The present disclosure relates to ferromagnetic semiconductor layers, electronic devices including the same, and methods of forming the same.
Semiconductor layers with strong magnetic properties may be beneficial to electronic devices such as magnetic bipolar transistors and magnetic storage devices. Ferromagnetic semiconductor layers may allow control of quantum spin state which may be critical for spintronic applications. Dilute magnetic semiconductors (DMS) have been researched to introduce ferromagnetism to semiconductor materials. However, DMS may have short-range ferromagnetic order, and the Curie temperature may not be high enough.
According to some embodiments of the present inventive concepts, ferromagnetic semiconductor layers may include an atomically thin transition metal dichalcogenide layer. The atomically thin transition metal dichalcogenide layer may include dopant metal atoms.
According to some embodiments of the present inventive concepts, methods of forming the ferromagnetic semiconductor layer may include reacting a first precursor gas including transition metal atoms with a second precursor gas including chalcogenide atoms and a third precursor gas including the dopant metal atoms to form a gaseous compound including the transition metal atoms, the chalcogenide atoms, and the dopant metal atoms and precipitating the atomically thin transition metal dichalcogenide layer on a substrate (e.g., a wafer having a diameter in a range of about 25 mm to 300 mm.
According to some embodiments of the present inventive concepts, electronic devices may include the ferromagnetic semiconductor layer therein.
Two dimensional materials (e.g., an atomically thin layer) may have unique optical, electrical, and mechanical properties compared with traditional three-dimensional materials. Therefore, processes of forming room-temperature ferromagnetic two dimensional materials have been researched. Recently, engineering has been performed to achieve room temperature ferromagnetic behavior of graphene. However, graphene may lack semiconducting properties due to its metallic conductivity. Semiconductors having ferromagnetism may be applicable to various electronic devices, for example, electric motors, transformers, magnetic storage, and spintronic devices. Therefore, two dimensional materials having strong room temperature magnetic properties and strong semiconductor properties (e.g., high carrier mobility) may be beneficial to various electronic devices.
Molybdenum disulfide (MoS2) has been considered as among materials suitable for spintronic applications due to its well-defined spin-splitting property. However, 2H phase pure (e.g., not intentionally doped) MoS2 may have no ferromagnetic property. To obtain ferromagnetic MoS2 thin film, various methods have been developed. For instance, defect engineering has been applied to create ferromagnetic moment. However, introduction of defects could lead to poor semiconducting functionalities of the MoS2 thin films. Doping MoS2 with magnetic metal atoms, such as Ni, Fe and Co, has been applied to create ferromagnetic moment in MoS2 thin films. However, sources of ferromagnetic moment of the MoS2 thin films may be unclear, and the MoS2 thin films do not show the long-range ferromagnetic order.
According to some embodiments of the present inventive concepts, an atomically thin MoS2 layer doped with platinum (Pt) atoms is provided. The MoS2 layer may have room-temperature ferromagnetic moment. Density Functional Theoretical (DFT) calculations suggest that one of sources of ferromagnetism may be the aligned Pt chains in grain boundaries of MoS2 polycrystalline films. The ferromagnetic moment may be controlled by changing concentrations of Pt atoms and lengths of the Pt chains, and the concentrations of Pt atoms and the lengths of the Pt chains may be controlled by changing an amount of Pt precursor during a process of forming the MoS2 layer. A thickness of the MoS2 layer may be controlled by changing Mo precursor amount. The ferromagnetic behavior may show dependence on a length of a Pt chain and a concentration of Pt atoms but may not show dependence on a number of MoS2 layers in a film.
In some embodiments, a MoS2 layer according to some embodiments of the present inventive concepts may include an edge free MoS2 film and Pt atoms, which are both paramagnetic, and may show room-temperature ferromagnetism. Density Function Theoretical (DFT) calculation suggests Pt atom chains in mirror grain boundaries may be among main sources of ferromagnetism. The presence of Pt atom chains was confirmed by high resolution Scanning Transmission Electron Microscopy (STEM) characterization. The Pt-doped MoS2 thin films show room-temperature ferromagnetism and semiconductor behavior (e.g., high carrier mobility). Additionally, the ferromagnetic behavior shows no layer dependence.
According to some embodiments of the present inventive concepts, a ferromagnetic semiconductor layer may include an atomically thin transition metal dichalcogenide layer that includes dopant metal atoms. The ferromagnetic semiconductor layers may be ferromagnetic semiconductor at room temperature (e.g., 300K). In some embodiments, the atomically thin transition metal dichalcogenide layer is a polycrystalline layer including multiple grains therein, and the dopant metal atoms may be in grain boundaries of the atomically thin transition metal dichalcogenide layer.
