Precursor composition for forming transition metal chalcogen compound film, and method for manufacturing transition metal chalcogen compound film using same

Abstract

An embodiment of the present invention is for reducing carbon by-products of a transition metal chalcogen compound film, and provides: a precursor composition for forming a transition metal chalcogen compound film, the precursor composition being characterized in that carbon and two chalcogen elements adjacent to the carbon are bonded by double bonds; a method for manufacturing a transition metal chalcogen compound film using same; and a transition metal chalcogen compound film manufactured thereby.

Description

Precursor composition for forming a transition metal chalcogenide film and method for manufacturing a transition metal chalcogenide film using the same

[0001] The present invention relates to a precursor composition for forming a transition metal chalcogenide film and a method for manufacturing a transition metal chalcogenide film using the same.

[0002] Transition metal chalcogenide compounds are layered compounds in which transition metal atoms are bonded to chalcogen atoms (such as S, Se, or Te), and are known as representative two-dimensional materials capable of maintaining a stable structure even at the atomic layer level. Due to their semiconductor properties with band gaps, changes in electrical and optical properties depending on the number of layers, and strong charge-spin-orbit coupling effects, these transition metal chalcogenide compounds are being presented as having broad application potential in the fields of next-generation semiconductor devices, optoelectronic devices, sensors, catalysts, and energy devices. In particular, there is a continuously increasing demand for technology to uniformly form single-layer or multi-layer transition metal chalcogenide films on large-area substrates due to the potential for integration with silicon-based semiconductor processes.

[0003] For such applications, it is important to grow transition metal chalcogenide films in the form of single crystals or highly crystalline thin films, and furthermore, securing uniform thickness, composition, and crystallinity on wafer-scale large-area substrates is recognized as a key challenge. To this end, vapor phase processes such as chemical vapor deposition (CVD), atomic layer deposition (ALD), and metal-organic chemical vapor deposition (MOCVD) are widely studied, and a method of forming transition metal chalcogenide films by reacting a transition metal precursor with a chalcogen source on a substrate is mainly used.

[0004] However, in conventional transition metal chalcogenide film formation processes, problems are frequently reported where carbon-containing byproducts are generated during the decomposition of transition metal precursors or chalcogen sources, or where amorphous carbon or carbon-based residues remain on the substrate due to side reactions. These carbon byproducts can cause a decrease in the crystallinity of transition metal chalcogenide films, degradation of electrical properties, and an increase in interfacial defects; in particular, they can have a fatal impact on device characteristics in single-layer or ultrathin structures. Furthermore, the extent of carbon byproduct generation tends to be highly dependent on process temperature, pressure, precursor flow rate, and the presence or absence of promoter gases, leading to concerns regarding reduced reproducibility and controllability of process conditions.

[0005] Furthermore, while conventional processes allow for relatively good film formation on specific substrates such as SiO₂ / Si, problems can arise where nucleation density, growth rate, and film uniformity vary significantly when the substrate type changes, such as between amorphous and crystalline substrates. Consequently, there is an increasing demand for technologies capable of stably forming transition metal chalcogenide films regardless of the substrate type. In particular, there is a limitation in that scaling to large-area or mass production processes is difficult when growth behavior changes significantly even with minute variations in process conditions.

[0006] As such, for the practical industrial application of transition metal chalcogenide films, film formation technology is required that can form uniform transition metal chalcogenide films on large-area substrates while suppressing the generation of carbon byproducts and providing excellent control over process conditions. In particular, since the characteristics of the precursors used in the transition metal chalcogenide film formation process directly affect the reaction pathway, the occurrence of side reactions, and the quality of the final film, continuous research is being conducted on precursors suitable for forming transition metal chalcogenide films.

[0007] [Prior Art Literature]

[0008] (Patent Document 0001) Republic of Korea Published Patent Application No. 10-2014-0115723

[0009] The technical problem to be solved by the present invention is to provide a precursor composition for forming a transition metal chalcogenide compound film capable of reducing carbon by-products by utilizing a novel chalcogen precursor, a method for manufacturing a transition metal chalcogenide compound film using the same, and a transition metal chalcogenide compound film using the same.

[0010] The technical problems that the present invention aims to solve are not limited to those mentioned above, and other unmentioned technical problems will be clearly understood by those skilled in the art to which the present invention belongs from the description below.

[0011] To achieve the above technical problem, one embodiment of the present invention may be characterized in that carbon and two chalcogen elements adjacent to the carbon are each bonded by a double bond.

[0012] The above precursor composition may be characterized by being represented by the following chemical formula 1.

[0013] [Chemical Formula 1]

[0014] X a =C=X b

[0015] In the above chemical formula 1, X a and X b Each can be independently selected from chalcogen elements.

[0016] The above X a and X b Each may be characterized by independently including one or more selected from the group consisting of sulfur (S), selenium (Se), and tellurium (Te).

[0017] The above X a is characterized as being oxygen, and the above X bIt may be characterized by including one or more selected from the group consisting of sulfur (S), selenium (Se), and tellurium (Te).

[0018] The above precursor composition may be characterized by further including one or more selected from the group consisting of O2, H2O, O3, O radicals, and carbon monoxide.

