Influence of different additives on the copper electroplating onto Au(111) and Cu(111) substrates [Elektronische Ressource] / von Corina Eleonora Täubert

Abteilung Elektrochemie
Universität Ulm







Influence of Different Additives
on the Copper Electroplating onto
Au(111) and Cu(111) Substrates



Dissertation
Zur Erlangung des Doktorgrades Dr. rer. nat.
der Fakultät für Naturwissenschaften
der Universität Ulm





von
Corina Eleonora Täubert
aus Bukarest

Ulm 2006

Der experimentelle Teil dieser Arbeit wurde in der Zeit von Februar 2002 bis Juli 2005 in der
Abteilung Elektrochemie der Universität Ulm angefertigt.

Wissenschaftlicher Betreuer: Prof. Dr. Dieter M. Kolb





















Amtierender Dekan: Prof. Dr. Klaus-Dieter Spindler

1. Gutachter: Prof. Dr. Dieter M. Kolb
2. Gutachter: Prof. Dr. Werner Tillmetz

Tag der Promotion: 9. November 2006




















Selbstständigkeitserklärung:

Hiermit erkläre ich, die vorliegende Dissertation selbstständig und ohne unerlaubte fremde
Hilfe angefertigt zu haben. Ich habe keine anderen als die angegebenen Quellen und
Hilfsmittel benutzt und sämtliche Textstellen, die wörtlich oder sinngemäß aus
veröffentlichten oder unveröffentlicthen Schriften entnommen wurden, und alle Angaben, die
auf mündlichen Auskünften beruhen, als solche kenntlich gemacht. Ebenfalls sind alle von
anderen Personen erbrachten Dienstleistungen als solche gekennzeichnet.




Ulm, den 26. Juli 2006 Corina Eleonora Täubert








To my husband,
Torsten
















Table of Contents

Table of Contents


1. Introduction...................................................................................................................... 1
2. Theoretical Part ............................................................................................................... 5
2.1. Metal-solution interphase – brief description of the electrical double layer .................. 5
2.2. Adsorption at electrode surfaces .................................................................................. 6
2.3. Electrochemical deposition.......................................................................................... 8
2.3.1. Metal deposition mechanisms ............................................................................. 10
2.3.2. Atomistic aspects of metal electrodeposition....................................................... 11
2.3.3. Nucleation .......................................................................................................... 13
2.3.4. Growth of nuclei................................................................................................. 14
2.3.5. Formation of compact 3D metal deposits ............................................................ 16
2.4. Some aspects of the industrial metal deposition ......................................................... 17
2.4.1. Effect of additives............................................................................................... 18
2.4.2. Current density and distribution.......................................................................... 21
3. Experimental Section ..................................................................................................... 23
3.1. Basic concepts of the experimental techniques........................................................... 23
3.1.1. Cyclic voltammetry ............................................................................................ 23
3.1.2. Scanning Tunneling Microscopy......................................................................... 24
3.2. Experimental procedures and devices ........................................................................ 27
3.2.1. Glassware cleaning ............................................................................................. 27
3.2.2. Sample preparation methods............................................................................... 28
3.2.3. Electrochemical cells .......................................................................................... 30
3.2.4. STM device ........................................................................................................ 31
3.2.5. STM cells ........................................................................................................... 32
3.2.6. Preparation of the STM tips ................................................................................ 34
3.2.7. List of chemicals and materials ........................................................................... 35

i Table of Contents
4. Characterisation of the Substrate Surface .................................................................... 37
4.1. Au(111) in sulphuric acid .......................................................................................... 37
4.2. Cu(111) in sulphuric acid .......................................................................................... 39
4.2.1. Electropolished Cu(111) in sulphuric acid........................................................... 40
4.2.2. Annealed Cu(111) in sulphuric acid .................................................................... 45
4.3. Cu(111) in perchloric acid ......................................................................................... 48
5. Influence of Different Additives on Copper Deposition onto Au(111) ......................... 51
5.1. Copper deposition from additive-free sulphuric acid electrolytes ............................... 53
5.1.1. Copper UPD onto Au(111) ................................................................................. 54
5.1.2. Bulk Cu deposition ............................................................................................. 73
5.2. Chloride .................................................................................................................... 81
5.2.1. Chloride adsorption on Au(111).......................................................................... 82
5.2.2. Chloride influence on Cu UPD in sulphuric acid electrolytes .............................. 83
5.2.3. Chloride influence on Cu bulk in sulphuric acid electrolytes ............................... 87
5.3. PEG + Chloride ......................................................................................................... 93
-5.3.1. PEG + Cl influence on Cu UPD from sulphuric acid electrolytes ....................... 94
-5.3.2. PEG + Cl influence on Cu bulk from sulphuric acid electrolytes ........................ 98
5.4. Mercaptopropanesulfonic acid (MPSA) ................................................................... 103
5.4.1. MPSA adsorption on Au(111)........................................................................... 106
5.4.2. MPSA effect on Cu UPD in sulphuric acid electrolytes..................................... 118
5.4.3. MPSA effect on Cu bulk in sulphuric acid electrolytes...................................... 122
5.4.4. SPS adsorption on Au(111)............................................................................... 127
6. Influence of Different Additives on Cu Deposition onto Cu(111)............................... 133
6.1. Mercaptopropionic acid (MPA) ............................................................................... 134
6.1.1. MPA adsorption on Cu(111)............................................................................. 136
6.1.2. MPA effect on Cu Deposition onto Cu(111) ..................................................... 143
6.2. Mercaptopropanesulfonic acid (MPSA) ................................................................... 151
6.2.1. MPSA adsorption on Cu(111)........................................................................... 151
6.2.2. MPSA effect on Cu deposition onto Cu(111) .................................................... 156
6.3. Bis(3-sodiumsulfopropyl)disulfide (SPS) ................................................................ 163
6.3.1. SPS adsorption on Cu(111)............................................................................... 163
6.3.2. SPS effect on Cu deposition onto Cu polycrystalline......................................... 167
i i Table of Contents
6.4. Mercaptopropanesulfonic acid + Chloride ............................................................... 171
-6.4.1. MPSA + Cl effect on Cu deposition onto Cu polycrystalline ............................ 171
-6.4.2. MPSA + Cl effect on Cu deposition onto Cu(111) ........................................... 172
7. Summary ...................................................................................................................... 181
8. Zusammenfassung........................................................................................................ 189
Bibliography............................................................................................................