KR100809629B1 - The confocal raman/uv-vis/fluorescence spectroscopy for the combinatorial structural analysis of novel catalysts, materials, and biomolecules - Google Patents

Abstract

A confocal Raman/UV-Vis/fluorescence spectroscopy for combinatorial structural analysis of novel catalysts, materials, and biomolecules is provided to effectively perform structure analysis and quantitative analysis of samples. A confocal Raman/UV-Vis/fluorescence spectroscopy for combinatorial structural analysis of novel catalysts, materials, and biomolecules includes an argon laser(101), a diode laser(134), an XYZ stage(132), a sample chamber(133), three monochrome light devices(123), an optical amplification tube(131), and a CCD detector(106). The argon laser has a wavelength of 488 to 514nm. The diode laser has a wavelength of 785nm. The XYZ stage is automatically controlled by a computer. The sample chamber includes an objective lens having various magnifications. The optical amplification tube and the CCD detector detect the signals.

Description

The confocal Raman / UV-Vis / Fluorescence spectroscopy for the combinatorial structural analysis of novel catalysts, materials, and biomolecules}

Figure 1 is a schematic diagram showing the main part of the confocal Raman / ultraviolet-visible / fluorescence spectrometer according to an embodiment of the present invention.

FIG. 2 is a Raman spectrum of Bi _4-x Ce _x Ti ₃ O ₁₂ (BCT, 0 <x <4), which is a ferroelectric thin film library according to an embodiment of the present invention. FIG. Figure 2 (b) shows the Raman spectrum according to the concentration of Ce of Bi _4-x Ce _x Ti ₃ O ₁₂ (BCT, 0 <x <4).

3 is a Raman spectrum of Bi _4-x Ce _x Ti ₃ O ₁₂ (BCT, 0 <x <1), which is a ferroelectric thin film library measured using the present invention, according to an embodiment of the present invention. ) Is a principle diagram related to the library preparation method, Figure 3 (b) shows the Raman spectrum according to the concentration of Ce of Bi _4-x Ce _x Ti ₃ O ₁₂ (BCT, 0 <x <1), Figure 3 (c) shows the magnitude of the stretching mode between Ti and O, one of the Raman vibration modes associated with the present structure, according to the concentration of Ce. FIG. 3 (d) shows the change in residual polarization of the BCT thin film array according to the concentration of Ce. It is shown.

4 is a Raman spectrum of Bi _4-x La _x Ti ₃ O ₁₂ (BLT, 0 <x <1), which is a ferroelectric thin film library according to an embodiment of the present invention, and FIG. 4 (a) is related to a library manufacturing method. Fig. 4 (b) is a Raman spectrum according to the concentration of La in Bi _4-x La _x Ti ₃ O ₁₂ (BLT, 0 <x <1), and Fig. 4 (c) is Raman related to the present structure. The size of the stretching mode between Ti and O, which is one of the vibration modes, is shown according to the concentration of La, and FIG. 4 (d) shows the residual polarization change of the BLT thin film array according to the concentration of La.

FIG. 5 is a Raman spectrum of a nanocomposite in which bonds are formed between various metals and carbons measured using the apparatus according to an embodiment of the present invention.

FIG. 6 is a Raman spectrum of Rh6G present on Rhodamine 6G (Rh6G) powder and a silver nanocluster dispersed in a solution and a submonolayer measured using the apparatus according to an embodiment of the present invention. FIG. Silver is the full Raman spectrum of Rh6G with or without the presence of nanoclusters, Figure 6 (b) shows an enlarged Raman spectrum of Rh6G powder.

Figure 7 shows the fluorescence spectrum of Y _3-x Al ₅ O ₁₂ : Cex measured by using the equipment according to an embodiment of the present invention.

Figure 8 shows the ultraviolet reflection and absorption spectrum of the TiO ₂ (anatase) powder measured by using the equipment according to an embodiment of the present invention.

9 shows ultraviolet / visible light reflection and absorption spectra of silver nanoclusters dispersed into submonolayers measured using the instrument in accordance with an embodiment of the present invention.

