CN117089821A - In-situ annealing preparation of pure-phase MoO 3 Method for producing films and use thereof - Google Patents
In-situ annealing preparation of pure-phase MoO 3 Method for producing films and use thereof Download PDFInfo
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- CN117089821A CN117089821A CN202310974387.XA CN202310974387A CN117089821A CN 117089821 A CN117089821 A CN 117089821A CN 202310974387 A CN202310974387 A CN 202310974387A CN 117089821 A CN117089821 A CN 117089821A
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- 238000000137 annealing Methods 0.000 title claims abstract description 31
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title description 5
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 230000005693 optoelectronics Effects 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 56
- 239000013078 crystal Substances 0.000 claims description 9
- 238000007747 plating Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 65
- 230000000052 comparative effect Effects 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012159 carrier gas Substances 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910016001 MoSe Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- CMIAIUZBKPLIOP-YZLZLFLDSA-N methyl (1r,4ar,4br,10ar)-7-(2-hydroperoxypropan-2-yl)-4a-methyl-2,3,4,4b,5,6,10,10a-octahydro-1h-phenanthrene-1-carboxylate Chemical compound C1=C(C(C)(C)OO)CC[C@@H]2[C@]3(C)CCC[C@@H](C(=O)OC)[C@H]3CC=C21 CMIAIUZBKPLIOP-YZLZLFLDSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- -1 trimethyl silicon methyl lithium n-hexane Chemical compound 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention relates to the field of optoelectronic devices, and discloses a method for preparing pure-phase MoO by in-situ annealing 3 A method of forming a film and use thereof. The method is performed in an atomic layer deposition chamber, comprising: (1) At 250-350 ℃ and in the presence of nitrogen, the silicon wafer, the metal precursor and the first O 3 Coating film treatment is carried out in an atomic layer deposition cavity to obtain MoO x A film; (2) At 400-500 ℃ and at a second O 3 In the presence of the MoO x Annealing the film in an atomic layer deposition cavity for 10-25min to obtain pure-phase MoO 3 A film; the metal precursor is a compound shown in a formula (1). The method provided by the invention has good crystallinity and simple process, omits the operation of taking out the film from the atomic layer deposition cavity to the tube furnace, and reduces the heat loss; and is also provided withShort annealing time and can rapidly realize MoO x Phase to MoO 3 And (5) regulating and controlling phases.
Description
Technical Field
The invention relates to the field of optoelectronic devices, in particular to a method for preparing pure-phase MoO by in-situ annealing 3 A method of forming a film and use thereof.
Background
Molybdenum oxide (MoO) 3 ) The film has various excellent characteristics of electrochromic, gasochromic, photochromic and the like, and also has good electrochromicChemical characteristics, thus MoO 3 Films are widely used in a variety of fields, for example, in gas sensors, organic optoelectronic devices, lithium ion batteries, and the like, while MoO 3 Also is synthesized MoS 2 、MoSe 2 、MoTe 2 And the raw materials of the two-dimensional material.
Atomic Layer Deposition (ALD) is used to prepare MoO for deposition of various optoelectronic devices 3 A desirable way of forming a film. However, ALD is currently employed to directly deposit MoO 3 All requiring O with longer cycle numbers or high energy 2 The plasma is realized, and most of the method needs to anneal in nitrogen, oxygen or air for a long time after the deposition is finished so as to obtain pure-phase MoO 3 Thus increasing the complexity of the process and external variables. Such that the deposited film may adsorb air and environmental impurities after sampling from the ALD chamber, and later affect film purity and performance.
CN113130214A discloses a NF@MoO 3 @NiCo-LDH composite material, preparation method and application thereof are realized by mixing MoO 3 Is compounded with NiCo-LDH to achieve the effect of enhancing electrochemical performance, thereby overcoming MoO 3 And the application limit of NiCo-LDH itself in the aspect of super capacitor electrode materials and the like. However, the annealing process is carried out in a tubular resistance furnace in an air atmosphere for 1.5-2.5 hours.
Therefore, the preparation method has the advantages of good crystallinity, simple process, short annealing time and capability of rapidly realizing MoO x Phase to MoO 3 The method for regulating the phase has important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art that the atomic layer deposition method prepares pure-phase MoO 3 And the defects of complex process, long annealing time and poor crystallinity.
