CN104745084B - A kind of chemical mechanical polishing liquid and application method for aluminium - Google Patents
A kind of chemical mechanical polishing liquid and application method for aluminium Download PDFInfo
- Publication number
- CN104745084B CN104745084B CN201310727881.2A CN201310727881A CN104745084B CN 104745084 B CN104745084 B CN 104745084B CN 201310727881 A CN201310727881 A CN 201310727881A CN 104745084 B CN104745084 B CN 104745084B
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- Prior art keywords
- acid
- application
- abrasive grains
- aluminium
- polishing
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Classifications
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- C—CHEMISTRY; METALLURGY
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-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/02—Light metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/02—Light metals
- C23F3/03—Light metals with acidic solutions
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Present invention is disclosed a kind of chemically mechanical polishings for aluminium.This polishing fluid at least contains a metal ion species.The addition of metal ion allows the polishing fluid of the present invention to have the removal rate of higher aluminium.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid more particularly to a kind of polishing fluids for polishing metal aluminium.
Background technology
Integrated circuit generally comprises millions of a active electronic elements.These active electronic elements pass through multiple-layer metallization
Interconnection layer connector is mounted in silicon substrate, and active electronic elements disconnected from each other by the access of metallization and touch originally for these
Point connection, to form complete functional circuit and component.In the manufacturing process of semiconductor metal is formed by following steps
Interconnection line or contact：Pattern is formed in the dielectric layer, groove or hole is formed by etching, in the trench deposited metal, then
Metal extra on dielectric layer is removed by flatening process, and makes the metal surface of deposition smooth, it is logical to form metal
Road or contact.
In the polishing process of entire semiconductor substrate, planarization have become it is of equal importance with lithography and etching and
One of complementary indispensable key technology.And it chemically-mechanicapolish polishes（CMP）Technique is most effective, most ripe at present
Planarization.Chemical-mechanical polishing system is the change for integrating the technologies such as cleaning, drying, on-line checking, end point determination
Mechanical Planarization is learned, is that integrated circuit improves life to miniaturization, multiple stratification, planarization, slimming development and integrated circuit
Production efficiency reduces cost, the indispensable technology of wafer global planarizartion.CMP process be exactly using a kind of mixture containing abrasive material and
Polishing pad wafer polishing surface.In typical cmp method, substrate is directly contacted with rotating polishing pad, is being served as a contrast
Bottom back side applies pressure.During polishing, gasket and operation console rotation, while the power to keep down in substrate back, by abrasive material
With chemism solution（Commonly referred to as polishing fluid or polishing slurries）It is applied on gasket, the polishing fluid and the wafer polished are thin
Film occurs chemical reaction and proceeds by polishing process.
And in CMP process, the selection of paste compound is then an important step in CMP step, is used
When, the active ingredient of polishing object slurry can react with base material is polished, to change polishing effect.Select suitable polishing
Slurry can not only accelerate the polishing speed of base material, can also effectively improve substrate surface flatness so that integrated circuit possesses more
Good operation performance.It is thus directed to different base materials, needs to select different polishing slurries, is imitated to the polishing of enhancing base materials
Fruit.
Aluminium resistivity is low, is easy to deposit and etch, is the production line back end used earliest（back-end-of-the-
line）Interconnection materials.And in production line front end（front-end-of-the-line）, with integrated circuit industry
Further development, the silicon dioxide layer of transistor have narrowed down to only the former 1/10th, the thickness of only 5 oxygen atoms
.As the insulator of spacer gates and lower layer, silicon dioxide layer cannot be reduced further, the electric leakage otherwise generated
Stream can allow transistor can not work normally.Source electrode can be made to drain electrode using transistor made of high k dielectric plus metal gates
Leakage current declines 5 times or more, and the leakage current of gate oxide dielectric reduces by 10 times or more, and the efficiency of transistor improves 20%, this
On hundreds of millions of chips of 45nm or less processing procedure Highgrade integrations, each transistor unit has such amplitude for the combination of sample
Promotion, will break through physics enhancing efficiency bottleneck.Traditional polysilicon gate is mismatched with high-g value, and aluminum metal grid can be with
It is mutually compatible with new high-g value.Therefore it needs to develop the polishing fluid and polishing process for being suitble to this front end aluminum metal grid polishing.