{The main part of the drawing is a description of the signs}

101: argon ion laser head 102: laser beam tuning mirror

103: laser mirror 104: shutter

105: ND filter 106: CCD detector

107: transmission grating 108: mirror

109: holographic notch filter 110: mirror

111: fiber optic cable 112: holographic notch filter

113: cut-up filter 114: beam tuning mirror

115: filter box 116: APD detector

117: system controller 118: CCD camera

119 beam splitter 120 laser mirror

121: ultraviolet / visible light source 123: monochromator

124: optical fiber cable 126: parabore focusing mirror

127: parabolic collimating mirror 128: beam tuning mirror

129: Parabora focusing mirror 130: Monochromator

131: PMT detector 132: sample stage

133: sample chamber 134: laser diode set

135: Raman spectrometer

The present invention at least a diameter of 300 ㎛ the micro sample 10 in the sample array integrated over ⁴ minutes associated with exactly confocal Raman, UV / visible light and fluorescence spectroscopy are combined composite system for evaluating the optical properties within a few hours will be.

Although numerous material synthesis experiments have been extensively carried out for the development of new materials and catalysts, the general rules that can be predicted with the composition, structure and reaction path of solid compounds have not been revealed to date. This is one big barrier to sustaining high cost and low efficiency research in the development of new materials of multi-component systems where synthesis and analysis of new compounds are based on existing knowledge and principles. For example, when 100 elements on the periodic table, which can make a composition consisting of three to six component systems or more, are used, the limitation of the search range through the existing experiment becomes even more obvious. For this reason, a more effective and economical approach to the development of new materials with useful properties needs to be extended to the scope of research not found in previous experiments. Part of the effort to solve this problem is the combinatorial semester technique. In other words, in a single experiment, more than 100 samples of various compositions are prepared in the form of thin films or powders and quickly characterized to find a material or catalyst having the desired physical properties. However, until now, performance has been limited to inorganic electronic materials whose performance is highly dependent on the composition. This is due to the lag behind the rapid development of sample array fabrication and the development of devices that can effectively structure and characterize it.

In order to solve this problem, modifications are inevitable in order to apply the structural analysis equipment mainly used in the existing experiments to the combination chemical technique. A typical example is a microbeam x-ray diffraction apparatus developed by Bruker. In order to analyze the micro sample array, the beam size of the x-ray was reduced to 100 μm using various optical lenses, and the increase in the signal-to-noise ratio was solved by mounting a high sensitivity detector. In addition, in order to scan more than 100 integrated samples on a substrate, the crystal structure of each sample may be analyzed using an XYZ stage moving by a computer program. The present invention aims to develop a confocal Raman, ultraviolet / visible and fluorescence spectrometer based on these basic components, i.e. minimizing beam size, high sensitivity detector and XYZ stage controlled by computer coordinates. .

Raman spectroscopy found that when the sample is irradiated with light in the visible region, the wavelength of the scattered light is slightly different from the wavelength of the irradiated light, and this difference is related to the chemical structure of the scattered sample. Leave. However, it did not spread as quickly as an infrared spectrometer. This means that the intensity of Raman scattering (or inelastic scattering) is less than one-hundredth of that of Rayleigh scattering (or elastic scattering), eliminating ray ray scattering with optical systems such as optical filters and detecting only the desired Raman scattering. This is due to the drawback that it is very difficult to develop a detector system. To overcome this, the visible light laser was developed along with the improved sensitivity of the optical amplification tube (PMT) used as a detector in the 1960s. In particular, as visible lasers are recognized as ideal light sources for obtaining the Raman spectrum, they have the appearance of a device called a dispersive Raman spectrometer. However, this equipment has a disadvantage in that it cannot measure impurities and samples that generate fluorescence, so it was used in a limited area until the 1980s. Recently, however, several long-wavelength lasers, such as diode lasers (785nm) and Nd / YAG lasers (1064nm), have been developed, and multichannel detectors based on CCDs (charged-coupled devices) instead of conventional optical amplification tubes have been developed. Solved the problem. In addition, to improve the signal-to-noise ratio of the Raman spectrometer, a notch filter or a monochromator is used to prevent the light of a wavelength longer than the wavelength of the light source to detect only the Raman scattering that we want. In particular, active research is being conducted until recently regarding the amplification of optical signals related to fine Raman scattering.

