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Electrochemical SPM

Version 5.30a
004-125-000

Copyright 2003, 2000 Veeco Instruments Inc.


All rights reserved.

Document Revision History: Title of Document

Revision Date Section(s) Affected Reference Approval

B 5/23/2003 Chs 3, 5, 6, 7, 9 Vinson Kelley

A 12/07/00 Initial Release 0376 M. Serry


Notices: The information in this document is subject to change without notice. NO WARRANTY OF ANY KIND IS MADE WITH REGARD TO
THIS MATERIAL, INCLUDING, BUT NOT LIMITED TO, THE IMPLIED WARRANTIES OF MERCHANTABILITY AND FITNESS FOR A
PARTICULAR PURPOSE. No liability is assumed for errors contained herein or for incidental or consequential damages in connection with the
furnishing, performance, or use of this material. This document contains proprietary information which is protected by copyright. No part of this
document may be photocopied, reproduced, or translated into another language without prior written consent.
Copyright: Copyright 2003 Veeco Instruments Inc. All rights reserved.
Trademark Acknowledgments: The following are registered trademarks of Veeco Instruments Inc. All other trademarks are the property of their
respective owners.

Product Names:
NanoScope
MultiMode
Dimension
BioScope
Atomic Force Profiler (AFP)
Dektak

Software Modes:
TappingMode
Tapping
TappingMode+
LiftMode
AutoTune
TurboScan
Fast HSG
PhaseImaging
DekMap 2
HyperScan
StepFinder
SoftScan

Hardware Designs:
TrakScan
StiffStage

Hardware Options:
TipX
Signal Access Module and SAM
Extender
TipView
Interleave
LookAhead
Quadrex

Software Options:
NanoScript
Navigator
FeatureFind

Miscellaneous:
NanoProbe

Origin: Veeco, 112 Robin Hill Rd., Santa Barbara, CA 93117, Tel: 805 967-2700
Web: www.veeco.com, www.di.com
Table of Contents
List of Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .v

List of Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix

Chapter 1 Rules of Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1

Chapter 2 SPM Fundamentals in Liquid Environments . . . . . . . . . .7


2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 AFM and STM in Liquid Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

Chapter 3 Electrochemical SPM Hardware . . . . . . . . . . . . . . . . . .11


3.1 Electrochemical SPMs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.1.1 Model ECM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.1.2 Model ECAFM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.1.3 Model ECLFM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.1.4 Model MMAFM-EC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.1.5 Model MMSECPM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2 Bipotentiostat/Galvanostat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2.1 Bipotentiostat/Galvanostat Model MMECAFM . . . . . . . . . . . . . . . . . . . . . . 15
3.2.2 Bipotentiostat/Galvanostat Model MMECPOT . . . . . . . . . . . . . . . . . . . . . . 15
3.3 Fluid Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.3.1 Fluid Cells for Electrochemical STM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.3.2 Fluid Cell for Electrochemical AFM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.4 Assembling ECSPM Hardware . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.4.1 Hardware for Model ECM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.4.2 Hardware for Other Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.4.3 STM in MMAFM-EC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

Chapter 4 AFM Electrochemical Fluid Cell Setup and Operation .25


4.1 Cleaning Fluid Cell Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4.2 Cleaning Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4.3 In Situ AFM Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4.3.1 Preparing the Sample. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4.3.2 Positioning the Cantilever Substrate on the GP . . . . . . . . . . . . . . . . . . . . . . 27
4.3.3 Positioning GP inside AFM Head . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.3.4 Imaging Dry without O-Ring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

Rev. B Digital Instruments Electrochemical SPM i


4.3.5 Imaging Dry with O-Ring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4.3.6 Installing the O-Ring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4.3.7 Introducing Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.3.8 Using TappingMode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.3.9 Connecting Electrodes to the Bipotentiostat/Galvanostat . . . . . . . . . . . . . . . 40

Chapter 5 STM Electrochemical Setup and Operation . . . . . . . . .41


5.1 Handling the Fluid Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.2 Cleaning Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.3 STM Imaging in an Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.3.1 Preparing the STM Fluid Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.3.2 Checking the Integrity of Fluid Cell Seal - Model MMTVFC . . . . . . . . . . . 45
5.3.3 Imaging Dry with a Bare Tip . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
5.3.4 Insulating the STM Tip . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.3.5 Imaging Dry with an Insulated Tip . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
5.3.6 Introduce Electrolyte into the Fluid Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

Chapter 6 Troubleshooting Common to ECAFM and ECSTM . . . .55


6.1 General ECSPM Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
6.1.1 Improper Electrical Connections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
6.1.2 Liquids and Scanners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
6.1.3 Persistent Leaks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
6.1.4 Chemical Reactivity and the Fluid Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
6.1.5 Colloidal Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
6.2 EC-Specific Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
6.2.1 Unexpected and Transient Peaks in Voltammogram . . . . . . . . . . . . . . . . . . . 57
6.2.2 Excessive Deposition of Solids on Sample . . . . . . . . . . . . . . . . . . . . . . . . . . 57
6.2.3 Deposition Not Imaged by SPM Probe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
6.2.4 Voltammogram Shows Jumpiness in Cell Current . . . . . . . . . . . . . . . . . . . . 58
6.3 Testing/Troubleshooting the Potentiostat/Galvanostat . . . . . . . . . . . . . . . 59

Chapter 7 Real-time Software and Voltametry Controls for EC . .61


7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
7.2 Real-time ECAFM and ECSTM Control Panels . . . . . . . . . . . . . . . . . . . 61
7.3 Electrode Controls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7.3.1 E . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7.3.2 Etip (STM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7.3.3 Ebias (STM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
7.3.4 I Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
7.3.5 Cell. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
7.3.6 Mode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
7.4 Voltam. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
7.4.1 Voltammogram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
7.4.2 Volt function (STM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
7.4.3 Elec area . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75

Rev. B Digital Instruments Electrochemical SPM ii


7.4.4 Voltam function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
7.4.5 I range . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
7.4.6 Volt max . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
7.4.7 Volt min . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
7.5 Temporal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
7.5.1 Temporal graph . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
7.5.2 Temporal function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
7.5.3 I range . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
7.5.4 Volt range . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
7.5.5 Time range . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
7.6 Ramping Controls. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
7.6.1 Ramp rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
7.6.2 Ramp max . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
7.6.3 Ramp min . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
7.6.4 Tip reference (STM only) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
7.6.5 Ramp electrode (STM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
7.6.6 Sample rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82

Chapter 8 Off-line Software for ECSPM . . . . . . . . . . . . . . . . . . . . .83


8.1 Off-line Software . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
8.1.1 Starting the Off-line Software . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
8.1.2 Display Environment (Image Screen) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
8.1.3 Graph Dialog Box . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88

Chapter 9 Running SECPM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .89


9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
9.2 Running SECPM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
9.2.1 Select Microscope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
9.2.2 SECPM-Specific Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93

Chapter 10 Maintenance and Support . . . . . . . . . . . . . . . . . . . . . .107


10.1 System Support. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
10.2 Maintenance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
10.3 O-Rings and Fluid Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
10.3.1 Approximate Dimensions (June 1997) . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
10.4 STM Tip Etching Procedure (Tungsten and Platinum-Iridium (Pt-Ir)) 109
10.5 NanoScope IIIa (or E, or 3) Control Box Adjustment to Match EC Equipment
109

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .115

Rev. B Digital Instruments Electrochemical SPM iii/(iv Blank)


List of Figures

Chapter ii List of Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v

Chapter iii List of Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix

Chapter 1 Rules of Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

Chapter 2 SPM Fundamentals in Liquid Environments . . . . . . . . . . . . . . . . . . 7


Figure 2.2a Force Curve Examples of High Adhesion and Low Adhesion . . . 8
Figure 2.2b Abbreviations Used in Electrochemical SPM. . . . . . . . . . . . . . . . 9

Chapter 3 Electrochemical SPM Hardware. . . . . . . . . . . . . . . . . . . . . . . . . . . . 11


Figure 3.1a Model ECM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Figure 3.1b Model ECAFM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Figure 3.1c Model ECLFM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Figure 3.1d Model MultiMode AFM-EC (MMAFM-EC). . . . . . . . . . . . . . . 13
Figure 3.1e Model MMECPOT with MMSECPM Head. . . . . . . . . . . . . . . . 14
Figure 3.1f SECPM Head . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Figure 3.2a MMECPOT DVM. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Figure 3.2b MMECPOT Bipotentiostat/Galvanostat . . . . . . . . . . . . . . . . . . . 16
Figure 3.3a Fluid Cells for Model ECM . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Figure 3.3b STM Fluid Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Figure 3.3c Electrochemical Fluid Cell for AFM . . . . . . . . . . . . . . . . . . . . . 19
Figure 3.3d The GP for AFM EC Fluid Cells . . . . . . . . . . . . . . . . . . . . . . . . 20
Figure 3.3e Microscope Head Configured for AFM Imaging . . . . . . . . . . . . 20
Figure 3.4a Short Ribbon Cable. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Figure 3.4b Cable Connection between Scanner and Potentiostat. . . . . . . . . 22
Figure 3.4c Jumper settings that support neither SECPM nor STS-EC (ver. 5.12
and below) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
Figure 3.4d Jumper settings for software versions that support STS under EC
control (ver.5.30a and up) but not SECPM. . . . . . . . . . . 23
Figure 3.4e Jumper settings for software versions that support SECPM but not STS
under EC control (ver. 5.30a).. . . . . . . . . . . . . . . . . . . . . 24
Figure 3.4f Jumper settings for software versions that support SECPM and STS
under EC control (ver. 5.30 and up).. . . . . . . . . . . . . . . . 24

Rev. B Digital Instruments Electrochemical SPM v


List of Figures

Chapter 4 AFM Electrochemical Fluid Cell Setup and Operation . . . . . . . . . 25


Figure 4.3a Ensure Conductivity between Scanner Cap and Samples Top Surface
26
Figure 4.3b Rotate Screws that Raise Head - Standard Scanner (right) and Vertical-
Engage Scanner (left). . . . . . . . . . . . . . . . . . . . . . . . . . . 26
Figure 4.3c Insert GP with Pits Matched to Steel Balls . . . . . . . . . . . . . . . . 27
Figure 4.3d Rotate the Clip until Ball Snaps into the Groove Machined Out of Top
Surface of the GP. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Figure 4.3e Use Tweezers to Place the Cantilever Substrate in the Inclined Groove
29
Figure 4.3f Verify that the Cantilever Substrate Is Seated within the Groove 29
Figure 4.3g Switches on Bipotentiostat/Galvanostat for MMAFM . . . . . . . 30
Figure 4.3h Prepare the Counter Electrode (CE) . . . . . . . . . . . . . . . . . . . . . 32
Figure 4.3i Secure the CE Wire. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
Figure 4.3j Attach the RE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
Figure 4.3k Position the O-Ring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Figure 4.3l Insert Luer Fittings into Remaining Holes . . . . . . . . . . . . . . . . . 36
Figure 4.3m Align the GP, O-Ring, and Head . . . . . . . . . . . . . . . . . . . . . . . 37
Figure 4.3n Electrode-lead Connections . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40

Chapter 5 STM Electrochemical Setup and Operation . . . . . . . . . . . . . . . . . . 41


Figure 5.3a ECM Fluid Cell Assembly . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
Figure 5.3b STM Fluid Cell, model MMTVFC, for MultiMode AFM . . . . 42
Figure 5.3c The MultiMode STM Fluid Cell, model MMTVFC2, exploded (left)
and assembled (right). . . . . . . . . . . . . . . . . . . . . . . . . . . 43
Figure 5.3d Assembled ECM Fluid Cell (with Electrode Wires Clipped on) Being
Placed on Sample Stage. . . . . . . . . . . . . . . . . . . . . . . . . 46
Figure 5.3e Assembled ECSTM on MultiMode Scanner and Base. . . . . . . . 46
Figure 5.3f Counter and Reference Electrodes Mounted on the TipView Head and
Connected to the Clip-Leads . . . . . . . . . . . . . . . . . . . . . 50
Figure 5.3g MMAFM Fluid Cell for STM and TipView Head with Electrodes in
Place and Assembled on the Scanner. . . . . . . . . . . . . . . 50
Figure 5.3h Electrochemically Etched Platinum-Iridium Tip Dip-Coated with
Apiezon Wax . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

Chapter 6 Troubleshooting Common to ECAFM and ECSTM . . . . . . . . . . . . 55


Figure 6.3a Dummy cell set-up for testing the Potentiostat/Galvanostat . . . 60

Chapter 7 Real-time Software and Voltametry Controls for EC . . . . . . . . . . . 61


Figure 7.2a NanoScope Control Window . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
Figure 7.2b Select Microscope Select. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
Figure 7.2c Microscope Select Dialog Box . . . . . . . . . . . . . . . . . . . . . . . . . 62
Figure 7.2d Real-time Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
Figure 7.2e Microscope/Calibrate/Detector . . . . . . . . . . . . . . . . . . . . . . . . . 63

vi Digital Instruments Electrochemical SPM Rev. B


List of Figures

Figure 7.2e Microscope / Calibrate / Detector . . . . . . . . . . . . . . . . . . . . . . . .63


Figure 7.2f Detector Calibration Dialog Box. . . . . . . . . . . . . . . . . . . . . . . . .64
Figure 7.2g Detector / Calibration Dialog Box: E-sens . . . . . . . . . . . . . . . . .64
Figure 7.2h Detector / Calibration Dialog Box: I cell Sens . . . . . . . . . . . . . .65
Figure 7.2i Microscope / Leakage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .66
Figure 7.2j Head Leakage Test Dialog Box . . . . . . . . . . . . . . . . . . . . . . . . . .66
Figure 7.2k Microscope / Offset. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .67
Figure 7.2l Head Offset Calibration Dialog Box . . . . . . . . . . . . . . . . . . . . . .67
Figure 7.2m Panels Pull-down Menu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .68
Figure 7.2n The Four Control Panels for ECAFM. . . . . . . . . . . . . . . . . . . . .69
Figure 7.2o The Four Control Panels for ECSTM . . . . . . . . . . . . . . . . . . . . .69
Figure 7.2p Control panels for SECPM . . . . . . . . . . . . . . . . . . . . . . . . . . .70
Figure 7.2q Potentio Pull-Down Menu . . . . . . . . . . . . . . . . . . . . . . . . . . . . .70
Figure 7.3a Electrode Controls Dialog Boxes . . . . . . . . . . . . . . . . . . . . . . . .72
Figure 7.4a Voltam Dialog Boxes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .75
Figure 7.5a Temporal Dialog Boxes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .77
Figure 7.6a Ramping Controls Dialog Boxes . . . . . . . . . . . . . . . . . . . . . . . .80

Chapter 8 Off-line Software for ECSPM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .83


Figure 8.1a Select Off-line . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .83
Figure 8.1b Select Off-line Icon. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .83
Figure 8.1c Off-line Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .84
Figure 8.1d Select View / Graph. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .84
Figure 8.1e ECAFM Image Screen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .85
Figure 8.1f ECSTM Image Screen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .85
Figure 8.1g Graph Dialog box . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .88

Chapter 9 Running SECPM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .89


Figure 9.1a SECPM Constant Potential Mode image of Sn60Pb40 alloy in
Glycerol at open circuit potential using uncoated PtIr tip at
potential setpoint of 100mV. The open circuit potential is -
520mV vs. a Pt quasi reference electrode. 5mm scan. . .90
Figure 9.1b An example of SECPM electrochemical potential spectroscopy. These
plots of potential (f) vs. probe-sample distance were recorded
above a HOPG sample in Glycerol as the probe approached
(white plot) and retracted (yellow plot) from the sample. 90
Figure 9.1c SECPM electrical configuration . . . . . . . . . . . . . . . . . . . . . . . . .91
Figure 9.2a NanoScope Control Window. . . . . . . . . . . . . . . . . . . . . . . . . . . .91
Figure 9.2b Microscope Select. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .92
Figure 9.2c Microscope Select Dialog Box . . . . . . . . . . . . . . . . . . . . . . . . . .92
Figure 9.2d Create Microscope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .93
Figure 9.2e Real-time Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .94
Figure 9.2f Microscope Mode. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .95
Figure 9.2g SECPM sens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .95

Rev. B Digital Instruments Electrochemical SPM vii


List of Figures

Figure 9.2h Head Offset . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96


Figure 9.2i Potential Setpoint . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Figure 9.2j Ptip . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Figure 9.2k SECPM example: HOPG in H2O, CE and RE: Pt wires, PtIr tip.98
Figure 9.2l SECPM Constant Potential Mode image of Sn60Pb40 alloy in Glycerol
99
Figure 9.2m Starting P-S Plot . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
Figure 9.2n Potential-Spectroscopy Controls . . . . . . . . . . . . . . . . . . . . . . . 101
Figure 9.2o Show All Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
Figure 9.2p SECPM Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
Figure 9.2q Feedback Type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Figure 9.2r Potential Setpoint . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
Figure 9.2s Data Type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
Figure 9.2t Trigger Mode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Figure 9.2u PS Plot on HOPG in H2O . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105

Chapter 10 Maintenance and Support . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107


Figure 10.5a Z Board for NanoScope IIIa. . . . . . . . . . . . . . . . . . . . . . . . . . 110
Figure 10.5b Z Board for NanoScope E or 3 . . . . . . . . . . . . . . . . . . . . . . . 111
Figure 10.5c Auxiliary Board for NanoScope IIIa.. . . . . . . . . . . . . . . . . . . 112
Figure 10.5d Auxiliary Board for NanoScope E or 3 . . . . . . . . . . . . . . . . . 112

Chapter 11 Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115

viii Digital Instruments Electrochemical SPM Rev. B


List of Tables

List of Tables

List of Figures v

List of Tables ix

Rules of Safety 1
Safety Symbols Key 2
Environmental Requirements 5

SPM Fundamentals in Liquid Environments 7

Electrochemical SPM Hardware 11

AFM Electrochemical Fluid Cell Setup and Operation 25

STM Electrochemical Setup and Operation 41

Troubleshooting Common to ECAFM and ECSTM 55

Real-time Software and Voltametry Controls for EC 61


EC ATM/STM Control Panel Parameters 68

Off-line Software for ECSPM 83

Running SECPM 89

Maintenance and Support 107


O-Ring and Fluid Cell Dimensions 108

Index 115

Rev. B Digital Instruments Electrochemical SPM ix/(x Blank)


Chapter 1 Rules of Safety

Please observe the following precautions as you work with the AFM:

Read the manuals!

Even if you have prior experience with the AFM/STM, be sure to go over the chapters in this
manual before doing any imaging work. Consult the relevant sections for an explanation of
software controls.

Follow good rules of engagement.

Engagement is the process of bringing the tip and sample surface together. This is not always
easy, and the software routine for controlling the process is complex. Some probes are prone to
damage if engaged too quickly or with too much force. Never attempt to manually engage using
coarse adjustment screws. Start with the tip and sample far apart; do not bring them too close to
save time waiting for the software-controlled engage sequence. The tip may be in contact with the
sample before you start the engage sequence. A little patience will buy time in the long run.

Never move the head while imaging.

The SPM head contains the tipholder. For AFM heads and older model STM heads for the
MultiMode, an X-Y translation stage is provided for moving the head, and tip, several millimeters
across the sample for coarse positioning adjustment. Even for relatively smooth samples, the head
should not be moved with the tip engaged. This can result in tip and sample damage. Always
disengage or move the tip up using the tip-up command in software before using the X-Y stage to
relocate the tip.

Never leave the controller ON without the NanoScope software running.

If the controller is left ON for an extended period without the NanoScope software running,
damage to the scanner may result.
This is a costly repair job.

Rev. B Digital Instruments Electrochemical SPM 1


Rules of Safety

Do not unplug cables to/from energized hardware. Turn power OFF first.

Unplugging energized hardware may result in damage to the AFM. Always turn OFF hardware
before making or breaking connections.

