了得網工業技術_-激子相互作用:原理和應用

編輯推薦

－激子相互作用：原理和應用在介紹經典的理論解釋和應用時加入大量科研*前沿的進展，保證讀者在能理解基礎概念的同時，對本領域的發展進展和熱點有一定了解。

內容簡介

本書從原理和應用兩個方向展開，詳細介紹了多種環境中的驅動催化反應和激子耦合驅動催化反應。主要可分為以下部分：基於表面增強拉曼散射（SERS）的驅動催化反應在大氣和液相中的機理和應用、基於針尖增強拉曼散射（TERS）的驅動催化反應在高真空中的機理和應用、激子耦合相互作用的物理模型和特性研究、激子耦合驅動催化反應在電化學液相中的應用，以及光電協同調控下的耦合驅動催化反應。通過介紹大量經典研究案例，結合相應理論計算與模型簡介，深入淺出地介紹了激子相互作用的意義與發展前景。
本書適用於有一定理論基礎的物理學本科生和有光學相關研究經歷的研究生和科研工作者。

CONTENTS

PlasmonExciton Interaction： Principlesand Applications
CONTENTS
CHAPTER 1Introduction

References

CHAPTER 2PlasmonDrivenChemical Reactions Based on
SERS in Atmosphere
2.1Brief introduction

