Fe-implanted ZnO: Magnetic precipitates versus dilution
Shengqiang Zhou, K. Potzger, G. Talut, H. Reuther, J. von Borany, R. Groetzschel, W. Skorupa, M. Helm, J. Fassbender, N. Volbers, M. Lorenz, T. Herrmannsdoerfer
Nowadays ferromagnetism is often found in potential diluted magnetic semiconductor systems. However, many authors argue that the observed ferromagnetism stems from ferromagnetic precipitates or spinodal decomposition rather than from carrier mediated magnetic impurities, as required for a diluted magnetic semiconductor. In the present paper we answer this question for Fe-implanted ZnO single crystals comprehensively. Different implantation fluences and temperatures and post-implantation annealing temperatures have been chosen in order to evaluate the structural and magnetic properties over a wide range of parameters. Three different regimes with respect to the Fe concentration and the process temperature are found: 1) Disperse Fe$^{2+}$ and Fe$^{3+}$ at low Fe concentrations and low processing temperatures, 2) FeZn$_2$O$_4$ at very high processing temperatures and 3) an intermediate regime with a co-existence of metallic Fe (Fe$^0$) and ionic Fe (Fe$^{2+}$ and Fe$^{3+}$). Ferromagnetism is only observed in the latter two cases, where inverted ZnFe$_2$O$_4$ and $α$-Fe nanocrystals are the origin of the observed ferromagnetic behavior, respectively. The ionic Fe in the last case could contribute to a carrier mediated coupling. However, their separation is too large to couple ferromagnetically due to the lack of p-type carrier. For comparison investigations of Fe-implanted epitaxial ZnO thin films are presented.
We report the structural and magnetic properties of ZnO single crystals implanted at 623 K with up to 10 at. % of Ni. As revealed by X-ray diffraction, crystalline fcc-Ni nanoparticles were formed inside ZnO. The magnetic behavior (magnetization with field reversal and with different temperature protocol) of all samples is well explained by a magnetic Ni-nanoparticle system. Although the formation of Ni:ZnO based diluted magnetic semiconductor cannot be ruled out, the major contribution to the magnetic properties stems from crystalline nanoparticles synthesized under these implantation conditi…
The magneto-transport properties of single proton-implanted ZnO and of Li(7\%)-doped ZnO microwires have been studied. The as-grown microwires were highly insulating and not magnetic. After proton implantation the Li(7\%) doped ZnO microwires showed a non monotonous behavior of the negative magneto-resistance (MR) at temperature above 150 K. This is in contrast to the monotonous NMR observed below 50 K for proton-implanted ZnO. The observed difference in the transport properties of the wires is related to the amount of stable Zn vacancies created at the near surface region by the proton implan…
Unwanted secondary phases are one of the major problems in diluted magnetic semiconductor creation. Here, the authors show possibilities to avoid such phases in Fe implanted and postannealed ZnO(0001) single crystals. While -Fe nanoparticles are formed after such doping in as-polished crystals, high temperature (1273 K) annealing in O2 or high vacuum before implantation suppresses these phases. Thus, the residual saturation magnetization in the preannealed ZnO single crystals is about 20 times lower than for the as-polished ones and assigned to indirect coupling between isolated Fe ions rather…
We present superparamagnetic clusters of structurally highly disordered Co-Zn-O created by high fluence Co ion implantation into ZnO (0001) single crystals at low temperatures. This secondary phase cannot be detected by common x-ray diffraction but is observed by high-resolution transmission electron microscopy. In contrast to many other secondary phases in a ZnO matrix it induces low-field anomalous Hall effect and thus is a candidate for magneto-electronics applications.
Unexpected ferromagnetism has been observed in carbon doped ZnO films grown by pulsed laser deposition [Phys. Rev. Lett. 99, 127201 (2007)]. In this letter, we introduce carbon into ZnO films by ion implantation. Room temperature ferromagnetism has been observed. Our analysis demonstrates that (1) C-doped ferromagnetic ZnO can be achieved by an alternative method, i.e. ion implantation, and (2) the chemical involvement of carbon in the ferromagnetism is indirectly proven.
Room-temperature ferromagnetism has been induced within ZnO single crystals by implant-doping with Fe ions. For an implantation temperature of 620 K and an ion fluence of 4x10^16 cm^-2, very tiny Fe particles, formed inside the host matrix, are responsible for the ferromagnetic properties. They were identified using synchrotron X-ray diffraction and Moessbauer spectroscopy. On the other hand, Fe ions implanted at a temperature of 253 K and an ion fluence of 4x10^15 cm^-2 are incorporated into the host matrix and develop a room temperature diluted magnetic semiconductor (DMS).
We investigated ZnO(0001) single crystals annealed in high vacuum with respect to their magnetic properties and cluster formation tendency after implant-doping with Fe. While metallic Fe cluster formation is suppressed, no evidence for the relevance of the Fe magnetic moment for the observed ferromagnetism was found. The latter along with the cluster suppression is discussed with respect to defects in the ZnO host matrix, since the crystalline quality of the substrates was lowered due to the preparation as observed by x-ray diffraction.
