CN117604623A - Hafnium tantalate monocrystal epitaxial film with modulation structure and preparation method thereof - Google Patents
Hafnium tantalate monocrystal epitaxial film with modulation structure and preparation method thereof Download PDFInfo
- Publication number
- CN117604623A CN117604623A CN202311575414.2A CN202311575414A CN117604623A CN 117604623 A CN117604623 A CN 117604623A CN 202311575414 A CN202311575414 A CN 202311575414A CN 117604623 A CN117604623 A CN 117604623A
- Authority
- CN
- China
- Prior art keywords
- single crystal
- hafnium
- hafnium tantalate
- epitaxial film
- zirconia
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 140
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title abstract description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000013078 crystal Substances 0.000 claims abstract description 122
- 239000000758 substrate Substances 0.000 claims abstract description 106
- 239000000919 ceramic Substances 0.000 claims abstract description 60
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 50
- 239000001301 oxygen Substances 0.000 claims abstract description 50
- 238000001816 cooling Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000013077 target material Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 27
- 238000005245 sintering Methods 0.000 claims description 22
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 19
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 7
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000008213 purified water Substances 0.000 claims description 6
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 32
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 238000011160 research Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 67
- 238000000151 deposition Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012720 thermal barrier coating Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000007373 indentation Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004098 selected area electron diffraction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
- C30B23/02—Epitaxial-layer growth
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
- C30B23/02—Epitaxial-layer growth
- C30B23/025—Epitaxial-layer growth characterised by the substrate
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
- C30B23/02—Epitaxial-layer growth
- C30B23/06—Heating of the deposition chamber, the substrate or the materials to be evaporated
- C30B23/063—Heating of the substrate
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/30—Niobates; Vanadates; Tantalates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6565—Cooling rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a hafnium tantalate monocrystal epitaxial film with a modulation structure and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a hafnium tantalate ceramic target and acid-treating the surface of a zirconia monocrystal substrate; heating the zirconia single crystal substrate to a first preset temperature and maintaining a first preset oxygen partial pressure; irradiating the surface of a hafnium tantalate ceramic target material by using excimer pulse laser; growing hafnium tantalate on the zirconia single crystal substrate to a preset thickness; and under the condition of a second preset oxygen partial pressure, adjusting the preset zirconia monocrystal substrate to a second preset temperature, carrying out in-situ annealing, and cooling to a third preset temperature to obtain the hafnium tantalate monocrystal epitaxial film. The method can realize epitaxial growth of the hafnium tantalate monocrystal film, and the obtained film has good ductility, single orientation characteristic, controllable thickness and surface flatness, and is beneficial to research on intrinsic performance of the hafnium tantalate material.
Description
Technical Field
The invention relates to the technical field of thermal protection, in particular to a hafnium tantalate monocrystal epitaxial film with a modulation structure and a preparation method thereof.
Background
The thermal barrier coating is an indispensable thermal protection technology of an advanced aeroengine, and extremely severe service environment brings extremely severe requirements on intrinsic thermal and mechanical properties of a coating material. This concept was first proposed by the united states aerospace agency in the twentieth century, 50, and so far only yttrium stabilized zirconia has been put to practical use, the root cause of which is the lack of thermal or mechanical properties of other materials. However, the YSZ material can generate tetragonal-monoclinic phase transformation at 1170 ℃ and is accompanied by 4% of volume strain and 7% of shear deformation, so that the coating is extremely easy to crack and fall off to fail, and therefore the YSZ material can not meet the service requirement of 1500 ℃ of the front air inlet of a new generation of aeroengine turbine, and development of a novel coating material is needed.
Among all the current thermal barrier coating ceramic materials, oxides of hafnium and tantalum generally show excellent high-temperature phase stability and mechanical properties, and the oxides of hafnium and tantalum can also form hafnium tantalate materials with modulated structures, and the chemical formula is Hf n Ta 2 O 2n+5 (n=4-10), the special modulation structure can promote lattice distortion, so that the crystal lattice is a typical high-entropy oxide, the phonon scattering probability is increased, and the material thermal conductivity is reduced; the high-temperature stability of the material can be further improved, so that the material has no phase change at room temperature to 2250 ℃, and the temperature is improved by more than 1000 ℃ compared with YSZ material; meanwhile, the material has wider component window, and can form a series of structural formulas of Hf along with the change of the ratio of hafnium to tantalum n Ta 2 O 2n+5 Hafnium tantalate material (n=4-10), which has a significant advantageous variation compared to YSZ (6-8% wt Y)The method comprises the steps of carrying out a first treatment on the surface of the Furthermore, hafnium tantalate also exhibits excellent mechanical toughness, which is far higher than other coating materials, even comparable to YSZ, especially hafnium tantalate also maintains 0.5 MPa-m at 1600 ℃ 1/2 Fracture toughness of (C). It can be seen that the high-toughness high-temperature-resistant hafnium tantalate material is an ideal material system for preparing advanced thermal barrier coatings.
