WO2002009158A2 - Structure semi-conductrice comportant une jonction a effet tunnel magnetique - Google Patents

Structure semi-conductrice comportant une jonction a effet tunnel magnetique Download PDF

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Publication number
WO2002009158A2
WO2002009158A2 PCT/US2001/022659 US0122659W WO0209158A2 WO 2002009158 A2 WO2002009158 A2 WO 2002009158A2 US 0122659 W US0122659 W US 0122659W WO 0209158 A2 WO0209158 A2 WO 0209158A2
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layer
monocrystalline
oxide
group
ferromagnetic
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PCT/US2001/022659
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English (en)
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WO2002009158A3 (fr
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Kurt Eisenbeiser
Jeffrey M. Finder
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Motorola, Inc.
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Priority to AU2001276980A priority Critical patent/AU2001276980A1/en
Publication of WO2002009158A2 publication Critical patent/WO2002009158A2/fr
Publication of WO2002009158A3 publication Critical patent/WO2002009158A3/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
    • 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
    • H01F10/32—Spin-exchange-coupled multilayers, e.g. nanostructured superlattices
    • H01F10/3213—Exchange coupling of magnetic semiconductor multilayers, e.g. MnSe/ZnSe superlattices
    • 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
    • H01F10/32—Spin-exchange-coupled multilayers, e.g. nanostructured superlattices
    • H01F10/324—Exchange coupling of magnetic film pairs via a very thin non-magnetic spacer, e.g. by exchange with conduction electrons of the spacer
    • H01F10/3254—Exchange coupling of magnetic film pairs via a very thin non-magnetic spacer, e.g. by exchange with conduction electrons of the spacer the spacer being semiconducting or insulating, e.g. for spin tunnel junction [STJ]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/51—Insulating materials associated therewith
    • H01L29/516—Insulating materials associated therewith with at least one ferroelectric layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B61/00—Magnetic memory devices, e.g. magnetoresistive RAM [MRAM] devices
    • 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
    • H10N50/10—Magnetoresistive devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N59/00—Integrated devices, or assemblies of multiple devices, comprising at least one galvanomagnetic or Hall-effect element covered by groups H10N50/00 - H10N52/00

Definitions

  • the present invention relates generally to compound semiconductor structures and devices and to a method for their fabrication, and more specifically to magnetic tunnel junction (MTJ) structures and devices and to the fabrication of MTJ devices on a monocrystalline semiconductor substrate .
  • MTJ magnetic tunnel junction
  • Magnetic tunnel junction (MTJ) devices have several applications in the microelectronics industry.
  • MTJ devices can be used to form magnetic nonvolatile memory elements, magnetic field sensors, and the like.
  • MTJ devices generally include two ferromagnetic layers separated by a thin insulating layer.
  • the MTJ devices are often fabricated by forming the ferromagnetic and insulating layers over strontium titanate substrates.
  • Such substrates are relatively expensive and are generally available only in relatively small forms (e . g. , substrates having a diameter less than about two inches) .
  • the performance of MTJ devices typically increases as the crystallinity of the ferromagnetic film increases .
  • an amount of change of resistance per amount of magnetic field applied to a ferromagnetic layer for a monocrystalline ferromagnetic material is typically higher than that of the same material in polycrystalline or amorphous form.
  • sharp interfaces between the insulating and ferromagnetic layers tend to improve performance of the MTJ device by reducing the noise of the device. Accordingly, methods for forming monocrystalline ferromagnetic and insulating materials, having sharp interfaces, on a substrate are desirable.
  • a large area thin film of high quality monocrystalline ferromagnetic material was available at low cost, a variety of semiconductor devices could advantageously be fabricated using that film at a low cost compared to the higher cost of fabricating such devices on strontium titanate substrates.
  • a thin film of high quality monocrystalline ferromagnetic material could be realized on a bulk wafer such as a silicon wafer, an integrated device structure could be achieved that took advantage of the best properties of both the silicon and the ferromagnetic material.
  • FIGS. 1 - 3 illustrate schematically, in cross section, device structures in accordance with various embodiments of the invention
  • FIG. 4 illustrates graphically the relationship between maximum attainable film thickness and lattice mismatch between a host crystal and a grown crystalline overlayer
  • FIG. 5 illustrates schematically, in cross-section, a magnetic tunnel junction fabricated on a monocrystalline semiconductor substrate
  • FIG 6 illustrates schematically, in cross-section, a magnetic tunnel junction stack fabricated on a monocrystalline semiconductor substrate
  • FIG. 7 illustrates schematically, in cross-section, the device of FIG. 6 illustrating a template layer
  • FIG. 8 illustrates schematically, in cross-section, the device of FIG. 6 illustrating monolithic integration between the magnetic tunnel junction and an integrated logic element formed in the monocrystalline semiconductor substrate;
  • FIGS. 9-18 illustrate schematically, in cross- section, additional device structures in accordance with various embodiments of the invention.
  • FIG. 1 illustrates schematically, in cross section, a portion of a microelectronic structure 20 in accordance with an embodiment of the invention.
