text:
# Photo-induced spin dynamics in ferromagnetic semiconductor 𝑝-(Ga,Mn)As

## Abstract

Spin dynamics in ferromagnetic $`p`$-(Ga,Mn)As ($`x`$ = 0.011, $`T_C`$ = 30 K) has been studied by carefully comparing the decay time of the photo-induced reflectivity change with the transient behavior of polar Kerr rotation induced by photo-generated carrier spins with a femtosecond light pulse of various polarizations. As to the rising process, the rate of Kerr rotation is found comparable to the generation rate of spin-polarized carriers. For the decay process, the Kerr rotation and reflectivity signal both show the same decay rate at above the $`T_C`$, whereas, below the $`T_C`$, the former becomes slower than the latter. The magnitude of Kerr rotation suggests that 102 Mn spins are revolved by injecting one hole spin. On the basis of these observations, collective rotation of ferromagnetically coupled Mn spins is discussed in terms of $`p`$-$`d`$ exchange interaction and successive transverse spin relaxation. Development of another long-lived behavior under external perpendicular magnetic fields is also disclosed.

In III-V based ferromagnetic semiconductors Ohno99 , carrier spins, especially hole spins play an important role in that they mediate long-range ferromagnetic coupling between magnetic ions through the $`p`$-$`d`$ exchange interaction Munekata ; Koshihara ; Ohno00 . This mechanism opens the ways to manipulate the orientation of ferromagnetically coupled Mn spins with spin-polarized carriers generated by photons without applied magnetic fields Oiwa . To pursue optical manipulation of magnetic properties, investigations of spin dynamics induced by optical pulses is indispensable.
In this letter, we are concerned with spin dynamics of ferromagnetically coupled Mn spin system in ferromagnetic, $`p`$-type (Ga,Mn)As epitaxial layers. This has been accomplished by carefully comparing the data obtained from femtosecond time-resolved photo-induced Kerr rotation spectroscopy with decay time of photo-induced change in reflectivity. While temporal profile of photo-induced Kerr rotation coincides with that of the photo-induced reflectivity above the Curie temperature ( $`T_C`$ = 30 K), discrepancy develops between the two profiles below $`T_C`$, as characterized by the prolonged relaxation rate in photo-induced Kerr rotation. The sign of rotation angle changes with the polarity of circularly polarized excitation light, and the rising rate of the rotation is found comparable to the generation rate of spin polarized carriers. The magnitude of the rotation indicates that 102 Mn spins are revolved per one hole spin. On the basis of these experimental results, ultrafast rotation of ferromagnetically coupled Mn spins is discussed. Development of a rather large, long-lived component under external perpendicular magnetic fields is also disclosed, and discussed in terms of temporal increase/decrease in hole-induced ferromagnetic coupling.
Samples were prepared by molecular beam epitaxy (MBE) on GaAs/GaAs(100) substrates at the substrate temperature of 250 C. Thickness and Mn contents $`x`$ of the (Ga,Mn)As epitaxial layer are 200 nm and 0.011, respectively. Because of the lattice mismatch between the (Ga,Mn)As layer and the substrate Shen , in-plane magnetic anisotropy is present in the (Ga,Mn)As layer. The Curie temperature, as measured by a superconducting quantum interference device (SQUID) magnetometer, is around 30 K. Hole concentration is inferred to be 1020 cm-3 or below, referring to the existing electrical transport data of (Ga,Mn)As with similar Mn contents Matsukura .

