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Article
Sub-Nanometer Atomic Layer Deposition for Spintronics in Magnetic
Tunnel Junctions Based on Graphene Spin-Filtering Membranes
Marie-Blandine Martin, Bruno Dlubak, Robert S Weatherup, Heejun
Yang, Cyrile Deranlot, Karim Bouzehouane, Frédéric Petroff, Abdelmadjid
Anane, Stephan Hofmann, John Robertson, Albert Fert, and Pierre Seneor
ACS Nano, Just Accepted Manuscript • DOI: 10.1021/nn5017549 • Publication Date (Web): 02 Jul 2014
Downloaded from http://pubs.acs.org on July 14, 2014

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Sub-Nanometer Atomic Layer Deposition for
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12 Spintronics in Magnetic Tunnel Junctions Based on
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16 Graphene Spin-Filtering Membranes
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21 Marie-Blandine Martin1, Bruno Dlubak1,2, Robert S. Weatherup2, Heejun Yang1,3, Cyrile
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Deranlot1, Karim Bouzehouane1, Frédéric Petroff1, Abdelmadjid Anane1, Stephan Hofmann2,
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26 John Robertson2, Albert Fert1 and Pierre Seneor1,*
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29 1 - Unité Mixte de Physique CNRS/Thales, 91767 Palaiseau, France, and University of Paris-
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32 Sud, 91405 Orsay, France
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34 2 - Department of Engineering, University of Cambridge, Cambridge CB21PZ, United Kingdom
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36 3 - Center for Integrated Nanostructure Physics, Institute of Basic Science, Sungkyunkwan
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39 University, Suwon 440-746, South Korea
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KEYWORDS: atomic layer deposition ; spintronics ; spin filter ; graphene ; dielectrics ;
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48 magnetic tunnel junction ;
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55 We report on the successful integration of low cost, conformal and versatile atomic layer
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57 deposited (ALD) dielectric in Ni-Al2O3-Co magnetic tunnel junctions (MTJ) where the Ni is
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coated with a spin-filtering graphene membrane. The ALD tunnel barriers, as thin as 0.6
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6 nm, are grown layer-by-layer in a simple, low vacuum, ozone-based process which yields
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8 high quality electron-transport barriers as revealed by tunneling characterization. Even
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under these relaxed conditions, including air exposure of the interfaces, a significant tunnel
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13 magnetoresistance is measured highlighting the robustness of the process. The spin filtering
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15 effect of graphene is enhanced leading to almost fully inversed spin polarization for the Ni
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18 electrode with -42%. This unlocks the potential of ALD for spintronics with conformal,
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20 layer-by-layer control of tunnel barriers in magnetic tunnel junctions towards low-cost
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22 fabrication and down-scaling of tunnel resistances.
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29 Atomic layer deposition (ALD) is a key technology for applications requiring ultra-thin,
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31 uniform, high quality, and conformal films. Owing to the chemically surface-limited growth
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33 mechanisms involved, ALD enables atomic control of the film thickness even for high aspect
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36 ratio substrates while being scalable and compatible with other industrial techniques such as roll-
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38 to-roll processing.1-3 These advantages are already exploited in a number of application,
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including for instance multilayer stacks in thin film electroluminescent flat panel displays,4,5 high
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43 quality dielectrics in dynamic random access memory (DRAM) capacitors,6,7 conformal
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45 passivation coatings for organic electronics e.g. organic light-emitting diodes (OLED),8,9 and
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48 conformal functionalization for porous biomaterials and bioelectronic devices.10,11 Furthermore,
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50 ALD grown ultra-thin, high-k gate dielectrics were industrially adopted for complementary metal
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52 oxide semiconductor (CMOS) logic technologies for high volume manufacturing as early as the
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55 45 nm node,12 and ALD is particularly well adapted for the high aspect ratio architectures such
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57 as FinFET and TriGate transistors used in the current 22 nm node.13,14
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6 To date, despite a number of pioneering attempts15-19 with promising results, the advantages of
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8 ALD have not been widely employed in the field of magnetic tunnel junctions for spintronics,
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which has instead had to rely on more complex physical deposition setups. Spin-valves, the
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13 active elements in technologies such as hard-drive read-heads and magnetic random-access
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15 memories (MRAM),20 would appear to be prime candidates to benefit from the use of ALD:15-17
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18 spin devices rely heavily on ultra-thin films such as nanometer-scale oxide tunnel barriers, whose
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20 quality and atomic composition crucially impact the electron’s spin polarization. A key issue has
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22 however remained: performing ALD directly on metallic spin sources (usually ferromagnets like
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25 Ni, Co, Fe and their alloys) leads to their oxidation during the fabrication and thus a quenching
