TWI810741B - Nickel-based detection substrate having high surface-enhanced raman scattering and manufacturing method thereof - Google Patents

Abstract

The present invention discloses a nickel-based detection substrate having high surface-enhanced raman scattering and its manufacturing method. A surface of a conductive substrate is roughen to obtain a rough surface, and a chemical nickel layer is disposed onto the rough surface to obtain the detection substrate having high surface-enhanced raman scattering. The chemical nickel layer comprises nickel and phosphorus. The conductive substrate is metal substrate or semiconductor substrate. The nickel-based detection substrate having high surface-enhanced raman scattering of present invention can be used to detect multiple substances and reused, and has high detection sensitivity. Thherefore, the present invention has excellent applicability.

Description

High surface-enhanced Raman scattering detection substrate containing nickel base and its manufacturing method

The invention relates to a nickel-based high-surface-enhanced Raman scattering detection substrate and a manufacturing method thereof. The prepared detection substrate has high sensitivity and wide applicability.

Raman scattering (Raman scattering) spectrum refers to the phenomenon that when atoms or molecules absorb photon energy, energy transfer occurs between atoms or molecules, resulting in the change of photon frequency after scattering, because different substances have different Raman spectra, Therefore, Raman spectroscopy can also be used to detect different substances or molecular structures, but the spontaneous Raman spectrum of substances is usually relatively weak, which increases the difficulty of substance detection; while Surface-Enhanced Raman Scattering (SERS) ) refers to a surface-sensitive technology that enhances Raman scattering by adsorbing molecules or nanostructures such as plasmonic magnetic silicon dioxide nanotubes on rough metal surfaces, so that Raman signals can be amplified to reduce the detection of substances difficulty. Currently, surface-enhanced Raman scattering can be used in different fields such as environmental substance detection or biomolecular detection. For example, the Republic of China Patent No. TW I619938B uses surface-enhanced Raman scattering technology to detect cancer cells in vitro.

However, at present, surface-enhanced Raman scattering substrates are mostly made of precious metals such as gold or silver, and the cost is quite high, and the manufacturing method is relatively complicated. Nano film on a substrate; then laser bombards the metal nano film to form a plurality of discontinuous and densely arranged metal nanoparticles, among which the metal nanoparticles are gold nanoparticles or silver nanoparticles. Therefore, the current preparation cost of surface-enhanced Raman scattering substrates is relatively high, which also limits the sensitivity and wide application of surface-enhanced Raman scattering substrates.

Today, in view of the fact that the existing detection substrates still have room for improvement in actual use, the inventor is a tireless spirit, assisted by his rich professional knowledge and many years of practical experience, and improved it, and based on this Research and create the present invention.

The present invention relates to a nickel-based high surface-enhanced Raman scattering (Surface-enhanced Raman spectroscopy, abbreviated as SERS) detection substrate and a manufacturing method thereof. The nickel-based high surface-enhanced Raman scattering detection substrate includes a conductor substrate and a device An chemical nickel layer on the conductive substrate, the conductive substrate has a rough surface, and the chemical nickel layer is arranged on the rough surface of the conductive substrate, wherein the chemical nickel layer includes nickel and phosphorus.

In one embodiment of the present invention, the conductive substrate is a metal substrate or a semiconductor substrate.

In one embodiment of the invention, the metal substrate is a brass substrate.

In one embodiment of the present invention, the rough surface of the metal substrate is made by a frosting method, a sandblasting method or a vapor phase etching method.

In an embodiment of the present invention, the chemical nickel layer includes 80-85 wt% nickel and 10-12 wt% phosphorus.

The manufacturing method of the high-surface-enhanced Raman scattering detection substrate containing nickel base of the present invention comprises: step 1, taking a conductor substrate, and performing roughening treatment on a surface of the conductor substrate, so that the conductor substrate has a rough surface; Step 2, disposing an electroless nickel layer on the rough surface of the conductive substrate to obtain the high surface enhanced Raman scattering detection substrate.

In one embodiment of the present invention, the conductive substrate is a metal substrate or a semiconductor substrate. When the conductive substrate is a metal substrate, the roughening treatment of the metal substrate is performed in step 1 by using a sandblasting method, a sandblasting method or a vapor phase etching method. ; And the metal substrate is a brass substrate.

