Method for producing metal nanoparticle-polymer composite thin film

Abstract

The present invention relates to a method for producing a metal nanoparticle-polymer composite thin film comprising uniformly shaped metal nanoparticles uniformly dispersed in a polymer matrix, and more particularly to a method for producing a gold nanoparticle-polymer composite thin film, comprising the steps of: (A) preparing a mixture of an ionic liquid and polyethylene oxide; (B) preparing a reaction solution by dissolving a gold nanoparticle precursor in the mixture; (C) producing a gold nanoparticle-polymer composite by applying plasma to the interface of the reaction solution; and (D) separating the gold nanoparticle-polymer composite from the reaction solution.

Claims

1. A method for producing a gold nanoparticle-polymer composite thin film, comprising the steps of: (A) preparing a mixture of an ionic liquid and a polyethylene oxide; (B) preparing a reaction solution by dissolving a gold nanoparticle precursor in the mixture; (C) producing a gold nanoparticle-polymer composite by applying plasma to an interface of the reaction solution; and (D) separating the gold nanoparticle-polymer composite from the reaction solution.

2. The method of claim 1, wherein the ionic liquid is a salt having a cation and an anion, the cation being substituted or unsubstituted 1-R-1-methylpyrrolidium or substituted or unsubstituted 1-R-3-methylimidazolium, wherein R is a C3 to C16 alkyl group, and the anion being BF4.sup., F.sup., Cl.sup., Br.sup. or I.sup..

3. The method of claim 1, wherein the polyethylene oxide is POE sorbitan fatty acid ester, POE alkyl phenyl ether, POE alkyl ether, or POE alkyl amine.

4. The method of claim 1, wherein a concentration of the gold nanoparticle precursor in the reaction solution is 0.01 to 1000 mM.

5. The method of claim 1, wherein the gold nanoparticle-polymer composite thin film has a thickness of 0.5 to 10 m.

6. The method of claim 1, wherein the gold nanoparticle-polymer composite thin film has a concentration gradient present along a section of the thin film.

7. The method of claim 2, wherein a concentration of the gold nanoparticle precursor in the reaction solution is 0.01 to 1000 mM.

8. The method of claim 2, wherein the gold nanoparticle-polymer composite thin film has a thickness of 0.5 to 10 m.

9. The method of claim 2, wherein the gold nanoparticle-polymer composite thin film has a concentration gradient present along a section of the thin film.

10. The method of claim 3, wherein a concentration of the gold nanoparticle precursor in the reaction solution is 0.01 to 1000 mM.

11. The method of claim 3, wherein the gold nanoparticle-polymer composite thin film has a thickness of 0.5 to 10 m.

12. The method of claim 3, wherein the gold nanoparticle-polymer composite thin film has a concentration gradient present along a section of the thin film.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 depicts a schematic view of a reaction according to one embodiment of the present invention, photographs showing a process of performing the reaction, and an SEM image and TEM image of a thin film produced through the reaction.

(2) FIG. 2 shows STEM-EDS mapping images of a gold nanoparticle-polymer composite thin film produced by one example of the present invention.

(3) FIG. 3 shows SEM images of a gold nanoparticle-polymer composite thin film produced by one example of the present invention.

(4) FIG. 4 depicts a sectional SEM image of a gold nanoparticle-polymer composite thin film produced by one example of the present invention and graphs showing STEM-EDS mapping of the thin film.

(5) FIG. 5 depicts SEM images showing the growth of gold nanoparticles in a gold nanoparticle-polymer composite thin film for varying plasma treatment times.

(6) FIG. 6 shows a high-resolution TEM image and FFT (Thermo Scientific, USA) image of pentagonal bipyramidal gold nanoparticles in a gold nanoparticle-polymer composite thin film.

(7) FIG. 7 depicts SEM images showing gold nanoparticle-polymer composite thin films formed using varying concentrations of a gold nanoparticle precursor in a solution.

(8) FIG. 8 depicts SEM images showing gold nanoparticle-polymer composite thin films formed using varying polymer contents.

(9) FIG. 9 depicts SEM section images and graphs showing the change in thickness of a gold nanoparticle-polymer composite thin film with a change in plasma treatment time.

DETAILED DESCRIPTION

(10) Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings and examples. However, these drawings and examples are only illustrative of the contents and scope of the technical idea of the present invention, and the technical scope of the present invention is not limited or modified thereby. It will be obvious to those skilled in the art that various modifications and alterations are possible based on this illustration without departing from the technical idea of the present invention.

