KR102307523B1 - Manufacuring method for polyphosphide precursor, manufacuring method for crystalline red phosphorus thin film and electronic device application - Google Patents

Abstract

The present invention relates to a method for preparing a polyphosphide precursor, a method for manufacturing a crystalline red phosphorus thin film, and application to an electronic device. ) to prepare a suspension by dissolving it in a solvent; heating the suspension; cooling the heated suspension to room temperature; separating the supernatant by centrifuging the cooled suspension; and purifying the supernatant to obtain a polyphosphide precursor; and passing the obtained polyphosphide precursor through an ion exchange resin.

Description

Manufacturing method of polyphosphide precursor, manufacturing method of crystalline red phosphorus thin film, and application of electronic device

The present invention relates to a method for preparing a polyphosphide precursor, a method for preparing a crystalline red phosphorus thin film, and application to an electronic device.

As the excellent electrical conductivity and charge mobility of graphene, a representative two-dimensional material, were discovered, great expectations were raised as a material for next-generation displays, electronic devices, and optoelectronic devices. It has limitations. Accordingly, black phosphorus received new attention as a two-dimensional material with a bandgap in its natural state, and the method of removing graphene was applied to black phosphorus, and several layers of the two-dimensional original layer were successfully removed. As it was revealed that this material has the highest electron mobility among two-dimensional semiconductor materials, it received explosive attention.

However, black phosphorus has a disadvantage in that it is easily oxidized when exposed to air and is quite expensive at about 1,700 $ per 1 g, as the manufacturing method is quite difficult. Therefore, many researchers are interested in cheap red phosphorus, which is another allotrope of black phosphorus, and in particular, red phosphorus with semiconductor properties has been reported very recently, and research is being actively conducted in various fields using it.

In general, the red phosphorus present is almost entirely composed of an amorphous phase. A type having crystallinity among allotropes of red phosphorus has been discovered relatively recently, and it has been reported that this type of red phosphorus has unique semiconductor properties.

However, to produce amorphous red phosphorus into crystalline red phosphorus, chemical vapor deposition (CVD) method is used to place amorphous red phosphorus in a sealed glass tube on a silicon substrate and requires addition of mineral materials and high-temperature heat treatment, so the synthesis process is quite difficult. There is a tricky problem.

The present invention is to solve the above problems, and an object of the present invention is to provide a polyphosphide capable of easily producing crystalline semiconductor red phosphorus at a relatively low temperature without complicated processes and any additives required to produce the crystalline semiconductor red phosphorus. An object of the present invention is to provide a method for preparing a precursor, a method for manufacturing a crystalline red phosphorus thin film, and an electronic device.

However, the problems to be solved by the present invention are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

A method for preparing a polyphosphide precursor according to an embodiment of the present invention includes preparing a suspension by dissolving red phosphorus powder in a solvent; heating the suspension; cooling the heated suspension to room temperature; separating the supernatant by centrifuging the cooled suspension; and purifying the supernatant to obtain a polyphosphide precursor.

In an embodiment, the preparing a suspension by dissolving the red phosphorus powder in a solvent may include dissolving the red phosphorus powder and a base in a polar solvent.

In one embodiment, the base is KOEt, t BuOK, LiHMDS, NaHMDS, MeONa, EtONa, t BuONa, n BuLi, K ₂ CO ₃ , Cs ₂ CO ₃ , K ₃ PO ₄ , DIPEA, NMM, DMAP, At least one selected from the group consisting of KOMe and Et ₃ N, wherein the polar solvent is dimethyl ether (DME), tetrahydrofuran (THF), dimethylformamide (DMF), N-methylformamide (NMF) ), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethylenediamine (En), formamide (FA), and may include at least one selected from the group consisting of dimethylacetamide .

In one embodiment, the heating of the suspension may be performed in a temperature range of room temperature to 100° C., and refluxing the suspension with cold water.

In one embodiment, the step of centrifuging the cooled suspension to separate the supernatant may include removing the residual solvent of the cooled suspension and then performing centrifugation by adding an organic solvent.

In one embodiment, the organic solvent is ethanol (EtOH), methanol (MeOH), propanol (PrOH), butanol (BuOH), isopropyl alcohol (IPA), isobutyl alcohol, dimethylacetamide (DMAC), dimethyl Formamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), triethylene phosphate (Triethylphosphate), trimethyl phosphate (Trimethylphosphate), hexane, benzene, toluene, xylene, acetone, methyl ethyl ketone (MEK), It may include at least one selected from the group consisting of methyl isobutyl ketone (MIBK), diisobutyl ketone, ethyl acetate, butyl acetate, dioxane, and diethyl ether.

In one embodiment, in the step of purifying the supernatant to obtain the polyphosphide precursor, an extraction organic solvent is added to the supernatant to precipitate a supernatant obtained from the crude solution, and then centrifugation is performed to perform a polyphosphide precursor. obtaining a; The polyphosphide precursor may be dissolved in a polar solvent and purified by adding a non-solvent; and may be to remove impurities by repeating the purification process using the non-solvent.

In one embodiment, the extraction organic solvent is chloroform (CHCl ₃ ), dichloromethane (CH ₂ Cl ₂ ), dichloroethane, diethyl ether, tetrahydrofuran, toluene, acetonitrile, tetrachloroethane, dioxane and At least one selected from the group consisting of acetone, and the polar solvent is dimethyl ether (DME), tetrahydrofuran (THF), dimethylformamide (DMF), N-methylformamide (NMF), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethylenediamine (En), formamide (FA) and at least one selected from the group consisting of dimethylacetamide, the non-solvent is iso From the group consisting of propyl alcohol, methyl ketone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dibutyl ketone, cyclohexanone, diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, ethyl acetate and methanol It may include at least any one selected.

In one embodiment, after the step of purifying the supernatant to obtain a polyphosphide precursor, passing the obtained polyphosphide precursor through an ion exchange resin; may further include.

In one embodiment, the step of passing the obtained polyphosphide precursor through an ion exchange resin, adding the obtained polyphosphide precursor in NMF with ^{K +} _{as a counter ion to NH 4} ⁺ resin beads to NH ₄ ^{A polyphosphide solution having +} may be centrifuged to prepare an ammonium polyphosphide solution.

A method for producing a crystalline red phosphorus thin film according to another embodiment of the present invention comprises the steps of preparing a polyphosphide precursor; coating the polyphosphide precursor on a substrate; and heat-treating the coated polyphosphide.

In one embodiment, the step of preparing the polyphosphide precursor may be prepared by the method for preparing a polyphosphide precursor according to an embodiment of the present invention.

In an embodiment, the coating of the polyphosphide precursor on the substrate is performed using the solution process, and the solution process is spin coating, drop casting, or dip. dip coating, roll coating, screen coating, spray coating, spin casting, flow coating, screen printing and inkjet printing (ink jet printing) and roll-to-roll (roll-to-roll) may include at least one selected from the group consisting of.

In one embodiment, the heat treatment is to be performed in a temperature range of 100 °C to 300 °C, and the heat treatment may be performed in air, nitrogen, argon, carbon monoxide, hydrogen, or a gas mixture thereof.

