CN112941631B - Zinc orthotitanate single crystal film and preparation method thereof - Google Patents
Zinc orthotitanate single crystal film and preparation method thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 88
- ZBFOLPMOGPIUGP-UHFFFAOYSA-N dizinc;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Zn+2].[Zn+2] ZBFOLPMOGPIUGP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 91
- 239000000758 substrate Substances 0.000 claims abstract description 46
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- -1 magnesium aluminate Chemical class 0.000 claims abstract description 11
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 118
- 239000010409 thin film Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 239000010936 titanium Substances 0.000 claims description 26
- 238000000137 annealing Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 125000002524 organometallic group Chemical group 0.000 claims description 12
- 238000011282 treatment Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000012159 carrier gas Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 27
- 239000004065 semiconductor Substances 0.000 abstract description 9
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- 238000004098 selected area electron diffraction Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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
- C30B29/22—Complex oxides
- C30B29/32—Titanates; Germanates; Molybdates; Tungstates
-
- 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
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a zinc orthotitanate single crystal film and a preparation method thereof. Diethyl zinc and tetra (dimethylamino) titanium are used as metal organic compound source materials, oxygen is used as oxidizing gas, a metal organic chemical vapor deposition device is adopted to grow a zinc titanate film on a magnesium aluminate crystal surface substrate under a vacuum condition, and the prepared film is annealed in the air to obtain the cubic zinc orthotitanate single crystal film. The zinc orthotitanate single crystal film material prepared by the invention has the advantages of regular lattice arrangement, complete structure, no twin crystal, high stability, good adhesion performance and wide application prospect in the field of semiconductor photoelectric devices.
Description
Technical Field
The invention relates to a zinc orthotitanate single crystal film and a preparation method thereof, belonging to the technical field of wide bandgap oxide semiconductor materials.
Background
The zinc orthotitanate belongs to functional materials and has wide application. Cubic zinc orthotitanate (Zn) 2 TiO 4 ) The wide band gap semiconductor material has the band gap width of about 3.29eV at room temperature, and has the advantages of high transmittance in a visible light region, stable physicochemical properties and the like. Zn 2 TiO 4 The material has good photoelectric characteristics and has application potential in the fields of luminescence, photocatalysis, dye-sensitized solar cells, gas-sensitive sensors and the like.
As for the production of the zinc orthotitanate material, a solution method, a sol-gel method, a sputtering method, and the like are mainly used, and for example, the publication nos.: CN1884095A (application No. 200610021323.4), CN103230812A (application No. 201310073213.2), and CN206076058U (application No. 201621112395.5). However, the currently prepared zinc orthotitanate material still has the following problems:
(1) most of the prepared zinc orthotitanate materials are in the forms of powder, polycrystalline films and nano structures, and the prepared materials are poor in crystallization quality and have many defects. At present, Zn is not seen 2 TiO 4 Bulk single crystal material is reported.
(2) The research on the zinc titanate mostly focuses on the improvement of the photocatalytic performance, luminescence performance and other performances of the material, and the research report related to the preparation of the single crystal thin film material is rare. One of the important reasons for restricting the development of zinc orthotitanate in the field of semiconductor electronic devices is the lack of zinc orthotitanate single crystal thin film materials, which limits the application of the zinc orthotitanate single crystal thin film materials in the field of semiconductor photoelectric devices.
(3) The high-performance zinc orthotitanate-based semiconductor device is manufactured by preparing a high-quality zinc orthotitanate single crystal film and obtaining a zinc orthotitanate film material with adjustable and controllable electrical properties by doping on the basis.
(4) The preparation of the zinc orthotitanate single crystal film requires a process suitable for growing the single crystal film and a single crystal substrate material matched with the crystal lattice of the zinc orthotitanate single crystal film. Currently, the most commonly used sapphire (alpha-Al) is used 2 O 3 ) And the silicon carbide (SiC) wafer and the gallium nitride (GaN) epitaxial wafer thereof are in a hexagonal structure, and are different from a cubic structure of a crystal form of zinc orthotitanate, if the materials are used as substrates to prepare the zinc orthotitanate, a triple-domain twin crystal structure can be formed, and the lattice mismatch is large. Therefore, a substrate material suitable for growing a zinc orthotitanate single crystal thin film is required to be found.