In one embodiment of the present invention, in the second step, the conductive substrate with a rough surface is soaked in a plating solution, and the chemical nickel layer is provided on the rough surface of the conductive substrate at a temperature of 80-100°C. , wherein the plating solution contains nickel sulfate, sodium citrate and sodium hypophosphite, and the pH value is between pH4-6.

In one embodiment of the present invention, the action temperature of step 2 is 88° C., and the pH value of the plating solution is pH5.

Therefore, the nickel-based high surface-enhanced Raman scattering detection substrate and its manufacturing method of the present invention are to roughen the surface of the conductor substrate first, and then use the self-catalysis reaction to carry out the reduction reaction on the rough surface, and deposit a Phosphorous chemical nickel layer, so the electroless nickel layer on the plated system can be evenly arranged on the rough surface to achieve a profiling coating effect; in addition, the chemical nickel layer plated on the present invention belongs to high phosphorus chemical nickel, and its phosphorus content is greater than 10%, so the prepared detection substrate will not be magnetic and suitable for analysis; and the cost of chemical nickel is low and non-toxic, which can also reduce the preparation cost of the detection substrate and improve safety.

In order to make the effect achieved by the technical means of the present invention more complete and clear, the detailed description is as follows. Please also refer to the disclosed drawings.

Please refer to the first figure, which is a schematic structural view of the nickel-based high surface-enhanced Raman scattering detection substrate of the present invention, which has a conductive substrate (1), and the conductive substrate (1) has a rough surface (11), and the rough surface ( 11) An chemical nickel layer (2) is provided on it; the chemical nickel layer (2) contains nickel and phosphorus, for example, contains 80-85 wt% nickel and 10-12 wt% phosphorus. The conductor substrate (1) can be a metal substrate or a semiconductor substrate, and the metal substrate can be a brass substrate.

In addition, the preparation method of the nickel-based high surface-enhanced Raman scattering detection substrate of the present invention includes: step 1, take a conductive substrate (1), and roughen a surface of the conductive substrate (1); the conductive substrate ( 1) It can be a metal substrate or a semiconductor substrate. When the conductive substrate (1) is a metal substrate, it is roughened by sandblasting, frosting or vapor phase etching, so that the conductive substrate (1) has a rough surface ( 11); Step 2, setting an chemical nickel layer (2) on the rough surface (11) of the conductor substrate (1), so as to obtain the nickel-based high surface-enhanced Raman scattering detection substrate, wherein the chemical nickel layer (2) Contains nickel and phosphorus, such as nickel containing 80-85 wt% and phosphorus of 10-12 wt%; in step 2, the conductor substrate (1) with rough surface (11) is soaked in a plating solution, at temperature Under the condition of 80-100 ℃, to set the chemical nickel layer (2) on the rough surface (11) of the conductor substrate (1), wherein the plating solution contains nickel sulfate, sodium citrate and sodium hypophosphite, and the pH value is between At pH 4-6, in a preferred embodiment, the action temperature of step 2 is 88° C., and the pH value of the plating solution is pH 5.

In addition, the scope of practical application of the present invention is further proved by the following specific examples, but it is not intended to limit the scope of the present invention in any form.

Embodiment 1. An electroless nickel layer is provided on the substrate to increase the intensity of the SERS signal obtained after detection.

First, take a brass substrate, soak it in a plating solution, and act for 150-180 seconds at 88°C to plate an electroless nickel layer on the brass substrate to obtain a nickel-plated brass substrate ; The brass referred to here is a copper-zinc alloy, and the plating solution used includes nickel ions (Ni ²⁺ ), reducing agent and complexing agent; in the embodiment of this case, the plating solution used can be the ENOVA of Coventya company 949 Semi-gloss high phosphorus chemical nickel plating solution; or the plating solution contains 10g/L nickel acetate, 23.5 g/L sodium citrate, and 17.5 g/L sodium phosphite hypophosphite) with a pH value of pH 5, nickel acetate provides nickel ions (Ni ²⁺ ), sodium citrate acts as a reducing agent, and sodium phosphite acts as a complexing agent.

