Distinct terahertz third-harmonic generation of many-body excitonic states

Changqing Zhu,1 Anneke Reinold,1 Patrick Pilch,1 Sergey Kovalev,1

Julian Heckötter,1 Doris Reiter,1 Manfred Bayer,1 Marc Assmann,1 and Zhe Wang1, ∗
1
Department of Physics, TU Dortmund University, 44227 Dortmund, Germany
The dynamics of an electron-hole plasma governed by strong Coulomb interaction is a challenging many-
body problem. We report on experimental realization of electron-hole many-body states in the picosecond time
scale, with tunable densities in a representative semiconductor Cu2 O. By using time-resolved optical-pump
terahertz third-harmonic-generation spectroscopy, we study the nonlinear terahertz dynamical characteristics of
the many-body electron-hole states. We find not only efficient and nonperturbative terahertz third-harmonic
yield associated with the excitonic formation, but also a nonmonotonic dependence of the excitonic nonlinear
response on the electron-hole density, reflecting the exciton dissociation at high charge density. Our results
arXiv:2501.09535v1 [cond-mat.str-el] 16 Jan 2025

provide an efficient excitonic sensing of the far-from-equilibrium electron-hole many-body states.

Excitonic dynamics plays a key role in various contexts, widely applied previously (see e.g. [9, 10, 17]). We observe
such as photosynthesis in chromophore molecules [1], energy strong THz third-harmonic emission of the nonthermal states
transport in semiconductor optoelectronic devices [2], and de- after the initial optical creation of electron-hole pairs, and
velopment of novel quantum technologies [3]. Similar to a utilize the nonlinear response to monitor the time-dependent
hydrogen atom stabilized by attractive Coulomb interaction of evolution of the far-from-equilibrium many-body states. By
an electron and a proton, an exciton is a quasiparticle formed carrying out a systematic investigation of the observed THz
as an attractively bound state of a negatively charged elec- third-harmonic generation as a function of pump-drive delay,
tron and a positively charged hole. To observe the hydro- optical pump fluence, and THz field strength, we find distinct,
genic Rydberg series of an exciton is, however, not straight- and a rich set of THz nonlinear characteristics of the strongly-
forward, because in a real material a concomitant excitation of correlated electron-hole many-body states.
unbound electron-hole pairs is hardly avoidable and the band Cuprous oxide Cu2 O is a highly suitable semiconductor
dispersion often deviates from parabolic [4–6]. While the hy- system chosen for the study of the involved many-body dy-
drogenic single-body description remains valid in the dilute namics. The canonical Rydberg excitons with principal quan-
charge density limit [7], the existence of exciton-exciton and tum number up to n = 30 were observed in Cu2 O [4, 5, 18],
exciton-plasma interactions renders the excitonic dynamics a while typically up to n = 5 in two-dimensional semicon-
representative many-body problem [8–10]. ductor crystals [6]. The lowest-lying exciton state is suffi-
From the time-dependent kinetic perspective, many-body ciently long-lived, i.e. ∼ 0.1 − 10 µs [19, 20], for a possi-
effects do not emerge instantaneously after a femtosecond ble realization of excitonic Bose-Einstein condensation [21–
laser pulse excitation (1 fs = 10−15 s) of unbound electron-hole 23]. Whereas bright excitons can be identified in conventional
pairs, but builds up in a characteristic time scale of several linear-response spectroscopy of thermal equilibrium state by
10 fs up to 0.1 picosecond (1 ps = 10−12 s) [9]. The many- measuring near-infrared/visible absorption [4] or photolumi-
body interactions govern the follow-up complex dynamical nescence [5], an access to dark excitonic states requires non-
processes, before the system relaxes to a quasi-equilibrium linear and/or nonequilibrium state spectroscopy that employs
state that consists of mainly the lowest-energy 1s excitons, two-photon processes [24–26] or intraexciton optical transi-
which takes typically several 100 ps [10]. While the quasi- tions [27–29]. In particular, a resonant optical transition ex-
equilibrium state can be well approximated by an indepen- citation of the 1s to 2p exciton states was resolved, at 10 ps
dent quasiparticle picture, it is a very challenging problem to after the creation of unbound electron-hole pairs, which de-
describe the strongly Coulomb correlated many-body dynam- termined a characteristic time scale of the 1s Rydberg exciton
ics from 0.1 to 10 ps after the initial excitation [11]. In this formation [27, 29].
ultrashort time interval, various dynamical processes occur si- We use a 100 fs laser pulse (800 nm, 1.55 eV) to induce
multaneously, including the formation of excitonic states from two-photon excitation of unbound electron-hole pairs in a nat-
unbound electron-hole pairs, the Coulomb collisions of one urally grown single crystal Cu2 O whose band gap is 2.172 eV
exciton with another bound or unbound electron-hole pair, as [29]. Generated by optical rectification of 800 nm pulse from
well as scattering of excitons or unbound charges by collec- the same laser system in a LiNbO3 crystal [30], an intense
tive excitations (for example, phonons or plasmons), see e.g. THz drive pulse is naturally synchronized to the pump pulse
[8–16]. with a tunable pump-drive time delay tpd [see Fig. 1(a)]. Due
Naturally matching the characteristic picosecond time to the centrosymmetric cubic structure of Cu2 O, the intraband
scale, an intense terahertz electromagnetic pulse (1 THz = even-order nonlinear susceptibilities vanish, hence we focus
1 ps−1 ) is used in this work to strongly interact with the on the third-order THz nonlinear responses. To prepare a nar-
nonequilibrium many-body states in order to reveal their non- rowband THz pulse with a central frequency f and to detect
linear characteristics, while linear THz probes have been third-order harmonic generation at 3 f , we use corresponding
 2

