LP980

Pride in Precision
Transient Absorption
Spectrometer
 Transient Absorption / Laser Flash Photolysis – Technical Overview

Transient Absorption / Laser Flash Photolysis is a tech- Transient absorption measurements are applicable to
nique for studying the transient chemical and biological liquid, gaseous, and solid samples. Liquids are usually
species generated by a short, intense light pulse from measured in a cuvette with the pump beam and the probe
a nanosecond pulsed laser source (pump pulse). This beam overlapping orthogonally (transverse excitation). In
intense light pulse creates short lived photo-excited inter- gaseous samples the concentration of the participating
mediates such as excited states, radicals, and ions. These molecules is much lower and a co-linear setup between
intermediates are generated in concentrations large the pump and probe beam is preferred to improve the
enough for chemical and physical interaction to occur signal to noise ratio.
and for direct observation of the associated temporally
changing absorption characteristics. Film samples, powders and non transparent bulk samples
are generally studied in a diffuse reflectance setup.
These absorption changes are recorded using a spectrally
continuous xenon lamp (probe source) forming the back- There are two modes of operation of the LP980:
ground in a single beam absorption spectrometer. The 1. Kinetic mode - LP980-K
probe source is operated in a pulsed mode to enhance 2. Kinetic and Spectral mode - LP980-KS
the photon flux for measurements in short time ranges,
allowing spectra and kinetics to be measured with tem-
poral resolutions from nanoseconds to milliseconds in
pulsed mode, and milliseconds to seconds in continuous
mode.

Kinetic
Kinetic Data Acquisition Spectral Data Acquisition

t t λ λ

Transient Absorption Spectrometer Kinetic Mode: transient absorption decays are

recorded at a single wavelength as a function of
Spectral Mode: time-gated transient absorption
spectra are measured at a specific time after excita-
time using a photodetector and a digital storage tion using an ICCD detector. Spectral mode meas-
oscilloscope. This mode provides very accurate urements provide the full picture of the transient

LP980
measurement of transient kinetics since a complete spectral features by exposing the sample to only a
LP980-K 4-10 time-resolved measurement of the transients is few laser shots. This is especially useful when study-
TRANSIENT ABSORPTION SPECTROMETER – made in a single flash experiment. Lifetimes from ing biological samples, which can easily undergo
KINETIC MODE nanoseconds to seconds can be measured over photo-degradation under high levels of light. Time
a wavelength range from 200 nm to 2550 nm resolutions down to 3 ns can be achieved with a
Spectrometer system for the measurements of transient (depending on the detector). spectral coverage from 200 nm to 930 nm.
absorption and laser-induced emission kinetics with the As a fully computer-controlled turn-key system,
ability to automatically generate transient spectra. the LP980 sets the standard for technical per- Spectral Slicing Kinetic Slicing

formance in transient absorption / laser flash

LP980 - System Overview 11-14 photolysis. Comprehensive software allows λ4 t4
TRANSIENT ABSORPTION SPECTROMETER for astonishing ease of use and the modular λ3 t3
λ2 t2
Configuration, layout, and specifications for the turn-key,
design concept enables maximum flexibility, λ1 t1
λ t
modular and unrivalled spectrometer. with unrivalled measurement modes all in one
instrument:
LP980-KS 15-19 t λ
Transient Absorption
TRANSIENT ABSORPTION SPECTROMETER – Time-resolved absorption spectra can be gener- Spectrally resolved absorption kinetics can be
KINETIC AND SPECTRAL MODE Laser-Induced Fluorescence (LIF)
ated in kinetic mode laser flash experiments by extracted from spectral mode measurements by
Spectrometer system for the direct measurements of automatic scanning through a pre-defined spectral automatically stepping the gate delay through a
Laser-Induced Breakdown Spectroscopy (LIBS)
range and subsequent data slicing. This technique predefined time range. Subsequent data slicing
time-gated transient absorption and laser-induced emis-
Ground and Excited-State Raman requires many laser shots, in particular when high reveals the details of the transient absorption
sion spectra as well as kinetic measurements.
spectral resolution is required. kinetics.