EXAMPLES

Example 1: Production of Gold Nanoparticle-Polymer Composite Thin Film

(11) (1) Production of Composite Thin Film in Reactor

(12) Triton X-100 (Sigma-Aldrich, USA) was added to [BMIM]BF4 (1-butyl-3-methylimidazolium tetrafluoroborate, Sigma-Aldrich) to a final concentration of 6.0 mol %, followed by stirring using a vortex mixer (KMC-1300V) for 15 minutes. 10 mg of HAuCl.sub.4.Math.xH.sub.2O (M.W.=339.79, Sigma-Aldrich) was added to 2.943 mL of the mixture solution, followed by sonication for 15 minutes.

(13) 0.5 ml of the prepared solution was placed in a Teflon reactor (70 mm15 mm) and treated with plasma using an atmospheric-pressure plasma system (Ar, 150 W, 5 lpm) for 10 minutes. The distance between the plasma electrode and the liquid was 2 mm. After the plasma treatment, a film floating in the reactor was separated, washed sequentially with water and ethanol, and dried at 60 C. for 1 hour.

(14) FIG. 1a) is a schematic view of the above-described reaction, and FIGS. 1b) and 1d) are photographs of an actual reactor after the reaction. FIG. 1b) is a photograph of a reaction solution containing a gold nanoparticle precursor dissolved therein, before plasma irradiation, and the reaction solution showed yellow color due to AuCl.sub.4.sup.. FIG. 1c) is a photograph after plasma treatment of the surface of the reaction solution, and shows a brown thin film formed at the interface of the reaction solution. FIG. 1d) shows the reaction solution remaining after separating the thin film from the reaction solution after plasma treatment, and as can be seen therein, the yellow color of the reaction solution was very light. Since the yellow color was attributable to the color of AuCl.sub.4.sup., it appears that the change in the color of the reaction solution reflects a change in the concentration of AuCl.sub.4.sup..

(15) Accordingly, the change in the UV spectrum of the reaction solution with a change in the plasma treatment time was observed, and the results of the observation are shown in FIG. 1e). As shown therein, as the plasma treatment time increased, the absorbance at 323 nm due to the absorption of AuCl.sub.4.sup. decreased gradually, and after 15 minutes of plasma treatment, the peak at 323 nm completely disappeared, indicating that AuCl.sub.4.sup. was no longer present in the solution. In addition, the absorbance band at 550 nm which is the absorption wavelength of gold nanoparticles was also not present, suggesting that AuCl.sub.4.sup. was not reduced to gold nanoparticles in the solution. The above results suggest that AuCl.sub.4.sup. in the solution was not reduced to gold nanoparticles in the solution by plasma treatment, but was reduced after moved from the solution to the thin film formed at the interface and dispersed therein.

(16) (2) Production of Composite Thin Film on Glass Substrate

(17) Triton X-100 (Sigma-Aldrich, USA) was added to [BMIM]BF4 (1-butyl-3-methylimidazolium tetrafluoroborate, Sigma-Aldrich) to a final concentration of 1.5 mol %, followed by stirring using a vortex mixer (KMC-1300V) for 15 minutes. 10 mg of HAuCl.sub.4.Math.xH.sub.2O (Sigma-Aldrich) was added to the mixture solution, followed by sonication for 15 minutes.

(18) 0.5 ml of the prepared solution was dropped on a 2020 mm glass substrate, and then treated with plasma using an atmospheric-pressure plasma system (Ar, 150 W, 5 lpm) for 10 minutes. The distance between the plasma electrode and the liquid thin film was 2 mm. The plasma-treated glass substrate was immersed in ethanol, and the thin film was separated from the glass substrate, washed sequentially with acetone and distilled water, and then dried at 60 C. for 1 hour.

Example 2: Structural Analysis of Gold Nanoparticle-Polymer Composite Thin Film

(19) The thin film produced in Example 1-(1) was imaged with low-magnification and high-magnification SEM (JSM-7000F, JEOL, Japan), and the images are shown in FIGS. 1f) and 1g). A TEM (JSM-7000F, JEOL, Japan) image of nanoparticles included in the thin film is shown in FIG. 1h). Wrinkles observed in FIG. if) were those formed in a process of transferring the thin film onto a silicon wafer for SEM image observation, and the SEM images of FIGS. 1f) and 1g) shows that particles having a uniform size were uniformly dispersed in the polymer thin film without being agglomerated. The scale bar in FIG. 1h) showing the TEM image indicates 100 nm, and suggests that Au nanoparticles had a particle size of about 100 nm and a clearly defined shape.

