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High-Accuracy LIBS with Nanosecond and Picosecond Time
Resolution Enabled by Ultrasensitive emICCD Technology“The PI-MAX4:1024EMB
emICCD camera seamlessly
combines the rapid gating
capabilities of an image
intensifier and the excellent
linearity of a back-illuminated,frame-transfer, 1024 x 1024
EMCCD detector...”Introduction
Laser-induced breakdown spectroscopy (LIBS) is considered one of the most convenient andefficient analytical techniques for trace elemental analysis in gases, solids, and liquids. Bothnon-invasive and non-destructive, LIBS requires little-to-no sample preparation and can easily
be performed either in the lab or in the field in hazardous industrial environments in real-time.
Remote measurements can be done from more than 50 meters’ distance.
During LIBS, typically, but not always, a short laser pulse generated at 1064 nm by an Nd:YAGlaser is focused on a sample (see Figure 1). Laser energy heats, vaporizes, atomizes, andionizes target material, generating a small area of plasma. Excited atoms and ions in theplasma emit secondary light that is collected and resolved by a spectrometer and directed toa high-speed, high-sensitivity photodetector. Each chemical element has a unique spectral
signature that can be discerned from the obtained spectra. As a result, the multi-elemental
composition of the sample can be determined instantly.

Figure 1.

A short laser pulse — direction andduration represented by red arrow —is focused on a solid sample. A small
amount of the material breaks down,
local heating occurs, and the expansionof high-pressure vapor creates asupersonic shock wave: free electrons(e-), ionic species (i), atomic species(a), molecular species (m), excitedspecies (*). Adapted from J. Braz.
Chem. Soc., Vol. 18, No. 3, 463–512,
2007.

e-ee- ee- eee-i* a*i+ae-e-m*

TimeTo satisfy LIBS’ competing requirements of high resolution and broad wavelength range, anechelle spectrometer is recommended. Unlike Czerny-Turner and Littrow spectrometers,echelle spectrometers use two dispersive elements, usually a prism and a grating. Thus, thespectrum is divided not only in the x-direction but also the y-direction. The primary advantageof this assembly is that the entire two-dimensional detection array is utilized and a fullspectrum is captured at high resolution, not just a small region.
In LIBS applications where a relatively low power laser can be used, the less intense
background continuum emission means a conventional CCD camera with a high-speed
mechanical chopper affords a suitable imaging solution. However, in LIBS applications
where a high-power, short-duration laser pulse is required (i.e., the lone laser pulse lasts1femtoseconds to nanoseconds, 10-15 to 10-9 sec), only a comparatively small amount of laser
energy is transferred to the sample. This short-duration pulse produces a weak emission
signal over the continuum that is very difficult, or even impossible, for a conventional CCD
camera to capture with good signal-to-noise (S/N) ratio — which is why gated, intensified CCD(ICCD) cameras are widely utilized to perform LIBS.
For challenging applications where ICCD camera sensitivity and dynamic range are notenough, an emICCD camera is recommended. This document presents data demonstrating
the improved performance of a new emICCD camera from Princeton Instruments (used inconcert with an echelle spectrometer from Lasertechnik Berlin, or LTB) that delivers ultrahighsensitivity for demanding LIBS applications on the nanosecond and picosecond timescales.
Princeton Instruments’ new emICCD camera technology overcomes ICCD sensitivity anddynamic range limitations by fiberoptically coupling an image intensifier to a back-illuminated,
electron-multiplying CCD (EMCCD) detector. Dual-gain control optimizes the emICCD
camera’s performance by adjusting both the intensifier and the EMCCD gains, thus permitting
better linearity and dynamic range (subsequently increasing S/N ratio).

Experimental Setup
LIBS setups for laboratories and in-the-field industrial settings rely on compact, relatively
inexpensive scientific-grade instruments. Figure 2 is a diagram of a typical LIBS setup, which
includes a pulsed laser, a mirror, a focusing lens, a sample holder/chamber, collecting optics,
an optical fiber, an echelle spectrometer, a gated ICCD camera, and a computer (not shown).

MirrorFigure 2.

A typical LIBS setup.

Pulsed Laser
Focusing Lens

Echelle SpectrometerCollecting Optics
SampleRotationOpticalstage Fiber

Gated ICCD
CameraThe LIBS spectra presented in the following section were acquired at Lasertechnik Berlin’s
test lab utilizing a setup similar to the one depicted in Figure 2. The experimental setup inBerlin included an LTB ARYELLE 200 echelle spectrometer, which was mated to aPI-MAX4:1024EMB emICCD camera from Princeton Instruments configured with asuper-red image intensifier fiberoptically bonded to a back-illuminated, frame-transfer EMCCD
detector. See Figure 3.

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Figure 3.

A Princeton Instruments
PI-MAX4:1024EMB emICCD camera
paired with an ARYELLE 200 echelle
spectrometer from Lasertechnik Berlin.

