CN114959896B - Hafnium oxide ferroelectric phase single crystal and preparation method thereof - Google Patents
Hafnium oxide ferroelectric phase single crystal and preparation method thereof Download PDFInfo
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- CN114959896B CN114959896B CN202210577546.8A CN202210577546A CN114959896B CN 114959896 B CN114959896 B CN 114959896B CN 202210577546 A CN202210577546 A CN 202210577546A CN 114959896 B CN114959896 B CN 114959896B
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- 229910000449 hafnium oxide Inorganic materials 0.000 title claims abstract description 103
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000013078 crystal Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 41
- 238000004093 laser heating Methods 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims description 45
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 210000001503 joint Anatomy 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 28
- 230000015654 memory Effects 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 238000005191 phase separation Methods 0.000 abstract description 3
- 238000004857 zone melting Methods 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004781 supercooling Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 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
- 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
-
- 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
- C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
- C30B13/16—Heating of the molten zone
- C30B13/22—Heating of the molten zone by irradiation or electric discharge
-
- 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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/02—Production of homogeneous polycrystalline material with defined structure directly from the solid state
Abstract
The application discloses a hafnium oxide ferroelectric phase monocrystal and a preparation method thereof, belonging to the technical field of ferroelectric memories, wherein the preparation method of the hafnium oxide ferroelectric phase monocrystal comprises the following steps: obtaining two hafnium oxide polycrystal material rods; setting two hafnium oxide polycrystal material rods in a collinear manner, and reserving a gap with a preset distance between the two hafnium oxide polycrystal material rods; and placing the gap in a laser heating area to grow ferroelectric single crystals to obtain hafnium oxide ferroelectric phase single crystals. The method can grow ferroelectric phase with large size and no macroscopic defect. The laser irradiation stability is good, the temperature uniformity of the heating area is high, the phase separation caused by the temperature non-uniformity can not occur, the component change is caused, the pollution problem is avoided, and the ferroelectric film quality is better.
Description
Technical Field
The application belongs to the technical field of ferroelectric memories, and particularly relates to a hafnium oxide ferroelectric phase monocrystal and a preparation method thereof.
Background
The ferroelectric film is a core material of a widely studied ferroelectric memory, is compatible with standard integrated circuit processes, can integrate high-speed and low-power consumption nonvolatile hafnium oxide-based ferroelectric field effect transistor (FeFET) memories with high density, has great application potential, and is an important development direction of novel semiconductor memories.
Currently, since the hafnium oxide based ferroelectric thin film in the FeFET is a polycrystalline, multiphase structure, the microstructure of randomly distributed ferroelectric/paraelectric grains, grain orientations, phase boundaries, etc. will cause performance differences between small area hafnium oxide based ferroelectric thin films, thus causing the problem of uniformity of the memory performance of the FeFET thereof. This is a technical bottleneck that hinders the industrialization of its FeFET memory.
Disclosure of Invention
The purpose of the application is to provide a hafnium oxide ferroelectric phase monocrystal and a preparation method thereof so as to solve the problem of polycrystal multiphase of a ferroelectric film and further realize uniformity of storage performance.
According to a first aspect of embodiments of the present application, there is provided a method for preparing a hafnium oxide ferroelectric phase single crystal, which may include:
obtaining two hafnium oxide polycrystal material rods;
setting two hafnium oxide polycrystal material rods in a collinear manner, and reserving a gap with a preset distance between the two hafnium oxide polycrystal material rods;
and placing the gap in a laser heating area to grow ferroelectric single crystals to obtain hafnium oxide ferroelectric phase single crystals.
In some alternative embodiments of the present application, the obtaining two hafnium oxide polycrystalline rods comprises:
heating and drying hafnium oxide raw material powder to obtain dried powder;
grinding and sintering the dried powder to obtain hafnium oxide powder;
and (3) performing pressing, shaping and sintering on the hafnium oxide powder to obtain the hafnium oxide polycrystalline material rod.
In some alternative embodiments of the present application, the hafnium oxide raw powder is a hafnium oxide powder or a doped hafnium oxide powder.
In some alternative embodiments of the present application, the doping element of the doped hafnium oxide powder is one or more of silicon, aluminum, zirconium, lanthanum, cerium, yttrium.
In some alternative embodiments of the present application, the preset distance is 1-1.5mm.
