University of Hulla

School of Engineering
Kingston upon Hull,
East Yorkshire HU6 7RX
United Kingdom
www.eng.hull.ac.uk

Renishaw plcb
Spectroscopy Products Division
Old Town, Wotton-under-Edge,
Gloucestershire GL12 7DW
United Kingdom
www.renishaw.com

Using Raman spectroscopy to study the effect of

boron on the mechanical properties of diamond

L.J. Browna, T. Smithb, E.J. Brookesa, I.P. Haywardb

Brookes et al1 have demonstrated that nitrogen content
affects the mechanical properties of diamonds, modifying
their plastic deformation behaviour. In the work presented
here, Raman stress mapping is used to reveal the stresses
around impressions on both type Ib and type IIb diamonds,
and give an insight into the different behaviour of the
diamonds, and in particular the effect of boron.

centre of
impression

[110]
surface
(100)

180 m
(including
n = 2.4
correction)

(110)
plane
though
centre

increasing
depth

Raman shift of
diamond band

300 m

1336 cm-1

Apparatus
Impressions were made using the University of Hull high
temperature rig, with a stylus-shaped cubic boron nitride
impressor at a chamber pressure of 10-2 Pa (10-4 torr). Two
impressions were studied, both made using 120 N force:
Type Ib diamond (synthetic, containing 80 ppm
substitutional N, impressed at 900 C for 50 minute).

4 cm-1

1331 cm-1

Figure 1
Raman maps of type Ib diamond

centre of
impression

[110]
surface
(100)

180 m
(including
n = 2.4
correction)

Type IIb diamond (synthetic, containing 10 ppm

uncompensated B, impressed at 1200 C for 50 minute).
Subsequent Raman spectroscopy measurements were made
using a Renishaw RM Series Raman microscope, with
514 nm excitation. Typical maps2 contained ~5600 spectra).

width (FWHM) of
diamond band
11 cm-1

(110)
plane
though
centre

300 m

increasing
depth

Raman shift of
diamond band
1336 cm-1

width (FWHM) of
diamond band
11 cm-1

1331 cm-1

4 cm-1

Figure 2
Raman maps of type IIb diamond

Analysis
The Raman shift of diamond 1332 cm-1 band increases with
compressive stress. Calibration of this shift to stress is very
complicated for non-hydrostatic stress fields; but we expect it
to be of similar magnitude to the hydrostatic value3, a shift of
-1

-1

2.4 cm GPa .
The Raman shift maps reveal that the geometries of the two
stress fields are broadly similar, with tensile regions below
the impressions and at the peripheries of the contact areas,
and compressive wings extending below the surface
diagonally away from the impressions. The stresses extend a
slightly greater distance from the type IIb impression than
from the type Ib impression, but less than may be expected
given the much higher temperature involved. We suggest that
this is because the boron hinders plastic deformation.

The maps of band width are harder to interpret because the

1332 cm-1 band width can be increased by disorder of the
diamond lattice, by stress fields that vary rapidly with
position, and by band splitting caused by non-hydrostatic
stress fields. The contribution of the last mechanism can be
determined by careful measurement of the polarization of the
Raman scattered light. These polarization measurements,
and further studies of the stress fields are ongoing.

References
1

E.J. Brookes, J.D. Comins, R.D. Daniel and R.M. Erasmus,

Diamond and Related Materials 9 (2000) 1115-1119
2

I.P Hayward, K.J. Baldwin, D.M. Hunter, D.N. Batchelder and

G.D. Pitt, Diamond and Related Materials 4 (1995) 617-621

The maximum stresses are much higher below the type IIb
diamond (ca. 10 GPa) than below the type Ib (ca. 5 GPa).
Work hardening seems to occur more rapidly in the IIb,
hindering movement of the dislocations and limiting slip. This
confines dislocations to the indentation area, resulting in
greater residual stresses.

S.K. Sharma, H.K. Mao, P.M. Bell, and JA Xu,

J. Raman Spec. 16 5 (1985) 350-352

Acknowledgements
We thank Dr. Kurt Baldwin, Dept. Physics and Astronomy,
U. of Leeds, for many helpful discussions, and De Beers
Industrial Diamond Division for kindly supplying the
diamonds.

P80