SYNTHESIS OF TETRATAENITE THIN FILMS VIA RAPID THERMAL ANNEALING
20190180933 ยท 2019-06-13
Assignee
Inventors
Cpc classification
H01F41/22
ELECTRICITY
B32B15/015
PERFORMING OPERATIONS; TRANSPORTING
International classification
H01F41/22
ELECTRICITY
Abstract
A method for synthesis of high anisotropy L1.sub.0 FeNi (tetrataenite) thin films is provided that combines physical vapor deposition via atomic layer sputtering and rapid thermal annealing with extreme heating and cooling speeds. The methods can induce L1.sub.0-ordering in FeNi thin films. The process uses a base composite film of a support substrate, a seed layer, a multilayer thin film of FeNi with alternating single atomic layers of Fe and Ni that mimics the atomic plane of the final L1.sub.0 FeNi alloy, and a capping layer. The Fe and Ni bilayers are grown on top of a Si substrate with a thermally oxidized SiO.sub.2 seed layer to mechanically strain the sample during rapid thermal annealing.
Claims
1. A method for synthesizing L1.sub.0 FeNi thin films, the method comprising: (a) providing a target composite of a narrow band gap substrate with a wide band gap seed layer and multiple repeats of atomic layers of Fe and Ni coupled to the seed layer; (b) rapidly heating the target composite in a vacuum over a period of less than 3 seconds to a temperature of 800 C. or above; (c) maintaining the temperature of the heated target composite at 800 C. or above over a period of less than 10,000 seconds; and (d) cooling the heated target composite to ambient temperature and pressure over a period of less than 1000 seconds.
2. The method of claim 1, wherein said target composite is heated to a temperature of 800 C. or above in a time period of between one second to two seconds.
3. The method of claim 1, wherein said temperature of the heated target composite is maintained over a period of 60 seconds to 90 seconds.
4. The method of claim 1, wherein said heated target composite undergoes rapid cooling to ambient temperature in a period of less than two (2) seconds.
5. The method of claim 1, wherein said Fe and Ni atomic layers comprise a bilayer of an atomic layer of Fe and an atomic layer of Ni, and wherein said target composite further comprises a capping layer on a top surface of said Fe and Ni bilayers to prevent oxidation.
6. The method of claim 5, wherein said capping layer comprises a layer of Fe.
7. The method of claim 1, wherein said substrate is a material selected from the group of materials consisting of Si, Ge, PbSe, PbS, InSb, Bi.sub.2Te.sub.3, alpha-Sn, SnTe, SnSe, and GaAs.
8. The method of claim 7, wherein said Si substrate of said target composite has a (100) orientation.
9. The method of claim 1, wherein said seed layer is a material selected from the group of materials consisting of SiO.sub.2, MgO, Al.sub.2O.sub.3, HfO.sub.2, and Gd.sub.2O.sub.3, and BN.
10. The method of claim 1, wherein said Fe and Ni atomic layers comprise a bilayer of an atomic layer of Fe and an atomic layer of Ni, regardless of the order, repeated 1000 times or less.
11. The method of claim 10, wherein said Fe and Ni atomic layers comprise a bilayer of an atomic layer of Fe and an atomic layer of Ni, regardless of the order, repeated 2 times to 30 times.
12. The method of claim 11, wherein said Fe and Ni bilayers have an atomic ratio of Fe to Ni within the range of 30:70 to 70:30.
13. The method of claim 12, wherein said Fe and Ni bilayers have an atomic ratio of Fe to Ni of 50:50.
14. A method for synthesizing a Tetrataenite (L1.sub.0 FeNi) thin film, the method comprising: (a) forming a wide band gap seed layer on a narrow band gap substrate; (b) applying multiple repeats of atomic layers of Fe and Ni to the seed layer of the substrate to produce a target composite; (c) rapidly heating the target composite in a vacuum over a period of less than 3 seconds to a temperature of 800 C. or above; (d) maintaining the temperature of the heated target composite at 800 C. or above over a period of less than 10,000 seconds; and (e) cooling the heated target composite to ambient temperature and pressure over a period of less than 1000 seconds.
