# Effect of Coulomb blockade on STM current through a granular film

\[

## Abstract

The electron transport through an array of tunnel junctions consisting of an STM tip and a granular film is studied both theoretically and experimentally. When the tunnel resistance between the tip and a granule on the surface is much larger than those between granules, a bottleneck of the tunneling current is created in the array. It is shown that the period of the Coulomb staircase(CS) is given by the capacitance at the bottleneck. Our STM experiments on Co-Al-O granular films show the CS with a single period at room temperature. This provides a new possibility for single-electron-spin-electronic devices at room temperature.

\]

Charging effects on single electron tunneling such as Coulomb blockade and Coulomb oscillation have attracted much interest. Recent advances in nano-technology enable us to fabricate small tunnel junctions where charging effects play an essential role. The I-V characteristics for double tunnel junction systems have been extensively studied, where the step-like structure called Coulomb staircase(CS) is observed when the resistances between the junctions are not equal. For these asymmetric double junction systems, the junction with a large resistance behaves like a bottleneck of the tunneling current and the central island is charged through the other junction up to the maximum charge. The tunneling current jumps when the maximum charge changes. Recently, the CS has been observed by using a tip of scanning tunneling microscope(STM) of nanometer-size in highly resistive granular films as well as metal-droplet systems . For a granular film, which is considered to be an array of tunnel junctions, the observed CS implies that a bottleneck exists in the conducting paths. However, the physics behind the CS in a granular film is not clear because it contains many granules with different size and the conducting path may form a three-dimensional network in a thick granular film.

Bar-Sadeh et al. have studied the STM current through a nonmagnetic granular film, Au-Al<sub>2</sub>O<sub>3</sub>, by using the cryogenic STM. They observed the CS at temperatures $`T=4.2`$ and 78 K, and analyzed the experimental data by using a triple barrier model. They assumed that the rate for tunneling between two granules is small and the number of excess electrons in each granule is treated independently. Because of these assumptions, the CS was given by the superposition of two different periods in their model: one was determined by the tunnel process between the STM tip and a granule, the other between another granule and the base electrode. On the contrary, as we will show later, the CS has a single period which is determined by the capacitance at the bottleneck.

In this Letter, we study the electron transport through an array of tunnel junctions consisting of an STM tip and a granular film both theoretically and experimentally. In this system, we can vary the tunnel resistance between the tip and a granule on the surface by changing the distance between them. When the tunnel resistance between the tip and a granule on the surface is much larger than those between granules, a bottleneck of the tunneling current is created in the array. Theoretically, we find that the period of the CS is given by the capacitance of the bottleneck even in a thick film with many granules between the tip and the base electrode. We present results from STM experiments on 10 nm- and 1$`\mu `$m-thick Co-Al-O granular films which have the CS with a single period at room temperature. We propose that tunnel magnetoresistance (TMR) oscillates with the same period as the CS for magnetic granular films. Our theoretical and experimental studies provide a new direction for single-electron-spin-electronic devices at room temperature.

Our setup is schematically shown in Figs. 1(a) and 1(b). The current flows from the STM tip to the base electrode through a granular film. The system with a thin granular film in panel (a) is modeled by the one-dimensional array of tunnel junctions as in panel (c). We will show that our experimental results for the 10 nm-thick film are well explained by this model with $`N=3`$. On the other hand, such a one-dimensional array is not appropriate for a thick granular film, because, as illustrated in Fig. 1(b), the conducting paths spread and form a three-dimensional network as the distance from the tip increases. We model this system by a one-dimensional array of $`N`$-junctions connected to a Bethe-lattice network with 3 nearest neighbors as shown in Fig. 1 (d). Each junction is characterized by a tunnel resistance $`R_j`$, capacitance $`C_j`$, and carrying charge $`Q_j`$. The number of excess electrons in the $`k`$-th granule is represented by $`n_k`$.