(a )
C o n d u c tio n b a n d values of tgate , as indicated by the dark blue arrow in Fig. 1(b).
tp d
A distinctly different THG feature occurs at positive tpd .
E le c tr o n
At tpd = 4.7 ps the duration of the THG trace appears to be
(3 f)
longer than that at tpd = 0.7 ps, which becomes even longer
P

(3 f) E
at tpd = 6 ps. This is not due to stretch of the THG tran-
O p tic a l sient in the time domain, but reflects the occurrence of a sec-
p u m p
H o le ond THG transient after (3 f )P . At a longer pump-drive de-
T H z d r iv e V a le n c e b a n d lay of tpd = 7.4 ps the second THG transient, as labelled by
(3 f )E , is temporally well-separated from the (3 f )P transient,
(b )
2
(c ) hence can be directly identified in our time-resolved measure-
tp d (p s ) Io = 0 .3 0 m J /c m (3 f)
-1 1 .3
p
1 0 0 * P ment. The (3 f )E transient does not shift with the optical pump
3 C u 2O
-7 .3
pulse in the time domain, but appears only when the THz drive
-3 .3 (3 f) P
pulse arrives, even for a quite long pump-drive delay, see e.g.
0 .7
4 K
tpd = 830 ps in Fig. 1(b). Such a long delay (i.e. ∼ 1 nanosec-
I3 f (n o rm .)

(3 f) E
4 .7 ond) corresponds to the characteristic time scale of the long-
E ( a r b . u n its )

2 -1
1 0
6 lived 1s Rydberg exciton state in Cu2 O [29]. As will be fur-
7 .4
ther discussed below, we can assign the (3 f )E transients as the
T o ta l T H G