To achieve the above object, a first aspect of the present invention provides an in-situ annealing method for preparing pure-phase MoO 3 A method of forming a thin film, the method performed in an atomic layer deposition chamber, comprising:
(1) At 250-350 ℃ and in the presence of nitrogen, the silicon chip, the metal precursor and the first stepOne O 3 Coating film treatment is carried out in an atomic layer deposition cavity to obtain MoO x A film;
(2) At 400-500 ℃ and at a second O 3 In the presence of the MoO x Annealing the film in an atomic layer deposition cavity for 10-25min to obtain pure-phase MoO 3 A film;
the metal precursor is a compound shown in a formula (1):
the silicon wafer is monocrystalline silicon wafer with crystal orientation p <100 >.
In a second aspect, the invention provides pure phase MoO prepared by the method of the first aspect 3 A film.
A third aspect of the invention provides the pure phase MoO of the second aspect x The application of the film in the field of optoelectronic devices.
Compared with the prior art, the method provided by the invention has good crystallinity and simple process, omits the operation of taking the film out of the atomic layer deposition cavity to a tube furnace, and reduces the heat loss; and the annealing time is short, and MoO can be rapidly realized x Phase to MoO 3 And (5) regulating and controlling phases.
Drawings
FIG. 1 shows a preferred method of preparing pure phase MoO according to the present invention 3 XRD pattern of the film;
FIG. 2 shows a preferred method of preparing pure phase MoO according to the present invention 3 XRD pattern of the film;
FIG. 3 is a MoO prepared in comparative example 1 provided by the present invention x XRD pattern of the film;
FIG. 4 is a MoO prepared in comparative example 2 provided by the present invention x XRD pattern of the film;
FIG. 5 is a MoO prepared in comparative example 3 provided by the present invention x XRD pattern of the film.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
It should be noted that, in the aspects of the present invention, the present invention is described only once in one aspect thereof without repeated description with respect to the same components or terms in the aspects, and those skilled in the art should not understand the limitation of the present invention.
As previously described, the first aspect of the present invention provides an in situ annealing process for preparing pure phase MoO 3 A method of forming a thin film, the method performed in an atomic layer deposition chamber, comprising:
(1) At 250-350 ℃ and in the presence of nitrogen, the silicon wafer, the metal precursor and the first O 3 Coating film treatment is carried out in an atomic layer deposition cavity to obtain MoO x A film;
(2) At 400-500 ℃ and at a second O 3 In the presence of the MoO x Annealing the film in an atomic layer deposition cavity for 10-25min to obtain pure-phase MoO 3 A film;
the metal precursor is a compound shown in a formula (1):
the silicon wafer is monocrystalline silicon wafer with crystal orientation p <100 >.
Preferably, the thickness of the silicon wafer is 480-520 μm.
In the present invention, the first O 3 And said second O 3 All are O 3 。
In the present invention, the metal precursor is a product prepared by the method of example 1 in the prior application CN 115448954a published by the inventor.
Preferably, in step (1), the first O 3 The volume flow rate of (2) is 300-1000sccm; and is also provided with
The first O 3 The introduction time is 1-10s.
Preferably, in the step (1), the metal precursor is introduced for a time of 0.1 to 8 seconds.
According to a preferred embodiment, the method of the present invention further comprises, in step (1), repeating the coating treatment 500 to 1500 times.
According to a preferred embodiment, the method of the present invention further comprises, in step (1), dividing the nitrogen gas into three streams and continuously introducing the three streams into the atomic layer deposition chamber while the film plating treatment is performed, wherein the volumetric flow rate of the first nitrogen gas is 200-400sccm, and the first O is 3 Introducing the second nitrogen into the atomic layer deposition cavity by taking the second nitrogen as carrier gas, wherein the volume flow rate of the second nitrogen is 100-200sccm; and the metal precursor is introduced into the atomic layer deposition cavity by taking the third nitrogen as carrier gas, and the volume flow rate of the third nitrogen is 100-200sccm.
Preferably, the method of the present invention further comprises, in step (2), the MoO within the atomic layer deposition chamber x Before the film is applied to the annealing treatment, the temperature of the atomic layer deposition cavity is heated to 400-500 ℃ at the speed of 3-5 ℃/min, the heat preservation treatment is carried out, and then the annealing treatment is carried out. The inventors found that in this preferred case, the pure phase MoO prepared according to the invention 3 The crystallization property of the film is better.