A crystalline red phosphorus thin film according to another embodiment of the present invention is manufactured by the method for manufacturing a crystalline red phosphorus thin film according to an embodiment of the present invention.

Polyphosphide precursor-capped nanoparticles according to another embodiment of the present invention, nanoparticles; and an inorganic ligand comprising a polyphosphide precursor coated on the surface of the nanoparticles.

In one embodiment, the nanoparticles may include at least one selected from the group consisting of a metal material, a semiconductor material, a magnetic material, a magnetic alloy, or a multi-component hybrid structure material.

In one embodiment, the nanoparticles are CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InP, InAs, InSb, SiC, PbS, Fe , Pt, Ni, Co, Al, Ag, Au, Cu, FePt, Fe ₂ O ₃ , Fe ₃ O ₄ , Ge, (NaYF ₄ :Yb ³⁺ ,Er ³⁺ ), (NaYF ₄ :Yb ³⁺ , Tm ³⁺ ), (NaGdF ₄ :Yb ³⁺ ,Er ³⁺ ), (NaYF ₄ :Yb ³⁺ ,Er ³⁺ /NaGdF ₄ ) and (NaGdF ₄ :Yb ³⁺ ,Er ³⁺ /NaGdF ₄ ) It may include at least one selected from the group consisting of.

In one embodiment, the attachment region of the inorganic ligand formed on the surface of the nanoparticles is -COOH, -NH ₂ , -(O)P(OH) ₂ , -SH and R ₃ N (where R is C1 to C24 alkyl group or C5 to C20 aryl group) may include at least one functional group selected from the group consisting of).

A nanoparticle-embedded fibrous phosphorus thin film according to another embodiment of the present invention includes polyphosphide precursor-capped nanoparticles according to an embodiment of the present invention.

An electronic device according to another embodiment of the present invention includes a crystalline red phosphorus thin film or a nanoparticle-embedded fibrous phosphorus thin film.

In an embodiment, the electronic device may include at least one functional group selected from the group consisting of a field effect transistor, a photosensor, a photodetector, a capacitor, a light emitting diode, and an image sensor.

The method for manufacturing a crystalline red phosphorus thin film according to an embodiment of the present invention can easily make a crystalline semiconductor red phosphorus thin film form at a relatively low temperature without expensive equipment and additives essential for the existing bulk or micro-scale crystalline semiconductor red phosphorus production method. It has great value in that it can be used, and since the manufactured thin film has semiconductor characteristics, it is expected to be widely applied to various electronic devices including field effect transistors and optical sensors based on this.

The solution process-based crystalline red phosphorus manufacturing technology according to an embodiment of the present invention has the advantage of being able to manufacture a large area on a desired substrate without limitation of a specific substrate, and at the same time does not require expensive equipment and complicated manufacturing steps required for manufacturing. Production cost can be significantly reduced.

The crystalline semiconductor red phosphorus produced as a thin film through an ink based on a polyphosphide precursor has semiconductor properties due to the characteristics of the material, so it can operate as a field effect transistor, a typical semiconductor device. In addition, since the developed ink contains polyphosphide anions, it can be used as an inorganic ligand on the surface of nanoparticles. Through this, a crystalline semiconductor red phosphorus thin film having a nanohetero structure containing nanoparticles capped with polyphosphide was ultimately prepared, and it was confirmed that the photoreactivity could be further improved through the introduction of nanoparticles.

1 is a view showing a crystalline semiconductor red thin film manufacturing process through a solution process according to an embodiment of the present invention.
2 is a photograph of a polyphosphide precursor solution dissolved in a polar solvent according to an embodiment of the present invention (DMF, DMSO, En, FA and NMF).
3 is an ESI-MS spectrum of a polyphosphide precursor solution purified in negative ionization mode according to an embodiment of the present invention.
4 is (a) SEM image of a fibrous red phosphorus thin film annealed at 250 ° C according to an embodiment of the present invention (inset is a _{photograph of a thin film on a Si/SiO 2} substrate), (b) polyphosphide precursor solution (black), dried UV-vis absorption spectra of (blue) and (red) phosphorus thin films annealed at 250 °C, (c) Raman spectra of fibrous red phosphorus thin films deposited on _{glass (black) or Si/SiO 2 (red) substrates, (d)} ) HRTEM images of solution-processed fibrous red phosphorus (inset shows corresponding SAED patterns).
5 is a scheme of a ligand exchange process between an inorganic polyphosphide ligand and nanoparticles according to an embodiment of the present invention.
Figure 6 shows Au nanoparticles and prepared polyphosphide-capped Au, InP, CdSe, PbS, FePt and NaGdF according to an embodiment of the present invention ₄ :Yb, Er nanoparticles for nanoparticles dispersed in NMF 2 A photograph showing the phase ligand exchange reaction.
7 is polyphosphide-capped nanoparticles according to an embodiment of the present invention (a) Au, (b) InP, (c) CdSe, (d) PbS, (e) FePt and (f) NaGdF ₄ :Yb , are TEM images of Er.
8 shows (a) absorption and (b) PL spectra of (black) organic and (red) polyphosphide-capped CdSe nanoparticles and (blue) polyphosphide precursor solutions according to an embodiment of the present invention, (c) ) FT-IR spectra of organic- and polyphosphide-capped nanoparticles of CdSe, FePt, PbS, InP and Au, (d) polyphosphide-capped FePt, PbS and CdSe nanoparticles and polyphosphide precursor solutions represents the ζ potential distribution of .
9 is a schematic diagram and an optical microscope image of an FET according to an embodiment of the present invention.
_{10 is a graph showing (a) Transfer (I D} vs V _G ) and (b) Output (I _D vs V _D ) characteristics of an FET having a fibrous red phosphorus thin film according to an embodiment of the present invention.
11 is a schematic diagram of an optical sensor made of crystalline red phosphorus according to an embodiment of the present invention and a graph of optical sensor characteristics of a nanoparticle-crystalline red phosphorus complex.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. In addition, the terms used in this specification are terms used to properly express the preferred embodiment of the present invention, which may vary according to the intention of the user or operator or customs in the field to which the present invention belongs. Accordingly, definitions of these terms should be made based on the content throughout this specification. Like reference numerals in each figure indicate like elements.

Throughout the specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

Throughout the specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components.

Hereinafter, the method for preparing the polyphosphide precursor of the present invention, the method for preparing the crystalline red phosphorus thin film, and the application of electronic devices will be described in detail with reference to Examples and drawings. However, the present invention is not limited to these examples and drawings.

Crystalline red phosphorus has recently emerged as a stable and cost-effective semiconductor material. However, despite its potential in electronic and optoelectronic fields, the widespread application of this material is still hampered by the limited synthetic route of ampoule-based chemical vapor deposition, which requires mineralizing agents. To solve this problem, we provide in the present invention the chemical synthesis of a soluble polyphosphide precursor that serves as an ink for a thin film fabrication solution, which is a crystalline fiber. The purified polyphosphide precursor formed crystalline fibrous phosphorus through thermal annealing at a low temperature of 250 °C without mineralizer. This anionic polyphosphide served as a surface-capping ligand for nanoparticles including metals, semiconductors and magnets.