In addition, CN106024398A (application No. 201610625265.X) discloses a dye-sensitized Zn for solar cell 2 TiO 4 The nanocrystalline film comprises a titanium suboxide layer as an underlayer and Zn 2 TiO 4 A nanocrystalline thin film of said Zn 2 TiO 4 The grain diameter of the nano crystal is 10-50nm, and the nano crystal is sintered into a film by adopting a sol-gel method. TW201317050A (application No. TW100139569) discloses a photocatalyst film for anti-bioadhesion comprising ZnTiO 3 、Zn 2 TiO 4 And Zn 2 Ti 3 O 8 At least one of the above methods is a sputtering method or a sol-gel method. The sol-gel method can prepare a gel film by a dipping, pulling or spin coating method, and then forms an inorganic film by drying and sintering, and is characterized in that the formed film is of an amorphous or polycrystalline structure, and the film has loose texture and many defects; the sputtering method can produce a thin film of an amorphous or polycrystalline structure, but is not suitable for epitaxial growth of a single crystal thin film. The quality of the film prepared by the sputtering method is superior to that of the film prepared by the sol-gel method. However, the CN106024398A and TW201317050A patents produce Zn 2 TiO 4 The film is a film with a nanocrystalline structure, the application of the film is a dye-sensitized film and a photocatalyst film of a solar cell respectively, and the requirement on the film structure is not high. Therefore, development of Zn having a good single crystal structure 2 TiO 4 The film has important significance in preparing devices with excellent performance in the fields of semiconductor electronic devices and photoelectric devices.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides high-quality zinc orthotitanate (Zn) 2 TiO 4 ) Single crystal thin filmAnd a method for preparing the same.
Interpretation of terms:
MOCVD: metal organic chemical vapor deposition.
The technical scheme of the invention is as follows:
the monocrystal film of zinc orthotitanate has the chemical composition of zinc orthotitanate and is cubic monocrystal.
According to the present invention, it is preferable that the crystal growth plane of the zinc orthotitanate single crystal thin film is Zn 2 TiO 4 (100) The internal lattice structure of the film is complete and has no twin crystal structure.
According to the invention, the growing bottom of the zinc orthotitanate single crystal film is MgAl 2 O 4 Substrate, zinc orthotitanate film and MgAl 2 O 4 The in-plane epitaxial relationship of the substrate is Zn 2 TiO 4 (100)//MgAl 2 O 4 (100) And Zn 2 TiO 4 [001]//MgAl 2 O 4 [001]。
According to the invention, the thickness of the zinc orthotitanate single crystal thin film is preferably 200-500 nm.
According to the invention, the zinc orthotitanate film is of a single crystal structure with regular lattice arrangement and complete structure, and provides a high-quality single crystal film for effective doping of the zinc orthotitanate film in the later period, so that the zinc orthotitanate film can be well applied to the fields of semiconductor electronic devices and photoelectric devices.
According to the present invention, the method for preparing the zinc orthotitanate single crystal thin film is a Metal Organic Chemical Vapor Deposition (MOCVD) method, wherein an organic metal Zn source and an organic metal Ti source are used as the metal organic compound raw materials, nitrogen is used as the carrier gas, oxygen is used as the oxidizing gas, and MgAl is added to the mixture 2 O 4 (100) Growing a zinc orthotitanate film on a single crystal substrate, and carrying out high-temperature annealing treatment on the grown amorphous film to obtain the zinc orthotitanate single crystal film.
