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Hyper Structured Molecules III 1st Edition Hiroyuki
Sasabe (Author) Digital Instant Download
Author(s): Hiroyuki Sasabe (Author)
ISBN(s): 9789056993511, 1420024884
Edition: 1
File Details: PDF, 39.43 MB
Year: 2002
Language: english
Hyper-Structured Molecules III
Hyper-Structured
Molecules Ill

Chemistry, physics and applications

Edited by
Hi royu ki Sasabe

Boca Raton London New York

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A TA Y L O R & F R A N C I S B O O K
First published 2002 by Taylor & Francis

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C ontents

Preface vii
List o f corresponding authors ix

1 Near field optical technologies: From imaging/

diagnostics to nano-fabrication/atom manipulation 1
M O T O IC H I OHTSU

2 Hybridization of scanning near-field optical

microscope with scanning tunneling microscope 31
KEN NAKAJIM A, RUGGERO M ICHELETTO, KEITA M ITSUI,
TAKASHI ISOSHIM A, M ASAHIKO H A R A , TATSUO W A DA,

HIROYUKI SASABE, A N D W OLFG A N G KNOLL

3 Organic spin clusters, fractals, and networks with

very high spin 46
AN D R ZEJ RAJCA

4 Single-molecule magnets 61
DANIEL RUIZ, GEORGE C HRISTO U, A N D
DAV ID N . H E N D R IC K SO N

5 From NLO-active alkynylmetal complexes to

organometallic dendrimers 90
MARK G. HUM PH R EY , A N D R EW M . M cD O N A G H ,
STEPHAN H O U BRECHTS, INGE ASSELBERGHS,
A N D R E PERSOO NS, TATSUO W A D A , HIROYUKI SASABE,
MAREK SA M O C , A N D BARRY LUTHER-DAVIES
vi Contents

6 A synthetic approach to rigid and dendritic

nano-sized Ruthenium complexes 100
M ASAHISA OSAW A, MIKIO H O S H IN O , A N D YASUO WAKATSUKI

7 Worm-like dendrimers with flexible carbosilane

branches 109
N . OUALI, S. M ERY, L. N O IR E Z , A N D A. SKOULIOS

8 Electrochemical construction of ordered porphyrin

polymers toward nano-molecular spin systems 123
FEIPENG W U, YASUHITO M A ED A , KAZUTAKA HIRAKAW A,

A N D HIROSHI SEGAWA

9 Chromogenic receptors as potentially

hyper-structured molecules 136
YUJI KUBO

10 Design and synthesis toward starburst C60-based

conducting polyanilines 150
LO N G Y. C H IA N G , VIJAYARAJ A N A N TH A R A J,
T A IZ O O N CAN TEEN W A LA , A N D LEE Y. W A N G

11 Exotic condensed states of matter: Discotic mesogen

and optically isotropic liquid crystals 172
M ICHIO SORAI A N D KAZUYA SAITO

12 Phototriggered reactions of DNA and their

applications 190
ISAO SAITO, KIYOHIKO KAWAI, TAKASHI N A K A M U R A ,
SHIGEO M A TSUD A , A N D K E N ZO FUJIM OTO

13 Optimized second-harmonic generation from

alternate-layer Langmuir-Blodgett films of a
transparent dye and poly (f-butyl methacrylate) 196
GEOFFREY J. ASHWELL A N D RAKESH R A N JA N

Index 209
Preface

Under the strategic research promotion program by Japan Science and

Technology Corporation, the Core Research for Evolutional Science and
Technology (CREST) program has been launched in March, 1996. The
Hyper-Structured Molecules and their Application to Organic Quantum
Devices group was approved as a member of the CREST program for five
years. The aims of this group are to design molecules such as dendritic
polymers and topologically controlled molecules and to handle these mol­
ecules by ‘molecular tweezers’ such as photon STM. Hyper-structured mol­
ecules are topologically well-defined molecules in two and/or three
dimensions, and are expected to show novel quantum effects in molecules
themselves and molecular sequences, e.g., light-emitting molecules, chemical
amplification, and molecular magnets.
The first International Forum on Hyper-Structured Molecules was held
in Kusatsu, Japan, on November 4 -6 , 1996, the second one held in Sap­
poro on May 30-June 1, 1997, the third in Otsu on June 9-11, 1998, and
the fourth in Oiso on June 29-July 1, 1999, to discuss the future of these
new molecules and their possible application to organic quantum devices.
The highlights of these forums are planned to be published as a series of
monographs which contribute to the understanding of the current status
and progress of this field. Already we have published two monographs,
Hyper-Structured Molecules I (in 1999) and II (in 2000). This monograph
on H yper-Structured M olecules III is based on the third and fourth forums
and covers molecular designs of dendrimers, oligomers, hyperbranched
polymers and/or high spin systems, molecular organizations and nanostruc­
tures, mesoscopic pattern formation, and scanning probe microscopy for
characterization and molecular handling.
I would like to express my sincere gratitude to all of the contributors to
the forums who made this new project a most promising research field.
The financial support by Japan Science and Technology Corporation is
viii Preface

also highly appreciated. Finally I would like to thank Gordon and Breach
Science Publishers for their continuous encouragement for this mono-
graph.