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 LP980-K - Kinetic Mode Transient Absorption Spectrometer
The LP980 Transient Absorption Spectrometer uses the In kinetic mode a photomultiplier detector is used and
Signal Detection and Data Acquisition
same basic optical-electrical setup for operation in both the transients are acquired using a fast, high resolution
the kinetic and the spectral mode, i.e. laser excitation oscilloscope. The LP980-K is supplied with a standard red sensitive with corresponding relative gains, varying from 1 to 1000.
source, probe source, sample compartment (including photomultiplier (PMT) which covers the spectral range
The LP980-K has been designed to meet the stringent For transient absorption and emission measurements in
optics, attenuators, laser shutter, and probe shutter), from 200 nm to 870 nm. The detector housing also ac-
demands of high quality research. At the same time it is a the near infra-red spectral region, InGaAs detectors (up
monochromator / spectrograph, and control electronics. commodates the high voltage power supply and the
true turn-key system suitable for routine applications, with to 2550 nm) are available as options.
The difference between the two modes is the detector voltage divider circuit.
ease of operation guaranteed by comprehensive software
and the data acquisition electronics. The output signal from the detector is directly recorded
and a user friendly interface. The photomultiplier detector system is designed to
by a digital storage oscilloscope with a minimum speci-
achieve a high dynamic range with exceptional current
fication of 200 MHz bandwidth, 2.25 GS/s sampling rate.
linearity. This is an essential requirement in measuring
Higher bandwidth and digitising rates are available as
small signals on a large signal background. The voltage
options. Instrument setup and data acquisition are fully
Operational Example divider and power supply are configured to support this
computer-controlled. The user does not need to be famil-
high linearity current mode by operating in a five stage
iar with detailed operation modes of oscilloscopes.
The sample being investigated is exposed to an intense dynode configuration.
The bandwidth of the oscilloscope, together with the ex-
probe pulse laser pump pulse, which creates the transient species, The PMT detector contains two outputs within the
citation laser pulse width and the detector response time,
and the probe source, which forms the background for same unit. The fast output has a rise-time of <3 ns and
contribute to overall instrumental response function of
the time dependent absorption measurement. is suitable for transients up to ca 1 ms. The slow output
the system. Hence, a significant increase in performance
small changes For time scales in the microsecond and nanosecond has a selectable range of output rise times and is recom-
in the plateau of only one of these parameters is of little benefit.
caused by the range the required high background level of the probe mended for timescales >1 ms, due to its improved signal
transient to noise ratio. The rise times vary for ca 10 μs to 10 ms
light is created by the intense flash from the pulsed xenon
lamp which – after some stabilisation period - reaches a
sufficiently flat plateau. This plateau level represents the Detection Limit
pre-photolysis background level of the transmitted light
through the sample. At a pre-set time after lamp trigger- The detection limit given by the RMS noise for single Detection improvement is made in proportion to the
ing, when the pulse plateau is flat, the excitation laser is shot measurements is ΔOD = 0.002 (fast detector) and number of pulses used in the measurement, e.g. 100
triggered creating the transient species under investiga- ΔOD = 0.0005 (slow detector option). pulses improves the signal-to-noise ratio by ten times and
tion. The absorption of the transient species is usually hence the detection limit improves to ΔOD = 0.0002 (fast
Data averaging is common in transient measurements in
time dependent and produces a time dependent change detector) and ΔOD = 0.00005 (slow detector).
order to improve the measurement’s signal-to-noise ratio.
in the transmission of the sample. For transient absorption measurements this improves the
After recording the time dependent transmission of the detection limit by decreasing the minimum ΔOD that can
sample, the optical density change is calculated using the be resolved.
level of the background light as 100% and the measure-
ment baseline as 0%.

The change in optical density, ΔOD, can then be analysed single shot measurement 10 shots average

using exponential least squares fitting algorithms, result-

ing in transient lifetimes or rate constants.
raw ΔOD(t) data
To protect the sample against unnecessary radiation
exposure between measurements and as a means to
fit result
control background measurements, high speed shutters
are operated to control the probe and laser beam prior
to entering the sample. For laser-induced emission meas-
urements the probe shutter remains permanently closed.

Demonstration of the detection limit and of the Signal-to-Noise improvement by signal averaging using the fast detector version
Sample: Erythrosin B in water
Measurement Conditions: lpump = 532 nm, Epump = 1 mJ, pulsed probe source, lprobe = 580 nm

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 Software Measurement Examples

The LP980-K spectrometer system is fully computer- switching between probe shutter open and probe shut- Transient Absorption and Photobleaching
controlled by means of the comprehensive L900 software ter closed then the result is a measurement of transient
In transient absorption, the presence of the transient
package. absorption which is corrected for emission.
species can cause the sample to have either increased or
A variety of different measurements and correction meth- The LP980-K data acquisition dialogue boxes allow the decreased levels of absorption relative to the absorption
ods are available. For example, if the probe shutter is direct import of data captured with the digital storage of the ground state species (positive ΔOD and negative
programmed to be closed during the measurement then oscilloscope. ΔOD respectively). While an increased absorption is as-
normal time-resolved emission measurements can be sociated with triplet-triplet or singlet-singlet transitions,
Data averaging can be made either within the oscilloscope
made. If a measurement sequence is made with alternate a reduction in the measured optical density is associated
in order to make effective use of high repetition rate
with either ground state depletion or sample emission.
sources, or the data can be transferred to the computer
memory and averaged there. Generally these effects can be separated spectrally, or
by means of their lifetimes. In some special cases (such
At the end of a measurement sequence, the raw data is
as with the ruthenium bipyridine complex) separation by
converted into optical density data.
lifetimes is not possible.
The L900 software package
offers a comprehensive library
of data analysis routines,
Triplet-Triplet Annihilation
including 1- to 4-exponential
and reconvolution fits, analysis Annihilation of excited states can take place if too many
of growth and decay kinetics. excited states are generated (due to high sample concen-
tration or excessive pump energies) whose lifetimes are
long compared to the diffusion times of the molecules. In
this case diffusion controlled collisions become possible
resulting in the de-activation of both molecules. Sample: Ruthenium bipyridine in water
Measurement Conditions: lpump = 355 nm, Epump = 8 mJ, pulsed probe
This example clearly shows the effect of laser energy on source, lprobe = 370 nm (top picture), lprobe = 450 nm (bottom picture),
single shot
the transient dynamics. Annihilation is a non-exponential Top picture: transient absorption at 370 nm
process but can be fitted with a series of exponential with Bottom picture: photobleaching at 450 nm

