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WO2019117559A1 - Film mince de métal de transition-dichalcogénure et son procédé de fabrication - Google Patents

Film mince de métal de transition-dichalcogénure et son procédé de fabrication Download PDF

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Publication number
WO2019117559A1
WO2019117559A1 PCT/KR2018/015585 KR2018015585W WO2019117559A1 WO 2019117559 A1 WO2019117559 A1 WO 2019117559A1 KR 2018015585 W KR2018015585 W KR 2018015585W WO 2019117559 A1 WO2019117559 A1 WO 2019117559A1
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Prior art keywords
thin film
transition metal
precursor
dicalcogenide
decalcogenide
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PCT/KR2018/015585
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English (en)
Korean (ko)
Inventor
박태주
김대현
김대웅
석태준
진현수
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Industry University Cooperation Foundation IUCF HYU
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Industry University Cooperation Foundation IUCF HYU
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Priority claimed from KR1020180147152A external-priority patent/KR102184699B1/ko
Application filed by Industry University Cooperation Foundation IUCF HYU filed Critical Industry University Cooperation Foundation IUCF HYU
Publication of WO2019117559A1 publication Critical patent/WO2019117559A1/fr
Priority to US16/874,802 priority Critical patent/US11649545B2/en
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering

Definitions

  • the present invention relates to a thin film of transition metal-decalcogenide and a method for producing the same, and more particularly, to a method of producing a thin film of transition metal-decalcogenide having uniform surface on a uniform thickness, Dimensionally transition metal-dicalcogenide thin films.
  • the structure of the transition metal-chalcogen compound is composed of a layered structure similar to graphene, it has excellent optical transparency and excellent mechanical flexibility, and can be used as a next generation flexible electronic device such as wearable device, flexible display and artificial electronic skin Has attracted attention.
  • the band gap of the transition metal-chalcogen compound is formed as a two-dimensional layer structure similar to graphene and is suitable as a semiconductor device.
  • the band gap has a band gap of 1 to 2 ev, Of the logic circuitry which was difficult to fabricate with the graphene of.
  • Transition metal-dicalcogenide compounds composed of the MX 2 structure are likely to be produced as semiconductor thin films.
  • M represents a transition metal element including Mo or W
  • X represents a chalcogen element including S, Se, and Te.
  • the transition metal-dicalcogenide compound is formed as a monolayer in the form of a bulk, it is possible not only to control the band gap value due to the fluctuation of the band structure, And a direct band gap semiconductor. This property is ideally applicable to a variety of optoelectronic devices such as photodiodes and solar cells.
  • the transition metal-dicalcogenide thin film has a thickness of three atoms.
  • the transition metal-dicalcogenide thin film of the single layer is composed of a structure in which one layer made of transition metal element-type atoms is interposed sandwiched between two layers made of chalcogen atoms.
  • the transition metal-decalcogenide thin film can be produced by a method of peeling from a multi-layered crystal.
  • the transition metal-decalcogenide thin film produced by the above method has a disadvantage in that the thickness thereof is not uniform and a long time is required in the manufacturing process.
  • a method for producing a transition metal-decalcogenide thin film using a conventional chemical vapor deposition method has been generalized.
  • Korean Laid-open Patent Publication No. 10-2017--0014319 discloses a method of controlling the pressure in a deposition chamber to control the amount of a chalcogen-containing precursor and a transition metal-containing precursor supplied into the deposition chamber, There is disclosed a method for preparing a two-dimensional transition metal-decalcogenide thin film by a chemical vapor deposition method of controlling a partial pressure ratio of the transition metal-containing precursor to the chalcogen-containing precursor.
  • the present invention is directed to a method for preparing a transition metal-dicalcogenide thin film, which comprises controlling the temperature of a base substrate in accordance with a bonding force between a transition metal and a ligand.
  • Another technical problem to be solved by the present application is to provide a method for producing a transition metal-dicalcogenide thin film comprising at least a part of a precursor is thermally decomposed and adsorbed on a base substrate.
  • Another aspect of the present invention is to provide a method of forming a transition metal-dicalcogenide thin film comprising forming a preliminary thin film and a step of preparing a transition metal-decalcogenide thin film, And a manufacturing method thereof.
  • Another aspect of the present invention is to provide a transition metal-dicalcogenide thin film including a precursor thin film and a gas atmosphere containing a chalcogen element in a chamber for forming the preliminary thin film, And a method for producing the same.
  • Another technical problem to be solved by the present application is to provide a uniform surface transition metal-dicalcogenide thin film.
  • Another technical problem to be solved by the present application is to provide a transition metal-dicalcogenide thin film of uniform thickness.
  • Another technical problem to be solved by the present application is to provide a large-area two-dimensional transition metal-dicalcogenide thin film.
