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Nonlinear photoacoustic response of suspensions of laser-synthesized plasmonic titanium nitride
nanoparticles
Melissa Maldonado, Avishek Das, Anderson Gomes, Anton Popov, Sergey Klimentov, Andrei Kabashin
To cite this version:
Melissa Maldonado, Avishek Das, Anderson Gomes, Anton Popov, Sergey Klimentov, et al.. Nonlin- ear photoacoustic response of suspensions of laser-synthesized plasmonic titanium nitride nanopar- ticles. Optics Letters, Optical Society of America - OSA Publishing, 2020, 45 (24), pp.6695.
�10.1364/OL.404304�. �hal-03160344�
To be published in Optics Letters:
© 2020 Optical Society of America Title:
Nonlinear Photoacoutic Response of Suspensions of Laser-Synthesized Plasmonic Titanium Nitride Nanoparticles
Authors:
Anderson S. Gomes,Andrei Kabashin,Melissa Maldonado Cantillo,avishek das,Sergey Klimentov,Anton Popov
Accepted:
31 October 20 Posted
10 November 20
DOI: https://doi.org/10.1364/OL.404304
Nonlinear Photoacoustic Response of Suspensions of Laser-Synthesized Plasmonic Titanium Nitride
Nanoparticles
M ELISSA E. M ALDONADO ,
1A VISHEK D AS ,
1A NDERSON S. L. G OMES ,
1,3,*A NTON A. P OPOV ,
2S ERGEY M. K LIMENTOV ,
2A NDREI V. K ABASHIN
2,31Departamento de Física, Universidade Federal de Pernambuco, Recife-PE 50670-901, Brazil
2 MEPhI, Institute of Engineering Physics for Biomedicine (PhysBio), Bio- nanophotonics Laboratory, 31 Kashirskoe sh., 115409, Moscow, Russia
3Aix Marseille Université, CNRS, LP3, Campus de Luminy, Case 917, 13288, Marseille, France *Corresponding author: [email protected]
Received XX Month XXXX; revisedXX Month, XXXX; accepted XX MonthXXXX; posted XX Month XXXX (Doc. ID XXXXX); published XX Month XXXX Nonlinear photoacoustic response from solutions of 40
nm plasmonic titanium nitride (TiN) nanoparticles (NPs) synthesized by laser ablation in liquid environment (acetone) is reported. Using photoacoustic Z-scan with 5 ns pumping pulses, values of effective nonlinear absorption coefficients βPA,eff were measured and found to be 3.27±0.17×10-8 cm/W, 6.41±0.17×10-8 cm/W and 3.22±0.17×10-8 cm/W for 600 nm, 700 nm and 800 nm pumping wavelengths, respectively. To take into account the influence of nonlinear scattering, absorption- dependent photoacoustic measurements were carried out together with the optical Z-scan and the obtained data were compared. The origin of the effective absorptive non-linearity is discussed based on combined nonlinear absorption in NPs, nonlinear scattering, and bubble generation triggered by NPs-mediated light absorption. Potential applications include biomedical diagnostics and therapy © 2020 Optical Society of America
http://dx.doi.org/10.1364/OL.99.099999
Titanium nitride (TiN) nanoparticles (NPs) present an alternative plasmonic material to noble metal counterparts, with a red-shifted plasmonic extinction band (600-800 nm) compared to Au and Ag NPs (520-550 nm and 400-420 nm, respectively) [1–3]. This feature makes them an attractive candidate for a variety of applications such as solar heat transducers [4], waveguides in the telecommunication range [5], functional arrays [6], electrochemical supercapacitors [7], etc.
Biomedicine looks as one of main beneficiaries of such remarkable plasmonic absorption, falling in the first biological transparency window (630-900 nm) even for relatively small NP sizes. As an example, TiN NPs have been successfully used as photothermal agents for cancer therapy and in vivo imaging [8–10]. The mechanism enabling such biomedical applications arises from linear optical absorption near the plasmonic resonance, which provides contrast in bioimaging [11] and initiate a photothermal effect [12]. On the other
hand, nonlinear optical (NLO) responses measured by optical Z-scan or other techniques can acquire important information on nonlinear absorption (NLA) and other characteristics, which can also help to unravel novel prospects for the development of imaging and therapy modalities. Such an expectation is confirmed by results of recent optical Z-scan studies reporting a strong NLO response using TiN NPs [13,14].