the long lifetime representing the “true” excited state

lifetime for the generated species. Oxygen Quenching of Transient Absorption Decays
Software Functionality
The triplet states of organic molecules are often quenched

The main challenge for the L900 software and the LP980 along with the digital storage oscilloscope. This task has by oxygen present in the solvent. Transient absorption

spectrometer controller is the correct time sequencing of been accomplished with the LP980 spectrometer; while measurements clearly reveal the sensitivity towards oxy-

the individual spectrometer components, i.e. pump laser, maintaining maximum flexibility in measurement modes gen. The measurement example below shows the effect

probe lamp, spectrograph, pump and probe port shutters the user has complete control. of different oxygen concentrations on the transient decay
times, from 0% (blue curve) to 20% oxygen (black curve).
Measurement Modes Control Features Data Manipulation and Display

• Measurement setup • Wavelength / slit control • ΔOD calculation

• Transient absorption • Grating selection (automatic and manual)
• Laser-induced fluorescence (LIF) • Pump laser flashlamp trigger • Arithmetic (+, -, x, /)
• Multiple spectral measurements • Pump laser Q-switch trigger • Scaling
• Time-resolved absorption • Probe source pulse current • Normalise
spectra (TRAS) • Pump and probe shutters • Baseline subtraction
• Time-resolved emission • Oscilloscope trigger • Data slicing – TRAS
spectra (TRES) • Data slicing – TRES
• Oscilloscope time base
• Stopflow mode for use with • Full data reconvolution using
• Oscilloscope voltage scale Sample: Anthracene in cyclohexane, partially degassed
optional stopped flow accessory non-linear least square fitting
• Signal offset Measurement Conditions: lpump = 355 nm, pulsed probe source, lprobe
routine = 423 nm, three different laser excitation pulse energies: Epump = 50 mJ
• Time shift / delay (red), Epump = 10 mJ (blue), Epump = 1 mJ (green).
• 2D, 3D, Contour plotting and text
• Optional temperature controlled Main figure (lower): measured change in optical density
Sample: Erythrosin B in water
sample holder Inset figure (upper): same data but scaled to same peak height. The
Measurement Conditions: lpump = 532 nm, Epump = 10 mJ, pulsed probe
green curve represents a single exponential decay with a lifetime of
• Optional cryostat mounting source, lprobe = 580 nm, 10 shots average
t = 271 μs
• Stopflow synchronisation

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 Measurement Examples Time-Resolved Absorption Spectra LP980-K - Technical Specifications

Spectrally Dependent Transient Kinetics The LP980-K Spectrometer hardware is computer- By automatically scanning through the spectral range System
controlled and enables the user to generate time- the probe background level can change. The changing The LP980-K is a system for the measurement of laser-induced transient absorption and emission decay kinetics with the ability to
Time-resolved transient absorption spectra can provide The delay characteristics (measured with a PMT) show automatically generate temporally resolved transient absorption and emission spectra
resolved absorption spectra in a two-fold process: background level does not have an effect on the value of
substantially more information than kinetic measurements different decay kinetics in each band. Spectral measure-
Firstly, a series of transient absorption measurements the optical density, but it has an effect on the noise of the
alone. The measurement of benzophenone in cyclohex- ments (measured with an ICCD camera) reveal that the Optional: Thin-film geometry, Co-linear excitation, diffuse reflectance geometry, Raman, Fluorescence and Phosphorescence lifetime
over a pre-defined range of probe wavelengths is individual measurements. The LP980-K has the software measurements, and Laser-Induced Breakdown Spectroscopy (LIBS) accessories are all available
ane shows two distinct absorption bands with maxima at longer wavelength band shifts towards the near-infrared
recorded, and, secondly, this data is sliced at desired option to either automatically reset the probe background
330 nm and 530 nm. spectral range with time.
time windows and delays from the laser pulse excitation. offset or to correct for this changing background level. Sensitivity
Minimum ΔOD 0.002 (single shot, fast detector option)
0.0005 (single shot, slow detector option)