8 .7 (3 f) E
featuring third-harmonic responses of excitons under the THz
1 2 .7
1
3 5 .7 -2
drive, while the (3 f )P radiation as THz THG of electron-hole
1 0
1 9 7 Io p (m J /c m 2
) plasma.
8 3 0 0 .0 8 0 .3 8 A second distinct behavior of the excitonic THG transient
0 .1 3 0 .5 1
0
N o p u m p 0 .3 0 0 .7 6 (3 f )E , which is characteristic for the nonequilibrium many-
-5 0 5 1 0 1 5 -2 0 0 2 0 4 0 6 0 4 0 0 8 0 0 body states, is the nonmonotonic dependence of its inten-
tg a te (p s ) P u m p - d r iv e d e la y tp d (p s ) sity on the pump-drive delay tpd . As can be directly seen
from the time-domain signal [Fig. 1(b)], the (3 f )E intensity
Figure 1. (a) Illustration of optical-pump THz-drive third-harmonic- at tpd = 12.7 ps is not only stronger than those at longer
generation measurement. (b) Time-domain traces of emitted THz pump-drive delays (e.g. tpd = 35.7 ps), but also than that
electric field E for various optical-pump THz-drive delays tpd at an of tpd = 8.7 ps. This is more evident in the representation of
optical-pump fluence of Iop = 0.30 mJ/cm2 and an f = 0.35 THz
the total integrated THG intensity I3 f in Fig. 1(c). At a criti-
drive peak field of E f = 120 kV/cm. The bottom trace represents
the background without optical pump. The emitted field after a 3 f cal value of Iop c
= 0.30 mJ/cm2 the maximum THG intensity
bandpass filter was gate-detected by electro-optic sampling with an achieved at tpd = 3.4 ps, as marked by the asterisk in Fig. 1(c),
800 nm laser pulse for tunable gate time tgate . (c) Total THG intensity is followed by a second smaller maximum at tpd = 12.7 ps,
I3f versus tpd for various pump fluences. as indicated by the arrow. Hence the second maximum as be-
ing due to the excitonic THG reflects the typical time scale
of exciton formation [29] after the excitation of electron-hole
THz bandpass filters with a 20% bandwidth. The time traces pairs, while the first maximum corresponds to the THG of the
of the THz pulses are detected via electro-optic sampling in a optically excited electron-hole plasma under the THz drive.
ZnTe crystal [31]. The sample temperature is 4 K in a helium A third nonlinear characteristic of the Coulomb correlated
flow optical cryostat. nonequilibrium many-body states is featured by the nonmono-
Results - Strong terahertz third harmonic generation (THG) tonic dependence of the excitonic THG signal (3 f )E on the
is observed by driving Cu2 O with an intense THz pulse af- electron-hole density, which is tunable by varying the pump-
ter an 800 nm optical excitation for varying the optical-pump pulse fluence. As shown in Fig. 1(c), with increasing pump
THz-drive delay tpd . Figure 1(b) presents the time-domain fluence, the maximum third-harmonic yield corresponding to
traces of the emitted THG electric field at various tpd ’s for the electron-hole plasma (3 f )P increases monotonically, while
an optical-pump fluence of Iop = 0.30 mJ/cm2 and a f = the position of this maximum shifts slightly to shorter pump-
0.35 THz drive with a peak field of E f = 120 kV/cm. Whereas drive delays. In contrast, the maximum of the excitonic THG
without optical excitation no THG is observed, a most effi- (3 f )E reaches a largest value at Iop c
= 0.30 mJ/cm2 , and
cient third-harmonic yield occurs at tpd = 3.4 ps [Fig. 1(c)]. the maximum position shifts monotonically towards longer
The negative values of tpd in the representation correspond to pump-drive delays (i.e. from 12.7 ps at 0.30 mJ/cm2 to 26.0 ps
the experimental settings that the optical pump pulse reaches at 0.76 mJ/cm2 , see arrows in Fig. 1(c)). For Iop < Iop c
the
the sample after the peak of the THz drive field. Even at (3 f )E maximum merges into the (3 f )P peak thus cannot be
tpd = −11.3 ps a weak THG trace labelled as (3 f )P is still resolved.
discernible i.e. after tgate = 13 ps [Fig. 1(b)], because the op- To further reveal nonlinear THz excitonic sensing of the
tical excitation pulse catches up the tail of the multicycle THz many-body states, we fix the pump-drive delay at tpd = 7.4 ps,
drive pulse whose duration is about 20 ps. With increasing tpd , where the (3 f )P and (3 f )E transients are well discriminated
the THG transient (3 f )P shifts continuously towards smaller in the time domain, and study their evolution with varying
 3

