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CN117865076B - A method for preparing a large-area two-dimensional alkali metal chalcogenide network - Google Patents

A method for preparing a large-area two-dimensional alkali metal chalcogenide network Download PDF

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CN117865076B
CN117865076B CN202410050469.XA CN202410050469A CN117865076B CN 117865076 B CN117865076 B CN 117865076B CN 202410050469 A CN202410050469 A CN 202410050469A CN 117865076 B CN117865076 B CN 117865076B
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copper
selenium
single crystal
substrate
potassium
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CN117865076A (en
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卢建臣
牛格非
高蕾
蔡金明
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00Selenium; Tellurium; Compounds thereof
    • C01B19/007Tellurides or selenides of metals
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/20Particle morphology extending in two dimensions, e.g. plate-like
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention relates to a preparation method of a large-area two-dimensional alkali metal chalcogenide network, belonging to the technical field of nano materials. Depositing selenium powder on the surface of a clean copper single crystal substrate at 25-30 ℃ in an ultrahigh vacuum environment, heating the copper single crystal substrate and the selenium powder deposited on the surface of the copper single crystal substrate to a growth temperature after the deposition is finished, annealing, cooling to room temperature to obtain an annealed selenium-copper carrying single crystal substrate, evaporating a potassium simple substance, depositing the potassium simple substance on the annealed selenium-copper carrying single crystal substrate, and maintaining the potassium-selenium carrying single crystal substrate at the room temperature to obtain a large-area two-dimensional potassium-selenium compound network. According to the method, by utilizing a strategy that selenium powder can chemically react with a copper substrate to form a compound, the selenium powder is deposited on the surface of the copper substrate so as to obtain a sample with copper selenium compounds and selenium atoms on the copper substrate, the sample is annealed, a potassium simple substance is deposited on the surface of the sample, and the sample is heated to room temperature, so that a sample with a network structure consisting of large-area two-dimensional potassium selenium compounds is finally obtained.

