PART Ⅰ:PREPARATION AND MATERIALS

LANGMUIR-BLODGETT FILMS

1.1 Introduction

1.2 L-B Films of Long-Chain Compounds

Fatty Acids

Amines

Other Long-Chain Compounds

1.3 Cyclic Compounds and Chromophores

1.4 Polymers and Proteins

1.5 Polymerization In Situ

1.6 Alternation Films(Superlattices)

1.7 Potential Applications

SELF-ASSEMBLED MONOLAYERS

2.1 Introduction

2.2 Monolayers of Fatty Acids

2.3 Monolayers of Organosilicon Derivatives

2.4 Monolayers of Alkanethiolates on Metal and Semiconductor Surfaces

2.5 Self-Assembled Monolayers Containing Aromatic Groups

2.6 Conclusions

PART Ⅱ:ANALYSIS OF FILM AND SURFACE PROPERTIES

SPECTROSCOPIC ELLIPSOMETRY

3.1 Introduction and Overview

3.2 Theory of Ellipsometry

3.3 Instrumentation

3.4 Determination of Optical Properties

Analysis of Single Ellipsometric Spectra:Direct Inversion Methods

Analysis of Single Ellipsometric Spectra:Least-Squares Regression Analysis Method

Analysis of Multiple Ellipsometric Spectra

3.5 Determination of Thin Film Structure

Thickness Determination for Monolayers

Microstructural Evolution in Thick Film Growth

3.6 Future Prospects

INFRARED SPECTROSCOPY IN THE CHARACTERIZATION OF ORGANIC THIN FILMS

4.1 Introduction

Specific Needs for Characterizing Organic Thin Films

General Principles and Capabilities of Infrared Spectroscopy for Surface and Thin Film Analysis

4.2 Quantitative Aspects

Spectroscopic Intensities

Electromagnetic Fields in Thin Film Structures

4.3 The Infrared Spectroscopic Experiment

General Instrumentation

Experimental Modes

Additional Aspects

4.4 Examples of Applications

Self-Assembled Monolayers on Gold by External Reflection

Octadecylsiloxane Monolayers on SiO2 by Transmission

Langmuir-Blodgett Films on Nonmetallic Substrates by External Reflection

RAMAN SPECTROSCOPIC CHARACTERIZATION OF ORGANIC THIN FILMS

5.1 Introduction

5.2 Fundamentals of Raman Spectroscopy

5.3 Instrumental Considerations

5.4 Raman Spectroscopic Approaches for the Characterization of Organic Thin Films

Integrated Optical Waveguide Raman Spectroscopy(IOWRS)

Total Internal Reflection Raman Spectroscopy

Surface Enhanced Raman Scattering

Normal Raman Spectroscopy

Resonance Raman Spectroscopy

Plasmon Surface Polariton Enhanced Raman Spectroscopy

Fourier Transform Raman Spectroscopy

Waveguide Surface Coherent Anti-Stokes Raman Spectroscopy(WSCARS)

5.5 Selected Examples of Thin Film Analyses

Raman Spectral Characterization of Langmuir-Blodgett Layers of Arachidate and Stearate Salts

Raman Spectral Characterization of Self-Assembled Monolayers of Alkanethiols on Metals

Surface Enhanced Resonance Raman Spectral Characterization of Langmuir-Blodgett Layers of Phthalocyanines

