Method for Producing a Multi-component Thin Film and a Multi-component Thin Film Produced Thereby

Abstract

The present invention relates to a method for manufacturing a thin film of a multi-component system and a thin film of a multi-component system, and more specifically, by utilizing a simple pyrolysis method, a thin film of a semiconductor material of a transition metal chalcogenide system can be easily manufactured, and said thin film of a semiconductor material of a multi-component system can be applied to a photodetector or a photoelectrochemical cell.

Description

Technology Field

[0001] The present invention relates to a method for manufacturing a multi-component thin film and a multi-component thin film manufactured using the same, and more specifically, to a method for manufacturing a multi-component transition metal chalcogen thin film for semiconductor materials applicable to photodetectors or photoelectrochemical cells and a multi-component thin film manufactured using the same. Background Technology

[0002] With the development of the electronics and energy-related industries, research is being conducted on two-dimensional materials that exhibit interesting properties to enhance the capabilities of nanophotonic and energy applications. In particular, among two-dimensional materials, transition metal dichalcogenides are receiving significant attention as materials for next-generation device applications because they not only possess high charge mobility but also exhibit excellent electrical, magnetic, and optical properties.

[0003] Transition metal dichalcogenides are compounds formed by combining various transition metals on the periodic table with group 16 chalcogen elements, such as sulfur (S), selenium (Se), and tellurium (Te), excluding oxygen. They can be represented by the chemical formula MX2. Representative examples of the transition metal elements (M) include molybdenum (Mo) and tungsten (W) from groups 4, 5, and 6, and the chalcogen elements (X) include group 16 elements such as sulfur (S), selenium (Se), and tellurium (Te).

[0004] These transition metal dichalcogenides are next-generation nanomaterials characterized by the existence of multiple structural phases and changes in electrical properties into conductors, semiconductors, and dielectrics through phase transitions, unlike graphene, which is a representative two-dimensional material having a single structural phase. Improving the physical properties of the transition metal chalcogenide materials is useful in various application fields such as optoelectronic and energy devices. Among the various methods for this, the development of ternary or multi-component semiconductors through the addition of heterogeneous elements is considered an excellent method for enabling band gap engineering and phase change of transition metal chalcogenides, thereby enabling multifunctionalization of materials and overall property improvement regardless of the application field.

[0005] As prior art related to this, Korean Patent Registration Publication No. 10-2109347 (Publication Date: May 12, 2020) discloses a technology for manufacturing a doped metal chalcogen thin film by first depositing dopant atoms on a substrate and then performing a heat treatment process of a metal precursor and a chalcogen precursor on the substrate on which the dopant atoms are deposited. Additionally, Korean Published Patent Application No. 2015-0129485 (Publication Date: November 20, 2015) discloses a technology for manufacturing a metal chalcogen thin film containing heterogeneous metal elements on a substrate by supplying a first metal precursor, a second metal precursor, and a chalcogen-containing gas.

[0006] However, research on the aforementioned transition metal chalcogenide-based multicomponent semiconductors is currently concentrated on performance enhancement tailored to specific functions or fields. Furthermore, there are limitations in that additional conditions are required to lower the activation energy in order to introduce specific components into the transition metal chalcogenides.

[0007] For example, a process for manufacturing multicomponent materials by doping transition metal chalcogenides with tellurium (Te) utilizes H2 gas to lower the activation energy; however, this method requires special caution during handling due to flammability and explosive risks, and also carries the limitation of requiring the use of promoters such as alkali metal catalysts.

[0008] Meanwhile, the solution process for heterogeneous element doping of transition metal chalcogenides involves dissolving a precursor in a solvent, coating it onto a substrate, and heat-treating it to form a thin film. This process can be carried out at relatively lower temperatures compared to CVD conditions and has the advantage of being applicable to various substrates. Furthermore, since the solution process enables mass production and is cost-effective, it is also suitable for industrial applications.

[0009] However, this method of doping heterogeneous elements through solution processes faces the difficulty of selecting a solvent that is well soluble in both the heterogeneous element precursor to be introduced into the transition metal chalcogenide and the transition metal chalcogenide precursor; furthermore, there are still limitations in ensuring doping uniformity by optimizing the solution concentration, coating conditions, and heat treatment conditions.

[0010] Therefore, there is an urgent need for a novel method for manufacturing multi-component thin films based on transition metal chalcogenides and for the development of multifunctional devices utilizing such films, in order to improve upon the problems of such manufacturing methods and overcome the limitations of solution processes. Prior art literature

[0011] Korean Patent Registration Publication No. 10-2109347 (Publication Date: May 12, 2020) Korean Published Patent Application No. 2015-0129485 (Publication Date: November 20, 2015) The problem to be solved

[0012] The present invention aims to provide a novel method for manufacturing ternary or multi-component thin films based on transition metal chalcogenides by adding a specific heterogeneous element to the transition metal chalcogenide or adding an oxide of said heterogeneous element in order to improve the physical properties of the transition metal chalcogenide.

