CN1955248B - Chemical mechanical polishing material for tantalum barrier layer - Google Patents

Chemical mechanical polishing material for tantalum barrier layer Download PDF

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Publication number
CN1955248B
CN1955248B CN2005100308564A CN200510030856A CN1955248B CN 1955248 B CN1955248 B CN 1955248B CN 2005100308564 A CN2005100308564 A CN 2005100308564A CN 200510030856 A CN200510030856 A CN 200510030856A CN 1955248 B CN1955248 B CN 1955248B
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chemical mechanical
mechanical polishing
polishing slurry
tetrazole
abrasive grains
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CN1955248A (en
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荆建芬
宋伟红
顾元
徐春
宋鹰
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Anji Microelectronics Shanghai Co Ltd
Anji Microelectronics Co Ltd
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Anji Microelectronics Shanghai Co Ltd
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Priority to CN2005100308564A priority Critical patent/CN1955248B/en
Priority to PCT/CN2006/002619 priority patent/WO2007048315A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32115—Planarisation
    • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

This invention relates to a chemical mechanical polishing paste used for tantalum barrier layer, including grinding particles, organic phosphonic acid, tetrazole compounds and vehicles. The invention of the chemical mechanical polishing paste can prevent metal materials from a partial and overall corrosion, reduce substrate surface pollutants, and reduce grind particle content, can achieve suitable selective polishing in different metal and oxides.