  • Another technical problem to be solved by the present application is to provide a monolayer transition metal-dicalcogenide thin film.
  • Another technical problem to be solved by the present application is to provide a thin film transistor having a high quantum efficiency as compared to a reference transition metal dichalcogenide thin layer made by atomic layer deposition, And to provide a transition metal-dicalcogenide thin film having a roughness.
  • Another object of the present invention is to provide a transition metal-dicalcium phosphate thin film which has a higher maximum peak value and a smaller standard deviation of the maximum peak value per region as compared with the reference transition metal- To provide a cogenerated thin film.
  • the present application provides a method for producing a transition metal-dicalcogenide thin film.
  • a method of making the transition metal-decalcogenide thin film comprises the steps of preparing a base substrate in a chamber, preparing a precursor containing a transition metal, providing the precursor on the base substrate And purifying the chamber a plurality of times to form a preliminary thin film on which the precursor is adsorbed on the base substrate; and heat treating the preliminary thin film in a gas atmosphere containing a chalcogen element , And a transition metal-dichalcogenide thin film is prepared.
  • the precursor may comprise the transition metal and the ligand coordinated.
  • the temperature of the base substrate can be controlled in the step of forming the preliminary thin film according to the bonding force between the transition metal and the ligand.
  • At least a part of the precursor may be thermally decomposed and adsorbed on the base substrate.
  • the preliminary thin film comprises completely covering the front surface of the base substrate, and at least a part of the preliminary thin film may include a layer of the precursor.
  • the at least a portion of the precursor thin film on which the precursor is laminated comprises a first portion and a second portion on the first portion, the precursor of the second portion being thermally decomposed, And adsorbed on the precursor of the first portion.
  • the transition metal-decalcogenide thin film is represented by the formula MX 2 wherein M is at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Zr, Nb, Mo, Tc, , Ta, W, Re, and Pt, and X may include at least one of the group consisting of S, Se, and Te.
  • the step of forming the preliminary thin film and the step of preparing the transition metal-decalcogenide thin film may be performed in chambers independent of each other.
  • a gas atmosphere including a chalcogen element may be provided in the chamber of the step of forming the preliminary thin film.
  • the transition metal-decalcogenide thin film may be prepared as a monolayer.
  • the preliminary thin film may completely cover the front surface of the base substrate.
  • the present application provides a transition metal-dicalcogenide thin film.
  • the transition metal-dicalcogenide thin film is a transition metal-dicalcogenide thin film including a transition metal and a chalcogen element
  • the transition metal-dicalcogenide thin film is a thin film of a transition metal- Compared to a reference transition metal-dichalcogenide thin layer, it can have a high quantum efficiency and a low surface roughness.
  • the transition metal-decalcogenide thin film has a maximum peak value higher than that of the reference transition metal-decalcogenide thin film and a standard deviation of the maximum peak value per region Can be small.
  • the transition metal-decalcogenide thin film may be MOS 2 .
  • a method of manufacturing a semiconductor device comprising: preparing a base substrate in a chamber; preparing a precursor containing a transition metal; providing the precursor on the base substrate; and purging the chamber a plurality of times Forming a preliminary thin film on which the precursor is adsorbed on the base substrate; and heat treating the preliminary thin film in a gas atmosphere containing a chalcogen element to form a transition metal dichalcogenide ) Thin film is prepared by the method of the present invention can be provided.
  • transition metal-dicalcogenide thin film As a result, a large-area two-dimensional transition metal-dicalcogenide thin film can be produced as a monolayer.
  • the transition metal-dicalcogenide thin film having a uniform surface and a thickness can be produced.
  • FIG. 1 is a flow chart for explaining a method of manufacturing a thin film according to an embodiment of the present invention.
  • FIG. 2 is a view for explaining a step of forming a preliminary film according to an embodiment of the present invention.
  • Figure 3 is an enlarged view of Figure 2A.
  • FIG. 4 is a view for explaining the thermal decomposition of a precursor according to an embodiment of the present invention.
  • FIG. 5 is a view for explaining the first and second portions of the preliminary thin film according to the embodiment of the present invention.
  • FIG. 6 is a view for explaining the step of heat-treating a preliminary thin film according to an embodiment of the present invention in a gas atmosphere including a chalcogen element.
  • Figure 7 is an enlarged view of Figure 6C.
  • FIG. 8 is a view illustrating a step of preparing a transition metal-dichalcogenide thin film according to an embodiment of the present invention.
  • Figure 9 is an enlarged view of Figure 8D.
  • FIG. 10 is a view for explaining a method for producing a transition metal-decalcogenide thin film according to a comparative example.
