Rare Metals2019年第12期

Design and fabrication of a new fluorescence enhancement system of silver nanoparticles-decorated aligned silver nanowires

Jian-Chao Wang Hong-Sheng Luo Ming-Hai Zhang Xi-Hong Zu Jie Zhang Yu-Xin Gu Guo-Bin Yi

School of Chemical Engineering and Light Industry,Guangdong University of Technology

Guangdong Provincial Key Laboratory of Advanced Coatings Research and Development,China National Electric Apparatus Research Institute Co.,Ltd.

作者简介:*Guo-Bin Yi e-mail:ygb702@163.com;

收稿日期:23 January 2018

基金:financially supported by the National Natural Science Foundation of China (No.51273048);Science and Technology Planning Project of Guangdong Province (No.2017B090915004);the Open Operation of Guangdong Provincial Key Laboratory of Advanced Coatings Research and Development (No.2017B030314105);

Design and fabrication of a new fluorescence enhancement system of silver nanoparticles-decorated aligned silver nanowires

Jian-Chao Wang Hong-Sheng Luo Ming-Hai Zhang Xi-Hong Zu Jie Zhang Yu-Xin Gu Guo-Bin Yi

School of Chemical Engineering and Light Industry,Guangdong University of Technology

Guangdong Provincial Key Laboratory of Advanced Coatings Research and Development,China National Electric Apparatus Research Institute Co.,Ltd.

Abstract:

A new substrate,aligned Ag nanowires decorated with silver nanoparticle composite structure(AgNWs@AgNPs),was fabricated to investigate metalenhanced fluorescence(MEF) and its mechanism.The new composite structure was fabricated via a three-phase interface assembly method followed by SnCl2 sensitization and AgNO3 reduction process.The size and distribution of the nanoparticles on silver nanowires increased with the sensitization and reduction cycles.The formation of AgNPs on the surfaces of AgNWs was confirmed by multiple characterization methods including scanning electron microscopy(SEM),transmission electron microscope(TEM),atomic force microscopy(AFM) and X-ray diffraction(XRD).The results show that the fluorescence intensity of the poly(3-hexylthiophene)(P3HT) on the composite structure was greatly enhanced compared with that on bare glass substrate,and the intensity increased with the increase in particle sizes and density.The mechanism was basedo n the increase in excitation rate and the radiation decay rate.The new type of substrate could serve as a good and efficient MEF substrate for high-performance fluorescence-based devices.

Keyword:

Fluorescence enhancement; Aligned Ag nanowires; Self-assembly; Mechanism;

Received: 23 January 2018

1 Introduction

Since the first experimental demonstraation by Drexhage and coworkers [ 1, 2] ,metal-enhanced fluorescence (MEF)has received much attention.Fluorescence-based devices have been widely used in the field of photonics,chemistry,biology,medicine and materials science [ 3] .The explanation for a significant enhancement can be based on three mechanisms:(1) a local electromagnetic field enhancement activates the adjacent fluorescent molecules,resulting in an increase in the excitation efficiency [ 4] ;(2) the radiative decay rate of the fluorophore is enhanced combined with an increase in the quantum yield and decreased lifetime of fluorescent species [ 5] ;and (3) when the emission wavelength of fluorophore is close to the surface plasmon resonance (SPR) wavelength of nanoscale metals,energy transfer between the fluorophore and the metal results in a radiation integration of excited-state fluorescent species and surface plasma,and thus,fluorescence intensity is enhanced [ 6] .

A set of methods,such as electron-beam lithography,nanosphere lithography,vapor deposition and electrochemical deposition,block copolymer self-assembly and self-assembly [ 7, 8, 9, 10, 11, 12] ,were used to fabricate ordered nanostrueture arrays as MEF substrates.However,most of these methods are complicated,of high cost or difficult for large-scale applications.Therefore,simnple,economical and large-area fabrication of efficient MEF substrates with uniform and dense periodic nanoarrays was still a challenge.Bae et al. [ 13] reported the enhanced fluorescence of high-aspect-ratio silver nanowires.Goh et al. [ 14] produced etched Ag nanowires to create more hot spots along the long axis direction of Ag nano wire for sensitive surfaceenhanced Raman scattering (SERS) detection.High curvature points created by the increase in surface roughness serve as new generated hot spots which broke the limitation of Ag nanowires with limited hot spots at the tips.Dai et al. [ 15] reported Ag nanowire and nanoparticle hybrid system.All these substrates exhibited a stronger SERS or fluorescence signal.Interfacial self-assembly method is a silnple and efficient method [ 16, 17] for the fabrication of various nanofilms of noble metal nanostructures.Tao et al. [ 18] used Langmuir-B lodgett technique to fabricate aligned silver nanowire films which served as excellent SERS substrates with large electromagnetic field enhancement factors.Chen et al. [ 16] fabricated aligned Ag nanowire films as uniform and repeatable SERS substrates by direct two-phase interfacial self-assembly method.Herein,self-assembly process was used to assemble aligned films of silver nanowires.The resulting planar plasmonic substrate was used as MEF substraates with high fluorescence enhancement.

Metal-enhanced fluorescence effect occurred at the surfaces of plasmonic nanostructure wwas mainly due to the concentration of electromagnetic near fields,which were associated with strong localized surfaace plasmon resonances [ 19] .The resonant oscillation of the surface plasmons could cause a large increase in the electromaagnetic field.Most recently,the development of nanoparticles on one-dimensional (1D) nanomaterials attracts gregreat interest in various fields [ 20, 21, 22, 23] .Among them,silver nanowire decorated with silver nanoparticles has received great attention in surface plasmon resonance.Tran et al. [ 24] investigated optical properties of silver nanowires densely decorated with silver nanoparticles,and the hybrid structure exhibited well-separated and fairly regular spots of localized emission/scattering.Wang et al. [ 25] fabricated novel 1D Ag NWs-Ag NPs substrate for detection of protoporphyrin IX based on metal fluorescence enhancement.The intensity enhancement mechanism was simply attributed to the coupling effect of Ag nanowires and Ag nanoparticles.Research results from Michaels et al. [ 26] showed that strong electric fields were located at the junction of two Ag nanoparticles.A series of studies showed that when a metal nanoparticle was placed in the near proximity of another metal nanoparticle/film with a gap of a few nanometers,electric fields in the gap were greatly enhanced [ 27, 28, 29, 30, 31] .The mechanism may be derived from the coupling of surface plasmon polaritons of a metal film with localized surface plasmons of metal nanoparticles [ 32] .The large electric fields resulted in strong fluorescence and Raman enhancement of probe molecule in such a given site.

