CN113668029B - Film formed by rough gold nanoparticles and preparation method and application thereof - Google Patents
Film formed by rough gold nanoparticles and preparation method and application thereof Download PDFInfo
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- 239000010931 gold Substances 0.000 title claims abstract description 218
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 217
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims description 33
- 239000010408 film Substances 0.000 claims abstract description 64
- 239000000758 substrate Substances 0.000 claims abstract description 57
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000010409 thin film Substances 0.000 claims abstract description 8
- 239000000975 dye Substances 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- 239000003792 electrolyte Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- SNXYSMKZWUVGEF-UHFFFAOYSA-K trichlorogold tetrahydrate Chemical compound O.O.O.O.Cl[Au](Cl)Cl SNXYSMKZWUVGEF-UHFFFAOYSA-K 0.000 claims description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 15
- 238000001514 detection method Methods 0.000 claims description 13
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- -1 gold ions Chemical class 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000004070 electrodeposition Methods 0.000 claims description 6
- 238000000861 blow drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 3
- 239000004744 fabric Substances 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 239000011521 glass Substances 0.000 description 28
- 238000001069 Raman spectroscopy Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 7
- 230000010354 integration Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000000479 surface-enhanced Raman spectrum Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C25D3/00—Electroplating: Baths therefor
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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Abstract
The invention relates to a film formed by rough gold nanoparticles, which mainly comprises a plurality of large gold nanoparticles positioned on a conductive substrate and a plurality of small gold nanoparticles coated on the surfaces of the large gold nanoparticles, wherein the large gold nanoparticles are stacked into a layer; the particle size of the small gold nanoparticles is 15-80nm, and the particle size of the large gold nanoparticles is 200-900nm. The thin film structure that coarse gold nanoparticle constitutes is connected by the gold nanoparticle stack of 2 to 4 layer surface irregularities and is formed, and this kind of structure makes has more gaps between them, can provide numerous SERS hot spots, and this kind of thin film structure has good structural homogeneity moreover, provides reliable guarantee for the homogeneity of SERS signal to the SERS sensitivity and the signal homogeneity that make the purpose product all obtain showing and promote. It can be used as an active substrate for surface enhanced Raman scattering to detect organic dyes.
Description
Technical Field
The invention relates to a gold nano material, a preparation method and application thereof, in particular to a film consisting of rough gold nano particles, a preparation method and application thereof.
Background
The Surface Enhanced Raman Scattering (SERS) spectrum technology can provide fingerprint information of molecular vibration and has the advantages of fingerprint identification, high sensitivity, high detection speed and the like. And the SERS spectrum is generated without separating from the SERS substrate. In order to realize the application of SERS detection technology, researchers have developed many types of SERS substrates. The gold nanostructure SERS substrate has the advantages of high chemical stability, excellent SERS activity, stable performance and the like, and is widely concerned. The signals of the SERS substrate mainly come from the hot spots of the electromagnetic field. Narrow noble metal nanogaps and nanoscale rough surfaces can both generate hot spots. Some beneficial attempts and efforts have been made to obtain gold nanostructures with a large number of hot spots, such as the article entitled "simple Fabrication of High-Density Sub-1-nm Gaps from Au nanoparticles as repeatable SERS Substrates", adv. Funct. Mater.2016,26,8137-8145 ("easy preparation of single-layer gold Nanoparticle films with High Density of Sub-nanogaps as Reproducible SERS Substrates", advanced functional materials, 2016, pp. 8137-8145, volume 26, 2016). The single-layer gold nanoparticle film mentioned in the article is a film assembled by single-layer gold nanoparticles and covered on a silicon chip substrate; the preparation method comprises the steps of firstly obtaining a monolayer film assembled by gold nanoparticles by using a liquid level self-assembly method, and then directly transferring the monolayer film to the surface of a clean silicon wafer to obtain a product. Although the product has stronger light absorption at 633nm and 785nm, the product and the