KR101108140B1 - A manufacturing method for Lay-by-Layer multilayer film and Lay-by-Layer multilayer film manufactured by the same - Google Patents

Abstract

A method of manufacturing a layer-by-layer multilayer thin film and a layer-by-layer multilayer thin film produced thereby are provided.
In the layer-by-layer multilayer thin film manufacturing method according to the present invention, the thin film forming the multilayer is mutually bonded by a nucleophilic substitution reaction, and the LbL multilayer thin film manufacturing method according to the present invention can be produced in a nonpolar solvent, thus, an LbL multilayer thin film. The range of solvent which can be used in a manufacturing method becomes wide. In addition, since the surface of the nanoparticle layer of the manufactured multilayer thin film has a hydrophobic property, it is possible to prevent the degradation of the thin film due to humidity, even when exposed to the air in the form of the final product. That is, the thin film obtained by the nucleophilic substitution reaction according to the present invention was shown to have both stable photoluminescence and moisture resistance in the air, compared to the LbL self-assembled thin film prepared with electrostatic properties. These results show that LbL growth of the patterned thin film is possible through nucleophilic substitution using micro-contact printing.

Description

A manufacturing method for Lay-by-Layer multilayer film and Lay-by-Layer multilayer film manufactured by the same

The present invention relates to a method for producing a layer-by-layer multilayer thin film and a layer-by-layer multilayer thin film prepared thereby, and more particularly, to a layer-by-layer multilayer thin film. The range is wider, and the surface of the nanoparticle layer of the manufactured multilayer thin film has hydrophobic properties, so that the layer-by-layer can be prevented from deterioration of the thin film due to humidity, even when exposed to the air in the form of the final product. A method for manufacturing a multilayer thin film and a layer-by-layer multilayer thin film produced thereby.

Layer-by-layer (LbL) self-assembly technology allows the thickness of the polymer and polymer / inorganic nanoparticle hybrid multilayer thin film to be controlled in thickness and has a chemical composition in nanometer units. It is recognized as a useful and convenient technology. The LbL technique is a technique for manufacturing a multilayer thin film, and may be described as a multilayer thin film technology through bonding between layers having different charges.

That is, traditional LbL self-assembly is described as self assembly between layers by electrostatic attraction of two oppositely charged materials in aqueous solution. Recently, LbL self-assembly has been attempted in polar solvents, especially alcohols, rather than aqueous solutions using hydrogen bonds, click chemistry, disulfide bonds, silanization, esterification, urethane bonds, and amidation. have. As is known to date, functional organic / inorganic nanocomposites have not been produced in nonpolar solvents.

Accordingly, an object of the present invention for solving the above problems is to provide a method for producing a LbL multilayer thin film that can be implemented in a non-polar solvent rather than an aqueous solution.

In addition, another object of the present invention is to provide a LbL multilayer thin film prepared by a method that can be implemented in a non-polar solvent.

Since the LbL multilayer thin film manufacturing method according to the present invention can be produced in a nonpolar solvent, the range of solvents that can be used in the LbL multilayer thin film manufacturing method is widened. In addition, since the surface of the nanoparticle layer of the manufactured multilayer thin film has a hydrophobic property, it is possible to prevent the degradation of the thin film due to humidity, even when exposed to the air in the form of the final product. That is, the thin film obtained by the nucleophilic substitution reaction according to the present invention was shown to have both stable photoluminescence and moisture resistance in the air, compared to the LbL self-assembled thin film prepared with electrostatic properties. These results show that LbL growth of the patterned thin film is possible through nucleophilic substitution using micro-contact printing.