The preparation method of the hafnium tantalate material mainly comprises the following steps: the materials prepared by the method all have polycrystalline characteristics, and the influence of factors such as pores, defects, grain boundaries and the like on thermal and mechanical properties of the materials cannot be avoided. The monocrystal is an optimal carrier for researching the intrinsic property of the material, and in order to reveal the excellent intrinsic thermal and mechanical properties of the hafnium tantalate material, the development of a monocrystal film preparation method of the material is needed, so that an ideal carrier can be provided for researchers to explore the origin of the high-toughness high-temperature-resistant property of the hafnium tantalate material, and theoretical guidance and experimental support can be provided for further perfecting the regulation and control mechanism of the hafnium tantalate thermal barrier coating.
Therefore, how to prepare a single crystal material of hafnium tantalate becomes a problem to be solved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a hafnium tantalate monocrystal epitaxial film with a modulation structure and a preparation method thereof. The technical problems to be solved by the invention are realized by the following technical scheme:
a method for preparing a hafnium tantalate single crystal epitaxial film with a modulated structure, the method comprising:
preparing a hafnium tantalate ceramic target;
treating the surface of the zirconia single crystal substrate by using acid to obtain a clean zirconia single crystal substrate;
heating the clean zirconia single crystal substrate to a first preset temperature and maintaining a first preset oxygen partial pressure;
shielding a clean zirconia single crystal substrate, and radiating the surface of the hafnium tantalate ceramic target material by using excimer pulse laser;
removing the shielding of the clean zirconia single crystal substrate to grow hafnium tantalate to a preset thickness on the clean zirconia single crystal substrate, so as to obtain a preset hafnium tantalate single crystal epitaxial film;
and under the condition of a second preset oxygen partial pressure, adjusting the preset zirconia monocrystal substrate to a second preset temperature, carrying out in-situ annealing, and cooling to a third preset temperature to obtain the hafnium tantalate monocrystal epitaxial film, wherein the second preset oxygen partial pressure is larger than the first preset oxygen partial pressure, and the crystal orientation of the hafnium tantalate monocrystal epitaxial film is kept consistent with that of the zirconia monocrystal substrate.
In one embodiment of the invention, a hafnium tantalate ceramic target is prepared comprising:
mixing hafnium oxide powder and tantalum oxide powder to obtain a uniformly mixed oxide mixture;
sintering the oxide mixture for the first time, and then cooling to room temperature to obtain a sintered oxide mixture;
pressing the sintered oxide mixture into a sheet shape at room temperature to obtain a ceramic sheet;
and (3) sintering the ceramic sheet for the second time, and then cooling to room temperature to obtain the hafnium tantalate ceramic target.
In one embodiment of the invention, the oxide mixture is subjected to a first sintering step, after which the temperature is reduced to room temperature, resulting in a sintered oxide mixture comprising:
and (3) sintering the oxide mixture for the first time at 1300-1500 ℃ for 12-24 hours, and then cooling to room temperature to obtain the sintered oxide mixture.
In one embodiment of the present invention, the ceramic wafer is sintered for the second time, and then the temperature is reduced to room temperature, so as to obtain the hafnium tantalate ceramic target, which comprises:
and sintering the ceramic sheet for the second time at 1400-1600 ℃ for 12-24 hours, and then cooling to room temperature to obtain the hafnium tantalate ceramic target.
In one embodiment of the present invention, treating a surface of a zirconia single crystal substrate with an acid to obtain a clean zirconia single crystal substrate comprises:
ultrasonic soaking is carried out on the zirconia single crystal substrate by utilizing dilute hydrochloric acid to obtain the zirconia single crystal substrate after soaking, wherein the concentration of the dilute hydrochloric acid is 0.1-1.0 mol/L, and the soaking time is 30-60 min;
and sequentially using ethanol and purified water to ultrasonically clean the soaked zirconia single crystal substrate, and drying to obtain the clean zirconia single crystal substrate.
In one embodiment of the present invention, heating the clean zirconia single crystal substrate to a first preset temperature and maintaining a first preset oxygen partial pressure comprises:
and heating the clean zirconia monocrystal substrate to 600-900 ℃, and introducing oxygen to maintain the oxygen partial pressure at 50-300 mTorr.
In one embodiment of the present invention, shielding a clean zirconia single crystal substrate, irradiating the surface of the hafnium tantalate ceramic target with an excimer pulse laser, comprising:
shielding the clean zirconia single crystal substrate by using a baffle plate, starting excimer laser, radiating the surface of the hafnium tantalate ceramic target by using excimer pulse laser, washing the target for 2000-5000 pulses, wherein the laser frequency is 5-10 Hz, and the laser power is 500-700 mJ.
In one embodiment of the present invention, removing the shadow of the clean zirconia single crystal substrate to grow hafnium tantalate to a predetermined thickness on the clean zirconia single crystal substrate to obtain a predetermined hafnium tantalate single crystal epitaxial film, comprising:
and removing a baffle plate shielding the clean zirconium oxide single crystal substrate to enable the hafnium tantalate to epitaxially grow to 50-400 nm on the surface of the zirconium oxide single crystal substrate, and then stopping laser radiation on the surface of the hafnium tantalate ceramic target material to obtain a preset hafnium tantalate single crystal epitaxial film.
