# Patent

## Title
Coherent spin field effect transistor

## Abstract

A coherent spin field effect transistor is provided by depositing a ferromagnetic base like cobalt on a substrate. A magnetic oxide layer is formed on the cobalt by annealing at temperatures on the order of 1000° K to provide a few monolayer thick layer. Where the gate is cobalt, the resulting magnetic oxide is Co3O4 (111). Other magnetic materials and oxides may be employed. A few ML field of graphene is deposited on the cobalt (III) oxide by molecular beam epitaxy, and a source and drain are deposited of base material. The resulting device is scalable, provides high on/off rates, is stable and operable at room temperature and easily fabricated with existing technology.

## Background
This application is a divisional of application Ser. No. 13/343,970, filed Jan. 5, 2012, pending, which is incorporated by reference herein.


The subject matter of this patent application was developed without federal or state funding. Although both inventors named herein are the beneficiaries of support from various corporate organizations, and are employed by Universities at which they work on subject matter including the development and characterization of materials formed by the direct growth of graphene on various substrates, no University time, compensation or apparatus was employed, involved or relied on in the development of the subject matter disclosed and claimed herein.
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to the development of a non-local spin valve, sometimes referred to as a spin field effect transistor, or spin-FET. Spin-FETS that can be operated at ambient temperatures offer the advantages of greater data storage in less space, with a reduced power consumption, and high sensitivity. Spin-FETS offer non-volatile solid state data storage the does not require the constant application of current to sustain it. Spin-FETS are, accordingly, an attractive technology to be used in the development of Magnetic Random Access Memory, or MRAMs. Spin-FETS also find application in logic devices, or combined logic and spin devices. Richter et al, Appl. Phys. Lett., 80 1291 (2002). Among the least consequential, but easily understood, effects of such advances is the ability to provide computing devices which need not consult a stored database before uploading, as most personal computers are arranged today. They offer an “instant on” capability: that is to say, nonvolatile memory and logic.
Background of the Technology
The spin-FET may have been first described as a desirable device to construct in 1990 (Datta et al, Appl. Phys. Lett., 56, 665 (1990)). These devices contemplate a non-magnetic layer which is used for transmitting and controlling the spin polarization of electrons from source to drain. A variety of field materials have been proposed over the years. Most of the concentrated effort in this field has looked at spin injection as a means of arriving at the capabilities offered by the theoretical spin-FET as described. Notwithstanding this effort, no room temperature spin-FET, that is scaleable, and reliable at low power consumption has yet been provided.
In one approach, the ability to deposit thin layers of cobalt on semi-conducting substrates such as GaAs was developed, in an effort to provide for a controlled magnetization perpendicular to the substrate. Bournel et al, Physics E, 10, 86-90 (2001). Ultimately, these researchers were unable to secure a stable, perpendicular magnetization for a ferromagnetic/semiconductor contact field, but research did demonstrate the ability to grow thin layers of oxidized Co on semiconductors such as gallium arsenide and silicon. As investigations into the provision of spin-FETs continue, the ability to adapt the resulting technology to existing materials will become increasingly important.
SUMMARY OF THE INVENTION
