WO2023171911A1 - Novel organotin compound, preparation method therefor, solution process composition comprising same, and thin film manufacturing method using same - Google Patents

Abstract

The present invention relates to an organotin compound, a preparation method therefor, a thin film manufacturing method using same, a solution process composition comprising the organotin compound, and a photosensor using same.

Description

Novel organotin compound, method for producing the same, composition for solution processing containing the same, and method for producing a thin film using the same

The present invention relates to a novel organotin compound, a method for producing the same, a composition for a solution process containing the same, and a method for producing a thin film using the same. More specifically, in producing a thin film through chemical vapor deposition or a solution process, Organotin compound with improved thermal stability and volatility and capable of easily producing high-quality tin thin films, tin oxide thin films or tin chalcogenide thin films at low temperatures, method for producing the same, composition for solution processing containing the same, and thin film using the same It relates to the manufacturing method.

Among the two-dimensional materials being studied recently, transition metal dichalcogenides (TMDC) materials are showing applicability in various fields.

For example, SnS and SnS ₂ have semiconductor properties with indirect band gap (Eg = 1.0-2.3 eV) and direct band gap (Eg = ∼2.2-2.5 eV), respectively, low environmental toxicity, and high optical absorption coefficient (10 ⁴ ~ 10 ⁵ cm ^-1 ), high theoretical capacity (645 mAh/g), and carrier mobility (∼230 cm ² /(V·s)) as a material that is attracting great attention, and is a hexagonal unit. Layered structures with cells and layers stacked along the c-axis by weak van der Waals forces, associated with large surface areas, can be attractive material properties for energy storage.

In particular, SnS and SnS ₂ nanostructures are suitable for applications in devices such as chemical and biological sensors, cathodes for Li-ion batteries, Na-ion batteries, photodetectors, dye-sensitized solar cells, and supercapacitors.

As an exemplary application, cadmium sulfide (CdS) thin films are mainly used for the buffer layer required in thin film solar cells such as CIGS and CZTS, but new buffer layer materials are required due to the toxicity and environmental pollution of cadmium. SnS, SnS ₂ , etc. are being studied as materials for the toothless buffer layer.

In addition, SnSe and SnSe ₂ have indirect band gaps of 0.9-1.3 eV and 1.7-2.2 eV, respectively, and have excellent charge mobility (~10 ⁴ cm ² /V·s) and are compatible with existing commercial materials such as silicon and gallium arsenide. Because it has a light absorption coefficient (10 ⁵ cm ^-1 ) that is 10 to 100 times higher than that of the tin (Sn)-based knife, research is being actively conducted on its use as a next-generation photoelectric device application material for detecting infrared and visible light. Key issues for device applications of cogenide layered materials include effective preparation of compositions for precursor synthesis or solution processing.

These nanostructures, nanocomposites, hybrids and heterostructures of SnS, SnS ₂ , SnSe and SnSe ₂ can be developed using various methods such as hydrothermal method, spray ultrasonic technology, chemical vapor deposition, continuous ion layer adsorption/reaction and vacuum deposition. It is synthesized according to a unique protocol, and is used as a metal precursor when producing thin films such as SnS, SnS _2, SnSe, SnSe ₂ , etc. using chemical vapor deposition (CVD), atomic layer deposition (ALD), or solution process-based thin film formation methods. Since the degree of deposition and deposition control characteristics are determined depending on the characteristics, the development of a metal precursor with excellent properties for thin film deposition is necessary.

In particular, when the organic tin precursor contains chalcogen atoms such as sulfur or selenium as a chalcogen component, it can contain both the tin component and the sulfur or selenium component in one molecule as a single source precursor, resulting in excellent properties for thin film deposition. There is a high possibility that this single-source precursor, as well as thin film manufacturing and application fields using it, are in need of research.

Regarding the method of manufacturing a thin film of such a transition metal chalcogenous material, as a prior art, in Korean Patent Publication No. 10-2020-0116724 and Korean Patent Publication No. 10-2021-0014353, amorphous disulfide is formed through an atomic layer deposition process. Although tin thin films have been manufactured, they do not contain a sulfur source in the organic tin precursor, so there is a limitation in manufacturing the thin film by separately providing a gaseous precursor such as hydrogen sulfide. Korean Patent Publication No. 10-2007- In No. 0044145 (publication date: April 27, 2007) and Korean Patent Publication No. 10-2020-0030233 (publication date: March 20, 2020), a metal chalcogen precursor is dissolved in an organic solvent for solution processing. Although the composition was prepared and coated and heat-treated on a substrate to produce an amorphous metal chalcogen thin film, they do not specifically disclose a composition for solution processing containing an organic tin precursor and a manufacturing process for a tin disulfide thin film using the same. No.

Therefore, as an organometallic compound that can be utilized for the various purposes described above, an organotin compound is made to contain both a tin component and a chalcogen component (sulfur (S), selenium (Se), or tellurium (Te)) in one molecule. A novel organometallic compound with improved thermal stability and the ability to easily form thin films at low temperatures that can be designed and used as a precursor in the manufacture of tin thin films, tin oxide thin films, or as a single-source precursor in the manufacture of tin chalcogenide thin films. There is a continuous need for development of a manufacturing process for thin films with improved physical properties using compositions for solution processing containing the same.

The first technical problem to be achieved by the present invention is to provide a precursor that has excellent solubility in organic solvents for use in solution processes and can easily produce tin thin films, tin oxide thin films, or tin chalcogenide thin films with good properties at low temperatures. To provide a novel organometallic compound.

In addition, the second technical problem to be achieved by the present invention is to provide a novel method for producing the organometallic compound.

In addition, the third technical problem to be achieved by the present invention is to provide a method of producing a tin thin film, a tin oxide thin film, or a tin chalcogenide thin film using the organometallic compound as a precursor.

In addition, the fourth technical problem to be achieved by the present invention is to form a thin film through a solution process, by producing a tin chalcogenide with excellent solubility in organic solvents, improved thermal stability, and a large area and high uniformity easily at low temperatures. The object is to provide a composition for solution processing containing an organic tin compound capable of producing a thin film.

In addition, the fifth technical problem to be achieved by the present invention is to provide an electronic device or sensor including a thin film manufactured using a composition for solution processing containing the organic tin compound.

In order to solve the above technical problems, the present invention provides an organometallic compound represented by the following [Chemical Formula A].

[Formula A]

In Formula A,

Wherein _{X 1} to

R ₁ to R ₁₆ are each the same or different and independently of each other hydrogen, deuterium, C ₁ -C ₁₀ linear, branched or cyclic alkyl group; and a C ₁ -C ₁₀ linear, branched or cyclic halogenated alkyl group,

The n1 to n4 are the same or different and are independently any integer selected from 1 to 3.

In addition, the present invention provides a method of producing a tin thin film, a tin oxide thin film, or a tin chalcogenide thin film using the organometallic compound represented by [Formula A] as a precursor.

In addition, the present invention provides one or more chalcogen precursors selected from sulfur (S), selenium (Se), and tellurium (Te); and an organic tin compound represented by the following compound B and an organic tin compound represented by the following compound B' Provided is a method for producing an organometallic compound represented by the formula A, which is characterized in that the organometallic compound represented by the formula A is prepared by using a tin compound as a reactant, respectively.