According to the invention, the zinc orthotitanate single crystal film has a cubic structure, and the crystal growth surface of the zinc orthotitanate single crystal film is Zn 2 TiO 4 (100) The internal crystal lattice structure of the film is complete and twin crystal junctions are avoidedEpitaxial relation Zn of structure, film growth 2 TiO 4 (100)//MgAl 2 O 4 (100) And Zn 2 TiO 4 [001]//MgAl 2 O 4 [001]。
According to the present invention, preferred MOCVD process conditions are as follows:
the pressure of the reaction chamber is 10-80 Torr;
the growth temperature is 450-600 ℃;
background N 2 The flow rate is 100-200 sccm;
the oxygen flow is 30-80 sccm;
flow rate of diethyl zinc source 6X 10 -7 ～4×10 -6 Moles/minute (mol/min);
titanium tetra (dimethylamino) source flow 3X 10 -7 ～2×10 -6 mol/min。
According to the invention, the growth rate of the zinc titanate film under the preparation process condition is preferably 1.0-8.0 nm/min.
According to the invention, the high-temperature annealing treatment of the normal zinc titanate film is preferably carried out in the air, wherein the annealing temperature is 900-1000 ℃, and is further preferably 930-970 ℃;
preferably, the annealing time is 15 minutes to 60 minutes.
According to the present invention, it is preferred to maintain the molar flow ratio of organometallic Zn source to Ti source at (1.5-2.5): 1, most preferably 2: 1.
According to the invention, after setting the pressures of the organic metal Zn source and Ti source steel cylinders and the cold trap temperature, the molar flow rates of the organic Zn source and Ti source are controlled by changing the flow rate of the carrier gas.
Most preferably, according to the present invention, the process conditions of MOCVD are as follows:
the pressure of the reaction chamber is 30 Torr;
the growth temperature is 550 ℃;
background N 2 The flow rate is 120 sccm;
flow rate of diethyl zinc source 2.2X 10 -6 mol/min；
Source stream of tetrakis (dimethylamino) titaniumAmount 1.1X 10 -6 mol/min；
The molar flow ratio of organometallic Zn source to Ti source was maintained at 2:1 throughout the preparation of the films.
According to the present invention, the growth rate of the zinc titanate thin film under the above-mentioned preparation process conditions was 2.5 nm/min.
According to the present invention, it is most preferable that the high temperature annealing treatment temperature for the zinc orthotitanate film in air is 950 ℃.
According to the invention, preferably, the organometallic Zn source is diethylzinc [ Zn (C) 2 H 5 ) 2 ]The organometallic Ti source is tetrakis (dimethylamino) titanium { Ti [ N (CH) 3 ) 2 ] 4 The oxidizing gas is oxygen.
According to the invention, the substrate is preferably magnesium aluminate (MgAl) 2 O 4 ) And (5) the single crystal wafer, wherein the polished crystal face of the substrate is (100).
According to the invention, the zinc orthotitanate obtained by the preparation method is a single crystal thin film material with a cubic structure, and the growth surface of the zinc orthotitanate thin film is Zn 2 TiO 4 (100)。
According to the present invention, the above method for producing a single crystal thin film of zinc orthotitanate, in a preferred embodiment, comprises the steps of:
(1) pumping the reaction chamber of MOCVD equipment to high vacuum state with vacuum degree of 4X 10 -5 ～6×10 -4 Pa, placing the cleaned magnesium aluminate substrate in a reaction chamber and heating to the growth temperature of 450-600 ℃;
(2) opening the nitrogen cylinder valve, and introducing background N into the reaction chamber 2 Background N 2 The flow rate is 100-200 sccm, the pressure of the reaction chamber is 10-80 Torr, and the reaction chamber is kept for 25-30 minutes;
(3) opening an oxygen cylinder valve, wherein the oxygen flow is 30-80 sccm, and keeping for 8-10 minutes;
(4) opening the valve of the organometallic Zn source bottle, and adjusting the flow of the diethyl zinc source to be 6 multiplied by 10 -7 ～4×10 -6 Keeping for 8-10 minutes at mol/min;
(5) opening the valve of the organic metal Ti source bottle, and adjusting the flow of the tetra (dimethylamino) titanium source to 3 multiplied by 10 -7 ～2×10 -6 Keeping for 8-10 minutes at mol/min;
(6) simultaneously introducing the gases in the steps (3), (4) and (5) into a reaction chamber, and keeping the time for 100-180 minutes; the growth rate of the zinc titanate film on the magnesium aluminate substrate is 1.0-8.0 nm/min;
(7) closing the organic metal Zn source bottle, the Ti source bottle and the oxygen bottle valve after the reaction is finished, and flushing the pipeline for 25-30 minutes by using nitrogen;
(8) and (3) placing the prepared film sample in a tubular furnace to carry out high-temperature annealing treatment, wherein the gas atmosphere is air, the annealing temperatures are 900 ℃, 950 ℃ and 1000 ℃, the heating rate is controlled to be 10 ℃/min, and the target temperature is kept for 0.5 hour to obtain the zinc orthotitanate single crystal film.