Description

Chemical mechanical polishing material for tantalum barrier layer
Technical field
The present invention relates to a kind of chemical mechanical polishing slurry, relate in particular to a kind of chemical mechanical polishing material for tantalum barrier layer.
Background technology
Development along with microelectronics, the very large scale integration chip integration has reached tens components and parts, characteristic dimension has entered nano level, and this just requires hundreds of procedure, especially multilayer wiring, substrate, medium in the microelectronic technique must pass through chemical-mechanical planarization.Very extensive integrated routing is just transformed to Cu by traditional Al.Compare with Al, it is low that the Cu wiring has resistivity, deelectric transferred energy rate height, and RC is short time of lag, can make the cloth number of plies reduce half, and cost reduces by 30%, shortens 40% advantage process period.The advantage of Cu wiring has caused that the whole world pays close attention to widely.
In order to guarantee the characteristic of Cu wiring and medium, at present multi-layer copper metallization is also used Ta or TaN does the blocking layer in the very large scale integration chip, therefore chemically machinery polished (CMP) slurry on Ta or TaN blocking layer has appearred being used for polishing in succession, as: US 6,719,920 patent disclosures a kind of polishing slurries that is used for the blocking layer; US 6,503,418 patent disclosures the polishing slurries on a kind of Ta blocking layer, contain organic additive in this polishing slurries; US 6,638, and 326 disclose the chemical-mechanical planarization composition of a kind of Ta of being used for and TaN, and CN 02116761.3 discloses the chemical and mechanical leveling polishing liquid of copper and tantalum in a kind of multilayer copper wire in large scale integrated circuit.But defectives such as these polishing slurries exist part and general corrosion, and ratio of defects is higher, and the polishing selectivity of different base is unreasonable.Therefore press for the chemical mechanical polishing slurry that is used for the blocking layer that exploitation makes new advances.
Summary of the invention
The objective of the invention is for above-mentioned the problems of the prior art, a kind of chemical mechanical polishing slurry that is used for the blocking layer is provided.
Above-mentioned purpose of the present invention realizes by following technical proposal: chemical mechanical polishing material for tantalum barrier layer of the present invention comprises abrasive grains, organic phospho acid, tetrazole compound and carrier.Owing to added organic phospho acid and tetrazole compound in the chemical mechanical polishing slurry of the present invention, so it has suitable polishing selectivity to different metal and oxide compound in polishing process, can prevent metal depression, obviously reduce organism, silicon-dioxide deposit and other metal ion residual of wafer surface.
Various compositions all can be with reference to prior art in the chemical mechanical polishing material for tantalum barrier layer of the present invention, in a preferred embodiment of the present invention, the concentration of this abrasive grains is 1～10%, the concentration of this organic phospho acid is 0.01～1%, the concentration of this tetrazole compound is 0.01～0.5%, this carrier is a surplus, and above % all refers to account for the total weight percent of whole chemical mechanical polishing slurry.
In the present invention, the size of this abrasive grains preferably is 20～200nm, more preferably is 30～100nm, is 70nm best.
Described organic phospho acid preferably is a 2-phosphonic acids butane group-1,2,4-tricarboxylic acid (PBTCA), ethylene diamine tetra methylene phosphonic acid and/or diethylene triamine pentamethylene phosphonic.
Described tetrazole compound (TRA) preferably is 5-methyl-tetrazole, 5-phenyl-1-hydrogen-tetrazole and/or 1-hydrogen-tetrazole.
Chemical mechanical polishing material for tantalum barrier layer of the present invention can also comprise 0.001～1% oxygenant.Described oxygenant can be various oxygenant of the prior art, preferably is hydrogen peroxide, Urea Peroxide, Peracetic Acid, benzoyl peroxide, Potassium Persulphate and/or ammonium persulphate, more preferably is hydrogen peroxide.
Abrasive grains of the present invention also can be with reference to prior art, and preferred silicon oxide, aluminum oxide, cerium oxide and/or polymer beads are as polyethylene or tetrafluoroethylene, more preferably silicon oxide.
The pH value of chemical mechanical polishing material for tantalum barrier layer of the present invention preferably is 2.0～4.0, more preferably be 3.0, the pH regulator agent can be various acid and/or alkali, so that pH regulator to desirable value is got final product, preferably is potassium hydroxide, nitric acid, thanomin and/or trolamine or the like.
Chemical mechanical polishing material for tantalum barrier layer of the present invention can also comprise tensio-active agent, stablizer, and inhibitor and/or sterilant are with the polishing performance of further raising substrate surface.
In the present invention, described carrier preferably is a water.
Chemical mechanical polishing material for tantalum barrier layer of the present invention can also comprise other additives, and as tensio-active agent, sterilant, stablizer and/or inhibitor or the like, these additives all can be with reference to prior art.
Positive progressive effect of the present invention is: chemical mechanical polishing material for tantalum barrier layer 1 of the present invention) can reduce the consumption of abrasive grains, make defective, scuffing, pickup and other residual obvious decline, thereby reduce the substrate surface pollutent; 2) have suitable polishing in the polishing process and select ratio; Can prevent the part and the general corrosion that produce in the medal polish process, improve the product yield.
Description of drawings
Fig. 1 is the surperficial microscope figure of the preceding blank tantalum wafer of polishing;
Fig. 2 is the surperficial microscope figure of the blank tantalum wafer in polishing back;
(TEOS refers to SiO to Fig. 3 among the figure for polishing back testing wafer surface microscope figure (amplifying 250 times) 2);
(TEOS refers to SiO to Fig. 4 among the figure for polishing back testing wafer surface SEM figure (amplifying 5000 times) 2).
Embodiment
Use non-limiting example to describe the present invention in detail below.
Embodiment 1～8 and comparative example 1 0
Table 1
Figure G05130856420051118D000041
Remarks: TRA1:5-methyl-tetrazole; TRA2:1-hydrogen-tetrazole; TRA3:5-phenyl-1-hydrogen-tetrazole; EDTMP: ethylene diamine tetra methylene phosphonic acid, DTPMP: diethylene triamine pentamethylene phosphonic; All the other compositions of above-mentioned chemical mechanical polishing slurry are water; 1 0Be comparative example 1 0
With each material in the following order: the deionized water of abrasive grains, half consumption, organic phospho acid, TRA, H 2O 2Order add in the reactor successively and stir, mend all the other deionized waters, use pH regulator agent (20%KOH or rare HNO at last 3, select according to the needs of pH value) be adjusted to required pH value and continue to be stirred to uniform fluid, can obtain chemical mechanical polishing slurry in static 10 minutes.
Effect embodiment 1
Use the foregoing description 1～8 and comparative example 1 respectively 0Chemical mechanical polishing slurry polish blank Ta, Cu, SiO 2Wafer, polishing condition is identical, and burnishing parameters is as follows: Logitech. polishing pad, downward pressure 2psi, rotary speed/rubbing head rotating speed=60/80rpm, polishing time 120s, chemical mechanical polishing slurry flow velocity 100mL/min.Polish results sees Table 2.
Table 2
Remarks: Surf. represents the pollutent situation of substrate surface.
The result shows: chemical mechanical polishing slurry of the present invention can be regulated Ta, Cu and SiO by adding organic acid and tetrazolium class material 2Removal speed, obtain suitable polishing selectivity when the concentration of adjusting abrasive grains, organic acid and tetrazolium class material, when adjusting oxidant concentration, can obtain better polishing selectivity.Fig. 1 is the surperficial microscope figure of the preceding blank Ta wafer of the chemical mechanical polishing slurry polishing of embodiment 1, Fig. 2 is the surperficial microscope figure of the blank Ta wafer after the chemical mechanical polishing slurry of embodiment 1 polishes, from Fig. 1 and 2 as can be seen, can be under low abrasive grains concentration, defective is obviously descended, and can prevent the part and the general corrosion that produce in the medal polish process, reduce the substrate surface pollutent, use the spot corrosion of the Ta wafer surface behind the chemical mechanical polishing slurry of the present invention can be obviously less, thereby improve the product yield.
Effect embodiment 2
To the silicon substrate wafer of sputter Ta/ electro-coppering after polish copper, polish with the chemical mechanical polishing slurry of embodiment 2,3,5 respectively again, polishing condition is identical, burnishing parameters is as follows: the Logitech. polishing pad, downward pressure 2psi, rotary speed/rubbing head rotating speed=60/80rpm, polishing time 120s, chemical mechanical polishing slurry flow velocity 100mL/min.Polish results sees Table 3.
Table 3
Chemical mechanical polishing slurry Testing wafer surface depression size ( ) Testing wafer surface contaminant situation
Embodiment 2 600 Do not have
Embodiment 3 450 Do not have
Embodiment 5 465 Do not have
The result shows: after using chemical mechanical polishing slurry of the present invention, testing wafer depression in the surface size obviously reduces, and the examination wafer surface does not have burn into pollutent and other residue.After the chemical mechanical polishing slurry polishing of embodiment 2, the testing wafer surface is amplified 250 times of nothings through microscope and is seen that there is (see figure 3) in pollutent; After the chemical mechanical polishing slurry polishing of embodiment 3, the testing wafer surface is not obviously seen pollution, corrosion etc. for 5000 times through the SEM amplification yet and is had (see figure 4).
Conclusion: chemical mechanical polishing material for tantalum barrier layer 1 of the present invention) can reduce the consumption of abrasive grains, make defective, scuffing, pickup and other residual obvious decline, thereby reduce the substrate surface pollutent; 2) have suitable polishing in the polishing process and select ratio; Can prevent the part and the general corrosion that produce in the medal polish process, improve the product yield.
The raw material that the foregoing description relates to is commercially available.