The free energy for the state characterized by the set of charges $`\{n_i\}(n_1,n_2,\mathrm{})`$ is given by

$$F(\{n_i\})=\underset{i}{}\frac{Q_i^2}{2C_i}(Q_1e\xi )V,$$
(1)   
where $`Q_1`$ represents the charge at the surface, $`\xi `$ is the number of electrons supplied by the voltage source and $`i`$ goes from 1 to $`N`$. When an electron tunnels through the $`k`$-th junction, the charge $`Q_i`$ deviates from its initial value by $`\delta Q_i^k`$. Let us consider the energy change due to the single electron tunneling, $`E_k^\pm `$, where the superscript $`+()`$ denotes the process that an electron tunnels upward(downward) through the $`k`$-th junction in Figs. 1(c) and 1(d). From Eq. (1), we obtain

$`E_k^\pm (\{n_i\})`$ $`=`$ $`{\displaystyle \underset{i}{}}\left(\stackrel{~}{{\displaystyle \underset{j<i}{}}}{\displaystyle \frac{\delta Q_j^k}{C_j}}\right)n_i+{\displaystyle \frac{1}{2}}{\displaystyle \underset{i}{}}{\displaystyle \frac{\left(\delta Q_i^k\right)^2}{C_i}}`$ (3)   
$`(\delta Q_1^k\pm e\delta _{1,k})V,`$   
where $`\stackrel{~}{_i}`$ represents the summation along the conducting path, and $`\delta _{1,k}`$ is Kronecker’s delta function. The deviation $`\delta Q_i^k`$ is determined by Kirchhoff’s law and is independent of the number of excess electrons $`\{n_i\}`$. The tunneling rate is obtained by using the golden rule  as

$$\mathrm{\Gamma }_k^\pm (\{n_i\})=\frac{E_k^\pm (\{n_i\})}{e^2R_k[\mathrm{exp}(E_k^\pm (\{n_i\})/T)1]}.$$
(4)   
By solving the master equation for the probability of states $`p(\{n_i\})`$ , the tunneling current through the $`k`$-th junction is obtained as

$$I_k=e\underset{\{n_i\}}{}p(\{n_i\})\left[\mathrm{\Gamma }_k^+(\{n_i\})\mathrm{\Gamma }_k^{}(\{n_i\})\right].$$
(5)   
For simplicity, we neglect the effect of residual fractional charge, cotunneling, spin accumulation and level quantization in the granules.

We first look at the I-V characteristics for a one-dimensional array of tunnel junctions with a bottleneck of the tunneling current between the tip and a granule on the surface. In Figs. 2(a) and 2(b), we present the numerical results for tunnel junctions with $`N=25`$ at $`T=0`$, $`N`$ being the number of junctions. Due to the charging energy in each junction, single electron tunneling is blocked as long as the bias voltage $`V`$ is lower than the threshold value $`V_T`$. From Eq. (3) the bias voltage $`V_T^k`$, above which the initial state $`(0,\mathrm{},0)`$ is unstable for electron tunneling through $`k`$-th junction, i.e., $`E_k^+(0,\mathrm{},0)<0`$, is given by

$$V_T^k=\frac{_i(\delta Q_i^k)^2/C_i}{2(\delta Q_1^k+e\delta _{1,k})}=\frac{e}{2}\left(\frac{1}{C_T}\frac{1}{C_k}\right).$$
(6)   
The last expression in Eq. (6) is easily obtained by considering the equivalent network shown in the inset of Fig. 2(a), where $`1/C_L=_{i<k}1/C_i`$ and $`1/C_R=_{i>k}1/C_i`$. The threshold voltage is given by $`V_T=\mathrm{min}_kV_T^k`$. As pointed out by Melsen et al., the Coulomb blockade region increases as the number of junctions, $`N`$, increases as shown in Figs. 2(a) and 2(b). For large $`N`$, the threshold voltage is expressed in terms of the average capacitance $`C`$ as $`V_T(e/2C)(N1)`$ and is proportional to the film thickness, because the total capacitance is inversely proportional to the layer thickness.

For a thick film with many granules between the tip and the base electrode, the conducting paths form a three-dimensional network as shown in Figs. 1(b) and 1(d). The decrease of the total capacitance for a junction network with increasing film thickness is much weaker than that for a one-dimensional array. Therefore, the threshold voltage $`V_T`$ of a thick film remains of the same order of the magnitude as that for a thin film. Later we will show that the experimental results for 1 $`\mu `$m-thick film are well explained by considering the junction network as the Bethe-lattice as shown in Fig. 1(d).

