Time-Resolved Absorption Spectrum Analysis System

Time-Resolved Absorption
Spectrum Analysis System
Measure the transient absorption spectrum in extremely short time !
Analysis of the formation and decay process of a reactive intermediate in a photoreaction in solutions, solids,
membranes, etc are possible.
Measure the transient absorption spectrum in extremely
short time in a high dynamic range with high S/N.
The time-resolved absorption spectrum analysis system is a
device to perform transient absorption spectrum
measurements in extremely short time. This system enables
to analyze the formation and decay process of a reactive
intermediate in a photoreaction in solutions, solids,
membranes, etc are possible. By using the streak camera
as the detector and performing multiple-wavelengths timeresolved measurements with a single shot, time-resolved
absorption spectra and transient absorption time-resolved
spectral images can be measured simultaneously, and you
can obtain images of irreversible phenomenon.
The newly developed High dynamic range streak camera
C7700 is employed as the detection device. Minute
transient absorption changes can also be measured in a
high dynamic range with high S/N.
Features
Measurements with the smallest optical
density (OD) of 0.005
(for single shot, OD value is 0.02 or less)
Simultaneous measurements of multiple
wavelengths using a single shot
High time resolution
Automatic measurements with computer
control
System configuration
ORCA-R2
Digital CCD camera
Spectrometer f=300 mm C11119-02
High dynamic range
streak camera
C7700
RELAY LENS
A2098
Image intensifier for C7700
V12303-01
Digital delay generator
DG535
Q-SW trigger
Spectrograph mount table
A11350-13
Flash lamp trigger
Streak camera transient
absorption measurement optics
Sample
High-output YAG laser
Shutter
Shutter
Data analyzer
C6743-94
2
Xe lamp 150 W/CW L8004 /
Xe lamp Break down L7013
Shutter controller
General performance
Nanosecond Q-SW YAG laser
Measurement time range
White light source
Picosecond mode-lock YAG laser
<7 ns
<70 ps
20 ns to1 ms
0.5 ns to 20 ns
Temporal resolution
Xe lamp 150 W/CW
Xe lamp Break down
Measurement OD value
0.005 (for single shot, 0.02 or less)
Simultaneous observation
wavelength width (W) and
100 gr/mm: W= 510 nm, Δλ<3.0 nm
wavelength resolution (Δλ)
300 gr/mm: W= 170 nm, Δλ<1.0 nm
150 gr/mm: W= 340 nm, Δλ<2.0 nm
600 gr/mm: W= 85 nm, Δλ<0.5 nm
Measurement wavelength range
250 nm to 750 nm
Number of channels
Time axis: 1024 ch
Wavelength axis: 1344 ch
Functions
The time-resolved absorption spectrum analyzing system is composed of a pump and probe lights, optics including shutters (a streak camera
transient absorption measurement optical system) a detector part (a spectrometer, a high dynamic range streak camera, and high sensitive
digital camera), delay generators, and a data analyzer. For example, a high-output Xenon lamp and a nano-second Q-SW YAG laser are
utilized as the pump and probe lights respectively. The pump and probe lights are operated the shutters on the transient absorption
measurement software in the data analyzer, and time resolved images such as Data Monitor, (Emission) and Dark images are measured by the
detector part. Transient absorption image is obtained from the time-resolved images by calculation with analysis functions.
Control functions
Analysis functions
Streak camera : time range, MCP gain
Spectrometer : grating selection, central wavelength setting,
slit width setting
Shutter
: shutter opening and closing for
excitation light and white light,
delay generator (delay value setting)
Display functions
Transient absorption time-resolved spectral images
Transient absorption time and wavelength profiles
Analyzing fluorescence images from Emission2
Emission2=Emission1-Dark
Measurement functions
Data measurements
(The white light is measured with both the pump light
and probe light shutters open.)
Data storage functions
Live image data (Data, Monitor, Emission1, Emission2, Dark,
Absorption1, and Absorption2 from the dialog box), spectrum
profiles, and time profiles can be saved as files. This does not
include fitting data.