[Compound B] [Compound B‘]

[Formula A]

In Compound _B , Compound B _{' ,} and Formula A, X ₁ to

In addition, the present invention provides a composition for solution processing for forming a tin chalcogenide thin film, comprising an organic tin compound represented by the following [Chemical Formula A].

[Formula A]

(In Formula A above,

Wherein _{X 1} to

R ₁ to R ₁₆ are each the same or different and independently of each other hydrogen, deuterium, C ₁ -C ₁₀ linear, branched or cyclic alkyl group; and a C ₁ -C ₁₀ linear, branched or cyclic halogenated alkyl group,

The n1 to n4 are each the same or different and independently from each other, any integer selected from 1 to 3.)

In addition, the present invention includes the steps of (a) coating the composition for solution processing according to the present invention on a substrate; and (b) heat treating the substrate coated with the composition for solution processing.

Additionally, the present invention provides a tin chalcogenide thin film prepared using the composition according to the present invention.

Additionally, the present invention provides an optical sensor including the tin chalcogenide thin film.

Additionally, the present invention provides an electronic device including the tin chalcogenide thin film.

The organometallic compound represented by [Formula A] of the present invention has thermal stability, tetrahydrofuran (THF), diethyl ether, hexane, toluene, benzene, and dimethyl. It has good solubility in organic solvents such as formamide (DMF) and acetone, and can form thin films with good characteristics, making it easy to form tin thin films containing tin components, tin oxide thin films, or tin chalcogenide thin films. It can be manufactured, and in particular, it contains a tin component and a sulfur component as a chalcogenide component in one molecule, so it can be used as a novel precursor for producing a tin chalcogenide thin film.

In addition, the composition for solution processing according to the present invention can form a thin film with good properties and thermal stability, making it possible to easily produce a large-area and highly uniform tin chalcogenide thin film.

In addition, the tin chalcogenide thin film manufactured using the composition for solution processing according to the present invention can exhibit superior semiconductor device or optical sensor performance compared to existing commercial materials.

Figure 1 is an X-ray crystal structure of Sn ₃ (dmamp) ₄ Se ₄ compound prepared according to Preparation Example 1 of the present invention.

Figure 2 shows the TGA measurement results for the Sn ₃ (dmamp) ₄ Se ₄ compound prepared according to Preparation Example 1 of the present invention.

Figure 3 shows the TGA measurement results for the Sn ₃ (dmamp) ₄ S ₄ compound prepared according to Preparation Example 2 of the present invention.

Figure 4 is a photograph (a) of a spin-coated thin film according to Example 1 of the present invention and an optical microscope photograph (b) of two-dimensional tin selenide prepared through a thermal decomposition process.

Figure 5 is a photograph showing a substrate on which a two-dimensional tin selenide thin film was formed, manufactured in Example 1, Example 3 to Example 5 of the present invention.

Figure 6 is a diagram showing the results of XPS analysis of thin film formation according to the thermal decomposition temperature of the Sn ₃ (dmamp) ₄ Se ₄ compound prepared according to Preparation Example 1 of the present invention.

Figure 7 is a diagram showing the Raman spectrum of two-dimensional tin selenide prepared according to Example 1 of the present invention.

Figure 8 is a diagram showing transmission electron micrographs (a, b) and energy dispersive X-ray mapping results (c to f) by element of the two-dimensional tin selenide thin film prepared according to Example 1 of the present invention.

Figure 9 is a figure (a) showing the results of Raman spectroscopy of two-dimensional tin selenide prepared according to Example 1 of the present invention and a figure (b) showing the results of spatial mapping by X-ray photoelectron spectroscopy.

Figure 10 is a diagram showing the results of measuring the structure and optical characteristics of an optical sensor manufactured using a two-dimensional tin selenide thin film manufactured according to Example 1 of the present invention.

Figure 11 is a diagram showing the results of measuring photocurrent according to temperature of an optical sensor manufactured using a two-dimensional tin selenide thin film manufactured according to Example 1 of the present invention.

Figure 12 shows the results of measuring photocurrent over time in visible light (532 nm) and near-infrared light (1064 nm) of an optical sensor manufactured using a two-dimensional tin selenide thin film manufactured according to Example 1 of the present invention. It's a picture.

Figure 13 is a diagram showing the photoelectric characteristics of the optical sensor manufactured using the two-dimensional tin selenide thin film prepared according to Example 1 of the present invention at the SWIR (Short-Wave IR) 1550 nm infrared wavelength.

Hereinafter, the present invention will be described in more detail. Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout the specification of the present application, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.

As a result of the present inventors' efforts to achieve the above technical tasks and develop a precursor for producing a tin thin film with excellent properties, the central tin atom and two neighboring tin atoms are formed into four identical or different chalcogen elements. It was possible to prepare an organic tin complex having a structure in which they are connected to each other as a bridge ligand structure, and each tin atom adjacent to the central tin atom is coordinated by two amino alkoxide ligands that are the same or different.

Here, in the case of the organotin complex, the remaining portions, excluding the central tin atom and the four chalcogen elements bonded thereto, are derived from the organotin compound represented by compound B below and the organotin compound represented by compound B', respectively. It corresponds to a moiety and is selected from sulfur (S), selenium (Se), and tellurium (Te) using the organic tin compound represented by compound B and the organic tin compound represented by compound B' as reactants. By reacting with one or more chalcogen precursors, the organometallic compound represented by the formula A according to the present invention can be produced.

[Compound B] [Compound B‘]

Here, the organic tin compound represented by compound B is an amino alkoxide ligand containing R1 to R4 (ligand B-1 below); and an amino alkoxide ligand containing R5 to R8 (ligand B-2 below); It has a structure in which an atom (N) and an oxygen atom (O) are each coordinated to a tin element,

[Ligand B-1] [Ligand B-2]

In addition, the organic tin compound represented by compound B' is an amino alkoxide ligand containing R9 to R12 (ligand B'-1 below); and an amino alkoxide ligand containing R13 to R16 (ligand B'-2 below). It has a structure in which the nitrogen atom (N) and oxygen atom (O) are each coordinated to the tin element.

[Ligand B’-1] [Ligand B’-2]

The organic tin compound of the present invention has a central structure in which four chalcogen elements are connected to the central tin atom to neighboring tin atoms as bridge ligands, and an amino alkoxide ligand (ligand B) coordinated in the compound B and compound B' -1, B-2, B'-1, B'-2) structure, it has excellent chemical and thermal stability, and is resistant to tetrahydrofuran (THF), diethyl ether, hexane, and toluene ( It has good solubility in organic solvents such as toluene, benzene, dimethylformamide (DMF), and acetone, and can facilitate the deposition of thin films even at relatively low temperatures, so that the organotin compounds (complexes) ) can be used as a precursor to produce a tin thin film, a tin oxide thin film, or a tin chalcogenide thin film.

Hereinafter, the composition and production method of the organic tin compound according to the present invention will be described in more detail.

The present invention provides an organometallic compound containing tin, represented by the following [Chemical Formula A].