[0013] In addition, the present invention aims to provide an electronic device comprising a multi-component thin film obtained using the above-described method for manufacturing a multi-component thin film. means of solving the problem

[0014] To achieve the above technical objectives, the present invention provides a method for manufacturing a thin film of a multi-component component comprising: (a) a step of coating a precursor comprising a transition metal source and a chalcogen source on a substrate; (b) a step of introducing, as an additional component, a heterogeneous element powder different from the transition metal or chalcogen component in step (a) or an oxide powder comprising said heterogeneous element into the substrate in the reaction chamber; and (c) a step of forming a thin film of a multi-component component comprising a transition metal chalcogenide and a heterogeneous element powder or an oxide component comprising said heterogeneous element by heating the substrate in the reaction chamber and said heterogeneous element powder or said heterogeneous element oxide powder.

[0015] In one embodiment, the substrate may comprise any one selected from silicon (Si), silicon oxide (SiO2), quartz, aluminum oxide (Al2O3), and graphene, or a mixture thereof.

[0016] In one embodiment, the chalcogen source in step (a) may be any one selected from sulfur (S), selenium (Se) and tellurium (Te).

[0017] In one embodiment, the transition metal in step (a) may be any one selected from molybdenum (Mo), tungsten (W), rhenium (Re), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), nickel (Ni), palladium (Pd), and platinum (Pt).

[0018] As one embodiment, the heating in step (c) may be in the range of 200°C to 650°C.

[0019] In one embodiment, the heterogeneous element in step (b) may be any one selected from Te, Re, Se, Ni, Pt, Pd, and V, or a mixture thereof.

[0020] In one embodiment, the substrate in step (a) may be a substrate on which a metal adhesive layer is formed.

[0021] In one embodiment, in step (a), the substrate may be coated with a precursor comprising a transition metal source and a chalcogen source by a solution process.

[0022] As one embodiment, the thin film of the multi-component system formed in step (c) may have a thickness of 3 to 100 nm.

[0023] As one embodiment, the thin film of the multi-component system formed in step (c) may be a thin film of the ternary or quaternary system.

[0024] In addition, the present invention provides a thin film of a multi-component system manufactured by the method for manufacturing a thin film of a multi-component system.

[0025] In addition, the present invention provides an electronic device comprising a thin film of a multi-component according to the thin film of the multi-component component. Effects of the invention

[0026] The method for manufacturing a multi-component thin film according to the present invention can produce a high-quality transition metal chalcogenide-based multi-component thin film using a simple pyrolysis method with a solution process precursor and a heterogeneous element powder or a heterogeneous element oxide powder as raw materials.

[0027] In addition, the thin film of a multi-component system in which heterogeneous elements are introduced into a transition metal chalcogenide according to the present invention can be utilized as a multi-functional device such as a photodetector and a photoelectrochemical cell, and by controlling the final application of the semiconductor material thin film obtained through temperature control during the pyrolysis process, it is possible to achieve quality optimization of individual semiconductor materials. Brief explanation of the drawing

[0028] FIG. 1 is a schematic diagram showing a method for manufacturing a thin film of a Mo-S-Te ternary component based on MoS2 as a transition metal chalcogenide in the manufacturing example of the present invention. Figure 2 is a figure showing the results of analyzing the phase change of MoS2 and Mo-S-Te ternary thin films prepared in Example 1 and Comparative Example 1 according to the present invention. Figure 3 is a graph showing the photoreactivity in the photoreactivity test in Example 1 and Comparative Example 1 according to the present invention. Figure 4 is a graph showing the photocurrent and long-term stability in the photoelectrochemical cell water splitting test in Example 2 and Comparative Example 2 according to the present invention. Specific details for implementing the invention

[0029] The following describes in detail the method for manufacturing a thin film of a multi-component system according to the present invention and electronic devices with target functions, such as photodetectors and photoelectrochemical cells, utilizing the same. However, this is merely illustrative and the present invention is not limited to the specific embodiments described illustratively.

[0030] The terms used in this invention have been selected to be as widely used as possible, taking into account the functions of the invention; however, these terms may vary depending on the intent of those skilled in the relevant field, case law, the emergence of new technologies, etc. Unless otherwise defined, technical and scientific terms used may have the meaning commonly understood by those skilled in the art to which this invention pertains.

[0031] In the specification and claims of the present invention, terms such as "comprising" or "having" mean that the features or components described in the specification exist, and unless specifically limited, this does not exclude the possibility that one or more other features or components may be added.