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27 of their spintronic performances. This has drastically limited the range of processes that can be
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used to fabricate spin-valve devices. Hence, although promising in terms of thickness and
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32 composition control, the application of water or ozone based ALD processes to magnetic tunnel
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34 junctions has so far been hindered by the associated ferromagnet oxidation.15-17
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39 Here we demonstrate the successful realization of graphene coated Ni/Al2O3/Co magnetic
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41 tunnel junctions based on sub-nanometer, ozone based ALD grown tunnel barriers. We are thus
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44 able to take advantage of the layer-by-layer thickness control, inherent to ALD, to down-scale
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46 the thickness and the resistance×area product of tunnel barriers. Measurements of large inverse
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48 tunnel magneto-resistance (TMR) signals highlight the almost full reversal of the graphene
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51 coated Ni spin polarization (P=-42%) compared to the max reported value (P=+46% for the
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53 highest quality Ni/Al2O3 interfaces21) and demonstrate the quality of the ALD barrier.
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RESULTS AND DISCUSSION
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6 In figures 1 and 2, we present the technological steps employed to integrate ALD grown tunnel
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8 barriers in vertical spin valves. Ni bottom electrodes are defined by a standard lift-off step and a
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subsequent chemical vapor deposition (CVD) process22,23 covers these electrodes with a
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13 continuous, few layer graphene coating. This yields a reduced and passivated Ni surface.24 This
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15 direct graphene growth method on patterned ferromagnetic electrodes is readily scalable, and
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18 avoids graphene transfer or exfoliation steps otherwise typical for the fabrication of graphene
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20 devices.25,26 A 1 µm2 junction is then defined in patterned resist (see figure 1). Next, after
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22 exposing the bottom electrode to air, ALD is performed with cycles of ozone and
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25 Tri[Methyl]Aluminum (TMA) pulses to grow ultra-thin Al2O3 layers (see methods). This
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27 fabrication flow results in electrodes fully covered with an Al2O3 thin film. We note that the
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growth of ultra-thin dielectrics on sp2-bonded graphene coatings has previously been considered
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32 challenging:27,28 both the preservation of the pristine graphene’s sp2 structure and the
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34 homogeneous wetting of the dielectric require careful engineering which has been particularly
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37 discussed for films deposited by evaporation or water-based ALD. In particular, ALD on
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39 graphene has been shown to require surface seeding (such as modified ALD cycles, inorganic
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41 clusters or molecular layers such as PTCA…) to increase wetting as required for ultra-low film
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44 thicknesses.27-29 Interestingly, the unseeded ozone-based ALD (O3-ALD) process used here is
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46 shown to be non-detrimental to the graphene layer (see figure 3), whilst yielding Al2O3 films
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48 homogeneous enough to be used as a tunnel barriers (see figures 4 and 5).
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53 As ozone is a powerful oxidant, its use in the process might be expected to result in significant
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oxidation of the graphene coating. We have thus investigated the impact of the whole O3-ALD
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growth process on CVD graphene monolayers using Raman spectroscopy, for 3 different growth
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6 temperatures (Tch): 80 °C, 150 °C and 200 °C (see figure 3). At the highest growth temperature
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8 of 200 °C, a strong Raman defect-enabled D peak (1350 cm-1) appears in the spectra, with an
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amplitude even exceeding that of the graphitic G peak (1600 cm-1) indicating a heavily degraded
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13 sp2 structure.30 Clearly at this high temperature, ozone reacts with the graphene layer introducing
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15 defects and forming functional groups such as epoxides on carbon sites.31,32 Remarkably,
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18 however, this reactivity decreases sharply with lower growth temperature. In particular, Raman
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20 spectra measured after the 80 °C growth of Al2O3 remain unchanged compared to those
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22 measured on bare as-grown CVD graphene (see figure 3): graphene appears to be inert to ozone
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25 during the 80 °C ALD process. These observations relate to the fact that ozone physisorption
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27 occurs on the graphene surface whilst further chemical bonding between the oxygen and carbon
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atoms requires a non-negligible activation energy barrier to be overcome.31,32 In the case of our
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32 80 °C O3-ALD process, the kinetics of this reaction are quenched for the exposure times
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34 considered. This inert process is thus considered in the following to grow ultra-thin Al2O3 films
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37 in complete magnetic tunnel junctions.
