C.
Müller
*a,
I.
Neckel
b,
M.
Monecke
c,
V.
Dzhagan
c,
G.
Salvan
c,
S.
Schulze
d,
S.
Baunack
e,
T.
Gemming
e,
S.
Oswald
e,
V.
Engemaier
e and
D. H.
Mosca
b
aTechnische Universität Chemnitz, Measurement and Sensor Technology, 09126 Chemnitz, Germany. E-mail: christian.mueller@etit.tu-chemnitz.de
bUniversidade Federal do Paraná, Departamento de Física, 81531-990 Curitiba, Brazil
cTechnische Universität Chemnitz, Solid Surfaces Analysis, 09126 Chemnitz, Germany
dTechnische Universität Chemnitz, Semiconductor Physics, 09126 Chemnitz, Germany
eIFW Dresden, Helmholtzstraße 20, 01069 Dresden, Germany
First published on 1st August 2016
We report the fabrication of Ni2.7Mn0.9Ga0.4/InGaAs bilayers on GaAs (001)/InGaAs substrates by molecular beam epitaxy. To form freestanding microtubes the bilayers have been released from the substrate by strain engineering. Microtubes with up to three windings have been successfully realized by tailoring the size and strain of the bilayer. The structure and magnetic properties of both, the initial films and the rolled-up microtubes, are investigated by electron microscopy, X-ray techniques and magnetization measurements. A tetragonal lattice with c/a = 2.03 (film) and c/a = 2.01 (tube) is identified for the Ni2.7Mn0.9Ga0.4 alloy. Furthermore, a significant influence of the cylindrical geometry and strain relaxation induced by roll-up on the magnetic properties of the tube is found.
In addition to epitaxial film growth, strain engineering offers an elegant approach to rearrange nanomembranes into three-dimensional micro- and nanotubes. Generally, the fabrication process requires a selective etching of the underlaying sacrificial layer to release the nanomembranes from their substrate and a certain amount of strain in the nanomembrane. Initially, molecular beam epitaxy (MBE) was used to fabricate strained bilayers based on semiconductors (i.e. InGaAs/GaAs26–28). More recently, first magnetic materials such as Fe3Si, have been introduced into epitaxial semiconductor/magnetic radial superlattices.29,30 In addition, other fabrication techniques were used to integrate magnetic materials into these rolled-up components.31–34 However, the integral magnetic properties of rolled-up Ni–Mn–Ga alloys and their potential for applications have not been studied yet. In this work, the fabrication of In0.2Ga0.8As/Ni–Mn–Ga nanomembranes on GaAs (001) substrate and their rolled-up freestanding counterparts is described in detail. We investigate the structural and magnetic properties with respect to the sample geometry.
X-ray diffraction (XRD) θ/2θ measurements were performed in Brag–Brentano geometry using Cu-Kα radiation. Atomic force microscopy (AFM) images were obtained using a 5600LS microscope from Agilent. Ex situ X-ray photoemission spectroscopy (XPS) studies were performed with a PHI 5600 X-ray Photoelectron Spectrometer. The non-monochromatic Mg-Kα (hν = 1254.6 eV) X-ray source provides a spectral resolution of 1.1 eV for the Ag 3d5/2 peak. Quantification calculations were done using standard single element sensitivity factors.
Magnetic measurements on the planar samples and microtubes were carried out in a vibrating sample magnetometer (Quantum Design Evercool II) with field cooling (FC) and zero-field cooling (ZFC) magnetization measurements with magnetic field applied along the key directions to the sample. The morphology of the samples was studied by optical microscopy and scanning electron microscopy (SEM) using a FEI NanoSEM 200. To investigate the InGaAs/Ni–Mn–Ga microtube cross section a lamella was prepared by focused ion beam (FIB) cutting in a Zeiss NVision40. The TEM investigations have been done in a FEI Tecnai F30 operating at of 300 kV. The STEM mode was used for EDX analysis and imaging using the high angle annular dark field detector (HAADF). The planar sample was prepared by mechanical polishing and Ar-ion etching at 3 keV. The cross section of the film was analyzed with an energy-filtered Philips CM 20 FEG high resolution transmission electron microscope (HRTEM) equipped with Gatan GIF operated at 200 kV.
