CN105506632A - Application of alkaline polishing solution in increment of copper film removal rate of GLSI (Great Large Scale Integration) copper wiring at low pressure - Google Patents

Application of alkaline polishing solution in increment of copper film removal rate of GLSI (Great Large Scale Integration) copper wiring at low pressure Download PDF

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Publication number
CN105506632A
CN105506632A CN201510997118.0A CN201510997118A CN105506632A CN 105506632 A CN105506632 A CN 105506632A CN 201510997118 A CN201510997118 A CN 201510997118A CN 105506632 A CN105506632 A CN 105506632A
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CN
China
Prior art keywords
copper film
application
polishing liquid
glsi
polishing solution
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Pending
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CN201510997118.0A
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Chinese (zh)
Inventor
刘玉岭
武鹏
孙鸣
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JINGLING MICRO-ELECTRONIC MATERIAL Co Ltd TIANJIN
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JINGLING MICRO-ELECTRONIC MATERIAL Co Ltd TIANJIN
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Priority to CN201510997118.0A priority Critical patent/CN105506632A/en
Publication of CN105506632A publication Critical patent/CN105506632A/en
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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
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • C23F1/34—Alkaline compositions for etching copper or alloys thereof
    • 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
    • C23F3/04—Heavy metals

Abstract

The invention relates to application of an alkaline polishing solution in increment of copper film removal rate of GLSI copper wiring at low pressure. The alkaline polishing solution mainly consists of a SiO2 abrasive material, an oxidant, an activating agent and a chelating agent; the pH value of the alkaline polishing solution is 9 to 13; the alkaline polishing solution is characterized in application of the chelating agent of the alkaline polishing solution in increment of the copper film removal rate at low mechanical pressure. The application of the alkaline polishing solution has the beneficial effects that the FA/O type chelating agent contains multi-hydroxyl and multi-amido alkaline large molecules, so the alkaline polishing solution plays an extremely strong complexation effect on copper ions in the solution, and reaction products stably exist and are easily soluble in water, so a high copper film removal rate is realized at low mechanical pressure.