(a ) (b ) (a ) (b )
tp = 7 .4 p s Io (m J /c m 2
) 1 0 1 (e ) tp d = 7 .4 p s 1 0 0 (3 f) E
d p
C u 2O
E f (k V /c m )
1 .5 2 (3 f) P (3 f) E Io = 0 .3 0 m J /c m 2
4 K 1 2 0
p

0 .7 6
0 (d ) 1 0 8 (3 f) P
1 0

E ( a r b . u n its )

I3 f (n o rm .)
1
0 .5 1
(3 f) 8 3 1 0 -1 ∝If
P
E ( a r b . u n its )

(3 f) (3 f)

I3 f (n o rm .)
P E
0 .3 0 6 3
1
-1
1 0 4 2
0 .2 5
∝ I f2 .3
(c ) h o le
2 3 C u 2O
0 .1 3
e le c tr o n I ocp 1 0 -2 ∝ I f3
N o d r iv e 4 K
-2 e x c ito n 0
1 0
0 .0 8 -5 0 5 1 0 0 .1 1
(3 f) E
∝ I o2p tg a te (p s ) D r iv e flu e n c e If ( n o r m .)
E f = 1 2 0 k V /c m N o p u m p
0
-3
1 0
-5 0 5 1 0 0 .0 1 0 .1 1 Figure 3. (a) Emitted THz field E measured with different drive
tg a te (p s ) P u m p flu e n c e Io p (m J /c m 2
) fields for tpd = 7.4 ps and Iop = 0.30 mJ/cm2 . (b) The obtained third-
harmonic yield of (3 f )P and (3 f )E exhibits very different dependen-
cies on the drive fluence, i.e. I(3 f )E ∝ I 2.3
f whereas I(3 f )P ∝ I f . The
Figure 2. (a) Emitted THz field traces at various optical-pump flu-
ences for tpd = 7.4 ps and a 0.35 THz drive peak field of 120 kV/cm. dashed line indicates a perturbative power-law dependence I3f ∝ If3 .
Two temporally separate THG transients are resolved and marked by
(3 f )P and (3 f )E , respectively. (b) Integrated intensity of these two
transients versus pump fluence. The dashed line indicates quadratic
the third-harmonic radiation [see Fig. 2(b), dashed line]. The
dependence I3 f ∝ Iop 2
for Iop < Iop
c
. (c) Sketch of unbound charges
and exciton in the dilute density limit. (d) Illustration of strongly cor- excitons in the presence of the charged particles (i.e. electrons
related many-body states of electron-hole plasma and excitons with and holes) are not independent from each other, but consti-
higher charge density. (e) In the high-density limit, the Coulomb in- tute together a highly correlated many-body state due to the
teraction within an exciton is completely screened, leaving behind a strong Coulomb interaction [Fig. 2(d)]. The interaction be-
strongly interacting electron-hole plasma. tween electrons and holes in the plasma can lead to the forma-
tion of excitons, while at the same time excitons are scattered
into electrons and holes in the plasma. Moreover, the electron-
pump fluence (or equivalently the charge density). As shown hole interaction within an exciton is screened by the other
in Fig. 2(a), the time-domain THG signal of (3 f )P increases charges in the plasma and excitons, hence the excitons become
monotonically with the pump fluence, whereas the (3 f )E sig- more and more fragile with increasing charge density. Above
c
nal first increases until the critical value of Iop = 0.30 mJ/cm2 a critical density (i.e. corresponding to Iop c
= 0.30 mJ/cm2 in
and then decreases. The pump-fluence dependence of the in- Fig. 2(b)), the excitons start to decay, which corresponds to the
tegrated intensity I3 f of these two temporally separated THG decrease of I(3 f )E , and finally evolve into a Mott phase where
transients (3 f )P and (3 f )E is presented in Fig. 2(b). At the only plasma remains [Fig. 2(e)]. For these strongly correlated
lowest fluences the THG intensity of the two transients is com- many-body states, which are formed just few picoseconds af-
parable and increases monotonically, which reflects a con- ter the optical excitation, our time-resolved measurement of
comitant increase of the optically excited charge-carrier and THz nonlinear responses can clearly unveil the signature of
exciton densities. The dependence on the optical pump flu- the excitons in presence of the plasma, thereby revealing their
2
ence follows essentially a quadratic behavior, i.e. I(3 f )P ∝ Iop evolution towards the Mott phase.
[see dashed line in Fig. 2(b)], which is consistent with the The distinction of the nonlinear THz excitonic dynamics
two-photon excitation of electron-hole pairs across the band is not only manifested by the charge-density dependent evo-
gap [Fig. 1(a)] [29]. At high fluences, i.e. Iop > Iop c
, the de- lution, but also by a characteristic difference of its depen-
crease of the excitonic THG intensity (3 f )E in contrast to the dence on the THz drive field. Figure 3(a) presents the emitted
continuous increase of plasma third-harmonic yield (3 f )P is third-harmonic radiation at various THz drive field strengths
a nonlinearity signature for a Mott phase of excitons due to for a fixed optical pump fluence of the critical value Iop c
=
the high density. Also the increase of the plasma THG devi- 0.30 mJ/cm and a pump-drive delay of tpd = 7.4 ps, where the
2