  • FIG. 11 is a graph showing a thickness characteristic of a transition metal-dicalcogenide thin film according to a comparative example corresponding to the temperature of the base substrate.
  • FIG. 12 is a graph showing the thickness characteristics of a transition metal-dicalcogenide thin film according to a comparative example corresponding to injection of a transition metal precursor.
  • FIG. 13 is a graph for comparing the thickness characteristics of the transition metal-dicalcium cyanide thin film according to the embodiment (M-ALD) and the comparative example (C-ALD) of the present invention.
  • FIG. 14 is a graph showing photoluminescence in order to confirm the luminescence efficiency of the transition metal-decalcogenide thin films according to Comparative Examples 1 to 5.
  • FIG. 14 is a graph showing photoluminescence in order to confirm the luminescence efficiency of the transition metal-decalcogenide thin films according to Comparative Examples 1 to 5.
  • FIG. 15 is a graph showing the photoluminescence of a transition metal-decalcogenide thin film according to Examples 1 to 5 of the present invention.
  • 16 is a graph for comparing photoluminescence of transition metal-dicalcogenide thin films according to Examples 1 to 5 (M-ALD) and Comparative Examples 1 to 5 (C-ALD) of the present invention.
  • Example 20 is a graph showing a Raman shift of a transition metal-dicalcogenide thin film according to Example 1, Example 3, and Example 5 of the present invention.
  • FIG. 21 is a graph showing a photograph of a transition metal-dicalcogenide thin film according to Example 3 of the present invention measured with an atomic force microscope and a length-height measurement.
  • FIG. 21 is a graph showing a photograph of a transition metal-dicalcogenide thin film according to Example 3 of the present invention measured with an atomic force microscope and a length-height measurement.
  • Example 22 is a graph showing a photograph of a transition metal-dicalcogenide thin film according to Example 1 of the present invention measured by atomic force microscope and a length-height measurement.
  • Example 23 is a photograph of a thin film of transition metal-dicalcium cyanide according to Example 3 of the present invention measured by a scanning electron microscope.
  • FIG. 24 is a photograph of a thin film of transition metal-dicalcogenide according to Example 1 measured by a scanning electron microscope.
  • FIG. 24 is a photograph of a thin film of transition metal-dicalcogenide according to Example 1 measured by a scanning electron microscope.
  • M-ALD transition metal-dicalcium cyanide thin films according to the embodiments of the present invention
  • C-ALD comparative examples
  • FIG. 26 is a photograph of a transition metal-dicalcogenide thin film according to an embodiment of the present invention measured by a scanning electron microscope.
  • FIG. 27 is an energy-dispersive X-ray spectroscopy (EDS) analysis graph of a transition metal-decalcogenide thin film according to an embodiment of the present invention.
  • EDS energy-dispersive X-ray spectroscopy
  • first, second, third, etc. in the various embodiments of the present disclosure are used to describe various components, these components should not be limited by these terms. These terms have only been used to distinguish one component from another. Thus, what is referred to as a first component in any one embodiment may be referred to as a second component in another embodiment.
  • Each embodiment described and exemplified herein also includes its complementary embodiment. Also, in this specification, 'and / or' are used to include at least one of the front and rear components.
  • connection &quot is used to include both indirectly connecting and directly connecting a plurality of components.
  • FIG. 2 is a view for explaining a step of forming a preliminary film according to an embodiment of the present invention
  • FIG. 3 is a cross-sectional view illustrating a method of manufacturing a thin film according to an embodiment of the present invention
  • FIG. 4 is a view for explaining thermal decomposition of a precursor according to an embodiment of the present invention
  • FIG. 5 is a view for explaining first and second portions of a preliminary thin film according to an embodiment of the present invention
  • FIG. 7 is an enlarged view of FIG. 6C, illustrating a step of heat-treating a preliminary thin film according to an embodiment of the present invention in a gas atmosphere including a Chalcogen element.
  • FIG. 8 is a view for explaining a step of manufacturing a transition metal-dichalcogenide thin film according to an embodiment of the present invention
  • FIG. 9 is an enlarged view of FIG. 8D
  • FIG. 10 is a cross- And a method for producing the transition metal-decalcogenide thin film according to the present invention.
  • a base substrate 110 may be prepared in a chamber (S110).
  • the chamber may be provided in a vacuum atmosphere.
  • the base substrate 110 may include at least one of an amorphous material or an oxide material.
  • the base substrate 110 may include SiO 2 and Al 2 O 3 .
  • the base substrate 110 may be a silicon substrate, a compound semiconductor substrate, a plastic substrate, or a glass substrate.
  • a precursor containing the transition metal 121 may be prepared (S120).
  • the precursor may comprise the transition metal 121 and the ligand 122.
  • the precursor may include the transition metal (121) coordinated to the ligand (122).