Therefore, the present invention investigates the potential of solution-treated fibrous phosphorus thin films as active channel layers in field effect transistors and photodetectors and demonstrates the photoresponse properties and initial performance for charge transport of these devices. The effect of semiconducting PbS nanoparticles embedded in fibrous phosphorus thin films on device performance was also studied. The synthesized polyphosphide precursors offer a wide range of opportunities for the facile preparation of ritalin red phosphorus and the chemical design of nanoparticles.

A method for preparing a polyphosphide precursor according to an embodiment of the present invention includes preparing a suspension by dissolving red phosphorus powder in a solvent; heating the suspension; cooling the heated suspension to room temperature; separating the supernatant by centrifuging the cooled suspension; and purifying the supernatant to obtain a polyphosphide precursor.

In one embodiment, the step of preparing the suspension by dissolving the red phosphorus powder in a solvent may include preparing the red phosphorus powder and the base in a polar solvent.

In one embodiment, the base is KOEt, t BuOK, LiHMDS, NaHMDS, MeONa, EtONa, t BuONa, n BuLi, K ₂ CO ₃ , Cs ₂ CO ₃ , K ₃ PO ₄ , DIPEA, NMM, DMAP, It may include at least one selected from the group consisting of KOMe and Et _{3 N.}

In an embodiment, the polar solvent is dimethyl ether (DME), tetrahydrofuran (THF), dimethylformamide (DMF), N-methylformamide (NMF), N,N-dimethylformamide (DMF) , dimethyl sulfoxide (DMSO), ethylenediamine (En), formamide (FA), and may include at least one selected from the group consisting of dimethylacetamide.

In the present invention, for example, red phosphorus powder is mixed with potassium ethoxide (KOEt) as a base to form a mixture, and the mixture is mixed with dimethyl ether (DME)/tetrahydrofuran (THF) as a polar solvent (1: 1 v/v).

In one embodiment, the heating of the suspension may be performed in a temperature range of room temperature to 100 °C. It may be heating at a temperature less than the boiling point of the polar solvent. It is preferred not to heat the solution above the boiling point of any component in the suspension. In the present invention, for example, it may be carried out in a temperature range of 60 ℃ to 90 ℃, 70 ℃ to 80 ℃.

In one embodiment, the suspension may be refluxed with cold water. Reflux by cold water may proceed simultaneously from the step of heating the suspension, and the reflux may continue even in the step of cooling the heated suspension. Reflux with cold water is more important in the step of heating the suspension than in the step of cooling the heated suspension.

In one embodiment, the step of centrifuging the cooled suspension to separate the supernatant may include removing the residual solvent of the cooled suspension and then performing centrifugation by adding an organic solvent.

In one embodiment, the residual solvent of the cooled suspension may be removed by flowing _{N 2 .}

In one embodiment, the organic solvent is ethanol (EtOH), methanol (MeOH), propanol (PrOH), butanol (BuOH), isopropyl alcohol (IPA), isobutyl alcohol, dimethylacetamide (DMAC), dimethyl Formamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), triethylene phosphate (Triethylphosphate), trimethyl phosphate (Trimethylphosphate), hexane, benzene, toluene, xylene, acetone, methyl ethyl ketone (MEK), It may include at least one selected from the group consisting of methyl isobutyl ketone (MIBK), diisobutyl ketone, ethyl acetate, butyl acetate, dioxane, and diethyl ether.

In one embodiment, the suspension from which the residual solvent has been removed can be obtained by adding absolute ethanol (EtOH) to the organic solvent to form a residue with a supernatant of the dark red suspension, and separating the dark red suspension into a supernatant. . The precipitate can then be precipitated by centrifugation.

In one embodiment, in the step of purifying the supernatant to obtain the polyphosphide precursor, an extraction organic solvent is added to the supernatant to precipitate a supernatant obtained from the crude solution, and then centrifugation is performed to perform a polyphosphide precursor. obtaining a; The method may further include dissolving the polyphosphide precursor in a polar solvent and purifying it by adding a non-solvent.

In one embodiment, the extraction organic solvent is chloroform (CHCl ₃ ), dichloromethane (CH ₂ Cl ₂ ), dichloroethane, diethyl ether, tetrahydrofuran, toluene, acetonitrile, tetrachloroethane, dioxane and It may include at least one selected from the group consisting of acetone. While the dissolution and precipitation are repeatedly performed by the extraction organic solvent, impurities other than the polyphosphide precursor, which is the target object to be obtained, remain eluted in the solution phase and removed, thereby improving the purity.

In an embodiment, the polar solvent is dimethyl ether (DME), tetrahydrofuran (THF), dimethylformamide (DMF), N-methylformamide (NMF), N,N-dimethylformamide (DMF) , dimethyl sulfoxide (DMSO), ethylenediamine (En), formamide (FA), and may include at least one selected from the group consisting of dimethylacetamide.

In one embodiment, the non-solvent is isopropyl alcohol, methyl ketone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dibutyl ketone, cyclohexanone, diethyl ether, dipropyl ether, dibutyl ether, tetra It may include at least one selected from the group consisting of hydrofuran, ethyl acetate and methanol.

In one embodiment, the impurities may be effectively removed by repeating the purification process using the non-solvent.

In one embodiment, the supernatant obtained from the crude solution can be precipitated by addition _{of chloroform (CHCl 3} ) as the extraction organic solvent followed by centrifugation. Then, the purified polyphosphide precursor may be dissolved in N-methylformamide (NMF) as a polar solvent, and repurified by adding isopropyl alcohol (IPA) as a non-solvent.

In the present invention, centrifugation may be performed for 1 minute to 10 minutes at a rotation speed of 100 rpm to 20000 rpm, 1000 rpm to 19000 rpm, 3000 rpm to 15000 rpm, or 5000 rpm to 14000 rpm. The supernatant can be easily recovered at the above centrifugation rotation speed and time, and energy waste can be minimized.

In one embodiment, after the step of purifying the supernatant to obtain a polyphosphide precursor, passing the obtained polyphosphide precursor through an ion exchange resin; may further include.

In one embodiment, the step of passing the obtained polyphosphide precursor through an ion exchange resin, adding the obtained polyphosphide precursor in NMF with ^{K +} _{as a counter ion to NH 4} ⁺ resin beads to NH ₄ ^{A polyphosphide solution having +} may be centrifuged to prepare an ammonium polyphosphide solution.

In one embodiment, the NH ₄ ⁺ resin beads may be prepared by mixing an acidic resin bead having ^{H +} _{as a cation with an aqueous solution of NH 4 Cl.}

In one embodiment, the obtained polyphosphide precursor _{is added to the NH 4} ⁺ resin bead of the ion exchange resin, vortexed and then centrifuged to separate from the resin bead, and toluene is added to the polyphosphide having _{NH 4} ⁺ The pid solution can be recovered. This process can be repeated 2 to 5 times to obtain a stable solution of ammonium polyphosphide by dissolving the last precipitate in N-methylformamide (NMF).

