# Single particle and collective excitations in the one-dimensional charge density wave solid K0.3MoO3 probed in real time by femtosecond spectroscopy.

## Abstract

Ultrafast transient reflectivity changes caused by collective and single particle excitations in the quasi one-dimensional charge-density wave (CDW) semiconductor K<sub>0.3</sub>MoO<sub>3</sub> are investigated with optical pump-probe spectroscopy. The temperature-dependence of non-equilibrium single particle excitations across the CDW gap and their recombination dynamics are reported for the first time. In addition, amplitude mode reflectivity oscillations are observed in real time. A $`T`$-dependent overdamped response is also observed which is attributed to relaxation of the phason mode.

Molybdenum oxides like K<sub>0.3</sub>MoO<sub>3</sub> and Rb<sub>0.3</sub>MoO<sub>3</sub> are well known for their interesting electronic properties arising from their one-dimensional (1D) chain structure. At room temperature they are highly anisotropic 1D metals. Upon cooling, they become susceptible to a Peierls instability on the 1D chains causing fluctuating local CDW ordering. Upon further cooling, as fluctuations are reduced, inter-chain interactions cause the CDWs on individual chains to become correlated, eventually undergoing a second-order phase transition to a three-dimensionally (3D) ordered state below $`T_c=183`$ K. The formation of a 3D CDW ordered state is concurrent with the appearance of a gap $`\mathrm{\Delta }_{CDW}`$ in the single particle (SP) excitation spectrum, while the collective excitations of the 3D CDW state are described by an amplitudon mode (AM) and a phase mode (phason).

In this Letter we report femtosecond time-domain transient reflectivity measurements on K<sub>0.3</sub>MoO<sub>3</sub> enabling for the first time real-time observation of the reflectivity modulations caused by collective CDW excitations. We report the $`T`$-dependence of the amplitude $`A(T),`$ frequency $`\omega _A(T),`$ and damping constant $`\tau _A(T)`$ of the AM and for the first time the $`T`$-dependence of the phason damping constant $`\tau _p(T)`$. We also report the $`T`$-dependence of electron-hole recombination lifetime $`\tau _s`$ across the CDW gap below, as well as above $`T_c`$. Up till now, enhaced coherent phonon oscillations associated with the formation of a CDW were observed below $`T_{c1}`$ in Mo<sub>4</sub>O<sub>11</sub>, but to our knowledge real-time observation of collective and SP excitations in CDW systems have not yet been reported.

In these experiments, an ultrashort laser pump pulse first excites electron-hole pairs via an interband transition in the material (step 1 in Fig.1a)). In a process which is similar in most materials including metals, semiconductors and superconductors, these hot carriers very rapidly release their energy via $`ee`$ and $`eph`$ collisions reaching states near the Fermi energy within $`\tau _i=10100`$ fs (step 2 in Fig.1a)) acting as an ultrashort SP injection pulse. If a CDW or superconducting gap is present in the SP excitation spectrum, it inhibits the final relaxation step resulting in a relaxation bottleneck and photoexcited carriers accumulate above the gap. This causes a transient change in reflectivity $`\Delta /`$ due to change in dielectric constant arising from excited state absorption processes of the type shown in step 3 in Fig.1a). The density of these accumulated photoinduced (PI) carriers, $`n_{sp}^{}`$ can thus be determined as a function of temperature and time after photoexcitation from the transient reflectivity change $`\Delta _s/S(T)e^{t/\tau _s}`$, where $`\tau _s`$ is the characteristic SP recombination time. The amplitude is given by $`S(T)n_{sp}^{}\rho _2\left|M_{12}\right|^2`$, where $`M_{12}`$ is the matrix element for the $`E_1`$ $``$ $`E_2`$ optical transition (Fig.1a)) and $`\rho _2`$ is the density of states in level $`E_2`$. Whereas $`\rho _2`$ and $`M_{12}`$ can be assumed to be $`T`$-independent in first approximation, $`n_{sp}^{}`$ is strongly $`T`$-dependent when $`k_BT\mathrm{\Delta }_{CDW}.`$ A $`T`$-dependence of $`n_{sp}^{}`$ has recently been calculated for various gap situations, which we can now compare with experiments.

In addition to the transient change of reflectivity due to SP excitations discussed above, a transient reflectivity signal is expected also from collective modes. The AM is of $`A_1`$ symmetry and involves displacements of ions about their equilibrium positions $`Q_0`$, which depend on the instantaneous surrounding electronic density $`n(t)`$. Since $`\tau _i<\mathrm{}/\omega _A,`$ the SP injection pulse may be thought of as a $`\delta `$-function-like perturbation of the charge density $`n_{sp}`$ and the injection pulse acts as a time-dependent displacive excitation of the ionic equilibrium position $`Q_0(t).`$ The response of the AM to this perturbation is a modulation of the reflectivity $`\Delta _A/`$ of the form $`A(T)e^{t/\tau _A}\mathrm{cos}(\omega _At+\varphi _0)`$ by the displacive excitation of coherent phonons (DECP) mechanism, known from femtosecond experiments on semiconductors and superconductors .