  • Microelectronic structure 20 includes a monocrystalline substrate 22, an accommodating buffer layer 24 comprising a monocrystalline material, and a layer 26 of ferromagnetic material, which is preferably monocrystalline.
  • the term "monocrystalline” shall have the meaning commonly used within the semiconductor industry.
  • the term shall refer to materials that are a single crystal or that are substantially a single crystal and shall include those materials having a relatively small number of defects such as dislocations and the like as are commonly found in substrates of silicon or germanium or mixtures of silicon and germanium and epitaxial layers of such materials commonly found in the semiconductor industry.
  • structure 20 also includes an amorphous intermediate layer 28 positioned between substrate 22 and accommodating buffer layer 24.
  • Structure 20 may also include a template layer 30 between the accommodating buffer layer and ferromagnetic material layer 26.
  • the template layer helps to initiate the growth of the ferromagnetic material layer on the accommodating buffer layer.
  • the amorphous intermediate layer helps to relieve the strain in the accommodating buffer layer and, by doing so, aids in the growth of a high crystalline quality accommodating buffer layer.
  • Substrate 22 in accordance with an embodiment of the invention, is a monocrystalline semiconductor wafer, preferably of large diameter.
  • the wafer can be of a material from Group IV of the periodic table, and preferably a material from Group IVA.
  • Group IV semiconductor materials include silicon, germanium, mixed silicon and germanium, mixed silicon and carbon, mixed silicon, germanium and carbon, and the like.
  • Substrate 22 can also be of a compound semiconductor material .
  • the compound semiconductor material of substrate 22 can be selected, as needed for a particular semiconductor structure, from any of the Group IIIA and VA elements (III-V semiconductor compounds) , mixed III-V compounds, Group II (A or B) and VIA elements (II-VI semiconductor compounds), and mixed II-VI compounds.
  • Examples include gallium arsenide (GaAs) , gallium indium arsenide (GalnAs) , gallium aluminum arsenide (GaAlAs) , indium phosphide (InP) , cadmium sulfide (CdS) , cadmium mercury telluride (CdHgTe) , zinc selenide (ZnSe) , zinc sulfur selenide (ZnSSe) , and the like.
  • GaAs gallium arsenide
  • GaAs gallium indium arsenide
  • GaAlAs gallium aluminum arsenide
  • InP indium phosphide
  • CdS cadmium sulfide
  • CdHgTe cadmium mercury telluride
  • ZnSe zinc selenide
  • ZnSSe zinc sulfur selenide
  • substrate 22 is a wafer containing silicon or germanium, and most preferably is a high quality monocrystalline silicon wafer as used in the semiconductor industry.
  • Accommodating buffer layer 24 is preferably a monocrystalline oxide or nitride material epitaxially grown on the underlying substrate .
  • amorphous intermediate layer 28 is grown on substrate 22 at the interface between substrate 22 and the growing accommodating buffer layer by the oxidation of substrate 22 during the growth of layer 24. The amorphous intermediate layer serves to relieve strain that might otherwise occur in the monocrystalline accommodating buffer layer as a result of differences in the lattice constants of the substrate and the buffer layer.
  • lattice constant refers to the distance between atoms of a cell measured in the plane of the surface. If such strain is not relieved by the amorphous intermediate layer, the strain may cause defects in the crystalline structure of the accommodating buffer layer. Defects in the crystalline structure of the accommodating buffer layer, in turn, would make it difficult to achieve a high quality crystalline structure in ferromagnetic material layer 26.
  • Accommodating buffer layer 24 is preferably a monocrystalline oxide or nitride material selected for its crystalline compatibility with the underlying substrate and with the overlying metallic oxide material.
  • the material could be an oxide or nitride having a lattice structure substantially matched to the substrate and to the subsequently applied ferromagnetic material.
  • Materials that are suitable for the accommodating buffer layer include metal oxides such as the alkaline earth metal titanates, alkaline earth metal zirconates, alkaline earth metal hafnates, alkaline earth metal tantalates, alkaline earth metal ruthenates, alkaline earth metal niobates, alkaline earth metal vanadates, perovskite oxides such as alkaline earth metal tin-based perovskites, lanthanum aluminate, lanthanum scandium oxide, and gadolinium oxide. Additionally, various nitrides such as gallium nitride, aluminum nitride, and boron nitride may also be used for the accommodating buffer layer.
  • metal oxides such as the alkaline earth metal titanates, alkaline earth metal zirconates, alkaline earth metal hafnates, alkaline earth metal tantalates, alkaline earth metal ruthenates, alkaline earth metal niobates, alkaline earth metal vanadates
  • these materials are insulators, although strontium ruthenate, for example, is a conductor.
  • these materials are metal oxides or metal nitrides, and more particularly, these metal oxide or nitrides typically include at least two different metallic elements and have a perovskite crystal lattice structure. In some specific applications, the metal oxides or nitride may include three or more different metallic elements .
  • Amorphous interface layer 28 is preferably an oxide formed by the oxidation of the surface of substrate 22, and more preferably is composed of a silicon oxide.
  • the thickness of layer 28 is sufficient to relieve strain attributed to mismatches between the lattice constants of substrate 22 and accommodating buffer layer 24.