In one embodiment, the polyphosphide precursor may be used by dissolving it in various polar solvents.

In an embodiment, the polar solvent is dimethyl ether (DME), tetrahydrofuran (THF), dimethylformamide (DMF), N-methylformamide (NMF), N,N-dimethylformamide (DMF) , dimethyl sulfoxide (DMSO), ethylenediamine (En), formamide (FA), and may include at least one selected from the group consisting of dimethylacetamide.

The method for preparing a polyphosphide precursor according to an embodiment of the present invention can easily prepare a solution polyphosphide precursor without any additives.

A method for producing a crystalline red phosphorus thin film according to another embodiment of the present invention comprises the steps of preparing a polyphosphide precursor; coating the polyphosphide precursor on a substrate; and heat-treating the coated polyphosphide.

1 is a view showing a crystalline semiconductor red thin film manufacturing process through a solution process according to an embodiment of the present invention.

Figure 1 (a) is a process of centrifugation during the process of preparing a polyphosphide precursor, Figure 1 (b) is a process for purifying the supernatant, Figure 1 (c) is a process for preparing a purified polyphosphide precursor indicates

In one embodiment, the step of preparing the polyphosphide precursor may be prepared by the method for preparing a polyphosphide precursor according to an embodiment of the present invention.

Figure 1 (d) shows a process of coating a polyphosphide precursor on a substrate.

In one embodiment, the substrate is not particularly limited, but at least one selected from the group consisting of silicon, metal, glass, ceramic, plastic film such as polyester or polyimide, rubber sheet, fiber, wood, and paper. may include. The substrate can be used after washing and degreasing, or it can be used after special pretreatment. The pretreatment method includes plasma, ion beam, corona, oxidation or reduction, heat, etching, ultraviolet (UV) irradiation, and a primer using a binder or additive. processing and the like can be exemplified.

In one embodiment, the coating of the polyphosphide precursor on the substrate may be performed using the solution process.

In one embodiment, the solution process is spin coating (spin coating), drop casting (drop casting), dip coating (dip coating), roll coating (roll coating), screen coating (screen coating), spray coating (spray) coating), spin casting, flow coating, screen printing and ink jet printing and roll-to-roll selected from the group consisting of It may include at least one.

In one embodiment, the solution process is a method of liquefying a material to be used using an organic solvent or the like, and then depositing it on a specific substrate by a technique such as spin coating or inkjet printing. Compared to the vacuum deposition method, this method has the advantage of being able to fabricate a device cheaply and quickly because it has a lower facility investment cost and faster process progress with small-scale equipment, thereby securing high applicability of the device.

1(e) shows a process of forming a crystalline red phosphorus thin film by heat treatment.

In one embodiment, the heat treatment may be performed in a temperature range of 100 °C to 300 °C. The heat treatment temperature may be 150 °C to 250 °C. For example, the coated polyphosphide precursor is thinned by heating at a rate of 5° C./min to 10° C. to reach a temperature in the above range. When the heating temperature is less than 100 °C, there is a problem that sufficient crystallinity does not occur, and when it is more than 300 °C, a problem of exceeding the boiling point of the solvent used as the reaction solvent occurs.

In one embodiment, the heat treatment may be performed in air, nitrogen, argon, carbon monoxide, hydrogen, or a mixed gas condition thereof.

The method for producing a crystalline red phosphorus thin film according to an embodiment of the present invention is a polyphosphide precursor dissolved without any additives at a relatively low temperature without expensive equipment and additives essential for the existing bulk or micro-scale crystalline semiconductor red phosphorus production method. can be used to easily prepare a crystalline red phosphorus thin film. In addition, it has the advantage of being able to manufacture a large area on a desired substrate without limitation of a specific substrate, and at the same time, expensive equipment and complicated manufacturing steps required for manufacturing are not required, so that the production cost can be greatly reduced. Therefore, overall manufacturing cost can be reduced compared to the prior art, and it can contribute to the commercialization of electronic devices based on this.

A crystalline red phosphorus thin film according to another embodiment of the present invention is manufactured by the method for manufacturing a crystalline red phosphorus thin film according to an embodiment of the present invention.

The crystalline red phosphorus thin film according to an embodiment of the present invention can be manufactured on a desired substrate with a large area. If the manufacturing process of the crystalline semiconductor red phosphorus thin film developed in the future can be optimized and comparable to the electrical properties of black phosphorus, it is expected to be widely used as a next-generation semiconductor material by replacing expensive black phosphorus with crystalline red phosphorus made from cheap red phosphorus as a raw material.

Polyphosphide precursor-capped nanoparticles according to another embodiment of the present invention, nanoparticles; and an inorganic ligand comprising a polyphosphide precursor coated on the surface of the nanoparticles.

In one embodiment, the polyphosphide precursor-capped nanoparticles are pre- Inorganic nanoparticles can be prepared. Since the prepared polyphosphide precursor ink contains polyphosphide anions, it can be used as an inorganic ligand on the surface of nanoparticles.

In one embodiment, the nanoparticles may include at least one selected from the group consisting of a metal material, a semiconductor material, a magnetic material, a magnetic alloy, or a multi-component hybrid structure material.

In one embodiment, the nanoparticles are CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InP, InAs, InSb, SiC, PbS, Fe , Pt, Ni, Co, Al, Ag, Au, Cu, FePt, Fe ₂ O ₃ , Fe ₃ O ₄ , Ge, (NaYF ₄ :Yb ³⁺ ,Er ³⁺ ), (NaYF ₄ :Yb ³⁺ , Tm ³⁺ ), (NaGdF ₄ :Yb ³⁺ ,Er ³⁺ ), (NaYF ₄ :Yb ³⁺ ,Er ³⁺ /NaGdF ₄ ) and (NaGdF ₄ :Yb ³⁺ ,Er ³⁺ /NaGdF ₄ ) It may include at least one selected from the group consisting of.

In one embodiment, the attachment region of the inorganic ligand formed on the surface of the nanoparticles is -COOH, -NH ₂ , -(O)P(OH) ₂ , -SH and R ₃ N (where R is C1 to C24 alkyl group or C5 to C20 aryl group) may include at least one functional group selected from the group consisting of).

The polyphosphide precursor-capped nanoparticles according to an embodiment of the present invention can prepare a crystalline semiconductor red thin film having a nanohetero structure. Therefore, it is expected to be widely used as a next-generation semiconductor material.

Nanoparticle-embedded fibrous phosphorus thin films according to another embodiment of the present invention include polyphosphide precursor-capped nanoparticles according to an embodiment of the present invention.

An electronic device according to another embodiment of the present invention includes a crystalline red phosphorus thin film or a nanoparticle-embedded fibrous phosphorus thin film.

In an embodiment, the electronic device may include at least one functional group selected from the group consisting of a field effect transistor, a photosensor, a photodetector, a capacitor, a light emitting diode, and an image sensor.

The electronic device according to an embodiment of the present invention can operate as an N-type field effect transistor, which is a typical semiconductor device, because the crystalline semiconductor red phosphorus manufactured as a thin film has semiconductor properties due to the characteristics of the material. In addition, the optical sensor using the polyphosphide precursor-capped nanoparticles can further improve the photoreactivity.