The $`\delta `$-function-like SP injection pulse also gives rise to the displacement of charges with respect to the ions, directly exciting the CDW phason. Since this is infrared-active, we expect the resulting change of the dielectric constant $`\mathrm{\Delta }ϵ/ϵ`$ to lead to a directly observable reflectivity transient, which for small $`\mathrm{\Delta }ϵ`$ can be approximated as $`\Delta _p/\mathrm{\Delta }ϵ/ϵ.`$ In equilibrium, we expect the phason to be pinned and at a finite frequency, but in non-equilibrium situation such as here, where the excess carrier kinetic energy may easily exceed the de-pinning energy, the mode may be de-pinned. In this case we may expect an overdamped reflectivity transient written as $`P(T)e^{t/\tau _p}\mathrm{cos}(\omega _pt+\varphi ),`$ with $`\omega _p0`$, but with a damping constant which is expected to be similar to that of the AM $`\tau _p\tau _A`$, i.e. $``$10 ps.

Summing all the contributions, in K<sub>0.3</sub>MoO<sub>3</sub> the photoinduced transient reflectivity signal is of the form:

$`\mathrm{\Delta }(t,T)/`$ $`=`$ $`A(T)e^{t/\tau _A}\mathrm{cos}(\omega _At+\varphi _0)`$ (2)   
$`+P(T)e^{t/\tau _p}+S(T)e^{t/\tau _s}+B(T).`$   
For completeness we have included an additional term $`B(T)`$ due to a long-lived background signal, which is also observed experimentally, and whose lifetime is longer than the inter-pulse separation of $`12`$ns. The different contributions to $`\Delta /`$ can be effecively distinguished experimentally by their very different time-dynamics, polarization- and $`T`$-dependences.

In the experiments reported here a mode-locked Ti:Sapphire laser with pulselength $`\tau _L100`$ fs at 800 nm was used. The PI change in reflectivity $`\Delta /`$ was measured using a photodiode and lock-in detection. The pump laser power was kept below 5 mW, exciting approximately 10<sup>18</sup>-10<sup>19</sup> carriers per cm<sup>3</sup>, and the pump/probe intensity ratio was $``$100. The steady-state heating effect was accounted for as described in Ref.. The experiments were performed on freshly cleaved K<sub>0.3</sub>MoO<sub>3</sub> single crystals with the laser polarization in the a-b plane, a being the  direction and b is the chain direction. The orientation of the crystal was determined by using an atomic force microscope, by the direction of the Mo-O chains.

In Fig.1a) we show $`\mathrm{\Delta }/`$ as a function of time at different temperatures. Below $`T_c`$, an oscillatory component is observed on top of a negative induced reflection, the latter exhibiting a fast initial decay followed by a slower decay. As $`T_c`$ is approached from below, the oscillatory signal dissappears, while the fast transient signal remains observed well above $`T_c,`$ as shown by the trace at 210K. For a quantitative analysis, we separate the different components of the signal according to their $`T`$-dependence and probe polarization anisotropies. In Fig.1b) we show the signal at $`T=45`$ and 110K with the oscillatory component and background $`B(T)`$ subtracted. The logarithmic plot enables us to clearly identify two components with substantially different lifetimes, one with $`\tau _s`$ 0.5 ps, and the other with $`\tau _p10`$ ps at low $`T.`$ Their amplitudes and relaxation times are analyzed by fitting two exponentials (Eq.(1)). For reasons which will become apparent, we attribute them to the SP relaxation $`S(T)`$ and phason relaxation $`P(T)`$ respectively. We note that $`P(T)`$ displays no sign of oscillatory response, in accordance with the expectation that the phason relaxation is overdamped in this type of experiment. The insert shows the dependence of the amplitude of the fast signal on the probe pulse polarization, showing maximum amplitude for $`\stackrel{}{E}a`$. In Fig.1c) we have plotted only the oscillatory component with its FFT spectrum, showing a peak at $`\nu _A=`$ 1.7 THz. In contrast to the transient signal the amplitude of the oscillatory signal is independent of polarization (Fig.2a)).