In this work,aligned silver nanowires decorated with silver nanoparticle (AgNWs@AgNPs) were fabricated using SnCl2 sensitization and AgNO3 reduction process without using any organic linking molecules.The mechanism of fluorescence enhancement of conjugated polymer poly(3-hexylthiophene)(P3HT) on silver nanoparticle-decorated aligned silver nanowires substrates was systematically investigated.The new type of substrate could serve as good and efficient MEF substrates for highperformance fluorescence-based devices.

2 Experimental

2.1 Materials

AgNO3 (99.8%,Sinopharm Chemical Reagent Co.,Ltd.,China),poly(vinylpyrrolidone)(PVP,average molecular weight of 58,000),copper (Ⅱ) chloride dihydrate,ethylene glycol (EG),SnCl2 (anhydrous) and hydrochloric acid were purchased from Shanghai Aladdin Bio-Chem Technology Co.,Ltd.P3HT (average molecular weight of Mw=30 kg·mol-1) was purchased from J&K Scientific Co.Ltd.,China.All the reagents above were used as received without any purification.Milli-Q water and absolute ethanol were used in all preparations.

2.2 Materials preparation

2.2.1 Fabrication of aligned Ag nanowire substrate

The AgNWs were synthesized by the polyol method [ 33] .In the polyol process,silver nitrate was reduced at 160℃with ethylene glycol as the solvent and reducing agent and PVP as wire-directing agent.Self-assembled AgNWs were prepared via a three-phase interface assembly [ 21] ,First of all,aqueous suspension of AgNWs (5 ml) was added to the liquid surface of 25 ml chloroform in a glass vessel.An interface was formed between two immiscible liquids.One milliliter acetone was added slowly.Minutes later,a sparkling mirror-like surface emerged.The ordered Ag nanowire films were then transferred onto glass slide.Residual solvent on the aligned Ag nanowires substrates was removed by natural volatilization at room temperature.

2.2.2 Decoration of aligned Ag nanowires with silver nanoparticle

The obtained self-assembled AgNWs films were immersed in a mixed aqueous solution of SnCl2 (0.02 mol·L-1) and HC1 (0.02 mol·L-1) for 2 min and were then rinsed in nanopure water.Then,the above SnCl2-sensitized aligned AgNWs films were immersed in 0.02 mol·L-1 aqueous solution of AgNO3 for 5 min and were then rinsed in nanopure water.The above preparation process was repeated four times.The samples were labeled as AgNWs,AgNWs@AgNPs-1,AgNWs@AgNPs-2,AgNWs@AgNPs-3 and AgNWs@AgNPs-4 representing the reaction cycles of 0,1,2,3 and 4,respectively.

2.2.3 Preparation of P3HT films

P3HT films on quartz glass and obtained AgNWs@AgNPs substrates were prepared by spin coating.In the typical fabrication process,30μl P3HT chlorobenzene solution(5 mg·ml-1) was spin-coated at a speed of 2000 r,min-1for 60 s.All samples were dried in a vacuum oven for at least 12 h to remove the residual solvent.The samples were labeled as P3HT,S0,S1,S2,S3 and S4 and then kept in dark to prevent deterioration until measurement.

2.3 Characterizations

Extinction spectra were obtained on a Shimadzu ultraviolet(UV)-2450 (Japan) spectrophotometer.The investigations were performed by atomic force microscope (AFM,JEOL JSM-7600F,Bruker),transmission electron microscope(TEM,JEM-1400PLUS,Hitachi) and X-ray diffractometer(XRD,X'Pert Powder,Holland) with Cu Kαradiation.The fluorescence spectra were measured on a FluoroMax-4Spectrofluorometer (HORIBA Jobin Yvon,France).The samples were excited by a Xe lamp at 557 nm for steadystate measurements.The fluorescence emission was measured between 490 and 800 nm.Raman spectroscopic analysis was performed on a laser Raman spectroscopy(HORIBA Jobin Yvon) equipped with an Ar ion laser as the excitation resource (633 nm).

3 Results and discussion

3.1 Fabrication of silver nanoparticle-decorated aligned Ag nanowires

The process for the preparation of AgNWs@AgNPs is schematically illustrated in Fig.1.The fabrication process consists of four steps:containing alignment in the interface,transferring onto the substrates,SnCl2 sensitization and AgNO3 reduction.Sn2+could be adsorbed on the surface of the AgNWs in which AgNWs were coated by a thin layer of PVP,which contains amine and carbonyl groups,serving as“molecular anchors”that bond the Sn2+to the surfaces of the membrane [ 34] .In addition,there are plenty of hydroxyl groups on the surface silver nanowires synthesized by polyol process [ 35] .When exposed to mixed solution of SnCl2 and HCl,the surface hydroxyl groups may be deprotonated,and negative oxygen sites were formed.Thus,Sn2+would be bound to negatively charged surfaces via electrostatic attraction.In the AgNO3 reduction,the spontaneous oxidation of surface Sn2+to Sn4+and reduction of Ag+to Ag0 took place,as shown in Eq.(1):

Fig.1 Schematic illustration of AgNWs@AgNPs substrate fabrica-tion process

SEM images of aligned AgNWs and AgNWs@AgNPs are shown in Fig.2.It is shown that the surface of AgNWs is smooth,and AgNWs are parallel to each other,forming a close contact,and highly arrayed structure.Some large intervals might be caused during the transfer of films from interface to substrate.For AgNWs@AgNPs,small silver seeds were formed along the longitude surface of AgNWs without destruction of the arrangement of Ag nano wires.With the further increase in reaction cycles,silver seed grew,and new silver seed was generated.Silver nanoparticles were uniformly immobilized along the long axis direction.Almost every AgNW was covered densely and uniformly with a great quantity of nanoparticles,leading to the shrinkage of gaps.It was observed that the size and distribution of silver nanoparticles on AgNWs substrates were controlled by the cycle times.

