US20220277896A1 - Mitigation of contamination of electroplated cobalt-platinum films on substrates - Google Patents
Mitigation of contamination of electroplated cobalt-platinum films on substrates Download PDFInfo
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- 239000000758 substrate Substances 0.000 title claims abstract description 54
- 238000011109 contamination Methods 0.000 title abstract description 7
- GUBSQCSIIDQXLB-UHFFFAOYSA-N cobalt platinum Chemical compound [Co].[Pt].[Pt].[Pt] GUBSQCSIIDQXLB-UHFFFAOYSA-N 0.000 title abstract 6
- 230000000116 mitigating effect Effects 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 46
- 230000004888 barrier function Effects 0.000 claims abstract description 41
- 238000000151 deposition Methods 0.000 claims abstract description 33
- 238000009792 diffusion process Methods 0.000 claims abstract description 29
- 238000000137 annealing Methods 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- AVMBSRQXOWNFTR-UHFFFAOYSA-N cobalt platinum Chemical compound [Pt][Co][Pt] AVMBSRQXOWNFTR-UHFFFAOYSA-N 0.000 claims description 106
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 37
- 239000010936 titanium Substances 0.000 claims description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 19
- 238000009713 electroplating Methods 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 6
- -1 tungsten nitride Chemical class 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 238000005240 physical vapour deposition Methods 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
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- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 4
- 229910052721 tungsten Inorganic materials 0.000 claims 4
- 239000010937 tungsten Substances 0.000 claims 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 2
- 229910003437 indium oxide Inorganic materials 0.000 claims 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims 2
- 229910052759 nickel Inorganic materials 0.000 claims 2
- 229910052758 niobium Inorganic materials 0.000 claims 2
- 239000010955 niobium Substances 0.000 claims 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 2
- 229910052715 tantalum Inorganic materials 0.000 claims 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 2
- 229910052720 vanadium Inorganic materials 0.000 claims 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 2
- 229910052726 zirconium Inorganic materials 0.000 claims 2
- 230000006872 improvement Effects 0.000 abstract description 7
- 239000010949 copper Substances 0.000 description 41
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
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- 238000006243 chemical reaction Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 230000005415 magnetization Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
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- 230000008020 evaporation Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WLQXLCXXAPYDIU-UHFFFAOYSA-L cobalt(2+);disulfamate Chemical compound [Co+2].NS([O-])(=O)=O.NS([O-])(=O)=O WLQXLCXXAPYDIU-UHFFFAOYSA-L 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical class [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/32—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying conductive, insulating or magnetic material on a magnetic film, specially adapted for a thin magnetic film
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00349—Creating layers of material on a substrate
- B81C1/0038—Processes for creating layers of materials not provided for in groups B81C1/00357 - B81C1/00373
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F10/00—Thin magnetic films, e.g. of one-domain structure
- H01F10/08—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers
- H01F10/10—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition
- H01F10/12—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition being metals or alloys
- H01F10/123—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition being metals or alloys having a L10 crystallographic structure, e.g. [Co,Fe][Pt,Pd] thin films
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F10/00—Thin magnetic films, e.g. of one-domain structure
- H01F10/26—Thin magnetic films, e.g. of one-domain structure characterised by the substrate or intermediate layers
- H01F10/30—Thin magnetic films, e.g. of one-domain structure characterised by the substrate or intermediate layers characterised by the composition of the intermediate layers, e.g. seed, buffer, template, diffusion preventing, cap layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
- H01F41/30—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates for applying nanostructures, e.g. by molecular beam epitaxy [MBE]
- H01F41/302—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates for applying nanostructures, e.g. by molecular beam epitaxy [MBE] for applying spin-exchange-coupled multilayers, e.g. nanostructured superlattices
- H01F41/309—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates for applying nanostructures, e.g. by molecular beam epitaxy [MBE] for applying spin-exchange-coupled multilayers, e.g. nanostructured superlattices electroless or electrodeposition processes from plating solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N35/00—Magnetostrictive devices
- H10N35/01—Manufacture or treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N50/00—Galvanomagnetic devices
- H10N50/01—Manufacture or treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/4902—Electromagnet, transformer or inductor
- Y10T29/49021—Magnetic recording reproducing transducer [e.g., tape head, core, etc.]
- Y10T29/49032—Fabricating head structure or component thereof
- Y10T29/49036—Fabricating head structure or component thereof including measuring or testing
- Y10T29/49043—Depositing magnetic layer or coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/4902—Electromagnet, transformer or inductor
- Y10T29/49021—Magnetic recording reproducing transducer [e.g., tape head, core, etc.]
- Y10T29/49032—Fabricating head structure or component thereof
- Y10T29/49036—Fabricating head structure or component thereof including measuring or testing
- Y10T29/49043—Depositing magnetic layer or coating
- Y10T29/49044—Plural magnetic deposition layers
Definitions
- CoPt cobalt-platinum
- a silicon substrate for example, is not electrically conductive enough to use electroplating to form CoPt permanent magnets on the Si substrate, or there may be dielectric layers on the Si substrate which prevent the use of electroplating processes. Therefore, it is necessary and customary to use an electrically conductive seed layer (e.g., a copper (Cu) seed layer) onto which electroplated CoPt films can be deposited.
- an electrically conductive seed layer e.g., a copper (Cu) seed layer
- CoPt layers require a high-temperature (e.g., between about 500-750° C.) heat treatment, such as an annealing treatment or step, to induce a phase transition for desirable magnetic properties.
- a high-temperature heat treatment such as an annealing treatment or step
- this high temperature step creates a variety of challenges for the integration of CoPt permanent magnets on substrates.