Hereinafter, the present invention will be described in detail with reference to the following Examples and Comparative Examples. However, the technical spirit of the present invention is not limited or limited thereto.

[Example]

ingredient

Potassium ethoxide (KOEt, 95 %, Aldrich), red phosphorus powder (Pred, -100 mesh, 98.9 %, Alfa Asear), 1,2-dimethoxyethane; DME , anhydrous, 99.5 %, Aldrich), tetrahydrofuran (THF, anhydrous, 99.9 %, Aldrich), ethyl alcohol (EtOH, anhydrous, ≥99.5 %, Aldrich), hexane (hexane, anhydrous, 95 %) , Aldrich), chloroform (chloroform, CHCl ₃ , 99.5 %, Samchun), N-methylformamide (N-methylformamide; NMF, 99 %, Aldrich), ethylenediamine (ethylenediamine; En, ≥99.5 %, Aldrich), dimethyl dimethyl sulfoxide (DMSO, anhydrous, ≥99.9%, Aldrich), formamide (FA, 99.5%, Alfa Aesar), N,N-dimethylformamide (N,N-dimethylformamide; DMF, anhydrous, 99.8 % , Alfa Aesar), isopropanol (IPA, 99.5 %, Samchun), cadmium oxide (CdO, 99.99 %, Aldrich), trioctylphosphine oxide (TOPO, 99 %, Aldrich), octa Decylphosphonic acid (octadecylphosphonic acid; ODPA, 97%, Aldrich), selenium (selenium, powder, 99.99%, Aldrich), trioctylphosphine (TOP, 90%, Aldrich), gold(III) chloride trihydrate ( gold(III) chloride trihydrate; HAuCl ₄ 3H ₂ O, 9 9.9 %, Aldrich), 1,2,3,4-tetrahydronaphthalene (1,2,3,4-tetrahydronaphthalene, tetralin, 97 %, Alfa Aesar), oleylamine; OAm, approximate C18 content 80-90 %, Acros Organics), borane tertbutylamine tertbutylamine complex (TBAB, 97 %, Aldrich), indium(III) chloride, 99.999 %, Aldrich), zinc(II) chloride (zinc(II) chloride, ≥98%, Aldrich), tris-(diethylamino)phosphine, 97%, Aldrich), oleic acid (oleic) acid; OA, 90 %, Aldrich), sulfur (sulfur, 99.998 %, Aldrich), lead(II) chloride, PbCl ₂ , reagent grade 99 %, Alfa Aesar), iron (III) acetylaceto nitrate (iron(III) acetylacetonate, 97 %, Aldrich), platinum (II) acetylacetonate (platinum(II) acetylacetonate, 97 %, Aldrich), 1,2-hexadecanediol (1,2-hexadecanediol, technical grade) , 90 %, Aldrich), gadolinium acetate hydrate 99.9 %, Aldrich, erbium acetate hydrate, 99.9 %, Aldrich), ytterbium acetate hydrate (99 %, Aldrich), sodium hydroxide (sodium hydroxide, 97 %, Aldrich), ammonium fluoride (99 %, Aldrich), methanol (methanol, 99.9 %, Daejung), 1-octadecene (ODE, > 90 %, Aldrich) and dioctyl ether (dio ctyl ether, ODE, 99%, Aldrich) was used. All other chemicals were used as received without further purification.

Synthesis of polyphosphide precursors

Polyphosphide precursors are described in published literature (Dragulescu-Andrasi, A.; Miller, LZ; Chen, B.; McQuade, DT; Shatruk, M. Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide. Angew. Chem., Int. Ed. 2016, 55, 3904-3908.) was synthesized with slight modifications. The initial poly all operations for the synthesis of phosphide precursor standard shoe Lenk (Schlenk) technology, or N ₂ - were carried out in a glove box filled (N ₂ filled glovebox) in an inert N ₂ atmosphere. First, 3.2 mmol of KOEt and Pred were added to a 100 mL 3-neck round bottom flask. The mixture was then dissolved in DME/THF (3.0 mL; 1:1 v/v). The suspension was heated from room temperature (RT) to 85° C. for 5 minutes at a heating rate of 12° C. min ^{−1 .} At that temperature, reflux with cold water was performed for 3 hours with continuous stirring. _{After cooling to room temperature, N 2} was sufficiently flowed to remove the residual solvent for drying of the resulting suspension, and 6 mL of anhydrous EtOH was injected into the flask. The dark red suspension dissolved in EtOH was separated as the supernatant and precipitated by centrifugation (13400 rpm, 5 min) in an _{N 2 -filled glove box.} The supernatant obtained from the crude solution was precipitated by addition of CHCl ₃ (1:3 v/v) followed by centrifugation (7800 rpm, 5 min). The purified polyphosphide precursor was dissolved in 6 mL of NMF and re-purified by adding 12 mL of IPA. The purification process by IPA can be repeated to effectively remove by-products, finally dissolved in En or NMF, and further _{stored in an N 2} -filled glove box.

cation exchange reaction

Cation exchange was carried out with an ion-exchange resin. In an N ₂ -filled glove box, 30 mg of NH ₄ ⁺ resin beads prepared by mixing acidic resin beads with ^{H +} _{as cations with an aqueous solution of NH 4} Cl were mixed with purified polyphosphorus in NMF with ^{K +} as counter ion. It was added to 1.0 mL of pid solution. The mixture was vortexed vigorously for 10 to 15 minutes, and the solution was separated from the resin beads by centrifugation (13400 rpm, 5 minutes). After adding toluene to the solution, _{a polyphosphide solution having NH 4} ⁺ as a counter ion was recovered and centrifuged. After repeating this process 3 times, finally, the precipitate was dissolved in 0.5 mL of NMF to make a stable solution of ammonium polyphosphide.