Check all connections before hardwiring external equipment.

External equipment that is hardwired into the AFM/STM (usually through the Signal Access
Module) requires special cautions. To prevent damage to your microscope, always check
connections carefully against documentation before powering up the system. For more information,
see Signal Access Module: Description and Use, Support Note #210.

Table 1.0a Safety Symbols Key

Symbol Definition
This symbol identifies conditions or practices that could
result in damage to the equipment or other property, and
in extreme cases, possible personal injury.
Ce symbole indique des conditions d'emploi ou des
actions pouvant endommager les quipements ou acces-
soires, et qui, dans les cas extrmes, peuvent conduire
des dommages corporels.
Dieses Symbol beschreibt Zustnde oder Handlungen die
das Gert oder andere Gegenstnde beschdigen knnen
und in Extremfllen zu Verletzungen fhren knnen.
This symbol identifies conditions or practices that involve
potential electric shock hazard.
Ce symbole indique des conditions d'emploi ou des
actions comportant un risque de choc lectrique.
Dieses Symbol beschreibt Zustaende oder Handlungen
die einen elekrischen Schock verursachen koennen.
This symbol identifies a laser hazard. Exposure could
result in eye damage.
Ce symbole indique un risque li un laser. Une exposi-
tion ce laser peut entraner des blessures aux yeux.
Dieses Symbol bedeutet Gefhrliche Laserstrahlung.
Laserstrahlung kann zu Beschdigung der Augen fhren.

2 Digital Instruments Electrochemical SPM Rev. B


Rules of Safety

CAUTION: Only qualified personnel aware of the hazards involved may perform service and
adjustments.

ATTENTION: Toute rparation ou talonnage doit tre effectu par des personnes qualifies et
conscientes des dangers potentiels.

VORSICHT: Service- und Einstellarbeiten sollten nur von qualifizierten Personen, die sich der
auftretenden Gefahren bewut sind, durchgefhrt werden.

CAUTION: Follow company and government safety regulations. Keep unauthorized


personnel out of the area when working on equipment.

ATTENTION: Il est impratif de suivre les prrogatives imposes tant au niveau gouvernmental
quau niveau des entreprises. Les personnes non autorises ne peuvent rester prs
du systme lorsque celui-ci fonctionne.

VORSICHT: Befolgen Sie die gesetzlichen Sicherheitsbestimmungen Ihres Landes. Halten Sie
nicht authorisierte Personen whrend des Betriebs fern vom Gert.

CAUTION: When imaging fluid samples, use extraordinary precautions against spillage. Do
not spill fluids on or around the sample holder, electronic boxes, or other
components containing electronic parts. Avoid spilling all corrosive fluids on
exposed surfaces; otherwise, damage may result! In the case of a spill,
immediately clean and dry all affected surfaces carefully.

ATTENTION: Lors dun travail en milieu liquide, prendre toute prcaution pour viter des
fuites. Les liquides ne doivent pas se rpandre sur la platine porte chantillons, le
botier lectronique ou tout autre partie du microscope contenant de
llectronique. Eviter tout fuite de liquide corrosif sur les surfaces exposes. Le
non respect de cette recommandation peut entraner des dommages. En cas de
fuite, nettoyer et scher immdiatement les surfaces touches.

VORSICHT: Falls Sie Proben in Flssigkeiten abbilden, lassen Sie uerste Vorsicht walten,
damit keine Flssigkeit verspritzt wird. Flssigkeiten drfen nicht auf die oder
nahe der Probenhalterung, der Elektronikbox oder anderen Komponenten, die
elektronische Bauteile enthalten, verspritzt werden. Vermeiden Sie bitte,
korrosive Flssigkeiten auf freiliegende Oberflchen zu verspritzen; andernfalls
wren Beschdigungen die Folge! Falls Sie Flssigkeit verspritzt haben, subern
und trocknen Sie alle betroffenen Flchen sorgfltig.

Rev. B Digital Instruments Electrochemical SPM 3


Rules of Safety

CAUTION: Voltages supplied to and within certain areas of the system are potentially
dangerous and can cause injury to personnel. Power-down everything and unplug
from sources of power before doing ANY electrical servicing. (Digital
Instruments/ Veeco Metrology Group personnel, only).

ATTENTION: Les tensions utilises dans le systme sont potentiellement dangereuses et


peuvent blesser les utilisateurs. Avant toute intervention lectrique, ne pas oublier
de dbrancher le systme. (Rserv au personnel de Digital Instruments/Veeco
Metrology Group seulement).

VORSICHT: Die elektrischen Spannungen, die dem System zugefhrt werden, sowie
Spannungen im System selbst sind potentiell gefhrlich und knnen zu
Verletzungen von Personen fhren. Bevor elektrische Servicearbeiten
irgendwelcher Art durchgefhrt werden ist das System auszuschalten und vom
Netz zu trennen. (Nur Digital Instruments/Veeco Metrology Group Personal).

CAUTION: Use of controls or adjustments or performance of procedures other than those


specified herein may result in hazardous laser light exposure. The use of optical
instruments with this product increases eye hazard.

ATTENTION: Toute utilisation, ou talonnage ou essai de modification, autre que ci-dessous


dcrits, peut entraner une exposition dangereuse la lumire du laser.
Lutilisation de systmes optiques avec ce produit peut entraner un danger pour
les yeux.

VORSICHT: Die falsche Verwendung dieses Gertes mit nicht in diesem Handbuch
beschriebenen Vorgehensweisen kann gefhrliche Laserstrahlung freisetzen.
Optische Instrumente, die zusammen mit diesem Produkt verwendet werden,
knnen evtl. Augenschden hervorrufen und verstrken.

CAUTION: Do not attempt to operate the standard air probe holder in a fluid environment.
Standard probe holders have exposed electrical signal lines that could short
circuit if exposed to a conducting fluid.

ATTENTION: En milieu liquide, ne pas utilizer le support de bras de levier standard prvu pour
une utilisation lair. Le support de bras de levier standard comporte des fils
lectroniques non protgs qui peuvent provoquer un court-circuit en cas de
contact avec un liquide conducteur.

VORSICHT: Versuchen Sie nicht, den Standard-Luft-Cantileverhalter in Flssigkeiten zu


betreiben. Am Standard-Cantileverhalter liegen elektrische Leitungen frei, die in
leitfhigen Flssigkeiten kurzgeschlossen werden knnten.

4 Digital Instruments Electrochemical SPM Rev. B


Rules of Safety

CAUTION: Always handle the atomic force microscope (AFM) head with care - it may be
damaged if dropped or crashed with force into samples.

ATTENTION: Prendre toute prcaution en cas de manipulation de la sonde. Celle-ci peut tre
trs abme si elle tombe ou scrase sur un chantillon.

VORSICHT: Bitte behandeln Sie das AFM mit Sorgfalt - ein Aufsetzen krftiges des Kopfes
auf die Probenoberflche kann zu Beschdigungen des Piezos fhren.

Provide the proper environmental conditions (see Table 1.0b) for system operation and
storage.

Table 1.0b Environmental Requirements

Equipment Use Condition Requirement


Operation Temperature 15C (59F) to 35C (95F)
Relative Humidity 45% to 80%, non-condensing
Storage Temperature 10C (50F) to 50C (122F)
Relative Humidity 35% to 90%, non-condensing

Use appropriate risk reduction measures when using flammable liquids.

Rev. B Digital Instruments Electrochemical SPM 5/(6 Blank)


Chapter 2 SPM Fundamentals in Liquid
Environments

2.1 Introduction
Electrochemical atomic force microscopy (AFM) and scanning tunneling microscopy (STM) allow
the microscopist to observe in situ electrochemical processes. Because of the variety and
complexity of electrochemical processes, no single procedure can accommodate all application
needs. Therefore, this manual provides general instructions and examples. Additional information
is available from Veeco applications and technical support teams.

This manual discusses only electrochemistry-specific hardware, operation, and software. You
should refer to your Veeco documentation set for details of basic hardware, operation, and image
processing.

2.2 AFM and STM in Liquid Electrolytes


Depending on the composition of the liquid and the physical and chemical properties of the SPM
probe and sample, operation of an SPM in a liquid can vary from slightly different to much
different than in air.

In STM an ionic liquid can conduct current between the sample, the tip, and the electrodes in the
electrochemical liquid cell. STM tips need to be insulated to minimize exposure to the liquid,
except at the tips apex, where tunneling current is to be established between the tip and sample
surface. STM in non-conducting liquids may be performed without insulating the tip.

In contact AFM in air, a thin layer of liquid adsorbed on the sample surface causes attractive forces
between the AFM tip and sample. These forces are greatly reduced or eliminated when the tip and
sample are immersed in liquid. For this reason, AFM tip-sample force curves in liquid are
generally, but not always, different from those in air. They show much less, and sometimes no,
adhesion between the tip and sample surface during the retract segment of the force curve cycle
(see examples in Figure 2.2a).

The fidelityand sometimes resolutionof contact AFM images in liquid may depend less on tip-
sample adhesive forces and more on the selection of the cantilever, as described below.

Rev. B Digital Instruments Electrochemical SPM 7


SPM Fundamentals in Liquid Environments
AFM and STM in Liquid Electrolytes

Figure 2.2a Force Curve Examples of High Adhesion and Low Adhesion

3135
High Adhesion Low Adhesion

Because the mechanical response time of AFM cantilevers in liquid is increased, to preserve image
fidelity scanning speeds during contact AFM in liquids may have to be kept lower than when
scanning in air. The increase in response time occurs because viscous damping in liquids is much
greater than that in air, and the cantilever drags some liquid along with it when moving through the
liquid (mass loading). For example, the viscous damping of an AFM cantilever in water is found to
be 12 orders of magnitude greater than in air.

The amount of viscous damping in liquids can vary considerably for different kinds of
commercially available cantilevers, depending on the cantilever geometry. Thus, the choice of AFM
cantilevers may affect the image quality in a liquid more dramatically than in air. Generally, among
the commonly used V-shaped nitride cantilevers, shorter and thicker cantilevers with larger spring
constants are better suited for AFM imaging in liquids. However, these cantilevers can be less
gentle on fragile and soft surfaces, as well as on loosely adsorbed species. Contact force must be
controlled in order to avoid relocation of electrochemically deposited material by the AFM
cantilever. You may need to experiment with various cantilevers to ascertain which ones better suit
the imaging requirements of each run.

Acidic or basic liquids may induce charging of the surface of the sample and the AFM tip. For
example, the surface of mica becomes negatively charged in acidic liquids (low pH). This type of
charging can complicate the structure of the electrical double layer, the properties of which greatly
influence electrochemical reactions on the surface of the sample. It can also significantly increase
the tip-sample contact force in AFM.

Since the AFM relies on optical detection of a laser beam, the optical properties of the electrolyte
can also affect the operation of the AFM. Opaque electrolytes diffuse the laser beam and in some
cases can block the beam. The presence of large colloidal particles in the electrolyte can interfere
with the operation of the AFM by sticking to the cantilever or by obscuring the path of the laser
beam as it enters and exits the fluid cell. Such particles can sometimes be by-products of
electrochemical reactions in the electrolyte. Air bubbles can create the same types of problems as
colloidal particles. The workaround for some of the common problems associated with air bubbles
and particles are described in Clearing Contaminants and Bubbles" on page 4-39.

The mechanism and rate of electrochemical reactions may depend on the geometry of the
electrochemical cell and the electrodes. The volume of the electrochemical cell in an SPM is
usually small compared to standard laboratory electrochemical cells, and the SPM probeeither
STM tip or AFM cantilever-tip assemblyis held close to, and often in contact with, the sample,
which is the working electrode.

8 Digital Instruments Electrochemical SPM Rev. B


SPM Fundamentals in Liquid Environments
AFM and STM in Liquid Electrolytes

Veeco personnel have sometimes observed noticeable differences in the surface area of the working
electrode beneath the AFM cantilever as compared with areas away from the cantilever. Diffusion
of reactant species from the bulk of the electrolyte to areas beneath the cantilever may be affected
by the proximity of the cantilever (and the scanning tip) to the surface of the working electrode.
This is also known as the tip-shielding effect.

Figure 2.2b Abbreviations Used in Electrochemical SPM

Abbreviation Definition
EC Electrochemical / Electrochemistry
GP Glass Piece
CE Counter Electrode
RE Reference Electrode
ECM an electrochemical STM which is commonly
(but incorrectly) referred to also as ECSTM
This microscope is shown in Figure 3.1a.

Rev. B Digital Instruments Electrochemical SPM 9/(10 Blank)


Chapter 3 Electrochemical SPM
Hardware

3.1 Electrochemical SPMs


Several Veeco SPM models are equipped with electrochemical hardware.

3.1.1 Model ECM

Model ECM is designed for STM imaging in air or in a fluid cell


Figure 3.1a Model ECM
with electrolyte and electrochemical potential control. The
Bipotentiostat/Galvanostat (see Bipotentiostat/Galvanostat on An Electrochemical STM
page 3-15) is integrated into the base of the ECM. Four scanner
types with maximum X-Y scan ranges of 1 m (model A) and 12
m (model D, DI, or E) can be used with the ECM. The J scanner
(120 m maximum scan size) can also be used with the ECM, but
not with the fluid cell that is designed for use with the ECM
sample stage.

CAUTION: Your model ECM must have the newer Potentiostat/Galvanostat board
(boards made after 3/1/92) installed to be capable of operating in the
Galvanostat mode. The older Potentiostat board (made prior to 3/1/92)
operates in the Potentiostat mode only.

Rev. B Digital Instruments Electrochemical SPM 11


Electrochemical SPM Hardware
Electrochemical SPMs

3.1.2 Model ECAFM

Figure 3.1b Model ECAFM


An Electrochemical AFM

Potentiostat/Galvanostat

With electrical and liquid leads Without electrical and liquid leads

Model ECAFM is designed for AFM imaging in air or in a fluid cell with electrolyte and
electrochemical potential control. The Potentiostat/Galvanostat (see Bipotentiostat/Galvanostat
on page 3-15) is separate from the microscope base (not integrated into the base, as it is in Model
ECM).

3.1.3 Model ECLFM

Figure 3.1c Model ECLFM


An Electrochemical AFM
Capable of LFM

Model ECLFM is designed for AFM and LFM (lateral force


microscopy) imaging in air or in a fluid cell with electrolyte and
electrochemical potential control. The Potentiostat/Galvanostat (see
Bipotentiostat/Galvanostat on page 3-15) is separate from the
microscope base.

Potentiostat/
Galvanostat

12 Digital Instruments Electrochemical SPM Rev. B


Electrochemical SPM Hardware
Electrochemical SPMs

3.1.4 Model MMAFM-EC

Figure 3.1d Model MultiMode AFM-EC (MMAFM-EC)

Potentiostat/
Galvanostat

AFM Configuration STM Configuration

Model MMAFM-EC is designed for STM, AFM, LFM, and TappingMode AFM imaging in air or
in a fluid cell with electrolyte and electrochemical potential control. However, while imaging with
TappingMode, the Veeco Bipotentiostat/Galvanostat may not be used for electrochemical potential
control; an external Potentiostat is then required.

CAUTION: The MultiMode AFM models equipped with a Phase Extender box may not be
interfaced with the Veeco Bipotentiostat/Galvanostat.

3.1.5 Model MMSECPM

Model MMSECPM is designed for STM, AFM, LFM, and TappingMode AFM imaging in air or in
a fluid cell with electrolyte and electrochemical potential control. However, while imaging with
TappingMode, the Veeco Bipotentiostat/Galvanostat may not be used for electrochemical potential
control; an external Potentiostat is then required. It is also capable of SECPM and STS-EC in fluids.

Rev. B Digital Instruments Electrochemical SPM 13


Electrochemical SPM Hardware
Electrochemical SPMs

Figure 3.1e Model MMECPOT with MMSECPM Head

Figure 3.1f SECPM Head

14 Digital Instruments Electrochemical SPM Rev. B


Electrochemical SPM Hardware
Bipotentiostat/Galvanostat

3.2 Bipotentiostat/Galvanostat
The Bipotentiostat/Galvanostat is used to monitor and control the electrochemical potentials and
currents in the electrochemistry (EC) cell. When conducting STM, the potentials of the STM tip
and the working electrode (sample) can be controlled simultaneously and independently (thus, a
Bipotentiostat).

Note: Note: This feature is not available on models ECAFM and ECLFM that are
equipped to do STM.

Additionally, the potential of the STM tip can be monitored and controlled relative to the reference
electrode (RE) or the working electrode (WE).

3.2.1 Bipotentiostat/Galvanostat Model MMECAFM

All the models shown in Section 3.1 include a digital voltmeter (DVM) and a hardware ON/OFF
potential-control switch on the Bipotentiostat/Galvanostat (see example in Figure 3.2b). This
mechanical ON/OFF switch together with a software switch in the Electrode Controls panel (see
Section 7.3.5) must be ON for the counter electrode to be connected to the Bipotentiostat/
Galvanostat circuitry. When both the hardware switch and the software switch are ON, you have
control over the EC cell potential in the Potentiostatic mode (or EC cell current in the Galvanostatic
mode), and the DVM on the Bipotentiostat/Galvanostat displays the working electrode potential.
When the potential control is OFF (i.e., when either one or both hardware and software switches are
OFF), the DVM displays the open-circuit (rest) potential of the EC cell.

3.2.2 Bipotentiostat/Galvanostat Model MMECPOT

Model MMECPOT is an upgrade of the earlier model, MMECAFM. In addition to having all the
features of the earlier model, it also enables STS (Scanning Tunneling Spectroscopy) measurements
in an electrochemical environment and SECPM (Scanning ElectroChemical Potential Microscopy).

Like its predecessor, the potentiostat/galvanostat has a digital voltmeter (DVM) in the front, shown
in Figure 3.2a. This DVM displays the working electrode potential. When the cell is turned OFF,
the DVM displays the open-circuit (rest) potential of the EC cell. Three switches, shown in Figure
3.2b, are located at the back of the potentiostat/galvanostat. The top switch turns the EC cell ON
and OFF and works in conjunction with a software switch found in the Electrode Potential Controls
window of the NanoScope EC software. The middle switch selects AFM (operates as a
potentiostat) or STM (operates as a bipotentiostat) modes of operation. The bottom switch selects
the GAIN of the current-to-voltage converter which is used to monitor the EC cell current. Three
different gain settings, 10, 100, 1000 A/V, correspond to three current ranges, 100, 1000 and
10,000 A.

Rev. B Digital Instruments Electrochemical SPM 15


Electrochemical SPM Hardware
Bipotentiostat/Galvanostat

Figure 3.2a MMECPOT DVM

Figure 3.2b MMECPOT Bipotentiostat/Galvanostat

To Scanner

To counter
electrode

To reference electrode

Specifications
Cell voltage range: 12V

Potential range: 2.5V

Potential resolution: 0.3mV

Reference impedance input: > 1013

Current range: 10mA

Minimum current resolution: 10nA

Current gains (3 decades): 10 A/V, 100A/V, 1000A/V

Output voltage compliance: 12V

16 Digital Instruments Electrochemical SPM Rev. B


Electrochemical SPM Hardware
Fluid Cells

3.3 Fluid Cells


The fluid cells for the AFM and STM are different. The procedure for assembling the cells can be
found in Chapter 4 (AFM) and Chapter 5 (STM).

3.3.1 Fluid Cells for Electrochemical STM

ECM Fluid Cell

The fluid cells for the ECM are shown in Figure 3.3a. Both the older and the newer designs are
open cells, meaning the electrolyte is exposed to the ambient air. The central circular feature is
where the electrolyte resides. The two pieces of wire terminating inside the circular area are the
reference and the counter electrodes (RE and CE). See Section 5.3.1 for instructions on assembling
the fluid cell.