The CS is classified into two types as shown in Figs. 2(a) and 2(b). The criterion is whether the capacitance $`C_1`$ of the bottleneck is the smallest of all of the junctions, i.e., whether $`V_T=V_T^1`$ or $`V_T=\mathrm{min}_{k1}V_T^k`$. A typical CS for $`V_T=\mathrm{min}_{k1}V_T^k`$ is given in Fig. 2(a), where electrons start to accumulate at the bottleneck once the bias voltage exceeds $`V_T`$. Until the accumulated electrons tunnel out through the bottleneck, the voltage drop caused by them forbids electrons to tunnel through the other junctions. Therefore, the stable state is given by $`(n_1,0,\mathrm{},0)`$ and the tunneling current jumps at the bias voltage where the number of accumulated electrons $`n_1`$ changes. This number $`n_1`$ is the minimum value satisfying the conditions

$$E_1^+(n_1,0,\mathrm{},0)<0,E_{k1}^+(n_1,0,\mathrm{},0)0.$$
(7)   
The first condition represents the accumulated electrons tunneling out through the first junction. The second indicates that electrons cannot tunnel through the other junctions, and is rewritten as $`(e^2/C_1)n_1eVV_T^{k1}`$. Therefore, the tunneling current jumps at the bias voltage $`V`$ given by

$$V=\underset{k1}{\mathrm{min}}V_T^k+(e^2/C_1)(n_11).$$
(8)   
From Eq. (8), one can easily see that the CS has a single period of $`e/C_1`$. The tunneling current for each plateau of the CS is approximately given by $`Ie\mathrm{\Gamma }_1^+(n_1,0,\mathrm{},0)`$.

On the other hand, if $`C_1`$ is the smallest, the tunneling current does not jump at $`V_T`$ as shown in Fig. 2(b). For $`V_T<V<\mathrm{min}_{k1}V_T^k`$, the tunneling current is approximately given by $`Ie\mathrm{\Gamma }_1^+(0,\mathrm{},0)`$. Once $`V`$ exceeds $`\mathrm{min}_{k1}V_T^k`$, electrons start to accumulate at the bottleneck and the I-V curve shows a CS. The bias voltage $`V`$ at which the tunneling current jumps is given by Eq.(8).

When the bottleneck is placed at another junction $`j(1<j<N)`$, the stable state is $`(0,\mathrm{},0,n_{j1}=n_j,n_j,0,\mathrm{},0)`$ and the period of the CS is determined by the capacitance $`C_j`$ at the bottleneck. The CS is classified into two types in the same way as those shown in Figs. 2(a) and 2(b). However, the criterion is whether the capacitance $`C_j`$ is the smallest or not.

The period of CS in a thick film shown in Figs. 1(b) and 1(d) is also determined from Eqs. (3) and (7), as long as the tip is coupled to a single granule on the surface and the bottleneck is created between them. Therefore, the voltage where the tunneling current jumps is given by Eq. (8). The CS has a single period determined by the capacitance at the bottleneck, even for a thick film.

We have performed STM experiments on Co-Al-O granular films. Samples with different thicknesses were prepared by an oxygen-reactive sputtering with a Co-Al alloy target; 10 nm- and 1 $`\mu `$m-thick Co<sub>36</sub>Al<sub>22</sub>O<sub>42</sub> films consisting of Co granules embedded in an Al-oxide matrix were deposited on glass substrates. For the 10 nm-thick Co<sub>36</sub>Al<sub>22</sub>O<sub>42</sub> film, a 200 nm-thick Co-Al alloy layer was inserted between the Co-Al-O granular film and the glass substrate as a base electrode. A conventional STM system was used for I-V measurements under high vacuum. The I-V curves were obtained by using a platinum tip at room temperature, and by placing the tip on a Co granule. The tunnel resistance between granules for Co-Al-O granular films is estimated to be about $`10^510^6\mathrm{\Omega }`$ from the average diameter of granules ($``$ 3 nm), the average intergranular distance ($``$ 1 nm), and electrical resistivity . On the other hand, the tunnel resistance between the tip and a granule on the surface, $`R_1`$, is about $`10^810^9\mathrm{\Omega }`$. Therefore, $`R_1`$ is $`10^210^4`$ times larger than the other tunnel resistances.