  • the precursor is provided on the base substrate 110 in a later step as the transition metal 121 and the ligand 122 are coordinated to each other, at least a portion of the precursor can easily be thermally decomposed have.
  • the base substrate 110 can be controlled.
  • the precursor is at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Zr, Nb, Mo, Tc, Ru, Pd, Hf, Ta, W, Re, . ≪ / RTI >
  • the precursor may include at least one of MoF 6 , MoCl 6 , and Mo (CO) 6 .
  • the precursor may be prepared in a solid state. That is, the precursor may be provided in a solid state at room temperature.
  • the step of providing the precursor on the base substrate 110 and the step of purging the chamber are repeated a plurality of times to form a preliminary thin film 120) (S130).
  • the precursor may include the transition metal 121 and the ligand 122, which are relatively weakly bonded to each other, and the transition metal 121, And when the precursor is provided on the base substrate 110 as the ligand 122 is coordinately bonded, at least a portion of the precursor can be readily thermally decomposed.
  • the temperature of the base substrate 110 can be controlled according to the coupling force between the transition metal 121 and the ligand 122, as described in step S120.
  • the temperature of the base substrate 110 may be increased in the step of forming the preliminary thin film 120 as the bonding force between the transition metal 121 and the ligand 122 is higher. Thereby, at least a part of the precursor can be easily thermally decomposed.
  • At least a portion of the precursor may be thermally decomposed, and at least a portion of the preliminary film 120 may comprise the precursor stacked.
  • the at least a portion of the preliminary thin film 120 in which the precursors are laminated comprises a first portion 123 and a second portion 124 on the first portion 123, ,
  • the precursor of the second portion 124 may be thermally decomposed and adsorbed on the precursor of the first portion 123.
  • the precursor when the transition metal 121 and the ligand 122 do not coordinate or control the temperature of the base substrate 110, Due to the binding force between the transition metal (121) and the ligand (122), the precursor may not be thermally decomposed. Accordingly, when forming the preliminary thin film 120 by providing the precursor on the base substrate 110, the preliminary thin film 120 may not completely cover the entire surface of the base substrate 110. Thus, it may be difficult to produce a single layer of the transition metal-dicalcogenide thin film 130.
  • the precursor when the precursor is provided on the base substrate 110 as the transition metal 121 and the ligand 122 are coordinated to each other as described above, May be thermally decomposed.
  • the higher the bonding force between the transition metal 121 and the ligand 122 the more the temperature of the base substrate 110 can be increased in the step of forming the preliminary thin film 120, And as shown in Figure 5, the precursor can be thermally decomposed. Accordingly, the precursor can be easily adsorbed on the base substrate 110, and therefore, the preliminary thin film 120 can be easily formed. In other words, the preliminary thin film 120 that completely covers the front surface of the base substrate 110 can be provided.
  • the preliminary thin film 120 completely covers the entire surface of the base substrate 110 by thermal decomposition of the precursor, and the thin film of the transition metal-dicalcogenide thin film 130, which will be described later,
  • the precursor may contain an amount of the precursor that is greater than the amount of the precursor required for the precursor. Accordingly, the transition metal-decalcogenide thin film 130 can be easily produced as a single layer, and the surface uniformity of the transition metal-decalcogenide thin film 130 to be manufactured can be improved.
  • the transition metal precursor and the chalcogen precursor can be alternately provided on the base substrate. Accordingly, the transition metal precursor may randomly grow on the base substrate, and thus the uniformity may be lowered when the transition metal-decalcogenide thin film is produced as a single layer. Further, the self-limiting reaction of the transition metal precursor may occur on the transition metal-decalcogenide thin film, and thus it is not easy to form a single layer and a transition metal-decalcogenide thin film having a uniform surface state .
  • the step of providing the precursor on the base substrate 110 and the step of purging the chamber are defined as one unit process, May be repeated a plurality of times.
  • the precursor may be adsorbed on the base substrate 110 at a high density to form the preliminary thin film 120.
  • the precursor when the unit process is not repeated a plurality of times, the precursor may not be adsorbed on the base substrate 110 at a high density. Accordingly, a process of transferring the base substrate 110 having the preliminary thin film 120 formed therein by a furnace for heat treatment performed after the unit process, and a process of heat-treating the preliminary thin film 120, The precursor of the preliminary thin film 120 may be lost and the quality of the transition metal-decalcogenide thin film 130 produced from the preliminary thin film 120 may be deteriorated.
  • the precursor in the preliminary thin film 120 can be provided at a high density,
  • the preliminary thin film 120 is transferred from the preliminary thin film 120 to the preliminary thin film 120 even if the precursor is lost in the process of transferring the preliminary thin film 120 to the furnace for heat treatment,
  • the degradation of the quality of the transition metal-decalcogenide thin film 130 can be minimized.
