Defects in Materials

Real-world materials do not have exactly uniform properties throughout; all materials
contain tiny inhomogeneities (or defects) in which the properties are substantially
different from that in the rest of the material.

Defects are central to any understanding of material characteristics. They determine a

whole host of material properties, including strength, ductility, resistivity, and opacity.
In some cases, defects can build up in a material until it fails, as has occurred with
some aircraft.

Defects in materials occur over a wide range of scales, as shown in Table I. At the
smallest scale, defects consist of single missing atoms (or vacancies) in the material.
At higher defect concentrations, the vacancies may connect into dislocations, the first
stage toward what may become a crack. Larger defects with no material in them are
called voids. In polymers, which are made up of long molecules, defects may
aggregate between molecules and form microscopic holes.

Defect Type Size Materials

Atomic
0.1 nm Metals
Vacancies

Dislocations 1 nm - 10 m Metals

Voids 0.1 nm - 1 m Metals

Holes 0.1 nm - 10 m Polymers

Table I. Defects range from single- atom vacancies through macroscopic voids and holes.

Positron Decay in Materials

The lifetime of a positron is directly related to the probability it will run into an
electron. Positrons in materials have lifetimes that are governed by the electron
density in the material; the higher the electron density, the shorter the lifetime.

Thus, positron spectroscopy is a sensitive probe of electron density in materials.

If the defect density is lower than the bulk density, then the defects contain fewer
electrons, so positrons in the defects have a longer lifetime. In addition, these defects
have fewer nuclei in them, so they attract and trap positrons, which are repelled by the
positive charge of nuclei.

These characteristics have made positron spectroscopy a standard, well-established

technique for defect detection and characterization in materials. As shown in Figure 1,
positrons occupy a unique niche in the array of techniques that can be used for these
studie

Figure 1. Positron annihilatio

n spectroscopy fills a special niche in the group of

techniques for general vacancy defect analysis. Shown are regions accessible to various standard
techniques: optical microscopy (OM), neutron scattering (nS), transmission electron microscopy
(TEM), scanning tunneling microscopy (STM), atomic force microscopy (AFM), and x-ray
scattering (XRS). Positron techniques are both highly sensitive and can resolve the size of atomic
vacancies at any depth in a sample. The solid green line outlines the range of interest for studies of
fine lines used as electronic interconnects on semiconductor chips.
Positron Annihilation Lifetime Spectroscopy

One type of positron annihilation spectroscopy that is a very sensitive probe of defect
density and size is positron annihilation lifetime spectroscopy. In this technique, the
lifetimes of a large number of positrons are recorded by detecting the entry of the
positron into the material and subsequently detecting the radiation emitted by
annihilation.

A graph of the number of positron decays as a function of time after entry into the
material (Figure 2) reveals two distinct decay constants, corresponding to two
lifetimes: a short lifetime for positrons that annihilate in the bulk material, and a
longer lifetime for positrons trapped in defects.

Figure 2. Positron annihilation lifetime spectroscopy. A plot of decay probability vs. time of entry into a material
reveals two decay constants: one corresponding to the lifetime in the bulk material, and another corresponding to the
lifetime in defects. The relative amplitude of the two decay signals gives the density of defects in the material, while
the lifetime in the defects gives the defect size.

The positron annihilation lifetimes can be measured by a variety of techniques, all

based on determining the time between positron entry into the sample and
annihilation. Implantation time can be determined by either detecting a gamma ray
produced at the same time as the positron (such as occurs in the decay of 22Na), by
detecting the time of passage of the positron through a detector as it impinges on the
sample, or by delivering the positrons in extremely short timed pulses. Positron
annihilation lifetime spectroscopy allows determination of both the defect density and size. The
relative amplitudes of the two decay curves gives the defect density, while the lifetimes can be
used to determine the defect size.

Positron lifetime spectroscopy is a well-understood technique. Measured results agree well with
theoretical prediction, so that observations can be interpreted unambiguously. Figure 3 shows the
excellent agreement observed between experiment and theory.
 Figure 3. Theoretical and experimental agreement for positron lifetimes in a wide variety of materials is
excellent. As a result, interpretation of measured positron lifetime spectra is quite straighforward.

High-Resolution Defect Analysis

To perform micro-analysis and thin-film analysis of defects, we are currently

developing an intense, pulsed, sub-micron size positron beam (a positron microprobe)
capable of 3-dimensional maps of buried defects and defect profiling in thin films and
at interfaces. This instrument can be used for either spot analysis or in scanning mode
to provide a three-dimensional map of defect concentrations. Our high current beam
and positron microprobe will provide high data rates while detecting and identifying
depth-dependent concentrations of vacancies, voids, gas-filled voids and other
negatively charged defects at typical depth and lateral resolutions of less than 0.1
micron.
 Figure 3. The positron microprobe is a small, high-intensity, pulsed, variable-energy positron
beam. Defect location is determined by controlling the positron beam size and energy to confine
the positrons to a volume of scale ~ r2d, where r ~ 1 m and d varies up to ~ 10 m.

The microprobe will allow detailed mapping and study of defects arising from a
number of mechanisms, summarized in Table II. Repeated stress can result in
dislocations, which may grow to become cracks or other failures. Once a crack has
appeared, the stress on the material around the crack is much greater. Defects tend to
cluster around grain boundaries, formed during the crystallization of the material.
Defects are also produced in materials by irradiation.

Grain Boundary Processing

Stress Crack Tip Resin vs. Fiber
Buried Interface Irradiation Work

Table II. Mechanisms for defect formation.