In one embodiment of the present invention, heating the preset zirconia single crystal substrate to a second preset temperature under a second preset oxygen partial pressure condition, performing in-situ annealing, and cooling to a third preset temperature to obtain a hafnium tantalate single crystal epitaxial film, including:
introducing oxygen and maintaining the oxygen partial pressure at 100-700 Torr, adjusting the preset zirconia monocrystal substrate to 700-1000 ℃, annealing in situ for 30-60 min, and cooling to room temperature-50 ℃ to obtain the hafnium tantalate monocrystal epitaxial film.
The invention also provides a hafnium tantalate single crystal epitaxial film with a modulation structure, and the hafnium tantalate single crystal epitaxial Bao Moli is prepared and formed by the preparation method of any one of the above embodiments.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, a hafnium tantalate ceramic target is prepared, a zirconium oxide single crystal substrate is treated by acid, then the zirconium oxide single crystal substrate is heated to a first preset temperature, a first preset oxygen partial pressure is maintained, then the zirconium oxide single crystal substrate is shielded, the surface of the hafnium tantalate ceramic target is irradiated by excimer pulse laser, then the shielding of the clean zirconium oxide single crystal substrate is removed, so that hafnium tantalate grows to a preset thickness on the surface of the zirconium oxide single crystal substrate in an epitaxial manner, the preset zirconium oxide single crystal substrate is adjusted to a second preset temperature under the condition of a second preset oxygen partial pressure, in-situ annealing is performed, and the temperature is reduced to a third preset temperature, so that the hafnium tantalate single crystal epitaxial film is obtained. The zirconium oxide substrate can form a pseudo-co-lattice matching relation with the hafnium tantalate, and the pulse laser can provide enough migration distance for the epitaxial growth of the hafnium tantalate, so that the epitaxial growth of the hafnium tantalate single crystal film can be realized by the method, the obtained film has good ductility, single orientation characteristics, controllable thickness and surface flatness, and is beneficial to research on the intrinsic performance of the hafnium tantalate material.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of a hafnium tantalate single crystal epitaxial film with a modulating structure according to an embodiment of the present invention;
FIG. 2 is an X-ray diffraction pattern of a hafnium tantalate epitaxial film prepared in accordance with the present invention;
FIG. 3 is a transmission electron microscope image of the interface of a hafnium tantalate epitaxial film prepared in accordance with the present invention;
FIG. 4 is a selected area electron diffraction pattern of a hafnium tantalate epitaxial film prepared in accordance with the present invention;
FIG. 5 is a graph of Young's modulus versus hardness for hafnium tantalate epitaxial films prepared in accordance with the present invention;
fig. 6 is an SEM image of the indentation area after microscopic weisse hardness test of the hafnium tantalate epitaxial film prepared in accordance with the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto.
Example 1
Referring to fig. 1, fig. 1 is a schematic flow chart of a preparation method of a hafnium tantalate single crystal epitaxial film with a modulation structure according to an embodiment of the present invention, and the preparation method of the hafnium tantalate single crystal epitaxial film with the modulation structure according to the embodiment of the present invention includes:
and step 1, preparing a hafnium tantalate ceramic target.
Specifically, the hafnium tantalate ceramic target material is prepared by a high-temperature solid phase method, the diameter of the hafnium tantalate ceramic target material is 1 inch, the thickness of the hafnium ceramic target material is 3-10 mm, the mass of the hafnium ceramic target material is 5-20 g, and the selected raw materials are hafnium oxide and tantalum oxide.
In one embodiment, step 1 may specifically include:
step 1.1, mixing hafnium oxide powder and tantalum oxide powder to obtain a uniformly mixed oxide mixture.
Specifically, according to the formula Hf of hafnium tantalate produced n Ta 2 O 2n+5 (n=4-10), ball milling hafnium oxide and tantalum oxide powder with corresponding molar ratio to obtain oxide mixture with homogeneous mixing.
Step 1.2, performing primary sintering on the oxide mixture, and then cooling to room temperature to obtain the sintered oxide mixture.
Alternatively, the temperature of the first sintering is 1300-1500 ℃.
Specifically, the oxide mixture is sintered for the first time at 1300-1500 ℃ for 12-24 hours, and then the temperature is reduced to room temperature, so as to obtain the sintered oxide mixture.
Optionally, the cooling rate is 5-10 ℃/min.
And 1.3, pressing the sintered oxide mixture into a tablet shape at room temperature to obtain the ceramic tablet.
Specifically, the phase purity of the obtained hafnium tantalate powder was confirmed by XRD (X-ray diffraction) before compacting, and after confirming that there was no problem, compacting was performed. During pressing, the sintered oxide mixture is pressed into tablets at room temperature by a tablet press, the mass is 5-20 g, the pressure is 10 tons, and the diameter of a die is 1 inch.
And 1.4, performing secondary sintering on the ceramic sheet, and then cooling to room temperature to obtain the hafnium tantalate ceramic target.
Optionally, the temperature of the second sintering is 1400-1600 ℃.
Optionally, the thickness of the hafnium tantalate ceramic target is 3-10 mm.