The advantage of such a Raman spectrometer is that it is very easy to analyze the structure of a sample dissolved in an aqueous solution because the spectrum is not interrupted by water or glass. This is an opportunity to extend the application to the biological field. In addition, when the laser is irradiated on inorganic materials, organic polymers, ionic solids, metal alloys, and biomolecules, local structural analysis using polarization phenomenon due to the interaction between the electric field and the electron cloud in the bond constituting the inorganic material It is also widely used as a tool.

In the 2000s, with the growing interest in microstructure analysis due to the remarkable advances in nanotechnology, a micro Raman system was developed that reduced the beam size in conventional Raman equipment to micro units for the above research applications. Is being used. One of them is being used to detect the process yield in order to prevent the process yield is reduced due to the fine foreign material adhered on the wafer in the semiconductor process is becoming increasingly integrated. In addition, it has been used to analyze the mechanism of interaction between liquid and solid molecules in polymer polymerization and to find micro size defects in semiconductor devices.

    As mentioned above, Raman spectroscopy is very useful for structural analysis of samples dissolved in aqueous solution, but not for quantitative analysis. It was developed to compensate for this UV / visible spectroscopy. The absorbed spectrum is obtained by irradiating light having a wavelength range of 200 to 900 nm to the sample dissolved in the aqueous solution, and the concentration of the sample dissolved in the solution can be quantified by the following equation.

A = -log T = log (P ₀ / P) = εbc (Beer's Law)

Where: A: Absorbance, T: Transmittance, b: Distance of light transmission, c: Concentration of chemical species to absorb light, P ₀ : Intensity of light before solution transmission, P: Intensity of light after solution penetration, ε: proportionality constant

Since most ultraviolet / visible spectroscopy are transmissive, the solution must be contained in a transparent cell, such as siliconized glass, which can pass these light sources well to suppress reflection and loss of light, and the absorption spectrum thus obtained is detected by the optical amplification tube. Will be. Recently, various sensing systems such as multi-channel detectors based on CCDs mentioned in Raman spectroscopy have been developed and applied to improve the time to acquire the spectrum by the optical amplifier tube and to reduce the ratio of signal to noise ratio. It is done. In addition, ultraviolet / visible spectroscopy is used to determine the fluorescence characteristics of the phosphor, which is a key material for the development of display materials.

As discussed here, the existing Raman, ultraviolet / visible and fluorescence spectrometers focus on measuring individual samples, and the development of detector systems and optical systems has been a priority. Therefore, it is not suitable for measuring a sample array in which 100 or more microsamples are integrated on a wafer or a substrate in a short time, and modification and supplementation thereof are inevitable.

The present invention has been made to solve the above problems, the object of which is to more efficiently by redesigning and manufacturing the existing Raman, UV / visible and fluorescence spectroscopy to be applicable to the combination chemistry techniques In addition to structural analysis of the sample, it is to perform quantitative analysis.

Confocal Raman / ultraviolet-visible / fluorescence spectrometer of the present invention to achieve the above object is a confocal Raman spectrometer for analyzing the structure of the sample by analyzing the wavelength change of the light reflected from the sample; Ultraviolet-visible light and fluorescence spectrometers that analyze the structure of the sample using the interaction between energy in the molecule and light energy; A sample chamber in which a sample for analyzing the structure is mounted in the Raman spectroscope and the ultraviolet-visible and fluorescence spectrometers; And a data input processor for controlling the sample chamber and data on the structure of the sample analyzed by the Raman spectrometer and the ultraviolet-visible and fluorescence spectrometers.

In the present invention, it is preferable that the sample chamber is provided with a highly integrated sample array in which at least 300 micrometer-sized microsamples are directly directed to 10,000 or more.

In the present invention, the data input processing unit preferably sets the coordinates of the sample chamber to move the stage.

