KR102123421B1 - Chalcogenized organic-inorganic hybrid perovskites compound and Fabrication Method thereof - Google Patents

Abstract

The method for producing a chalcogenated organic-inorganic perovskite compound according to the present invention includes a) a component A, a halide of a monovalent organic cation; As the B component, a metal halide selected from one or more of halide of tetravalent metal, halide of trivalent metal, and halide of divalent metal; As C component, nanoparticles which are chalcogenides of 2 to 4 metals; And a solvent for dissolving components A and B; forming a precursor by applying a precursor solution comprising; And b) heat-treating the precursor to contain cations, monovalent organic cations and bivalent to tetravalent metal ions derived from the B component and bivalent to tetravalent metal ions derived from the C component. And producing a chalcogenated organic-inorganic perovskite compound containing a halogen anion derived from component A and the component B and a chalcogen anion derived from component C.

Description

Chalcogenized organic-inorganic perovskite compound and its manufacturing method {Chalcogenized organic-inorganic hybrid perovskites compound and Fabrication Method thereof}

The present invention relates to a method for producing a chalcogenated organic-inorganic perovskite compound, and to a method for preparing an organic-inorganic perovskite compound in which material stability is significantly improved by strong ion bonding.

The organic-inorganic perovskite compound, also referred to as an organometal halide perovskite compound, consists of organic cations (A), metal cations (M) and halogen anions (X), and perovskites It is a material represented by the chemical formula of AMX ₃ having a structure. In detail, the organic-inorganic perovskite compound represented by the chemical formula of AMX ₃ is a form in which A organic cations are located in the middle in a three-dimensional network in which the MX ₆ octahedron is corner-sheared.

These organic-inorganic perovskite compounds have very low material prices, excellent low-temperature process or low-cost solution process, and are excellent in commerciality. Active research has been conducted in various fields such as light emitting devices, memory devices, sensors, and photovoltaic devices. In addition, efficiency of up to 20% in perovskite-based solar cells using an organic-inorganic perovskite compound as a light absorber is reported (Republic of Korea Patent Publication No. 2014-0035284), more and more for organic-inorganic perovskite compounds Interest is growing.

However, organic/inorganic perovskite compound materials, such as easily decomposed or deteriorated, have poor stability and have difficulty in yarn use. This low stability is due to the weak ionic bond strength of the organic-inorganic perovskite compound in which the monovalent halogen anion binds the monovalent organic cation and the divalent metal cation.

Republic of Korea Patent Publication No. 2014-0035284

The present invention provides a method for preparing an organic-inorganic perovskite compound using a solution coating method and a solid-phase diffusion method, which are the strengths of the organic-inorganic perovskite compound, and the stability of the material is significantly improved by strong ion bonding.

The method for producing a chalcogenated organic-inorganic perovskite compound according to the present invention includes a) a component A, a halide of a monovalent organic cation; As the B component, a metal halide selected from one or more of halide of tetravalent metal, halide of trivalent metal, and halide of divalent metal; As C component, nanoparticles which are chalcogenides of 2 to 4 metals; And a solvent for dissolving at least components A and B; forming a precursor by applying a precursor solution comprising; And b) heat-treating the precursor to contain cations, monovalent organic cations, and bivalent to tetravalent metal ions derived from component B and bivalent to tetravalent metal ions derived from component C. As anions, components A and B And producing a chalcogenated organic-inorganic perovskite compound containing a halogen anion derived from a component and a chalcogen anion derived from a C component.

In the method for preparing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, the precursor solution of step a) is a component B-C component, and any one of the following I) to X) substance sets It may contain the above.

I) Halogens of divalent metals-Nanoparticles that are chalcogenides of tetravalent metals

II) Halides of divalent metals-Nanoparticles that are chalcogenides of trivalent metals

III) Halides of divalent metals and halides of tetravalent metals-nanoparticles that are chalcogenides of tetravalent metals

IV) Halides of divalent metals and halides of trivalent metals-nanoparticles that are chalcogenides of trivalent metals

V) Halides of divalent metals and halides of tetravalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of divalent metals

VI) Halides of divalent metals and halides of trivalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of trivalent metals

VII) Halides of divalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of tetravalent metals

VIII) Halides of divalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of trivalent metals

IX) Halides of trivalent metals-Chalcogenides of trivalent metals

X) Halides of tetravalent metals-Chalcogenides of tetravalent metals

In the method for producing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, the precursor solution is a monovalent organic cation derived from component A: metal and C component of metal halide derived from component B The molar ratio of the metal of the chalcogenide of the metal derived from may be 1:1.

In the method for preparing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, the precursor solution contains chalcogenide nanoparticles of a tetravalent metal as a C component or a tetravalent metal as a B component Contains halide or contains halide of tetravalent metal and chalcogenide nanoparticles of tetravalent metal as component B and C, and is derived from component B, component C or component B and component C in the precursor solution. A valence metal: a molar ratio of chalcogen derived from chalcogenide nanoparticles of a 2 to 4 valent metal of the C component may be 1:2.

In the method for producing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, the precursor solution contains chalcogenide nanoparticles of a trivalent metal as a C component, or a trivalent metal as a B component. Contains halide, or contains the halide of a trivalent metal and the chalcogenide nanoparticles of a trivalent metal as components B and C, and is derived from components B, C, or B and C in the precursor solution. A valence metal: The molar ratio of chalcogen derived from the chalcogenide nanoparticles of the C to C tetravalent metal may be 1:1.

In the method of manufacturing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, the precursor solution is a chalcogen source (source); And at least a solvent for dissolving the chalcogen source.

In the method for preparing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, the chalcogen source may be a chalcogen or a chalcogen compound selected from S, Se, and Te.

In the method of manufacturing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, at least a solvent dissolving the chalcogen source may be a hydrazine-based solvent.

In the method for producing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, the hydrazine-based solvent may be anhydrous hydrazine, hydrazine hydrate, hydrazine derivative, hydrazine derivative hydrate, or a combination thereof.

In the method for producing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, the hydrazine derivative or the hydrazine derivative in a hydrate state is methyl hydrazine, dimethyl hydrazine, and ethylenediamine (ethylenediamine), 1,3-diaminopropane, phenylenediamine, ethylamine, propylamine, diethylamine, or combinations thereof Can be.

In the method for preparing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, the precursor solution contains chalcogenide nanoparticles of a tetravalent metal as a C component or a tetravalent metal as a B component Contains halide or contains halide of tetravalent metal and chalcogenide nanoparticles of tetravalent metal as component B and C, and is derived from component B, component C or component B and component C in the precursor solution. Valence metal: The molar ratio of chalcogenide nanoparticles of chalcogenide nanoparticles and chalcogenide sources of 2 to 4 of the C component may satisfy 1:1.

In the method for producing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, the precursor solution contains chalcogenide nanoparticles of a trivalent metal as a C component, or a trivalent metal as a B component. Contains halide, or contains the halide of a trivalent metal and the chalcogenide nanoparticles of a trivalent metal as components B and C, and is derived from components B, C, or B and C in the precursor solution. Valence metal: The molar ratio of chalcogenide nanoparticles of chalcogenide nanoparticles and chalcogenide sources of the C to 2 tetravalent metal may satisfy 1:1.

In the method for producing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, in component B, a metal of a tetravalent metal halide, a trivalent metal halide, and a divalent metal halide metal Silver is a metal that is different from each other, and the halide of the tetravalent metal is a metal selected from one or more of titanium (Ti), tin (Sn), cerium (Ce), zirconium (Zr), molybdenum (Mo), and tungsten (W). Halide of the trivalent metal, and antimony (Sb), bismuth (Bi), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), scandium (Sc), yttrium ( Y), Lanthanum (La), Cerium (Ce), Iron (Fe), Ruthenium (Ru), Chromium (Cr), Vanadium (V) and Titanium (Ti). In the B component, the halide of the divalent metal is copper (Cu), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), chromium (Cr), palladium (Pd), cadmium (Cd) ), germanium (Ge), tin (Sn), lead (Pb), and ytterbium (Yb).

In the method for producing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, in the C component, a chalcogenide of a divalent metal, a chalcogenide of a trivalent metal, and a chalcogen of a tetravalent metal The cargo is a chalcogenide of different metals, the chalcogenide of the divalent metal satisfies the following formula (1), the chalcogenide of the trivalent metal satisfies the following formula (2), and the chalcogenide of the tetravalent metal: Formula 3 may be satisfied.