5.6 Prospects for Raman Spectroscopic Characterization of Thin Films

SURFACE POTENTIAL

6.1 Introduction

6.2 Origins of the Contact Potential Difference and Surface Potential

The Work Function

Contact Potential Difference and Surface Potential

Surface Potential Changes Induced by Adsorbates

6.3 Measurement of Surface Potential

Capacitance Techniques

Ionizing-Probe Technique

6.4 Surface Potentials of Organic Thin Films

Air-Water Interface:Surface Potential of Langmuir Monolayers

Air-Solid Interface:Surface Potential of L-B and Related Films

6.5 Conclusions

X-RAY DIFFRACTION

7.1 Introduction

7.2 Basic Principles

7.3 Structure Normal to Film Plane

7.4 Structure Within the Film Plane

7.5 Summary

HIGH RESOLUTION EELS STUDIES OF ORGANIC THIN FILMS AND SURFACES

8.1 Introduction

8.2 The Scattering Mechanism

Dipole Scattering

Impact Scattering

Resonance Scattering

8.3 The Spectrometer

8.4 EELS Versus Other Techniques:Advantages and Disadvantages

8.5 Examples

Resolution Enhancement

Linearity

Depth Sensitivity

Molecular Orientation

Local Versus Long-Range Interactions

Surface Segregation

8.6 Conclusions

WETTING

9.1 Introduction

9.2 Contact Angles

9.3 Techniques for Contact Angle Measurements

Axisymmetric Drop Shape Analysis-Profile(ADSA-P)

Axisymmetric Drop Shape Analysis-Contact Diameter(ADSA-CD)

Capillary Rise Technique

9.4 Phase Rule for Moderately Curved Surface Systems

9.5 Equation of State for Interfacial Tensions of Solid—Liquid Systems

9.6 Drop Size Dependence of Contact Angle and Line Tension

9.7 Contact Angles in the Presence of a Thin Liquid Film

9.8 Effects of Elastic Liquid-Vapor Interfaces on Wetting

SECONDARY ION MASS SPECTROMETRY AS APPLIED TO THIN ORGANIC AND POLYMERIC FILMS

10.1 Introduction and Background

Overview of the SIMS Method and Experiment

Ion Formation Mechanisms

Comparisons to Other Surface Analysis Techniques

The Motivation for Thin Organic Films as Model Systems

10.2 Qualitative Information:Mechanisms of Secondary Molecular Ion Formation

Structure-Ion Formation Relationships

Applications to Self-Assembled Film Chemistry

10.3 The Study of Sampling Depth in the SIMS Experiment

10.4 Quantitation in SIMS

Development of Quantitation Methods

Application of Quantitative Schemes to Thin Film Chemistry

10.5 Imaging Applications

10.6 Summary and Prospects

X-RAY PHOTOELECTRON SPECTROSCOPY OF ORGANIC THIN FILMS

11.1 Introduction

11.2 Experimental Considerations

11.3 Binding Energy Shifts

11.4 XPS of Molten Films

11.5 Angular Dependent XPS

11.6 ETOA XPS of Self-Assembled Monolayers

11.7 Conclusions

MOLECULAR ORIENTATION IN THIN FILMS AS PROBED BY OPTICAL SECOND HARMONIC GENERATION

12.1 Introduction

12.2 Experimental Considerations

12.3 Molecular Nonlinear Polarizability Calculation

12.4 Measurements of the Surface Nonlinear Susceptibility

12.5 Molecular Orientation Calculation

Case 1:βZZZ only

Case 2:βZXX only

Case 3:βXXZ(=βXZX)only

Case 4:βZZZ and βZXX

Case 5:βZXX and βXXZ(=βXZX)

12.6 Absolute Molecular Orientation Measurements

12.7 Summary and Conclusions

APPENDIX:TECHNIQUE SUMMARIES

1 Auger Electron Spectroscopy(AES)

2 Dynamic Secondary Ion Mass Spectrometry(Dynamic SIMS)

3 Fourier Transform Infrared Spectroscopy(FTIR)

4 High-Resolution Electron Energy Loss Spectroscopy(HREELS)

5 Low-Energy Electron Diffraction(LEED)

6 Raman Spectroscopy

7 Scanning Electron Microscopy(SEM)

8 Scanning Tunneling Microscopy(STM)and Scanning Force Microscopy(SFM)

9 Static Secondary Ion Mass Spectrometry(Static SIMS)

10 Transmission Electron Microscopy(TEM)

11 Variable-Angle Spectroscopic Ellipsometry(VASE)

12 X-Ray Diffraction XRD)

13 X-Ray Fluorescence(XRF)

14 X-Ray Photoelectron Spectroscopy(XPS)

Index