Preferably, in step (2), the second O 3 The volume flow rate of (2) is 300-1000ccm. The inventors have found that in this preferred case, the final preparation of pure phase MoO can be improved 3 Crystallization properties of the film.
More preferably, the second O is continuously introduced while the annealing treatment is performed 3 Until the annealing treatment is completed.
According to a preferred embodiment, the method of the present invention further comprises, in step (1), preheating the metal precursor to 100-130 ℃ before the coating treatment is performed, and applying the metal precursor to the coating treatment.
According to a preferred embodiment, the method of the present invention further comprises, in step (2), during said step of applying to said MoO x After the film is annealed, the atomic layer deposition cavity is cooled to 15-30 ℃ under the vacuum degree of 0-4hPa, and the pure-phase MoO is obtained 3 And the average cooling rate is 1-5 ℃/min. The inventors have found that in this preferred case other problems of atmosphere disturbances or the introduction of foreign substances in the outside air can be avoided.
Preferably, the pressure of the plating treatment and the annealing treatment are each independently 1 to 15hPa.
As previously mentioned, the second aspect of the present invention provides a pure phase MoO prepared by the method of the first aspect 3 A film.
As previously mentioned, a third aspect of the present invention provides the pure phase MoO of the second aspect 3 The application of the film in the field of optoelectronic devices.
In the present invention, the room temperature or room temperature referred to in the following examples is 25.+ -. 3 ℃ unless otherwise specified.
The present invention will be described in detail by way of examples, and unless otherwise specified, all materials used are commercially available.
Silicon wafer: the silicon wafer is a circular monocrystalline silicon wafer with the thickness of 500+/-20 mu m and the diameter of 150mm, the crystal orientation of the silicon wafer is p <100>, and the silicon wafer is purchased from Zhejiang crystal phototechnology Co., ltd.
Atomic layer deposition instrument: model R-200, available from Finnish-picsun, inc., has an atomic layer deposition cavity 8 inches in diameter and 100mm in height.
Preparing a metal precursor:
reference is made to the method of example 1 in the patent application publication CN 115448954a, comprising:
s1, under the nitrogen atmosphere, firstly, filling a 1L Schlenk bottle (history)Lycra bottle) was added with 20g sodium molybdate, 400mL ethylene glycol dimethyl ether, 54mL triethylamine, 24mL tert-butylamine and 112mL trimethylchlorosilane, heated under reflux at 80℃for 24 hours, filtered to remove the precipitate, and the resulting filtrate was evaporated to dryness under reduced pressure to give (tBuN) 2 Mo(Cl 2 )-dme；
S2, 10.65g (tBuN) was added to a 500mLSchlenk flask under nitrogen atmosphere 2 Mo(Cl 2 ) -dme, 200mL toluene was added, 50mL pyridine was then added, followed by stirring at room temperature (400-700 rpm) for overnight reaction, and Mo-0.5 orange solid (intermediate) was obtained after evaporation of the solvent under reduced pressure;
s3, adding Mo-0.5 intermediate (10.4 g,22.3 mmol) into a 500mL Schlenk bottle under nitrogen atmosphere, adding toluene (200 mL), dripping trimethyl silicon methyl lithium n-hexane solution (82 mL,45.1 mmol) with the concentration of 0.55M/L into the reaction liquid through a constant pressure dropping funnel, stirring overnight at room temperature (400-700 rpm), evaporating the solvent under reduced pressure, adding 150mL n-hexane, filtering through diatomite, evaporating the filtrate to obtain a black reddish liquid crude product, and performing reduced pressure rectification on the obtained liquid crude product with the vacuum degree of 0.2torr and the rectification temperature of 120 ℃ to obtain the metal precursor.