preparation method thereof have defects; firstly, gold nanoparticles in a product are only a single layer, which not only restricts the SERS activity of the product, but also has extremely high uniformity to be damaged by water waiting for detection solution, thereby seriously affecting the uniformity of SERS signals of the product; secondly, the preparation method cannot obtain a product with high SERS activity and the uniformity of the SERS signal of the product cannot be damaged by water waiting for a detection solution. For this reason, a method of electrodepositing a gold nanoparticle-assembled thin film on a conductive substrate sputtered with a gold film has been developed, such as patent application No. 2017103043375, filed 5, 3/2017, entitled "gold nanoparticle-assembled thin film and method for preparing the same" and invention patent of use thereof. The film is a film which is formed by mutually adhering a plurality of layers of gold nanoparticles to form a thickness of 200nm-2 mu m and is coated on a conductive substrate, wherein the particle size of the gold nanoparticles is 30-120nm; the method comprises the steps of sputtering gold on the surface of a conductive substrate to obtain the conductive substrate with the surface covered with a gold film, placing the conductive substrate with the surface covered with the gold film in a gold electrolyte by taking a graphite sheet as an anode and taking the conductive substrate with the surface covered with the gold film as a cathode, and performing electrodeposition under constant current to obtain the target product. The gold electrolyte is a mixed solution of 0.2-10g/L chloroauric acid aqueous solution and 2-200g/L polyvinylpyrrolidone (PVP) aqueous solution, and although the film assembled by multiple layers of gold nanoparticles is obtained by the preparation method, the preparation method and the product appearance have space for improving. For example, a sputtering method is adopted to sputter a layer of gold film on the surface of conductive glass, so that the preparation method is heavily dependent on a sputtering instrument; secondly, the surface of the gold nanoparticles obtained by sputtering is smooth, and even if gaps exist among the gold particles to increase SERS hot spots, the hot spot amount is still limited; and thirdly, the surface active agent polyvinylpyrrolidone is added into the gold electrolyte, the surface active agent can be adsorbed on the surface of the prepared gold nanoparticle and is not easy to remove, and when a low-concentration molecule to be detected is detected, an SERS signal of the polyvinylpyrrolidone can be generated, so that an interference signal is generated for SERS detection.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a film consisting of rough gold nanoparticles, a preparation method and application thereof. The film composed of the rough gold nanoparticles is formed by mutually connecting and overlapping the gold nanoparticles on the conductive substrate, the gold nanoparticles have numerous SERS hot spots and uniform structure, and the uniformity and high detection sensitivity of SERS signals are ensured.
The film formed by the rough gold nanoparticles comprises a plurality of large gold nanoparticles positioned on a conductive substrate and a plurality of small gold nanoparticles coated on the surfaces of the large gold nanoparticles, wherein the large gold nanoparticles are stacked into a layer; the particle size of the small gold nanoparticles is 15-80nm, and the particle size of the large gold nanoparticles is 200-900nm. The large gold nanoparticles are rough and uneven in surface to form rough gold nanoparticles due to the aggregation and coating of a plurality of small gold nanoparticles on the surface of the large gold nanoparticles.
Meanwhile, the preparation method of the film formed by the rough gold nanoparticles comprises the steps of uniformly dispersing a gold seed crystal solution on the surface of the conductive substrate, drying, and uniformly attaching gold seed crystals on the surface of the conductive substrate; then, the conductive substrate attached with the gold seed crystal is taken as a negative electrode, the rectangular graphite flake is taken as an anode, the gold electrolyte is taken as the electrolyte, and carrying out electrodeposition on the conductive substrate with the gold seed crystal attached to the surface, and carrying out post-treatment to obtain the gold-doped copper-based conductive material. The conductive substrate in the present invention is common, such as conductive glass (indium tin oxide (ITO) glass substrate), silicon wafer substrate, fluorine-doped tin dioxide conductive glass substrate, etc. can be used. The invention relates to a rough gold nanoparticle structure, which is formed by growing large gold nanoparticles on a gold seed crystal on a conductive substrate, electrodepositing gold chloride in a solution to form small gold nanoparticles, and gathering and coating the small gold nanoparticles on the large gold nanoparticles to form a rough structure.