Time-resolved polar Kerr rotation measurements, by means of pump-and-probe technique, were carried out to study spin dynamics. Light source was a cw mode-locked Ti:Sapphire laser pumped by a cw frequency-doubled Nd:YAG laser. Duration and repetition rate of laser pulses were $``$120 fs and 78 MHz, respectively. The laser pulse, whose central photon energy was tuned at 1.579 eV, was split in pump and probe pulses by a beam-splitter. The value of photon energy was slightly higher than the band gap of (Ga,Mn)As, and was appropriate to generate low-energy electrons and holes in the samples. Intensity of the pump pulse impinging on samples was varied between 1 and 5$`\times `$1016 photons/pulse/cm3. Polarization of pump pulses was controlled by a quarter-wave plate to be either in a linear or right- ($`\sigma ^+`$) / left- ($`\sigma ^{}`$) handed circular polarization so that spin de-polarized or polarized carriers was respectively generated in the samples. The probe pulse of 1$`\times `$1015 photons/pulse/cm3 was fixed in a linear polarization so that the information as to spin dynamics was represented as a pump-induced change in Kerr rotation angle of the probe pulse. The change in the rotation angle was measured by means of the balancing detection technique with an accuracy of 10-4 deg. Dynamics of photo-generated carrier was studied by the pump-induced change in reflectivity. In this experiment, polarization of pump and probe pulses were both in linear polarization. Both time-resolved Kerr rotation and reflectivity experiments were carried out at temperatures ranging from 10 to 80 K, either under the applied magnetic field of 0 or 1 Tesla along the direction normal to the sample plane (Faraday configuration).
We first start with time-resolved photo-induced change in reflectivity and Kerr rotation above $`T_C`$. As shown in Fig.1(b), the reflectivity signal rises steeply at zero picosecond (ps) and decays rapidly. From the single exponential decay curve, the decay time of the reflectivity signal is estimated to be 25$`\pm `$1 ps. This fast decay time is most likely attributed to the crystal defects formed during the low-temperature (LT) epitaxial growth. It is known that LT-GaAs and Be doped LT-GaAs ($`p`$-LT-GaAs:Be) epitaxial layers contain excess ionized As and associated defects that work as electron and hole traps, which give rise to the reflectivity and differential transmission signal of sub-picosecond Gupta ; Loch ; Hamil . The present (Ga,Mn)As is heavily $`p`$-type, so that hole traps are most likely saturated. On the other hand, the electron traps are not saturated, especially under the present low excitation density. In fact, the decay time of the reflectivity signal is independent on the excitation density, as shown in the inset. Consequently, the observed reflectivity signal mainly reflects the initial trapping time of the photo-generated electron Loch ; Hamil . This suggests that photo-generated holes stay longer in the valence band than the decay time of the reflectivity.
Turning eyes on the behavior of time-resolved Kerr rotation signals (Fig.1(a)), the temporal profile is very similar to that observed for the reflectivity change. The rotation angle is symmetric with respective to the circular polarization, being positive and negative for the excitation of $`\sigma ^+`$ and $`\sigma ^{}`$, respectively. For the linearly polarized excitation, the rotation signal vanishes. These results indicate that the Kerr rotation profile at 50 K is governed by spin relaxation of carriers generated by the circularly polarized pump pulse. Most likely, it is free electrons, but not holes, that are primarily responsible for the Kerr signal, since spin relaxation time of holes is known to be very fast, being less than a few ps in GaAs Damen ; Hilton . Our inference is based on the assumption that band structure of (Ga,Mn)As at above the Curie temperature can be approximated with that of a non-magnetic GaAs, at least in the vicinity of $`\mathrm{\Gamma }`$ point.
Below $`T_C`$, the decay of Kerr rotation signal becomes clearly slower than that of reflectivity signal, as shown in the data taken at $`T`$ = 20 K (Figs.2(a) and (b)). As to the dependence of polarization of pump pulse on the sign of Kerr rotation angle, the relationship observed at temperatures above $`T_C`$ holds also below $`T_C`$ for both fast and slow components. Looking the data carefully, we notice that a slower component is superimposed on a fast decay component. A single exponential fit of the Kerr rotation signal results in the overall decay time constant of 30 ps. More precise analysis with bi-exponential curve fitting $`[A_1\mathrm{exp}(t/\tau _1)+A_2\mathrm{exp}(t/\tau _2)]`$ yields $`\tau _1`$ = 13 ps for the fast component and $`\tau _2`$ = 54 ps for the relatively slow component. The fast component coincides with the photo-generated electron trapping time obtained from the reflectivity data. The contribution of the relatively slow component becomes smaller with increasing temperature. The application of the bi-exponential fit became rather difficult for data taken at 30 K and higher. With single exponential fit, however, we were able to notice the presence of the relatively slow component up to around the Curie temperature, as shown in the inset in Fig. 2. As a whole, above $`T_C`$, spin relaxation occurs with the same time constant as that of the electron trapping, whereas, below $`T_C`$, spin relaxation slows down. This clearly indicates that the development of long-range ferromagnetic alignment of Mn spins, accompanied by the spin-polarized-hole bands, seems to be responsible for the occurrence of relatively slow decay.
Within hole spin coherence time, photo-generated hole spins are aligned perpendicular to the sample plane and interact with ferromagnetically coupled Mn ions through the $`p`$-$`d`$ exchange interaction. This gives rise to the generation of a perpendicular effective magnetic field, and results in immediate rotation of Mn spins from lateral to perpendicular direction. Comparing the magnitude of Kerr rotation at the peak of photo-induced rise with the value of Kerr rotation angle at saturation magnetization, the numbers of rotated Mn is estimated to be about 1018 cm-3 per excitation pulse; namely, one hole spin rotates about 102 of Mn spins, assuming the quantum efficiency of photo-carriers to be unity. This fact strongly suggests the occurrence of collective rotation of ferromagnetically-coupled Mn spins, which could be a new type of excitation. In the previously reported cw-excitation experiments Oiwa , the number of rotated Mn spins was deduced to be 106-7 cm-3 per one hole spin. In the cw-experiments, continuous generation of spin-polarized hole makes it possible to accumulate hole spins. This results in the enhanced numbers of rotated Mn spins.
The relaxation process of the rotated Mn ion spins can be viewed as transverse spin relaxation through the Larmor precession. The magnetic field that drives the precession comes from in-plane magnetic anisotropy of 0.2 Tesla, as estimated from the difference in $`MH`$ product between in-plane and out-of-plane magnetization data Ani . This field, with a gyromagnetic constant of electron $`\gamma `$ = 2.2$`\times `$105 m/As, gives rise to the oscillation time of about 200 ps, being not so far from the decay time constant obtained experimentally. The absence of oscillatory behavior in Kerr rotation signal may either be due to free induction decay or homogeneous relaxation. Knowing that the decay profile is not Gaussian but exponentional, we are able to conclude that the homogeneous relaxation is the predominant process. In other words, there is a strong damping factor being present in the Larmor precession in the present case. The origin of damping may be phonon scatterings.
Another interesting behavior has been found in the situation where initial spin states are aligned perpendicular to the sample plane. Examples are shown in Fig. 3 by the data taken with $`H_{}`$ = 1T at which magnetization is saturated along the direction normal to the sample plane. A new component, being characterized by slowly-increasing ($`\tau `$ = 150 ps) and decreasing ($`\tau `$ = 500 ps) behaviors, appears below $`T_C`$ ($`T`$ = 20 K, curve ‘a’) in addition with the fast-decaying component. The magnitude of induced Kerr rotation at the maximum (40 mdeg) is fairly large, being comparable to 10% of the saturation at 20 K. Furthermore, the long-lived Kerr rotation signal is independent on the polarization of pump pulse, suggesting that it is not a spin relaxation process but an energy relaxation process that is taking place. Here, we should recall that the lifetime of holes is long because of the predominance of electron trapping over hole trapping in the $`p`$-type sample. Mn states, if they can weakly bind holes Hirakawa ; Takahashi , would also contribute to increasing the hole lifetime. Within the lifetime of photo-generated holes, ferromagnetic coupling is enhanced, making Mn-spin subsystem possible to further align parallel at the given finite temperature. This is a relatively slow process, because the change in relative alignment between Mn spins is always accompanied by the changes in energy and momentum of hole-spin subsystem through emission and absorption of phonons. Compared with the complicated rising process, the decaying process is more straightforward; we believe that this process is dominated by the recombination between holes and trapped electrons.
The long-lived component is still observable above the Curie temperature, as seen in the data taken at 50 K (curve ‘b’). Hole injection causes the variation of the Curie temperature to a slightly higher temperature, which results in enhancement in the paramagnetic susceptibility at higher temperature side near $`T_C`$. The effect vanishes completely at 70 K (curve ‘c’) which is far from $`T_C`$. The long-lived component is also observable in ferromagnetic samples with different Mn contents of 0.068 (data not shown). In this case, the rise and decay time constants are much longer than the $`x`$ = 0.011 sample. In summary, our experimental results show that optical manipulation of ferromagnetically coupled Mn spin system is possible in various time scales with III-V-based magnetic alloy semiconductors.
This work was started at “Photomagnetic semiconductor” project (1999-2002) of Kanagawa Academy of Science and Technology, Kanagawa, Japan, and has been being continued with partial support from Scientific Research in Priority Areas “Semiconductor Nanospintronics” (2002 - ) of The Ministry of Education, Culture, Sports, Science and Technology, Japan.