Photoacoustic (PA) response of absorptive materials provides another attractive opportunity for NPs characterization, which arises from the transformation of absorbed photons into heat. Such a phenomenon forces microscopic expansions and subsequent contractions (after cooling), which in turn generate acoustic waves in the surrounding medium. There is a myriad of applications of photoacoustic techniques, from spectroscopy [15] to multiscale imaging and tomography [16]. When the photoacoustic process takes place in a liquid ambience, nanobubbles and microbubbles can also be generated [17,18]. Photoacoustic Z-scan (PAZ-scan) presents a modification of optical Z-scan, which detects the generation of photoacoustic waves in the NLO regime, while an optical pulse is nonlinearly absorbed by the sample and converted into sound waves [19]. The method has advantages over the optical Z-scan, since it relies solely on the material’s absorption, can work with opaque samples and be used with a wide range of excitation wavelength, while scattering does not contribute to the recorded signals. An advanced implementation of this technique, termed OPAZ, combines optical Z- scan and PAZ-scan to obtain a better understanding of the NLA in optical materials [20].
In this letter, for the first time we report a quantitative characterization of nonlinear photoacoustic response (NPR) of suspensions of laser-synthesized TiN NPs using OPAZ-scan. The laser- synthesized NPs were chosen as a new appealing object for biomedical applications, combining unique physico-chemical characteristics (spherical shape, controllable size under low size dispersion, absence of toxic impurities, high stability in aqueous or organic solvents, etc.) [21] with high safety in biological models in vitro and in vivo [22], which makes them advantageous compared to counterparts prepared by conventional methods, including chemical synthesis [1], epitaxy growth [6], electrochemical [7] and hydrothermal synthesis [8]. We measured effective nonlinear absorption coefficients βPA,eff and discuss
th of (fsea na Ti ve lab 1(10 Ru Th co
Fig sca th SE Str sca Te In 1bdis ma ma co an
Fig Op (Fwa br su ex co [2
e role of nonlinea f this work.
Solutions of TiN s) laser ablation arlier successfull anomaterials, inc N target (Good ertically in a glass
boratory reagen (a). A laser beam 00 µJ pulse energ ussia) was focuse he ablation time olloid was 50 μg/m
g. 1. (a) Schema anner and F-thet e focal spot over EM image (inset) ructural propert anning transmis escan, Czech Rep st., UK). STEM co b). Statistical ana
stribution with aximum (Fig. 1b ain elements in orresponding to o nd titanium oxide
g. 2. EDS (a) and o ptical characteriz FluoroMax, Horib
avelengths below road extinction b urface plasmon r xtinction coefficie omparable to the
7]), although it i
ar loss mechanis N NPs were synth from a solid targ ly applied for luding Au NPs [2 dFellow, hot pre s cuvette and im t, >99.5% purity from a Yb:KGW gy, 10 kHz repet ed via a F-theta l was 20 min. M mL, as determine
atic of laser synt ta lens, which ma
the target, 3 – ab and size distribut ies and chemical sion electron mi public) coupled w onfirmed the form alysis of STEM i
40 nm mode s b). EDS analysis n the compositio other elements (O e coating of NPs su
optical absorptio zation of NPs b a) revealed a stro w 400 nm due t band around 600 resonances (SPR ent at plasmonic extinction coeffic is lower than tha
sms, as a part of n hesized by metho get in liquid amb the fabrication 23,24] and Si NP essed, 99.5% pu mmersed in aceto
y), as schematic laser (1030 nm, 2 tition rate, TETA lens having 100 Mass concentratio
ed by gravimetric
thesis. 1 –mirror ake possible cons blation chamber w tion of laser-synt l composition we icroscopy (STEM with an EDS dete mation of spheric images revealed size and 40 nm revealed titanium on of formed N O, Si) originated urface (Fig. 2a).
n (b) spectra of 4 by UV-Vis-NIR s ong absorption in to interband tran 0-900 nm due t R) by TiN NPs (F
c peak 18 L/(g*
cient of 40 nm Au at of 40 nm Ag N
novel contributio ods of femtosecon bience, which we
of a variety Ps [25,26]. Briefly
urity) was plac one (Sigma Aldric cally shown in F
270 fs pulse leng A 10 model, Aves mm focal distan on of the obtain c method.