Hiroyuki Sasabe
Project Leader of HSM, CREST, JST
List of corresponding authors

Motoichi Ohtsu, Prof.

Interdisciplinary Graduate School
Tokyo Institute of Technology
4259 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan
Tel: +81-45-924-5455; Fax: +81-45-924-5487
E-mail: [email protected]

Ken Nakajima, Dr.

Frontier Research Systems (FRS)
The Institute of Physical & Chemical Research
2-1 Hirosawa, Wako, Saitama 351-0198, Japan
Tel.: +81-48-462-1111; Fax: +81-48-462-6337
E-mail: [email protected]

Andrzej Rajca, Prof.

Department of Chemistry
University of Nebraska Lincoln
Lincoln, Nebraska 68588, U.S.A.
Tel: +1-402-9196; Fax: +1-402-472-9402
E-mail: [email protected]

David N. Hendrickson, Prof.

Department of Chemistry and Biochemistry
University of California, San Diego
9500 Gilman Drive, Dept 0358, La Jolla, CA 92093-0358, U.S.A.
Tel: +1-619-534-5580; Fax: +1-619-534-534-5383
E-mail: [email protected]

Mark G. Humphrey, Dr.

Department of Chemistry, Australian National University
Canberra, ACT 0200, Australia
Tel: +61-2-6249-2927; Fax: +61-2-6249-0760
E-mail: [email protected]

Masahisa Osawa, Dr.

The Institute of Physical 8c Chemical Research
2-1 Hirosawa, Wako, Saitama 351-098, Japan
x List of corresponding authors

Tel.: +81-48-462-1111; Fax: +81-48-462-4665

E-mail: [email protected]

Stephane Mery, Dr.

Institute de Physique et Chimie des Materiaux de Strasbourg (IPCMS)
23 rue du Loess, F-67037 Strasbourg Cedex, France
TeL: +33-388-10 71 65; Fax: +33-388-10 7246
E-mail: [email protected]

Hiroshi Segawa, Prof.

Department of General System Studies
Graduate School of Arts and Sciences
The University of Tokyo
3-8-1 Komaba, Meguro-ku, Tokyo 153, Japan
TeL: +81-3-5454-6579; Fax: +81-3-5454-6998
E-mail: [email protected]

Yuji Kubo, Prof.

Department of Applied Chemistry
Faculty of Engineering
Saitama University
255 Shimo-Okubo, Urawa, Saitama 338-8570, Japan
TeL: +81-48-858-3514; Fax: +81-48-855-2889
E-mail: [email protected]

Long Y. Chiang, Prof.

Center for Condensed Matter Sciences
National Taiwan University
1 Roosevelt Road, Section 4, Taipei, Taiwan 10764, ROC
TeL: +886-2-2365 5403; Fax: +886-2-2365 5404
E-mail: [email protected]

Michio Sorai, Prof.

Research Center for Molecular Thermodynamics
Graduate School of Science
Osaka University
1-1 Machikaneyama-cho, Toyonaka 560-0043, Japan
TeL: 06-6850-5523; Fax: 06-6850-5526
E-mail: [email protected]

Isao Saito, Prof.

Department of Synthetic Chemistry and Biological Chemistry
Kyoto University
Kyoto 606-8501, Japan
TeL: 075-753-5656; Fax: 075-753-5676
E-mail: [email protected]

Geoffrey J. Ashwell, Prof.

Centre for Molecular Electronics
Cranfield University
Cranfield MK430AL, UK
TeL: +44-1234-754224; Fax: +44-1234-750875
E-mail: [email protected]
Chapter I

N ear field optical technologies:

From imaging/diagnostics to
nano-fabrication/atom
manipulation
Motoichi Ohtsu*

I. BASIC FEATURES OF AN OPTICAL NEAR FIELD

AND RELATED SYSTEMS

The meaning and importance of optical near field phenomena can be studied
in the framework of general optical processes, such as a light-scattering pro­
cess involving two atomic-scale objects, i.e., the sample and probe [1],
An incident light wave drives an effective field both inside and outside
the sample. For observation of the effective field near the sample, the fol­
lowing two requirements have to be met:

1 The probe must have dimensions as small as the sample (this require­
ment determines the penetration depth of the effective field, since the
effective field corresponds to the electromagnetic correlation produced
in the sample itself);
2 The probe tip must be placed near the sample, where an effective field
with a short penetration depth maintains its significance.