In some embodiments, the dopant metal atoms may be in the grain boundaries of the atomically thin transition metal dichalcogenide layer and may not be in the grains of the atomically thin transition metal dichalcogenide layer. The dopant metal atoms may form a linear chain, and ferromagnetic momentum may vary according to a number of the dopant metal atoms included in the linear chain. For example, the linear chain of the dopant metal atoms comprises more than 5 dopant metal atoms (e.g., 6 dopant metal atoms, 7 dopant metal atoms, 8 dopant metal atoms, 9 dopant metal atoms, 10 dopant metal atoms, 11 dopant metal atoms, 12 dopant metal atoms, 13 dopant metal atoms, 14 dopant metal atoms, 15 dopant metal atoms, 16 dopant metal atoms, 17 dopant metal atoms, 18 dopant metal atoms, 19 dopant metal atoms, or 20 dopant metal atoms).
For example, the dopant metal atoms may include iron (Fe) atoms, nickel (Ni) atoms, cobalt (Co) atoms, platinum (Pt) atoms, magnesium (Mg) atoms, rhenium (Re) atoms, and/or Niobium (Nb) atoms. The atomically thin transition metal dichalcogenide layer may include, for example, MoS2, WS2, WSe2, MoSe2, MoTe2, WTe2, and/or an alloy thereof.
In some embodiments, the atomically thin transition metal dichalcogenide layer may be a monolayer film or a film including less than 10 layers (e.g., 1 layer, 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers, 8 layers, 9 layers). The atomically thin transition metal dichalcogenide layer may have a thickness of about 10 nm or less (e.g., 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, or 10 nm).
In some embodiments, the ferromagnetic semiconductor layer may have a magnetic momentum equal to or greater than 500 emu/cm (e.g., 500 emu/cm, 510 emu/cm, 520 emu/cm, 530 emu/cm, 540 emu/cm, 550 emu/cm, 600 emu/cm, 650 emu/cm) and coercivity equal to greater than 70 Oe (e.g., 70 Oe, 80 Oe, 90 Oe, 100 Oe, 110 Oe, 120 Oe) at a temperature of 300K.
In some embodiments, an atomic percentage of the dopant metal atoms in the ferromagnetic semiconductor layer is equal to or greater than 3 at. % (e.g., 3 at. %, 3.5 at. %, 4 at. %, 4.5 at. %, 5 at. %, 5.5 at. %, 6 at. %, 6.5 at. %, 7 at. %, 7.5 at. %, 8 at. %, 8.5 at. %, 9 at. %, 9.5 at. %, or 10 at. %).
The atomically thin transition metal dichalcogenide layer of the ferromagnetic semiconductor layer may be formed using methods similar to the method discussed in U.S. Pat. No. 9,527,062. Processes according to some embodiments of the present inventive concepts may be the same as or similar to the process discussed in U.S. Pat. No. 9,527,062, in some aspects, but may further include using a precursor including dopant metal atoms for in-situ doping of dopant metal atoms to the atomically thin transition metal dichalcogenide layer.
The method may include sublimating a first precursor powder including transition metal atoms, a second precursor powder including chalcogenide atoms, and a third precursor powder including dopant metal atoms to provide a first precursor gas including the transition metal atoms, a second precursor gas including the chalcogenide atoms, and a third precursor gas including the dopant metal atoms, respectively.
The method may also include reacting the first precursor gas with the second precursor gas and the third precursor gas to form a gaseous compound including the transition metal atoms, the chalcogenide atoms, and the dopant metal atoms. The gaseous compound may be transferred toward a substrate (e.g., a wafer having a diameter in a range of about 25 mm to 300 mm) using a carrier gas and then may be diffused onto the substrate. The diffused gaseous compound may be precipitated on the substrate.
In some embodiments, the carrier gas may be a mixture of argon and hydrogen, and a volume ratio of argon to hydrogen is in a range of 80:20 to 99:1 (e.g., 80:20, 85:15, 90:10, 95:5, and 99:1). For example, the first precursor powder may include MoCl5, MoCl3, MoO2Cl2, MoOCl3, WCl6, MoO3, WO3, Mo(CO)6, W(CO)6, a compound comprising Mo and/or a compound comprising W. For example, the second precursor powder may include sulfur powder, and a third precursor powder may include Platinum (II) acetyl acetonate (Pt(acac)2).