Figure 3.3a Fluid Cells for Model ECM

Older Design Newer Design

STM Fluid Cell for MMAFM

The STM fluid cell for the MultiMode is an open cell design, meaning the liquid in the cell is
exposed to the ambient air. The connections to the counter and reference electrodes are not
integrated into this cell. In the newer model, these connections are facilitated by two Teflon screws
on the STM head (the TipView head Figure 3.3b-B). In the older model, the connections are made
by running the electrode wires through two small holes in the ceramic crossbar that also holds the
STM tip (See Figure 3.3b-C). The STM fluid cell for MMAFM and the new and old designs of the
STM TipView head are shown in Figure 3.3b. Instructions for assembling the STM TipView head
and the fluid cell are found in Section 5.3.1.

Rev. B Digital Instruments Electrochemical SPM 17


Electrochemical SPM Hardware
Fluid Cells

Figure 3.3b STM Fluid Cells


Model MultiMode AFM (A), New Tip View Head (B), and
Old Tip View Head (C)
A B

O-ring
Sample
Screws for secur-
ing counter and
reference elec-
trodes (shown by
dark circles)

C
Assembled
cell

Holes for securing counter


and reference electrode.

3.3.2 Fluid Cell for Electrochemical AFM

The fluid cell for AFM consists of the machined glass piece (GP), sometimes referred to as the
cantilever substrate holder, an O-ring which fits into the GP, and the sample surface. The cell is
constructed by inserting the O-ring into the groove on the bottom of the GP and then placing the
assembly on the sample so that the O-ring is in contact with the sample surface (see Figure 3.3c).
The O-ring seals the volume called the fluid cell. The fluid cell is a closed cell in that the electrolyte
and sample area inside the cell are not exposed to ambient air when electrolyte is injected into the
cell. (See Chapter 4 for instructions on how to assemble the fluid cell.)

18 Digital Instruments Electrochemical SPM Rev. B


Electrochemical SPM Hardware
Fluid Cells

Figure 3.3c Electrochemical Fluid Cell for AFM

Laser Diode
Position
Sensitive
Detector

Flow-thru
Glass Piece (GP)
Fluid
Chamber
Cantilever/Tip

~12

O-ring Seal
Sample

3122a
The machined GP has a gold-plated, stainless steel wire clip that holds the cantilever substrate
rigidly in place (see Figure 4.3f). When the GP is in place on the microscope head, the cantilever
substrate (and the integrated cantilever) are tilted at about 12 degrees with respect to the sample
surface (assuming the sample surface is flat and level as it rests on the piezoelectric scanner cap).

CAUTION: Do not rest GP with the cantilever side in contact with the support surface.
Always rest GP with the cantilever side facing up. This protects the gold-coating
on the clip and the anti-reflection coating on the bottom (cantilever) side.

Four tapered channels are machined into the GP (three through the side, one through the top) to
provide flow capability and allow insertion of the reference and counter electrodes. Standard male
Luer fittings are used with three channels machined into the side of the glass holder. The narrow
fourth channel extends through the top of the glass holder and is used for inserting the counter
electrode into the cell.

Figure 3.3d shows the GP for AFM EC in two configurations: TappingMode AFM (on the left with
attachments) and contact mode AFM (on the right without attachments).

CAUTION: The TappingMode design is for use with the MMAFM-EC only. The contact
mode design can be used in all three models (ECAFM, ECLFM, and the
MMAFM-EC).

Rev. B Digital Instruments Electrochemical SPM 19


Electrochemical SPM Hardware
Fluid Cells

Figure 3.3d The GP for AFM EC Fluid Cells


TappingMode Cell (left) and Contact Mode Cell (right)
Counter electrode
insertion hole

Counter Electrode

Reference Electrode

Luer fittings
(electrolyte
inlet/outlet ports)

TappingMode Cell Contact Mode Cell

Figure 3.3e shows the final configuration of the head of a microscope capable of AFM imaging
(model ECAFM, ECLFM, or MMAFM-EC) and the GP of the electrochemical fluid cell with the
electrolyte flow tubes and the electrodes attached.

Figure 3.3e Microscope Head Configured for AFM Imaging

Some users have reported reduced electrolyte contamination by not using the tubes, and instead by
connecting a fresh syringe directly to a Luer fitting and injecting just enough electrolyte from the
syringe to fill the liquid cell (i.e., without an output tube to drain excess electrolyte).

20 Digital Instruments Electrochemical SPM Rev. B


Electrochemical SPM Hardware
Assembling ECSPM Hardware

3.4 Assembling ECSPM Hardware

3.4.1 Hardware for Model ECM

The Bipotentiostat/Galvanostat is integrated into the base for model ECM.

Reference Chapter 5 for fluid cell assembly instructions.

3.4.2 Hardware for Other Models

1. Place ECAFM, ECLFM, or MMAFM-EC base on the Bipotentiostat/Galvanostat.

2. Align the DVM displays from the two units. The three steel balls on the bottom plate of the
microscope align with the three magnets imbedded in the top ring of the Bipotentiostat/
Galvanostat.

3. Connect the microscope and the Bipotentiostat/Galvanostat using the short, standard 25-pin
type ribbon cable (see Figure 3.4a).

Figure 3.4a Short Ribbon Cable

Short
Ribbon
Cable

Note: There are two 9-pin connectors on the Bipotentiostat/Galvanostatone male


and one female.

CAUTION: DO NOT CONNECT THE SCANNER TO THE MICROSCOPE BASE,


which is usually done during AFM imaging. Using the extension cable provided,
connect the scanner to the female 9-pin connector on the Bipotentiostat/
Galvanostat as shown in Figure 3.4b. The microscopes head connects to the
base in the usual manner (See Figure 3.4b).

Rev. B Digital Instruments Electrochemical SPM 21


Electrochemical SPM Hardware
Assembling ECSPM Hardware

Figure 3.4b Cable Connection between Scanner and Potentiostat

Head connects to
base as usual.

Scanner cable

Extension cable
connected to the
adapter on the
Potentiostat and to
the scanner cable.

4. Connect the clip-lead electrode wire assembly (orange and purple wires) to the male 9-pin
connector on Bipotentiostat/Galvanostat.

Connections

When used with NanoScope Microscopes, the microscope base sits on top of the potentiostat/
galvanostat which is connected by a 25-pin, D-sub connector to the NanoScope controller. A short
ribbon cable connects the potentiostat/galvanostat to the microscope. A male 9-pin micro-D
connector, the cell connector, near the top of the potentiostat/galvanostat provides reference and
counter electrode connections to the cell for ECAFM or ECSTM. An extension cable, which plugs
into a female 9-pin micro-D connector at the top of the potentiostat/galvanostat, mates to the
scanner replacing the usual connection on the scanner support ring.

Jumpers

The PCB board has 4 jumpers. Jumper J1, when capped, enables the mechanical ON/OFf switch on
the Potentiostat/Galvanostat. When J1 is uncapped, this switch is disabled. The default setting is
capped (switch enabled). Jumper J6 allows digital signal D0 from the nanoScope controller to
either switch the cell ON/OFF (when capped to the CELL side, shown in) or switch between STM/
SECPM modes. Jumper J7, includes (when capped to the VR+B side, shown in Figure 3.4d and
Figure 3.4f) or excludes (when capped to the VR side shown in Figure 3.4c andFigure 3.4e) the
Bias Voltage and Reference Voltage summing junction. To support STS under electrochemistry, cap
the VR+B side. Jumper J8 should be left uncapped to meet the CE standard. NanoScope software
version 5.30 and above support SECPM. NanoScope software versions 5.30a and above support
STS under EC. The jumper settings are shown below.

22 Digital Instruments Electrochemical SPM Rev. B


Electrochemical SPM Hardware
Assembling ECSPM Hardware

If, for some reason, you have hardware (MMECPOT) that supports SECPM and STS-EC but are
running an early version of software that does not support these features, set the jumpers as shown
in Figure 3.4c.

Figure 3.4c Jumper settings that support neither SECPM nor STS-EC (ver. 5.12 and below)

J7 to VR side

J1 Capped
J6 to CELL
side

If, for some reason, you have hardware (MMECPOT) that supports SECPM and STS-EC but are
running an early version of software that does not support SECPM, set the jumpers as shown in
Figure 3.4d.

Figure 3.4d Jumper settings for software versions that support STS under EC control (ver.5.30a and up) but not
SECPM.

J7 to VR+B

J1 Capped
J6 to CELL
Side

Version 5.30 supports SECPM but not STS-EC - set the jumpers as shown in Figure 3.4e.

Rev. B Digital Instruments Electrochemical SPM 23


Electrochemical SPM Hardware
Assembling ECSPM Hardware

Figure 3.4e Jumper settings for software versions that support SECPM but not STS under EC control (ver.
5.30a).

J7 to VR

J1 Capped

J6 to SPM
side

Version 5.30 supports SECPM and STS-EC - set the jumpers as shown in Figure 3.4f.

Figure 3.4f Jumper settings for software versions that support SECPM and STS under EC control (ver. 5.30 and
up).

J7 to VR+B

J1 Capped

J6 to SPM
side

3.4.3 STM in MMAFM-EC

The connections between the Bipotentiostat/Galvanostat, scanner, and STM TipView head are the
same as those between the Bipotentiostat/Galvanostat, scanner, and optical head in the AFM
configuration of the model ECAFM. See Chapter 5 for instructions to assemble the STM fluid cell
for the MultiMode.

24 Digital Instruments Electrochemical SPM Rev. B


Chapter 4 AFM Electrochemical Fluid
Cell Setup and Operation

4.1 Cleaning Fluid Cell Elements

CAUTION: Cleanliness is important when preparing and working with the fluid cell. Wear
fresh, clean latex gloves when handling pieces of the fluid cell and the sample.
Electrochemical experiments are extremely susceptible to even small amounts of
contaminants.

You can clean various pieces of the AFM fluid cell assembly and attachments (such as the glass
piece and Luer fittings) in an ultrasonic bath by immersing them in deionized water in a container
made of Teflon or other soft material. Do not place the glass piece of the fluid cell directly in
contact with the metal bath because the glass may be damaged or scratched during cleaning. Make
sure the glass piece rests on the Teflon container with the cantilever side facing up. This prevents
the gold-coated clip from rubbing against the container bottom during cleaning. Do not use abrasive
cleaning solutions to clean the glass piece, for you may damage the anti-reflective coating on the
bottom surface of the glass piece.

4.2 Cleaning Electrodes


Thoroughly clean the electrode wires. If you are using platinum or other high-melting-point wires,
a hydrogen flame (with no oxygen mixed) does an excellent job of cleaning the electrode.
Otherwise use fine sandpaper to remove metal oxide from the surface and clean with isopropyl
alcohol and a lint-free clean room paper. Complete the process with a long rinse in deionized water.

4.3 In Situ AFM Imaging

4.3.1 Preparing the Sample

The working electrode wire from the Bipotentiostat/Galvanostat connects to the sample via the
metal cap on the AFM scanner. The top surface of the sample (the side in contact with the
electrolyte) must have a low resistive path to the scanner cap, so that it is electrically connected to
the Potentiostat.

Rev. B Digital Instruments Electrochemical SPM 25


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

Figure 4.3a Ensure Conductivity between Scanner Cap and Samples Top
Surface

1. Pressing a drop of silver epoxy between the sample and the puck works well if the sample is
entirely conductive. If the sample rests on an insulating substrate, add some of the silver
epoxy to the edge of the sample and to the conductive portion of the sample so that an
electrical path is created to the puck. Whatever method is used, prepare your sample so that
there is no more than 10 ohms resistance between the samples top surface and the scanner
cap.

2. Place the sample on the scanner cap.

3. On older model scanners (which have three head-support screws for lowering and raising the
head) rotate the two manual screws in front and the one stepper-motor-controlled screw in
the rear to raise the scanner approximately 7 mm, or more if the sample is thick (see Figure
4.3b). On vertical engage scanners there is only a single, motor-controlled, head-support
screw. Raise this screw so that the scanner outer shell is approximately 5 mm above the base
of the scanner inner cylinder (see Figure 4.3b.)

Figure 4.3b Rotate Screws that Raise Head - Standard Scanner (right) and
Vertical-Engage Scanner (left)

7 mm
Head
Elevation
(Larger
for Thick
Samples)

4. Place the glass piece (GP) of the fluid cell (without the cantilever substrate) into the
microscope head and ensure proper positioning of machined pits of the GP on the two small
steel balls inside the head.

26 Digital Instruments Electrochemical SPM Rev. B


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

Figure 4.3c Insert GP with Pits Matched to Steel Balls

Pits on the GP (see figure


on next page)

Clamp

Steel balls

5. Secure the GP in place by tightening the clamp onto the GP as is done with a regular
cantilever substrate holder in air. Place head on scanner and secure with springs as usual.

6. Lower the microscope head on the scanner while making sure that the sample clears the GP
by at least 1 mm. This clearance allows the cantilever substrate to be mounted on the GP
without contact to the sample surface prior to engaging the microscope.

7. Once you check the clearance, remove the GP from inside the head so you can place a
cantilever substrate in it.

4.3.2 Positioning the Cantilever Substrate on the GP

The fluid cell must be disassembled if you discover a misaligned or loosely held cantilever
substrate. Therefore, proper positioning of the cantilever substrate inside the GP is very important.

1. Rotate the clip so that the small silicone ball is in the groove machined out of the top surface
of the GP (see Figure 4.3d).

Rev. B Digital Instruments Electrochemical SPM 27


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

Figure 4.3d Rotate the Clip until Ball Snaps into the Groove Machined
Out of Top Surface of the GP

Pits on the
GP that Plunger
match steel
balls in AFM Silicone ball
head

Rotate clip until


silicone ball
snaps into groove

Groove

2. Place the GP upside down (spring side down, cantilever side up) on a hard surface, such as a
glass tabletop. The plunger, which is the assembly of the gold-plated clip and the spring that
it is threaded through, should be in contact with the hard surface.

Note: Press the GP down gently so the gold-plated clip rises on the cantilever side of
the GP. The plunger spring tends to bring the clip back onto the GP, so you
must maintain gentle pressure until the cantilever substrate is in place.

3. Place the cantilever substrate inside the machined groove. This groove is inclined at
approximately 12 degrees so that the cantilever substrate and cantilever clear the sample
during imaging. (See Figure 4.3e and Figure 4.3f.)

4. Gently release pressure on the GP and allow the plunger spring to pull the wire clip so that
the clip hugs the cantilever substrate tightly against the inclined groove of the GP.

5. To maximize stability, position the cantilever substrate so it is lined up against one side of
the groove. Ensure that the cantilever substrate is not raised out of the inclined groove and
made unstable.

28 Digital Instruments Electrochemical SPM Rev. B


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

Figure 4.3e Use Tweezers to Place the Cantilever Substrate in the


Inclined Groove

Figure 4.3f Verify that the Cantilever Substrate Is Seated within the Groove

Cantilever Wire clip


substrate

3 Lift wire clip by pressing


1 plunger on opposite side.
3
8 Insert cantilever substrate
with tweezers, then release
Insert cantilever clip.
substrate into
inclined groove
Inclined Groove
Press on plunger

6. After positioning the cantilever substrate in the GP, check again to ensure the silicone ball of
the plunger is seated inside the groove provided for it on the other side of the GP. This
prevents the wire clip from sliding off the cantilever substrate and releasing the cantilever
substrate from the GP.

4.3.3 Positioning GP inside AFM Head

Place the GP inside the microscope head, ensuring that the pits on the GP are properly positioned
on the two small steel balls inside the head. (See Figure 4.3c.)

1. Lower the clamp (See Figure 4.3c) until the clamp makes good contact with the GP and holds
it tightly in place.

Rev. B Digital Instruments Electrochemical SPM 29


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

4.3.4 Imaging Dry without O-Ring

Turn the hardware potential control switch on the Bipotentiostat/Galvanostat to the OFF position.

MultiMode Users Only

On the MMAFM-EC Bipotentiostat/Galvanostat, three switches control electrochemical operation


of the microscope (See Figure 4.3g). The top switch turns the EC cell ON and OFF (this switch
works together with a software switch which is in the Electrode Potential Controls window of the
NanoScope EC software); the middle switch selects AFM or STM operation, and the bottom switch
selects GAIN of the current-to-voltage-converter, which monitors electrochemical cell current. The
three different gain settings (10, 100, 1000 A/V) correspond to three current ranges: 100, 1000,
10,000 A. A software parameter needs to be set to the appropriate gain, as described below.

Figure 4.3g Switches on Bipotentiostat/Galvanostat for MMAFM

Set the switches as follows:

1. On MultiMode AFM, base set the microscope mode control switch to AFM/LFM.

2. On Bipotentiostat/Galvanostat, set AFM/STM function switch to AFM.

3. Set the gain of the current-to-voltage converter on the Bipotentiostat/Galvanostat to a value


appropriate to your EC experiment.

4. Set the software parameter as follows:

a. From the real-time menu, click on Microscope / Calibrate/ Detector. The Detector
Calibration dialog box appears.

b. In the Detector Calibration dialog box, set the sensitivity of Auxiliary input channel A
(Aux A sens) to the same value that you selected on the GAIN switch on the
Bipotentiostat/Galvanostat.

30 Digital Instruments Electrochemical SPM Rev. B


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

All Users

1. From the real-time menu click on Microscope / Select.

2. From the displayed options select the EC version of the software (e.g., ECAFM or
MMAFM-EC).

3. Align the laser on the cantilever and adjust the photodetector to center the reflected laser
beam spot on the detector.

Note: Detailed information on laser alignment is found in the MultiMode Scanning


Probe Microscope Instruction Manual and the AFM/LFM Scanning Probe
Microscope Instruction Manual.

4. Lower the microscope head to bring the tip closer to the sample.

a. In regular scanners turn the two manual height adjustment screws in front
counterclockwise, and lower the back screw using the stepper motor. Be sure the head is
level side-to-side and slightly raised in the back prior to the final, motorized approach
for engaging the microscope. If the head is not level upon engage, the stability of O-ring
contact with samples and the quality of fluid cell seal is almost always jeopardized.

b. In vertical engage scanners use the stepper motor (there are no manual height
adjustment screws). Leveling the head is not an issue with vertical engage scanners.

5. Engage the microscope and obtain a stable image in contact mode.

Note: This cannot be done in TappingMode because the liquid necessary to oscillate
the cantilever is not yet in the fluid cell.

6. Withdraw the microscope once (raising the tip a few microns from the sample surface) and
observe the difference (the A-B signal) in the DVM. This is the signal that is usually used to
monitor cantilever deflection. Here, we use it as a diagnostic tool. If it has changed much
from the value prior to the previous engage, the GP may not be seated well inside the head, or
the cantilever substrate may be unstable in its position on the GP. Use a piece of paper to
examine the reflected beam entering the detector. If the beam shape has changed (e.g., has
become diffuse or asymmetric) or if the sum signal (A+B) has dropped much, pull the GP out
of the head and examine the cantilever substrate position within the inclined groove. Verify
that the clip is secured in its position. Make necessary adjustments, including the tip-sample
clearance, and reposition the GP inside the head. Then tighten the clamp, position the laser
on the back of the cantilever, adjust the detector, and engage the microscope.

7. Once you are satisfied with the mechanical stability of the GP and you have assured yourself
that the microscope is imaging normally, withdraw the microscope four or five times using
Real-time / Motor / Withdraw. This usually raises the tip about 30 to 50 microns from the
sample surface. Each click of the Withdraw raises the head by approximately the same
distance, which varies with each scanner.

8. Reengage the microscope and keep track of the approach distance prior to engage as
indicated by the Motor or Tip display counter on the bottom (status bar) of the control
monitor (see Figure 7.2c).

Rev. B Digital Instruments Electrochemical SPM 31


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

CAUTION: You need to remember this approach distance for the next engage, which will
be with the O-ring in place. Determine the approximate number of microns of
approach the four to five withdraws equals by engaging and then withdrawing
the microscope several times, each time with the same number of repeated
executions of the Withdraw command. Finally withdraw one last time (again
with the same number of clicks on Withdraw), in order to place the O-ring in the
GP.