Time Resolution
Instrument Response Function 7 ns (100 MHz acq. bandwidth, fast detector option)*
(FWHM) 10 μs (slow detector option)
100 ns (InGaAs detector option)
* Faster IRFs are available with suitable oscilloscope(s) and laser(s). Contact Edinburgh Instruments for more information.
Lasers with pulse width >6 ns will result in a broadened instrument response

Laser Excitation Source **

Single Wavelength Flashlamp pumped Q-switched Nd:YAG laser,
operating at 1064 nm, 532 nm, 355 nm or 266 nm**
Tuneable Dye Laser, tunable range dependent on dye
OPO, tuneable between 410 nm - 710 nm (signal).
Idler and UV doubler options possible to extend the range from
Sample: Benzophenone in cyclohexane <210 nm to >2000 nm
Sample: Anthracene in cyclohexane, partially degassed ** A fully tested laser system can be supplied by Edinburgh Instruments, or alternately supplied by the customer
Measurement Conditions: Left: lpump = 355 nm, Epump = 8 mJ, pulsed probe source, lprobe = 330 nm (green), lprobe = 530 nm (red), single shot
Right: lpump = 355 nm, Epump = 8 mJ, pulsed probe source, spectral range 290 nm - 600 nm, gate width = 200 ns, delay (green) = 0 ns, Measurement Conditions: lpump = 355 nm, Epump = 5 mJ, pulsed probe source, lprobe = 390 nm to 440 nm in 1 nm steps using a PMT, spectral
delay (red) = 600 ns, delay (blue) = 1200 ns. resolution = 1 nm, 16 averages per decay. Probe Source
Fit Results: at 330 nm: t = 1100 ns; at 530 nm: t1= 151 ns (φ1 = 22%); t2 = 1126 ns (φ2 = 78%) Left: raw data obtained in kinetic mode, Right: data after spectral slicing
Type Pulsed / steady state xenon arc lamp, 150 W, ozone free
Pulsed Operation: Rep. Rate - 10 Hz to single shot
The spectrometer operating software can perform For the advanced analysis of complex data sets an option- Pulse Current - Up to 100 A
Pulse Duration - 0.2 ms – 6 ms
Data Slicing and Data Correction standard curve fitting of individual ΔOD(t) curves. The al software package is available. The advanced analysis

L900 allows for automated fluorescence background

standard analysis is based on exponential decay models, software offers batch and global fitting of multiple ΔOD(t) Monochromator
Kinetic and spectral data sets can be viewed and analysed
taking into account the Gaussian statistics of the raw data. curves and can also test the measurements for second
in various ways using the L900 software. Data slicing can subtraction, as well as probe subtraction. This is in ad- Type 300 mm focal length, Czerny-Turner with Triple Grating Turret
order decay kinetic models Filter Wheel Integrated, automatic filter wheel for 2nd order light removal
be used to convert a set of kinetic decay data into spectral dition to subtraction of the laser (pump) noise from the Slits 5 mm to 10 mm (continuously adjustable), motorised
data and vice versa. Additionally, transient absorption resulting spectra. These correction facilities ensure the Stray Light Rejection 1:105
Grating Plane, ruled grating, 1800 grooves/mm, 500 nm blaze
data can be corrected by making additional fluorescence most accurate data is represented The automatic selec-
Dispersion 1.8 nm/mm
measurements and then subtracting them in order to ex- tion of high-pass filters in the monochromator filter wheel Options Gratings with 150 – 2400 grooves/mm, optimised from UV-NIR
Mirror Motorised to select detector
pose the true underlying transient absorption behaviour. inhibits second-order grating effects.
Detector
Type PMT with 5 stage dynode chain for high current linearity
Spectral Range 200 nm – 870 nm
Window Material UV Glass
Detector Impedance 50 Ω (amplified-fast detector, <3 ns rise time), 1 kΩ (slow
detector, <100 ms rise time)
Options InGaAs detectors (900 nm - 2550 nm)

Data Acquisition
Oscilloscope Fully remote controlled by operating software, or manually
controlled when off-line
Bandwidth 100 MHz as standard (300 MHz and 500 MHz optional)
Sampling Rate 1.25 GS/s
Interface Ethernet

Sample: Ruthenium bipyridine in water

Software
Measurement Conditions: lpump = 355 nm, Epump = 9 mJ, pulsed probe source, lprobe = 340 nm to 700 nm in 10 nm steps using a PMT
Raw data and fitted curves of the set of 80 time-resolved measurements of an anthracene example. Operating System Windows ®
Left: data after spectral slicing without fluorescence correction, slicing 0 to 450 ns in 50 ns slices Data Manipulation ΔOD calculation (with / without background correction),
Right: data after spectral slicing with fluorescence correction, slicing 0 to 450 ns in 50 ns slices Data were analysed with FLASH software (optional) using Global Analysis of a second order kinetic decay model, globally linking the rate constant. The
result of the fit is a global second order rate constant of 1.8x103 (M ms)-1 and a wavelength dependence of the amplitude as shown in the insert. numerical fits by Marquardt-Levenberg algorithm, analysis of
growth and decay kinetics, Time-Resolved Absorption Spectra