In the present invention, it is preferable that the Raman analyzer selects a laser in the visible and infrared regions.

In the present invention, it is preferable that the data input processing unit enables image mapping using an avalanche photo diode (APD).

In the present invention, the ultraviolet-visible light and the fluorescence analyzer preferably detects the beam reflected from the sample chamber in the optical amplification tube by using two mirrors.

In the present invention, it is preferable that the fluorescence analyzer enables the emission and excitation mode of the sample molecules, and the UV / visible light analyzer enables the reflection and absorption scan mode of the sample molecules.

The present invention integrates a confocal Raman system and an ultraviolet / visible and fluorescence spectrometer to simultaneously measure the Raman spectrum, fluorescence properties, ultraviolet / visible absorption spectrum of various materials and catalysts, thereby facilitating qualitative and quantitative analysis.

In addition, we implemented an automated system to drive the x-y stage by a computer program for structural analysis of a library of more than 100 micron-sized microsamples. In this case, the most important question is how to obtain a good signal-to-noise spectrum when the microsample array is irradiated with a fine beam size in a short time. The confocal Raman spectrometer features a holographic monochromator and a highly sensitive back-illuminated photo array detector to reduce analysis time and improve signal-to-noise ratio.

Therefore, a high quality spectrum can be obtained without damaging a sample. In addition, objective magnifications of various magnifications can be used to minimize the size of the beam down to about 1 micron.

In the fluorescence and ultraviolet / visible absorption spectra, scanning in the range of 200-900 nm is possible by replacing two light sources with ultraviolet / visible light instead of laser light. In particular, because of the absorption spectrum as well as the emission (excitation) and the excitation (excitation) mode is possible, it is very effective in analyzing the fluorescence and composition of the sample. In addition, the program was developed so that all analysis and evaluation could be performed automatically by computer.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. In adding reference numerals to components of the following drawings, it is determined that the same components have the same reference numerals as much as possible even if displayed on different drawings, and it is determined that they may unnecessarily obscure the subject matter of the present invention. Detailed descriptions of well-known functions and configurations will be omitted.

Figure 1 is a schematic diagram showing the main part of the confocal Raman / ultraviolet-visible / fluorescence spectrometer according to an embodiment of the present invention.

Referring to FIG. 1, an argon laser (wavelength: 488, 514 nm) 101 or a diode laser (wavelength: 785 nm) 134 and an ultraviolet / visible light source 121 may be exchanged and used. XYZ stage 132 automatically controlled by the sample chamber, the sample chamber 133 equipped with objective lenses (2x-90x) of various magnifications for focusing at the time of sample measurement, and 3 monochromatic light devices for light resolution (123). And a high sensitivity optical amplifier tube 131 and a CCD detector 106 for detecting a signal.

In the confocal Raman spectrum analysis, argon 101 or a diode laser 134 is used as a light source, and the incident laser is irradiated perpendicularly to the sample 132 through an objective lens to focus. Light scattered from the sample 132 is analyzed by the CCD detector 106 cooled in liquid nitrogen through an optical fiber through an objective lens parallel to the incident laser. In addition, the CCD camera 118 allows viewing of the surface of each sample array on a wafer or substrate through a computer screen. The magnification for this depends on the magnification of the objective lens (2 times-90 times) located at the top inside the sample chamber 133. The method of inputting coordinates differs depending on the shape of the fine sample array integrated on one wafer as the fine point, and a program for this has been developed.

For example, if the overall shape where the entire sample is placed is a rectangle, the coordinates of the upper left point and the lower right point are moved by XY stage to check the coordinates and input them into the program. At this time, each sample should be placed at a predetermined distance on the wafer. After we have done this and run it in the program, we will continuously measure the spectrum according to our position. Since the number of samples is as small as 50 or as many as 400 or more, the measurement time is mainly short from 10 to 30 seconds. In addition, as mentioned above, confocal Raman uses a high-sensitivity optical array detector system (1340 X 400 pixels, manufactured by Princeton) and a holographic monochromator to improve the signal-to-noise ratio. In addition, image mapping is possible using the APD module.