[Formula A]

In Formula A,

Wherein X1 to

R ₁ to R ₁₆ are each the same or different and independently of each other hydrogen, deuterium, C ₁ -C ₁₀ linear, branched or cyclic alkyl group; and a C ₁ -C ₁₀ linear, branched or cyclic halogenated alkyl group,

The n1 to n4 are the same or different and are independently any integer selected from 1 to 3.

Here, in the organometallic compound represented by [Formula A], four chalcogen atoms are bonded to each other as a bridge structure between the central atom, a tin atom, and two adjacent tin atoms, so that three tin atoms are formed in one molecule. It has a unique structure containing an atom and four chalcogen atoms, and through this it has excellent chemical and thermal stability, and is resistant to tetrahydrofuran (THF), diethyl ether, hexane, and toluene ( It has good solubility in organic solvents such as toluene, benzene, dimethylformamide (DMF), and acetone, and facilitates the deposition of tin thin films, tin oxide thin films, or tin chalcogenide thin films even at relatively low temperatures. In particular, a metal chalcogenide thin film can be easily formed in a solution process.

In addition, in the organometallic compound according to the present invention, R ₁ in the amino alkoxide ligand of [Formula A], R ₂ , R ₅ , R ₆ , R ₉ , R ₁₀ , R ₁₃ and R ₁₄ are the same or different and independently of each other, a linear alkyl group of C ₁ -C ₂ ; C ₁ -C ₂ linear halogenated alkyl group; C ₃ -C ₆ branched or cyclic alkyl group; and C ₃ -C ₆ branched or cyclic halogenated alkyl group; It is preferable to use any one selected from among, and in this case, it has excellent chemical-thermal stability and has a fast deposition rate of the thin film even at a relatively low temperature, so it can be used as a metal thin film, a metal oxide thin film, or a metal chalcogenide ( It can have very desirable properties as a precursor of a metal component for forming a thin film (metal sulfide, metal selenium, metal tellurium).

In addition, as a more preferred embodiment of the present invention, the R ₁ , R ₂ , R ₅ , R ₆ , R ₉ , R ₁₀ , R ₁₃ and R ₁₄ may be the same or different and independently selected from CH ₃ , CF ₃ , C ₂ H ₅ , CH(CH ₃ ) ₂ and C(CH ₃ ) ₃ .

In addition, in the organometallic compound according to the present invention, R ₃ in the amino alkoxide ligand of [Formula A], R ₄ , R ₇ , R ₈ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ are each the same or different and independently of each other a linear alkyl group of C ₁ -C ₂ ; C ₁ -C ₂ linear halogenated alkyl group; C ₃ -C ₆ branched or cyclic alkyl group; and C ₃ -C ₆ branched or cyclic halogenated alkyl group; It is preferable to use any one selected from among, and in this case, it has excellent chemical-thermal stability and has a fast deposition rate of the thin film even at a relatively low temperature, so it can be used as a metal thin film, a metal oxide thin film, or a metal chalcogenide ( It can have very desirable properties as a precursor of a metal component for forming a thin film (metal sulfide, metal selenium, metal tellurium).

In addition, in a more preferred embodiment of the present invention, R ₃ , R ₄ , R ₇ , R ₈ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ may each be the same or different and independently from one another selected from CH ₃ , CF ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ .

Additionally, in one embodiment of the present invention, n1 to n4 may each be 1, and as a result, the tin atom may be in a stable state by having a coordination structure of a 5-membered ring with the amino alkoxide ligand.

In addition, _{in one} embodiment of the present invention, _the chalcogen elements in the organometallic compound, X ₁ to A ligand containing the above substituents R ₅ to R ₈ ; A ligand containing the above substituents R ₉ to R ₁₂ ; and a ligand containing the substituents R ₁₃ to R ₁₆ may be the same as each other.

Meanwhile, the present invention can provide a method for producing a tin thin film, a tin oxide thin film, or a tin chalcogenide thin film using the organometallic compound represented by the formula A as a metal precursor, and a thin film obtained by the manufacturing method, , This can be performed by a chemical vapor deposition (CVD) method, an atomic layer deposition (ALD) method, or a solution process method that can form a thin film by dissolving the precursor in a solvent and coating it.

Here, the chemical vapor deposition (CVD) method, atomic layer deposition (ALD), or solution process appropriately adjusts the growth rate and thin film formation temperature conditions according to each process condition to achieve optimal thickness and density. Branches can produce thin films.

More specifically, when using the chemical vapor deposition (CVD) method, the reactant containing the organometallic compound precursor of the present invention is supplied in a gaseous state to a reactor containing a substrate of various types or shapes, thereby forming an annotation on the substrate. It can form a thin film, a tin oxide thin film, or a tin chalcogenide thin film.

In addition, in the present invention, when using atomic layer deposition (ALD), a reactant containing the organometallic compound represented by formula A in the present invention as a precursor is supplied to the deposition chamber in pulse form to form a pulse on the wafer surface. A precise single-layer film can be formed by causing a chemical reaction.

In addition, in the present invention, when forming a thin film of the organometallic compound represented by Formula A through a solution process, the organometallic compound (precursor) is dissolved in a solvent, coated on the substrate, and then heated or energy is applied from the outside. As a result, a tin thin film, a tin oxide thin film, or a tin chalcogenide thin film can be formed. Preferably, the organometallic compound represented by the formula A has the advantage of simultaneously containing a tin component and a chalcogen component in one molecule. At the same time, tetrahydrofuran (THF), diethyl ether, hexane, toluene, benzene, dimethylformamide (DMF), and acetone By having good solubility in organic solvents such as the like, a tin chalcogenide thin film can be easily formed through a solution process without adding additional chalcogenide components (sulfur, selenium, or tellurium components).

Additionally, the present invention provides a photoresist composition containing the organometallic compound represented by [Formula A].

Since the photoresist composition according to the present invention contains a structural unit in which an organic group of a specific structure is bonded to a tin atom in an organometallic compound, it has relatively excellent sensitivity and can be easily handled compared to conventional organic and/or inorganic photoresists. there is.

In a preferred embodiment, in the photoresist composition, the organometallic compound represented by Formula A is contained in an amount of 0.1% by weight to 80% by weight, preferably 0.5% by weight to 50% by weight, based on the total weight of the composition. More preferably, it may be included in an amount of 1% to 30% by weight.

In a preferred embodiment, the photoresist composition may optionally include an organic solvent, for example, aromatic compounds (e.g., xylene, toluene), alcohols (e.g., 4-methyl-2 -Pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol, propylene glycol monomethyl ether), ethers (e.g., anisole, tetrahydrofuran), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone), mixtures thereof, etc., but are limited thereto. That is not the case.

In a preferred embodiment, the photoresist composition may further include a resin in addition to the organotin compound represented by Chemical Formula A and a solvent.

Additionally, the photoresist composition according to the present invention may further include additives in some cases. Examples of the additives include surfactants, cross-linking agents, leveling agents, or combinations thereof.

Additionally, a pattern can be formed using the photoresist composition according to the present invention, and the pattern forming method includes forming a film to be etched on a substrate; forming a photoresist film by applying the photoresist composition described above on the etching target film; patterning the photoresist film to form a photoresist pattern; and etching the etch target layer using the photoresist pattern as an etch mask.