(Formula 1)

MaChal

In Formula 1, Ma is Cu ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ²⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Pb ²⁺ and in Yb ^2+, and one or a divalent metal ion selected two or more, Chal is S ^- a knife kojen anion is selected from at least one or both ^-, Se ^-, and Te.

(Formula 2)

Mb ₂ Chal ₃

In Formula 2, Mb is Sb ³⁺ , Bi ³⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Sc ³⁺ , Y ³⁺ , La ³⁺ , Ce ³⁺ , Fe ³⁺ , Ru ^3+, Cr ^3+, V and trivalent metal ions ³⁺ and select at least one or two in Ti ^3+, Chal is S ^- a knife kojen anion is selected from at least one or both ^-, Se ^-, and Te.

(Formula 3)

McChal ₂

In formula 3, Mc is ^{Ti 4+, Sn 4+, Ce 4+} , Zr 4+, Mo , and one or metal ions, tetravalent selected two or more in the ⁴⁺ and W ^4+, Chal is S ^-, Se ^-, and Te ^- is a chalcogenide anion selected from one or two or more.

In the method of manufacturing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, the average diameter of the C component nanoparticles may be 0.5 nm to 20 nm.

In the method of manufacturing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, the heat treatment in step b) may be performed at 100 to 250°C.

In the method of manufacturing a chalcogenated organic-inorganic perovskite compound according to an embodiment of the present invention, the heat treatment in step b) may be performed in an inert atmosphere or a hydrogen atmosphere.

The method for producing a chalcogenated perovskite compound according to the present invention contains a chalcogen anion having a strong binding strength compared to a halogen anion by solid-phase reaction through low-temperature heat treatment at 250° C. or less based on a solution process excellent in commerciality, There is an advantage in that a chalcogenated perovskite compound having significantly improved thermal, chemical, and optical stability of a material can be prepared.

Hereinafter, a method for producing a chalcogenated organic-inorganic perovskite compound of the present invention will be described in detail. At this time, unless there are other definitions in the technical terms and scientific terms to be used, it has a meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention in the following description and the accompanying drawings Descriptions of well-known functions and configurations that may be obscured are omitted.

In the present invention, the chalcogenated organic-inorganic perovskite compound (hereinafter, the chalcogenated perovskite compound) means an organic-inorganic perovskite compound containing a divalent chalcogenide anion as an anion. Specifically, the chalcogenated organic-inorganic perovskite compound is composed of an organic cation (A), a metal cation (M) and an anion (X), based on a compound that satisfies the formula of AMX ₃ having a perovskite structure , MX ₆ octahedron may represent a compound in which a chalcogen anion and a halogen anion are located in the place of X (anion).

The method for producing a chalcogenated perovskite compound according to the present invention includes a) a component A, a halide of a monovalent organic cation; As the B component, a metal halide selected from one or more of halide of tetravalent metal, halide of trivalent metal, and halide of divalent metal; As C component, nanoparticles which are chalcogenides of 2 to 4 metals; And a solvent for dissolving components A and B (hereinafter, a solvent for a halide); forming a precursor by applying a precursor solution comprising; And b) heat-treating the precursor to contain cations, monovalent organic cations, and bivalent to tetravalent metal ions derived from component B and bivalent to tetravalent metal ions derived from component C. As anions, components A and B And producing a chalcogenated organic-inorganic perovskite compound containing a halogen anion derived from a component and a chalcogen anion derived from a C component.

As described above, the manufacturing method according to the present invention contains a tetravalent metal ion and/or a trivalent metal ion, together with a monovalent organic cation as a cation, by solid phase diffusion by application and heat treatment of a precursor solution, and anion As a result, a chalcogenide containing a halogen anion and a chalcogen anion can be prepared. The chalcogenated organic-inorganic perovskite compound prepared in step b) contains a chalcogen anion, which is a divalent anion, so that the ionic bond between anions and cations is greatly increased, and the conventional perovskite contains only halogen anions as anions. It has the advantage that the stability of the material is significantly improved compared to the organometal halide of the skye structure. Furthermore, as it also contains a trivalent to tetravalent metal ion together with a divalent chalcogen anion, its stability can be further improved.

In the method for producing a chalcogenide according to the present invention, component A may be a source of monovalent organic cations constituting a perovskite structure. In addition, as component A is a halide of a monovalent organic cation, component A can serve as a source of halogen anions forming a perovskite structure.

Component B may be a source of metal ions that make up the perovskite structure. Specifically, since the B component is a metal halide selected from one or more of a halide of a tetravalent metal, a halide of a trivalent metal, and a halide of a divalent metal, the B component has 2 to 4 metal ions (2 It may be a source of one or more metal ions selected from valence metal ions, trivalent metal ions, and tetravalent metal ions. In addition, since the B component is a halide of a divalent to tetravalent metal (a halide of a tetravalent metal, a halide of a trivalent metal and a halide of a divalent metal, a metal halide selected from one or more), the B component The halogen anion forming the silver perovskite structure may serve as another source.

The C component is a nanoparticle that is a chalcogenide of a 2-4 tetravalent metal, and is a chalcogen located at the position of X (anion) of MX ₆ (M=metal ion, X=anion) octahedron in the perovskite structure. It can be a source of negative ions. Specifically, the precursor of step a) may be a source for supplying the chalcogen anion through a solid phase diffusion reaction during the heat treatment of step b). By this solid phase diffusion reaction, a chalcogen anion is supplied to the site of X (anion) of MX ₆ (M=metal ion, X=anion) octahedron, and chalcogenide can be prepared. In addition, as the nanoparticle C component is a chalcogenide of a 2-4 tetravalent metal, the C component is a 2-4 tetravalent metal ion (divalent metal ion, trivalent metal ion, and tetravalent metal) forming a perovskite structure. Other sources of one or more metal ions selected from metal ions).

As described above, component A can be a source of monovalent organic cations and halogen anions, component B can be a source of 2-4 tetravalent metal ions and other sources of halogen anions, and component C is a source of chalcogen anions. And other sources of bivalent metal ions.

As a specific example, the precursor solution of step a) is a material pair of component B-C, and may contain any one or more of the following material sets of I) to X).

I) Halogens of divalent metals-Nanoparticles that are chalcogenides of tetravalent metals

II) Halides of divalent metals-Nanoparticles that are chalcogenides of trivalent metals

III) Halides of divalent metals and halides of tetravalent metals-nanoparticles that are chalcogenides of tetravalent metals

IV) Halides of divalent metals and halides of trivalent metals-nanoparticles that are chalcogenides of trivalent metals

V) Halides of divalent metals and halides of tetravalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of divalent metals

VI) Halides of divalent metals and halides of trivalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of trivalent metals

VII) Halides of divalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of tetravalent metals

VIII) Halides of divalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of trivalent metals

IX) Halides of trivalent metals-Chalcogenides of trivalent metals

X) Halides of tetravalent metals-Chalcogenides of tetravalent metals

When the precursor solution contains a substance set of I) as a substance pair of component B-C (halogen of divalent metal-nanoparticle which is a chalcogenide of tetravalent metal), component B is a source of divalent metal ions And other sources of halogen anions, and component C can be a source of tetravalent metal ions and a source of chalcogen anions.

When the precursor solution contains the substance set of II) as a substance pair of the component B-C (halogen of a divalent metal-nanoparticle which is a chalcogenide of a trivalent metal), the component B is a source of divalent metal ions And other sources of halogen anions, and component C may be a source of trivalent metal ions and a chalcogen anion.

When the precursor solution contains a substance set of III) as a substance pair of component B-C (halogen of a divalent metal and halide of a tetravalent metal-a nanoparticle that is a chalcogenide of a tetravalent metal), component B Silver is a source of divalent metal ions and tetravalent metal ions and other sources of halogen anions, and the C component can be a source of tetravalent metal ions and a source of chalcogen anions.

When the precursor solution contains a substance set of IV) as a substance pair of component B-C (halogen of a divalent metal and halide of a trivalent metal-a nanoparticle that is a chalcogenide of a trivalent metal), component B Silver is a source of divalent metal ions and trivalent metal ions and other sources of halogen anions, and component C can be a source of trivalent metal ions and a source of chalcogen anions.

Precursor solution is a substance set of B component-C component V (halogen of divalent metal and halide of tetravalent metal-nanoparticles which are chalcogenides of divalent metals and chalcogenides of tetravalent metals) Phosphorus nanoparticles), component B is a source of divalent metal ions and tetravalent metal ions and other sources of halogen anions, and component C is a source of divalent metal ions and tetravalent metal ions and chalcogen anions. It can be a source.