Figure 1 is a step of the LbL multilayer thin film manufacturing method according to an embodiment of the present invention.
2 is a graph of FTIR analysis of BMPA-QD, PAMA and PAMA / BMPA-QD multilayer thin films.
3 is a graph showing a frequency change over time, and FIG. 4 is a graph showing a frequency change with increasing number of layers in a multilayer thin film.
5 is an SEM and AFM image of a (PAMA / BMPA-QD) 1 multilayer thin film.
6 is a high resolution emission electron spectrometer (HR_TEM) image of BMPA-QD of an LbL thin film with high packing density (fill density).
FIG. 7 shows a) SEM, AFM images of (PAMA / MAA-QD) 1 multilayer thin films fabricated on silicon substrates, and b) HR-TEM images of MAA-QD layers adsorbed with a TEM grid coated with PAMA. to be.
FIG. 8 is a graph showing the absorption strength of BMPA-QD according to the total number of process cycles in which the first process of depositing the BMPA-QD layer in toluene and the second process of depositing the PAMA layer in ethanol cross each other.
9 is a diagram showing that the thickness of the BMPA-QD / PAMA multilayer thin film increases proportionally with the number of layers.
10 is a microscopic image of a water contact angle.
Fig. 11 is the PL spectrum of the (PAMA / BMPA-QD) n multilayer thin film.
12 is a PL spectrum of the (PAMA / BMPA-QD) ₁₀ multilayer thin film of the present invention, (PAMA / MAA-QD) ₁₀ multilayer thin film of Comparative Example 1 and (PAMA / BCM-QD) ₁₀ multilayer thin film of Comparative Example 2 to be.
FIG. 13 shows PL for (PAMA / BMPA-QD) ₁₀ multilayer thin films over time, (PAMA / MAA-QD) ₁₀ multilayer thin films of Comparative Example 1 and (PAMA / BCM-QD) ₁₀ multilayer thin films of Comparative Example 2 It shows the spectrum.

With respect to the embodiments of the present invention disclosed in the text, specific structural to functional descriptions are merely illustrated for the purpose of describing embodiments of the present invention, embodiments of the present invention may be implemented in various forms and It should not be construed as limited to the embodiments described in.

Hereinafter, with reference to the accompanying drawings, it will be described in detail a preferred embodiment of the present invention. The same reference numerals are used for the same constituent elements in the drawings and redundant explanations for the same constituent elements are omitted. In addition, unless otherwise indicated, the subscript means the number of layers of the multilayer thin film, and the material of the layer is separated by "/".

In the present invention, an organic / inorganic multilayered LbL self-assembled body was prepared in a nonpolar solvent using a Nucleophilic Substitution Reaction (SN). That is, the present invention manufactures a multilayer thin film through substitution reaction between end groups of the constituent material rather than electrostatic attraction between the multilayer thin film constituents.

That is, the LbL self-assembled multilayer thin film according to the present invention includes a first thin film including a first compound having a halogen group terminated with a specific carbon, and a functional group having a non-covalent electron pair for bonding with the carbon from which the halogen group is released. It consists of a 2nd thin film containing the 2nd compound which has a terminal, The said 1st thin film and a 2nd thin film are couple | bonded according to the substitution reaction between a halogen group and a functional group. In an embodiment of the present invention, the first thin film includes quantum dots (QD), nanoparticles, metal particles, and the like, and the first compound of the first thin film encapsulates the quantum dots and the like. Thus, particles having electrical properties, such as quantum dots, do not directly bond to the second thin film, but instead a thin film (first thin film) encapsulating the particles binds to the second thin film, and the bonding is not electrostatic attraction. It is a covalent bond following a nuclear substitution reaction.

According to an embodiment of the present invention, a quantum dot (QD) of CdSe @ ZnS is encapsulated using 2-bromo-2-methylpropionic acid (BMPA) as a first compound in toluene or hexane which is a nonpolar solvent. One thin film was prepared. As the end group in the BMPA, the bromine (Br) group then becomes a substitution reaction site in the multilayer thin film. As the end group of the material coating the metal particles, such as QD, a halogen group such as bromine has an excellent nucleophilic substitution site. Will be provided.

In addition, in a nucleophilic substitution reaction (particularly, an SN2 reaction in which an end group such as a halogen group is first released), a reactor (substituent group) that binds to the leaving cationic carbon with the leaving group is also important. An amine group was used.