Meanwhile, the present invention provides a chalcogen precursor selected from sulfur (S), selenium (Se), and tellurium (Te); an organic tin compound represented by the following compound B; and an organic tin compound represented by the following compound B' Provided is a method for producing an organometallic compound represented by the formula A, which is characterized in that the organometallic compound represented by the formula A is prepared by using a tin compound as a reactant, respectively.

[Compound B] [Compound B‘]

[Formula A]

Here _, in Compound B _, Compound B' _, and Formula A, X ₁ to

In addition, in a more preferred embodiment of the present invention, the chalcogen precursor may be selected from sulfur, triphenylphosphine sulfide, selenium, triphenylphosphine selenide, tellurium, and triphenylphosphine telluride. It is not limited.

That is, the organometallic compound represented by the formula A of the present invention is one or more chalcogen precursors selected from sulfur (S) and selenium (Se); and an organotin compound represented by the following compound B and the following compound B'. The indicated organic tin compounds are used as reactants, respectively;

an organic tin compound represented by compound B, in which a ligand containing the substituents R ₁ to R ₄ and a ligand containing the substituents R ₅ to R ₈ are coordinated; and a ligand containing the substituents R ₉ to R ₁₂ and the above an organotin compound represented by compound B', coordinated with a ligand containing substituents R ₁₃ to R ₁₆ ; these are each bonded to two chalcogen elements, and the four chalcogen elements thus represented are also represented by compound B An organometallic compound represented by the above [Formula A] can be produced by bonding to a tin atom (center metal) derived from an organotin compound or an organotin compound represented by Compound B' below.

Here, in compound B according to the present invention, R ₁ to R ₈ are each preferably a C ₁ -C ₂ linear alkyl group; C ₁ -C ₂ linear halogenated alkyl group; C ₃ -C ₆ branched or cyclic alkyl group; and C ₃ -C ₆ branched or cyclic halogenated alkyl group; It may be any one selected from among, and more preferably, R ₁ to R ₈ are the same or different and independently of each other, CH ₃ , CF ₃ , C ₂ H ₅ , CH(CH ₃ ) ₂ and C(CH ₃ ) It can be any one of ₃ .

In addition, in compound B' according to the present invention, R ₉ to R ₁₆ are each preferably a C ₁ -C ₂ linear alkyl group; C ₁ -C ₂ linear halogenated alkyl group; C ₃ -C ₆ branched or cyclic alkyl group; and C ₃ -C ₆ branched or cyclic halogenated alkyl group; It may be any one selected from among, and more preferably, R ₉ to R ₁₆ are the same or different and independently of each other, CH ₃ , CF ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) It can be any one of ₃ .

Additionally, in the method for producing an organometallic compound represented by Formula A of the present invention, a ligand comprising the substituents R ₁ to R ₄ in the compound B; A ligand containing the above substituents R ₅ to R ₈ ; A ligand containing the above substituents R ₉ to R ₁₂ in compound B'; and the ligand containing the substituents R ₁₃ to R ₁₆ may be the same as each other.

In addition, when an organic solvent is used in producing the organometallic compound represented by the formula A, suitable types of organic solvents include hexane, toluene, tetrahydrofuran, hexane, cyclohexane, diethyl ether, acetone, and dimethyl. Formamide, etc. may be mentioned, but it is not limited thereto, and diethyl ether or hexane may be preferably used.

The reaction can preferably be carried out in the organic solvent at a temperature range of -30 to 150°C, preferably -10 to 40°C for 12 to 24 hours, and when reacted at a low temperature, the formula A The yield of the displayed compound may be high.

At this time, during the production reaction of the compound represented by Formula A, in order to separate the product from the by-products or unreacted products produced together, recrystallization, sublimation, distillation, extraction, or column chromatography is used. By separating using, etc., novel organometallic compounds of high purity can be obtained.

The high-purity organometallic compound represented by Chemical Formula A thus obtained may be solid or liquid at room temperature.

In addition, the present invention can exhibit superior optical sensor performance compared to existing commercial materials when manufacturing a thin film using a composition for solution processing containing the organic tin compound represented by the formula A, and at the same time, it can exhibit large-area optical sensor performance compared to existing commercial materials. And a highly uniform tin chalcogenide thin film can be produced.

Hereinafter, the composition for solution processing containing an organic tin compound according to the present invention and the method for manufacturing a tin chalcogenide thin film using the same will be described in more detail.

The present invention provides a composition for solution processing for forming a tin chalcogenide thin film, comprising an organic tin compound represented by the following [Chemical Formula A].

[Formula A]

In Formula A,

Wherein _{X 1} to

R ₁ to R ₁₆ are each the same or different and independently of each other hydrogen, deuterium, C ₁ -C ₁₀ linear, branched or cyclic alkyl group; and a C ₁ -C ₁₀ linear, branched or cyclic halogenated alkyl group,

The n1 to n4 are the same or different and are independently any integer selected from 1 to 3.

Here, by using a composition for solution processing containing the compound represented by the formula A, it is possible to have excellent chemical and thermal stability, and to manufacture a large-area and highly uniform tin chalcogenide thin film of excellent quality, Accordingly, it is possible to manufacture a tin chalcogenide thin film that can exhibit superior optical sensor performance compared to existing commercial materials.

Here, the amino alkoxide ligand coordinated to each outer tin atom rather than the central tin atom in the organic tin compound in the composition for solution processing of the present invention is Ligand B-1, Ligand B-2, Ligand B'-1, and It may include ligand B'-2.

[Ligand B-1] [Ligand B-2]

[Ligand B’-1] [Ligand B’-2]

In addition, R ₁ , which is a substituent bonded to the carbon atom connected to the oxygen atom (O) in the amino alkoxide ligand of [Formula A] in the composition for solution processing according to the present invention, R ₂ , R ₅ , R ₆ , R ₉ , R ₁₀ , R ₁₃ and R ₁₄ are the same or different and independently of each other, a linear alkyl group of C ₁ -C ₅ ; C ₁ -C ₅ linear halogenated alkyl group; C ₃ -C ₇ branched or cyclic alkyl group; and a C ₃ -C ₇ branched or cyclic halogenated alkyl group; It is preferably any one selected from among, and more preferably, a C ₁ -C ₂ linear alkyl group; C ₁ -C ₂ linear halogenated alkyl group; C ₃ -C ₆ branched or cyclic alkyl group; and C ₃ -C ₆ branched or cyclic halogenated alkyl group; It is preferable to use any one selected from among, and in this case, tin chalcogenide (tin sulfide, tin selenium, tin Tellurium) can have very desirable properties as a precursor of a metal component for forming a thin film.

In addition, as a more preferred embodiment of the present invention, the R ₁ , R ₂ , R ₅ , R ₆ , R ₉ , R ₁₀ , R ₁₃ and R ₁₄ may be the same or different and independently selected from CH ₃ , CF ₃ , C ₂ H ₅ , CH(CH ₃ ) ₂ and C(CH ₃ ) ₃ .