The experimental I-V curves for a 10 nm-thick Co<sub>36</sub>Al<sub>22</sub>O<sub>42</sub> film are plotted in Fig. 3 (a). There exist two or three granules between the tip and base electrode. Even at room temperature, the tunneling current shows a clear CS with a single period. The I-V curves for a 1 $`\mu `$m-thick Co<sub>36</sub>Al<sub>22</sub>O<sub>42</sub> film are plotted in Fig. 4(a). We also find the CS with a single period. Note that for this thick film, 200 to 300 Co granules exist in the direction perpendicular to the film plane between the tip and the substrate. Let us now analyze our experimental results by using the theory presented above.

We first examine the I-V curves for the 10 nm-thick film. A triple tunnel junction model with a bottleneck between the tip and a granule on the surface is used for the calculation. The calculated I-V curves are shown in Fig. 3 (b). Parameter values were chosen in the ranges estimated from the experiments. We find that the theoretical curves explain the experimental ones very well.

For the thick film, on the other hand, the conducting paths are considered to form a three-dimensional network inside the film; this is a more complicated system compared to the thin granular films for which the CS was observed so far. The value of the threshold voltage $`V_T0.5`$V is not explained by the one-dimensional array model, because the threshold voltage $`V_T`$ is proportional to the layer thickness in this model and is about 100 times larger than that for 10 nm-thick film; this is in contrast with the experimental data.

As mentioned before, this discrepancy can be resolved by considering a network of the conducting paths. We describe the thick film as a one-dimensional array connected to a Bethe-lattice network as shown in Fig. 1(d). The bottleneck is created between the tip and a granule on the surface. Therefore, the stable states are given by $`(n_1,0,\mathrm{},0)`$ and the tunneling current jumps when the number of accumulated electrons $`n_1`$ changes. The voltage where the current jumps is given by Eq. (8) and the CS has a single period of $`e/C_1`$ even for a thick film. The equivalent network to obtain the threshold voltage for $`k`$-th junction $`V_T^k`$ is shown in Figs. 4 (b) and 4(c), where we assume, for simplicity, the same capacitance $`C`$ for all junctions. The key point is that for electron tunneling in the one-dimensional array, the Bethe-lattice network is replaced by its total capacitance as shown in Fig. 4 (b). The total capacitance for the Bethe-lattice is $`C/2`$ and the bias voltage $`V`$ at which the tunneling current jumps (see Eq. 8) is given by $`V=(e/2C)(N+1)+(e/C)(n_11)`$. The experimental results shown in Fig. 4(a) are consistent with our model with $`N2`$.

The TMR in tunnel junctions with ferromagnetic electrodes  and magnetic granular films  is another attractive topic. Recently, the TMR oscillations in asymmetric double tunnel junctions with ferromagnetic electrodes have been studied. The condition for TMR oscillations is that the tunneling current shows the CS and the magnetic field dependence of the tunnel resistance is not the same for all tunnel junctions. The TMR oscillations with the same period as the CS may be observed for magnetic granular films. Our calculation shows that the amplitude of the TMR oscillation is about 5% at room temperature for the curve A in Fig. 3(b).

In summary, the electron transport through an array of tunnel junctions consisting of an STM tip and a granular film has been studied both theoretically and experimentally. When the tunnel resistance between the tip and a granule on the surface is much larger than those between granules, a bottleneck is created in the array and a CS with a single period is observed in the I-V curve. We predicted that the period of the CS is given by the capacitance at the bottleneck even in a thick film with many granules between the tip and the base electrode. Our STM experiments on 10 nm- and 1$`\mu `$m-thick Co-Al-O granular films confirmed the CS with a single period at room temperature. TMR oscillations for magnetic granular films are also predicted. Our theoretical and experimental studies provide a new direction for single-electron-spin-electronic devices at room temperature.

We thank P. M. Levy for reading the manuscript. This work is supported by a Grant-in-Aid from Scientific Research Priority Area for Ministry of Education, Science, Sports and Culture of Japan, a Grant from the Japan Society for Promotion of Science, and NEDO Japan.