Nanoparticles and trivalent metal chalcogenides where the precursor solution is a B-C-VI substance pair (halide of divalent metal and halide of trivalent metal-chalcogenide of divalent metal) Phosphorus nanoparticles), component B is a source of divalent metal ions and trivalent metal ions and other sources of halogen anions, and component C is a source of divalent metal ions and trivalent metal ions and chalcogen anions. It can be a source.

The precursor solution contains a substance set of VII) (halogens of divalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of divalent metals) as a substance pair of component B-C. In case, the B component is a source of divalent metal ions and other sources of halogen anions, and the C component can be a source of divalent metal ions and tetravalent metal ions and a source of chalcogen anions.

The precursor solution contains the substance set of VIII) as a substance pair of component B-C (halogen of a divalent metal-nanoparticle which is a chalcogenide of a divalent metal and nanoparticle that is a chalcogenide of a trivalent metal) In case, the B component is a source of divalent metal ions and other sources of halogen anions, and the C component can be a source of divalent metal ions and trivalent metal ions and a source of chalcogen anions.

When the precursor solution contains a substance set (halide of a trivalent metal-chalcogenide of a trivalent metal) as a substance pair of component B-C, component B is a source of trivalent metal ions and halogen anion Is a different source, and the C component can be a source of trivalent metal ions and a source of chalcogen anions.

When the precursor solution contains a substance set (X halide of tetravalent metal-chalcogenide of tetravalent metal) as a substance pair of component B-C, component B is a source of tetravalent metal ions and halogen anion Is a different source, and the C component can be a source of tetravalent metal ions and a source of chalcogen anions.

At this time, as described above based on the material pair of component B-C, the precursor solution contains a halide of a 3-4 tetravalent metal as a B component, and/or a chalcogen of a 3-4 tetravalent metal as a C component May contain cargo. This is for stably securing charge neutralization as the chalcogenated perovskite compound contains a divalent chalcogen anion.

Hereinafter, each component contained in the precursor solution will be described in more detail.

The halide of the monovalent organic cation as component A (hereinafter, an organic halide) may mean a compound of a monovalent organic cation (A) and a halogen anion (X).

Specifically, the organic halide may be the following Chemical Formula 4.

(Formula 4)

AHal

In the formula (4), A is a monovalent cation, A is an organic ammonium ion, amidinium group ion or organic ammonium ion and amidinium ion, and Hal is a halogen ion. In formula 4, Hal is Cl ^- may be one or two or more kinds selected from a halogen anion ^-, Br ^-, F ^-, and I.

In Chemical Formula 4, A may be one organic cation belonging to the following Chemical Formulas 5 to 7 or two organic cations belonging to the Chemical Formulas 5 to 7 and different from each other. Formulas 5 to 6 correspond to the case where the monovalent cation is a monovalent organic ammonium ion, and Formula 7 corresponds to the case where the monovalent cation is an amidinium group ion.

(Formula 5)

R ₁ -NH ₃ ⁺

In Formula 5, R ₁ is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl.

(Formula 6)

R ₂ -C ₃ H ₃ N ₂ ⁺ -R ₃

In Formula 6, R ₂ is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl, and R ₃ is hydrogen or C1-C24 alkyl.

(Formula 7)

In the formula (7), R ₄ to R ₈ are, independently of each other, hydrogen, amino, C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl. R ₄ to R ₈ in the formula (7) independently of each other may be hydrogen, amino or C1-C24 alkyl, specifically hydrogen, amino or C1-C7 alkyl, more specifically hydrogen, amino or methyl, and more specifically R ₄ is hydrogen, amino or methyl, and R ₅ to R ₈ may each be hydrogen. As a specific and non-limiting example, the amidinium-based ion is formamidinium (NH ₂ CH=NH ₂ ⁺ ) ion, acetamidinium (NH ₂ C(CH ₃ )=NH ₂ ⁺ ) Or Guamidinium (NH ₂ C(NH ₂ )=NH ₂ ⁺ ).

In this case, the two types of organic cations belonging to the formulas 5 to 7 and different from each other may not be interpreted as being limited to only organic cations belonging to the different formulas in the formulas 5 to 7, and the same formula (Formula 5, Formula 6, or Formula 7) ), but different organic ligands (R _{1 for} Formula 5, R ₂ and/or R ₃ for Formula ₆ , R ₄ , R ₅ , R ₆ , R ₇ and/or R _{8 for} Formula 7) It should be interpreted as including the organic cation having.

When two different organic cations are contained, in Formula 4, A is A ¹ _(1-k) A ² _k (real number where 0<k<1, A ¹ and A ² belong to Formulas 5 to 7, and Different two kinds of organic cations).

In this case, when both the organic ammonium ion which is the organic cation belonging to the formula 5 to 6 and the amidinium-based ion belonging to the formula 7 are contained, it is more advantageous for charge transfer. When the organic cation contains both the organic ammonium ion and the amidinium-based ion, the total number of moles of the monovalent organic cation is 1, which will contain 0.7 to 0.95 amidinium-based ions and 0.3 to 0.05 organic ammonium ions. Can be. That is, in Formula 4, A may be A ¹ _(1-k) A ² _k , wherein A ¹ is an amidinium-based ion, A ² is an organic ammonium ion, and k is a real day of 0.3 to 0.05. Can be.

Considering the use of the organic-inorganic perovskite compound, the monovalent organic cation may be appropriately changed, but when considering the use of a semiconductor device or an optical device, in Formula 4, when A contains an organic ammonium ion, organic ammonium The ions may be R ₁ -NH ₃ ⁺ , and R ₁ may be C ₁ -C ₂₄ alkyl, preferably C ₁ -C 7 alkyl, more preferably methyl.

The component B may be a metal halide selected from at least one of a halide of a tetravalent metal, a halide of a trivalent metal, and a halide of a divalent metal. At this time, the tetravalent metal in the halide of the tetravalent metal, the trivalent metal in the halide of the trivalent metal, or the divalent metal in the halide of the divalent metal, a metal having only a tetravalent oxidation state (only a trivalent metal Of course, it cannot be interpreted as being limited to a metal having only oxidized water or a metal having only divalent oxidized water: tetravalent metals are trivalent to tetravalent oxidized water, divalent to tetravalent oxidized water, divalent to pentavalent oxidized water, trivalent It should be construed to mean a halide of a transition metal, post-transition metal or metalloid having two or more oxidation numbers, such as an oxidation number of 5 to 5, but having at least a tetravalent oxidation number. Halides of transition metals, post-transition metals, or metalloids having at least two oxidation numbers, such as valent oxidation numbers, divalent to trivalent oxidation numbers, divalent to tetravalent oxidation numbers, trivalent to pentavalent oxidation numbers, etc. Similarly, a divalent metal has two or more oxidation numbers, such as divalent to tetravalent oxidation number, divalent to trivalent oxidation number, divalent to pentavalent oxidation number, etc., but having at least divalent oxidation number It should be construed to mean a halide of a transition metal, post-transition metal or metalloid.

Accordingly, when the B component contains a halide of a divalent metal, the halide of the divalent metal should not be interpreted as being limited to a dihalide, and a halide of the trivalent metal is limited to a trihalide analysis. It should not be, and the halides of tetravalent metals should not be interpreted as being limited to tetrahalides. Specifically, the halide of the B-4 divalent metal, which is a component B, may be a halogenated bond of a number corresponding to a known oxidation number of the metal. As a practical example, when the component B contains a halide of a tetravalent metal, the halide of the tetravalent metal is not only a tetrahalide (MHal ₄ , M is a tetravalent metal, Hal is a halogen), but also known Depending on the oxidation number, dihalides (MHal ₂ , M is a tetravalent metal, Hal is halogen) may also be included.

As described above, the component B may be a metal halide selected from one or two or more halides of a tetravalent metal, a halide of a trivalent metal, and a halide of a divalent metal.

The halide of the tetravalent metal may be a metal halide selected from one or more of titanium (Ti), tin (Sn), cerium (Ce), zirconium (Zr), molybdenum (Mo) and tungsten (W). . Halides of trivalent metals are antimony (Sb), bismuth (Bi), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), scandium (Sc), yttrium (Y), lanthanum It may be a metal halide selected from (La), cerium (Ce), iron (Fe), ruthenium (Ru), chromium (Cr), vanadium (V) and titanium (Ti). Halides of divalent metals are copper (Cu), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), chromium (Cr), palladium (Pd), cadmium (Cd), germanium ( Ge), tin (Sn), lead (Pb), and ytterbium (Yb).