In the ultraviolet / visible and fluorescence spectrometers, deuterium lamps are used as ultraviolet light sources and tungsten lamps as visible light lamps instead of laser light sources. In the ultraviolet / visible spectrum and fluorescence characteristics analysis, the optical amplification tube 131 is mainly used and is designed to use a CCD detector. Since visible light and ultraviolet light are not light sources emitted from short wavelengths such as lasers, the size of the beam cannot be minimized with an optical lens. Therefore, it was possible to minimize to 300 ㎛ using the optical fiber 124. Unlike conventional equipment for the analysis of micro sample arrays, the mirror 126 is not transmissive but reflects light from the UV / visible region at a slight angle to the sample using a mirror 126 to mirror the opposite light signal generated. It is reflected by the mirror 127 and finally detected by the optical amplification tube (PMT) 131. This allows structural analysis of thin film and powder libraries of dozens or more of samples at the same time while driving the XY stage. In addition, scanning in the range of 200-900 nm is possible in the fluorescence and ultraviolet / visible light absorption spectra, and in particular, the emission and excitation modes are possible in the fluorescence, which is very effective for fluorescence characteristics and component analysis of the sample. In addition, the program was developed so that all analysis and evaluation could be performed automatically by computer. Visible / ultraviolet spectroscopy is also the same because the coordinate setup and scanning of the microsample array share the XY stage with the confocal Raman spectrometer.

Therefore, this equipment can realize the Raman spectrum, fluorescence, and ultraviolet / visible absorption spectrum of the library sample with high concentration of fine samples at the same time without changing the sample in one device.

Hereinafter, an embodiment in which the actual thin film according to the spectrometer of the present invention is measured will be described.

Example 1 Analysis of Ferroelectric Bi _4-x Ce _x Ti ₃ O ₁₂ (BCT, 0 <x <4) Thin Film Array Structure Using Confocal Raman System

In order to fabricate (Bi, Ce) ₄ Ti ₃ O ₁₂ thin film arrays, Bi ₂ O ₃ , TiO ₂ , and CeO ₂ targets were used as the respective metal precursors and sputtered by Pt / TiO ₂ / SiO ₂ / Si The time exposed during deposition to stack on the substrate and change the Bi / Ce ratio in the x-axis direction as shown in Fig. 2 (a) can be produced by a computer controlled shutter. After the deposition, heat treatment was carried out in an oxygen atmosphere at 400 ° C. for 1 hour and then reheated at 700 ° C. for 1 hour for crystallization. Figure 2 (b) shows the spectrum scanned at regular intervals along the x-axis direction using the confocal Raman system. At this time, the laser intensity was 40 mW, and the measurement time for each sample was 10 seconds. The light source was an argon laser with a wavelength of 488 nm. According to this spectrum, three peaks (260, 550, 847 cm ^-1 ) and shoulder (317cm ^-1 ) related to TiO ₆ observed in bismuth layered structure were observed in the concentration range of Ce concentration (x) within 0.8. This is evidence that Bi ₂ O ₃ / CeO ₂ / TiO ₂ is well mixed. Here, the B _2g and B _3g modes coming out of 260cm ^-1 are combined to represent the bent vibration between Ti and O, and the peak coming out of 550cm ^-1 is the vibration mode in which oxygen located at the two peaks of TiO ₆ moves in opposite directions. It is involved in the warping of TiO ₆ . The peak at 847 cm ⁻¹ represents the stretching mode between Ti and O. Finally, the shoulder at 317 cm ^-1 is a combination of the above two bend vibration modes and stretching vibration modes. However, as the concentration of Ce increases, the peak at 847 cm ^-1 , which indicates the stretching vibration between Ti and O, gradually decreases and almost disappears from the fourth (Bi / Ce = 3.2 / 0.8) spectrum. In addition, it was observed that the other two peaks also shifted to Raman spectra (205, 460, 608 cm ⁻¹ ) occurring in the CeO ₂ structure rather than the bismuth layered structure. Through this, the sample can be uniformly formed in the concentration of Ce within 0.8, through which it was possible to predict the composition range having the desired ferroelectric properties.