In some alternative embodiments of the present application, the heating rate of the laser heating zone is between 30-60 ℃/min.
In some alternative embodiments of the present application, the placing the gap in a laser heating zone for growing a ferroelectric single crystal to obtain a hafnium oxide ferroelectric phase single crystal includes:
placing the gap in a laser heating area and rotating the two hafnium oxide polycrystal material rods in opposite directions;
when two ends of the two hafnium oxide polycrystal material rods, which are close to each other, are in a molten state, the two hafnium oxide polycrystal material rods are in butt joint;
oxygen is introduced to enable the crystal to grow in the oxygen atmosphere so as to obtain the hafnium oxide ferroelectric phase monocrystal.
In some alternative embodiments of the present application, the counter-rotation is at a rotation rate of 20-25r/min.
In some optional embodiments of the present application, after the step of placing the gap in a laser heating area to perform growth of a ferroelectric single crystal to obtain a hafnium oxide ferroelectric phase single crystal, the method for preparing a hafnium oxide ferroelectric phase single crystal further includes:
continuously introducing oxygen and cooling for 1-2 hours.
According to a second aspect of embodiments of the present application, there is provided a hafnium oxide ferroelectric phase single crystal prepared by the method for preparing a hafnium oxide ferroelectric phase single crystal according to any one of the embodiments of the first aspect.
The technical scheme of the application has the following beneficial technical effects:
according to the method, the hafnium oxide polycrystal rod is heated in a laser heating mode, so that a large-size ferroelectric phase without macroscopic defects can be grown. The heating temperature of the laser heating zone melting method can reach 3000 ℃ at most, so that the requirement of high melting point of hafnium oxide can be met, and the growing mode has higher heating temperature and can bring greater supercooling degree, so that the prepared hafnium oxide crystal is in a ferroelectric phase. In addition, the laser irradiation stability is good, the temperature uniformity of the heating area is high, the phase separation caused by the temperature non-uniformity can not occur, the component change is caused, the pollution problem is avoided, and the quality of the ferroelectric film is better.
Drawings
FIG. 1 is a flow chart of a method for producing a hafnium oxide ferroelectric phase single crystal according to an exemplary embodiment of the present application;
FIG. 2 is a phase change barrier diagram of a hafnium oxide phase in an exemplary embodiment of the present application;
FIG. 3 is a horizontal schematic view of an adjustment device in an exemplary embodiment of the present application;
FIG. 4 is a top view of a growth process in an exemplary embodiment of the present application;
fig. 5 is a growth schematic in an exemplary embodiment of the present application.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail below with reference to the accompanying drawings. It should be understood that the description is only exemplary and is not intended to limit the scope of the present application. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the concepts of the present application.
A layer structure schematic diagram according to an embodiment of the present application is shown in the drawings. The figures are not drawn to scale, wherein certain details may be exaggerated and some details may be omitted for clarity. The shapes of the various regions, layers and relative sizes, positional relationships between them shown in the drawings are merely exemplary, may in practice deviate due to manufacturing tolerances or technical limitations, and one skilled in the art may additionally design regions/layers having different shapes, sizes, relative positions as actually required.
It will be apparent that the embodiments described are some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
In the description of the present application, it should be noted that the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In addition, the technical features described below in the different embodiments of the present application may be combined with each other as long as they do not collide with each other.
The method for preparing the hafnium oxide ferroelectric phase monocrystal provided in the embodiment of the application is described in detail below through specific examples and application scenes thereof with reference to the accompanying drawings.
As shown in fig. 1, in a first aspect of the embodiments of the present application, there is provided a method for preparing a hafnium oxide ferroelectric phase single crystal, which may include:
s110: obtaining two hafnium oxide polycrystal material rods;
s120: setting two hafnium oxide polycrystal material rods in a collinear manner, and reserving a gap with a preset distance between the two hafnium oxide polycrystal material rods;
s130: and placing the gap in a laser heating area to grow ferroelectric single crystals to obtain hafnium oxide ferroelectric phase single crystals.
