Application

Note: 51122
Analysis of Diamonds by FT-IR Spectroscopy
Stephen Lowry, Ph.D., Thermo Fisher Scientific, Madison, WI, USA

Introduction The Thermo Scientific Nicolet™ 6700 FT-IR spectrometer

Key Words Diamonds are by far the most popular gemstone in equipped with an optimized beam condenser or reflection
America and many other parts of the world. Because of accessory has the sensitivity to rapidly acquire high quality
• Diamond Simulants
this popularity and the high prices of quality gemstones, spectra from faceted diamonds. When the system is
• HPHT Detection there is a large market for cheaper stones that resemble configured with the Thermo Scientific TQ Analyst™ multi-
diamonds as well as diamonds that have been treated to variate analysis software, automated workflows can be
• Hydrogen and Boron
improve their appearance. Detecting these stones can be a created to automatically analyze the spectral data and
• Nitrogen Aggregates significant problem for diamond buyers if these stones are quickly report the results. Once the stone has been properly
represented as natural diamonds by unscrupulous sellers. positioned in the instrument, a complete analysis can be
FT-IR spectroscopy can be a useful tool for buyers and completed in less than a minute with no effect on the
sellers to determine whether diamonds are natural. stone itself.
Diamonds are unique among gemstones because they
are composed of a single element (carbon), while virtually Experimental
all other gems contain multiple elements including significant
Rapid Confirmation that a Stone is a Diamond
amounts of oxides. The infrared spectrum of diamond is
equally unique and can be used to easily confirm that a Automatic material confirmation is a technique that has
stone is actually a diamond. A diamond consists of crystalline been extensively used in the pharmaceutical industry to
carbon and the extreme conditions required to create them ensure that incoming material is correctly labeled.
also provide a way for trace amounts of other elements to Reference spectra are acquired from all of the materials that
be trapped in the crystal matrix. The most important trace are used in the products and then a computer algorithm is
element is nitrogen, which can be found in different forms in employed to calculate the similarity of the spectrum from
the diamond crystal. These nitrogen aggregates create unique the incoming material with the reference spectrum from
features in the infrared spectrum and are key in classifying the specified material. In this case, a reference spectrum
diamonds. Hydrogen, boron and carbonates are other from a type IIa diamond was used to develop a Similarity
important trace elements, all of which have identifiable Match method using the TQ Analyst software. A match
features in the infrared spectral region. While it is easy to value is then computed. The value will be 100 if the spec-
confirm that a stone is a diamond, it is much more difficult trum from the sample is identical to the reference and zero
to determine if it is synthetic or treated. Laboratory grown if there is no similarity between the two spectra. Since the
high pressure-high temperature (HPHT) diamonds are now spectra for all diamonds are slightly different, the match
commercially available and their identification is one of the value will always be less than 100. In our experience, setting
major challenges for the gem industry today. The infrared
a threshold for a pass of 80 gave no false positives and yet
peaks corresponding to the nitrogen aggregates or presence
accepted a certain amount of variance in the sample spectra.
of other elements can be used to provide valuable evidence
The major exception that was found was Type IIb diamonds
that a stone is not natural. In this application note, we will
with high boron levels which severely distorted the phonon
describe several techniques based on FT-IR spectroscopy
region. The only features observed in a spectrum of pure
that are extremely valuable to gemological laboratories.
diamond are the phonon bands from the crystal lattice
structure that are observed in the 1500 cm-1 to 4000 cm-1
spectral region. There are three phonon bands but the
one phonon band is not infrared active. An example of
analyzing a typical diamond is shown in Figure 2.

Figure 1: The Thermo

Scientific Nicolet 6700
FT-IR spectrometer and
4X beam condenser

The 4X beam condenser photo is courtesy

of the Gemological Institute of America, ©2002.
All rights reserved. Reprinted by permission.
 Many diamond spectra have a peak in the 1360 cm-1
region which has been attributed to the formation of
platelets in the crystal. This peak is interesting in that it
both shifts and broadens depending on the overall makeup
of the sample. Curve resolution, or peak fitting, is a tech-
nique that can be very effective in this type of situation.
This technique synthesizes peaks based on a pre-defined
line shape and minimizes the difference between the actual
spectrum and a linear combination of the synthetic peaks.
The following figure shows two platelet peaks that are
shifted by several wavenumbers.

Figure 2: Diamond confirmation based on TQ Analyst Similarity Match

Classifying Diamonds
A technique used extensively in quantitative analysis is
Classical Least Squares (CLS). The basis of CLS is the
assumption that the spectrum from a sample that is a
mixture of known materials can be modeled by a linear
combination of the spectra from the pure reference materials.
In this case we are using spectra from diamonds with well
defined nitrogen aggregates: Type IaA, Type IaB and Type
Figure 4: Characterizing the Platelet Peak in two diamond spectra by Curve Fitting
Ib. Because we do not know the actual concentrations of
nitrogen in the spectra, we have arbitrarily assigned the The results of the Peak Resolve™ curve fit reveal that
value to be 100 ppm so the actual values reported here are the Full Width at Half Maximum (FWHM) has gone from
relative to the arbitrary value for illustrative purposes. 3.2 cm-1 to 4.8 cm-1 as the peak has shifted from 1359 cm-1
to 1364 cm-1. A closer examination of the curve fit results
also shows that the peaks are asymmetric and can be fitted
better with two synthetic peaks.

Figure 3: Quantitative analysis of nitrogen aggregates by CLS

The results of this example CLS method are shown

above. Although the calculated standard error terms
indicate that all three nitrogen types are present, adding
more standards to the method might resolve any questions
about the presence of the Type Ib aggregates.
Assisting in the Detection of Synthetic Diamonds Conclusions In addition to these
offices, Thermo Fisher
Besides the platelet peak, several other peaks in the spectrum Numerous gemological laboratories employ FT-IR on a
Scientific maintains
can be helpful in trying to identify treated stones. In many daily basis to characterize diamonds and other gemstones.
a network of represen-
of these cases the amount of nitrogen in the diamond is In this application note, we have provided several examples
tative organizations
very low, so it can be difficult to confirm the presence of where the combination of a Thermo Scientific Nicolet
throughout the world.
particular peaks. In this example, a simple CLS method series FT-IR spectrometer and an optimized accessory has
was developed to confirm the presence and measure the been used with multivariate statistical analysis techniques
intensity of peaks at 3107 cm-1, 1344 cm-1 and 1332 cm-1. to provide a rapid, reliable information source of great
A key advantage to the CLS approach is that a standard importance to classifying gemstones. By automating
error term is reported with the analysis. While it is not a these methods, the results are consistent and supported
rigorous statistical confidence level, if the peak intensity is by a quality, or confidence, metric. In many cases, FT-IR Africa
three to five times the reported error term, the presence of is used by an operator to rapidly screen out the samples +43 1 333 5034 127
a peak has been confirmed. An example for a sample that clearly pass or fail the test, allowing the outliers to Australia
+61 2 8844 9500
containing very low levels of nitrogen is shown below in be examined by an expert. Austria
Figure 5. In this example all three peaks are present at +43 1 333 50340
detectable levels. Belgium
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+86 10 8419 3588
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Figure 5: Measuring low level peaks in the diamond spectrum by CLS
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