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Optical Spectroscopy


Ossila broadband white light source and spectroscopy transmission holder
The Ossila Broadband White Light Source and Spectroscopy Transmission Holder set up for visible spectroscopy

Optical spectroscopy (or UV-Vis spectroscopy) is a versatile and non-invasive technique that can be used to study a wide range of materials. You can use this technique to probe solutions, thin films, and bulk devices in order to determine material properties and molecular structure. Optical spectroscopy can also used for biological and industrial purposes.

Optical spectroscopy is fairly easy to set up. All you need is an optical spectrometer and a calibrated light source. The type of optical spectroscopy you should do depends on both the sample itself and what material property you wish to investigate. Additionally, the type of light source you need depends on the type of spectroscopy you wish to perform. 

The main types of optical spectroscopy are luminescence, absorbance and reflectance spectroscopy which measure how a sample emits, absorbs and reflects light respectively.

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What is Optical Spectroscopy?


In broad terms, optical spectroscopy uses light in the UVA, visible and IR regions of the electromagnetic spectrum (anywhere between 190 - 1000 nm) to probe materials. By directing this light source through or reflecting it off a sample; you can use an optical spectrometer to measure how this light interacts with the sample. This works as light is split into its constituent wavelength components using a grating or prism. The spectrometer outputs the intensity of the light as a function of wavelength, and from this, you can gain important information about the electronic structure of the material.

A typical set up for spectroscopy consists of a spectrometer, the sample (usually held in either a transmission holder or cuvette holder), and a light source. These may be connected together with optical fibers ("coupled") and/or bolted to an optical table or breadboard plate. You can perform optical spectroscopy using a range of different light sources, categorised as either monochromatic or broadband sources. The type of measurement you wish to take determines which type of light source you should use. In general, monochromatic sources are used to excite materials (for example, in fluorescence measurements) whereas broadband sources are used for absorption, transmission and reflection measurements.

Need more information about Spectrometers? Please refer to our guide on How Spectrometers Work

To get started with the Ossila Optical Spectrometer, simply plug it in to a computer via the supplied USB-C cable and launch the spectroscopy software. The spectrometer can be controlled via serial commands (please see the Optical Spectrometer user manual for details) but the spectroscopy software is the easiest way to interface with the device, take measurements, and save and analyse data.

We recommend waiting for around 30 minutes for the internal temperature of the spectrometer to stabilise before taking any measurements.

Ambient light

We recommend performing measurements in the dark where possible. This reduces the effects of ambient light, which can interfere with spectroscopic measurements. The measurement apparatus (i.e. spectrometer, light source, and sample holder) should also be firmly secured (e.g. on an optical breadboard) before starting measurements, as any changes in position during the measurement will affect the results.

Jablonski Diagrams


The most common way to illustrate electronic and vibrational states and the transitions between them is using Jablonski diagrams. The energy levels are arranged vertically according to energy levels and horizontally according to multiplicity. An example Jablonski diagram is shown below.

Jablonski diagram
Jablonski diagram showing the singlet ground state (S0), the first two singlet excited states (S1 and S2), and the first triplet excited state (T1) (black lines). The vibrational energy levels (v0, v1, v2, and v3) are denoted by the grey lines.

Radiative transitions (such as absorption and fluorescence) are indicated by straight arrows, while non-radiative transitions (such as internal conversion and intersystem crossing) tend to be indicated by wavy arrows.

To find out more information on Jablonski diagrams, see Jablonski Diagrams

Transmittance 


Transmission measurements allow you to quantify how opaque a sample is to a particular wavelength of light. The transmittance, T , of a sample is defined as the ratio of light incident on the sample, I0 , to the intensity of light emerging from the other side of the sample, I:

This technique is complementary to absorbance spectroscopy, as you can work out the absorbance spectrum of a sample from the transmittance spectrum. You can also use transmittance spectrometry to measure the optical transparency of materials. For example, for optoelectronic devices, top contacts and top facing transport layers should be transparent in the visible region to reduce parasitic absorption. 

For transmittance measurements, light from a broadband light source is transmitted through a sample, and the transmitted light is detected by an optical spectrometer. 

