Edited by

Mohamed Mehdi Chehimi

Aryl Diazonium Salts

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Aryl Diazonium Salts

New Coupling Agents in Polymer and Surface Science

Edited by Mohamed Mehdi Chehimi

The Editor

Dr. Mohamed Mehdi ChehimiUniversity Paris DiderotSorbonne Paris CitéITODYSUMR CNRS 708615 rue J-A de Baïf75013 ParisFrance

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

Library of Congress Card No.: applied for

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© 2012 Wiley-VCH Verlag & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany

All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.

Print ISBN:    978-3-527-32998-4ePDF ISBN:   978-3-527-65047-7ePub ISBN:    978-3-527-65046-0mobi ISBN:    978-3-527-65045-3oBook ISBN:  978-3-527-65044-6

Cover Design  Adam-Design, WeinheimTypesetting  Toppan Best-set Premedia Limited, Hong KongPrinting and Binding  Markono Print Media Pte Ltd, Singapore

V

To Jean Pinson, with gratitude

VII

Contents

1 AttachmentofOrganicLayerstoMaterialsSurfacesbyReductionofDiazoniumSalts  1

JeanPinson1.1  A Brief Survey of the Chemistry and Electrochemistry  

of Diazonium Salts  11.2  The Different Methods that Permit Grafting of Diazonium Salts  31.2.1  Electrochemistry  31.2.2  Reducing Substrate, Homolytic Dediazonation,  

Reaction with the Substrate  41.2.3  Reducing Reagent  51.2.4  Neutral and Basic Media  61.2.5  Ultrasonication  61.2.6  Heating and Microwave  61.2.7  Mechanical Grafting  71.2.8  Photochemistry  71.3  The Different Substrates, Diazonium Salts, and Solvents  

that Can Be Used  71.3.1  Substrates  71.3.2  Diazonium Salts  91.3.3  Solvents  101.4  Evidence for the Presence of a Bond between the Substrate  

and the Organic Layer  111.4.1  Stability of the Layer  111.4.2  Spectroscopic Evidence for a Bond  121.5  From Monolayers to Multilayers  131.5.1  Monolayers  141.5.2  Layers of Medium Thickness  161.5.2.1  Thick Layers  191.6  Structure and Formation of Multilayers  21

Preface XV ListofContributors XVII

VIII Contents

1.6.1  Chemical Structure  211.6.2  The Spatial Structure of the Layers  221.6.3  Compactness of the Layers  231.6.4  Swelling of the Layer  241.6.5  Electron Transfer through the Layers  241.6.6  The Formation Mechanism of Multilayers  251.7  Conclusion  27 References  27

2 Aryl–SurfaceBonding:ADensityFunctionalTheory(DFT)SimulationApproach  37

NanShao,ShengDai,andDe-enJiang2.1  Introduction  372.2  Density Functional Theory  382.3  Bonding between Aryl and Various Substrates  382.3.1  On Graphite/Graphene  392.3.1.1  On the Basal Plane  392.3.1.2  On the Edges of Graphene  422.3.2  On Carbon Nanotubes  442.3.3  On Metal Surfaces  452.4  Summary and Outlook  48  Acknowledgments  49 References  50

3 PatternedMolecularLayersonSurfaces  53 AlisonJ.Downard,AndrewJ.Gross,andBradleyM.Simons3.1  Methods Based on Scanning Probe Lithography  533.1.1  AFM  543.1.2  SECM  543.1.3  Spotting  563.2  Methods Based on Soft Lithography  573.2.1  Printing  573.2.2  Molds  593.2.3  Nanosphere Lithography  593.3  Methods Based on Lithography  603.4  Methods Based on Surface-Directed Patterning  623.4.1  Modification of Si Surfaces  633.4.2  Modified Electrode Arrays  643.5  Summary and Conclusions  66 References  68

4 AnalyticalMethodsfortheCharacterizationofArylLayers  71 KarstenHinrichs,KatyRoodenko,JörgRappich,

MohamedM.Chehimi,andJeanPinson4.1  Introduction  714.2  Scanning Probe Microscopies  71

Contents IX

4.3  UV–VIS Spectroscopy: Transmission, Reflection,  and Ellipsometry  72

4.4  IR Spectroscopy  724.4.1  Transmission Spectroscopy  734.4.2  Reflection Spectroscopy  744.4.3  Infrared Spectroscopic Ellipsometry (IRSE)  754.4.4  IRSE Surface Characterization  774.4.5  InSitu IR Spectroscopy: ATR and IRSE  794.5  Raman Spectroscopy and Surface-Enhanced Raman  

Scattering (SERS)  834.6  X-ray Photoelectron Spectroscopy (XPS)  844.7  X-ray Standing Waves (XSW)  914.8  Rutherford Backscattering  934.9  Time of Flight Secondary Ion Mass Spectroscopy  934.10  Electrochemistry  944.11  Contact Angle Measurements  964.12  Conclusion  96 References  98