(20) The components of the produced thin film were analyzed by STEM-EDS (scanning transmission electron microscopy energy dispersive spectrometry). FIG. 2 depicts STEM-EDS mapping images, and shows that all elements, including Au, C, F, N and O, were uniformly dispersed. This indicates that the produced thin film is a gold nanoparticle-polymer composite thin film comprising gold nanoparticles dispersed in the polymer matrix.

(21) FIG. 3a) is an SEM image (scale bar: 10 m) of the gold nanoparticle-polymer composite thin film transferred onto a silicon wafer, and FIGS. 3b) and 3c) are enlarged SEM images (scale bar: 1 m) of the top surface and bottom surface, respectively, indicated in FIG. 1a). To produce the gold nanoparticle-polymer composite, HAuCl.sub.4.Math.xH.sub.2O was dissolved in [BMIM]BF.sub.4 containing 3 mol % of Triton X-100 solution to a molar concentration of 10 mM, and then treated with plasma for 10 minutes according to the method of Example 1-(2), and the produced composite was separated. FIG. 3 shows that the concentration of gold nanoparticles differs between the top surface and the bottom surface. This suggests that the polymer thin film was first formed at the interface by the cross-linking reaction between Triton X-100 and the ionic liquid, and AuCl.sub.4.sup. from the solution was inserted into pores formed by the cross-linking reaction, and then grown into gold nanoparticles by plasma, and the polymer thin film was grown in the direction from the top surface to the bottom surface, thereby producing the gold nanoparticle-polymer composite thin film. Since the bottom surface of the thin film was in contact with the solution containing AuCl.sub.4.sup. dissolved therein, the size of the gold nanoparticles was as small as about 50 nm, and increased gradually toward the top surface, and was about 100 to 150 nm in the middle-height portion of the thin film.

(22) FIG. 4 depicts a SEM image of the section of the gold nanoparticle-polymer composite thin film and EDS mapping along the section, and shows the size and distribution of gold nanoparticles in the section of the composite thin film. In FIG. 4b), the left (0 m) indicates the top surface, and the right indicates the bottom surface. From FIG. 4, it can be seen that the concentration of gold nanoparticles did differ along the section, but at the same thickness, the variation in the size of the gold nanoparticles was small and the gold nanoparticles were uniformly dispersed.

Example 3: Analysis of Growth of Gold Nanoparticles for Varying Plasma Treatment Times

(23) In order to examine the process of growth of gold nanoparticles in a polymer matrix, gold nanoparticle-polymer composite thin films were produced while changing the plasma treatment time to 2 min, 6 min, 10 min and 15 min. The produced gold nanoparticle-polymer composite thin films were observed with SEM and TEM, and the results of the observation are sequentially shown in FIGS. 5a) to 5d). The content of Triton X-100 relative to [BMIM]BF.sub.4 was 6 mol %, and the concentration of the gold nanoparticle precursor was 10 mM.

(24) It was clearly observed that gold nanoparticles were formed after 2 minutes of plasma irradiation. It can be seen that the gold nanoparticles had an irregular shape and a size of about 20 nm and were single-twinned particles uniformly dispersed in the polymer thin film. When plasma was irradiated for 6 minutes, the size of the gold nanoparticles increased to about 60 nm, and the shape of the particles also greatly changed to polygonal bipyramidal particles, such as trigonal bipyramidal, tetragonal bipyramidal, pentagonal bipyramidal, and truncated trigonal bipyramidal particles. FIG. 6 shows a TEM image and FFT (Thermo Scientific, USA) image of a pentagonal bipyramidal nanoparticle, and shows that the pentagonal bipyramidal nanoparticle was a single crystal having a single twin plane indicated by the yellow line. It is known that a pentagonal bipyramidal nanoparticle consists of five tetrahedral crystals having the (111) plane and acts as the nucleus of nanocrystal growth of gold nanoparticles. When the plasma treatment time increased to 10 minutes, AuCl.sub.4.sup. moved from the solution to the polymer thin film and around the nucleus, and was then reduced slowly, thereby producing clearly defined nanoparticles having a uniform size of about 100 nm, such as octahedral, decahedral, dodecahedral, and truncated trigonal bipyramidal nanoparticles. As the gold nanoparticles grew, the concentration of AuCl.sub.4.sup. in the solution present under the gold nanoparticle-polymer composite thin film decreased gradually.