ates from a perturbative quadratic dependence, reflecting an excitonic THG is clearly distinguished from the plasma THG
enhanced Coulomb interaction among the electrons and holes in the time domain. Without a THz drive no 3 f radiation is
at high densities. detectable within our experimental uncertainties. Hence both
Figure 2(c)-(e) illustrate the evolution of the many-body the THz drive and the optical pump [see also Fig. 1(b)] are
states excited by the 800 nm laser pulses as a function of required for the observation of the THz third-harmonic radia-
charge-carrier density (or equivalently, of laser fluence). At tion.
very low pump fluences [Fig. 2(c)], both the electron-hole The plasma THG I(3 f )P starts to appear already at a rela-
plasma density and the exciton density increase continuously, tively low THz drive field (e.g. 23 kV/cm), while the exci-
which, under the THz drive, leads to a quadratic increase of tonic THG I(3 f )E is hardly discernible. With increasing drive
 4

0
field strength, both the plasma and the exciton THG increases 1 0
tp = 4 .7 p s Io (m J /c m 2
)
d p
continuously, in contrast to the nonmonotonic dependence on 1 .5 2
0 .3 0
the optical pump fluence (see Fig. 2). In comparison with that 1 0 -1
0 .1 9

A m p litu d e ( n o r m .)
3 f 0 .1 3
of plasma, the enhancement of the excitonic THG is much
0 .0 8
faster, which becomes even dominant over the plasma THG f
-2
1 0
at the highest drive fields available to our experiment. The
temporal separation of the exciton and plasma THG enables -3
1 0
a separate evaluation of their intensity, the result of which is C u 2O
N o p u m p
presented as a function of the THz drive pulse fluence I f in 4 K
-4
Fig. 3(b). Interestingly, neither of the two THG transients 1 0
0 .3 5 0 .7 0 1 .0 5 1 .4 0
exhibits a cubic power law dependence on I f , which is in F re q u e n c y (T H z )
clear contrast to a perturbative third-order nonlinear response.
Whereas the plasma THG exhibits essentially a linear depen- Figure 4. Broadband THz emission spectrum of optically excited
dence I(3 f )P ∝ I f , the dependence of the excitonic THG fol- electron-hole plasma under an f = 0.35 THz drive at a fixed, short
lows a nonperturbative power-law dependence I(3 f )E ∝ I 2.3 f , pump-drive delay of tpd = 4.7 ps for various pump fluences Iop . The
which refute a trivial interpretation by a perturbative nonlin- spectrum without optical pump characterizes the spectral profile of
ear susceptibility. the transmitted THz drive pulse, where above ∼ 0.5 THz reflects the
experimental noise level. With increasing fluence the emission spec-
Discussions - Our results have provided a systematic THz tra are broadening, which effectively enhances the spectral weight at
nonlinear characterization of the strongly correlated nonequi- 3f.
librium electron-hole many-body states. The observed distinct
difference in the THz fluence dependencies of the plasma and
the exciton THG indicates two different mechanisms for the Within the framework of Boltzmann transport theory, one
generation of the third harmonic radiation. As will be dis- can take into account scattering processes and show that the
cussed below, one mechanism roots in the nonparabolicity nonperturbative power-law dependence results from a strong
of the exciton dispersion relation, while the other is because THz field driven nonlinear kinetics (see e.g. Refs. [34, 35]).
of the highly nonthermal nature of the far-from-equilibrium Based on this mechanism, we can naturally ascribe the ob-
electron-hole plasma. served THz THG to the field-driven kinetics of holes from