Spectroscopy set up for transmission measurement

Absorbance


Absorbance spectroscopy measures the amount of light which can be absorbed by a sample as a function of wavelength. Just like transmittance spectroscopy, light is transmitted through a sample from a broadband light source. From this transmittance spectrum, you can work out the amount of light that has been absorbed.

This is a very useful technique. Depending on the sample it can help inform you about a wide range of material properties such as: 

  • Electronic structure and the properties of molecules in a solution or thin film.
  • Volume concentration, film thickness or molar concentration.
  • Optical density of bacterial cultures (used to monitor bacteria growth).

You can also use this technique as a non-invasive means of tracking changes in systems or materials (i.e. phase changes, glass transitions in polymers or changes in pH of some solvent systems). 

To find out more information on absorbance, see Absorption Spectroscopy

Photoluminescence


Photoluminescence spectroscopy measures the photoluminescence of a sample. This is when a sample or material absorbs electromagnetic energy in the form of a photon, and then emits this energy in the form of another, lower energy photon. This is also known as radiative emission or radiative recombination. PL spectroscopy is complementary to absorbance spectroscopy. Unlike chemiluminescence or electroluminescence, one key feature about photoluminescence is that it requires absorbance of a photon.

You can use Photoluminescence to investigate key electronic properties about different materials. It is useful for testing optoelectronic and photonic devices. Common uses of PL spectroscopy include: 

  • Studying optical properties of materials used in electronic devices, i.e. solar cells, LEDs. 
  • Characterising semiconductors.
  • Studying biological samples.

Photoluminescence should occur isotopically and so you can measure the PL spectrum of a sample at various angles. This means that you will need to optimise the design dependent your sample. In all cases, you should use a high energy light source - either UV laser or UV monochromatic light sources. This will excite the electrons into their excited states and the spectrometer will detect the emitted light. You may need to use a filter to remove the laser signal.

There are two main types of photoluminescence: fluorescence and phosphorescence.

Fluorescence

Fluorescence involves the relaxation of an electron through a singlet-singlet transition and happens on a nano second timescale. This means that once an electron has absorbed a photon, it almost immediately relaxes and re-emits another lower energy photon. This short lifetime means that fluorescence emission occurs only while the sample is being illuminated.

Phosphorescence

Phosphorescence occurs over a longer time scale. Phosphorescence requires a triplet-singlet transition which is much less likely to occur than a singlet-singlet transition. The longer lifetime of phosphorescence means that phosphorescent materials emit light continually after being illuminated. Therefore, these materials glow.

Chemiluminescence


Chemiluminescence is when a sample emits a photon because of a chemical reaction. This occurs when the chemical reaction creates a product which is in an excited state. This product then returns to its ground state through the emission of a photon or through the transfer of energy to a luminescent material. Like phosphorescence, this causes the material to glow. However, unlike photoluminescence, there is no initial illumination to cause this excited state.

We often see this process in nature - for example, in glow-worms, fireflies and jellyfish. It also has extensive biological applications, such as for acting labels for immunoassays or for probing DNA. You could also use chemiluminescence for synthetic purposes such as for creating glow sticks or detecting pollution levels in the atmosphere. 

Electroluminescence


Electroluminescence is the emission of light in response to an electric current or electric field being applied across the material. This is used in optoelectronic materials, often semiconductors. Excess electrons are injected into excited states by doping the material (e.g. to create a p-n junction), or by applying a strong electric field across it. These electrons then relax back to their ground state, emitting a photon. 

Electroluminescence is used in dashboard displays and in some nightlights. However, the most common use of electroluminescence is in light emitting diodes. 

Diffuse Reflectivity 


Reflectance spectroscopy studies the way that light scatters off a surface or sample. There are many types of reflectance spectroscopy, but two main types are specular and diffuse reflection. Specular reflectance is used to measure more ideal reflectors such as mirrors. It can be a useful property to examine when you are determining a materials suitability for a certain use. Diffusive reflection measures the way light reflects or scatters off a textured or rough surface. 

  

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Contributing Authors


  • David Coles
  • Kristy McGhee
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