The method of the embodiment heats the hafnium oxide polycrystal rod by a laser heating mode, and can grow the hafnium oxide monocrystal with large size and no macroscopic defect. The heating temperature of the laser heating zone melting method can reach 3000 ℃ at most, so that the requirement of high melting point of hafnium oxide can be met, and the growing mode has higher heating temperature and can bring greater supercooling degree, so that the prepared hafnium oxide crystal is in a ferroelectric phase. In addition, the laser irradiation stability is good, the temperature uniformity of the heating area is high, the phase separation caused by the temperature non-uniformity can not occur, the component change is caused, the pollution problem is avoided, and the ferroelectric film quality is better.
As shown in fig. 2, it is found that a larger phase change potential barrier exists in the process of monoclinic phase transition of ferroelectric phase to stable phase, and a ferroelectric single crystal can be obtained by heating hafnium oxide to tetragonal phase and then cooling the sample by adjusting a larger supercooling degree. The requirement of the process on temperature is very high, and the heating temperature of the laser heating zone melting method can reach 3000 ℃ at most, so that the requirement of high melting point of hafnium oxide can be met firstly, and the second growth mode has higher heating temperature and can bring greater supercooling degree, so that the prepared hafnium oxide crystal is in a ferroelectric phase.
For a clearer description, the following description will be given for the above steps, respectively:
first, step S110: two hafnium oxide polycrystal material rods were obtained.
Hafnium oxide polycrystal material in this stepThe rod may be hafnium oxide (HfO 2 ) May also be doped hafnium oxide (HfO 2 ). Wherein the doping element is one or a combination of more of silicon (Si), aluminum (Al), zirconium (Zr), lanthanum (La), cerium (Ce) and yttrium (Y).
Specifically, the hafnium oxide polycrystal material rod can be prepared by the following method:
in the first step, raw material powder is prepared. Hafnium oxide and oxide powder doped with elements are prepared, and the powder is placed in a box furnace and heated and dried at 900 ℃ for one night, so that moisture in a sample is taken out, and the moisture is prevented from affecting the subsequent grain growth.
And secondly, preparing uniformly mixed raw material powder. Mixing the powder dried in the previous step according to the stoichiometric ratio of the doping ratio, grinding, then placing into an open zirconia crucible with the diameter of 100mm multiplied by 100mm, placing into a box-type furnace, slowly heating to 1500 ℃, and sintering for 20 hours. Taking out the powder after sintering, cooling to room temperature, taking out the powder, grinding the powder for the second time, and repeating the previous step, and sintering at 1500 ℃ for 20 hours. And grinding the sintered sample again to obtain uniform hafnium oxide powder.
Thirdly, preparing the hafnium oxide polycrystal material rod. Grinding and refining the raw material powder prepared in the last step, adding an alcohol solution, and uniformly mixing. Placing the powder into a rubber tube, vacuumizing the rubber tube for 10-15 minutes, and pressing the powder into a material rod. And drying the rubber tube containing the hafnium oxide material rod, and removing the outer rubber tube. And (3) placing the hafnium oxide material rod into a box furnace to sinter for 10-15 hours at 1600 ℃ to obtain the hafnium oxide polycrystalline material rod.
Then step S120: and arranging the two hafnium oxide polycrystal material rods in a collinear way, and leaving a gap with a preset distance between the two hafnium oxide polycrystal material rods.
The laser device can be adjusted first, and in an exemplary embodiment, seven laser light sources are arranged in the device, each light source is controlled by an independent power supply, the maximum power of each light source is 200W, and the laser wavelength is 800-1100nm. The width of the laser beam is adjusted to be larger than the width of the polycrystalline rod, and the laser irradiation position is adjusted up and down to be in the same horizontal plane. Then the laser source is adjusted back and forth so that the focus is at the center point of the horizontal plane. Installing the polycrystalline rods prepared in the third step in a laser heating zone melting method device platform, and butting up and down to form a straight line which is positioned at the focus of the laser adjusted in the last step. The gap between the upper and lower material bars is 1-1.5mm, so that the gap between the upper and lower polycrystalline bars is positioned at the horizontal plane of laser irradiation.
Finally, step S130: and placing the gap in a laser heating area to grow ferroelectric single crystals to obtain hafnium oxide ferroelectric phase single crystals.
