The present invention relates to materials useful as semiconductors with a ferromagnetic property, and more specifically, to iron-doped transition metal dichalcogenide monolayers with ferromagnetism stable at or above room temperature.
Semiconductors possess enormous utility in the computing fields, and electronics in general. Specifically, dilute magnetic semiconductors (DMSs) are a class of semiconductor materials that exhibit both ferromagnetism and semiconductor properties, which include Mn-doped Pb1-xSnxTe and GaAs among others. Of particular interest, DMS materials allow for the manipulation of quantum spin states, which makes them promising candidates for a variety of applications. However, current implementations of such technology are not viable for practical applications, as the useful ferromagnetic properties of known DMS materials degrade at temperatures well below room temperature.
The present invention provides for in situ doping of irons into MoS2, which facilitates the fabrication of two-dimensional (2D) dilute magnetic semiconductors that retain their useful properties below, at, and above room temperature.
By the fabrication methods of the present invention, the class of available ferromagnetic 2D materials has been expanded to include the iron doped DMS material of the present invention, the first in its class with Curie temperature (TC) above room temperature. Stable DMS at normal operating temperatures will open new opportunities towards realizing on-chip magnetic manipulation at room temperature.
Its capability of controlling quantum spin states makes DMS a promising candidate for spintronics applications. Spintronic devices control the quantum spin state, which enables almost total spin polarization. This would allow for the development of spin transistors, which rely on the ability of electrons to exhibit one of two states of spin. In turn, the electrons set in particular states of spin may be used to store information.
As such, previously proposed magnetically-sensitive devices are made out of magnetic semiconductors. However, such materials have a Tc at and above which the ferromagnetic materials (FM) lose their permanent magnetic field. The previous highest observed ferromagnetic TC was 110 K in Mn-doped GaAs, which is still far below room temperature. Such low ferromagnetic TC prevents DMSs from realizing their desirable properties in practical applications.
Doping transition metal impurities into transition metal dichalcogenide (TMD) monolayers obtains atomically thin DMSs. Such new 2D DMS systems provide potential opportunities to achieve a ferromagnetic TC close to or higher than room temperature.
Vanadium-doped compounds, such as V:MoTe2 and V:WSe2, have been shown to possess a Tc higher than room temperature. However, these materials were fabricated using mechanical exfoliation before post-growth doping, which severely limits their practical applications due to their lack of scalability, in the case of V:MoTe2, and low-yield in fabrication, in the case of V:WSe2. The V:MoTe2 requires a post-growth method, which is time consuming, and the V:WSe2 requires a solution-based synthesis to obtain the material. Such solution-based synthesis has a low yield and cannot be scaled up for practical applications.
In contrast, the present invention involves utilizing a low-pressure chemical vapor deposition (LPCVD) growth method to synthesize Fe:MoS2 monolayers, while simultaneously doping iron into MoS2. The LPCVD-grown 2D materials have a high potential to be scaled up. Furthermore, this is accomplished while also achieving a DMS with a Tc above room temperature.
Specifically, in one embodiment, the present invention provides for the creation of in situ doped Fe:MoS2 monolayers, which constitute an entirely new class of iron-based van der Waal s ferromagnets with semiconducting properties at room temperature, as well as high magnetic field strength. These monolayers displayed, at room temperature, comparable magnetic field strength to their metallic counterparts that are based on monolayers of CrI3 or CrBr3 at cryogenic temperatures.
These properties are conducive to applications such as on-chip magnetic manipulation of quantum states. The present invention enables applications relating, for instance, to such categories as quantum information science, and minimizing bit storage in spintronics, spintronic devices (spin-injection sources) and memory devices.
In particular, two-dimensional (2D) spintronic devices, including 2D spin-transfer torque magnetoresistive random-access memory (2D STT MRAM) can be developed. In this vein, a 2D STT-MRAM is presented, which is a solid state magnetic memory in the form of a magnetic tunnel junction (MTJ). The STT-MRAM comprises three elements: the free layer, the fixed layer and the tunnel barrier.