Accordingly, the B component is titanium halide, tin halide, cerium halide, zirconium halide, molybdenum halide, tungsten halide, antimony halide, bismuth halide, aluminum halide, gallium halide, indium halide , Thallium halide, scandium halide, yttrium halide, lanthanum halide, iron halide, ruthenium halide, chromium halide, vanadium halide, titanium halide, copper halide, nickel halide, cobalt halide, It may be one or two or more halides selected from manganese halide, chromium halide, palladium halide, cadmium halide, germanium halide, lead halide, and ytterbium halide. At this time, the halogen of the halide may be one or two or more selected from I, Br, F and Cl. However, as described above, when the B component contains only a halide of a divalent metal, it is advantageous that the C component contains chalcogenide nanoparticles of a trivalent to tetravalent metal.

Component C may include nanoparticles that are chalcogenides of divalent or tetravalent metals. Specifically, the chalcogenide of the divalent metal, the chalcogenide of the trivalent metal, and the chalcogenide of the tetravalent metal are chalcogenides of different metals, and the chalcogenide of the divalent metal satisfies Formula 1 below. , The chalcogenide of the trivalent metal may satisfy the following formula (2), and the chalcogenide of the tetravalent metal may satisfy the following formula (3).

(Formula 1)

MaChal

In Formula 1, Ma is Cu ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ²⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Pb ²⁺ and in Yb ^2+, and one or a divalent metal ion selected two or more, Chal is S ^- a knife kojen anion is selected from at least one or both ^-, Se ^-, and Te. Specifically, in the formula 1, the chalcogen anion, Chal, may be one or two or more selected from S ² , Se ² and Te ² .

(Formula 2)

Mb ₂ Chal ₃

In Formula 2, Mb is Sb ³⁺ , Bi ³⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Sc ³⁺ , Y ³⁺ , La ³⁺ , Ce ³⁺ , Fe ³⁺ , Ru ^3+, Cr ^3+, V and trivalent metal ions ³⁺ and select at least one or two in Ti ^3+, Chal is S ^- a knife kojen anion is selected from at least one or both ^-, Se ^-, and Te. Specifically, the chalcogen anion in formula 2, Chal may be one or two or more selected from S ² , Se ² and Te ² .

(Formula 3)

McChal ₂

In formula 3, Mc is ^{Ti 4+, Sn 4+, Ce 4+} , Zr 4+, Mo , and one or metal ions, tetravalent selected two or more in the ⁴⁺ and W ^4+, Chal is S ^-, Se ^-, and Te ^- is a chalcogenide anion selected from one or two or more. Specifically, in the general formula (3), the chalc which is a chalcogen anion may be one or two or more selected from S ² , Se ² and Te ² .

Component C may include one or two or more chalcogenide nanoparticles satisfying Formulas 1 to 3, wherein when the C component contains two or more chalcogenide nanoparticles, two or more chalcogenides Cargoes cannot be interpreted as being limited to chalcogenides belonging to chemical formulas different from each other in Chemical Formulas 1 to 3, and belong to the same chemical formula (Chemical Formula 1, Chemical Formula 2, or Chemical Formula 3), but also include halides of two or more different metals. It should be interpreted as meaning.

Chalcogenide nanoparticles of divalent or tetravalent metals contained as C component in the precursor solution may have an average diameter of 0.5 nm to 20 nm, and advantageously 0.5 to 10 nm. These fine-sized nanoparticles can act as a material source of chalcogen and/or metal more quickly and easily through solid phase diffusion even at low temperatures during the heat treatment of step b). Also, the chalcogen and/or metal in the precursor It is advantageous because nanoparticles as a material source can be more homogeneously distributed.

In the chalcogenide production method according to an embodiment of the present invention, the precursor solution is a monovalent organic cation derived from component A: a metal halide metal derived from component B and a metal chalcogenide derived from component C The metal may have a molar ratio of 1:1. That is, the precursor solution includes: the number of moles of the organic halide of component A contained in the precursor solution: the number of moles of metal resulting from all metal halide of component B in the precursor solution and all metal chalcogens of component C in the precursor solution. The sum of the number of moles of metal originating from the cargo can satisfy a ratio of 1:1. Such a component: a chalcogenide having a perovskite structure can be more stably manufactured by a molar ratio between a metal of component B and a metal of component C.

In the method for producing a chalcogenide according to an embodiment of the present invention, the precursor solution contains chalcogenide nanoparticles of a tetravalent metal as component C, or a halide of a tetravalent metal as component B, or component B And a halide of a tetravalent metal and chalcogenide nanoparticles of a tetravalent metal as component C, and a tetravalent metal derived from component B, component C or component B and component C in the precursor solution: of component C The molar ratio of chalcogen (based on element) derived from chalcogenide nanoparticles of 2 to 4 valent metal may be 1:2.

As described above, the precursor solution may include a B component, a C component, or a tetravalent metal (metal ion) derived from the B component and the C component, wherein the total number of moles of the tetravalent metal contained in the precursor solution: C The molar ratio between the number of moles of chalcogen (based on the element) contained in the nanoparticles of the component may satisfy 1:2. The molar ratio between the tetravalent metal ion and the chalcogen anion may be independent of whether the divalent metal ion is contained, and the divalent metal ion content, and b) is caused by charge neutralization of the chalcogenated perovskite compound prepared in step It may be a molar ratio.

Precursor solution is a substance pair of component B-C containing a tetravalent metal, as described above, I) a halide of a divalent metal-a nanoparticle that is a chalcogenide of a tetravalent metal, III) a halogen of a divalent metal Halides of cargoes and tetravalent metals-nanoparticles that are chalcogenides of tetravalent metals, V) halides of divalent metals and halides of tetravalent metals-nanoparticles that are chalcogenides of divalent metals and tetravalent metals Chalcogenide nanoparticles, VII) divalent metal halide-divalent metal chalcogenide nanoparticles and tetravalent metal chalcogenide nanoparticles and X) tetravalent metal halide-tetravalent And a set of materials selected from one or more of chalcogenides of metals.

A component: The molar ratio between the metal of component B and the metal of component C satisfies 1:1, that is, the number of organic halides contained in the precursor solution: total metal contained in the precursor solution (metal ions derived from component B) And the molar ratio of the metals contained in the C component satisfies 1:1, and the total molar number of the tetravalent metals contained in the precursor solution: the molar ratio between the moles of the chalcogen (based on the element) contained in the nanoparticles of the C component When 1:2 is satisfied, a chalcogenated perovskite compound satisfying the following formula 8 (following formula 8') or the following formula 9 may be prepared by a solid phase diffusion reaction by the heat treatment in step b). .

(Formula 8)

AM ^IV HalChal ₂

In Formula 1, A is a monovalent organic cation, M ^IV is a tetravalent metal ion, Hal is a monovalent halogen anion, and Chal is a divalent chalcogen anion. Specifically, in Formula 8, Chal is S ^2-, Se ^2- and may be alone or in combination of two or more selected from Te ^2-, Hal is I ^- 1 kind selected from ^-, Br ^-, F ^- and Cl Alternatively, it may be two or more, and M ^IV may be one or two or more selected from Ti ⁴⁺ , Sn ⁴⁺ , Ce ⁴⁺ , Zr ⁴⁺ , Mo ⁴⁺ and W ⁴⁺ .

As a material pair of component B-C, in which the chalcogenated perovskite compound of Formula 8 can be prepared, the above-mentioned, X) halide of a tetravalent metal-a substance set of a chalcogenide of a tetravalent metal Can be lifted.

In Chemical Formula 8, when the chalcogenated perovskite compound contains a tetravalent metal ion, but contains two or more different tetravalent metal ions, Chemical Formula 8 may be represented by the following Chemical Formula 8''.