In the above preparation method, preferably, the gold seed solution may be prepared by: dissolving gold chloride tetrahydrate and polyvinylpyrrolidone (K29-32) in deionized water to form a mixed solution, uniformly dispersing hydrochloric acid in the mixed solution, adding sodium borohydride, and reducing gold ions to prepare a gold seed crystal solution; the size of the gold seed crystal is 5-15nm. More preferably, the gold seed solution may be prepared by the following method: completely dissolving 1-5mg of gold chloride tetrahydrate and 0.1-0.5g of polyvinylpyrrolidone (K29-32) in 20mL of deionized water to form a mixed solution, uniformly dispersing 200 mu L of hydrochloric acid with the concentration of 20-30g/L into the mixed solution, then adding 1-5mg of sodium borohydride into the mixed solution, reducing gold ions to prepare a gold seed crystal solution, sealing the gold seed crystal solution in a conical flask, and standing for 24 hours for use.
In the above preparation method, preferably, the gold electrolyte may be prepared by: firstly, preparing a gold chloride aqueous solution, and then adding hydrochloric acid into the gold chloride aqueous solution to prepare a gold electrolyte. A more preferred method of preparing the gold electrolyte may be: completely dissolving 2-10mg of gold chloride tetrahydrate in 15mL of deionized water to obtain a gold chloride aqueous solution, and adding 200 mu L of hydrochloric acid with the concentration of 20-30g/L into the gold chloride aqueous solution to obtain the gold electrolyte.
In the above preparation method, preferably, the gold seed solution may be uniformly covered in a range of 2 to 4cm 2 Drying the substrate at 60-90 deg.c to form gold seed crystal film.
In the above preparation method, preferably, the post-treatment may include water washing, soaking, and blow-drying. More preferably, the gold seed crystal solution can be soaked in deionized water for 15-30min after being washed by the deionized water, and the soaking function is to remove the extremely small amount of the surfactant remained in the gold seed crystal solution.
In addition, the inventor researches and discovers that the obtained film formed by the rough gold nanoparticles can be used as an active substrate for surface enhanced Raman scattering so as to be used for detecting organic dyes, such as rhodamine 6G which can be used for detecting trace dyes.
Preferably, the excitation light of the laser Raman spectrometer has a wavelength of 532nm, a power of 0.1-2mW, and an integration time of 1-30s.
In the invention, the method for uniformly attaching the gold seed crystals on the surface of the conductive substrate does not adopt magnetron sputtering or ion sputtering because the magnetron sputtering and the ion sputtering depend on a sputtering instrument, the cost is high, the method is complex, and the gold film formed by the magnetron sputtering and the ion sputtering is finer and more compact, a compact gold film can be formed after electrodeposition, and the coarse particles cannot be generated or the generated coarse particles are very few. The invention is that gold seed crystal solution is evenly dispersed on the surface of the conductive substrate and then dried.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the thin film structure composed of rough gold nanoparticles is formed by overlapping and connecting a plurality of (2-4) layers of gold nanoparticles with uneven surfaces, the thin film formed by the plurality of layers of rough gold nanoparticles has more gaps between the rough gold nanoparticles and can provide a plurality of SERS hot points, and the thin film structure has good structural uniformity and provides reliable guarantee for uniformity of SERS signals, so that SERS sensitivity and signal uniformity of target products are remarkably improved.
Secondly, the gold electrolyte in the invention mainly comprises gold chloride tetrahydrate and hydrochloric acid, and does not contain a common surfactant such as PVP, so that the cleanliness of the surface of a film consisting of product gold nanoparticles is ensured, favorable conditions are provided for obtaining pure SERS signals of molecules of an object to be detected, and the interference of the SERS signals of the surfactant polyvinylpyrrolidone in detection on the result is avoided.
Thirdly, the prepared target product is used as an SERS active substrate, and multiple multi-batch tests are carried out on rhodamine 6G under different concentrations, and when the concentration of the rhodamine 6G to be tested is as low as 8 multiplied by 10 -9 The method can still effectively detect the target product when the concentration is mol/L, and the uniformity and repeatability of the detected signal are very good at any point on the target product and any point on different batches of products.