15. The method of claim 14, wherein said multiple repeats of atomic layers of Fe and Ni are applied to the seed layer of the substrate by magnetron sputtering in a vacuum chamber performed with the substrate held at a temperature of approximately 220 C.
16. The method of claim 14, wherein said Fe and Ni atomic layers comprise a bilayer of an atomic layer of Fe and an atomic layer of Ni, regardless of the order, repeated 1000 times or less.
17. The method of claim 16, wherein said Fe and Ni bilayers have an atomic ratio of Fe to Ni within the range of 30:70 to 70:30.
18. The method of claim 14, further comprising: applying a capping layer on a top surface of said atomic layers of Fe and Ni of said target composite to prevent oxidation.
19. The method of claim 18, wherein said capping layer comprises a layer of Fe.
20. The method of claim 14, wherein said substrate is a material selected from the group of materials consisting of Si, Ge, PbSe, PbS, InSb, Bi.sub.2Te.sub.3, alpha-Sn, SnTe, SnSe, and GaAs.
21. The method of claim 14, wherein said seed layer is a material selected from the group of materials consisting of SiO.sub.2, MgO, Al.sub.2O.sub.3, HfO.sub.2, and Gd.sub.2O.sub.3 and BN.
22. The method of claim 14, wherein said target composite is heated to a temperature of 800 C. or above in a time period of between one second to two seconds.
23. The method of claim 14, wherein said temperature of the heated target composite is maintained over a period of 60 seconds to 90 seconds.
24. The method of claim 14, wherein said heated target composite undergoes rapid cooling to ambient temperature in a period of less than two (2) seconds.
25. A target composite for use in synthesizing L1.sub.0 FeNi thin films, comprising: (a) a narrow band gap substrate; (b) a wide band gap seed layer on a top surface of the narrow band gap substrate; (c) a plurality of bilayers of an atomic layer of Fe and an atomic layer of Ni, regardless of the order, repeated 1000 times or less, coupled to the seed layer; and (d) a capping layer on a top surface of the plurality of bilayers.
26. The composite of claim 25, wherein said capping layer comprises a layer of Fe.
27. The composite of claim 25, wherein said substrate is a material selected from the group of materials consisting of Si, Ge, PbSe, PbS, InSb, Bi.sub.2Te.sub.3, alpha-Sn, SnTe, SnSe, and GaAs.
28. The composite of claim 25, wherein said seed layer is a material selected from the group of materials consisting of SiO.sub.2, MgO, Al.sub.2O.sub.3, HfO.sub.2, and Gd.sub.2O.sub.3 and BN.
29. The composite of claim 25, wherein said Fe and Ni bilayers have an atomic ratio of Fe to Ni within the range of 30:70 to 70:30.
30. The composite of claim 29, wherein said Fe and Ni bilayers have an atomic ratio of Fe to Ni of 50:50.
Description
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0019] The technology described herein will be more fully understood by reference to the following drawings which are for illustrative purposes only:
[0020]
[0021]
[0022]
[0023]
[0024]
[0025]
DETAILED DESCRIPTION
[0026] Referring more specifically to the drawings, for illustrative purposes, embodiments of methods for the synthesis of L1.sub.0 FeNi (tetrataenite) thin films are generally shown. Several embodiments of the technology are described generally in
[0027] Generally, the synthesis of L1.sub.0 FeNi thin films is used to illustrate the technology. Although the methods are demonstrated in the domain of FeNi thin films, the apparatus and methods can be adapted and applied to other alloyed materials, including CoPt, CoPd, FePd, etc.
