CN101130876A - Metal anti-corrosion rinsing liquid used for semiconductor manufacture process - Google Patents
Metal anti-corrosion rinsing liquid used for semiconductor manufacture process Download PDFInfo
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- CN101130876A CN101130876A CNA2006100304568A CN200610030456A CN101130876A CN 101130876 A CN101130876 A CN 101130876A CN A2006100304568 A CNA2006100304568 A CN A2006100304568A CN 200610030456 A CN200610030456 A CN 200610030456A CN 101130876 A CN101130876 A CN 101130876A
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Abstract
The present invention relates to a metal anticorrosion cleaning liquor which can be used in the semiconductor production process. It is characterized by that said cleaning liquor includes one kind or several kinds of chemical additives which not only can be used for removing various residua from metal surface, but also can be used for effectively preventing metal surface from corroding.
Description
Technical field
The present invention relates to a kind of scavenging solution, relate in particular to the metal anti-corrosion rinsing liquid that is used for manufacture of semiconductor.
Background technology
Typical scavenging solution has deionized water, superoxol and weak ammonia, they are mainly used in cleans debris in the last technology, such as after CMP (Chemical Mechanical Polishing) process, the polishing fluid that the metallic surface is residual, after over etching goes high light resistance technology, residual go the high light blocking solution and through the debris behind the depositing operation etc.After wherein last technology debris is cleaned, thereby the organic substance residues that the metallic surface still may exist some to be introduced by scavenging solution influences next manufacturing process, perhaps the corrosion of metallic surface still exists, the corrosion of metallic surface can influence metallic surface Flatness quality also makes defect level high, thereby has reduced product yield and earning rate.
Some scavenging solutions are disclosed, comprise carboxylic acid such as the scavenging solution in the U.S. US2002169088 patent, nitrogenous compound and phosphoric acid (carboxylic acid, phosphoric acid, amine acid).Acidic cleaning solution in No. 2005093031 patents of world patent WO comprises organic acid and nitrogenous inhibitor.Alkaline cleaning fluid in No. 2005085408 patents of world patent WO comprises organic acid and nitrogenous inhibitor.Scavenging solution among the Chinese patent CN01104317.2 comprises organic acid, corrosion inhibitor, and hydramine, many alcohol compounds, these all are the using method about scavenging solution or scavenging solution.Scavenging solution in the U.S. Pat 6147002 is the scavenging solution about a kind of acidic aqueous solution, and it also comprises the fluorine-containing material of 0.5～5 weight %, and this scavenging solution is suitable for cleaning the ic component of copper metal semiconductor wafer.But the scavenging solution in the above-mentioned patent, or contain toxicant, unfriendly to environment; Or cleaning efficiency is not high enough, or has residual to defectives such as subsequent technique generation detrimentally affects; Or the cleaning use range is narrow, and for example the scavenging solution of US6443814 patent is merely able to clean the wafer of copper-containing metal layer.
Therefore, being necessary to develop a kind of cleaner for metal, can effectively to remove the metallic surface various residual, reduces the interference to subsequent technique greatly.
Summary of the invention
To the objective of the invention is in order addressing the above problem, to provide a kind of semi-conductor that is used for to make that effectively to remove the metallic surface various residual, reduce interferential scavenging solution greatly subsequent technique.
Above-mentioned purpose of the present invention realizes by following technical proposal: this scavenging solution comprises a kind of carrier, and effectively the removing metallic surface is various residual also to comprise one or more, effectively prevents the organic acid chemical additive of corrosion.
Described organic acid chemical additive is the composition of organic carboxyl acid, organic phospho acid or organic sulfonic acid and their formation salt formation.
Described organic carboxyl acid be citric acid, oxalic acid, tartrate, succsinic acid or toxilic acid with in one or more combination.
Described organic phospho acid comprises one or more the combination in alkyl phosphonic acid, phenyl-phosphonic acid, 1-hydroxyl vinyl-1,1-di 2 ethylhexyl phosphonic acid, methylene phosphonic acid, vinyl-diamines-4, methylene phosphonic acid, tetramethylene base-triamine-5-methylene phosphonic acid or the polyamino polyether base tetramethylene phosphonic acid.
Described organic sulfonic acid comprises one or more the combination in methylsulphonic acid, ethylsulfonic acid, dimethyl sulfonic acid or the butyl sulfonic acid lactone.
Described nitrogenous amino acid and its formation salt comprise glycine, L-Ala, leucine, Isoleucine, Xie Ansuan, Gelucystine, halfcystine, methionine(Met), Threonine, Serine, phenylalanine, tyrosine, tryptophane, proline(Pro), oxyproline, the combination of one or more in L-glutamic acid, aspartic acid, Methionin or the arginine.