9. Remove the GP from the head in order to place the electrodes and the O-ring in the GP.

4.3.5 Imaging Dry with O-Ring

Attaching the Counter Electrode (CE)

1. Wrap the clean CE with Teflon tape so that it fits snugly into the tapered hole in the top of
the fluid cell.

Note: If the electrode wire is very thin, you can more easily wrap it with Teflon tape
by making a loop with the electrode and wrapping the free end of the wire
around the body of the wire (like making a noose) to increase the wire
thickness. Be sure the looped CE is still thin enough to fit inside the fluid cell
without contacting the cantilever substrate and sample. (See step 6 below.)

Figure 4.3h Prepare the Counter Electrode (CE)

Wrap the CE with Teflon tape

Insert the CE into


the tapered hole

Loop the electrode wire


if necessary to increase
the thickness of the wire

32 Digital Instruments Electrochemical SPM Rev. B


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

2. Carefully insert the Teflon-wrapped CE into the tapered hole, making sure that the CE
extends far enough on the opposite side to be in contact with the electrolyte, but not far
enough to contact the sample.

3. Verify that the wire does not contact the sample or interfere with the cantilever or the
incident or reflected laser beam by inserting the GP in the head and examining the A-B and
A+B signals of the AFM.

CAUTION: Any electrolyte escaping through this hole to the top surface of the GP can
interfere with the incident or reflected laser beam and compromise the fluid cell
seal.

4. Make sure the CE port is sealed well with Teflon tape.

5. With a sharp tweezer, gently squeeze extra Teflon into the hole in small quantities until
sealed.

Note: Be careful not to chip away at the GP with the tweezers.

Note: If the CE is thin enough, you may bend the exposed portion of the CE in the
fluid cell volume into a curve and extend it over a larger portion above the
sample. This increases the area of the counter electrode exposed to the
electrolyte in the fluid cell. This also sometimes makes it easier for the AFM tip
to access and image sites of deposition and removal of material on the sample
without having to translate the sample stage much beneath the AFM tip.

6. If in the fluid cell volume the CE is too long, trim the excess length and/or pull out the slack
through the tapered hole.

Note: If you looped the CE (as suggested in step 1 above), then do not trim it as
electrical connection in the trimmed (disjointed) loop may be compromised.
Instead, pull the slack through the tapered hole.

7. On the top side of the GP, wrap the loose end of the CE around the steel post on top of the
GP a few times to ensure that the electrode cannot easily be pulled loose from the cell.

Rev. B Digital Instruments Electrochemical SPM 33


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

Figure 4.3i Secure the CE Wire

Wrap CE wire around


post to secure

Attaching the Reference Electrode (RE)

1. Wrap the clean reference electrode (RE) with Teflon tape so that it fits snugly into the left-
hand tapered hole of the fluid cell (Figure 4.3j).

Figure 4.3j Attach the RE

Reference Electrode
(RE)

2. Leave enough RE wire extending outside the port so that a clip lead can be attached. Be sure
enough electrode wire is extending towards the electrolyte so that the end of the RE is as
close to the electrolyte as possible.

3. Insert extra teflon tape using tweezers to seal the port. Be careful not to chip away at the GP
with tweezers.

34 Digital Instruments Electrochemical SPM Rev. B


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

4.3.6 Installing the O-Ring

Placing the O-Ring

The fluid cell is the volume encapsulated between the GP, the O-ring, and the surface of the sample.

1. With a pair of clean tweezers, place the O-ring on the circular groove machined into the GP.

Figure 4.3k Position the O-Ring

Note: The O-ring must be secure in the groove so that it cannot fall off when the GP
is inverted. If the O-ring is pushed too far into the groove, there may be
inadequate contact between the O-ring and the sample when the GP is placed
back in the head, and thus no seal when the liquid is introduced. The O-ring
must contact the sample all around, defining a circular boundary, before the tip
contacts the sample; otherwise, the fluid cell is not sealed. Remember that the
tip is only few 10s of micrometers above the sample since the last withdraw
command in Section 4.3.4.

2. Push the O-ring partially, but not entirely, into the circular groove (Figure 4.3k).

3. Press the O-ring in the groove equally all around.

4. Connect the silicone tubes to the GP via the male Luer fittings as shown in Figure 4.3l.
Sometimes, a syringe alone is simpler and works better than a tube for fluid injection (see
Section 4.3.2). Users are encouraged to experiment.

Rev. B Digital Instruments Electrochemical SPM 35


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

Figure 4.3l Insert Luer Fittings into Remaining Holes

Positioning the GP inside AFM Head with O-Ring Installed

Properly positioning the GP in the head is critical. Without an O-ring, positioning the GP in the
head was easy because the steel balls in the head and the matching pits machined out of the GP
were in contact before the clamp securing the GP was tightened. But with the O-ring inserted, the
balls and pits are not necessarily matched when the clamp is lowered, because the O-ring contacts
the sample before the balls fit into the pits.

1. Carefully position the GP inside the head using the Luer fittings to handle the GP.

2. Visually align the two pits on the bottom of the GP with the matching steel balls in the head.

3. Lower the GP onto the sample until the O-ring makes contact with the sample surface.

36 Digital Instruments Electrochemical SPM Rev. B


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

Figure 4.3m Align the GP, O-Ring, and Head

Pits
O-Ring

3125

Steel balls

4. Slowly lower the clamp. As the clamp starts pushing down on the rear of the GP, gently press
down on the front edge of the GP to uniformly press the O-ring into the circular groove of the
GP.

5. Tighten the clamp.

Note: If the clamp is tight enough, and the GP is properly aligned in the head, the tip
should be about 40-50 microns above the sample surface (assuming that you
withdrew four or five times after the last engage in Section 4.3.4 step 8).

6. Examine the sum (A+B) and the difference (A-B) signals of the detector. They should be
nominally unchanged from the setup without the O-ring in place (Section 4.3.4). If there is a
small change in the sum signal, slightly realigning the detector might adjust it. If there is a
large change in the signals, or if the sum signal has gone to zero, the GP is probably not
properly positioned. Examine the positioning of the GP inside the head and make
adjustments. If the GP appears properly positioned, check the cantilever substrate to be sure
it has not been moved inadvertently during the insertion of the O-ring. If it has, realign the
cantilever substrate and make necessary adjustments to the reflected laser beam going into
the detector. But if you do so, you will lose the distance between tip and sample after last
withdraw in Section 4.3.4. So, it is a good idea to click on Withdraw some more in order to
increase the tip sample clearance before re-inserting the GP in the head.

7. Once you are satisfied with the alignment and stability of the parts involved, engage the
microscope in contact mode with a small scan size (<1m).

8. If you did not have to readjust the cantilever substrate on the GP, the microscope should
engage within about 40-50 microns of approach, assuming it was withdrawn four or five

Rev. B Digital Instruments Electrochemical SPM 37


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

times after the previous engage in Section 4.3.4. If the approach continues for much longer,
either the GP is not aligned properly or the clamp is not low enough on the GP. Check the GP
alignment and ensure the clamp is tight. If problems persist, withdraw several times
consecutively (to increase sample clearance) and repeat engage without the O-ring, then
reinsert the O-ring and try again. If the difference (A-B) signal drifts during the approach, it
may be a sign of misalignment, but wait at least until the expected distance of approach
elapses before interrupting the approach. Sometimes optical interference and other effects
give rise to this drift, but the microscope engages before drift is too large, and you can then
withdraw once and adjust the A-B and A+B signals with the tip very close to the surface.

Compensating for O-Ring Distortion

The motion of the piezo tube in the X and Y directions moves the sample. This movement deforms
the elastic O-ring, which is restrained in the circular groove of the GP. Conversely, the O-ring puts
a small amount of strain on the piezo tube in X-Y motion.

If the O-ring pushes too hard on the sample surface, features may appear squeezed in some areas of
the AFM image as the X-Y scan of the piezo tube is hampered by the O-ring. If the seal between the
O-ring and the sample surface is not tight, the fluid can leak out of the fluid cell. A balance must be
obtained to eliminate the compression of the features in the image without compromising the seal.

Once a stable configuration is obtained for the head/scanner assembly, withdraw the microscope
twice to raise the tip above the sample surface. Then insert the electrolyte, as described in Section
4.3.7.

4.3.7 Introducing Electrolyte

Inserting Liquid Electrolyte into the Fluid Cell

CAUTION: Before introducing electrolyte into the fluid cell, issues such as chemical
reactivity, concentration, and colloidal composition of the electrolyte should be
considered. These are discussed briefly in Chapter 2.

1. Make sure the Bipotentiostat/Galvanostat potential control switch is in the OFF position.

2. Introduce the liquid electrolyte into the fluid cell, using a syringe and tubing or any
customized fittings to suit the special needs of your experiments. Some users have
successfully attached a micropump to circulate liquids with small flow rates.

38 Digital Instruments Electrochemical SPM Rev. B


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

Adjusting the Photodiode Detector

Adjust the photodiode detector to the new optical path length traveled by the laser beam.

1. With no liquid in the cell, the laser beam reflecting off the cantilever strikes the air/glass
interface at a non-zero angle, i.e., the beam is not perpendicular to the interface. Once the
liquid is introduced into the cell, the laser beam now strikes a liquid/glass interface. The
reflected beam travels toward photodiode detector at a new angle. Therefore, the position of
the photodiode must be readjusted to locate the reflected beam back on the center of the
detector.

2. Because the angle of incidence of the laser beam going into the glass is zero (normal
incidence), you usually do not have to readjust the position of the laser beam on the
cantilever. When the beam enters the GP, it is perpendicular to the glass whether the
interface is air/glass or liquid glass.

3. Once the reflected laser beam is properly directed into the detector, engage the microscope
and adjust the scan parameters to obtain an image of the surface.

Clearing Contaminants and Bubbles

After introducing the electrolyte into the cell, if you cannot get good sum (A+B) and difference (A-
B) signals by adjusting the detector, a gas bubble or particulate contaminant may be blocking the
optical path of the laser beam. The presence of small bubbles can often be detected with an optical
microscope looking down into the head.

1. If a gas bubble or a particulate contaminant is trapped in contact with any part of the
cantilever, the optical path of the incident laser beam may be blocked or altered. Do not
adjust the position of the laser beam relative to the cantilever because the bubble or
contaminant may be pushed away, requiring yet another adjustment. Instead, clear any
contaminants and bubbles out of the path of the incident and the reflected laser beam before
proceeding.

2. Flowing liquid into and out of the cell repeatedly often clears contaminants and bubbles.
Sometimes it is helpful to increase the flow velocity to create a moderate jet of liquid through
the cell. Be very careful, however, for an excessively fast flow can jeopardize the integrity of
the fluid cell seal and cause leakage.

4.3.8 Using TappingMode

If you have a MultiMode TappingMode fluid cell, after engaging in contact mode, withdraw,
change operation mode to TappingMode, and engage in TappingMode.

Note: The electrochemical potential control of the cell cannot be realized with the
Veeco software-controlled Bipotentiostat/Galvanostat when operating the AFM
in TappingMode. An external Potentiostat is required and additional grounding
issues need to be addressed, but all electrical and fluid connections to the GP
may be left in place.

Rev. B Digital Instruments Electrochemical SPM 39


AFM Electrochemical Fluid Cell Setup and Operation
In Situ AFM Imaging

4.3.9 Connecting Electrodes to the Bipotentiostat/Galvanostat

1. Once the reflected laser beam is properly directed into the detector, engage the microscope
and adjust the scan parameters to obtain an image of the surface.

2. Connect the counter electrode and reference electrode to the Bipotentiostat/Galvanostat


using the cable assembly with the 9-pin connector at one end and clip-leads at the other:

a. Connect the 9-pin connector to the 9-pin socket on the small connector box mounted on
the side of the Bipotentiostat/Galvanostat.

b. Connect the orange lead of the cable assembly to the reference electrode and the purple
lead to the counter electrode (See Figure 4.3n).

Figure 4.3n Electrode-lead Connections

CE

Purple lead

RE
Orange
lead

40 Digital Instruments Electrochemical SPM Rev. B


Chapter 5 STM Electrochemical Setup
and Operation

5.1 Handling the Fluid Cell


Cleanliness is important when preparing and working with the fluid cell. Wear fresh, clean
laboratory gloves when handling pieces of the fluid cell and the sample. Electrochemical
experiments are extremely susceptible to even small amounts of contaminants.

You can immerse pieces of the fluid cell in deionized water in a container, then clean in an
ultrasonic bath.

5.2 Cleaning Electrodes


Thoroughly clean the electrode wires. If you are using a platinum wire, a hydrogen (no oxygen
mixed) flame does an excellent job of cleaning the electrode. Otherwise, use fine sandpaper to
remove metal oxide from the surface and clean with isopropyl alcohol and a lint-free cleanroom
paper. Finish with a long rinse in deionized water.

5.3 STM Imaging in an Electrolyte

5.3.1 Preparing the STM Fluid Cell

ECM Fluid Cell

To assemble the fluid cell for model ECM, place the sample and elements of the fluid cell (supplied
with the electrochemistry kit) together as shown in Figure 5.3a.

Rev. B Digital Instruments Electrochemical SPM 41


STM Electrochemical Setup and Operation
STM Imaging in an Electrolyte

Figure 5.3a ECM Fluid Cell Assembly

Reference Electrode

Top Piece Counter Electrode


(Material: KelF)

Reference Electrode Contact

Counter Electrode Contact

O Ring
Sample (Working Electrode)
Invar Stage

Screws

Assembled Cell

STM Fluid Cell for the MMAFM-EC

The MultiMode uses an STM fluid cell that rests on top of the piezoelectric scanner. Assemble the
STM fluid cell for the MultiMode as depicted in Figure 5.3b.

Figure 5.3b STM Fluid Cell, model MMTVFC, for MultiMode

Top Piece
(material: KelF)

O-ring
Sample

Steel Plate

Screws

42 Digital Instruments Electrochemical SPM Rev. B


STM Electrochemical Setup and Operation
STM Imaging in an Electrolyte

STM Fluid Cell MMTVFC for the MMAFM-EC

Model MMTVFC fluid cell has been superseded by model MMTVFC2 fluid cell, shown in Figure
5.3c. The following improvements have been incorporated into this design:

The cell top is made of Teflon, chemists favorite material that is compatible with nearly
all chemicals and is suitable for critical cleaning, e.g. in hot acid

A ridge machined on the cell top replaces the O-rings used in the model MMTVFC fluid
cell. This simplifies assembly and eliminates possible contamination from the O-rings.

Normally, two (rather than three) screws are used to hold the cell-top, sample and cell
bottom together, therefore accommodating larger samples than the earlier model
MMTVFC

Note: The sample should not be smaller than 9.8 mm square or diameter. The
maximum sample size is 12 mm by 16 mm.

Note: This design is meant to get users started. For specific samples, customers may
need to design unique cells.

Figure 5.3c The MultiMode STM Fluid Cell, model MMTVFC2, exploded (left) and assembled (right).

Rev. B Digital Instruments Electrochemical SPM 43


STM Electrochemical Setup and Operation
STM Imaging in an Electrolyte

Conductivity of Working Electrode

Place the sample on the steel plate (invar stage). The sample must be either conductive or
semiconducting. The setup must provide a conductive path from the top surface of the sample
(exposed to the electrolyte) to the steel plate. If the bulk of the sample is not conductive, use silver
epoxy, another conductive adhesive, or a metal clip to provide the electrical connection, but this
connection should be made outside the O-ring so that it does not become a participant in the
electrochemical reactions in the electrolyte. Whatever method you use to create the conductive
path, there should be no more than 10 ohms resistance between the sample surface and the steel
plate or invar stage on which the sample rests.

Assembling Fluid Cell Model MMTVFC

Place the KelF top piece on the sample so that the O-ring covers the central area of the sample. To
reduce the possibility of a leaky cell, ensure that the O-ring does not rest on the sample surface
where there are noticeable bumps or scratches, and do not place the O-ring too close to an edge of
the sample.

1. Keep the O-ring level as you tighten the assembling screws which hold the cell together. The
screws must be tight, but excessive torque may cause thread damage in the KelF and /or an
undesired bending of the KelF fluid cell, possibly causing leakage.

Assembling Fluid Cell Model MMTVFC2

1. Align the cell bottom, sample and cell top so you can put two screws through two diagonal
threaded holes to sandwich the sample.

2. Tighten the two screws (shown as 1&2) evenly. Do not over-tighten, otherwise the threads in
the Teflon top could be damaged.

3. Loosen the screws slightly to release the stress built up on the sample. This diminishes one of
the major causes of drift.

4. If the sample bottom is not conducting (for instance, gold film on mica), an electrical
connection has to be made from the top surface to the cell bottom. Use the 3rd screw (shown
as screw3) to press down a piece of aluminum foil onto the top surface, and wrap the
aluminum foil to contact the cell bottom.

Note: The connection for the bias or working electrode is made through the scanner
top.

5. Fill the cell with the liquid to be used. Watch for leakage. If leakage is observed, tighten the
cell further. Do not overfill the cell, usually fill to less than half of the cell volume.

6. It is easier to adjust the tip-sample separation before filling the cell. Check for leakage after
filling. Leakage may destroy the scanner due to the high voltage applied for scanning;

44 Digital Instruments Electrochemical SPM Rev. B


STM Electrochemical Setup and Operation
STM Imaging in an Electrolyte

CAUTION: If leakage is seen during imaging, stop immediately. Use KimWipes to clean and
dry the scanner.

5.3.2 Checking the Integrity of Fluid Cell Seal - Model MMTVFC

Introduce a few drops of the electrolyte into the cell and monitor the cell for a minute or two. If the
cell is leaking, wick off the electrolyte from the cell using a piece of low-lint paper or lint-free
cleanroom wipes.

1. If the cell is leaky, visually examine it for the cause. If you can identify a problem, try to
solve it by adjusting the assembling screw pressure or repositioning the sample underneath
the O-ring. Sometimes rough sample topography compromises the O-rings seal; this
requires repositioning the sample with the smoothest parts in contact with the O-ring, or a
little extra tightening of the screws.

2. If you cannot identify the cause of leakage through visual examination, loosen the screws,
clean the sample surface and the O-ring, and reassemble the cell.

3. If leaking persists, consider the composition of the electrolyte (see Section 6.1.3).

Note: The remainder of this chapter describes a step-by-step method to enable you to
image with STM with a coated tip in a liquid electrolyte. This sequence of steps
has proven efficient in reducing chances of crashing the tip into the surface or
scratching the surface with a tip that is fully coated and cannot conduct a
tunneling current.

5.3.3 Imaging Dry with a Bare Tip

Once a leak-free cell is assembled, start with a dry sample surface, and place the fluid cell in its
place on the microscope.

Model ECM

1. Slide the fluid cell in place on the sample stage, and connect clip-lead wires to electrode
screws (orange wire for RE, purple wire for CE). See Figure 5.3d.

2. Turn the hardware potential control switch on the Bipotentiostat/Galvanostat to the OFF
position.

Rev. B Digital Instruments Electrochemical SPM 45


STM Electrochemical Setup and Operation
STM Imaging in an Electrolyte

Figure 5.3d Assembled ECM Fluid Cell (with Electrode Wires Clipped on)
Being Placed on Sample Stage

Purple lead to Orange lead to


Counter Electrode Reference Electrode
(CE) (RE)

Model MMAFM

1. Place the assembled fluid cell on top of the scanner as shown in Figure 5.3e. The clip-lead
assembly is not yet needed as the CE and RE are not yet in place.

2. Turn the hardware potential control switch on the Bipotentiostat/Galvanostat to the OFF
position.

Figure 5.3e Assembled ECSTM on MultiMode Scanner and Base.