In to aluminium polishing process, because the hardness of aluminium is smaller, in order to obtain good polishing effect, a system there has been at present
Arrange the research for the polishing fluid being applicable in for the base material containing aluminium.
As Chinese patent CN1238812A, United States Patent (USP) US7186654B2, U.S. US20080200098A1 are each provided with
The slurry of chemically mechanical polishing for polished aluminum, however the polishing slurries in above-mentioned patent contain the strong oxygen of such as ammonium persulfate
Agent, aluminium oxide is as abrasive grains, and in practical polishing process, ammonium persulfate is unstable, and online service life is short, and this
A little oxidizing species are difficult to control so that excessive corrosion occurs for aluminium or base material；And it is produced by these strong oxidizers to remove
Raw thick alumina layer, which must use aluminium oxide to cause the surface of aluminium recess occur as abrasive grains, makes the surface of base material go out
Existing scratch etc., seriously affects the flatness of base material, and in polishing process, the polishing speed of aluminium is low.United States Patent (USP)
US5209816A provides a kind of polishing slurries for aluminium, is effectively improved the polishing speed of aluminium, however because of its slurry
PH value is smaller, causes the corrosion of aluminium, the surface smoothness of base material low.
Meanwhile in the chemical mechanical polishing liquid of the prior art, often promote such as copper or tungsten using metal ion
A kind of polishing fluid for polishing copper is disclosed in polishing speed, such as US6541384, containing oxidant, bivalent cupric ion has
Machine acid and azole compounds.It is to be noted, however, that catalyst of the bivalent cupric ion as oxidant, does not participate in directly
In the redox reaction of metal material.Meanwhile there is also use metal ion nonmetallic materials is promoted to throw in the prior art
The precedent of optical speed, but the addition of metal ion are to change the zeta current potentials of abrasive grains, avoid abrasive grains
Reunite, or is allowed to more easily promote polishing speed with material surface effect is polished.In the prior art, there has been no for
The research directly affected between metal cation and polishing base material.
Invention content
Present invention is disclosed a kind of chemically mechanical polishings for aluminium.This polishing fluid at least contains a metal ion species.
The addition of metal ion allows the polishing fluid of the present invention to have the removal rate of higher aluminium.
Polishing fluid in the present invention further can also contain at least one complexing agent and a kind of abrasive grains.
Wherein, complexing agent is organic acid, organic phospho acid and ammonia carboxylic compound, and organic acid is acetic acid, oxalic acid, citric acid, wine
It is one or more in stone acid, malonic acid, succinic acid, malic acid, lactic acid, gallic acid and sulfosalicylic acid；Described is organic
Phosphonic acids be 2- phosphonobutanes -1,2,4- tricarboxylic acids, aminotrimethylenephosphonic acid, 1-hydroxy ethylidene-1,1-diphosphonic acid, ethylene diamine tetra methylene phosphonic acid,
Diethylene triamine pentamethylene phosphonic, 2- hydroxyethylidene diphosphonic acids guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid and polyamino polyether base methylenephosphonic acid
In it is one or more；The ammonia carboxylic compound is selected from glycine, alanine, valine, leucine, proline, phenylpropyl alcohol ammonia
Acid, tyrosine, tryptophan, lysine, arginine, histidine, serine, aspartic acid, threonine, glutamic acid, asparagine,
Glutamine, nitrilotriacetic acid, ethylenediamine tetra-acetic acid, hexamethylene tetraacethyl, ethylenediamine disuccinic acid, diethylene triamine pentacetic acid (DTPA) and
It is one or more in triethylenetetramine hexaacetic acid；The content of complexing agent is weight percentage 0.05~10wt%, preferably 0.1
~3wt%.