The weight percent content of organic carboxyl acid chemical additive of the present invention preferably is 0.05～5%.
The weight percent content of described organic phospho acid chemical additive preferably is 0.02～0.5%.
The weight percent content of described organic sulfonic acid chemical additive preferably is 0.02～1%.
The weight percent content of described chemistry of amino acids additive preferably is 0.05～5%.
Scavenging solution of the present invention also comprises the anticorrosion inhibitor of PH conditioning agent, tensio-active agent and/or polymer metal.
The anticorrosion inhibitor of described polymer metal is copolymerization, phosphono-carboxylic acids multipolymer, vinylformic acid-acrylate-sulfonate terpolymer or the vinylformic acid-acrylate-phosphonic acids-sulfonate tetrapolymer of copolymerization, acrylic compounds and the esters of acrylic acid of polyacrylic compounds, acrylic compounds and cinnamic copolymerization, acrylic compounds and MALEIC ANHYDRIDE.
The anticorrosion inhibitor scope of described polymer metal molecular weight is 2,000～3, and 000,000.
Described polycarboxylic acid and/or its salt are formula I compound:
Formula I
Wherein, R
1, R
2Be hydrogen atom or carbonatoms by oneself less than 3 alkyl, R
3Be H, K, Na or NH
4
Described polyacrylic compounds preferably is a polyacrylic acid.
Described polyacrylic compounds molecular weight ranges preferably is 5,000～30,000.
Described polyacrylic compounds weight percent content preferably is 10ppm～5000ppm.
Scavenging solution of the present invention comprises that also nitrogen-containing heterocycle compound is benzotriazole, pyrazoles and/or imidazoles.
Described scavenging solution comprises that also the nitrogen-containing heterocycle compound content that is weight percentage is 0～0.1%.
The pH value scope of scavenging solution of the present invention preferably is 2～7.
Described carrier is alcohols and/or water.
The purposes of scavenging solution of the present invention in metal substrate.
Described metal substrate is copper, aluminium, tantalum, tantalum nitride, titanium, titanium nitride, silver or golden.
In the present invention, described scavenging solution can be used for during following technology makes: in polishing, etching (going to high light resistance back), deposition and other protection steps.
Because this chemical additive is used for scavenging solution of the present invention, reduce interference to subsequent technique, reduce the surface pitting of metallic substance greatly, lower the surface corrosion degree, thereby reduced defective, improved cleaning efficiency and product yield, increased earning rate.
Positive progressive effect of the present invention is: thereby scavenging solution of the present invention can reduce Corrosion of Metallic Materials degree (1) greatly defective is obviously descended; (2) improved the Flatness quality of metallic surface greatly; (3) improve product yield (4) and improve the technological operation window.
Description of drawings
Figure 1A is for using scanning electronic microscope (SEM) figure of the copper/tantalum/silica sphere after conventional clean solution (1% citric acid, 0.1% benzotriazole) cleans;
Figure 1B is scanning electronic microscope (SEM) figure of the copper/tantalum/silica sphere after the cleaning solution in the embodiment of the invention 1 cleans;
Fig. 2 A is scanning electronic microscope (SEM) figure of the copper/tantalum/silica sphere behind the use conventional clean solution (1% citric acid, 0.1% benzotriazole);
Fig. 2 B is scanning electronic microscope (SEM) figure of the copper/tantalum/silica sphere after cleaning solution cleans in the embodiment of the invention 2.
Embodiment
Embodiment 1
The scavenging solution (pH=2.4) that will contain 2%citric acid (citric acid) and polyacrylic acid (molecular weight 5000) 10ppm and water and be surplus is used for the Cu/SiO 2 surface after the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.Wash result is seen Figure 1A, 1B.
The result shows that bright line partly be a metal among the figure, the wafer (as Figure 1A) of use conventional clean liquid, and the metallic surface has more serious residual; Use the metallic surface (as Figure 1B) after scavenging solution of the present invention cleans smooth, do not see obviously residual or corrosion, ratio of defects obviously descends, the roughness of metallic surface be improved significantly.
Embodiment 2
The scavenging solution (pH=2.5) that will contain 0.5% polyamino polyether base tetramethylene phosphonic acid and water and be surplus is used for the Cu/SiO 2 surface after the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.Wash result is seen Fig. 2 A, 2B.
The result shows, uses the wafer (as Fig. 2 A) of conventional clean liquid, and there is more serious corrosion the metallic surface; Use the smooth of metallic surface (as Fig. 2 B) after scavenging solution of the present invention cleans, do not see obviously residual or corrosion, ratio of defects obviously descends, the roughness of metallic surface be improved significantly.