r, 2 –galvanomet stant movement with a target. (b) A thesized TiN NPs
ere measured by M) system (MAIA ector (X-act, Oxfo cal NPs (inset of F a log-normal si m full-width-at-ha m and nitrogen NPs, while signa
from the substra
40 nm TiN NPs.
spectrophotomet n the ultraviolet f nsitions [13] and to the excitation Fig. 2b) with ma
*cm). This value u NPs (25 L/(g*cm NPs (159 L/(g*cm ons
nd ere of y, a ced ch, Fig.
gth, sta, ce.
ned
ter t of An
y a A 3, ord Fig.
alf-ize as als ate
ter d a for of ass is m) m)
[28]) w extinctio plasmon of simil than hu The e optical was tun nm, op controll optimiz The firs the inpu using a scan, wh the len moved The TiN axis an ultrasou MHz w the surf was col open ap 30 μm.
Fig. 3. E photoac The r left colu differen simulta right co ranging was mu reprodu scan sig (rather naturall apertur To u energy the well
where α and r=1
which is a champ on coefficient of T nic feature in nea lar size (14 L/(g uge 150 nm Au ba
experimental set source, we used ned to three diffe
erating at 10 H led by two Glan ze the beam diam
st one was sent t ut power, while
125 mm focal len here the sample m ns was placed o
in small steps to N colloid was plac nd was mounte und coupling. Th water immersion face of the sampl llected by a phot perture Z-scan. T
Experimental setu coustic Z-scan (O results of OPAZ-s umn (Fig. 4a, 4c, nt fluences, at aneously measure
olumn, (Fig. 4b, g from 0.71 J/cm2 uch better in the
ucible, and Fig. 4 gnal obtained wit than saturated a ly inverted, since re Z-scan signal ca understand our r
compared to the l-known Tauc’s e
α is the linear ab 1/2 for direct allo
pion in this field TiN NPs is very h ar IR region: TiN g*cm) [29]) and
ased core-shell N tup for the OPAZ- d an optical param
ferent wavelength Hz and 5 ns puls n polarizers, follo meter. The beam to a reference ph the second one ngth lens. In cont moves through th on a motorized
enable scanning ced in a 2 mm qu ed in a cell co he reflected PA s transducer (Oly le for a better co todetector (PD2) The beam diamet
up to simultaneou OPAZ). See text fo
scan for the TiN c , 4e) shows the p
three different ed open aperture 4d, 4f). The da
2 up to 1.32 J/cm case of the PAZ-s shows a represen th open aperture absorption) proce
e it is solely due an be due to both results, it is impo
e TiN bandgap, w equation [31], rep
/
bsorption coeffic owed transitions
d. More importan high among mate NPs outperform have slightly low Ps (21 L/(g*cm) -scan is shown in metric oscillator ths: 600 nm, 700 ses. The inciden owed by a teles m was split into t
hotodetector (PD was focused ont trast to conventio he focus of the len translation stage of the sample alo uartz cuvette at 45 ontaining distille
ignal was detect ympus V312-N-SU oupling. The tran
) for the measur ter at the focus (z
usly measure op or further details.
colloid are shown photoacoustic sig t wavelengths, e optical Z-scan is ata were obtaine m2, and the signal- scan. The measur ntative example.
e directly implies ess. The photoaco
to absorption w h absorption and ortant to verify t which can be ca produced in eq. 1
cient, A is the op s. Using linear ab
ntly, the mass erials having a m Au nanorods wer extinction
[30]).
n Fig. 3. As the (OPO) which 0 nm and 800 nt power was cope, used to two channels.
D1) to control to the sample onal optical Z- ns, in our case e, which was ong the Z-axis.