If these requirements are met, the small sample and the probe form an
interacting subsystem. As a result, the effective field of the sample turns out
to be an internal field of a coupled system, which produces a light wave
scattered from the probe and reaching the photodetector. This approach to
detecting an optical near field event is the essence of the near field optical
analysis of material systems.
The requirements of implementing this approach have been supported
theoretically. That is, the near field optical microscopy (NOM) process can,

* Also with (1) Ohtsu’s Photon Control Project, Exploratory Research for Advanced Techno­
logy, Japan Science and Technology Corporation, STA, Japan, 4th-floor, Tenko building
17, 687-1 Tsuruma, Machida-shi, Tokyo, 194-0004, Japan (2) Near Field Photonics
Group, Kanagawa Academy of Science and Technology, KSP East 408B, 3-2-1 Sakado,
Takatsu-ku, Kawasaki, Kanagawa 213-0012, Japan.
2 M. Ohtsu

to some extent, be described in terms of conventional electromagnetic theories,

thus demonstrating several basic features of optical near field interaction
[2]. Among them, two results justifying these requirements are:

1 Size-dependent localization. The theory has described the short-range

nature and spatial locality of the optical interaction of two closely
spaced objects. An important point is that the result is scaled not by
wavelength but by the sizes of the object and the probe. It should be
emphasized here that a field calculation alone is not sufficient for the
theoretical description of a NOM process. Instead, one should consider
an interacting sample-probe system as an important subsystem separated
from a global NOM process. When the sample-probe system is irradi­
ated by an evanescent wave with a wavelength larger than that of the
sample-probe system, the transferred optical intensity can be calculated
on the basis of conventional Mie scattering and Kirchhof’s integral.
Therefore, the result is related to the far-field observation of the
sample-probe scattering. A rapid decay of the transferred intensity can
be clearly shown by increasing the sample-probe distance. The size-
dependent localization of optical near field interaction is one of the
most important features of a general NOM system. This feature was
confirmed by accurate experimental work [3].
2 Size-resonance behavior. The transferred optical intensity takes a max­
imum when the sizes of the sample and probe are equal. This size-
resonance behavior is also important in the general NOM process.
That is, the near-field optical interaction between sample and probe
exhibits a kind of resonance character with respect to spatial frequency.

To extract optical near field phenomena from the whole light-scattering

process, one needs to use a probe that is sensitive only to high-spatial-fre-
quency components relevant to the local effective field around the sample,
as well as a signal-processing scheme that eliminates the signal background.
This is why the technique of fabricating fine probes is of primary import­
ance. It should be noted that the probe as a spatial-frequency filter must
have a specific bandwidth that corresponds to the locality of the effective
field confined around the sample.
There is current interest in combined NO M operations using several dif­
ferent types of scanning probe microscopes, such as STM and AFM. One of
the most popular techniques is a shear force-controlled positioning of the
NOM probe, which utilizes the atomic force between the sample’s surface
and a laterally vibrating probe. The amplitude modulation of the resonant
vibration of a NO M probe due to the atomic force exerted by the sample’s
surface provides a measure of the sample-probe separation. Although the
combined operation might be attractive, one must pay attention to interfer­
ence between fundamental processes, that is, one must be aware that inter­
 Near field optical technologies 3

action-type microscopes employ a process of destructive measurement.

When the types of interaction combined are very different in their natures
and in their scales of relevant spatial sizes, time constants, and material
characters, and so on, the combined apparatus provides much useful
information. However, if their ranges are in competition with each other,
the results obtained are very different from the expected ones. In fact, in
some situations, a seemingly different measurement of a specimen may res­
ult in a similar image owing to interference. This difficulty is often referred
to as an ‘artifact’ problem.

2. PROBES

One of the most realistic and commonly used methods for the preparation
of the probe is sharpening an optical fiber to a very small apex. By employ­
ing the scanning technique already established in STM and AFM, the probe
with the apex of sharpened fiber works under precise distance control.
Figure 1 shows schematics of typical fiber probes, introducing the termino­
logy for each part. A conventional optical fiber is sharpened by chemical
etching in buffered hydrofluoric acid. An apex (diameter d - 2 a ) can easily
be made small, and a minimum apex size of only a few nanometers has been
already achieved. In NOM , only the apex interacts electromagnetically

Figure I C ross-sectional structure of a typical fiber probe.