(Formula 8'')

(1-k)(AMa ^IV HalChal ₂ )/k(AMb ^IV HalChal ₂ )

In Formula 8'', A is a monovalent organic cation, Ma ^IV and Mb ^IV are different tetravalent metal ions, Hal is a monovalent halogen anion, Chal is a divalent chalcogen anion, and k is 0<k <1 real number, specifically, 0.3≤k≤0.7. In more detail, the formula 8 '', Chal is S ^2-, Se ^2- and may be alone or in combination of two or more selected from Te ^2-, Hal is I ^-, Br ^-, F ^- and Cl ^- selected from It may be one or two or more, Ma ^IV is one selected from Ti ⁴⁺ , Sn ⁴⁺ , Ce ⁴⁺ , Zr ⁴⁺ , Mo ⁴⁺ and W ⁴⁺ , and Mb ^IV is different from Ma ^IV However, it may be one selected from Ti ⁴⁺ , Sn ⁴⁺ , Ce ⁴⁺ , Zr ⁴⁺ , Mo ⁴⁺ and W ⁴⁺ . Formula 8'' is AMa ^IV HalChal ₂ AMb ^IV HalChal ₂ and AMa ^IV HalChal ₂ , as well as the meaning of solid solutions homogeneously employed in each other within a single perovskite structure It should also be construed to include the meaning of a complex phase (so-called double perovskite structure) in which two perovskite compounds of AMb ^IV HalChal ₂ are mixed. Formula 8'' may also be referred to as AMa ^IV _k Mb ^IV _(1-k) HalChal ₂ , and this notation should not be construed as being limited only to the solid solution as described above.

(Formula 9)

(1-x)(AM ^II Hal ₃ )/x(AM ^IV HalChal ₂ )

In Formula 9, A is a monovalent organic cation, M ^II is a divalent metal ion, M ^IV is a tetravalent metal ion, Hal is a monovalent halogen anion, Chal is a divalent chalcogen anion, and 0<x <1 is a mistake. Specifically, in Formula 9, Chal is S ^2-, Se ^2- and may be alone or in combination of two or more selected from Te ^2-, Hal is I ^- 1 kind selected from ^-, Br ^-, F ^- and Cl Or may be two or more, M ^IV may be one or two or more selected from Ti ⁴⁺ , Sn ⁴⁺ , Ce ⁴⁺ , Zr ⁴⁺ , Mo ⁴⁺ and W ⁴⁺ , M ^II is Cu ^{1 selected from 2+} , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ²⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Pb ²⁺ and Yb ²⁺ . It may be a species or two or more species.

Formula 9 is AM ^II Hal ₃ AM ^IV HalChal ₂ and AM ^II Hal ₃ as well as the meaning of solid solutions homogeneously employed in each other within a single perovskite structure The meaning of the complex phase in which two perovskite compounds of AM ^IV HalChal ₂ are mixed should also be interpreted to include this, and this complex phase should be interpreted to include a double layer perovskite structure. Formula 9 may also be expressed as AM ^II _(1-x )M ^IV _x Hal _(3-2x) Chal _2x , and this notation should not be interpreted as being limited only to the _{solid solution} as described above.

As a material pair of component B-C, in which the chalcogenated perovskite compound of formula 9 can be prepared, I) the above-mentioned, I) halide of a divalent metal-nanoparticle which is a chalcogenide of a tetravalent metal, III) Halides of divalent metals and halides of tetravalent metals-nanoparticles that are chalcogenides of tetravalent metals, V) halides of divalent metals and halides of tetravalent metals-chalcogenides of divalent metals Phosphorus nanoparticles and tetravalent metal chalcogenide nanoparticles and VII) divalent metal halide-divalent metal chalcogenide nanoparticles and tetravalent metal chalcogenide nanoparticles And substance sets.

When the precursor solution contains both a divalent metal and a tetravalent metal, the content of the chalcogen anion in the chalcogenated perovskite compound prepared by the tetravalent metal ion content can be determined. Accordingly, in terms of significantly improving the material stability of the chalcogenated perovskite compound, it is advantageous that the precursor solution contains the C component such that x is 0.3 or more, and in one specific example, the precursor solution has an x of 0.3 ≤ It is advantageous to contain the C component such that x is a real number of 1, a more specific example, and x is a real number of 0.3 ≤ x ≤ 0.7. Furthermore, in terms of the more stable formation of the perovskite compound, in a more specific example, the precursor solution preferably contains the C component such that x is 0.5.

In the method for producing a chalcogenide according to an embodiment of the present invention, the precursor solution contains chalcogenide nanoparticles of a trivalent metal as component C, or a halide of a trivalent metal as component B, or component B And trivalent metal halide and trivalent metal chalcogenide nanoparticles as component C, and trivalent metal derived from component B, component C or component B and component C in the precursor solution: The molar ratio of chalcogen (based on element) derived from chalcogenide nanoparticles of 2 to 4 valent metal may be 1:1.

As described above, the precursor solution may include a B component, a C component, or a trivalent metal (metal ion) derived from the B component and the C component, wherein the total number of moles of the trivalent metal contained in the precursor solution: C The molar ratio between the number of moles of chalcogen (based on the element) contained in the nanoparticles of the component may satisfy 1:1. The molar ratio between the trivalent metal ion and the chalcogen anion may be independent of the content of the divalent metal ion, and the content of the divalent metal ion, and b) by charge neutralization of the chalcogenated perovskite compound prepared in step It may be a molar ratio.

Precursor solution is a substance pair of component B-C containing a trivalent metal, as described above, II) a halide of a divalent metal-a nanoparticle that is a chalcogenide of a trivalent metal, IV) a halogen of a divalent metal Halides of cargoes and trivalent metals-nanoparticles that are chalcogenides of trivalent metals, VI) halides of divalent metals and halides of trivalent metals-nanoparticles and trivalent metals that are chalcogenides of divalent metals Chalcogenide nanoparticles, VIII) divalent metal halide-divalent metal chalcogenide nanoparticles and trivalent metal chalcogenide nanoparticles and IX) trivalent metal halide-trivalent And a set of materials selected from one or more of chalcogenides of metals.

The number of moles of organohalides contained in the precursor solution: The ratio of the number of moles of the total metal (metal ions derived from component B and the metal contained in component C) contained in the precursor solution satisfies 1:1, and is contained in the precursor solution. Total number of moles of trivalent metal: When the molar ratio between moles of chalcogen (based on element) contained in C component nanoparticles satisfies 1:1, by solid phase diffusion reaction by heat treatment in step b), the following formula 10 (Or a chalcogenated perovskite compound satisfying the following formula 10) or the following formula 11 may be prepared.

(Formula 10)

AM ^III Hal ₂ Chal

In Formula 10, A is a monovalent organic cation, M ^III is a trivalent metal ion, Hal is a monovalent halogen anion, and Chal is a divalent chalcogen anion. Specifically, in formula 10, Chal is S ^2-, Se ^2- and may be alone or in combination of two or more selected from Te ^2-, Hal is I ^- 1 kind selected from ^-, Br ^-, F ^- and Cl Or it may be two or more, M ^III is Sb ³⁺ , Bi ³⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Sc ³⁺ , Y ³⁺ , La ³⁺ , Ce ³⁺ , Fe ³⁺ , Ru ³⁺ , Cr ³⁺ , V ³⁺ and Ti ³⁺ may be selected from one or two or more. When the chalcogenated perovskite compound contains trivalent metal ions, but contains two or more different trivalent metal ions, M ^III in Formula 10 is Ma ^III _k Mb ^III _(1-k) (0< It can be replaced by a real number with k<1, specifically 0.3≤k≤0.7). At this time, Ma ^III and Mb ^III are Sb ^{3 +} , Bi ^{3 +} , Al ^{3 +} , Ga ^{3 +} , In ^{3 +} , Tl ^{3 +} , Sc ^{3 +} , Y ³⁺ , La ³⁺ , Ce ^{3 +} , Fe ^{3 +,} and may be ^{Ru 3 +, Cr 3 +,} V 3+ and Ti ^{3 +} 3 is a metal ion of two or more selected from the.

As a material pair of component B-C, in which the chalcogenated perovskite compound of formula (10) can be prepared, the above-mentioned IX) halide of a trivalent metal-chalcogenide of a trivalent metal can be mentioned.

When the chalcogenated perovskite compound contains trivalent metal ions, but contains two or more different trivalent metal ions that are different from each other, Formula 10 may be represented by the following Formula 10''.