5 degrees to Z ed water for ted using a 10 U) in front of smitted beam rement of the z=0) was w0 =
en Z-scan and .
n in Fig 4. The gnal for three whereas the s shown in the ed at fluences -to-noise ratio rements were The optical Z- an absorptive oustic signal is while the open
scattering.
the excitation alculated from
:
(1) ptical constant bsorption data
fro to an th1.7 co th ex th Frap th tab be vasca th th int
Fig NL ph wi
ab cu
om Fig. 2(b), the g results for TiN f nd the conduction e band gap energ 77 eV, and 1.5 eV onduction band a e nonlinear resp xpected a contrib e excitation wav rom the obtained ppears at the cen e NPR was clear ble I). This effec ecause of the sma alues of NLA coef
an. The role of a e NLA process, s e dominant effe tensities.
g. 4. Experiment LR from TiN hotoacoustic Z-sc
ith open aperture To calculate the bsorptive respon urve using the eq.
gap energy was c films [13]. To ind n band of TiN, the gy (Eg). In this wo V) were lower tha and two-photon-
onse the plasmo bution of plasmo velength was in t d results, we can nter of the plasm
rly higher than a ct did not appea all scattering effe fficient obtained
plasmonic enhan similar to that in ect for the NLA
tal results (dots) NP with the O can measuremen e, simultaneously e nonlinear coeff se, we employed
(2) [33]:
∑
calculated to be ab duce a transition e photon energy m ork, the excitation an the Eg. Therefo induced d electr n band, just like on resonances at the resonant reg anticipate that th monic band, aroun at the other two ar in the optical ect leading to the
by the optical an ncement in TiN i Au NPs. Howev in our sample
and theoretical OPAZ setup. L nts; right column (
y measured.
fficients arising fr d the open apert
/
bout 3.7 eV, simil n between d ban must be larger th n energies (2.06 e ore, electrons in t rons contributed in [13,32]. We al high intensities gion of the samp he plasmonic effe nd 700 nm, whe o wavelengths (s domain, probab e differences in t nd photoacoustic s therefore clear ver, we believe th is the TPA for
fits (lines) of t eft column (a- (d-f): optical Z-sc
from the nonline ture optical Z-sc
⁄ (
lar nds han the eV, to lso as ple.
ere ect see bly the r in Z- hat all
the c):
can
ear can
(2)
The nor I is the the sam z is the scatterin On th is pro
where which characte thus, we process complex interact generat therefor coefficie
The nor with the
In a NP influenc the for microbu optical mechan cannot d one of N In the can be o call this above-m photoac can be should b formats regimes NLA co suspens powder [13]. In optical obtaine losses d Another measur photoac sensitiv nonline depend
~ 6.16 β βPA,eff to increase words, absorpt projecte coefficie
rmalized transm e intensity at focu mple with a linear e Rayleigh length ng was neglected he other hand, in oportional to the a
is the incident li depends on th teristics. The PA s e can expect that s. In this case, t x interaction bet tion can include tion of bubbles re we replaced ent. Then,
rmalized photoac e PA signal norm
Ps suspension, a ced by losses ari rmation of mic ubbles is often
Z-scan does not nisms, while the directly different NLA of NPs.
e first approxima obtained from eq s an effective NLA mentioned mech
coustics. Table I a compared to oth be careful when s (NPs or thin fil s, some qualitativ oefficient obtaine
sion is within the rs at similar puls
the case of TiN NLA was one ed in nanosecond
due to scattering r important aspe rements are als coustic Z-scan.
ve to scattering ear scattering ma dent. At 600nm, β
βOZ-SCAN, and at 80 βOZ-SCAN ratio nea e of relative porti high extinction tion rather than i ed applications ent at the plasmo
mission is proport us,
r coefficient α , L h of the beam. In d.