2.2Plasmondriven oxidationreactions

CONTENTS

PlasmonExciton Interaction： Principles
and Applications

CONTENTS

CHAPTER 1Introduction

References

CHAPTER 2PlasmonDriven
Chemical Reactions Based on

SERS in Atmosphere

2.1Brief introduction

2.2Plasmondriven oxidation
reactions

2.2.1Genuine SERS spectrum of PATP

2.2.2Experimental and theoretical
investigations of

plasmondriven oxidation
reactions

2.3Plasmondriven reduction
reactions

2.4Priority between plasmondriven
oxidation and

reduction reactions

References

CHAPTER 3PlasmonDriven
Surface Catalytic Reactions Monitored by

Electrochemical SERS in Liquid

3.1Introduction

3.2Designed apparatus

3.3Plasmondriven reduction
reactions in liquid

3.3.1Laserintensitydependent

3.3.2Potentialdependent

3.3.3LSPRdependent

3.3.4pHdependent

3.4Plasmondriven oxidation
reactions

3.5Priority between plasmondriven
surface catalytic

reactions in liquid

References

CHAPTER 4PlasmonDriven
Surface Catalysis Reactions Monitored by

TERS in High Vacuum

4.1Introduction of TERS

4.2Brief history of TERS

4.3Setup of TERS

4.4Plasmondriven surface
catalytic reactions

References

CHAPTER 5PlasmonExciton CoDriven
Surface Catalytic Reactions

5.1Introduction

5.2Mechanisms

5.2.1Free space spontaneous emission

5.2.2Spontaneous emission in cavities

5.3Femtosecond absorption

5.4Applications

References

CHAPTER 6PlasmonExciton CoDriven
Catalytic Reactions Based on

Electrochemical SERS

6.1Introduction

6.2Plasmonexciton codriven
reduction reactions

6.3Plasmonexciton codriven
oxidation reactions

6.4The priority in the plasmonexciton codriven

catalytic reactions

6.5Conclusions

References

CHAPTER 7ElectroOptical
Synergy on PlasmonExciton CoDriven Surface

Reduction Reactions

7.1Introduction

7.2Properties of electrooptical
device

7.2.1Optical measurements

7.2.2Electrical measurements

7.3Plasmonexciton codriven
surface reduction reactions

7.3.1Laser intensitydependent
surface reduction

reactions

7.3.2Biasvoltagedependent
surface reduction reaction

7.3.3Gatevoltagedependent
surface reduction reaction

References

Acknowledgements

在線試讀

CHAPTER 1Introduction
In this book,from principles to applications,we introduce plasmondriven and plasmonexciton codriven surface catalytic reactions in atmosphere,liquid and high vacuum environments.Since the discovery of plasmondriven chemical reaction in 2010［1,2］,plasmonic chemistry has been one of important branches of plasmonics［3,4］.While,the lifetime of plasmonic hot electrons generated from plasmon decay is about 150 femtoseconds,which is too short to surface catalytic reaction,and then the probability and efficiency of plasmondriven chemical reactions are low.To increase them,the lifttime and amounts of plasmonic hot electrons should be significantly increased.
The plasmonexciton coupling interaction for surface catalytic reactions has been reported in 2015,in which the probability and efficiency of plasmonexciton codriven chemical reactions have been significantly increased,where the lifetime of hot electrons has been enlarged to several hundred picoseconds［58］.The ultrafast femtosecond pumpprobe absorption spectroscopy reveals the nature of plasmonexcition coupling interactions,and demonstrates the ultrafast electron transfer between the plasmon metal and the exciton semiconductor.
To further improve the probability and efficiency of plasmonexciton codriven chemical reactions,the gate voltage and the bias voltage and current have also been employed by us.The electrooptical synergy has been applied in plasmonexcitoncodriven surface reduction reactions in 2017［9］.The voltage manipulates plasmonexciton codriven chemical reactions can reach up to higher probability and efficiency in surface catalytic reactions.
In this book,we introduce plasmonic chemistry in the field of surface catalytic reactions in detail,including the principles and applications of interactions among plasmon,exciton and molecule on the plasmonic nanostructure covered by monolayer semiconductors.The book is suitable for the research scientists,Ph.D.candidates and bachelor students,who would like to learn or study plasmonexciton codriven chemical reactions.

CHAPTER 1Introduction
In this book,from principles to applications,we introduce plasmondriven and plasmonexciton codriven surface catalytic reactions in atmosphere,liquid and high vacuum environments.Since the discovery of plasmondriven chemical reaction in 2010［1,2］,plasmonic chemistry has been one of important branches of plasmonics［3,4］.While,the lifetime of plasmonic hot electrons generated from plasmon decay is about 150 femtoseconds,which is too short to surface catalytic reaction,and then the probability and efficiency of plasmondriven chemical reactions are low.To increase them,the lifttime and amounts of plasmonic hot electrons should be significantly increased.
The plasmonexciton coupling interaction for surface catalytic reactions has been reported in 2015,in which the probability and efficiency of plasmonexciton codriven chemical reactions have been significantly increased,where the lifetime of hot electrons has been enlarged to several hundred picoseconds［58］.The ultrafast femtosecond pumpprobe absorption spectroscopy reveals the nature of plasmonexcition coupling interactions,and demonstrates the ultrafast electron transfer between the plasmon metal and the exciton semiconductor.
To further improve the probability and efficiency of plasmonexciton codriven chemical reactions,the gate voltage and the bias voltage and current have also been employed by us.The electrooptical synergy has been applied in plasmonexcitoncodriven surface reduction reactions in 2017［9］.The voltage manipulates plasmonexciton codriven chemical reactions can reach up to higher probability and efficiency in surface catalytic reactions.
In this book,we introduce plasmonic chemistry in the field of surface catalytic reactions in detail,including the principles and applications of interactions among plasmon,exciton and molecule on the plasmonic nanostructure covered by monolayer semiconductors.The book is suitable for the research scientists,Ph.D.candidates and bachelor students,who would like to learn or study plasmonexciton codriven chemical reactions.