(Formula 10'')

(1-k)(AMa ^III Hal ₂ Chal)/k(AMb ^III Hal ₂ Chal)

In Formula 10'', A is a monovalent organic cation, Ma ^III and Mb ^III are different tetravalent metal ions, Hal is a monovalent halogen anion, Chal is a divalent chalcogen anion, and k is 0<k <1 real number, specifically, 0.3≤k≤0.7. In more detail, the formula 1 '', Chal is S ^2-, Se ^2- and may be alone or in combination of two or more selected from Te ^2-, Hal is I ^-, Br ^-, F ^- and Cl ^- selected from May be one or two or more, Ma ^III is Sb ³⁺ , Bi ³⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Sc ³⁺ , Y ³⁺ , La ³⁺ , Ce ^{3+, Fe 3+, Ru 3+,} Cr 3+, V 3+ and is one element selected from among Ti ^3+, Mb ^III, but is different from ^{Ma III Sb 3 +, Bi 3} +, Al 3 +, Ga ^{+ 3,} in ^{+ 3,} Tl ^{+ 3,} Sc ^3+, Y ^3+, La ^{+ 3,} Ce ^{+ 3,} Fe ^{+ 3,} Ru ^{+ 3,} Cr ^{+ 3,} V ³⁺ and Ti ^{3 +} 1 is selected from It can be a species. Formula 1'' is AMa ^III Hal ₂ Chal AMb ^III Hal ₂ Cha, as well as the meaning of solid solutions homogeneously employed in each other within a single perovskite structure, as well as AMa ^III Hal ₂ Chal It should also be interpreted to include the meaning of the complex phase (so-called double perovskite structure) in which two perovskite compounds of AMb ^III Hal ₂ Chal are mixed. Formula 10'' may also be expressed as AMa ^III _k Mb ^III _(1-k) Hal ₂ Chal, and this notation should not be construed as being limited to the employment only, as described above.

(Formula 11)

(1-x)(AM ^II Hal ₃ )/x(AM ^III Hal ₂ Chal)

In Formula 11, A is a monovalent organic cation, M ^II is a divalent metal ion, M ^III is a trivalent metal ion, Hal is a monovalent halogen anion, Chal is a divalent chalcogen anion, and 0<x <1 is a mistake. Specifically, in formula 11, Chal is S ^2-, Se ^2- and may be alone or in combination of two or more selected from Te ^2-, Hal is I ^- 1 kind selected from ^-, Br ^-, F ^- and Cl Or it may be two or more, M ^III is Sb ³⁺ , Bi ³⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Sc ³⁺ , Y ³⁺ , La ³⁺ , Ce ³⁺ , Fe ³⁺ , Ru ³⁺ , Cr ³⁺ , V ³⁺ and Ti ³⁺ may be selected from one or two or more, M ^II is Cu ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ²⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Pb ²⁺ and Yb ²⁺ may be selected from one or more.

Formula 11 is AM ^II Hal ₃ AM ^III Hal ₂ Chal and AM ^II Hal ₃ as well as the meaning of solid solutions homogeneously employed in each other in a single perovskite structure The meaning of the complex phase in which two perovskite compounds of AM ^III Hal ₂ Chal are mixed should also be interpreted to include this, and this complex phase should be interpreted to include a double layer perovskite structure. Formula 11 may also be expressed as AM ^II _(1-x )M ^III _x Hal _(3-x) Chal _x , and this notation should not be interpreted as being limited only to the solid solution as described above.

Similar to Formula 9, when the chalcogenated perovskite compound contains a divalent metal ion and a divalent metal ion, the content of the chalcogen anion may be determined by the content of the trivalent metal ion. Accordingly, in terms of significantly improving the material stability of the chalcogenated perovskite compound, and accordingly, in terms of significantly improving the material stability of the chalcogenated perovskite compound, the precursor solution has an x of 0.3. It is advantageous to contain the C component so that it is the above, and as a specific example, the precursor solution contains the C component such that x is a real number of 0.3 ≤ x <1, and more specifically, x is a real number of 0.3 ≤ x ≤ 0.7. It is advantageous. Furthermore, in terms of the more stable formation of the perovskite compound, in a more specific example, the precursor solution preferably contains the C component such that x is 0.5.

As a material pair of component B-C, in which the chalcogenated perovskite compound of Formula 11 can be prepared, the above-mentioned, II) nanoparticles which are halides of divalent metals-chalcogenides of trivalent metals, IV) Halides of divalent metals and halides of trivalent metals-Nanoparticles that are chalcogenides of trivalent metals, VI) Halides of divalent metals and halides of trivalent metals-Chalcogenides of divalent metals Phosphorus nanoparticles and trivalent metal chalcogenide nanoparticles and VIII) divalent metal halide-one or more selected from divalent metal chalcogenide nanoparticles and trivalent metal chalcogenide nanoparticles And substance sets.

The solvent for the halide contained in the precursor solution may be any solvent that dissolves the above-mentioned organic halide and a halide of a 2 to 4 metal. Specifically, the solvent for the halide may be a polar organic solvent, and as a specific and non-limiting example, the polar organic solvent is gamma-butyrolactone, formamide, dimethylformamide, diformamide, acetonitrile, tetra Hydrofuran, dimethylsulfoxide, diethylene glycol, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, acetone, α-terpineol, β-terpineol, dihydro terpineol , 2-methoxy ethanol, acetylacetone, methanol, ethanol, propanol, ketone, methyl isobutyl ketone, or the like, but is not limited thereto.

The solvent for the halide is sufficient as long as the amount of the organic halide (component A) and the halide of the 2 to 4 metal (component B) can be completely dissolved. As a specific and non-limiting example, the precursor solution may contain 0.1 to 100 parts by weight, specifically 1 to 50 parts by weight of a polar organic solvent, based on 1 part by weight of component A, which is an organic halide.

In the method for producing a chalcogenated perovskite compound according to an embodiment of the present invention, the precursor solution, together with the above-described A component, B component, C component and solvent, chalcogen source and at least chalcogen source It may further contain a soluble solvent (hereinafter referred to as a chalcogen solvent). The chalcogenide source may act as a source of another chalcogen element independent of the C component in the preparation of the chalcogenated perovskite compound.

A chalcogenated perovskite compound is prepared by a solid phase reaction, but based on a solution application method of applying a precursor solution, the chalcogen source is a heterogeneous organic/inorganic ligand (different to molecular) with different chalcogens. In the case of a compound combined with ), the risk of not producing a chalcogenated perovskite compound by simple solution application and low temperature heat treatment or producing a high quality chalcogenated perovskite compound by an undesired amount of impurities This is very big.

Accordingly, it is advantageous that the chalcogen source is a chalcogen (chalcogen metal) or a chalcogen compound selected from S, Se, and Te. In this case, the chalcogenide compound may include one chalcogenide compound selected from S, Se and Te, two or more chalcogenide compounds selected from S, Se and Te, or a combination thereof. As a specific and preferred example, the chalcogenide source may be one or two or more selected from S, Se, Te and S ₂ (disulfur).

As the precursor solution contains the chalcogen source together with the chalcogen solvent, the chalcogen source dissolved in the chalcogen solvent, specifically, the chalcogen dissolved in the chalcogen solvent (chalcogen metal) and/ Or it may contain a chalcogenide compound.

The chalcogen solvent may be a solvent that dissolves at least a chalcogen (chalcogen metal) to chalcogen compound. Specifically, the solvent for chalcogen may be a hydrazine-based solvent. The hydrazine-based solvent may be anhydrous hydrazine, hydrazine hydrate (N ₂ H ₄ ·xH ₂ O (1≤x≤5)), hydrazine derivative, hydrazine derivative hydrate, or a combination thereof.

Hydrazine derivatives or hydrazine derivatives in the hydrate state are methyl hydrazine, dimethyl hydrazine, ethylenediamine, 1,3-diaminopropane, and phenylenediamine , Ethylamine, propylamine, diethylamine, or a combination thereof.

The solvent for chalcogen is sufficient as long as the chalcogen source is sufficiently dissolved. As a specific example, the precursor solution may contain 10 to 10 ⁵ parts by weight of a chalcogen solvent, specifically a hydrazine-based solvent, based on 1 part by weight of a chalcogen source, preferably chalcogen (metal chalcogen). More specifically, the precursor solution may contain 50 to 10 ⁵ parts by weight of a hydrazine-based solvent, based on 1 part by weight of a chalcogen source, preferably chalcogen (metal chalcogen).

When the precursor solution further contains a chalcogen source and a solvent for chalcogen, the precursor solution together with the component A, the solvent for halide, and the solvent for chalcogen, any one or more of the material sets of I') to X') below It may contain.