Specifically, the ceramic sheet is sintered for the second time at 1400-1600 ℃ for 24 hours, and then the temperature is reduced to room temperature with the temperature reduction rate of 5-10 ℃/min. The secondary sintering can enable the obtained hafnium tantalate ceramic target material to be more compact, and prevent particles/powder from splashing during laser irradiation.
And 2, treating the surface of the zirconia single crystal substrate by using acid to obtain the clean zirconia single crystal substrate.
Specifically, the zirconia single crystal substrate was a single-sided polished yttrium-stabilized zirconia single crystal substrate having a crystal orientation of (011) and a chemical composition of 7% by weight Y 2 O 3 And 93% by weight ZrO 2 。
In one embodiment, step 2 may specifically include:
step 2.1, carrying out ultrasonic soaking on the zirconia single crystal substrate by utilizing dilute hydrochloric acid to obtain a soaked zirconia single crystal substrate, wherein the concentration of the dilute hydrochloric acid is 0.1-1.0 mol/L, and the soaking time is 30-60 min;
and 2.2, sequentially using ethanol and purified water to ultrasonically clean the soaked zirconia single crystal substrate, and then blowing to dry to obtain the pure zirconia single crystal substrate.
Specifically, ethanol and purified water are sequentially used for ultrasonic cleaning of the soaked zirconia single crystal substrate, the cleaning time is 30-60 min, and the zirconia single crystal substrate is dried by high-purity compressed air to obtain the clean zirconia single crystal substrate.
And 3, heating the clean zirconia single crystal substrate to a first preset temperature, and maintaining a first preset oxygen partial pressure, wherein the preset temperature and the oxygen partial pressure are beneficial to the migration and nucleation process of hafnium tantalate particles.
Optionally, the first preset temperature is 600-900 ℃, and the first preset oxygen partial pressure is 50-300 mTorr.
Specifically, the clean zirconia single crystal substrate is heated to 600-900 ℃, and oxygen is introduced to maintain the oxygen partial pressure at 50-300 mTorr.
That is, the epitaxial growth of the single crystal thin film of the present embodiment may employ an excimer pulse laser as an excitation source, and thus, first, a hafnium tantalate ceramic target and a clean zirconia single crystal substrate are placed on a target holder and a heating substrate of a pulse laser deposition apparatus, respectively. Setting the back ground vacuum of the pulse laser deposition equipment to be lower than 1 multiplied by 10 -7 And (3) Torr, heating the clean zirconia single crystal substrate to 600-900 ℃, slowly introducing oxygen, and maintaining the oxygen partial pressure at 50-300 mTorr.
And 4, shielding the clean zirconia single crystal substrate, radiating the surface of the hafnium tantalate ceramic target by using excimer pulse laser, wherein the selected excimer pulse laser has high energy density, and can effectively excite the hafnium tantalate ceramic target with high melting point.
Specifically, a baffle plate is used for shielding a clean zirconia single crystal substrate, then excimer laser is started, the surface of a hafnium tantalate ceramic target is irradiated by excimer pulse laser, 2000-5000 pulses are washed, the laser frequency is 5-10 Hz, and the laser power is 400-750 mJ.
And 5, removing shielding of the clean zirconia single crystal substrate, so as to grow hafnium tantalate to a preset thickness on the clean zirconia single crystal substrate, and obtaining the preset hafnium tantalate single crystal epitaxial film.
Specifically, the baffle plate shielding the clean zirconia single crystal substrate is removed, so that hafnium tantalate is epitaxially grown to 50-400 nm on the surface of the zirconia single crystal substrate, the laser radiation of the surface of the hafnium tantalate ceramic target is stopped, and the growth of the hafnium tantalate film is stopped.
And 6, under the condition of a second preset oxygen partial pressure, adjusting the preset zirconia monocrystal substrate to a second preset temperature, performing in-situ annealing to reduce the oxygen defect concentration in the hafnium tantalate film, achieving the purpose of further improving the crystallinity of the film, and then cooling to a third preset temperature to obtain the hafnium tantalate monocrystal epitaxial film, wherein the second preset oxygen partial pressure is larger than the first preset oxygen partial pressure, the crystal orientation of the hafnium tantalate monocrystal epitaxial film is kept consistent with that of the zirconia monocrystal substrate, and the selected area electron diffraction line shows that the hafnium tantalate monocrystal epitaxial film has a typical modulation structure.
Optionally, the second preset oxygen partial pressure is 100-700 Torr, the second preset temperature is 700-1000 ℃, and the third preset temperature is room temperature-50 ℃.
Specifically, oxygen is introduced and the oxygen partial pressure is maintained at 100-700 Torr, the preset zirconia monocrystal substrate is adjusted to 700-1000 ℃, after in-situ annealing is performed for 30-60 min, the temperature is reduced to room temperature-50 ℃, and the hafnium tantalate monocrystal epitaxial film is obtained.
