CHEM3033CHEM3033

Surface and Bulk characterisation of solids

Prof. D.G. Billing

Course outline and contentCourse outline and content

Introduction Importance of surface chemistryImportance of surface chemistry Surface vs BulkSurface vs Bulk Analytical Chem of SurfacesAnalytical Chem of Surfaces Surface processes / a clean surfaceSurface processes / a clean surface Types of techniques and resultsTypes of techniques and results UHVUHV

Surface techniques. ESCA/XPSESCA/XPS AESAES SIMSSIMS SPM / AFMSPM / AFM

Bulk techniques. DSC, DTA, TGADSC, DTA, TGA XRFXRF XRDXRD

Course assessment.Course assessment.

Coursework component Assignment Assignment

Describe the basic principles of operation and at least one Describe the basic principles of operation and at least one application of one of the more common surface or bulk application of one of the more common surface or bulk characterisation techniquescharacterisation techniques

50% principles & 50% application50% principles & 50% application

10-15 pages.10-15 pages.

Wikipedia warning – don’t just copy. At least use own words, Wikipedia warning – don’t just copy. At least use own words, diagrams and examples.diagrams and examples.

No practicals Use time to read background material and work on Use time to read background material and work on

assignment.assignment.

References (Intro & Surface)References (Intro & Surface)

JC Vickerman (ed) ‘Surface Analysis’, Johan Wiley and Sons, New York 1997.

J. Chem. Ed, 61 (1984), 402-409, 483-489, 593-599

JF Watts & J Wolstenholme, ‘An Introduction to Surface Analysis by XPS and AES’, Wiley,2003

EM McCash, ‘Surface Chemistry’, OUP, 2001

IntroductionIntroduction

Interfaces between states of matter has interested “scientists” for thousands of years.

Solid surfaces are particularly important to everyday life.

90% of the world’s industrial output of materials such as fertilizers and plastics are produced via het. cat.

Consequences of lower coordination no.Consequences of lower coordination no.

Unbalanced forces at the surface means that the surface area is at a relative high energy compared to the bulk.

The electronic structure of the surface is different from the bulk

Crystallographic structure of surface is different.

The binding or ‘adsorption’ of gases is strongly favoured at the surface.

Surface vs BulkSurface vs Bulk

Operational definitionOperational definition

The surface region is that volume of the solid that the measurement technique or probe samples.

Therefore different techniques could sample different surfaces.

How many atoms in a surface?How many atoms in a surface?

Assume a cube of materials 1cm1cm33 (Density = 1 mol in 1 cm (Density = 1 mol in 1 cm33))

Ratio of surface to bulk is : 10101515/10/102323 = 10 = 10-8-8

Generally only probe 1 mm2 ie 1013 atoms, and about 10 layers deep, ie 1014 atoms.

Information required:Information required:

To understand the properties and reactivity of a surface, the following info is required:

The physical topographyThe physical topography The chemical compositionThe chemical composition The chemical structureThe chemical structure The atomic structureThe atomic structure The electronic stateThe electronic state A detailed description of bonding of molecules at the A detailed description of bonding of molecules at the

surface.surface.

No one technique can provide all this

Techniques for studying surfacesTechniques for studying surfaces

Note: Issues of measurement relate to both penetration and emission.In XPS X-rays penetrate to 10000 A, but it is still a surface sensitive technique!

Surface SensitivitySurface Sensitivity

Sample ChargingSample Charging

Build up of charge can occur on a surface. (esp. if it is non-conducting)

Leads to spectral distortion and peak shifts.

Insulators > semiconductors > conductors

Remove the problem: Surface conductionSurface conduction Stray electronsStray electrons CalibrationCalibration Flood-gunFlood-gun

ContaminationContamination

Contamination & surface layer normally samples!

Usually composed of species absorbed onto the surface. From atmosphere,From atmosphere, HandlingHandling Vacuum systemsVacuum systems

Quantification aspectsQuantification aspects

Extremely sensitive to the distribution of the measured species on the surface.

Angle of take offAngle of take off

Depth profiling via etchingDepth profiling via etching

ResolutionResolution

Why is UHV required for surface studies ?Why is UHV required for surface studies ?

Ultra high vacuum is required for most surface science experiments for two principal reasons :

To enable atomically clean surfaces to be prepared for To enable atomically clean surfaces to be prepared for study, and such surfaces to be maintained in a study, and such surfaces to be maintained in a contamination-free state for the duration of the contamination-free state for the duration of the experiment. experiment.

To permit the use of low energy electron and ion-based To permit the use of low energy electron and ion-based experimental techniques without undue interference experimental techniques without undue interference from gas phase scattering.from gas phase scattering.

To put these points in context we shall now look at the variation of various parameters with pressure

1. Gas Density1. Gas Density

2. Mean Free Path of Particles in the Gas Phase2. Mean Free Path of Particles in the Gas Phase

3. Incident Molecular Flux on Surfaces3. Incident Molecular Flux on Surfaces

4. Gas Exposure - the "Langmuir" 4. Gas Exposure - the "Langmuir"

5. Sticking Coefficient & Surface Coverage5. Sticking Coefficient & Surface Coverage

How long will it take for a clean surface to become covered with a How long will it take for a clean surface to become covered with a complete monolayer of adsorbate ? complete monolayer of adsorbate ?

       Time / ML ~ ( 1019 / F )        [ s ]

This is dependent upon the flux of gas phase molecules incident upon the surface, the actual coverage corresponding to the monolayer and the coverage-dependent sticking probability….

however , it is possible to get a minimum estimate of the time required by assuming a unit sticking probability (i.e. S = 1) and noting that monolayer coverages are generally of the order of 1015 per cm2 or 1019 per m2 . Then

Summary - Variation of Parameters with PressureSummary - Variation of Parameters with Pressure

For most surface science experiments there are a number of factors For most surface science experiments there are a number of factors necessitating a high vacuum environment : necessitating a high vacuum environment :

For surface spectroscopy, the mean free path of probe and detected particles (ions, atoms, electrons) in the vacuum environment must be significantly greater than the dimensions of the apparatus in order that these particles may travel to the surface and from the surface to detector without undergoing any interaction with residual gas phase molecules. This requires pressures better than 10-4 Torr. There are, however, some techniques, such as IR spectroscopy, which are "photon-in/photon-out" techniques and do not suffer from this requirement.(On a practical level, it is also the case that the lifetime of channeltron and multiplier detectors used to detect charged particles is substantially reduced by operation at pressures above 10-6 Torr).

Most spectroscopic techniques are also capable of detecting molecules in the gas phase; in these cases it is preferable that the number of species present on the surface substantially exceeds those present in the gas phase immediately above the surface - to achieve a surface/gas phase discrimination of better than 10:1 when analysing ca. 1% of a monolayer on a flat surface this requires that the gas phase concentration is less than ca. 1012 molecules cm-3 ( = 1018 molecules m-3), i.e. that the (partial) pressure is of the order of 10-4 Torr or lower.

In order to begin experiments with a reproducibly clean surface, and to ensure that significant contamination by background gases does not occur during an experiment, the background pressure must be such that the time required for contaminant build-up is substantially greater than that required to conduct the experiment i.e. of the order of hours. The implication with regard to the required pressure depends upon the nature of the surface, but for the more reactive surfaces this necessitates the use of UHV (i.e. < 1 x 10-9 Torr).