The angles between silver nanowires and horizontal line were measured through the ImageJ.In Fig.2b-f,77%-85%nanowires were aligned in one direction±5°(Table 1).Standard deviation (σ) provides the degree of dispersion (Table 1).

where N is the number of silver nano wires,Xi is the angle between nanowire and the horizontal direction andμis the arithmetic mean of the angle of all the silver nano wires.The results appeared to reflect that most of the silver nanowires were parallel to each other and only a few silver nanowires were in disorder which are formed during the transfer of films from interface to substrate.

3.2 Morphology and crystallinity

To further analyze the size and morphology of silver nanoparticles decorated on silver nanowires and the interface areas of two kinds of nanoparticles,TEM experiments were performed.Figure 3 shows typical TEM images of as-synthesized Ag nanowires and AgNWs@AgNPs.The surface of as-synthesized silver nano wires was very smooth.After one sensitization and reduction reaction cycle,many silver nanoparticles appeared on the surface of Ag nanowires along the long axis.The average diameter of AgNPs was about 36.8 nm.The size and number of AgNPs grew with sensitization and reduction cycles,and the diameters were 45.6,53.3 and65.8 nm,for AgNWs@AgNPs-2,AgNWs@AgNPs-3 and AgNWs@AgNPs-4,respectively.Besides,the formed Ag nanoparticles were more uniform and denser on the surface of the nano wire with more reaction cycles.Moreover,it was obvious that there were large interface areas between AgNPs and AgNWs,suggesting that Ag nanoparticles were firmly anchored to the surface of Ag nanowires even after the ultrasonic process during sample preparation for TEM,and only a few unbond AgNPs were observed.An HRTEM image of AgNW s@AgNPs-1 shows the simultaneous presence of different crystallographic planes (Fig.3f),showing the expected spacings of 0.254 and 0.204 nm for(111) and (200) crystal planes of Ag.

Fig.2 SEM images of a,b aligned AgNWs film and c-f AgNWs@AgNPs-1,AgNWs@AgNPs-2,AgNWs@AgNPs-3 and AgNWs@AgNPs-4,respectively

  下载原图

Table 1 Frequency of (μ±5°) and standard deviation of nanowires in Fig.2b-f

Fig.3 TEM images of a AgNWs and b-e AgNWs@AgNPs-1,AgNWs@AgNPs-2,AgNWs@AgNPs-3 and AgNWs@AgNPs-4,respectively;f HRTEM image of AgNWs@AgNPs-l

Figure 4 shows AFM height images of as-synthesized Ag nanowires and AgNPs-decorated Ag nano wires.Morphological differences between two types of nano wires were clearly observed.The as-synthesized silver nano wire shows a very smooth surface along the long axis,whereas for the AgNWs@AgNPs,the formation of AgNPs on the surface of aligned Ag nanowires can be clearly distinguished.A large amount of silver nanoparticles coated with Ag nanowires show a highly roughened surface along the longitudinal axis.AFM height images of aligned substrates are presented in Fig.4c,d to provide direct topographical comparisons between both types of substrates.Almost all the Ag nanowires were uniformly decorated with AgNPs,forming a new type of highly roughened nanowire without adverse effect on alignment of Ag nanowires.

Figure 5 shows typical XRD patterns of AgNWs and AgNWs@AgNPs-4.Both XRD patterns have five distinct diffraction peaks,and the peak positions of both types of AgNWs were consistent with each other.The diffraction pattern for the AgNWs@AgNPs-4 film has five peaks at38.10°,44.38°,64.43°,77.84°and 81.33°,corresponding to(111),(200),(220),(311) and (222) of fee silver according to JCPDS No.04-783.The diffraction peaks were sharp and intense,and no other peaks can be observed.It was indicated that AgNWs and newly formed AgNPs were not oxidized during and after the reaction and preserved high purity and good crystalline nature.

Fig.4 AFM topography of single as-synthesized a AgNWs and b AgNWs@AgNPs-1 on silicon substrate.AFM images of c aligned AgNWs substrates and d aligned AgNWs@AgNPs-3 substrates

Fig.5 XRD patterns of as-synthesized Ag nano wires and AgNWs@AgNPs-4

3.3 Metal-enhanced fluorescence

Figure 6 shows fluorescence emission spectra of P3HT on bare glass substrate and different AgNWs@AgNPs substrates.For comparison,the intensity of spectrum of P3HT was magnified to five times of its original data.Two emission peaks of P3HT were observed at 660 and 725 nm,respectively.The fluorescence intensity of the P3HT on bare glass substrate was the weakest,the fluorescence intensity on the aligned Ag nanowires was stronger,and the fluorescence emission on AgNWs@AgNPs was further increased.The fluorescence intensity of P3HT on aligned Ag nano wires was about 17.5 times higher than that on bare glass substrate.Compared with aligned Ag nanowires,enhancement factors of silver nanoparticle-decorated Ag nano wires substrates at 725 nm were 1.51,2.33,3.18 and3.88,respectively.It was indicated that the fabricated AgNWs@AgNPs substrate could significantly enhance the fluorescence emission for P3HT.Moreover,the intensity of P3HT was increased with the increase in size and distribution of nanoparticles.