[0019] The above precursor composition may be characterized by further including an inert gas.

[0020] To achieve the above technical objective, another embodiment of the present invention provides a method for manufacturing a transition metal chalcogenide film, comprising the steps of: positioning a substrate in a chamber; supplying the aforementioned precursor composition for forming a transition metal chalcogenide film and a transition metal precursor into the chamber; and forming a transition metal chalcogenide film on the substrate positioned in the chamber.

[0021] In the step of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor in a gaseous form into the chamber, the transition metal precursor may be characterized by comprising one or more metals selected from the group consisting of molybdenum (Mo), tungsten (W), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), rhenium (Re), and platinum (Pt), their metal carbonyls, their oxides, their dioxo compounds, their halides, or their oxyhalides.

[0022] The step of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor in gaseous form into the chamber may further include the step of supplying a promoter.

[0023] In the step of supplying the above promoter, the promoter may be characterized by comprising one or more selected from the group consisting of halogen compounds, halogen chalcogenide compounds, oxidizing agents, and alkali metal compounds.

[0024] The step of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber may be characterized by supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber sequentially.

[0025] The step of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber may be characterized by simultaneously supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber.

[0026] The step of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber may further include the step of purging after supplying one or more of the precursor composition for forming a transition metal chalcogenide film or the transition metal precursor into the chamber.

[0027] The step of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor in gaseous form into the chamber may further include the step of supplying one or more selected from the group consisting of O2, H2O, O3, O radicals, and carbon monoxide.

[0028] The step of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor in a gaseous form into the chamber may further include the step of supplying an inert gas.

[0029] The step of forming a transition metal chalcogenide compound film on the substrate may be characterized by being performed through any one of a chemical vapor deposition (CVD) process, an atomic layer deposition (ALD) process, and a chalcogenization process.

[0030] The step of forming a transition metal chalcogenide film on the substrate may be characterized by being performed in a temperature range of 300 ℃ to 1200 ℃.

[0031] The step of forming a transition metal chalcogenide film on the substrate may be characterized by being performed in a temperature range of 600 ℃ to 1100 ℃.

[0032] To achieve the above technical objective, another embodiment of the present invention provides a transition metal chalcogenide film prepared by the method for preparing a transition metal chalcogenide film described above.

[0033] To achieve the above technical problem, another embodiment of the present invention provides a semiconductor device comprising the transition metal chalcogenide film described above.

[0034] The precursor composition for forming a transition metal chalcogenide film according to the present invention can reduce carbon by-products of the transition metal chalcogenide film.

[0035] In addition, the precursor composition for forming a transition metal chalcogenide film according to the present invention can reduce the occurrence of side reactions when forming a transition metal chalcogenide film.

[0036] In addition, the precursor composition for forming a transition metal chalcogenide film according to the present invention can form a large-area uniform transition metal chalcogenide film regardless of the type of substrate.

[0037] In addition, the precursor composition for forming a transition metal chalcogenide film according to the present invention can form a high-quality transition metal chalcogenide film even at low temperatures.

[0038] The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description of the invention or the claims.

[0039] Figure 1 is a flowchart illustrating the method for manufacturing a transition metal chalcogenide film of the present invention.

[0040] Figure 2 is a schematic diagram showing the structure of a transition metal chalcogenide film of the present invention.

[0041] Figure 3 is an SEM image showing the surface analysis results of the transition metal chalcogenide film of the present invention.

[0042] Figure 4 is a graph showing the structural and optical properties of the transition metal chalcogenide film of the present invention.

[0043] Figure 5 is a graph showing the results of the uniformity analysis of the transition metal chalcogenide film of the present invention grown on a SiO2 / Si substrate.

[0044] Figure 6 is a graph showing the results of the uniformity analysis of the transition metal chalcogenide film of the present invention grown on an amorphous substrate.

[0045] Figure 7 is an SEM image showing the surface analysis results of the transition metal chalcogenide film of the present invention on a crystalline substrate.

[0046] Figure 8 is a graph showing the structural and optical properties of the transition metal chalcogenide film of the present invention on a crystalline substrate.

[0047] Figure 9 is a graph showing the carbon byproduct reduction characteristics of the transition metal chalcogenide film of the present invention when no promoter is injected.

[0048] Figure 10 is a graph showing the carbon byproduct reduction characteristics of the transition metal chalcogenide film of the present invention when a promoter is injected.

[0049] Figure 11 is a graph showing the results of evaluating side reactions and process controllability according to the precursor composition for forming a transition metal chalcogenide film of the present invention.

[0050] Figure 12 is a graph showing the carbon byproduct reduction characteristics according to the growth temperature of the transition metal chalcogenide film of the present invention.

[0051] Figure 13 is an SEM image of a transition metal chalcogenide compound film of the present invention grown on a crystalline sapphire substrate at a growth temperature of 1050 ℃.

[0052] Figure 14 is an SEM image showing the surface analysis results according to the growth pressure of the transition metal chalcogenide film of the present invention.

