CN101362986B - Aqueous cleaning compositions for semi-conductor copper processing - Google Patents
Aqueous cleaning compositions for semi-conductor copper processing Download PDFInfo
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- CN101362986B CN101362986B CN200710138062A CN200710138062A CN101362986B CN 101362986 B CN101362986 B CN 101362986B CN 200710138062 A CN200710138062 A CN 200710138062A CN 200710138062 A CN200710138062 A CN 200710138062A CN 101362986 B CN101362986 B CN 101362986B
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Abstract
The invention relates to a water phase cleaning composition which is used in or after the chemical mechanical planarization during the copper processing of an integrated circuit, and the water phase cleaning composition comprises 0.05 to 20 percent by weight of nitrogen-containing heterocyclic organic base, 0.05 to 50 percent by weight of alkylol amine, 0.01 to 10 percent by weight of quaternary ammonium hydroxide and water. When the water phase cleaning composition is used in or after the planarization process of a semiconductor, the cleaning composition can effectively remove residual pollutants from the surface of a chip and simultaneously give the better surface roughness to the surface of the chip.
Description
Technical field
The present invention relates to a kind of aqueous phase cleaning composition that is used for integrated circuit copper processing chemical-mechanical planarization (CMP).
Background technology
About semiconductor element, just develop now towards the direction of littler live width, higher long-pending volume density.When the unicircuit minimum feature is reduced to below 0.25 micron, become the main key that influences the element arithmetic speed by the resistance and the caused time lag of dielectric layer stray capacitance (RC delay) of plain conductor itself.Therefore, in order to improve the arithmetic speed of element, the dealer changes gradually in the processing of the high-order below 0.13 micron and adopts the copper plain conductor and replace traditional aluminum-copper alloy lead at present.
The technology of chemical-mechanical planarization (Chemical Mechanical Planarization) is applied in the processing of copper plain conductor; Not only can overcome the problem that is difficult for being difficult to define pattern because of the copper metal etch; And grinding the back is the plane of universe property planarization (global planarity), is easy to the carrying out of multi-layer conductor leads processing.The principle of chemical-mechanical planarization is to match with chemical assistant through the abrasive grains in the lapping liquid; Make the wafer surface material is produced abrasion; Make the smooth higher position of air spots remove speed thus because of pressurized produces height greatly; And the smooth lower of air spots has because of pressurized is little and removes speed more slowly, thereby reaches the purpose of universe property planarization.
In the process of lapping of chemical-mechanical planarization, a large amount of fine ground particles and chemical assistant in the lapping liquid, and the chip that the wafer abrasion are peeled off may be attached to wafer surface.General wafer common pollutent after grinding is metals ion, organic cpds or abrasive grains etc.Do not remove above-mentioned pollutent if there is effective wash procedure, will influence the carrying out of following process and the output and the reliability of reduction element so.Therefore, in the CMP processing or its follow-up wash procedure, become can successful Application CMP in the gordian technique of semiconductor machining.
With how using benzotriazole in the lapping liquid (benzotriazole, BTA) or derivatives thereof is as corrosion inhibitor in copper processing.Grind in the produced pollution thing of back at the copper processed wafer, be difficult to most remove with the BTA organic residue, major cause is that BTA is binding on the copper conductor with the chemisorption mode.Tradition only utilizes electrostatic repulsion, ultrasonic oscillation and Z 150PH (PVA) brush the mode of physical removal such as to scrub, and is difficult for that excellent cleaning effect is arranged.
Dielectric layer between traditional metal (inter-metal dielectric layer) and tungsten plug (W plug) often use ammonia soln and/or fluorochemicals to clean behind chemical-mechanical planarization, but above-mentioned solution and be not suitable for the wafer of copper plain conductor.Ammonia soln can corrode copper metallic face unevenly, and causes the phenomenon of roughening.Fluorochemicals such as hydrofluoric acid not only can make roughened copper surfaceization so, and for avoiding its harmful to human and environment, need pay more costs in personnel safety guard and liquid waste disposal.