  • the precursor in the preliminary thin film 120 may be formed into a plurality of layers. Also, as the number of repetition of the unit process increases, the thickness of the preliminary thin film 120 can be increased.
  • the precursor may be provided in a solid state at room temperature. Accordingly, the precursor is easily adsorbed on the base substrate 110, so that the preliminary thin film 120 to which the precursor is adsorbed at high density can be manufactured.
  • the preliminary thin film 120 is heat-treated in a gas atmosphere containing a chalcogen element 125 to form a transition metal-dichalcogenide thin film 130 (S140).
  • the gas atmosphere may include at least one of the group consisting of S, Se, and Te.
  • the gas atmosphere may contain H 2 S.
  • the heat treatment of the preliminary thin film 120 may be performed at a temperature of 600 ° C or higher. If more than the temperature of the heat treatment step 600 °C, the produced transition metal-radical chalcogenides thin film 130, of the formula MX 2, denoted as (M: chalcogen elements (125): a transition metal (121) element, and X) Structure.
  • the precursor provided in the unit process is Mo (CO) 6
  • the gas containing the chalcogen element 125 provided in the heat treatment process is H 2 S
  • the temperature of the heat treatment process is 600 ° C.
  • the transition metal-decalcogenide thin film 130 to be manufactured may contain MoS 2 .
  • the preliminary thin film 120 may be cooled at room temperature in a state where heat remains.
  • the preliminary thin film 120 may be cooled to room temperature at a temperature of 150 ° C or higher.
  • the chalcogen element provided on the preliminary thin film 120 in the heat- may be deteriorated.
  • the chalcogen element 125 provided on the preliminary thin film 120 By minimizing the loss, degradation of the quality of the transition metal-decalcogenide thin film 130 to be manufactured can be minimized.
  • the transition metal-decalcogenide thin film 130 may be manufactured as a monolayer.
  • the transition metal-decalcogenide thin film 130 ⁇ A 1g ⁇ E 2g interval) may be 20 cm -1 days.
  • a 1g represents out-of-plane vibration
  • E 2g represents in-plane vibration.
  • a 1g and E 2g may have a sensitive thickness dependence. For example, A 1 g may increase as the thickness increases, and E 2 g may decrease as the thickness increases. Therefore, it can be determined whether the transition metal-decalcogenide thin film 130 is a single layer or a plurality of layers according to the intervals of? A 1 g to E 2 g .
  • the interval of? A 1 g to E 2 g of MoS 2 is 20 cm -1 .
  • the transition metal-decalcogenide thin film 130 fabricated according to one embodiment may be MoS 2 produced as a single layer.
  • the step of forming the preliminary thin film 120 and the step of fabricating the transition metal-decalcogenide thin film 130 may be performed in chambers independent of each other.
  • the step of forming the preliminary thin film 120 (S130) and the step of fabricating the transition metal-decalcogenide thin film 130 (S140) may be performed in a separate facility.
  • the precursor can be adsorbed on the base substrate 110 at a high density, The decline in the quality of the transition metal-decalcogenide thin film 130 can be minimized even if the precursor of the transition metal-decalcogenide film 120 is partially lost.
  • a transition metal precursor and a chalcogen precursor are alternately provided on a base substrate, and even though a reaction site exists due to physical contact between the transition metal precursors And may not be adsorbed on the base substrate (screening effect). In addition, due to the large size of the transition metal precursor, thin film formation can be disturbed (Steric hindrance effect).
  • the transition metal-decalcogenide thin film 130 does not grow at random and is easily manufactured into a single layer .
  • the unit process may be repeated a plurality of times, so that the precursor in the preliminary film 120 can be provided at a high density, as shown in FIG.
  • the preliminary thin film 120 on which the transition metal precursor has been adsorbed may substantially cover the entire surface of the base substrate 110, whereby the preliminary thin film 120 is formed of the transition metal- The thin film 130 can be manufactured.
  • a method of manufacturing a semiconductor device comprising: preparing a base substrate 110 in a chamber; preparing a precursor containing a transition metal; providing the precursor on the base substrate 110; Forming a preliminary thin film (120) on which the precursor is adsorbed on the base substrate (110) by repeatedly performing a step of performing heat treatment on the preliminary thin film (120) in a gas atmosphere containing a chalcogen element, A method of fabricating a thin film of transition metal-decalcogenide thin film including a step of producing a transition metal-decalcogenide thin film 130 may be provided.
  • transition metal-dicalcogenide thin film having a higher maximum peak value and a smaller standard deviation of the maximum peak value in each region can be provided in comparison with the above-mentioned reference transition metal-decalcogenide thin film in Raman spectrum measurement.