Figure 1 is a step of the LbL multilayer thin film manufacturing method according to an embodiment of the present invention.

Referring to FIG. 1, in one embodiment of the present invention, a poly (amidoamine) dendrimer (PAMA) including an amine group having a non-covalent electron pair becomes a compound of the second thin film, and BMPA including a halogen group such as bromine is It binds to the QD (BMPA-QD) thin film coated with the first compound. That is, bromine, which is an end group of the first compound encapsulating QD in the first thin film, and an amine group, which is another end group of the compound (second compound) constituting the second thin film, undergo a nucleophilic substitution reaction, thereby producing an LbL multilayer thin film. .

The above embodiment will be described in more detail below.

Example  One

Example  1-1

matter

CdSe @ ZnS (QD), having a size of 5.3 nm and stabilized with oleic acid, was prepared in a toluene solvent according to known techniques. For ligand exchange, BMPA (3.34 wt%) was added to QD-dispersed toluene and heated to 40 ° C. for 2 hours to prepare CdSe @ ZnS (BMPA-QD) encapsulated with BMPA.

Example  1-2

Multilayer Thin Film Lamination

BMPA-QD dispersed in toluene or hexane and PAMA dispersed in ethanol were prepared at a concentration of 1 mg / mL. Prior to the LbL self-assembly shown at the bottom of FIG. 1, the quartz or silicon substrate was cleaned with an RCA solution (H 2 O: NH 3: H 2 O 2: 5: 1: 1 v / v / v).

The substrate was first immersed in a solution containing PAMA, which is a second thin film, for 10 minutes, then washed twice with ethanol, and then dried slightly with nitrogen. Thus, a substrate coated with PAMA is completed. The substrate coated with PAMA is then immersed for 30 minutes in a nonpolar solvent in which BMPA-QD, which is the first thin film, is dispersed, washed with toluene, and dried with nitrogen. Thereafter, the obtained substrate was again immersed in the PAMA solution for 10 minutes. By repeating the immersion process, a multilayer thin film (PAMA / BMPA-QD multilayer thin film) having a desired number of layers was prepared.

Example  1-3

Measure

UV-vis and photoluminescense spectra were analyzed using a Perkin Elmer Lambda 35 UV-vis spectrometer and a fluorescence spectrometer (Perkin Elmer LS 55), respectively. The PL spectrum of the PAMA / BMPA-QD multilayer thin film was measured at an excitation wavelength of 300 nm. The mass of the layer deposited after each immersion step was analyzed using a QCM apparatus (QCM200, SRS). The resonance frequency of the QCM electrode was about 5 MHz , and PAMA and BMPA-MP, octakis-MP, Δm, were calculated by changing the QCM frequency using Equation 1 below, which is the Sauerbrey equation.

(Where Δm _A is the change in mass per unit area of quartz crystal, μg / cm 2)

The surface morphology of the (PAMA / BMPA-QD) n multilayer thin film obtained according to an embodiment of the present invention was analyzed using FE-SEM (model: JSM-7401F, JEOL).

Example  1-4

Patterned  Preparation of Multilayer Thin Film

Photo-crosslinkable PS-N ₃ (M _n = 28.0 kg mol ⁻¹ ) was synthesized by eversible addition fragmentation transfer (RAFT) polymerization. PS-N ₃ (about 2 wt% in toluene) was deposited on a silicon substrate at a rate of 4000 rpm and then spincoated. Thereafter, the PS-N ₃ was optically crosslinked with UV ( l = 254 nm) through a patterned shadow mask. The silicon substrate coated with PS-N ₃ was again immersed in the PAMA solution (ethanol) and the BMPA-QD dispersion in the manner described above to grow the BMPA-QD / polymer multilayer thin film only in the hydrophilic region.

analysis

According to the above-described method, the multilayer thin film of QD / polymer structure obtained by nucleophilic substitution reaction has both stable photoluminescence in air and excellent moisture resistance compared to LbL self-assembled thin film manufactured with electrostatic properties. Appeared. Furthermore, it is possible to grow LbL into a patterned thin film through a nucleophilic substitution reaction using micro-contact printing, which will be described in detail below.

