- Nano Review
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Investigations of ripple pattern formation on Germanium surfaces using 100-keV Ar+ ions
© Sulania et al.; licensee Springer. 2015
Received: 11 November 2014
Accepted: 12 January 2015
Published: 28 February 2015
We have investigated the formation of nanoripples on the surface of germanium, Ge(100), due to the effect of 100-keV Ar + ion irradiation. The irradiation was carried out at different incidence angles from 0° to 75° in steps of 15° with respect to the surface normal with a fixed ion fluence of approximately 3 × 1017 ions/cm2. Atomic force micrographs show an increase in surface roughness from 0.5 to 4.3 nm for the pristine sample and the sample irradiated at 60° incidence angle due to cos−1(θ) dependence on sputtering yield. With increase in angle of incidence, there is transition observed from nanodots to aligned nanodots perpendicular to the direction of the beam. There is an increase in size of the nanostructures observed from 44 to 103 nm with angle of incidence. The formation of nanoripples initiates at an angle of θ ~ 45°. Ripple pattern formation has taken place on the Ge surface in the energy regime of 100 keV as compared to the other reports which had been carried out using very low energy ions. Raman spectra reveal that the near surface of crystalline Ge samples becomes amorphous due to interaction of Ar+ ions due to creation of defects through collision cascades.
Ion beam is a unique tool used for creating nanopatterns at the surfaces of a desired substrate. Earlier low-energy ion irradiation techniques had been used extensively for etching purposes to clean materials’ surfaces for device applications. As an outcome of the etching process, formation of various surface patterns such as ripples or dots or pits has been observed by many research groups [1-4]. The ordering of these surface patterns depends upon the ion beam parameters such as time of bombardment, energy of the ions used, and angle of incidence of the ion beam. With proper control of ion beam parameters and proper understanding of the physics of ion-solid interactions and defect dynamics, fabrication of surface nanostructures can be achieved in a desired manner [5,6]. As a consequence of low-energy ion irradiation, the near-surface region of the target material gets amorphized due to creation of point defects through the process of collision cascades. Collision cascade or displacement cascade is the sequential collisions of atoms, which is induced due to the incoming energetic particle within a solid target. If the energy of the incoming ion in a collision cascade is higher than the threshold displacement energy of the atom in a material, the atom will be displaced from its lattice site with production of point defects such as vacancy or interstitial. Having passed the surface plane, the incident ion will undergo further collisions generating secondary recoils or cascades. These collision cascades are statistical in nature and follow a Gaussian-like depth distribution, f(x)dx, thus leading to the formation of nanostructures on the surface of a material through the process of self-assembly [5,7-10]. The formation of ripples due to Ar+ ion bombardment was observed by Navez et al. on the surface of glass during the etching process . These ripples have the same analogy as the ripples which occur naturally on sand dunes in deserts and the river beds or sea water due to the flow of air. The first efforts to explain this experimentally observed phenomenon were put by Bradley and Harper . They proposed a linear theory based upon Sigmund’s theory of sputtering . According to the linear theory, the main mechanism governing such changes on the surface is the competition or interplay between the roughening induced by ion bombardment and smoothening due to surface diffusion. It could explain many of the experimental findings but did not explain the saturation phenomenon of ripple amplitude and formation of dots or pits on the surfaces as observed by many of the experimental groups on various target materials. The understanding of these features could be achieved only by adding non-linear terms in the linear theory, and thus, non-linear theories came into the picture which could explain most of the experimental findings [14,15].