format: text

text:
# Intrinsic thermal vibrations of suspended doubly clamped single-wall carbon nanotubes

## Abstract

We report the observation of thermally driven mechanical vibrations of suspended doubly clamped carbon nanotubes, grown by chemical vapor deposition (CVD). Several experimental procedures are used to suspend carbon nanotubes. The vibration is observed as a blurring in images taken with a scanning electron microscope. The measured vibration amplitudes are compared with a model based on linear continuum mechanics.

carbon nanotubes,nanomechanics,mechanical harmonic oscillator,NEMS

Carbon nanotubes (NTs) form a material with unique mechanical properties Ebbesen ; Poncharal ; Wagner ; Ruoff ; Walters . The high Young’s modulus and low specific weight qualify single-wall carbon nanotubes (SWNTs) as ultimate mechanical resonators. Similar to lithographically patterned SiC beams, whose resonance frequency has recently crossed the border from MHz to GHz Roukes1 , it would be highly desirable to integrate NTs into nanoelectromechanical systems (NEMSs) and to electrically excite the mechanical vibration modes Roukes2 . A first step in this direction has been the observation of electrically driven mechanical vibrations of multi-wall carbon nanotubes Poncharal . Nanometer-sized resonators oscillate at high frequencies, but simultaneously have small vibration amplitudes, which are difficult to measure. At cryogenic temperatures, the resonant adsorption of an external electromagnetic field could successfully be measured using superconducting elements attached to a freely suspended NT Reulet . At room temperature a tunnelling probe in the form of, for example, an STM tip would be a versatile detector. Integrating a sensitive measuring transducer with a NT nanomechanical oscillator is however challenging. In a first step, it would be desirable if the mechanical vibrations could be imaged directly. Here, we report on the observation of thermal vibrations of suspended doubly clamped SWNTs, imaged by scanning electron microscopy (SEM).

Thermally driven excitations of multi-wall carbon nanotubes (MWNTs), clamped at one end only, were first investigated by Treacy et al. Ebbesen . The mechanical oscillation appeared in the images, which were collected with a transmission electron microscope (TEM), as a blurring that increased towards the free end of the MWNTs.