4 M, Ohtsu

with the sample. The tapered part has a simple conical shape and the cone
angle 9 is clearly defined. The apex radius and the cone angle can be varied
by controlling the etching condition. The exterior surface of the probe is
coated with opaque metal, such as aluminum or gold, to avoid the illu­
mination of excitation light or the detection of the background signal
through the side wall of the tapered part. The very end of the metal coating
is removed to allow the sharpened glass part, including the apex, to pro­
trude. The aperture with a diameter of df (also called the foot diameter)
makes a contribution, as will be discussed later. We call the protruded glass
part and the metal-coated part the tapered core and the metallized tapered
core, respectively.
The metallized tapered core is regarded as a metal-cladding (metallic)
waveguide where excitation or signal light passes through. Since the metallic
waveguide has a complex loss mechanism, e.g., the existence of a cutoff
diameter and absorption by the metal cladding, the optimization of the
structure of the waveguide is essential. The constitutive material and struc­
ture of the fiber waveguide also determine several other important factors,
including polarization preservation and the propagation feature of ultra­
violet light.
To perform NO M application, one has to fabricate a nanometric probe
which works a sensitive scatterer and/or a selective generator of high
spatial frequency components of a localized optical near field. NO M
employing a scatterer-type probe and a generator-type probe are defined as
collection-mode (c-mode) NO M and illumination-mode (i-mode) N O M 1,
respectively. For illumination-collection mode (i-c mode) NOM 2, one requires
a probe functioning as both a generator and a scatterer of the optical near
field.
To fabricate a probe with an apex diameter less than 10 nm, the selective
etching technique was developed [4,5]. The core is tapered by immersing a
high-G e02 doped fiber in a buffered hydrogen fluoride solution. The cone
angle is controlled from 20° to 180° for an apex diameter less than 10 nm.
Further, selective etching is the most highly reproducible technique among
existing fabrication techniques.
In imaging applications requiring high spatial resolution, a tapered probe
or a metallized probe with a nanometric apex diameter and a small cone

1 In the c-mode NOM, the light is incident to the total internal reflection. The three dimen­
sional optical near field generated and localized on the sample surface is scattered by a
probe and part of the scattered field is detected and collected through the sample and the
probe. The principle of operation of i-mode NOM is similar except that the probe acts as a
generator of the optical near field which illuminates the sample surface. The field scattered
by the sample is collected by conventional optics.
2 In the i-c mode NOM, a sample is excited by an optical near field on the probe. The light
generated on the sample is scattered and collected by the probe.
 Near field optical technologies 5

angle has to be fabricated because the resolution capability of the probe is

determined by its parameters such as the cone angle and the apex diameter.
However, the throughput3 of a metallized probe is decreased by decreasing
the cone angle. In spectroscopic applications where one must cope with
extremely low detected power, the probe should have high throughput in
i-mode and be highly sensitive in c-mode. In the i-mode NOM , to avoid
thermal damage to the sample and the probe, the probe should be used
with an input power as low as possible. Therefore, the resolution capability
and throughput of the tapered probe have to be optimized depending on
the application of NO M to imaging or spectroscopy. This optimization
should be done through tailoring the probe. Furthermore to obtain a highly
resolved image, a metallized probe must be tailored so as to have a protrud­
ing tip emerging from a metallic film.
In order to fabricate application-oriented probes, we have developed
some methods [6] which were based on hybrid selective etching of specially
designed multistep index fibers [7,8] and preferential etching of the metal
covering the apex [9-11]. We succeeded in fabricating application-oriented
probes such as a protrusion-type probe with high resolution capability [7,8]
and preferential etching of the metal covering the apex [9-11], a double­
tapered probe with high throughput [12], a triple-tapered probe with high
resolution capability and high throughput [7,8], and an ultraviolet probe
with a pure silica core [6,7].
Using G e0 2-doped fibers such as dispersion compensating fiber (DCF)
and a double-cladding fiber, we fabricated application-oriented probes and
carried out NO M applications such as imaging a biological sample, and a
spectroscopic study of semiconductor devices in visible and infrared regions.
However, UV-emitting devices and materials have been little studied by
these probes because the G e0 2-doped fiber has optical absorption and
luminescence at around 363 nm and 394 nm, respectively. To overcome this
difficulty and to realize highly spatially resolved imaging at near-UV
region, we succeeded in fabricating a UV single-tapered probe [6] and a UV
triple-tapered probe [7] which have a pure silica core and a double core,
respectively. To fabricate a UV triple-tapered probe, for example, we
developed a multistep index fiber with the double core involving a sub­
wavelength core and a pure silica core. In the following text, this fiber is
called a double core fiber.
In general, a serious problem of the fiber probe is its low throughput.
The essential cause of the low throughput is the guiding loss along (or