Edinburgh Instruments Ltd. has a policy of continuous product development and reserve the right to amend specifications without prior notice (Jan 2016)

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 Laser Pump Source LP980 - Transient Absorption Spectrometer Dual Sample Chamber and Beam Geometry

In Transient Absorption / Laser Flash Photolysis, transient Spectra Physics (Quanta-Ray Pro, Lab and Indi). OPOs Transient Absorption (TA) (Standard) Laser-Induced Fluorescence (LIF) (Standard)
species are generated using a short pulse, high peak by Continuum and OPOTEK can have their wavelengths suitable for liquids (shown) and film samples suitable for liquids (shown) and film samples
power laser, known as the pump pulse. Suitable lasers in- tuned from within the L900 software.
clude fixed wavelength lasers, particularly Nd:YAG lasers Laser Beam Steering Chamber Laser Beam Steering Chamber
Generally, flashlamp pumped Nd:YAG lasers have pulse
(fundamental wavelength 1064 nm) and their harmonics
widths in the range 5 ns - 7 ns. Pulse energies at the fun-
(at wavelengths 532 nm, 355 nm and 266 nm), or tunable
damental wavelength range typically from 50 mJ - 1000 LP Controller
lasers, particularly optical parametric oscillators (OPOs).
Other lasers sometimes used include nitrogen or excimer
mJ, dropping with each non-linear stage of harmonic Laser Beam Dual Sample
lasers and dye lasers.
generation to between 2 mJ - 20 mJ at 266 nm.
Power Supply Steering Chamber Chamber
When pumped by the third harmonic of the Nd:YAG laser
The LP980 has been designed with the ultimate flexibil-
at 355 nm, OPOs provide broadly tuneable output from
Electronics Chamber
ity in mind. It can be supplied either as a turn-key, fully
both signal and idler bands spanning the range from 410 Dual Sample Dual Sample
tested and performance guaranteed spectrometer, with Spectrograph Chamber
Probe Beam Chamber
Chamber
Probe Beam Chamber
nm – 2400 nm. Additional frequency doubling can extend
integrated laser to suit individual need and budget, or
the wavelength tuneability to the UV down to 210 nm.
as a system with comprehensive trigger and command
pulses to control virtually any commercially available laser.
Type II OPOs are generally preferred as they do not suffer Probe Lamp Quasi-Co Linear (Optional) Diffuse Reflectance (Optional)
from a gap in tunability around the degenerate wave- Readout suitable for low absorption liquid and gas samples suitable for powders and non-transparent film samples
Edinburgh Instruments have experience of integrating length at 710 nm although they characteristically have a
lasers from a wide variety of manufacturers including slightly reduced pulse energy. With a pump pulse energy
Laser Beam Steering Chamber Laser Beam Steering Chamber
Continuum (Minilite and Surelite I and II Nd:YAG lasers, of 100 mJ at 355 nm OPOs have peak output energy of
broadband or narrow band OPOs, Horizon OPO I or II), up to 35 mJ at 450 nm and several mJ over a wide tuning
Quantel (Q-Smart, Brilliant, Brilliant B and Brio Nd:YAG range. Edinburgh Instruments are happy to advise on the
with optional Rainbow OPO), OPOTEK (Opolette and optimum laser for particular applications and budget.
Vibrant OPOs), Ekspla (Lasers and OPO systems),