No. 6139763 announcement of people's such as Ina USP is a kind of can be effectively from the abrasive composition of substrate removal tantalum metal, and its reductive agent (like oxalic acid) and water by abrasive grain, the oxygenant of oxidable tantalum metal, reducible tantalum oxide is formed.This abrasive composition can further comprise hexahydropyrazine (piperazine, a kind of nitrogen heterocyclic ring organic bases).Teaching according to people such as Ina; Hexahydropyrazine can act on the copper laminar surface at process of lapping, thereby prevents the generation of surface damage, and for example subside (recesses), dish fall into (dishing) or abrasion (erosion); It also can protect lapped face, to impel the surface of accomplishing as the minute surface.People such as Ina not teaching or suggestion can be used for hexahydropyrazine the water scavenging solution of semiconductor copper planarization process.
The USP the 6th of Small; 546; No. 939 (No. the 396202nd, Taiwan patent) discloses a kind of method from metal or dielectric layer surface removal chemical residue, its with pH value between enough time of removal chemical residue of 3.5 to 7 waterborne compositions contacting metal or dielectric layer surface.This waterborne compositions comprises: a kind of organic acid of single, double or trifunctional base, the alkali of the quaternary ammonium compound of buffering capacity, volatile caustic, azanol, hydroxylammonium salt or diamine salt, and bursine (choline hydroxide).
People's such as Small USP the 6th; 498; Disclose a kind of clean-out system No. 131; It is made up of non-ionics, amine, quaternary ammonium compound and the surperficial setting-up agent that is selected from terepthaloyl moietie, Ucar 35, polyoxyethylene and its mixture, in order to clean the resistates of chemical-mechanical planarization processing.
People's such as Naghshineh USP discloses a kind of clean-out system the 6th, 492, No. 308, and it is made up of tetra-alkyl ammonium hydroxide, polarity organic amine and corrosion inhibitor, contains copper integrated circuit in order to cleaning.
The USP of Nam discloses a kind of clean-out system the 5th, 863, No. 344, and it is made up of TMAH, acetate and water, and in order to clean semiconductor components, wherein acetate is 1 to about 50 to the preferable volumetric ratio of TMAH.
People's such as Masahiko USP discloses a kind of cleaning for the 6th, 716, No. 803 and has the method for copper conductor in its surperficial semiconducter substrate, and the clean-out system that said method is used comprises tensio-active agent and nitrogenous alkaline matter.
People's such as Ward USP discloses a kind of clean-out system the 5th, 988, No. 186, and it is made up of water soluble polar solvent, organic amine and phenyl ring corrosion inhibitor, in order to remove the organic or inorganic material.
The liquid cleaner of No. 20060229221 a kind of low metal etch speed of (No. the 200706647th, Taiwan publication) announcement of U.S.'s publication of people such as Walker, it is made up of hydroxide level Four ammonium, alkanolamine and water, is used for the cleaning microelectronic substrate.
Old people's the U.S.'s publication No. 20070066508 (No. the 200641121st, Taiwan publication) that waits discloses a kind of aqueous cleaning compositions for semi-conductor copper processing; It is made up of nitrogen heterocyclic ring organic bases, hydramine and water, is used for cleaning containing the copper conductor wafer behind the unicircuit processing chemical-mechanical planarization.
Progress along with semiconductor wafer processing; The plain conductor width has narrowed down to 32 rice how; The problem that new planarization process still has many need to overcome; For example the wide wafer surface of nanowire surfaceness possible deviation and live width after processing treatment open circuit/short-circuit test (open/short test) and reliability test (reliability test) of dwindling back copper conductor wafer more is easy to generate deterioration.Industrial community is cleaned processing to the copper conductor wafer and is still needed more can effectively remove the cleaning liquid composition that remains in the pollutent on the copper conductor wafer surface and reduce the number of defects of wafer surface than prior art.
Summary of the invention
The present invention provides in a kind of chemical-mechanical planarization in copper processing or the aqueous phase cleaning composition that uses behind the chemical-mechanical planarization, and it comprises nitrogen heterocyclic ring organic bases, hydramine, hydroxide level Four ammonium and water.Aqueous phase cleaning composition of the present invention can be removed the pollutent that remains in after the grinding on the wafer surface, the number of defects that reduces wafer surface effectively, and can give wafer preferable surfaceness after contacting one period working lipe with the cupric semiconductor wafer.
Description of drawings
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Embodiment
Aqueous phase cleaning composition of the present invention in composition total weight, comprises the nitrogen heterocyclic ring organic bases of 0.05-20 weight %, the hydramine of 0.05-50 weight %, hydroxide level Four ammonium and the water of 0.01-10 weight %.