Spectra and Observations
Figure 4 presents a LIBS spectrum of a solid sample (i.e., 402 stainless steel) acquired usinga PI-MAX4:1024EMB emICCD camera mated to an ARYELLE 200 echelle spectrometer.
By utilizing the echelle spectrometer to divide the spectrum in the x-direction as well as they-direction, the charge-coupled device’s entire 1024 x 1024 detection array can be leveraged
to capture the full spectrum, matching the spectral resolution of the ARYELLE 200.

Figure 4.

Full spectrum of 402 stainlesssteel acquired via LIBS using
PI-MAX4:1024EMB emICCD
camera paired with ARYELLE
200 echelle spectrometer. Data
courtesy of Lasertechnik Berlin.

Figure 5 compares LIBS spectra of 402 stainless steel acquired utilizing the LTB echelle
spectrometer paired with an emICCD camera (spectrum rendered using a gold line) and astandard ICCD camera (spectrum rendered using a blue line), respectively.

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Figure 5.

LIBS spectra acquired using emICCD
camera (gold line) and standard
ICCD camera (blue line) paired withechelle spectrometer. Data courtesy ofLasertechnik Berlin. Two-dimensional
plot created using LTB’s Sophi
software.

The emICCD camera (PI-MAX4:1024EMB) was fitted with a super-red intensifier, whereas thestandard ICCD camera (PI-MAX4:1024f) was fitted with a red-blue intensifier. The emICCD
camera, with its dual-gain mechanism, was observed to be ~3x to ~5x more sensitive. Had thesame super-red intensifier been used for both cameras, it is expected that the sensitivity withthe emICCD camera across the full spectral range, from 200 nm to 900 nm, would have been
~3x better than with the standard ICCD camera. The solid sample, the megapixel detector
array size, the intensifier gate/delay times, the laser excitation wavelength, and other key
experimental parameters were identical.
Figures 6 and 7 provide a closer look at these spectra in the UV and NIR regions, respectively.
Thanks to its use of a CCD featuring electron-multiplying detection technology, the emICCD
camera system clearly demonstrates superior sensitivity and resolution in the spectral regionsof interest when compared to the standard gated ICCD camera.

Figure 6.

Close-up of LIBS spectra in the UV
region: emICCD camera (gold line)
and standard ICCD camera (blue line)
paired with echelle spectrometer. Data
courtesy of Lasertechnik Berlin. Twodimensional plot created using LTB’sSophi software.

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Figure 7.

Close-up of LIBS spectra in the NIR
region: emICCD camera (gold line)
and standard ICCD camera (blue line)
paired with echelle spectrometer. Data
courtesy of Lasertechnik Berlin. Twodimensional plot created using LTB’sSophi software.

Enabling Technology
The PI-MAX4:1024EMB emICCD camera seamlessly combines the rapid gating capabilities
of an image intensifier and the excellent linearity of a back-illuminated, frame-transfer,
1024 x 1024 EMCCD detector in order to deliver quantitative, ultra-high-sensitivity
performance for LIBS applications executed on nano- and picosecond timescales.
This fiberoptically bonded Princeton Instruments PI-MAX®4 camera system provides<500 psec gate widths using standard fast-gate intensifiers while preserving quantum
efficiency. Its integrated SuperSynchro timing generator allows camera users to set gate
pulse widths and delays under GUI software control, and significantly reduces the inherent
insertion delay (~27 nsec).
Complete control over all PI-MAX4:1024EMB hardware features is simple with the latest
version of Princeton Instruments’ LightField® data acquisition software (available as an option).
Precision intensifier gating control and gate delays, as well as a host of novel functions foreasy capture and export of spectral data, are provided via the exceptionally intuitive LightField
user interface.
The PI-MAX4:1024EMB uses a high-bandwidth (125 MB/sec or 1000 Mbps) GigE datainterface to afford camera users real-time image transmission. This interface supports remote
operation from more than 50 meters away.

SummaryLaser-induced breakdown spectroscopy generally requires little if any sample preparationand is easy to perform in hazardous industrial environments in real-time. Hence, it is a very
attractive analytical tool. LIBS applications are utilized in many diverse fields. Areas thatbenefit from LIBS include geology, mining, construction, exploration of planets, environmental

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monitoring, analysis of biological samples, archaeology, architecture, military/defense,
forensic science, combustion processes, the metal industry, and the nuclear industry.
Unique PI-MAX4 emICCD cameras from Princeton Instruments provide high-performance,
cost-efficient, and user-friendly solutions for performing ultra-high-sensitivity LIBS applications
on nanosecond and picosecond timescales. All instrumentation-related functions are fully
controlled via software that includes quantitative algorithms as well as script language forcomplex automated measurement tasks.

Resources
For more information about PI-MAX4 ICCD and emICCD cameras, please visit:
http://www.pi-max4.com

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