Fig.6 Steady-state fluorescence spectra of P3HT films on bare quartz glass substrate and different AgNWs@AgNPs substrates excited by 557-nm excitation light source

3.4 Extinction spectra and excite enhancement

Figure 7 shows the evolution of ultraviolet-visible (UV-Vis) spectra of aligned AgNWs and silver nanoparticlesdecorated aligned silver nanowire substrates with increasing cycles of sensitization and reduction.The plasmon resonance peaks of silver nanowire located at about 322 and350 nm correspond to the transverse plasmon resonance and quadrupole resonance excitation of nanowires,respectively [ 36] .The SPR is extremely sensitive to size,morphology and arrangement of AgNWs [ 37, 38] .After one cycle of silver nanoparticle deposition,plasma resonance peaks of Ag nano wires changed obviously.The intensity of transverse plasmon resonance peaks declined clearly,and a new absorption bands appeared at about 450 nm.With increasing cycles of sensitization and reduction process,new peak strengthened continuously,indic ating the formation of silver nanoparticles.Furthermore,a slight red shift was observed,suggesting the size growth of the nanoparticles.It can be seen that the color of the substrates gradually changed from silver gray to dark yellow.Moreover,the formation of AgNPs on the surface of AgNWs also resulted in a tiny band shift of AgNWs to longer wavelength.It was demonstrated that there was the coupling of the AgNPs and AgNWs.The enhancement of the extinction intensity coupled with the emergence of new SPR of AgNPs contributed to larger overlap between SPR of AgNWs@AgNPs films and absorption peaks of P3HT (520,557 and 603 nm).Larger overlap was favorable for the enhancement of the excitation rate,which is beneficial to enhanced fluorescence of P3HT.

Fig.7 UV-Vis spectra of aligned as-synthesized nanowires and silver nanoparticle-decorated aligned silver nanowires with different sensitization and reduction cycles (1,2,3 and 4) and absorption spectrum of P3HT film on quartz

3.5 Energy transfer analysis

Metal-enhanced fluorescence is also strongly influenced by the energy transfer between the fluorophore and the metal substrate.When a fluorophore is excited,intramolecular energy transfer occurs from the excited fluorophore to the metal,resulting in metal nanoparticles to emit fluorescence with the same wavelength,and thus,fluorescence intensity is enhanced.The energy transfer from fluorophore to adjacent nanoparticle occurs only in the range of the SPR frequency [ 39] .Figure 8 shows that the emission peak positions of the P3HT film were outside the surface plasmon resonance region of the aligned AgNWs@AgNPs films,leading to a low energy transfer from the excited conjugated polymer P3HT to aligned AgNWs@AgNPs films.Therefore,energy transfer from fluorescence polymer to AgNWs@AgNPs substrate is quite negligible.

3.6 Electromagnetic field enhancement and Raman analysis

To further demonstrate the mechanism of MEF,surfaceenhanced resonance Raman scattering was also carried out in our work.Raman enhancement was mainly caused by local electromagnetic field enhancement [ 40] .Figure 9a shows the Raman spectra of the P3HT films on bare glass substrate and different AgNWs@AgNPs substrates.The characteristic Raman peaks at 715,1380 and 1450 cm-1were assigned to the P3HT C-S-C ring deformation,C-C skeletal stretching deformation and C=C stretching.respectively [ 41] .It can be seen that the peak positions were consistent with different substrates,indicating no morphology or chemistry change in P3HT at the presence of AgNWs@AgNPs substrates.The spectroscopic band intensity was greatly enhanced by the inclusion of AgNWs@AgNPs,and the peak intensities were gradually enhanced with the increase in size and density of decorated nanoparticles.The observed Raman enhancement reflects the coherence enhancements in electromagnetic field due to the AgNWs@AgNPs,which may also contribute to the enhanced fluorescence.

Fig.8 Extinction spectra of aligned AgNWs@AgNPs-3 films and emission spectra P3HT film on quartz glass

Fig.9 a Raman spectra of P3HT films on bare glass substrate and different aligned AgNWs@AgNPs films;b illustration of electromagnetic field enhancement mechanism of MEF based on AgNWs@AgNPs substrate

Electromagnetic field of plasmonic nanostructure can alter the excitation and emission of fluorophore,and energy transfer between fluorophore and adjacent metal to enhance the fluorescence intensity [ 42] .The mechanism of the electromagnetic field enhancement is shown in Fig.9b.Tran et al. [ 24] studied the optical properties of a hybrid structure of a silver nanowire densely decorated with silver nanoparticles.Upon light radiation,regularly distributed spots of localized emission/scattering were observed along the AgNWs.The phenomenon was attributed to collective interactions of the localized surface plasmon resonances(LSPRs) of AgNPs with propagating surface plasmons(SPPs) on the AgNWs.The structure of our silver nano wire decorated with silver nanoparticles was similar to the system of Tran [ 24] .We make an analogy to show that our AgNWs@AgNPs substrates exhibit similar character.On the other hand,the enhancement of electromagnetic field in nanoparticle-nanoparticle or nanoparticle-nanowire gaps was much greater.Our AgNWs@AgNPs substrates have more hot spots than that from an inpidual nanowire through finite method [ 43] .Similarly,our silver nanoparticle-nanoparticle,nanoparticle-nanowire or nanowirenanowire gaps also contributed to total electromagnetic fields.So,for our silver nanoparticles-decorated aligned silver nanowire,electromagnetic field at these gaps was greatly enhanced.As a result,fluorescence and Raman intensity of P3HT were enhanced for electromagnetic field enhancement.

