Third harmonic generation in air ambient

and laser ablated carbon plasma

Cite as: Phys. Plasmas 22, 123302 (2015); https://doi.org/10.1063/1.4937419
Submitted: 30 September 2015 • Accepted: 25 November 2015 • Published Online: 11 December 2015

Ravi Pratap Singh, Shyam L. Gupta and Raj K. Thareja

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© 2015 AIP Publishing LLC.

 PHYSICS OF PLASMAS 22, 123302 (2015)

Third harmonic generation in air ambient and laser ablated carbon plasma
Ravi Pratap Singh,a) Shyam L. Gupta, and Raj K. Thareja
Department of Physics, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh 208016, India
(Received 30 September 2015; accepted 25 November 2015; published online 11 December 2015)
We report the third harmonic generation of a nanosecond laser pulse (1.06 lm) in air ambient and
in the presence of nanoparticles from laser ablated carbon plasma. Significant decrease in the
threshold of third harmonic generation and multi-fold increment in the intensity of generated third
harmonic is observed in presence of carbon plasma. The third harmonic in air is due to the quasi-
resonant four photon process involving vibrationally excited states of molecular ion of nitrogen
due to electron impact ionization and laser pulse. Following optical emission spectroscopic obser-
vations we conclude that the presence of C2 and CN in the ablated plume play a vital role in the
C 2015 AIP Publishing LLC.
observed third harmonic signals. V
[http://dx.doi.org/10.1063/1.4937419]

I. INTRODUCTION depending upon material properties and the intensity of laser

Laser produced plasmas are being extensively studied
because of their wide range of scientific and technological
applications ranging from the fabrication of thin films, labo-
ratory models of astrophysical plasma, as a source of highly
charged ions and XUV radiation, nanoparticle formation,
analysis of soils and hazardous materials, and harmonic gen-
eration.1–5 Several successful attempts have been made by
various research laboratories to generate harmonics using
various nonlinear media, including birefringent crystals,
noble gases, and ionized metal vapour. The efforts are in pro-
gress to discover the new processes that can enhance the har-
monic efficiency, generation of high order harmonics, and
to increase the conversion efficiency of preferred harmon-
ics.5–11 The first experiment for generation of optical har-
monics was reported in 1961 by Franken et al.7 who
produced the second harmonic in quartz crystal using a ruby
laser. Later Maker and Terhune10 reported third harmonic
generation (THG) in crystals, glasses, and liquids. Noble
gases are generally preferred as nonlinear media for high
order harmonic generation due to their larger ionization
potential compared with ordinary gases and also they are
free from optical damage problem; however, availability of
limited noble gases and generation of only odd harmonics
due to symmetry imposes constraints. The recent reports on
remote atmospheric sensing have shown that availability of
UV laser in ambient air could revolutionize the field.12 The
lasing in air has been shown either by femtosecond laser fila-
mentation or by electrons impact excitation of neutral nitro-
gen molecules in air in the ultraviolet regime. Nonlinear
wavelength conversion in air has also been discussed as a
potential source of air lasing.13–16
A laser ablated plasma plume is a complex mixture of
atoms, electrons, neutrals, ions, nanoparticles/clusters, and
molecules. It has been reported that the harmonic generation
is sensitive to the plume constituents and harmonics can be
generated in the plasma through various possible processes
a)
Author to whom the correspondence should be addressed. Electronic mail:
ravips@iitk.ac.in
pulse. Recent work of Lopez-Arias et al.17 for low order har-
monic generation using nanosecond and picoseconds laser
pulses also shows that efficient harmonic generation at opti-
mum delay between ablating and driving pulses depends on
the thermo-physical properties of target material and laser
pulse width.
Recently, there has been renewed interest in the applica-
tion of plasma as a nonlinear medium because ions, molecules,
and nanoparticle/clusters present in plasma have higher ioniza-
tion potential and/or increased polarizability that contribute to
harmonic generation.5,18 Finite size and surfaces of nanopar-
ticles/clusters introduce the anharmonicity that in-turn results
in a size-dependent susceptibility.19 The response of constitu-
ents in the presence of E-field of laser pulse leads to the polar-
ization of the medium which can be expressed as P ¼ e0 ðvðxÞ E
þ vð2xÞ E2 þ vð3xÞ E3 þ :::Þ. Under the influence of weak laser
field the charge distribution of these clusters get weakly per-
turbed and bound electrons contribute towards the lower order
harmonic generation. Third harmonic generation, in general,
is described by the third-order polarization. The intensity of
generated third harmonic (I(3x)) depends on input laser inten-
sity of fundamental (I(x)), third ordered nonlinear susceptibil-
ity (v(3x)(3x)), the number of contributors (N), and the phase
matching function (F) as Ið3xÞ / ðNvð3xÞ ð3xÞÞ2 I3 ðxÞF.20
The thrust of experimental and theoretical study in this area
of research is to understand the laser interaction with plume
constituents and to relate it to their macroscopic nonlinear
response. In this report, we have presented detailed study of
the third harmonic (TH) generation in air and carbon plasma
using nanosecond laser pulses of 1.06 lm and attempted to cor-
relate the contribution of plasma species, in particular, nano-
particles/clusters, to the enhancement of third harmonic
generation efficiency.
II. EXPERIMENTAL
A schematic of the experimental setup is shown in Fig. 1.
The carbon plasma was produced inside the plasma chamber
by irradiating the graphite target in air ambient at atmospheric
pressure with 8 ns pulses of 1064 nm from Nd:YAG laser