Experimental Example  One

IR  analysis

The Br terminal of BMPA-QD and NH2 terminal of PAMA were identified using Fourier transform infrared spectroscopy (FTIR).

2 is a graph of FTIR analysis of BMPA-QD, PAMA and PAMA / BMPA-QD multilayer thin films.

Referring to FIG. 2, the FTIR spectra of the PAMA / BMPA-QD multilayer thin films show characteristic peaks in the wavelength range of 1190 and 1100 cm ⁻¹ when compared with the FTIR results of BMPA-QD and PAMA, which represent primary amine and Br groups. Corresponding to the characteristic bands of secondary aliphatic amines obtained from the nucleophilic substitution reaction therebetween. In addition, when compared with PAMA, the multilayer thin film (PAMA / BMPA-QD) obtained in the present invention shows a low peak at 1550 cm ⁻¹ , which corresponds to the NH bend mode of the amine group, which corresponds to PAMA and The driving force to assemble and bind BMPA-QD proves to be a nucleophilic substitution reaction. Thus, the FTIR spectrum indicates that the driving force of the BMPA-QD and PMMA bond is a nucleophilic substitution between Br and NH ₂ .

QCM  analysis

Kinetic studies on BMPA-QD adsorption in the PAMA layer were performed through quartz crystal microgravimeter (QCM).

3 is a graph showing a frequency change over time, and FIG. 4 is a graph showing a frequency change with increasing number of layers in a multilayer thin film.

Referring to Figure 3, the LbL multilayer thin film manufacturing method according to an embodiment of the present invention follows a typical adsorption endothermic behavior, the amount of BMPA-QD adsorbed on the PAMA layer reaches a ballast (flat group) within 30 minutes Able to know. That is, referring to Figure 3, the frequency shift (△ F) and the mass change of the BMPA-QD adsorbed on PAMA layer (△ m) was reached on the ballast in 30 minutes (231 ± 5 Hz and ~ 4081ng / cm ²⁾ . The results suggest that BMPA-QD remains stable in the LbL self-assembly process, but that continuous mass increase is induced by QD aggregation as the adsorption time increases.

The QCM analysis clearly shows that the LbL preparation of BMPA-QD / PAMA multilayer thin films is by nucleophilic substitution reaction between NH2-Br.

In addition, referring to FIG. 4, -ΔF of each layer of PAMA is 9 ± 2 Hz, which corresponds to Δm (mass increase) of ˜158 g. In addition, -ΔF of the QD layer is 221 ± 4 Hz, which corresponds to Δm (mass increase) of ˜3904 g. As it viewed in consideration of the density of the CdSe core (core) and a ZnS shell layer (surface layer), respectively ^{5.81 g cm -3 and 3.89 g cm} -3 in level, the number density of the QD in the QD layers each about 1.3 x 10 ¹² cm ^- Calculated to ² , which corresponds to a packing density of 58%. In particular, considering the packing density of randomly packed aggregated particles having a level of 64%, it can be seen that the packing density of the LbL according to the present invention is considerably high.

BMPA - QD  Surface analysis

Coated BMPA-QD surfaces were analyzed using SEM (Scanning Electron Microscopy) and Atomic Force Microscopy (AFM).

5 is an SEM and AFM image of a (PAMA / BMPA-QD) 1 multilayer thin film. The measured RMS surface roughness was 1.5 nm level.

Referring to FIG. 5, it can be seen that as the adsorption time elapses, the QD of the surface increases, but large sized QD aggregates are not found.

QD Packing density

 The high resolution emission electron spectrometer (HR_TEM) results for BMPA-QD of LbL thin films with high packing density (fill density) are shown in FIG. 6.

Referring to FIG. 6, HR-TEM analysis results show that there is no large void between QDs.