Synthesis of organic-capped nanoparticles

Ban et al. (Ban, HW; Park, S.; Jeong, H.; Gu, DH; Jo, S.; Park, SH; Park, J.; Son, JS Molybdenum and Tungsten Sulfide Ligands for Versatile Functionalization of All-Inorganic Nanocrystals. J. Phys. Chem. Lett. 2016, 7, 3627-3635.) and Tessier et al. (Tessier, MD; Dupont, D.; De Nolf, K.; De Roo, J.; Hens, Z. Economic and Size-Tunable Synthesis of InP/ZnE (E = S, Se) CdSe nanoparticles (3.5 nm size) and InP nanoparticles (2.7 nm size) were synthesized. Au nanoparticles (6.0 nm size) were slightly adjusted to Zhu et al. (Zhu, W.; Michalsky, R.; Metin, O.; Lv, H.; Guo, S.; Wright, CJ; Sun, X.; Peterson). , AA; Sun, S. Monodisperse Au Nanoparticles for Selective Electrocatalytic Reduction of CO2 to CO. J. Am. Chem. Soc. 2013, 135, 16833-16836.). Here, _{under N 2} atmosphere, 0.2 g of HAuCl ₄ was dissolved in 20 mL of a mixture of tetralin and OAm (1:1 v/v) at room temperature for 1 hour. Liu et al. (Liu, C.; Wu, X.; Klemmer, T.; Shukla, N.; Weller, D.; Roy, AG; Tanase, M.; FePt nanoparticles (2.5 nm size) were synthesized according to the publication of Laughlin, D. Reduction of Sintering during Annealing of FePt Nanoparticles Coated with Iron Oxide. Chem. Mater. 2005, 17, 620-625. PbS nanoparticles (6.7 nm size) were obtained with slight modifications from Weidman et al. (Weidman, MC; Beck, ME; Hoffman, RS; Prins, F.; Tisdale, WA Monodisperse, Air-Stable PbS Nanocrystals via Precursor Stoichiometry Control. ACS Nano 2014 , 8, 6363-6371.) was synthesized according to the experimental procedure reported. The sulfur precursor solution was heated using a heating mantle with a heating rate of ^{5 °C min -1 for 20 minutes.} NaGdF ₄ :Yb, Er nanoparticles (10.0 nm size) were prepared according to the reported procedure with slight modifications. Specifically, gadolinium acetate hydrate (0.78 mmol), ytterbium acetate hydrate (0.20 mmol) and erbium acetate hydrate (0.02 mmol) were added to a 3-neck flask containing OA (10 mL) and ODE (15 mL). The mixture was heated to 150° C., held for 40 minutes and then cooled to room temperature. Sodium hydroxide (2.5 mmol) and ammonium fluoride (4.0 mmol) were dissolved in methanol.

Each methanol solution was added to the reactor and stirred at 50 °C for 30 min. The mixture was then heated to 110° C. with stirring under vacuum for 15 minutes to remove methanol. The flask was switched to an Ar atmosphere, and the temperature was raised to 310° C. at a rate of ^{10° C. min −1 and maintained for 1 hour.} Finally, the reactor was cooled to room temperature, ethanol was added to precipitate nanoparticles, and recovered by centrifugation. The product was dispersed in hexane and stored in the refrigerator.

Ligand exchange reactions for various colloidal nanoparticles with polyphosphide anions

All surface modification processes were _{performed in an N 2} -filled glove box. In a typical two-phase ligand exchange process, 0.5 mL of nanoparticles in ^{hexane (20 mg mL -1} ) are placed in a vial containing 1.5 mL of polyphosphide dissolved in ^{NMF (70 mg mL -1 ), and the upper hexane phase} (phase) and the formation of the lower NMF phase. This immiscible two-phase mixture was carried out under vigorous stirring until complete phase transition of the nanoparticles from the upper non-polar phase to the lower polar phase was achieved. After ligand exchange, the upper colorless hexane was completely discarded. To purify the nanoparticles, the residual bottom solution containing polyphosphide-capped inorganic nanoparticles was precipitated by addition of 1.5 mL of IPA followed by centrifugation (13400 rpm, 5 min). Precipitated nanoparticles capped with polyphosphide were dispersed in 1 mL of fresh NMF for further experiments.

Mixed solution of polyphosphide and nanoparticles

Solutions for pure fibrous phosphorus thin films were prepared by purified polyphosphide precursors dissolved in ^{En or NMF (200 mg mL -1 ).} PbS-nanoparticle-embedded fiber phosphorus thin film ink was prepared by polyphosphide-capped PbS nanoparticle solution with excess polyphosphide ligand. Specifically, the ligand exchange reaction proceeds with a combination of 40 mg of PbS nanoparticles ^{in hexane (15 mg mL −1} ) and 150 mg of purified polyphosphide in ^{NMF (50 mg mL −1 ).} After ligand exchange, both polyphosphide ligand and polyphosphide capped PbS nanoparticles in NMF were precipitated by excess IPA to concentrate the solution to a high concentration. Then, the precipitate was dispersed in 0.5 mL of fresh NMF and used as an ink.

device fabrication

A heavily doped n-type Si wafer covered with a thermally grown SiO ₂ layer (100 nm) was used as the gate substrate. To form the source/drain (S/D) electrodes, Ti/Au (7/40 nm) was thermally deposited onto the substrate, and various pairs of channel length (L) and width (W) (W/L = 13200 μm) Contacts in the interdigitated structure with /3 μm, 7800 μm/5 μm and 3800 μm/10 μm) were photolithographically patterned. The substrate with the S/D electrode was washed with acetone, rinsed with IPA, and dried with _{N 2 before use.}

The solution for the pure fiber phosphorus thin film and the PbS nanoparticle-embedded fiber phosphorus thin film was spin-coated on the cleaned substrate. The spin-coated film was pre-baked on a hot plate at 100° C. for 20 seconds to evaporate residual solvent and then annealed at 250° C. for 30 minutes. All device fabrication procedures were _{performed in an N 2} -filled glove box.

Measurement of material properties

Electrospray ionization mass spectrometry (ESI-MS) data were recorded on a JEOL JMS-T100LP AccuTOF LC-plus time-of-flight mass spectrometer. The instrument was calibrated with dithranol for accurate mass spectrometry. Microstructure characterization was performed using a Nova-NanoSEM230, FEI scanning electron microscopy (SEM) operating at 10 kV. Raman spectra were acquired using a Witec alpha 300R confocal Raman microscope with a 532 nm laser wavelength and an excitation power of 0.7 mW. High-resolution transmission electron microscopy (HRTEM) images and selected area electron diffraction (SAED) patterns were collected using a JEOL JEM-2100F microscope operating at 200 kV. For the preparation of HRTEM specimens, a powder form of heat-treated polyphosphide was carefully dropped onto a transmission electron microscopy (TEM) grid coated with a carbon film. TEM images of nanoparticles were acquired using a JEOL-2100 instrument accelerated at 200 kV. TEM specimens of nanoparticles dispersed in various solvents were prepared by drop casting onto carbon-coated copper TEM grids and dried completely in a vacuum chamber. The UV-vis absorption spectrum of the nanoparticle solution was acquired at room temperature (RT) using a Shimadzu UV-2600 spectrophotometer. Optical photoluminescence (PL) spectra were obtained using a Cary Eclipse fluorescence spectrophotometer. The UV-vis absorption and diffuse reflection spectra of the red phosphor films were measured using a Cary 5000 UV-vis-NIR-spectrophotometer. Analysis of trace element composition was performed by inductively coupled plasma optical emission spectrometry (ICP-OES) using a Varian 700-ES. Fourier transform infrared (FT-IR) spectroscopy spectra were acquired in attenuated total reflection mode using a 670/620 Varian FT-IR spectrometer. High power X-ray diffraction patterns were collected at room temperature (RT) using a Rigaku D/Max2500V diffractometer equipped with a Cu-rotating anode X-ray source. Zeta (ζ)-latent data were acquired using a Malvern Zetasizer Nano-ZS90.

Device Characteristics Measurement

All electrical and photoelectric measurements were performed using a Keithley 4200 semiconductor parameter analyzer in an _{N 2 -filled glove box.} Field-effect mobilities were extracted in the saturation regime and calculated using Equation 1:

[Equation 1]

I _D = μC _i (W/2L) (V _G -V _th ) ²

(where C _i is the capacitance per unit area (30.0 nF cm ^-2 ), and V _th is the threshold voltage).