According to the invention, the pressed hafnium tantalate ceramic target is sintered twice, so that the obtained hafnium tantalate ceramic target is more compact, splashing of particles/powder is prevented during laser irradiation, then the zirconium oxide single crystal substrate is heated to a first preset temperature and maintained at the first preset oxygen partial pressure, migration and nucleation processes of hafnium tantalate particles are facilitated, then the surface of the hafnium tantalate ceramic target is irradiated by using excimer pulse laser, and therefore the high-melting-point hafnium tantalate ceramic target can be effectively excited, after the growth of the zirconium oxide single crystal substrate is finished, the grown zirconium oxide single crystal substrate is adjusted to a second preset temperature under the condition of the second preset oxygen partial pressure, in-situ annealing is performed, so that the oxygen defect concentration in the hafnium tantalate film is reduced, the purpose of further improving the crystallinity of the film is achieved, and then the temperature is reduced to a third preset temperature, and the hafnium tantalate single crystal epitaxial film is obtained. By the method, the hafnium tantalate film prepared by the method has good ductility, single orientation characteristic, modulation structure, controllable thickness and surface flatness and good mechanical property.
The invention is based on pulse laser deposition technology, and can realize epitaxial growth of hafnium tantalate monocrystal film by adjusting parameters such as laser energy density and frequency, vacuum cavity oxygen partial pressure, substrate temperature, growth time, in-situ annealing and the like, and the obtained film has better ductility, single orientation characteristic, controllable thickness and surface flatness, and is beneficial to research on intrinsic performance of hafnium tantalate material.
Example two
The embodiment provides a specific preparation method of a hafnium tantalate monocrystal epitaxial film with a modulation structure on the basis of the first embodiment, wherein the preparation method comprises the following steps:
step 1: hafnium tantalate ceramic target material prepared by high-temperature solid phase method, and the chemical formula of the prepared material is Hf 6 Ta 2 O 17 。
Specifically, hafnium oxide (HfO 2 ) And tantalum oxide (Ta) 2 O 5 ) Powder according to the mole ratio of 6:1, ball milling for 24 hours to obtain a uniformly mixed oxide mixture, performing primary sintering at 1400-1500 ℃ for 12-24 hours at a cooling rate of 10 ℃/min, cooling to room temperature, and confirming the obtained Hf by utilizing X-ray diffraction 6 Ta 2 O 17 The phase purity of the powder is pressed into tablets at room temperature by a tablet press, the mass of the powder is 5-20 g, the pressure of the press is 10 tons, the diameter of a die is 1 inch, the obtained ceramic tablet is sintered for the second time, the sintering temperature is 1500-1600 ℃, the sintering time is 24 hours, the cooling rate is 5 ℃/min, and the powder is cooled to the room temperature, so that the compact hafnium tantalate ceramic target material, namely Hf, is obtained 6 Ta 2 O 17 The thickness of the ceramic target material is 3-10 mm.
Step 2: ultrasonic soaking in dilute hydrochloric acid for 30-60 min at concentration of 0.1-1.0 mol/L, ultrasonic washing with alcohol and purified water for 30-60 min, and blowing with compressed air.
Step 3: hf is set 6 Ta 2 O 17 The ceramic target is placed on a target holder of a pulse laser deposition device, and a cleaned (011) yttrium stabilized zirconia monocrystal substrate is stuck on a heating substrate of the pulse laser deposition device by silver paste and is solidified by a heat table.
Step 4: the back vacuum of the cavity of the device for depositing the pulse laser is lower than 1 multiplied by 10 -7 And (3) Torr, heating the zirconia single crystal substrate to 700-850 ℃, and slowly introducing oxygen, wherein the oxygen partial pressure is maintained at 50-200 mTorr.
Step 5: the baffle is used for shielding the surface of the substrate, excimer laser is started, the surface of the target is irradiated, 2000 pulses are washed, the frequency of the laser is 5-10 Hz, and the power of the laser is 500-700 mJ.
Step 6: baffle plate before removing substrate to realize Hf 6 Ta 2 O 17 And (3) growing a film, and stopping growing when the film is deposited to 50-400 nm, and closing the laser.
Step 7: introducing oxygen and maintaining the oxygen partial pressure at 200-400 Torr, setting the substrate temperature at 800-1000 ℃, annealing in situ for 30-60 min, cooling to room temperature-50 ℃ to obtain Hf consistent with the crystal orientation of the zirconia monocrystal substrate 6 Ta 2 O 17 The monocrystal extends the film, and the microscopic atomic structure arrangement of the film presents the characteristic of a modulating structure.
Example III
The embodiment provides a preparation method of a specific hafnium tantalate single crystal epitaxial film with a modulation structure on the basis of the first embodiment, wherein the preparation method comprises the following steps:
step 1: hafnium tantalate ceramic target material prepared by high-temperature solid phase method, and the chemical formula of the prepared material is Hf 8 Ta 2 O 21 。
Specifically, hafnium oxide (HfO 2 ) And tantalum oxide (Ta) 2 O 5 ) Powder according to a molar ratio of 8:1, mixing, ball milling for 24 hours to obtain a uniformly mixed oxide mixture, and performing primary sintering at 1400-1500 ℃ for 12-to-10 DEG of sintering time24h, cooling at a rate of 5 ℃/min, cooling to room temperature, and confirming the obtained Hf by X-ray diffraction 8 Ta 2 O 21 The phase purity of the powder is pressed into tablets at room temperature by a tablet press, the mass of the powder is 5-20 g, the pressure of the press is 10 tons, the diameter of a die is 1 inch, the obtained ceramic tablet is sintered for the second time, the sintering temperature is 1500-1600 ℃, the sintering time is 24 hours, the cooling rate is 5 ℃/min, and the powder is cooled to the room temperature, so that the compact hafnium tantalate ceramic target material, namely Hf, is obtained 8 Ta 2 O 21 The thickness of the ceramic target material is 3-10 mm.