Image file format : TIFF, ITEX
Profile file format : TEXT file
Analyzing transient absorption operation images
For nonfluorescent samples
Absorption1=-log10 ([Date-Dark]/[Monitor-Dark])
For fluorescent samples
Absorption2=-log10 ([Date-Emission]/[Monitor-Dark])
Monitor measurements
(The white light is measured with only the probe light
shutter open.)
Emission measurements
(The fluorescence is measured with only the pump light
shutter open.)
Dark measurements
(The dark current is measured with both the pump light and
probe light shutters closed.)
Absorption2
Transient absorption operation image,
example of transient spectrum profile display
3
Operating principle
Using a streak camera as the detector
Sweep electrodes
(electrons are swept in the direction
from top to bottom)
Sweep circuit
Trigger
signal
Image intensifier
Streak image on
phosphor screen
Lenses
Light intensity
Time
Space
Time
Slit
Space
Phosphor screen
MCP
(electrons light)
(which multiplies
Accelerating
The intensity of the incident light
electrons)
can be read from the brightness
electrode
of the phosphor screen, and the
Streak tube
(accelerates the electron)
time and space from the position
of the phosphor screen.
Photocathode
(photons electrons)
Fig. 1 Operating principle of streak tube
[Streak camera operating principle]
The streak camera is a device that measures and displays the
temporal variations of the incident light intensity as the
luminance distribution using the positions (spatially) on the
screen by converting incident light into electrons and
performing a high speed sweep of the electrons from top to
bottom. Figure 1 shows the operating principle of the streak
tube at the heart of the streak camera.
The light pulse being measured passes through the slit and the
lenses and the image of the light is formed as the slit image on
the photocathode of the streak tube. Even now, there is a slight
lag both temporally and spatially and four light pulses with
different light intensities pass through the slit before reaching
the photocathode. Because the photocathode also converts
the light pulses into electrons proportional to the intensity of the
incident light, the four light pulses are converted into electrons
in order and accelerated by the accelerating electrode before
being conducted towards the phosphor screen. The highspeed sweeping is performed by applying high voltage to the
sweep electrodes, timed to the passage between the
electrodes of the groups of electrons created from the four light
pulses. Because each successive group of electrons arrives a
bit later than the previous group, they are deflected at slightly
different angles in the perpendicular direction and then
bombarded against the phosphor screen where they are
converted back into light.
The streak image obtained on the phosphor screen through the
image intensifier can be read by a digital camera that has been
The fluorescence image of the first incident light pulse is
positioned at the top of the phosphor screen with successive
light pulses appearing lower on the screen in order. In other
words, the perpendicular direction on the phosphor screen
serves as the time axis. In addition, the brightness of each
fluorescence image is proportional to the intensity of the
corresponding incident light pulse. The horizontal positions of
the fluorescence images correspond to the horizontal positions
of the incident light.
Therefore, the spectral images by the spectrometer are formed
on the photocathode and the temporal variations in the light
intensity that occur in each wavelength can be measured by
performing the streak sweep.
4
[Simultaneous measurements of multiple
wavelengths]
As explained in the "Streak camera operating principle"
section, time-resolved spectrum measurements of multiple
wavelengths can be performed simultaneously by combining
the C7700 with the spectrometer. Figure 2 shows an example
of a three-dimensional display of time-resolved spectrum
photometry.