3.7 Fluorescence lifetime measurement

Enhancement of the radiative decay rate is related to metalenhanced fluorescence,usually accompanied by a decrease in fluorescence lifetime [ 44] .To further study the mechanism of the fluorescence enhancement of AgNWs@AgNPs substrates,time-resolved fluorescence spectroscopy was carried out.Figure 10 shows time-resolved decay curves of the P3HT films on bare glass substrate and different AgNWs@AgNPs substrates at 475-nm excitation.Monoexponential function was used to fit the experimental data.

Fig.10 Time-resolved decay curves of P3HT films on bare glass substrate and different aligned AgNWs@AgNPs films

  下载原图

Table 2 Fitting lifetime of P3HT

Goodness of fit was determined by R2 value

whereτis the lifetime,A represents the value of weighting factor of fluorescence decay,t is the time and y0 stands for weighting factor of nonradiative decay.Time-resolved decay curves of P3HT on bare glass are significantly different from the other curves,while for different silver nanowires substrates,there is no significant difference.The average lifetime of P3HT films on glass was found to be the longest,while for different AgNWs@AgNPs substrates,the fluorescence lifetime slightly shortened.Moreover,the fluorescence lifetime of P3HT is found to decrease with the increase in the number of fabrication cycles,and the data are listed in Table 2.This would partially demonstrate the observed fluorescence enhancement.The result shows that the emission enhancement is not only a result of increase in the absorption rate of P3HT,but also the result of the increase in radiative decay.

4 Conclusion

In this study,silver nanoparticles-decorated aligned silver nanowires (AgNWs@AgNPs) films were prepared as MEF substrates.Experimental results show that the size and distribution of nanoparticle were tuned by sensitization and reduction cycles.The fluorescence intensity of the P3HT on the fabricated substrates increased with the ihcrease in particle sizes and density.The mechanism of metal-enhanced fluorescent enhancement was based on the enhancement of the excitation rate from the larger overlap between SPR of AgNWs@AgNPs films and absorption peaks of P3HT,and the decrease in fluorescence lifetime of P3HT with the increase in the number of fabrication cycles.In a word,the fluorescence enhancement may be the result of an increase in both excitation rate and the radiation decay rate.Owning to the enhancement of fluorescence intensity and easy preparation,the silver nanoparticles-decorated aligned silver nanowire substrates are the suitable choice for good and efficient MEF sensing applications.

参考文献

[1] Drexhage KH,Kuhn H,Schafer FP.Variation of the fluorescence decay time of a molecule in front of a mirror.Ber Bunsenges Phys Chem.1968;72(2):329.

[2] Drexhage KH.Influence of a dielectric interface on fluorescence decay time.J Lumin.1970;1-2(Supplement C):693.

[3] Bauch M,Toma K,Toma M,Zhang QW,Dostalek J.Plasmon-enhanced fluorescence biosensors:a review.Plasmonics.2014;9(4):781.

[4] Tanabe K.Field enhancement around metal nanoparticles and nanoshells:a systematic investigation.J Phys Chem C.2008;112(40):15721.

[5] Goldys EM,Drozdowicz-Tomsia K,Xie F,Shtoyko T,Matveeva E,Gryczynski I,Gryczynski Z.Fluorescence amplification by electrochemically deposited silver nanowires with fractal architecture.J Am Chem Soc.2007;129(40):12117.

[6] Saraswat S,Desireddy A,Zheng DS.Guo LJ,Lu HP,Bigioni TP,Isailovic D.Energy transfer from fluorescent proteins to metal nanoparticles.J Phys Chem C.2011;115(35):17587.

[7] Flauraud V,Regmi R,Winkler PM,Alexander DTL,Rigneault H.van Hulst NF.Garcia-Parajo MF,Wenger J.Brugger J.In-plane plasmonic antenna arrays with surface nanogaps for giant fluorescence enhancement.Nano Lett.2017;17(3):1703.

[8] Pang J,Thcodorou IG,Centeno A,Petrov PK,Alford NM,Ryan MP,Xie F.Gold nanodisc arrays as near infrared metal-enhanced fluorescence platforms with tuneable enhancement factors.J Mater Chem C.2017;5(4):917.

[9] Geddes CD,Parfenov A,Roll D,Fang JY,Lakowicz JR.Electrochemical and laser deposition of silver for use in metal-enhanced fluorescence.Langmuir.2003;19(15):6236.

[10] Shin DO,Mun JH,Hwang GT,Yoon JM,Kim JY,Yun JM,Yang YB,Oh Y,Lee JY,Shin J,Lee KJ,Park S,Kim JU,Kim SO.Multicomponent nanopatterns by directed block copolymer self-assembly.ACS Nano.2013;7(10):8899.

[11] Mistark PA,Park S,Yalcin SE,Lee DH,Yavuzcctin O,Tuominen MT,Russell TP,Achermann M.Block-copolymer-based plasmonic nanostructures.ACS Nano.2009;3(12):3987.

[12] Punj D.Regmi R,Devilez A.Plauchu R,Moparthi SB,Stout B.Bonod N,Rigneault H,Wenger J.Self-assembled nanoparticle dimer antennas for plasmonic-enhanced single-molecule fluorescence detection at micromolar concentrations.ACS Photonics.2015;2(8):1099.

[13] Bae S,Han H,Bae JG,Lee EY,Im SH,Kim DH,Seo TS.Growth of silver nanowires from controlled silver chloride seeds and their application for fluorescence enhancement based on localized surface plasmon resonance.Small.2017;13(21):1603392.

[14] Goh MS,Lee YH,Pedireddy S,Phang IY,Tjiu WW,Tan JMR,Ling XY.A chemical route to increase hot spots on silver nanowires for surface-enhanced Raman spectroscopy application.Langmuir.2012;28(40):14441.

[15] Dai ZG,Xiao XH,Liao L,Ying JJ,Mei F,Wu W,Ren F,Li WQ,Jiang CZ.Enhanced and polarization dependence of surface-enhanced Raman scattering in silver nanoparticle arraynanowire systems.Appl Phys Lett.2013;102(16):1052.