Fig. 2 Ni 2p3/2, Mn 2p3/2 and Ga 2p3/2 XPS peaks of Ni2.7Mn0.9Ga0.4 after surface cleaning with Ar-ions. |
The peaks appear at 852 eV, 639 eV and 1116 eV, respectively. The short Ar ion sputtering step removed surface contaminations, e.g. native oxide, and carbon species, and increased significantly the intensity of the Ni 2p3/2, Mn 2p3/2 and Ga 2p3/2 peaks, enabling to determine the composition of the alloy to Ni2.7Mn0.9Ga0.4. It is known from earlier works35 that the composition is strongly related to the sputtering time. To prove the composition, EDX-analysis was performed inside a SEM (not shown). From the measurements similar composition were obtained for the Ni–Mn–Ga alloy with deviations of <4 at% from the XPS data.
To examine the crystal structure more in detail TEM experiments were performed on the films. Fig. 4(a) shows the cross section of the film. The GaAs, AlAs, InGaAs and Ni–Mn–Ga layers can be clearly identified by their different mass-thickness contrast. However, the interface between Ni–Mn–Ga and InGaAs is not clearly visible, allowing only an estimation of the layer thickness. The diffraction pattern taken from the Ni–Mn–Ga layer shows a combination of diffuse rings and spots, indicating a polycrystalline nature (Fig. 4(b)). After analyzing the position of the (112) and (200) diffraction rings a body centered tetragonal, L10 structure (I4/mmm) with lattice parameter a = b = 3.58 Å, c = 7.27 Å, and c/a = 2.03 was found. This result is comparable with diffraction data for Ni2Mn1.2Ga0.8 of ref. 36, reporting a = b = 3.7 Å, c = 7.1 Å. Shao Meng et al.37 found a = b = 3.9 Å, c = 6.4 Å for Ni2.1Mn0.9Ga. However, in the present work an alloy with significant higher amount of Ni was obtained.
After releasing the strained InGaAs/Ni–Mn–Ga bilayers from the substrate rolled-up double microtubes orientated along the GaAs (100) axis with a typical radius of 2.5 μm, measured by scanning electron microscopy (SEM), and a length of several millimeters were obtained (Fig. 5(a) and (b)).
Fig. 5 Optical microscopy images: (a) taken from the tube array. The rolling direction is indicated with bright arrows. (b) Showing two rolled-up double tubes with ∼5 μm diameter. |
Fig. 6 summarizes the results from cross-sectional microscopic analysis. According to the tube radius and the stripe size microtubes with three periods are obtained (Fig. 6(a) and (b)). Defined FIB thinning of tubular structures was adversely affected by the cavity and loose rolling. During lamella preparation only one of the twin tubes shown in Fig. 5(b) survived. The lower layer in Fig. 6(b) is material redeposited during FIB milling (mainly GaAs). The layer thickness of InGaAs and for the Ni–Mn–Ga layer was measured to 20 nm and 40 nm, respectively, in agreement with the nominal deposition parameters and the AFM investigations. The Ni–Mn–Ga layer appears polycrystalline with grain sizes of about 20 nm. An EDX line scan was were carried out over the marked line of the layer stack (Fig. 7(a)). The element intensities allow to clearly distinguish between the three different materials NiMnGa, InGaAs, and GaAs redeposited during FIB cutting (Fig. 7(b)). The compositional analysis of the NiMnGa layer of the tube gave Ni2.7MnGa0.3 which is close to the XPS data. The oxygen signal is higher in the NiMnGa layer than in the GaAs without remarkable enrichment at the interfaces. This probably originates from oxygen incorporated during deposition. Similar results were observed in other rolled-up structures.29
Fig. 7 (a) EDX line scan and HAADF brightness inside the rolled up structure. (b) HAADF-STEM image with location of the EDX line scan. The image is located near the right edge of the marked area in Fig. 6(a). The line scan spans from a partly thinned NiMnGa layer (upper) to GaAs redeposited in the hollow tube interior. |
The crystal structure of the rolled-up Ni–Mn–Ga was investigated by HRTEM (Fig. 6(c)). The diffraction pattern shows a combination of rings and spots, indicating a polycrystalline layer. Based on the diffractions rings the crystalline structure can be indexed as body centered tetragonal, L10 structure (I4/mmm; a = b = 3.51 Å, c = 7.06 Å, c/a = 2.01).