  • Atmosphere can be provided.
  • a gas atmosphere including the chalcogen element 125 may be firstly provided.
  • a preliminary transition metal-dicalcogenide thin film in which the transition metal 121 and the chalcogen element 125 of the preliminary thin film 120 are combined can be produced.
  • the step of providing a gas atmosphere comprising the chalcogen element 125 may be performed at least once.
  • step S140 in the preliminary transition metal-dicalcogenide thin film prepared in another facility, that is, another chamber, separate from the chamber provided with the gas atmosphere including the chalcogen element 125, A gas atmosphere including the kogen element 125 may be provided secondarily.
  • a transition metal-dicalcogenide thin film 130 in which the transition metal 121 and the chalcogen element 125 of the preliminary transition metal-decalcogenide thin film are combined can be prepared.
  • a SiO 2 wafer having a thickness of 300 nm was prepared.
  • Mo (CO) 6 was prepared as a precursor containing a transition metal.
  • the preliminary thin film was heat-treated at 900 ° C for 1 minute in a gas atmosphere containing 5% H 2 S and then cooled at 150 ° C at room temperature to prepare a transition metal-dicalcogenide thin film according to Example 1.
  • Example 2 Preparing a transition metal-decalcogenide thin film in the same manner as in the above-described Example 1, performing the step of providing the Mo (CO) 6 on the SiO 2 wafer and purging the chamber 9 times, A transition metal-dicalcogenide thin film according to Example 2 was prepared.
  • Example 3 Preparing a transition metal-decalcogenide thin film in the same manner as in the above-mentioned Example 1, performing the step of providing the Mo (CO) 6 on the SiO 2 wafer and purging the chamber 10 times, A transition metal-dicalcogenide thin film according to Example 3 was prepared.
  • Mo (CO) 6 was prepared as a precursor containing a transition metal.
  • H 2 S was prepared as a precursor containing a chalcogen element.
  • transition metal-decalcogenide thin films according to Examples 1 to 5 and Comparative Examples 1 to 5 of the present invention can be summarized as shown in Table 1 below.
  • FIG. 11 is a graph showing the thickness characteristics of the transition metal-decalcogenide thin film according to the comparative example corresponding to the temperature of the base substrate
  • FIG. 12 is a graph showing the thickness characteristics of the transition metal-
  • FIG. 13 is a graph for comparing the thickness characteristics of a transition metal-decalcogenide thin film according to the embodiment (M-ALD) and the comparative example (C-ALD) of the present invention.
  • the thickness of the transition metal-decalcogenide thin film according to the comparative example increases.
  • the thickness of the transition metal-decalcogenide thin film rapidly increases after 180 ° C., and it is difficult to control the thickness of the transition metal-decalcogenide thin film according to the temperature in the temperature range of 180 ° C. or more.
  • the process window range of the transition metal-decalcogenide thin film according to the comparative example is as narrow as 160 to 180.
  • the thickness of the transition metal-decalcogenide thin film according to the comparative example is increased, but the thickness of the transition metal-decalcogenide thin film is not saturated Able to know.
  • the thickness of the transition metal-decalcogenide thin film according to the embodiment (M-ALD) of the present invention is about the same as that of the transition metal-decalcogenide thin film according to the comparative example (C-ALD) 5.5 times thinner. Accordingly, when the method for producing a transition metal-decalcogenide thin film according to an embodiment of the present invention is used, it is possible to precisely control the injection amount of the precursor and thus to produce the transition metal-dicalcogenide thin film with improved uniformity .
  • FIG. 14 is a graph showing photoluminescence of a transition metal-decalcogenide thin film according to Comparative Examples 1 to 5
  • FIG. 15 is a graph showing the photoluminescence of a transition metal-dicalcene thin film according to Examples 1 to 5 of the present invention.
  • 16 is a graph showing the change in the transition metal-dicalogy according to Examples 1 to 5 (M-ALD) and Comparative Examples 1 to 5 (C-ALD) Is a graph for comparing the light emission of the thin film.
  • the transition metal-dicalcogenide when the method for producing a thin film of transition metal-dicalcium cyanide according to Examples 1 to 5 and Comparative Examples 1 to 5 of the present invention is used, the transition metal-dicalcogenide It can be seen that the thin film can be manufactured as a single layer. However, it can be confirmed that the transition metal-dicalcogenide thin films according to Examples 1 to 5 of the present invention have better quantum efficiency than the transition metal-decalcogenide thin films according to Comparative Examples 1 to 5.
  • the PL peak was divided by the peak intensity of MoS 2 only and normalized.
  • the PL intensity ratio of the transition metal-dicalcogenide (MoS 2 ) thin film to the raman peak can be proportional to the quantum efficiency of the transition metal-decalcogenide thin film of the single layer.
