UNIVERSITY OF ILLINOIS, URBANA CHAMPAIGN

Cathodoluminescence Spectroscopy

by Anshuman Kumar

Final Report for the requirements of the course Optical Spectroscopy (PHYS-552)

in the Department of Physics

December 2010

Abstract

This report discusses some of the basic aspects of Cathodoluminiscence(CL) Spectroscopy, with special reference to plasmonics. CL setup oers several advantages. The multimode imaging capabilities of the electron microscope enable the correlation of optical properties (via cathodoluminescence) with surface morphology (secondary electron mode) at the nanometre scale. But perhaps most intriguingly, the small beam can probe a single selected nanostructure. The report is divided into three chapters and a bibliography. Chapter one discusses a general overview of CL and provides the mathematical background of the eld of a moving charge in presence of an interface. Chapter two gives some idea of the experimental setup involved, without going into much detail. Chapter three lists two applications of CL: one involving a study of plasmon modes in a annular shaped nanoresonator; the second application deals with probing the gap plasmon modes in a metal-sphere & metal lm conguration. In both these examples, I havent delved into the theory of plasmonics itself, but just attempted to highlight how CL gives us a means to probe some of these resonances, by varying excitation location.

Contents
Abstract List of Figures i iii

1 Introduction: Overview, History and 1.1 Introduction . . . . . . . . . . . . . . 1.2 History . . . . . . . . . . . . . . . . 1.3 Principles of the technique . . . . . . 1.4 Mathematical Theory . . . . . . . . 1.4.1 Transition Radiation . . . . . 1.4.2 Surface Plasmons . . . . . . . 2 Experimental Setup

Mathematical Formulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. . . . . .

. . . . . .

. . . . . .

1 1 1 2 3 4 6 8 10

3 Examples from Literature 3.1 Plasmonic Modes of Annular Nanoresonators Imaged by Spectrally Resolved Cathodoluminescence[1] . . . . . . . . . . . . . . . . . . . . . . . 3.1.1 Fabrication of Nanoresonators . . . . . . . . . . . . . . . . . . . . 3.1.2 CL measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2 Gap and Mie Plasmons in Individual Silver Nanospheres near a Silver Surface[2] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.1 What we expect? . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.2 Fabrication of the nanostructures . . . . . . . . . . . . . . . . . . 3.2.3 CL measurement . . . . . . . . . . . . . . . . . . . . . . . . . . .

. 10 . 10 . 10 . . . . 13 13 13 13

Bibliography

17

ii

List of Figures
1.1 1.2 Cherenkov radiation glowing from a spent fuel core of the High Flux Isotope Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Evanescent character of of the electromagnetic eld produced by a fast electron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CL setup incorporated in a Scanning Electron Microscope . . . . . . . . . Panchromatic CL imaging of Ag annular nanoresonators . . . . . . . . Spectrally resolved imaging of plasmonic modes in an Ag annular nanoresonator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Excitation of gap and Mie plasmons in supported silver nanospheres . . Schematic representation of the charge distribution in gap and Mie plasmons excited in silver spheres supported on silver for dierent beam congurations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Angular and position dependence of the emission from gap and dipole Mie plasmons in supported spheres . . . . . . . . . . . . . . . . . . . . . 3 5 8

2.1 3.1 3.2 3.3 3.4

. 11 . 12 . 14

. 15 . 16

3.5

iii

Chapter 1

Introduction: Overview, History and Mathematical Formulation

1.1 Introduction

Cathodoluminescence(CL)[3][4] is basically the emission of photons from a specimen stimulated using an electron beam. A common example of the CL process is the screen of a television CRT monitor. Here, the electron beam generated by a cathode ray tube, impacts a luminiscent material causing it to emit light. Today, CL is used in the elds of geology, minerology, materials science and fundamental experimental physics. Usually these are used, in conjunction with a scanning electron microscope, to examine the internal structure of semiconductors, rocks, ceramics, glass and to study surface plasmon modes in nanostructures. This conguration of CL setup oers several advantages. The multimode imaging capabilities of the electron microscope enable the correlation of optical properties (via cathodoluminescence) with surface morphology (secondary electron mode) at the nanometre scale. The broad energy range of the electrons can excite wide-bandgap materials, such as diamond- or gallium-nitride-based structures that are not easily excited by conventional optical means. But perhaps most intriguingly, the small beam can probe a single selected nanostructure.