1070-664X/2015/22(12)/123302/5/$30.00 22, 123302-1 C 2015 AIP Publishing LLC

V
123302-2 Singh, Gupta, and Thareja
FIG. 1. Experimental set up for the study of third harmonic generation
(THG).
system (Indi series from Spectra Physics). The radiation was
focussed to a spot size of 300 lm using a focussing lens of
40 cm. In order to avoid the possible erosion of the target, the
target holder was continuously rotated using a stepper motor.
Another Q-switched Nd:YAG laser at 1064 nm wavelength
and of 8 ns pulse width (Spectra Physics Lab-190) was used
as a probe beam. The energy of the probe beam was varied by
using a beam attenuator (Topag; DA 10-1064). The probe
beam was focussed using a focussing lens of 30 cm at 1 mm
distance from the target surface in a direction parallel to the
target surface. The delay in probe beam with respect to pump
beam was controlled using a delay generator (Stanford
Research System, DG535). The delay between the pump and
probe beams is monitored on an oscilloscope using two identi-
cal fast photodiodes placed at equal optical distances from the
target and illuminated by the part of pump and probe beam. In
order to separate out the fundamental wavelength from the
TH, we have used a combination of IR and UV reflecting mir-
rors. The filtered TH is then detected using a fiber coupled
spectrograph (Andor Shamrock SR 303i) attached to an exter-
nally triggered gated intensified charge-coupled device
(ICCD) (ICCD, DH-720, ANDOR Technology, USA) whose
gate opening is synchronized with the probe beam. For spec-
troscopic observations a 12 00 l/mm grating and 100 lm slit,
which yields spectral resolution of 0.1 nm was used. To
identify the plasma species, we have recorded the optical
emission spectra of plasma in presence and absence of probe
beam by imaging (1:1) the plasma plume using a quartz lens
of 10 cm onto the input of an optical fiber coupled ICCD spec-
trograph (same as used for recording the TH signal). The opti-
cal emissions of plasma were recorded perpendicular to the
probe beam direction under similar experimental conditions
as used for third harmonic generation.
III. RESULTS AND DISCUSSION
When the laser is focussed in gases and its intensity in
the focal region exceeds gas breakdown threshold, the elec-
trical breakdown of gases takes place and a luminous spark
associated with this breakdown is observed in the focussed
region. This spark is due to the visible emissions of electron-
ically excited/ionized atoms/molecules of the gases. The
breakdown threshold of a gas strongly depends on the laser
wavelength, pulse-width, intensity, focal spot, and dust or
Phys. Plasmas 22, 123302 (2015)
impurities present in the gas.2 The atmospheric air is pre-
dominantly nitrogen. Since the ionization potential of N2
(15.6 eV) is much larger than the single photon energy
(1.15 eV) of the fundamental wavelength (1.06 lm) of
Nd:YAG laser, the air breakdown can be achieved either by
multi-photon or cascade breakdown process. For the multi-
photon ionization to dominate, Ps < 107 Torr-s; where P is
ambient pressure and s is the laser pulse width.21 For our
study, P ¼ 760 Torr and s ¼ 8 ns that leads to Ps ¼ 6.18
 106 > 107 Torr-s. This implies that the cascade ioniza-
tion predominates the observed air breakdown. We observed
a threshold of 110 mJ/pulse for air breakdown, consistent
with the literature.22 To see the third harmonic signal gener-
ated in the air breakdown, 355 nm reflecting mirror was used
along the propagation direction of probe beam to reflect TH
towards an optical fiber coupled with spectrograph for detec-
tion. The energy of the probe beam was varied from 10 mJ to
500 mJ and no pump was used. We did not observe the third
harmonic of 1064 nm laser pulse in air for energies below its
breakdown threshold and thus conclude that only excited
molecular nitrogen contribute towards the third harmonic
processes. However, with increase in probe laser pulse
energy (>110 mJ) the third harmonic signal is observed that
increases with energy of the probe beam and follows the
cubic dependence,23 Ið3xÞ / I3 ðxÞ on the laser pulse energy
up to 300 mJ (Fig. 2). This confirms the non-linear character
of the emissions at third harmonic of 1064 nm laser pulse.
However, with further increase in laser pulse energy above
300 mJ, the TH signal does not increase, which can be attrib-
uted to a combination of effects like medium heating
induced by self focusing/defocusing of the laser beam, etc.24
The optical emission spectra in the direction normal to
the probe beam propagation direction do not show any signa-
ture of 355 nm. The observation of TH signal only along the
probe beam direction indicates its generation due to the non-
linear processes taking place along the beam direction. The
possible explanation of TH generated in air is the quasi-
resonant four photon process taking place from vibrationally
excited states of molecular ion of nitrogen. The electrons
absorb laser energy through inverse bremsstrahlung (IB)
FIG. 2. Variation of peak intensity of third harmonic TH with respect to
probe pulse energy in air (without carbon plasma) at 103 mbar. Inset shows
the cubic fit for TH up to 300 mJ.
123302-3 Singh, Gupta, and Thareja Phys. Plasmas 22, 123302 (2015)