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41 Given the low wettability of the carbon sp2 structure, another challenge is the formation of
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44 continuous, ultra-thin, pinhole-free tunnel barriers on graphene. Despite it so far not being
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46 achievable by evaporation,33 we previously reported that sputtering led to high quality Al2O3
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48 films on graphene down to a thickness of 1 nm.34 However, growing Al2O3 films thinner than 1
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51 nm on graphene by sputtering did not yield continuous layers. In particular, AFM
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53 characterisation of a 0.6 nm tunnel barrier, produced by sputtering a 0.4 nm film of metallic Al
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that was further oxidized in a 50 Torr O2 atmosphere (as for the high quality 1 nm tunnel
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barrier34), reveals a particularly high roughness (RMS>0.7 nm, even in excess of the targeted
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6 nominal film thickness). In fact, at these lower thicknesses the coalescence of Al islands is not
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8 achieved following the sputtering process, leading to severely pinholed films. In stark contrast,
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0.6 nm of Al2O3 obtained by the O3-ALD process on graphene shows significantly higher
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13 homogeneity and no observable pinholes, as confirmed by AFM. The measured root mean
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15 square (RMS) roughness of 0.25 nm for the 0.6 nm ALD film is comparable to what is achieved
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18 for the thicker, high quality, 1 nm, sputtered films. These characteristics underline that the
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20 inherent attributes of ALD are well-suited for the needs of spintronics devices in terms of
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22 producing conformal, ultra-thin, high quality, films. Indeed, in the following the <1 nm films
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25 grown by ALD are shown to be homogeneous enough to act as quality tunnel barriers.
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These ultra-thin electron transparent tunnel barriers grown by O3-ALD are then integrated into
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32 1 µm² vertical graphene coated Ni/Al2O3/Co magnetic tunnel junctions. The tunnel junctions are
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34 contacted by a Au-capped ferromagnetic Co top electrode to probe their charge and spin
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37 transport properties (as shown schematically in the Fig. 4a). We first consider their electron
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39 tunneling properties. In Fig. 4b, a typical I-V transport characterization of a full tunneling spin-
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41 valve is shown. We observe a strong non-linear behavior. Next, in figure 4c, the measured
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44 resistances of devices for the 3 different Al2O3 thicknesses are presented. Here, we note in
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46 particular that the 1 nm ALD tunnel barriers have resistances in the mega-ohm range, equivalent
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48 to results obtained with sputtered tunnel barriers.24 The reduction of the number of ALD growth
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51 cycles allows the probing of electrical properties of thinner Al2O3 films (see Figure 4c):
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53 strikingly, the resistances measured for 0.6 nm, 0.8 nm and 1 nm barriers scale exponentially
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with their thickness, and show an increase by a factor 2 to 5 from 300K down to 1.4K. By
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comparison, junctions fabricated with a low-temperature water-based ALD process28
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6 systematically showed short-circuit characteristics with much lower resistances. Figure 4d shows
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8 a typical dI/dV spectrum measured at 1.4K in these junctions. This spectrum contains a ~120
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meV gap-like feature which is characteristic of electron tunneling into graphene layers: at low
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13 biases, vertical tunneling is quenched due to the momentum mismatch between the tunneling
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15 electron and the available in-plane electron states in graphene, while at higher biases additional
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18 inelastic tunneling paths are activated.35 These different electrical characterizations highlight the
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20 high quality of the Al2O3 layers grown by O3-ALD as tunnel barriers.36 Thus the simple and low
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22 cost O3-ALD process presented here remarkably leads to well-wetted tunnel barriers on the
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25 bottom electrode with control down to extremely low thicknesses of 0.6 nm, below what is
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32 We now discuss the spin transport properties of these tunnel devices. In figure 5, a magneto-