Cleaning combination of the present invention utilizes alcohol amine compound that the copper laminar surface is carried out inhomogeneity etching, makes that the surfaceness of copper conductor does not produce deterioration after the etching.Nitrogen provides not share electron pair on the heterocycle of nitrogen heterocyclic ring organic bases, and it can carry out the key knot with copper conductor, thereby the organic pollutant of avoiding breaking away from copper conductor adsorbs back again.Hydroxide level Four ammonium then is the clean ability that further promotes wafer surface.
The group that the optional free hexahydropyrazine of nitrogen heterocyclic ring organic bases used in the present invention, 2-(1-hexahydropyrazine) ethanol, 2-(1-hexahydropyrazine) ethamine and its mixture are constituted, preferable use hexahydropyrazine.The content of nitrogen heterocyclic ring organic bases used in the present invention in composition total weight, is 0.05-20 weight %, is preferably 0.1-15 weight %, is more preferred from 0.15-10 weight %.
The group that optional free thanomin, diethylolamine, trolamine, Propanolamine, Mono Methyl Ethanol Amine, methyldiethanolamine and its mixture of hydramine used in the present invention constituted, the preferable group that constitutes by thanomin, diethylolamine, trolamine and its mixture that is selected from.The content of hydramine used in the present invention in composition total weight, is 0.05-50 weight %, is preferably 0.1-45 weight %, is more preferred from 0.15-40 weight %.
Hydroxide level Four ammonium used in the present invention can be selected from tetraalkylammonium hydroxide, the preferable group that is made up of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium and its mixture that is selected from.The content of hydroxide level Four ammonium used in the present invention in composition total weight, is 0.01-10 weight %, is preferably 0.02-10 weight %, is more preferred from 0.05-8 weight %.
The lapping liquid that general copper processing chemical-mechanical planarization uses often contains the wafer surface after tensio-active agent and corrosion inhibitor (like the BTA or derivatives thereof) very easily remain in grinding, and the physical method that said organic residue is difficult to only depend on general using electrostatic repulsion, ultrasonic oscillation and Z 150PH (PVA) brush to scrub is removed.Nitrogen heterocyclic ring organic bases that cleaning combination of the present invention contained and alcohol amine compound can promote the saturation solubility of cleaning combination to organic residue (like BTA), thereby can provide bigger motivating force with dissolving BTA particulate.Mode in conjunction with conventional physical is removed is used disclosed cleaning combination, can reach good wash result.
Cleaning combination of the present invention can directly use, or with re-using after the ultrapure water dilution.For saving production, transportation and warehouse cost, the compsn of higher concentration is provided usually, use with ultrapure water dilution back in use side again.The multiple of dilution uses situation according to reality and determines, generally between 10 to 60 times.Under the specific demand situation, as saving the treatment time, cleaning combination stoste that can concentration is higher is directly in order to clean wafers.
Can use under the cleaning combination normal temperature of the present invention, this cleaning combination is contacted one period working lipe with the cupric semiconductor wafer, can remove the pollutent that remains on the wafer surface effectively, keep the preferable surfaceness of copper conductor simultaneously.Generally speaking, when working concentration is low, need long duration of contact (for example, 1-3 minute), when working concentration is higher, only need short duration of contact (for example, being shorter than 1 minute).When reality is used, can seek the processing optimization (Process Optimization) of cleaning combination concentration and duration of contact through examination mistake mode (try anderror).
Cleaning combination of the present invention can clean the wafer surface through planarization on the board of carrying out chemical-mechanical planarization, also can independently clean the wafer surface through planarization on the cleaning machine.
Following examples will be further described the present invention, be not in order to limiting scope of the present invention, and any have modification and a change that common knowledge the knowledgeable can reach easily in this technology, and it all is covered by in the scope of the present invention.
Embodiment
Cleaning combination with nitrogen heterocyclic ring organic bases, hydramine and the different compositions of hydroxide level Four ammonium preparation tool; Cleaning combination dilutes 30 times with ultrapure water on cleaning machine Ontrak; Copper blank wafer to grinding is cleaned, and scavenging period two minutes, clean-out system flow are 600 milliliters of PMs.Measure copper wafer surface blemish number with TOPCON WM-1700 wafer measuring fine particles appearance after cleaning completion, use AFM (AFM) to measure the surfaceness (Ra) of copper wafer in addition.