Recently theoretical works predict that some semiconductors (e.g. ZnO) doped with magnetic ions are diluted magnetic semiconductors (DMS). In DMS magnetic ions substitute cation sites of the host semiconductor and are coupled by free carriers resulting in ferromagnetism. One of the main obstacles in creating DMS materials is the formation of secondary phases because of the solid-solubility limit of magnetic ions in semiconductor host. In our study transition metal ions were implanted into ZnO single crystals with the peak concentrations of 0.5-10 at.%. We established a correlation between stru…
The structural and magnetic properties of V doped ZnO are presented. V ions were introduced into hydrothermal ZnO single crystals by ion implantation with fluences of 1.2*10^16 to 6*10^16 cm^-2. Post-implantation annealing was performed in high vacuum from 823 K to 1023 K. The ZnO host material still partly remains in a crystalline state after irradiation, and is partly recovered by annealing. The V ions show a thermal mobility as revealed by depth profile Auger electron spectroscopy. Synchrotron radiation x-ray diffraction revealed no secondary phase formation which indicates the substitution…
We simulated and experimentally investigated the sputter yield of ZnO and GaAs nanowires, which were implanted with energetic Mn ions at room temperature. The resulting thinning of the nanowires and the dopant concentration with increasing Mn ion fluency were measured by accurate scanning electron microscopy (SEM) and nano-X-Ray Fluorescence (nanoXRF) quantification, respectively. We observed a clear enhanced sputter yield for the irradiated nanowires compared to bulk, which is also corroborated by iradina simulations. These show a maximum if the ion range matches the nanowire diameter. As a c…
The existence of semiconductors exhibiting long-range ferromagnetic ordering at room temperature still is controversial. One particularly important issue is the presence of secondary magnetic phases such as clusters, segregations, etc... These are often tedious to detect, leading to contradictory interpretations. We show that in our cobalt doped ZnO films grown homoepitaxially on single crystalline ZnO substrates the magnetism unambiguously stems from metallic cobalt nano-inclusions. The magnetic behavior was investigated by SQUID magnetometry, x-ray magnetic circular dichroism, and AC suscept…
Transition metals implanted in single crystal MgO can precipitate out at grain boundaries or remain embedded in bulk. Using first-principles calculations based on density functional theory we have calculated the thermodynamic stability and diffusion coefficients of the implanted ions to explain Fe and Ni precipitation in MgO. Experimentally it has been observed that some of the Fe atoms precipitate out, while few Fe atoms in 2+ and 3+ charge states remain embedded in the lattice. Our simulation shows that at 600 K (typical annealing temperature) while neutral iron in MgO would migrate 1 $μ$m i…
Ion implantation is an interesting method to dope semiconducting materials such as zinc oxide provided that the implantation-induced defects can be subsequently removed. Nitrogen implantation followed by anneals under O2 were carried out on zinc oxide nanowires in the same conditions as in a previous study on bulk ZnO [J. Appl.Phys. 109, 023513 (2011)], allowing a direct comparison of the defect recovery mechanisms. Transmission electron microscopy and cathodoluminescence were carried out to assess the effects of nitrogen implantation and of subsequent anneals on the structural and optical pro…
Magnetic anisotropies of Co-implanted ZnO (0001) films grown on single-crystalline Al2O3 (11-20) substrates have been studied by ferromagnetic resonance (FMR) technique for different cobalt implantation doses. The FMR data show that the easy and hard axes have a periodicity of 60 degrees in the film plane, in agreement with the hexagonal structure of the ZnO films. This six-fold in-plane magnetic anisotropy, which is observed for the first time in ZnO-based diluted magnetic semiconductors, is attributed to the substitution of cobalt on Zn sites in the ZnO structure, and a clear indication for …
We have studied the structural, magnetic and electronic properties of Co-implanted ZnO (0001) films grown on Al2O3 (1120) substrates for different implantation doses and over a wide temperature range. Strong room temperature ferromagnetism is observed with magnetic parameters depending on the cobalt implantation dose. A detailed analysis of the structural and magnetic properties indicates that there are two magnetic phases in Co-implanted ZnO films. One is a ferromagnetic phase due to the formation of long range ferromagnetic ordering between implanted magnetic cobalt ions in the ZnO layer, th…
We report on the stability and magnetic state of ion implanted $^8$Li in single crystals of the semiconductor ZnO using $β$-detected nuclear magnetic resonance. At ultradilute concentrations, the spectra reveal distinct Li sites from 7.6 to 400 K. Ionized shallow donor interstitial Li is stable across the entire temperature range, confirming its ability to self-compensate the acceptor character of its (Zn) substitutional counterpart. Above 300 K, spin-lattice relaxation indicates the onset of correlated local motion of interacting defects, and the spectra show a site change transition from dis…
