CN114645321B - Co 9 S 8 Method for preparing single crystal transition metal sulfide film - Google Patents

Co 9 S 8 Method for preparing single crystal transition metal sulfide film Download PDF

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CN114645321B
CN114645321B CN202210300347.2A CN202210300347A CN114645321B CN 114645321 B CN114645321 B CN 114645321B CN 202210300347 A CN202210300347 A CN 202210300347A CN 114645321 B CN114645321 B CN 114645321B
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single crystal
transition metal
metal sulfide
film
crystal transition
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CN114645321A (en
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乔梁
陶思旭
周祥寅
高云冲
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University of Electronic Science and Technology of China
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/02—Epitaxial-layer growth
    • C30B23/025—Epitaxial-layer growth characterised by the substrate
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/002—Controlling or regulating
    • 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
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
    • 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

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  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention belongs to the field of pulse laser deposition technology and transition metal sulfide film preparation, and particularly provides Co 9 S 8 A method for preparing a single crystal transition metal sulfide thin film is used to obtain a high quality epitaxial sulfide thin film. The method prepares Co for the first time by using a pulse laser deposition method through CoS target preparation and deposition parameter accurate design 9 S 8 Single crystal epitaxial films, compared to Co 9 S 8 Powder or block, co 9 S 8 The single crystal epitaxial film can have better physical properties, and Co is compared with the existing transition metal sulfide film 9 S 8 The single crystal epitaxial film has the advantages of high crystallization quality, thin thickness and good electric transport performance; in conclusion, the method prepares Co for the first time based on the pulse laser deposition method 9 S 8 The single crystal epitaxial film has the advantages of high quality, thin thickness and good electric transport performance, provides a good foundation for the application of the single crystal epitaxial film in the field of energy sources, and has simple preparation process and low preparation cost.