1.2

History

Although the phenomenon of luminescence was recognized as early as the seventeenth century, systematic observations and discussio of cathodoluminiscence did not take place 1

Chapter 1. Introduction: Overview, History and Mathematical Formulation until around 1960s.

Early CL studies were carried out using a CL microscope, which is basically a petrographic microscope to which a cathode gun is attached. Subsequently, the scanning electron microscope has been utilized to generate high resolution and high magnication CL images. CL was mostly employed for determining characteristics of geological materials. However, with the advent of nanotechnology, CL measurements are now routinely used to investigate localized surface plasmons excited by electron impact. Here, the photon emission of a metal nanostructure is induced via a high energy electron beam and collected using a suitable detection pathway. The advantage of this technique is that by scanning the electron beam over the particle surface, spatial prole of these modes can be eciently mapped out by light collection at particular resonance wavelengths . This technique is also found to work for propogating Surface Plasmon Polaritons.

1.3

Principles of the technique

The main emission processes involved in CL are Cherenkov radiation and transition radiation. It turns out that each of these processes is coherent with the eld generated by the incoming electron. Besides, although the generation of SPPs can be considered as an indirect process (2-step), it is still coherent emission. This kind of coherence between dierent sources of emission can result in interesting interference phenomenon, which can be used for easy characterization. However, there are also incoherent emission channels associated with electron-hole pair generated which eventually recombine and emit. But in metals, which are the major focus of this report, electronic relaxation proceeds much faster than radiative recombination, hence one can safely consider the incoherent contribution to CL to be a minor contribution only. Now we provide a brief overview of the emission processes involved. Cherenkov Radiation When a charged particle passes through a medium with speed greater than the speed of light in that medium, it emits Cherenkov Radiation. The basic idea here is that these charged particlespolarize the molecules of the medium, which return to their ground state rapidly resulting in an emission of radiation. A classic example of this is the characteristic blue-glow of nuclear reactors. See for instance, gure 1.1.

Chapter 1. Introduction: Overview, History and Mathematical Formulation

Figure 1.1: Cherenkov radiation glowing from a spent fuel core of the High Flux Isotope Reactor[Wikipedia].

However, this emission is not important for metals, since the disruption in the local electromagnetic eld can be restored without emission of a photon. Transition Radiation This kind of emission occurs when a charged particle passes through a boundary between two media of dierent dielectric constants. It is usually a result of the time dependent variation of the dipole moment formed by the incident charged particle and its image charge inside the other dielectric. This radiation can be explained by noting that since the electric eld of the particle is dierent in each medium, the particle has to get rid of the dierence when it crosses the boundary. This results in a net energy loss of the particle. In view of the above two phenomena, if metals are bombarded with an electron beam, the excitation of bulk or surface plasmons can ocur if the moving charge couples to the free electrons in the metal. This eect becomes apparent in Electron Energy Loss Experiments (EELS)

1.4

Mathematical Theory

We know that an electron moving with a constant velocity in free space does not result in a radiation. However, in the presence of a boundary of another material, it induces a polarization charge, which together with the original electron can be considered to be a dipole. In a metal, there are two channels available for the dipole to decay: (a) transition radiation emission into the far eld and (b) generation of surface plasmons. We look at both these processes in the following subsections[5].