Description

Alkalescence polishing liquid improves the application that GLSI thin copper film copper film removes speed at low pressures
Technical field
The invention belongs to chemically machinery polished, particularly relate to a kind of alkalescence polishing liquid and improve the application that GLSI thin copper film copper film removes speed at low pressures.
Background technology
Metallic copper, due to its outstanding electrical properties, makes thin copper film occupy most of market of integrated circuit metal interconnection line.Along with the reduction of device size, the increasing of the increase of wafer size and the metal line number of plies, the quality of every one deck planarization all affects the serviceability of last unicircuit finished product.Chemically machinery polished is the technology that uniquely can realize local and global planarizartion at present, and whether the maturation of chemical Mechanical Polishing Technique directly affects the development of unicircuit.
Chemically machinery polished requires the reason of low pressure: (1) is along with the development of microelectronics, the integrated level of unicircuit is more and more higher, 13 layers have been reached before metal line number of layers, copper film thins down, if operating pressure is excessive in chemically machinery polished, copper film is easily caused to come off.(2) in order to reduce the Resistance-Capacitance delay time, medium with low dielectric constant material widely uses in integrated circuits, but the advanced low-k materials of porous fragility can the avalanche because polish pressure is excessive.(3) polishing pad has elasticity, and the increase of polish pressure can cause the removal speed of copper film surface pocket too fast, and height speed difference diminishes, and is unfavorable for planarization.
For the chemically machinery polished of thin copper film, adopt acid polishing slurry in the world more.Its principle is: the oxidized rear mantoquita easily forming solubility with acid-respons of copper, thus reaches the object of removal copper.And along with unicircuit is to 28nm and following fast development, acid polishing slurry is more and more not suitable for using in chemically machinery polished, reason has: it is on the low side that (1) removes speed.In acid polishing slurry, the chemical reaction rate using suppression etching reagent to reduce copper surface pocket, reaches planarization object more.But suppress the use of etching reagent again can the overall removal speed reducing copper, the removal speed that acid polishing slurry is lower be difficult to reach industry needs.(2) polish pressure is excessive.For improving polishing speed, industrial usual employing improves the method for polish pressure, this low polish pressure contradiction just required with advanced low-k materials.(3) environmental protection pressure.Acid polishing slurry environmental pollution is serious, and meeting etching apparatus, causes metal ion pollution, cause workpiece degradation.Suppress etching reagent to have toxicity more.Have many sections of bibliographical informations in recent years, Novel stop layer material Ru, in acid polishing slurry, can generate volatilizable poisonous RuO 4.
According to the prediction of " ITRS ", by 2024, the minimum feature of transistor will reach about 7nm.Therefore be badly in need of exploitation and under lower pressure, the very fast method removing speed can be had to great scale integrated circuit thin copper film copper film.Be difficult to the bottleneck overcome under the pressure of acid polishing slurry, industry turns to the cmp method of alkaline route sight.Alkalescence route is primarily dealt with problems the oxide compound and oxyhydroxide such as CuO, Cu that are copper 2o, CuOH, Cu (OH) 2water-fast problem in the basic conditions.At present, the FA/O type macromole sequestrant of Microelectronic Institute of Hebei University of Technology independent research solves the oxide compound undissolved international headache in the basic conditions of copper, by the combination of macromole inner complex and cupric ion, under low pressure copper film is reached and remove speed faster, meet industry needs.
Summary of the invention
The object of the invention is to the deficiency overcoming above-mentioned technology, and provide a kind of alkalescence polishing liquid to improve the application of GLSI thin copper film copper film removal speed at low pressures, FA/O type sequestrant in alkalescence polishing liquid contains the alkaline macromole of poly-hydroxy polyamines base, extremely strong complexing action is had to the cupric ion in solution, its reaction product stable existence and soluble in water, achieves and remove speed to the height of copper film under low mechanical pressure.
The present invention for achieving the above object, by the following technical solutions: a kind of alkalescence polishing liquid improves GLSI thin copper film copper film at low pressures and removes the application of speed, primarily of SiO 2the alkalescence polishing liquid of abrasive material, oxygenant, promoting agent and sequestrant composition, its pH value 9 ~ 13, is characterized in that: the sequestrant of described alkalescence polishing liquid removes the application of speed under low mechanical pressure to the height of copper film.
Described alkalescence polishing liquid by following composition by weight % Homogeneous phase mixing make,
Nano-meter SiO_2 2abrasive material 5 ~ 80%, deionized water 10 ~ 80%
Oxygenant 0.5 ~ 6% promoting agent: 0.5 ~ 5%
Sequestrant 3 ~ 6%.
Described Nano-meter SiO_2 2the concentration of abrasive material is 20 ~ 80wt%, particle diameter is 50 ~ 120nm.
Described sequestrant is one or more mixing in FA/O II type sequestrant, FA/O IV type sequestrant or glycine.
Described promoting agent is one or more mixing in FA/O I type nonionogenic tenside, dodecyl phenol polyethenoxy ether or polyoxyethylene octylphenol ether.
Described oxygenant is H 2o 2, KClO 3or KNO 3in one.