In order to see whether a similar experiment is possible with doubly clamped SWNTs, we will first estimate the expected amplitude in thermal equilibrium at room temperature. A schematics with coordinate system is shown in Fig. 1a. Assuming that linear continuum mechanics is a good approximation, the equation of motion for the vertical displacement $`\xi `$ is given by Liftshiz

$$\frac{^2\xi }{t^2}+\left(\frac{YI}{\rho A}\right)\frac{^4\xi }{x^4}=0\text{.}$$
(1)
Here, $`\rho `$ is the mass density, $`A`$ the cross-sectional area, $`Y`$ the Young’s modulus, and $`I=\pi d^4/64`$ the moment of inertia, which depends only on the diameter $`d`$. Applying the proper boundary conditions, the spectrum of eigenfrequencies is obtained:

$$\omega _i=\frac{\beta _i^2}{L^2}\sqrt{\frac{YI}{\pi d\rho _{2d}}}\text{ }(i=1,2,3\mathrm{})\text{ ,}$$
(2)
where $`L`$ is the suspended length, $`\rho _{2d}`$ is the surface mass density of a graphite sheet ($`7.710^7`$ kgm-2)and $`\beta _1=4.73`$, $`\beta _2=7.85`$, and $`\beta _3=11.0`$ for the first three modes.

The equipartition theorem predicts that each vibration mode carries the energy $`k_BT`$ in thermal equilibrium at temperature $`T`$, where $`k_B`$ is the Boltzmann constant. Together with the appropriate solutions of Eq. (1), one obtains an expression for the variance of the maximum deflection amplitude, which for the fundamental frequency ($`i=1`$) occurs in the middle:

$$\sigma _1^2<\xi _1^2(L/2)>=\frac{k_BTL^3}{\gamma _1YI},$$
(3)
where $`\gamma _1=192`$ Blanter . Table 1 summarizes the eigenfrequencies and the thermal vibration amplitudes at room temperature of a ‘typical’ SWNT with diameter $`d=1.5`$ nm and Young’s modulus $`Y=1`$ TPa for different (practically feasible) suspension lengths $`L=0.25`$$`\mu `$m. This table demonstrates that thermal vibration amplitudes can be of appreciable magnitude, of order $`10`$ nm ($`L=1`$$`\mu `$m). Since state-of-the-art scanning electron microscopes have resolutions well below $`10`$ nm, thermal vibration should appear on SEM images.

There are already many reports on the fabrication of suspended NTs. For example, SWNTs were grown between distant silicon towers Dai1 ; Dai3 , spread over metal posts Roth , or grown over solid terraces Dai2  and etched trenches Walters . Though devices with suspension lengths of $`L5`$$`\mu `$m were realized and imaged with SEM, the thermal vibration has surprisingly not yet been reported, although it should readily have shown up in respective SEM images, provided the reported SWNTs were single SWNTs. In the work of Dai and coworkers Dai1 ; Dai2 ; Dai3 , the SWNTs were coated with a metal layer to increase the contrast in the SEM, whereas others have explicitly reported on suspended ropes of SWNTs or MWNT Ruoff ; Roth , which are inherently stiffer.

Carbon nanotubes are synthesized by chemical vapor deposition (CVD) as previously reported us . We would like to emphasize that not all grown NTs are individual SWNTs. This will be explained further in the text. To account for the possible influence of substrate during imaging in SEM, we have suspended NTs using three different methods.

Method I, shown in Fig. 1b, is based on the work of Nygård et al. Nygard . The NTs are grown on thermally oxidized ($`400`$ nm) Si substrates. Electrical contacts are patterned by electron-beam lithography (EBL), followed by evaporation (Ti/Au) and lift-off. The SiO2 is etched in buffered HF us1 . To stop etching, the sample is heavily rinsed in water followed by isopropanol. With this method we find it possible to suspend NTs over distances up to $`1`$$`\mu `$m. For larger lengths, the surface tension of the etchant tends to pull the NT down to the substrate.

In method II, shown in Fig. 1c, the NTs are grown across predefined trenches. We start with a Si substrate with layers of $`800`$ nm of SiO2 and $`200`$ nm of Si3N4. Slits of width $`15`$$`\mu `$m and length $`10`$$`\mu `$m are first etched into the top Si3N4 layer using a CHF3-based plasma etching process Hoss . Next, the slit is further wet-etched into SiO2 and the Si substrate using HF and KOH us2 , respectively. This results in deep trenches $`3.5`$$`\mu `$m, a prerequisite for NTs to bridge the trenches in the CVD growth process.

In method III, shown in Fig. 1d, slits are defined in Si3N4 membranes of thickness $`150`$ nm and lateral size $`0.5`$ mm following a similar procedure as in method II.

The key difference between the three methods is the depth of suspension. It is $`400`$ nm, $`3.5`$$`\mu `$m, and $`\mathrm{}`$ for methods I-III, respectively. The samples are imaged with SEM (Philips XL30 FEG) at room temperature. To generate an image, a focused electron beam is raster scanned.