3 When a metallized tapered fiber is used as a generator-type probe for an i-mode NOM
employing an objective lens, the throughput is defined as the relative output power to the
input power.
6 M. Ohtsu

inside) the metallized tapered core. In order to increase the throughput,

excitation of the plasmon mode is utilized in the metallized tapered core.
It should be noted that an increase in throughput requires some tailoring
of the probe structure. This is because the guiding loss in the metallized
tapered core is still high even if the HE-plasmon mode is excited. Since the
guiding loss in the core is due to the loss in the metal cladding, the easiest
way to decrease the loss is to shorten the length of the tapered core. Probes
developed to increase the throughput are:

1 Triple-tapered probe [13]. A triple-tapered structure, as is shown by

Figure 2(a), was introduced to reduce the loss in a tapered core, to
focus the light, and to excite effectively the HEn mode. A focused ion
beam and selective chemical etching were used for fabrication. Figure
2(b) shows the measured relation between the aperture diameter and
the throughput. By this measurement, over a 1000-fold increase in the
throughput of the triple-tapered probe with the aperture diameter
d{< 100 nm was confirmed in comparison with the conventional single­
tapered probe. Figure 2(c) shows the measured spatial distribution of
the output light intensity at the apex of the probe with d{ = 60 nm and
its cross-sectional profile. By this measurement, existence of the localized
optical near field on the triple-tapered apertured probe can be confirmed,
which is due to the third taper with a small cone angle.
2 A protruded metallized probe with an aperture [14]. Figure 3(a) explains
schematically its cross-sectional structure. Two metallic films were
coated on separately at the apex and the foot of the tapered core. The
metallic film on the apex was to increase the scattering efficiency, and
to enhance the optical near field intensity for the c-mode and i-mode
NOM s, respectively, by which an improvement in measurement sensit­
ivity was expected. The metallic film on the foot formed an aperture to
suppress the detection and generation of light with low spatial Fourier
components, by which increase in the contrast of the image was
expected. Figure 3(b) shows a SEM micrograph of the fabricated
probe, where the gold-coated apex diameter, d, is 35 nm (the uncoated
apex diameter is smaller than 5 nm). The thickness of the gold film at
the foot is 100 nm, and the aperture diameter (i.e., the foot diameter),
df, is 400 nm. Figure 3(c) shows the measured spatial distribution of the
output light intensity at the apex of the fabricated probe in Figure 3(b)
and its cross-sectional distribution. The high intensity at the center of
the butterfly represents the effect of the metal coating on the apex.
Here, the butterfly-shaped distribution in this figure corresponds to the
HEn mode which depends on the size and structure of the aperture.
The half-width of the central peak is 150 nm, which is the convolution
of the apex diameter of the metallized core and the aperture diameter
of the probe scanned for the measurement. Figure 3 clearly confirms
 Near field optical technologies 7

Figure 2 (a) Cross-sectional structure o f a triple-tapered core and its SEM micrograph
obtained prior to coating a metallic film, (b) measured relation betw een the
aperture diameter df and the throughput. O pen circles and closed circles rep­
resent the values for a triple-tapered probe and conventional single-tapered
probe, respectively, (c) measured spatial distibution of the output light intensity
at the apex o f the probe with df = 60 nm (inset) and the its cross-sectional profile
taken along the line indicated by the tw o arrows in the inset. Full width at the
half maximum of the cross-sectional profile is 160 nm.

the effect of the metal coating on the apex in enhancing the optical field
intensity.
3 M etallized probe exciting a localized plasmon [15]. A technique that
excites a localized plasmon on the apex probe for NOM was employed.
Vapor deposition and heating of several tens nm thick gold films on
a 1 nm thick germanium-covered tapered optical fiber probe made
highly adherent and smooth overlayers. A collection-mode NO M
system combining a tunable dye laser was used to excite a localized
plasmon. Dependence of the detected intensity on the excitation photon
energy is shown in Figure 4. In this figure, open circles represent
8 M. Ohtsu

Figure 3 (a) Cross-sectional structure o f a protruded metallized probe with an aperture,