The zinc orthotitanate single crystal epitaxial film prepared by the invention has many unique advantages, the film has complete crystal lattice structure, no twin crystal, good adhesiveness, high stability and very wide application prospect.
Compared with the existing zinc titanate film, the zinc orthotitanate film prepared by the invention has the following excellent effects:
1. the zinc orthotitanate thin film of the present invention is a single crystal thin film having a cubic structure. The growth surface of the zinc orthotitanate film is Zn 2 TiO 4 (100)，Zn 2 TiO 4 Film and MgAl 2 O 4 The in-plane epitaxial relationship of the substrate is Zn 2 TiO 4 [001]//MgAl 2 O 4 [001]。
2. The zinc orthotitanate monocrystal film has the advantages of complete lattice structure, no twin crystal inside, regular and ordered atomic arrangement and few lattice defects, and is suitable for manufacturing zinc orthotitanate based electronic devices and transparent semiconductor devices.
3. The method for preparing the zinc orthotitanate single crystal film of the invention optimizes the substrate and finds that magnesium aluminate MgAl is selected 2 O 4 (100) The crystal face is used as a substrate, and a single crystal film can be obtained; meanwhile, the invention optimizes the heat treatment temperature, and the Zn can be successfully obtained only by controlling the heat treatment temperature to 950-1000 DEG C 2 SnO 4 A single crystal thin film.
4. The results of various structural representations show that the zinc orthotitanate film has a good single crystal structure and high stability, can be effectively doped to obtain the zinc orthotitanate film with stable and controllable electrical properties, and has wide application prospects in the field of photoelectric devices.
Drawings
FIG. 1 is an X-ray theta-2 theta scanning diffraction pattern of a zinc orthotitanate film after non-annealing and different temperature annealing treatments. Abscissa Degree: degree, ordinate Intensity/a.u.: intensity (arbitrary units).
FIG. 2 shows the Zn film after 950 ℃ heat treatment in example 1 2 TiO 4 {220} plane and substrate MgAl 2 O 4 X-ray in-situ phi scan of {220} plane, where (a) is the substrate MgAl 2 O 4 (iii) diffraction spectrum of {220} plane, (b) thin film Zn 2 TiO 4 Diffraction spectra of {220} plane.
FIG. 3 shows Zn after 950 ℃ heat treatment in example 1 2 TiO 4 Film and MgAl 2 O 4 High Resolution Transmission Electron Microscopy (HRTEM) pattern at the substrate interface.
FIG. 4 shows Zn after 950 ℃ heat treatment in example 1 2 TiO 4 Film and MgAl 2 O 4 A Selected Area Electron Diffraction (SAED) pattern at the substrate interface.
Detailed Description
The invention is further described below by reference to the drawings, examples and comparative examples, but is not limited thereto.
Example 1:
using magnesium aluminate single crystal wafer as substrate, Zn (C) with purity of 99.9999% 2 H 5 ) 2 And Ti [ N (CH) 3 ) 2 ] 4 The zinc titanate film material is prepared by MOCVD technology by using ultrahigh pure nitrogen as carrier gas and high pure oxygen as oxidizing gas as organic metal source and through heat treatment at 950 deg.c.