Fig. 2 Example of a three-dimensional
display of time-resolved
spectrum photometry
Measurement example
Measurement of transient absorption time-resolved spectrum
-1
355 nm excitarion
Time-resolved transient absorption spectral image
of the triplet-triplet absorption of anthracene in
supercritical carbon dioxide (40 :, 10.9 MPa)
0
Time (μs)
2
Data courtesy of :
National Institute of Advanced Industrial Science and Technology
Supercritical Fluid Research Center (Sendai City, Japan)
Researcher:
Dr. Takafumi Aizawa
4
6
8
310 320 330 340 350 360 370 380 390 400 410 420 430 440 450 460
Wavelength (nm)
0.8
τ=2 μS
τ=4 μS
τ=6 μS
0.6
Absorbance
Extinction coefficient / M-1cm-1
τ=0 μS
0.7
0.5
0.4
-2
0
2
4
Delay time / us
6
0.3
0.2
0.1
55000
50000
45000
40000
35000
30000
25000
20000
0.0
370
380
390
400
410
420
430
440
8
9
10
11
Triplet-triplet absorption spectral of anthracene in
supercritical carbone dioxide (40 :, 10.9 MPa)
13
14
15
Pressure dependency of the molar extinction coefficient
of triplet anthracene (40 :)
Time-resolved transient absorption spectral streak
image of the singlet-singlet absorption of C60
-1
0
Data courtesy of:
Tohoku University, Institute for Chemical Reaction Science
Professor Osamu Ito
2
Time (ns)
12
Pressure / MPa
Wavelength / nm
4
6
8
310 320 330 340 350 360 370 380 390 400 410 420 430 440 450 460
wavelength (nm)
-1
Simultaneous observation
of singlet-singlet and
triplet-triplet absorption
spectrum of Anthracene
solution
2
0,2
0,15
Δ OD
Time (ns)
0
4
0,1
0,05
6
0
8
0
310
320
330
340
350
360
370
380
390
400
Wavelength (nm)
410
420
430
440
450
460
1
2
3
4
5
Time (ns)
5
Specifications
High dynamic range streak camera C7700-01
The streak camera is an ultra high-speed
detector with 5 ps temporal resolution. By
combining with the spectrometer, transient
absorption spectrums can be measured using
with a single shot because multiple
wavelengths can be observed simultaneously.
Streak camera transient absorption measurement optics
The streak camera transient absorption measurement optics contains
3 kinds of optics: a white light input optics, an excitation optics, and
2 optical laser shutters.
Measurements can be performed accurately in the 250 nm to 750 nm
measurement wavelength range. Excitation optics is composed of 2
triple wavelength YAG laser mirrors for 532 nm, 355 nm, and 266 nm
laser lines.
S-20 (spectral response : 200 nm to 850 nm)
Photocathode
Measurement wavelength range 250 nm to 750 nm
Effective photocathode area 7 mm × 17.4 mm
Phosphor screen
P-43 (φ25 mm)
Laser Mirror
Dielectric multilayer mirror (for 532 nm, 355 nm, 266 nm)
Sweep time
0.5 ns, 1 ns, 2 ns, 5 ns, 10 ns, 20 ns, 50 ns, 100 ns,
200 ns, 500 ns, 1 μs, 2 μs, 5 μs, 10 μs, 20 μs, 50 μs,
100 μs, 200 μs, 500 μs, and 1 ms
Sample holder
10 mm cell holder, Thin film sample holder
Laser Shutter (A6538)
Rotating solenoid, 2 heads
(1 for pump light / 1 for probe light)
Temporal resolution
Less than 5 ps (maximum speed range)
Jitter
± 20 ps
Trigger delay (typ.)
Approx. 25 ns (0.5 ns)
Maximum repetition
1 kHz (0.5 ns range)
The ORCA-R2 Digital CCD camera is used
to read the streak images. The CCD element
is cooled to -35 ˚C and measurements are
possible with high S/N by substantially
decreasing the dark current.
Spectral response
105
Radiation sensitivity (μA/W)
ORCA-R2 Digital CCD camera C10600-10B
104
103
102
101
100
10-1
200
400
600
800
1000
Effective number of pixels
1344 (wavelength axis) × 1024 (time axis)
Pixel size
6.45 μm × 6.45 μm
Cooling temperature
-35 : (forced air cooling with a peltier device)
Average reading noise
6 electrons
A/D
12 bit or 16 bit
Frame rate
8.5 Hz (full resolution)
Exposure time
10 μs to 4200 s
Wavelength (nm)
Spectrometer f=300 mm C11119-02
The spectrometer is ideally suited for
combination with the streak camera. Since
an optical system that corrects for
astigmatism is used, the light condensing
efficiency at the detector is high and highsensitivity measurements are possible.
Digital delay generator DG535 C13430-01
The digital delay generator is a general unit
used to match the timing of the streak
camera and pulse laser.