Our invention resides in a new type of non-local spin valve or spin field effect transistor (spin-FET), based upon graphene deposited directly onto a magnetically polarizeable electrically insulating or semiconducting substrate such as an oxide, and with the oxide dielectric, with net interface spin polarization, formed on top of a base ferromagnetic layer. In essence, the polarization of the substrate will result in polarization of the transition metal ions of the oxide dielectric at both the top and bottom interfaces, which will in turn lead to polarization of the graphene valence/conduction band electrons. Using appropriate magnetically polarizable source and drain electrodes, a low power, high on-off rate spin-FET can be constructed gated by the bottom base ferromagnetic layer, separated from what amounts to a narrow conduction channel by a dielectric oxide. An example of this is shown in FIG. 1.
In developing this new or non-local spin-FET, although the applicants do not wish to be bound by this explanation, ferromagnetic polarization of the base layer, or gate, is effective to polarize the metal ions in the magnetic oxide at both the top and bottom interfaces. At the top interface, the one in intimate contact with the graphene conduction channel, these ions will undergo exchange interactions with the graphene valence/conduction band electrons. Such “proximity polarization” has been predicted for graphene [1]. Strong ion/conduction electron exchange interactions have been observed in impurity-doped oxide quantum dots, resulting in magnetic behavior in closed shell systems [2-4].
In elementary terms, in FET operation, when the polarization of the source and drain are in the same direction as that of the graphene, there will be a low non-local resistance (high current) between the source and drain. Switching the polarization of the base layer (or gate) will change the polarization of the graphene, and if it no longer matches the polarization of the source or drain, the non-local resistance will be much higher. This provides the basis for the non-local spin-valve, or coherent spin-FET.
In a “conventional” graphene-based spin valve (FIG. 2), as demonstrated by Tombros, et al, [5], and by Cho, et al. or Han, et al [6, 7] graphene injection from a polarized electrode occurs through a tunneling barrier, such as alumina or magnesia [8]. The electrons are polarized by an external applied magnetic field as they travel through the graphene. The spin density is thus characterized by classical diffusion kinetics, based on the long spin diffusion length of graphene [5], and limited by the grain boundary density of graphene, and also (in the case of SiO2) by silica/graphene phonon interactions that limit the electron mobility [5, 9]. For these reasons—substrate phonon interference and grain-boundary densities, the performance (i.e., non-local resistance) of conventional graphene-based spin valves at room temperature has been disappointingly poor for practical device applications. [5-7].
In contrast, the inventive coherent spin-FET's properties derive from the fact that magnetic exchange interactions between oxide conduction electrons and oxide cations will result in the formation of magnetic polarons (FIG. 3a), as shown, which are stabilized relative to the ground state by ion/conduction electron exchange interactions (FIG. 3b). Since in this case the conduction band wavefunction itself is polarized, rather than individual electrons, we term such spin transport as coherent. Thus, magnetic polaron transport in graphene should be relatively independent of graphene grain boundary density. Further, such exchange interactions persist to and above room temperature, as there are relatively few avenues for spin relaxation and other phonon-mediated decay pathways. Further, if the ferromagnetic gate retains polarization at or above room temperature, no applied external magnetic field will be required to maintain polarization of graphene electrons, as the device should operate at remanance.



BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated herein and constitute part of this specification, illustrate exemplary embodiments of the invention, and, together with the general description given above and the detailed description given below, serve to explain the features of the invention.
FIG. 1 is schematic of a proposed non-local Spin Field Effect Transistor (spin-FET), based on direct graphene growth on a magnetically polarizable oxide.
FIG. 2 is a graphene-based non-local spin valve based on diffusion of individual spin-polarized electrons through the graphene layer. (From Tombros, et al.)
FIG. 3 is schematic illustration of magnetic polaron formation: (a) Alignment of graphene conduction band electrons with Co+2 ions yields polarization of the conduction electrons by; (b) formation of a magnetic polaron, stabilized by the exchange interactions; and (c) spin-field effect transistor (spin-FET) geometry for testing this effect, which offers a low current, high on/off ratio non-local resistance even at 300 K.



DETAILED DESCRIPTION OF THE INVENTION
Referring initially to the schematic illustration in FIG. 1, and recognizing that this is a “conventional representation” and that structure and dimensions will be subject to modification depending on the ultimate application envisioned, the formation of each layer of the coherent spin-FET of the invention is described. This is best begun with a discussion of the field itself, as shown.
Graphene—this film must consist of (111)-oriented, sp2 carbon (graphene), as either a single layer or several layers, as desired to control potential oxide/graphene interactions such as charge transfer [10, 11]. This layer can be deposited by molecular beam epitaxy, or possibly by chemical or physical vapor deposition.
The deposition of graphene on a substrate has been described at some length in U.S. patent application Ser. No. 12/543,053 and U.S. patent application Ser. No. 12/980,763, both of which are included herein-by-reference. Additional advances in the control over few layer graphene deposition are provided in U.S. Provisional Patent
Application Ser. Nos. 61/490,650 and 61/497,971, both of which are incorporated herein-by-reference. The controlled direct growth of graphene by MBE (layer-by-layer growth of macroscopically continuous graphene sheets on Co3O4(111) at 1000 K by carbon molecular beam epitaxy (MBE) from a graphite rod source) is described in detail in U.S. Provisional Patent Application Ser. No. 61/522,600. The disclosure of this pending application is incorporated herein-by-reference. Any of the methods described in the incorporated applications can be used to form the graphene field, with a preference for controlled molecular beam epitaxy.
Magnetic Oxide, Source and Drain: This material electrically isolates the graphene from the ferromagnetic gate layer, and allows polarization of the graphene valence/conduction electrons via polarization of the cations in the magnetic oxide. Potential candidates include Co3O4(111), Fe3O4(111), NiO(111), and potentially spinels such as CoFe2O4(111), as well as Cr2O3(111), BaFe2O4. A critical feature is the polarization within the ion layer adjacent to the graphene (FIG. 1). The polarization of the ions must be ferromagnetic within each layer, even if adjacent ion layers in the oxide are polarized antiferromagnetically to each other. A uniform ferromagnetic polarization within the surface layer is needed to polarize the graphene electrons. Further, the direction of polarization is important. If the oxide ions are polarized in a direction parallel to the surface plane, then the graphene will be similarly polarized, and so must the source and drain. In that case, appropriate source/drain materials could be Co, Ni, Fe, or various alloys. However, if the oxide cations are polarized perpendicularly to the surface plane, then the source and drain should have easy axes of magnetization perpendicular to the plane, and should be made of materials such as Permalloy, Co—Pd alloys and multilayers, Co—Pt alloys and multilayers, Fe—Pt alloys and multilayers, some L1o ferromagnetic compounds, etc. Similar nickel-iron alloys, and triblends, such as Molybdenum permalloy, may also be used.
Note, since NiO(111) has the same rocksalt structure as MgO(111), deposition of graphene may result in oxide reconstruction, destroying the chemical equivalence of graphene A sites and B sites [12], removing the HOMO/LUMO equivalence at the Dirac point and opening a band gap, as set forth in U.S. patent application Ser. No. 12/980,763. Development of bandgap potential in graphene bearing materials may provide important electronic advantages, in addition to preserving spintronic adaptability.
Ferromagnetic Gate: This layer should have its axis of magnetic polarization that is easily switchable and ideally has a low coercive field for multifunction logic gates, and be ferromagnetic at room temperature. Appropriate materials include Co, Ni, or Fe.
EXAMPLE
In order to prepare a coherent spin-FET of the invention, a sapphire (aluminum oxide (0001)) substrate is prepared for deposition. An electron beam evaporator may be used to reduce movement between chambers and improve productivity, switching in various targets for deposition. Thus, a fifty angstrom layer of cobalt may be deposited under conventional conditions on the substrate at 750° K in UHV. This deposition is followed by an oxidation anneal at 1000° K which results in surface segregation of dissolved oxygen and the development of a thin layer of Co3O4 (111) (may be 2-5 ML thick). Graphene (2 or 3 ML) is deposited on the Co3O4 using molecular beam epitaxy at 1000° K, yielding a macroscopically continuous graphene film of approximately 3 ML thickness. Graphene may also be deposited via CVD and PVD processes, as disclosed, but MBE is preferred, not only because of the fine control and developed information for this method, but because it is compatible with the other process steps in the formation of the coherent spin-FET of the invention. This leads to high productivity.
In this example, the coherent spin-FET is finished with the application of Co source and drain, and connected in the device for use. On magnetization, it is stable and exhibits a very high on/off rate with low power consumption at temperatures substantially above room temperature. Thus, referring to FIG. 1, the coherent spin-FET prepared has a gate of cobalt, with an insulating layer of cobalt oxide (Co3O4). A few ML layer of graphene is deposited over the magnetic oxide, with Co source and drain. Application of a field to the device gives a durable, low power, high on/off rate spin-FET that is operable at room temperature. The resulting coherent spin-FET gives on/off rates (or switching rates) of at least 107-108 per second depending on the materials and conditions selected.
REFERENCES