Example 2 Analysis of Bi _4-x Ce _x Ti ₃ O ₁₂ (BCT, 0 <x <1) Thin Film Array Structure Using Confocal Raman System

Based on the conclusion that in Example 1, the concentration (x) of Ce has ferroelectricity in a concentration range of less than 1, each metal precursor material was laminated by sputtering as shown in FIG. 3 (a) to (Bi, Ce) ₄ Ti ₃ An O ₁₂ thin film array was prepared as shown in FIG. 2 (a). In this case as well, in order to change the Bi / Ce ratio in the x-axis direction, a shutter controlled by a computer was used to control the exposure time during deposition. After deposition, heat treatment was carried out at 400 ° C. for 1 hour in an oxygen atmosphere and then reheated at 700 ° C. for 5 hours for crystallization. Figure 3 (b) shows a spectrum scanned at regular intervals along the x-axis direction using the confocal Raman system. At this time, the laser intensity was 40 mW, and the measurement time for each sample was 30 seconds. The light source was an argon laser with a wavelength of 488 nm.

According to this spectrum, BCT film sample in the entire region that the concentration of Ce 1 or less are bismuth three peaks associated with the TiO ₆ observed in the layered structures ^{(260, 550, 847 cm -1} ) and the shoulder (317cm ^-1) a Was observed, which is consistent with the above results. However, it was easy to observe that as the concentration of Ce increases, the size of the peak at 847 cm ⁻¹ , which indicates a stretching vibration between Ti and O, gradually decreases. This (Figure 3 (c)) which spontaneous while the sample is subjected to restriction on the movement of oxygen when rotated about an axis parallel to the polarization direction when applied and an electric field in has a TiO ₆ structure of this TiO ₆ is slightly expanded polarization It is due to the mechanism that occurs. Therefore, this peak is deeply related to the spontaneous polarization value of the ferroelectric and may be one reason for predicting the appearance of excellent ferroelectric characteristics in the region of low Ce concentration. As the concentration of Ce gradually decreased, it was confirmed that the residual polarization value increased. However, when the concentration of Ce was too small (x <0.3), electrical characteristics could not be measured in spite of the large stretching vibration mode of Ti and O at 847 cm ^-1 . This is because when too small amount of Ce (x <0.3) is substituted at Bi site, it promotes the stationary immobilization which reduces the movement of ferroelectric domain. This acts as a stress when an electric field is applied, which means that the stress appears as a new phase or a defect, thereby increasing the leakage current density. Therefore, confocal Raman equipment is difficult to predict the exact optimal composition, but it is likely that the equipment is an efficient equipment for predicting the composition region where the optimal composition is located.

Example 3 Analysis of Bi _4-x La _x Ti ₃ O ₁₂ (BLT, 0 <x <1) Thin Film Array Using Confocal Raman System

Unlike Examples 1 and 2, (Bi, La) ₄ Ti ₃ O ₁₂ thin film array was manufactured by stacking each metal precursor material by sputtering as shown in FIG. 4 (a) using La ₂ O ₃ target instead of CeO ₂ . It was. In this case as well, in order to change the Bi / La ratio in the x-axis direction, a shutter controlled by a computer was used for the exposure time during deposition. After deposition, heat treatment was carried out at 400 ° C. for 1 hour in an oxygen atmosphere and then reheated at 700 ° C. for 5 hours for crystallization. Figure 4 (b) shows the spectrum scanned at regular intervals along the x-axis direction using the confocal Raman system. At this time, the laser intensity was 40 mW and the measurement time per sample was 30 seconds. The light source was an argon laser with a wavelength of 488 nm.