Embodiment 3
To contain 0.2% methylsulphonic acid, polyacrylic acid (molecular weight 5000) 5000ppm and water are the Cu/SiO 2 surface after the scavenging solution (pH=2.5) of surplus is used for the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.
Embodiment 4
To contain the Cu/SiO 2 surface after the scavenging solution that 1% citric acid and water are surplus (pH=2.5) is used for the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.
Embodiment 5
The scavenging solution (pH=2.5) that will contain 0.1%Glycine (glycine) and polyacrylic acid (molecular weight 5000) 100ppm and water and be surplus is used for the aluminium/silica sphere after the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.
Embodiment 6
To contain 0.1% butane phosphono-1,2,4-tricarboxylic acid and water are the Cu/SiO 2 surface after the scavenging solution (pH=2.1) of surplus is used for the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.
Embodiment 7
To contain 0.2% cyclohexyl-diamines-4, methylene phosphonic acid and water are the tantalum/tantalum nitride/silica sphere after the scavenging solution (pH=2.1) of surplus is used for the chemical mechanical polishing liquid polishing.
(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.
Embodiment 8
To contain 0.02% cyclohexyl-diamines-4, methylene phosphonic acid and 0.5%Citric acid water are the titanium/silica sphere after the scavenging solution (pH=3.0) of surplus is used for the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.
Embodiment 9
To contain 0.05% butane phosphono-1,2,4-tricarboxylic acid and 0.8% citric acid and water are the Cu/SiO 2 surface after the scavenging solution (pH=3.5) of surplus is used for the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.
Embodiment 10
To contain 0.5% butane phosphono-1,2,4-tricarboxylic acid and 2-acrylamido-2-methyl propane sulfonic acid 10ppm and water are the Cu/SiO 2 surface after the scavenging solution (pH=3.5) of surplus is used for the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min;
(4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.
Raw material used in the present invention and reagent are the commercially available prod.
Embodiment 11
The scavenging solution (pH=3.0) that will contain 1% phenyl-phosphonic acid and 0.05% tartrate and water and be surplus is used for the titanium/silica sphere after the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.
Embodiment 12
The scavenging solution (pH=3.0) that will contain 1% dimethyl sulfonic acid and 5% succsinic acid and water and be surplus is used for the titanium surface after the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.
Embodiment 13
The scavenging solution (pH=3.0) that will contain 1% butyl sulfonic acid lactone and 0.05% methionine(Met) and water and be surplus is used for the titanium/silica sphere after the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.
Embodiment 14
The scavenging solution (pH=7.0) that will contain 5% oxyproline and polyacrylic acid 5000ppm (molecular weight is 20,000) and water and be surplus is used for the titanium/silica sphere after the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.
Embodiment 15
The scavenging solution (pH=7.0) that will contain 1% aspartic acid and polyacrylic acid 10ppm (molecular weight is 10,000) and water and be surplus is used for the titanium/silica sphere after the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.
Embodiment 16
To contain 0.1% cyclohexyl-diamines-4, methylene phosphonic acid and polyacrylic acid 500ppm (molecular weight is 30,000) and water are the tantalum/silica sphere after the scavenging solution (pH=7.0) of surplus is used for the chemical mechanical polishing liquid polishing.(1) technology of chemical mechanical polishing liquid polish copper metal is: the rotating speed 50-70rpm of overdraft 1.0-2.0psi, polishing disk, rubbing head rotating speed 70-90rpm, polishing fluid flow velocity 200-300ml/min, polishing time 1-2min; (2) then at rotating speed 25rpm, the rubbing head rotating speed 25rpm of overdraft 1.5psi, polishing disk, use conventional clean liquid and this invention scavenging solution respectively, the scavenging solution flow velocity is at 300ml/min, polishing time 0.5-1min; (3) with scavenging solution and polyvinyl alcohol (PVA) round brush wafer surface is scrubbed 2min, the round brush rotating speed is 300rp, cleaning head rotating speed 280rpm, scavenging solution flow 300ml/min; (4) scrub 2min with deionized water and PVA round brush again, the round brush rotating speed is 300rpm cleaning head rotating speed 280rpm, de-ionized water flow rate 300ml/min.
Raw material used in the present invention and reagent are the commercially available prod.
Claims (24)
1. a scavenging solution that is used for the semi-conductor anticorrosive metal is characterized in that: comprise a kind of carrier, comprise that also one or more effective metallic surfaces of removing are various residual, effectively prevent the organic acid chemical additive of corrosion simultaneously.
2. scavenging solution as claimed in claim 1 is characterized in that: described organic acid chemical additive is the composition of organic carboxyl acid, organic phospho acid, organic sulfonic acid or nitrogenous amino acid and their formation salt formation.