Those skilled in the art can be readily appreciated that, metal cation should include have it is higher than polished material
Standard electrochemical oxidation-reduction potential.The standard electrode potential of metal cation i.e. in the present invention is more than -1.66V, preferably
Copper ion, silver ion, iron ion etc., when above-mentioned metal cation is added in polishing fluid in a salt form, for respective metal sun
Ion, matched anion are sulfate, nitrate, phosphate, carbonate etc..A concentration of the 1 of the metal ion~
1000ppm.Preferably 5~500ppm
Abrasive grains are metal oxide particle commonly used in the art in the present invention, are silica, adulterated al or covering
Silica, aluminium oxide, ceria, titanium dioxide and/or the macromolecule abrasive grains of aluminium.Preferably silica.Grinding
The weight percent concentration of particle is preferably 0.1~20wt%；More preferably 0.2~5wt%.The grain size of abrasive grains be 20~
200nm, preferably 20~120nm.
The pH value of the polishing fluid of the present invention is preferably 3~10.
Can also include other typical additives such as pH adjusting agent, viscosity modifier, antifoaming agent etc. in the slurry of the present invention
To reach polishing effect.
And it should be noted that as described in the background before, due to the gold in polishing fluid according to the present invention
Belong to cation, it is different from the effect of metal cation in the prior art, it is not used as the catalyst of oxidant, therefore preferably
Ground does not contain the oxidant such as hydrogen peroxide in polishing fluid of the invention.
The polishing fluid of the present invention can prepare concentration sample, be diluted with deionized water using preceding.
The positive effect of the present invention is that：Additional oxidation need not be added in the chemical mechanical polishing liquid of the present invention
Agent, it is only necessary to by the way that specific metal ion and complexing agent are added in Silica abrasive particle, you can make aluminium have higher
Polishing speed, the problems such as avoiding the surface tear brought using alumina abrasive particles and oxidant, and reduce and be produced into
This.
Specific implementation mode
The advantages of the present invention is further explained below by specific embodiment, but protection scope of the present invention is not only limited to
In following embodiments.
Examples 1 to 46
Table 1 gives the Examples 1 to 46 of the chemical mechanical polishing liquid of the present invention, is formulated by given in table, by all groups
Divide and be uniformly mixed, mass percent is supplied to 100% with water.With KOH or HNO3Adjust required pH value.As described below hundred
Point content is mass percentage content.Chemical reagent used is market buying in formula.
1 polishing fluid Examples 1 to 46 of table
Effect example
Table 2 gives the chemical mechanical polishing liquid embodiment and comparative example formula of the present invention.It is formulated by given in table, by institute
There is component to be uniformly mixed, mass percent is supplied to 100% with water.With KOH or HNO3Adjust required pH value.Following institute
It is mass percentage content to state percentage composition.Chemical reagent used is market buying in formula.
Using the polishing fluid of comparison polishing fluid and the present invention, to empty piece aluminium（Al）Chip is polished.The throwing of the aluminium of gained
Optical speed is shown in Table 2.
Empty piece polishing condition：2inch aluminium chips, polishing machine platform be Logitech LP50, lower pressure 3psi, polishing disk and
Rubbing head rotating speed 70/65rpm, polishing pad IC1010 polish flow velocity 50ml/min, polishing time 1min
The formula and aluminium removal rate of the chemical mechanical polishing liquid embodiment and comparative example of 2 present invention of table
As shown in Table 2, with not plus compared with the comparative example 1 and 2 of metal ion, variety classes are added in embodiment 47~60
After the metal ion of concentration, the removal rate of aluminium greatly improves.
After oxidant hydrogen peroxide is added compared with embodiment 48 it is found that in the system by comparative example 3, aluminium will be substantially reduced
Removal rate.
It should be understood that wt% of the present invention refers to mass percentage.Above to the specific implementation of the present invention
Example is described in detail, but it is intended only as example, and the present invention is not restricted to particular embodiments described above.For this
It is any to the equivalent modifications that carry out of the present invention and to substitute also all among scope of the invention for field technology personnel.Therefore,
Impartial conversion and modification made by without departing from the spirit and scope of the invention, all should be contained within the scope of the invention.