Further applications include 2D devices and/or applications including controllability via strain and gating, heterostructures, magnetic sensors, terahertz magneto-optical devices, multiferroics and topological quantum computing.
For a better understanding of the present invention, reference is made to the following detailed description of various exemplary embodiments considered in conjunction with the accompanying drawings, in which:
Various embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely illustrative of the invention that can be embodied in various forms. In addition, each of the examples given in connection with the various embodiments is intended to be illustrative, and not restrictive. Further, the figures are not necessarily to scale, and some features may be exaggerated to show details of particular components (and any size, material and similar details shown in the figures are intended to be illustrative and not restrictive). Therefore, specific details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the disclosed embodiments.
Subject matter will now be described more fully hereinafter with reference to the accompanying drawings, which form a part hereof, and which show, by way of illustration, specific exemplary embodiments. Subject matter may, however, be embodied in a variety of different forms and, therefore, covered or disclosed subject matter is intended to be construed as not being limited to any exemplary embodiments set forth herein, it being understood that such exemplary embodiments are provided merely to be illustrative. Among other things, for example, subject matter may be embodied as methods, devices, components, materials, compositions or systems. The following detailed description is, therefore, not intended to be taken in a limiting sense.
Throughout the specification, terms may have nuanced meanings suggested or implied in context beyond an explicitly stated meaning. Likewise, the phrase “in one embodiment” as used herein does not necessarily refer to the same embodiment and the phrases “in another embodiment” and “other embodiments” as used herein do not necessarily refer to a different embodiment. It is intended, for example, that covered or disclosed subject matter includes combinations of the exemplary embodiments in whole or in part.
In general, terminology may be understood at least in part from usage in context. For example, terms, such as “and”, “or”, or “and/or,” as used herein may include a variety of meanings that may depend at least in part upon the context in which such terms are used. Typically, “or” if used to associate a list, such as A, B, or C, is intended to mean A, B, and C, here used in the inclusive sense, as well as A, B, or C, here used in the exclusive sense. In addition, the term “one or more” as used herein, depending at least in part upon context, may be used to describe any feature, structure, or characteristic in a singular sense or may be used to describe combinations of features, structures or characteristics in a plural sense. Similarly, terms, such as “a,” “an,” or “the,” may be understood to convey a singular usage or to convey a plural usage, depending at least in part upon context. In addition, the term “based on” may be understood as not necessarily intended to convey an exclusive set of factors and may, instead, allow for existence of additional factors not necessarily expressly described, again, depending at least in part on context.
In one embodiment, the present invention allows for creation of a 2D DMS that can be realized via in situ synthesis of iron-doped MoS2 (Fe:MoS2) monolayers. In alternate embodiments, other doped TMD compounds may be produced, such as those comprising WS2, MoSe2 and WSe2, using the methods of the present invention. In one embodiment, the in situ doping and the growth of the material are simultaneously achieved via LPCVD growth. In one embodiment, Fe:MoS2 monolayers are grown onto an SiO2 substrate in this manner, while FeCl3 (anhydrous) on a Si substrate can also be used as the Fe source for doping.
In one embodiment, prior to growth, a thin MoO3 layer is prepared using physical vapor deposition (PVD) of e-beam-evaporated MoO3 (e.g., in pellets) onto a Si substrate with thermal oxides of a suitable thickness (e.g., 300 nm-thick). Next, another SiO2/Si substrate contacts the MoO3-deposited substrate face-to-face. In alternate embodiments, SiC and sapphire substrates may be used for the MoO3 and/or FeCl3.
A manufacturing flow chart for obtaining Fe: MoS2 monolayers is shown in
Specifically, 2D iron-doped transition metal dichalcogenides are obtained by the aforementioned method. The substrate used can be varied (e.g., SiC or sapphire), or the doped monolayer may be transferred to another desired substrate when formed, as appropriate to the intended application.