For photoresponse measurement, the device was exposed to white light (100 mW cm ⁻² ) under dark conditions, and the current was measured. Responsivity (R) value is the device [P _in (A _active /A _spot )] (where P _in is the total power of the light source, A _active is the active area of the FET, and A _spot is the total area of the light spot exposed on the substrate) ) was extracted from the photocurrent divided by the incident light power on the active region (ie, the difference between _{I D before and after exposure; I ph} = I _{D, light-on} -ID _{, light-off ).} FET devices have an interdigitated structure of source and drain electrodes. Since most of the charge transport occurs in the FET channel created by interdigitated electrodes, we set A _active to the region of _{A active} × L _{active .} On the other hand, the total area (A _active ) of the light spot exposed on the substrate safely covers the entire area of the FET device. Accordingly, the incident optical power to the active region of the device may be provided in terms _{of P in} (A _active /A _spot).

Results and discussion

1 is a view showing a crystalline semiconductor red thin film manufacturing process through a solution process according to an embodiment of the present invention. A schematic representation of the synthesis of polyphosphide precursor solutions and solution-based preparation of fibrous phosphorus thin films. For the initial polyphosphide-precursor synthesis, the reported chemical route was modified, in which amorphous red phosphorus was reacted with potassium ethoxide to produce a potassium mixture of polyphosphide powder. In order to remove any unreacted precursors and by-products, the synthesized polyphosphide powder was further purified by dispersing the synthesized polyphosphide powder in ethanol and removing the insoluble precipitate. This step is important to obtain a high purity polyphosphide precursor. The purified precursor was readily soluble in various polar solvents. 2 is a photograph of a polyphosphide precursor solution dissolved in a polar solvent according to an embodiment of the present invention (DMF, DMSO, En, FA and NMF).

3 is an ESI-MS spectrum of a polyphosphide precursor solution purified in negative ionization mode according to an embodiment of the present invention. Referring to FIG. 3 , the electrospray ionization mass spectrum of the purified precursor solution of DMSO in negative ionization mode shows multiple peaks in the mass-to-charge ratio (m/z) range of 150-500.

4 is (a) SEM image of a fibrous red phosphorus thin film annealed at 250 ° C according to an embodiment of the present invention (inset is a _{photograph of a thin film on a Si/SiO 2} substrate), (b) polyphosphide precursor solution (black), dried UV-vis absorption spectra of (blue) and (red) phosphorus thin films annealed at 250 °C, (c) Raman spectra of fibrous red phosphorus thin films deposited on _{glass (black) or Si/SiO 2 (red) substrates, (d)} ) HRTEM images of solution-processed fibrous red phosphorus (inset shows corresponding SAED patterns). The bottom vertical line in Fig. 4(c) shows the peaks from the reference for IV and V types.

5 is a scheme of a ligand exchange process between an inorganic polyphosphide ligand and nanoparticles according to an embodiment of the present invention. Molecular inorganic anions such as chalcogenidometallates, metal-free anions and polyoxometallates have been actively used as surface capping ligands for various nanoparticles. These ligands provide a negative charge to the surface to electrostatically stabilize the nanoparticle surface, allowing colloidal stability of the nanoparticles in polar solvents.

Figure 6 shows Au nanoparticles and prepared polyphosphide-capped Au, InP, CdSe, PbS, FePt and NaGdF ₄ :Yb,Er nanoparticles according to an embodiment of the present invention 2 for nanoparticles dispersed in NMF A photograph showing the phase ligand exchange reaction. The feasibility of current polyphosphide anions as capping ligands was demonstrated by typical two-phase ligand exchange reactions of polyphosphides in solutions with various colloidal nanoparticles: metallic Au, semiconducting InP, CdSe and PbS, magnetic FePt. and luminescent NaGdF ₄ :Yb,Er upconverting nanoparticles.

7 is polyphosphide-capped nanoparticles according to an embodiment of the present invention (a) Au, (b) InP, (c) CdSe, (d) PbS, (e) FePt and (f) NaGdF ₄ :Yb , are TEM images of Er. Referring to FIG. 7 , the polyphosphide anion performed all expected surface ligand functions. That is, all polyphosphide-capped nanoparticles showed good colloidal stability in polar solvents; Preserve their main structure as evidenced by TEM analysis.

8 shows (a) absorption and (b) PL spectra of (black) organic and (red) polyphosphide-capped CdSe nanoparticles and (blue) polyphosphide precursor solutions according to an embodiment of the present invention, (c) ) FT-IR spectra of organic- and polyphosphide-capped nanoparticles of CdSe, FePt, PbS, InP and Au, (d) polyphosphide-capped FePt, PbS and CdSe nanoparticles and polyphosphide precursor solutions represents the ζ-dislocation distribution of .

9 is a schematic diagram and an optical microscope image of an FET according to an embodiment of the present invention. Referring to Fig. 9, a fibrous thin film was irradiated by fabricating a bottom electrode, bottom gate FET with electronic and optoelectronic properties.

_{10 is a graph showing (a) Transfer (I D} vs V _G ) and (b) Output (I _D vs V _D ) characteristics of an FET having a fibrous red phosphorus thin film according to an embodiment of the present invention. Both curves show an n-type gate effect with an average on/off ratio of 3.1 x 10 ³ and excellent linear/saturation behavior, so solution-treated fibrous phosphorus is likely to be used as an active material in electronic devices. This is the first report on the n-type semiconductor properties of crystalline red phosphorus. Only the previously reported vacuum-grown red phosphorus exhibited p-type behavior.

11 is a schematic diagram of an optical sensor made of crystalline red phosphorus according to an embodiment of the present invention and a graph of optical sensor characteristics of a nanoparticle-crystalline red phosphorus complex.

11 (a) is a time-dependent photocurrent (incident light amount: 100 mW cm ^-2 ) graph of an FET having a fibrous red thin film according to exposure to white light. The inset shows a schematic of a selectively light-exposed FET with a fibrous red thin film. _{Fig. 11 (b) is an I D} vs V _G curve of pure and polyphosphide-capped PbS-nanoparticle-containing fibrous red thin films before and after exposure to white light. Figure 11 (c) is a view showing the photosensitivity of the pure and polyphosphide-capped PbS-nanoparticle-containing fibrous red phosphorus thin film. The inset is a schematic diagram of a fibrous phosphorus thin film containing polyphosphide-capped PbS nanoparticles under white light exposure. Fig. 11(d) shows the band alignment at the junction of fibrous phosphorus and PbS nanoparticles.

