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. 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