[0032] Singular expressions used in the present invention and claims include plural expressions unless the context clearly specifies them as singular. Additionally, plural expressions include singular expressions unless the context clearly specifies them as plural.

[0033] Furthermore, the numerical range used in the present invention includes lower and upper limits, all values ​​within the range, increments logically derived from the form and width of the defined range, all of the specified values, and all possible combinations of upper and lower limits of the numerical range defined in different forms. Unless otherwise specifically defined in the present invention, values ​​outside the numerical range that may occur due to experimental error or rounding are also included in the defined numerical range.

[0034] The inventors have completed the present invention by recognizing that, in order to introduce a heterogeneous element or an oxide of a heterogeneous element into a two-dimensional thin film material based on a transition metal chalcogenide, a multicomponent thin film containing a heterogeneous element based on a transition metal chalcogenide can be manufactured by heating and introducing the powder of the heterogeneous element or the oxide of the heterogeneous element into a gaseous state during a thermal decomposition process of a precursor containing a transition metal component and a chalcogenide component, and that the characteristics of the thin film finally obtained can be optimized according to the application through simple thermal decomposition temperature control.

[0035] The method for manufacturing a thin film of a multi-component system according to the present invention comprises: (a) a step of coating a precursor comprising a transition metal source and a chalcogen source on a substrate; (b) a step of introducing, as an additional component, a heterogeneous element powder different from the transition metal or chalcogen component in step (a) or an oxide powder comprising said heterogeneous element into the substrate in the reaction chamber; and (c) a step of forming a thin film of a multi-component system comprising a transition metal chalcogenide and a heterogeneous element or an oxide component comprising said heterogeneous element by heating the substrate in the reaction chamber and said heterogeneous element powder or said heterogeneous element oxide powder.

[0036] Hereinafter, a method for manufacturing a thin film of the multi-component system according to the present invention will be described in more detail.

[0037] According to the present invention, step (a) is a step of coating a precursor comprising a transition metal source and a chalcogen source on a substrate; wherein a precursor for manufacturing a transition metal chalcogenide thin film is coated on the substrate.

[0038] Here, the substrate for forming the transition metal chalcogenide thin film in step (a) is not limited to any specific type and may include, for example, one selected from silicon (Si), silicon oxide (SiO2), quartz, aluminum oxide (Al2O3), polyimide (PI), polydimethylsiloxane (PDMS), and graphene, or a mixture thereof, but is not limited thereto.

[0039] In addition, the transition metal in the precursor containing the transition metal source and the chalcogen source used in step (a) above may be any of the transition metals of periods 4, 5, and 6 of the periodic table, and preferably may be any one selected from molybdenum (Mo), tungsten (W), rhenium (Re), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), nickel (Ni), palladium (Pd), platinum (Pt), and tin (Sn), but is not limited thereto.

[0040] In addition, the chalcogen source in the precursor containing the transition metal source and the chalcogen source used in step (a) above may be any one selected from sulfur (S), selenium (Se), and tellurium (Te), or a mixture thereof, and preferably may be sulfur (S) or selenium (Se).

[0041] Accordingly, if the precursor containing the transition metal source and chalcogen source is not introduced, it may be thermally decomposed by heating in step (c) to form a transition metal chalcogenide thin film, and at this time, the transition metal chalcogenide component in the generated transition metal chalcogenide thin film may be one selected from MoS2, MoSe2, MoTe2, WS2, WSe2, WTe2, ReS2, ReSe2, and ReTe2, or a composite component thereof, but is not limited thereto.

[0042] As a preferred example of the precursor in the present invention, the precursor comprises a transition metal and a chalcogen element, and one or more selected from (NH4)2MoS4, (NH4)2WS4, (NH4)2MoSe4, (NH4)2ReO4, (NH4)2[VO(tart)H2O], (NH4)2PtCl6, (NH4)2PdCl6, (NH4)2TiF6, (NH4)2ZrF6, but are not limited thereto.

[0043] In addition, the substrate obtained in step (a) of the present invention may be coated by any one or a combination thereof selected from chemical vapor deposition (CVD), atomic layer deposition (ALD), and a solution process, but preferably, the precursor comprising the transition metal source and chalcogen source may be coated by a solution process.

[0044] Here, the above solution process is a process for forming a thin film by dissolving a precursor in an organic solvent, coating it on a substrate, etc., and then thermally decomposing it. The organic solvent used at this time can be used without limitation in type as long as it is a solvent capable of dissolving the precursor and being removed by evaporation during thermal decomposition. Suitable organic solvents include, but are not limited to, toluene, tetrahydrofuran, hexane, cyclohexane, acetonitrile, dimethylformamide, dimethyl sulfoxide (DMSO), isopropyl alcohol (IPA), ethylene glycol, etc., and more preferably, acetonitrile, dimethylformamide, dimethyl sulfoxide (DMSO), isopropyl alcohol (IPA), and ethylene glycol.