Claims (9)

1. chemical mechanical polishing material for tantalum barrier layer, it comprises abrasive grains, organic phospho acid, tetrazole compound and carrier;
Wherein, the concentration of this abrasive grains is 1～10wt%, and the concentration of this organic phospho acid is 0.01～1wt%, and the concentration of this tetrazole compound is 0.01～0.5wt%;
Described tetrazole compound is 5-methyl-tetrazole, 5-phenyl-1-hydrogen-tetrazole and/or 1-hydrogen-tetrazole; And
The pH value of this chemical mechanical polishing slurry is 2.0～4.0.
2. chemical mechanical polishing slurry according to claim 1 is characterized in that, this carrier is a surplus.
3. chemical mechanical polishing slurry according to claim 1 is characterized in that this abrasive grains is of a size of 20～200nm.
4. chemical mechanical polishing slurry according to claim 3 is characterized in that this abrasive grains is of a size of 30～100nm.
5. according to each described chemical mechanical polishing slurry of claim 1～4, it is characterized in that described organic phospho acid is a 2-phosphonic acids butane group-1,2,4-tricarboxylic acid, ethylene diamine tetra methylene phosphonic acid and/or diethylene triamine pentamethylene phosphonic.
6. according to each described chemical mechanical polishing slurry of claim 1～4, it is characterized in that this chemical mechanical polishing slurry also comprises the oxygenant of 0.001～1wt%.
7. chemical mechanical polishing slurry according to claim 6 is characterized in that described oxygenant is hydrogen peroxide, Urea Peroxide, Peracetic Acid, benzoyl peroxide, Potassium Persulphate and/or ammonium persulphate.
8. according to each described chemical mechanical polishing slurry of claim 1～4, it is characterized in that this abrasive grains is silicon oxide, aluminum oxide, cerium oxide and/or polymer beads.
9. according to each described chemical mechanical polishing slurry of claim 1～4, it is characterized in that this chemical mechanical polishing slurry also comprises tensio-active agent, stablizer and/or sterilant.
CN2005100308564A 2005-10-28 2005-10-28 Chemical mechanical polishing material for tantalum barrier layer Active CN1955248B (en)

Priority Applications (2)

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PCT/CN2006/002619 WO2007048315A1 (en) 2005-10-28 2006-10-08 A chemical mechanical polishing paste for tantalum barrier layer

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CN101153205A (en) * 2006-09-29 2008-04-02 安集微电子（上海）有限公司 Chemical mechanical polishing solution for polishing low dielectric materials
CN101457122B (en) * 2007-12-14 2013-01-16 安集微电子（上海）有限公司 Chemical-mechanical polishing liquid for copper process
CN101906269A (en) * 2009-06-08 2010-12-08 安集微电子科技(上海)有限公司 Slurry for metal chemical and mechanical polishing and using method thereof
JO3244B1 (en) * 2009-10-26 2018-03-08 Amgen Inc Human il-23 antigen binding proteins
CN102477259B (en) * 2010-11-30 2015-05-27 安集微电子（上海）有限公司 Chemically mechanical polishing slurry
CN104726028A (en) * 2013-12-18 2015-06-24 安集微电子（上海）有限公司 Chemical mechanical polishing liquid and use method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6803353B2 (en) * 2002-11-12 2004-10-12 Atofina Chemicals, Inc. Copper chemical mechanical polishing solutions using sulfonated amphiprotic agents
CN101263583A (en) * 2005-09-09 2008-09-10 旭硝子株式会社 Polishing compound, method for polishing surface to be polished, and process for producing semiconductor integrated circuit device

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US7736405B2 (en) * 2003-05-12 2010-06-15 Advanced Technology Materials, Inc. Chemical mechanical polishing compositions for copper and associated materials and method of using same
TWI288046B (en) * 2003-11-14 2007-10-11 Showa Denko Kk Polishing composition and polishing method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6803353B2 (en) * 2002-11-12 2004-10-12 Atofina Chemicals, Inc. Copper chemical mechanical polishing solutions using sulfonated amphiprotic agents
CN101263583A (en) * 2005-09-09 2008-09-10 旭硝子株式会社 Polishing compound, method for polishing surface to be polished, and process for producing semiconductor integrated circuit device

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