5 ModificationofNano-objectsbyArylDiazoniumSalts  103

Dao-JunGuoandFakhradinMirkhalaf5.1  Introduction  1035.2  Electrochemical Modification of Nano-objects  

by Reduction of Diazonium Salts  1055.2.1  Surface Modification of Carbon Nano-objects via Electrochemical 

Reduction of Aryl Diazonium Cations  1055.2.2  Surface Modification of Metal and Metal Oxide Nano-objects via 

Electrochemical Reduction of Aryl Diazonium Cations  1115.3  Chemical Modification of Nano-objects by Reduction  

of Diazonium Salts  1125.3.1  Surface Modification of Carbon Nano-objects via Chemical Reduction  

of Aryl Diazonium Cations  1125.3.2  Surface Modification of Metal and Metal Oxide Nano-objects via 

Chemical Reduction of Aryl Diazonium Cations  1165.4  Summary and Conclusions  119  Acknowledgments  120 References  120

6 PolymerGraftingtoArylDiazonium-ModifiedMaterials:MethodsandApplications  125

SarraGam-Derouich,SamiaMahouche-Chergui,HatemBenRomdhane,andMohamedM.Chehimi

6.1  Introduction  1256.2  Methods for Grafting Coupling Agents from Aryl Diazonium 

Compounds  127

X Contents

6.3  Grafting Macromolecules to Surfaces through Aryl Layers  1306.3.1  Binding Macromolecules to Surfaces by a Grafting  

from Strategy  1306.3.1.1  Surface-Initiated Atom Transfer Radical Polymerization  

(SI-ATRP)  1306.3.1.2  Surface-Initiated Reversible Addition–Fragmentation  

Chain Transfer (SI-RAFT)  1426.3.1.3  Surface-Initiated Photopolymerization  1436.3.1.4  Alternative Methods  1466.3.2  Attachment of Macromolecules through Grafting  

onto Strategies  1476.3.2.1  Photochemical Attachment  1476.3.2.2  Ring Opening  1486.3.2.3  Acylation  1496.3.2.4  Click Chemistry  1496.3.2.5  Diazotation of Substrates and Macromolecules  1506.4  Adhesion of Polymers to Surfaces through Aryl Layers  1516.5  Conclusion  153 References  153

7 GraftingPolymerFilmsontoMaterialSurfaces:TheOne-StepRedoxProcesses  159

GuyDeniau,SergePalacin,AliceMesnage,andLorraineTessier7.1  Cathodic Electrografting (CE) in an Organic Medium  1607.1.1  Direct Cathodic Electrografting of Vinylic Polymers  1607.1.2  Indirect Cathodic Electrografting  1627.2  Surface Electroinitiated Emulsion Polymerization (SEEP)  1647.2.1  Characterization of Poly(Butyl Methacrylate) Films  1667.2.2  Determination of the Film Structure  1677.2.3  Reduction of Protons and the Role of Hydrogen Radicals  1697.2.4  Mechanism of SEEP  1707.3  Chemical Grafting via Chemical Redox Activation (Graftfast™)  1717.3.1  Process without Vinylic Monomer  1727.3.2  Process with Vinylic Monomer  1747.3.2.1  Type of Materials  1747.3.2.2  Parameters Controlled in the Process  1747.4  Summary and Conclusions  177 References  178

8 ElectrograftingofConductiveOligomersandPolymers  181

JeanChristopheLacroix,JalalGhilane,LuisSantos,GaelleTrippe-Allard,PascalMartin,andHyacintheRandriamahazaka

8.1  Introduction  1818.2  Conjugated Oligomers and Polymers  181

Contents XI

8.3  Surface Grafting Based on Electroreduction  of Diazonium Salts  184

8.4  Polyphenylene and Oligophenylene-Tethered Surface Prepared by the Diazonium Reduction of Aniline or 4-Substituted Aniline  187

8.5  n-Doping and Conductance Switching of Grafted Biphenyl, Terphenyl, Nitro-biphenyl and 4-Nitroazobenzene Mono- and Multilayers  187

8.6  p-Doping and Conductance Switching of Grafted Oligo-Phenylthiophene or Oligothiophene Mono- and Multilayers  190

8.7  p-Doping and Conductance Switching of Grafted Oligoaniline Mono- and Multilayers  192

8.8  Conclusion and Outlook  193 References  195

9 TheUseofArylDiazoniumSaltsintheFabricationofBiosensorsandChemicalSensors  197

J.JustinGooding,GuozhenLiu,andAliciaL.Gui9.1  Introduction  1979.1.1  Sensors and Interfacial Design  1979.1.2  Molecular Level Control over the Fabrication  

of Sensing Interfaces  1989.2  The Important Features of Aryl Diazonium Salts  

with Regard to Sensing  2009.3  Sensors and Biosensors Fabricated Using Aryl  

Diazonium Salts  2019.3.1  Chemical Sensors – Sensors Fabricated via the Immobilization  

of Chemical Recognition Species  2019.3.2  Biosensors  2059.3.2.1  Enzyme Biosensors  2069.3.2.2  Immunobiosensors  2089.3.2.3  DNA-Based Biosensors  2109.3.2.4  Cell-Based Biosensors  2139.4  Conclusions  213 References  214