FIG. 7 shows a) SEM, AFM images of (PAMA / MAA-QD) 1 multilayer thin films fabricated on silicon substrates, and b) HR-TEM images of MAA-QD layers adsorbed with a TEM grid coated with PAMA. to be.

According to the research results so far, PAMA / MMA-QD multilayer thin film can be produced and grown in water under the electrostatic action, the packing density of this QD was much less than 15% (see Fig. 7). . Thus, the high packing density of hydrophobic BMPA-QD is believed to be due to the small size of the BMPA ligand, not the ion, ie the electrostatic and steric repulsion, long region between QDs due to the ligand which does not carry an electrostatic charge. This is because the repulsive force does not exist.

Multi-layered  Multi-layer thin film analysis and surface chemistry

FIG. 8 is a graph showing the absorption strength of BMPA-QD according to the total number of process cycles in which the first process of depositing the BMPA-QD layer in toluene and the second process of depositing the PAMA layer in ethanol cross each other.

Referring to FIG. 8, an increase in the total number of process cycles corresponds to an increase in the number of layers in the multilayer thin film, and the increase in absorption intensity indicates a linear characteristic, and further, an LbL growth process of the BMPA-QD / PAMA multilayer thin film can be seen. .

9 is a diagram showing that the thickness of the BMPA-QD / PAMA multilayer thin film increases proportionally with the number of layers.

Referring to FIG. 9, the average thickness of each layer was about 10 nm above the sizes of CdSe @ ZnS QD and PAMA, which can be seen through the SEM cross-sectional image inserted in FIG. 9.

10 is a microscopic image of a water contact angle. Odd and even numbers here denote layers laminated with PAMA and BMPA-QD layers, respectively.

Referring to FIG. 10, as shown in the inserted portion in FIG. 10, the PAMA layer is characterized by hydrophilicity by the end group of NH ₂ , and the water contact angle is 7 degrees. In contrast, the BMPA-QD layer is hydrophobic because of Br and methyl groups, with a water contact angle of about 115 degrees. Therefore, according to the process of the present invention in which the BMPA-QD layer and the PAMA layer are laminated alternately, the water contact angle difference of each of the finally obtained multilayer films is 90 degrees to 180 degrees, more preferably between 90 degrees and 120 degrees. Therefore, from the above results, the present invention not only enables LbL growth in the nonpolar solvent of the BMPA-QD / PAMA multilayer thin film, but also the surface chemical properties of the BMPA-QD still have hydrophobicity, and the final obtained through LbL growth. It can be seen the advantages of the present invention that the surface properties of the thin film can be freely adjusted according to the process.

Furthermore, due to this hydrophobic character, the multilayer thin film prepared according to the present invention has excellent moisture resistance.

Fluorescence ( Photoluminescence , PL Characteristics

PL (and electrofluorescence) has a very important meaning in the technical application of a composite thin film having a puller / QD structure. This is because such optical fluorescence property of the multilayer thin film is a very important factor that can determine the optical properties of the thin film for optical applications or the electrical device performing the bio / medical image processing.

However, in the production of polymer / QD composite films, the use of conventional LbL self-assembly techniques is limited for several reasons, one of which is because the PL properties of QDs embedded in multilayer thin films are generally low. In the conventional LbL self-assembly technique performed in an aqueous solution or polar solvent environment, QD is mainly prepared directly in an aqueous solution or polar solvent in which the LbL self-assembly process is performed, or obtained through ligand exchange or phase transfer. However, the QD manufactured in this manner weakens and deteriorates the PL characteristics according to the LbL self-assembly process and the long time use of the thin film. Recent studies have reported that when small-sized thiol ligands with hydrophilic properties are integrated at high density, this significantly reduces the quantum yield of QDs.