Please refer to the second picture, take a silicon substrate, a nickel-free brass substrate, and the above-mentioned nickel-plated brass substrate, drop the sodium nitrate aqueous solution, and detect the signal intensity of the surface-enhanced Raman scattering (SERS) ;According to the second figure, the three substrates can detect a signal at the Raman shift (Raman shift) of 1000-1200 1/cm, and the detection limit concentration of the silicon substrate and the nickel-free brass substrate is 10 ^{- 3} M, while the detection limit concentration of the nickel-plated brass substrate is 10 ^-4 M, and the SERS signal intensity of the nickel-plated brass substrate is higher than that of the other two groups.

Embodiment 2. Brass substrate roughening treatment enhances surface-enhanced Raman scattering intensity

In this embodiment, the surface of the brass substrate is roughened with sandpaper, or with sandblasting, or by vapor phase etching, to produce a rough surface; wherein the sandblasting is The brass substrate is treated by dry sandblasting or wet sandblasting; and the vapor phase etching method is to cut the brass substrate into 1.45 X 4.4 cm ² , place it in a container with 3 mL of ammonia solution, seal the container, and Etching is carried out at room temperature, and the action time is 1~3 hrs. After the etching is completed, the brass substrate is taken out, washed with deionized water and then dried. The ratio of ammonia water to pure water in the ammonia solution is between 1:1- 1:5.

Then this brass substrate with a rough surface was plated with an electroless nickel layer by the method of Example 1 to obtain a nickel-plated brass substrate; finally, 10 ^-4 M was dropped on the surface of different brass substrates and 10 ⁻⁵ M sodium nitrate aqueous solution, and detect the SERS intensity of each substrate.

Please refer to the third picture, the surface of all the brass substrates has been plated with chemical nickel layer, while the surface of the brass substrate of the control group has not been roughened; according to the third picture, the control group only has 10 ^-4 M The sodium nitrate aqueous solution can detect the SRES signal, but cannot detect the 10 ^-5 M sodium nitrate (NaNO ₃ ) aqueous solution; among them, both the frosted group and the sandblasting group can measure the 10 ^-4 M and 10 ^-5 M nitric acid Sodium aqueous solution, and the intensity of SERS signal is higher than that of the control group, but the SERS signal intensity of the frosted group is higher than that of the sandblasting group; the nickel-plated brass substrate of the meteorological etching group can also detect 10 ^-4 M and 10 ^- The SERS signal intensity of ⁵ M sodium nitrate aqueous solution was higher than that of the control group, but lower than that of the frosted and sandblasting groups. Therefore, frosting treatment is used in the subsequent steps to roughen the surface of the brass substrate.

Then, sand the surface of the brass substrate with different thicknesses of sandpaper, and then plate the roughened brass substrate with an electroless nickel layer to obtain different detection substrates; the thickness of the sandpaper is presented by the number of sandpaper, the number The sandpaper with a larger number means that the number of particles per unit area is larger and the thickness is finer. Please refer to the fourth picture. In this embodiment, #200, #400, #600, #800, and #1000 sandpaper are used for sanding, and the detection concentration of the finally obtained detection substrate is between 10 ^-4 -10 ^-8 M Sodium nitrate aqueous solution; according to the results in the fourth figure, only the detection substrate prepared by sanding with #600 sandpaper can detect the sodium nitrate aqueous solution with a concentration between 10 ^-4 -10 ^-8 M, and the SERS signal intensity is also all It is higher than other groups, so the brass substrate is roughened with #600 sandpaper.

Then, the brass substrate that is ground with #600 sandpaper is nickel-plated with the chemical nickel layer plating method described in Example 1, but in this embodiment, different detection substrates are prepared with different nickel-plating times, and then plated The nickel time is 150 seconds, 180 seconds, 210 seconds and 240 seconds respectively; then use different detection substrates prepared to detect sodium nitrate aqueous solution with a concentration between 10 ^-4 -10 ^-8 M; please refer to the fifth figure, only The detection substrate with a nickel plating time of 180 seconds can measure five different concentrations of sodium nitrate aqueous solution, and its SERS signal intensity is also higher than that of other groups; therefore, the brass substrate is roughened with #600 sandpaper and treated with The nickel plating time is the production condition of 180 seconds, and the detection substrate is prepared.

Please refer to Figure 6, which is a scanning electron microscope photo of the surface of the nickel-plated brass inspection substrate. The inspection substrate is roughened with #600 sandpaper, and the nickel plating time is 180 seconds. Made, and it is referred to as high SERS detection substrate in follow-up specification; Further analysis this detection substrate surface chemical nickel layer element content (atomic %), it contains the nickel of 83.33% and the phosphorus of 10.72%; This analysis shows The electroless nickel layer plated in this case is high-phosphorus electroless nickel with a phosphorus content greater than 10%, which can make the electroless nickel layer non-magnetic and more suitable for analysis.