Chapter 1. Introduction: Overview, History and Mathematical Formulation

1.4.1

Transition Radiation

Consider an electron moving with a velocity v along the z axis. This electron is incident from the lower half space of z < 0, which is considered vacuum (
1

= 1) and corsses the

1

inrface with the upper half consisting of a dielectric of permittivity given by ( identies the medium 1,2):

= )

at time t=0. The electromagnetic elds are expected to satisfy Maxwells Equations (j

H=0

(1.1)

E=

1 H c t

(1.2)

jE

= 4

(1.3)

H=

4 j E + j c t c

(1.4)

The charge and current densities associated with the moving electron can be written as:

(z, t) = e (z vt)

(1.5)

j(z, t) = ev (z vt) To solve these equations, we use the method of fourier transforms:

(1.6)

H(r, t) =

1 (2 )4

deit

d3 qH(q, z, )eiqr

(1.7)

The fourier transforms of the sources are found to be:

(k, ) =

e ( k v ) (2 )

(1.8)

j(k, ) = v(k, )

(1.9)

Chapter 1. Introduction: Overview, History and Mathematical Formulation

The next task is to to decompose the elds H into a a bulk component and an induced component near interfaces. The solution for the bulk part is relatively straight-forward and one gets: 4ieQ iz/v t e 2 c kj q 2

Hbulk (Q, z, ) = j

(1.10)

and Q is the in plane momentum vector. = z where t Q Performing an inverse fourier transform of the above equation over momentum, we obtain:

Hbulk (r, ) = j

2e iz/v e K1 ( ) vc v

(1.11)

where is the perpendicular distance form the electron trajectory, is the lorentz is the azimuthal angle and K1 is the modied Bessel function contraction factor, of second kind. From this equation, one can see that the moving electron acts as a broadband source of electromagnetic eld. However, due to the nature of the Bessel function, the eld decays away from the electron trajectory. I have attached a gure1.2 from a paper which uses dierent variables for these quantities but shows the ideas well.

Figure 1.2: Evanescent character of of the electromagnetic eld produced by a fast electron[3]

Chapter 1. Introduction: Overview, History and Mathematical Formulation

There are some important observations related to this bulk eld. The eld diverges at the location of the electron trajectory. Hence it means that the resolution of the experiments is only limited by the size of the beam spot. However we must also consider the response of teh material as delocalized, which reduces the actual resolution. Next, we turn our attention to the induced eld, which is evaluated to be
ikzj |z | Hind j t j (Q, z, ) = 2ekj sj e

(1.12)

where kzj =

2 Q2 , s = 1 and s = 1 and s are the boundary coecients kj 1 2 j

calculated using appropriate boundary conditions on parellel components of the electric and magnetic elds. The actual expressions are: /v 2 + kz 2 2Qi/c [ 2 kz 1 2 + kz 2 1 q 2 k1 2Qi/c /v 2 + kz 1 [ 2 kz 1 2 + kz 2 1 q 2 k1 /v 1 + kz 2 1 ] 2 q 2 k2

1 (Q) =

(1.13)

2 (Q) =

/v 1 + kz 1 2 ] 2 q 2 k2

(1.14)

Using the above two expressions, we get the expression for the induced eld as
0

Hind j (r, ) = iesj where J1 is the rst order Bessel function.

QdQj eikzj |z | J1 (QR)

(1.15)

Since in experiments, we observe the CL signal in the far eld, far away from the actual impact point of the electron, it is clear that the eld detected there cannot arise from the evanescent bulk elds. Hence it is the induced elds that we observe.

1.4.2

Surface Plasmons

An electron incident on a metal surface also excites SPPs. The results of the previous section can be used to derive the plasmon generation rate. The wave-vector condition describing SPPs is given by: kz 1
2

+ kz 2

=0

(1.16)

Using a Taylor expansion around the plasmon wave-vector, Qp one gets:

ikzj |z | 1 Hind H1 (Qp R) j ( ) = eQp Aj e

(1.17)

Chapter 1. Introduction: Overview, History and Mathematical Formulation

1 is the rst Hankel function and A = (Q Q ) where H1 j j p

Chapter 2

Experimental Setup
As discussed in the previous chapter, CL measurements rely on the detection of radiation emitted when a sample is bombarded by an electron beam. In order to carry out spectroscopy, the emitted radiation has to be spectrally resolved. On the other hand, for imaging, one requires spatial resolution of the position from which the emission originates. However, as proved in the previous section, the spatial resolution of the CL is determined by the excitation source and not detection. A schematic of the CL setup incorporated in a Scanning Electron Microscope is shown in gure 2.1.

Figure 2.1: CL setup incorporated in a Scanning Electron Microscope.