Kotov et al. Reported that the PL strength of polyelectrolyte / citrate stabilized CdSe @ ZnS composite film was increased to 50 to 500 times when irradiated with external light for several days and surface oxidation proceeded to external oxygen in QD. Doing. In addition, it is reported that the PL band blue shifted to a considerable level with the exposure time with the increase of the PL intensity. To date, producing polymer / QD multilayer thin films with the inherent PL properties of QD has been considered a significant challenge. In this situation, the present inventors completed the LbL self-assembly process of CdSe @ ZnS QD stabilized with hydrophobic BMPA in a nonpolar solvent by nucleophilic substitution of the terminal Br group of BMPA with an amine (NH ₃ ) group of PAMA. The general process is as described with reference to the above embodiments and drawings.

In general, CdSe @ ZnS QD has a CdSe core of 4nm and a thickness of 1nm, consisting of a ZnS shell layer stabilized with oleic acid as described above, is prepared in hexane or toluene. Stabilizers, such as oleic acid, are replaced with BMPA via ligand exchange, resulting in CdSe @ ZnS QD stabilized with BMPA, which is named BMPA-QD throughout this specification as described above. However, this ligand exchange reduces the quantum yield of QDs in coumarin by 59% to 30%.

For comparison, the oleic acid stabilizer of QD was phase-changed from toluene solvent to aqueous solution solvent and exchanged with mercapto acetic acid (MAA) to prepare a QD coated with negatively charged MAA, which is MAA-QD throughout this specification. Is referred to.

The relative quantum yield of MAA-QD was about 9% at pH 9, since the use of hydrophilic thiol ligands to replace the original hydrophobic ligands drastically reduced the quantum yield of PL. Therefore, in order to prevent such a sudden decrease in quantum yield, in the present invention, BMPA-QD dispersed in hexane or toluene and PAMA solution in ethanol were used in the LbL growth process (see FIG. 1). The nucleophilic substitution reaction can be carried out for 30 minutes at room temperature in a non-aqueous solvent such as hexane, toluene and ethanol as described above.

Fig. 11 is the PL spectrum of the (PAMA / BMPA-QD) n multilayer thin film.

Referring to FIG. 11, the PL strength of BMPA-QD increases as the number of layers increases, but the maximum PL may be slightly red shifted. This result is judged to be because energy is transferred from the small QD to the larger QD in the BMPA-QD layer.

For comparison, two different CdSe @ ZnS QD / PAMA multilayer thin films were prepared according to the conventional LbL method based on electrostatic action in water. The first multilayer thin film was a multilayer thin film prepared using mercaptoacetic acid (MAA) as a stabilizer of CdSe @ ZnS QD (Comparative Example 1). The second multilayer thin film was derived from block copolymer micelles (BCMs) consisting of polystyrene cores, in which QD was put, and a poly (acrylic acid) corona was prepared in a conventional manner (comparative example 2). The maximum concentration of QD in BCM was 0.57 mg / mL, and the quantum yield of BCM-QD was about 19%.

12 is a PL spectrum of the (PAMA / BMPA-QD) ₁₀ multilayer thin film of the present invention, (PAMA / MAA-QD) ₁₀ multilayer thin film of Comparative Example 1 and (PAMA / BCM-QD) ₁₀ multilayer thin film of Comparative Example 2 to be.

Referring to FIG. 12, the PL strength of the (PAMA / BMPA-QD) ₁₀ thin film was about 510 times higher than that of the (PAMA / MAA-QD) ₁₀ thin film, and the PL of the (PAMA / BCM-QD) ₁₀ thin film. It was about 10 times higher than strength. The large difference in PL strength of the three films is due to the high quantum yield of BMPA-QD in the multilayer thin film of the present invention and the high density filling (coverage, coverage) properties of BMPA per layer, as well as the MAA-QD and BCM in the LbL self-assembly process. This is because the PL characteristic of QD deteriorates. In order to better understand this phenomenon, the long-term PL stability of the QD / PAMA multilayer thin film was analyzed in a dark room temperature environment.

FIG. 13 shows PL for (PAMA / BMPA-QD) ₁₀ multilayer thin film, (PAMA / MAA-QD) ₁₀ multilayer thin film of Comparative Example 1, and (PAMA / BCM-QD) ₁₀ multilayer thin film of Comparative Example 2 It shows the spectrum.