  • the defect i.e., bilayer
  • the position of the PL peak shifts to the right and the intensity can also decrease.
  • the transition metal-decalcogenide thin film is a single layer, the highest intensity peak can be observed.
  • the transition metal-decalcogenide thin films according to Examples 1 to 5 of the present invention were made into a single layer.
  • the peaks and intensities observed in the transition metal-decalcogenide thin films may vary depending on the measurement position.
  • peaks and intensities observed in the transition metal-decalcogenide thin films in all regions can be uniform.
  • the luminescence efficacity of the transition metal-decalcogenide thin films according to the comparative examples was 1.25 times, while the luminescence efficacity of the transition metal-decalcogenide thin films according to the embodiments of the present invention was relatively high, 11.5 times.
  • FIG. 17 is a PL mapping for examining the luminescence efficiency of the transition metal-decalcogenide thin films according to Comparative Examples 1 to 5, and Fig. 18 is a graph showing the luminescence efficiency of the transition metal-dicalcogenide thin film according to Examples 1 to 5 of the present invention
  • FIG. 19 is a graph showing a variation in thickness of a transition metal-dicalcogenide thin film according to Examples 1 to 5 and Comparative Examples 1 to 5 of the present invention.
  • FIG. 20 is a graph showing a Raman shift of a transition metal-dicalcogenide thin film according to Example 1, Example 3, and Example 5 of the present invention.
  • the Raman shift data of the transition metal-decalcogenide thin film according to the embodiments and the comparative examples of the present invention can be confirmed.
  • the Raman shift of the transition metal-decalcogenide thin film was about 20.1 cm -1 , indicating that the transition metal-decalcogenide thin film was formed as a single layer.
  • the uniformity of the transition metal-decalcogenide thin film having a size of 5 cm was measured. As a result, it was found that the transition metal-decalcogenide thin film according to the embodiments of the present invention, It can be seen that the uniformity of the cogenide thin film is excellent.
  • the distance between two peaks of the transition metal-diccoconjugate thin film according to Example 5 of the present invention is larger than 20 cm -1 . Accordingly, it can be seen that the transition metal-decalcogenide thin film partially includes a bilayer. Meanwhile, it can be seen that the distance between the two peaks of the transition metal-dicalcogenide thin film according to Example 3 of the present invention agrees with 20 cm -1 . Thus, it can be seen that the transition metal-decalcogenide thin film is formed as a single layer. From these experimental results, it can be seen that when the number of repetitions of the step of providing Mo (CO) 6 and the step of purging the chamber is 10 cycles, the transition metal-decalcogenide thin film can be easily prepared as a single layer have.
  • FIG. 21 is a graph showing a photograph of a transition metal-dicalcogenide thin film according to Example 3 of the present invention measured with an atomic force microscope and a length-height measurement
  • FIG. 22 is a graph 1 is a graph showing a measurement of a transition metal-dicalcogenide thin film according to an atomic force microscope and a length-height measurement.
  • the transition metal-decalcogenide thin film according to Example 3 and Example 1 of the present invention is a monolayer having an average thickness of 0.6 nm within an average length of 12 ⁇ Can be confirmed.
  • the thickness deviation of the transition metal-decalcogenide thin film according to Example 3 of the present invention is +0.5 to -0.1, whereas the thickness variation of the transition metal-decalcogenide thin film according to Example 1 is +1.5 to- 1 < / RTI >
  • the number of repetitions of the step of providing Mo (CO) 6 and the step of purging the chamber is 10 cycles, it means that the thickness distribution is uniform within a range of 12 mu m in average length.
  • FIG. 23 is a photograph of a thin film of transition metal-dicalcium cyanide according to Example 3 of the present invention measured by a scanning electron microscope.
  • FIG. It is an electron microscope photograph.
  • the transition metal-decalcogenide thin film according to Example 3 of the present invention has an area of 500 x 500 nm as compared with the transition metal-diccoconjugate thin film according to Example 1 It can be seen that the surface is uniform.
  • M-ALD transition metal-dicalcium cyanide thin film according to the embodiments of the present invention
  • C-ALD comparative examples
  • EDS energy-dispersive X-ray spectroscopy
  • the transition metal-decalcogenide thin films according to the embodiments and the comparative examples of the present invention can be confirmed to contain MoS 2 in a chemical structure. 26 and 27, it can be confirmed that MoS 2 having a thickness of 0.6 nm is uniformly deposited as a monolayer. According to the results, according to the method for producing a transition metal-decalcogenide thin film according to an embodiment of the present invention, the transition metal-dicalcogenide thin film having a thickness of 0.6 nm, which includes MoS 2 in a chemical composition, As shown in FIG.