References

［1］FANG Y,LI Y,XU H,et al.Ascertaining p,p′dimercaptoazobenzene produced from paminothiophenol by selective catalytic coupling reaction on silver nanoparticles［J］.Langmuir,2010,26： 77377746.
［2］HUANG Y H，ZHU P,LIU G K,et al.When the signal is not from the original molecule to be detected： chemical transformation of paraaminothiophenol on Ag during the SERS measurement［J］.J.Am.Chem.Soc.,2010,132： 92449246.
［3］SUN M T,XU H X.A novel application of plasmonics： plasmondriven surfacecatalyzed reactions［J］.Small,2012,8： 2777.
［4］ZHANG Z,XU P,YANG X,et al.Surface plasmondriven photocatalysis in ambient,aqueous and highvacuum monitored by SERS and TERS［J］.Journal of Photochemistry and Photobiology C： Photochemistry Reviews,2016,27： 100112.
［5］DING Q Q,SHI Y,CHEN M D,et al.Ultrafast dynamics of plasmonexciton interaction of Ag nanowiregraphene hybrids for surface catalytic reactions［J］.Sci.Rep.,2016,6： 32724.
［6］DING Q,LI R,CHEN M,et al.Ag nanoparticlesTiO2 film hybrid for plasmonexciton codriven surface catalytic reactions［J］.Applied Materials Today,2017,9： 251258.
［7］YANG X,YU H,GUO X,et al.Plasmonexciton coupling of monolayer MoS2Ag nanoparticles hybrids for surface catalytic reaction［J］.Materials Today Energy,2017,5： 7278.
［8］LIN W,SHI Y,YANG X,et al.Physical mechanism on excitonplasmon coupling revealed by femtosecond pumpprobe transient absorption spectroscopy［J］.Materials Today Physics,2017,3： 33.
［9］CAO E,GUO X,ZHANG L,et al.Electrooptical synergy on plasmonexcitoncodriven surface reduction reactions［J］.Advanced Materials.Interfaces,2018,5： 1700869.

CHAPTER 2PlasmonDriven Chemical Reactions Based on SERS in AtmosphereCHAPTER 2PlasmonDriven Chemical Reactions Based on SERS in Atmosphere

2.1Brief introduction
It is widely known that Raman scattering can be measured as the fingerprint of specific molecules.And the major obstacle is that the intensity and resolution are relatively weak.Hence,as a developed technology,surfaceenhanced Raman scattering (SERS) was found in 1974 by Fleischmann［1,2］,which has more general applications on fingerprint vibrational spectroscopy with singlemolecule sensitivity［3］.
With the developed properties,SERS has been widely used in many fields,such as sensors,biology and material science［1,410］.Two enhancement mechanisms of plasmonenhanced Raman scattering are widely accepted,which are electromagnetic enhancement (EME) and chemical enhancement (CE)［7,1114］.The EME attributes to the localized surface plasmon resonance (LSPR) mainly on the rough metal surfaces radiated by a laser［12］.And the EME is considered as a nonselective amplification mechanism for enhancing the Raman signals of all vibration modes of adsorbed molecules of 1010-1011.However,the CE,which is up to 103,can result in some specific Raman peaks being selectively enhanced enormously instead.And the CE,which mainly attributed to the charge transfer mechanism,can be considered as a resonance Raman process between the ground electronic state of the moleculemetal hybrid system and the metalmolecule charge transfer electronic state［1518］.
Since its discovery,SERS had been long regarded as a noninvasive technique.The Raman peaks of paraaminothiophenol (PATP) at 1140 cm-1,1391 cm-1 and 1440 cm-1 on Ag nanoparticles （NPs） were once considered as the enhanced “b2 modes” induced by CE［1928］,because the selective and tremendous enhancements only of the four “b2 modes” could not be explained by the EME［24］.However,Fujishima and coworkers doubted that the “b2 modes” may come from other surface azobenzene species［29］.In 2010,Wu and coworkers predicted that “b2 modes” were assigned to the NN bond of p,p′dimercaptoazobenzene (DMAB) theoretically,which was generated from PATP on Ag NPs through a surface catalytic reaction,and their chemical structures are shown in Fig.21.For further reinterpretation,Sun and coworkers［30］ investigated the existence of DMAB,and Huang studied the relation between the chemical transfer and the power density of laser in conventional SERS.In the meantime,surface mass spectroscopy (SMS) and SERS measurements on the synthesized DMAB convincingly support the proposal［22,28,3147］.