Number of output channels 4 ch (A, B, C, and D output terminals)
Focal length
300 mm
Output level
TTL, ECL, NIM, and VAR 50 Ω / HIGH
Aperture ratio
F/4
Delay setting range
0 ps to 999.9 s
Incident slit
10 μm to 3000 μm in 1 μm steps
Delay resolution
5 ps
Built-in gratings
(Typical example)
100 gr/mm : W=510 nm, Δλ<3.0 nm
150 gr/mm : W=340 nm, Δλ<2.0 nm
300 gr/mm : W=170 nm, Δλ<1.0 nm
600 gr/mm : W=85 nm, Δλ<0.5 nm
Internal delay time
85 ns
Cycle frequency
Single to 1 MHz
Jitter
Approx. 100 ps
Interface
GPIB
GPIB control
Central wavelength setting, grating selection
Delay unit C1097-05
Spectrograph mount table A11350-13
The spectrograph mount table is used to secure the spectrometer
and streak camera when they are connected.
6
The delay unit is used to adjust the
operation timing of streak camera with the
laser pulse.
Delay range
31.75 ns
Delay setting range
30 ps, 60 ps, 120 ps, 250 ps, 500
ps, 1 ns, 2 ns, 4 ns, 8 ns, 16 ns
Xe lamp Break down L7013
Xe lamp 150 W/CW L8004
Radiation intensity (μW/cm2nm2) at 50 cm
The Xe lamp 150 W/CW is a highly stable white light source without
shaking or movement at the source of the arc light.
100
10
1
0.1
0.01
200
300
400
500
600
700
The Xe lamp Break down can generates
extremely bright white light from 250 nm to
750 nm with 50 ns pulse width (FWHM) by
focusing the fundamental wavelength (1064
nm) of the high output picosecond laser
onto the Xe cell.
This is different from ordinary pulse xenon
lamps and allows you to obtain smooth spectra without bright lines.
By combining with a high-output picosecond laser, transient
absorption measurements are possible in the picosecond region.
Emission wavelength range 250 nm to 750 nm
Radiation wavelength
220 nm to 2000 nm
Emission time width
Approx. 50 ns (FWHM)
Radiation intensity
250 nm : 0.52 μW/cm2 . nm-1 at 50 cm
500 nm : 2.00 μW/cm2 . nm-1 at 50 cm
Stability
OD corresponding value less than ± 0. 005 1
Noise
OD corresponding value less than ± 0.02
Power consumption
150 W
Window material
Ozoneless quartz
Light output stability
Drift : ± 0.5 %/h (typ.)
Fluctuation : 1.0 % (Max.)
2
1
This is the baseline shaking when the absorption operation is performed and
was determined from two single shot measurements of the white light output
when a 20 mJ/pulse YAG laser light was directed at the L7013.
2
This is the noise level when the absorption operation is performed and was
determined from a single shot measurement of the white light under the same
conditions as in.
Image intensifier for C7700 V12303-01
Excitation light source
The image intensifier is an option to
enhance the streak image at the phosphor
screen of the streak tube 1000 times and
output it.
Photoelectric surface
Bialkali
Luminance gain
1000 (Max.)
MCP
Built-in
The YAG laser is the excitation light source for transient absorption
measurements. The system can be enhanced by combining with the
lasers from various manufacturers.
Laser handling mirror for T-Absorption A8005 (optional)
The laser handling mirror is used to direct the YAG laser in the optical
system.
Data analyzer C6743-94
Coating
Dielectric multilayer film mirror
Reflection wavelength
1.06 μm, 532 nm, 355 nm, and 266 nm
The data analyzer is used to control each device such as the streak
camera and spectrometer and to collect and analyze data.
Memory
4 GB
Hard disk
500 GB
Color display
>23 inch
Frame grabber board
IEEE1394B
I/O board
PCle-DI0024
Software
Control functions
Streak camera : time range, MCP gain
Spectrometer : grating selection, central wavelength setting,
slit width setting
Shutter opening and closing for excitation light and white light
Delay generator : delay value setting
Measurement
functions
Data measurements
Monitor measurements : white light only measured
Emission measurements : fluorescence only measured
: dark current measured
Dark measurements
Analysis functions
For nonfluorescent samples :
Absorption1=-log10 ([Data-Dark]/[Monitor-Dark])
For fluorescent samples :
Absorption2=-log10 ([Data-Emission]/[Monitor-Dark])
Display functions
Transient absorption time-resolved spectral images
Transient absorption time and wavelength profiles
Data storage
functions
Image file format : TIFF, ITEX
Profile file format : TEXT file
Coaxial excitation optics (optional)
This is an optical system to excite the excitation light on the same
axis as the white light. The excitation light is reflected by the dichroic
mirror and is directed at the sample on the same axis. This excitation
light is removed by the color filter installed after the sample. This
optical system is used to perform transient absorption measurements
of solution samples, film, and membrane samples in a cell with a 2
mm optical path length.