Example 3. Analysis of detection properties of high SERS detection substrate

The brass substrate was roughened with #600 sandpaper, and the high SERS detection substrate was prepared under the production conditions of nickel plating time of 180 seconds, and the detection properties were analyzed.

Please refer to Figure 7 first, which is the SERS analysis chart obtained by detecting 10 ^-4 M, 10 ^-5 M, 10 ^-6 M, 10 ^-7 M and 10 ^-8 M sodium nitrate aqueous solution using the above-mentioned high SERS detection substrate It can be observed from Figure 7 that even if the concentration of sodium nitrate is 10 ^-8 M, the high SERS detection substrate can detect signals, that is, the high SERS detection substrate has high sensitivity and can be used to detect low concentration substances.

Please refer to the eighth figure again, the SERS intensity values obtained by measuring different concentrations of sodium nitrate aqueous solution with a high SERS detection substrate are subjected to regression analysis, and the regression coefficient (R ² ) is found to be 0.96, which has a good linear regression, which is the present invention The high SERS detection substrate can also be used to make a calibration line to quantify the concentration of the detected substance.

Also, please refer to Figure 9, measuring 10 ^-4 M sodium nitrate aqueous solution, 10 ^-4 M zinc sulfate (ZnSO ₄ ) solution and 10 ^-4 M 4-adenosine triphosphate (4-adenosine triphosphate, 4-ATP) solution SERS analysis diagram; the ninth figure shows that when the high SERS detection substrate measures the three solutions, peaks can be observed at different Raman shifts, and the high SERS detection substrate can indeed distinguish the detection of the three solutions; at the same time See Figure 10, which is the SERS signal intensity of three solutions detected by the high SERS detection substrate; the results of Figures 9 and 10 show that the high SERS detection substrate can detect many different substances.

Example 4. Reusable Analysis of High SERS Detection Substrate

In this embodiment, the high SERS detection substrate is first used to detect 10 ^-6 M sodium nitrate aqueous solution to obtain a detection value, then the high SERS detection substrate is washed with water and dried in the shade, and then the same high SERS detection substrate is used to detect 10 ^-6 M sodium nitrate aqueous solution; repeat the above steps to obtain the detection value each time, record and compare the difference in the detection results under the condition of repeatedly using the high SERS detection substrate, in this embodiment, use the same high SERS The detection process of the detection substrate was repeated 10 times by the above steps.

Please refer to the eleventh figure, which is the SERS analysis chart obtained by repeating 10 times of detection. There is little difference in the line type of the results of the 10 tests, and obvious peaks can be observed at the same Raman shift; the twelfth picture is 10 test results and analysis diagrams of SERS signal intensity, the average error value of the ten test results is 3%, the difference is quite small, that is, the nickel-based high SERS detection substrate of the present invention can indeed be reused.

To sum up, the nickel-based high surface-enhanced Raman scattering detection substrate of the present invention has the following advantages:

1. The nickel-based high-surface-enhanced Raman scattering detection substrate of the present invention first roughens the surface of the conductor substrate, and then utilizes an autocatalytic reaction to uniformly deposit chemical nickel on the rough surface of the conductor substrate; the surface of the conductor substrate Roughening treatment can improve the specific surface area of the conductor substrate surface, and the chemical nickel layer deposited by the self-catalytic reaction can effectively achieve the effect of profiling; in addition, the chemical nickel layer of the present invention is a high-phosphorus chemical nickel layer with a phosphorus content greater than 10%. , non-magnetic, which can make the nickel-based high surface-enhanced Raman scattering detection substrate more applicable to analysis.

2. The nickel-based high surface-enhanced Raman scattering detection substrate of the present invention can detect a variety of different substances, is widely used, and can be used to detect low-concentration substances, and its detection limit concentration can reach 10 ^-8 M; The detection results obtained by the invention of the nickel-based high surface-enhanced Raman scattering detection substrate have good regression coefficients and can also be used for concentration quantification.