[0053] The present invention will be described below with reference to the attached drawings. However, the present invention may be implemented in various different forms and is therefore not limited to the embodiments described herein. Furthermore, in order to clearly explain the present invention in the drawings, parts unrelated to the explanation have been omitted, and similar parts throughout the specification have been given similar reference numerals.

[0054] Throughout the specification, when it is stated that a part is "connected (connected, in contact, combined)" with another part, this includes not only cases where they are "directly connected," but also cases where they are "indirectly connected" with other members interposed between them. Furthermore, when it is stated that a part "includes" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but rather allows for the inclusion of additional components.

[0055] The terms used herein are merely for describing specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “comprising” or “having” are intended to indicate the presence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0056] Embodiments of the present invention will be described in detail below with reference to the attached drawings.

[0057]

[0058] A precursor composition for forming a transition metal chalcogenide film according to one embodiment of the present invention will be described.

[0059] A precursor composition for forming a transition metal chalcogenide film according to one embodiment of the present invention may be characterized in that carbon and two chalcogen elements adjacent to the carbon are each bonded by a double bond.

[0060] The above chalcogen precursor may be characterized by being represented by the following chemical formula 1.

[0061] [Chemical Formula 1]

[0062] X a =C=X b

[0063] In the above chemical formula 1, X a and X b Each can be independently selected from chalcogen elements.

[0064] As one embodiment, the X a and X bEach may be characterized by independently comprising one or more selected from the group consisting of sulfur (S), selenium (Se), and tellurium (Te), but the above X a and X b The types of are not limited to the examples above.

[0065] For example, the precursor composition for forming a transition metal chalcogenide film according to the present invention may be any one selected from the group consisting of CS2, CSe2, and CTe2.

[0066] The above precursor composition for forming a transition metal chalcogenide film is X a =C=X b When expressed as such, the ratio of chalcogen to carbon is high, which may be advantageous for supplying chalcogen monomers, and accordingly, the occurrence of side reactions and the formation of carbon byproducts may be reduced during the formation of transition metal chalcogen compound films.

[0067] As one embodiment, the X a is characterized as being oxygen, and the above X b It may be characterized by including one or more selected from the group consisting of sulfur (S), selenium (Se), and tellurium (Te).

[0068] For example, the precursor composition for forming a transition metal chalcogenide film according to the present invention may be any one selected from the group consisting of OCS, OCSe, and OCTe.

[0069] The above precursor composition for forming a transition metal chalcogenide film is O=C=X- b If indicated as such, C=X versus C=O bond b The low bond decomposition energy can be advantageous for supplying chalcogen monomers, and the low reactivity and high thermal stability of C=O, an intermediate separated from chalcogen during the formation of transition metal chalcogen compound films, can reduce the occurrence of side reactions and the formation of carbon byproducts.

[0070] The above precursor composition may be characterized by further including one or more selected from the group consisting of O2, H2O, O3, O radicals, and carbon monoxide.

[0071] If the above precursor composition further comprises one or more selected from the group consisting of O2, H2O, O3, and O radicals, the oxygen present in the O2, H2O, O3, or O radicals combines with carbon within the precursor composition, thereby enabling a smoother supply of chalcogen monomers during the process of forming the transition metal chalcogen compound film.

[0072] If the above precursor composition further includes carbon monoxide, the carbon monoxide can control the ligand attachment of the transition metal precursor during the process of forming the transition metal chalcogenide film, thereby allowing the reaction between the precursor composition and the transition metal precursor to occur at a more appropriate location.

[0073] The above precursor composition may be characterized by further including an inert gas.

[0074] The above inert gases are argon (Ar) and nitrogen (N- 2- It may include ) etc., but can be used without limitation as long as it can be used as a carrier gas, and is not limited to the above examples.

[0075] The present invention includes a precursor composition for forming a transition metal chalcogenide film in which carbon and at least one chalcogen element are bonded by a double bond, thereby suppressing side reactions during the process of forming a transition metal chalcogenide film and reducing carbon by-products.

[0076]

[0077] Referring to FIG. 1, a method for manufacturing a transition metal chalcogenide film according to another embodiment of the present invention will be described.

[0078] Figure 1 is a flowchart illustrating the method for manufacturing a transition metal chalcogenide film of the present invention.

[0079] Referring to FIG. 1, a method for manufacturing a transition metal chalcogenide film according to one embodiment of the present invention may include the step of positioning a substrate in a chamber (S100); the step of supplying a precursor composition for forming a transition metal chalcogenide film according to any one of claims 1 to 6 and a transition metal precursor into the chamber (S200); and the step of forming a transition metal chalcogenide film on the substrate positioned in the chamber (S300).

[0080] First, the substrate can be positioned inside the chamber (S100).

[0081] The above substrate may be one or more selected from the group consisting of conductors, semiconductors, and insulators, and its crystal structure is not limited to amorphous or crystalline, but may include any crystalline state between these.

[0082] The above chamber can be used without any special restrictions on type or structure, provided that it is a chamber that can be used in the process performed in the step (S300) of forming a transition metal chalcogenide film described later.

[0083] Secondly, the aforementioned precursor composition for forming a transition metal chalcogenide film and the transition metal precursor can be supplied into the chamber (S200).