Description

Co 9 S 8 Method for preparing single crystal transition metal sulfide film
Technical Field
The invention belongs to the field of pulse laser deposition technology and transition metal sulfide film preparation, and particularly provides Co 9 S 8 A method for preparing a single crystal transition metal sulfide thin film.
Background
The transition metal sulfide thin film plays an important role in the fields of photoelectric devices, photovoltaic cells, thermoelectric devices, sensors and the like, the transition metal sulfide thin film prepared at present is mostly rough and has high-density defects, the film thickness is dozens of micrometers, and the limited performance and the high-density defects enable people to transfer the research direction to high-quality single crystals and extremely thin epitaxial thin films. However, it is very difficult to deposit a sulfide epitaxial thin film directly on an oxide substrate by a one-step method due to the mismatch of lattice parameters and thermal expansion, etc.; meanwhile, the traditional top-down technology cannot realize the accuracy control of the nanometer level; therefore, it remains a considerable challenge to obtain high quality epitaxial chalcogenide films on larger substrates.
Disclosure of Invention
The invention aims to provide Co 9 S 8 Preparation method of single crystal transition metal sulfide film, co is prepared for the first time 9 S 8 Single crystal epitaxial film with excellent electrical performance and good stability, for studying Co 9 S 8 Provide samples for a range of good performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
co 9 S 8 The preparation method of the single crystal transition metal sulfide thin film comprises the following steps:
step 1, grinding, tabletting and high-temperature calcining CoS powder serving as a reaction material to obtain a CoS target material;
step 2, sequentially carrying out ultrasonic cleaning on the YSZ substrate by adopting acetone, alcohol and deionized water, and drying the YSZ substrate by using nitrogen for later use;
step 3, placing the CoS target material and the YSZ substrate in a sputtering chamber of a pulse laser deposition system, setting the distance between the target material and the substrate to be 55mm, and setting the vacuum degree of the back of the pulse laser deposition system to be 4.5 multiplied by 10 -4 Pa, a growth temperature of 500-600 ℃, a pulse laser repetition frequency of 9Hz and a pulse laser energy density of 1.6J/cm 2 Depositing and growing Co on a YSZ substrate by a pulsed laser deposition system to obtain Co with the deposition pulse number of 18000-30000 pulses 9 S 8 A single crystal transition metal sulfide thin film.
Further, in the step 1, the amount of CoS powder is 1g-2g.
Further, in the step 1, grinding is carried out in a vacuum glove box, and the grinding time is 25min-30min.
Further, in the step 1, tabletting is carried out by adopting a tabletting machine, the pressure is set to be 15-20 Mpa, the tabletting time is set to be 8-10 min, the tabletting machine and the ceramic gasket are transferred into a quartz tube together after tabletting is finished, and then a vacuum tube sealing machine is used for vacuumizing and tube sealing.
Further, in the step 1, the high-temperature calcination is performed by using a tube furnace, the corundum tube is firstly placed in the tube furnace, and then the quartz tube filled with the target material is placed in the corundum tube to prevent the quartz tube from being cracked due to volatilization of sulfides, wherein the parameters of the high-temperature calcination are as follows: heating from room temperature to 750 deg.C at a heating rate of 5 deg.C/min, and maintaining for 10-12 h.
Further, in the step 3, the CoS target is subjected to surface polishing by using sand paper, then is adhered to a target holder by using conductive carbon, and the YSZ substrate is adhered to a substrate table by using conductive silver paste.
Further, the Co 9 S 8 The thickness of the single crystal transition metal sulfide thin film is 60nm-100nm.
The invention has the beneficial effects that:
the invention provides a Co 9 S 8 The preparation method of the single crystal transition metal sulfide film comprises the steps of preparing a CoS target material and accurately designing deposition parameters by a pulse laser deposition method, and preparing Co for the first time 9 S 8 Epitaxial film of single crystal, compared with Co 9 S 8 Powder or block, co 9 S 8 The single crystal epitaxial film can have better physical properties, and Co is compared with the existing transition metal sulfide film 9 S 8 The single crystal epitaxial film has the advantages of high crystallization quality, thin thickness and good electric transport performance; in conclusion, the method prepares Co for the first time based on the pulse laser deposition method 9 S 8 The single crystal epitaxial film has the advantages of high quality, thin thickness and good electric transport performance, provides a good foundation for the application of the single crystal epitaxial film in the field of energy, and can be preparedSimple process and low preparation cost.