    [1] H. Haugen, D. Huertas-Hernando, A. Brataas. Spin transport in proximity-induced ferromagentic graphene. Physcal Review B. 77 (2008) 115406.
    [2] R. Ozwaldowski, I. Zutic, A. G. Petukhov. Magnetism in closed-shell quantum dots: Emergence of magnetic bipolarons. Phys Rev Lett. 106 (2011) 177201.
    [3] d. R. Yakovlev, W. Ossau, G. Landwehr, R. N. Bicknell-Tassius, A. Waag, S. Schmeusser. Two dimensional exciton magnetic polaron in CdTe/Cd1-xMnxTe. Sol St Commun 82 (1992) 29-32.
    [4] D. R. Yakovlev, W. Ossau, G. Landwehr, R. N. Bicknell-Tassius, A. Waag, S. Schmeusser. Two dimensional exciton magnetic polaron in CdTe/Cd1-xMnxTe quantum well structures. Sol St Commun 82 (1992) 29-32.
    [5] N. Tombros, C. Jozsa, M. Popinciuc, H. T. Jonkman, B. J. v. Wees. Electronic spin transport and spin precession in single graphene layers at room temperature. Nature. (2007) 571-574.
    [6] S. Cho, Y. Chen, M. S. Fuhrer. Gate-tuneable graphene spin valve. Applied Physics Letters. 91 (2007) 123105.
    [7] W. Han, K. Pi, H. Wang, M. McCreary, Y. Li, W. Bao, P. Wei, J. Shi, C. N. Laun, R. K. Kawakami. Spin transport in graphite and graphene spin valves. Proceedings of SPIE. 7398 (2009) 739819-1.
    [8] B. Dlubak, P. Seneor, A. Anane, C. Barraud, C. Deranlot, D. Deneuve, B. Servet, R. Mattana, F. Petroff, A. Fert. Are Al2O3 and MgO tunnel barriers suitable for spin injection in graphene? Appl Phys Lett. 97 (2010) 092502.
    [9] V. E. Dorgan, M. Bae, E. Pop. Mobilty and saturation velocity in graphene on SiO2. Appl Phys Lett. 97 (2010) 082112.
    [10] J. A. Kelber, S. Gaddam, C. Vamala, S. Eswaran and P. A. Dowben. Proc. SPIE 8100 (2011) 8100 DY 1-13.
    [11] M. Zhou, F. L. Pasquale, P. A. Dowben, A. Boosalis, M. Schubert, V. Darakchieva, R. Yakimova, J. A. Kelber. Direct graphene growth on Co3O4(111) by molecular beam epitaxy. J Phys: Cond Matt. (2011) in press.
    [12] S. Gaddam, C. Bjelkevig, S. Ge, K. Fukutani, P. A. Dowben, J. A. Kelber. Direct graphene growth on MgO: Origin of the band gap. J Phys Cond Matt. 23 (2011) 072204.


While the present invention has been disclosed both generically and with reference to specific embodiments and examples, these alternatives are not intended to be limiting unless reflected in the claims set forth below. The invention is limited only by the provisions of the claims, and their equivalents, as would be recognized by one of skill in the art to which this application is directed.

## Claims

1. A method of forming a coherent spin field effect transistor (spin-FET), comprising a cobalt base layer or gate, a cobalt oxide layer overlaying said base layer, a layer of graphene deposited over said magnetic oxide layer, a separated source and drain both in electrical contact with said graphene layer, wherein polarization of ions in layers within said magnetic oxide layer overlaying said base layer and adjacent said graphene layer is ferromagnetic within the layers comprising:
(A) forming said gate layer by deposition of said cobalt, followed by annealing to segregate surface oxygen to form a few monolayer thick cobalt oxide layer; and
(B) depositing said graphene layer on said cobalt oxide layer by one or more of molecular beam epitaxy (MBE), chemical vapor deposition (CVD) and powder vapor deposition (PVD) and thereafter forming said source and drain on said graphene.

2. The method of claim 1, wherein said gate layer is comprised of cobalt deposited at 750° K in HUV and said gate layer is annealed at 1000° K in HUV to form said magnetic oxide layer.

3. The method of claim 1, wherein said graphene layer is formed by MBE conducted at 1000° K in HUV.

4. A method of forming a coherent spin field effect transistor (spin-FET), comprising a ferromagnetic base layer or gate, a magnetic oxide layer overlaying said base layer, a layer of graphene deposited over said magnetic oxide layer, and an electrical contact with said graphene layer, said method comprising:
(A)forming said gate layer of cobalt,
(B) forming said magnetic oxide of chrome oxide on said gate layer,
(C) depositing said graphene layer over said chrome oxide and annealing said graphene layer, and
(D)forming an electrical contact with said annealed graphene.

5. The method of claim 4, wherein said graphene is deposited by molecular beam epitaxy (MBE), chemical vapor deposition (CVD) or plasma vapor deposition (PVD).

6. The method of claim 5, wherein said graphene is deposited using MBE.