[0028] Turning now to
[0029] At block 12 a silicon oxide seed layer is formed on a base silicon substrate. In one embodiment, silicon wafers with (100) orientation are thermally treated in a heating furnace with oxygen, creating thin layers of SiO.sub.2 (130 nm to 200 nm) on the Si surface. Other materials with a large enough band gap as compared to the heating energy, such as MgO, Al.sub.2O.sub.3, HfO.sub.2, Gd.sub.2O.sub.3, and BN, may be used as the seed layer in block 12. Other substrates with a similar narrow band gap as Si, such as Ge, PbSe, PbS, InSb, Bi.sub.2Te.sub.3, alpha-Sn, SnTe, SnSe, and GaAs, may be used as the substrate at block 12.
[0030] Alternating atomic layers of Fe and Ni are then applied to the SiO.sub.2 surface of the substrate at block 14 of
[0031] It will be seen that any number of alternating metal bilayer repeats can be applied at block 14. In one preferred embodiment, the composite has repeated deposits within the range of one to approximately thirty bilayers of Fe/Ni. However, some composites can be thicker using as many as 1000 alternating atomic layers of Fe and Ni or the other selected materials.
[0032] The alternating monolayers of Fe and Ni are preferably in an approximately 50-50 ratio, mimicking the final atomic planes of the L1.sub.0 FeNi. However, the Fe and Ni bilayers may have an atomic ratio of Fe to Ni within the range of approximately 30:70 to approximately 70:30.
[0033] The composite film may be capped at block 16 of
[0034] One preferred embodiment of the starting composite film 26 is shown schematically in cross-section in
[0035] In the embodiment shown in
[0036] The starting composite film 26 is processed at the steps of blocks 18 to 24 of
[0037] At the step of block 18 of
[0038] The temperature of the substrate heater is elevated to approximately 800 C. or above at block 20, as measured at the substrate heater window thermocouple. The sample initially sits in the adjacent load lock chamber at room temperature, with the load lock valve closed, as shown in
[0039] Accordingly, this process rapidly heats up the composite FeNi films 26 at a rate up to 400 C./second, which is much faster than the maximum heating rate of 40-50 C./second that is typically possible in conventional RTA systems. The preferred rate of this ultrafast heating of the composite film at block 20 is within the range of approximately 100 C./second to approximately 2000 C./second.
[0040] At block 22, the sample is preferably exposed directly to the heater at 800 C. or above for a period of time. The time of exposure at block 22 is preferably between approximately 10 seconds to approximately 10,000 seconds and more preferably between approximately 60 to approximately 90 seconds.
[0041] Once heating is completed, the film is then immediately transferred out of the heat bath and moved into a transfer load lock at room temperature at block 24. This process again typically takes less than 1000 seconds takes and often takes only 1 to 2 seconds. The load lock may then be immediately evacuated with >99.95% pure Nitrogen. Once the load lock reaches 1 atmosphere, in 1-2 minutes, the sample is immediately removed from the sample platter (which is still very warm) and placed in contact with a thermal sink such as another metal platform to quickly bring the sample substrate to room temperature. The rapid heating and cooling cycle is important to achieve the L1.sub.0 FeNi phase, usually over the course of less than 10 minutes.
[0042] One heating apparatus embodiment is depicted schematically in the side views of
[0043] The apparatus shown in
[0044] As shown in
[0045] The sample platter 46 and transfer rod 44 allow the placement of the platter 42 into the load lock 38 and eventually into a heating chamber 36, directly below a substrate heater box 42 for rapid heating of the composite film 26 as shown in
[0046] The technology described herein may be better understood with reference to the accompanying examples, which are intended for purposes of illustration only and should not be construed as in any sense limiting the scope of the technology described herein as defined in the claims appended hereto.
Example 1
[0047] In order to demonstrate the operational principles of the apparatus and synthesis methods, FeNi composite films were produced and processed using the processing steps shown generally in
[0048] Sample A: sputtered at room temperature;
[0049] Sample B: sputtered at 220 C.;
[0050] Sample C: sputtered at 220 C., followed by RTA at 800 C. for 60 s;
[0051] Sample D: sputtered at 220 C., followed by RTA at 800 C. for 90 s.
