What is a Spectrometer?

At the very outset, it is important to understand the term “spectrometer”. A spectrometer is a device that separates and analyses the individual spectral components of a physical phenomenon to produce analytical results of interest. The spectrum – while most naturally associated with light by most – could be also be mass, magnetic, electron etc. leading to a large variety of types of spectrometry, such as optical spectrometry, photoelectron spectrometry, mass spectrometry etc.

What’s an Optical Emission Spectrometer (OES)? or What’s an Atomic Emission Spectrometer (AES)

Optical spectrometry refers to the analysis of a light spectrum separated by wavelengths. It can be of two types – absorption or emission. An Atomic Optical/Emission Spectrometer (AES / OES) is one that analyses an optical (light) spectrum emitted by an excited sample. The excitation could be by a number of means, such as application of a spark, plasma, flame etc. That said, the term “OES” is now almost ubiquitously used by people to refer to the arc-spark OES technique.

What principles does arc/spark Optical Emission Spectrometer work on?

Arc / Spark OES works on two very basic principles of physics:

  • Electrons in atoms absorb energy (get “excited”) and move into higher energy states (also called orbits) when energy is applied. When this  energy source is removed, the electrons fall into the ground state and release the absorbed energy in the form of photons.
  • No two different element’s atoms can emit photons at the same wavelength. Consequently, every wavelength is unique to a single element  alone.

This means that once we know the wavelength of the photon emitted, we know which element is emitting it!

Spark OES

How does an arc/spark OES work?

In an arc/spark OES, the principles outlined above are leveraged to analyze metallic (by and large – but more on this later) samples to assess exactly which elements are present in it – and in what proportion. The output of the OES is a detailed assessment of the elemental composition of the sample in weight percentages.

First up, there is a need to “spark” the sample. The sample is therefore first prepared, i.e. one face of the sample is made absolutely uniform, clean, flat and as free from surface flaws as possible. Suitable methods of sample preparation must be used for this. The prepared sample is then placed on the sample stand as shown below. The sample stand has a hole in it which the sample must cover. Below this, there is an electrode at a fixed distance from the sample’s exposed surface. This entire spark enclosure is filled with Argon when analysis is to be done. Then, a high current is applied to the sample.

The extremely high levels of DC current create a plasma in the Argon-purged atmosphere of the spark chamber, and a rapid series of high-energy sparks is therefore created between the electrode and the sample. Application of these sparks causes a part of the sample to vaporise. The vaporised atoms in the plasma absorb energy and their electrons move to higher energy-states with each spark. With each removal, the electrons move back into ground state and emit photons. Given the large number of elements simultaneously emitting photons, a composite emission is generated. This composite light is made to fall upon a diffraction grating.

The diffraction grating separates each individual wavelength and creates a spectrum inside what is called the “optical chamber”.

The spectrum can now clearly be analysed! The basis for analysis is of course, simplicity itself. We know the wavelengths that characterize each element. Further, the stronger the intensity of the emission at an element’s wavelength, the higher its concentration. Were to have a database containing the concentration levels that different intensity values correspond to for each wavelength of interest to us, we could simply look up the emission intensity against this database and say with conviction what the concentration of individual elements is.

Spark Optical Emission Spectrometer

How the first spectrometers worked

The first instruments (very early) had to work without photoemitters. The earliest researchers therefore had to rely on more mundane analog methods! They simply placed a photographic plate upon which the diffracted spectrum would fall. This plate was then developed and studied to arrive at the required results.

The first move to automation – the introduction of PMT detectors

In the 1930s however, there emerged the photomultiplier tube (PMT), a vacuum tube that emits electrons when light is incident upon it. Spectrometers therefore rapidly moved to using PMTs. A PMT was therefore placed inside the optical chamber in precise position for each wavelength that the user wished to analyse. Along with this, there was also a computer connected to the spectrometer. The computer stored the database against which the PMTs’ outputs were compared to arrive at the elemental composition required. This automated the process and not only made it far more rapid and convenient, but also far more accurate and error-free.

Working of Spectrometer

This worked very well for decades – but, as ever, technology moved on. PMTs clearly had a load of drawbacks:

Flexibility was absent – once bought, that’s that!

  • No ability at all to modify once made
  • Even a single element increase meant a new OES!

Cost and tedium was still very high

  • Detectors, cards etc. were extremely expensive
  • Regular profiling needed, vacuum pumps etc.

The revolution – the death of PMTs and rise of CCD and then CMOS:

The introduction of CCD (Charge Coupled Device) and now CMOS (Complementary metal-oxide semiconductor) detectors solved literally every issue that the PMT devices posed and also offered several more upsides to spectrometer makers and users. Just a few of these are:

Unmatched flexibility

  • Every wavelength is captured – so can be analysed
  • No limitation of space as CCDs are small

Instruments became smaller and less expensive

  • High-res grating & CCDs results in shorter focal lengths
  • Fewer detectors mean fewer cards and lower cost

Low tedium and low running costs!

  • No need for profiling etc. – as all this is automated
  • No vaccum and efficient electronic = lower running costs

Spectrometers therefore rapidly shifted towards using these devices and today, the modern OES exclusively comprises of optics with these devices.

What are the types of OES available today, then?

While modern OES design focuses exclusively on CMOS / CCD detectors, there remain some legacy instrument models in the market which still feature PMT detectors. Just as when the shift to DSLRs began, it didn’t immediately see all analog SLRs immediately withdrawn, so too, while the fall in PMT OES marketshare has been precipitous, there are still a handful of models with this technology that remain in the market. For the most part, the OES of today can therefore be classed into three types as shown below. All this said, PMT OES are now virtually obsolete and form a very small fraction of the overall market.

types of OES

What do the results appear like?

The results of an OES are completely quantitative and appear as weight percentages.

A typical analytical result would appear as below:

Is there anything more to know about OES?

Of course! As with any field, this is merely the beginning. For more, do refer to:

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