Use of Formulations Based On Choline Chloride-Malonic Acid Deep Eutectic Solvent for Back End of Line Cleaning in Integrated Circuit Fabrication

Persistent Link:
http://hdl.handle.net/10150/283692
Title:
Use of Formulations Based On Choline Chloride-Malonic Acid Deep Eutectic Solvent for Back End of Line Cleaning in Integrated Circuit Fabrication
Author:
Taubert, Jenny
Issue Date:
2013
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
Interconnection layers fabricated during back end of line processing in semiconductor manufacturing involve dry etching of a low-k material and deposition of copper and metal barriers to create copper/dielectric stacks. After plasma etching steps used to form the trenches and vias in the dielectric, post etch residues (PER) that consist of organic polymer, metal oxides and fluorides, form on top of copper and low-k dielectric sidewalls. Currently, most semiconductor companies use semi aqueous fluoride (SAF) based formulations containing organic solvent(s) for PER removal. Unfortunately, these formulations adversely impact the environmental health and safety (EHS) requirements of the semiconductor industry. Environmentally friendly "green" formulations, free of organic solvents, are preferred as alternatives to remove PER. In this work, a novel low temperature molten salt system, referred as deep eutectic solvent (DES) has been explored as a back end of line cleaning (BEOL) formulation. Specifically, the DES system comprised of two benign chemicals, malonic acid (MA) and choline chloride (CC), is a liquid at room temperature. In certain cases, the formulation was modified by the addition of glacial acetic acid (HAc). Using these formulations, selective removal of three types of PER generated by timed CF₄/O₂ etching of DUV PR films on Cu was achieved. Type I PER was mostly organic in character (fluorocarbon polymer type) and had a measured thickness of 160 nm. Type II PER was much thinner (25 nm) and consisted of a mixture of organic and inorganic compounds (copper fluorides). Further etching generated 17 nm thick Type III PER composed of copper fluorides and oxides. Experiments were also conducted on patterned structures. Cleaning was performed by immersing samples in a temperature controlled (30 or 40° C) double jacketed vessel for a time between 1 and 5 minutes. Effectiveness of cleaning was characterized using SEM, XPS and single frequency impedance measurements. Type II and III residues, which contained copper compounds were removed in CC/MA DES within five minutes through dissolution and subsequent complexation of copper by malonic acid. Removal of Type I PER required the addition of glacial acetic acid to the DES formulation. Single frequency impedance measurement appears to be a good in situ method to follow the removal of the residues. High water solubility of the components of the system in conjunction with their environmental friendly nature, make the DES an attractive alternative to SAF.
Type:
text; Electronic Dissertation
Keywords:
Characterization of Post Etch Residue; Deep Eutectic Solvents; Post Etch Residue Cleaning; Materials Science & Engineering; Back End of Line Cleaning
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Graduate College; Materials Science & Engineering
Degree Grantor:
University of Arizona
Advisor:
Raghavan, Srini

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleUse of Formulations Based On Choline Chloride-Malonic Acid Deep Eutectic Solvent for Back End of Line Cleaning in Integrated Circuit Fabricationen_US
dc.creatorTaubert, Jennyen_US
dc.contributor.authorTaubert, Jennyen_US
dc.date.issued2013-
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractInterconnection layers fabricated during back end of line processing in semiconductor manufacturing involve dry etching of a low-k material and deposition of copper and metal barriers to create copper/dielectric stacks. After plasma etching steps used to form the trenches and vias in the dielectric, post etch residues (PER) that consist of organic polymer, metal oxides and fluorides, form on top of copper and low-k dielectric sidewalls. Currently, most semiconductor companies use semi aqueous fluoride (SAF) based formulations containing organic solvent(s) for PER removal. Unfortunately, these formulations adversely impact the environmental health and safety (EHS) requirements of the semiconductor industry. Environmentally friendly "green" formulations, free of organic solvents, are preferred as alternatives to remove PER. In this work, a novel low temperature molten salt system, referred as deep eutectic solvent (DES) has been explored as a back end of line cleaning (BEOL) formulation. Specifically, the DES system comprised of two benign chemicals, malonic acid (MA) and choline chloride (CC), is a liquid at room temperature. In certain cases, the formulation was modified by the addition of glacial acetic acid (HAc). Using these formulations, selective removal of three types of PER generated by timed CF₄/O₂ etching of DUV PR films on Cu was achieved. Type I PER was mostly organic in character (fluorocarbon polymer type) and had a measured thickness of 160 nm. Type II PER was much thinner (25 nm) and consisted of a mixture of organic and inorganic compounds (copper fluorides). Further etching generated 17 nm thick Type III PER composed of copper fluorides and oxides. Experiments were also conducted on patterned structures. Cleaning was performed by immersing samples in a temperature controlled (30 or 40° C) double jacketed vessel for a time between 1 and 5 minutes. Effectiveness of cleaning was characterized using SEM, XPS and single frequency impedance measurements. Type II and III residues, which contained copper compounds were removed in CC/MA DES within five minutes through dissolution and subsequent complexation of copper by malonic acid. Removal of Type I PER required the addition of glacial acetic acid to the DES formulation. Single frequency impedance measurement appears to be a good in situ method to follow the removal of the residues. High water solubility of the components of the system in conjunction with their environmental friendly nature, make the DES an attractive alternative to SAF.en_US
dc.typetexten_US
dc.typeElectronic Dissertationen_US
dc.subjectCharacterization of Post Etch Residueen_US
dc.subjectDeep Eutectic Solventsen_US
dc.subjectPost Etch Residue Cleaningen_US
dc.subjectMaterials Science & Engineeringen_US
dc.subjectBack End of Line Cleaningen_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.disciplineMaterials Science & Engineeringen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorRaghavan, Srinien_US
dc.contributor.committeememberUhlmann, Donald R.en_US
dc.contributor.committeememberSaez, Eduardo A.en_US
dc.contributor.committeememberMuralidharan, Krishnaen_US
dc.contributor.committeememberRaghavan, Srinien_US
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