[0052] Magnetic measurements were performed at room temperature using a PMC Corp. Model 3900 vibrating sample magnetometer (VSM) and a Quantum Designs superconducting quantum interference device (SQUID) magnetometer, with applied magnetic field both in the plane and perpendicular to the film plane. Graphs of magnetic hysteresis loops measured in the in-plane geometry (top) and the out-of-plane geometry (bottom) for Sample A, Sample B and Sample D for comparison are shown in
[0053] Magnetic hysteresis loops for the Sample FeNi thin films were measured before and after the RTA process, for each deposition temperature and RTA processing time, as shown in
[0054] Sample B exhibited a similar hysteresis loop with a coercivity of 20 Oe in plane [
[0055] In Sample C, the coercivity increased to 430 Oe in-plane and 420 Oe out-of-plane (not shown) as a result of the application of rapid thermal annealing processing steps. The processing steps and longer exposure (RTA treatment for 90 s at 800 C.) of Sample D produced even more dramatic results. The coercivity exhibited the greatest increase, up to 753 Oe in-plane [a 63-fold increase,
Example 2
[0056] To better understand the microstructure of the samples, TEM studies and electron diffraction were performed on each sample. For Sample A, plan-view TEM showed small, polycrystalline grains which corresponded to the electron diffraction patterns that exhibited several peaks (rings) associated with a polycrystalline fcc phase. A similar effect was observed in Sample B.
[0057] For Sample C and Sample D, sizable ordered crystalline regions were clearly visible in TEM images. The corresponding electron diffraction patterns exhibited discrete spots along the rings, consistent with improved crystallinity. The observed straining in the lattice was consistent with a transformation from a fcc phase in samples A and B to a fct phase in samples C and D with a larger c lattice parameter. Furthermore, morphology analysis carried out by scanning electron microscopy confirms that the annealed samples retain the continuous film structure, in contrast to the presence of voids seen in similarly processed films.
[0058] To quantitatively assess the degree of L1.sub.0 ordering, the magnetic anisotropy constant was measured by evaluating the hard axis saturation field (HK) in a hysteresis loop measured by SQUID. From the saturation field values and correcting for demagnetization, an anisotropy constant of 610.sup.6 erg cm.sup.3 for Sample D was derived.
[0059] To further examine the degree of L1.sub.0 ordering, a first-order reversal curves (FORC) method was used to qualitatively and quantitatively capture the A1 to L1.sub.0 phase transition in FeNi. For the FORC measurements, the sample is first saturated by a positive magnetic field. The field is then swept to a reversal field, HR, and the magnetization M(H, H.sub.R) was measured as the field is increased back up to positive saturation. These set of points map out a reversal curve associated with a particular value of H.sub.R. This was then repeated for a set of H.sub.R values, creating a family of FORC's. The FORC distribution was then extracted. The extracted FORC distribution was then normalized to the measured saturation magnetization.
[0060] FORC distributions measured for Sample A and Sample D in the out-of-plane geometry were observed. For sample A, the FORC distribution showed only a peak near H.sub.C=0, reflecting a magnetically soft phase with small coercivities. This is consistent with the chemically-disordered cubic A1 FeNi phase before the RTA processing. For sample D, the FORC distribution exhibited two distinct features: 1) a FORC ridge near H.sub.C=0, much like Sample A, which indicated that some fraction of the disordered cubic phase still remained post RTA; and 2) a peak centered near H.sub.C 1.2 kOe, indicative of a magnetically hard high coercivity phase. This high-coercivity phase is consistent with the emergence of an L1.sub.0 phase in the thin film, which was not present prior to RTA processing.