  • Example 6 Preparing a transition metal-decalcogenide thin film in the same manner as in the above-described Example 1, performing the step of providing the Mo (CO) 6 on the SiO 2 wafer and purging the chamber 20 times, A transition metal-dicalcogenide thin film according to Example 6 was prepared.
  • a thin film of transition metal-decalcogenide was prepared in the same manner as in Example 6, except that the preliminary thin film was heat-treated at 800 ° C for 1 minute in a gas atmosphere containing 5% H 2 S, Cooled to prepare a transition metal-dicalcogenide thin film according to Example 7.
  • the transition metal-dicalcogenide thin film was prepared in the same manner as in Example 6, except that the preliminary thin film was heat-treated at 600 ° C for 1 minute in a gas atmosphere containing 5% H 2 S, Cooled to prepare a transition metal-dicalcogenide thin film according to Example 8.
  • a thin film of transition metal-decalcogenide was prepared in the same manner as in Example 6, except that the preliminary thin film was heat-treated at 400 ° C for 1 minute in a gas atmosphere containing 5% H 2 S, Cooled to prepare a transition metal-dicalcogenide thin film according to Comparative Example 6.
  • the transition metal-dicalcogenide thin films according to Example 7 and Example 8 and Comparative Example 6 can be summarized as shown in Table 2 below.
  • the transition metal-decalcogenide thin film annealed at 400 ° C. according to Comparative Example 6 showed no peaks at the MoS 2 wavelength.
  • a peak of MoS 2 wavelength can be observed.
  • the transition metal-decalcogenide thin films according to Examples 6 to 8 of the present invention include MoS 2 .
  • the transition metal-decalcogenide thin film according to the embodiment of the present invention can be utilized in various technical fields such as semiconductor devices and display devices.

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Abstract

L'invention concerne un procédé de fabrication d'un film mince de métal de transition-dichalcogénure. Le procédé de fabrication d'un film mince de métal de transition-dichalcogénure peut comprendre les étapes consistant à : préparer un substrat de base à l'intérieur d'une chambre ; préparer un précurseur comprenant un métal de transition ; effectuer de manière répétée, de multiples fois, une étape de fourniture du précurseur sur le substrat de base et une étape de purge de la chambre, ce qui permet de former, sur le substrat de base, un film mince préliminaire dans lequel le précurseur est adsorbé ; et fabriquer un film mince de métal de transition-dichalcogénure par traitement thermique du film mince préliminaire dans une atmosphère gazeuse comprenant un élément chalcogène.
PCT/KR2018/015585 2017-12-13 2018-12-10 Film mince de métal de transition-dichalcogénure et son procédé de fabrication Ceased WO2019117559A1 (fr)

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CN113072099A (zh) * 2020-01-03 2021-07-06 中国科学院上海微系统与信息技术研究所 TMDs二维材料薄膜、器件及制备方法
CN117156358A (zh) * 2023-10-30 2023-12-01 深圳市增长点科技有限公司 一种高回弹性扬声器复合振膜及具有该振膜的耳机扬声器

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KR20170048873A (ko) * 2015-10-27 2017-05-10 연세대학교 산학협력단 Cvd를 이용한 전이금속 칼코겐 화합물 합성 방법

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KR20140115723A (ko) * 2013-03-22 2014-10-01 경희대학교 산학협력단 칼코겐 화합물의 2차원 대면적 성장 방법, cmos형 구조체의 제조 방법, 칼코겐 화합물의 막, 칼코겐 화합물의 막을 포함하는 전자 소자 및 cmos형 구조체
KR20150098904A (ko) * 2014-02-21 2015-08-31 엘지전자 주식회사 금속 칼코게나이드 박막의 제조 방법 및 그 박막
KR20170014319A (ko) * 2015-07-29 2017-02-08 한국표준과학연구원 2 차원 전이금속 디칼코지나이드의 제조 방법
KR20170048873A (ko) * 2015-10-27 2017-05-10 연세대학교 산학협력단 Cvd를 이용한 전이금속 칼코겐 화합물 합성 방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113072099A (zh) * 2020-01-03 2021-07-06 中国科学院上海微系统与信息技术研究所 TMDs二维材料薄膜、器件及制备方法
CN113072099B (zh) * 2020-01-03 2022-07-08 中国科学院上海微系统与信息技术研究所 TMDs二维材料薄膜、器件及制备方法
CN117156358A (zh) * 2023-10-30 2023-12-01 深圳市增长点科技有限公司 一种高回弹性扬声器复合振膜及具有该振膜的耳机扬声器
CN117156358B (zh) * 2023-10-30 2024-02-02 深圳市增长点科技有限公司 一种高回弹性扬声器复合振膜及具有该振膜的耳机扬声器

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