Laser Induced Breakdown Spectroscopy
During LIBS, a short laser pulse is focused on a sample. Laser energy heats, vaporizes, atomizes, and ionizes sample material, generating a small area of plasma. Excited atoms and ions in the plasma emit a secondary light which is collected and spectrally resolved by a spectrophotometer and analyzed by a light detector. Each chemical element has a unique spectral signature which can be discriminated from the obtained spectra. As a result, the multi-elemental composition of the sample can be determined. Applying some special techniques provides an opportunity to simultaneously determine particle size distribution in aerosols.
2.1 Spectral coverage vs. resolution
2.2 Light sensitivity
3. General Applications
LIBS is considered one of the most convenient and efficient analytical techniques for trace elemental analysis in gases, solids, and liquids. Some of its major advantages include:
Real-time measurements: online monitoring and quality control of industrial processes
Noninvasive, nondestructive technique: valuable samples can be reused, sensitive materials can be analyzed, suitable for in-situ biological analysis
Remote measurements can be done from up to 50 meters distance: can be used in hazardous environments and for space exploration missions on other planets
Compact and inexpensive equipment: can be widely used in industrial environments, perfect for field measurements
High-spatial resolution: can obtain 2D chemical and mechanical profiles of virtually any solid material with up to 1 µm precision
Non or very little sample preparation is required: reduced measurement time, greater convenience, less opportunity for sample contamination
Samples can be in virtually any form: gas, liquid, or solids
Analysis can be performed with a very small amount of sample (nanograms): very useful in chemistry for characterization of new chemicals and in material science for characterization of new composite materials or nanostructures
Virtually any chemical element can be analyzed, such as heavier elements unavailable for X-ray fluorescence
Analysis can be done on extremely hard materials like ceramics and superconductors; these materials are difficult to dissolve or sample to perform other types of analysis
In aerosols both particle size and chemical composition can be analyzed simultaneously
2.1 Spectral Coverage vs. Resolution
Compact echelle spectrometers designed for LIBS applications are offered by several manufacturers.
In the rare occasion that an application requires even higher resolution, the Acton Series of spectrometers with their long focal lengths are extremely useful. The latest models use toroid mirrors with improved spectral quality.
An inconvenience of Czerny-Turner high-resolution spectrometers (as compared to echelle spectrometers) is that they only provide a relatively narrow range of spectral coverage during one laser shot. For a PI-MAX 3:1024 detector with 1024 horizontal pixels, each of which is 26 Ám wide, the theoretical field of view is 26.6 mm. But since a standard 25 mm intensifier is used, the field of view is 25 mm.
For example, if you decided to utilize a 2400 groove/mm grating in the Acton Series 2500 in order to enhance resolution, the linear dispersion will be 0.6 nm/mm while the spectral coverage will be 0.6*25 = 15 nm. To cover a spectral range between 300 and 600 nm (for example), you will need to perform at least 20 laser shots each time, moving the spectrometer grating to a new position and "gluing" all 20 spectra together. This is a very standard procedure which can be done painlessly and automatically with Princeton Instruments software. The only disadvantage to this is that acquisition of one spectrum could take up to a few dozen seconds or longer, which is why the echelle spectrometer has become extremely popular, especially in industrial and field applications where real-time measurements such as online quality control is a must.
2.2 Light sensitivity
Typically, the laser pulse in LIBS applications lasts for femto- to nanoseconds (10-15 to 10-9 s). Especially in applications where non-invasive and non-destructive analysis is required, a relatively small amount of laser energy is transferred to the sample. Therefore, one laser pulse produces a weak emission signal which is hard or impossible to collect with conventional CCD detectors. That is why intensified CCDs (ICCDs) are widely used in LIBS.
To improve the emitting signal on the order of 10-30 times, a scheme with two orthogonal lasers beams is often used. In this dual-scheme, the first and usually more powerful laser pulse ablates and atomizes sample material while the second one heats the ablated material even further, allowing it to improve the intensity of atomic or ionic lines. Factors such as the level of laser excitation energy for both pulses and the time delay between the pulses play a crucial role in achieving signal intensity enhancement. This technique increases the sensitivity of LIBS by at least one order of magnitude and allows for a greater possible number of applications.
If measurement time duration is not an issue, a regular CCD, such as the PIXIS 1024 (1024x1024 pixels, 13 µm pixel size), can be used together with the an echelle spectrometer for LIBS applications. To obtain the reasonable light level required for a non-intensified CCD, long exposure time measurements should be performed. In this case, plasma emission signal is accumulated on the CCD from a multiple laser pulse. However, one should be careful about excessive accumulation of background noise and low signal-to-noise ratio. It is especially important when performing measurements in the open air without an enclosed sample chamber. Since the CCD stays open for a long period of time, all sources of stray light in the room should be eliminated and measurements should be conducted in darkness. The PIXIS 1024 CCD usually proves a more sophisticated system than the PI-MAX 3 ICCD because intensified CCDs are prone to permanent damage by excessive light levels. Extra care should be taken so as not to expose ICCDs to the bright sources of light like laser reflections. In the case of a regular CCD, it is difficult to damage with excessive light.
3. General Applications
The fact that LIBS generally requires little-to-no sample preparation, simple instrumentation, and can easily be performed on-the-field in hazardous industrial environments in real-time, it is a very attractive analytical tool. The following are a few examples of real life applications, where LIBS is successfully used:
Express-analysis of soils and minerals (geology, mining, construction)
Exploration of planets (such as projects using LIBS for analyzing specific conditions on Mars and Venus to understand their elemental composition)
Environmental monitoring (Real-time analysis of air and water quality, control of industrial sewage and exhaust gas emissions)
Biological samples (non-invasive analysis of human hair and teeth for metal poisoning, cancer tissue diagnosis, bacteria type detection, detection of bio-aerosols and bio-hazards, anthrax, airborne infectious disease, viruses, sources of allergy, fungal spores, pollen). Replacing antibody, cultural, and DNA types of analysis
Archeology (analysis of artifacts restoration quality)
Architecture (quality control of stone buildings and glasses restoration)
Army and Defense (detection of biological weapons, explosives, backpack-based detection systems for homeland security)
Forensic (gun shooter detection)
Combustion processes (analysis of intermediate combustion agents, combustion products, furnace gases control, control of unburned ashes)
Metal industry (in-situ metal melting control, control of steel sheets quality, 2D mapping of Al alloys)
Nuclear industry (detection of cerium in U-matrix, radioactive waste disposal)
PI-MAX4 ICCD Camera
- The ultimate in precision and intelligence
- For gating to <500 picoseconds
- With Gen II or Gen III image intensifier
PIXIS CCD Cameras
- Lifetime vacuum guarantee for worry-free operation
- Deep cooling without the need for liquid circulators
- Up to 1000 spectra/sec data acquisition
IsoPlane Imaging Spectrographs
- Eliminates field astigmatism and greatly reduces coma.
- Produces crisp, detailed images across the focal plane.
- Preserves intensity - sharp spectral lines of constant width and height.
Acton Series Monochromators & Spectrographs
- Positrak™ grating stabilization offers simple calibration
- Optimized coatings for higher throughput
- Interchangeable grating turrets with a wide selection of gratings
Echelle spectrometer vendors
- LTB ARYELLE - (download the Tech Note)
- Applied Spectra