table 2.
Table 2
Data can draw from table 2, use regular solution (contrast 1) polishing, and it is 50A/min only that polysilicon is removed speed, but uses solution of the present invention to polish, and can be increased to more than the 200A/min removing speed, more up to more than the 800A/min.After polysilicon polished with above-mentioned solution, the surface was observed under optics and electron microscope without special cleaning step, all found particle residue on the surface, did not also find mechanical scratch.And by general general knowledge as can be known, the polishing fluid that contains abrasive grains after polishing, some grinding particle residues of existence or mechanical scratch that the polysilicon rear surface all can be more or less, the effect that depends on follow-up cleaning that its final surface particles residual effect is bigger.This shows, adopt this solution to polish advantage with low defective.
Claims (11)
1. solution that is used for silicon polishing and cleaning, it comprises: water and at least a compound.
2. solution according to claim 1, it is characterized in that described compound is selected from the guanidine class or contains compound, the amides of guanidine radicals or contain compound, the azole of amide group or contain the compound and the ureas of azoles base or contain in the compound of urea groups one or more.
3. as solution as described in the claim 2, it is characterized in that, described guanidine class or the compound that contains guanidine radicals are selected from guanidine, N1,N1-Dimethylbiguanide, phenformin, Moroxydine, 1, one or more in the acid salt of one or more in 1 '-hexyl two [5-(rubigan) biguanides] and the poly hexamethylene biguanide and above-claimed cpd.
4. as solution as described in the claim 2, it is characterized in that described amides or the compound that contains amide group are selected from Cellmic C 121,1,6-hexanolactam and N, one or more in N '-methylene-bisacrylamide.
5. as solution as described in the claim 2, it is characterized in that described azole or the compound that contains the azoles base are selected from benzotriazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 5-carboxyl-3-amino 1,2, one or more in the amino tetrazole of 4-triazole and 5-.
6. as solution as described in the claim 2, it is characterized in that described ureas or the compound that contains urea groups are selected from one or more in biuret, methylolurea and the L-urea groups Beta Alanine.
7. solution according to claim 1 is characterized in that described compound is the compound that contains two or more at least functional groups in guanidine functional group, azoles functional group, urea functional group and the amide functional group in the molecule simultaneously.
8. as solution as described in the claim 7, it is characterized in that, described compound is selected from (E)-1-(2-chloro-1,3-thiazole-5-ylmethyl)-3-methyl-2-nitroguanidine, N '-methyl-N " (2-(((5-methyl isophthalic acid H-imidazol-4 yl) methyl) sulfo-) ethyl)-N-dicyanodiamide hydrochloric acid, benzophenone guanidine methyl esters, 2; 4-diamino-6-methyl isophthalic acid; 3, one or more in the 5-triazine.
9. solution according to claim 1 is characterized in that, the total content of described compound in solution be 0.001～30wt% or on be limited to the maxima solubility of each compound in the aqueous solution.
10. solution according to claim 1 is characterized in that described solution further contains the complexing agent of metal ion and/or the inhibitor of silicon.
11., it is characterized in that the complexing agent of described metal ion is selected from one or more in ethylenediamine tetraacetic acid (EDTA), oxalic acid, citric acid and the Succinic Acid as solution as described in the claim 10; The inhibitor of described silicon is selected from one or more in polyoxyethylene glycol, tween and the quaternary amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100526618A CN101906272A (en) | 2009-06-08 | 2009-06-08 | Solution for polishing and cleaning silicon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100526618A CN101906272A (en) | 2009-06-08 | 2009-06-08 | Solution for polishing and cleaning silicon |
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| Publication Number | Publication Date |
|---|---|
| CN101906272A true CN101906272A (en) | 2010-12-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2009100526618A Pending CN101906272A (en) | 2009-06-08 | 2009-06-08 | Solution for polishing and cleaning silicon |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212315A (en) * | 2010-04-08 | 2011-10-12 | 福吉米株式会社 | Polishing composition and polishing method |
| CN106381069A (en) * | 2016-08-23 | 2017-02-08 | 蚌埠精科机床制造有限公司 | A method of preparing a grinding lubricant used for a hyperfine polishing machine tool |
| CN108048227A (en) * | 2017-12-18 | 2018-05-18 | 清华大学 | A kind of optical material cleaning solution |
-
2009
- 2009-06-08 CN CN2009100526618A patent/CN101906272A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212315A (en) * | 2010-04-08 | 2011-10-12 | 福吉米株式会社 | Polishing composition and polishing method |
| CN102212315B (en) * | 2010-04-08 | 2015-05-13 | 福吉米株式会社 | Polishing composition and polishing method |
| CN106381069A (en) * | 2016-08-23 | 2017-02-08 | 蚌埠精科机床制造有限公司 | A method of preparing a grinding lubricant used for a hyperfine polishing machine tool |
| CN108048227A (en) * | 2017-12-18 | 2018-05-18 | 清华大学 | A kind of optical material cleaning solution |
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Application publication date: 20101208 |