To deduce the vibration amplitude quantitatively two assumptions have to be made: 1) the intensity profile of the electron beam centered at coordinate $`(x,y)`$ has a Gaussian distribution and 2) the measured intensity of secondary electrons reflects the (time-averaged) probability $`P(x,y)P_x(\xi )`$ to find the NT at position $`(x,y)`$ convoluted with the intensity profile of the primary beam. 1) is a convenient assumption and 2) should hold, because scanning in SEM is slow as compared to the vibration of the NT. The latter results in a blurring of the NT in SEM images. An example of a vibrating suspended NT is shown in Fig. 2a. The vibration is observed as a blurring, which is largest in the middle. In contrast, the NT appears sharp at the edges of the trench, limited by the finite resolution of the SEM. To deduce the vibration amplitude, more precisely the variance $`\sigma ^2(x)\xi ^2(x)`$, we note that $`P_x(\xi )`$ is Gaussian and determined by Boltzmann statistics. The deconvolution is simple because of assumption 1). We only need to extract $`\sigma ^2(x)`$ from the intensity distribution of the SEM image perpendicular to the NT and subtract $`\sigma ^2(0)`$. To do so, we average the intensity profile in $`\mathrm{\Delta }x`$ slices as shown in Fig. 2b and fit it to a Gaussian. Such an analysis was first done for MWNT cantilevers by Krishnan et al. Ebbesen1 .

Figure 2b shows a SEM image of a suspended doubly clamped vibrating NT fabricated by method I. The free suspension length is relatively short, i.e. $`L650`$ nm. Applying the analysis procedure mentioned above, the maximum rms vibration amplitude is determined to be $`\sigma =27\pm 5`$ nm. We have also analyzed $`\sigma `$ as a function of $`x`$ and compare the result with analytical curves for the first three eigenmodes in Fig. 2c. The agreement between the measured points and the theoretical curves is reasonably good. Matching between experiment and theory is improved if the first and second modes are taken into account, each of which carries $`kT`$ energy. Contributions from higher order modes decay very rapidly and can be neglected. Note, there is one fitting parameter $`Yd^4`$, which will be discussed below.

Figure 3a shows another NT grown over Si3N4 membrane. Here, the suspension length is rather large, i.e. $`L6.2`$$`\mu `$m. Correspondingly, the observed blurring is much larger. The maximum rms vibration amounts to $`\sigma =80\pm 5`$ nm. Applying Eq. (3) and assuming the typical high Young’s modulus value of SWNTs of Y=1 TPa the diameter of this NT is estimated to be $`d=2\pm 0.5`$ nm.

The SEM image displayed in Fig. 3b shows three suspended NTs. Though grown in one run, only one NT seems to vibrate, namely the middle one. This, at first sight surprising result, points to a variability of NTs that are grown during one and the same process. The only parameter in our experiment, which is not predetermined, is $`Yd^4`$, see Eq. (3). Though different values for the Young’s modulus were reported, we suspect that the diameter $`d`$ is the cause for the variability, because it enters in the fourth power. The absence of visible vibrations for the upper and lower NT in Fig. 3b suggests that these have a larger diameter. They may be multi-wall nanotubes or ropes of tubes. In fact, the lower one must be a rope, because a clear branching is observed at the right end (highlighted by a circle). Having looked through a large number of samples, the fraction of vibrating tubes is very small (a few %). This is a clear indication that not all of the grown NTs are SWNTs.

We summarize the measured rms vibration of several NTs in table 2. Determined are $`L`$ and $`\sigma (L/2)`$. Using Eq. (3), we obtain an estimate for $`Yd^4`$, which is given in the third column. What is immediately noticed is the large spread in $`Yd^4`$ of more than two orders of magnitude. Unfortunately, we are not able to unambiguously deduce the Young’s modulus $`Y`$ and diameter $`d`$, independently. We have tried to measure the diameter using atomic-force microscopy (AFM). Due to surface roughness and the strong $`d^4`$ dependence, the error bar is too large to deduce $`Y`$ with an acceptable accuracy. For the discussion we instead rely on an average diameter for SWNTs, which we have obtained from electrical measurements of contacted semiconducting NTs us . We have analyzed the band-gap, which is inversely proportional to the diameter $`d`$, of more than $`10`$ semiconducting SWNTs and obtained as an average $`d=1.6\pm 0.3`$ nm. We note, that taking this diameter, the estimated Young’s modulus (column $`4`$ in table 2, denoted by $`Y_{1.6}`$) has an accuracy of ‘only’ $`75`$ %. Well graphitized NTs have a large Young’s modulus. For example, $`Y=1.4\pm 0.4`$ TPa was reported for SWNTs grown by laser ablation Ebbesen1 , whereas $`1`$ TPa was found in simulations independent of helicity and number of shells Lu . In column $`5`$ of table 2 we therefore also list the diameter $`d_1`$, which we deduce from the measured $`Yd^4`$, assuming $`Y=1`$ TPa. $`d_1`$ is varying between 0.58 to $`2.0`$ nm. Since we have never observed SWNTs with diameters $`<1`$ nm in TEM, the first two NTs (row $`1`$ and $`2`$), both belonging to samples prepared by method I, cannot have a large Young’s modulus $`Y1`$ TPa. Taking $`d`$ to be $`1.6`$ nm leads to a modulus of only $`Y_{1.6}20`$ GPa. Because method I uses HF-etching we suspect that the NT’s are affected during this process step. It is possible that CVD-grown SWNTs are not perfect so that wet etching can proceed starting at defect sites. In contrast to method I, the as-grown CVD NTs of methods II and III yield consistent results, which are in agreement with a large Young’s modulus of $`1`$ TPa and with the diameter, which we have deduced by electrical measurements. Though we observe ropes and small diameter MWNTs (only a few number of shells) in TEM, their diameter is typically larger than $`2`$ nm. This strongly suggests that the NTs of row $`36`$ in table 2 are single-wall carbon nanotubes.