In some embodiments, the method may be performed at a temperature in a range of about 300° C. to about 1000° C. (e.g., 300° C., 350° C., 400° C., 450° C., 500° C., 550° C., 600° C., 650° C., 700° C., 750° C., 800° C., 850° C., 900° C., 950° C., and 1000° C.) and at a pressure in a range of about 1 Torr to 4 Torr (e.g., 1 Torr, 1.5 Torr, 2 Torr, 2.5 Torr, 3 Torr, 3.5 Torr, and 4 Torr).
In some embodiments, the first precursor gas, the second precursor gas, and the third precursor gas may be supplied at a flow rate of in a range of about 20 sccm to about 80 sccm (e.g., 20 sccm, 25 sccm, 30 sccm, 35 sccm, 40 sccm, 45 sccm, 50 sccm, 55 sccm, 60 sccm, 65 sccm, 70 sccm, 75 sccm, and 80 sccm).
In some embodiments, the substrate may include a silicon substrate and a silicon oxide layer, and the atomically thin transition metal dichalcogenide layer may be formed on the silicon oxide layer such that the silicon oxide layer may extend between the silicon substrate and the atomically thin transition metal dichalcogenide layer.
The ferromagnetic semiconductor layer according to some embodiments of the present inventive concepts may be included in various electronic devices. For example, the ferromagnetic semiconductor layer may be included in a single-photon emitter, a magnetic field sensor, a magneto-optical device, a transistor, or a memory device.
In some embodiments, the ferromagnetic semiconductor layer may be included in a gate electrode of a transistor. In some embodiments, the ferromagnetic semiconductor layer may be included in a data storage element of a memory device (e.g., a magnetoresistive random-access memory)
The following examples describe some embodiments of the present inventive concepts. While embodiments of the present inventive concepts are described in connection with the following examples and the corresponding text and figures, there is no intent to limit embodiments of the present inventive concepts to this description.
Pt doped MoS2 films were synthesized using a chemical vapor deposition process similar in at least some aspects to that discussed in U.S. Pat. No. 9,527,062. Molybdenum chloride (MoCl3) powder (99.99%, Sigma-Aldrich), sulfur powder (99%, Sigma-Aldrich), and Platinum (II) acetylacetonate (Pt(acac)2) (97%, Sigma-Aldrich) were used as Molybdenum, sulfur and platinum precursors respectively. Argon (Ar)/H2 (Vol ratio 95:5) mixture gas was used as the carrier gas. Receiving substrates are 300 nm SiO2/Si wafers (university wafers Inc). Typical synthesis conditions include a temperature of 850° C., a flow rate of 50 sccm, and a pressure around 2 Torr. The films with different Pt dopant concentrations were prepared by controlling the P (acac)2 precursor amounts.
Raman and photoluminescent (PL) measurements were carried out using a Horiba xPlora system equipped with an excitation wavelength at 532 nm. Atomic Force Microscopy (AFM) measurements were performed at an asylum MFP-3000 atomic force microscope. X-ray Photoelectron Spectroscopy (XPS) measurements were carried out at X-ray photoelectron spectroscope (SPECS System with PHOIBOS 150 analyzer using an Mg Kα X-ray source). Annular dark-field (ADF) STEM images and HRTEM images were acquired using an aberration-corrected JEOL JEM-ARM200CF scanning transmission electron microscope operated at 80 kV. ADF images were processed with a deconvolution filter to improve the contrast. Magnetization measurements were performed at 5K-300K in a Quantum Design SQUID VSM. The magnetic field was applied parallelly or vertically to the samples that were mounted on a diamagnetic quartz sample holder to measure the in-plane and out-plane magnetic moments respectively.
The field-effect transistor device was fabricated by evaporating Ti/Au (5/200 nm) electrodes directly onto top of Pt-MoS2 films on SiO2/Si substrates with 300 nm thick silicon oxide. A copper grid (100 mesh, 30 microns spacing, Ted Pella) was placed on top of the thin film as mask for the electrode fabrication. This gives a relatively large channel with a length L=30 μm and a width W=230 μm. The electrical measurements were performed in ambient conditions using a probe station (Karl Suss PSM6).