Example 1
This example is illustrative of a preferred in situ annealing process for preparing pure phase MoO provided by the present invention 3 The method for preparing the film comprises the following steps:
(1) Placing a silicon wafer in an atomic layer deposition cavity, introducing first nitrogen at a volume flow rate of 300sccm, introducing the metal precursor preheated to 110 ℃ into the atomic layer deposition cavity by taking the third nitrogen at a volume flow rate of 150sccm as carrier gas, and then introducing first O by taking the second nitrogen at a volume flow rate of 150sccm as carrier gas 3 Introducing into an atomic layer deposition cavity, and coating the silicon wafer 1000 times at 300 ℃ under the pressure of 11hPa to obtain MoO x A film;
wherein the first O 3 The volume flow rate of (2) is 700sccm, and the introducing time is 5s;
the metal precursor is introduced for 2s;
(2) Heating the atomic layer deposition cavity to 400 ℃ at a speed of 5 ℃/min, preserving heat, and continuously introducing the second O at a volume flow rate of 700ccm 3 The MoO was then subjected to a pressure of 2hPa x Annealing the film in the atomic layer deposition cavity for 15min, cooling the atomic layer deposition cavity to room temperature at a vacuum degree of 1hPa at a cooling rate of 1 ℃/min to obtain the pure-phase MoO with a thickness of 57nm 3 A film, designated C1;
FIG. 1 shows the pure phase MoO in this example 3 XRD pattern (X-ray diffraction analysis pattern) of film (C1), wherein it is represented by stable orthorhombic phase alpha-MoO 3 Diffraction of (PDF 005-0508) is at 12.8, 25.7, 39.0 is diffraction peaks of crystal planes (020), (040), and (060), respectively. Description of the embodiment implementing MoO x Conversion of the crystalline phase of the film to pure phase MoO 3 Is a target of (a).
Example 2
This example is illustrative of a preferred in situ annealing process for preparing pure phase MoO provided by the present invention 3 The method for preparing the film comprises the following steps:
(1) Placing a silicon wafer in an atomic layer deposition cavity, introducing first nitrogen at a volume flow rate of 300sccm, introducing the metal precursor preheated to 110 ℃ into the atomic layer deposition cavity by taking the third nitrogen at a volume flow rate of 150sccm as carrier gas, and then introducing first O by taking the second nitrogen at a volume flow rate of 150sccm as carrier gas 3 Introducing into an atomic layer deposition cavity, and coating the silicon wafer 1000 times at 300 ℃ under the pressure of 11hPa to obtain MoO x A film;
wherein the first O 3 The volume flow rate of (2) is 700sccm, and the introducing time is 5s;
the metal precursor is introduced for 2s;
(2) Heating the atomic layer deposition cavity to 500 ℃ at a speed of 4 ℃/min, preserving heat, and continuously introducing the second O at a volume flow rate of 700ccm 3 At the same time, the MoO is pressed at a pressure of 2hPa x Annealing the film in an atomic layer deposition chamberTreating for 15min, cooling the atomic layer deposition cavity to room temperature under vacuum degree of 1hPa at cooling rate of 1 ℃/min to obtain the pure phase MoO with thickness of 58nm 3 The film was designated as C2.
FIG. 2 shows the pure phase MoO in this example 3 XRD pattern (X-ray diffraction analysis pattern) of film (C2), wherein it is represented by stable orthorhombic phase alpha-MoO 3 Diffraction of (PDF 005-0508), diffraction peaks of (110) and (021) appear at 12.8, 25.7 and 39.0 are diffraction peaks of crystal planes (020), (040) and (060), respectively, showing pure phase MoO prepared in this example 3 The crystallinity of the film is good.
Comparative example 1
This comparative example was conducted in a similar manner to example 1 except that in step (1), the temperature of the plating treatment was 350℃to obtain MoO 3 The film was designated DC1.
FIG. 3 shows MoO in this comparative example x XRD pattern of film without molybdenum suboxide phase MoO x The diffraction peak of crystal face of (2.75.ltoreq.x.ltoreq.2.89) is mainly weaker orthorhombic phase alpha-MoO 3 Small bulges formed by the peaks of (2). The transformation of the crystalline phase in this comparative example is illustrated, but the transformation process is slower.
Comparative example 2
This comparative example was conducted in a similar manner to example 1 except that the annealing treatment in step (2) was not conducted, specifically, the MoO obtained in step (1) was directly conducted x The film was cooled to room temperature to give the product, designated DC2.
FIG. 4 shows the XRD pattern (X-ray diffraction analysis pattern) of DC2 in this comparative example, in which a strong diffraction peak appears at 22.1℃and a weaker diffraction peak appears at 45.0℃and these two diffraction peaks are molybdenum suboxide phases MoO x (x is more than or equal to 2.75 and less than or equal to 2.89). XRD showed weaker orthorhombic phase alpha-MoO 3 Small bulges formed by the peaks of (2). Description of MoO in DC2 in this comparative example x Mainly in the sub-oxidation state.
Comparative example 3
This comparative example was conducted in a similar manner to example 1, except that,in the step (2), the annealing treatment temperature is 350 ℃, and MoO is obtained x The film was designated DC3.
FIG. 5 shows the XRD pattern (X-ray diffraction analysis pattern) of DC3 in this comparative example, in which a strong diffraction peak appears at 22.1℃and a weaker diffraction peak appears at 45.0℃and these two diffraction peaks are molybdenum suboxide phases MoO x (x is more than or equal to 2.75 and less than or equal to 2.89). XRD showed weaker orthorhombic phase alpha-MoO 3 Small bulges formed by the peaks of (2). Description of MoO in DC3 in this comparative example x Mainly in the sub-oxidized form, the crystal phase transition has no obvious effect.
From the above results, the in-situ annealing method provided by the invention can prepare pure-phase MoO 3 The film is simple in process, the operation of taking out the film from the atomic layer deposition cavity to the tube furnace is omitted, and the heat loss is reduced; short annealing time and can rapidly realize MoO x Phase to MoO 3 Regulating and controlling phases; and the pure phase MoO obtained 3 The crystallinity of the film is good.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. In-situ annealing preparation of pure-phase MoO 3 A method of forming a thin film, the method performed in an atomic layer deposition chamber, comprising:
(1) At 250-350 ℃ and in the presence of nitrogen, the silicon wafer, the metal precursor and the first O 3 Coating film treatment is carried out in an atomic layer deposition cavity to obtain MoO x A film;
(2) At 400-500 ℃ and at a second O 3 In the presence of the MoO x Annealing the film in an atomic layer deposition cavity for 10-25min to obtain pure-phase MoO 3 A film;
the metal precursor is a compound shown in a formula (1):
the silicon wafer is monocrystalline silicon wafer with crystal orientation p <100 >.
2. The method of claim 1, wherein in step (1), the first O 3 The volume flow rate of (2) is 300-1000sccm; and is also provided with
The first O 3 The introduction time is 1-10s.
3. A method according to claim 1 or 2, wherein in step (1) the metal precursor is introduced for a time of 0.1-8s.
4. The method according to claim 1 or 2, wherein the method further comprises, in the step (1), repeating the plating treatment 500 to 1500 times.
5. The method according to claim 1 or 2, wherein in step (2), the second O 3 The volume flow rate of (2) is 300-1000ccm.
6. The method according to claim 1 or 2, wherein the method further comprises, in step (1), preheating the metal precursor to 100-130 ℃ before the plating treatment, and applying the metal precursor to the plating treatment.
7. The method according to claim 1 or 2, wherein the method further comprises, in step (2), at said step of applying to said MoO x After the annealing treatment is carried out on the film, the temperature is reduced to 15-30 ℃ under the vacuum degree of 0-4hPa, and the pure-phase MoO is obtained 3 And the average cooling rate is 1-5 ℃/min.
8. The method according to claim 1 or 2, wherein the pressure of the plating treatment and the annealing treatment is each independently 1-15hPa.
9. Pure phase MoO prepared by the method of any one of claims 1-8 3 A film.
10. Pure phase MoO as claimed in claim 9 3 The application of the film in the field of optoelectronic devices.
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| US20130313534A1 (en) * | 2012-05-24 | 2013-11-28 | Agency For Science, Technology And Research | Method of preparing molybdenum oxide films |
| CN105274483A (en) * | 2015-09-29 | 2016-01-27 | 扬州大学 | Preparation method of negative thermal expansion material Sc2W3O12 thin film |
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| CN109786503A (en) * | 2018-12-29 | 2019-05-21 | 浙江师范大学 | The method that monocrystalline silicon surface is passivated with molybdenum oxide |
| CN115448954A (en) * | 2022-10-11 | 2022-12-09 | 中山大学 | ALD precursor molybdenum complex and preparation method thereof |
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| US20130313534A1 (en) * | 2012-05-24 | 2013-11-28 | Agency For Science, Technology And Research | Method of preparing molybdenum oxide films |
| US20170316847A1 (en) * | 2014-11-07 | 2017-11-02 | Plansee Se | Metal oxide thin film, method for depositing metal oxide thin film and device comprising metal oxide thin film |
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| CN109786503A (en) * | 2018-12-29 | 2019-05-21 | 浙江师范大学 | The method that monocrystalline silicon surface is passivated with molybdenum oxide |
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