To our knowledge there are no reports on the Young’s modulus of CVD-grown SWNT. Though we are not able to accurately determine $`Y`$, our results suggest that CVD-grown SWNTs can have a large modulus of order $`Y1`$ TPa. The exception are wet-etched NTs, for which our data suggest $`Y1`$ TPa. Small Young’s modulus have previously been reported for CVD-grown MWNTs Salvetat .

In conclusion, we have demonstrated that it is possible to observe thermally driven vibrations of suspended doubly clamped SWNTs in SEM. From the measured rms vibration amplitude, the Young’s modulus $`Y`$ of CVD-grown SWNTs has been estimated. Only a small fraction of suspended NTs are seen to vibrate, although they are suspended over a comparable length and grown at the same time. This suggests that the majority of grown tubes are not single SWNTs, but rather ropes and MWNTs, a finding, which is supported by TEM. We suspect that this is the reason why thermal vibrations of SWNTs has not already been observed before.

###### Acknowledgements.

We acknowledge support and technical assistance with TEM imaging by A. Engel, G. Gantenbein and H. Stahlberg of the Biocenter and discussions with L. Forró. This work has been supported by COST (BBW), the Swiss NFS and the NCCR on Nanoscience.


text:
# Local density of states induced by anisotropic impurity scattering in a d-wave superconductor

## Abstract

We study a single impurity effect on the local density of states in a d-wave superconductor accounting for the momentum-dependent impurity potential. We show that the anisotropy of the scattering potential can alter significantly the spatial dependence of the quasiparticle density of states in the vicinity of the impurity.

A search for the symmetry of the cuprate superconducting state involves among others theoretical studies of the disordered systems 1 ; 2 ; 3 . The most direct probe of a simple defect impact on superconductivity is provided by the scanning tunneling microscopy (STM) measurement of the position-dependent quasiparticle density of states. The STM images of Zn and Ni substitutions at the planar Cu sites in $`\mathrm{Bi}_2\mathrm{Sr}_2\mathrm{CaCu}_2\mathrm{O}_{8+\delta }`$ reveal a distinct four-fold symmetry of the local density of states (LDOS) 4 ; 5  predicted for the d-wave superconductor response to disorder 6 ; 7 . In addition to providing detailed information on the superconducting state, this kind of experiment may shed light on the nature of the quasiparticle scattering centers. Although the main feature of the four-fold symmetry of the tunneling currents is captured by the model of isotropic impurity scattering the observed spatial dependence of the quasiparticle density of states is far more complex, and may originate from a non trivial structure of the impurity potential. This aspect of the quasiparticle scattering process has been raised in the discussion of macroscopic measurements in these compounds 8 ; 9 ; 10 ; 11 . It has been shown that the unexpected for the d-wave superconductivity weak impurity-induced suppression of the critical temperature can be understood within a scenario of a momentum-dependent (anisotropic) impurity scattering potential 12 ; 13 ; 14 ; 15 . In the present paper we discuss the effect of anisotropic impurity potential on the local density of states in the vicinity of a single impurity and verify to what extend this scenario can reproduce the STM maps of $`\mathrm{Bi}_2\mathrm{Sr}_2\mathrm{CaCu}_2\mathrm{O}_{8+\delta }`$. There are studies of the momentum-dependent impurity scattering which indicate the existence of the impurity-bound states even for the potential strength far from resonant 16 . Therefore, we focus here on the symmetry of the LDOS and its spatial dependence. For this purpose and for analytical simplicity we consider scattering in the Born approximation. Hereafter we show that the anisotropy of the scattering potential alters the local density of states in the d-wave superconductor but preserves its tetragonal symmetry. Compared to the effect of the isotropic impurity potential it enhances the spatial variation of the quasiparticle density of states and can lead to a long-range spatial modulation of the LDOS spectra. We note that the anisotropy of the impurity potential, if the same as the anisotropy of the superconducting order parameter, enhances the relative magnitude of oscillations in the LDOS for the direction of a gap maximum, especially in the vicinity of the impurity, whereas the impurity potential with maxima in the nodal region inverts this tendency and leads to a larger quasiparticle density of states along the gap node direction.

We consider the momentum-dependent impurity potential 12 ; 13 ; 14 ; 15 ; 15a

$$\widehat{v}(𝐤,𝐤^{})=\left[v_i+v_af\left(𝐤\right)f\left(𝐤^{}\right)\right]\widehat{\tau }_3$$
(1)
where $`v_i`$, $`v_a`$ are isotropic and anisotropic scattering amplitudes, respectively, $`f\left(𝐤\right)`$ is the anisotropy function, and $`\widehat{\tau }_i`$ ($`i=1,2,3`$) are Pauli matrices. We assume $`f\left(𝐤\right)=\pm 1`$ such as its Fermi surface (FS) average vanishes, i.e., $`f={\displaystyle _{FS}}𝑑S_kn(𝐤)f\left(𝐤\right)=0`$, where $`n(𝐤)`$ is the normalized angle resolved FS density of states, $`{\displaystyle _{FS}}𝑑S_kn(𝐤)=1`$. Potential determined by $`f\left(𝐤\right)=sgn\left(k_x^2k_y^2\right)=sgn\left(cos2\varphi \right)`$, which is in phase with the d-wave superconducting order parameter leads to a particularly moderate suppression of the critical temperature 12 ; 15 ; 15a . In the above $`\varphi `$ is a polar angle.