Description

Preparation method of large-area two-dimensional alkali metal chalcogenide network
Technical Field
The invention relates to a preparation method of a large-area two-dimensional alkali metal chalcogenide network, belonging to the technical field of nano materials.
Background
In recent decades, the demand for secondary batteries having high energy/power density and low cost has been increasing due to rapid consumption of fossil energy and increasingly serious energy crisis. Accordingly, development of alternative to conventional electrochemical energy storage systems has attracted increasing attention. In recent years, alkali metal chalcogenides have been widely studied in the energy field as electrodes and electrolytes, and particularly, the characteristics of high energy and low cost in the presence of potassium ions are considered as attractive candidate materials in next-generation energy storage systems. However, most polyselenide compounds are characterized by large volume changes, so that the circulating performance is still not ideal. It would be possible to find a non-conventional, non-stoichiometric class of selenides to provide a new choice.
For potassium selenium compounds, the proportion of elements in the phase diagram is mostly included. If the surface physical chemistry method is utilized, the material with the element proportion which does not exist in the phase diagram can be prepared, and then the subsequent experimental means can be known and designed according to the morphology, so that a meaningful strategy is provided for practical application.
Disclosure of Invention
Aiming at the problems and the defects existing in the prior art, the invention provides a preparation method of a large-area two-dimensional alkali metal chalcogenide network. According to the method, by utilizing a strategy that selenium powder can chemically react with a copper substrate to form a compound, the selenium powder is deposited on the surface of the copper substrate so as to obtain a sample with copper selenium compounds and selenium atoms on the copper substrate, the sample is heated to a growth temperature and then annealed, then a potassium simple substance is deposited on the surface of the sample, and the sample is heated to room temperature and then annealed, so that the sample with a network structure consisting of large-area two-dimensional potassium selenium compounds is finally obtained. The invention is realized by the following technical scheme.
A method for preparing a large-area two-dimensional alkali metal chalcogenide network, comprising the steps of:
step 1, depositing selenium powder on the surface of a clean copper single crystal substrate at 25-30 ℃ in an ultra-high vacuum environment;
Step 2, after the deposition of the step 1 is finished, heating the copper monocrystalline substrate and selenium powder deposited on the surface of the copper monocrystalline substrate to a growth temperature, carrying out annealing treatment, and then cooling to room temperature to obtain an annealed selenium-copper carrying monocrystalline substrate;
And step 3, evaporating and depositing a potassium simple substance on the annealed selenium-copper carrying single crystal substrate obtained in the step 2, and then maintaining at room temperature to obtain a large-area two-dimensional potassium-selenium compound network.
The preparation process of the copper single crystal substrate in the step 1 comprises the following steps:
step 1.1, carrying out argon ion sputtering treatment on a copper single crystal in an ultrahigh vacuum cavity to obtain a copper substrate;
And step 1.2, heating the copper substrate obtained in the step 1.1 to 450 ℃, and keeping for 10-30min to obtain the copper single crystal substrate.
And in the step 1, the selenium powder is evaporated at the evaporation temperature of 120-125 ℃ and is deposited for 15-20 min to clean the surface of the copper single crystal substrate.
In the step 2, the growth temperature is 100-400 ℃, the annealing treatment (namely, the growth temperature is kept) is carried out for 10-30 min, and through the step, the deposited selenium atoms and potassium simple substances can interact and fully diffuse to form a large-area two-dimensional potassium-selenium compound network structure.
And in the step 3, the evaporation temperature of the potassium simple substance is 620-630 ℃, and the potassium simple substance is deposited for 10-15 min to the annealed selenium-copper-carrying monocrystal substrate.
And in the step 3, the temperature is kept at room temperature for 15-30 min.
The step of evaporating the selenium powder and the potassium simple substance is to evaporate the selenium powder and the potassium simple substance by thermal resistance type heating and direct current heating and deposit the selenium powder and the potassium simple substance on the copper single crystal substrate.
The beneficial effects of the invention are as follows:
The network structure composed of the large-area two-dimensional potassium selenium compound prepared by the method is a novel single-layer two-dimensional material and can be directly applied to two-dimensional electronic information devices.
Drawings
FIG. 1 is a scanning tunneling microscope image of a large-area two-dimensional potassium selenium compound network prepared in example 1 of the present invention;
FIG. 2 is a view showing atomic resolution images, cell structures and cycle charts of a scanning tunneling microscope with a large-area two-dimensional potassium-selenium compound network prepared in example 1 of the present invention;
Fig. 3 is a scanning tunneling microscope image with a large-area two-dimensional potassium-selenium compound network prepared in example 1 of the present invention, a scanning tunneling microscope image with a large-area two-dimensional potassium-selenium compound network simulated by a calculation method, and a corresponding optimized atomic configuration image of the potassium-selenium compound network.
Detailed Description
The invention will be further described with reference to the drawings and detailed description.
Test instrument and apparatus:
Cryogenic scanning tunneling microscope available from Omacron, germany.
K-cell molecular Evaporation source from Omacron, germany.
Argon ion gun from Omicron, germany.
Raw materials:
Selenium powder was purchased from Sigma-Aldrich and had a purity of 99.99%.
Copper single crystal purchased from MaTecK with 99.999% purity.
The potassium simple substance is purchased from SAES and has the purity of 99.99 percent.
Example 1
The preparation method of the large-area two-dimensional alkali metal chalcogenide network comprises the following steps:
Step 1, depositing selenium powder on the surface of a clean copper single crystal substrate at a temperature of 125 ℃ for 15min to 30 ℃ under an ultrahigh vacuum environment (the vacuum degree is better than 1x10 -9 mbar) by utilizing a thermal resistance type K-cell molecular evaporation source;
the preparation process of the clean copper single crystal substrate comprises the following specific steps:
Step 1.1, performing argon ion sputtering treatment on the copper single crystal in an ultrahigh vacuum cavity (the vacuum degree is superior to 1x10 -9 mbar) by using an argon ion gun to obtain a copper substrate;
step 1.2, heating the copper substrate obtained in the step 1.1 to 450 ℃, and keeping for 10min to obtain a copper single crystal substrate;
Step 2, after the deposition of the step 1 is finished, heating the copper single crystal substrate and selenium powder deposited on the surface of the copper single crystal substrate to a growth temperature of 400 ℃, carrying out annealing treatment for 30min, and then cooling to room temperature to obtain an annealed selenium-copper carrying single crystal substrate;
and step 3, evaporating a potassium simple substance at 630 ℃, depositing for 10min to the annealed selenium-copper carrying monocrystal substrate obtained in the step 2, and then maintaining at room temperature for 30min to obtain a large-area two-dimensional potassium-selenium compound network.
The large-area two-dimensional potassium selenium compound network prepared by the invention is observed by a scanning tunnel microscope, as shown in figure 1.
FIG. 2 is an atomic resolution image of a large-area two-dimensional potassium selenium compound network scanning tunneling microscope, and cell size and period thereof. From FIG. 2, it can be seen that the cell size of the large-area two-dimensional potassium selenium compound network cell is 1.51nm.
Fig. 3 is an experimentally and computationally simulated scanning tunneling microscope atomic resolution image of a large-area two-dimensional potassium selenium compound network structure prepared according to the preparation method of the embodiment of the present invention. It can be directly and effectively demonstrated that the network structure of the large-area two-dimensional potassium selenium compound prepared by the preparation method of the embodiment of the invention is composed of selenium atoms and potassium atoms.
Example 2
The preparation method of the large-area two-dimensional alkali metal chalcogenide network comprises the following steps:
Step 1, depositing selenium powder on the surface of a clean copper single crystal substrate for 20 minutes to 25 ℃ at the evaporation temperature of 120 ℃ by utilizing a thermal resistance type K-cell molecular evaporation source under an ultra-high vacuum environment (the vacuum degree is superior to 1x10 -9 mbar);
the preparation process of the clean copper single crystal substrate comprises the following specific steps:
Step 1.1, performing argon ion sputtering treatment on the copper single crystal in an ultrahigh vacuum cavity (the vacuum degree is superior to 1x10 -9 mbar) by using an argon ion gun to obtain a copper substrate;
Step 1.2, heating the copper substrate obtained in the step 1.1 to 450 ℃, and keeping for 30min to obtain a copper single crystal substrate;
step 2, after the deposition of the step 1 is finished, heating the copper single crystal substrate and selenium powder deposited on the surface of the copper single crystal substrate to a growth temperature of 100 ℃, carrying out annealing treatment for 10min, and then cooling to room temperature to obtain an annealed selenium-copper carrying single crystal substrate;
And 3, evaporating a potassium simple substance at 620 ℃, depositing for 15min on the annealed selenium-copper carrying monocrystal substrate obtained in the step 2, and then keeping at room temperature for 30min to obtain a large-area two-dimensional potassium-selenium compound network.
Example 3
The preparation method of the large-area two-dimensional alkali metal chalcogenide network comprises the following steps:
Step 1, depositing selenium powder on the surface of a clean copper single crystal substrate at the evaporation temperature of 122 ℃ for 18min to 28 ℃ in an ultra-high vacuum environment (the vacuum degree is superior to 1x10 -9 mbar unit) by utilizing a thermal resistance type K-cell molecular evaporation source;
the preparation process of the clean copper single crystal substrate comprises the following specific steps:
Step 1.1, performing argon ion sputtering treatment on the copper single crystal in an ultrahigh vacuum cavity (the vacuum degree is superior to 1x10 -9 mbar) by using an argon ion gun to obtain a copper substrate;
Step 1.2, heating the copper substrate obtained in the step 1.1 to 450 ℃, and keeping for 20min to obtain a copper single crystal substrate;
step 2, after the deposition of the step 1 is finished, heating the copper single crystal substrate and selenium powder deposited on the surface of the copper single crystal substrate to a growth temperature of 300 ℃, carrying out annealing treatment for 20min, and then cooling to room temperature to obtain an annealed selenium-copper carrying single crystal substrate;
And 3, evaporating a potassium simple substance at 625 ℃, depositing for 13min on the annealed selenium-copper carrying monocrystal substrate obtained in the step 2, and then keeping at room temperature for 25min to obtain a large-area two-dimensional potassium-selenium compound network.
While the present invention has been described in detail with reference to the drawings, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.

