Transient absorption Manual

1/ Principle of transient absorption technique

Transient absorption (TA) spectroscopy is the pump-probe technique which monitors the carrier
dynamics of materials.

** By using two pulses, including the pump pulse for exciting the samples and the weaker following
probe pulse, we can monitor the differential transmission (or transmittance) change (∆T/T = (T on –
Toff)/Toff) via time delay between pump and probe pulses, where T on and Toff are the probe transmission
with and without a pump.

** The photo-induced bleaching (PIB) represents the specific resonant inter-band transitions, while the
photo-induced absorption (PIA) indicates intra-band excitation of photo-generated free carriers.

+ If we get the positive of differential transmission (∆T/T > 0 or ∆A/A < 0), we called photobleaching (PB)

+ If the differential transmission is negative (∆T/T < 0 or ∆A/A > 0), we will get the photo-induced
absorption (PIA) as shown below:
** For example:

Transient absorption map

 Extract the spectrum from the map

Transient absorption spectrum
 Reflection mode
** Notably, we can also measure the reflection mode in transient absorption spectroscopy which we will
measure the differential reflectance (∆R/R), instead of the differential transmittance (∆T/T).

+ The obtained results (∆R/R) would be similar to the transmission mode (∆T/T), for example:

The spectrum and the kinetics of reflectance mode (∆R/R)

 2/ Operation of transient absorption system
** The laser line outside the pump-probe HARPIA system:

1/ Pump generation.

With specific wavelengths, we have the corresponding configurations for the output port selector.

G2 G3 G4
** With different wavelengths, we have the specific configuration which we need to check the position
and the corresponding filter which we need and put it in the suitable positions.

** Note: The button shown above could control the electronic part in the laser system (not regarded to
the PC).

2/ Pump alignment

a/ Pump-beam turn on in the monitor.

b/ Check the pump beam inside the HARPIA.

+ Check the pump beam after the iris 1 to ensure that the beam is in the center.
+ If not, we should change the mirror which we can only touch two screws to modify the horizontal and
vertical direction as shown below.

** Please do not use the diagonal screw which can cause the mirror position change.
3/ Probe alignment inside HARPIA

+ Check the probe beam after the iris 1, 2, and 3 to ensure that the probe beam is in the center.

a/ Iris 1 – near field

+ If the probe beam after iris 1 is not in the center, we should check the lens outside the HARPIA.

b/ Change the far-field.

+ Check the probe beam after the Iris 4

+ Open the lens as shown above and change the far-field position with horizontal and vertical direction.

** Please do not touch the diagonal spot, it can change the mirror position.

c/ Probe beam checking.

+ Insert the camera inside the probe beam.

+ Turn on the software on the monitor and connect the cab to the computer.

+ Click on the camera name.

+ We can control the probe beam intensity by changing the exposure and gain.

** Note: please do not make the saturated probe beam intensity.

+ Use the oscillate function on the HARPIA to inspect the stability of the probe beam.

d/ Align the delay line.

+ Use the mirror 2 to align delay line with the far field.

4/ White-light continuum generation

a/ Focus the probe beam on the sample stage.

** Please do not use the parabolic mirrors (5 and 6) as shown below to focus the probe beam which can
cause the shape change to either horizontal or vertical ellipticity of the beam.
b/ Checking the probe light in the slit (detector).

+ Make the probe light brightest and in the center of the slit using the aluminum mirror 8 (horizontal).

+ We can change the probe spectrum shape by the modulator as shown in the probe line in the image
above.
c/ Intensity probe spectrum check

+ To check the spectrum, choose the “Diagnostics tab” of the HARPIA software -> choose the “Measure”
button below.

+ Change the probe ND filter the HARPIA software on the monitor (pump/probe/detector).

** Click this button if the tab did not appear

+ We can also move the iris to modify the white light intensity until we see the most stable probe
spectrum on the monitor.
** Please note that do not make the red circle (the right-side image below) of the white light after the
CaF2/YAG crystal due to the high intensity which can damage the crystal of white-light continuum
generation.

+ We can check the stability of one specific probe wavelength (nm) which we can change the x and y
scale to see the clearer intensity.
d/ Choose the center wavelength of the probe to check the probe spectrum you want.

For example, if you choose 660 nm as shown above, the covered probe spectrum wavelength will range
from 400 nm – 660 nm (center wavelength) – 900 nm

Or if in the NIR range, if you choose 1300 nm as the center wavelength, the probe spectrum range will be
ranging from 1000 nm – 1300 – 1600 nm

5/ Pump-probe overlap

a/ Turn on the software and choose the “Pump-probe” tab.

+ We should choose the value of spectra per acquisition: 500

** When we open the cover of HARPIA, automatically the notice “interlock disabled” will appear.

b/ Click the “Measure continuously” position to check the probe spectrum and the signal.

c/ Pump-probe overlap

+ Make the pump-probe overlap by the screws (orange arrows in the image) by changing the positions of
the pump beam in the x and y direction.
+ Make the best overlapping between pump and probe to obtain the highest signal.

6/ Time zero setting

+ The time when the signal (red line) started to occur is set as the zero-delay time.

+ Press this button and choose “Set current delay as zero” as shown below:
7/ Measurement

a/ Choose the tab Configuration.

b/ Choose the “New” tab –> Transient Absorption Measurement

+ Press the number on runs (1, 2,…).

1/ We can manually write as you want which delay times

For example: -10, -9,-8,…0, 0.05, 0.1, 0.15,…1, 1,1,…2, 2.5,….3,…

2/ Choose the preset step

+ Or you can choose the “Add the linear space” position and then adding the delay time you want and
step
For example:

From To Step

-1 1 0.05
c/ Click the “Pump-probe” tab -> Run -> Write the measurement file information

** When you want to change from Visible to NIR range, please change:

1/ The grating:

+ Turn off the HARPIA software, and detector.

+ Change the grating (the green and red color should be duplicated).
2/ Change the VIS -> NIR or opposite array detector

3/ Change the probe crystal

+ Vis: CaF2

+ NIR: YAG crystal

4/ Change the filter from Vis -> NIR.

 REFLECTION MODE
** In our system, we can also measure the reflection mode as well, not only the transmission one.

+ In such a case, we have the new alignment of the probe beam as shown below:

+ Please remove the mirror 7 (transmission mode) when you use the reflection mode.

+ The process of measurements for the reflection mode is similar to the above steps for the transmission
mode.