We study the effect of the impurity potential (1) on the quasiparticle states using the one particle Green’s function of the $`d_{x^2y^2}`$-wave superconducting state in the particle-hole notation

$$\widehat{G}_0(𝐤,\omega _n)=\left[i\omega _n\widehat{\tau }_0\xi _𝐤\widehat{\tau }_3\mathrm{\Delta }\left(𝐤\right)\widehat{\tau }_1\right]^1$$
(2)
where $`\mathrm{\Delta }(𝐤)=\mathrm{\Delta }\left(k_x^2k_y^2\right)=\mathrm{\Delta }cos2\varphi `$ represents the superconducting order parameter, $`\omega _n`$ is the Matsubara frequency, $`\xi _𝐤=\epsilon _𝐤\epsilon _F`$ is the quasiparticle energy in the normal state, $`\epsilon _F`$ is the Fermi energy, and $`\widehat{\tau }_0`$ is the identity matrix. For simplicity we assume a parabolic dispersion and a two-dimensional (planar) superconductivity. Neglecting the anisotropy of the Fermi surface we concentrate on the feature of coupled anisotropies of the order parameter and the impurity potential. The impurity effect is studied at zero temperature by the analytic continuation of (2)

$$\widehat{G}_0(𝐤,\omega )=\widehat{G}_0(𝐤,\omega _n)_{i\omega _n=\omega +i0^+}$$
(3)
In order to discuss the real space distribution of the quasiparticle states we take a two-dimensional Fourier transform of the Green’s function (3), which for the parabolic band $`\epsilon _𝐤=k^2/2m`$ and for positive $`\omega `$ smaller than the Fermi energy reads

$$\widehat{G}_0(𝐫,\omega )=\underset{\mathrm{}}{\overset{\mathrm{}}{}}\frac{d^2k}{\left(2\pi \right)^2}e^{i\mathrm{𝐤𝐫}}\widehat{G}_0(𝐤,\omega )=\frac{i\pi m}{2\left(2\pi \right)^2}\underset{0}{\overset{2\pi }{}}𝑑\varphi _𝐤\left[\frac{\omega \widehat{\tau }_0+\mathrm{\Delta }\left(𝐤\right)\widehat{\tau }_1}{\sqrt{\omega ^2\mathrm{\Delta }^2\left(𝐤\right)}}\left(e^{i𝐤_+𝐫}+e^{i𝐤_{}𝐫}\right)+\widehat{\tau }_3\left(e^{i𝐤_+𝐫}e^{i𝐤_{}𝐫}\right)\right]$$
(4)
where similarly to the three-dimensional case 17  $`k_\pm =\sqrt{2m}\left[\epsilon _F\pm \sqrt{\omega ^2\mathrm{\Delta }^2\left(𝐤\right)}\right]^{1/2}`$ and $`Im\sqrt{\omega ^2\mathrm{\Delta }^2\left(𝐤\right)}0`$. For negative $`\omega `$ one must multiply the imaginary part of (4) by $`sgn\left(\omega \right)`$. Here $`\mathrm{}=1`$.

We consider the impurity effect in the Born approximation, that is, proceed with the perturbative expansion of the Green’s function up to the second order term in the scattering potential $`\widehat{v}`$. The linear correction results from the impurity-induced change of the Fermi energy

$$\delta \widehat{G}^{}(𝐤,𝐤^{},\omega )=\widehat{G}_0(𝐤,\omega )\widehat{v}(𝐤,𝐤^{})\widehat{G}_0(𝐤^{},\omega )$$
(5)
while the quadratic term represents the proper Born correction and takes the finite quasiparticle life-time into account

$$\delta \widehat{G}^{\prime \prime }(𝐤,𝐤^{},\omega )=\widehat{G}_0(𝐤,\omega )\widehat{\mathrm{\Sigma }}_B(𝐤,𝐤^{})\widehat{G}_0(𝐤^{},\omega )$$
(6)
where the self-energy $`\widehat{\mathrm{\Sigma }}_B`$ is determined by

$$\widehat{\mathrm{\Sigma }}_B(𝐤,𝐤^{})=\underset{𝐤^{\prime \prime }}{}\widehat{v}(𝐤,𝐤^{\prime \prime })\widehat{G}_0(𝐤^{\prime \prime },\omega )\widehat{v}(𝐤^{\prime \prime },𝐤^{})$$
(7)
Both corrections are evaluated for a single impurity which means that the self-energy is not determined self-consistently. We have neglected changes to the absolute value of the order parameter in the vicinity of the impurity which will not change the symmetry of LDOS images but their absolute magnitudes. The total correction to the Green’s function reads

$$\delta \widehat{G}(𝐤,𝐤^{},\omega )=\delta \widehat{G}^{}(𝐤,𝐤^{},\omega )+\delta \widehat{G}^{\prime \prime }(𝐤,𝐤^{},\omega )$$
(8)
and its real space transform is given by