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34 transport characterization obtained at 1.4K is presented. Independent switching of the
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37 magnetizations of the top and bottom ferromagnetic electrodes allows the observation of two
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39 resistance states, revealing spin-dependent tunneling across the ALD layer. The large magneto-
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41 resistance (MR) measured confirms that the graphene passivation layer preserves a spin
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44 polarization for the bottom electrode following the ALD step. In contrast to unsuccessful
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46 previous studies where ALD was performed directly on top of ferromagnetic metals,15-17 here we
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48 show that the graphene layer prevents the ferromagnet from oxidizing while allowing a spin
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51 polarized current to be extracted. We obtain up to
 = = -31% from the device

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54 characterization presented in figure 5, where Rp and Rap are the device resistances in the parallel
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4 and Pbot of the top and bottom interfaces with
 = , following ref. 39. Taking the



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7 largest value of the Co/Al2O3 spin polarization we measure in reference devices40 (Ptop = +32%),
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9 we derive a large Pbot = -42% for the air exposed graphene coated nickel/alumina. This negative
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sign was expected to arise from the nickel/graphene interface.24,41 Strikingly, this is comparable
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14 in amplitude to the max reported P = +46% value difficultly achieved for the highest quality
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16 Ni/Al2O3 interfaces.21 Hence this corresponds to a practically full inversion of the spin
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19 polarization vs. graphene-free Ni/Al2O3 spin sources. The ability to achieve high spin signal
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21 amplitude from a Ni/Al2O3 source is remarkable when considering how difficult it has been to
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23 raise its spin polarization above +10% in state of the art tunneling experiments21,42-44 and that the
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26 surface here has been exposed to air in this simple ex-situ process. We note that the pre-cleaning
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28 inherent to the O3-ALD process used is able to remove contaminants from the air-exposed
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electrode. Another possible origin of this large MR signal could be the homogeneity of the Al2O3
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33 layers grown by ALD. Indeed, high quality sputtered Al2O3 tunnel barriers are usually produced
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35 by oxidizing a thin metallic Al film. This results in a gradient in the extent of oxidation through
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the layer while tunnel barriers grown by ALD are oxidized layer by layer, providing a more
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40 homogeneous material.1,2 Following from the work presented herein, the layer-by-layer ALD
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42 growth of other tunnel barriers such as MgO can be foreseen. This may ultimately lead to higher
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45 spin polarization and drastically reduced resistances.
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49 CONCLUSION
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52 The ability to produce conformal, high quality dielectrics in a layer-by-layer manner,
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54 combined with its notable simplicity and low cost has led ALD to supersede other deposition
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techniques in many advanced microelectronics applications. Still, despite several attempts, its
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use has not been widely adopted for magnetic tunnel junctions where an industry-compatible
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6 alternative to sputtering has remained elusive. By demonstrating the fabrication of functional
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8 spin valves based on ultrathin and efficient ALD tunnel barriers, we unveil here the potential of
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ALD for spintronics and more particularly magnetic tunnel junctions. While this is only the first
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13 step, ALD has a high potential and may open new avenues for the development of scaled-up spin
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15 circuits, such as MRAMs45 and envisioned all-spin logic architectures,46,47 offering closer
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18 integration with conventional processes of the microelectronics industry.
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22 METHODS
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25 10 µm-wide Ni electrodes are defined by e-beam lithography, evaporation of 150 nm of Ni and
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27 subsequent lift-off. Reduction and graphene-passivation of the Ni surface is achieved by a CVD
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process22-24 performed in a custom-built coldwall reactor whose base pressure is 5.10-7 mbar.