The presence of Fe atoms in the MoS2 lattice was verified using scanning transmission electron microscopy (STEM) and Raman spectroscopy. Photoluminescence spectroscopy revealed a new Fe-related emission at 2.28 eV in the Fe:MoS2 monolayers that is stable up to room temperature.
This in situ synthesis of Fe:MoS2 monolayers realizes a new class of iron-based van der Waals ferromagnets with semiconducting properties at room temperature. Using such methods one can readily fabricate an Fe:MoS2 material-based spin transistor, and memory (magnetoresistive random access memory, i.e. MRAM) devices in the future.
The achievement of ferromagnetism in 2D crystals, combined with their rich electronics and optics, could open up numerous opportunities. The flexibility of the layer stacking process facilitates the creation of van der Waals heterostructures between layered ferromagnets and a diverse set of other 2D materials. In contrast to the traditional magnetic thin films, 2D materials largely decouple from the substrates, allow electrical control, are mechanically flexible, and are open to chemical functionalization. These attributes make 2D magnets accessible, engineerable, and integrable into emergent heterostructures for previously unachieved properties and applications.
In particular, the present invention can be used to develop 2D STT MRAM devices. While conventional STT MRAM devices use a metallic ferromagnet as a free layer, which demands high energy to change the direction of magnetization, the devices of the present invention can use Fe:MoS2 in 2D STT MRAM, which will ensure much lower energy consumption. Furthermore, this 2D STT MRAM application provides room temperature operation, and can be applied to curved and bendable surfaces.
In an embodiment of the present invention, a 2D STT-MRAM is proposed, which includes a solid state magnetic memory in the form of a magnetic tunnel junction (MTJ). The STT-MRAM cell has a free layer, a fixed layer and a tunnel barrier. The free layer stores information in its magnetic state. The fixed layer provides a reference frame required for reading and writing.
The STT-MRAM functionality is powered by the tunneling magnetoresistance (TMR) effect for the reading of memory and the STT effect for the writing to memory. This TMR effect causes the resistance of the MTJ to change dramatically, which enables the magnetic state of the free layer to be sensed and, thus, stored information to be read.
The free layer can be a 2D magnetic semiconductor layer, and the fixed layer can be made of another magnetic layer, which does not switch during the memory operation. The tunnel barrier is a thin (˜10 Å) insulating, non-magnetic layer between the free layer and the fixed layer. In one embodiment, the insulating layer is crystalline MgO. In another embodiment, the insulating layer (i.e., tunneling barrier) comprises hexagonal boron nitride.
The fixed layer has a fixed magnetization direction; the free layer can change its magnetization direction. A spacer (i.e., nonmagnetic metal) or tunneling barrier (insulator) is fixed between the two layers in GMR and TMR structures, respectively.
Unlike ferromagnetic metals used in conventional STT-MRAM designs, Fe:MoS2, a 2D ferromagnetic semiconductor with a lower coercivity field, requires much less energy to change its direction of magnetization. The 2D MTJ structure can be readily fabricated and integrated into the current STT-MRAM structure via placing 2D ferromagnetic semiconductor monolayer as the free layer.
Parallel magnetization of one STT-MRAM cell is illustrated schematically in
The fabrication methods for integrating Fe:MoS2 into the device architecture have generally been well-established. To fabricate 2D STT MRAM, the bottom electrode and bottom insulator can be fabricated via standardized lift-off photolithography and sputtering. The free layer (e.g., Fe:MoS2 monolayers) can be transferred onto the surface with polymer-based methods which have been well-established in the past 20 years.
The fixed layer, insulator, and free layer structure can be easily fabricated and integrated into current STT MRAM structures via replacing the top free layer with the inventive 2D ferromagnetic semiconductor monolayer.