(b) SEM micrograph, (c) measured spatial distibution o f the output light intens­
ity at the apex o f the probe (inset) and the its cross-sectional profile taken
along the line indicated by the tw o arrows in the inset. Full width at the half
maximum o f the main peak o f the cross-sectional profile is 150 nm.

experimental values for the metallized probe, and a theoretical curve

was fitted to them based on a local field theory involving a radiation
damping factor [16,17]. For reference, closed circles represent the
values for an uncoated probe. Comparison between the open circles and
the closed circles confirms the realization of the local field enhance-
 Near field optical technologies 9

Figure 4 D ependence o f the detected intensity on the excitation photon energy. O pen
circles and closed circles represents the results for the metallized probe and
uncoated probe, respectively. The solid curve is the theoretical result fitted to
the open circles.

ment in the metallized probe. The resonant photon energy in the

metallized probe was about 2.11 eV, corresponding to 588 nm in wave­
length. This local field enhancement could be estimated to generate
only in the close proximity of the substrate. The detected intensity at
the resonant point was about six times as high as that of the uncoated
probe. Theoretical enhancement of the near field, however, is esti­
mated to be about 150 times the incident intensity. This difference is
due to the experimental fact that many of the unwanted low spatial
Fourier frequency com ponents and far-field com ponents of the light
were included in the detected light intensity for the uncoated probe.

Functional probes are the ones which have a functional material on the
apex of an optical fiber probe. Comparison between functional probes and
conventional probes described above allows one to recognize the signific­
ance and applications of functional probes. Functional probes can be
regarded as optical fiber sensors directed into miniaturization. Appropriate
10 M. Ohtsu

applications of functional probes are energy transfer, optical nonlinearity,

chemical/biological sensing, and so on. Local investigation of conditions
and environments as well as the optical field, including the optical near
field, is also possible.
We have developed a fixation method which uses a micropipette with a
micromanipulator system in order to fix selectively the functional material
onto the apex of the fiber probe. This method enables one to attach various
kinds of material. Since the fixation method selects the material to immob­
ilize on the probe tip, we have to consider the requirements for the mater­
ials imposed by the micropipette fixation method: (1) The materials must
be liquid or dissolved in solvents in order to fill a micropipette; (2) the
materials must be fixed on the probe surface by adsorption, which is the
result of the intermolecular force between the glass surface and the matter.
Polar substances are more appropriate than nonpolar ones for attaching to
a glass surface with a polarity which is the same as that of the silanol group
(Si-OH), because then the dipole-dipole interaction works more effectively;
(3) the capillary effects (e.g., capillary condensation and capillary rise) of
using a micropipettes should be taken into account, because they can influ­
ence chemical properties such as viscosity, concentration, and components
of the material in the micropipette.
Dyes such as phenolphthalein have been used as a fluorescent indicator
of pH in analytical chemistry. This idea suggests that by using fixing mater­
ials like the fluorescent indicator, we can obtain chemical sensing probes
which will enable us to measure the spatial distribution and temporal
evolution of the ion concentration in a cell. Chemical sensing probes fixed
with a plasticized poly(vinyl chloride) (PVC) membrane were developed,
which have been extensively used as a lipophilic membrane in ion-selective
sensors operated in an optical mode [18] as well as in an electrical one.
Much effort has been focused on the miniaturization of optical sensors
using the plasticized PVC [19,20].
We have fabricated a chemically etched probe with lipophilic fluorescein,
and measured temporal variation of the fluorescence intensity induced by a
change in the Na+ concentration. In order to reject the contribution of photo-
bleaching, we have fabricated another type of the probe to acquire the
signal representing the spectral wavelength shift. That is, we used a heat-
pulled probe with lipophilic 7-hydroxycoumarin, whose SEM micrograph
is shown in the inset of Figure 5. This figure also shows the temporal vari­
ation of the ratio between the two fluorescence intensities. One is a longer
wavelength than the isosbestic point of the fluorescence spectra, and the
other is shorter. This ratio is proportional to the magnitude of the spectral
wavelength shift. The response time to a change in Na+ was 10 s.
By replacing the nontailed ionophoren-5 (C14-DTM16C5) [21], the
stability of the optical signals is improved [22]. This can be explained by
the fact that the tail of the ionophor reacts like an anchor that prevents the
 Near field optical technologies II

Figure 5 SEM micrograph of the chemical sensing probe with lipophilic 7-hydroxycou-
marin fixed on the apex (inset) and the tim e dependency o f the fluorescence
intensity ratio. The Na+ concentration was changed from 0 to 0.03 M at the
time t = 100 s. A scale bar in the inset is for 10|im.

ionophore, which includes Na+, from leaching into the aqueous phase due
to attachment to plasticized PVC.