  • layer 28 has a thickness in the range of approximately 0.5-5 nm.
  • the ferromagnetic material of layer 26 can be selected, as desired for a particular structure or application.
  • Exemplary materials suitable for ferromagnetic material layer 26 include a general chemical formula of (A ⁇ B ⁇ ) C0 3 where x ranges from 0 to 1 and where A is lanthanum or neodymium, B is strontium, barium, calcium, or lead, and .C is Mn, (Mn y Co 1 _ y ) or (Mn-Ni ⁇ where y and z are greater than zero and less than one.
  • Suitable template materials chemically bond to the surface of the accommodating buffer layer 24 at selected sites and provide sites for the. nucleation of the epitaxial growth of the subsequent ferromagnetic material layer 26.
  • template layer 30 has a thickness ranging from about one to about ten monolayers .
  • FIG. 2 illustrates, in cross section, a portion of a microelectronic structure 40 in accordance with a further embodiment of the invention.
  • Structure 40 is similar to the previously described structure 20, except that an additional insulating layer 32 is positioned above ferromagnetic material 26 and a second additional layer of ferromagnetic material 33 is formed over insulating layer 32.
  • Insulating material suitable for layer 32 may include any insulating material listed above in connection with accommodating buffer layer 24, and ferromagnetic material layer 33 may include any ferromagnetic material listed above in connection with layer 26.
  • Layer 33 is typically about 1-6 nm and preferably less than about 2.5 nm.
  • Structure 34 is similar to structure 40, except that structure 34 includes an amorphous layer 36, rather than accommodating buffer layer 24 and amorphous interface layer 28.
  • amorphous layer 36 may be formed by first forming an accommodating buffer layer and an amorphous interface layer in a similar manner to that described above. The accommodating buffer layer is then exposed to an anneal process to convert the monocrystalline accommodating buffer layer to an amorphous layer.
  • Amorphous layer 36 formed in this manner comprises materials from both the accommodating buffer and interface layers, which amorphous layers may or may not amalgamate. Thus, layer 36 may comprise one or two amorphous layers. Formation of amorphous layer 36 between substrate 22 and additional buffer layer 32 (subsequent to layer 32 formation) relieves stresses between layers 22 and 32 and provides a true compliant substrate for subsequent processing--e.gr., ferromagnetic material layer 26 formation.
  • layer 30 serves as an anneal cap during layer 36 formation and as a template for subsequent ferromagnetic material layer 26 formation. Accordingly, layer 30 is preferably thick enough to provide a suitable template for layer 26 growth (at least one monolayer) and thin enough to allow layer 30 to form as a substantially defect free monocrystalline layer (often less than about ten monolayers) .
  • monocrystalline substrate 22 is a silicon substrate oriented in the (100) direction.
  • the silicon substrate can be, for example, a silicon substrate as is commonly used in making complementary metal oxide semiconductor (CMOS) integrated circuits having a diameter of about 200-300 mm.
  • accommodating buffer layer 24 is a monocrystalline layer of Sr g Ba 1 . g Ti0 3 and the amorphous intermediate layer is a layer of silicon oxide (SiO x ) formed at the interface between the silicon substrate and the accommodating buffer layer.
  • the composition of layer 24 is selected to obtain one or more lattice constants closely matched to corresponding lattice constants of the subsequently formed layer 26.
  • the accommodating buffer layer can have a thickness of about 2 to about 100 nm and preferably has a thickness of about 10 nm. In general, it is desired to have an accommodating buffer layer thick enough to isolate the ferromagnetic layer from the substrate to obtain the desired properties. Layers thicker than 100 nm usually provide little additional benefit while increasing cost unnecessarily; however, thicker layers may be fabricated if needed.
  • the amorphous intermediate layer of silicon oxide can have a thickness of about 0.5-5 nm, and preferably a thickness of about 1.5-2.5 nm.
  • ferromagnetic material layer 26 is a layer of LaSrMn0 3 having a thickness of about 5 nm to about 500 and preferably a thickness of about 20 nm to about 70 n .
  • the thickness generally depends on the application for which the layer is being prepared.
  • a structure is provided that is suitable for MTJ applications.
  • the substrate is preferably a silicon wafer as described above.
  • a suitable accommodating buffer layer material is Sr g Ba 1 . g Ti0 3 , where g ranges from zero to one, having a thickness of about 2-100 nm and preferably a thickness of about 5-15 nm.
  • the ferromagnetic material can be, for example LaSrMn0 3 , and layers 26 and 33 thickness can be about 5 nm to about 500 and preferably about 20 nm to about 70 nm.
  • Layer 32, which is interposed between ferromagnetic layers 26 and 33 includes Sr g Ba 1 . g Ti0 3 , where g ranges from zero to one, having a thickness of about 2.5 nm.
  • substrate 22 is a monocrystalline substrate such as a monocrystalline silicon or gallium arsenide substrate.
  • the crystalline structure of the monocrystalline substrate is characterized by a lattice constant and by a lattice orientation.
  • accommodating buffer layer 24 is also a monocrystalline material and the lattice of that monocrystalline material is characterized by a lattice constant and a crystal orientation.