For excitation, a focussed electron beam of a SEM is used. The accelerating voltage of the beam is tunable between 1-30keV. Beam current is a function of aperture size and voltage, and can be varied between several pA to tens of nA. Beam currents in the range of tens of nA provide an electron impact rate which is signicantly slower than the electron relaxation processes in most noble metals important for plasmonics. Hence is it 8

Chapter 2. Experimental Setup

safe to consider single electron excitations. We can also accurately position the electron beam to an accuracy of tens of nanometres over the sample. The emitted light is detected using a parabolic mirror which is placed a few millimetres above the sample in such a way that its focal point coincides iwth the sample. The size of this focus is usually in tens of microns. The mirror is arranged to as to have a large acceptance angle. The light collected from the focal point is reected as a parellel beam through a holllow waveguide tube and focussed onto the entrance slits of a monochromator.

Chapter 3

Examples from Literature

In this chapter, we briey discuss two examples, from recent literature, of the application of cathodoluminescence.

3.1

Plasmonic Modes of Annular Nanoresonators Imaged by Spectrally Resolved Cathodoluminescence[1]

In this study, the authors excite plasmonic modes in engineered annular nanoresonators on Ag and Au surfaces, using a highly localized electron beam source and use spectrally resolved CL imaging to probe the plasmon eld intensity as a function of excitation position. The details of the experiment are given below.

3.1.1

Fabrication of Nanoresonators

Nanoresonators are fabricated on Ag surface. The Ag structures were prepared by evaporation on a quartz substrate and Focussed Ion Beam was used to patter the annular rings. Each annular resonator has a central plateau and ve concentric rings separated by grooves 50nm deep with varying grating ring period and center diameter.

3.1.2

CL measurement

CL measurements were performed using a eld emission SEM operating at 30keV, which used a usual mirror based detection system. The electron beam spot size was 5nm (which is also the limit of spatial resolution). To get spectrally resolved images, the emitted light, after passing through the mirror, is sent to grating monochromator, which is set to 10

Chapter 3. Examples from Literature

11

a specic wavelength, each time. Secondary electron and CL images are simultaneously recorded. In order to get panchromatic images, the emitted light is directly focussed on the broadband PMT detection system. Figure 3.1 shows the panchromatic CL images of nano-resonators in Ag with 315nm grating period and three dierent center diameters. These images represent the radiation collected from the entire resonator as a function of the electron beam excitation position on the structure. Bright regions correspond to greater emitted photon intensity. From this gure, it is clear that the high intensity is observed for excitation near at the edges of the center and of the concentric rings (The locally increased emission inside the grooves is attributed to scattering from roughness in the polycrystalline Ag lm). The CL prole clearly shows peaks in emission when the electron beam dwells near an edge. An overall decay in emission intensity is observed as the electron beam moves outward from the center. Thus, we see that a higher emitted photon intensity is obtained for electron beam excitation in the center of the structure, indicating that more ecient excitation and/or more ecient outcoupling occurs in this region. This eect was justied using simulations, the description of which is not within the scope of the present paper.

Figure 3.1: Panchromatic CL imaging of Ag annular nanoresonators with 315 nm period and center sizes of (a) 620 nm, (b) 1.07 m, and (c) 1.70 m. (d) SEM image taken concurrently with panchromatic CL image of structure in (c). (e) Line proles from regions indicated by the dashed line in (c) and (d) illustrating strong emission when the electron beam is positioned at an edge and decreasing intensity as the beam moves outward from the center[1].

Chapter 3. Examples from Literature

12

Another study that they carried out was to experimentally probe the plasmonic modes, as shown in gure 3.2. At = 350 nm, which is very close to the Ag surface plasmon resonance, nearly uniform emission occurs for excitation anywhere in the structure. Near resonance, surface plasmon propagation lengths are very short and thus no resonator modes can build up. Several dierent modes are observed at longer wavelengths, as illustrated in (c) part of Figure 3.2. At = 700 nm, CL data show bright emission for excitation near the edges of the center plateau, but uniform emission from the rest of the structure. In gure 3.2, the rst subscript s of Ms,n describes the symmetry of the mode: s=0 means that the eld prole has a node at the centre of the plateau and s=1 stands for an antinode. Numerical methods like FDTD and BEM, given in the gure, are common in the parlance of plasmonics people and the interested reader is requested to read the relevant references provided to gure out the meanings of these terms.