3. BASIC FEATURES OF OPTICAL NEAR FIELD

IMAGING

The quality of the imaging is influenced by various factors such as the

probe parameters, sample-probe separation, and the polarization of the
illuminating light. We have demonstrated that the power spectral analysis
could be employed as a potential tool for evaluation of near field optical
images [23]. As a reference sample, we employed colloidal gold particles
of 20 nm-diameter fixed on a glass substrate. It was found that the power
spectral density of the near field image resembles the Airy pattern due to a
circular dot with the first minimum occurring at the spatial frequency
5.6 x l 0 7m -1. This corresponds to an estimated particle diameter of
22 nm. From a comparison with the theoretical power spectral density of
randomly distributed circular dots, the transfer function of NO M has been
estimated. It has been found that the resolution estimated using - 3 dB
12 M. Ohtsu

cutoff value obtained from the transfer function was 0.8 nm which is
much higher than that determined by aperture size. The highly resolving
ability of the present NO M system was attributed to the confinement of
very high spatial frequency optical near fields around the apex of the aper­
ture probe.

4. IMAGING BIOLOGICAL SAMPLES

Biological specimens have been investigated with optical microscopes such

as the differential interference contrast microscope and the confocal micro­
scope. Although they provide a way to monitor the biological process in
real time [24], their resolution is limited by the diffraction of the light. One
possible method avoiding diffraction is through the use of scanning probe
microscopes [25], including the NOM . With NOM , it is also possible to
attach specific biomolecules with fluorescing dye labels in order to investig­
ate the spatial distribution and functional properties of the molecules with
a resolution well beyond the diffraction limit. We have succeeded in
imaging some biological specimens, namely, Salmonella, neurons, microtu­
bules, fibroblasts, and DNA, in order to demonstrate the high-resolution
capability of our NOM .
In order to conduct observation of DNA, the double stranded plasmid
DNA with a ring structure (puc 18 and 2868 base pairs) was used as the
sample. It was diluted with distilled water to a final concentration of 5 ng/
\il. A quantity of 2 |l l 1 of this diluted DNA solution was dropped onto the
center of a wet-treated sapphire surface, and then this surface was blown
dry with compressed air. The terrace width and step height of the sapphire
surface had been chosen carefully. The terrace width was adjusted to be 1
to 1.5 ]im and the step height to be around 2 nm by varying the annealing
conditions while fabricating the sapphire substrate. Figure 6 shows the
NO M image of DNA. The image was obtained under a constant sample-
probe separation of less than 5 nm with the optical near field intensity as
the control signal. In the image, the bright string structures correspond to
D N A strands. As can be seen, both single and supercoiled structures are
present. The pixel size is 5 nm x 5 nm. This image was taken under the
incident electric field being parallel to the sample surface. The full width
at half maximum of the bright string as indicated by white arrows is
around 20 nm. In this case, the observed intensity variation in comparison
to the base level was around 20% and the base level fluctuations were less
than 1%. Recently, by improving the performance of our NO M system,
the observed width of a single strand has been reduced to 4nm when
the pixel size was 2 n m x 2 n m [26]. As the control is done optically, it is
easier to extend the operation in liquid or fluid environments [27] which
opens up the possibility of directly manipulating the DNA structure or
 Near field optical technologies 13

Figure 6 The c-m ode NOM image o f D N A obtained under a constant sample-probe sep­
aration less than 5nm with the optical near field intensity as th e control signal.
The full width at the half maximum o f the bright strand, as indicated by the
w hite arrows, is around 20 nm.

conducting investigation on the individual segment of the double helix

structure itself.

5. DIAGNOSING SEMICONDUCTOR
NANO-MATERIALS AND DEVICES

We have carried out the near-field photoluminescence (PL) spectroscopy of

semiconductor micro/nano structures fabricated on opaque substrates. In
these experiments, several specific techniques are necessary compared with the
standard measurements shown in the previous sections, from the viewpoints
of probe structures, optical configurations, signal detentions, and so on.
In the study of semiconductors, the N O M has been employed in two
different ways. First, spatially resolved spectroscopy has been successfully
implemented to determine the optical structures and responses of photonic
devices and materials, tracing their surface topography [28-30]. Second,
N O M can be used as a probe for local excitation and collection to achieve
single particle spectroscopy, i.e., the observation of individual PL spectra of
inhomogeneously broadened systems such as the islands of quantum dots
[31-33]. Recent rapid progress with pulsed laser sources and photodetec­
tors enables us to combine the near-field method with conventional
14 M. Ohtsu