[0061] To quantify the degree of L1.sub.0 ordering, the L1.sub.0 phase fraction can be calculated by integrating the region associated with the hard phase pre- and post-RTA processing. Since the total FORC distribution can be integrated to retrieve the total magnetization of the sample, it is possible to separately integrate the regions corresponding to each phase, and compare against the total magnetization to determine the approximate percentage of each phase present in the sample as a measure of the L1.sub.0 ordering. Sample A showed that 88% of the magnetization was composed of the low-coercivity disordered phase, while sample D shows that 68% of the magnetization is composed of the high-coercivity (L1.sub.0) phase, an increase by a factor of nearly 6. While this does not show 100% L1.sub.0 ordering, it does demonstrate that the process can successfully induce a large degree of L1.sub.0 ordering in FeNi thin films.
[0062] From the description herein, it will be appreciated that that the present disclosure encompasses multiple embodiments which include, but are not limited to, the following:
[0063] 1. A method for synthesizing L1.sub.0 FeNi thin films, the method comprising: (a) providing a target composite of a narrow band gap substrate with a wide band gap seed layer and multiple repeats of atomic layers of Fe and Ni coupled to the seed layer; (b) rapidly heating the target composite in a vacuum over a period of less than 3 seconds to a temperature of 800 C. or above; (c) maintaining the temperature of the heated target composite at 800 C. or above over a period of less than 10,000 seconds; and (d) cooling the heated target composite to ambient temperature and pressure over a period of less than 1000 seconds.
[0064] 2. The method of any preceding embodiment, wherein the target composite is heated to a temperature of 800 C. or above in a time period of between one second to two seconds.
[0065] 3. The method of any preceding embodiment, wherein the temperature of the heated target composite is maintained over a period of 60 seconds to 90 seconds.
[0066] 4. The method of any preceding embodiment, wherein the heated target composite undergoes rapid cooling to ambient temperature in a period of less than two (2) seconds.
[0067] 5. The method of any preceding embodiment, wherein the target composite further comprises a capping layer on a top surface of the bilayers to prevent oxidation.
[0068] 6. The method of any preceding embodiment, wherein the capping layer comprises a layer of Fe.
[0069] 7. The method of any preceding embodiment, wherein the substrate is a material selected from the group of materials consisting of Si, Ge, PbSe, PbS, InSb, Bi.sub.2Te.sub.3, alpha-Sn, SnTe, SnSe, and GaAs.
[0070] 8. The method of any preceding embodiment, wherein the Si substrate of the target composite has a (100) orientation.
[0071] 9. The method of any preceding embodiment, wherein the seed layer is a material selected from the group of materials consisting of SiO.sub.2, MgO, Al.sub.2O.sub.3, HfO.sub.2, and Gd.sub.2O.sub.3, and BN.
[0072] 10. The method of any preceding embodiment, wherein the Fe and Ni atomic layers comprise a bilayer of an atomic layer of Fe and an atomic layer of Ni, regardless of the order, repeated 1000 times or less.
[0073] 11. The method of any preceding embodiment, wherein the Fe and Ni atomic layers comprise a bilayer of an atomic layer of Fe and an atomic layer of Ni, regardless of the order, repeated 2 times to 30 times.
[0074] 12. The method of any preceding embodiment, wherein the Fe and Ni bilayers have an atomic ratio of Fe to Ni within the range of 30:70 to 70:30.
[0075] 13. The method of any preceding embodiment, wherein the Fe and Ni bilayers have an atomic ratio of Fe to Ni of 50:50.
[0076] 14. A method for synthesizing a Tetrataenite (L1.sub.0 FeNi) thin film, the method comprising: (a) forming a wide band gap seed layer on a narrow band gap substrate; (b) applying multiple repeats of atomic layers of Fe and Ni to the seed layer of the substrate to produce a target composite; (c) rapidly heating the target composite in a vacuum over a period of less than 3 seconds to a temperature of 800 C. or above; (d) maintaining the temperature of the heated target composite at 800 C. or above over a period of less than 10,000 seconds; and (e) cooling the heated target composite to ambient temperature and pressure over a period of less than 1000 seconds.