The temperature rising rate in the laser heating zone melting method device can be slowly regulated to be 30-60 ℃/min, and the rotating speed of the hafnium oxide polycrystal rod in the fixed zone melting method device is 20-25r/min. When the top ends of the upper hafnium oxide polycrystal rod and the lower hafnium oxide polycrystal rod are just in a molten state, the upper hafnium oxide polycrystal rod and the lower hafnium oxide polycrystal rod are butted by slowly moving, after the butt joint is successful, the morphology of the hafnium oxide crystal is stable, the crystal growth rate is 20mm/h, the crystal grows in an oxygen atmosphere, and the oxygen inlet rate is 0.5-1L/min.
The heating is performed by using laser, and the heating temperature is high. Because the laser beam is used, the control of the heating area is better, the penetration of the melt to the top (raw material part) of the sample can be restrained, more stable raw material supply is obtained, and meanwhile, the upper and lower rotation directions of the sample are opposite, so that the temperature of the heating area is more uniform and concentrated.
After the step S130, the laser light source is turned off after the growth is completed, oxygen is continuously introduced, the cooling time is 1-2 hours, and the hafnium oxide ferroelectric monocrystal can be obtained after the cooling is completed.
In some embodiments, the obtaining two hafnium oxide polycrystalline material rods comprises:
heating and drying hafnium oxide raw material powder to obtain dried powder;
grinding and sintering the dried powder to obtain hafnium oxide powder;
and (3) performing pressing, shaping and sintering on the hafnium oxide powder to obtain the hafnium oxide polycrystalline material rod.
In some embodiments, the hafnium oxide raw powder is a hafnium oxide powder or a doped hafnium oxide powder.
In some embodiments, the doping element of the doped hafnium oxide powder is one or more of silicon, aluminum, zirconium, lanthanum, cerium, yttrium.
In some embodiments, the predetermined distance is 1-1.5mm.
In some embodiments, the heating rate of the laser heating zone is between 30-60 ℃/min.
In some embodiments, the placing the gap in a laser heating zone for growing a ferroelectric single crystal to obtain a hafnium oxide ferroelectric phase single crystal comprises:
placing the gap in a laser heating area and rotating the two hafnium oxide polycrystal material rods in opposite directions;
when two ends of the two hafnium oxide polycrystal material rods, which are close to each other, are in a molten state, the two hafnium oxide polycrystal material rods are in butt joint;
oxygen is introduced to grow the crystals in an oxygen atmosphere to obtain a single crystal ferroelectric phase.
In some embodiments, the counter-rotation has a rotation rate of 20-25r/min.
In some embodiments, after the gap is placed in the laser heating area for growing the ferroelectric single crystal to obtain a single crystal ferroelectric phase, the method for preparing the single crystal ferroelectric phase further includes:
continuously introducing oxygen and cooling for 1-2 hours.
In one embodiment of the present application, a method for preparing a single crystal ferroelectric phase is provided, which may include:
first hafnium oxide HfO 2 And zirconia ZrO 2 The powder is put into a box-type furnace and heated and dried at 900 ℃ for one night so as to remove moisture in the sample and avoid the moisture from affecting the subsequent grain growth.
And secondly, preparing the HZO powder which is uniformly mixed. The HZO powder can be HfO doped with Zr 2 Powder, the step is to mix the powder dried in the previous step according to the stoichiometric ratio of 1:1 and grind the mixture finely, then put the mixture into an open zirconia crucible with phi of 100mm multiplied by 100mm, then put the mixture into a box-type furnace, slowly heat the mixture to 1500 ℃ and sinter the mixture for 20 hours.Taking out the powder after sintering, cooling to room temperature, taking out the powder, grinding the powder for the second time, and repeating the previous step, and sintering at 1500 ℃ for 20 hours. And grinding the sintered sample again to obtain uniform HZO powder.
Grinding and refining the HZO powder prepared in the last step, adding an alcohol solution, and uniformly mixing. HZO powder was placed in a rubber tube having a diameter of 3mm, and after evacuating the rubber tube for 15 minutes, the powder was pressed into a rod under a pressure of 8000 PSI. And drying the rubber tube containing the HZO material rod, and removing the outer rubber tube. And (5) placing the HZO material rod into a box furnace to sinter for 10 hours at 1600 ℃ to obtain the HZO polycrystalline rod.
The laser beam width was adjusted to be larger than the width of the polycrystalline rod as shown in fig. 3, and the laser irradiation position was adjusted up and down to be in the same horizontal plane as shown in fig. 2. Then the laser source is adjusted back and forth so that the focus is at the center point of the horizontal plane.