$$\delta \widehat{G}(𝐫,\omega )=\underset{𝐤,𝐤^{}}{}e^{i\left(𝐤𝐤^{}\right)𝐫}\delta \widehat{G}(𝐤,𝐤^{},\omega )$$
(9)
Function (9) determines the position dependent impurity-induced change of the quasiparticle density of states near a single impurity

$$\delta N(𝐫,\omega )=\frac{1}{\pi }Im\left\{\delta G_{11}(𝐫,\omega )\right\}$$
(10)
We have evaluated the LDOS for equal impurity scattering strength in isotropic and anisotropic channel $`\pi N_0v_i=\pi N_0v_a=0.1`$, where $`N_0`$ is the density of states per spin at the Fermi level in the normal state, and for the coherence length $`\xi _0=12\pi k_F^1`$. The distance scale in the figures is set by $`k_F^1`$. We observe a pronounced spatial variation of the quasiparticle density of states for anisotropic impurity potential. This feature is in agreement with the result of an enhanced LDOS due to a finite range of the scattering potential 18 . In Figs. 1a-c we show the distance dependence of the impurity-induced change to the LDOS at the quasiparticle energy $`\omega =1.1\mathrm{\Delta }`$ along the a-axis ($`\varphi =0`$), i.e., gap maximum, and nodal ($`\varphi =\pi /4`$) direction for isotropic scattering (Fig. 1a) and two representative anisotropic impurity potentials (1): $`f\left(𝐤\right)=sgn\left(k_x^2k_y^2\right)=sgn\left(cos2\varphi \right)`$ which is in phase with the d-wave order parameter (Fig. 1b), and $`f\left(𝐤\right)=sgn\left(k_xk_y\right)=sgn\left(sin2\varphi \right)`$ (Fig. 1c) scattering out of the order parameter phase. We note that the impurity potential in phase with the order parameter enhances the magnitude of oscillations in the LDOS for the direction of a gap maximum, especially in the vicinity of the impurity, whereas the out of phase impurity potential inverts this tendency and leads to a larger quasiparticle density of states in the nodal regions. Significant is also very weak anisotropy of the LDOS near the isotropic impurity (Fig. 1a) where discernible differences between $`\varphi =0`$ and $`\varphi =\pi /4`$ directions occur at a distance of about $`50k_F^1`$ from impurity 6 . It shows that visible spatial distribution of intensity maxima and minima in the STM maps is induced by the anisotropy of defect potential. Therefore, we suggest that the apparent anisotropy of the experimental images 4 ; 5  may possibly result in part from the presence of the momentum-dependent scattering potential. We have also performed the LDOS calculation for quasiparticles below the gap threshold energy and displayed them for $`\omega =0.1\mathrm{\Delta }`$ in Figs. 2a-c. Another interesting feature of the anisotropic scattering is a presence of a long-range spatial modulation of the LDOS for the impurity potential in phase with the d-wave order parameter, i.e., $`f\left(𝐤\right)=sgn\left(k_x^2k_y^2\right)`$. Such a modulation is absent for isotropic or out of phase scattering (Fig. 3). We summarize our discussion by showing in Figs. 4-5 comprehensive pictures of the STM images at the frequencies $`\omega =1.1\mathrm{\Delta }`$ and $`\omega =0.1\mathrm{\Delta }`$ around simple defects of isotropic and anisotropic Born potential in the ab plane of the d-wave superconductor. The potential strength, coherence length and distance units have been fixed as in Figs. 1-3. The quasiparticle density of states is given in the units of the FS two-spin density of states $`N(0)`$, $`N(0)=2N_0`$, and varies from the lowest (black) to the highest (white) value according to the scale in each figure. We have checked that similarly to the effect on the critical temperature 13  any other scattering potential which is orthogonal to the order parameter(in the sense of the FS integral as the scalar product) gives qualitatively the same LDOS as the discussed above $`f\left(𝐤\right)=sgn\left(sin2\varphi \right)`$, i.e., out of phase potential. The effect of potentials in phase with the order parameter like $`f\left(𝐤\right)=cos2\varphi `$ agrees qualitatively with $`f\left(𝐤\right)=sgn\left(cos2\varphi \right)`$. Therefore, both studied anisotropies can be considered representative for the impurity potential (1). Although we have restricted our study to nonmagnetic impurity scattering, as a closing remark we note that inclusion of spin $`S=1/2`$, $`1`$ or $`3/2`$ scattering does not contribute any quantitative change to the results for the impurity potential obeying the Born approximation.
Concluding, we have shown that the anisotropy of the impurity potential enhances the quasiparticle LDOS in the vicinity of the impurity and leads to discernible differences of its intensity in horizontal and diagonal direction. Depending on its symmetry the impurity potential can rotate the LDOS maxima and minima by $`45^{}`$ degrees and can induce a long-range spatial modulation of the quasiparticle density of states but cannot change the induced by the d-wave superconductivity four-fold symmetry of the STM images.
Note added in proof: A similar modulation to the one in Fig. 3(b) is seen along the gap nodal direction for the potential out of the order parameter phase.
We would like to acknowledge helpful discussions with Dr. L. Borkowski. The work was supported in part by KBN grant No. 5P03B05820.