Drawings
FIG. 1 shows Co prepared in examples 1, 2 and 3 of the present invention 9 S 8 Calibration of single crystal films XRD patterns were measured for YSZ (002) orientation.
FIG. 2 shows Co prepared in example 1 of the present invention 9 S 8 Calibration of single crystal films YSZ (002) orientation was measured as a RSM plot.
FIG. 3 shows Co prepared in example 1 of the present invention 9 S 8 Alignment of single crystal films YSZ (202) measured Phi-Scan plot.
FIG. 4 shows Co prepared in examples 1, 2 and 3 of the present invention 9 S 8 Temperature change resistance diagram of the single crystal thin film.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
The present embodiment provides a Co 9 S 8 The preparation method of the single crystal transition metal sulfide film specifically comprises the following steps:
step 1, weighing 2g of CoS powder, and grinding for 30min in a vacuum glove box by using an agate mortar; tabletting with a tabletting machine after grinding, wherein the tabletting pressure is 20Mpa and the time is 10min; after tabletting is finished, putting the pressed target material and the ceramic gasket into a quartz tube together, and performing vacuum tube sealing by using a vacuum tube sealing machine, wherein the vacuum degree of the sealed tube is controlled to be 4.5 multiplied by 10 -4 pa; after the tube sealing is finished, putting the quartz tube into a tube furnace for target sintering, wherein the sintering temperature is 750 ℃, the heat preservation time is 12h, the heating rate is 5 ℃/min, and the CoS target can be obtained after sintering is finished;
step 2, ultrasonically cleaning the YSZ substrate by using acetone, alcohol and deionized water in sequence, wherein the cleaning time is 5min respectively; drying the cleaned product by using a nitrogen gun;
step 3, polishing the sintered target material smoothly by using fine sand paper, and adhering the target material to a target material support by using conductive carbon adhesive; adhering a YSZ substrate to a substrate table by using conductive silver paste, and quickly drying the silver paste by using a heating table; the target material and the base materialThe pieces are put into a pulsed laser deposition system together, and the distance between the target material and the substrate is controlled to be 55mm; co deposition growth on YSZ substrates in pulsed laser deposition systems 9 S 8 The deposition growth parameters of the monocrystal transition metal sulfide film are as follows: the vacuum degree is controlled at 4.5X 10 -4 pa, temperature of 600 ℃, laser frequency of 9Hz, and energy density of 1.6J/cm 2 The number of laser pulses was 18000pulses, and Co having a thickness of 60nm was obtained 9 S 8 Single crystal transition metal sulfide thin films.
Example 2
The present embodiment provides a Co 9 S 8 The only difference between the preparation method of the single crystal transition metal sulfide thin film and the embodiment 1 is that: in step 3, the number of laser pulses is changed from 18000pulses to 30000pulses, and Co with a thickness of 60nm to 100nm is obtained 9 S 8 A single crystal transition metal sulfide thin film.
Example 3
The present embodiment provides a Co 9 S 8 The preparation method of the single crystal transition metal sulfide thin film is only different from the preparation method of the embodiment 1 in that: in the step 3, the growth temperature is changed from 600 ℃ to 700 ℃, and other growth conditions are kept unchanged 9 S 8 A single crystal transition metal sulfide thin film.
FIG. 1 shows Co prepared in examples 1, 2 and 3 9 S 8 The XRD pattern measured for the aligned (002) orientation of the film shows that the peaks appearing on the film are all peaks aligned with the orientation of the substrate, indicating that our film is epitaxially grown.
FIG. 2 shows Co prepared in example 1 9 S 8 The RSM of the film obtained by calibrating YSZ (002) orientation shows that the epitaxial relationship between the film and the substrate is good.
FIG. 3 shows Co prepared in example 1 9 S 8 The Phi-Scan plot of the film measured by the alignment YSZ (202) shows that the film has 4 peaks in the range of 0-360 degrees, which indicates that the film has four-fold symmetry and shows good epitaxial relationship between the film and the substrate.
FIG. 4 shows Co prepared in examples 1, 2 and 3 9 S 8 The temperature-change resistance data of the film shows that Co is obtained according to the data 9 S 8 The resistance of the sample is below 10 ohm, the change trend of the resistance-temperature change resistance along with the temperature is known, co 9 S 8 The sheet resistance exhibits a metallic characteristic as the resistance increases with temperature, and higher temperature and thicker films have more excellent electrical properties.
While the invention has been described with reference to specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise; all of the disclosed features, or all of the method or process steps, may be combined in any combination, except mutually exclusive features and/or steps.