The $`T`$-dependences of the single oscillatory component frequency $`\nu _A`$ and damping $`\mathrm{\Gamma }_A=1/(\pi \tau _A)`$ derived from fits to the real-time oscillations are shown in Fig.2a). Since the oscillation frequency $`\nu _A`$ shows clear softening as T<sub>c</sub> is approached from below, the contribution from coherent phonons as observed in Ref. can be excluded. The measured $`\nu _A`$ and $`\mathrm{\Gamma }_A`$ closely follow the expected behaviour for the AM and are in good agreement with previous spectroscopic neutron and Raman data. The amplitude of the modulation $`A(T)`$ falls rather more rapidly with $`T`$ than $`\nu _A`$ and is rather isotropic in the $`ab`$ plane.

In Fig.2b) and c) we have plotted the $`T`$-dependence of $`\tau _p`$ and $`P(T)`$. At $`T=`$50 K, $`\tau _p=12\pm 2`$ ps, in agreement with the $`\mathrm{\Gamma }=0.050.1`$ THz linewidths of the pinned phason mode in microwave and IR experiments. With increasing temperature $`\tau _p`$ is approximately constant up to 90 K and then falls rapidly as $`TT_c`$. The decrease of $`\tau _p`$ near $`T_c`$ is consistent with increasing damping due to thermal phase fluctuations arising from coupling with the lattice and SP excitations. The amplitude $`P(T)`$ exhibits somewhat different behaviour. It appears to first show an increase with increasing $`T`$, and then drops as $`TT_c`$. Such $`T`$-dependence behaviour has been previously observed - but not yet satisfactorily explained - for the threshold field in some non-linear conductivity experiments.

Let us now turn to the transient reflectivity signal due to photoexcited SP excitations. The $`T`$-dependence of the PI signal amplitude below $`T_c`$ for a $`T`$-dependent gap $`𝚫(T)`$ \- for simplicity using a BCS-like $`T`$-dependence - is given by:

$$S(T)n_{sp}^{}=\frac{_I/(𝚫(T)+k_BT/2)}{1+\gamma \sqrt{\frac{2k_BT}{\pi 𝚫(T)}}\mathrm{exp}(𝚫(T)/k_BT)},$$
(3)   
where $`_I`$ is the pump laser intensity per unit cell and $`\gamma `$ is a constant, depending on the materials’ parameters. Plotting Eq.(2) as a function of temperature in Fig.3a), we find that the amplitude $`S(T)`$ obtained from the fits to the data agrees remarkably well with the theory for $`T<T_c`$: $`S(T)`$ is nearly constant up to nearly 100 K, then increases slightly and then drops very rapidly near $`T_c`$. The value of the gap $`\mathrm{\Delta }(0)`$=850K$`\pm 100`$K obtained from the fit of Eq.(2) with $`\gamma =`$ 10 is in good agreement with other measurements . In contrast to the response of the collective modes $`A(T)`$ and $`P(T),`$ both of which dissappear within 10-20 K below $`T_c`$, $`S(T)`$ remains observable up to nearly 240 K, i.e. appears to show a pseudogap up to 50 K above $`T_c.`$ This is - in contrast to the behaviour below $`T_c`$ \- clearly incompatible with a BCS-like description of the gap and suggests the fluctuating presence of the gap well above $`T_c`$. The polarization anisotropy of the signal $`S(T)`$ for $`T>T_c`$ is the same as for $`T<T_c`$ (Fig.1b)), strongly suggesting that the origin of the signal $`S(T)`$ above $`T_c`$ is the same as below $`T_c`$ i.e. SP gap excitations.

The $`T`$-dependence of the relaxation time $`\tau _s`$ (Fig.3b)) is qualitatively different to $`\tau _p`$ and $`\tau _A`$. As $`TT_c,`$ $`\tau _s`$ appears to diverge and then drops to $`\tau _s0.25`$ ps above $`T_c`$. Such behaviour is in agreement with expected $`T`$-dependence of SP relaxation across the gap. The dominant recombination mechanism across the gap is phonon emission via phonons whose energy $`\mathrm{}\omega _p>2\mathrm{\Delta }`$. As the gap closes near $`T_c`$, more low-energy phonons become available for reabsorption and the recombination mechanism becomes less and less efficient. The recombination lifetime near $`T_c`$ can be shown to be inversely proportional to the gap as $`\tau _s1/\mathrm{\Delta }(T)`$. The solid line in Fig.3b) shows a fit to the data using a BCS-like $`T`$-dependent gap $`\mathrm{\Delta }_{BCS}(T)`$ with $`T_c^{3D}`$=183 K.