[0045] In addition, in the composition for the solution process, the content of the precursor based on the total composition content may be 0.3 to 80 wt%, preferably 0.7 to 50 wt%, more preferably 1 to 20 wt%, even more preferably 1.5 to 15 wt%, and even more preferably 2 to 10 wt%.

[0046] More specifically, the coating method by the above solution process may include spin coating, dip coating, or slot die coating methods, and the precursor coating layer obtained after the coating process may be thermally decomposed by heating in step (c) to form a transition metal chalcogenide layer.

[0047] In addition, the present invention may additionally include a step of hydrophilizing the substrate prior to step (a), preferably selected from UV light treatment, plasma treatment, or discharge treatment, through which the precursor compound can be uniformly coated over the entire surface of the substrate.

[0048] In addition, the present invention may further include a drying step for removing organic solvent from the substrate obtained after step (a). At this time, the drying step may preferably be carried out for about 1 minute to 1 hour at a temperature range of 80 to 200 ℃, thereby removing at least 50 wt% of organic solvent, preferably 70 wt% of organic solvent, and more preferably 80 wt% of organic solvent.

[0049] Next, in step (b) according to the present invention, a heterogeneous element powder or an oxide powder containing a heterogeneous element, which is different from the coated substrate in step (a) and the transition metal chalcogenide component coated on the substrate, is introduced into the reaction chamber.

[0050] Here, the heterogeneous element in the heterogeneous element powder or oxide powder containing the heterogeneous element is a component that is uniformly doped onto a transition metal chalcogenide thin film to form a multi-component thin film in the present invention, and the heterogeneous element component or the heterogeneous element oxide component can be uniformly doped onto the layered structure of the transition metal chalcogenide or inside the layered structure according to the thermal division process by heating in step (c).

[0051] In one embodiment, the heterogeneous element in step (b) is tellurium (Te), rhenium (Re), It may be any one selected from selenium (Se), nickel (Ni), platinum (Pt), palladium (Pd), and vanadium (V), or a mixture thereof.

[0052] Meanwhile, the reaction chamber used in step (b) of the present invention is not limited to any specific type and can be used as long as it corresponds to a reactor capable of maintaining a size and temperature that can perform a pyrolysis process as the substrate and the heterogeneous element powder or the oxide powder containing the heterogeneous element are heated in the subsequent step (c); for example, an atmospheric pressure chamber or a reduced pressure chamber may be used.

[0053] Subsequently, in step (c) according to the present invention, by heating the substrate and the heterogeneous element powder or the oxide powder containing the heterogeneous element in the reaction chamber, the precursor in the substrate undergoes a pyrolysis process to form a transition metal chalcogenide thin film, and the heterogeneous element powder or the oxide powder containing the heterogeneous element is sublimated or vaporized by heating, and the heterogeneous element component or the heterogeneous element oxide component is doped by reaction with the transition metal chalcogenide during the process of forming the transition metal chalcogenide thin film on the substrate, thereby enabling the production of a thin film of a multi-component component.

[0054] That is, the present invention allows for the easy formation of a thin film of a multi-component system comprising a transition metal chalcogenide and a heterogeneous element or an oxide component comprising a heterogeneous element by simply heating a substrate coated with a precursor comprising a transition metal source and a chalcogen source, and the heterogeneous element powder or the heterogeneous element oxide powder in a reaction chamber.

[0055] At this time, the heating process for the pyrolysis and reaction may be carried out in a mixed gas atmosphere comprising any one inert gas selected from helium, nitrogen, and argon, or a mixture thereof.

[0056] More specifically, the heating process for the pyrolysis and reaction may be performed by placing a sample boat, such as a quartz boat containing a substrate coated with the precursor and a powder of a heterogeneous element (or an oxide containing a heterogeneous element), into a reaction chamber, and the pyrolysis process may be carried out under an atmosphere of one or more inert gases selected from Ar, He, and N2.

[0057] In addition, in the present invention, the heating conditions for the thermal decomposition and reaction of the substrate coated with the precursor in step (c) and the heterogeneous element powder or the oxide powder containing the heterogeneous element may be in the range of 200 ℃ to 650 ℃, preferably in the range of 250 ℃ to 600 ℃, and more preferably in the range of 280 ℃ to 550 ℃.

[0058] In the case of a multi-component thin film produced according to the present invention, the physical properties of the formed thin film may vary depending on the temperature conditions for heating in step (c). For example, when MoS2 is used as a transition metal chalcogenide thin film and Te is introduced as a heterogeneous element, under the heating conditions for thermal decomposition, at 250 to 350 ℃, it can be applied as a photodetector device that detects light in the wavelength range of 532 to 1550 nm, and under the conditions of 450 to 550 ℃, it can be applied as a photoelectrochemical cell that generates hydrogen through solar-based water splitting.