  • the lattice constants of the accommodating buffer layer and the monocrystalline substrate must be closely matched or, alternatively, must be such that upon rotation of one crystal orientation with respect to the other crystal orientation, a substantial match in lattice constants is achieved.
  • the terms "substantially equal” and “substantially matched” mean that there is sufficient similarity between the lattice constants to permit the growth of a high quality crystalline layer on the underlying layer .
  • FIG. 4 graphically illustrates the relationship of the achievable thickness of a grown crystal layer of high crystalline quality as a function of the mismatch between the lattice constants of the host crystal and the grown crystal.
  • Curve 42 illustrates the boundary of high crystalline quality material. The area to the right of curve 42 represents layers that has a large number of defects. With no lattice mismatch, it is theoretically possible to grow an infinitely thick, high quality epitaxial layer on the host crystal . As the mismatch in lattice constants increases, the thickness of achievable, high quality crystalline layer decreases rapidly.
  • substrate 22 is a (100) or (111) oriented monocrystalline silicon wafer and accommodating buffer layer 24 is a layer of strontium barium titanate. Substantial matching of lattice constants between these two materials is achieved by rotating the crystal orientation of the titanate material by 45° with respect to the crystal orientation of the silicon substrate wafer.
  • a silicon oxide layer in this example serves to reduce strain in the titanate monocrystalline layer that might result from any mismatch in the lattice constants of the host silicon wafer and the grown titanate layer.
  • a high quality, thick, monocrystalline titanate layer is achievable.
  • layers 26 and 33 are layers of epitaxially grown ferromagnetic material and that crystalline material is also characterized by a crystal lattice constant and a crystal orientation.
  • the lattice constant of layer 26 differs from the lattice constant of substrate 22.
  • the accommodating buffer layer must be of high crystalline quality.
  • substantial matching between the crystal lattice constant of the host crystal, in this case, the monocrystalline accommodating buffer layer, and the grown crystal is desired.
  • a crystalline buffer layer between the host oxide and the grown metallic oxide layer can be used to reduce strain in the grown monocrystalline ferromagnetic material layer that might result from small differences in lattice constants. Better crystalline quality in the grown monocrystalline ferromagnetic material layer can thereby be achieved.
  • Insulating layer 32 is also characterized by a crystal lattice constant and a crystal orientation.
  • insulating material 32 is selected such that it can be orientates such that a lattice constant of layer 32 substantially matches the lattice constants for layers 26 and 33.
  • the following example illustrates a process, in accordance with one embodiment of the invention, for fabricating a microelectronic structure such as the structures depicted in FIGS. 1 - 3. The process starts by providing a monocrystalline semiconductor substrate comprising silicon.
  • the semiconductor substrate is a silicon wafer having a (100) orientation.
  • the substrate is preferably oriented on axis or, at most, about 0.5° off axis.
  • At least a portion of the semiconductor substrate has a bare surface, although other portions of the substrate, as described below, may encompass other structures.
  • bare in this context means that the surface in the portion of the substrate has been cleaned to remove any oxides, contaminants, or other foreign material.
  • bare silicon is highly reactive and readily forms a native oxide.
  • the term "bare” is intended to encompass such a native oxide.
  • a thin silicon oxide may also be intentionally grown on the semiconductor substrate, although such a grown oxide is not essential to the process in accordance with the invention.
  • the native oxide layer In order to epitaxially grow a monocrystalline oxide layer overlying the monocrystalline substrate, the native oxide layer must first be removed to expose the crystalline structure of the underlying substrate.
  • the following process is preferably carried out by molecular beam epitaxy (MBE) , although other epitaxial processes may also be used in accordance with the present invention.
  • the native oxide can be removed by first thermally depositing a thin layer of strontium, barium, a combination of strontium and barium, or other alkali earth metals or combinations of alkali earth metals in an MBE apparatus.
  • strontium is used, the substrate is then heated to a temperature of about 750° C to cause the strontium to react with the native silicon oxide layer.
  • the strontium serves to reduce the silicon oxide to leave a silicon oxide-free surface.
  • the resultant surface which exhibits an ordered 2x1 structure, includes strontium, oxygen, and silicon.
  • the ordered 2x1 structure forms a template for the ordered growth of an overlying layer of a monocrystalline oxide .
  • the template provides the necessary chemical and physical properties to nucleate the crystalline growth of an overlying layer.
  • the native silicon oxide can be converted and the substrate surface can be prepared for the growth of a monocrystalline oxide layer by depositing an alkali earth metal oxide, such as strontium oxide, strontium barium oxide, or barium oxide, onto the substrate surface by MBE at a low temperature and by subsequently heating the structure to a temperature of about 750°C. At this temperature, a solid state reaction takes place between the strontium oxide and the native silicon oxide, causing the reduction of the native silicon oxide and leaving an ordered 2x1 structure with strontium, oxygen, and silicon remaining on the substrate surf ce. Again, this forms a template for the subsequent growth of an ordered monocrystalline oxide layer.
  • an alkali earth metal oxide such as strontium oxide, strontium barium oxide, or barium oxide
  • the substrate is cooled to a temperature in the range of about 200-800°C and a layer of strontium titanate is grown on the template layer by molecular beam epitaxy.