Taking two polycrystalline rods prepared in the third step, one polycrystalline rod is used as seed crystal, the other polycrystalline rod is used as raw material, the polycrystalline rods are installed in a laser heating zone melting method device platform and are butted up and down to form a straight line, and the straight line is positioned at the focus of laser adjusted in the last step. The gap was 1.5mm so that the gap between the upper and lower polycrystalline rods was located at the level of laser irradiation.
The temperature of the laser heating zone melting method device is slowly regulated, and the power of the device is controlled at 95%. The rotating speed of the HZO polycrystal rod in the fixed zone melting device is 20r/min. And as shown in fig. 5, the up-and-down rotation is reversed. When the top ends of the upper and lower HZO polycrystalline rods are just in a molten state, the upper and lower rods are slowly moved to be butted, and after the butt joint is successful, the morphology of the HZO crystal is stable, so that the crystal growth rate is 20mm/h, the crystal grows in an oxygen atmosphere, and the oxygen inlet rate is 0.5L/min.
After the growth is completed, the laser light source is turned off, oxygen is continuously introduced, the cooling time is 2 hours, and the HZO ferroelectric single crystal can be obtained after the cooling is completed.
In another embodiment of the present application, a method for preparing a hafnium oxide ferroelectric phase single crystal is provided, which may include:
first hafnium oxide HfO 2 With yttrium oxideY 2 O 3 The powder is put into a box-type furnace and heated and dried at 900 ℃ for one night so as to remove moisture in the sample and avoid the moisture from affecting the subsequent grain growth.
Secondly, preparing uniformly mixed Y: hfO (HfO) 2 And (3) powder. Mixing the powder dried in the previous step according to the stoichiometric ratio of hafnium, hf and yttrium in the Y ratio of 8:1, grinding the mixture, then placing the mixture into an open zirconia crucible with phi of 100mm multiplied by 100mm, then placing the crucible into a box-type furnace, slowly heating the crucible to 1500 ℃, and sintering the crucible for 20 hours. Taking out the powder after sintering, cooling to room temperature, taking out the powder, grinding the powder for the second time, and repeating the previous step, and sintering at 1500 ℃ for 20 hours. Grinding the sintered sample again to obtain uniform Y: hfO2 powder.
And (3) carrying out the preparation of Y in the last step: hfO (HfO) 2 Grinding and refining the powder, adding alcohol solution, and mixing uniformly. Y: hfO (HfO) 2 The powder was placed in a rubber tube having a diameter of 3mm, and after evacuating the rubber tube for 15 minutes, the powder was pressed into a rod under a pressure of 8000 PSI. Will contain Y: hfO (HfO) 2 And after the rubber tube of the material rod is dried, removing the outer rubber tube. Y: hfO (HfO) 2 Placing the material rod into a box furnace to be sintered for 10 hours at 1600 ℃ to obtain Y: hfO (HfO) 2 A polycrystalline rod.
Seven laser light sources are arranged in the device, each light source is controlled by an independent power supply, the maximum power of each light source is 200W, and the laser wavelength is 800-1100nm. The laser beam width was adjusted to be larger than the width of the polycrystalline rod as shown in fig. 3, and the laser irradiation position was adjusted up and down to be in the same horizontal plane as shown in fig. 2. Then the laser source is adjusted back and forth so that the focus is at the center point of the horizontal plane.
Taking two polycrystalline rods prepared in the third step, one polycrystalline rod is used as seed crystal, the other polycrystalline rod is used as raw material, the polycrystalline rods are installed in a laser heating zone melting method device platform and are butted up and down to form a straight line, and the straight line is positioned at the focus of laser adjusted in the last step. The gap was 1.5mm so that the gap between the upper and lower polycrystalline rods was located at the level of laser irradiation.
The temperature of the laser heating zone melting method device is slowly regulated, and the power of the device is controlled at 95%. Y in the fixed zone melting apparatus: hfO (HfO) 2 Polycrystalline rodThe rotational speed of (2) is 20r/min. And as shown in fig. 5, the up-and-down rotation is reversed. When the upper Y and the lower Y: when the top end of the HfO2 polycrystalline rod is just in a molten state, the upper rod and the lower rod are slowly moved to be in butt joint, and after the butt joint is successful, the following steps are that: hfO (HfO) 2 The crystal morphology is stable, the crystal growth rate is 20mm/h, the crystal grows in the oxygen atmosphere, and the oxygen inlet rate is 0.5L/min.