According to this spectrum, BLT film sample in the entire region that the concentration of La less than or equal to 1 are bismuth three peaks associated with the TiO ₆ observed in the layered structures ^{(260, 550, 847 cm -1} ) and the shoulder (317cm ^-1) a Was observed. As with the BCT array, it was easy to observe that the size of the peak at 847 cm ^-1 gradually decreases as the substitution concentration of La increases, as in the BCT array (Fig. 4 (c)). It can be one of the reasons for predicting the appearance of excellent ferroelectric characteristics in the region of low concentration. In fact, as shown in Fig. 4 (d), the ferroelectric characteristics are reduced when the concentration of La (x) is between 0.25 and 0.33. It was confirmed that it is very excellent. However, at too small a concentration (x <0.2), the electrical properties could not be measured despite the large stretching mode between Ti and O. This is due to the immobilization of the ferroelectric domain, which occurs when too little La is substituted at the Bi site, as mentioned above.

Example 4 Structure Analysis of Metallic Carbon Nanocomposites as Hydrogen Storage Materials Using Confocal Raman System

 In order to prepare a metal-nano composite having a predetermined structure, a nano-frame such as SBA-15 was prepared by the following method. First, 380 mL of 1.6M hydrochloric acid solution and 10 g of Pluronic P123 from BASF were stirred at room temperature, and 22 g of tetraethylorthosilicate (TEOS) was added thereto, and the mixture was maintained at 35 ° C for 12 hours. . Thereafter, the mixture was maintained at 100 ° C. for 24 hours, followed by filtration and drying, and then calcined at 550 ° C. for 2 hours to prepare a SBA-15 nano-frame having a predetermined structure.

The metal precursor solution was added to the nano-frame so that 2.5 mol% of the metal was impregnated on the basis of 1 g of the nano-frame (SBA-15) thus prepared, and the mixed solution was dried with a vacuum dryer to form the metal precursor outside the nano-frame. Was dispersed. Preferred metal precursors are nitrides or chlorides. This impregnation process is a process of uniformly inducing the metal precursor into the nano-frame by vacuum drying the solution containing the metal precursor and the nano-frame. Then 2.5 g of sucrose, 0.28 g of sulfuric acid and 10 g of water were added and mixed uniformly. Thereafter, the mixture was reacted at 100 ° C. and 160 ° C. for 6 hours, and then carbonized in a vacuum atmosphere at 900 ° C. Then, using a 5wt% hydrofluoric acid aqueous solution to dissolve and remove the nano-frame, washed to prepare a metal-carbon composite having a nanostructure. At this time, a variety of silver (Ag), gold (Au), cobalt (Co), chromium (Cr), copper (Cu), magnesium (Mg), nickel (Ni), tungsten (W), zirconium (Zr) Metal-carbon nanocomposite libraries with transition metals were synthesized and analyzed using confocal Raman equipment. At this time, the measurement time for each sample was 10 seconds, and the laser intensity was 12 mW because it contained carbon. As shown in FIG. 5, the molybdenum-bonded carbon nanocomposite showed an amorphous form in which two peaks occurring in carbon nanotubes were hardly observed. In contrast, when the metals such as chromium, cobalt, and copper were combined, 1350 and 1587 The characteristic peaks of carbon nanotubes at cm ⁻¹ were easily distinguished.

Example 5 Rh6G Detection on Silver Nanoclusters Using Confocal Raman System

This system is capable of detecting biomolecules, and FIG. 6 is a spectrum of Rh6G, which is a label for detecting biomolecules on silver nanoclusters. The silver nanocluster solution was prepared by reducing an aqueous solution of nitrogen oxide (AgNO ₃ , Aldrich) at 95 ^° C. with sodium citrate (Aldrich) and reducing it for 30 minutes. At this time, about 2 wt% of polypyrrolidone (Aldrich) was added as a molecular agent to disperse the produced silver nanoparticles, and the average size of the produced nanoparticles was about 50 nm. As a substrate for dispersing nanoclusters, slide glass is used to remove organic and metal contaminants, and a silane compound containing amino group (APTMS, Aldrich) is used as a binder for connecting the nanoclusters and glass. ) Was used. The surface treated glass was immersed in a plastic petric dish containing silver nanocluster solution for at least 8 hours, washed three times with distilled water, and dried with nitrogen. At this time, the nanocluster formed a submonolayer on the glass. Rh6G (Rhodamine 6G, Aldrich), a label for biomolecule detection, was dissolved in distilled water containing 50% ethanol to prepare a 1 mM Rh6G aqueous solution. The silver nanocluster dispersed glass was immersed in the prepared aqueous solution for about 2 hours, washed three times or more with tertiary distilled water, and dried with a nitrogen gun. As shown in FIG. 6, the amplification of the Raman signal by the silver nanoclusters was confirmed. This signal amplification results in the formation of surface plasmons by interaction between the incident visible light laser (488 nm) and the silver nanoclusters, leading to the formation of an amplified electromagnetic field between the nanoparticles. The amplified electromagnetic field was able to detect high sensitivity of Rh6G in trace amounts between nanoparticles. At this time, the analysis time of the Raman spectrum was 1 second, and it was possible to confirm the possibility of analyzing several samples in a short time.