Table one: surface imperfection number and roughness behind the cleaning combination cleaning copper wafer
By the result of above-mentioned compsn 1 to 11, relatively number 1,8 and 10 cleaning combinations, numbering 2,9 and 11 cleaning combinations can be known, use nitrogen heterocyclic ring organic bases, hydramine and hydroxide level Four ammonium when simultaneously, can obtain minimum copper wafer and clean back surface imperfection number.And relatively number 1 to 7 and 12; Wafer surface blemish number after ultrapure water cleans is the poorest; Numbering 1 to 7 cleaning combination is except obviously significantly reducing copper wafer surface blemish number, and will copper wafer surface roughness remains on and do not have a corrodibility ultrapure water and clean the identical level of copper wafer surface afterwards.
Claims (9)
- One kind in chemical-mechanical planarization or the aqueous phase cleaning composition that uses behind the chemical-mechanical planarization, it comprises the nitrogen heterocyclic ring organic bases of (a) 0.05-20 weight %; (b) hydramine of 0.05-50 weight %; (c) the hydroxide level Four ammonium of 0.01-10 weight %; (d) water,Wherein said organic bases is selected from hexahydropyrazine, 2-(1-hexahydropyrazine) ethanol, 2-(1-hexahydropyrazine) ethamine and its mixture; Said hydramine is selected from thanomin, diethylolamine, trolamine, Propanolamine, Mono Methyl Ethanol Amine, methyldiethanolamine and its mixture, and said hydroxide level Four ammonium is selected from tetraalkylammonium hydroxide.
- 2. compsn according to claim 1, wherein said hydramine are selected from thanomin, diethylolamine, trolamine and its mixture.
- 3. compsn according to claim 1, wherein said tetraalkylammonium hydroxide are selected from tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium and its mixture.
- 4. compsn according to claim 1, the consumption of wherein said nitrogen heterocyclic ring organic bases are 0.1-15 weight %.
- 5. compsn according to claim 4, the consumption of wherein said nitrogen heterocyclic ring organic bases are 0.15-10 weight %.
- 6. compsn according to claim 1, the consumption of wherein said hydramine are 0.1-45 weight %.
- 7. compsn according to claim 6, the consumption of wherein said hydramine are 0.15-40 weight %.
- 8. compsn according to claim 1, the consumption of wherein said hydroxide level Four ammonium are 0.02-10 weight %.
- 9. compsn according to claim 8, the consumption of wherein said hydroxide level Four ammonium are 0.05-8 weight %.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200710138062A CN101362986B (en) | 2007-08-08 | 2007-08-08 | Aqueous cleaning compositions for semi-conductor copper processing |
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| CN200710138062A CN101362986B (en) | 2007-08-08 | 2007-08-08 | Aqueous cleaning compositions for semi-conductor copper processing |
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| CN101362986A CN101362986A (en) | 2009-02-11 |
| CN101362986B true CN101362986B (en) | 2012-09-05 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1006166A1 (en) * | 1998-12-01 | 2000-06-07 | Fujimi Incorporated | Polishing composition and polishing method employing it |
| CN1865423A (en) * | 2005-05-20 | 2006-11-22 | 长兴开发科技股份有限公司 | Aqueous phase cleaning composition for semiconductor copper manufacture process |
| TW200706647A (en) * | 2005-03-30 | 2007-02-16 | Advanced Tech Materials | Aqueous cleaner with low metal etch rate |
-
2007
- 2007-08-08 CN CN200710138062A patent/CN101362986B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1006166A1 (en) * | 1998-12-01 | 2000-06-07 | Fujimi Incorporated | Polishing composition and polishing method employing it |
| TW200706647A (en) * | 2005-03-30 | 2007-02-16 | Advanced Tech Materials | Aqueous cleaner with low metal etch rate |
| CN1865423A (en) * | 2005-05-20 | 2006-11-22 | 长兴开发科技股份有限公司 | Aqueous phase cleaning composition for semiconductor copper manufacture process |
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| CN101362986A (en) | 2009-02-11 |
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Address after: Kaohsiung City, Taiwan, China Patentee after: Xinming Materials Co.,Ltd. Address before: No. 2, KEBA Road, Zhuxiang Road, Nanke Kaohsiung Park, Tainan Science and Industry Park, Kaohsiung County, Taiwan, China Patentee before: Changxing Development Technology Co.,Ltd. |
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Effective date of registration: 20230927 Address after: Delaware Patentee after: Integ Ltd. Address before: Taiwan, Kaohsiung, China Patentee before: Xinming Materials Co.,Ltd. |