Figure 3.2: Spectrally resolved imaging of plasmonic modes in an Ag annular nanoresonator with 620 nm center diameter and 315 nm grating period. (a) Spectrally resolved CL images at the indicated wavelengths (b) SEM image of nanoresonator indicating the scan region for the CL images in (a). (c) Line proles of modes M0,0 , M1,0 , andM0,1 from nite element (FDTD) simulated time-averaged electric eld intensity, probability of CL emission from BEM simulations, and spectrally resolved CL images at the indicated wavelengths. The corresponding surface topography is shown in gray[1].

In summary, the above application demonstrates high-resolution spectrally resolved CL imaging as a powerful tool to reveal plasmonic modes in Ag annular nanoresonators. Such a study of plasmonic modes excitation via excitation at precise (highly resolved) excitation regions on the nanostructure, is a novelty of the CL method.

Chapter 3. Examples from Literature

13

3.2

Gap and Mie Plasmons in Individual Silver Nanospheres near a Silver Surface[2]

In this study, CL is used to study the plasmons conned in the gap between silver nanospheres and silver planar surfaces using angle and space resolved CL. Plasmons in individual nanoparticles are excited by an electron beam, giving rise to light emission that is analyzed as a function of photon-energy, emission direction, and position of the beam spot. The gap plasmons obtained by bringing a nanoparticle close to a metal surface have been recently used to produce controlled 1010 enhancement factors in surface-enhanced Raman scattering (SERS). However, gap plasmons are extremely sensitive to the distance between metals, and therefore their analysis requires studying individual structures. In view of what we discussed above, CL seems to be the obvious choice for such a study.

3.2.1

What we expect?

The gap is a region of huge induced-charge pileup, so it has a large inuence on the plasmons of the nanoparticles. The emergence of a gap mode with m = 0 azimuthal symmetry relative to the rotational axis of the particle-surface system results in the aforesaid large pileup of induced charge near the gap, which is compensated by opposite charges distributed over the rest of the particle. But the sphere can also support Mie modes that are almost unperturbed with respect to the isolated particle, and in particular, the sphere dipole parallel to the surface remains rather unaected by the interaction with the substrate. We want to use CL to study these properties.

3.2.2

Fabrication of the nanostructures

Silver particles of size 50-600nm were obtained by evaporating silver in Ar atmosphere. The silver lm is deposited on either evaporated silver lms or TEM carbon lms.

3.2.3

CL measurement

Unlike the previous case, here angle resolved spectral CL is measured. In order to do this, a TEM is used and ellipsoidal and parabolic mirrors are used for light collection. A CCD camera provides an image of the mirror. The emission angle can be found out from the position in the mirror image. Here the beam energy is 200keV and the beam size is about 10nm.

Chapter 3. Examples from Literature

14

Our main experimental results are summarized in Figure 3.3. A collection of CL spectra from individual spheres are shown in Figure 3.3(a)(c) for dierent particle sizes. Figure 3.3(a),(b) corresponds to the emission recorded when the electron beam is passing nearly grazing with respect to the particle surface, as shown in the upper insets. The spectra are displays a number of maxima, the position of which is nearly insensitive to the substrate, as deduced from the fact that their energies are almost the same when the particles are deposited on either a carbon lm or a silver substrate.

Figure 3.3: Excitation of gap and Mie plasmons in supported silver nanospheres. Mie plasmons are resolved in the cathodoluminescence emission when the spheres are excited by a grazing electron beam, as observed in the spectra measured for particles of dierent size deposited on either (a) a 10 nm carbon lm or (b) an optically thick silver surface. Gap plasmons are observed at lower energies in silver particles deposited on silver when the beam spot is close to the center of the spheres, as shown in (c). The size-dependent measured energies of both multipolar Mie plasmons (extracted from (a) and (b)) and gap plasmons (taken from (c)) are represented in (d) (symbols) and compared to the calculated cathodolulminescence intensity from self-standing particles under grazing incidence (background density plot). The size-dependence of the gap plasmon obtained from a simple analytical model and from full numerical simulations is shown as pink and yellow solid curves, respectively. The emission is collected over the upper hemisphere (backward emission) in all cases. The arrows in (ac) indicate the position of dipole (red), quadrupole (green), hexapole (blue), and gap (black) plasmons[2].