3. The nickel-based high surface-enhanced Raman scattering detection substrate of the present invention can be used repeatedly, and the error value of the signal intensity measured during repeated use is extremely small, so the detection result will not be affected even when it is used repeatedly.

In summary, the nickel-based high surface-enhanced Raman scattering detection substrate and its manufacturing method in this case can indeed achieve the expected use effect through the above disclosed embodiments, and the present invention has not been disclosed before the application , Sincerely has fully complied with the provisions and requirements of the Patent Law. ￠It is really convenient to file an application for a patent for invention according to the law, and ask for the review and approval of the patent.

However, the above-mentioned descriptions are only preferred embodiments of the present invention, and are not intended to limit the protection scope of the present invention; those who are familiar with the art generally make other equivalents according to the characteristic scope of the present invention Changes or modifications should be considered as not departing from the design scope of the present invention.

1: Conductor substrate 11: Rough surface

2: chemical nickel layer

Figure 1: A schematic diagram of a high surface-enhanced Raman scattering (SERS) detection substrate of the present invention.

Figure 2: SERS signal analysis diagram of nickel-plated and nickel-free detection substrates.

Figure 3: Analysis of the SERS signal intensity of the detection substrate affected by different roughening treatments.

Figure 4: The impact of the thickness of the sandpaper used for grinding on the SERS signal intensity analysis of the detection substrate.

Figure 5: The impact of nickel plating time on the SERS signal intensity analysis of the detection substrate.

Figure 6: a scanning electron microscope photo of the surface of the high SERS detection substrate of the present invention.

Figure 7: Analysis chart of the detection limit concentration of the high SERS detection substrate of the present invention.

Figure 8: The regression analysis chart of the detection of different concentrations of substances detected by the high SERS radiation detection substrate of the present invention.

Figure 9: SERS analysis chart (1) of different substances detected by the high SERS detection substrate of the present invention.

Figure 10: SERS analysis chart (1) of different substances detected by the high SERS detection substrate of the present invention.

Fig. 11: SERS analysis diagram (1) of repeated use of the high SERS detection substrate of the present invention.

Figure 12: SERS analysis chart (2) of the reused high SERS detection substrate of the present invention.

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1: Conductor substrate 11: Rough surface 2: chemical nickel layer

Claims (10)

A nickel-based high-surface-enhanced Raman scattering detection substrate includes a conductive substrate and an chemical nickel layer disposed on the conductive substrate, wherein the conductive substrate has a rough surface, and the chemical nickel layer is disposed on the conductive substrate On rough surfaces, where the electroless nickel layer contains nickel and phosphorous. The nickel-based high surface-enhanced Raman scattering detection substrate as described in claim 1, wherein the conductive substrate is a metal substrate or a semiconductor substrate. The nickel-based high surface-enhanced Raman scattering detection substrate as described in claim 2, wherein the metal substrate is a brass substrate. The nickel-based high-surface-enhanced Raman scattering detection substrate as claimed in Claim 2, wherein the rough surface of the metal substrate is produced by a frosting method, a sandblasting method or a vapor phase etching method. The nickel-based high surface-enhanced Raman scattering detection substrate as claimed in claim 1, wherein the chemical nickel layer contains 80-85wt% nickel and 10-12wt% phosphorus. A method for manufacturing a nickel-based high-surface-enhanced Raman scattering detection substrate, comprising: step 1: taking a conductive substrate, and roughening a surface of the conductive substrate, so that the conductive substrate has a rough surface; Step 2: disposing an electroless nickel layer on the rough surface of the conductive substrate to obtain the high surface-enhanced Raman scattering detection substrate, wherein the electroless nickel layer includes nickel and phosphorus. The manufacturing method according to claim 6, wherein the conductive substrate in the step 1 is a metal substrate or a semiconductor substrate. The manufacturing method according to claim 7, wherein the conductive substrate is a metal substrate, and the roughening treatment of the metal substrate is performed by a sanding method, a sandblasting method or a vapor phase etching method. The manufacturing method according to claim 7, wherein the metal substrate is a brass substrate. According to the manufacturing method described in claim 6, in step 2, the conductive substrate with the rough surface is soaked in a plating solution, and acted at a temperature of 80-100°C to coat the rough surface of the conductive substrate The chemical nickel layer is provided, wherein the plating solution contains nickel sulfate, sodium citrate and sodium hypophosphite, and the pH value is between pH4-6.