46 Digital Instruments Electrochemical SPM Rev. B


STM Electrochemical Setup and Operation
STM Imaging in an Electrolyte

MultiMode Users Only

On the MMAFM-EC Bipotentiostat/Galvanostat, three switches control electrochemical operation


of the microscope. The top switch turns the EC cell ON and OFF (this switch works together with a
software switch which is in the Electrode Potential Controls window); the middle switch selects
AFM or STM operation, and the bottom switch selects GAIN of the current-to-voltage converter,
which monitors electrochemical cell current. The three different gain settings (10, 100, 1000 A/V)
correspond to three current ranges: 100, 1000, 10,000 A. A software parameter needs to be set to
the appropriate gain, as described below.

Set the switches as follows:

1. On the MultiMode base, set the microscope mode control switch to STM.

2. On the Bipotentiostat/Galvanostat, set the AFM/STM function switch to STM.

3. Set the gain of the current-to-voltage converter on the Bipotentiostat/Galvanostat to a value


appropriate to your EC experiment (10, 100, or 1000 A/V).

4. Set the software parameter as follows:

a. From the real-time menu, click on Microscope / Calibrate/ Detector. A dialog box
appears entitled Detector Calibration.

b. In the Detector Calibration dialog box, set the sensitivity of Auxiliary input channel A
(Aux A sens) to the same value as that you selected on the GAIN switch on the
Bipotentiostat/Galvanostat (10, 100, or 1000 A/V).

All Users

1. Place a bare (un-coated) STM tip in the tip holder on the microscope head.

There are three versions of the STM heads for MMAFM. They are all called TipView head.

a. In older models of the TipView head (See Figure 3.3b-C), insert the STM tip some 3
mm, then kink the STM tip slightly and insert an additional 3 mm (or more, depending
on the length of the STM tip). The kink holds the tip in place.

b. In newer models of the TipView head (See Figure 3.3b-B), the tipholder is slightly bent
so there is no need to kink the tip.

2. Lower the head towards the sample, ensuring that the tip clears the sample surface when the
head is resting on the sample stage in model ECM or on the scanner in model MMAFM.

Note: When holding the tip with tweezers, do not hold by the coated part, or the
coating may crack.

Rev. B Digital Instruments Electrochemical SPM 47


STM Electrochemical Setup and Operation
STM Imaging in an Electrolyte

Note: Make sure the tip is lower than the counter electrode (CE) and reference
electrode (RE), so the CE and RE do not contact the surface before the tip does.
This does not apply to open circuit conditions where the CE and the RE are not
used

Note: The liquid level should be lower than the uncoated part of the tip

3. Connect the STM head to the 9-pin connector on the microscope base.

4. Connect the clip-lead assembly (orange and purple wires) to the male 9-pin connector on the
microscope base (on the Bipotentiostat/Galvanostat for model MMAFM).

5. Connect the microscope base (the Bipotentiostat/Galvanostat for model MMAFM) to the
NanoScope controller.

6. In MMAFM, connect the microscope base to the Bipotentiostat/Galvanostat using the short
25-pin ribbon cable.

7. Connect the NanoScope controller to the computer.

Leveling the Head - Necessary for Model ECM, Good Practice for MultiMode STM

It is important that the head is level in model ECM. A significant tilt can distort the image as well as
limit tip access to the sample in the vertical, Z-direction.

With the TipView head of the MultiMode, the sample is raster-scanned beneath the tip, and a tilted
scanning head is less of a problem than it is in ECM.

1. Using the screws on the sample stage of the ECM (or on the bottom of the MMAFM
scanner), lower the head (and thus the tip) toward the sample surface in such a way that the
microscope head is level left-to-right.

a. In model ECM you must turn all three screws manually, because the stepper motor does
not have a hardware switch to turn it. The ECM head starts out with the rear slightly
lower than the front, and in the final pre-engage configuration, the rear raises in order to
lower the tip, which is in the front, towards the sample surface.

b. In model MMAFM-EC, the TipView head is slightly tilted with the rear slightly raised
prior to the final engage command. In the final approach, the rear (motor-driven) screw
is lowered in order to lower the TipView head and engage the microscope.

c. In model MMAFM-EC with a standard scanner, use the two manual screws and the
stepper motor hardware switch to adjust the tilt of the head. There is no leveling
problem in model MMAFM-EC using a vertical engage scanner, because a single
motor-driven screw lowers and raises the head, keeping it parallel to the base of the
microscope. With the TipView head of the MultiMode, the sample is raster-scanned
beneath the tip, and a tilted scanning head is not an issue.

2. Engage the microscope with a small Scan size (e.g., 100 nm) and ensure you have a properly
engaged head.

48 Digital Instruments Electrochemical SPM Rev. B


STM Electrochemical Setup and Operation
STM Imaging in an Electrolyte

3. Examine the head from the side and from the front. If the head is not leveled, withdraw the
microscope and adjust the position of the three screws that determine the height and
orientation of the head. Reengage and reexamine the head. Repeat this until you are satisfied
the head is leveled.

Note: (For model ECM only) The ultimate test of head levelness in ECM is scanning
in height mode (constant-current mode) on a flat, smooth sample over a large
scan area and setting the Real-time planefit parameter to Offset. Use a small
Scan rate (e.g., <1Hz) to avoid damaging the tip.

Note: In this mode if there is a significant tilt in the head, you see it in the height
image. You can test the levelness in the Y-direction by setting the Scan angle to
90 degrees, making the microscope scan fast in the Y-direction, and you do not
have to wait for a whole image to be scanned to determine any tilt in the Y-
direction. If the slow scan Real-time Planefit parameter is set to Line, the tilt
in Y-direction is not depicted in the real-time image. Note also that this test on a
rough sample can damage the tip, especially at high scan rates.

CAUTION: If atomic resolution is important to your experiment, do not use this test with the
same tip you plan on using for atomic resolution.

4. Reduce the Scan size (e.g., 10 nm) and try to achieve atomic resolution if the surface is
atomically flat. Optimize scanning parameters to obtain a stable image and increase the Scan
size.

5. Obtain a stable image and withdraw the microscope three or four times. This raises the tip
20-40 microns above the sample surface.

Mounting Electrodes

1. Take the head off the microscope carefully, ensuring that the tip does not contact anything.

Note: If the tip comes in contact with an object, put the head back, reengage the
microscope, and examine the quality of the image. If the tip picked up debris, or
was damaged, or lost its sharpness, change the tip. Even if the apex did not
contact an object, the tip may have been bent as a result of contact. Since this
changes the separation between tip and sample surface, it is a good idea to
reengage and withdraw a couple of times to have the tip raised a known amount
above the sample surface.

2. In model MMAFM, mount the counter and reference electrodes, as shown in Figure 5.3f and
Figure 5.3g.

Rev. B Digital Instruments Electrochemical SPM 49


STM Electrochemical Setup and Operation
STM Imaging in an Electrolyte

Figure 5.3f Counter and Reference Electrodes Mounted on the TipView Head
and Connected to the Clip-Leads

3. Mount these electrodes so that when you put the head back on the scanner, you can bend the
electrodes so that they both reach deep into the cell, but none must contact the working
electrode (sample). Use the two Teflon screws to anchor (tighten) the electrodes to the body
of the TipView head (see Figure 5.3g).

Figure 5.3g MMAFM Fluid Cell for STM and TipView Head with Electrodes
in Place and Assembled on the Scanner

Teflon screw

Note: Electrochemical reactions depend on the geometry and the relative positioning
of the electrodes. You can have as much of each electrode in the cell as you
wish, and in any geometric configuration, as long as none interferes with the
operation of the STM tip or contacts the sample.

4. Connect the reference and counter electrodes to orange and purple clip-leads, respectively.
The clip-lead assembly should be connected to the Bipotentiostat/Galvanostat. Make sure the
hardware potential control switch on the Potentiostat is in the OFF position.

50 Digital Instruments Electrochemical SPM Rev. B


STM Electrochemical Setup and Operation
STM Imaging in an Electrolyte

5.3.4 Insulating the STM Tip

For STM imaging in an electrolyte, the lower portion of the STM tip must be coated with an
insulating material. Some coating processes require melting the insulating material onto the tip,
which may expose the tip, piezoelectric tube, and other parts of the microscope head to heat.
Images obtained immediately after coating the tip may show noticeable thermal drift, which
subsides with time.

Two commonly used coating materials are hot-melt glue (usually a polyethylene-based glue) and
apiezon wax. Hot-melt glue insulates tips well in most electrolytes. Veecos EC kit contains a
supply of hot-melt glue and apiezon wax. If the electrolyte reacts with hot-melt glue, use apiezon
wax.

Coating the Tip: Method 1

You need a glue gun and a heat gun (or blow dryer with hot air blowing capability).

1. Use glue gun to melt the glue.

2. Insert the tip into the melted glue and then pull away. Wait a few seconds for the glue to cool
and become fixed.

3. Very briefly (1-2 seconds) expose the end of the tip to a stream of hot air (from heat gun or
blow dryer). Hold the head so that the tip is pointing straight down vertically when you do
the brief exposure to heat. This will expose the tip apex.

Coating the Tip: Method 2

1. Strip a piece of very clean wire, which might consist of several threads, and cut a 5 cm piece
off of a thin thread. This piece is used to apply melted glue to the STM tip, so it is best if this
thread is much thinner than the STM tip.

2. Turn on the heat gun or glue gun and position it safely so that you can easily bring the tip to
the stream of hot air, preferably without having to handle the gun.

3. With the head removed from the microscope, use a clean pair of tweezers to place a small
amount (about the volume of the STM tip protruding from the tipholder) of hot-melt glue on
the shaft of the tip, halfway up from the tip apex toward the tipholder. If the piece keeps
falling off the tip, keep trying with fresh pieces of glue. Do not put contaminated glue on the
tip.

4. Pick up the thin thread wire in one hand and with the other hand bring the microscope head
close to the heat gun, exposing the tip to hot air and melting the glue onto the tip.
Immediately use the thin wire to drag the melted glue around the shaft and down toward the
tip apex. Then pull straight away from the tip apex as you remove the head away from the
heat so that a thin string of melted glue extends from the tip to the thin wire. Do not break the
string by pulling on it. In a few seconds, the glue will cool and solidify on the tip.

Rev. B Digital Instruments Electrochemical SPM 51


STM Electrochemical Setup and Operation
STM Imaging in an Electrolyte

5. The tip is now coated, and must be exposed at the apex for imaging. Bring the tip into the
stream of hot air for a very brief period (one second is often enough) then remove it from the
heat. The string of glue quickly melts, and the apex of the tip is exposed as the glue briefly
flows and pulls back from the apex.

CAUTION: If with the naked eye you can see an exposed portion of the tip, you probably
exposed the apex to the heat for too long a period (more than two seconds is
almost always too long). Too long an exposure to heat often causes a major
problem laterlarge Faradic currents through the tip in electrolyte.

Coating the Tip: Method 3

For STM to work in liquid, especially electrolyte solutions, the tip has to be isolated (except the
very end of the tip) so as to reduce the area exposed to the solution to suppress leakage current,
which would otherwise overwhelm the tunneling current signal and make STM imaging in solution
impossible. Equally important, albeit less critical, SECPM tips have to be coated for better
performance. A variety of materials and methods have been used for tip coating; the method of
using Apiezon Wax-Naphtha mix is by far the simplest of its kind and is best suitable for use in
aqueous solution.

The Mix

The mix contains, by weight, 50:50 of Apiezon Wax (Apiezon Wax W, Kurt J. Lesker Company)
and Naphtha (VM&P Naphtha Klean Strip, VM-46), Apiezon wax is first ground, then dissolved in
Naphtha and stirred overnight to make a viscous, uniform mix.

CAUTION: Take the same precautions as for naphtha. Please read the MSDS of both
Apiezon Wax and Naphtha. Dont use near an open flame, and dont inhale. Use
in a chemical hood whenever possible.

DANGER: Severe Fire and Explosion Hazard


Flammable liquid
Do not store near flames or elevated temperatures
Dispose in accordance with applicable local, state, and federal regulations

DANGER: Acute Inhalation Hazard


May cause dizziness, headache, nausea, and watering of eyes
Severe overexposure may cause irritation of respiratory tract, drowsiness, and
unconsciousness
Use only with adequate ventilation under engineered air control system designed
to provide maximum protection

52 Digital Instruments Electrochemical SPM Rev. B


STM Electrochemical Setup and Operation
STM Imaging in an Electrolyte

DANGER: Harmful or Fatal if Swallowed


May cause gastrointestinal irritation, nausea, vomiting, an diarrhea

WARNING: Avoid Contact with Skin


May cause skin irritation upon prolonged or repeated contact
Use impermeable gloves

CAUTION: Avoid Contact with Eyes


May cause eye irritation
Use ANSI approved chemical work goggles or full length face shield

Tip Coating Procedure

1. Dip the tip into the Mix by 3-4mm, pull straight out slowly (so it does not drag a big drop of
wax) and wait for a few minutes to let air-dry.

2. One dipping-pulling-drying cycle usually will coat the tip to a leakage current of a few
nanoamperes. More cycles will bring the leakage current further down; picoamperes leakage
can usually be reached within 2-4 cycles.

3. The leakage current can be checked using NanoScope STM

Start the NanoScope software, go to Real-time window, select STM or MMSTM,


under Menu Item MICROSCOPE, click OFFSET.

Mount the tip into the STM holder.

Read the offset in air.

Read the offset in the liquid to be used.

Note: The leakage current varies with different solutions, bias voltage and potential of
the sample when under electrochemical control.

The difference between the above two readings is the leakage current of the tip.

4. If the leakage current is still too big for use, rinse and re-coat the tip as necessary.

5. Keep the tip and let it air-dry for several hours before use.

Note: Although mechanically cut tips (Pt-Ir) may be coated and work in liquid,
electrochemically etched tips are almost always better for coating due to the
usually favorable conic geometry and smoother surface.

Figure 5.3h shows an example of tips coated using this procedure.

Rev. B Digital Instruments Electrochemical SPM 53


STM Electrochemical Setup and Operation
STM Imaging in an Electrolyte

Figure 5.3h Electrochemically Etched Platinum-Iridium Tip Dip-Coated with Apiezon Wax

5.3.5 Imaging Dry with an Insulated Tip

1. Place the head back on the microscope carefully and set the Scan size to a small value (e.g.,
10 nm).

2. Engage the microscope.

If the head lowers much more than the amount it was raised by successive withdrawals
at the end of leveling the head segment in Section 5.3.3, the tip may still be insulated
at the apex and tunneling is not possible. Withdraw several times, then re-expose the
apex to heat for a very brief period and engage the microscope once more.

CAUTION: The tip or sample may already have been damaged.

3. Once engaged, optimize the scan parameters. Increase Scan size gradually and optimize the
parameters accordingly. Obtain a stable image and withdraw twice so as to raise the top from
the sample surface about 20 microns.

4. Remove the microscope head to fully expose the fluid cell for easy introduction of
electrolyte. Removing the head prior to introducing the electrolyte into the fluid cell also
reduces the chances of getting electrolyte on the scanner in model ECM.

5.3.6 Introduce Electrolyte into the Fluid Cell

1. With the head removed, use a syringe or a pipet to drop electrolyte into the fluid cell. In
model ECM, make sure the reference and counter electrodes are partially submerged inside
the electrolyte by realigning them if necessary.

2. Place the head back on the microscope carefully so that the tip does not touch anything in
transit. In a MMAFM ensure the counter and reference electrodes are partially submerged in
the electrolyte, then adjust them if necessary without touching any part of the STM tip.
Secure the TipView head on the MMAFM with springs. You are now ready to engage and
image in the electrolyte.

54 Digital Instruments Electrochemical SPM Rev. B


Chapter 6 Troubleshooting Common to
ECAFM and ECSTM

6.1 General ECSPM Considerations

6.1.1 Improper Electrical Connections

Poor or improper electrical connections between various elements of the ECSPM will cause
malfunctions. Check all electrical connections and settings whenever a problem arises which might
have its root in the electrical wiring and switches.

Connections include those between:

the Potentiostat/Galvanostat and the microscope base

the microscope base and the controller

the electrodes and the clip-leads

the Potentiostat/Galvanostat and the clip-lead assembly

the microscope head and/or scanner and the microscope base

Setups include the AFM/STM and Gain selection switches on the MMAFM and the cell potential
ON/OFF switch on the Potentiostat/Galvanostat on all models.

6.1.2 Liquids and Scanners

The elements of the SPM near the fluid cell are not waterproof. They are water resistant, meaning
they are designed to withstand the presence of water on them for short periods of time. Leaks of
electrolyte must be dried and cleaned as soon as possible after they are detected. The piezoelectric
scanners are particularly susceptible to leaks. They need to be dried and cleaned anytime there is a
leak or a suspected leak near them.

Rev. B Digital Instruments Electrochemical SPM 55


Troubleshooting Common to ECAFM and ECSTM
General ECSPM Considerations

6.1.3 Persistent Leaks

If you encounter persistent leaking of electrolyte from the fluid cell, consider the composition of
the electrolyte. Low surface tension of the electrolyte may be the main cause. If possible, eliminate
from the electrolyte any surfactants and other components having very low surface tension. If such
components are essential to the composition of the electrolyte, try applying a small amount of high
vacuum grease to a clean O-ring, and restart with a clean sample surface and clean cell. We
recommend Dow Corning High Vacuum Grease (Dow Corning Corp., Midland, Michigan, U.S.A.),
which contains silica, amorphous, fumed, and polydimethylsiloxane.

6.1.4 Chemical Reactivity and the Fluid Cell

The elements of the fluid cell are not chemically inert. Strong acids and bases react with the surface
in the fluid cell. It is important to keep the concentration of reactants in electrolytes low. Special
caution should be taken for concentrations above 0.2 mol. If you are not sure about the chemical
compatibility of the GP, of the AFM fluid cell, or the KelF piece of the STM fluid cell with an
electrolyte, drop a small amount of the electrolyte on a side of the GP away from the fluid cell area
and monitor reactivity equal to the expected period of time the electrolyte is to remain in contact
with the fluid cell. Keep in mind that the bottom surface of the AFM fluid cell is coated with a thin
film of nonreflective material. Call Veeco if you are uncertain of chemical compatibility between
fluid cell and electrolyte.

6.1.5 Colloidal Electrolytes

The colloidal composition of an electrolyte may affect the reflected laser beam in AFM by diffusing
the beam and possibly blocking a large fraction of the beam, which is supposed to reach the
detector. Large colloidal particles can also stick to the cantilever and tip, altering the optical path
length and tip-sample interaction.

In some cases even with electrolytes which are chemically compatible with a fluid cell, large
concentrations of the solute may cause problems, including solidification of solute on the AFM
cantilever or the STM tip, deposition of solids onto the GP in the AFM, and unwanted crystal
formation on all three (working, reference, and counter) electrodes in both AFM and STM.

56 Digital Instruments Electrochemical SPM Rev. B


Troubleshooting Common to ECAFM and ECSTM
EC-Specific Problems

6.2 EC-Specific Problems

6.2.1 Unexpected and Transient Peaks in Voltammogram

The presence of impurities and contaminants in the fluid cell is the most detrimental factor affecting
SPM in an electrolyte with cell potential control. In AFM, where the fluid cell allows for electrolyte
circulation through the tubing, the cleanliness of the tubes and the syringes is just as important as
that of the elements of the fluid cell. The presence of contaminants can lead to noise and to
anomalous and transient peaks in the voltammogram.

6.2.2 Excessive Deposition of Solids on Sample

If not monitored well, continuous cathodic currents may deposit a thick layer of solid on the
sample. If the deposition rate is high enough, the deposited layer may become so thick that the Z-
piezo retracts to its limit. The feedback mechanism and the Z-piezo can then no longer compensate
for further growth of the deposited layer, and the SPM probe is pushed into the sample.