[0077] 15. The method of any preceding embodiment, wherein the multiple repeats of atomic layers of Fe and Ni are applied to the seed layer of the substrate by magnetron sputtering in a vacuum chamber performed with the substrate held at a temperature of approximately 220 C.
[0078] 16. The method of any preceding embodiment, wherein the Fe and Ni atomic layers comprise a bilayer of an atomic layer of Fe and an atomic layer of Ni, regardless of the order, repeated 1000 times or less.
[0079] 17. The method of any preceding embodiment, wherein the Fe and Ni bilayers have an atomic ratio of Fe to Ni within the range of 30:70 to 70:30.
[0080] 18. The method of any preceding embodiment, further comprising: applying a capping layer on a top surface of the atomic layers of Fe and Ni of the target composite to prevent oxidation.
[0081] 19. The method of any preceding embodiment, wherein the capping layer comprises a layer of Fe.
[0082] 20. The method of any preceding embodiment, wherein the substrate is a material selected from the group of materials consisting of Si, Ge, PbSe, PbS, InSb, Bi.sub.2Te.sub.3, alpha-Sn, SnTe, SnSe, and GaAs.
[0083] 21. The method of any preceding embodiment, wherein the seed layer is a material selected from the group of materials consisting of SiO.sub.2, MgO, Al.sub.2O.sub.3, HfO.sub.2, and Gd.sub.2O.sub.3 and BN.
[0084] 22. The method of any preceding embodiment, wherein the target composite is heated to a temperature of 800 C. or above in a time period of between one second to two seconds.
[0085] 23. The method of any preceding embodiment, wherein the temperature of the heated target composite is maintained over a period of 60 seconds to 90 seconds.
[0086] 24. The method of any preceding embodiment, wherein the heated target composite undergoes rapid cooling to ambient temperature in a period of less than two (2) seconds.
[0087] 25. A target composite for use in synthesizing L1.sub.0 FeNi thin films, comprising: (a) a narrow band gap substrate; (b) a wide band gap seed layer on a top surface of the narrow band gap substrate; (c) a plurality of bilayers of an atomic layer of Fe and an atomic layer of Ni, regardless of the order, repeated 1000 times or less, coupled to the seed layer; and (d) a capping layer on a top surface of the plurality of bilayers.
[0088] 26. The composite of any preceding embodiment, wherein the capping layer comprises a layer of Fe.
[0089] 27. The composite of any preceding embodiment, wherein the substrate is a material selected from the group of materials consisting of Si, Ge, PbSe, PbS, InSb, Bi.sub.2Te.sub.3, alpha-Sn, SnTe, SnSe, and GaAs.
[0090] 28. The composite of any preceding embodiment, wherein the seed layer is a material selected from the group of materials consisting of SiO.sub.2, MgO, Al.sub.2O.sub.3, HfO.sub.2, and Gd.sub.2O.sub.3 and BN.
[0091] 29. The composite of any preceding embodiment, wherein the Fe and Ni bilayers have an atomic ratio of Fe to Ni within the range of 30:70 to 70:30.
[0092] 30. The composite of any preceding embodiment, wherein the Fe and Ni bilayers have an atomic ratio of Fe to Ni of 50:50.
[0093] Although the description herein contains many details, these should not be construed as limiting the scope of the disclosure but as merely providing illustrations of some of the presently preferred embodiments. Therefore, it will be appreciated that the scope of the disclosure fully encompasses other embodiments which may become obvious to those skilled in the art.
[0094] In the claims, reference to an element in the singular is not intended to mean one and only one unless explicitly so stated, but rather one or more. All structural, chemical, and functional equivalents to the elements of the disclosed embodiments that are known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the present claims. Furthermore, no element, component, or method step in the present disclosure is intended to be dedicated to the public regardless of whether the element, component, or method step is explicitly recited in the claims. No claim element herein is to be construed as a means plus function element unless the element is expressly recited using the phrase means for. No claim element herein is to be construed as a step plus function element unless the element is expressly recited using the phrase step for.