  • the MBE process is initiated by opening shutters in the MBE apparatus to expose strontium, titanium and oxygen sources .
  • the ratio of strontium and titanium is approximately 1:1.
  • the partial pressure of oxygen is initially set at a minimum value to grow stochiometric strontium titanate at a growth rate of about 0.3-0.5 nm per minute. After initiating growth of the strontium titanate, the partial pressure of oxygen is increased above the initial minimum value.
  • the overpressure of oxygen causes the growth of an amorphous silicon oxide layer at the interface between the underlying substrate and the growing strontium titanate layer.
  • the growth of the silicon oxide layer results from the diffusion of oxygen through the growing strontium titanate layer to the interface where the oxygen reacts with silicon at the surface of the underlying substrate .
  • the strontium titanate grows as an ordered monocrystal with the crystalline orientation rotated by 45° with respect to the ordered 2x1 crystalline structure of the underlying substrate. Strain that otherwise might exist in the strontium titanate layer because of the small mismatch in lattice constant between the silicon substrate and the growing crystal is relieved in the amorphous silicon oxide intermediate layer.
  • the monocrystalline strontium titanate may be capped by a template layer that is conducive to the subsequent growth of an epitaxial layer of a desired material.
  • the MBE growth of the strontium titanate monocrystalline layer can be capped by terminating the growth with 1-2 monolayers of titanium, 1- 2 monolayers of titanium-oxygen or with 1-2 monolayers of strontium-oxygen.
  • the ferromagnetic material is grown using MBE or other suitable techniques.
  • the structure illustrated in FIG. 2 can be formed by the process discussed above with the addition of an insulating layer deposition step.
  • Insulating material for layer 32 may be epitaxially formed over layer 26 using the method described above in connection with layer 24 formation, with the exception that an amorphous interface layer is preferably not formed between layer 26 and layer 32. Accordingly, the insulating layer is preferably formed using condition that favor stochiometric growth of layer 26.
  • Structure 34 may be formed by growing an accommodating buffer layer, forming an amorphous oxide layer over substrate 22 as described above .
  • the accommodating buffer layer and the amorphous oxide layer are then exposed to an anneal process sufficient to change the crystalline structure of the accommodating buffer layer from monocrystalline to amorphous, thereby forming an amorphous layer such that the combination of the amorphous oxide layer and the now amorphous accommodating buffer layer form a single amorphous oxide layer 36.
  • Layer 26 is then subsequently grown over layer 32.
  • the anneal process may be carried out subsequent to growth of layer 26.
  • layer 36 is formed by exposing substrate 22, the accommodating buffer layer, the amorphous oxide layer, and layer 30 or a suitable cap layer to a rapid thermal anneal process with a peak temperature of about 700°C to about 1000°C and a process time of about 10 seconds to about 10 minutes.
  • a rapid thermal anneal process with a peak temperature of about 700°C to about 1000°C and a process time of about 10 seconds to about 10 minutes.
  • other suitable anneal processes may be employed to convert the accommodating buffer layer to an amorphous layer in accordance with the present invention.
  • laser annealing or "conventional" thermal annealing processes may be used to form layer 36.
  • Ferromagnetic layer 52 e . g.
  • (La ⁇ r ⁇ ) Mn0 3 is epitaxially grown using sputter deposition. More particularly, the (La k Sr x _ k )Mn0 3 layer is grown by RF magnetron sputtering (face to face configuration) from a (La k Sr x _ k )Mn0 3 target. The deposition is performed with oxygen as sputter gas, and a substrate temperature of about 400 °C.
  • the process described above illustrates a process for forming a semiconductor structure including a silicon substrate, an overlying oxide layer, and a ferromagnetic material layer by the processes of molecular beam epitaxy and RF sputtering.
  • the process can also be carried out by the process of chemical vapor deposition (CVD) , metal organic chemical vapor deposition (MOCVD) , migration enhanced epitaxy (MEE) , atomic layer epitaxy (ALE) , physical vapor deposition (PVD) , chemical solution deposition (CSD) , pulsed laser deposition (PLD) , or the like.
  • CVD chemical vapor deposition
  • MOCVD metal organic chemical vapor deposition
  • MEE migration enhanced epitaxy
  • ALE atomic layer epitaxy
  • PVD physical vapor deposition
  • CSSD chemical solution deposition
  • PLD pulsed laser deposition
  • monocrystalline accommodating buffer layers such as alkaline earth metal titanates, zirconates, hafnates, tantalates, vanadates, ruthenates, and niobates, peroskite oxides such as alkaline earth metal tin-based perovskites, lanthanum aluminate, lanthanum scandium oxide, and gadolinium oxide can also be grown.
  • other metallic oxide layers can be deposited overlying the monocrystalline oxide accommodating buffer layer and/or the ferromagnetic layer.
  • Each of the variations of ferromagnetic material and monocrystalline oxide layers may use an appropriate template for initiating the growth of the respective layer.
  • FIG. 5 illustrates schematically, in cross-section, a semiconductor structure 90 in accordance with the present invention.