In Cu2 O, different from the lowermost conduction band Γ+6 the nonparabolic band Γ+7 , both for excitons and plasma. It is
with a parabolic dispersion relation in the vicinity of the Γ worth noting that a fully quantum-mechanical description of
point, the dispersion relation of the uppermost valence band the many-body nonlinear kinetics driven by intense THz field
Γ+7 is characterized by a clear nonparabolicity due to spin- remains an outstanding theory problem [36].
orbit coupling [see Fig. 1(a) for an illustration] [32, 33]. In the The observed linear dependence of the plasma THG inten-
Hamiltonian in addition to the parabolic terms H P (k x , ky , kz ) = sity (i.e. I(3 f )P ∝ I f ) deviates rather far from the perturbative
−a1 k2x − a2 ky2 − a3 kz2 with coefficients a1,2,3 and the quasi- cubic power law, strongly suggesting a different mechanism
momentum components k x,y,z , the nonparabolic terms up to than for the excitonic THG (i.e. I(3 f )E ∝ I 2.3 f ). To investigate
the second order are in general of the form H NP (k x , ky , kz ) = the plasma THG further, we shift the pump-drive time delay
−c1 |k x ||ky | − c2 |ky ||kz | − c3 |kz ||k x | where the coefficients c1,2,3 to tpd = 4.7 ps, where the emitted THG is dominated by the
arise due to spin-orbit and orbit-orbit coupling [33]. To clar- plasma contribution [see Fig. 1(b)], and measure the emitted
ify the responsibility of the nonparabolicity for the observed THz field in the time domain without a 3f bandpass filter for
THG, we can consider a simplified model for a linearly po- various pump fluences. The derived THz emission spectra in
larized THz drive field along the x-axis with an idealized si- the frequency domain are presented in Fig. 4.
nusoidal waveform E f sin(2π f t). Under the drive of this field,
Without the optical pump, we observe just the transmission
the parabolic terms will lead to a velocity of the charged quasi-
of the THz drive pulse through the sample [see also Fig. 1(b)],
particles vP (t) ∝ ∂H
P
∂k x = −2a1 k x ∝ cos(2π f t), hence the emit- which is centered at the frequency of f = 0.35 THz with-
ted THz electric field ∝ ∂ j∂t(t) ∝ sin(2π f t) with the time-
P
out resolvable spectral weight at 3 f above the noise level. In
dependent current density jP (t) = nvP (t), which is again a contrast, with an optical pump, already at a low pump fluence
sinusoidal waveform with the fundamental frequency f . In of 0.08 mJ/cm2 , one can see an evident change of the THz
contrast, the nonparabolic terms give rise to vNP (t) ∝ ∂H
NP
∂k x = emission spectrum, which is characterized by a broadening
∓(c1 |ky | + c3 |kz |), which for the linearly polarized THz field re- beyond the spectrum of the THz drive pulse, both towards the
sults in a time-dependent current density jNP (t) = nvNP (t) of a lower and higher frequencies. With increasing pump fluence,
rectangular waveform in an idealized scenario. Consequently, the broadening is further enhanced in the frequency domain.
the emitted THz electric field, which is proportional to ∂ j ∂t (t) ,
NP
At the highest pump fluence, the high-frequency limit of the
contains high-order harmonics. This idealized model has al- broadband emission spectrum reaches up to about 1.5 THz
ready captured the essence of the physics, although the energy above the experimental noise level. These results show that
loss due to inelastic scattering in real materials is neglected. the stimulated THz emission due to the plasma is of broad-
 5

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