In addition, in the organometallic compound according to the present invention, R ₃ , which is a substituent bonded to the nitrogen atom (N) in the amino alkoxide ligand of [Formula A], R ₄ , R ₇ , R ₈ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ are each the same or different and independently of each other a linear alkyl group of C ₁ -C ₅ ; C ₁ -C ₅ linear halogenated alkyl group; C ₃ -C ₇ branched or cyclic alkyl group; and a C ₃ -C ₇ branched or cyclic halogenated alkyl group; It is preferable that it is any one selected from among, and more preferably, a C ₁ -C ₂ linear alkyl group; C ₁ -C ₂ linear halogenated alkyl group; C ₃ -C ₆ branched or cyclic alkyl group; and C ₃ -C ₆ branched or cyclic halogenated alkyl group; It is preferable to use any one selected from among, and in this case, tin chalcogenide (tin sulfide, tin selenium, tin Tellurium) can have very desirable properties as a precursor of a metal component for forming a thin film.

In addition, in a more preferred embodiment of the present invention, R ₃ , R ₄ , R ₇ , R ₈ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ may each be the same or different and independently from one another selected from CH ₃ , CF ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ .

In addition, in one embodiment of the present invention, n1 to n4 in the amino alkoxide ligand of [Formula A] may each be 1 or 2, whereby the tin atom has a coordination structure of a 5-membered ring or a 6-membered ring with the amino alkoxide ligand. It can represent a stable state by having, and more preferably, n1 to n4 are each 1, and the tin atom can have the structure of an amino alkoxide ligand and a 5-membered ring.

In addition, in one embodiment of the present invention _{, the} chalcogen elements _{X 1} to A ligand containing the above substituents R ₅ to R ₈ ; A ligand containing the above substituents R ₉ to R ₁₂ ; and a ligand containing the substituents R ₁₃ to R ₁₆ may be the same as each other.

That is, in the tin complex represented by _[ Formula A] _, all chalcogen elements X ₁ to X ₄ are sulfur atoms _, or all X ₁ to It may be an atom, and in this case, the chalcogen element is the same, so that the tin complex can be avoided from being obtained in various types, which has the advantage of easy purification and separation of the finally obtained tin complex, and also the tin chalcogen to be produced. There is an advantage in that a tin chalcogenide thin film can be manufactured by ensuring that only the desired chalcogen elements are included in the thin film.

In addition, a ligand containing the above substituents R ₁ to R ₄ ; A ligand containing the above substituents R ₅ to R ₈ ; A ligand containing the above substituents R ₉ to R ₁₂ ; and the ligand containing the substituents R ₁₃ to R ₁₆ ; by using the same type, it is possible to avoid obtaining the tin complex in various types, which has the advantage of easy purification and separation of the finally obtained tin complex. Since the diameter of the amino alkoxide ligand in the tin complex can be adjusted to be the same, the reaction can be carried out under uniform conditions when forming a thin film.

In addition, the composition for solution processing containing the organic tin compound represented by Formula A has good solubility in organic solvents, enabling thin film formation in the presence of organic solvents. In this case, the composition for the solution process contains a chalcogen component in the organic tin compound represented by Chemical Formula A, and tin chalcogen is produced under the solution process without the addition of additional chalcogen components (sulfur, selenium, or tellurium components). A cargo thin film can be easily formed.

At this time, the organic solvent mixed with the organic tin compound is not particularly limited, and is preferably hexane, heptane, octane, nonane, benzene, toluene, xylene, One or more non-polar organic solvents selected from cyclohexane and cyclooctane or mixtures thereof may be used, or acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, N-methylpyrroli One or more polar organic solvents selected from copper, tetrahydrofuran, ethyl acetate, and acetone, or mixtures thereof, may be used.

Here, the composition for solution processing of the present invention can be prepared by adding the organic tin compound represented by [Formula A] into an organic solvent and mixing and stirring for 5 minutes to 3 days, preferably 30 minutes to 12 hours. .

Here, the composition for solution processing of the present invention may contain 10 to 99.95 wt% of the organic solvent, preferably 50 to 99.9 wt%, and more preferably 80 to 99.8 wt%, based on the entire composition. It may contain, more preferably, 90 to 99.3 wt%, and even more preferably, 92 to 99 wt%.

In addition, the composition for solution processing of the present invention contains 0.05 to 90 wt%, preferably 0.1 to 50 wt%, and more preferably 0.2 to 20 wt% of the organic tin compound represented by [Formula A], based on the entire composition. wt%, more preferably 0.5 to 15 wt%, more preferably 0.7 to 10 wt%, and even more preferably 1 to 8 wt%. You can.

Meanwhile, the present invention can provide a method for producing a tin chalcogenide thin film using a composition for solution processing containing the organic tin compound represented by the formula A, and a thin film obtained by the production method.

More specifically, the present invention includes the steps of coating a substrate with a composition for solution processing containing the organic tin compound represented by Formula A; and (b) heat-treating or applying external energy to a substrate coated with the composition for solution processing. It is possible to provide a method for producing a tin chalcogenide thin film comprising ) is melted and coated on a substrate, followed by heat treatment or application of energy to form a thin film.

At this time, the type of substrate used may be one selected from SiO ₂ , SiO ₂ /Si, sapphire, glass and quartz, plastic and flexible glass (Willow glass). In this case, an example of the plastic is polyethylene terephthalate. Phthalate (polyethylene terephthalate, PET), polyimide (PI), etc. may be used, but are not limited thereto.

Meanwhile, in order to improve the formation of a coating film of the composition for solution processing when the organic solvent in the composition for solution processing is a polar organic solvent, before step (a), the surface of the substrate may be treated to make it hydrophilic. At this time, the hydrophilic treatment of the substrate may preferably be selected from UV light treatment, plasma treatment, or discharge treatment, and through this, the composition for solution processing can be evenly dispersed on the surface of the substrate to improve coating power.

Methods for coating the composition for solution processing on a substrate include spin coating, dip coating, roll coating, screen coating, spray coating, and spin. Coating methods such as spin casting, flow coating, screen printing, ink jet, or drop casting can be used, and are the most desirable coating in terms of convenience and uniformity. The method may be spin coating, e.g., first coating at a speed of 300 to 1500 rpm; and secondary coating at a speed of 1000 to 2500 rpm; preferably, primary coating at a speed of 700 to 900 rpm; and secondary coating at a speed of 1500 to 1700 rpm.

Additionally, in the present invention, after forming the coating film, a heat treatment step to remove the organic solvent remaining on the substrate may be additionally included. The heat treatment step may be a drying step, and may specifically be performed at a temperature of 50 to 150°C. At this time, the heat treatment time is not limited as long as the polar organic solvent can be removed, but can be adjusted in the range of 10 seconds to 10 minutes.

Heat treatment used to form a two-dimensional tin chalcogenide by thermal decomposition of ligands bonded to tin atoms after the formation of the coating film, or optionally after a heat treatment step to remove the organic solvent remaining on the substrate. The temperature may be in the range of 200 to 700°C, preferably in the range of 250 to 600°C, more preferably in the range of 280 to 500°C, and the heat treatment time may be 10 seconds to 12 hours, preferably Heat treatment may be performed for 1 minute to 1 hour, for example, in an inert gas atmosphere such as argon or nitrogen at a temperature ranging from 250 to 700°C, preferably in the range of 250 to 600°C. Preferably, it can be carried out in the range of 280 to 500°C, and this can be appropriately adjusted or changed depending on the components and properties of the desired thin film.