Step 2: ultrasonic soaking in dilute hydrochloric acid for 30-60 min at concentration of 0.1-1.0 mol/L, ultrasonic washing with alcohol and purified water for 30-60 min, and blowing with compressed air.
Step 3: hf is set 8 Ta 2 O 21 The ceramic target is placed on a target holder of a pulse laser deposition device, and a cleaned (011) direction yttrium stabilized zirconia monocrystal substrate is stuck on a heating substrate of the pulse laser deposition device by silver paste and is solidified by a heat table.
Step 4: the back vacuum of the cavity of the device for depositing the pulse laser is lower than 1 multiplied by 10 -7 And (3) Torr, heating the substrate to 700-900 ℃, and slowly introducing oxygen, wherein the oxygen partial pressure is maintained at 100-300 mTorr.
Step 5: the baffle is used for shielding the surface of the substrate, excimer laser is started, the surface of the target is irradiated, 2000 pulses are washed, the frequency of the laser is 5-10 Hz, and the power of the laser is 600-750 mJ.
Step 6: baffle plate before removing substrate to realize Hf 8 Ta 2 O 21 And (3) growing a film, and stopping growing when the film is deposited to 50-400 nm, and closing the laser.
Step 7: introducing oxygen and maintaining the oxygen partial pressure at 400-700 Torr, setting the substrate temperature at 900-1000 ℃, annealing in situ for 30-60 min, cooling to room temperature-50 ℃ to obtain Hf consistent with the crystal orientation of the zirconia monocrystal substrate 8 Ta 2 O 21 Single crystal epitaxial film and microscopic atomic structure of the filmThe arrangement exhibits a modulating structural feature.
Referring to FIG. 2, FIG. 2 shows the Hf prepared in the present invention 6 Ta 2 O 17 、Hf 8 Ta 2 O 21 The X-ray diffraction pattern of the epitaxial film only shows 2 diffraction peaks in the range of 30-80 degrees, belonging to YSZ (022) and Hf respectively 6 Ta 2 O 17 、Hf 8 Ta 2 O 21 (022) The crystal face proves that the film obtained by the invention has single orientation and presents typical epitaxial growth characteristics, namely the growth direction of the film is consistent with the direction of the substrate.
Referring to FIG. 3, FIG. 3 shows the Hf prepared in the present invention 6 Ta 2 O 17 、Hf 8 Ta 2 O 21 Transmission electron microscopy at the epitaxial thin film interface. The difference in atomic number results in a difference in image contrast, hf 6 Ta 2 O 17 、Hf 8 Ta 2 O 21 The region is light gray and YSZ is dark gray, thus the Hf can be seen 6 Ta 2 O 17 、Hf 8 Ta 2 O 21 The film thickness is uniform, the interface between the film and the YSZ substrate is flat and clear, the interdiffusion phenomenon is not detected, the atomic lattice of the film can be matched with the substrate, and dislocation or other interface defects are not detected. The atomic lattice in the film is uniform in distribution, no secondary phase is detected, and the Hf prepared by the invention is proved 6 Ta 2 O 17 、Hf 8 Ta 2 O 21 The sample is a single-orientation epitaxial film, and the film has good crystal quality and ductility, and is suitable for developing Hf 6 Ta 2 O 17 、Hf 8 Ta 2 O 21 Study of intrinsic properties.
Referring to FIG. 4, FIG. 4 shows the Hf prepared in the present invention 6 Ta 2 O 17 、Hf 8 Ta 2 O 21 The diffraction pattern of the modulating structure, i.e. weak satellite spots on both sides of the main spot, can be observed by selective electron diffraction patterns of the epitaxial film.
Referring to FIG. 5, FIG. 5 shows the Hf prepared in the present invention 6 Ta 2 O 17 、Hf 8 Ta 2 O 21 Young's modulus and hardness graph of epitaxial film, test adopts nanoindentation continuous stiffness method, hf 6 Ta 2 O 17 、Hf 8 Ta 2 O 21 The Young's modulus of the epitaxial film is 242.0GPa and 230.0GPa, and the hardness is 22.0GPa and 21.0GPa.
Referring to FIG. 6, FIG. 6 shows the Hf prepared in the present invention 6 Ta 2 O 17 、Hf 8 Ta 2 O 21 In the SEM image of the indentation area of the epitaxial film after the microWelch hardness test, besides the quadrangular pyramid mark of the normal Welch indentation is maintained on the surface of the film, cracks are generated along the top end of the mark, which proves that the applied external force is more suitable. In addition, the water ripple-shaped fold patterns are arranged near the cracks, so that the further expansion of the cracks can be effectively prevented, and the special toughening property of the hafnium tantalate material is reflected.