(25) When the plasma treatment time further increased to 15 minutes, the gold nanoparticles grew to a size of about 150 nm and had a side with a sharp edge. Most of the nanoparticles were octahedral and truncated trigonal bipyramidal nanoparticles, which were face-centered cubic single crystals having (110) and (111) planes.

(26) Regardless of the plasma treatment time, all the nanoparticles were uniformly dispersed in the polymer matrix without being agglomerated, and had a uniform particle size. Meanwhile, as the plasma treatment time became longer, the thickness of the thin film gradually became thicker.

Example 4: Analysis of Formation of Composites at Varying Concentrations of Gold Nanoparticle Precursor

(27) In order to analyze the effect of the concentration of the gold nanoparticle precursor in the solution on the formation of the composite thin film, gold nanoparticle-polymer composite thin films were produced by plasma treatment under conditions in which the concentrations of the gold nanoparticle precursor were 5, 10, 40 and 80 mM. The surfaces of the thin films were observed with a SEM, and the results of the observation are sequentially shown in FIGS. 7a) to 7d). The content of Triton X-100 relative to [BMIM]BF.sub.4 was 6 mol %, and atmospheric pressure plasma treatment (Ar, 150 W, 5 lpm) was performed for 10 minutes.

(28) As can be expected, as the concentration of the gold nanoparticle precursor in the solution increased, the concentrations of gold nanoparticles in the composite thin film also increased, and a gold nanoparticle-polymer composite thin film comprising gold nanoparticles uniformly dispersed therein without being agglomerated was formed.

Example 5: Analysis of Formation of Composites Using Varying Polymer Contents

(29) In order to analyze the effect of the polymer content on the formation of the composite thin film, gold nanoparticle-polymer composite thin films were produced by plasma treatment under conditions in which the contents of Triton X-100 were 1.5, 3, 6 and 12 mol %. The surfaces of the thin films were observed with a SEM, and the results of the observation are sequentially shown in FIGS. 8a) to 8d). The concentration of the gold nanoparticle precursor was 10 mM, and atmospheric pressure plasma treatment (Ar, 150 W, 5 lpm) was performed for 10 minutes.

(30) As the content of Triton X-100 increased, the thickness of the composite thin film formed decreased. When the content of Triton X-100 was 1.5 mol %, the thickness was the greatest. When the content of Triton X-100 was 1.5 mol %, the size of the gold nanoparticles was very small, and the crystal shape was also not clear. This is believed to be because when the content of Triton X-100 was low, the thickness of the polymer layer formed increased and the growth of the gold nanoparticles was also slow. As the content of Triton X-100 increased, the size of the particles formed increased, reached the greatest at 6 mol %, and then showed a tendency to decrease.

Example 6: Evaluation of the Effect of Gold Nanoparticle Precursor on Thickness of Composite Thin Film

(31) In order to evaluate the effect of the gold nanoparticle precursor on the growth of the composite thin film, the thickness of the polymer thin film produced was compared between when the gold nanoparticle precursor was present (the concentration of the precursor in the solution was 10 mM) and when the gold nanoparticle precursor was not present. FIGS. 9a) to 9e) are SEM section images of composite thin films produced by 1 min, 2 min, 5 min, 10 min and 20 min of plasma treatment, respectively, and show that a thin film having a uniform thickness was formed by plasma treatment and as the plasma treatment time increased, the thickness increased gradually. FIG. 9f) is a graph showing the thickness of the produced thin film as a function of the plasma treatment time. In this figure, the red color indicates the thickness of the gold nanoparticle-polymer composite thin film produced with the addition of 10 mM of the gold nanoparticle precursor, and the blue color indicates the thickness of the polymer thin film produced without the addition of the gold nanoparticle precursor.

(32) The thickness of the polymer thin film produced without the addition of the gold nanoparticle precursor was as thin as about of the thickness of the composite thin film produced by plasma treatment for the same time. It could be seen that, regardless of the presence or absence of the gold nanoparticle precursor, as the plasma treatment time increased, the thickness of the thin film produced increased gradually, and then no longer increased after about 10 to 15 minutes.