I') Halides of divalent metals-Nanoparticles that are chalcogenides of tetravalent metals-Chalcogen source

II') Halides of divalent metals-Nanoparticles that are chalcogenides of trivalent metals-Chalcogen source

III') Halides of divalent metals and halides of tetravalent metals-Nanoparticles that are chalcogenides of tetravalent metals-Chalcogen source

IV') Halides of divalent metals and halides of trivalent metals-Nanoparticles that are chalcogenides of trivalent metals-Chalcogen source

V') Halides of divalent metals and halides of tetravalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of tetravalent metals-chalcogen source

VI') Halides of divalent metals and halides of trivalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of trivalent metals-chalcogen source

VII') Halides of divalent metals-Nanoparticles that are chalcogenides of divalent metals and Nanoparticles that are chalcogenides of tetravalent metals-Chalcogen source

VIII') Halides of divalent metals-Nanoparticles that are chalcogenides of divalent metals and Nanoparticles that are chalcogenides of trivalent metals-Chalcogen source

IX') Halides of Trivalent Metals-Chalcogenides of Trivalent Metals-Chalcogen Sources

X') Halide of tetravalent metal-Chalcogenide of tetravalent metal-Chalcogen source

Even when the precursor solution further contains a chalcogen source and a chalcogen solvent, the precursor solution is a monovalent organic cation derived from component A: a metal halide metal derived from component B, and a metal sword derived from component C. The molar ratio of the metal of the kogenide may satisfy 1:1. That is, the molar ratio of the monovalent organic cations contained in the precursor solution to the total metal contained in the precursor solution may satisfy 1:1.

When the precursor solution further contains a chalcogen source and a chalcogen solvent, the precursor solution contains a tetravalent metal chalcogenide nanoparticle as a C component, a tetravalent metal halide as a B component, or B As a component and a C component, a halide of a tetravalent metal and a chalcogenide nanoparticle of a tetravalent metal may be contained, and a tetravalent metal derived from a B component, a C component, or a B component and a C component in a precursor solution: a C component The molar ratio of chalcogenide (based on the element) derived from chalcogenide nanoparticles and chalcogen source of the 2-4 tetravalent metal may be 1:2.

That is, the precursor solution may include a B component, a C component, or a tetravalent metal (metal ion) derived from the B component and the C component, and may include a C component and a chalcogen derived from the chalcogen source, wherein , The total number of moles of the tetravalent metal contained in the precursor solution: The molar ratio between the C component and the chalcogen (based on the element) contained in the chalcogen source may satisfy 1:2. The molar ratio between the tetravalent metal ion and the chalcogen anion may be independent of whether the divalent metal ion is contained and the divalent metal ion content.

When the precursor solution further contains a chalcogen source and a solvent for chalcogen, the precursor solution is a substance pair containing a tetravalent metal, the aforementioned I') halide of a divalent metal-a chalcogen of a tetravalent metal Cargo nanoparticles-chalcogen source, III') divalent metal halide and tetravalent metal halide-tetravalent metal chalcogenide nanoparticles-chalcogen source, V') divalent metal halide And halides of tetravalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of tetravalent metals-chalcogen sources, VII') halides of divalent metals-chalcogens of divalent metals Cargo nanoparticles and tetravalent metal chalcogenide nanoparticles-chalcogen source, and X') tetravalent metal halide-tetravalent metal chalcogenide-a set of substances selected from chalcogen sources Can be lifted.

A component: The molar ratio between the metal of component B and the metal of component C satisfies 1:1, that is, the number of organic halides contained in the precursor solution: total metal contained in the precursor solution (metal ions derived from component B) And the ratio of the number of moles of the metal contained in the C component satisfies 1:1, and the total number of moles of the tetravalent metal contained in the precursor solution: the molar ratio between the C component and the chalcogen contained in the chalcogen source (based on the element) is 1 : When 2 is satisfied, a chalcogenated perovskite compound that satisfies the above formula (8) or the following formula (9) is prepared by a solid phase diffusion reaction by heat treatment in step b). Can be.

When the precursor solution further contains a chalcogen source and a chalcogen solvent, the precursor solution contains a trivalent metal chalcogenide nanoparticle as a C component, a trivalent metal halide as a B component, or B As a component and a C component, a halide of a trivalent metal and a chalcogenide nanoparticle of a trivalent metal may be contained, and a trivalent metal derived from the B component, C component, or B component and C component in the precursor solution: C component The molar ratio of chalcogenide (based on element) derived from chalcogenide nanoparticles and chalcogen source of the 2 to 4 valent metal may be 1:1.

That is, when the precursor solution further contains a chalcogen source and a chalcogen solvent, the precursor solution may include a B component, a C component, or a trivalent metal (metal ion) derived from the B component and the C component, wherein , The total number of moles of the trivalent metal contained in the precursor solution: The molar ratio between the C component and the chalcogen (based on the element) contained in the chalcogen source may satisfy 1:1. The molar ratio between the trivalent metal and the chalcogen may be independent of whether the divalent metal is contained and the divalent metal content.

When the precursor solution further contains a chalcogen source and a solvent for chalcogen, the precursor solution is a pair of substances containing a trivalent metal, as described above, II') a halide of a divalent metal-a chalcogen of a trivalent metal Cargo nanoparticles-chalcogen source, IV') divalent metal halide and trivalent metal halide-trivalent metal chalcogenide nanoparticles-chalcogen source, VI') divalent metal halide And halides of trivalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of trivalent metals-chalcogen sources, VIII') halides of divalent metals-chalcogens of divalent metals Nanoparticles that are cargoes and nanoparticles that are chalcogenides of trivalent metals-chalcogen sources, and IX') halides of trivalent metals-chalcogenides of trivalent metals-a set of one or more substances selected from chalcogen sources Can be lifted.

The number of moles of organohalides contained in the precursor solution: The ratio of the number of moles of the total metal (metal ions derived from component B and the metal contained in component C) contained in the precursor solution satisfies 1:1, and is contained in the precursor solution. When the molar ratio between the total number of moles of the trivalent metal:C component and the number of moles of chalcogen (based on the element) contained in the chalcogen source satisfies 1:1, by the solid phase diffusion reaction by heat treatment in step b), Chalcogenated perovskite compounds satisfying Formula 10 (including Formula 10'' below) or Formula 11 may be prepared.

When the precursor solution further contains a chalcogen source and a solvent for chalcogen, in order to stably dissolve each component in the solvent, components A and B are dissolved in a solvent for a halide, and the chalcogen source is a solvent for chalcogen. Of course, after dissolving in, it is advantageous to mix the two solutions. In this case, the C component can be added to the liquid in which the A component and the B component are dissolved, the liquid in which the chalcogen source is dissolved, or a mixed liquid of these two liquids.

In step a), the application of the precursor solution may be used as long as it is a method commonly used for application in a liquid or dispersed phase. As a specific example, application of the precursor solution may include deep coating, spin coating, casting, screen printing, inkjet printing, electrostatic hydraulic printing, micro contact printing, imprinting, gravure printing, reverse offset printing, or gravure offset printing. However, it is not limited thereto.

In step a), the precursor solution can be applied on a support, the support can be an optically transparent or opaque support, and can be a physically, flexible or rigid support. As an example of a flexible transparent support, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polycarbonate (PC), polypropylene (PP), triacetyl cellulose (TAC), polyethersulfone ( PES), polydimethylsiloxane (PDMS), and other polymer substrates, but are not limited thereto. An example of the rigid transparent support may be glass, but is not limited thereto. Furthermore, the support to which the precursor solution is applied not only serves to physically support the applied solution, but also in a device including a chalcogenated perovskite compound as a component, a lower configuration of the chalcogenated perovskite compound The element may be a preformed support. As a specific example, when the device is a photovoltaic device (solar cell), the support may include an electrode; Or a charge carrier and an electrode; may be a transparent substrate having a group. Of course, before application of the precursor solution, the components previously provided on the support can be appropriately changed according to a known structure of a device including a conventional organic-inorganic perovskite compound.

In step a), after drying of the precursor solution, natural drying, drying under reduced pressure, drying at a temperature of 100° C. or less, and drying by combinations thereof may be performed. Drying can optionally be performed if necessary.

By the step a), a precursor in which the C component nanoparticles are homogeneously dispersed and distributed can be prepared. At this time, the precursor may include an organometal halide produced by spontaneous crystallization, and the nanoparticles (component C) are homogenized in the form of inclusion in an organometal halide. It can be distributed. In addition, when the precursor solution further includes a chalcogen source and a chalcogen solvent, the precursor may further contain chalcogen in units of units to clusters.

Step b) is a step of heat-treating the precursor obtained in step a) to produce chalcogenide, and when heat treatment of step b), chalcogenide may be prepared by a solid phase diffusion reaction. In detail, by solid phase diffusion during heat treatment, the chalcogen element and the 2-4 tetravalent metal provided from nanoparticles, optionally nanoparticles, and chalcogen sources are supplied to the organometallic halide, and chalcogenide can be prepared. It is a matter of course that during the heat treatment for the solid-state reaction, an excess amount of halogen contained in the precursor (which exceeds the content according to Chemical Formulas 8 to 11) can be removed with a halogen (Hal ₂ gas) gas.