[0059] The multi-component thin film according to the present invention, obtained according to this method, is formed by simultaneously performing a doping process through the vaporization or sublimation of the heterogeneous element component or heterogeneous element oxide component during the thermal decomposition process of each transition metal component and chalcogen component coated on the substrate. The formation of the transition metal chalcogenide thin film can be simplified and large-area through a solution process, and the additional heterogeneous element component can be easily mass-produced through the sublimation or vaporization of the heterogeneous element powder or heterogeneous element oxide powder. Consequently, this method offers many advantages over conventional methods in forming transition metal chalcogenide-based multi-component thin films. In particular, when doping the transition metal chalcogenide with tellurium (Te), it has the advantage of being able to form a large-area multi-component thin film without using H2 valence or a promoter such as an alkali metal catalyst to lower the activation energy.

[0060] In addition, the thin film of the multi-component component formed in step (c) of the present invention may have a thickness of 3 to 100 nm, preferably 3 to 80 nm, and more preferably 5 to 60 nm. Here, the thin film of the multi-component component can be appropriately adjusted by the user within the above range according to reaction conditions and application.

[0061] In addition, the thin film of the multi-component system formed in step (c) of the present invention can form various thin films of the multi-component system by changing the type of transition metal, the type of chalcogen, and the type of heterogeneous element component to be doped.

[0062] For example, in the case of a ternary thin film, a thin film can be formed by selecting one type of transition metal source, one type of chalcogen source, and one type of heterogeneous element component.

[0063] More specifically, the thin film of the ternary component formed in step (c) above may comprise one transition metal chalcogenide component selected from MoS2, MoSe2, MoTe2, WS2, WSe2, WTe2, ReS2, ReSe2, or ReTe2, and may additionally comprise one type selected from Se and Te as a transition metal or chalcogen different from the transition metal chalcogenide component.

[0064] As another example, in the case where the thin film of the multi-component system formed in step (c) above is a quaternary system thin film, the thin film can be formed by configuring one of the transition metal source, chalcogen source, and heterogeneous element components as two types and each of the remaining components as one type.

[0065] More specifically, the quaternary thin film according to the present invention comprises one component selected from MoS2, MoSe2, MoTe2, WS2, WSe2, WTe2, ReS2, ReSe2, or ReTe2 as a transition metal chalcogenide, and may additionally comprise a transition metal oxide component different from the transition metal chalcogenide component, and the additional transition metal oxide component may react with the transition metal chalcogenide to form a thin film.

[0066] In addition, when the multi-component thin film in the present invention is a pent-component thin film, the thin film can be formed by configuring one of the transition metal source, chalcogen source, and heterogeneous element components as three types and each of the remaining components as one type, or by configuring two of the transition metal source, chalcogen source, and heterogeneous element components as two types and each of the remaining one as one type.

[0067] The method for manufacturing a multi-component thin film according to the present invention has the advantage of being able to easily introduce a heterogeneous element or a heterogeneous element oxide component into a transition metal chalcogenide-based thin film and form a multi-component thin film with a more uniform and wider area than conventional methods, by reacting the precursor with the thermally decomposed product of the precursor in a substrate coated with the precursor through the sublimation or vaporization process of the heterogeneous element powder or the oxide powder containing the heterogeneous element in step (c).

[0068] More specifically, in the case of chemical vapor deposition used to manufacture transition metal chalcogenide ternary semiconductors according to conventional technology, the material size is technically limited to flakes of tens of μm, and methods using plasma processes are limited in application due to complex processes and high manufacturing costs resulting from the equipment used. In contrast, the present invention has the advantage of being able to form ternary, quaternary, or multi-component semiconductor thin films over a larger area than conventional methods through a pyrolysis process combined with the coating of a precursor and the introduction of heterogeneous elements.

[0070] In addition, the present invention provides a thin film of a multi-component system manufactured by the method for manufacturing a thin film of a multi-component system according to the present invention, and also provides an electronic device comprising the thin film of a multi-component system.

[0071] The above multi-component thin film is a thin film formed in a form in which a heterogeneous element is doped into a transition metal chalcogenide base, and since band engineering of the transition metal chalcogenide material is possible and a phase transition between 2H and 1T' can be induced, the multi-component semiconductor material with heterogeneous element added according to the present invention can be individually optimized to have physical properties desired by the user.

[0072] Accordingly, an electronic device comprising a thin film of a multi-component system manufactured according to the present invention can be applied as an individualized, optimized ternary semiconductor photodetector or a semiconductor photoelectrochemical cell.