Fourthly, the preparation method is scientific and effective. Uniformly covering a layer of gold seed crystal solution film on the surface of the conductive substrate, and then carrying out electrodeposition to prepare a film formed by rough gold nanoparticles; the formed film has multiple layers of rough gold nanoparticles, and finally, the film formed by the target product of the multiple layers of gold nanoparticles with high density and controllable SERS hot points is prepared, and the film has the advantages of higher SERS sensitivity, structural uniformity and signal uniformity, is convenient to prepare in batches with large area, high density and highly controllable structural parameters simply and cheaply, and further can be used as an active substrate of SERS to measure trace organic matters attached to the active substrate.
Drawings
FIG. 1 is a result of characterization of the obtained objective product using a Scanning Electron Microscope (SEM);
FIG. 2 is a graph showing a graph including (a) 1X 10 -6 mol/L、(b)2×10 -7 mol/L、(c)4×10 -8 mol/L、(d)8×10 - 9 mol/L rhodamine 6G, a target product is characterized by using a copolymerization laser Raman spectrometer.
Detailed Description
The following examples are further illustrative of the present invention as to the technical content of the present invention, but the essence of the present invention is not limited to the following examples, and one of ordinary skill in the art can and should understand that any simple changes or substitutions based on the essence of the present invention should fall within the protection scope of the present invention.
The preparation method of the material comprises the steps of bombarding conductive glass by plasma in an oxygen atmosphere to increase the surface hydrophilicity of the conductive glass, and then uniformly attaching a certain amount of gold seed crystals to the surface of the conductive glass so that a uniform film is formed on the surface of the conductive glass by the gold seed crystal solution.
Example 1
Step 1, uniformly dripping 80 mu L of gold seed crystal solution on an ITO conductive substrate to obtain conductive glass covered with the gold seed crystal solution, and drying in an oven at 80 ℃ to obtain the conductive substrate covered with a gold seed crystal solution film; the preparation method of the gold seed crystal solution comprises the following steps: completely dissolving 1mg of gold chloride tetrahydrate and 0.1g of polyvinylpyrrolidone (K29-32) in 20mL of deionized water to form a mixed solution, uniformly dispersing 200 mu L of hydrochloric acid with the concentration of 20g/L into the mixed solution, then adding 2mg of sodium borohydride into the mixed solution, reducing gold ions to obtain a gold seed crystal solution, sealing the gold seed crystal solution, and standing for 24 hours for use.
Step 2, placing the conductive glass covered with the gold seed crystal solution film prepared in the step into gold electrolyte, taking the conductive glass attached with the gold seed crystal as a negative electrode and a rectangular graphite sheet as an anode, electrodepositing gold on the conductive glass, using the electrolyte at 40 ℃ and 50 muA cm -2 Carrying out electrodeposition for 4 hours to obtain a film consisting of rough gold nanoparticles; the preparation method of the gold electrolyte comprises the following steps: 10mg of gold chloride tetrahydrate is completely dissolved in 15mL of deionized water to obtain a gold chloride aqueous solution, and 200 mu L of hydrochloric acid with the concentration of 30g/L is added into the gold chloride aqueous solution to obtain a gold electrolyte.
And 3, cleaning the film consisting of the rough gold nanoparticles by using deionized water for three times, soaking for twenty minutes, cleaning the product, and blowing the product by using argon to dry to obtain the target product.
The target product prepared in example 1 is characterized by using a Scanning Electron Microscope (SEM), and as a result, as shown in fig. 1, the SEM image in fig. 1 shows that the target product is a film composed of rough gold nanoparticles, and a plurality of small gold nanoparticles are aggregated and coated on the surface of the large gold nanoparticles, so that the surface thereof is rough and uneven, forming rough gold nanoparticles, and the film composed of rough gold nanoparticles is composed of a plurality of layers (about 2 to 4 layers) of uneven gold nanoparticles.
For the component containing 1X 10 -6 mol/L、2×10 -7 mol/L、4×10 -8 mol/L、8×10 -9 And (3) characterizing a target product of the rhodamine 6G in mol/L by using a confocal laser Raman spectrometer to obtain a result shown in a figure 2, wherein the wavelength of exciting light of the laser Raman spectrometer is 532nm, the power is 0.1-2mW, and the integration time is 1-30s. As can be seen from FIG. 2, the SERS activity of the prepared SERS substrate is very high, and the detection concentration is as low as 8 x 10 -9 The rhodamine 6G with mol/L can still obtain a stronger SERS spectrum, and the characteristic peak is more obvious.