In such cases the Z-center position indicator on the image monitor drifts up, indicating that the
piezo is retracting. If not compensated for, the Z-center position indicator drifts all the way to the
top of its range, and the word limit appears in red letters next to it. You can use motor/step
motor/tip up to raise the probe, thus bringing the Z-center position close to center (0V). Damage
to an STM tip is usually worse than to an AFM tip.

6.2.3 Deposition Not Imaged by SPM Probe

Sometimes the voltammogram indicates reduction taking place, but nothing is deposited where the
SPM probe is scanning. This usually occurs when most of the deposition on the sample is taking
place near the counter electrode and away from the SPM probe. Another possible cause is the tip-
shielding effect (see Section 6.2). Mounting the counter electrode closer to the scan area helps you
have a better chance to image where some deposition is taking place on the sample surface.

This can also occur because reduced species are being deposited in the scan area, but they are so
loosely bound to the sample surface that the AFM cantilever force is great enough to push aside the
deposited material.

In STM operation if the deposited material is not conductive enough, an STM tip tries to push
through it to reach the conducting substrate underneath. In this case the image might look very
noisy because the tunneling current is not always maintained.

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Troubleshooting Common to ECAFM and ECSTM
EC-Specific Problems

6.2.4 Voltammogram Shows Jumpiness in Cell Current

First check that all electrodes are making contact with the electrolyte in the cell. A common STM
problem is the evaporation over time of some electrolytes in the open fluid cell. Also,
electrochemical current running through electrolytes can cause decomposition and accelerate
evaporation of liquid.

Next check that the reference and/or counter electrodes are not covered by solids or have not
oxidized during the electrochemical reaction to the point that the electrode exposed to the
electrolyte has significantly changed its properties. In this case try cleaning and refurbishing the
electrodes, or simply replace them with new electrode wires. Platinum wire may be cleaned
extremely well in an oxygen-free hydrogen flame. Also, check that the reference, counter, and
working electrodes are not touching each other.

58 Digital Instruments Electrochemical SPM Rev. B


Troubleshooting Common to ECAFM and ECSTM
Testing/Troubleshooting the Potentiostat/Galvanostat

6.3 Testing/Troubleshooting the Potentiostat/Galvanostat


A simple way to test whether the Potentiostat/Galvanostat functions properly uses a dummy cell.

Set up the Microscope as follows (Figure 6.3a):

1. Place the SPM base atop the potentiostat/galvanostat. Align vertically, with the DVM display
directly over that of the potentiostat/galvanostat below. The bases three steel balls align with
three magnets embedded in the top ring of the potentiostat.

2. Connect the potentiostat to the SPM base by using the short ribbon cable having a male, 25-
pin, D-type connector at one end and a female 25- pin D-type connector at the other end. The
mating connectors are located on the left side of the microscope when viewed from the front.

3. Use the 9-pin, micro-D extension cable to connect the scanner into the 9- pin, socket on the
potentiostat

4. Connect the ECSPM to the NanoScope controller by using the 5-foot ribbon cable. Mate the
end of the cable having the 25-pin connector to the potentiostat, and the other end having the
37-pin connector to the front panel of the controller.

5. Using the GAIN switch on the potentiostat, select the gain as appropriate

6. Start the EC version of the software; any ECSPM can be selected for the dummy cell test.

7. Use the MICROSCOPE / CALIBRATE / DETECTOR command to set the sensitivity of the
Auxiliary input channel A (Aux A Sens.) to the value selected in step #5 above.

8. Connect RE (orange) and CE (purple) of the cell connector to one end of a 10k resistor, and
connect the scanner cap (WE) to the other end of the resistor, dont short the scanner cap to
the scanner shell.

9. Turn on the cell using the mechanical and software switches.

Note: The software switch might be disabled when configured for SECPM.

10. Start the Nanoscope Software, run CV (cyclic voltametry, Chapter 7).

11. A linear CV means the Potentiostat works properly. If there is no current, make sure the cell
is ON, and the connections to CE and WE are solid. If the Potential jumps around, check the
connection to RE.

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Troubleshooting Common to ECAFM and ECSTM
Testing/Troubleshooting the Potentiostat/Galvanostat

Figure 6.3a Dummy cell set-up for testing the Potentiostat/Galvanostat

Resistor

Cell Connectors Scanner

Scanner Extension Cable

Microscope Base

Ribbon Cable
Potentiostat/
Galvanostat

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Chapter 7 Real-time Software and
Voltametry Controls for EC

7.1 Introduction
The ECSPM software has a Real-time scanning and data collection mode, and an Off-line data
analysis and display mode. Both the Real-time and Off-line modes provide several pull-down
command menus.

The Real-time command menus contain the commands which allow the microscope to be set up
and data to be collected. Commands in the Real-time menus control the operation of the
microscope.

Commands in the Off-line menu control the handling, processing, and analysis of the collected
data. See Chapter 8 for a description of the Off-line commands.

7.2 Real-time ECAFM and ECSTM Control Panels


This chapter discusses ECAFM and ECSTM. SECPM is discussed in Chapter 9.

Upon starting the NanoScope software, youll see the following window (see Figure 7.2a):

Figure 7.2a NanoScope Control Window

Clicking the di logo, youll see a pull-down menu (See Figure 7.2b).

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Real-time Software and Voltametry Controls for EC
Real-time ECAFM and ECSTM Control Panels

Figure 7.2b Select Microscope Select

If you are going to do image/data analysis, you can select Off-line from this menu and go to
Chapter 8 of this manual to see the description of Off-line software parameters. You can select Off-
line also by clicking on its icon, which is under the di logo and to the right.

If you are going to image and collect data with your EC-SPM, that is, if you are going to run the
Real-time software, first, you need to ensure you have the proper microscope selected. Click
Microscope Select. The following dialog box appears (see Figure 7.2c).

Figure 7.2c Microscope Select Dialog Box

In the dialog box, choose the electrochemical SPM you are going to run, and click OK. Depending
on what microscopes you own and have configured for your NanoScope control station, you may
see any of the choices shown here, as well as others that are not shown here; e.g., MMAFM,
Dimension, BioScope, etc. Once you make the choice, the control station updates the software to
run the microscope you selected. (For additional information on the options in this dialog box,
reference the SPM Command Reference Manual.

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Real-time Software and Voltametry Controls for EC
Real-time ECAFM and ECSTM Control Panels

The Real-time software environment can be invoked by either choosing Real-time from the pull-
down menu under the di logo (see Figure 7.2b) or by clicking the icon that has a picture of a
microscope on it (see Figure 7.2b). The Real-time software environment looks like this:

Figure 7.2d Real-time Environment

On the bottom-left corner of this window, youll see which microscope is selected; here, it is EC
MMSTM, which stands for Electrochemical MultiMode STM.

The Potentio pull-down item in this environment is the only one that is entirely specific to
electrochemical SPM. But there are other items that are also specific to electrochemical SPM, and
are under Microscope and Panels pull-down items.

Description of individual Real-time software parameters for electrochemical SPM follows.

Microscope

Figure 7.2e Microscope/Calibrate/Detector

Figure 7.2e Microscope / Calibrate / Detector

The Detector Calibration dialog box appears.

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Real-time Software and Voltametry Controls for EC
Real-time ECAFM and ECSTM Control Panels

Figure 7.2f Detector Calibration Dialog Box

Serial number refers to the scanner you are using; here, it is a J scanner for a MultiMode AFM.
The two electrochemistry-specific parameters in this dialog box are:

E Sens.

This parameter should be set to 0.25 V/V for all electrochemistry SPMs, with the very few
exceptions of those model ECMs that date back to 1991-1992. If you are unsure, please call Veeco
for help.

Figure 7.2g Detector / Calibration Dialog Box: E-sens

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Real-time Software and Voltametry Controls for EC
Real-time ECAFM and ECSTM Control Panels

I cell Sens.

This parameter is used, together with a hardware switch, to set the gain of the current-to-voltage
converter that converts electrochemical cell current to voltage. Even though the software allows
typing in many values for this parameter, there are only three acceptable gain settings: 10A/Volts,
100A/Volts, and 1000A/Volts. On the MultiMode SPMs bi-potentiostat/galvanostat, there is a
hardware switch that must be set to the same value as selected here in the software (see Figure
7.2h), otherwise the electrochemical cell current data will be recorded incorrectly. On other SPM
models, namely, ECM, AFM, and LFM, there is no hardware switch, but there is a jumper that
serves the same purpose. That jumper is in the base of the microscope for model ECM and in the
bipotentiostat/galvanostat for models AFM and LFM.

All other parameters in the Detector Calibration box should be set as seen in Figure 7.2h.
Figure 7.2h Detector / Calibration Dialog Box: I cell Sens

Microscope/Leakage (for model ECM only)

This is not a parameter. It is a testing tool that is used only when the model ECM microscope is not
engaged. In the scanners for model ECM, the STM tip is in close proximity to one of the Y-
piezoelectric elements of the scanner tube. Even though the tip is supposed to be electrically
isolated from this piezoelectric element, sometimes the quality of the insulation is compromised.
This may happen, for example, with long term exposure to high humidity and reactive chemicals.
As a result, when a voltage is applied to the scanner, i.e., during STM imaging, the voltage can
induce an unwanted current through the STM tip.

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Real-time Software and Voltametry Controls for EC
Real-time ECAFM and ECSTM Control Panels

Figure 7.2i Microscope / Leakage

When Microscope/leakage is invoked, the controller applies a high voltage to the Y-piezoelectric
element and measures the current through the STM tip holder. This measurement is done
repeatedly (Passessee dialog box below) and the value of the measured current is updated with
each pass until you click on Quit.

Figure 7.2j Head Leakage Test Dialog Box

The value of this leakage current should be near zero. If this value is comparable to or larger than
the STM setpoint current, then the STM images will be affected adversely, or in some cases, the
microscope will false-engage. If this happens, place the scanner in a dry environment for a while
and redo the test. Also, you can use a cotton swab and alcohol to clean the area around the tip
holder and where the tip holder attaches to the piezoelectric scanner (do not use other chemicals to
clean this area). If the problem persists, the scanner needs to be sent back for repair.

There is a section on this feature in your SPMs Command Reference Manual. Read that short
section; it has more useful information that is relevant to electrochemistry applications as well, but
which is not duplicated here.

Microscope/Offset (STM only)

This is not a parameter. It is a testing tool that is used when the microscope is not engaged. For
regular STM, that is, STM without electrochemistry, it is used for adjusting the offset current on the
STM head preamplifier. So, when you invoke this, a dialog box appears and instructs you to
Adjust head offset which is not related to electrochemistry (See your SPM Command Reference
Manual for more detail on this.)

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Real-time Software and Voltametry Controls for EC
Real-time ECAFM and ECSTM Control Panels

Figure 7.2k Microscope / Offset

Figure 7.2l Head Offset Calibration Dialog Box

But you can also use this to test, on all STMs not just model ECM the quality of the coating of
the STM tip when STM is performed in liquid. Once the coated tip is mounted in the tip holder,
place the microscope head on the microscope base (model ECM) or the tip-view STM head on the
microscope scanner (Models MMAFM, AFM, LFM) as if you are going to engage and image with
STM, but do not engage the microscope. Instead, first make sure the STM tip is in the electrolyte
and then invoke Microscope/Offset to measure the current through the STM tip.

If this measured current is comparable with the STM setpoint current, then the STM images will be
adversely affected if you engage the microscope now. If the current is larger than the STM setpoint
current, then the microscope will false engage when you invoke the Engage command. A large
offset current measured here indicates that there is too much current going through the STM tip just
by inserting the tip in the electrolyte. Most likely, the tip is exposed to the electrolyte more than is
acceptable for STM imaging, i.e., the quality of the tip coating is not good enough. You have to re-
coat the tip.

There is a section on this feature in your SPMs Command Reference Manual. Read that short
section; it has more useful information which is relevant to electrochemistry applications as well,
but which is not duplicated here.

Panels

There are four (4) items under the Panels pull-down menu that are specific to electrochemical SPM.
These are Ramping Controls, Electrode Controls, Voltam, and Temporal, (see Figure 7.2m).

Each of these choices opens a panel in the Real-time software environment. These panels are
slightly different in AFM vs. STM models and in potentiostat vs. galvanostat mode. In the next
section, the parameters in each of these four panels are described and, when applicable, the range of
values for each parameter is given. In addition, the Other Controls panel selects STM or SECPM
mode.

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Real-time Software and Voltametry Controls for EC
Real-time ECAFM and ECSTM Control Panels

Figure 7.2m Panels Pull-down Menu

Table 7.2a lists the parameters and the control panel in which they are found. These can be seen in
Figure 7.2n and Figure 7.2o.

Table 7.2a EC ATM/STM Control Panel Parameters


PARAMETER PANEL EC
Cell [On/Off] Electrode Controls AFM/STM
E Electrode Controls AFM/STM
Elec area Voltam AFM/STM
Ebias Electrode Controls STM
Etip Electrode Controls STM
I cell Electrode Controls AFM/STM
I range Voltam AFM/STM
I range Temporal AFM/STM
Microscope mode Other Controls STM/SECPM
Mode [Pot/Gal] Electrode Controls AFM/STM
Ramp electrode Ramping Controls STM
Ramp rate Ramping Controls AFM/STM
Ramp max Ramping Controls AFM/STM
Ramp min Ramping Controls AFM/STM
Sample rate Ramping Controls AFM/STM
Temporal function Temporal AFM/STM
Temporal graph Temporal AFM/STM
Time range Temporal AFM/STM
Tip reference Ramping Controls STM
Voltam function Voltam AFM/STM
Voltammogram Voltam AFM/STM
Volt function Voltam STM
Volt max Voltam AFM/STM
Volt min Voltam AFM/STM
Volt range Temporal AFM/STM

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Real-time Software and Voltametry Controls for EC
Real-time ECAFM and ECSTM Control Panels

Figure 7.2n The Four Control Panels for ECAFM

Figure 7.2o The Four Control Panels for ECSTM

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Real-time Software and Voltametry Controls for EC
Real-time ECAFM and ECSTM Control Panels

Figure 7.2p Control panels for SECPM

Potentio

There are six (6) items under the Potentio pull-down menu: Hold, Increase, Decrease, CV
Increase, CV Decrease, and Stop All. All of these are specific to electrochemistry.

Figure 7.2q Potentio Pull-Down Menu

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Real-time Software and Voltametry Controls for EC
Real-time ECAFM and ECSTM Control Panels

Choosing each one of these items invokes new instructions in the hardware that control the
electrochemical cell voltage or current by altering the status and direction of the ramping of the
ramp electrode (see below for details). Note that at any time, the choice last made (and still in
effect) appears at the bottom-left of the Real-time software window; here, it is Ramping: CV Inc
for CV Increase (see figure above). Description of each of these items under the Potentio menu
follows.

Hold: Stops any ramp. Holds the potentiostat at current values. Continues reading cell potential,
currents, and updates data values.

Increase: Increases cell potential from the current value to ramp max. If current potential is larger
than ramp max, there is no change.

Decrease: Decreases cell potential from the current value to ramp min. If the current potential is
less than ramp min, there is no change.

CV Increase: Starts a cyclic ramping from the current value to the ramp maximum, then to the
minimum; repeats the cycle.

CV Decrease: Starts a cyclic ramping from the current value to the ramp minimum, then to the
maximum; repeats the cycle.

Stop All: Stops the reading and updating of the potentiostat. The cell potential is still controlled at
the last set value.

Note: If the present potentiostat value is outside the ramp limits, cyclic ramping will
first ramp to the nearest limit and then continue to cycle.

Note: When NanoScope software is shutdown and exited, the hardware will control
the electrochemical cell potential according to the last command executed. For
example, if CV Increase was used last, then the electrochemical cell potential
will continue to ramp cyclically. As soon as NanoScope software is invoked
again, the electrochemical cell electrodes will be set to zero volts.

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Real-time Software and Voltametry Controls for EC
Electrode Controls

7.3 Electrode Controls


Figure 7.3a Electrode Controls Dialog Boxes

Electrode Controls Electrode Controls


E: 2fl .flfl mV E: 2fl .flfl mV

I cell: 2.2fl A Etip: 6fl mV

Cell [On/Off]: Off Ebias: 4fl mV

Mode [Pot/Gal]: Potentio I cell: 2.2fl A

Cell [On/Off]: Off

3141 Mode [Pot/Gal]: Potentio

EC AFM EC STM

7.3.1 E

Description: E is the potential applied between the working


electrode and the reference electrode. E = Vsample -
Vreference electrode.
Range or Settings: -4500 through 4500 mV
Notes: If E is ramped (see Section 7.6), E in the Electrode
Controls panel is not updated and does not correspond
to the true value of E. This is indicated by Ramping
appearing in the field for E.
Feedback electronics in the Bipotentiostat-Galvanostat
control the potential of the counter electrode to
maintain the desired working-electrode potential.
E is not accessible in the Galvanostat mode, because in
that mode, electrochemical cell current controls E.

7.3.2 Etip (STM)

Description: Etip is the potential applied between the tip and the
reference electrode. But note that the tip is held at
ground, and the voltage of the reference electrode is the
parameter that is controlled.
Range or Settings: -4500 through 4500 mV
Notes: If Etip is ramped, Etip is not updated in the Electrode
Controls panel and does not correspond to the true
value of Etip (this is indicated by Ramping).
Do not set Etip = E while running the STM; it is the
same thing as setting the bias voltage to zero and
therefore crashes the tip into the sample.
Etip is not accessible in the Galvanostat mode.

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Electrode Controls

7.3.3 Ebias (STM)

Description: Ebias is the potential applied between the tip and the
working (sample) electrode.
Range or Settings: -4500 through 4500 mV
Notes: Ebias is relative to the working electrode and is the
potential which drives the tunneling current. Ebias =
Etip - E or in other words, Ebias = Vtip - Vsample. But
again, note that the tip is held at ground.
If E, Etip, or Ebias is ramped, it is not updated
(indicated by Ramping) in the ECSTM Electrode
Controls panel.
Do not set Ebias = 0 while running the STM; it crashes
the tip into the surface.
Ebias is not accessible in the Galvanostat mode.

7.3.4 I Cell

Description: In the Galvan mode, I Cell displays the


electrochemical cell current.
Range or Settings: -100 A to 100 A at 10 A/V (gain setting of
Bipotentiostat/Galvanostat)
-1000 A to 1000 A at 100 A/V
-10 mA to 10 mA at 1000 A/V
Notes: Not accessible in the Potentiostat mode.
The current range depends on the jumper or switch
selection on the Potentiostat/Galvanostat board: 10,
100, and 1000 A/V.

CAUTION: You must have the newer Potentiostat/Galvanostat board (boards made after 3/1/
92) installed in the model ECM to operate in the Galvanostat mode. The older
Potentiostat board (made prior to 3/1/92) operates in the Potentiostat mode only.

7.3.5 Cell

Description: In both the Potentiostat and the Galvanostat modes,


Cell indicates the On/Off status of the electrochemical
cell.
Range or Settings: On - Cell is active and feedback is on.
Off - Cell is open and the DVM displays the open cell
potential.

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Electrode Controls

CAUTION: When switching between the Galvanostat and Potentiostat modes, Cell switch
should be Off to prevent current surges.

7.3.6 Mode

Description: The setting of Mode indicates the microscopes


operating mode.
Range or Settings: Potentio (Potentiostat) or Galvan (Galvanostat)
operating mode
Notes: In Potentio mode, cell potential matches E when Cell
is closed.
In Galvan mode, cell current matches I Cell.

CAUTION: You must have the newer Potentiostat/Galvanostat board (boards made after 3/1/
92) installed in the model ECM to operate in the Galvanostat mode. The older
Potentiostat board (made prior to 3/1/92) operates in the Potentiostat mode only.