  • Semiconductor structure 90 includes a monocrystalline semiconductor substrate 92, a monocrystalline insulator layer 94 overlying substrate 92, and a magnetic tunnel junction device 96 overlying the insulator layer.
  • insulator layer 94 is a monocrystalline oxide layer epitaxially grown over the substrate.
  • FIG. 6 illustrates schematically, in cross-section, a semiconductor structure 98 generally analogous to the structure shown in FIG. 5.
  • FIG. 5 illustrates schematically, in cross-section, a semiconductor structure 98 generally analogous to the structure shown in FIG. 5.
  • first layer 100 and third layer 104 are capable of exhibiting ferromagnetic properties.
  • first layer 100 and second layer 102 may be epitaxially grown on their respective underlying layers.
  • second layer 102 is advantageously a monocrystalline insulator layer.
  • one or both of first layer 100 and third layer 104 may also be monocrystalline layers.
  • substrate 92 is silicon.
  • Insulator layer 94 is preferably a monocrystalline material selected from the group consisting of metal oxides and metal nitrides . More particularly, insulating layer 94 is preferably selected from the following materials: alkali earth metal titanates, zirconates, hafnates, tantalates, ruthenates, niobates and vanadates, perovskites including tin based perovskites, lanthanum aluminate, lanthanum scandium oxide, gadolinium oxide, gallium nitride, and aluminum nitride .
  • first layer 100 is preferably a monocrystalline oxide, for example, a manganite perovskite, but may be made from any suitable material having a composition (A,B)C0 3 where A is selected form the group consisting of lanthanum and neodymium, B is selected from the group consisting of strontium, barium, calcium, and lead, and C is selected from the group consisting of Mn, (Mn,Co), and (Mn,Ni) .
  • A is selected form the group consisting of lanthanum and neodymium
  • B is selected from the group consisting of strontium, barium, calcium, and lead
  • C is selected from the group consisting of Mn, (Mn,Co), and (Mn,Ni) .
  • Third layer 104 is preferably a monocrystalline oxide, for example, a manganite perovskite, but may also be made from any of the materials described above in connection with first layer 100.
  • Second insulator layer 102 is preferably a monocrystalline oxide having a thickness in the range of 1 to 6 nm, and is preferably lattice matched to first layer 100. In a particularly preferred embodiment, second insulator layer 102 is at a thickness less than about 2.5 nm and is lattice matched within about four percent to first layer 100.
  • second insulator layer 102 is preferably configured to provide an atomically sharp interface with first layer 100.
  • Second insulator layer 102 may be made from a material selected from the group consisting of alkali earth metal titanites, zirconates, hafnates, tantalates, ruthenates, niobates and vanadates, perovskites including tin based perovskites, lanthanum aluminate, lanthanum scandium oxide, and gadolinium oxide.
  • first layer 100, second layer 102, and third layer 104 may be patterned to form, at least in part, a magnetic tunnel junction device in accordance with generally known fabrication techniques.
  • a magnetic tunnel junction device By fabricating a magnetic tunnel junction device on a monocrystalline [ e . g. , silicon) substrate 92 in accordance with the present invention, substantially reduced cost may be realized by the scalability afforded by monocrystalline substrate 92.
  • FIG. 7 illustrates schematically, in cross-section, a semiconductor structure 106 similar to structure 98 shown in FIG. 6, but also including a template 118 overlying insulator layer 94.
  • Template layer 118 advantageously terminates insulator layer 94 and may be made from oxygen and an element selected from strontium, barium, calcium, or lead.
  • Template layer 118 is preferably in the range of 1 to 10 monolayers in thickness.
  • FIG. 8 illustrates schematically, in cross-section, a semiconductor structure 110 generally analogous to the structures shown in FIGS. 5 - 7, and further illustrating an integrated logic element 130, such as a metal oxide semiconductor (e. g. , CMOS) circuit formed at least partially in substrate 92.
  • logic element 130 may be electrically connected to the magnetic tunnel junction by an interconnection 108.
  • interconnection 108 connects logic element 130 to second layer 102.
  • FIG. 9 illustrates schematically, in cross-section, a semiconductor structure 112 generally analogous to that shown in FIGS . 5 - 8.
  • Semiconductor 112 includes a strain relief layer 114, for example, an amorphous oxide layer underlying insulator layer 94.
  • amorphous oxide layer 114 is generally analogous to intermediate layer 28 discussed above in connection with FIGS. 1 and 2.
  • FIG. 10 illustrates schematically, in cross-section, a semiconductor structure 116 generally analogous to structure 98 of FIG. 6.
  • Semiconductor structure 116 includes magnetic tunnel junction 96 sandwiched between a first electrical contact layer 120 formed underlying and electrically contacting first layer 100, and a second electrical contact layer 122 overlying and electrically contacting third layer 104.
  • layers 120 and 122 preferably comprise a monocrystalline electrically conductive oxide layer, and be made from a material selected from the group consisting of (La k Sr 1 . k ) Co0 3 , SrRu0 3 , SrCr0 3 , and SrV0 3/ , where k is greater than zero and less than one .