[16] Chen CF,Hao JM,Zhu LY,Yao YQ,Meng XG,Weimer WN,Wang QWK.Direct two-phase interfacial self-assembly ofaligned silver nanowire films for surface enhanced Raman scattering applications.J Mater Chem A.2013;1(43):13496.

[17] Liu JW,Zhang SY,Qi H,Wen WC,Yu SH.A general strategy for self-assembly of nanosized building blocks on liquid/liquid interfaces.Small.2012;8(15):2412.

[18] Tao A,Kim F,Hess C,Goldberger J,He RR,Sun YG,Xia YN,Yang PD.Langmuir-blodgett silver nanowire monolayers for molecular sensing using surface-enhanced Raman spectroscopy.Nano Lett.2003;3(9):1229.

[19] Lee SJ,Morrill AR,Moskovits M.Hot spots in silver nanowire bundles for surface-enhanced Raman spectroscopy.J Am Chem Soc.2006;128(7):2200.

[20] Zhang D,Zhang L,Shi L.Fang C.Li H,Gao R,Huang L,Zhang J.In situ supported MnO_x-CeO_x on carbon nanotubes for the low-temperature selective catalytic reduction of NO with NH_3.Nanoscale.2013;5(3):1127.

[21] Peng C,Wang W.Zhang W,Liang Y,Zhuo L.Surface plasmon-driven photoelectrochemical water splitting of TiO_2 nanowires decorated with Ag nanoparticles under visible light illumination.Appl Surf Sci.2017;420:286.

[22] Khandare L,Terdale S.Gold nanoparticles decorated MnO_2nanowires for high performance supercapacitor.Appl Surf Sci.2017;418:22.

[23] Han J,Zhang D,Maitarad P,Shi L,Cai S,Li H,Huang L,Zhang J.Fe_2O_3 nanoparticles anchored in situ on carbon nanotubes via an ethanol-thermal strategy for the selective catalytic reduction of NO with NH3.Catal Sci Technol.2015;5(1):438.

[24] Tran ML,Centeno SP,Hutchison JA,Engelkamp H,Liang D,Van Tendeloo G,Sels BF,Hofkens J,Uji-i H.Control of surface plasmon localization via self-assembly of silver nanoparticles along silver nanowires.J Am Chem Soc.2008;130(51):17240.

[25] Wang YJ,Zu XH,Yi GB,Luo HS,Huang HL,Song XL.Ag nanowire-Ag nanoparticle hybrids for the highly enhanced fluorescence detection of protoporphyrin IX based on surface plasmon-enhanced fluorescence.Chin J Chem.2016;34(12):1321.

[26] Michaels AM,Jiang J,Brus L.Ag nanocrystal junctions as the site for surface-enhanced Raman scattering of single Rhodamine 6G molecules.J Phys Chem B.2000;104(50):11965.

[27] Zhao LB,Liu XX,Zhang M,Liu ZF,Wu DY,Tian ZQ.Surface plasmon catalytic aerobic oxidation of aromatic amines in metal/molecule/metal junctions.J Phys Chem C.2016;120(2):944.

[28] Jiang J,Bosnick K,Maillard M,Brus L.Single molecule Raman spectroscopy at the junctions of large Ag nanocrystals.J Phys Chem B.2003;107(37):9964.

[29] Jia CC.Migliore A,Xin N,Huang SY,Wang JY,Yang Q.Wang SP,Chen HL,Wang DM,Feng BY,Liu ZR,Zhang GY,Qu DH,Tian H,Ratner MA,Xu HQ,Nitzan A,Guo XF.Covalently bonded single-molecule junctions with stable and reversible photoswitched conductivity.Science.2016;352(6292):1443.

[30] Dasari R,Zamborini FP.Surface enhanced Raman spectroscopy at electrochemically fabricated silver nanowire junctions.Anal Chem.2016;88(1):675.

[31] Schmelzeisen M,Zhao Y,Klapper M,Mullen K,Kreiter M.Fluorescence enhancement from inpidual plasmonic gap resonances.ACS Nano.2010;4(6):3309.

[32] Mock JJ,Hill RT,Degiron A,Zauscher S,Chilkoti A,Smith DR.Distance-dependent plasmon resonant coupling between a gold nanoparticle and gold film.Nano Lett.2008;8(8):2245.

[33] Wang JC.Luo HS,Zhang MH,Zu XH,Li ZW.Yi GB.Aligned chemically etched silver nanowire monolayer as surface-enhanced Raman scattering substrates.Nanoscale Res Lett.2017;12(1):587.

[34] Menon VP,Martin CR.Fabrication and evaluation of nanoelectrode ensembles.Anal Chem.1995;67(13):1920.

[35] Wan J,Cai W,Meng X,Liu E.Monodisperse water-soluble magnetite nanoparticles prepared by polyol process for high-performance magnetic resonance imaging.Chem Commun.2007;47(47):5004.

[36] Chen DP,Qiao XL,Qiu XL,Chen JG,Jiang RZ.Large-scale synthesis of silver nanowires via a solvothermal method.J Mater Sci-Mater Electron.2011;22(1):6.

[37] Okamoto H,Imura K.Near-field imaging of optical field and plasmon wavefunctions in metal nanoparticles.J Mater Chem.2006;16(40):3920.

[38] Felidj N,Grand J,Laurent G,Aubard J,Levi G,Hohenau A,Galler N.Aussenegg FR,Krenn JR.Multipolar surface plasmon peaks on gold nanotriangles.J Chem Phys.2008;128(9):94702.

[39] Singh MP,Strouse GF.Involvement of the LSPR spectral overlap for energy transfer between a dye and Au nanoparticle.J Am Chem Soc.2010;132(27):9383.

[40] Jang HY,Kim SK,Park S.Electromagnetic field enhancement in the multilayer of metallic nanomesh films:synthesis and application as surface-enhanced Raman scattering substrates.J Phys Chem C.2015;119(19):10585.