Detectors
Probe Source Dual Sample Dual Sample
Probe Beam Chamber Probe Beam Chamber
Chamber Chamber
In a conventional absorption spectrometer, the time aver- The LP980 contains a built-in lamp pulser with particular
Probe Beam
aged absorption of a sample is measured from the light emphasis on pulse flatness, reproducibility and minimum
Chamber
level being attenuated whilst passing through the sample. ripple. An optional Halogen lamp can be added in order Accessories
In flash photolysis the temporal change of the attenu- to facilitate long lifetime measurements (milliseconds and
ated light following laser excitation is measured. As these higher). Raman measurement module Laser-Induced Breakdown Spectroscopy module
changes often occur in the nanosecond time range, the The Raman accessory contains notch and dichroic filters A type of atomic emission spectroscopy. With this up-
Monochromator / Spectrograph Detectors
available light level in the probe beam may be too low for and an objective lens. It can be used with an ICCD grade the laser is focused to form a plasma, which atom-
an acceptable signal to noise ratio. In order to overcome and a narrow linewidth laser to measure ground-state ises and excites the sample. In principle, Laser-Induced
pulsed Xe, unscaled The LP980 spectrometer has a three grating turret mono- and is blazed at 500 nm. It offers a spectral range of 540 Kinetic Mode (K) Spectral Mode (S)
this and to provide sufficient probe light levels, a pulsed Raman spectra. Excited-state Raman is also possible with breakdown Spectrocopy (LIBS) can analyse any matter
chromator/spectrograph which gives maximum flexibility nm with the standard 25 mm long detector array. Other The LP980 in its kinetic mode is supplied, as standard, with Spectral mode allows the user to study the full time-gated
probe source is used. continuous Xe, scaled appropriate lasers. Please contact EI for more details. regardless of its physical state.
in wavelength coverage and spectral resolution, for both grating options with wavelength coverage of 270 nm and a red sensitive photomultiplier which covers the spectral transient spectra within one flash of the pump laser. This
The best way of supplying a broad band, stable light pulse the UV-VIS and near IR spectral ranges. 135 nm are available upon request. Stopped flow accessory Temperature control systems
range from 200 nm to 870 nm. An optional detector is also is especially useful when studying samples that are not
with a flat time profile is by using a xenon arc lamp oper- available with extended spectral range up to 1010 nm. photostable. A rapid kinetic accessory for manual multi-mixing Oxford Instruments liquid nitrogen or helium cryostats
The monochromator/spectrograph has a symmetric A combination of up to three different gratings can be
ated by adding a “super current pulse” to the low current capabilities is available to allow stopped flow analysis. It with ITC controllers are used when low temperature
continuous Xe, unscaled Czerny-Turner optical configuration with a focal length of fitted to the grating turret. The selection of the grating For transient absorption and emission measurements The LP980 in spectral mode utilises a gated ICCD camera
simmer supply. A pulsed xenon lamp exhibits a significant comprises a sample handling unit fitted with three 1.0 ml measurements are required. The cryostat is provided with
300 mm and a constant aperture of F/4.1. type and the requested spectral position is made by a further into the near infrared (NIR), InGaAs photodiodes optimised for spectroscopy applications. The ICCD is
increase in the emitted photon flux during the period of drive syringes, 600 mm long umbilical, manual or software an adapter to fit into the standard sample chamber, which
micro-stepping drive controlled from the system software. can be used with coverage up to 2550 nm. There are 3 gated so that transient spectra from a few nanoseconds
the pulse, compared with the photon flux from the same For kinetic (K) mode, UV-VIS operation the system is fitted controlled drive, and 12.5 mm square mixing/observation is controlled by the L900 software.
This gives unparalleled accuracy and reproducibility in the different InGaAs detectors to choose from. These cover to seconds can be recorded.
lamp in steady-state operation over the equivalent time with a standard 1800 g/mm grating. It has a linear disper- cuvette
Xenon arc lamp emission spectrum monitored over a 3 ms period. Lamp spectral performance of the system. A temperature controlled cuvette
period. During pulsed operation, the colour temperature in continuous operation (red curve - unscaled; black curve - scaled) and sion of 1.8 nm/mm, blazed at 500 nm, and a wavelength spectral ranges up to 1650 nm, 2050 nm and 2550 nm.
There are various ICCD options available based on spec- Film Sample Holder holder with range of -10°C to
in pulsed operation with a current pulse of 150 A (blue curve). Spectra
of the arc is dramatically increased over its steady state were measured using an ozone-free Xenon bulb and are corrected for
coverage from 200 nm to 900 nm. For near IR operation A unique feature of the monochromator is the computer- The LP980 employs NIR PMTs to make Laser-Induced tral coverage and minimum gate widths. To discuss which
Vertically mounted sample +105°C (extended versions avail-
equivalent and as a result, the emission profile is shifted the responsivity of the detection system. the standard grating has 600 g/mm, with a blaze wave- controlled beam steering mirror at the exit port, allowing Fluorescence (LIF) measurements using the Multi-Channel camera is best suited to your requirements please contact able), and ±0.02°C precision, is
holder for transparent thin-
towards the UV and the spectrum is less structured. length of 1 μm, covering the spectral range from 600 nm rapid selection of detectors (e.g. photomultiplier and Scaling (MCS) photon counting technique. This is used for us directly.
film and slide samples at 45 also available.
to 2.7 μm InGaAs detector or single element and array detector) example in singlet oxygen analysis.
degrees, with rotational and X-Y
without the need for mechanical or optical adjustment.
For time-gated measurement applications in the kinetic/ movement control.
spectral (KS) mode, the standard grating has 150 g/mm