  • FIG. 11 illustrates schematically, in cross-section, a semiconductor structure 124 including a monocrystalline semiconductor (e . g. , silicon) substrate 92, a monocrystalline oxide layer 94, preferably epitaxially grown overlying substrate 92, and a magnetic tunnel junction device 96.
  • Magnetic tunnel junction device 96 preferably includes a first layer 100 made of a monocrystalline ferromagnetic material, a second layer 102 made from a monocrystalline insulator material which overlies and forms an atomically sharp interface with first layer 100, and a third layer 104 made from a ferromagnetic material.
  • Second layer 102 is preferably sufficiently thin to allow carrier tunneling therethru.
  • Third layer 104 advantageously exhibits an ordered crystalline structure.
  • first layer 100, second layer 102, and third layer 104 are each monocrystalline materials epitaxially grown on their underlying layer.
  • Second layer 102 is preferably an electrically insulating oxide selected from the group consisting of alkali earth metal titanates, zirconates, hafnates, tantalates, ruthenates, niobates and vanadates, perovskites including tin based perovskites, lanthanum aluminate, lanthanum scandium oxide, and gadolinium oxide.
  • FIG. 12 illustrates schematically, in cross-section, a semiconductor structure 126 including substrate 92 having logical element 130 formed at least partially therein, insulating layer 94 and magnetic tunnel junction 96.
  • Semiconductor structure 126 further includes amorphous oxide layer 114, and an electrical interconnect 132 configured to electrically couple logic element 130 to layer 104.
  • Insulator layer 94 is preferably a monocrystalline oxide layer made from Sr g Ba 1 _ g Ti0 3 , where g ranges , from zero to one.
  • Monocrystalline layer 102 is preferably an oxide having a thickness in the range of 1 to 6 nm, and is advantageously lattice matched to within four percent of layer 100.
  • the various semiconductor structure illustrated and described herein may be fabricated using any of the processing techniques described above in connection with FIGS. 1-3. By fabricating the magnetic tunnel junction devices discussed herein on monocrystalline semiconductor substrate 92, monolithic integration between the magnetic tunnel junction structure and microelectronic structures associated with substrate 92 is enabled.
  • FIG. 13 illustrates schematically, in cross-section, an integrated magnetic tunnel junction circuit 140.
  • Semiconductor structure 140 includes a template layer 142 overlying substrate 92, as well as insulator layer 94.
  • amorphous oxide layer 114 is advantageously fabricated during the step of epitaxially growing insulator layer 94 on substrate 92.
  • a second template layer 144 may be advantageously fabricated on insulator layer 94.
  • Second template layer 144 facilitates the epitaxial growth of first ferromagnetic oxide layer 100.
  • second insulative oxide layer 102 is preferably epitaxially grown on first ferromagnetic oxide layer 100.
  • Semiconductor structure 140 of FIG. 13 illustrates the photolithographic patterning of first layer 100, second layer 102 and third layer 104 to permit the magnetic tunnel junction to be monolithically integrated with logic element 130 associated with substrate 92.
  • an electrical interconnect 134 provides electrical contact between logic element 130 and each of first layer 100 and third layer 104.
  • interconnect 134 is configured to contact an electrode 136 associated with third layer 104 and an electrode 138 associated with first layer 100.
  • the monocrystalline layers may be grown using any suitable process, including MBE, MOCVD, MEE, CVD, PVD, PLD, CSD, and ALE. Indeed, these techniques may be employed to grow any of the layers illustrated herein, as appropriate.
  • a template layer may be formed by terminating the growth of the underlying monocrystalline layer with 1 to 10 monolayers of oxygen and a material selected from the group consisting of strontium, barium, calcium and lead.
  • a preferred method of fabricating a magnetic tunnel junction structure 146 will now be described in conjunction with FIG. 14.
  • the monocrystalline silicon substrate 92 is first provided. Thereafter, a number of layers are sequentially deposited to form a semiconductor stack, using any combination of the deposition processes described herein.
  • insulator layer 94 comprising a layer of Sr g Ba 1 . g Ti0 3 , where g ranges from zero to one is deposited on substrate 92.
  • Ferromagnetic layer 100 is then deposited on insulator layer 94, ferromagnetic layer 100 is preferably a material of the composition (A,B)C0 3 where A is selected from the group consisting of lanthanum and neodymium, B is selected from the group consisting of strontium, barium, calcium and lead, and C is selected from the group consisting of Mn, (Mn,Co), and (Mn, Ni) .
  • Insulative tunnel oxide layer 102 is then deposited on layer 100.
  • Ferromagnetic layer 104 suitably of a material similar to that of layer 100, is then deposited on layer 102.
  • FIG. 15 illustrates schematically, in cross-section, a semiconductor structure 156 generally analogous to structure 146 of FIG. 14 further illustrating amorphous layer 114 and logic element 130 formed at least partially within substrate 92.
  • FIG. 16 illustrates schematically, in cross-section, a semiconductor structure 158 generally analogous to structure 146 of FIG. 14 further illustrating the step of patterning one or more of layers 100, 102, and 104 to thereby yield respective nodes 150, 152 and 154, which may correspond to any desired combination of voltage or current nodes.