For example, as a more preferable example in the heat treatment process for thermal decomposition of the composition for solution process containing the organic tin compound represented by the formula A, a pressure of 0.5 torr to 760 torr, preferably a pressure of 1 torr to 20 torr removing the organic solvent by heating in the range of 50 to 120° C.; and thermal decomposition under a pressure of 0.5 torr to 760 torr, preferably 1 torr to 20 torr, at a temperature of 200 to 700°C.

At this time, in the heat treatment step, the heat treatment may be performed in an inert gas atmosphere such as nitrogen or argon gas, and through this, thermal decomposition can be achieved in a more stable state.

Additionally, the present invention can provide a tin chalcogenide thin film manufactured by the above tin chalcogenide thin film manufacturing method. That is, through the thermal decomposition process according to the present invention, a tin chalcogenide thin film with a high quality and uniform surface can be formed, and the thin film can be formed in the form of a single layer or multilayer with a two-dimensional structure.

Additionally, the present invention can provide an optical sensor including the tin chalcogenide thin film or an electronic device (Device) including the tin chalcogenide thin film.

In the case of the optical sensor according to the present invention, it is possible to increase the area of the tin chalcogenide thin film and at the same time have a high-quality, uniform surface, so that it can be used not only as a general optical sensor such as visible light and near infrared (Near IR), but also as a SWIR (Short IR) sensor. -Wave IR) It has the advantage of being applicable as an infrared sensor.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for illustrating the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited thereto.

(Example)

Preparation Example 1. Synthesis of Sn ₃ (dmamp) ₄ Se ₄

Sn(dmamp) ₂ (0.395 g, 1 mmol) is dissolved in diethyl ether (dmamp: 1-dimethylamino-2-methyl-2-propanolate). Selenium powder (0.079 g, 1 mmol) was added and stirred in an ice bath for 15 hr. The solvent is removed under reduced pressure. The compound was recrystallized using diethyl ether and hexane solvent to obtain pale yellow crystals.

¹ H NMR (C ₆ D ₆ , 500 MHz): δ1.14 (s, 3H), 1.32 (s, 3H), 2.17&2.20 (s, 1H), 2.31&2.34 (d, 1H), 2.66 (s, 3H), 2.84 (s, 3H). Anal Calcd. for C ₂₄ H ₅₆ N ₄ O ₄ Se ₄ Sn ₃ : C, 25.84; H, 5.29; N, 4.90. Found: C, 25.36; H, 4.97; N, 4.93.

In addition, a crystal of the Sn3(dmamp)4Se4 compound obtained in Preparation Example 1 was obtained, and the X-ray crystal structure is shown in FIG. 1.

Preparation Example 2. Synthesis of Sn ₃ (dmamp) ₄ S ₄

Sn(dmamp) ₂ (1.19 g, 3 mmol) is dissolved in diethyl ether (dmamp: 1-dimethylamino-2-methyl-2-propanolate). Sulfur powder (0.128 g, 4 mmol) was added and stirred at room temperature for 15 hr. The solvent is removed under reduced pressure. The compound was recrystallized using diethyl ether and hexane solvent to obtain pale yellow crystals.

¹ H NMR (C ₆ D ₆ , 500 MHz): δ1.17 (s, 3H), 1.34 (s, 3H), 2.17&2.19 (s, 1H), 2.38&2.40 (d, 1H), 2.71 (s, 3H), 2.83 (s, 3H). Anal Calcd for C ₂₄ H ₅₆ N ₄ O ₄ S ₄ Sn ₃ : C, 30.37; H, 5.95; N, 5.90, S, 13.51. Found: C, 30.81; H, 5.97; N, 5.49, S, 12.63.

<Analysis of thermal properties of prepared organometallic compounds>

In order to evaluate the possibility of the organometallic compounds synthesized in Preparation Examples 1 and 2 as precursors for forming thin films, thermogravimetric analysis (TGA) was performed to measure their thermal stability and decomposition temperature.

In the TGA method, the product was heated to 900 °C at a rate of 10 °C/min, and nitrogen gas was injected at a pressure of 1.5 bar/min.

The TGA graph of the tin precursor compound (Sn ₃ (dmamp) ₄ Se ₄ ) synthesized in Preparation Example 1 is shown in Figure 2, and the TGA of the tin precursor compound (Sn ₃ (dmamp) ₄ S ₄ ) synthesized in Preparation Example 2 The graph is shown in Figure 3.

As can be seen in FIG. 2, the mass of the tin precursor compound according to Preparation Example 1 decreased by 65.2% from 200 ℃ to 286 ℃, and then the mass decrease was observed from 700 ℃ to 839 ℃. It is presumed that in the first mass reduction section, the ligand coordinated to the tin precursor compound decomposes first to produce Sn ₃ Se ₄ , and as the temperature rises, thermal decomposition occurs in the second mass reduction section to generate Sn.

In addition, as can be seen in FIG. 3, the mass of the tin precursor compound (Sn ₃ (dmamp) ₄ S ₄ ) according to Preparation Example 2 decreased by 52.05% from 100 ℃ to 303 ℃, and then from 700 ℃ to 860 ℃. Mass loss was observed up to ℃. It is presumed that in the first mass reduction section, the ligand coordinated to the tin precursor compound first decomposes to produce Sn ₃ S ₄ , and as the temperature rises, thermal decomposition occurs in the second mass reduction section to generate Sn.

Examples 1 to 6: Preparation of two-dimensional tin selenide thin films

Example 1. Thin film formation using 5 wt% solution of Sn ₃ (dmamp) ₄ Se ₄ compound

Sn ₃ (dmamp) ₄ Se ₄ prepared in Preparation Example 1 was dissolved in DMF and stirred at room temperature for 60 minutes to prepare a solution with a concentration of 5 wt%. The obtained composition solution was spin-coated at a speed of 800 rpm for 10 seconds on a hydrophilic-treated SiO ₂ (300 nm)/Si(001) substrate by surface treatment with UV light for 60 seconds, and spin-coated at 1600 rpm for 30 seconds. Thus, a substrate on which a Sn ₃ (dmamp) ₄ Se ₄ thin film is formed is manufactured.

After placing the coated substrate in a hot plate and heating it at a temperature of 100° C. for 2 minutes to remove the solvent, the substrate on which the solvent-removed Sn ₃ (dmamp) ₄ Se ₄ thin film was formed was placed in a thermal reactor ( It was placed inside a furnace, injected with 1000 sccm of Ar at a pressure of 1.5 Torr and a temperature of 300°C, and heat treated for 10 minutes to synthesize two-dimensional tin selenide.

The chemical composition of the thin film formed according to the thermal decomposition reaction in Example 1 was confirmed through A doublet peak related to the bonding state (Sn2+) could be observed.

In addition, a photograph of the spin-coated thin film according to Example 1 of the present invention is shown in FIG. 4(a), and an optical microscope photograph of a two-dimensional tin selenide thin film manufactured through a thermal decomposition process is shown in FIG. 4(a). As shown in b), it can be confirmed that the two-dimensional tin selenide (SnSe) according to Example 1 was uniformly formed on the SiO2/Si substrate, as shown in FIG. 2(b).