Example 2
The preparation method comprises the following specific steps:
step 1, uniformly dripping 100 mu L of gold seed crystal solution on an ITO conductive substrate to obtain conductive glass covered with the gold seed crystal solution, and drying in an oven at 80 ℃ to obtain the conductive substrate covered with a gold seed crystal solution film;
step 2, placing the conductive glass covered with the gold seed crystal solution prepared in the step into gold electrolyte, taking the conductive glass attached with the gold seed crystal as a negative electrode and the rectangular graphite flake as an anode, and electrodepositing gold on the conductive glass to obtain a film consisting of rough gold nanoparticles; the preparation method of the gold electrolyte comprises the following steps: completely dissolving 8mg of gold chloride tetrahydrate in 15mL of deionized water to obtain a gold chloride aqueous solution, and adding 200 mu L of 28g/L hydrochloric acid into the gold chloride aqueous solution to obtain a gold electrolyte. The preparation method of the gold seed crystal solution comprises the following steps: completely dissolving 2mg of gold chloride tetrahydrate and 0.2g of polyvinylpyrrolidone (K29-32) in 20mL of deionized water to form a mixed solution, uniformly dispersing 200 mu L of 23g/L hydrochloric acid into the mixed solution, adding 3mg of sodium borohydride into the mixed solution, reducing gold ions to obtain a gold seed crystal solution, sealing the gold seed crystal solution, and standing for 24 hours for use.
And 3, cleaning the film consisting of the rough gold nanoparticles by using deionized water for three times, soaking for twenty minutes, cleaning the product, and blowing the product by using argon to dry to obtain the target product.
The prepared film consisting of the rough gold nanoparticles is used as an active substrate for surface enhanced Raman scattering, and a laser Raman spectrometer is used for measuring rhodamine 6G attached to the film, wherein the wavelength of exciting light of the laser Raman spectrometer is 532nm, the power is 0.1-2mW, and the integration time is 1-30s. Detection concentration of 8X 10 -9 When the rhodamine is 6G at mol/L, the concentration is 614cm -1 The intensity of the characteristic peak was 125 count units.
Example 3
The preparation method comprises the following specific steps:
step 1, uniformly dripping 120 mu L of gold seed crystal solution on an ITO conductive substrate to obtain conductive glass covered with the gold seed crystal solution, and drying in an oven at 80 ℃ to obtain the conductive substrate covered with a gold seed crystal solution film;
step 2, placing the conductive glass covered with the gold seed crystal solution prepared in the step into a gold electrolyte, taking the conductive glass attached with the gold seed crystal as a negative electrode and a rectangular graphite sheet as an anode, and electrodepositing gold on the conductive glass to obtain a film consisting of rough gold nanoparticles; the preparation method of the gold electrolyte comprises the following steps: 6mg of gold chloride tetrahydrate is completely dissolved in 15mL of deionized water to obtain a gold chloride aqueous solution, and 200 mu L of hydrochloric acid with the concentration of 25g/L is added into the gold chloride aqueous solution to obtain a gold electrolyte. The preparation method of the gold seed crystal solution comprises the following steps: completely dissolving 3mg of gold chloride tetrahydrate and 0.3g of polyvinylpyrrolidone (K29-32) in 20mL of deionized water to form a mixed solution, uniformly dispersing 200 mu L of hydrochloric acid with the concentration of 25g/L into the mixed solution, adding 4mg of sodium borohydride into the mixed solution, reducing gold ions to obtain a gold seed crystal solution, sealing the gold seed crystal solution, and standing for 24 hours for use.
And 3, cleaning the film consisting of the rough gold nanoparticles with deionized water for three times, soaking for twenty minutes, cleaning the product, and blow-drying with argon gas to obtain the film consisting of the rough gold nanoparticles shown in the figure 1.
The prepared film consisting of the rough gold nanoparticles is used as an active substrate for surface enhanced Raman scattering, and a laser Raman spectrometer is used for measuring rhodamine 6G attached to the film, wherein the wavelength of exciting light of the laser Raman spectrometer is 532nm, the power is 0.1-2mW, and the integration time is 1-30s. The detection concentration is 4 multiplied by 10 -8 When rhodamine 6G is used in mol/L, it is 614cm -1 The intensity of the characteristic peak was 459 count units.
Example 4
Step 1, uniformly dripping 110 mu L of gold seed crystal solution on an ITO conductive substrate to obtain conductive glass covered with the gold seed crystal solution, and drying in an oven at 80 ℃ to obtain the conductive substrate covered with a gold seed crystal solution film;
step 2, placing the conductive glass covered with the gold seed crystal solution prepared in the step into gold electrolyte, taking the conductive glass attached with the gold seed crystal as a negative electrode and the rectangular graphite flake as an anode, and electrodepositing gold on the conductive glass to obtain a film consisting of rough gold nanoparticles; the preparation method of the gold electrolyte comprises the following steps: 4mg of gold chloride tetrahydrate is completely dissolved in 15mL of deionized water to obtain a gold chloride aqueous solution, and 200 mu L of hydrochloric acid with the concentration of 23g/L is added into the gold chloride aqueous solution to obtain a gold electrolyte. The preparation method of the gold seed crystal solution comprises the following steps: completely dissolving 4mg of gold chloride tetrahydrate and 0.4g of polyvinylpyrrolidone (K29-32) in 20mL of deionized water to form a mixed solution, uniformly dispersing 200 mu L of hydrochloric acid with the concentration of 26g/L into the mixed solution, adding 4mg of sodium borohydride into the mixed solution, reducing gold ions to obtain a gold seed crystal solution, sealing the gold seed crystal solution, and standing for 24 hours for use.
And 3, cleaning the film consisting of the rough gold nanoparticles by using deionized water for three times, soaking for twenty minutes, cleaning the product, and blowing the product by using argon to dry to obtain the target product.
The prepared film consisting of the rough gold nanoparticles is used as an active substrate for surface enhanced Raman scattering, and a laser Raman spectrometer is used for measuring rhodamine 6G attached to the film, wherein the wavelength of exciting light of the laser Raman spectrometer is 532nm, the power is 0.1-2mW, and the integration time is 1-30s. The detection concentration is 2 multiplied by 10 -7 When the rhodamine is 6G at mol/L, the concentration is 614cm -1 The intensity of the characteristic peak is 714 count units.
Example 5
Step 1, uniformly dripping 120 mu L of gold seed crystal solution on an ITO conductive substrate to obtain conductive glass covered with the gold seed crystal solution, and drying in an oven at 80 ℃ to obtain the conductive substrate covered with a gold seed crystal solution film;
step 2, placing the conductive glass covered with the gold seed crystal solution prepared in the step into a gold electrolyte, taking the conductive glass attached with the gold seed crystal as a negative electrode and a rectangular graphite sheet as an anode, and electrodepositing gold on the conductive glass to obtain a film consisting of rough gold nanoparticles; the preparation method of the gold electrolyte comprises the following steps: 2mg of gold chloride tetrahydrate is completely dissolved in 15mL of deionized water to obtain a gold chloride aqueous solution, and 200 mu L of hydrochloric acid with the concentration of 20g/L is added into the gold chloride aqueous solution to obtain a gold electrolyte. The preparation method of the gold seed crystal solution comprises the following steps: completely dissolving 5mg of gold chloride tetrahydrate and 0.5g of polyvinylpyrrolidone (K29-32) in 20mL of deionized water to form a mixed solution, uniformly dispersing 200 mu L of hydrochloric acid with the concentration of 30g/L into the mixed solution, then adding 5mg of sodium borohydride into the mixed solution, reducing gold ions to obtain a gold seed crystal solution, sealing the gold seed crystal solution, and standing for 24 hours for use.
And 3, cleaning the film consisting of the rough gold nanoparticles with deionized water for three times, soaking for twenty minutes, cleaning the product, and blow-drying with argon to obtain the target product.