To complete the data analysis, we show in Fig.4 the amplitude of the slowly-decaying background signal $`B(T)`$ as a function of $`T`$. Its anomalous $`T`$-dependence clearly rules out a thermal origin. The lifetime $`\tau >10^8`$s deduced from the amplitude of $`B(T)`$ at ”negative times” i.e. from the preceding pulse, strongly suggests excitations involving localized states. From a fit to an Arrhenius law $`B(T)=B_0\mathrm{exp}[E_a/k_BT],`$ we obtain an activation energy $`E_a/\mathrm{\Delta }(0)0.6\pm 0.2`$, suggesting that the process involves the excitation of carriers from intra-gap states into the SP continuum $`E_1`$. As the gap closes, excitations from intra-gap states to the SP states are no longer possible, explaining the $`T`$-dependence of the signal above $`T_c`$. The microscopic origin of these states is most likely trapped defects, but the possibility of a collective excitation cannot be excluded at this stage. We note that a long-lived signal with a similar $`T`$-dependence was recently observed in time-resolved experiments on the cuprate superconductor YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7-δ</sub> and attributed to localized intra-gap states.

The real-time optical data presents some qualitatively new information on the SP and collective excitations in quasi-1D materials. We have found that because of the qualitatively different time-, polarization- and $`T`$-characteristics, the responses of the different components can be effectively separated. Apart from directly extracting the $`T`$-dependences of $`A(T)`$, $`\nu _A(T)`$ and $`\tau _A(T)`$, we also observe an overdamped mode, which we have assigned to relaxation of the phason mode. In addition to the observation of the $`T`$-dependence of photoinduced SP population as predicted by theory, we find - also in agreement with calculations \- that the SP recombination time across the gap diverges as $`\tau _s1/\mathrm{\Delta }`$ as $`TT_c`$. From the fact that the SP population appears to persist above $`T_c`$, the data shows clear evidence for the existence of a pseudogap for SP excitations above $`T_c`$ and suggests the fluctuating presence of a SP gap, rather than fluctuations of the order parameter, which would appear as a tail also in the SP relaxation time $`\tau _s`$ above $`T_c`$ \- but does not. Finally, we should mention that many of the features, particularly the $`T`$-dependence of the SP excitation amplitude and the SP recombination lifetime is very similar to the behaviour recently reported in cuprates. We note that although coherent oscillations were reported in YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7-δ</sub>, no $`T`$-dependence of the oscillation frequency was reported, and they were attributed not to any collective electronic mode, but to $`c`$-axis phonons.

FIG 1. a) The transient reflection $`\mathrm{\Delta }R/R`$ from K<sub>0.3</sub>MoO<sub>3</sub> after photoexcitation by a 100 fs laser pulse at a number of temperatures above and below $`T_c^{3D}=183`$ K. The constant background signal $`B(T)`$ was substracted and offset for clarity. b) The time-evolution of transient signal with the oscillatory component subtracted shown at $`T`$=45 K and 110 K, displayed on a logarithmic scale to emphasise the difference in relaxation times $`\tau _p`$ and $`\tau _s`$. The insert shows the amplitude $`S(T)`$ as a function of probe pulse polarization below (solid squares), and above $`T_c^{3D}`$ (open circles) with respect to the crystal  direction. c) The oscillatory transient signal $`\mathrm{\Delta }R_A/R`$ after subtraction of the decay components $`B`$, $`S`$ and $`P`$. The fit is made using the first term in Eq.(1). The insert shows the FFT spectrum of the signal.

FIG 2. a) The amplitude $`A(T)`$ (diamonds), frequency $`\nu _A`$ (squares) and damping constant $`\mathrm{\Gamma }_A=1/(\pi \tau _A)`$ (full circles) as a function of $`T`$. Data from Refs. (open circles) and  (open triangles) are also included. The insert shows the amplitude $`A(T)`$ as a function of probe polarization with respect to the crystal  direction. b) $`\tau _p`$ as a function of $`T`$ (circles). The amplitudon decay time $`\tau _A`$ is plotted for comparison (squares). c) $`P(T)`$ as a function of $`T`$.

FIG 3. a) The $`T`$-dependence of $`S(T)`$ . The fit to the data for $`S(T)`$ is shown using Eq.(2) with a BCS-like gap $`\mathrm{\Delta }_{BCS}(T)`$ opening at $`T_c^{3D}=183`$ K. b) The SP relaxation time $`\tau _s`$ as a function of $`T`$ and a fit using Eq.(25) of Ref..

FIG 4. The $`T`$-dependence of the long-lived signal $`B\left(T\right)`$. The line is an Arrhenius fit of the signal amplitude below $`T_{c\text{ }}`$with $`E_a=60`$meV. The insert shows the amplitude $`B(T)`$ as a function of probe pulse polarization with respect to the crystal  direction.

The authors wish to acknowledge L.Degiorgi and P.Monceau for very useful discussions and K.Kočevar for the AFM analysis. A part of this work was performed under the auspices of the EU ULTRAFAST project.