Example 2. Thin film formation using 3 wt% solution of Sn ₃ (dmamp) ₄ Se ₄ compound

Meanwhile, in order to change the thickness of the SnSe thin film, a thin film was formed and tested in the same manner as in Example 1, except that the concentration of the Sn ₃ (dmamp) ₄ Se ₄ solution was changed to 3 wt%. In this case, a uniform thin film was also formed. This was confirmed through an optical microscope and actual photos.

Examples 3 to 5. Thin film formation using 5 wt% solution of Sn ₃ (dmamp) ₄ Se ₄ compound according to substrate type

A two-dimensional tin selenide thin film was manufactured in the same experiment as in Example 1 except that the type of substrate according to Table 1 below was changed, and the thin films according to Example 1 and Examples 3 to 5 were formed. The substrate is shown in Figure 5.

	Example 1	Example 3	Example 4	Example 5
Board	2 inches SiO2/Si wafer	2 inches Quartz	Quartz	polyimide

As shown in FIG. 5, the two-dimensional tin selenide prepared by the composition for solution processing according to the present invention is uniformly deposited on a 2-inch large-area substrate or large-area flexible substrate at a relatively low temperature of 300°C. It can be confirmed that tin selenide can be formed.

Example 6. Thin film formation using 1% solution of Sn ₃ (dmamp) ₄ Se ₄ compound

The Sn ₃ (dmamp) ₄ Se ₄ compound prepared in Preparation Example 1 was dissolved in DMF and stirred at 40 ° C. for 14 hours to prepare a 1 wt% precursor solution. The obtained precursor solution was spin coated on a hydrophilic treated SiO ₂ (300 nm)/Si(001) substrate at a speed of 2000 rpm for 30 seconds and heat treated at 100 ^o C for 1 minute to form a Sn ₃ (dmamp) ₄ Se ₄ spin coating layer. After placing the substrate on which the spin coating layer was formed in the reactor, Ar (1000 sccm) was injected and heat treated for 30 minutes at temperatures of 300, 400, and 600 ^o C to synthesize the final thin film, and the thermal decomposition reaction (thin film synthesis) temperature The chemical composition of the thin film formation according to the change was confirmed through X-ray photoelectron spectroscopy (XPS) and is shown in Figure 6.

As shown in FIG. 6, when the thermal decomposition temperature is 400 ^o C and 600 ^o C, it can be confirmed that the Sn related peak is oxidized Sn ⁴⁺ through the Sn 3 d core level spectrum, and there is no Se 3 d related peak. As a result of performing thermal decomposition at a temperature of 300 ^o C, SnSe-related bonding states (Sn ²⁺ ) and SnSe _2- related bonding state (Sn ⁴⁺ ) peaks coexist in the Sn 3 d core level spectrum. can confirm.

In addition, the Se 3d core level spectrum results show that doublet peaks related to SnSe and SnSe ₂ overlap, and the survey spectrum results show peaks related to the SiO ₂ /Si substrate, indicating that it is a very thin thin film with a thickness of less than 10 nm. It can be confirmed that this was formed.

<Thin film property evaluation experiment>

1. Raman spectroscopy

The Raman spectrum of the two-dimensional tin selenide thin film prepared in Example 1 according to Raman spectroscopy is shown in FIG. 7. As shown in FIG. 4, it was confirmed that a vibration mode corresponding to the SnSe structure was observed as a result of the Raman spectroscopy analysis. More specifically, It can be confirmed that the tin selenide layered material was successfully synthesized through the observation of Ag ² , B ² _3g , Ag ³ , and Ag ⁴ , which are typical phonon modes of tin selenide thin films.

2. Transmission electron microscopy/energy dispersive X-ray mapping (EDS)

Transmission electron micrographs and energy-dispersive X-ray element-specific mapping results for the two-dimensional tin selenide thin film prepared in Example 1 are shown in FIG. 8. As shown in FIG. 8, looking at the transmission electron micrograph (FIG. 8a, b) of the two-dimensional tin selenide thin film synthesized according to the present invention, the thickness of the produced tin selenide thin film layer is ~10 nm, and the number of layers is It can be confirmed that it is ~15, and looking at the mapping results for each energy-dispersive It can be confirmed that the ratio is about 1:1 (21.6 at%: 21.0 at%), indicating that a SnSe thin film has been formed.

3. Raman spectroscopy and X-ray photoelectron spectroscopy

The results of Raman spectroscopy (200 x 200 μm ² ) and X-ray photoelectron spectroscopy (XPS, 3 x 6 mm ² ) for the two-dimensional tin selenide thin film prepared in Example 1 are shown in FIG. 9. As shown in FIG. 9, the spatial mapping results of the two-dimensional tin selenide thin film synthesized according to the present invention by Raman spectroscopy (FIG. 9a) and It can be confirmed that selenide was synthesized.

<Manufacture and characteristic evaluation of optical sensor>

1. Manufacturing of optical sensor

Cr with a thickness of 3 nm and Au with a thickness of 70 nm were sequentially deposited on the tin selenide thin film synthesized on the SiO2/Si substrate according to Example 1 in selective areas using thermal evaporation and a shadow mask. So two-terminal An optical sensor was manufactured and its composition and optical characteristics were measured and shown in Figure 10.

Here, Figure 10a shows the structure and voltage/current characteristic results of Cr/Au and tin selenide thin films, Figure 10b shows photocurrent in visible light (532 nm), and Figure 10c shows photocurrent in visible light (532 nm). ), Figure 10d shows the photocurrent in near-infrared rays (1064 nm), and Figure 10e shows the light response time in near-infrared rays (1064 nm). At this time. The photocurrent characteristics were measured using an optical chopper and a photocurrent measurement device (KEITHLEY, 6514 system electrometer) to control the On-Off of the visible light and near-infrared laser to measure the current change in the optical device.

2. Analysis of optical characteristic measurement results of optical sensor

As shown in FIG. 10, the optical sensor manufactured from the tin selenide thin film according to the present invention has a photocurrent of 142 μA and 48 μA from a visible light (532 nm) and near-infrared (1064 nm) light source, respectively, and the response time is It was found to be 62 μs and 374 μs in visible light and near-infrared light, respectively.

In addition, the photoresponsivity was confirmed to be 56.8 A/W@20 mW/cm2, 532 nm, and the maximum photoresponsivity was 366 A/W@0.2 mW/cm2, 532 nm. The obtained results show that the existing two-dimensional It was confirmed that it exhibits superior characteristics compared to optical sensors based on semiconductor materials.

In addition, the photocurrent according to temperature in visible light (532 nm) of the optical sensor manufactured using the two-dimensional tin selenide thin film in the present invention was measured, and the results are shown in FIG. 11. As shown in FIG. 11, it can be confirmed that the optical sensor manufactured according to the present invention maintains very stable photocurrent characteristics at room temperature (before heating) and in all temperature ranges from 100 to 160°C.