10 DiazoniumCompoundsinMolecularElectronics  219 RichardMcCreeryandAdamJohanBergren10.1  Introduction  21910.2  Fabrication of Molecular Junctions Using Diazonium Reagents  22210.2.1  Substrates for Diazonium-Derived Molecular Junctions  22210.2.2  Surface Modification Using Diazonium Chemistry  22310.2.3  Application of Top Contacts  22510.3  Electronic Performance of Diazonium-Derived  

Molecular Junctions  22610.3.1  Surface Diffusion Mediated Deposition (SDMD)  22710.3.2  Structural Control of Molecular Junction Behavior  230

XII Contents

10.3.3  Redox Reactions in Molecular Junctions  23210.3.4  Microfabricated Molecular Devices Made  

with Diazonium Chemistry  23310.4  Summary and Outlook  235  Acknowledgments  236 References  236

11 ElectronicPropertiesofSiSurfacesModifiedbyArylDiazoniumCompounds  241

JörgRappich,XinZhang,andKarstenHinrichs11.1  Introduction  24111.2  Experimental Techniques to Characterize Electronic Properties  

of Si Surfaces in Solutions  24211.2.1  InSitu Photoluminescence and Photo Voltage Measurements  24211.2.2  InSitu PL and PV Measurements during 

Electrochemical Grafting  24411.2.3  Reaction Scheme of the Electrochemical Grafting via  

Diazonium Ions  24511.2.4  Change in IPL and UPV during Electrochemical Grafting 

onto Si Surfaces  24611.2.5  Change in Band Bending and Work Function after  

Electrochemical Grafting onto Si Surfaces  24811.2.6  pH Dependence and Enhanced Surface Passivation  24911.3  Conclusion and Outlook  251  Acknowledgments  252 References  252

12 Non-DiazoniumOrganicandOrganometallicCouplingAgentsforSurfaceModification  255

FetahI.Podvorica12.1  Amines  25512.1.1  Characterization of the Grafted Layer  25712.1.1.1  Electrochemical Methods  25712.1.1.2  Surface Analysis Techniques  25812.1.2  Chemical Grafting  25912.1.3  Localized Electrografting  26012.1.4  Grafting Mechanism  26112.1.5  Applications  26212.2  Arylhydrazines  26412.3  Aryltriazenes  26612.4  Alcohols  26712.4.1  Observation and Characterization of the Film  26812.4.2  Applications  26912.5  Grignard Reagents  27012.5.1  Characterization of the Layers  27112.5.2  Grafting Mechanism  272

Contents XIII

12.6  Onium Salts  27212.6.1  Iodonium Salts  27212.6.2  Sulfonium Salts  27312.6.3  Ammonium Salts  27312.7  Alkyl Halides  27412.8  Conclusion  275 References  276

13 VariousElectrochemicalStrategiesforGraftingElectronicFunctionalMoleculestoSilicon  283

DineshK.Aswal,ShankarPrasadKoiry,andShivKumarGupta13.1  Introduction  28313.2  Architecture of Hybrid Devices  28413.2.1  Molecular Dielectrics and Wires  28513.2.2  Molecular Diodes  28613.2.3  Resonant Tunnel Diodes  28613.2.4  Molecular Transistors  28613.3  Electrografting of Monolayers to Si  28713.3.1  Essential Requirements  28713.3.2  Experimental Process of Electrografting  28713.4  Negative Differential Resistance Effect in a Monolayer  

Electrografted Using a Diazonium Complex  28813.4.1  Electrografting of DHTT  28813.4.2  NDR Effect in DHTT Monolayers  29013.5  Dielectric Monolayers Electrografted Using Silanes  29313.5.1  Mechanism of Electrografting  29313.5.2  Electrical Characterization  29413.6  Molecular Diodes Based on C60/Porphyrin-Derivative Bilayers  29513.6.1  Fabrication Process  29613.6.1.1  Electrografting of Acceptor C60 Layer on Si  29613.6.1.2  Self-Assembly of Donor Porphyrin Derivative Layer on C60/Si  29713.6.2  Rectification Characteristics of D–A Bilayers  29813.7  Memory Effect in TPP-C11 Monolayers Electrografted  

Using a C=C Linker  30113.7.1  Electrografting of TPP-C11 Monolayer  30113.7.2  Electrical Bistability and Memory Effect  30313.8  Summary  305 References  305

14 PatentsandIndustrialApplicationsofArylDiazoniumSaltsandOtherCouplingAgents  309

JamesA.Belmont,ChristopheBureau,MohamedM.Chehimi,SarraGam-Derouich,andJeanPinson

14.1  Introduction  30914.2  Patents  30914.2.1  The Surface Chemistry of Diazonium Salts  309