3. scavenging solution as claimed in claim 2 is characterized in that: described organic carboxyl acid is one or more the combination in citric acid, oxalic acid, tartrate, succsinic acid or the toxilic acid.
4. scavenging solution as claimed in claim 2; it is characterized in that: described organic phospho acid comprises alkyl phosphonic acid, phenyl-phosphonic acid, 1-hydroxyl vinyl-1; 1-di 2 ethylhexyl phosphonic acid, methylene phosphonic acid; vinyl-diamines-4, methylene phosphonic acid, butane phosphono-1; 2, the combination of one or more in 4-tricarboxylic acid, cyclohexyl-diamines-4, methylene phosphonic acid, tetramethylene base-triamine-5-methylene phosphonic acid or the polyamino polyether base tetramethylene phosphonic acid.
5. scavenging solution as claimed in claim 2 is characterized in that: described organic sulfonic acid comprises in methylsulphonic acid, ethylsulfonic acid, dimethyl sulfonic acid or the butyl sulfonic acid lactone one or more combination.
6. scavenging solution as claimed in claim 2, it is characterized in that: described nitrogenous amino acid comprises glycine, L-Ala, leucine, Isoleucine, Xie Ansuan, Gelucystine, halfcystine, methionine(Met), Threonine, Serine, phenylalanine, tyrosine, tryptophane, proline(Pro), oxyproline, the combination of one or more in L-glutamic acid, aspartic acid, Methionin or the arginine.
7. scavenging solution as claimed in claim 2 is characterized in that: the weight percent content of described organic carboxyl acid chemical additive is 0.05～5%.
8. scavenging solution as claimed in claim 2 is characterized in that: the weight percent content of described organic phospho acid chemical additive is 0.02～1%.
9. scavenging solution as claimed in claim 2 is characterized in that: the weight percent content of described organic sulfonic acid chemical additive is 0.02～1%.
10. scavenging solution as claimed in claim 2 is characterized in that: the weight percent content of described chemistry of amino acids additive is 0.05～5%.
11. as the arbitrary described scavenging solution of claim 1 to 10, it is characterized in that: described scavenging solution also comprises the anticorrosion inhibitor of PH conditioning agent, tensio-active agent and/or polymer metal.
12. scavenging solution as claimed in claim 11 is characterized in that: the anticorrosion inhibitor of described polymer metal is copolymerization, phosphono-carboxylic acids multipolymer, vinylformic acid-acrylate-sulfonate terpolymer or the vinylformic acid-acrylate-phosphonic acids-sulfonate tetrapolymer of copolymerization, acrylic compounds and the esters of acrylic acid of polyacrylic compounds, acrylic compounds and cinnamic copolymerization, acrylic compounds and MALEIC ANHYDRIDE.
13. scavenging solution as claimed in claim 11 is characterized in that: the anticorrosion inhibitor molecules amount of described polymer metal is 2,000～3,000,000.
14. scavenging solution as claimed in claim 13 is characterized in that: the anticorrosion inhibitor weight percent content of described polymer metal scope is 0～20%.
15., it is characterized in that the anticorrosion inhibitor of described polymer metal is that polycarboxylic acid and/or its salt are formula I compound as the described scavenging solution of claim 12～14:
Formula I
Wherein, R
1, R
2Be hydrogen atom or carbonatoms by oneself less than 3 alkyl, R
3Be H, K, Na or NH
4
16. scavenging solution as claimed in claim 15 is characterized in that: described polyacrylic compounds is a polyacrylic acid.
17. scavenging solution as claimed in claim 15 is characterized in that: described polyacrylic compounds molecular weight is 5,000～30,000.
18. as claim 11 or 15 described scavenging solutions, it is characterized in that: described polyacrylic compounds weight percent content is 10ppm～5000ppm.
19. as claim 4 or 5 described scavenging solutions, it is characterized in that: described scavenging solution comprises that also nitrogen-containing heterocycle compound is benzotriazole, pyrazoles and/or imidazoles.
20. scavenging solution as claimed in claim 19 is characterized in that: described scavenging solution comprises that also the nitrogen-containing heterocycle compound content that is weight percentage is 0～0.1%.
21. scavenging solution as claimed in claim 1 is characterized in that: the pH value scope of described scavenging solution is 2～7.
22. scavenging solution according to claim 1 is characterized in that: described carrier is alcohols and/or water.
23. the purposes of scavenging solution as claimed in claim 1 in metal substrate.
24. the purposes of scavenging solution as claimed in claim 23 in metal substrate is characterized in that: described metal substrate is copper, aluminium, tantalum, tantalum nitride, titanium, titanium nitride, silver or golden.
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