MoS2 monolayers were synthesized via LPCVD. Prior to growth, a thin MoO3 layer was prepared using physical vapor deposition (PVD) of MoO3 onto a Si substrate with 300 nm-thick thermal oxides. Another SiO2/Si substrate contacted the MoO3-deposited substrate face-to-face. Fe:MoS2 monolayers were grown onto the SiO2/Si substrate. The Fe doping was achieved in the following sequence: Fe3O4 particles were evenly cast onto the SiO2/Si substrate before contacting the MoO3-deposited substrate. To ensure a uniform distribution of Fe3O4 particles, the substrate was washed using deionized (DI) water, so that a thin layer of water was created on the SiO2 surface, prior to applying the Fe3O4 particles. The substrate was then annealed at 110° C. for 5 min on a hot plate. For the growth, the furnace was heated up with a ramping rate of 18° C. min−1 and held for 15 min at 850° C. During the heating procedure, an argon gas (30 s.c.c.m.) was supplied at 300° C. and, subsequently, a hydrogen gas (15 s.c.c.m. of) was delivered at 760° C. Sulfur was supplied when the furnace temperature reached 790° C. After the growth, a few millimeters size of Fe: MoS2 monolayers were obtained.
As explained above, the in-situ Fe doping of monolayer MoS2 was realized by growing MoS2 with Fe3O4 via the LPCVD contact-growth method. To eliminate the effects of local disorders in the substrate, both as-grown MoS2 and Fe:MoS2 monolayers were encapsulated into thin-film hBN. A scanning electron microscopy (SEM) image of Fe:MoS2 monolayers was obtained, and triangular island-like domains were observed, which are typical for similar MoS2-CVD growth techniques. As substitution of Fe atoms at Mo sites is thermodynamically favorable, Fe dopant atoms replace Mo host atoms in the MoS2 crystal. To gain further insight into the atomic structure of the Fe:MoS2 monolayer, high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) was employed. Compared with Mo (Z=42) atoms, Fe (Z=26) has ˜40% smaller atomic number. As the magnitude of the forward-scattered electron intensity is dependent on the atomic number, it is expected that Fe atoms produce lower relative intensity, which is clearly visible for the substitutionally doped Fe atoms in the STEM image. The corresponding STEM intensity scan in
To verify the growth of monolayer Fe:MoS2 domains, the samples were characterized using atomic force microscopy (AFM). The AFM image occasionally showed the onset of the growth of the next layer, (i.e., the bilayer of Fe:MoS2 with its typical snowflake-like pattern). Bilayer growth was further evident from
Evolution of PL intensity as a function of temperature for Fe:MoS2 and MoS2 monolayers are shown in
Transition metal ions show unequal amounts of light absorption when excited with left- and right-handed circular polarizations. At the atomic level, the light absorption is closely related to the magnetically induced Zeeman shifts. Therefore, performing MCD spectroscopy can give insights into the magnetic properties of the material.
In situ substitutional doping of Fe atoms in MoS2 monolayers via LPCVD has been demonstrated. The presence of Fe atoms in the MoS2 lattice was verified using STEM and Raman spectroscopy. PL spectroscopy revealed an unambiguous Fe-related emission at 2.28 eV in Fe:MoS2 monolayers, which is stable up to RT. These findings extend the class of available ferromagnetic van der Waals materials with ferro-magnetism at or above RT and open opportunities towards applications such as on-chip magnetic manipulation in quantum information science or in minimizing bit storage in spintronics.
It will be understood that the embodiments described herein are merely exemplary and that a person skilled in the art may make many variations and modifications without departing from the spirit and scope of the invention. All such variations and modifications, including those represented in
This application claims priority to U.S. Provisional Patent Application Ser. No. 63/034,812 filed Jun. 4, 2020, the entire disclosure of which is incorporated herein by reference.
Filing Document | Filing Date | Country | Kind |
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PCT/US2021/036034 | 6/4/2021 | WO |
Number | Date | Country | |
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63034812 | Jun 2020 | US |