Germanium (Ge) is being chosen over Si-based devices due to its high carrier mobility which shows improved results in metal-oxide-semiconductor field-effect transistors (MOSFET) technology when used with high-k dielectric materials [16-18]. The Si/Ge-based heterostructure is being studied by many research groups for its usefulness in photocurrent applications, absorption, photoluminescence spectroscopy, etc. . Carbone et al. bombarded Ge(001) with 1-keV Xe+ ions in a GISAXS setup in ESRF at Grenoble, France. They observed the early stage of ripple formation on Ge(100) surfaces under near-normal ion beam sputtering with a wavelength of 42 nm . Yehuda et al. studied the dynamics of defect creation in amorphous Ge thin films with a thickness of 200 to 300 nm using Ar+ ions in the energy range of 15 to 110 eV at 30° incidence . They observed formation of voids in the films, with the films remaining amorphous in nature. It is further concluded that the incident ion energy does not affect the formation of defects but rather ion fluence plays a crucial role in defect creation. Ziberi et al. observed the formation of well-ordered nanodots and nanoripples on Si and Ge surfaces during low-energy ion beam erosion with a mean wavelength of approximately 45 nm upon bombarding it with different ions and variable energies from 0.5- to 1.5-keV ion energies. They also observed an increase in wavelength with increases in ion energies [22,23]. Chason et al. studied the surface roughening of Ge(001) due to 200-eV Xe+ ion bombardment during the molecular beam epitaxy to see the surface diffusivity of Ge on Ge(100) . It was found that the initially smooth surfaces reach a steady state roughness which depends on the temperature and incident ion adatom flux. Sulania et al. observed the formation of an amorphized Ge layer on crystalline Ge(100) due to the impact of 1.5-keV Ar atoms incident at 0° with respect to the surface normal . It is concluded that the nanostructure formation does take place on Ge but the structures are not well organized and non-uniform in size. The size of the structures and rms roughness increase with increases in ion fluence. Teichmann et al. studied the ripple coarsening behavior on the surfaces of Ge, Si, Al2O3, and SiO2 using ions with energies of 600 and 1,200 eV at ion incidence angles of 65° and 75°. The ion fluence was varied from 1.1 × 1017 to 1.3 × 1019 ions/cm2. They observed the coarsening process to be independent of the material used . Zhou et al. studied the formation of ripple using a focused ion beam (FIB)-scanning electron microscope setup using 30-keV Ga+ on the Ge(001) surface . It is concluded that the ripple direction changes with the change in fast scan direction of FIB. As the dose of Ga+ is increased to 8.67 × 1015 ions/cm2, nanostructured networks are formed on the surface of Ge(001). In another work using FIB on GaAs, Xu et al. found ordered droplets of Ga on the surface of GaAs and observed an increase in size with ion fluence . Wu et al. observed the formation of self-organized nanoripples on thin films of SrTiO3 deposited on STO under the influence of FIB irradiation at different ion beam currents with a characteristic wavelength of approximately 375 nm and amplitude of approximately 100 nm .
All the above studies on Ge had been carried out at a very low energy regime of the ions or electrons (0.07 to 1.5 keV) with the main motivation of studying the defect formation on Ge with low-energy ion irradiation. In few of the reports, FIB is used to form the ordered structures on the surfaces of various materials to ensure the concentrated impact of the ion beam onto the surface to form structures.
The range of the low-energy Ar ion of few keVs is approximately 200 Å inside Ge. The electronic and nuclear energy losses of 1.5-keV Ar are 4.3 and 33.5 eV/Å, respectively. On the other hand, the range of 100-keV Ar ion inside Ge is approximately 722 Å, and the electronic and nuclear energy losses are 36.5 and 59.6 eV/Å, respectively (as estimated by SRIM 2003) . Clearly, the dominating process is the nuclear energy through which the energy is deposited within the system and the changes in surface morphology occur due to collision cascade. Therefore, in this paper, we report the formation of Ge nanoripples due to the impact of medium-range energy ions of 100 keV. Moreover, the angle of incidence variation on Ge has not been studied in detail for such a large range starting from 0° to 75° incidence with respect to the surface normal. Therefore, in this study, we investigate the formation of surface nanostructuring on the Ge(100) surface due to the effect of change in incidence angle of the 100-keV Ar+ ion beam.