As described above, although the embodiments have been described with reference to the limited embodiments and drawings, various modifications and variations are possible from the above description by those skilled in the art. For example, even if the described techniques are performed in an order different from the described method, and/or the described components are combined or combined in a different form from the described method, or replaced or substituted by other components or equivalents Appropriate results can be achieved. Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (22)

preparing a suspension by dissolving red phosphorus powder in a solvent;
heating the suspension;
cooling the heated suspension to room temperature;
separating the supernatant by centrifuging the cooled suspension; and
purifying the supernatant to obtain a polyphosphide precursor;
including,
After the step of purifying the supernatant to obtain a polyphosphide precursor,
passing the obtained polyphosphide precursor through an ion exchange resin;
further comprising,
A method for preparing a polyphosphide precursor.
According to claim 1,
The step of preparing a suspension by dissolving the red phosphorus powder in a solvent,
Dissolving the red phosphorus powder and the base in a polar solvent,
A method for preparing a polyphosphide precursor.
3. The method of claim 2,
The base is KOEt, t BuOK, LiHMDS, NaHMDS, MeONa, EtONa, t BuONa, n BuLi, K ₂ CO ₃ , Cs ₂ CO ₃ , K ₃ PO ₄ , DIPEA, NMM, DMAP, KOMe and Et ₃ N At least one selected from the group consisting of
The polar solvent is dimethyl ether (DME), tetrahydrofuran (THF), dimethylformamide (DMF), N-methylformamide (NMF), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) ), which comprises at least one selected from the group consisting of ethylenediamine (En), formamide (FA) and dimethylacetamide,
A method for preparing a polyphosphide precursor.
According to claim 1,
Heating the suspension comprises:
It is carried out in a temperature range of room temperature to 100 °C,
The suspension is subjected to reflux with cold water,
A method for preparing a polyphosphide precursor.
According to claim 1,
Separating the supernatant by centrifuging the cooled suspension,
After removing the residual solvent of the cooled suspension, centrifugation is performed by adding an organic solvent,
A method for preparing a polyphosphide precursor.
6. The method of claim 5,
The organic solvent is ethanol (EtOH), methanol (MeOH), propanol (PrOH), butanol (BuOH), isopropyl alcohol (IPA), isobutyl alcohol, dimethylacetamide (DMAC), dimethylformamide (DMF), Dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), triethylene phosphate (Triethylphosphate), trimethyl phosphate (Trimethylphosphate), hexane, benzene, toluene, xylene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) ), which comprises at least one selected from the group consisting of diisobutyl ketone, ethyl acetate, butyl acetate, dioxane and diethyl ether,
A method for preparing a polyphosphide precursor.
According to claim 1,
Purifying the supernatant to obtain the polyphosphide precursor,
adding an extraction organic solvent to the supernatant to precipitate a supernatant obtained from the crude solution, followed by centrifugation to obtain a polyphosphide precursor;
dissolving the polyphosphide precursor in a polar solvent and purifying by adding a non-solvent;
further comprising,
To remove impurities by repeating the purification process with the non-solvent,
A method for preparing a polyphosphide precursor.
8. The method of claim 7,
The extraction organic solvent is _{selected from the group consisting of chloroform (CHCl 3} ), dichloromethane (CH ₂ Cl ₂ ), dichloroethane, diethyl ether, tetrahydrofuran, toluene, acetonitrile, tetrachloroethane, dioxane and acetone at least one of which is
The polar solvent is dimethyl ether (DME), tetrahydrofuran (THF), dimethylformamide (DMF), N-methylformamide (NMF), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) ), ethylenediamine (En), formamide (FA), and at least one selected from the group consisting of dimethylacetamide,
The non-solvent is isopropyl alcohol, methyl ketone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dibutyl ketone, cyclohexanone, diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, ethyl acetate and Which comprises at least one selected from the group consisting of methanol,
A method for preparing a polyphosphide precursor.
delete According to claim 1,
The step of passing the obtained polyphosphide precursor through an ion exchange resin,
By adding the polyphosphide precursor obtained above in NMF having ^{K +} as a counter ion _{to NH 4} ⁺ _{resin beads to centrifuge the polyphosphide solution having NH 4} ⁺ to prepare an ammonium polyphosphide solution,
A method for preparing a polyphosphide precursor.
Preparing a polyphosphide precursor prepared by the method for preparing the polyphosphide precursor of claim 1;
coating the polyphosphide precursor on a substrate; and
heat-treating the coated polyphosphide;
containing,
A method for producing a crystalline red phosphorus thin film.
delete 12. The method of claim 11,
The step of coating the polyphosphide precursor on the substrate,
It is carried out using a solution process,
The solution process is spin coating (spin coating), drop casting (drop casting), dip coating (dip coating), roll coating (roll coating), screen coating (screen coating), spray coating (spray coating), spin casting ( Spin casting), flow coating (flow coating), screen printing (screen printing) and ink jet printing (ink jet printing) and roll-to-roll (roll-to-roll) comprising at least one selected from the group consisting of that is,
A method for producing a crystalline red phosphorus thin film.
12. The method of claim 11,
The heat treatment is to be carried out in a temperature range of 100 ℃ to 300 ℃,
The heat treatment is to be performed in air, nitrogen, argon, carbon monoxide, hydrogen or a mixed gas condition thereof,
A method for producing a crystalline red phosphorus thin film.
A crystalline red phosphorus thin film produced by the method of claim 11 .
nanoparticles; and
An inorganic ligand comprising a polyphosphide precursor prepared by the method for preparing the polyphosphide precursor of claim 1 coated on the surface of the nanoparticles;
containing,
Polyphosphide precursor-capped nanoparticles.
17. The method of claim 16,
The nanoparticles, including at least one selected from the group consisting of a metal material, a semiconductor material, a magnetic material, a magnetic alloy, or a multi-component hybrid structure material,
Polyphosphide precursor-capped nanoparticles.
17. The method of claim 16,
The nanoparticles are CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InP, InAs, InSb, SiC, PbS, Fe, Pt, Ni, Co , Al, Ag, Au, Cu, FePt, Fe ₂ O ₃ , Fe ₃ O ₄ , Ge, (NaYF ₄ :Yb ³⁺ ,Er ³⁺ ), (NaYF ₄ :Yb ³⁺ ,Tm ³⁺ ), ( NaGdF ₄ :Yb ³⁺ ,Er ³⁺ ), (NaYF ₄ :Yb ³⁺ ,Er ³⁺ /NaGdF ₄ ) and (NaGdF ₄ :Yb ³⁺ ,Er ³⁺ /NaGdF ₄ ) at least selected from the group consisting of which includes any one,
Polyphosphide precursor-capped nanoparticles.
17. The method of claim 16,
The attachment region of the inorganic ligand formed on the surface of the nanoparticles is -COOH, -NH ₂ , -(O)P(OH) ₂ , -SH and R ₃ N (where R is a C1 to C24 alkyl group or C5 To include at least one functional group selected from the group consisting of a C20 aryl group),
Polyphosphide precursor-capped nanoparticles.
A nanoparticle-embedded fibrous phosphorus thin film comprising the polyphosphide precursor-capped nanoparticles of claim 16 .
An electronic device comprising the crystalline red phosphorus thin film of claim 16 or the nanoparticle-embedded fibrous phosphorus thin film of claim 20 .
22. The method of claim 21,
The electronic device will include at least one functional group selected from the group consisting of a field effect transistor, a photosensor, a photodetector, a capacitor, a light emitting diode, and an image sensor,
electronic device.

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