[0084] In the step (S200) of supplying the precursor composition for forming a transition metal chalcogen compound film and the transition metal precursor into the chamber, the chalcogen precursor composition and the transition metal precursor of the composition for forming a transition metal chalcogen compound film may be injected in a gaseous form, and may be injected independently, simultaneously, or sequentially; however, the method of injecting the chalcogen precursor composition and the transition metal precursor of the composition for forming a transition metal chalcogen compound film is not limited to the above examples. When the chalcogen precursor composition and the transition metal precursor of the composition for forming a transition metal chalcogen compound film are injected in a gaseous form, they are advantageous in terms of flow rate control, uniform supply over a large area, and reproducibility, and thus can have advantages in mass production.

[0085] The above precursor composition for forming a transition metal chalcogen compound film may be characterized by carbon and at least one chalcogen element being bonded by a double bond.

[0086] In the step (S200) of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber, a specific description of the composition overlapping with the aforementioned precursor composition for forming a transition metal chalcogenide film is omitted. However, even if the description of such composition is omitted, it is not intended that such components are not included in any embodiment.

[0087] In the step (S200) of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber, the transition metal precursor may include one or more metals selected from the group consisting of molybdenum (Mo), tungsten (W), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), rhenium (Re), and platinum (Pt), their metal carbonyls, their oxides, their dioxo compounds, their halides, or their oxyhalides, but the types of the transition metal precursor are not limited to the above examples.

[0088] For example, the transition metal precursor according to the present invention may be Mo(CO)6.

[0089] The step (S200) of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber may further include the step (S250) of supplying a promoter.

[0090] The above-mentioned precursor composition for forming a transition metal chalcogenide film, the transition metal precursor, and the promoter may each be injected independently, simultaneously, or sequentially, but the order or method of injection is not limited to the above examples.

[0091] In the step of supplying the promoter (S250), the promoter may include one or more selected from the group consisting of halogen compounds, halogen chalcogenide compounds, oxidizing agents, and alkali metal compounds, and preferably may include one or more of Cl-2, HCl, S2Cl2, Se2Cl2, SeOCl2, O2, and H2O, but the examples of the promoter are not limited to the examples above.

[0092] For example, the promoter according to the present invention may include Cl2.

[0093] In one embodiment, the promoter according to the present invention may further include an organic ligand or radical in the alkali metal.

[0094] For example, the promoter according to the present invention may be PP (potassium propionate, C3H5KO2) containing an organic ligand to an alkali metal.

[0095] When PP is used as the above promoter, it can be supplied in a gaseous form due to the high vapor pressure of PP.

[0096] Due to the step (S250) of supplying the promoter, the nucleation density and grain size of the transition metal chalcogenide film can be controlled, the number of defects in the film can be reduced, film formation can be promoted by lowering the energy barrier in the intermediate path of the synthesis reaction, and the transition metal chalcogenide film can be formed at a lower temperature by forming a low-melting point intermediate material.

[0097] In the step (S200) of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber, the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor may be injected sequentially according to the process or simultaneously.

[0098] In one embodiment, when the step (S300) of forming a transition metal chalcogenide compound film on a substrate located within the chamber described below is performed through an ALD process, the precursor composition for forming the transition metal chalcogenide compound film and the transition metal precursor can be sequentially supplied into the chamber.

[0099] At this time, depending on the process, the precursor composition for forming the transition metal chalcogenide film may be supplied first and then the transition metal precursor may be supplied later, or the transition metal precursor may be supplied first and then the precursor composition for forming the transition metal chalcogenide film may be supplied later.

[0100] In one embodiment, when the step (S300) of forming a transition metal chalcogenide film on a substrate located within the chamber described below is performed through a CVD process, the precursor composition for forming the transition metal chalcogenide film and the transition metal precursor can be supplied simultaneously into the chamber.

[0101] In the step (S200) of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber, the supply of the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor may be performed once or multiple times depending on the thickness, composition, or crystal characteristics of the thin film.

[0102] The step (S200) of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber may further include the step of purging after supplying one or more of the precursor composition for forming a transition metal chalcogenide film or the transition metal precursor into the chamber.

[0103] The purging step described above may be performed by additionally supplying an inert gas, such as nitrogen (N2) or argon (Ar), into the chamber, but the purging method is not limited to the above example and can be performed without limitation as long as it can remove the precursor or reaction byproduct remaining in the chamber.

[0104] The purging step may be performed after the supply of the precursor composition for forming the transition metal chalcogenide film, or after the supply of the transition metal precursor, and may be performed repeatedly between the supply of each precursor or after the supply of each precursor depending on the process.

[0105] The step (S200) of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber may further include the step of supplying one or more selected from the group consisting of O2, H2O, O3, O radicals, and carbon monoxide.

[0106] In the step of supplying one or more selected from the group consisting of O2, H2O, O3, O radicals, and carbon monoxide, one or more selected from the group consisting of O2, H2O, O3, O radicals, and carbon monoxide may be injected simultaneously with the precursor composition for forming a transition metal chalcogenide film or the transition metal precursor, may be injected sequentially, or may be injected independently of each, but the order or method of injection is not limited to the above examples.