Fig.21The molecular structures of (a) PATP,(b) DMAB and (c) 4NBT,respectively

Many PATPAg junction models are used for theoretical studies whether the “b2 modes” of PATP can be reproduced.After considering several cases,it can be concluded that the “b2 modes” of PATP agree well with ag modes of DMAB［48］.As an additional evidence,Huang also found that when the laser intensity decreased,the intensities of the “b2 modes” of PATP would diminish.The characteristic that the intensities of “b2 modes” depend on the laser intensity［33］ conflicts with the photondriven charge transfer (PDCT) model due to the quasiresonanceenhanced Raman.In PDCT model,the intensities of the “b2 modes” should be tuned by the wavelength and the potential instead of the laser power.The details will be introduced later［24］.
After confirming that the surface plasmons (SPs) can not only enhance the Raman signals of molecules but also induce the surface catalytic reactions,the systematic works on the novel application of SPs on both plasmondriven oxidation and reduction reactions have been reviewed［49］.
In this chapter,we mainly focus on the novel phenomenon of plasmondriven surface catalytic reactions in the atmosphere.As mentioned above,PATP is widely used in investigating the deeper mechanism of plasmondriven surface oxidation reactions,which can be oxidized to DMAB with the help of SPs.On the other hand,4nitrobenzenethiol (4NBT) is a proper candidate for plasmondriven reduction reactions.Then,for further investigation,we thoroughly study several cases which have different conditions such as adjusting the substrates and the wavelengths of laser.Finally,to comprehensively study the problem,we also take the priority between the plasmondriven oxidation and reduction reactions in the atmosphere.
2.2Plasmondriven oxidation reactions
The plasmondriven surface catalytic reactions are related to many aspects.To thoroughly address this problem,we will divide it into several parts.First,we will introduce the genuine SERS spectrum of PATP,which indicates that SPs are able to only enhance the Raman signals of PATP without inducing the catalytic reactions.Then,plasmondriven oxidation reactions on different substrates will be presented,such as Au/Ag/Au film and hybrid systems.Normally,threedimensional finitedifference time domain (3DFDTD) method is used for deeper investigating the differences between the effects of substrates on the CMEs.Besides,the CE can be stimulated using dependent density functional theory.Moreover,the effect of the wavelengths of laser,as well as the mechanism of the plasmondriven oxidation reactions will also be investigated.
2.2.1Genuine SERS spectrum of PATP
Before proving the existence of surfacecatalyzed reaction that DMAB can be produced from PATP on several substrates,the genuine SERS spectrum of PATP itself needs to be confirmed.However,the phenomenon is hard to observe because the monomer of PATP is easy to convert to dimer in the atmosphere.
With the help of the designed substrate,the SERS spectrum of PATP can be obtained without the “b2 modes”.The SERS spectrum fits well with the NRS spectrum and the theoretical Raman spectrum of PATP,indicating that PATP on the special substrate does not be oxidized to DMAB,as shown in Fig.22.The substrate is prepared as Ag nanowireAg film junction structure,where the thickness of the Ag film is about 120 nm and the diameter of Ag nanowire is about 300 nm.The advantages of this substrate can be concluded in two parts.First,the metallic nanowire can disperse the plasmon,so the effect of plasmon coupling can be reduced noticeably compared with in the hot spots between NPs［50］.The other reason is that the number of molecules between the Ag nanowire and Ag film can be well controlled by adjusting the concentration of PATP solutions.When the number of PATP molecule is controlled in small quantities,DMAB cannot be produced easily.As a result of the two aspects,the plasmondriven oxidation reactions can be well controlled and even avoided.

Fig.22(a) Normal Raman scattering NRS spectrum of PATP powder； (b) genuine SERS spectrum； (c) the stimulated Raman spectrum of PATP［51］

To further investigate the mechanism,the related calculations are presented which indicate that the plasmon enhancement based on the Ag nanowireAg film system is too weak to induce the plasmondriven oxidation reactions.As a control group,Fig.23 is presented where the radius of NPs is 40 nm and the distance is 1 nm.The incident laser is chosen as a plane wave with a wavelength of 633 nm.And according to the calculation,it is obvious that the EM enhancement in the gap between the Ag nanowire and Ag film is much weaker than that between Ag NP,which explains why genuine SERS of PATP can be observed in the hybrid system.In a word,the EME plays a key role in affecting surface catalytic reactions.