7
Dimensional outlines (Unit : mm)
High dynamic range streak camera C7700-01 (Approx. 26 kg)
85±0.5
275±1
106.6±3
285±1
160.5±3 (C-mount)
C7700
HIGH DYNAMIC RANGE STREAK CAMERA
A1976-04
160±0.5
310±1
A2098
40.5±1
390±1
Spectrometer f=300 mm C11119-02 (Approx. 16 kg)
ORCA-R2 Digital CCD camera C10600-10B
Camera head (Approx. 1.1 kg)
14
13.5±2
3.5±1
90±3
124
205
31±1
1-32UN C-mount (D=7)
215
26
217
337
0.5±0.2
51
95±1
254
95±1
1/4-20UNC (D=5)
10
Spectrograph mount table A11350-13 (Approx. 10 kg)
ORCA-R2 Digital CCD camera C10600-10B
Camera control unit (Approx. 2.8 kg)
74±1
232±2
200
300
6.9±1
400
420±1
6-M6
308±2
300
90.5
980±2
★ ORCA is registered a trademark of Hamamatsu Photonics K.K.
★ Product and software package names noted in this documentation are trademarks or registered trademarks of their respective manufacturers.
●
●
●
The university, institute, or company name of the researchers, whose measurement data is published in this brochure, is subject to change.
Subject to local technical requirements and regulations, availability of products included in this promotional material may vary. Please consult your local sales representative.
Information furnished by HAMAMATSU is believed to be reliable. However, no responsibility is assumed for possible inaccuracies or omissions.
Specifications and external appearance are subject to change without notice.
© 2015 Hamamatsu Photonics K.K.
HAMAMATSU PHOTONICS K.K.
www.hamamatsu.com
HAMAMATSU PHOTONICS K.K., Systems Division
812 Joko-cho, Higashi-ku, Hamamatsu City, 431-3196, Japan, Telephone: (81)53-431-0124, Fax: (81)53-435-1574, E-mail: [email protected]
U.S.A.: Hamamatsu Corporation: 360 Foothill Road, Bridgewater, N.J 08807, U.S.A., Telephone: (1)908-231-0960, Fax: (1)908-231-1218 E-mail: [email protected]
Germany: Hamamatsu Photonics Deutschland GmbH.: Arzbergerstr. 10, D-82211 Herrsching am Ammersee, Germany, Telephone: (49)8152-375-0, Fax: (49)8152-265-8 E-mail: [email protected]
France: Hamamatsu Photonics France S.A.R.L.: 19, Rue du Saule Trapu, Parc du Moulin de Massy, 91882 Massy Cedex, France, Telephone: (33)1 69 53 71 00, Fax: (33)1 69 53 71 10 E-mail: [email protected]
United Kingdom: Hamamatsu Photonics UK Limited: 2 Howard Court,10 Tewin Road, Welwyn Garden City, Hertfordshire AL7 1BW, UK, Telephone: (44)1707-294888, Fax: (44)1707-325777 E-mail: [email protected]
North Europe: Hamamatsu Photonics Norden AB: Torshamnsgatan 35 16440 Kista, Sweden, Telephone: (46)8-509-031-00, Fax: (46)8-509-031-01 E-mail: [email protected]
Italy: Hamamatsu Photonics Italia S.r.l.: Strada della Moia, 1 int. 6 20020 Arese (Milano), Italy, Telephone: (39)02-93581733, Fax: (39)02-93581741 E-mail: [email protected]
China: Hamamatsu Photonics (China) Co., Ltd.: B1201 Jiaming Center, No.27 Dongsanhuan Beilu, Chaoyang District, Beijing 100020, China, Telephone: (86)10-6586-6006, Fax: (86)10-6586-2866 E-mail: [email protected]
Cat. No. SHSS0005E04
AUG/2015 HPK
Created in Japan