Hf prepared by the present example 8 Ta 2 O 21 The epitaxial film is obvious in that the hafnium tantalate film prepared by the method is good in ductility, has single orientation characteristic, is controllable in thickness and surface flatness, shows excellent mechanical properties, and is beneficial to research on other intrinsic properties of the hafnium tantalate material by researchers.
Example IV
The present embodiment further provides a hafnium tantalate single crystal epitaxial film having a modulating structure on the basis of the above embodiments, the hafnium tantalate single crystal epitaxial film being prepared by any one of the methods of the first to third embodiments, the crystal orientation of the hafnium tantalate single crystal epitaxial film being consistent with the crystal orientation of the zirconium oxide single crystal substrate, and the hafnium tantalate single crystal epitaxial film having a modulating structure.
In the description of the present invention, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Further, one skilled in the art can engage and combine the different embodiments or examples described in this specification.
Although the invention is described herein in connection with various embodiments, other variations to the disclosed embodiments can be understood and effected by those skilled in the art in practicing the claimed invention, from a study of the drawings, the disclosure, and the appended claims. In the claims, the word "comprising" does not exclude other elements or steps, and the "a" or "an" does not exclude a plurality. A single processor or other unit may fulfill the functions of several items recited in the claims. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. Modifications made by those skilled in the art without departing from the spirit of the invention should be considered as falling within the scope of the invention.
Claims (10)
1. A method for preparing a hafnium tantalate single crystal epitaxial film with a modulating structure, which is characterized by comprising the following steps:
preparing a hafnium tantalate ceramic target;
treating the surface of the zirconia single crystal substrate by using acid to obtain a clean zirconia single crystal substrate;
heating the clean zirconia single crystal substrate to a first preset temperature and maintaining a first preset oxygen partial pressure;
shielding a clean zirconia single crystal substrate, and radiating the surface of the hafnium tantalate ceramic target material by using excimer pulse laser;
removing the shielding of the clean zirconia single crystal substrate to grow hafnium tantalate to a preset thickness on the clean zirconia single crystal substrate, so as to obtain a preset hafnium tantalate single crystal epitaxial film;
and under the condition of a second preset oxygen partial pressure, adjusting the preset zirconia monocrystal substrate to a second preset temperature, carrying out in-situ annealing, and cooling to a third preset temperature to obtain the hafnium tantalate monocrystal epitaxial film, wherein the second preset oxygen partial pressure is larger than the first preset oxygen partial pressure, and the crystal orientation of the hafnium tantalate monocrystal epitaxial film is kept consistent with that of the zirconia monocrystal substrate.
2. The method for preparing a modulated structure hafnium tantalate single crystal epitaxial film of claim 1, wherein preparing the hafnium tantalate ceramic target comprises:
mixing hafnium oxide powder and tantalum oxide powder to obtain a uniformly mixed oxide mixture;
sintering the oxide mixture for the first time, and then cooling to room temperature to obtain a sintered oxide mixture;
pressing the sintered oxide mixture into a sheet shape at room temperature to obtain a ceramic sheet;
and (3) sintering the ceramic sheet for the second time, and then cooling to room temperature to obtain the hafnium tantalate ceramic target.
3. The method for preparing a modulated hafnium tantalate single crystal epitaxial film according to claim 2, wherein the oxide mixture is sintered for the first time and then cooled to room temperature to obtain a sintered oxide mixture, comprising:
and (3) sintering the oxide mixture for the first time at 1300-1500 ℃ for 12-24 hours, and then cooling to room temperature to obtain the sintered oxide mixture.
4. The method for preparing a modulated hafnium tantalate single crystal epitaxial film according to claim 2, wherein the steps of sintering the ceramic wafer for the second time and then cooling to room temperature to obtain the hafnium tantalate ceramic target material comprise:
and sintering the ceramic sheet for the second time at 1400-1600 ℃ for 12-24 hours, and then cooling to room temperature to obtain the hafnium tantalate ceramic target.
5. The method for producing a modulated hafnium tantalate single crystal epitaxial film according to claim 1, wherein the step of treating the surface of the zirconia single crystal substrate with an acid to obtain a clean zirconia single crystal substrate comprises:
ultrasonic soaking is carried out on the zirconia single crystal substrate by utilizing dilute hydrochloric acid to obtain the zirconia single crystal substrate after soaking, wherein the concentration of the dilute hydrochloric acid is 0.1-1.0 mol/L, and the soaking time is 30-60 min;
and sequentially using ethanol and purified water to ultrasonically clean the soaked zirconia single crystal substrate, and drying to obtain the clean zirconia single crystal substrate.
6. The method of preparing a modulated structure hafnium tantalate single crystal epitaxial film of claim 1 wherein heating the clean zirconium oxide single crystal substrate to a first predetermined temperature and maintaining a first predetermined oxygen partial pressure comprises:
and heating the clean zirconia monocrystal substrate to 600-900 ℃, and introducing oxygen to maintain the oxygen partial pressure at 50-300 mTorr.