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Voltam

7.4 Voltam
Figure 7.4a Voltam Dialog Boxes

Voltam Voltam
Voltammogram: Display Voltammogram: Display
Elec area: .5 cm 2 E
Volt function:
Voltam function: Current
Elec area: .5 cm 2
I range: 2 A
Voltam function: Current
Volt max: 1 mV
I range: 2 A
Volt min: 1 mV
Volt max: 1 mV
Reset 1 mV
Volt min:

Reset
3142

EC AFM EC STM

7.4.1 Voltammogram

Description: Enables hiding or displaying voltammogram.


Range or Settings: Display, Hide

7.4.2 Volt function (STM)

Volt function defines which potential is plotted on the


Description:
voltammogram along the horizontal axis.
Range or Settings: E: Cell potential is plotted along horizontal axis vs. cell
current along vertical axis.
Etip: Tip potential is plotted vs. tip current.
Etip should be selected when ramping the tip (Ramp
electrode set to Tip [see Section 7.6]).
When Etip is selected, Temporal graph (see Section
7.5) automatically selects Itip, which is tip current,
Notes:
with the appropriate current range in nA.
Even though software allows selection of Itip (Voltam
function, see Section 7.4.4) together with E, the
displayed graph will be meaningless.

7.4.3 Elec area

Description: Area of the working electrode exposed to electrolyte.

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Voltam

7.4.4 Voltam function

Description: Voltam function determines which quantity is plotted


along the vertical axis of the voltammogram. (Itip can
be plotted only vs. Etip.)
Range or Settings: Current - The cell current is plotted as a function of the
working electrode voltage.
Cur Dens - The cell current density is plotted as a
function of the working electrode voltage. Current
density is current divided by electrode area.
Log Cur - The log of the cell current is plotted as a
function of the working electrode voltage (log base e,
or natural log).
Lg Cur Dens - The log of the cell current density is
plotted as a function of the working electrode voltage
(log base e, or natural log).
Charge - The charge (integrated current) is plotted as a
function of the working electrode voltage.
Chrg Dens - The charge density through working
electrode (integrated current density) is plotted as a
function of the working electrode voltage.
Itip (STM) - Tip current is plotted as a function of Etip
when Volt function = Etip.
Note: Even though the software option exists to select Itip
with E (from volt function), the displayed graph is
meaningless.

7.4.5 I range

Description: I range controls the vertical scale of the graph.


Range or Settings: Current - [A], 1 through 4500 depending on gain
selection

Cur Dens - [A/cm2]


Log Cur - [log(A)] (log base e, or natural log)

Lg Cur Dens - [log (A/cm2)]


(log base e, or natural log)
Charge - [mC], 1 through 1000

Chrg Dens - [mC/cm2]


Notes: The only function available for experiments with the tip
potential scanned (Ramp electrode set to Tip) is
Current.
All functions are available for experiments with the
reference potential scanned (Ramp electrode set to
Work).

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Temporal

7.4.6 Volt max

Description: Volt max is the voltage corresponding to the right-hand


side of the voltammogram graph.
Range or Settings: Volt min + 20 mV through 3000 mV (see Section 7.4.7
for Volt min).
Notes: Changing the value of Volt max zooms the
voltammogram graph in or out.

7.4.7 Volt min

Description: Volt min is the voltage corresponding to the left-hand


side of the voltammogram graph.
Range or Settings: -5000 mV through Volt max - 200 mV
Notes: Changing the value of Volt min zooms the
voltammogram graph in or out.

7.5 Temporal
Figure 7.5a Temporal Dialog Boxes
Temporal Temporal
Temporal graph: Display Temporal graph: Display

Temporal function: Current Temporal function: Current

I range: 2. A I range: 2. A

Volt range: 2 mV Volt range: 2 mV

Time range: 1 s Time range: 1 s

Reset Reset

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EC AFM EC STM

7.5.1 Temporal graph

Description: Allows you to display or hide the temporal graph.


Range or Settings: Display, Hide

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Temporal

7.5.2 Temporal function

Description: Temporal function determines which current or


current-related quantity is plotted (in blue) on the
temporal graph vs. time (along the horizontal axis).
Range or Settings: Current - The cell current is plotted as a function of the
working electrode voltage.
Cur Dens - The cell current density is plotted as a
function of the working electrode voltage. Current
density is Current divided by Electrode area (in
Voltam window).
Log Cur - The log of the cell current is plotted as a
function of the working electrode voltage (log base e,
or natural log).
Lg Cur Dens - The log of the cell current density is
plotted as a function of the working electrode voltage
(log base e, or natural log).
Charge - The charge (integrated current) through the
working electrode is plotted as a function of the
working electrode voltage.
Chrg Dens - The charge density (integrated current
density) is plotted as a function of the working
electrode voltage.
Itip (STM) - Plotted as a function of time when Volt
function = Etip. (See Voltam window for Etip.)
Notes: The only function available for experiments with the tip
potential scanned (Ramp electrode set to Tip) is the tip
current.
All functions are available for experiments with the
reference potential scanned (Ramp electrode set to
Work).

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Temporal

7.5.3 I range

Description: I range sets the vertical scale of the temporal graph for
the current (blue) plot.
Range or Settings: Current - [A], 1 through 4500 (gain dependent)

Cur Dens - [A/cm2]


Log Cur - [log(A)] (log base e, or natural log)

Lg Cur Dens - [log (A/cm2] (natural log, base e)


Charge - [mC], 1 through 1000

Chrg Dens - [mC/cm2]


0 (zero) is always in the center of the graph.
Notes: Graph limits are plus or minus one-half of the range.

7.5.4 Volt range

Description: Volt range sets the voltage range along the vertical axis
of the temporal graph for the voltage (yellow) plot.
Range or Settings: 200mV through 10,000mV
Notes: 0 (zero) volts is always in the center of graph.
Graph limits are plus or minus one-half of the range.

7.5.5 Time range

Description: Time range sets the time range of the temporal graph
(along horizontal axis).
Range or Settings: 40 through 6,000 seconds
Notes: If the plot fits in the time range, the left edge is 0 (zero)
seconds. If the plot reaches the right edge of the graph,
the current and voltage plots shift left one division of
the graph (Chart Recorder mode).
The time limits on the graph are incremented to show
the new limits.
The time range may be changed at any time to display
the most recent data at any resolution.
Time range is limited to the maximum time that can be
stored (see Section 7.6.6).

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Ramping Controls

7.6 Ramping Controls


Figure 7.6a Ramping Controls Dialog Boxes

Ramping Controls Ramping Controls


Ramp rate: 25.fl mV/S Ramp rate: 25.fl mV/S

Ramp max: 5flfl mV Ramp max: 5flfl mV

Ramp min: 5flfl mV Ramp min: 5flfl mV

Sample rate: 1fl .fl Hz Tip reference: Work

Ramp electrode: Work


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7.6.1 Ramp rate

Description: The setting of Ramp rate indicates the rate at which


potential/current is ramped.
Range or Settings: 0.1 through 1000V/s (Potentiostat mode)
0.1 through 1000A/s (Galvanostat mode) depending
on gain.
Notes: One of the Potentio menu commands (see section 7.2;
Figure 7.2o) must be selected for the ramp to be placed
on the electrodes in either Potentiostat or Galvanostat
mode.

7.6.2 Ramp max

Description: The Ramp max setting indicates the maximum of the


ramp potential applied to the electrodes. When the
ramped electrode attains a potential above this setting,
the ramp either stops or reverses direction.
Range or Settings: -4500 through 4500mV for the Potentiostat mode (but
greater than Ramp min)
-450 through 450A for the Galvanostat mode (but
greater than Ramp min)
Notes: When an Increase/Decrease command is selected from
the Potentio (Figure 7.2o) menu, the ramped voltage or
current stays constant when it attains its limit. The
Cyclic Voltametry (CV) Increase/Decrease command
causes the ramp to reverse direction when Ramp Max
is reached.
The Increase/Decrease or the CV Increase/Decrease
command must be selected from the Potentio menu to
start the ramp.

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7.6.3 Ramp min

Description: The Ramp min setting indicates the minimum of the


ramp potential applied to the electrodes in the
Potentiostat mode or the minimum of the ramp current
in the Galvanostat mode. When the ramped electrode
reaches this setting, the ramp either stops or reverses
direction.
Range or Settings: -4500 through 4500mV for the Potentiostat mode (but
less than Ramp max)
-450 through 450A for the Galvanostat mode (but less
than Ramp max)
Notes: When an Increase/Decrease command is selected from
the Potentio menu, the ramped voltage or current stays
constant when it attains its limit. The CV Increase/
Decrease command causes the ramp to reverse
direction when Ramp min limit is reached.
The Increase/Decrease or the CV Increase/Decrease
command must be selected from the Potentio menu to
start the ramp.

7.6.4 Tip reference (STM only)

Description: The setting of Tip reference indicates whether the


STM tip potential is measured relative to the working
electrode or the reference electrode.
Range or Settings: Work - The tip potential is measured relative to the
working electrode.
Ref - The tip potential is measured relative to the
reference electrode.
Notes: The Etip item is held constant in the ECSTM
Electrode Controls panel when the Tip reference item
is set to Ref.
The Ebias item is held constant in the ECSTM
Electrode Controls panel when the Tip reference item
is set to Work.
When the Ramp electrode item is set to Work and the
Tip reference item is set to Work, the tip is ramped
along with the working electrode. This maintains a
constant potential difference between the tip and
working electrodes.
Tip reference is set to Work in the Galvanostat mode.

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7.6.5 Ramp electrode (STM)

Description: The Ramp electrode setting indicates which electrode


is ramped by the Potentio menu (Figure 7.2o)
commands.
Range or Settings: Work - The working electrode potential is ramped.
Tip - The tip potential is ramped
Notes: When the Increase/Decrease command is selected
from the Potentio menu, the ramped parameter stops
when it reaches its limit. Increase indicates that the
ramp starts in the positive direction (ramping towards
the setting of Ramp max). Decrease indicates that the
ramp starts in the negative direction (towards the setting
of Ramp min). The CV commands cause the ramp to
reverse direction when the limit is reached.
When the Ramp electrode item is set to Work and the
Tip reference item is set to Work, the tip is ramped
along with the working electrode. This maintains the
potential difference set between the tip and working
electrodes.
The ramping starts at the current setting of the E item or
the Ebias item.
When ramping the tip (Ramp electrode = Tip), Etip is
plotted vs. Itip. The Volt function in the Graph
Control panel should be changed to Etip for the
voltammogram.
Ramp electrode is set to Work in the Galvanostat
mode.

7.6.6 Sample rate

Description: The Sample rate is the rate at which electrochemical


data is read and recorded from the electrochemical cell.
Range or Settings: 0.1 to 100Hz
Notes: The lowest rate that gives enough data points for the
experiment should be used. About 60,000 data points
can be stored. 10Hz provides data for 100 minutes.
The maximum setting is adjusted so that enough data is
saved to cover the Time range set in the Temporal
graph.

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Chapter 8 Off-line Software for ECSPM

8.1 Off-line Software


Off-line software for electrochemical SPM image and data analysis is covered in this section.
Again, this manual covers only those features that are specific to electrochemical SPM (STM or
AFM). For additional information about Off-line software commands which are not
electrochemistry-specific, please refer to your SPMs Command Reference Manual.

8.1.1 Starting the Off-line Software

The Off-line software environment can be invoked by choosing Off-line from the pull-down menu
under the di logo,

Figure 8.1a Select Off-line

or by clicking on its icon, which is under the di logo and to the right.

Figure 8.1b Select Off-line Icon

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Off-line Software

The menu and icons at the top of the Off-line environment looks like the picture below. (There may
be one or more panels open below the icons when you get to this screen. Here we show none.)

Figure 8.1c Off-line Environment

To view the SPM (STM or AFM) image alone, without the electrochemical data, select Image from
the menu.

If you want to display and re-scale the electrochemical data attached to an ECSTM or EC-AFM
image, then select View/Graph.

Figure 8.1d Select View / Graph

When View/Graph is selected, one of the following two screens appear in the image window
depending on the SPM mode in which the data was captured, (i.e., ECSTM or ECSFM).

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Figure 8.1e ECAFM Image Screen

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Figure 8.1f ECSTM Image Screen

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Also, a dialog box appears (see Figure 8.1a) in the control window to allow you to scale and
analyze the electrochemical data.

Here, we first describe the display environment (image screen) and the electrochemistry parameters
that appear on the image screen (see Section 8.1.2). Then we describe the parameters in the dialog
box (see Figure 8.1g, Section 8.1.3). The numeric, text, and graphic representation of the
electrochemical data on the image screen update as you change the parameters in the dialog box.

8.1.2 Display Environment (Image Screen)

The image and two plots are arrayed vertically in the image screen. The text to the left of plots
describes the state of the hardware at the time of capture.

In the Voltammogram (top plot), a current is plotted along the vertical axis versus a voltage along
the horizontal axis. This can be Itip vs. Etip or I vs. E or one of the calculated values, current
density, charge, etc. vs., E. Note that the calculated values are all based on the electrochemical cell
current, I, and not on STM tip current, Itip.

In the Temporal (bottom plot), the horizontal axis is always time. A voltage (yellow) and a current
(blue) are plotted versus time. The voltage can be the electrochemical cell potential, E, or the
voltage applied to the STM tip which is Etip. The current can be electrochemical cell current, I, or
one of its derivative quantities; e.g., charge, current density, etc.; or it can be the current through
the STM tip which is Itip.

The time scale on the Temporal graph does not necessarily correspond to the time required to
capture an SPM image for the following reasons.

1. If the time to capture an image exceeds the time to record the maximum of the 60,000
electrochemical data points that can be stored, only the last 60,000 data points are saved. The
data points prior to the last 60,000 data points are lost. Time zero on the Temporal graph
reflects the start of the last 60,000 data points.

2. To display on the Temporal graph only a portion of the stored data points, for example, the
last 30,000 of 60,000 data points recorded using a Sample rate of 100 Hz, define Time start
equal 300 seconds (one-half of the maximum of 600 seconds) and Time end equal 600
seconds in the Graph control panel for the Off-line software. In this case, time zero on the
Temporal graph would actually be the first data point after the 300-second marker.

A mouse click-and-hold-and-drag may be used in the Temporal plot and the Image to display data
at any point in the experiment. The marker in the Temporal plot will follow the position of the
cursor as the mouse is dragged (click and hold) in the plot, staying on the current vs. time plot line
(See Figure 8.1a or Figure 8.1b). The electrochemical cell data at the position of the marker is
displayed to the left of the Temporal plot.

A marker on the Voltammogram will indicate the corresponding data as potential vs. current. The
white vertical line in the Temporal plot indicates, in time, when the first line of the SPM image was
captured. As the Temporal marker is moved to the right of the line, a horizontal line on the SPM
image will move to the scan line that was captured at approximately the same time. In addition, the
mouse may drag (click-and-hold) the line on the image to any scan line, and this will move the

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Temporal and Voltammogram markers to the appropriate positions and update the
electrochemical cell data display.

Note that it is possible to have data displayed in the Temporal plot across such a time window that it
does not correspond to any of the data in the SPM image. This is because when an SPM image is
captured, the last 60,000 electrochemical data points are also recorded in the file, and only a portion
of the electrochemical data recorded may correspond to the time required to capture the SPM
image; i.e., the image may have taken less time to capture than the last 60,000 electrochemical data
points.

Voltam

Voltam function - Indicates the quantities plotted along horizontal and vertical axes of the
voltammogram. When this parameter is Itip, the current through STM tip is plotted vs. Etip. All
other settings (e.g., current, charge) have the electrochemical cell parameter plotted vs. E.

Tip reference (STM only) - Indicates whether the STM tip potential is relative to the working or
reference electrode.

Ramp electrode - Indicates which electrode (working or STM tip) was ramped at time of capture.

Ramp rate - Indicates the ramp rate at the time of capture.

Sample rate - The rate of electrochemical data recording at the time of capture.

Temporal

Temporal Function - Indicates what parameter is plotted in blue along the vertical axis vs. time
along horizontal axis.

I (plot) - Cell current at marker position.

E (plot) - Cell potential at marker position.

Etip (STM only) - Potential of the tip relative to the working electrode when Tip reference is set to
Work.

Ebias (STM only) - E - Etip.

Time - Time at marker position relative to start of Temporal plot. The data is normally displayed
using the Temporal Time range at the time of capture (see sections 6.5.5 and 6.6.6).

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8.1.3 Graph Dialog Box

Figure 8.1g Graph Dialog box

Voltam Graph

Voltam function - Selects from Charge, Chrg Dens, Current, Cur Dens, Log Cur, Lg Cur Dens, or
Tip Current options.

I range - Controls the vertical scale of the Voltammogram graph.

Volt max - Voltage corresponding to the right edge of the Voltammogram graph.

Volt min - Voltage corresponding to left edge of Voltammogram graph.

Temporal Graph

Temporal function - Selects from Charge, Chrg Dens, Current, Cur Dens, Log Cur, Lg Cur Dens,
or Tip Current options.

I range - Controls the current scale of the Temporal graph.

Time start - Start time of displayed data (left edge of plot).

Time end - Ending time of displayed data (right edge of plot).

Note: The system will record the current and voltage vs. time data starting from time
= 0 in the Temporal graph. The current is integrated starting at time = 0 of the
Temporal graph. Any data that fits into the Temporal graph will be displayed.
Voltammogram will display data within the time range of the Temporal graph.

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Chapter 9 Running SECPM

9.1 Introduction
Veeco offers three different options for electrochemical Scanning Probe Microscopy (SPM):
Electrochemical Scanning Tunneling Microscopy (ECSTM), Electrochemical Atomic Force
Microscopy (ECAFM) and Scanning Electrochemical Potential Microscopy (SECPM). SECPM
offers in-situ imaging or potential mapping with nanometer-scale resolution. SECPM measures the
potential difference between its potentiometric probe and the sample, immersed in an electrolyte or
a polar liquid, enabling the user to profile the electrochemical potential, , which changes rapidly
with distance across the electrical double layer at solid/liquid interfaces.

SECPM has three modes of operation:

Constant Potential Mode: In this mode, SECPM uses SPM feedback to adjust the
position (height) of the probe relative to the sample surface to maintain a constant value
of . When the probe raster-scans the sample surface (in X and Y), the constant potential
mode can generate topographic images of the sample surface (Figure 9.1a).

Constant Height Mode: In this mode, SECPM feedback is turned off, and, when the
probe is raster-scanned, SECPM maps the electrochemical potential distribution across
the sample surface.

Spectroscopic Mode (or Potential Profiling): SECPMs raster-scanning (in X,Y) is


disabled in this mode. Instead, the probe is scanned (in Z) across the electrical double
layer, and the SECPM records a plot of the measured potential, , vs. distance traveled
(Figure 9.1b).

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Introduction

Figure 9.1a SECPM Constant Potential Mode image of Sn60Pb40 alloy in Glycerol at open circuit potential
using uncoated PtIr tip at potential setpoint of 100mV. The open circuit potential is -520mV vs. a Pt quasi
reference electrode. 5m scan.

Figure 9.1b An example of SECPM electrochemical potential spectroscopy. These plots of potential () vs.
probe-sample distance were recorded above a HOPG sample in Glycerol as the probe approached (white plot)
and retracted (yellow plot) from the sample.

The basic electrical configuration of SECPM is shown in Figure 9.1c. The STM configuration
substitutes a galvanometer, which measures current, for SECPMs potentiometer, which measures
voltage.

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Figure 9.1c SECPM electrical configuration

9.2 Running SECPM

9.2.1 Select Microscope

Select Microscope

Upon starting the NanoScope software, you will see the window shown in Figure 9.2a.

Figure 9.2a NanoScope Control Window

Clicking the di logo, youll see a pull-down menu shown in Figure 9.2b.

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Figure 9.2b Microscope Select

To image and collect data with your EC-SPM - that is, if you are going to run the Real-time
software - you must first select the proper microscope. Click Microscope Select, shown in Figure
9.2b. The dialog box shown in Figure 9.2c appears.