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32 Samples are heated in a 1 mbar atmosphere of H2 to 600 ºC at 300 ºC/min and annealed for 15
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34 min. The H2 is removed and then the samples are exposed to a 10-5 mbar atmosphere of C2H2 at
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37 600 ºC for 15 min. Finally, the samples are cooled in vacuum at ∼100 ºC/min. This growth
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39 results in a few layer graphene (2-5 layers) coating which prevents the oxidation of the Ni
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41 surface as checked by in- and ex-situ XPS measurements.24 Complete spin valves are then
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44 fabricated using ALD tunnel barriers. 1 µm2 windows are opened in a UVIII resist layer above
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46 the electrode by a second e-beam lithography step. Al2O3 layers of different thicknesses (0.6 nm,
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0.8 nm, 1 nm) are grown by ALD using a Cambridge Nanotech Savannah system. The junctions
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51 are then contacted by a Co(15 nm)/Au(80 nm) top electrode sputtered through a shadow mask to
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ALD is performed with the growth chamber temperature (Tch) held at 80 ºC, low enough to
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6 promote adsorption and quench ozone reactivity with graphene, yet high enough to enable
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8 complete ALD reactions. Ozone (500 Torr, 20 sec purges) and Tri[Methyl]Aluminum (1 Torr, 60
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sec purges) pulses are sequentially carried with a growth rate of 1A per cycle. Before the growth,
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13 the graphene layers are exposed to a 500 Torr ozone atmosphere for 60 sec to promote
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15 adsorption and subsequent homogeneous nucleation. CVD-like reactions in the chamber during
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18 the ALD process are prevented as checked by ellipsometry and breakdown measurements in
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20 mm2 test structures. The quenching of the reactivity of the complete 80 ºC ozone process with
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22 the graphene coating is probed by Raman spectroscopy with a Renishaw InVia system using a
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25 532 nm laser. The roughness of the sputtered and ALD grown tunnel barriers on graphene are
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27 characterized using AFM in tapping mode.
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33 FIGURES
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36 Figure 1. Optical profilometer image of a device. Junctions (1 µm2) are opened in a masking
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38 resist on graphene coated Ni electrodes derived by a direct CVD step.
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Figure 2. Schematic of the ozone-based atomic layer deposition process on graphene coated
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44 electrodes. Ozone and Tri[Methyl]Aluminum (TMA) pulses are supplied resulting in an electron
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46 transparent Al2O3 tunnel barrier.
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Figure 3. Raman spectra of CVD monolayer graphene on SiO2 obtained after the growth of 1 nm
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52 Al2O3 by different ozone-ALD processes. In the case of the 80 °C process the Raman spectrum
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54 remains unchanged from as-grown graphene, indicating the preservation of the structural order
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of the graphene sp2 lattice.
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Figure 4. Electrical characterizations of ALD grown tunnel barriers on graphene coated
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6 electrodes obtained at 1.4K. (a) Scheme of the graphene coated Ni/ALD Al2O3/Co tunnel
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8 junction, (b) I-V curve measured for a 1 nm tunnel barrier with Resistance.Area product of about
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20 MOhm.µm2, (c) Exponential dependence of the resistance with the ALD barrier thickness as
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13 compared to 1 nm sputtered tunnel barriers, (d) dI/dV curve showing the typical gap-like feature
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15 arising from electron tunneling into graphene through ALD Al2O3.
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Figure 5. Large magneto-resistance signal obtained in graphene coated Ni/ALD Al2O3/Co
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21 junctions. The inversed sign of the magneto-resistance arise from the negative spin polarisation
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23 of the bottom electrode driven by the Ni/graphene interface spin filtering effect.
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AUTHOR INFORMATION
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32 Corresponding Author
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35 *pierre.seneor@thalesgroup.com
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41 ACKNOWLEDGMENT
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45 R.S.W. acknowledges a Research Fellowship from St. John’s College, Cambridge. P.S.
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47 acknowledges the Institut Universitaire de France for junior fellowship. S.H. acknowledges
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49 funding from ERC Grant InsituNANO (No. 279342) and EPSRC under grant GRAPHTED (Ref.
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52 EP/K016636/1). This research was partially supported by the EU FP7 work programme under
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54 Grant GRAFOL (No. 285275) and Graphene Flagship (No. 604391).
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