Using the prepared film consisting of rough gold nanoparticles as an active substrate for surface-enhanced Raman scattering, and measuring rhodamine 6G attached to the film by using a laser Raman spectrometer, whereinThe wavelength of exciting light of the laser Raman spectrometer is 532nm, the power is 0.1-2mW, and the integration time is 1-30s. The detection concentration is 1 × 10 -6 When the rhodamine is 6G at mol/L, the concentration is 614cm -1 The intensity of the characteristic peak was 1143 count units.
It should be noted that the technical contents described above are only explained and illustrated to enable those skilled in the art to know the technical spirit of the present invention, and therefore, the technical contents are not to limit the scope of the present invention. The scope of the invention is defined by the appended claims. It should be understood by those skilled in the art that any modification, equivalent replacement, and improvement made based on the spirit of the present invention should be considered to be within the spirit and scope of the present invention.
Claims (8)
1. A film composed of rough gold nanoparticles comprises a plurality of large gold nanoparticles and a plurality of small gold nanoparticles, wherein the large gold nanoparticles are positioned on a conductive substrate, the small gold nanoparticles are coated on the surfaces of the large gold nanoparticles, and the large gold nanoparticles are stacked; the particle size of the small gold nanoparticles is 15-80nm, and the particle size of the large gold nanoparticles is 200-900nm;
the preparation method of the film formed by the rough gold nanoparticles comprises the steps of uniformly dispersing a gold seed crystal solution on the surface of a conductive substrate, drying, and uniformly attaching gold seed crystals on the surface of the conductive substrate; then, taking the conductive substrate attached with the gold seed crystals as a negative electrode, taking the rectangular graphite flake as an anode, taking gold electrolyte as electrolyte, carrying out electrodeposition on the conductive substrate attached with the gold seed crystals on the surface, and carrying out post-treatment to obtain the gold seed crystal; the preparation method of the gold electrolyte comprises the following steps: firstly, preparing a gold chloride aqueous solution, and then adding hydrochloric acid into the gold chloride aqueous solution to prepare a gold electrolyte.
2. The rough gold nanoparticle-comprising film of claim 1, wherein the gold seed solution is prepared by the following method: dissolving gold chloride tetrahydrate and polyvinylpyrrolidone in deionized water to form a mixed solution, uniformly dispersing hydrochloric acid in the mixed solution, adding sodium borohydride, and reducing gold ions to prepare a gold seed crystal solution; the grain size of the gold seed crystal is 5-15nm.
3. The rough gold nanoparticle-formed film according to claim 1, wherein the gold seed solution is uniformly covered in a range of 2 to 4cm 2 Drying the substrate at 60-90 deg.c to form gold seed crystal film.
4. The membrane composed of rough gold nanoparticles as claimed in claim 2, wherein 1-5mg of gold chloride tetrahydrate and 0.1-0.5g of polyvinylpyrrolidone are completely dissolved in 20mL of deionized water to form a mixed solution, 200 μ L of hydrochloric acid with a concentration of 20-30g/L is uniformly dispersed in the mixed solution, then 1-5mg of sodium borohydride is added to the mixed solution to reduce gold ions to prepare a gold seed solution, the gold seed solution is sealed in a conical flask and is used after standing for 24 h.
5. The membrane of rough gold nanoparticles as claimed in claim 1, wherein 2-10mg of gold chloride tetrahydrate is completely dissolved in 15mL of deionized water to obtain an aqueous gold chloride solution, and 200 μ L of hydrochloric acid with a concentration of 20-30g/L is added to the aqueous gold chloride solution to obtain the gold electrolyte.
6. The membrane of rough gold nanoparticles as claimed in claim 1, wherein the post-treatment comprises washing with water, soaking, blow-drying; after being washed by deionized water, the cloth needs to be soaked in the deionized water for 15-30min.
7. Use of a thin film of rough gold nanoparticles as claimed in claim 1 as an active substrate for surface enhanced raman scattering for the detection of organic dyes.
8. The use of the film as an active substrate for Surface Enhanced Raman Scattering (SERS) for detecting the trace dye rhodamine 6G as claimed in claim 7.
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