In addition, the photocurrent over time for one month was measured in visible light (532 nm) and near-infrared light (1064 nm) of the optical sensor manufactured using the two-dimensional tin selenide thin film in the present invention, and the results are shown in Figure 12. The results are shown, and as shown in FIG. 12, it can be confirmed that the optical sensor manufactured according to the present invention maintains the photocurrent characteristics without deterioration even after one month in both visible light (532 nm) and near infrared light (1064 nm). there is.

In addition, to investigate the applicability of the optical sensor manufactured using the two-dimensional tin selenide thin film in the present invention not only to optical sensors such as visible light and near infrared (Near IR) but also to SWIR (Short-Wave IR) infrared sensors, SWIR The photoelectric characteristics of a light source with a wavelength of 1550 nm (121.24 mW/cm2, 20 V) were measured and shown in Figure 13. As shown in Figure 13, the possibility of application as an optical sensor for SWIR detection can be confirmed. .

In addition, the performance indicators of the optical sensor manufactured using the two-dimensional tin selenide thin film in the present invention for wavelengths in the visible light, near-infrared (Near IR), and short-wave IR (SWIR) infrared regions are shown in Table 2 below. shown in

Wavelength (nm)	Photoresponsivity (A/W)	EQE (%)	Detectivity (Jones)	Response time (s)
532	5.89	1370	1.8 x 10 11	6.2 x 10 -5
1064	1.2	140	3.7 x 10 10	3.7 x 10 -4
1550	0.14	11.2	4.3 x 10 9	2.3 x 10 -1

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements can be made by those skilled in the art using the basic concept of the present invention as defined in the following claims. It falls within the scope of invention rights.

The tin chalcogenide thin film manufactured using the composition for solution processing according to the present invention has excellent semiconductor device or optical sensor performance compared to existing commercial materials and has industrial applicability.

Claims (22)

1. An organometallic compound represented by the following [Chemical Formula A].

   [Formula A]

   

   In Formula A,

   Wherein _{X 1} to

   R ₁ to R ₁₆ are each the same or different and independently of each other hydrogen, deuterium, C ₁ -C ₁₀ linear, branched or cyclic alkyl group; and a C ₁ -C ₁₀ linear, branched or cyclic halogenated alkyl group,

   The n1 to n4 are the same or different and are independently any integer selected from 1 to 3.
2. According to paragraph 1,

   The R ₁ , R ₂ , R ₅ , R ₆ , R ₉ , R ₁₀ , R ₁₃ and R ₁₄ are the same or different and independently of each other, a linear alkyl group of C ₁ -C ₂ ; C ₁ -C ₂ linear halogenated alkyl group; C ₃ -C ₆ branched or cyclic alkyl group; and C ₃ -C ₆ branched or cyclic halogenated alkyl group; An organometallic compound characterized in that it is any one selected from among.
3. According to paragraph 1,

   The R ₁ , R ₂ , R ₅ , R ₆ , R ₉ , R ₁₀ , R ₁₃ and R ₁₄ is the same or different and is independently selected from CH ₃ , CF ₃ , C ₂ H ₅ , CH(CH ₃ ) ₂ and C(CH ₃ ) ₃ .
4. According to paragraph 1,

   The R ₃ , R ₄ , R ₇ , R ₈ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ are each the same or different and independently of each other a linear alkyl group of C ₁ -C ₂ ; C ₁ -C ₂ linear halogenated alkyl group; C ₃ -C ₆ branched or cyclic alkyl group; and C ₃ -C ₆ branched or cyclic halogenated alkyl group; An organometallic compound characterized in that it is any one selected from among.
5. According to paragraph 1,

   The R ₃ , R ₄ , R ₇ , R ₈ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ are each the same or different and independently selected from CH ₃ , CF ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ Organometallic compounds made of.
6. According to paragraph 1,

   An organometallic compound wherein n1 to n4 are each 1 or 2.
7. According to paragraph 1,

   X ₁ to X ₄ are the same as each other,

   A ligand containing the above substituents R ₁ to R ₄ ; A ligand containing the above substituents R ₅ to R ₈ ; A ligand containing the above substituents R ₉ to R ₁₂ ; and a ligand containing substituents R ₁₃ to R ₁₆ are the same as each other.
8. A method of producing a tin thin film, a tin oxide thin film, or a tin chalcogenide thin film using any one organometallic compound selected from claims 1 to 7 as a metal precursor.
9. According to clause 8,

   A method of producing a tin thin film, a tin oxide thin film, or a tin chalcogenide thin film, wherein the process of growing the thin film is performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD) or a solution process.
10. One or more chalcogen precursors selected from sulfur (S), selenium (Se), and tellurium (Te);

    Formula A in claim 1, wherein an organometallic compound represented by the following formula A is prepared by using an organic tin compound represented by the following compound B and an organic tin compound represented by the following compound B', respectively, as reactants. A method for producing an organometallic compound represented by .

    [Compound B] [Compound B‘]

    

    [Formula A]

    

    In Compound B _, Compound B' _{, and} Formula A, X ₁ to
11. A composition for solution processing for forming a tin chalcogenide thin film, comprising an organic tin compound represented by the following [Chemical Formula A].

    [Formula A]

    

    (In Formula A above,

    Wherein _{X 1} to

    R ₁ to R ₁₆ are each the same or different and independently of each other hydrogen, deuterium, C ₁ -C ₁₀ linear, branched or cyclic alkyl group; and a C ₁ -C ₁₀ linear, branched or cyclic halogenated alkyl group,

    The n1 to n4 are each the same or different and independently from each other, any integer selected from 1 to 3.)
12. According to clause 11,

    The R ₁ , R ₂ , R ₅ , R ₆ , R ₉ , R ₁₀ , R ₁₃ and R ₁₄ is the same or different and is independently selected from CH ₃ , CF ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) _3. A composition for solution processing, wherein .
13. According to clause 11,

    The R ₃ , R ₄ , R ₇ , R ₈ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ are each the same or different and independently selected from CH ₃ , CF ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ A composition for a solution process.
14. According to clause 11,

    X ₁ to X ₄ are the same as each other,

    A ligand containing the above substituents R ₁ to R ₄ ; A ligand containing the above substituents R ₅ to R ₈ ; A ligand containing the above substituents R ₉ to R ₁₂ ; and a ligand containing substituents R ₁₃ to R ₁₆ are the same as each other.
15. According to clause 11,

    The composition for a solution process is characterized in that it contains an organic solvent.
16. According to clause 15,

    A composition for a solution process, characterized in that it contains 0.05 to 90 wt% of an organic tin compound represented by [Chemical Formula A], based on the entire composition.
17. Coating a composition for a solution process selected from claims 11 to 16 on a substrate; and

    (b) heat treating the substrate coated with the composition for solution processing.
18. According to clause 17,

    In step (b), the heat treatment step is a method of producing a tin chalcogenide thin film, characterized in that it is performed in the range of 200 to 700 ° C.
19. According to clause 17,

    Before step (a), the method of producing a tin chalcogenide thin film, characterized in that the surface of the substrate is hydrophilic treated.
20. A tin chalcogenide thin film manufactured by the method for producing a tin chalcogenide thin film according to claim 17.
21. An optical sensor comprising the tin chalcogenide thin film according to claim 20.
22. An electronic device comprising the tin chalcogenide thin film according to claim 20.

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