[0107] In the step of supplying one or more selected from the group consisting of O2, H2O, O3, O radicals, and carbon monoxide, if one or more selected from the group consisting of O2, H2O, O3, and O radicals are supplied, the oxygen present in the O2, H2O, O3, or O radicals combines with carbon in the precursor composition, thereby allowing the chalcogen monomer to be supplied more smoothly during the process of forming the transition metal chalcogen compound film.

[0108] When carbon monoxide is supplied in the step of supplying one or more selected from the group consisting of O2, H2O, O3, O radicals, and carbon monoxide, the carbon monoxide controls the ligand attachment of the transition metal precursor during the process of forming the transition metal chalcogenide film, thereby allowing the reaction between the precursor composition and the transition metal precursor to occur at a more appropriate location.

[0109] The step (S200) of supplying the precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber may further include the step of supplying an inert gas.

[0110] In the step of supplying the inert gas, the inert gas may be injected simultaneously with the precursor composition for forming a transition metal chalcogenide film or the transition metal precursor, or sequentially, or independently thereof, but the order or method of injection is not limited to the above examples.

[0111] The above inert gases are argon (Ar) and nitrogen (N- 2- It may include ) etc., but can be used without limitation as long as it can be used as a carrier gas, and is not limited to the above examples.

[0112] Finally, a transition metal chalcogenide film can be formed on a substrate located within the chamber (S300).

[0113] The step (S300) of forming a transition metal chalcogenide film on the substrate may be performed through any one of a chemical vapor deposition (CVD) process, an atomic layer deposition (ALD) process, and a chalcogenization process, but the method of forming the transition metal chalcogenide film is not limited to the above examples, and other thin film formation processes capable of forming the transition metal chalcogenide film may be applied.

[0114] For example, the step (S300) of forming a transition metal chalcogenide compound film on the substrate according to the present invention can be performed through a CVD process, and more specifically, through a metal-organic chemical vapor deposition (MOCVD) process.

[0115] The step (S300) of forming a transition metal chalcogenide film on the substrate can be performed in a temperature range of 300 ℃ to 1200 ℃, and more preferably in a temperature range of 600 ℃ to 1100 ℃, but the temperature range is not limited to the above example.

[0116] The step (S300) of forming the transition metal chalcogenide film may be performed in a pressure range of 3 Torr to 500 Torr, but the pressure range is not limited to the above example.

[0117] The method for manufacturing a transition metal chalcogenide film of the present invention enables the growth of a uniform transition metal chalcogenide film regardless of the type or crystal structure of the substrate by manufacturing the transition metal chalcogenide film using the aforementioned precursor composition for forming a transition metal chalcogenide film.

[0118]

[0119] Referring to FIG. 2, a transition metal chalcogen compound film according to another embodiment of the present invention will be described.

[0120] Figure 2 is a schematic diagram showing the structure of a transition metal chalcogenide film of the present invention.

[0121] Referring to FIG. 2, a transition metal chalcogenide film according to one embodiment of the present invention may be characterized by being manufactured according to the method for manufacturing a transition metal chalcogenide film described above.

[0122] The above transition metal chalcogenide film may have a layered structure in which a plane of the transition metal is sandwiched between two planes of chalcogen atoms. The transition metal and the chalcogenide film may be bonded by covalent bonds, and the layered structure may be maintained by weak van der Waals forces between the layers, and may be in a single crystal or polycrystalline state.

[0123] The above transition metal chalcogenide film can preferably be formed as a single layer, but if necessary, such single layers can be stacked vertically to form multiple layers.

[0124] When the above transition metal chalcogenide film is multilayer, the interlayer thickness based on the distance between the transition metals of each layer may be 6.5 Å.

[0125] In one embodiment, the transition metal chalcogenide film may be MoS2.

[0126] The transition metal chalcogenide film of the present invention is manufactured using a chalcogen precursor in which the molecular fraction of chalcogen elements relative to carbon is large, thereby reducing carbon byproducts compared to conventional transition metal chalcogenide films.

[0127]

[0128] A semiconductor device according to another embodiment of the present invention will be described.

[0129] A semiconductor device according to one embodiment of the present invention may include the transition metal chalcogenide film described above.

[0130] Since the above semiconductor device is identical to the configuration of a conventional semiconductor device except that it includes a transition metal chalcogenide compound film according to the present invention in a material film requiring high dielectric properties within the device, a detailed description of the configuration of the semiconductor device is omitted in this specification.

[0131] In this case, “high-K characteristics” refers to characteristics where the dielectric constant is greater than the dielectric constant of silicon dioxide (i.e., about 4.1 or higher).

[0132]

[0133] The present invention will be explained in more detail below through manufacturing examples, comparative examples, and experimental examples. However, the present invention is not limited to the following manufacturing examples and experimental examples.

