Synthesis and Characterization of Silver Nanowires by Solvothermal Method

Anh Luu, Josh Doorn, Cuikun Lin, Stanley P. May*

Abstract Recently, silver nanowires are of great interest at this time to the scientific community due to their application in microelectronics, optical devices, surface enhanced Raman scattering (SERS) and surface enhanced fluorescence (SEF). How to synthesize and control the length and diameter of the silver nanowires is the research topic now. In this paper, silver nanowires were prepared by a facile solvothermal method. A solution, solution A, is prepared by dissolving AgNO3 (Silver Nitrate) in Ethylene Glycol. Another solution, solution B, is prepared by dissolving NaCl (Sodium Chloride) and Polyvinylpyrrolidone (PVP) in Ethylene Glycol. The two prepared solutions were mixed together under vigorous stirring. And then obtained mixed solution was transferred into an Autoclave and heated at 160oC in an oven. The Autoclave is to ensure that the solution is under high pressure (>1000psi) so that {111} facet of the silver nanowires will grow much faster rather than {100} facet. In order to understand the growth mechanism and control the length and diameter of silver nanowires, different concentration of PVP, silver nitrate, sodium chloride and different temperature and reaction time were used. After the silver nanowires are synthesized, the shape of the nanowires was determined using Atomic Force Microscopy (AFM) in Pardee 309. The absorption spectrum was performed by a UV-Vis absorption spectrometer in room Churchill-Haines 127. Powder X-Ray Defraction (XRD) was run on the nanowires in Akeley by Sarah Chadima. The obtained silver nanowires have potential application in optical devices and metal enhanced luminescence. Further work will be done to control the morphology of the silver nanostructures.

I. Introduction Silver nanowires have attracted a great amount of attention because they have extensive application in surface-enhanced Raman scattering (SERS) and surface-enhance florescence (SEF). In the literature, they reported a brief experiment on silver nanowires by solvothermal method. It should be noted that the paper didnt mention the molecular weight of PVP. The PVPs purpose is to ensure that the nanowires grow longer on one axis than another by binding to the {100}faucets more that the {111} faucets1. Sodium Chloride is used in the creation of nanowires to produce AgCl. The resulting AgCl is used as seeds for the nanowire growth2. In our experiment, we varied the reactants of the silver nanowires to determine the effects of varying reactants will affect the aspect ratio of silver nanowires. II. Experimental Silver nanowires were synthesized by solvothermal method. Solvothermal method is a method that uses a high heat and pressure. An autoclave is a device that allows the heating of the nanowires to high temperatures in order to create high pressure without exploding. Typically, first AgNO3 was dissioved in Ethylene Glycol (EG, 99%). And then Polyvinylpyrrolidone (PVP) and NaCl was dissolved in Ethylene Glycol (EG, 99%) at 120 C under vigorous stirring at 600 rpms. Then PVP/NaCl/EG solution was added into the solution of AgNO3/EG solution drop by drop under vigorous stirring. The solution was allowed to mix for 5 minutes and then transferred in a 125 mL autoclave. Once the autoclave was securely sealed, it was placed in an oven for 7 hours3. After 7 hours, the autoclave is cooled to room temperature. At the high temperature and pressure the resulting reaction is as follows4: 2 HOCH2CH2OH 2 CH3CHO + 2 H2O Ethylene GlycolAcetaldehyde+Water 2 Ag+ + 2 CH3CHO CH3CO OCCH3 + 2 Ag + 2 H+ SilverIon+Acetaldehyde2,3-Butanedione+Silver Metal+Hydrogen Ion The nanowires were then precipitated with acetone in plastic test tubes and centrifuged at 5000 rpm so that the nanowires would separate from the solution and stick to the bottom of the test tube. The nanowires were then cleaned three times by dissolving them with methanol,