11 12
www.ed inst.com 13 14
 LP980-KS - Technical Specifications
LP980-KS - Kinetic / Spectral Mode Transient Absorption Spectrometer
System
The LP980-KS is a combined system for the measurement of laser-induced transient absorption and emission decay kinetics AND
spectra with the ability to automatically convert and fully analyse the kinetic and spectral information. Wavelength specific kinetic Signal Detection and Data Acquisition
measurements are made using a photomultiplier and oscilloscope, while time-gated spectral measurements are obtained using an
The generation of spectra in kinetic mode by successive The LP980-KS has an array detector fitted to the spectro-
image-intensified CCD camera. measurements at different wavelengths requires many graph exit port to measure a full range of wavelengths
The LP980-KS uses an externally triggerable, gated ICCD The ICCD camera is a software-controlled device with its
The LP980-KS technical specification includes all specifications from the LP980-K plus the additional: excitation flashes. This can sometimes be problematic simultaneously. By means of a swing mirror and a slit at
camera optimised for spectroscopy applications. The hardware / software interface located in the spectrometer
because of sample photodegradation and instability. This the second exit port, a kinetic detector can still be fitted
ICCD detector has the high sensitivity of a photomulti- control computer. This permits all image intensifiers pa-
is true in particular when highly spectrally resolved results to the spectrometer.
Sensitivity plier as well as nanosecond time resolution. It combines rameters, CCD parameters, and data transfer operations
(with small wavelength steps) are anticipated.
Minimum ΔOD 0.0005 (single shot) - ICCD camera The array detector is a CCD camera with an integrated the highest quality scientific grade CCD array detector to be fully controlled by the L900 spectrometer software.
An efficient method to overcome these issues is to use the gated image intensifier (ICCD). The device exhibits a high with image intensifier, gating and delay circuits, and CCD
LP980-KS – the kinetic and spectral mode version of the sensitivity and allows time-resolved spectra to be meas- cooling fully integrated into one compact detector.
Time Resolution
LP980 laser flash photolysis spectrometer. ured in a window as narrow as 3 ns.
Minimum Gate Width 7 ns * (3 ns, ultrafast option available) The CCD multi-channel detector has a characteristic high
(FWHM) dynamic range and an ultra-low readout noise.
* Lasers with pulse width >6 ns will result in a broadened instrument response
The gain of the image intensifier is user adjusted so the
Monochromator / Spectrograph sensitivity of the detector can be set to the best level for
Type 300 mm focal length Czerny-Turner with Triple Grating Turret Operational Example the measurement. At low gain the sensitivity is compara-
Filter Wheel Integrated, automatic filter wheel for 2nd order ligth removal ble to that of a normal CCD detector. When operated at
Slits 25 mm to 10 mm (continuously adjustable), motorised
The continuous spectral output of the high gain the ICCD detector can detect single photons.
Grating K-mode grating AND plane, ruled grating, 150 grooves/mm,
500 nm blaze, 540 nm coverage xenon lamp forms the background
Dispersion 21.6 nm/mm
light level for time -gated spectra.
Spectral Coverage 540 nm (active horizontal ICCD dimension: 25 mm)
Andor iSTAR
Spectral Resolution 0.56 nm (spectral coverage / 960 pixels) The spectral characteristics of this background spectrum
Options Gratings with 300 grooves/mm or 270 nm coverage and (black curve), and
background light is determined by spectra after laser
0.28 nm resolution
many factors, such as the xenon lamp excitation
Mirror Motorised to select detector Detection Limit
output, monochromator efficiency,
Detector ICCD spectral responsivity and sample The information from the CCD detector can be read with transferred to the computer, or in image mode, where
LP980-K PMT detector plus: ground state absorption characteristics. a rate of 1 μs/pixel for fast results or with read-out rates all pixels are read individually and the information of the
Type Image intensified CCD camera ΔOD curves calculated
from the raw data above of up to 32 μs/pixel for the lowest possible readout noise. vertical columns is averaged in the computer memory.
Spectral Range 200 nm – 850 nm After laser excitation the continuous
Min. Optical Gate Width 7 ns (FWHM) In addition, the CCD may be cooled down to -25oC (with For laser flash photolysis experiments the latter mode is
Active Pixels 960 x 256
background will be modified according
additional water circulation) for further noise reduction desired as it improves the dynamic range, at the cost of a
Active Area 25 mm x 6.7 mm to the transient features of the sample,
Cooling -10°C (-25°C with additional water circulation) and minimal baseline drift when measurements are made slower experimental repetition rate.
depending on image intensifier gate
Option 3 ns min. optical gate width over extended periods.
300 nm - 930 nm spectral range width and delay. The detection limit of the ICCD array detector is ΔOD =
The LP980-S can operate the ICCD in either fast vertical 0.0005 for a single shot measurement. It can be further
Data Acquisition The optical density change is calculated from the
binning mode, where the information contained in the 256 enhanced by signal averaging.
differences between background and measurement
ICCD Fully remote controlled by operating software vertical pixels are accumulated on the CCD before being
Fast Vertical Binning 16-bit data resolution after sample excitation.
Image 24-bit data resolution
For comparison, the bottom figure demonstrates the
ground state absorption and emission of the same single shot measurement 10 shots average
Software
Ru(Bpy) sample. The effect of the ground state and
Operating System Windows ®
Data Manipulation ΔOD calculation, mathematical, smoothing, automatic kinetic
excited state phenomena on the ΔOD spectra can
spectra acquistion, transformation into kinetics by data slicing, clearly be seen.
2D, 3D graphics, contour plotting