Fig.23The calculation of EMEs in (a) Ag NP dimer； (b) Ag nanowireAg film hybrid system［51］
（Colored picture attached at the end of the book）

2.2.2Experimental and theoretical investigations of plasmondriven oxidation reactions
After realizing that the EME plays a crucial role in the surface catalytic reactions,there are other several factors we need to reveal whether they are vital in SERS.First of all,the incident laser is indispensable to produce the SPs and further induces the surface catalytic reactions,where the timedependent SERS spectra can be used to reveal the relationship.The wavelength of laser also affects the probability and efficiency of plasmondriven surface catalytic reactions in many aspects significantly.Besides,the substrate should be available instead of dispersing plasmons.
1. Laserdependent plasmondriven oxidation reactions
In this part,we will introduce the effects of incident laser on plasmondriven oxidation reactions,which are divided into two important parts as the timedependent and wavelengthdependent SERS catalytic reactions.Before investigating the effect of these conditions,there is no doubt that the laser exists or not plays a decisive role in plasmondriven surface catalytic reactions.According to the surface mass spectroscopic (SMS) measurement,PATP adsorbed on Ag electrodes (r=40 nm) can transform to DMAB with the help of highpower laser.The spectra of PATP adsorbed on Ag electrodes under radiation show that there is a “H H-Ph-N=N-Ph-S” fragment of 245.5(see Fig.24(a)(i)),as well as a “K S-Ph-NH2” fragment.So the absence of 245.5 peak reveals that DMAB cannot be formed of PATP without irradiation (Fig.24(a)(ii)),and the blank roughened Ag electrodes were used as control group (Fig.24(a)(iii)).In a word,there is no doubt that the incident laser is indispensable for the plasmondriven oxidation reactions and the assumption that “b2 modes” correspond to the ag modes of DMAB is well supported again.

Fig.24(a) Surface mass spectra of PATP on roughened Ag electrode (i) with laser and (ii) without laser,and (iii) SMS of Ag electrode without PATP,respectively； (b) The Raman spectra of (i) PATP and (ii) DMAB on the roughened Ag electrodes,respectively［52］

Will the plasmondriven surface catalytic reaction happen as soon as the incident laser is applied? If not,how to find the most suitable parameters?
According to Fig.25,we can observe that the SERS catalytic reactions of PATP have a tight relation with the delay time.When the concentration of PATP is 5×10-6 M1 M=1 mol/L.,we can conclude that the intensity of Raman signals increases from 0 to 27 min,and then begin to drop.In the range from 1100 cm-1 to 1500 cm-1,the NN (1390 cm-1 and 1432 cm-1) and C—N (1143 cm-1) modesrelated peaks grow faster than other modes,indicating the formation of DMAB from PATP on Ag NPs.
The dynamic process of the catalytic reactions can be interpreted as below.After the PATP molecules adsorbed on the Ag NPs through a thio group,DMAB starts to be produced when the intensity obviously increases.And while the Ag NPs aggregate together,the signals of DMAB become harder to detect.Those processes exist simultaneously while the priority changes at different conditions.To verify the assumption,the timedependent SERS spectra of PATP with the concentration at 5×10-4 M were also investigated (Fig.25(c)),and the regular pattern changed obviously,indicating that the heavy concentration would lead to a reduction in the formation process.And the most suitable delay time of laser is changed when the concentration changes.Figure 25(d) shows that if the concentration of Ag sol is reduced to only half,the time of formation will be extended.In a word,we can find out that the time of laser should be adjusted to achieve the maximum efficiency of plasmondriven surface catalytic reactions when other conditions change.
The Fig.3(h) in Ref.［30］ shows that the DMAB can be produced when PATP adsorbed on Ag substrates at 1064 nm where the three enhanced Raman peaks occurred,even the EM enhancement is relatively weak according to the calculation.Besides,several experiments that DMAB was able to be produced from PATP at 1064 nm on different substrates were taken by many groups［53］.
2. Substratedependent plasmondriven oxidation reactions
As we all known,SERS depends on the marriage between the adsorbed molecules and the plasmonic nanostructure.And among many available substrates for plasmondriven surface catalytic reactions,the Ag and Au NPs substrates are most competitive candidates due to the stability in air,compared with copper.Another important reason for choosing noble metals is that their LSPR regimes cover most of the visible and nearinfrared wavelength range which are suitable for measuring Raman signals.
Several investigations focus on optimizing substrate for enhancement factors,including different plasmonic materials or shapes［5456］.
It is found that the SERS enhancement will be improved when the noble metal

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