[0134]

[0135] <Preparation Example 1> Preparation of the transition metal chalcogenide film of the present invention

[0136] After loading the substrate into the CVD chamber, the chamber was purged with nitrogen, and the pressure inside the chamber was set to 100 Torr and the temperature to 350 °C. Subsequently, impurities and foreign substances present on the surface of the substrate were removed using hydrogen. Afterward, while controlling the chamber pressure to 3 to 10 Torr and the temperature to 350 °C to 800 °C and maintaining them constant, Mo(CO)6 was injected into the chamber at a flow rate of 5 sccm and COS at a flow rate of 40 sccm to proceed with a CVD reaction to form a MoS2 compound film on the substrate. At this time, if necessary, an accelerator may be injected simultaneously. After the reaction was completed, the chamber was purged with nitrogen and cooled to room temperature to produce a MoS2 compound film on the substrate.

[0137]

[0138] <Experimental Example 1> Evaluation of the structural and optical properties of the transition metal chalcogenide film of the present invention

[0139] Figure 3 is an SEM image showing the surface analysis results of the transition metal chalcogenide film of the present invention. (a) is an SEM image of the case where no promoter is injected, (b) is an SEM image of the case where Cl2 is injected as a promoter at a flow rate of 0.5 sccm, and (c) is an SEM image of the case where PP (potassium propionate, C3H5KO2) is injected as a promoter at a flow rate of 10 sccm at 50 ℃.

[0140] Figure 4 is a graph showing the structural and optical properties of the transition metal chalcogenide film of the present invention. In Figure 4, 'chlorine non-supply' means the case where no promoter is injected, and 'chlorine supply' means the case where Cl2 is injected as a promoter at a flow rate of 0.5 sccm. (a) and (b) are graphs showing the results of Raman spectrum analysis, and (c) is a graph showing the results of photoluminescence spectrum analysis.

[0141] Referring to Fig. 3, it was confirmed that MoS2 gradually forms a film as it grows into triangular to round crystal grains, and that the size of the crystal grains increases when a promoter is injected simultaneously. Through this, it was confirmed that by utilizing COS, which is the precursor composition for forming a transition metal chalcogenide compound film according to the present invention, triangular crystal grains with a size of 10 to 200 nm merge to form a continuous compound film at the mono layer to bi layer level, and it was confirmed that the size of the crystal grains can be controlled depending on the presence and type of the promoter.

[0142] Referring to Fig. 4a, the Raman peak is at 380 cm⁻¹ -1 Nearby and 420 cm -1 It was confirmed that it was observed in the vicinity, and referring to Fig. 4b, it was confirmed that no peak attributed to carbon was observed in the Raman spectrum. Additionally, referring to Fig. 4c, it was confirmed that a strong photoluminescence peak attributed to the MoS2 compound film was observed, and it was confirmed that the size of the peak increased when Cl2 was used as a promoter. Through this, it was confirmed that the MoS2 compound film was formed normally in a single layer form, and that the formation of carbon byproducts was reduced by the precursor composition for forming transition metal chalcogenide compound films of the present invention.

[0143]

[0144] <Experimental Example 2> Evaluation of the uniformity of the transition metal chalcogenide film of the present invention according to substrate

[0145] Figure 5 is a graph showing the results of the uniformity analysis of the transition metal chalcogenide film of the present invention grown on a 4-inch SiO2 / Si substrate.

[0146] Figure 6 is a graph showing the results of the uniformity analysis of the transition metal chalcogenide compound film of the present invention grown on a 4-inch fused silica wafer substrate, which is an amorphous substrate.

[0147] Figure 7 is an SEM image showing the surface analysis results of the transition metal chalcogenide film of the present invention on a crystalline sapphire substrate.

[0148] FIG. 8 is a graph showing the structural and optical properties of the transition metal chalcogenide film of the present invention on a crystalline substrate. (a) and (b) are graphs showing the results of Raman spectrum analysis, and (c) is a graph showing the results of photoluminescence spectrum analysis.

[0149] Referring to FIGS. 5 and 6, it was confirmed that Raman spectra measured at different locations (1 to 10) on the SiO2 / Si substrate and the fused silica wafer substrate were similar to each other in terms of peak position and shape. Additionally, referring to FIGS. 7 and 8, it was confirmed that the MoS-2 compound film formed on the sapphire substrate also gradually formed a film while growing into triangular to round crystal grains, with a Raman peak at 380 cm⁻¹. -1 Nearby and 420 cm -1 It was confirmed that while peaks attributed to carbon were observed in the vicinity, no peaks attributed to carbon were observed.

[0150] Through this, it was confirmed that the transition metal chalcogenide film prepared according to the method for preparing a transition metal chalcogenide film of the present invention can be grown uniformly regardless of the type of substrate.

[0151]

[0152] <Experimental Example 3> Evaluation of Carbon Byproduct Reduction Characteristics of the Transition Metal Chalcogenide Film of the Present Invention

[0153] FIG. 9 is a graph showing the carbon byproduct reduction characteristics of the transition metal chalcogenide film of the present invention when no promoter is injected. (a) and (b) are graphs showing the results of Raman spectrum analysis when DMTS is used as a chalcogenide precursor, and (c) and (d) are graphs showing the results of Raman spectrum analysis when COS, which is an embodiment of the precursor composition for forming a transition metal chalcogenide film of the present invention, is used.

[0154] Figure 10 is a graph showing the carbon byproduct reduction characteristics of the transition metal chalcogenide film of the present invention when a promoter is injected. At this time, O2 was used as the promoter and injected simultaneously with COS at a flow rate of 30 sccm.

[0155] Referring to Figures 9a and 9b, when DMTS was used as the chalcogen precursor, a Raman signal attributed to amorphous carbon was observed along with a peak attributed to the MoS2 compound film, whereas referring to Figures 9c, 9d and 10, it was confirmed that for the MoS2 compound film according to the present invention, a peak attributed to the MoS2 compound film was observed, but the Raman signal attributed to amorphous carbon was significantly reduced.

[0156] Through this, it was confirmed that carbon byproducts can be reduced when a transition metal chalcogenide film is formed using the precursor composition for forming a transition metal chalcogenide film of the present invention.

[0157]

[0158] <Experimental Example 4> Analysis of Manufacturing Process Conditions for the Transition Metal Chalcogenide Film of the Present Invention

[0159] 4-1. Evaluation of the growth rate and controllability of side reactions of the transition metal chalcogenide film of the present invention according to the flow rate of the precursor composition for forming a transition metal chalcogenide film of the present invention

[0160] FIG. 11 is a graph showing the results of evaluating side reactions and process controllability according to the precursor composition for forming a transition metal chalcogenide film of the present invention. (a) is the case where no promoter is injected, and (b) is Cl as the promoter. 2- This represents the case where is injected at a flow rate of 0.5 sccm.

[0161] Table 1 below shows the area ratio of a MoS2 compound film formed on the surface of a substrate according to the flow rate of COS, which is a precursor composition for forming a transition metal chalcogenide compound film according to the present invention.

[0162] Flow rate (sccm) of precursor composition for forming transition metal chalcogenide film Formation range of MoS2 compound film relative to substrate (%) 107.93 320 12.73 930 35.36 440 60.464

[0163] Referring to Figure 11 and Table 1, when H2S is used as a chalcogen precursor, the intensity of the A1g peak does not increase steadily due to side reactions even when the flow rate of H2S increases. In contrast, when COS, which is an embodiment of the precursor composition for forming a transition metal chalcogen compound film according to the present invention, is used as a chalcogen precursor, the occurrence of side reactions is suppressed, and it was confirmed that the flow rate of COS increases steadily compared to H2S. Furthermore, it was confirmed that it increases more steadily when Cl2 is used as a promoter. Through this, it was confirmed that the growth behavior of the transition metal chalcogen compound film can be stably controlled by the precursor composition for forming a transition metal chalcogen compound film according to the present invention.

[0164]

[0165] 4-2. Evaluation of Carbon Byproduct Reduction Characteristics of the Transition Metal Chalcogenide Compound Film of the Present Invention According to Process Temperature Conditions

[0166] Figure 12 is a graph showing the carbon byproduct reduction characteristics according to the growth temperature of the transition metal chalcogenide film of the present invention.

[0167] Figure 13 is an SEM image of a transition metal chalcogenide compound film of the present invention grown on a crystalline sapphire substrate at a growth temperature of 1050 ℃. At this time, Mo(CO)6 was supplied at a flow rate of 4 sccm and COS at a flow rate of 50 sccm, and the growth was performed for 40 minutes at a growth pressure of 100 Torr.

[0168] Referring to FIG. 12, it was confirmed that peaks attributable to the MoS2 compound film were observed under various process temperature conditions ranging from 350 °C to 800 °C, while Raman signals attributable to amorphous carbon remained at a relatively low level. Additionally, referring to FIG. 13, when using the precursor containing COS of the present invention, a growth pattern with aligned MoS2 crystal orientations was observed on a crystalline sapphire substrate even at 1050 °C, thereby confirming that epitaxial growth is possible. Through this, it was confirmed that the precursor composition for forming a transition metal chalcogenide compound film of the present invention can stably form a transition metal chalcogenide compound film with the formation of carbon byproducts suppressed over a wide temperature range from a low temperature region (350 °C) to a high temperature region (1050 °C).

[0169]

[0170] 4-3. Evaluation of Surface Characteristics of the Transition Metal Chalcogenide Film of the Present Invention According to Process Pressure Conditions

[0171] Figure 14 is an SEM image showing the surface analysis results according to the growth pressure of the transition metal chalcogenide film of the present invention.

[0172] Referring to Fig. 14, it was confirmed that the nucleation density of the MoS2 compound film decreases as the process pressure increases, and the nucleation density of the MoS2 compound film increases as the process pressure increases. Through this, it was confirmed that the nucleation density and the grain size of the transition metal chalcogenide compound film can be controlled by adjusting the process pressure conditions in the method for manufacturing the transition metal chalcogenide compound film of the present invention.

[0173]

[0174] Thus, it was confirmed that carbon by-products of a transition metal chalcogenide film can be reduced by manufacturing a transition metal chalcogenide film using the precursor composition for forming a transition metal chalcogenide film of the present invention, in which carbon and at least one chalcogen element are bonded by a double bond.

[0175]

[0176] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will understand that other specific forms can be easily modified without altering the technical spirit or essential features of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single unit may be implemented in a distributed manner, and components described as distributed may likewise be implemented in a combined form.