[0073] The following describes the application of the multi-component thin film according to the present invention as a multifunctional device, such as a photodetector and / or photoelectrochemical cell.

[0074] As an example of an electronic device comprising the thin film of the multi-component system according to the present invention, a photodetector or a photoelectrochemical cell can be manufactured by the method for manufacturing the multi-component thin film of the present invention described above.

[0075] In one embodiment, a photodetector obtained using the method for manufacturing a thin film of a ternary component according to the present invention may include: a substrate; a semiconductor layer of a ternary thin film formed according to the method for manufacturing a thin film of a ternary thin film according to the present invention, formed on the substrate; and an electrode bonded to the semiconductor layer of the ternary thin film.

[0076] Here, the electrode may be deposited by methods such as photolithography, ion beam lithography, and an electrode patterning process including a shadow mask, for example, by performing electrode patterning using a shadow mask and then depositing the electrode through thermal vapor deposition.

[0077] In addition, as the type of metal for the electrode, one or more types selected from cobalt, iron, nickel, chromium, gold, silver, copper, aluminum, platinum, tin, tungsten, ruthenium, palladium, or cadmium may be used, but are not limited thereto.

[0078] In addition, a photoelectrochemical cell using the method for manufacturing a thin film of a ternary component according to the present invention may include a substrate; and a semiconductor layer of a ternary thin film formed according to the method for manufacturing a thin film of a ternary component according to the present invention, formed on the substrate.

[0079] The inventors can provide a device suitable for an application with individualized optimization according to the thermal decomposition temperature by controlling the temperature range in the heating process in step (c) when forming a ternary semiconductor with a heterogeneous element added to a transition metal chalcogenide layer.

[0080] In one embodiment, the bandgap energy between the conduction band and the valence band in the semiconductor of the ternary thin film may be 1.5 eV or less. When the bandgap energy is preferably 1.0 eV or less, and more preferably 0.5 eV or less, the detection wavelength band of the photodetector may be further expanded.

[0081] In one embodiment, the semiconductor of the ternary thin film may include a crystal structure of 1T' phase (1T phase) and 2H (2H phase), and may operate as a 1T'-2H phase transition structure. By operating the ternary semiconductor layer as described above, it exhibits metalloid characteristics, the conductivity of the ternary semiconductor is improved, and the band gap is reduced, allowing for a wide detection wavelength and high photocurrent. Additionally, electrochemical dynamics are enhanced, allowing for excellent photoelectrochemical water splitting characteristics.

[0082] In addition, in one embodiment, the ternary semiconductor layer is based on MoS2, and the different heterogeneous elements may include Te. Photodetectors and photoelectrochemical cells manufactured from ternary semiconductors containing MoS2 and Te can induce bandgap engineering and 1T'-2H phase transition, thereby exhibiting superior performance as multifunctional devices compared to conventional ones and individualized optimization according to thermal decomposition temperature.

[0083] In one embodiment, the semiconductor layer of the ternary thin film included in the photodetector of the present invention can be utilized as a photosensor for detecting light in the wavelength range of 532 to 1550 nm.

[0084] More specifically, the photosensor according to the present invention may be a visible light photosensor that detects light in a wavelength range of 532 to 780 nm, and the photosensor may also be an infrared sensor that detects light in a wavelength range of 780 to 1550 nm.

[0085] In one embodiment, the ternary semiconductor layer included in the photoelectrochemical cell of the present invention can produce hydrogen through water splitting at 0 V vs. RHE when sunlight is incident.

[0086] Hereinafter, embodiments of the present invention will be further described with reference to specific experimental examples and drawings. The following embodiments and comparative examples are merely illustrative of the present invention and are not intended to limit the appended claims. It is obvious to those skilled in the art that various changes and modifications to the embodiments are possible within the scope and spirit of the present invention, and that such variations and modifications fall within the scope of the appended claims.

[0087] [Comparative Preparation Example 1: Preparation of a thin film of MoS2 binary components]

[0088] Without introducing heterogeneous element components, (NH4)2MoS4 was stirred in ethylene glycol at room temperature for 60 minutes as a source precursor for coating on a substrate, as shown in Fig. 1, and the resulting solution was spin-coated on a substrate hydrophilically treated via a UV irradiation process at a rotation speed of 3000 rpm for 40 seconds. After spin-coating, the sample was immediately annealed at 100 °C for 1 minute to remove the solvent.

[0089] The generated (NH4)2MoS4 film was heat-treated in a heat treatment furnace at a pressure of 3 Torr for 30 minutes at 280 °C (first step) under an Ar (1000 sccm) atmosphere, and then pyrolyzed at 500 °C (second step) for 30 minutes to synthesize a pure MoS2 layer.