  • patterning one or more of layers 100, 102 and 104 may produce a magnetic tunnel junction device of any desired configuration.
  • FIG. 17 illustrates schematically, in cross-section, a semiconductor structure 160 generally analogous to structure 158 of FIG. 16, further including the additional step of depositing a layer of conductive material 180 and patterning layer 180 to produce respective nodes 164, 166 and 168.
  • an interconnect 170 is suitably fabricated into semiconductor structure 160 to connect one or more of nodes ( e . g. , electrodes) 164-168 with logic element 130.
  • the processes and structures shown in FIGS. 12-17 illustrate, inter alia, the advantages of fabricating magnetic tunnel junction devices on a monocrystalline semiconductor substrate to thereby enable the monolithic integration of magnetic tunnel junction devices with logic elements associated with the substrate.
  • FIG. 12-17 illustrate, inter alia, the advantages of fabricating magnetic tunnel junction devices on a monocrystalline semiconductor substrate to thereby enable the monolithic integration of magnetic tunnel junction devices with logic elements associated with the substrate.
  • Conductive oxide layer 172 is preferably fabricated by the step of depositing a material selected from the group consisting of (La k Sr ⁇ Co0 3 , SrRu0 3 , SrCr0 3 , and SrV0 3 , where k is greater than zero and less than one.
  • the terms "comprises,” “comprising, “ or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

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Abstract

L'invention concerne des couches épitaxiales de haute qualité de matériaux ferromagnétiques pouvant être développées sur de grandes tranches de silicium (22), en développant premièrement une couche tampon d'accommodation (24) sur une galette de silicium. La couche tampon d'accommodation est composée d'oxyde monocristallin séparée de la tranche de silicium par une couche interface amorphe (28) d'oxyde de silicium. Ladite couche interface amorphe dissipe la déformation et permet de développer une couche tampon d'accommodation d'oxyde monocristallin de haute qualité. Tout décalage entre la couche tampon d'accommodation et le substrat de silicium sous-jacent est atténué grâce à la couche interface amorphe. Cette technique permet de fabriquer des appareils (96) en utilisant des matériaux ferromagnétiques sur un substrat semi-conducteur monocristallin. Le procédé de la présente invention permet en particulier de réaliser des appareils de jonction à effet tunnel magnétique sur du silicium.
PCT/US2001/022659 2000-07-24 2001-07-18 Structure semi-conductrice comportant une jonction a effet tunnel magnetique WO2002009158A2 (fr)

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US6759081B2 (en) 2001-05-11 2004-07-06 Asm International, N.V. Method of depositing thin films for magnetic heads
US7037574B2 (en) 2001-05-23 2006-05-02 Veeco Instruments, Inc. Atomic layer deposition for fabricating thin films
US7494927B2 (en) 2000-05-15 2009-02-24 Asm International N.V. Method of growing electrical conductors
US9607842B1 (en) 2015-10-02 2017-03-28 Asm Ip Holding B.V. Methods of forming metal silicides
US9634106B2 (en) 2008-12-19 2017-04-25 Asm International N.V. Doped metal germanide and methods for making the same
US10553440B2 (en) 2008-12-19 2020-02-04 Asm International N.V. Methods for depositing nickel films and for making nickel silicide and nickel germanide

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US8025922B2 (en) 2005-03-15 2011-09-27 Asm International N.V. Enhanced deposition of noble metals
CN111816760B (zh) * 2019-04-11 2023-07-14 上海磁宇信息科技有限公司 一种磁性随机存储器磁性存储单元及其形成方法

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Publication number Priority date Publication date Assignee Title
US7494927B2 (en) 2000-05-15 2009-02-24 Asm International N.V. Method of growing electrical conductors
WO2002045167A2 (fr) * 2000-11-30 2002-06-06 Asm International N.V. Films minces pour dispositifs magnetiques
WO2002045167A3 (fr) * 2000-11-30 2003-05-30 Asm Microchemistry Oy Films minces pour dispositifs magnetiques
US7220669B2 (en) 2000-11-30 2007-05-22 Asm International N.V. Thin films for magnetic device
KR100869326B1 (ko) * 2000-11-30 2008-11-18 에이에스엠 인터내셔널 엔.브이. 자기장치용 박막
US6759081B2 (en) 2001-05-11 2004-07-06 Asm International, N.V. Method of depositing thin films for magnetic heads
US7037574B2 (en) 2001-05-23 2006-05-02 Veeco Instruments, Inc. Atomic layer deposition for fabricating thin films
US9634106B2 (en) 2008-12-19 2017-04-25 Asm International N.V. Doped metal germanide and methods for making the same
US10553440B2 (en) 2008-12-19 2020-02-04 Asm International N.V. Methods for depositing nickel films and for making nickel silicide and nickel germanide
US10043880B2 (en) 2011-04-22 2018-08-07 Asm International N.V. Metal silicide, metal germanide, methods for making the same
US9607842B1 (en) 2015-10-02 2017-03-28 Asm Ip Holding B.V. Methods of forming metal silicides
US10199234B2 (en) 2015-10-02 2019-02-05 Asm Ip Holding B.V. Methods of forming metal silicides

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