n the PAZ-scan, absorption coeffi
, ight intensity, and he material prop signal is indepen t it describes pure the photoacousti tween intense in the nonlinear ab around NPs due
to include the
coustic signal for malized by the far-
as in our case, t ising from nonlin crobubbles [16–
neglected in su t measure the inf e PAZ-scan is no
tiate the contribu ation, the values f qs. (1 – 5). These A coefficient, βPA
hanisms leading also shows resul her literature val comparing the d lm) and differen ve comparison c ed from optical Z e same order of m
e duration, but d thin films in the order of magnit d regime. One re and bubble form ect is that the ob so not far from
As mentioned g effect. Therefo ay slightly affects βPA,eff ~ 1.36 βOZ-SC
00nm it is βPA,eff ~ ar the plasmonic r
ion of absorption in the plasmon increase of scatte
of TiN NPs co onic band centra
tional to the NLA is the effectiv L is the sample t n eq. (2), the effec the acoustic sign icient , i.e.,
d Γ is the Grüneis perties and the ndent of the scatte
e light absorptive tic signal is prod
cident light and bsorption by NPs
e to their high effective nonline
r PAZ-scan is give -field component
⁄
the absorptive e near scattering [3 –18], although t uch measuremen fluence of either ot affected by s ution of microbub for an effective N values are given
A,eff, due to the in to the NPR, as lts of the optical lues. Notice that, data, since TiN ar nt spectro-tempo can be made. Fro Z-scan results for magnitude to thos different excitatio
femtosecond reg tude higher tha eason could be th mation, since it is btained values fro m those obtain
before, the PAZ ore, one can c the result and it
CAN, at 700nm it g
~ 2.62 βOZ-SCAN. Th resonance indica n in total extinctio ic peak is due t ering. This fact is olloids. The high
al resonance con
A coefficient, β.
ve thickness of thickness, and ct of nonlinear nal amplitude
(3) sen coefficient e laser beam ering process;
e nature of the duced by the TiN NPs. This s, but also the photoheating, ear absorption
(4) en by [17,18], t:
(5) effects can be
34], or due to the effect of nts. Since the r of those two scattering, we bbles from the NLA coefficient n in table I. We nfluence of the s detected by Z-scan, which although one re in different oral excitation om table I, the r the TiN NPs se obtained in on wavelength gime [14], the an our values he absence of s not a colloid.
om the optical ed from the Z-scan is not conclude that is wavelength grows to βPA,eff
he increase of ates significant on, or, in other to increase of s beneficial for her nonlinear nfirms the role
of plasmonic enhancement. On the other hand, one important issue is related to the fact that in the photoacoustic measurements, the photons absorbed by TiN NPs are transformed into heat, which is very likely to create microbubbles. In order to clarify the role of such microbubbles, time resolved studies should be performed, as in [16,17], where microbubbles in gold colloids were studied. Therefore, the NLA values obtained in our work could be affected by this phenomenon, and further experiments are required to verify this possibility.
Table I Calculated values of the NLA coefficient for TiN NPs in this work and comparison with literature values
AExcitation intensity one order of magnitude higher than in the present work.
B52nm thick thin film.
In conclusion, effective values of optically induced nonlinear photoacoustics response of suspensions of 40nm TiN NPs were reported for the first time using a combined technique for simultaneous optical and photoacoustic detection. Using the OPAZ- scan method, it was shown that nonlinear scattering can affect the results, as a loss mechanism influencing the nonlinear absorption.
Furthermore, bubble formation due to heating cannot be ruled out and further experiments are required to clarify this issue. Such bubbling effects are important for NPs mediated laser ablation of biological tissues and can be used for potential theranostics applications [16].
The plasmonic enhancement in the TiN NPs can also be exploited for biomedical applications such as photothermal therapy [9,10,21], which can be extended by serial PA tomography [35], as demonstrated with gold NP.
Funding. This work was funded by INCT of Photonics Program supported by CNPq, CAPES and FACEPE (Grant 465.763/2014-6) for optical characterization and the Russian Science Foundation (Project 19-72-30012) for fabrication and characterization of TiN NPs.
Acknowledgements. A.D. thanks the PNPD Program, CAPES/UFPE, for a post-doctoral fellowship. ASLG thanks CNPq for grant PQ-1A 307259/2015-3.
Disclosures. The authors declare no conflicts of interest.
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Sam ple
Preparatio n method/
solvent λ , nm
size, NP nm
βPA,eff
×10-8, cm/W
βOZ- SCAN
×10-8, cm/W
Ref (τexc)
TiN Laser ablation/
acetone 600 700 800
40 40 40
3.27
±0.17 6.41
±0.32 3.22
±0.16 2.40 1.04 1.23
This work (5 ns)
TiN Commerci
al powder 532 55 --- 8.31 [13] A (7 ns)
TiN Thin film 780 --- --- -68
[14]B (150 fs, 1 kHz)
TiN Thin film 155
0 --- --- -66
(150 [14]
fs, 1 kHz)
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