After the growth is completed, the laser light source is turned off, oxygen is continuously introduced, the cooling time is 2 hours, and the Y: hfO can be obtained after the cooling is completed 2 Ferroelectric single crystals.
In a second aspect of embodiments of the present application, there is provided a hafnium oxide ferroelectric phase single crystal prepared by the method for preparing a hafnium oxide ferroelectric phase single crystal according to any one of the embodiments of the first aspect.
The embodiments of the present application have been described above with reference to the accompanying drawings, but the present application is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and many forms may be made by those of ordinary skill in the art without departing from the spirit of the present application and the scope of the claims, which are also within the protection of the present application.
Claims (7)
1. A method for producing a hafnium oxide ferroelectric phase single crystal, comprising:
obtaining two hafnium oxide polycrystal material rods;
setting two hafnium oxide polycrystal material rods in a collinear manner, and reserving a gap with a preset distance between the two hafnium oxide polycrystal material rods, wherein the preset distance is 1-1.5mm;
placing the gap in a laser heating zone to grow ferroelectric single crystals to obtain hafnium oxide ferroelectric phase single crystals, wherein the heating rate of the laser heating zone is between 30 and 60 ℃/min;
the step of placing the gap in a laser heating area to grow the ferroelectric single crystal to obtain the hafnium oxide ferroelectric phase single crystal comprises the following steps:
placing the gap in a laser heating area and rotating the two hafnium oxide polycrystal material rods in opposite directions;
when two ends of the two hafnium oxide polycrystal material rods, which are close to each other, are in a molten state, the two hafnium oxide polycrystal material rods are in butt joint;
oxygen is introduced to enable the crystal to grow in the oxygen atmosphere so as to obtain the hafnium oxide ferroelectric phase monocrystal.
2. The method for producing a hafnium oxide ferroelectric phase single crystal according to claim 1, wherein the obtaining two hafnium oxide polycrystal material rods comprises:
heating and drying hafnium oxide raw material powder to obtain dried powder;
grinding and sintering the dried powder to obtain hafnium oxide powder;
and (3) performing pressing, shaping and sintering on the hafnium oxide powder to obtain the hafnium oxide polycrystalline material rod.
3. The method for producing a hafnium oxide ferroelectric phase single crystal according to claim 2, wherein the hafnium oxide raw material powder is hafnium oxide powder or doped hafnium oxide powder.
4. A method for producing a hafnium oxide ferroelectric phase single crystal according to claim 3, wherein the doping element of the doped hafnium oxide powder is one or more of silicon, aluminum, zirconium, lanthanum, cerium, yttrium.
5. The method for producing a hafnium oxide ferroelectric single crystal according to claim 1, wherein the rotation rate of the counter rotation is 20 to 25r/min.
6. The method for producing a hafnium oxide ferroelectric phase single crystal according to claim 1, wherein after said placing said slit in a laser heating zone for growing a ferroelectric single crystal to obtain a hafnium oxide ferroelectric phase single crystal, said method for producing a hafnium oxide ferroelectric phase single crystal further comprises:
continuously introducing oxygen and cooling for 1-2 hours.
7. A hafnium oxide ferroelectric phase single crystal prepared by the method for producing a hafnium oxide ferroelectric phase single crystal according to any one of claims 1 to 6.
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| KR20170004274A (en) * | 2015-07-01 | 2017-01-11 | 에스케이하이닉스 주식회사 | Method of fabricating hafnium oxide and semiconductor device having the same |
| US20220325439A1 (en) * | 2019-09-04 | 2022-10-13 | The Johns Hopkins University | Functional metal oxides and methods of making same |
| US11855204B2 (en) * | 2020-04-20 | 2023-12-26 | Unist (Ulsan National Institute Of Science And Technology) | Ultra high-density memory and multi-level memory device and method of fabricating the same |
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| CN108330540A (en) * | 2018-04-12 | 2018-07-27 | 山东大学 | Hafnium oxide single crystal fiber and the preparation method and application thereof |
| CN111554568A (en) * | 2020-05-19 | 2020-08-18 | 湘潭大学 | Preparation method of hafnium oxide based ferroelectric film |
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