- FIG. 1 illustrates an example device including a cobalt-platinum (CoPt) permanent magnet formed on a substrate according to an example embodiment described herein.
- CoPt cobalt-platinum
- FIG. 2 illustrates an example device including a CoPt permanent magnet formed on a substrate having a titanium nitride (TiN) diffusion barrier layer according to an example embodiment described herein.
- TiN titanium nitride
- FIG. 3 shows example cross-section scanning electron microscope images of the CoPt magnets deposited into photoresist-defined molds with different thicknesses after annealing according to examples described herein.
- FIG. 4 shows x-ray diffraction (XRD) measurements for CoPt layer samples with different film thicknesses according to examples described herein.
- FIG. 5 shows the average grain size and the L10 phase volume fraction for CoPt layer samples according to examples described herein.
- FIGS. 6A and 6B present out-of-plane magnetization curves for CoPt layer samples deposited with and without a TiN layer, respectively, according to examples described herein.
- FIG. 7 illustrates an example device including a CoPt permanent magnet formed on a substrate having a TiN barrier layer and platinum (Pt) seed layer according to an example embodiment described herein.
- FIGS. 8A and 8B present in-plane and out-of-plane magnetization curves for 0.4 ⁇ m-thick CoPt layer samples deposited, respectively, upon Cu, Co, and Pt seed layers according to examples described herein.
- FIG. 9 shows XRD measurements for CoPt layer samples with different barrier and/or seed layers according to examples described herein.
- FIG. 10 shows a process for the manufacture of a CoPt permanent magnet on a substrate according to an example embodiment described herein.
- CoPt Equiatomic cobalt-platinum
- Ku magnetocrystalline anisotropy constant
- M s saturation magnetization
- a CoPt layer In the as-deposited state, a CoPt layer possesses a disordered A1 crystallographic phase, with relatively soft magnetic properties (e.g., ⁇ 0 H ci ⁇ 0.0125 T, squareness or remanence/saturation magnetization (M r /M s ) ⁇ 0.05).
- a thermal annealing process step at a relatively high temperature e.g., usually >500° C.
- the tetragonal crystal lattice yields high magnetocrystalline anisotropy and plays a key role in yielding hard CoPt permanent magnets.
- electroplating is a variation-prone process, in that factors such as plating conditions (e.g., pH levels, current characteristics, temperature, agitation, deposition time), electrolyte composition, substrate or seed layer type and/or composition impact the morphology and overall properties of the plated layer.
- plating conditions e.g., pH levels, current characteristics, temperature, agitation, deposition time
- electrolyte composition, substrate or seed layer type and/or composition impact the morphology and overall properties of the plated layer.
- an investigation of the influence of current density, seed layer, and anneal temperature/time on the crystallographic structure and magnetic properties of 3-20 ⁇ m-thick electroplated CoPt magnets has identified process-induced variations.
- CoPt magnets having thicknesses of hundreds of nanometers to a few microns may be desired for certain micro device and system applications.
- the effects of thickness variation on the magnetic properties of electroplated CoPt magnets, and particularly an unexpected reduction in magnetic properties observed in CoPt magnets having a thickness of less than about 3 ⁇ m, are described herein.
- the deterioration in the magnetic properties of CoPt magnets having thicknesses less than 3 ⁇ m on Si substrates is identified to be the result of various factors, including (a) metal-silicide reactions between the metal seed layers or CoPt layers with Si substrates and (b) inter-diffusion of the metal seed layers with the CoPt layers, both of which occur during annealing.
- a diffusion barrier such as a TiN diffusion barrier, between the silicon and reactive metals is shown to eliminate the silicide reaction and thereby improve the magnetic properties of thinner electroplated CoPt magnets.
- inter-diffusion between the seed layer or diffusion barrier with the CoPt layer still remains.
- seed layers other than copper such as cobalt Co and platinum Pt, for example, can be used as described herein.
- the CoPt layers may be deposited directly onto a suitable diffusion barrier, so long as the diffusion barrier is electrically conductive enough for electroplating.
- FIG. 1 illustrates an example device 10 including a CoPt permanent magnet formed on a substrate.
- the device 10 includes a substrate 100 , a titanium (Ti) layer 102 , a Cu layer 104 , and a CoPt layer 106 .
- the substrate 100 , Ti layer 102 , Cu layer 104 , and CoPt layer 106 are not necessarily drawn to scale in FIG. 1 .
- the device 10 is provided as a representative example of a structure through which a CoPt permanent magnetic layer can be formed, through electroplating the CoPt layer 106 upon the Cu layer 104 , but is not intended to be limiting as other structures are within the scope of the embodiments.
- the substrate 100 can be embodied as any material or combination of materials suitable for use as a supporting substrate for the devices described herein.
- the substrate 100 can be embodied as a single crystal silicon or a silicon compound, such as 100, 110, or 111-oriented single crystal silicon, polycrystalline silicon, silicon dioxide, silicon carbide, or silicon nitride, or combinations thereof, germanium, gallium arsenide, quartz, ceramic or ceramic compounds, glass, polymers or conductive polymers, or any combinations thereof.
- the substrate 100 may also include one or more films on its surface, such as silicon oxide, silicon dioxide, silicon carbide, polysilicon, aluminum, copper, gold, or any combinations thereof.
- CoPt layers with thicknesses ranging from 0.5 ⁇ m to 5 ⁇ m were deposited into photoresist-defined molds (i.e., 3.5 mm ⁇ 3.5 mm square and 5 ⁇ m ⁇ 50 ⁇ m arrays) on a (100)-oriented Si substrate coated with a 10 nm Ti adhesion layer and a 100 nm Cu seed layer.