[0090] [Preparation Example 1: Preparation of a thin film of Mo-S-Te ternary components]

[0091] As shown in FIG. 1, for the preparation of a Mo-S-Te ternary thin film, the same method as the process according to Comparative Preparation Example 1 above is used, except that after coating and annealing (NH4)2MoS4 on a substrate, Te powder (0.2 g) is added to a crucible in a reaction chamber and heated in a heat treatment furnace at 280 °C (first step) under an Ar (1000 sccm) atmosphere at a pressure of 3 Torr for 30 minutes. 30 It was heat-treated for minutes, and then heat-treated at 300 °C (second step) for 30 minutes to produce MoSTe-300 The layer was synthesized.

[0092] For the fabrication of another thin film, following the heat treatment in the first step above, MoSTe-500 is pyrolyzed at 500 °C (second step) for 30 minutes. The layer was synthesized.

[0093] [Preparation Example 2: Preparation of Re-Mo-SO quaternary thin film semiconductor material]

[0094] As shown in Figure 1, for the fabrication of a Mo-S-Re-O quaternary thin film, the source precursor (NH4)2MoS4 was stirred in ethylene glycol at room temperature for 60 minutes, and the resulting solution was spin-coated onto a substrate hydrophilically treated by UV irradiation at a rotation speed of 2000 rpm for 20 seconds. After spin-coating, the sample was immediately annealed at 130 °C for 1 minute to remove the solvent.

[0095] After performing the annealing above, ReO3 powder (0.01 g) was added to a crucible in the reaction chamber and placed in a heat treatment furnace. As before, thermal decomposition was carried out at a temperature of 600 °C under an atmosphere of Ar (1000 sccm) at a pressure of 3 Torr for 30 minutes to form a quaternary thin film.

[0096] [Example 1: Mo-S-Te ternary semiconductor-based photodetector]

[0097] A SiO2 / Si substrate having a semiconductor formed from a Mo-S-Te ternary thin film prepared in Preparation Example 1 was patterned using a shadow mask, and then an electrode was deposited by performing a thermal vapor deposition process. Specifically, a photodetector was fabricated by depositing chromium (Cr) to a thickness of 3 nm as an adhesive layer on each pattern, and then depositing gold (Au) to a thickness of 70 nm on top of it.

[0098] [Comparative Example 1: MoS2 2D Semiconductor-based Photodetector]

[0099] A SiO2 / Si substrate formed with pure MoS2 obtained according to the MoS2 synthesis process of Comparative Manufacturing Example 1 was used.

[0100] Electrode formation was carried out using a shadow mask and thermal vapor deposition process in the same manner as in Example 1 above, and a photodetector was fabricated by depositing a 3 nm thick chromium adhesive layer and a 70 nm thick gold layer on MoS2.

[0101] [Example 2: Mo-S-Te ternary semiconductor-based photoelectrochemical cell]

[0102] The semiconductor of the Mo-S-Te ternary thin film from Preparation Example 1 above was prepared on a Ti / Si photocathode substrate, and titanium (Ti) was used as an intermediate adhesive layer. More specifically, a photoelectrochemical cell was fabricated by depositing Ti as an adhesive layer with a thickness of 10 nm on a Si photocathode and forming the ternary thin film obtained through Preparation Example 1 above thereon.

[0103] [Comparative Example 2: MoS2 2D Semiconductor-based Photoelectrochemical Cell]

[0104] A Ti / Si substrate on which pure MoS2 was formed according to the MoS2 synthesis process of Comparative Manufacturing Example 1 was used, and a photoelectrochemical cell was fabricated by depositing Ti as an adhesive layer with a thickness of 10 nm in the same manner as in Example 2, and forming a MoS2 thin film on it through Comparative Manufacturing Example 1.

[0105] [Test Example 1: Thin Film Analysis Test]

[0106] Figure 2 shows the results of analyzing the structural characteristics of the MoS2 and Mo-S-Te ternary semiconductors prepared in Example 1 and Comparative Example 1 using X-ray photoelectron spectroscopy (XPS; Thermo VG Scientific).

[0107] More specifically, Figure 2 above shows the XPS analysis results of Example 1 and Comparative Example 1. When compared to the upper graph of Figure 2 according to Comparative Example 1, the formation of a Mo-S-Te ternary thin film and a 1T'-2H phase transition were confirmed in Example 1 according to the middle and lower graphs of Figure 2. In addition, it was confirmed that the 1T'-2H phase transition was greater at a temperature of 300 °C than at a temperature of 500 °C.

[0108] [Test Example 2: Photoreactivity Test]

[0109] Figure 3 shows the results of testing the photoresponsiveness of the photodetectors prepared in Example 1 and Comparative Example 1 according to the present invention using a semiconductor parameter analyzer (4200-SCS, Keithley) and a laser source (λ = 532, 1064 and 1550 nm).