<Example 6> Measurement of Luminescence Characteristics of Y _3-x Al ₅ O ₁₂ / Ce _x Phosphors by UV / Visible Spectroscopy System

The system can measure in excitation and emission modes. In this embodiment, emission intensity and excitation intensity values for Y _3-x Al ₅ O ₁₂ / Ce _x material, which is one of the green emitters, are measured. Measurements were made to confirm physical characteristics of the degree of luminescence, and FIG. 7 is a spectrum measured by an ultraviolet / visible spectroscopic system.

Example 7 Measurement of Optical Properties of Silver Nanoclusters for TiO ₂ Photocatalyst and Biomolecule Detection Using UV / Visible Spectroscopy System

The system is capable of measuring the electron transfer properties of inorganic oxides and the wavelength at which surface plasmon resonance (SPR) occurs on metal nanostructures in reflection and absorption scan modes. As shown in FIG. 8, the electron transition of TiO ₂ used as a photocatalyst was confirmed to occur at about 350 nm. In addition, as shown in FIG. 9, in the case of the silver nanoclusters having the extreme layer formed on the glass, the SPR wavelength was found at about 400 nm.

As described above, it has been described with reference to the preferred embodiment of the present invention, but those skilled in the art various modifications and changes of the present invention without departing from the spirit and scope of the present invention described in the claims below I can understand that you can.

As described above, according to the present invention, structural analysis of various materials such as catalysts, ferroelectrics, hydrogen storage materials, and metal nanomaterials and biomolecules is very performed by an analysis system combining confocal Raman, ultraviolet / visible and fluorescence spectroscopy. It is easy and is not limited by the shape of the sample.

In addition, while significantly reducing the time and cost of conventional analysis, the structure of multi-component materials and catalysts can be analyzed, and the relationship between performance and structure can be explored based on the design of new materials and development of new drugs and disease diagnosis chips. It can help in the bio field.

Claims (8)

A sample chamber on which a sample for analyzing a structure is placed; A confocal Raman spectrometer for analyzing a structure of the sample by analyzing a wavelength change of light reflected from the laser beam; An ultraviolet-visible light and fluorescence spectrometer for analyzing the structure of the sample by using an interaction between energy in a molecule and light energy; And And a system controller that controls the sample chamber and analyzes spectral data on the structure of the sample analyzed by the Raman spectrometer and the ultraviolet-visible and fluorescence spectrometers. The method of claim 1, The sample chamber is a spectrometer, characterized in that the high-density sample array that is integrated with more than 10000 micrometers of at least 300㎛ size is installed. The method of claim 1, The control of the sample chamber is characterized in that for setting the coordinates of the sample chamber to move the stage. The method of claim 1, And the laser is selectable in the visible and infrared regions. The method of claim 1, And the system controller maps an image of the sample structure to an optical signal detected by an avalanche photo diode (APD). The method of claim 1, And the ultraviolet-visible light and fluorescence analyzer reflects the optical signal generated after irradiating the sample to a mirror and detects the optical signal in the optical amplification tube. The method of claim 1, The fluorescence analyzer spectrometer, characterized in that to enable the emission and excitation mode of the sample molecules. delete

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