Demonstration of the detection limit and of the Signal-to-Noise improvement by signal averaging
Sample: Erythrosin B in Water
Measurement Conditions: lpump = 532 nm, Epump = 1 mJ, pulsed probe source, 10 μs gate width, 1 μs gate delay

Edinburgh Instruments Ltd. has a policy of continuous product development and reserve the right to amend specifications without prior notice (Jan 2016)

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 Software Measurement Examples

The L900 software package controls both the LP980-K, ki- Comprehensive spectral calibration features are available, Time-Gated Transient Absorption Spectra
netic mode operation as well as the LP980-KS, kinetic and and automatic software subtraction of camera dark noise
Anthracene has distinct spectral bands when viewed Magenta curve (200 ms after laser pulse): the fluorescence
spectral mode operation. This ensures full compatibility is provided.
in the nanosecond and microsecond timescales, as the has gone and the transient absorption bands become
between the two modes as well as a user friendly software
A variety of different spectral measurement and cor- features of fluorescence and transient absorption can be more distinct.
environment for systems able to operate in either mode.
rection options can be made. For example, with the seen in the two graphs below.
Blue curve (400 ms after laser pulse): the transient absorp-
The user can view pixel bitmaps of the CCD image to probe shutter permanently closed normal time-resolved
Green curve (immediately after laser pulse): fluorescence tion decay continues.
assess the quality of the image at the ICCD photocath- emission spectra are taken. If a measurement sequence
superimposed on transient absorption. The large, but fast
ode. This is particularly useful for setup and optimisation is made with a fixed gain and fixed gate width, but with
decaying, fluorescence alone can be seen on the plot on
purposes prior to measurement sequences. incremental increase of the gate delay, a map of time-
the right.
resolved spectra is automatically generated. These can be
For standard measurements, 2D images of the raw data
sliced to produce kinetic decays at a given wavelength.
and the resulting optical densities are the preferred plot
options.

Sample: Anthracene in cyclohexane, partially degassed Sample: Anthracene in cyclohexane, partially degassed
Measurement Conditions: TA: lpump = 355 nm, Epump = 10 mJ, pulsed Measurement Conditions: LIF: lpump = 355 nm, Epump = 10 mJ, spectral
probe source, spectral range 300 nm - 500 nm, gate width = 1 ms range 300 nm - 500 nm, gate width= 50 ns

Time-Gated Laser-Induced Fluorescence Spectra

The LP980 has an enhanced capability that no other
transient absorption spectrometer on the market can do.
It can also capture laser-induced fluorescence spectra in
the ultraviolet, visible and near-infrared spectral ranges.
Software Functionality In addition to this, the spectra can be time-resolved.

While maintaining full flexibility for users who want to have their minds focussed entirely on the sample and The graph on the right shows ruthenium bipyridine laser-

use the ICCD in specific setup modes (like restriction of transient absorption results. It will take a newcomer only a induced time-resolved fluorescence spectra.

image size, modification of data transfer rates, use of few minutes to become familiar with the requirements for Green curve immediately after laser pulse
fast vertical binning mode), particular attention has been standard measurements in the spectral mode. Magenta curve 100 ns after laser pulse
Blue curve 200 ns after laser pulse
paid to make the software user friendly for scientists who
Orange curve 300 ns after laser pulse
Measurement Modes Control Features Data Manipulation and Display Turquoise curve 400 ns after laser pulse

• Measurement setup • Wavelength / slit control • ΔOD calculation

• Transient absorption • Grating selection • Arithmetic (+, -, x, /, append)
• Laser-induced fluorescence (LIF) • Spectrograph port selection • Scaling
• Laser-induced breakdown (LIBS) • Pump laser flashlamp trigger • Normalise
• Ground and excited-state Raman • Pump laser Q-switch trigger • Baseline subtraction
• Multiple spectral measurements • Probe source pulse current • Smoothing
• Time-gated absorption maps • Pump and probe shutters • Data slicing
• Time-gated emission maps • ICCD gain • 2D, 3D, Contour plotting and text
• ICCD gate delay
• ICCD gate width
• ICCD temperature
• Cryostat
Sample: Ruthenium Bipyridine in water
• Temperature-controlled Measurement Conditions: (LIF) lpump = 450 nm, Epump = 10 mJ, spectral
cuvette holder range 450 nm - 800 nm, gate width = 100 ns

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 Printed: Jan 2016

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