[0110] More specifically, the current characteristics according to light irradiation at wavelengths of 532 nm, 1064 nm, and 1550 nm are compared and shown in FIG. 3, and the photoresponsiveness of Example 1 according to the middle and lower graphs of FIG. 3 is shown to be superior to the photoresponsiveness of Comparative Example 1 according to the upper graph of FIG. 3.

[0111] In particular, Figure 3 confirmed that the ternary semiconductor pyrolyzed at 300 °C, which has a larger 1T'-2H phase transition than the Mo-S-Te ternary semiconductor pyrolyzed at 500 °C, exhibited the best sensitivity.

[0112] [Test Example 3: Photoelectrochemical water splitting test]

[0113] Figure 4 shows the results of testing the performance and stability of the photoelectrochemical cells prepared in Example 2 and Comparative Example 2 using a three-electrode system and an electrochemical analyzer (potentiostat / galvanostat 263A).

[0114] More specifically, Figure 4 shows a graph comparing photocurrent characteristics and stability graphs due to photoelectrochemical water splitting upon solar irradiation. It was confirmed that the photoelectrochemical cell prepared in Example 2 has superior performance compared to the photoelectrochemical cell prepared in Comparative Example 2. In particular, regarding the Mo-S-Te ternary semiconductor thermally decomposed at 300 °C and 400 °C in Example 2, the photocurrent characteristics at 300 °C and 400 °C are higher than at 500 °C, but the stability at 500 °C is significantly superior. This confirms that the ternary thin film semiconductor thermally decomposed at 500 °C, which has higher crystallinity, exhibits stable performance even if the 1T'-2H phase change ratio is lower.

[0115] That is, according to Figure 4 above, this means that individualized optimization of materials for each test field is possible by controlling the thermal decomposition temperature of the ternary thin film according to the present invention.

[0116] From the above results, it can be confirmed that the method for manufacturing a thin film of a multi-component system according to the present invention can manufacture a ternary or multi-component semiconductor with excellent performance over a large area, and by applying it to multi-functional devices such as photodetectors and photoelectrochemical cells, it can provide a multi-functional device exhibiting improved performance compared to conventional devices, as well as enable individual optimization for each test field through simple thermal decomposition temperature control.

Claims

Claim 1 (a) a step of coating a precursor comprising a transition metal source and a chalcogen source on a substrate; (b) a step of introducing, as an additional component, a heterogeneous element powder different from the transition metal or chalcogen component in step (a) or an oxide powder comprising said heterogeneous element into the substrate in the reaction chamber; and (c) a step of forming a thin film of a multi-component component comprising a transition metal chalcogenide and a heterogeneous element or an oxide component comprising said heterogeneous element by heating the substrate in the reaction chamber and said heterogeneous element powder or said heterogeneous element oxide powder; comprising a method for manufacturing a thin film of a multi-component component. Claim 2 A method for manufacturing a thin film of a multi-component structure according to claim 1, wherein the substrate comprises one selected from silicon (Si), silicon oxide (SiO2), quartz, aluminum oxide (Al2O3), polyimide (PI), polydimethylsiloxane (PDMS) and graphene, or a mixture thereof. Claim 3 A method for manufacturing a thin film of a multi-component system according to claim 1, wherein in step (a), the chalcogen source is selected from sulfur (S), selenium (Se), and tellurium (Te). Claim 4 A method for manufacturing a thin film of a multi-component system according to claim 1, wherein in step (a), the transition metal is selected from molybdenum (Mo), tungsten (W), rhenium (Re), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), nickel (Ni), palladium (Pd), platinum (Pt), and tin (Sn). Claim 5 A method for manufacturing a thin film of a multi-component system according to claim 1, characterized in that the heating in step (c) is in the range of 200 ℃ to 650 ℃. Claim 6 In claim 1, the heterogeneous elements in step (b) above are Te, Re, Se, Ni, Pt, Pd, V A method for manufacturing a thin film of a multi-component system, characterized by being one of the components selected from or a mixture thereof. Claim 7 A method for manufacturing a thin film of a multi-component system according to claim 1, wherein in step (a), the substrate is coated with a precursor comprising a transition metal source and a chalcogen source by a solution process. Claim 8 A method for manufacturing a thin film of a multi-component component according to claim 1, characterized in that the thin film of the multi-component component formed in step (c) has a thickness of 3 to 100 nm. Claim 9 A method for manufacturing a thin film of a multi-component system according to claim 1, wherein the thin film of the multi-component system formed in step (c) is a thin film of a ternary or quaternary system. Claim 10 A thin film of a multi-component system manufactured according to any one of claims 1 to 9. Claim 11 An electronic device comprising a thin film of a multi-component system according to Clause 10.

Images