We report on the structural and magnetic properties of a cobalt-implanted ZnO film grown on a sapphire substrate. X-ray diffraction and transmission electron microscopy reveal the presence of a (10-10)-oriented hexagonal Co phase in the Al2O3 sapphire substrate, but not in the ZnO film. Co clusters, with a diameter of is about 5-6 nm, form a Co rich layer in the substrate close to the ZnO/Al2O3 interface. Magnetization measurements indicate that there exist two different magnetic phases in the implanted region. One originates from the Co clusters in Al2O3, the other one belongs to a homogeneou…
Although zinc oxide is a promising material for the fabrication of short wavelength optoelectronic devices, p-type doping is a step that remains challenging for the realization of diodes. Out of equilibrium methods such as ion implantation are expected to dope ZnO successfully provided that the non-radiative defects introduced by implantation can be annealed out. In this study, ZnO substrates are implanted with nitrogen ions, and the extended defects induced by implantation are studied by transmission electron microscopy and X-ray diffraction (XRD), before and after annealing at 900^{\circ}C. …
In the last decade, transition-metal-doped ZnO has been intensively investigated as a route to room-temperature diluted magnetic semiconductors (DMSs). However, the origin for the reported ferromagnetism in ZnO-based DMS remains questionable. Possible options are diluted magnetic semiconductors, spinodal decomposition, or secondary phases. In order to clarify this question, we have performed a thorough characterization of the structural and magnetic properties of Co- and Ni-implanted ZnO single crystals. Our measurements reveal that Co or Ni nanocrystals (NCs) are the major contribution of the…
We report room temperature ferromagnetism in as-implanted Eu doped ZnO (ZnO:Eu). To address the origin of ferromagnetism ab initio calculations of ZnO:Eu system are performed. Results show that the ferromagnetism is induced by ZnO point defects as Eu ions in perfect ZnO tend to align antiferromagnetically.
The results of XPS core-level and valence band measurements, photoluminescence spectra of a-SiO2 implanted by Zn-ions (E=30 keV, D=1*1017 cm^-2) and Density Functional Theory calculations of electronic structure as well as formation energies of structural defects in silica glass induced by Zn-ion implantation are presented. Both theory and experiment show that it is energetically more favorable for implanted zinc ions to occupy the interstitial positions instead of cation substitution. As a result, the Zn-ions embedded to interstitials, form chemical bonds with the surrounding oxygen atoms, fo…
In this paper, a correlation between structural and magnetic properties of Fe implanted ZnO is presented. High fluence Fe^+ implantation into ZnO leads to the formation of superparamagnetic alpha-Fe nanoparticles. High vacuum annealing at 823 K results in the growth of alpha-Fe particles, but the annealing at 1073 K oxidized the majority of the Fe nanoparticles. After a long term annealing at 1073 K, crystallographically oriented ZnFe2O4 nanoparticles were formed inside ZnO with the orientation relationship of ZnFe2O4(111)[110]//ZnO(0001)[1120]. These ZnFe2O4 nanoparticles show a hysteretic be…
In the past decade, room temperature ferromagnetism was often observed in transition metal doped semiconductors, which were claimed as diluted magnetic semiconductors (DMS). Nowadays intensive activities are devoted to clarify wether the observed ferromagnetism stems from carrier mediated magnetic impurities, ferromagnetic precipitates, or spinodal decomposition. In this paper, we have correlated the structural and magnetic properties of transition metal doped ZnO, TiO2, and Si, prepared by ion implantation. Crystalline precipitates, i.e., transition metal (Co, Ni) and Mn-silicide nanocrystals…
We review pitfalls in recent efforts to make a conventional semiconductor, namely ZnO, ferromagnetic by means of doping with transition metal ions. Since the solubility of those elements is rather low, formation of secondary phases and the creation of defects upon low temperature processing can lead to unwanted magnetic effects. Among others, ion implantation is a method of doping, which is highly suited for the investigation of those effects. By focussing mainly on Fe, Co or Ni implanted ZnO single crystals we show that there are manifold sources for ferromagnetism in this material which can …
During the past years there has been renewed interest in the wide-bandgap II-VI semiconductor ZnO, triggered by promising prospects for spintronic applications. First, ferromagnetism was predicted for dilute magnetic doping. In comprehensive investigation of ZnO:Co thin films based on the combined measurement of macroscopic and microscopic properties, we find no evidence for carrier-mediated itinerant ferromagnetism. Phase-pure, crystallographically excellent ZnO:Co is uniformly paramagnetic. Superparamagnetism arises when phase separation or defect formation occurs, due to nanometer-sized met…
Boron (B) has the potential for generating an intermediate band in cubic silicon carbide (3C-SiC), turning this material into a highly efficient absorber for single-junction solar cells. The formation of a delocalized band demands high concentration of the foreign element, but the precipitation behavior of B in the 3C polymorph of SiC is not well known. Here, probe-corrected scanning transmission electron microscopy and secondary-ion mass spectrometry are used to investigate precipitation mechanisms in B-implanted 3C-SiC as a function of temperature. Point-defect clustering was detected after …