[41] Yang YZ,Sun L,Ou JM,He YT,Lin XF,Yuan ZK,Lin WS,Hong W,Yu DS,Chen XD,Qiu ZR.Plasmonic effects and the morphology changes on the active material P3HT:PCBM used in polymer solar cells using Raman spectroscopy.J Raman Spectrosc.2016;47(8):888.

[42] Cui QL,He F,Li LD,Mohwald H.Controllable metal-enhanced fluorescence in organized films and colloidal system.Adv Colloid Interface.2014;207:164.

[43] Hao J,Liu T,Huang Y,Chen G,Liu A,Wang S,Wen W.Metal nanoparticle-nanowire assisted SERS on film.J Phys Chem C.2015;119(33):19376.

[44] Lakowicz JR,Ray K,Chowdhury M,Szmacinski H,Fu Y.Zhang J,Nowaczyk K.Plasmon-controlled fluorescence:a new paradigm in fluorescence spectroscopy.Analyst.2008;133(10):1308.

[1] Drexhage KH,Kuhn H,Schafer FP.Variation of the fluorescence decay time of a molecule in front of a mirror.Ber Bunsenges Phys Chem.1968;72(2):329.

[2] Drexhage KH.Influence of a dielectric interface on fluorescence decay time.J Lumin.1970;1-2(Supplement C):693.

[3] Bauch M,Toma K,Toma M,Zhang QW,Dostalek J.Plasmon-enhanced fluorescence biosensors:a review.Plasmonics.2014;9(4):781.

[4] Tanabe K.Field enhancement around metal nanoparticles and nanoshells:a systematic investigation.J Phys Chem C.2008;112(40):15721.

[5] Goldys EM,Drozdowicz-Tomsia K,Xie F,Shtoyko T,Matveeva E,Gryczynski I,Gryczynski Z.Fluorescence amplification by electrochemically deposited silver nanowires with fractal architecture.J Am Chem Soc.2007;129(40):12117.

[6] Saraswat S,Desireddy A,Zheng DS.Guo LJ,Lu HP,Bigioni TP,Isailovic D.Energy transfer from fluorescent proteins to metal nanoparticles.J Phys Chem C.2011;115(35):17587.

[7] Flauraud V,Regmi R,Winkler PM,Alexander DTL,Rigneault H.van Hulst NF.Garcia-Parajo MF,Wenger J.Brugger J.In-plane plasmonic antenna arrays with surface nanogaps for giant fluorescence enhancement.Nano Lett.2017;17(3):1703.

[8] Pang J,Thcodorou IG,Centeno A,Petrov PK,Alford NM,Ryan MP,Xie F.Gold nanodisc arrays as near infrared metal-enhanced fluorescence platforms with tuneable enhancement factors.J Mater Chem C.2017;5(4):917.

[9] Geddes CD,Parfenov A,Roll D,Fang JY,Lakowicz JR.Electrochemical and laser deposition of silver for use in metal-enhanced fluorescence.Langmuir.2003;19(15):6236.

[10] Shin DO,Mun JH,Hwang GT,Yoon JM,Kim JY,Yun JM,Yang YB,Oh Y,Lee JY,Shin J,Lee KJ,Park S,Kim JU,Kim SO.Multicomponent nanopatterns by directed block copolymer self-assembly.ACS Nano.2013;7(10):8899.

[11] Mistark PA,Park S,Yalcin SE,Lee DH,Yavuzcctin O,Tuominen MT,Russell TP,Achermann M.Block-copolymer-based plasmonic nanostructures.ACS Nano.2009;3(12):3987.

[12] Punj D.Regmi R,Devilez A.Plauchu R,Moparthi SB,Stout B.Bonod N,Rigneault H,Wenger J.Self-assembled nanoparticle dimer antennas for plasmonic-enhanced single-molecule fluorescence detection at micromolar concentrations.ACS Photonics.2015;2(8):1099.

[13] Bae S,Han H,Bae JG,Lee EY,Im SH,Kim DH,Seo TS.Growth of silver nanowires from controlled silver chloride seeds and their application for fluorescence enhancement based on localized surface plasmon resonance.Small.2017;13(21):1603392.

[14] Goh MS,Lee YH,Pedireddy S,Phang IY,Tjiu WW,Tan JMR,Ling XY.A chemical route to increase hot spots on silver nanowires for surface-enhanced Raman spectroscopy application.Langmuir.2012;28(40):14441.

[15] Dai ZG,Xiao XH,Liao L,Ying JJ,Mei F,Wu W,Ren F,Li WQ,Jiang CZ.Enhanced and polarization dependence of surface-enhanced Raman scattering in silver nanoparticle arraynanowire systems.Appl Phys Lett.2013;102(16):1052.

[16] Chen CF,Hao JM,Zhu LY,Yao YQ,Meng XG,Weimer WN,Wang QWK.Direct two-phase interfacial self-assembly ofaligned silver nanowire films for surface enhanced Raman scattering applications.J Mater Chem A.2013;1(43):13496.

[17] Liu JW,Zhang SY,Qi H,Wen WC,Yu SH.A general strategy for self-assembly of nanosized building blocks on liquid/liquid interfaces.Small.2012;8(15):2412.

[18] Tao A,Kim F,Hess C,Goldberger J,He RR,Sun YG,Xia YN,Yang PD.Langmuir-blodgett silver nanowire monolayers for molecular sensing using surface-enhanced Raman spectroscopy.Nano Lett.2003;3(9):1229.

[19] Lee SJ,Morrill AR,Moskovits M.Hot spots in silver nanowire bundles for surface-enhanced Raman spectroscopy.J Am Chem Soc.2006;128(7):2200.