That means after roll-up the same lattice type as for the film is observed. When comparing the results from the microtube with the film, a slight mismatch between the lattice parameters of 2%, 3% and 1%, respectively for a, c and c/a can be found. The difference can be seen as an indication for tensile strain in the NiMnGa film. During roll-up of the strained bilayer relaxation can take place, accompanied by a decrease of the lattice parameters of NiMnGa. At the same time the compressed InGaAs layer (a = 5.85 Å for the film) is released.
Saturation magnetizations Ms of 560 emu cm−3 at 4 T were obtained when taking into account the film dimensions. Measurements along both in-plane directions exhibit atypical easy axis rectangular loop with a coercivity (Hc) of ∼25 mT. The coercivity along [001] is significant larger (100 mT) and the hysteresis curve is more tilted.
After roll-up the in-plane magnetization curves exhibit a smoother shape, indicating harder switching behavior (Fig. 8(b)).
Furthermore, the hysteresis curve of the in-plane direction (0°, tube long axis) coincides with the out-of-plane direction (tube short axis). The coercivity along [001] is significant larger (∼130 mT) and the hysteresis curve is more tilted. These results indicate that shape anisotropy of the tube plays a minor role. The polycrystalline character of the NiMnGa layer and the absence of a pronounced microstructure allow us to attribute this change of anisotropy due to magnetoelastic effect (stress). Then the change of stress induced by roll-up along the 90° direction can be estimated from the intersection of both hysteresis curves measured along 90°. This gives an average anisotropy field of HA = 2K/Ms of 65 mT, which is related to an anisotropy constant of K = 18.4 kJ m−3. The difference of stress can be calculated from K = 3/2λsσ, where λs is the magnetostrictive constant and σ is the stress. Using a value for NiMnGa of λs = 1.3 × 10−4 (ref. 38) one obtains a difference of stress between film and rolled-up tube of 94 MPa, indicating a higher tensile stress along the 90° axis of the film. The orientation of the easy axis of the film seems to be supported by this stress, originating from the lattice mismatch between GaAs and InGaAs/Ni–Mn–Ga bilayer. After roll-up stress release occurs preferentially along the 90° axis (rolling axis) and therefore tilting of the hysteresis curve is observed. As expected from geometry all perpendicular directions to the long tube axis behave similar. Similar observations after roll-up were made in.29 Roll-up of the strained bilayer induces compression of NiMnGa along the 90° axis. Probably, a tensile strength remains along the 0° direction due to incomplete underetching between neighbouring tubes, resulting in similar magnetization curves as observed in Fig. 8(b). Strain relaxation also can be seen as the reason for strong increase of coercivity along the 0° and 90° axis. Important to note, that the result from stress evolution found by magnetization measurements is in agreement with our data from TEM, showing a small drop of the lattice parameters after roll-up.
In addition, the temperature dependence of the ZFC and FC magnetizations is shown in Fig. 9 measured in the range 10 ≤ T ≤ 400 K under a magnetic field of 50 mT. Film (Fig. 9(a)) and tubes (Fig. 9(b)) show similar results. The ZFC magnetization initially increases with decreasing temperature and passes a maximum at Tmax = 150 K, indicating a transition from superparamagnetic to ferromagnetic behavior. Above Tmax the samples become magnetically isotropic, which is also observed in the in-plane hysteresis loops measured at 300 K (Fig. 8(c)). Whereas below Tmax a splitting of the FC and ZFC curves is observed, implying the presence of magnetically blocked states. The ZFC-FC irreversibility found in this work is consistent with reports on polycrystalline Ni50Mn35Ga15 samples with tetragonal structure.39,40 Similar to aforementioned mentioned works no martensitic transformations can be seen in the magnetization curves due to the nanocrystalline nature.
Fig. 9 ZFC and FC magnetization curves for a cooling field of 50 mT with the magnetic field applied along the 0° direction: (a) of Ni53Mn28Ga19 films and (b) after roll-up. |
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