Beneficial effect: compared with prior art, alkalescence polishing liquid of the present invention utilizes FA/O type sequestrant to contain the alkaline macromole of poly-hydroxy polyamines base, extremely strong complexing action is had to the cupric ion in solution, its reaction product stable existence and soluble in water, achieves and remove speed to the height of copper film under low mechanical pressure.Use hydrogen peroxide as the oxygenant in polishing fluid, oxidation products is water, on whole copper metallization chemical mechanical polishing environment without impact.FA/O type sequestrant can react with cupric ion efficiently, and enhance the chemical action in chemically machinery polished, cooperative mechanical effect, achieves based on chemical action, and mechanical effect is auxiliary chemically machinery polished.Less mechanical effect, improves wafer quality after polishing, again saves the energy, extend service life of equipment.Use tensio-active agent to improve mass transfer effect on polishing interface, contribute to improving and remove crystal column surface quality after speed and polishing.What after using lower polish pressure to efficiently solve polishing, crystal column surface may exist steps on limit, locally crosses the problems such as throwing, has saved the energy simultaneously, has extended equipment life.Not containing corrosion inhibitor in alkalescence polishing liquid, contained chemical composition not etching apparatus, free from environmental pollution, environmental protection pressure is little.Nano-meter SiO_2 used 2grinding abrasive is stable existence in alkalescence polishing liquid.
Embodiment
The specific embodiment of the present invention is described in detail below in conjunction with preferred embodiment.
Present embodiments provide a kind of alkalescence polishing liquid and improve the application that GLSI thin copper film copper film removes speed at low pressures, primarily of SiO 2the alkalescence polishing liquid of abrasive material, oxygenant, promoting agent and sequestrant composition, its pH value 9 ~ 13, the sequestrant of described alkalescence polishing liquid removes the application of speed under low mechanical pressure to the height of copper film.Described alkalescence polishing liquid by following composition by weight % Homogeneous phase mixing make,
Nano-meter SiO_2 2abrasive material 5 ~ 80%, deionized water 10 ~ 80%
Oxygenant 0.5 ~ 6% promoting agent: 0.5 ~ 5%
Sequestrant 3 ~ 6%.
Described Nano-meter SiO_2 2the concentration of abrasive material is 20 ~ 80wt%, particle diameter is 50 ~ 120nm.
Described sequestrant is one or more mixing in FA/O II type sequestrant, FA/O IV type sequestrant or glycine.
Described promoting agent is one or more mixing in FA/O I type nonionogenic tenside, dodecyl phenol polyethenoxy ether or polyoxyethylene octylphenol ether.
Described oxygenant is H 2o 2, KClO 3or KNO 3in one.
Embodiment 1:
Under alkalescence polishing liquid proportioning and low pressure, copper metallization chemical mechanical polishing processing parameter requires:
Preparation alkalescence polishing liquid 3340g; Select Nano-meter SiO_2 2abrasive material 1200g, abrasive concentration is 20 ~ 80wt%, and abrasive size 50nm puts into 1800g deionized water while stirring, then gets FA/O IV type sequestrant 120g respectively, FA/O I type nonionogenic tenside 100g and H 2o 2120g adds aforesaid liquid while stirring.Adjust ph 9 ~ 13, the 3340g thin copper film alkalescence polishing liquid after stirring.
Glossing parameter is: pressure 5.516KPa, flow 200mL/L, rotating speed 60rpm/min, temperature 22 DEG C, polishing time 3min.
Polishing speed is 856nm/min, and rate non-uniformity controls 0.08.
Embodiment 2:
Under alkalescence polishing liquid proportioning and low pressure, copper metallization chemical mechanical polishing processing parameter requires:
Preparation alkalescence polishing liquid 3400g; Select Nano-meter SiO_2 2abrasive material 1500g, abrasive concentration is 20 ~ 80wt%, and abrasive size 70nm puts into 1500g deionized water while stirring, then gets FA/O II type sequestrant 150g respectively, dodecyl phenol polyethenoxy ether 100g and KClO 3150g adds aforesaid liquid while stirring.Adjust ph 9 ~ 13, the 3400g thin copper film alkalescence polishing liquid after stirring.
Glossing parameter is: pressure 4.827KPa, flow 150mL/L, rotating speed 60rpm/min, temperature 20 DEG C, polishing time 3min.
Polishing speed is 915nm/min, and rate non-uniformity controls 0.06.
Embodiment 3:
Under alkalescence polishing liquid proportioning and low pressure, copper metallization chemical mechanical polishing processing parameter requires:
Preparation alkalescence polishing liquid 3500g; Select Nano-meter SiO_2 2abrasive material 2000g, abrasive concentration is 20 ~ 80wt%, and abrasive size 120nm puts into 1000g deionized water while stirring, then gets FA/O IV type sequestrant and glycine 200g, FA/O I type nonionogenic tenside and agent polyoxyethylene octylphenol ether 100g and H respectively 2o 2200g adds aforesaid liquid while stirring.Adjust ph 9 ~ 13, the 3500g thin copper film alkalescence polishing liquid after stirring.
Glossing parameter is: pressure 4.137KPa, flow 150mL/L, rotating speed 65rpm/min, temperature 25 DEG C, polishing time 3min.
Polishing speed is 986nm/min, and rate non-uniformity controls 0.07.
Use in copper metallization chemical mechanical polishing in the relevant manufactures of acid polishing slurry, polishing work pressure is between 10.34 ~ 20.69KPa, and the polishing speed obtained is also only upper and lower at 800nm/min.Its polish pressure is 2 ~ 5 times that obtain identical polishing speed use polish pressure in the present invention, not only causes energy dissipation, and excessive polish pressure is unfavorable for the stable of production line, reduces the stably manufactured time of production line, affects production efficiency.
Use in copper metallization chemical mechanical polishing in the relevant manufactures of alkalescence polishing liquid, except condition (< 6.895KPa) polishing speed in low mechanical pressure is difficult to meet except need of production, the silicon sol of Large stone can not stable existence in its polishing fluid, particle diameter can only be used at the silicon sol of 15 ~ 30nm as polish abrasive, the too small then polishing speed of abrasive size is little, can not meet industrial application.
Principle of work
Oxidizing rear formation cupric oxide in the polished liquid of copper, the oxide compound hydrolysis cupric ion of copper under alkaline condition, the FA/O type sequestrant that Tianjin Jingling Electronic Material Technology Co., Ltd sells contains the alkaline macromole of poly-hydroxy polyamines base, extremely strong complexing action is had to the cupric ion in solution, and its reaction product stable existence and soluble in water, under low mechanical pressure, achieve and speed is removed to the height of copper film.Reaction principle is as follows:
Cu+H 2O 2→CuO
Cu(OH) 2fCu 2++2OH -
Above-mentioned detailed description of the application that this kind of alkalescence polishing liquid improves GLSI thin copper film copper film removal speed at low pressures being carried out with reference to embodiment; illustrative instead of determinate; several embodiments can be listed according to institute's limited range; therefore in the change do not departed under general plotting of the present invention and amendment, should belong within protection scope of the present invention.