[20] Zhang D,Zhang L,Shi L.Fang C.Li H,Gao R,Huang L,Zhang J.In situ supported MnO_x-CeO_x on carbon nanotubes for the low-temperature selective catalytic reduction of NO with NH_3.Nanoscale.2013;5(3):1127.

[21] Peng C,Wang W.Zhang W,Liang Y,Zhuo L.Surface plasmon-driven photoelectrochemical water splitting of TiO_2 nanowires decorated with Ag nanoparticles under visible light illumination.Appl Surf Sci.2017;420:286.

[22] Khandare L,Terdale S.Gold nanoparticles decorated MnO_2nanowires for high performance supercapacitor.Appl Surf Sci.2017;418:22.

[23] Han J,Zhang D,Maitarad P,Shi L,Cai S,Li H,Huang L,Zhang J.Fe_2O_3 nanoparticles anchored in situ on carbon nanotubes via an ethanol-thermal strategy for the selective catalytic reduction of NO with NH3.Catal Sci Technol.2015;5(1):438.

[24] Tran ML,Centeno SP,Hutchison JA,Engelkamp H,Liang D,Van Tendeloo G,Sels BF,Hofkens J,Uji-i H.Control of surface plasmon localization via self-assembly of silver nanoparticles along silver nanowires.J Am Chem Soc.2008;130(51):17240.

[25] Wang YJ,Zu XH,Yi GB,Luo HS,Huang HL,Song XL.Ag nanowire-Ag nanoparticle hybrids for the highly enhanced fluorescence detection of protoporphyrin IX based on surface plasmon-enhanced fluorescence.Chin J Chem.2016;34(12):1321.

[26] Michaels AM,Jiang J,Brus L.Ag nanocrystal junctions as the site for surface-enhanced Raman scattering of single Rhodamine 6G molecules.J Phys Chem B.2000;104(50):11965.

[27] Zhao LB,Liu XX,Zhang M,Liu ZF,Wu DY,Tian ZQ.Surface plasmon catalytic aerobic oxidation of aromatic amines in metal/molecule/metal junctions.J Phys Chem C.2016;120(2):944.

[28] Jiang J,Bosnick K,Maillard M,Brus L.Single molecule Raman spectroscopy at the junctions of large Ag nanocrystals.J Phys Chem B.2003;107(37):9964.

[29] Jia CC.Migliore A,Xin N,Huang SY,Wang JY,Yang Q.Wang SP,Chen HL,Wang DM,Feng BY,Liu ZR,Zhang GY,Qu DH,Tian H,Ratner MA,Xu HQ,Nitzan A,Guo XF.Covalently bonded single-molecule junctions with stable and reversible photoswitched conductivity.Science.2016;352(6292):1443.

[30] Dasari R,Zamborini FP.Surface enhanced Raman spectroscopy at electrochemically fabricated silver nanowire junctions.Anal Chem.2016;88(1):675.

[31] Schmelzeisen M,Zhao Y,Klapper M,Mullen K,Kreiter M.Fluorescence enhancement from inpidual plasmonic gap resonances.ACS Nano.2010;4(6):3309.

[32] Mock JJ,Hill RT,Degiron A,Zauscher S,Chilkoti A,Smith DR.Distance-dependent plasmon resonant coupling between a gold nanoparticle and gold film.Nano Lett.2008;8(8):2245.

[33] Wang JC.Luo HS,Zhang MH,Zu XH,Li ZW.Yi GB.Aligned chemically etched silver nanowire monolayer as surface-enhanced Raman scattering substrates.Nanoscale Res Lett.2017;12(1):587.

[34] Menon VP,Martin CR.Fabrication and evaluation of nanoelectrode ensembles.Anal Chem.1995;67(13):1920.

[35] Wan J,Cai W,Meng X,Liu E.Monodisperse water-soluble magnetite nanoparticles prepared by polyol process for high-performance magnetic resonance imaging.Chem Commun.2007;47(47):5004.

[36] Chen DP,Qiao XL,Qiu XL,Chen JG,Jiang RZ.Large-scale synthesis of silver nanowires via a solvothermal method.J Mater Sci-Mater Electron.2011;22(1):6.

[37] Okamoto H,Imura K.Near-field imaging of optical field and plasmon wavefunctions in metal nanoparticles.J Mater Chem.2006;16(40):3920.

[38] Felidj N,Grand J,Laurent G,Aubard J,Levi G,Hohenau A,Galler N.Aussenegg FR,Krenn JR.Multipolar surface plasmon peaks on gold nanotriangles.J Chem Phys.2008;128(9):94702.

[39] Singh MP,Strouse GF.Involvement of the LSPR spectral overlap for energy transfer between a dye and Au nanoparticle.J Am Chem Soc.2010;132(27):9383.

[40] Jang HY,Kim SK,Park S.Electromagnetic field enhancement in the multilayer of metallic nanomesh films:synthesis and application as surface-enhanced Raman scattering substrates.J Phys Chem C.2015;119(19):10585.

[41] Yang YZ,Sun L,Ou JM,He YT,Lin XF,Yuan ZK,Lin WS,Hong W,Yu DS,Chen XD,Qiu ZR.Plasmonic effects and the morphology changes on the active material P3HT:PCBM used in polymer solar cells using Raman spectroscopy.J Raman Spectrosc.2016;47(8):888.

[42] Cui QL,He F,Li LD,Mohwald H.Controllable metal-enhanced fluorescence in organized films and colloidal system.Adv Colloid Interface.2014;207:164.

[43] Hao J,Liu T,Huang Y,Chen G,Liu A,Wang S,Wen W.Metal nanoparticle-nanowire assisted SERS on film.J Phys Chem C.2015;119(33):19376.

[44] Lakowicz JR,Ray K,Chowdhury M,Szmacinski H,Fu Y.Zhang J,Nowaczyk K.Plasmon-controlled fluorescence:a new paradigm in fluorescence spectroscopy.Analyst.2008;133(10):1308.