7. The method for preparing a modulated structure hafnium tantalate single crystal epitaxial film according to claim 1, wherein shielding a clean zirconia single crystal substrate, irradiating the surface of the hafnium tantalate ceramic target with excimer pulse laser, comprises:
shielding the clean zirconia single crystal substrate by using a baffle plate, starting excimer laser, radiating the surface of the hafnium tantalate ceramic target by using excimer pulse laser, washing the target for 2000-5000 pulses, wherein the laser frequency is 5-10 Hz, and the laser power is 500-700 mJ.
8. The method for preparing a modulated hafnium tantalate single crystal epitaxial film according to claim 1, wherein the step of removing the shield of the clean zirconium oxide single crystal substrate to grow hafnium tantalate to a predetermined thickness on the clean zirconium oxide single crystal substrate to obtain a predetermined hafnium tantalate single crystal epitaxial film comprises:
and removing a baffle plate shielding the clean zirconium oxide single crystal substrate to enable the hafnium tantalate to epitaxially grow to 50-400 nm on the surface of the zirconium oxide single crystal substrate, and then stopping laser radiation on the surface of the hafnium tantalate ceramic target material to obtain a preset hafnium tantalate single crystal epitaxial film.
9. The method for preparing a modulated hafnium tantalate single crystal epitaxial film according to claim 1, wherein heating the pre-set zirconium oxide single crystal substrate to a second pre-set temperature under a second pre-set oxygen partial pressure condition, performing in-situ annealing, and cooling to a third pre-set temperature to obtain the hafnium tantalate single crystal epitaxial film, comprising:
introducing oxygen and maintaining the oxygen partial pressure at 100-700 Torr, adjusting the preset zirconia monocrystal substrate to 700-1000 ℃, annealing in situ for 30-60 min, and cooling to room temperature-50 ℃ to obtain the hafnium tantalate monocrystal epitaxial film.
10. A hafnium tantalate single crystal epitaxial film having a modulated structure, characterized in that the hafnium tantalate single crystal epitaxial film is produced by the production method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311575414.2A CN117604623A (en) | 2023-11-23 | 2023-11-23 | Hafnium tantalate monocrystal epitaxial film with modulation structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311575414.2A CN117604623A (en) | 2023-11-23 | 2023-11-23 | Hafnium tantalate monocrystal epitaxial film with modulation structure and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117604623A true CN117604623A (en) | 2024-02-27 |
Family
ID=89943617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311575414.2A Pending CN117604623A (en) | 2023-11-23 | 2023-11-23 | Hafnium tantalate monocrystal epitaxial film with modulation structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117604623A (en) |
-
2023
- 2023-11-23 CN CN202311575414.2A patent/CN117604623A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7461851B2 (en) | Semiconductor Film | |
| CN109851377B (en) | Laser-induced high-temperature solid-phase reaction for generating A2B2O7Method for forming thermal barrier coating material | |
| JP7159450B2 (en) | Underlying substrate and manufacturing method thereof | |
| CN104499047A (en) | Substrate for realizing heteroepitaxial growth of large-size monocrystal diamond and preparation method thereof | |
| CN101186493B (en) | Method for increasing bismuth layer structure piezoelectricity ferroelectric ceramic material density | |
| CN112813385B (en) | Calcium bismuth niobate thin film with c-axis preferred orientation and preparation method thereof | |
| Shoup et al. | Sol-gel synthesis of LaAlO3; Epitaxial growth of LaAlO3 thin films on SrTiO3 (100) | |
| Yoon et al. | Epitaxial growth of sol-gel PLZT thin films | |
| CN116575121A (en) | Monocrystalline Cr with high orientation 2 AlC material and preparation method thereof | |
| CN117604623A (en) | Hafnium tantalate monocrystal epitaxial film with modulation structure and preparation method thereof | |
| JP7124207B2 (en) | Underlying substrate | |
| JP2008198396A (en) | Manufacturing method of superconductive oxide material | |
| CN108409318A (en) | A kind of preparation method of the adjustable stronitum stannate cobalt thin film of energy gap | |
| CN113677833B (en) | Semiconductor film | |
| WO2021048950A1 (en) | Semiconductor film | |
| JP7265624B2 (en) | semiconductor film | |
| Park et al. | Orientation control of sol-gel-derived lead zirconate titanate film by addition of polyvinylpyrrolidone | |
| Ikuta et al. | STM observation on the initial growth of amorphous and microcrystalline silicon films | |
| JP7320070B2 (en) | Underlying substrate and manufacturing method thereof | |
| JP7439117B2 (en) | Underlying substrate and its manufacturing method | |
| RU2341847C1 (en) | Method of making silicon carbide films on silicon substrate | |
| JP4465461B2 (en) | Method for producing perovskite oxide epitaxial thin films | |
| CN1160806C (en) | Process for preparing Si base Bi4 Ti3 O12 ferroelectric film | |
| CN115505880B (en) | Bismuth calcium niobate thin film material with periodic nanoscale microcrack structure and preparation method thereof | |
| Kim et al. | Epitaxial growth of PbZr0. 5Ti0. 5O3 thin films on (001) LaAlO3 by the chemical solution deposition method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |