# Kinetics of Electric field induced oxygen ion migration in epitaxial metallic oxide films

## Abstract

In this paper we report the observation of curent induced change of resistance of thin metallic oxide films. The resistance changes at a very low current (current density $`J10^3`$ A/cm<sup>2</sup>). We find that the time dependence associated with the processes (increase of resistance) show a streched exponential type dependence at lower temperature, which crosses over to a creep type behavior at $`T`$ 350 K. The time scale associated shows a drastic drop in the magnitude at $`T`$ 350 K, where a long range diffusion sets in increasing the conductivity noise. The phenomena is like a ”glass-transition” in the random lattice of oxygen ions.

In recent years metallic oxides like LaNiO<sub>3</sub>, RuSrO<sub>3</sub>, La<sub>0.5</sub>Ca<sub>0.5</sub>SrO<sub>3</sub> etc. are being used as interconnects or electrodes in the field of oxide electronics. Many of these oxides belong to the ABO<sub>3</sub> class of oxides which are structurally similar to high $`T_c`$ superconductors. In many of these oxides oxygen/oxygen defect is a particularly mobile species and the activation energy for diffusion is often $``$ 1eV.  The high mobility of oxygen species can lead to two generic problems in use of these oxides as interconnects or electrodes in electronic applications. First, the conductivity noise in these oxides can be substantially large which mainly arises from long range diffusion of oxygen . The second problem is that the current or field induced changes in the resistivities of the films can occur for a prolonged period. This phenomenon of current induced resistance change have been first seen in high $`T_c`$ oxides and studied in films of YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7</sub> in which oxygen is a mobile species . It has been concluded that the current induced resistivity change arises due to electromigration of oxygen ions. These problems are of concern because they can seriously limit their applications and cause reliability linked problems.

In this paper we investigated the kinetics of the electric field induced resistivity changes as a function of temperature in epitaxial thin films of a typical normal metallic oxide LaNiO<sub>3-δ</sub> which has a cubic ABO<sub>3</sub> structure. The material is metallic in stoichiometric form ($`\delta `$=0) and its electrical properties have been investigated extensively . Our experiment consisted of high precision resistivity measurement as well as estimation of low frequency resistance fluctuations. The investigation has led to three very important results which are of significance in determining the stability of the these oxides as interconnects or electrodes. The observations are : (1) a very small current and field can induce a long time drift in the resistivity of the film, (2) the time scales associated with the changes are strongly temperature dependent and (3) at $`T`$ 340 K - 350 K there is a drastic reduction in the time scales associated with the process and the kinetics of the resistivity variation changes over from a stretched exponential behavior (at lower temperatures) to a creep type behavior at higher temperatures. At these temperatures the conductivity noise also shows a rapid increase.

All the experiments reported here are done with thin epitaxial films (thickness $``$ 150 nm) of LaNiO<sub>3</sub> grown on LaAlO<sub>3</sub> substrate by pulsed laser ablation. Details of growth and characterization has been given elsewhere.  Films with room temperature resistivity $`\rho _{rt}`$ = 1.6 m$`\mathrm{\Omega }`$.cm were patterned for resistance and noise measurements. The resistance measurements were done with a precision of 1 ppm and the noise measurement using a five probe geometry  was done with precision of spectral power $`10^{19}`$ V<sup>2</sup>/Hz. All the data are taken at thermal equilibrium where the temperature was controlled to within $`\pm `$5 mK.

In figure 1 we show a typical current induced change in the observed resistance $`R`$ at three characteristics temperatures. The measurements shown here were made with a current of 100 mA. This corresponds to a current density $`J`$ 5$`\times `$10<sup>4</sup> A/cm<sup>2</sup> and an electric field $`E`$ 10<sup>2</sup> V/cm. $`J`$ was so chosen that it was not high enough to cause a rupture and at the same time not so low that no perceptible change occurs. (We find that there is a threshold associated with this phenomena with $`J_{threshold}`$ 10<sup>3</sup> A/cm<sup>2</sup> and the exact value depends on the history of the material). Immediately after applying the current the resistance ($`R`$) drops slightly in a scale of few minutes. Then it starts to increase. We call this the ”damage”-($`d`$) process. Over several hundred minutes $`R`$ changes by about $``$ 2-3%. Then the current was reversed. On reversal of current $`R`$ falls typically by $``$ 1% and then starts to increase again. We call this drop in resistance the ”recovery” ($`r`$) process. The time scale involved in the $`r`$process is much smaller than that involved in the $`d`$process and it is quite similar to the early resistance drop seen on initial application of the current. The current stressing experiments were done for 270 K $`<T<`$ 400 K. Similar $`r`$ and $`d`$processes were seen in epitaxial films of high $`T_c`$ cuprates at room temperature . It was concluded  that the resistance change is a consequence of the oxygen ion migration and while the $`r`$process heals defects, the $`d`$process increases the defect and disorder. In this letter however we donot discuss this issue and focus on the kinetics instead, in particular its temperature dependence.

It is also important to note that the process occurs at low current/field. The current density $`J`$ used in the experiment is much less than the typical electromigration threshold observed in metallic interconnects. Interestingly this is also less than the threshold of $`J`$ 10<sup>6</sup> A/cm<sup>2</sup> observed in high $`T_c`$ cuprates .

In order to obtain quantitative evaluation of the time scales we first fitted the data to the following functional form.

$$\mathrm{\Delta }R(t)=\mathrm{\Delta }R_r(t)+\mathrm{\Delta }R_d(t)$$
(1)   
where the subscripts refer to the $`r`$process and the $`d`$process. Here we assume that the two processes take place simultaneously. However they are well separated in time and thus it is possible to analyze the data unambiguously. Both $`\mathrm{\Delta }R_r`$ and $`\mathrm{\Delta }R_d`$ follow $`streched`$ exponential dependence on time $`t`$. For $`\mathrm{\Delta }R_d`$ an additional creep component shows up at $`T`$ = 350 K and dominates the $`t`$ dependence at higher $`T`$. Thus we can write :

$$\mathrm{\Delta }R_r=\mathrm{\Delta }R_{0r}\left[1e^{\left(t/\tau _r\right)^{\beta _r}}\right]$$
(2)   
at all $`T`$.

$$\mathrm{\Delta }R_d=\mathrm{\Delta }R_{0d}\left[1e^{\left(t/\tau _d\right)^{\beta _d}}\right]+\nu t$$
(3)   
where $`\nu `$ = 0 for $`T<`$ 350 K. At low temperatures ($`T<`$ 330 K) $`\tau _d`$ being very large compared to the measurement time $`t`$ an unambiguous and independent determination of $`\tau _d`$ and $`\mathrm{\Delta }R_{0d}`$ is not possible. Instead, $`\tau _dt`$ allows us to make the assumption that

$$\mathrm{\Delta }R_d=\left(\frac{t}{K}\right)^{\beta _d}$$
(4)   
where,

$$K=\frac{\tau _d}{\left(\mathrm{\Delta }R_{0d}\right)^{1/\beta _d}}$$
(5)   
The data are fitted to the eqns.1-5 and the parameters are obtained. Typical time dependence of the resistance is shown figure 1. The inset to figure 1 shows a few fits to the data according to the equations above.

The time scale for the recovery process $`\tau _r`$ follows an Arrhenius relation with $`T`$ with an activation energy $`E_r`$ = 0.79 eV which is the same as the activation energy for migration of oxygen ions in these materials.  This shows that the process of current induced change in $`R`$ has its origin in oxygen ion migration. Also the exponent $`\beta _r`$ 0.8 implying that the underlying process is not too different from a simple Debye relaxation ($`\beta `$ = 1).

The temperature dependence of the time scale for the d-process, $`\tau _d`$ is shown in figure 2. In this case we show the temperature dependence of $`K`$ (see eqn 5) which in turn shows the T dependence of $`\tau _d`$ since the T dependence of $`\mathrm{\Delta }R_{0d}`$ is less severe. We find that $`K`$ (and hence $`\tau _d`$) has a weak temperature dependence for $`T<`$ 340 K. But at $`T`$ = 350 K, $`K`$ drops drastically. In the same graph we have also shown the $`T`$ dependence of the creep rate $`\nu `$. This is small near $`T`$ = 350 K and increases rapidly at higher $`T`$. The creep rate also follows an Arrhenius temperature dependence with activation energy, $`E_d`$ = 0.84 eV. This again is similar to $`E_r`$ and is similar to the activation energy for oxygen ion migration. The physical process underlying the resistance change is thus related to the migration of oxygen ions.

Figure 2 clearly shows that there is onset of long range diffusion at $`T`$ 350 K which gives rise to the creep. The effect of long range diffusion for $`T`$ 350 K can be seen also in the conductivity noise (denoted by $`\gamma /n`$, normalized noise magnitude, $`n`$ being the carrier concentration) which we show in the lower part of figure 2. One can see that at the onset of the long range diffusion the temperature dependence of the noise shows an upturn at $`T`$ 350 K. The fact that the extra noise observed at $`T`$ 350 K arises from long range diffusion has been shown before.  Below this temperature long range diffusion is frozen-in. The situation is thus similar to the process of glass-transition where at certain characteristic temperature range the long range diffusion freezes on cooling.

Evidence of a glass-transition like freezing at $`T`$ 350 K can be seen also in the $`T`$ dependence of the streched exponential exponent $`\beta _d`$ which is shown in figure 3. The value of the exponent $`\beta _d`$ is high in the ”molten” state ($`T>`$ 350 K) signifying nearly single Debye type relaxation associated with the oxygen migration. However, in the frozen state ($`T<`$ 350 K) the value of $`\beta _d`$ sharply decreases to $``$ 0.4-0.6 implying that there is an hierarchy of the relaxation process as in a glass . Interestingly, in a recent noise studies at low temperatures ($`T<`$ 20 K) we found clear evidence of two-level systems of low energy in this crystalline material as one generally find in conventional glasses . In that study we were able to conclude that these ”glass like” low energy excitations occur in the randomly frozen lattice of oxygen ions. The observation of kinetic freezing at $`T`$ 350 K thus very well connects to the observation of low energy excitation.

The observation of a glass like freezing of the oxygen migration is a new result. (However, there exists evidence from calorimetric studies of a glass-transition like phenomena of the excess oxygen in a related compound La<sub>2</sub>NiO<sub>4</sub> .) We feel that this new phenomena will be extremely important in determining the usability of oxide films as interconnects or electrodes. The important lesson from our investigation is that the characteristic temperature, where the ”glass-transition” of oxygen ions occur should be at a fairly high temperature if these oxide interconnects have to be used in application with low noise and stability against field-induced oxygen ion migration.

Figure Captions

Figure 1: Time dependence of resistance at various temperatures. The data at 400 K depicts creep-type behavior and the change in resistance is irreversible. The inset shows the type of fit that can be obtained with the phenomenological equations described in the text.

Figure 2: Temperature dependence of K (see text) and normalized noise magnitude. Current density for noise measurement was $``$ 10<sup>3</sup> A/cm<sup>2</sup>. The dotted line in the noise curve is guide to the eye showing the expected temperature dependence due to localized movements of atoms/vacancies.

Figure 3: Temperature dependence of the exponent $`\beta _d`$ in the long range diffusion regime.