Claims (7)

1. Co 9 S 8 The preparation method of the single crystal transition metal sulfide thin film comprises the following steps:
step 1, grinding, tabletting and high-temperature calcining CoS powder serving as a reaction material to obtain a CoS target material;
step 2, sequentially carrying out ultrasonic cleaning on the YSZ substrate by adopting acetone, alcohol and deionized water, and drying the YSZ substrate by using nitrogen for later use;
step 3, placing the CoS target material and the YSZ substrate in a sputtering chamber of a pulse laser deposition system, setting the distance between the target material and the substrate to be 55mm, and setting the vacuum degree of the back of the pulse laser deposition system to be 4.5 multiplied by 10 -4 Pa, a growth temperature of 500-600 ℃, a pulse laser repetition frequency of 9Hz and a pulse laser energy density of 1.6J/cm 2 Depositing and growing Co on a YSZ substrate by a pulsed laser deposition system to obtain Co with the deposition pulse number of 18000-30000 pulses 9 S 8 Single crystal transition metal sulfide thin films.
2. Co as set forth in claim 1 9 S 8 The method for preparing the single crystal transition metal sulfide thin film is characterized in that in the step 1, the dosage of CoS powder is 1g～2g。
3. Co as set forth in claim 1 9 S 8 The preparation method of the single crystal transition metal sulfide film is characterized in that in the step 1, grinding is carried out in a vacuum glove box, and the grinding time is 25-30 min.
4. Co as set forth in claim 1 9 S 8 The preparation method of the single crystal transition metal sulfide film is characterized in that in the step 1, tabletting is carried out by adopting a tablet machine, the pressure is set to be 15Mpa-20Mpa, the tabletting time is set to be 8min-10min, the tablet is transferred into a quartz tube together with a ceramic gasket after the tabletting is finished, and then a vacuum tube sealing machine is used for vacuumizing and tube sealing.
5. Co as defined in claim 1 9 S 8 The preparation method of the single crystal transition metal sulfide film is characterized in that in the step 1, high-temperature calcination is carried out by adopting a tubular furnace, firstly, a corundum tube is placed in the tubular furnace, then, a quartz tube filled with a target material is placed in the corundum tube to prevent the quartz tube from being cracked due to volatilization of sulfides, and the parameters of the high-temperature calcination are as follows: heating from room temperature to 750 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 10-12 h.
6. Co as set forth in claim 1 9 S 8 The preparation method of the single crystal transition metal sulfide film is characterized in that in the step 3, the CoS target material is subjected to surface polishing by using sand paper and then is adhered to a target holder by using conductive carbon, and the YSZ substrate is adhered to a substrate table by using conductive silver paste.
7. Co as set forth in claim 1 9 S 8 The preparation method of the single crystal transition metal sulfide thin film is characterized in that the Co 9 S 8 The thickness of the single crystal transition metal sulfide thin film is 60nm-100nm.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4623426A (en) * 1982-06-22 1986-11-18 Hughes Aircraft Company Low temperature process for depositing epitaxial layers
JPH06122596A (en) * 1992-08-26 1994-05-06 Mitsubishi Kasei Corp Production of deposited thin film
CN111525128A (en) * 2020-04-20 2020-08-11 电子科技大学 Ruthenium-doped sulfur vacancy-containing transition metal sulfide electrode and preparation method thereof
CN114892276A (en) * 2022-04-01 2022-08-12 电子科技大学长三角研究院(湖州) Spinel sulfide thin film material and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120227663A1 (en) * 2011-03-08 2012-09-13 Purdue Research Foundation Oxide metal semiconductor superlattices for thermoelectrics
KR20200113238A (en) * 2018-01-22 2020-10-06 킹 압둘라 유니버시티 오브 사이언스 앤드 테크놀로지 Large-scale synthesis of 2D semiconductors by epitaxial phase transition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4623426A (en) * 1982-06-22 1986-11-18 Hughes Aircraft Company Low temperature process for depositing epitaxial layers
JPH06122596A (en) * 1992-08-26 1994-05-06 Mitsubishi Kasei Corp Production of deposited thin film
CN111525128A (en) * 2020-04-20 2020-08-11 电子科技大学 Ruthenium-doped sulfur vacancy-containing transition metal sulfide electrode and preparation method thereof
CN114892276A (en) * 2022-04-01 2022-08-12 电子科技大学长三角研究院(湖州) Spinel sulfide thin film material and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Vala L.Laser-Induced Reactive Deposition of Nanostructured CoS2- and Co2CuS4-Based Films with Fenton Catalytic Properties.《EUROPEAN JOURNAL OF INORGANIC CHEMISTRY》.2019,(第undefined期),第1220-1227页. *
刘劲松.脉冲激光诱导的分子定取向动力学研究.《中国优秀硕士学位论文全文数据库基础科学辑》.2019,(第undefined期),A005-175页. *
陶思旭.过渡金属硫化物薄膜的外延生长和物性研究.《中国优秀硕士学位论文全文数据库基础科学辑》.2023,(第undefined期),A005-1078. *

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