Figure 9.2c Microscope Select Dialog Box

In the dialog box, choose the electrochemical SPM you are going to run, and click OK. Depending
on what microscopes you own and have configured for your NanoScope control station, you may
see any of the choices shown here, as well as others that are not shown here; e.g., MMAFM,
Dimension, BioScope, etc. Having made your choice, the control station updates the software to
run the microscope you selected. (For additional information on the options in this dialog box,
reference the SPM Command Reference Manual).

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Create Microscope

If the microscope is not listed, create one as follows: in the Microscope Select dialog box click
NEW. When an Equipment-New dialog box pops up, choose the CONTROLLER and MICROSCOPE
from the pull down lists and click SCANNER for scanner selection. See Figure 9.2d.

Figure 9.2d Create Microscope

9.2.2 SECPM-Specific Parameters

This chapter discusses SECPM. ECAFM and ECSTM are discussed in Chapter 7.

The Real-time software environment can be invoked by either choosing Real-time from the pull-
down menu under the di logo (see Figure 9.2b) or by clicking the icon that has a picture of a
microscope on it (also shown in Figure 9.2b). The Real-time software environment is shown in
Figure 9.2e.

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Figure 9.2e Real-time Environment

Microscope Mode

The SECPM head integrates a STM preamplifier and a SECPM potentiometer; the head works in
either STM mode or SECPM mode via software control. The Microscope mode can be switched in
Other Controls > Microscope Mode, shown in Figure 9.2f.

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Figure 9.2f Microscope Mode

SECPM Sens(itivity)

SECPM SENS is the sensitivity of the SECPM potentiometer, which the user sets in accordance
with the GAIN setting on the SECPM head. In Feedback Controls panel, shown in Figure 9.2g,
choose the appropriate SECPM SENS from the pull down list.

Figure 9.2g SECPM sens

Head Offset

Clicking MICROSCOPE > OFFSET brings up the Head Offset box, shown in Figure 9.2h. Check
and record this offset value after SECPM SENS is set. This enables you to check the potential
difference before engaging while the tip is far from the sample surface.

Note: The tip potential changes with the potential applied to the sample-working
electrode.

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Figure 9.2h Head Offset

This can be useful in two ways:

1. It can be viewed as the upper limit of the POTENTIAL SETPOINT, since the POTENTIAL
SETPOINT is normally smaller than this value, because the tip-sample potential difference
gets smaller as the tip gets closer to the sample surface.

2. It can also be used to check whether the microscope mode switch is working properly.
Without adding liquid or solution and while tip is far from sample surface (e.g. the head is
not on the scanner top), the offset should be near 0V in STM mode. In SECPM mode this is
floating and may typically reach a maximum of 10 times the SECPM SENS.

Potential Setpoint

POTENTIAL SETPOINT is the tip-sample potential difference the feedback holds constant in
Constant Potential Mode (see Constant Potential Mode on Page 89). Since the tip-sample potential
difference gets smaller as the tip gets closer to the sample surface, a smaller setpoint means a
smaller tip-sample separation. Therefore, smaller setpoints tend to give higher resolution. However,
POTENTIAL SETPOINTs smaller than 5mV are more likely to cause the tip to crash. To reduce the
possibility of a tip crash, it is good practice to set the setpoint slightly less than that seen in
Microscope Offset (see Head Offset on page 95).

Figure 9.2i Potential Setpoint

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Ptip

PTIP, shown in Figure 9.2j, denotes the tip-sample potential difference. This is not to be confused
with ETIP in the STM mode, which is the tip potential with respect to the reference electrode (RE).
Choosing PTIP in the Voltam/Volt window results in a plot of PTIP vs. E-working electrode (WE)
potential in the Voltam display, and PTIP vs. Time in the Temporal plot. An example is shown in
Figure 9.2k. The sample is HOPG in H2O with Pt wires used for both the CE and RE and a PtIr tip.

Figure 9.2j Ptip

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Figure 9.2k SECPM example: HOPG in H2O, CE and RE: Pt wires, PtIr tip.

SECPM Imaging Settings

Adjust the GAINs, SCAN RATE, POTENTIAL SETPOINT in the Scope Mode. GAIN settings are
sensitive to the tip being used; larger gains usually work better for well-coated tips. The INTEGRAL
GAIN can be as high as 200, and the PROPORTIONAL GAIN can be as high as 1024. Slowly increase
the GAINs until the cantilever begins to oscillate. Cantilever oscillation is most easily observed in
Scope Mode. Good practice for SECPM imaging changes the SCAN SIZE gradually, e.g. 500nm-
>1m->2m This is also the case for SCAN RATE. A lower SETPOINT favors better tracking and
higher resolution; however, this means large tip-sample interactions which is unfavorable for soft
materials.

For imaging HOPG in a pure polar liquid, Veeco recommends the following initial settings:

SCAN SIZE: < 500 nm

SCAN RATE: < 2 Hz

INTEGRAL GAIN: 5

PROPORTIONAL GAIN: 10

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POTENTIAL SETPOINT: 2/3 of TIP POTENTIAL (seen in Head Offset before engaging)

Figure 9.2l shows a SECPM Constant Potential Mode image of Sn60Pb40 in Glycerol using an
open circuit potential and an uncoated PtIr tip at a potential setpoint of 100mV. This sample was
made by melting the alloy and pressing it against a glass slide. The open circuit potential is -520mV
referenced to a Pt quasi-reference electrode. The following settings were used:

SCAN SIZE: 5m

SCAN RATE: 0.5 Hz

INTEGRAL GAIN: 12

PROPORTIONAL GAIN: 30

POTENTIAL SETPOINT: 100mV

Figure 9.2l SECPM Constant Potential Mode image of Sn60Pb40 alloy in Glycerol

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SECPM Spectroscopy: Potential Profiling

The Spectroscopic Mode enables the Potential-Separation profile to be acquired by recording PTIP
while approaching and retracting the tip to/from the sample surface by ramping the Z-voltage of the
piezo. This shows how the potential changes across the electrical double layer at solid/liquid
interfaces. This unique piece of information is fundamental to understanding electrochemical
processes.

To invoke this function, click VIEW > P-S PLOT, shown in Figure 9.2m. This opens the dialog
boxes shown in Figure 9.2n.

Figure 9.2m Starting P-S Plot

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Figure 9.2n Potential-Spectroscopy Controls

Critical parameters are visible by default. Some parameters, used less frequently, are hidden by
default. These can be shown by clicking the top left corner of the dialog box and checking SHOW
ALL ITEMS (see Figure 9.2o). Checking a hidden parameter makes that parameter visible in the
default view.

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Figure 9.2o Show All Parameters

Figure 9.2p SECPM Parameters

Ramp Channel

Select Z for P-S (Potential Spectroscopy) plots.

Ramp size

RAMP SIZE specifies the Z-distance over which the piezo travels.

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Running SECPM
Running SECPM

Scan rate:

The SCAN RATE is the (ramp) rate at which the tip approaches and retracts from the surface.

Forward/Reverse Velocity

The Z-velocity of the tip. You can set either the velocity or the rate and the other variable will be
automatically updated.

Number of Samples

NUMBER OF SAMPLES is the number of data points (in Z) for each plot. Plot detail is directly
proportional to this

Feedback Type

FEEDBACK TYPE, selected from a pull-down list, shown in Figure 9.2q, is used to control the tip-to-
sample separation and helps avoid tip crashes that can be caused by piezo drift.

Figure 9.2q Feedback Type

The following FEEDBACK TYPEs are available:

NONE: Open loop (i.e., no feedback).

PIXEL: Turns feedback on at each data point. This is rarely used.

RAMP: Turns feedback on after each ramp (1/2 cycle), both approach and retract.

CYCLE: Turns feedback on once per cycle when the tip is nearest to the sample.

Rev. B Digital Instruments Electrochemical SPM 103


Running SECPM
Running SECPM

Feedback Counts

FEEDBACK COUNTS specifies the amount of time (in DSP clock cycles, 16 s) that feedback will be
on. Allow sufficient time for the control system to settle. A FEEDBACK COUNTS value greater than
1000 is recommended.

Potential Setpoint

POTENTIAL SETPOINT, found in the Feedback Controls panel, shown in Figure 9.2r, sets the value
(in Volts) of the closest point of the tip to the sample surface.

Figure 9.2r Potential Setpoint

Data Type

Choose POTENTIAL as the DATA TYPE, found in the Channel 1 panel, shown in Figure 9.2s.

Figure 9.2s Data Type

Trigger Mode

Set TRIGGER MODE, found in the Scan Mode panel (see Figure 9.2t), OFF.

104 Digital Instruments Electrochemical SPM Rev. B


Running SECPM
Running SECPM

Figure 9.2t Trigger Mode

Figure 9.2u shows a Potential-Spectroscopy (P-S) plot taken on HOPG in H2O.

Figure 9.2u PS Plot on HOPG in H2O

Rev. B Digital Instruments Electrochemical SPM 105/(106 Blank)


Chapter 10 Maintenance and Support

10.1 System Support


Contact Veeco, 112 Robin Hill Rd., Santa Barbara, CA 93117, Tel. 805-967-1400, with questions
regarding MultiMode hardware and software. Veeco can be found on the web at http://
www.veeco.com.

Refer to the Maintenance chapter of the MultiMode Scanning probe Microscope Instruction
Manual for MultiMode-specific issues.

10.2 Maintenance
MultiMode AFMs do not require periodic maintenance if always operated at a room temperature
comfortable to the operator.

See Chapter 4 and Chapter 5 for cell and electrode cleaning procedures.

10.3 O-Rings and Fluid Cells

10.3.1 Approximate Dimensions (June 1997)

Veecos O-rings are made of at least three different materials: silicone for AFM fluid cells, EDP for
AFM and STM fluid cells, and Teflon for STM fluid cells. EDP, which is black, is less chemically
inert than Teflon.

Table 10.3a summarizes measured and calculated dimensions of O-rings and fluid cells.

Rev. B Digital Instruments Electrochemical SPM 107


Maintenance and Support
O-Rings and Fluid Cells

Table 10.3a O-Ring and Fluid Cell Dimensions

Sample
O-Ring O-Ring O-Ring Surface Approx. Cell
Inner Dia. Outer Dia. Thickness Area Volume
Fluid Cell
(mm 0.05 (mm 0.05 (mm 0.05
(O-Ring) (mm2 calculated
mm) mm) mm)
measured measured measured 0.07 mm2) see noteb
calculated
AFM 5.70 11.25 2.72 56 150 mm3
(silicone) (0.15 ml)*
AFM 5.70 11.25 2.63 56 150 mm3
(EDP) (0.15 ml)*
ECSTM 7.61 11.28 1.84 70 see notea
(Teflon)
ECSTM 7.61 11.22 1.85 70 see notea
(EDP)
TipView 6.05 9.64 1.82 48 see notea
STM
(Teflon)
TipView 6.05 9.69 1.83 49 see notea
STM
(EDP)

a.The volume of the fluid in the TipView STM and ECSTM fluid cells may be estimated by
multiplying the tabulated Surface Area by the height of the fluid in the cell. The maximum
possible heights of fluid above the sample surface in the STM cells are approximately 3.25 mm
for ECSTM (model ECM) fluid cells and 3.8 mm for TipView STM fluid cells.
b. Cell volume excludes volume of input/output Luer fitting ports and electrode insertion ports.

* For AFM fluid cells, the volume depends on 1) the fraction of the O-rings thickness which is
pushed into the circular groove of the machined glass piece, and 2) the amount of pressure on the
O-ring as it sits on the sample.

The volume of the electrolyte in cells is roughly estimated and may vary for all fluid cells, but more
so with the STM cells because the operator determines the level of the electrolyte in the fluid cell.

Note, however, that in TipView STM and ECSTM fluid cells, the diameter of the circle defining the
cylindrical cell cross-sectional area is constant near the sample, but above a certain height from the
sample surface the diameter increases. This makes for a larger range of values possible for fluid
volume in STM fluid cells.

108 Digital Instruments Electrochemical SPM Rev. B


Maintenance and Support
STM Tip Etching Procedure (Tungsten and Platinum-Iridium (Pt-Ir))

10.4 STM Tip Etching Procedure (Tungsten and Platinum-


Iridium (Pt-Ir))
1. Prepare an aqueous solution of 1 M KOH (potassium hydroxide) for a tungsten tip, or 6-10 M
KOH (or NaOH) for a Pt-Ir tip.

2. Immerse a 0.010-inch diameter tungsten wire 3 mm into the KOH solution. A convenient
way to support the wire is by inserting it into a 22-gauge syringe needle. Friction will support
the wire and allow easy control of the wire depth in solution.

3. Immerse a counter electrode (Au, Pt, or stainless steel) wire several inches into the KOH
solution.

4. Connect a variable voltage, AC source (variac) to the tungsten wire and counter electrode.

5. Apply an AC voltage between the tip wire and counter electrode. Bubbles can be observed
rising from the wires. Suggested voltages for a tungsten tip: 5-8V and for a Pt-Ir tip: 20-25V.
Users are encouraged to experiment with shape (i.e., sinusoidal or square wave, etc.),
amplitude and frequency of the applied voltage.

6. Turn off the current when the wire has shortened to the extent that less than 1 mm is still
immersed in the solution. Experimentation with the etching times gives you an idea of the
variety of tip shapes that it is possible to make with this method.

More complex procedures claim to result in significantly sharper tips.1

Veeco sells ready-to-image Platinum (part number: PT-ECM) and Tungsten (part number: TT-
ECM) tips.

10.5 NanoScope IIIa (or E, or 3) Control Box Adjustment to


Match EC Equipment
It is necessary to adjust the analog control and the analog-to-digital circuits in the NanoScope IIIa
(E or 3) control box to match specific electrochemical equipment used. These adjustments are made
at the time the entire NanoScope control system is tested.

1. If you have added electrochemistry capability to your system, the Bias, Analog1, and AUX
A/D need to be adjusted so the signals going to and from the EC equipment are accurate. The
AUX A/D offset changes with temperature, so you need to let the control box warm up for at
least one hour with the cover on prior to making its final adjustment.

1.Mircea Fotino, Tip sharpening by normal and reverse electrochemical etching, Review of Scientific
Instruments, 1993, 64(1), 159.

Rev. B Digital Instruments Electrochemical SPM 109


Maintenance and Support
NanoScope IIIa (or E, or 3) Control Box Adjustment to Match EC Equipment

2. Make a dummy cell by connecting the counter electrode (CE) and the
CE RE
reference electrode (RE) (orange and purple leads from the EC
equipment, respectively) to one side of a 10K resistor. Connect the other
side of the resistor to the working electrode (WE - the scanner cap or

ECM sample holder). Turn the EC equipment switch to On.
10K
3. Run the Z program and under Microscope / Select, choose an ECSTM
device. If you do not have ECSTM, select an ECAFM device and ignore
all the following instructions regarding bias or Ebias. WE

4. Under EC Controls, select Cell: On and Mode: Potentio.

5. On the menu bar, select Potentio / Hold. Make sure the Temporal graph is set to Display
by selecting View / Image Mode and Ok. Monitor the cell I current and E voltage on the
display monitor.

Bias Adjustment

1. Turn off the power to the NSIIIa (or E, or 3) controller box, open it, and connect a
multimeter red lead to the ground test point on the Z board (see Figure 10.5a for NanoScope
IIIa or see Figure 10.5b for NanoScope E or 3). Connect the black lead to the WE side of the
10K resistor (scanner cap or ECM sample holder). Set the meter for 100-200mV DC. Turn
the controller on.

2. (If you do not have equipment that uses Bias settings, skip to Analog 1 Adjustment on
page 10-111.) Under the EC Controls, set E and EBias to 0mV. Adjust the Bias Offset
trim pot on the Z board until the multimeter reads 0mV.

Figure 10.5a Z Board for NanoScope IIIa.

Gain
Offset

Ground Test Point

110 Digital Instruments Electrochemical SPM Rev. B


Maintenance and Support
NanoScope IIIa (or E, or 3) Control Box Adjustment to Match EC Equipment

Figure 10.5b Z Board for NanoScope E or 3

3. Set EBias to 100mV. Adjust the Bias Gain trim pot until the meter reads 100mV.

4. Check EBias at 0 and 100mV again. If necessary, readjust the Bias Offset and Gain.

Analog 1 Adjustment

1. Set E and EBias to 0V. (If using a profile that has Ebias, make sure Ebias remains at 0V,
because the multimeter is really measuring Etip, which is only equal to E when Ebias is 0V.)
Connect the black multimeter lead to the CE and RE side of the resistor (orange and purple
leads from the EC equipment). Adjust the Analog 1 Offset trim pot on the AUX board until
the multimeter reads 0mV (see Figure 10.5c for NanoScope IIIa or see Figure 10.5d for
NanoScope E or 3).

Rev. B Digital Instruments Electrochemical SPM 111


Maintenance and Support
NanoScope IIIa (or E, or 3) Control Box Adjustment to Match EC Equipment

Figure 10.5c Auxiliary Board for NanoScope IIIa.

Offset Gain

A/D Offset

Analog 1

Figure 10.5d Auxiliary Board for NanoScope E or 3

2. Set E to 100mV. Adjust the Analog 1 Gain trim pot until you measure 100mV.

3. Check E at 0 and 100mV again. If necessary, readjust the Analog 1 Offset and Gain.

112 Digital Instruments Electrochemical SPM Rev. B


Maintenance and Support
NanoScope IIIa (or E, or 3) Control Box Adjustment to Match EC Equipment

A/D Converter Adjustment

1. This adjustment must be made when the control box is fully warmed up. Set E and EBias to
0mV. Adjust the A/D Offset trim pot until E and I on the display monitor are near zero.
You need to close the cover and wait for the controller to warm up. Make this adjustment
quickly. The A/D cools down if the cover is off for just a short time.

2. Set E for various values and check that the I current display is proportional. The 10K resistor
should give you a 10mV/1A ratio. It is normal for the noise level of the A/D to account for
the four least significant bits.

Rev. B Digital Instruments Electrochemical SPM 113/(114 Blank)


Index

Head Offset Dialog Box 67

B I
I Cell 73
bipotentiostat/galvanostat 15
I cell Sens 65
C
Cantilever Substrate I Range 76, 79
Imaging
positioning 2729
preparing the sample 2527
Cell 73
M
Cleaning 25
Microscope Select Dialog Box 62, 92
D
MMAFM-EC model 13
Detector Calibration Dialog Box 64
Mode 74
Dry Image 3034
Model
E ECAFM 12
E 72 ECLFM 12
E sens 64 MMAFM-EC 13
Ebias 73 O
ECAFM Control Panels 69 Operator
ECAFM model 12 safety 12
ECLFM model 12 O-ring
ECSTM Control Panels 69 installation 35
Elec Area 75 R
Electrode Controls Dialog Boxes 72 Ramp Electrode 82
Electrolyte 38 Ramp Max 80
Environmental Requirements 5 Ramp Min 81
Etip 72 Ramp Rate 80
F Ramping Controls Dialog Boxes 80
fluid cell S
AFM 18 Safety 12
ECM 17 sample
G preparation for imaging 2527
GP Sample Rate 82
positioning 29 STM
H imaging 4154
Symbols
hardware 21
Hazard Symbols thermal hazard 2
thermal 2 T
Head Leakage Dialog Box 66 Temporal Dialog Boxes 77

Rev. B Digital Instruments Electrochemical SPM 115


Index

Temporal Function 78
Temporal Graph 77
Thermal Hazard
symbol definition 2
Time Range 79
Tip Reference 81
Troubleshooting 5558
Tungsten Tip
etching procedure 109
V
Volt Function 75
Volt max 77
Volt Min 77
Volt Range 79
Voltam Dialog Boxes 75
Voltam Function 76
Voltammogram 75

116 Digital Instruments Electrochemical SPM Rev. B