The method comprises the following steps:
(1) pumping the MOCVD reaction chamber to high vacuum degree of 2 × 10 -4 Pa, placing the magnesium aluminate substrate in a reaction chamber and heating to the temperature of 550 ℃;
(2) opening nitrogen gasA bottle valve for introducing background N into the reaction chamber 2 Background N 2 The flow rate is 120sccm, the pressure of the reaction chamber is 30Torr, and the reaction chamber is kept for 25 minutes;
(3) opening an oxygen cylinder valve, wherein the oxygen flow is 50sccm and keeping for 10 minutes;
(4) opening the valve of the organometallic Zn source bottle, and adjusting the flow of the diethyl zinc source to be 2.2 multiplied by 10 -6 Mol/min, hold for 10 minutes;
(5) opening the valve of the organic metal Ti source bottle, and adjusting the flow of the tetra (dimethylamino) titanium source to be 1.1 multiplied by 10 -6 Mol/min, hold for 10 minutes;
(6) oxygen in the step (3) and carrier gas N carrying organic metal Zn source in the step (4) 2 And step (5) carrier gas N carrying Ti source 2 Simultaneously introducing the mixture into a reaction chamber, and keeping the reaction chamber for 120 minutes; the growth rate of the zinc titanate film on the magnesium aluminate substrate is 2.5 nm/min;
(7) after the reaction, the organic metal Zn and Ti source bottles and the oxygen cylinder valves are closed, and the pipeline is flushed with nitrogen for 25 minutes.
(8) And (3) placing the prepared film sample in a tubular furnace for high-temperature annealing treatment, wherein the gas atmosphere is air, the annealing temperature is 950 ℃, the heating rate is controlled to be 10 ℃/min, and the target temperature is kept for 30 min. And after the annealing treatment is finished, naturally cooling to room temperature, and taking out the sample.
The film prepared in this example 1 was a cubic phase zinc orthotitanate single crystal film, and the growth surface of the film was Zn 2 TiO 4 (100) The film has complete crystal lattice structure and no twin crystal. The out-of-plane epitaxial relationship of the film and the substrate is Zn 2 TiO 4 (100)//MgAl 2 O 4 (100) In-plane epitaxial relationship of Zn 2 TiO 4 [001]//MgAl 2 O 4 [001]。
The X-ray theta-2 theta scanning diffraction pattern of the zinc orthotitanate film sample prepared in this example is shown in FIG. 1. Zn after 950 ℃ annealing treatment determined by the diffraction spectrum of the sample 2 TiO 4 The (400) diffraction peak of the film is strongest, and the full width at half maximum of the diffraction peak is the smallest, about 0.20 degrees, which indicates that the crystallization quality of the film is the best. Zn 2 TiO 4 The film isEdge [100 ]]Single orientation, the growth relation between the film and the substrate is Zn 2 TiO 4 (100)//MgAl 2 O 4 (100)。
Zn of the present example 2 TiO 4 Thin film {220} plane and substrate MgAl 2 O 4 X-ray in-situ phi-scan of the {220} plane, as shown in figure 2. Due to Zn 2 TiO 4 Only 4 diffraction peaks appear in the {220} plane in-situ phi scan spectrum of the film, and the diffraction peaks and MgAl are combined 2 O 4 The positions of the {220} plane in-situ phi-scan diffraction peaks are consistent, so that Zn can be judged 2 TiO 4 The film is single crystal, the crystal lattice structure of the film is complete, and twin crystals do not exist inside the film. The in-plane epitaxial relationship between the film and the substrate is Zn 2 TiO 4 [001]//MgAl 2 O 4 [001]。
The High Resolution Transmission Electron Microscopy (HRTEM) pattern at the interface of the zinc orthotitanate film prepared in this example with the magnesium aluminate substrate is shown in fig. 3. From FIG. 3, Zn can be clearly and visually seen 2 TiO 4 Film and MgAl 2 O 4 The regular arrangement of the lattice of the substrate, the crystal planes and orientations are marked on the figure, and the test results are consistent with the X-ray phi scan conclusion.