FIG. 3. Variation of TH of probe pulse

(90 mJ) in presence of carbon plasma
(at 100 mJ pump pulse) with respect to
delay between pump and probe pulse.

absorption and if the energy gained by the electrons is suffi- clusters towards THG. The presence of these clusters/nano-
cient, they can impact ionize the N2 through the following particles in the medium is supported by the scanning electron
reaction23 microscopic (SEM) images of the deposition on the target
! ! (discussed later in the text). In order to investigate the contri-
X
þ Xþ
bution of nanoparticles/clusters further, we varied the probe
 þ
e þ N2 X 1
! N2 X 2
þ 2e : (1)
g g
pulse energy in the carbon plasma at 1.5 ls delay with
respect to ablation event (Fig. 4). We observed lower thresh-
Since the air plasma species after excitation move towards old of THG in presence of carbon plasma (30 mJ) as com-
the laser beam due to its recoil momentum, there pared with air only (110 mJ; Fig. 2). Observation of TH for
is probability of interaction of molecular ion with the energies much lower (25%) than the air breakdown thresh-
remaining part of the laser pulse. During this process, the old and 4-fold increase in the maximum output TH intensity
molecular nitrogen ions get excited to the higher vibrational indicate significant contributions from carbon plasma con-
P stituents. We observed the conversion efficiency of 104 in
N2þ ðB2 þ Þ levels which subsequently decay to the state
Pu presence of the carbon plasma plume. Third harmonic gener-
N2þ ðX2 þg Þ by emitting photons of energy (3h)
23
ated in carbon plasma follows the cubic dependence up to
! ! 200 mJ; however, after that up to 400 mJ it increases slowly
X
þ X
þ
N2þ B2
 3h ! N2þ X 2
: (2) with probe energy and with further increase in probe energy
u g it shows a decrease in third harmonic intensity (Fig. 4). In
order to correlate the effect of probe energy variation on
With the increase in probe energy the density of N2þ and TH third harmonic and plume species, we recorded the optical
signal intensity increase initially. However, the relative pop- emission spectroscopy (OES) of carbon plasma in presence
ulation of NII emissions starts dominating over N2þ species and absence of probe pulse. The optical emission in the
and a decrease in the intensity of generated third harmonic direction normal to the carbon plasma expansion was imaged
signal is observed at larger probe beam energy. This con- on to the optical fiber-spectrograph arrangement. Figure 5
firms the contributions of N2þ species toward THG. shows optical emission from carbon plasma for different
In order to study the contribution of the laser ablated probe beam energy at fixed pump energy used for carbon
carbon plasma towards the THG, we ablated the graphite tar- ablation of 100 mJ. Plasma emissions corresponding to NII
get using 100 mJ of the pump pulse and passed the probe (399.5 nm and 566.7 nm), NIII (400.4 nm), and CII (392 nm
pulse parallel to and 1 mm away from the target surface at
different delays with respect to pump pulse. Figure 3 shows
that TH signal intensity observed at 90 mJ of probe pulse first
increases, attains maximum 1.5 ls and then slowly decays
with time, showing its presence up to 500 ls. In our previous
study, we have observed that carbon plasma is predominately
populated by C2 and CN species 1.5 ls under similar ex-
perimental conditions.25 The molecular emissions and the
TH signal follow; both peak at 1.5 ls and then decrease.
This indicates that these species might be contributing
towards the THG at earlier temporal delays. The laser pro-
duced plasmas are well documented to have abundance of
nanoparicles/clusters of respective target material at longer
temporal delays.26–28 These nanoparticles/clusters are
formed due to recombination of molecular species and arrive
late in the interaction zone. Thus, the plateau and the
FIG. 4. Variation in TH signal in presence of carbon plasma (at constant
decrease of TH intensity at longer temporal delays may be pump pulse energy of 100 mJ) with respect to probe pulse energy at 1.5 ls
attributed to the contributions from carbon nanoparticles/ delay between pump and probe pulse.
123302-4 Singh, Gupta, and Thareja
426.7 nm, and 657.8 nm) start appearing along with the C2
(d3 pg ! a3 pu ) band system corresponding to Dv ¼ 1, 0, and
1 and CN band (B2Rþ  X2Rþ) corresponding to Dv ¼ 0,
1 at lower probe energy.
For probe energy less than 200 mJ/pulse, the emission
from C2 and CN predominate the emission spectra. However,
increasing the probe energy beyond 200 mJ we observe the
lines corresponding to ionized nitrogen (nitrogen breakdown)
and carbon excited species (CII at 426.7 and CII at 657.8 nm)
Phys. Plasmas 22, 123302 (2015)
FIG. 5. OES of carbon plasma in dif-
ferent spectral range at 1.5 ls delay
with respect to pump beam (100 mJ) at
varying probe pulse energy; 90 mJ
(red), 115 mJ (blue), 215 mJ (dark
cyan), 300 mJ (magenta), 400 mJ (dark
yellow), 570 mJ (navy), and no probe
(black).
and the emission from C2 and CN decreases. Therefore, over-
all molecular density increases slowly with probe energy,
resulting in increase in third harmonic intensity up to 400 mJ
(Fig. 4). At probe energies greater that 400 mJ/pulse, the mo-
lecular bands disappear and optical emission spectra is domi-
nated by ionic lines.25 This implies a large concentration of
electrons and ionic species compared with C2 and CN in the
interaction zone of plasma, resulting in decrease of TH inten-
sity for probe energy greater than 400 mJ.
FIG. 6. (a) TH signal at different pump
pulse energies at constant probe pulse
energy (90 mJ) at 103 mbar. Inset shows
the variation of the peak intensity of TH
signal with respect to probe pulse energy
at constant probe pulse energy (90 mJ).
(b) The scanning electron micrograph
showing the back deposited nanopar-
ticles on the ablated target with 100 mJ
pump pulse in air ambient at 103 mbar.
123302-5 Singh, Gupta, and Thareja
We further varied the pump beam energy starting from
10 mJ and up to 100 mJ at constant probe energy of 90 mJ.
The pump energy is not exceeded above 100 mJ so as to
keep it well below the breakdown threshold of air (110 mJ).
We observed that the third harmonic yield strongly depends
on the pump beam energy as shown in Fig. 6(a). It shows a
linear variation with pump energy (inset, Fig. 6(a)).
Increase in the ablation energy and the high ambient pres-
sure increases the probability of recombination processes;
this increases C2 and CN species in carbon plasma plume.
The observation of increase in C2 and CN species along
with an increase in the TH intensity with increase in the
ablation intensity further confirmed the contributions of
these clusters towards THG. The laser ablated plasma is
populated by the nanoparticles/clusters at the later stages of
plasma evolution. The higher ambient pressure pushes these
nanospecies backward resulting in back deposition on the
target surface. The analysis of ablated target surface
showed the presence of deposited nanoparticles (Fig. 6(b));
the presence of nanoparticles can influence the plasma and
could even enhance the efficiency of higher harmonics due
to the higher local concentration of neutral atoms in the
nanoparticles.29
IV. CONCLUSION
In summary, our experimental investigation shows that
TH of a nanosecond fundamental wavelength (1.06 lm) of
Nd:YAG laser could be generated in air at atmospheric pres-
sure due to electron impact excitation/ionization of nitrogen
molecule. C2 and CN molecules and clusters/nanoparticles
enhance the TH signal in the presence of carbon plasma.
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