- the resulting structures showed an unexpected reduction in magnetic properties for the CoPt layers less than about 2-3 ⁇ m thick. This effect may be a consequence of metal-silicide reactions that occur at the substrate Ti/Cu interface during annealing, leading to the formation of a non-magnetic layer at the interface.
- FIG. 2 illustrates an example device 20 including a CoPt permanent magnet formed on a substrate having a TiN diffusion barrier layer.
- the device 20 includes the substrate 100 , a TiN diffusion barrier layer 108 , the Ti layer 102 , the Cu layer 104 , and the CoPt layer 106 . Again, the device 20 is not necessarily drawn to scale.
- the device 20 is provided as a representative example of a structure through which a CoPt permanent magnetic layer can be formed, through electroplating the CoPt layer 106 upon the Cu layer 104 , but is not intended to be limiting as other structures are within the scope of the embodiments.
- CoPt layers were electroplated into photoresist-defined molds (i.e., 3.5 mm ⁇ 3.5 mm square and 5 ⁇ m ⁇ 50 ⁇ m arrays) on a (100)-oriented Si substrate using one of two types of seed layers.
- Type A samples used a 10 nm Ti adhesion layer and a 100 nm Cu conductive layer.
- Type B samples used a TiN diffusion barrier layer, followed by a 10 nm Ti adhesion layer and a 100 nm Cu conductive layer.
- the TiN diffusion barrier layer was achieved by reactive sputtering of Ti in nitrogen, and the Ti adhesion and Cu seed layers were direct current sputtered.
- the electroplating bath for the CoPt layer consisted of 0.1 M of cobalt sulfamate, 0.025 M of diamine dinitrito platinum (II), and 0.1 M of ammonium citrate salts in a 100 mL solution.
- CoPt layers were plated at room temperature, at a pH of 7 using 100 mA/cm2 currents and subsequently annealed in a forming gas ambient (4% H2+96% N2) at 700° C. with a ramp rate of 20° C./min for 40 mins.
- CoPt layers of various thicknesses between ⁇ 0.5 ⁇ m and ⁇ 5 ⁇ m were obtained by varying the deposition time. Table 1 presents the deposition time and corresponding film thickness for samples A1-A5 and B1-B3.
- EDS Energy dispersive x-ray spectroscopy
- SEM scanning electron microscope
- FIG. 3 shows example cross-section SEM images of the CoPt magnets deposited into the photoresist-defined molds with different thicknesses after annealing according to examples described herein. Images of samples A1-A3 and B1-B3, corresponding to those identified in Table 1, are shown in FIG. 3 .
- samples without a TiN layer i.e., Type A samples A1-A3
- a rough, pulverized appearance of the metal-substrate interface is observed, particularly in the 0.4 ⁇ m-thick film of the A1 sample.
- this damaged interface is a consequence of a metal-silicide reaction between the Si substrate and the TiN/Cu layers at temperatures 200° C.
- a 25-nm TiN layer was used (refer to Type B samples in Table 1 and the structure shown in FIG. 2 ).
- the use of the TiN layer shows a significant improvement.
- An improvement of the Si substrate/TiN/Cu layer interface is observed as shown for the Type B samples in FIG. 3 .
- a new problem arises in the poorer adhesion of the electroplated CoPt layer to the Cu seed layer. Particularly, the larger 3.5 mm ⁇ 3.5 mm layers delaminated, but the smaller 5 ⁇ m ⁇ 50 ⁇ m layers did not.
- FIG. 4 shows XRD measurements for CoPt layer samples with different film thicknesses according to examples described herein.
- the diffraction patterns confirm the presence of Co- and Cu-silicides in the Type A samples, with strong peak intensities for the 0.4 ⁇ m-thick sample without TiN.
- FIG. 4 also confirms the elimination of the silicides in the Type B samples with the introduction of the TiN barrier layer.
- FIG. 5 shows the average grain size and the L10 phase volume fraction for CoPt layer samples A1-A5 (with TiN) and B1-B3 (without TiN).
- An increase in the L10 volume fraction is observed with increasing film thickness for both sets of samples.
- the low volume fraction obtained in the thinner films is attributed to the formation of metal silicides from interface reactions, inhibiting the progress of the transformation for the Type A samples, and a contamination of the CoPt magnetic film by the Cu seed layer for the Type B samples.
- FIGS. 6A and 6B present out-of-plane magnetization curves for CoPt layer samples deposited with and without a TiN layer, respectively.
- FIG. 6A relatively poor magnetic properties are exhibited by the 0.4 ⁇ m-thick sample without a TiN layer, owing to the large volume fraction of non-magnetic silicides. The magnetic properties improve with thickness suggesting the existence of a “good” magnetic layer on top of a “poor” layer. Films at 3.5 ⁇ m and above show properties consistent with previously-reported 3 to 20 ⁇ m-thick layers. As shown in FIG.
- FIG. 7 illustrates an example device 30 including a CoPt permanent magnet formed on a substrate having a TiN barrier layer and a Pt seed layer according to an example embodiment described herein. As compared to the device 20 in FIG. 2 , the device 30 includes a Pt layer 110 rather than the Cu layer 104 . The device 30 is not necessarily drawn to scale.
- the device 30 is provided as a representative example of a structure through which a CoPt permanent magnetic layer can be formed, through electroplating the CoPt layer 106 upon the Pt layer 110 , but is not intended to be limiting as other structures are within the scope of the embodiments.
- the method by which the device 30 can be manufactured is described in further detail below with reference to FIG. 10 .
- FIGS. 8A and 8B present in-plane out-of-plane magnetization curves for 0.4 ⁇ m-thick CoPt layer samples, respectively, deposited upon Cu, Co, and Pt seed layers.
- the magnetic properties are improved with the use of the Co seed layer and further improved with the use of the Pt seed layer, for both the in-plane out-of-plane magnetization curves.
- the magnetic properties are improved as compared to a Cu seed layer for both the Co and Pt seed layers. Additionally, the magnetic properties improve with thickness beyond 0.4 ⁇ m-thick CoPt layers.
- seed layers other than copper such as Co and Pt seed layers
- the use of seed layers other Cu can provide a greater than two times increase in coercivity and about a two times increase in squareness.
- other platinum-group elements such as Palladium (Pd), Ruthenium (Ru), Rhodium (Rh), Osmium (Os), or Iridium (Ir) seed layers may be used in place of Cu.
- metals that inter-diffuse more slowly with the CoPt may be preferable as seed layers to those that diffuse more quickly.
- FIG. 9 shows XRD measurements for CoPt layer samples with different barrier and/or seed layers according to examples described herein.
- the diffraction patterns confirm the elimination of Si (e.g., when a Si substrate is used) by using the TiN barrier layer.
- the diffraction patterns also show that there are no (or minimal) crystals of face-centered cubic (FCC) Co within the CoPt layer when deposited on a Pt seed layer.
- FCC Co in the CoPt layer reduces the overall coercivity of the CoPt layer.
- the elimination of FCC Co in the CoPt layer is desired.
- FIG. 10 shows a process for the manufacture of a CoPt permanent magnet on a substrate according to an example embodiment described herein.
- the process includes providing a substrate.
- Any suitable substrate can be relied upon among the embodiments, including a single crystal silicon or a silicon compound, such as 100, 110, or 111-oriented single crystal silicon, polycrystalline silicon, silicon dioxide, silicon carbide, or silicon nitride, or combinations thereof, germanium, gallium arsenide, quartz, ceramic or ceramic compounds, glass, polymers or conductive polymers, or any combinations thereof.
- the substrate can include one or more films on its surface, such as silicon oxide, silicon dioxide, silicon carbide, polysilicon, aluminum, copper, gold, or any combinations thereof.
- the process includes depositing a TiN barrier layer over the substrate.
- the TiN barrier layer can be deposited over the substrate in any suitable way, such as by using a physical vapor deposition process.
- the TiN barrier layer can be deposited by evaporation or sputtering of Ti in an atmosphere of nitrogen.
- the TiN barrier layer can be deposited at a thickness of about 25 nm, although other thicknesses are within the scope of the embodiments.
- the TiN barrier layer can be omitted, in which case the step at reference numeral 1004 can be skipped.
- the process includes depositing a Ti layer over the TiN barrier layer.
- the Ti layer can be deposited in any suitable way, such as by using evaporation or sputtering of Ti in a vacuum.
- the Ti layer can be deposited at a thickness of about 10 nm, although other thicknesses are within the scope of the embodiments.
- the process includes depositing a metal seed layer over the Ti layer.
- the metal seed layer can be deposited in any suitable way, such as by using evaporation or sputtering of the metal in a vacuum.
- the metal seed layer can be deposited at a thickness of about 100 nm, although other thicknesses are within the scope of the embodiments.
- a Cu metal seed layer can be deposited at reference numeral 1006 .
- seed layers other than CU such as Co and Pt, for example, can be used.
- Ru or Ir seed layers can be used as metal seed layers.
- metals which diffuse more slowly may be preferable to those that diffuse more quickly as seed layers among the embodiments.
- the process includes depositing a CoPt magnetic layer over the metal seed layer.
- the CoPt magnetic layer can be deposited through electroplating, for example, or another suitable method.
- An electroplating bath consisting of about 0.1 M of cobalt sulfamate, 0.025 M of diamine dinitrito platinum (II), and 0.1 M of ammonium citrate salts in a 100 mL solution, for example, can be used for electroplating the CoPt magnetic layer, although other bath compositions can be used.
- the CoPt magnetic layer can be electroplated at room or other temperatures, at a pH of about 7 using 100 mA/cm2 or any other suitable pH and current.
- the CoPt magnetic layer can be formed at a relatively thin thickness of hundreds of nanometers to a few microns while still maintaining good magnetic properties.
- the process includes annealing the CoPt magnetic layer.
- the CoPt magnetic layer can be annealed in a suitable forming gas at a suitable temperature and ramp rate for a period of time to induce a crystallographic ordering in the CoPt magnetic layer from the disordered A1 phase with a face-centered cubic structure to an ordered L10 equilibrium phase having a face-centered tetragonal structure.
- an improvement of the substrate/TiN/Ti/metal seed layer interface can be achieved after annealing, without (or with less) delamination, and with substantial improvements in the magnetic properties of the CoPt magnetic layer.
- Additional layers can also be deposited upon the CoPt magnetic layer for building MEMS devices, for example, or for other reasons.
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Abstract
Description
- This application is a continuation of the co-pending U.S. Non-provisional application Ser. No. 16/801,978, filed Feb. 26, 2020, U.S. Non-provisional application Ser. No. 16/801,978 claims priority and benefit to the divisional application of co-pending U.S. Non-Provisional application Ser. No. 15/404,716, filed Jan. 12, 2017, U.S. Non-Provisional application Ser. No. 15/404,716 claims the benefit of U.S. Provisional Application No. 62/277,669, filed Jan. 12, 2016, and the benefit of U.S. Provisional Application No. 62/320,773, filed Apr. 11, 2016, the contents of all of which applications are herein incorporated by reference in their entireties.
- This invention was made with government support under grant number IIP-1439644 awarded by the National Science Foundation. The government has certain rights in this invention.
- Because of the advantages offered by electroplating, such as cost efficiency, ease of fabrication and scalability, shape controllability, and the ability to integrate with other micro-electro-mechanical system (MEMS) processes, the electrodeposition of cobalt-platinum (CoPt) permanent magnets has been widely studied as an attractive and practical fabrication technique for various MEMS applications.
- Because most MEMS are built on substrates, it is also desirable to have a process to integrate CoPt permanent magnets onto substrates. Generally, however, a silicon substrate, for example, is not electrically conductive enough to use electroplating to form CoPt permanent magnets on the Si substrate, or there may be dielectric layers on the Si substrate which prevent the use of electroplating processes. Therefore, it is necessary and customary to use an electrically conductive seed layer (e.g., a copper (Cu) seed layer) onto which electroplated CoPt films can be deposited.
- Once formed, CoPt layers require a high-temperature (e.g., between about 500-750° C.) heat treatment, such as an annealing treatment or step, to induce a phase transition for desirable magnetic properties. Unfortunately, this high temperature step creates a variety of challenges for the integration of CoPt permanent magnets on substrates.
- For a more complete understanding of the embodiments and the advantages thereof, reference is now made to the following description, in conjunction with the accompanying figures briefly described as follows:
-
FIG. 1 illustrates an example device including a cobalt-platinum (CoPt) permanent magnet formed on a substrate according to an example embodiment described herein. -
FIG. 2 illustrates an example device including a CoPt permanent magnet formed on a substrate having a titanium nitride (TiN) diffusion barrier layer according to an example embodiment described herein. -
FIG. 3 shows example cross-section scanning electron microscope images of the CoPt magnets deposited into photoresist-defined molds with different thicknesses after annealing according to examples described herein. -
FIG. 4 shows x-ray diffraction (XRD) measurements for CoPt layer samples with different film thicknesses according to examples described herein. -
FIG. 5 shows the average grain size and the L10 phase volume fraction for CoPt layer samples according to examples described herein. -
FIGS. 6A and 6B present out-of-plane magnetization curves for CoPt layer samples deposited with and without a TiN layer, respectively, according to examples described herein. -
FIG. 7 illustrates an example device including a CoPt permanent magnet formed on a substrate having a TiN barrier layer and platinum (Pt) seed layer according to an example embodiment described herein. -
FIGS. 8A and 8B present in-plane and out-of-plane magnetization curves for 0.4 μm-thick CoPt layer samples deposited, respectively, upon Cu, Co, and Pt seed layers according to examples described herein. -
FIG. 9 shows XRD measurements for CoPt layer samples with different barrier and/or seed layers according to examples described herein. -
FIG. 10 shows a process for the manufacture of a CoPt permanent magnet on a substrate according to an example embodiment described herein. - The drawings illustrate only example embodiments and are therefore not to be considered limiting of the scope of the embodiments described herein, as other embodiments are within the scope of this disclosure. The elements and features shown in the drawings are not necessarily drawn to scale, emphasis instead being placed upon clearly illustrating the principles of the embodiments. Additionally, certain dimensions or positionings may be exaggerated to help visually convey certain principles. In the drawings, similar reference numerals between figures designate like or corresponding, but not necessarily the same, elements.
- Equiatomic cobalt-platinum (CoPt) in the ordered L10-phase is known to exhibit relatively strong magnetic properties (e.g., magnetocrystalline anisotropy constant (Ku)=4.9 MJ/m3, μ0Hci≥1 T, and saturation magnetization (Ms)=1 T) and good corrosion resistance, making it a magnetic material of considerable interest in several fields, such as the power micro-electro-mechanical system (MEMS) community, among others. In the as-deposited state, a CoPt layer possesses a disordered A1 crystallographic phase, with relatively soft magnetic properties (e.g., μ0Hci<0.0125 T, squareness or remanence/saturation magnetization (Mr/Ms)<0.05). A thermal annealing process step at a relatively high temperature (e.g., usually >500° C.) can be used to induce a crystallographic ordering in the CoPt layer from the disordered A1 phase with a face-centered cubic structure to an ordered L10 equilibrium phase having a face-centered tetragonal structure. The tetragonal crystal lattice yields high magnetocrystalline anisotropy and plays a key role in yielding hard CoPt permanent magnets.
- Because most MEMS are built on substrates, it would be desirable to have a reliable and robust process to integrate CoPt permanent magnets onto substrates. Some substrates, however, are not electrically conductive enough to use an electroplating process to form CoPt permanent magnets onto them, or there may be other dielectric layers on the substrates which prevent the use of electroplating processes. Therefore, it is necessary and customary to use an electrically conductive seed layer, such as a copper (Cu) seed layer, onto which electroplated CoPt layers or films can be deposited.
- However, as noted above, electroplating is a variation-prone process, in that factors such as plating conditions (e.g., pH levels, current characteristics, temperature, agitation, deposition time), electrolyte composition, substrate or seed layer type and/or composition impact the morphology and overall properties of the plated layer. For example, an investigation of the influence of current density, seed layer, and anneal temperature/time on the crystallographic structure and magnetic properties of 3-20 μm-thick electroplated CoPt magnets has identified process-induced variations.
- While studies have focused on multi-micron thick CoPt magnets, CoPt magnets having thicknesses of hundreds of nanometers to a few microns may be desired for certain micro device and system applications. The effects of thickness variation on the magnetic properties of electroplated CoPt magnets, and particularly an unexpected reduction in magnetic properties observed in CoPt magnets having a thickness of less than about 3 μm, are described herein. The deterioration in the magnetic properties of CoPt magnets having thicknesses less than 3 μm on Si substrates is identified to be the result of various factors, including (a) metal-silicide reactions between the metal seed layers or CoPt layers with Si substrates and (b) inter-diffusion of the metal seed layers with the CoPt layers, both of which occur during annealing. The use of a diffusion barrier, such as a TiN diffusion barrier, between the silicon and reactive metals is shown to eliminate the silicide reaction and thereby improve the magnetic properties of thinner electroplated CoPt magnets. However, inter-diffusion between the seed layer or diffusion barrier with the CoPt layer still remains. To further improve the magnetic properties of thinner electroplated CoPt layers, seed layers other than copper, such as cobalt Co and platinum Pt, for example, can be used as described herein. In other embodiments, the CoPt layers may be deposited directly onto a suitable diffusion barrier, so long as the diffusion barrier is electrically conductive enough for electroplating.
- Turning to the drawings,
FIG. 1 illustrates anexample device 10 including a CoPt permanent magnet formed on a substrate. Thedevice 10 includes asubstrate 100, a titanium (Ti)layer 102, aCu layer 104, and aCoPt layer 106. Thesubstrate 100,Ti layer 102,Cu layer 104, andCoPt layer 106 are not necessarily drawn to scale inFIG. 1 . - The
device 10 is provided as a representative example of a structure through which a CoPt permanent magnetic layer can be formed, through electroplating theCoPt layer 106 upon theCu layer 104, but is not intended to be limiting as other structures are within the scope of the embodiments. The method by which the device 10 (and other devices described herein) can be manufactured, including electroplating and annealing theCoPt layer 106, is described in further detail below with reference toFIG. 10 . It should also be appreciated that other layers can be deposited upon theCoPt layer 106 in certain cases as described below. - The
substrate 100 can be embodied as any material or combination of materials suitable for use as a supporting substrate for the devices described herein. As non-limiting examples, thesubstrate 100 can be embodied as a single crystal silicon or a silicon compound, such as 100, 110, or 111-oriented single crystal silicon, polycrystalline silicon, silicon dioxide, silicon carbide, or silicon nitride, or combinations thereof, germanium, gallium arsenide, quartz, ceramic or ceramic compounds, glass, polymers or conductive polymers, or any combinations thereof. In some cases, thesubstrate 100 may also include one or more films on its surface, such as silicon oxide, silicon dioxide, silicon carbide, polysilicon, aluminum, copper, gold, or any combinations thereof. - Consistent with the example structure of the
device 10 shown inFIG. 1 , CoPt layers with thicknesses ranging from 0.5 μm to 5 μm were deposited into photoresist-defined molds (i.e., 3.5 mm×3.5 mm square and 5 μm×50 μm arrays) on a (100)-oriented Si substrate coated with a 10 nm Ti adhesion layer and a 100 nm Cu seed layer. The resulting structures showed an unexpected reduction in magnetic properties for the CoPt layers less than about 2-3 μm thick. This effect may be a consequence of metal-silicide reactions that occur at the substrate Ti/Cu interface during annealing, leading to the formation of a non-magnetic layer at the interface. - To address the unexpected reduction in magnetic properties for CoPt layers less than about 2-3 μm thick, a TiN diffusion barrier layer was added to inhibit the silicide reaction and thereby maintain strong magnetic properties (e.g., Hci of about 800 kA/m, Mr/Ms=0.8) in micron-thick electroplated CoPt layers. In that context,
FIG. 2 illustrates anexample device 20 including a CoPt permanent magnet formed on a substrate having a TiN diffusion barrier layer. Thedevice 20 includes thesubstrate 100, a TiNdiffusion barrier layer 108, theTi layer 102, theCu layer 104, and theCoPt layer 106. Again, thedevice 20 is not necessarily drawn to scale. Thedevice 20 is provided as a representative example of a structure through which a CoPt permanent magnetic layer can be formed, through electroplating theCoPt layer 106 upon theCu layer 104, but is not intended to be limiting as other structures are within the scope of the embodiments. The method by which the device 20 (and other devices described herein) can be manufactured, including electroplating and annealing theCoPt layer 106, is described in further detail below with reference toFIG. 10 . It should also be appreciated that other layers can be deposited upon theCoPt layer 106 in certain cases as described below. - Consistent with the example structures of the
device 20 shown inFIG. 2 , CoPt layers were electroplated into photoresist-defined molds (i.e., 3.5 mm×3.5 mm square and 5 μm×50 μm arrays) on a (100)-oriented Si substrate using one of two types of seed layers. Type A samples used a 10 nm Ti adhesion layer and a 100 nm Cu conductive layer. Type B samples used a TiN diffusion barrier layer, followed by a 10 nm Ti adhesion layer and a 100 nm Cu conductive layer. The TiN diffusion barrier layer was achieved by reactive sputtering of Ti in nitrogen, and the Ti adhesion and Cu seed layers were direct current sputtered. The electroplating bath for the CoPt layer consisted of 0.1 M of cobalt sulfamate, 0.025 M of diamine dinitrito platinum (II), and 0.1 M of ammonium citrate salts in a 100 mL solution. CoPt layers were plated at room temperature, at a pH of 7 using 100 mA/cm2 currents and subsequently annealed in a forming gas ambient (4% H2+96% N2) at 700° C. with a ramp rate of 20° C./min for 40 mins. CoPt layers of various thicknesses between ˜0.5 μm and ˜5 μm were obtained by varying the deposition time. Table 1 presents the deposition time and corresponding film thickness for samples A1-A5 and B1-B3. -
TABLE 1 Deposition times and film thickness of electroplated CoPt. Deposition Time Film Thickness Sample Layers (min) (μm) A1 Si/Ti/Cu 5 0.4 A2 Si/Ti/Cu 15 1.3 A3 Si/Ti/ Cu 30 2.6 A4 Si/Ti/ Cu 45 3.5 A5 Si/Ti/ Cu 60 5.2 B1 Si/TiN/Ti/Cu 5 0.4 B2 Si/TiN/Ti/Cu 15 1.3 B3 Si/TiN/Ti/ Cu 30 2.6 - Energy dispersive x-ray spectroscopy (EDS) was used to confirm the chemical composition of the CoPt films, and an FEI Nova NanoSEM 430 scanning electron microscope (SEM) was used to image the films and to measure the film thickness. Crystallographic structure analysis was carried out using x-ray diffraction (XRD) patterns from a Panalytical X'Pert Powder diffractometer. In-plane and out-of-plane magnetic measurements were made with an ADE EV9 vibrating sample magnetometer (VSM).
-
FIG. 3 shows example cross-section SEM images of the CoPt magnets deposited into the photoresist-defined molds with different thicknesses after annealing according to examples described herein. Images of samples A1-A3 and B1-B3, corresponding to those identified in Table 1, are shown inFIG. 3 . For samples without a TiN layer (i.e., Type A samples A1-A3), a rough, pulverized appearance of the metal-substrate interface is observed, particularly in the 0.4 μm-thick film of the A1 sample. As confirmed by XRD, this damaged interface is a consequence of a metal-silicide reaction between the Si substrate and the TiN/Cu layers attemperatures 200° C. As the film thickness increases, the effects of the metal-silicide reactions become less noticeable and the microstructure of the CoPt layer becomes clearly defined. This trend was also observed in samples A4 and A5 (not shown inFIG. 3 ) with film thickness of 3.5 μm and 5.2 μm, respectively. - To mitigate the silicide reaction, a 25-nm TiN layer was used (refer to Type B samples in Table 1 and the structure shown in
FIG. 2 ). The use of the TiN layer shows a significant improvement. An improvement of the Si substrate/TiN/Cu layer interface is observed as shown for the Type B samples inFIG. 3 . However, a new problem arises in the poorer adhesion of the electroplated CoPt layer to the Cu seed layer. Particularly, the larger 3.5 mm×3.5 mm layers delaminated, but the smaller 5 μm×50 μm layers did not. -
FIG. 4 shows XRD measurements for CoPt layer samples with different film thicknesses according to examples described herein. The diffraction patterns confirm the presence of Co- and Cu-silicides in the Type A samples, with strong peak intensities for the 0.4 μm-thick sample without TiN.FIG. 4 also confirms the elimination of the silicides in the Type B samples with the introduction of the TiN barrier layer. -
FIG. 5 shows the average grain size and the L10 phase volume fraction for CoPt layer samples A1-A5 (with TiN) and B1-B3 (without TiN). An increase in the L10 volume fraction is observed with increasing film thickness for both sets of samples. The low volume fraction obtained in the thinner films is attributed to the formation of metal silicides from interface reactions, inhibiting the progress of the transformation for the Type A samples, and a contamination of the CoPt magnetic film by the Cu seed layer for the Type B samples. -
FIGS. 6A and 6B present out-of-plane magnetization curves for CoPt layer samples deposited with and without a TiN layer, respectively. InFIG. 6A , relatively poor magnetic properties are exhibited by the 0.4 μm-thick sample without a TiN layer, owing to the large volume fraction of non-magnetic silicides. The magnetic properties improve with thickness suggesting the existence of a “good” magnetic layer on top of a “poor” layer. Films at 3.5 μm and above show properties consistent with previously-reported 3 to 20 μm-thick layers. As shown inFIG. 6B , substantial improvements in magnetic properties are also observed for the samples including a TiN layer, especially those with film thicknesses of 1.3 μm and above, although the 0.4 μm-thick film still exhibits relatively poor magnetic properties which may be attributed to the aforementioned contamination of the CoPt magnetic layer by the Cu seed layer during annealing. - To address the contamination of the CoPt magnetic layer by the Cu seed layer during annealing, seed layers other than copper, such as cobalt Co and platinum Pt, for example, can be used. In that context,
FIG. 7 illustrates anexample device 30 including a CoPt permanent magnet formed on a substrate having a TiN barrier layer and a Pt seed layer according to an example embodiment described herein. As compared to thedevice 20 inFIG. 2 , thedevice 30 includes aPt layer 110 rather than theCu layer 104. Thedevice 30 is not necessarily drawn to scale. Thedevice 30 is provided as a representative example of a structure through which a CoPt permanent magnetic layer can be formed, through electroplating theCoPt layer 106 upon thePt layer 110, but is not intended to be limiting as other structures are within the scope of the embodiments. The method by which thedevice 30 can be manufactured is described in further detail below with reference toFIG. 10 . -
FIGS. 8A and 8B present in-plane out-of-plane magnetization curves for 0.4 μm-thick CoPt layer samples, respectively, deposited upon Cu, Co, and Pt seed layers. As shown, the magnetic properties are improved with the use of the Co seed layer and further improved with the use of the Pt seed layer, for both the in-plane out-of-plane magnetization curves. As compared to the results shown inFIGS. 6A and 6B , the magnetic properties are improved as compared to a Cu seed layer for both the Co and Pt seed layers. Additionally, the magnetic properties improve with thickness beyond 0.4 μm-thick CoPt layers. Thus, the use of seed layers other than copper, such as Co and Pt seed layers, for example, reduce the contamination of the CoPt magnetic layer during annealing. Particularly, the use of seed layers other Cu can provide a greater than two times increase in coercivity and about a two times increase in squareness. In other embodiments, other platinum-group elements, such as Palladium (Pd), Ruthenium (Ru), Rhodium (Rh), Osmium (Os), or Iridium (Ir) seed layers may be used in place of Cu. Among the embodiments, metals that inter-diffuse more slowly with the CoPt may be preferable as seed layers to those that diffuse more quickly. -
FIG. 9 shows XRD measurements for CoPt layer samples with different barrier and/or seed layers according to examples described herein. The diffraction patterns confirm the elimination of Si (e.g., when a Si substrate is used) by using the TiN barrier layer. The diffraction patterns also show that there are no (or minimal) crystals of face-centered cubic (FCC) Co within the CoPt layer when deposited on a Pt seed layer. FCC Co in the CoPt layer reduces the overall coercivity of the CoPt layer. Thus, the elimination of FCC Co in the CoPt layer, as much as possible, is desired. -
FIG. 10 shows a process for the manufacture of a CoPt permanent magnet on a substrate according to an example embodiment described herein. Atreference numeral 1002, the process includes providing a substrate. Any suitable substrate can be relied upon among the embodiments, including a single crystal silicon or a silicon compound, such as 100, 110, or 111-oriented single crystal silicon, polycrystalline silicon, silicon dioxide, silicon carbide, or silicon nitride, or combinations thereof, germanium, gallium arsenide, quartz, ceramic or ceramic compounds, glass, polymers or conductive polymers, or any combinations thereof. In some cases, the substrate can include one or more films on its surface, such as silicon oxide, silicon dioxide, silicon carbide, polysilicon, aluminum, copper, gold, or any combinations thereof. - At
reference numeral 1004, the process includes depositing a TiN barrier layer over the substrate. The TiN barrier layer can be deposited over the substrate in any suitable way, such as by using a physical vapor deposition process. For example, the TiN barrier layer can be deposited by evaporation or sputtering of Ti in an atmosphere of nitrogen. The TiN barrier layer can be deposited at a thickness of about 25 nm, although other thicknesses are within the scope of the embodiments. In some embodiments, the TiN barrier layer can be omitted, in which case the step atreference numeral 1004 can be skipped. - At
reference numeral 1006, the process includes depositing a Ti layer over the TiN barrier layer. The Ti layer can be deposited in any suitable way, such as by using evaporation or sputtering of Ti in a vacuum. The Ti layer can be deposited at a thickness of about 10 nm, although other thicknesses are within the scope of the embodiments. Atreference numeral 1008, the process includes depositing a metal seed layer over the Ti layer. The metal seed layer can be deposited in any suitable way, such as by using evaporation or sputtering of the metal in a vacuum. The metal seed layer can be deposited at a thickness of about 100 nm, although other thicknesses are within the scope of the embodiments. A Cu metal seed layer can be deposited atreference numeral 1006. However, to avoid the contamination of the CoPt magnetic layer, which is deposited over the metal seed layer atreference numeral 1010, by Cu during annealing, seed layers other than CU, such as Co and Pt, for example, can be used. In other embodiments, Ru or Ir seed layers can be used as metal seed layers. In general, metals which diffuse more slowly may be preferable to those that diffuse more quickly as seed layers among the embodiments. - At
reference numeral 1010, the process includes depositing a CoPt magnetic layer over the metal seed layer. The CoPt magnetic layer can be deposited through electroplating, for example, or another suitable method. An electroplating bath consisting of about 0.1 M of cobalt sulfamate, 0.025 M of diamine dinitrito platinum (II), and 0.1 M of ammonium citrate salts in a 100 mL solution, for example, can be used for electroplating the CoPt magnetic layer, although other bath compositions can be used. The CoPt magnetic layer can be electroplated at room or other temperatures, at a pH of about 7 using 100 mA/cm2 or any other suitable pH and current. As described herein, based in part on the use of the TiN barrier layer and/or the Co or Pt metal seed layers, the CoPt magnetic layer can be formed at a relatively thin thickness of hundreds of nanometers to a few microns while still maintaining good magnetic properties. - At
reference numeral 1012, the process includes annealing the CoPt magnetic layer. The CoPt magnetic layer can be annealed in a suitable forming gas at a suitable temperature and ramp rate for a period of time to induce a crystallographic ordering in the CoPt magnetic layer from the disordered A1 phase with a face-centered cubic structure to an ordered L10 equilibrium phase having a face-centered tetragonal structure. Again, based in part on the use of the TiN barrier layer and/or the Co or Pt metal seed layers, an improvement of the substrate/TiN/Ti/metal seed layer interface can be achieved after annealing, without (or with less) delamination, and with substantial improvements in the magnetic properties of the CoPt magnetic layer. Additional layers can also be deposited upon the CoPt magnetic layer for building MEMS devices, for example, or for other reasons. - Although embodiments have been described herein in detail, the descriptions are by way of example. The features of the embodiments described herein are representative and, in alternative embodiments, certain features and elements may be added or omitted. Additionally, modifications to aspects of the embodiments described herein may be made by those skilled in the art without departing from the spirit and scope of the present invention defined in the following claims, the scope of which are to be accorded the broadest interpretation so as to encompass modifications and equivalent structures.
Claims (17)
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US15/404,716 US10614953B2 (en) | 2016-01-12 | 2017-01-12 | Mitigation of contamination of electroplated cobalt-platinum films on substrates |
US16/801,978 US11532433B2 (en) | 2016-01-12 | 2020-02-26 | Method of manufacturing electroplated cobalt-platinum films on substrates |
US17/663,737 US20220277896A1 (en) | 2016-01-12 | 2022-05-17 | Mitigation of contamination of electroplated cobalt-platinum films on substrates |
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US11532433B2 (en) | 2022-12-20 |
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