The high resolution transmission electron microscopy selected area electron diffraction pattern at the interface of the zinc orthotitanate film prepared in this example and the magnesium aluminate substrate is shown in fig. 4. Zn is shown in FIG. 4 2 TiO 4 Film and MgAl 2 O 4 The round point-shaped diffraction spots of the substrate are regularly and orderly arranged and present typical single crystal characteristics, crystal faces corresponding to the film and the diffraction spots of the substrate are marked in the figure, the epitaxial relationship is identical with the X-ray phi scanning conclusion, and the Zn with the cubic structure is proved to be obtained by the invention 2 TiO 4 A single crystal thin film.
Example 2:
with MgAl 2 O 4 (100) Preparing zinc titanate film material as substrate by MOCVD technique and carrying out heat treatment. The film was prepared by the same procedure as in example 1, except that the heat treatment temperature was 1000 ℃ and the time was 30 minutes. Prepared Zn 2 TiO 4 The film has a single epitaxial orientation of (400) crystal plane, but is trueExample 1 comparison, Zn 2 TiO 4 (400) The intensity of the diffraction peak of the crystal face is obviously reduced, and the full width at half maximum is increased, which indicates that the crystallization quality of the film of the sample subjected to the annealing treatment at 1000 ℃ is reduced.
Example 3:
with MgAl 2 O 4 (100) Preparing zinc titanate film material as substrate by MOCVD technique and carrying out heat treatment. The film formation process was the same as in example 1 except that the heat treatment temperature was 900 ℃ for 30 minutes. Prepared Zn 2 TiO 4 The film had a single epitaxial orientation with (400) crystal planes, but in comparison with examples 1 and 2, Zn 2 TiO 4 (400) The intensity of the diffraction peak of the crystal face is obviously weaker, which indicates that the crystallization quality of the film is reduced in the sample annealed at 900 ℃.
Comparative example 1: preparing the zinc titanate film material by the MOCVD technology.
With polished MgAl 2 O 4 (100) For the substrate, the film formation process was the same as in example 1, except that the annealing temperature was 800 ℃ and the target temperature was maintained for 30 minutes. Analysis of the test results in FIG. 1 shows that the film annealed at 800 ℃ did not form significant Zn 2 TiO 4 Diffraction peak, preparation of Zn 2 TiO 4 The film is in an amorphous or microcrystalline structure.
Comparative example 2: sapphire (alpha-Al) 2 O 3 ) And (0001) preparing the zinc titanate film material by using the MOCVD technology on the substrate.
The zinc titanate preparation method and annealing process were the same as in example 1, except that polished sapphire α -Al was used 2 O 3 (0001) Surface is substrate material, Zn is prepared 2 TiO 4 The film is of a polycrystalline structure.
Comparative example 3: zirconium oxide (ZrO) 2 ) (100) preparing the zinc titanate thin film material by using a substrate and MOCVD technology.
The zinc titanate preparation method and annealing process were the same as in example 1, except that zirconia ZrO was used 2 (100) Zn prepared as a substrate material 2 TiO 4 The film is of a polycrystalline structure.
Comparative example 4:
the film preparation process conditions were as described in example 1, except that:
using MgAl 2 O 4 (110) Is a substrate. Preparation of Zn 2 TiO 4 The film is of a polycrystalline structure.
Comparative example 5:
the film preparation process conditions were as described in example 1, except that:
using MgAl 2 O 4 (111) Is a substrate. Preparation of Zn 2 TiO 4 The film is of a polycrystalline structure.