Pure MoS2 monolayer films and Pt-doped MoS2 monolayer films on SiO2/Si substrates were synthesized using some aspects of a self-limiting chemical vapor deposition method discussed in U.S. Pat. No. 9,527,062. The edges of MoS2 have been reported to possess ferromagnetism. Therefore, edge-free continuous thin films were synthesized. It was confirmed that the doped and undoped films are very uniform in both composition and structure, and the films cover the SiO2/Si supporting substrates with no observable crakes or cracks as shown in
For comparison, magnetic behavior of a pure MoS2 monolayer, a Pt-doped MoS2 monolayer, and a bare SiO2/Si substrate were measured using SQUID. Both the edge free MoS2 monolayer and a bare SiO2/Si substrate show paramagnetic behavior at all measured temperatures. While, Pt-MoS2 films show ferromagnetic moment not only at low temperature (5K) but also at room temperature (300K) at certain Pt dopant concentrations as shown in
To further confirm that the Pt atom chains in the grain boundaries are a source of the magnetism on Pt-MoS2 films, an edge-free monolayer Pt-MoS2 film was prepared. The edge-free monolayer Pt-MoS2 films include various amounts of grain boundaries with different length per unit area due to different grain sizes which is determined by the quality of the film. Meanwhile, Pt chains with different length and concentrations could be obtained. In general, the higher the quality, the longer but less boundaries per unit area will be in the films. The quality is closely affected by the ratio of the precursor Pt(acac)2 to MoCl3. Therefore, to control the length and concentration of Pt chains, different platinum precursor amounts were used during the CVD synthesis while keeping the Mo precursor amount constant. The accurate platinum amount in Pt-MoS2 films were obtained by XPS measurement (
The quality of MoS2 film also showed significant influence on the magnetic orders of the doped films. Two films with the same Pt concentration but different qualities were prepared. The ferromagnetic moments show difference for these two samples. The one with better quality (higher PL) shows much stronger ferromagnetic moment that the one with lower quality (lower PL) as shown in
To test the semiconductor behavior of Pt-MoS2 films, a field-effect transistor device was fabricated. Reasonable gating behavior and mobility was obtained from the Pt-MoS2 film with room temperature ferromagnetism. This matches the observation of reasonable strong PL signals on those Pt-MoS2 films.
MoS2 films with their grain boundaries decorated by Pt chains with different concentrations and length were fabricated and showed both strong semiconductor properties and room-temperature ferromagnetism. The ferromagnetic moment may depend on a length of the Pt chains and may not have dependence on a number of layers. The fabricated Pt-MoS2 films showed in-plane and out-plane ferromagnetism.
It will be understood that the present inventive concepts are not limited to particular embodiments described herein, and as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
All publications and patents cited in this specification are herein incorporated by reference in a matter consistent with the present application as if each individual publication or patent were specifically and individually indicated to be incorporated by reference and are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited.
Functions or constructions well-known in the art may not be described in detail for brevity and/or clarity. Embodiments of the present inventive concepts will employ, unless otherwise indicated, techniques of nanotechnology, organic chemistry, material science and engineering and the like, which are within the skill of the art.
It should be noted that ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. It will be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “about 0.1% to about 5%” should be interpreted to include not only the explicitly recited values of about 0.1% to about 5%, but also include individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g., the phrase “x to y” includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’ and less than ‘y’. The range can also be expressed as an upper limit, e.g., ‘about x, y, z, or less’ and should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘less than x’, less than y′, and ‘less than z’. Likewise, the phrase ‘about x, y, z, or greater’ should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘greater than x’, greater than y′, and ‘greater than z’. In some embodiments, the term “about” can include traditional rounding according to significant figures of the numerical value. In addition, the phrase “about ‘x’ to ‘y’”, where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about ‘y’”.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts belong. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.
The articles “a” and “an,” as used herein, mean one or more when applied to any feature in embodiments of the present inventive concepts described in the specification and claims. The use of “a” and “an” does not limit the meaning to a single feature unless such a limit is specifically stated. The article “the” preceding singular or plural nouns or noun phrases denotes a particular specified feature or particular specified features and may have a singular or plural connotation depending upon the context in which it is used. As used herein the term “and/or” includes any and all combinations of one or more of the associated listed items. Like reference numbers refer to like elements throughout.
The following claims are provided to ensure that the present application meets all statutory requirements as a priority application in all jurisdictions and shall not be construed as setting forth the scope of the present invention.
This application claims priority to U.S. Provisional Application Ser. No. 62/811,085, entitled ROOM-TEMPERATURE FERROMAGNETIC SEMICONDUCTOR LAYERS ELECTRONIC DEVICES INCLUDING THE SAME, AND METHODS OF FORMING THE SAME, filed in the USPTO on Feb. 27, 2019, the disclosure of which is hereby, incorporated by reference herein in its entirety.
This invention was made with government support under grant number 1741693 awarded by the National Science Foundation. The government has certain rights in the invention.
Number | Date | Country | |
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62811085 | Feb 2019 | US |