precipitating them with acetone, and centrifuging them. The nanowires were then dissolved with methanol and either spin coated or dropped and dried onto glass slides. An AFM image was generated in 309 Pardee by Cuikun Lin. Absorption measurements taken in 127 ChurchillHaines by Cuikun Lin, Ahn Luu, and Josh Doorn. Powder X-Ray Defraction (XRD) was run by Sarah Chadima in Akeley. In order to understand the growth mechanism of the nanowires, the concentrations of the precursors are varied as listed in the following table. Synthesis Date Parameter Varied 5/15/09 Original Process 5/14/09 5/18/09 5/20/09 5/21/09 5/22/09 Less AgNO3 More NaCl Less PVP More PVP Different MW PVP 5/25/09 5/26/09 6/4/09 No NaCl More AgNO3 Shorter Reaction Time 6/5/09 Very Short Reaction Time 6/8/09 Longer Reaction Time 6/10/09 Lower Temperature 6/15/09 Different MW PVP
Need to Analyze* Need to Analyze* Need to Analyze* Need to Analyze* Need to Analyze* Need to Analyze* Need to Analyze* Need to Analyze* Need to Analyze* Need to Analyze* Need to Analyze* Need to Analyze*

Nanowire diameter 71 nm

Nanowire length 4m

Nanoparticle diameter -

42 nm 90 nm 80 nm 302 nm

456 nm 2.9m 4.9 m 27m

76 nm 52 nm 586nm

235 nm 87 nm
Need to Analyze*

26 m 6m
Need to Analyze*

193nm Need to Analyze*

TABLE 1: Different parameters used to create the silver nanowires.

II. Results and Discussion Trial 1: AFM data on the silver nanowires synthesized by Anh Luu and Josh Doorn on May 14, 2009.

FIGURE 1: AFM image of silver nanowires synthesized on May 14, 2009, by Anh Luu and Josh Doorn (14may09Ag NW b level Z(SEN) rev).

FIGURE 2: Absorption spectrum of silver nanowires synthesized on May 14, 2009 (14May09a.wav)

Nanowire diameter Average Value 14030 nm

Nanowire length 46080 nm

Nanoparticle diameter 15030 nm

TABLE 2: Average diameter and length of the Nanowires as well as diameter of Nanoparticles synthesized on May 14, 2009. From Figure 1, Figure 2, and Table 2, the major parts of the products are silver nanoparticles ~76nm. Trial 2: AFM data on the silver nanowire synthesized by Anh Luu and Josh Doorn on May 15, 2009.

FIGURE 3: AFM image of silver nanowires synthesized on May 15, 2009, by Anh Luu and Josh Doorn (15may09Ag NW b level Z(SEN) rev & 15may09Ag NW c level Z(SEN) rev).

FIGURE 4: Absorption spectrum of silver nanowires synthesized on May 15, 2009 (15May09a.wav)

FIGURE 5: Powder X-Ray Diffraction of silver nanowires synthesized on May 15, 2009. Nanowire diameter Average Value 17040 nm Nanowire length 4000900 nm

TABLE 3: Average diameter and length of the Nanowires synthesized on May 15, 2009.This is the best result we obtained. The sample is very uniform with ~70nm in diameter and 4m in length. Trial 3: AFM data on the silver nanowire synthesized by Anh Luu and Josh Doorn on May 18, 2009.

FIGURE 6: AFM image of silver nanowires synthesized on May 18, 2009, by Anh Luu and Josh Doorn (18may09Ag NW e level Z(SEN) rev).

FIGURE 7: Absorption spectrum of silver nanowires synthesized on May 18, 2009 (18May09a.wav)

FIGURE 8: Powder X-Ray Diffraction of silver nanowires synthesized on May 18, 2009. Nanowire diameter Average Value 13020 nm Nanowire length 2900800 nm Nanoparticle diameter 13020 nm

TABLE 4: Average diameter and length of the Nanowires as well as diameter of Nanoparticles synthesized on May 18, 2009.In this experiment, we increased the concentration of NaCl based on the results of May 15. The obtained sample consists of silver nanoparticles and silver nanowires. Comparing with the results of May15, increase of concentration of NaCl will form more seeds resulting in shorter nanowires and more nanoparticles. Trial 4: AFM data on the silver nanowire synthesized by Anh Luu and Josh Doorn on May 20, 2009.

FIGURE 9: AFM image of silver nanowires synthesized on May 20, 2009, by Anh Luu and Josh Doorn (20may09Ag NW d level Z(SEN) rev).

FIGURE 10: Absorption spectrum of silver nanowires synthesized on May 20, 2009 (20May09a.wav) Nanowire diameter Average Value 36050 nm Nanowire length 50003000 nm

TABLE 5: Average diameter and length of the Nanowires synthesized on May 20, 2009.In this experiment, we decreased the concentration of PVP. Decrease of concentration of PVP slow down the growth rate of silver nanowires resulting in non-uniform nanowires. Trial 5: AFM data on the silver nanowire synthesized by Anh Luu and Josh Doorn on May 21, 2009.

FIGURE 11: Absorption spectrum of silver nanowires synthesized on May 21, 2009 (21May09a.wav) Trial 6: AFM data on the silver nanowire synthesized by Anh Luu and Josh Doorn on May 22, 2009.

FIGURE 12: AFM image of silver nanowires synthesized on May 22, 2009, by Anh Luu and Josh Doorn (22may09Ag NW a level Z(SEN) rev).

FIGURE 13: Absorption spectrum of silver nanowires synthesized on May 22, 2009 (22May09a.wav)

FIGURE 14: Powder X-Ray Diffraction of silver nanowires synthesized on May 22, 2009. Nanowire diameter Average Value 75060 nm Nanowire length 2800023000 nm Nanoparticle diameter 1100200 nm

TABLE 6: Average diameter and length of the Nanowires as well as diameter of Nanoparticles synthesized on May 22, 2009. The molecular weight of PVP was changed to 58,000 this time. From the literature, the interaction between PVP and {100} sides are stronger than others, leaving {111} side to receive the coming silver atom, which results in long silver nanowires. The bonding capability of 58,000 PVP is weaker than that of 1.3M PVP, resulting in bigger diameter5. Trial 7: AFM data on the silver nanowire synthesized by Anh Luu on May 25, 2009.

FIGURE 15: AFM image of silver nanowires synthesized on May 25, 2009, by Anh Luu (25may09Ag NW b1 level Z(SEN) rev).

FIGURE 16: Absorption spectrum of silver nanowires synthesized on May 25, 2009 (25May09a.wav)

FIGURE 17: Powder X-Ray Diffraction of silver nanowires synthesized on May 25, 2009. Nanowire diameter Average Value 58060 nm Nanowire length 2600021000 nm Nanoparticle diameter 67090 nm

TABLE 7: Average diameter and length of the Nanowires as well as diameter of Nanoparticles synthesized on May 25, 2009. In this experiment, sodium chloride was not added. Trial 8: AFM data on the silver nanowire synthesized by Anh Luu on May 26, 2009.

FIGURE 18: AFM image of silver nanowires synthesized on May 26, 2009, by Anh Luu (26may09Ag NW a level Z(SEN) rev).

FIGURE 19: Absorption spectrum of silver nanowires synthesized on May 26, 2009 (26May09a.wav)

FIGURE 20: Powder X-Ray Diffraction of silver nanowires synthesized on May 26, 2009. Nanowire diameter Average Value 44040 nm Nanowire length 60001500 nm

TABLE 8: Average diameter and length of the synthesized on May 26, 2009. In this experiment, AgNO3 concentration was increased. Conclusion Silver nanowires were successfully prepared by a solvothermal method. The resulting nanowires were characterized by AFM, UV-vis absorbance, and XRD. By varying the concentration of precursors, silver nanowires with different length and diameter were obtained. As the seed source, the concentration of NaCl has major effects on the length of nanowires. Higher concentrations of NaCl (seeds) results in shorter nanowires. The molecular weight of the capping

agent, PVP, affects both diameter and length of silver nanowires. A higher molecular weight of PVP makes thinner, shorter, and much more uniform silver nanowires due to better capping ability of PVP to silver. Future work will involve measuring the samples that have not yet been measure to determine if the conclusion about PVPs affect on the nanowire growth stays true. The measurements will also reveal the effects of temperature and reaction time on the growth of the silver nanowires.

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