From the plots, one can infer that the interaction between Mie modes and the substrate is weak for grazing trajectories( since, as aforesaid, the position of maxima are nearly independent of substrate). The only signicant eect of the substrate is a small red

Chapter 3. Examples from Literature

15

shift of the modes with a silver substrate as compared to the modes observed with a thin carbon lm, which seems to originate in the attractive interaction with image charges. However, we have an interesting observation when the beam spot is positioned at the center of the particles which are deposited on the silver substrate, there is a new peak which appears at low energies. This new mode disappears in case of carbon lm substrate. This is attributed to the gap mode, it being highly sensitive to the substrate. Remarkably, the substrate plays a dominant role in this case, even though the external excitation produced by the electron is initially located far from the gap region (actually, the electron is likely to undergo strong collisions with silver atoms for diameters above 100 nm). A physical picture of what is happening is presented via simulations in gure 3.4.

Figure 3.4: Schematic representation of the charge distribution in gap and Mie plasmons excited in silver spheres supported on silver for dierent beam congurations (lower part), alongside the calculated electric near-eld intensity component corresponding to the frequencies of these modes for 140 nm particles (upper part)[2].

In order to conrm this picture, we can look at the angular distribution of emitted light as shown in gure 3.5. The dipole picture clearly explains gure 3.5 in view of the model of g 3.4. In conclusion, using the power of high spatial resolution oered by CL imaging, we could study the Mie and Gap plasmons in this conguration. The present study demonstrates that spectral CL provides the necessary power for a more detailed investigation of the gap

Chapter 3. Examples from Literature

16

Figure 3.5: Angular and position dependence of the emission from gap and dipole Mie plasmons in supported spheres. A dipole Mie plasmon is observed at 2.5 eV in (a) and (b), which show the measured light intensity as a function of emission angle and energy for an 140 nm silver sphere supported on a carbon lm and a silver substrate, respectively, and excited by a grazing electron beam and a central trajectory, respectively (see insets of Figure 1a,c). An additional gap plasmon feature is observed at 1.4 eV in (b). The beam-position dependence of the emission with the silver substrate is shown in (c). The angular patterns of emission for dipole and gap plasmons are represented in (d) (symbols), as compared to the calculated emission from both a dipole placed right at a silver planar substrate and oriented normal to it (red curved) and a dipole parallel to the substrate at a distance of 70 nm (i.e., the sphere radius; blue curve)[2].

mode as a function of spacing, which should be of great importance for understanding the mechanisms involved in ultrasensitive analysis based on plasmon connement.

Bibliography
[1] Carrie E. Hofmann, Ernst Jan R. Vesseur, Luke A. Sweatlock, Henri J. Lezec, F. Javier Garca de Abajo, Albert Polman, and Harry A. Atwater. cence. Nano Letters, 7(12):36123617, 2007. Plasmonic URL modes of annular nanoresonators imaged by spectrally resolved cathodoluminesdoi: 10.1021/nl071789f. http://pubs.acs.org/doi/abs/10.1021/nl071789f. [2] N. Yamamoto, S. Ohtani, and F. Javier Garcia de Abajo. Gap and mie plasmons in individual silver nanospheres near a silver surface. Nano Letters, 0(0), 0. doi: 10.1021/nl102862x. URL http://pubs.acs.org/doi/abs/10.1021/nl102862x. [3] F. J. Garc a de Abajo. Optical excitations in electron microscopy. Rev. Mod. Phys., 82(1):209275, Feb 2010. doi: 10.1103/RevModPhys.82.209. [4] Martin Kuttge. Cathodoluminescence plasmon microscopy. Ph.D. thesis, March 2009. [5] J.D. Jackson. Classical electrodynamics. 2007.

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