[0177] The scope of the present invention is defined by the claims set forth below, and all modifications or variations derived from the meaning and scope of the claims and equivalent concepts thereof should be interpreted as being included within the scope of the present invention.

Claims

1. A precursor composition for forming a transition metal chalcogen compound film, characterized in that carbon and two chalcogen elements adjacent to the carbon are each bonded by a double bond.

2. In Paragraph 1, A precursor composition for forming a transition metal chalcogenide film, characterized by being represented by the following chemical formula 1: [Chemical Formula 1] X a =C=X b In the above chemical formula 1, X a and X b Each is independently selected from chalcogen elements.

3. In Paragraph 2, The above X a and X b A precursor composition for forming a transition metal chalcogenide film, characterized by each independently comprising one or more selected from the group consisting of sulfur (S), selenium (Se), and tellurium (Te).

4. In Paragraph 2, The above X a It is characterized by being oxygen, The above X b A precursor composition for forming a transition metal chalcogenide film, characterized by comprising one or more elements selected from the group consisting of sulfur (S), selenium (Se), and tellurium (Te).

5. In Paragraph 1, A precursor composition for forming a transition metal chalcogenide film, characterized in that the above precursor composition further comprises one or more selected from the group consisting of O2, H2O, O3, O radicals, and carbon monoxide.

6. In Paragraph 1, A precursor composition for forming a transition metal chalcogenide film, characterized in that the above precursor composition further comprises an inert gas.

7. A step of positioning the substrate inside the chamber; A step of supplying a precursor composition for forming a transition metal chalcogenide film according to any one of claims 1 to 6 and a transition metal precursor into the chamber; and A method for manufacturing a transition metal chalcogenide film, characterized by including the step of forming a transition metal chalcogenide film on a substrate located within the chamber.

8. In Paragraph 7, In the step of supplying the above-mentioned precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber, A method for preparing a transition metal chalcogenide film, characterized in that the above transition metal precursor comprises one or more metals selected from the group consisting of molybdenum (Mo), tungsten (W), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), rhenium (Re), and platinum (Pt), their metal carbonyls, their oxides, their dioxo compounds, their halides, or their oxyhalides.

9. In Paragraph 7, The step of supplying the precursor composition for forming the transition metal chalcogenide film and the transition metal precursor into the chamber is: A method for manufacturing a transition metal chalcogenide film characterized by further including a step of supplying a promoter.

10. In Paragraph 9, In the step of supplying the above promoter, A method for manufacturing a transition metal chalcogenide compound film, characterized in that the above promoter comprises one or more selected from the group consisting of halogen compounds, halogen chalcogenide compounds, oxidizing agents, and alkali metal compounds.

11. In Paragraph 7, The step of supplying the precursor composition for forming the transition metal chalcogenide film and the transition metal precursor into the chamber is: A method for manufacturing a transition metal chalcogenide film characterized by sequentially supplying the above-mentioned precursor composition for forming a transition metal chalcogenide film and the transition metal precursor into the chamber.

12. In Paragraph 7, The step of supplying the precursor composition for forming the transition metal chalcogenide film and the transition metal precursor into the chamber is: A method for manufacturing a transition metal chalcogenide film characterized by simultaneously supplying the precursor composition for forming the transition metal chalcogenide film and the transition metal precursor into the chamber.

13. In Paragraph 7, The step of supplying the precursor composition for forming the transition metal chalcogenide film and the transition metal precursor into the chamber is: A method for manufacturing a transition metal chalcogenide film, characterized by further including the step of purging after supplying one or more of the above-mentioned precursor composition for forming a transition metal chalcogenide film or a transition metal precursor into the chamber.

14. In Paragraph 7, The step of supplying the precursor composition for forming the transition metal chalcogenide film and the transition metal precursor into the chamber is: A method for manufacturing a transition metal chalcogenide film, characterized by further including the step of supplying one or more selected from the group consisting of O2, H2O, O3, O radicals, and carbon monoxide.

15. In Paragraph 7, The step of supplying the precursor composition for forming the transition metal chalcogenide film and the transition metal precursor into the chamber is: A method for manufacturing a transition metal chalcogenide film characterized by further including a step of supplying an inert gas.

16. In Paragraph 7, A method for manufacturing a transition metal chalcogenide film, characterized in that the step of forming a transition metal chalcogenide film on the substrate is performed through any one of a chemical vapor deposition (CVD) process, an atomic layer deposition (ALD) process, and a chalcogenization process.

17. In Paragraph 7, A method for manufacturing a transition metal chalcogenide film, characterized in that the step of forming a transition metal chalcogenide film on the substrate is performed in a temperature range of 300 ℃ to 1200 ℃.

18. In Paragraph 7, A method for manufacturing a transition metal chalcogenide film, characterized in that the step of forming a transition metal chalcogenide film on the substrate is performed in a temperature range of 600 ℃ to 1100 ℃.

19. A transition metal chalcogenide film prepared by the method for preparing a transition metal chalcogenide film of claim 7.

20. A semiconductor device comprising the transition metal chalcogenide film of claim 19.

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