Claims (13)
1. a kind of application of chemical mechanical polishing liquid in improving aluminium removal rate, which is characterized in that the chemically mechanical polishing
Liquid at least contains the metal ion that a kind of standard electrode EMF is more than -1.66V, a kind of abrasive grains and a kind of complexing agent, wherein
The metal ion is one or more in copper ion, silver ion, and the pH value of the chemical mechanical polishing liquid is 3~10.
2. application as described in claim 1, which is characterized in that a concentration of 1~1000ppm of the metal ion.
3. application as claimed in claim 2, which is characterized in that a concentration of 5~500ppm of the metal ion.
4. application as described in claim 1, which is characterized in that the complexing agent is selected from organic acid, organic phospho acid and ammonia carboxylation
It closes one or more in object.
5. application as claimed in claim 4, which is characterized in that the organic acid is acetic acid, oxalic acid, citric acid, tartaric acid, third
It is one or more in diacid, succinic acid, malic acid, lactic acid, gallic acid and sulfosalicylic acid；The organic phospho acid is 2- phosphines
Sour butane -1,2,4- tricarboxylic acids, aminotrimethylenephosphonic acid, 1-hydroxy ethylidene-1,1-diphosphonic acid, diethylene triamine pentamethylene phosphonic, 2- hydroxyls
It is one or more in phosphono-acetic acid, ethylene diamine tetra methylene phosphonic acid and polyamino polyether base methylenephosphonic acid；The ammonia carboxylation is closed
Object is selected from glycine, alanine, valine, leucine, proline, phenylalanine, tyrosine, tryptophan, lysine, smart ammonia
Acid, histidine, serine, aspartic acid, threonine, glutamic acid, asparagine, glutamine, nitrilotriacetic acid, ethylenediamine tetrem
It is one or more in acid, ethylenediamine disuccinic acid, diethylene triamine pentacetic acid (DTPA) and triethylenetetramine hexaacetic acid.
6. application as described in claim 1, which is characterized in that a concentration of mass percent 0.05 of the complexing agent~
10%.
7. application as claimed in claim 6, which is characterized in that a concentration of mass percent 0.1~3% of the complexing agent.
8. application as described in claim 1, which is characterized in that the abrasive grains are silica, adulterated al or aluminium coating
Silica, aluminium oxide, ceria, titanium dioxide and/or macromolecule abrasive grains.
9. application as claimed in claim 8, which is characterized in that the abrasive grains are silica.
10. application as described in claim 1, which is characterized in that the concentration of the abrasive grains is weight percentage 0.1~
20%.
11. application as claimed in claim 10, which is characterized in that the concentration of the abrasive grains is weight percentage 0.2~
5%.
12. application as described in claim 1, which is characterized in that the grain size of the abrasive grains is 20~200nm.
13. application as claimed in claim 12, which is characterized in that the grain size of the abrasive grains is 20~120nm.