Referring to FIG. 13, the (PAMA / BMPA-QD) ₁₀ multilayer thin film according to the present invention shows a slight change after a storage period of one month, whereas the multilayer thin films of Comparative Examples 1 and 2 have a storage period of only one week. It can be seen that the PL strength decreases significantly. This means that the hydrophobic nature of BMPA-QD and its self-assembled layer prevents PL quenching by hydrolysis and / or oxidation in the atmospheric environment. Therefore, the inherent PL properties of the QD of the multilayer thin film according to the present invention can be protected by the hydrophobic property of the surface.

In conclusion, in the present invention, an LbL self-assembled multilayer thin film is prepared by nucleophilic substitution reaction between a bromine group which is a halogen group and an amino group having a lone pair. Particularly high hydrophobic QDs are prepared in nonpolar solvents, polymers are prepared in polar solvents and combined together into one composite multilayer thin film. The multilayer thin film manufacturing method according to the present invention enables QD / polymer multilayer thin film, in particular, the packing density of QD is close to 58%, and shows excellent and stable PL behavior due to the hydrophobic property of the surface. These results are quite useful from a technical point of view, and to date, similarly to the prior art of preparing LbL multilayer thin films in an electrostatic manner in a water-soluble solvent (polar solvent), a method for producing an LbL multilayer thin film according to the present invention based on a nucleophilic substitution reaction. The BMPA-QD / PAMA multilayer thin film can be grown only in the desired area of the patterned substrate. This is shown in SI Figure S6.

The above method according to the present invention means that a wide range of hydrophobic materials (ie Fe2O3, Pt, Au or QD nanoparticles) can be grown from an organic solvent to a composite multilayer by LbL self-assembly process. This is because the multilayer thin film manufacturing method depends on the reaction between the nanoparticles and the end groups of the polymer. That is, rather than depending on the properties of the nanoparticles themselves and the polymers themselves, it depends on the properties of the end groups of the constituent materials forming the multilayer thin film. Therefore, the multilayer thin film manufacturing method according to the present invention has excellent industrial applicability in manufacturing thin film-based electronic devices such as nonvolatile memories.

Claims (8)

In the manufacturing method of the layer-by-layer multilayer thin film,
The multilayer thin film is mutually bonded by a nucleophilic substitution reaction, wherein the multilayer thin film comprises a first thin film including a first compound having a halogen group as a terminal group and a second compound having a functional group having a lone pair as a terminal A second thin film comprising a, wherein the first thin film and the second thin film is coupled according to the substitution reaction between the halogen group and the functional group, wherein the first thin film has a higher water contact angle than the second thin film Method of manufacturing a layer-by-layer multilayer thin film. delete The method according to claim 1,
The first thin film includes quantum dots, nanoparticles, or metal particles, and the first compound or second compound of the first thin film encapsulates the quantum dots, nanoparticles, or metal particles. Method for producing a multilayer thin film. The method according to claim 3,
The method of manufacturing the layer-by-layer multilayer thin film,
Stacking a second thin film on the substrate by first immersing the substrate in a solution containing the second compound; And
And immersing the substrate on which the second thin film is laminated in a solution containing the first compound, thereby laminating the first thin film on the second thin film, wherein the second thin film and the first thin film Method for producing a layer-by-layer multilayer thin film characterized in that it is bonded by a nucleophilic substitution reaction. The method of claim 4,
The solution comprising the first compound and the solution containing the second compound is a non-aqueous solution, the solution containing the second compound is a non-polar solution, characterized in that the manufacturing method of the layer-by-layer multilayer thin film. delete The method according to claim 1,
The first compound is 2-bromo-2-methylpropionic acid (BMPA), and the second compound is a poly (amidoamine) dendrimer method of manufacturing a layer-by-layer multilayer thin film. A layer-by-layer multilayer thin film produced by the method for producing a layer-by-layer multilayer thin film according to claim 1.

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