The heat treatment of step b) for solid phase reaction may be performed at 100 to 250°C, specifically 100 to 200°C. The heat treatment may be performed in an inert atmosphere or a hydrogen atmosphere, but is not limited thereto. In this case, the inert atmosphere may be nitrogen, argon, helium, or a mixed gas atmosphere thereof, and the hydrogen atmosphere may be hydrogen gas itself or an inert gas atmosphere containing hydrogen. The inert gas containing hydrogen may contain 1 to 80% by volume of hydrogen, but is not limited thereto.

(Example 1)

Dimethylformamide is used as a polar organic solvent and mixed so that 0.5 mol of PbI ₂ (1 mol based on I) and 0.5 mol of SnS ₂ nanoparticles (average size 7 nm) (1 mol based on S) relative to 1 mol of CH ₃ NH ₃ I To prepare a precursor solution, coat it on a substrate, and heat-treat it in an inert atmosphere at 200° C. to CH ₃ NH ₃ Pb ^II _0.5 Sn ^IV _0.5 I ₂ S[0.5(CH ₃ NH ₃ Pb ^II I ₃ )/0.5(CH ₃ NH ₃ Sn ^IV IS ₂ )] was prepared (double) perovskite compound. As a result of X-ray diffraction analysis, it was confirmed that the perovskite crystal phase was well formed.

(Example 2)

Dimethylformamide as a polar organic solvent, 0.5 mol of SnI ₂ (1 mol based on I), 0.5 mol of PbS nanoparticles (average size 4 nm) (0.5 mol based on S), and anhydrous hydrazine relative to 1 mol of CH ₃ NH ₃ I ( Anhydrous hydrazine) dissolved in S ₂ 0.25 moles (0.5 moles based on S) to prepare a precursor solution, coated on a substrate, and then heat-treated at 200° C. in an inert atmosphere for CH ₃ NH ₃ Pb ^II _0.5 Sn ^IV _0.5 I _A double perovskite compound of ₂ S [0.5 (CH ₃ NH ₃ Pb ^II I ₃ )/0.5 (CH ₃ NH ₃ Sn ^IV IS ₂ )] was prepared. As a result of X-ray diffraction analysis, it was confirmed that the perovskite crystal phase was well formed.

As described above, the present invention has been described by specific matters and limited embodiments and drawings, but it is provided to help a more comprehensive understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention Various modifications and variations can be made by those skilled in the art.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and should not be determined, and all claims that are equivalent or equivalent to the scope of the claims as well as the claims described below belong to the scope of the spirit of the invention. .

Claims (17)

a) As component A, a halide of a monovalent organic ammonium ion; As a component B, a metal halide selected from one or more of halide of tetravalent metal and halide of divalent metal; C component, nanoparticles that are chalcogenides of divalent metals or tetravalent metals; And a solvent for dissolving components A and B; forming a precursor by applying a precursor solution comprising the precursor; And
b) a metal ion selected from at least one selected from divalent metal ions and tetravalent metal ions derived from the monovalent organic cation and the B component, and having a perovskite structure by heat-treating the precursor; Chalcogenated organic-inorganic waste containing bivalent or tetravalent metal ions derived from component C and containing halogen anions derived from component A and component B and chalcogen anions derived from component C as anions. A method of manufacturing a chalcogenated organic-inorganic perovskite compound comprising the steps of preparing a lob-sky compound. According to claim 1,
The precursor solution of step a) is a component B-C, a chalcogenated organic-inorganic perovskite compound containing at least one of the following material sets of I), III), V), VII), and X) Method of manufacturing.
I) Halogens of divalent metals-Nanoparticles that are chalcogenides of tetravalent metals
III) Halides of divalent metals and halides of tetravalent metals-nanoparticles that are chalcogenides of tetravalent metals
V) Halides of divalent metals and halides of tetravalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of divalent metals
VII) Halides of divalent metals-nanoparticles that are chalcogenides of divalent metals and nanoparticles that are chalcogenides of tetravalent metals
X) Halides of tetravalent metals-Chalcogenides of tetravalent metals According to claim 1,
The precursor solution is a chalcogenide organic/inorganic waste material having a molar ratio of monovalent organic cations derived from component A: metal halide metal derived from component B and metal chalcogenide derived from component C: 1 Method of manufacturing a lobsky compound. According to claim 1,
The precursor solution contains chalcogenide nanoparticles of a tetravalent metal as a C component, a tetravalent metal halide as a B component, or a tetravalent metal halide and a tetravalent metal as a B component and a C component. Contains a chalcogenide nanoparticle, a tetravalent metal derived from the B component, C component or B component and C component in the precursor solution: derived from the chalcogenide nanoparticle of the divalent or tetravalent metal of the C component Method for producing a chalcogenated organic-inorganic perovskite compound having a molar ratio of chalcogen to 1:2.
delete According to claim 3,
The precursor solution is a chalcogen or a chalcogen source which is a compound between chalcogens; And at least a solvent for dissolving the chalcogen source; wherein the chalcogen is selected from S, Se, and Te, or two or more, and the chalcogen compound is selected from S, Se, and Te. A method for producing a chalcogenated organic-inorganic perovskite compound that is a chalcogenide compound of S, Se, Se, and two or more chalcogenide compounds selected from or combinations thereof.
delete The method of claim 6,
The solvent for dissolving the chalcogen source is anhydrous hydrazine, hydrazine hydrate, methyl hydrazine, dimethyl hydrazine, ethylenediamine, 1,3-diaminopropane (1,3-diaminopropane), phenylenediamine, ethylamine, propylamine, diethylamine, or a combination of chalcogenated organic and inorganic perovskite compounds Manufacturing method.

delete delete The method of claim 6,
The precursor solution contains chalcogenide nanoparticles of a tetravalent metal as a C component, a tetravalent metal halide as a B component, or a tetravalent metal halide and a tetravalent metal as a B component and a C component. Contains a chalcogenide nanoparticle, a tetravalent metal derived from the B component, C component, or B component and C component in the precursor solution: chalcogenide nanoparticles and chalcogen of the 2-4 tetravalent metal of the C component Method for producing a chalcogenated organic-inorganic perovskite compound having a molar ratio of chalcogen derived from a source of 1:2. delete According to claim 1,
In the B component, the metal of the halide of the tetravalent metal and the halide of the divalent metal are different metals, and in the B component, the halide of the tetravalent metal is titanium (Ti), tin (Sn), cerium Halogen of a metal selected from (Ce), zirconium (Zr), molybdenum (Mo) and tungsten (W), and in the B component, the halide of the divalent metal is copper (Cu), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), chromium (Cr), palladium (Pd), cadmium (Cd), germanium (Ge), tin (Sn), lead (Pb) and Method for producing a chalcogenated organic-inorganic perovskite compound which is a halide of one or more metals selected from ytterbium (Yb). According to claim 1,
In the component C, the chalcogenide of the divalent metal and the chalcogenide of the tetravalent metal are chalcogenides of different metals, and the chalcogenide of the divalent metal satisfies the following formula (1), and the knife of the tetravalent metal Cogenide is a method for producing a chalcogenated organic-inorganic perovskite compound satisfying the following Chemical Formula 3.
(Formula 1)
MaChal
(In Formula 1, Ma is Cu ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ²⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Pb ²⁺ and in the Yb ²⁺ is a divalent metal ion selected at least one, or both, Chal is S ^-, Se ^- Te and ^- in a knife kojen anion selected more than one or two)
(Formula 3)
McChal ₂
(In the formula 3, Mc is ^{Ti 4+, Sn 4+, Ce 4+} , Zr 4+, Mo , and one or metal ions, tetravalent selected two or more in the ⁴⁺ and W ^4+, Chal is S ^-, Se ^- And Te ^- is a chalcogen anion selected from one or more) According to claim 1,
Method for producing a chalcogenated organic-inorganic perovskite compound having an average diameter of the C component nanoparticles of 0.5 nm to 20 nm. According to claim 1,
The heat treatment of step b) is a method for producing a chalcogenated organic-inorganic perovskite compound performed at 100 to 250°C. According to claim 1,
The heat treatment of step b) is a method for producing a chalcogenated organic-inorganic perovskite compound performed in an inert atmosphere or a hydrogen atmosphere.