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| CN201310727881.2A CN104745084B (en) | 2013-12-25 | 2013-12-25 | A kind of chemical mechanical polishing liquid and application method for aluminium |
| PCT/CN2014/093685 WO2015096631A1 (en) | 2013-12-25 | 2014-12-12 | Chemical mechanical polishing slurry for aluminum and use thereof |
| TW103143424A TWI642769B (en) | 2013-12-25 | 2014-12-12 | Chemical mechanical polishing slurry for polishing aluminium and method thereof |
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| US10066126B2 (en) * | 2016-01-06 | 2018-09-04 | Cabot Microelectronics Corporation | Tungsten processing slurry with catalyst |
| CN107641808A (en) * | 2016-07-21 | 2018-01-30 | 北京洁航箭达环保科技有限公司 | A kind of aluminium Special cleaning brightener and preparation method thereof |
| CN109269867B (en) * | 2018-09-11 | 2020-12-11 | 大连理工大学 | Tungsten-nickel-iron alloy polishing liquid and alloy surface polishing and metallographic preparation method |
| CN109321141B (en) * | 2018-11-02 | 2019-12-03 | 山东天岳先进材料科技有限公司 | A method of preparing the stability-enhanced silicon carbide chemical mechanical polishing liquid of pH |
| CN114686110A (en) * | 2020-12-30 | 2022-07-01 | 安集微电子科技（上海）股份有限公司 | A chemical mechanical polishing liquid |
| CN115198275B (en) * | 2022-06-07 | 2024-02-09 | 湖北奥美伦科技有限公司 | Sand surface aluminum alloy masking agent and preparation method and application thereof |
| CN115044777B (en) * | 2022-07-11 | 2024-01-16 | 斯尔特环保设备(浙江)有限公司 | Method for efficiently recycling metal-containing phosphoric acid polishing solution |
| CN115928073B (en) * | 2022-11-28 | 2025-01-07 | 广东红日星实业有限公司 | A grinding liquid and its preparation method and application |
| CN116926551A (en) * | 2023-08-08 | 2023-10-24 | 山东创新板材有限公司 | Polishing solution for aluminum alloy and preparation method thereof |
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| CN1434846A (en) * | 2000-05-12 | 2003-08-06 | 日产化学工业株式会社 | Polishing composition |
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| JP4213858B2 (en) * | 2000-02-03 | 2009-01-21 | 花王株式会社 | Polishing liquid composition |
| CN1480499A (en) * | 2002-09-05 | 2004-03-10 | 御币岛化学有限公司 | Chemical polishing liquid |
| KR100504606B1 (en) * | 2002-12-27 | 2005-08-03 | 제일모직주식회사 | Slurry Composition for Chemical Mechanical Polishing of Aluminium with Improved Removal Rate and Dispersability |
| JP3917593B2 (en) * | 2004-02-05 | 2007-05-23 | 株式会社東芝 | Manufacturing method of semiconductor device |
| KR100497413B1 (en) * | 2004-11-26 | 2005-06-23 | 에이스하이텍 주식회사 | Slurry for tungsten-chemical mechanical polishing and method for manufacturing of the same |
| US20060118760A1 (en) * | 2004-12-03 | 2006-06-08 | Yang Andy C | Slurry composition and methods for chemical mechanical polishing |
| US20060124026A1 (en) * | 2004-12-10 | 2006-06-15 | 3M Innovative Properties Company | Polishing solutions |
| US7731864B2 (en) * | 2005-06-29 | 2010-06-08 | Intel Corporation | Slurry for chemical mechanical polishing of aluminum |
| CN1900206B (en) * | 2005-07-21 | 2011-01-05 | 安集微电子（上海）有限公司 | Chemical and mechanical polishing liquid and its use |
| US8425797B2 (en) * | 2008-03-21 | 2013-04-23 | Cabot Microelectronics Corporation | Compositions for polishing aluminum/copper and titanium in damascene structures |
| CN101649162A (en) * | 2008-08-15 | 2010-02-17 | 安集微电子（上海）有限公司 | Polishing solution used for chemical mechanical grounding |
| 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 |
| CN102051126B (en) * | 2009-11-06 | 2014-11-05 | 安集微电子（上海）有限公司 | Polishing solution for tungsten chemical mechanical polishing |
| CN102373013A (en) * | 2010-08-24 | 2012-03-14 | 安集微电子（上海）有限公司 | Chemically mechanical polishing solution |
| CN102477258B (en) * | 2010-11-26 | 2015-05-27 | 安集微电子（上海）有限公司 | Chemically mechanical polishing liquid |
| CN102820223A (en) * | 2011-06-08 | 2012-12-12 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing method for simultaneously polishing phase-change material and tungsten |
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| CN1434846A (en) * | 2000-05-12 | 2003-08-06 | 日产化学工业株式会社 | Polishing composition |
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| TW201525123A (en) | 2015-07-01 |
| CN104745084A (en) | 2015-07-01 |
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