We have used 100-keV Ar + ions to bombard the samples of Sb-doped Ge(100) at 300 K. The angle of incidence of the ion beam with respect to the surface normal has been changed from θ ion = 0°, 15°, 30°, 45°, 60°, and 75° keeping the other parameters constant. The base pressure of the chamber during bombardment was around 2 × 10−6 mbar. An ion fluence of 3 × 1017 ions/cm2 was used (corresponding to a bombardment time of approximately 27 min at a flux of 18.5 μA/cm2). The ion fluence was chosen from the study on fluence dependence on Ge using 500-keV Ar4+ ion energy (not reported here). Below this fluence, the surface patterning was not observed but only roughness was visible on the surface of Ge(100) as observed in our previous experiment with medium-range energy ions. The angle variation was obtained by changing the angle of the ladder on which samples were mounted by rotating it. The experiment was performed in the material science beam line of the Low Energy Ion Beam (LEIB) facility of IUAC, New Delhi. We analyzed the results obtained with the help of atomic force microscopy (AFM) micrographs by observing the change in shape, size, and roughness variation of the structures obtained on the surface of Ge. The surfaces of pristine and bombarded samples were investigated by using AFM Nanoscope IIIa Multimode from Digital Instruments, Canberra, USA. All measurements were conducted in air using silicon-nitride (RTES) tips from Bruker (Singapore) with a nominal tip radius of <10 nm. The micro-Raman measurements were performed on the pristine and irradiated samples using a Renishaw inVia micro-Raman setup (Renishaw, Gloucestershire, UK) using an Ar ion laser with an excitation wavelength of 514.5 nm. The AFM and Raman measurements were performed at the Inter University Accelerator Centre (IUAC), New Delhi.
Nanopattern formation takes place on the surface due to the interplay between the surface diffusion term which could be ion induced or thermal diffusion on the surface or a combination of both and sputtering of the material from the surface due to the impact of energetic ions onto the surface. According to the BH theory, the ripple formation takes place on the surface due to the difference in the sputtering rates at different surface curvatures. The troughs are eroded faster as compared to the crests . In the case of a binary compound, the difference in the sputtering rates also plays a significant role in the pattern formation onto a surface due to different masses present inside the material. The lighter element will sputter more readily than the one with higher mass, as seen by different research groups for InP , GaAs , Gasb , etc. But for the single element material, it may be difficult to achieve the ripple formation, although there are contradictory reports on this especially for the cases of Si targets [2,10] but not so clearly visible on Ge . We have observed ripple pattern formation on the Ge surface; however, the structures are not continuous but are chains of nanodots, and there was continuous ripple formation on InP. This also supports the theory proposed by Bradley et al. in their PRL report  which suggested that ripples readily form on a binary compound rather than on a single element material. The rms roughness increases with increases in incidence angles with cos−1(θ) dependence on sputtering yield. Further surface roughness is maximum for 60° and minimum for 75° incidences, respectively.
The formation of nanostructures is observed on Ge by changing the incidence angle of the ion beam. The nanodots are observed for normal incidence angle, and these nanodots are aligned perpendicular to the direction of the beam as the incidence angle is increased. The surface roughness of the irradiated samples is found to increase with increase in angle of incidence from 0.3 to 4.6 nm. The size of the nanostructures increases from 44 to 103 nm, and the ripple wavelength increases from 97 to 140 nm with angle of incidence. The micro-Raman analysis revealed that the Ge is getting amorphized upon irradiation due to interaction of the Ar+ ion with Ge atoms, creating defects through collision cascades.
The authors would like to thank Mr. Kedar Mal for delivering the stable beam during the experiment. The authors would also like to thank Mr. Subodh Kumar for the micro-Raman measurements. The financial support from DST under the IRHPA project for the SPM facility at IUAC, New Delhi, is gratefully acknowledged.
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