Claims (8)
1. The monocrystal film of zinc orthotitanate is characterized in that the chemical composition of the monocrystal film is zinc orthotitanate, and the monocrystal film is a monocrystal with a cubic structure;
the crystal growth surface of the zinc orthotitanate single crystal film is Zn 2 TiO 4 (100) The internal lattice structure of the film is complete and has no twin crystal structure; the growth substrate of the zinc orthotitanate single crystal film is MgAl 2 O 4 Substrate, zinc orthotitanate film and MgAl 2 O 4 The in-plane epitaxial relationship of the substrate is Zn 2 TiO 4 （100）//MgAl 2 O 4 (100) And Zn 2 TiO 4 [001]// MgAl 2 O 4 [001]；
The zinc orthotitanate single crystal film is prepared by the following method:
the MOCVD method is adopted, and an organic metal Zn source and an organic metal Ti source are used as metal organic compound raw materials, nitrogen is used as a carrier gas, oxygen is used as an oxidizing gas, and MgAl is added into the mixture 2 O 4 (100) Growing a zinc orthotitanate film on a single crystal substrate, and carrying out high-temperature annealing treatment on the grown amorphous film to obtain the zinc orthotitanate single crystal film;
the MOCVD process conditions are as follows:
the pressure of the reaction chamber is 10-80 Torr;
the growth temperature is 450 ℃ and 600 ℃;
background N 2 Flow rate100-200 sccm；
Oxygen flow is 30-80 sccm;
flow rate of diethyl zinc source 6X 10 -7 -4×10 -6 Moles/minute (mol/min);
titanium tetra (dimethylamino) source flow 3X 10 -7 -2×10 -6 mol/min；
Annealing the normal zinc titanate film in air at the high temperature of 900-1000 ℃;
the organometallic Zn source is diethylzinc [ Zn (C) 2 H 5 ) 2 ]The organometallic Ti source is tetrakis (dimethylamino) titanium { Ti [ N (CH) 3 ) 2 ] 4 }。
2. The zinc orthotitanate single crystal thin film as claimed in claim 1, wherein the thickness of said zinc orthotitanate single crystal thin film is 200-500 nm.
3. A method for producing a zinc orthotitanate single crystal thin film according to claim 1, comprising the steps of:
the MOCVD method is adopted, and an organic metal Zn source and an organic metal Ti source are used as metal organic compound raw materials, nitrogen is used as a carrier gas, oxygen is used as an oxidizing gas, and MgAl is added into the mixture 2 O 4 (100) Growing a zinc orthotitanate film on a single crystal substrate, and carrying out high-temperature annealing treatment on the grown amorphous film to obtain the zinc orthotitanate single crystal film;
the MOCVD process conditions are as follows:
the pressure of the reaction chamber is 10-80 Torr;
the growth temperature is 450 ℃ and 600 ℃;
background N 2 The flow rate is 100-;
the oxygen flow is 30-80 sccm;
flow rate of diethyl zinc source 6X 10 -7 -4×10 -6 Moles/minute (mol/min);
titanium tetra (dimethylamino) source flow 3X 10 -7 -2×10 -6 mol/min；
Annealing the normal zinc titanate film in air at the high temperature of 900-1000 ℃;
the organometallic Zn source is diethylzinc [ Zn (C) ] 2 H 5 ) 2 ]The organometallic Ti source is tetrakis (dimethylamino) titanium { Ti [ N (CH) 3 ) 2 ] 4 }。
4. The method for preparing a zinc orthotitanate single crystal thin film as claimed in claim 3, wherein the annealing temperature is 930-970 ℃.
5. The method of producing a zinc orthotitanate single crystal thin film according to claim 3, wherein the annealing time is 15 minutes to 60 minutes.
6. The method of producing a zinc orthotitanate single crystal thin film according to claim 3, wherein the molar flow ratio of the organometallic Zn source to the Ti source is maintained at (1.5-2.5): 1.
7. the method of producing a zinc orthotitanate single crystal thin film according to claim 6, wherein the molar flow ratio of the organometallic Zn source to the Ti source is maintained at 2:1 at all times during the production of the thin film.
8. The method of producing a zinc orthotitanate single crystal thin film according to claim 3, wherein the substrate is magnesium aluminate (MgAl) 2 O 4 ) And (3) a single crystal wafer, wherein the polished crystal plane of the substrate is (100).
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