Claims (6)

1. alkalescence polishing liquid improves the application that GLSI thin copper film copper film removes speed at low pressures, primarily of SiO 2the alkalescence polishing liquid of abrasive material, oxygenant, promoting agent and sequestrant composition, its pH value 9 ~ 13, is characterized in that: the sequestrant of described alkalescence polishing liquid removes the application of speed under low mechanical pressure to the height of copper film.
2. alkalescence polishing liquid according to claim 1 improves GLSI thin copper film copper film at low pressures and removes the application of speed, it is characterized in that: described alkalescence polishing liquid by following composition by weight % Homogeneous phase mixing make,
Nano-meter SiO_2 2abrasive material 5 ~ 80%, deionized water 10 ~ 80%
Oxygenant 0.5 ~ 6% promoting agent: 0.5 ~ 5%
Sequestrant 3 ~ 6%.
3. alkalescence polishing liquid according to claim 1 and 2 improves the application that GLSI thin copper film copper film removes speed at low pressures, it is characterized in that: described Nano-meter SiO_2 2the concentration of abrasive material is 20 ~ 80wt%, particle diameter is 50 ~ 120nm.
4. alkalescence polishing liquid according to claim 1 and 2 improves the application that GLSI thin copper film copper film removes speed at low pressures, it is characterized in that: described sequestrant is one or more mixing in FA/O II type sequestrant, FA/O IV type sequestrant or glycine.
5. alkalescence polishing liquid according to claim 1 and 2 improves the application that GLSI thin copper film copper film removes speed at low pressures, it is characterized in that: described promoting agent is one or more mixing in FA/O I type nonionogenic tenside, dodecyl phenol polyethenoxy ether or polyoxyethylene octylphenol ether.
6. alkalescence polishing liquid according to claim 1 and 2 improves the application that GLSI thin copper film copper film removes speed at low pressures, it is characterized in that: described oxygenant is H 2o 2, KClO 3or KNO 3in one.
CN201510997118.0A 2015-12-24 2015-12-24 Application of alkaline polishing solution in increment of copper film removal rate of GLSI (Great Large Scale Integration) copper wiring at low pressure Pending CN105506632A (en)

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Application Number Priority Date Filing Date Title
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1398938A (en) * 2002-05-10 2003-02-26 河北工业大学 Chemical and mechanical leveling polishing liquid for multilayer copper wire in large scale integrated circuit
CN1861321A (en) * 2006-06-09 2006-11-15 河北工业大学 Method for controlling planeness during chemically mechanical polishing for ULSI multiple-layered copper wiring
CN1861320A (en) * 2006-06-09 2006-11-15 河北工业大学 Method for controlling disc-like pit during chemically mechanical polishing for ULSI multiple-layered copper wiring
CN101966688A (en) * 2010-07-21 2011-02-09 河北工业大学 Low-pressure CMP (Chemico-mechanical Polishing) method for grand-scale integrated circuit copper wiring surface

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1398938A (en) * 2002-05-10 2003-02-26 河北工业大学 Chemical and mechanical leveling polishing liquid for multilayer copper wire in large scale integrated circuit
CN1861321A (en) * 2006-06-09 2006-11-15 河北工业大学 Method for controlling planeness during chemically mechanical polishing for ULSI multiple-layered copper wiring
CN1861320A (en) * 2006-06-09 2006-11-15 河北工业大学 Method for controlling disc-like pit during chemically mechanical polishing for ULSI multiple-layered copper wiring
CN101966688A (en) * 2010-07-21 2011-02-09 河北工业大学 Low-pressure CMP (Chemico-mechanical Polishing) method for grand-scale integrated circuit copper wiring surface

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