Claims (2)

1. A method for preparing a large-area two-dimensional alkali metal chalcogenide network, which is characterized by comprising the following steps:
step 1, depositing selenium powder on the surface of a clean copper single crystal substrate at 25-30 ℃ in an ultra-high vacuum environment;
Step 2, after the deposition of the step 1 is finished, heating the copper monocrystalline substrate and selenium powder deposited on the surface of the copper monocrystalline substrate to a growth temperature, carrying out annealing treatment, and then cooling to room temperature to obtain an annealed selenium-copper carrying monocrystalline substrate;
step 3, evaporating and depositing a potassium simple substance on the annealed selenium-copper carrying monocrystal substrate obtained in the step 2, and then maintaining at room temperature to obtain a large-area two-dimensional potassium-selenium compound network;
The preparation process of the copper single crystal substrate in the step 1 comprises the following steps:
step 1.1, carrying out argon ion sputtering treatment on a copper single crystal in an ultrahigh vacuum cavity to obtain a copper substrate;
Step 1.2, heating the copper substrate obtained in the step 1.1 to 450 ℃, and keeping for 10-30min to obtain a copper single crystal substrate;
In the step 1, selenium powder is evaporated at the evaporation temperature of 120-125 ℃ and deposited for 15-20 min to clean the surface of a copper single crystal substrate;
the growth temperature in the step2 is 100-400 ℃, and the annealing treatment is carried out for 10-30 min;
And in the step 3, the evaporation temperature of the potassium simple substance is 620-630 ℃, and the potassium simple substance is deposited for 10-15 min to the annealed selenium-copper-carrying monocrystal substrate.
2. The method for preparing a large-area two-dimensional alkali metal chalcogenide network according to claim 1, wherein the step 3 is performed at room temperature for 15-30 min.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102344714A (en) * 2010-05-18 2012-02-08 罗门哈斯电子材料有限公司 A group 6a/group 3a ink and methods of making and using same
CN113463031A (en) * 2021-07-23 2021-10-01 昆明理工大学 Method for simultaneously preparing and regulating three types of single-layer copper selenide superstructures

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7867551B2 (en) * 2006-09-21 2011-01-11 Solopower, Inc. Processing method for group IBIIIAVIA semiconductor layer growth

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102344714A (en) * 2010-05-18 2012-02-08 罗门哈斯电子材料有限公司 A group 6a/group 3a ink and methods of making and using same
CN113463031A (en) * 2021-07-23 2021-10-01 昆明理工大学 Method for simultaneously preparing and regulating three types of single-layer copper selenide superstructures

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