time-resolved spectroscopy or nonlinear spectroscopy. These techniques

provide physical insights into the ultrafast dynamic processes of excited
carriers and elemental excitations. Furthermore, in the last few years,
NO M operation at low temperature has been an indispensable technique
for the fundamental investigation and understanding of the intrinsic optical
properties of semiconductors.
In these experiments, we encounter serious problems which are particu­
lar to the optical investigation of semiconductors. One of the problems is
concerned with the conversion of electromagnetic modes generated by a
small aperture. Since semiconductors have large refractive indices, the optical
near field are easily coupled into the propagating modes due to the interac­
tion with semiconductor surfaces. This conversion results in reduced NOM
resolving power. In order to retain the optical near field in the optically
dense semiconductors, should be much smaller than the wavelength of
the excitation light, which causes low excitation efficiency. The diffusion of
photoexcited carriers brings about another problem. In the detection of PL
images and spectra, an illumination-collection mode is an essential technique
in order to prevent the deterioration of the resolution, which is determined
by the carrier diffusion length. By solving these problems, we have studied
novel-structured semiconductor photonic devices, as are described below:

1 An accurate correspondence between the local optical responses and

the structures of semiconductor light-emitting devices was demon­
strated by using an illumination-mode NOM [29]. We studied the
novel-structured lateral p-n junctions grown on patterned G a A s(lll)A
substrate. The junctions were one-step grown at the upper and the
lower end of the slope, taking advantage of the amphoteric nature of Si
in GaAs. Measuring the spatially resolved photoluminescence spectra,
we precisely determined the position and the width of the transition
region of p-n junctions. The illumination-collection mode was also
employed to map the two-dimensional emission efficiency with higher
resolution, which was not affected by carrier diffusion.
2 Near field photocurrent measurements with multiwavelength excita­
tion sources were applied to the investigation of a lateral p-n junction
described in (1) [34]. In order to probe the internal properties of this
device, propagation modes into the sample were utilized retaining high
resolution with the contribution of a penetration depth smaller than
the aperture diameter. By systematically varying the penetration depth
over a wide range up to 900 nm, photocurrent signals due to internal
optical response clearly appeared. The capability of ‘tomographic’ dia­
gnostics was demonstrated and the slant angle of the p-n interface was
determined to be 30° ± 8°.
3 Lateral p-n junctions were characterized through the spatially resolved
detection of light emission by current injection using a collection-mode
 Near field optical technologies 15

NO M [30]. Although the width of the transition region determined

from the spatially resolved PL measurements was much wider in the
lower junction than in the upper one, the broadness of the junction,
which is observed for the first time owing to the high resolution of the
detection system, was the same for both junctions.
A single InGaAs quantum dot PL spectra and images were obtained
using a low-temperature NO M [35]. By modifying the commonly used
NO M , a high spatial resolution and high detection efficiency were
achieved simultaneously. Local collection of the emission signal
through an aperture contributed to the single-dot imaging. Tailoring
the tapered structure of the fiber probe enabled us to obtain the emis­
sion spectra of single dots in the weak excitation region, where the car­
rier injection rate was about 107excitons/s per dot. By employing such
a technique, the evolution of single-dot PL spectra with excitation
intensity is shown by Figure 7. By a precise investigation of this figure,
i.e., the excitation power dependencies of individual dots, two-dimen­
sional identification of their emission origins was obtained for the first
time. Figure 8 summarizes the result of this identification.
Nonlinear absorption spectroscopy of a single InGaAs quantum dot
was carried out in order to investigate the possibility of realizing nano­
metric optical switching, modulation, and so on, by utilizing the
gigantic optical nonlinearity due to the concentration of oscillator
strength at narrow spectral region [36]. Setup of NO M system was
almost equivalent to that of (4). For the measurement of the nonlinear
transmission of single quantum dot, cw pump-probe technique was
employed. Photoexcited carriers were generated in quantum dots by the
pump beam (633 nm wavelength) passing through the aperture. The
nonlinear change of the absorption coefficient due to the occupation of
carriers in quantized states of single quantum dot was probed by the
transmitted light (920 nm wavelength), which was collected through
the same aperture. The pump and probe lights were modulated at the
frequencies and f2, respectively. Nonlinear transmission signal (fx- f2)
was extracted by means of synchronous lock-in detection. Figure 9
shows the dependence of the signal intensity on the pump power dens­
ity. In the weak excitation region, the signal intensity linearly increased
with the pump power. Above 300 W/cm2 excitation, the signal intensity
saturates due to the continuous occupation of carriers in a quantized
state. This figure also shows that the PL intensity saturated at the same
excitation intensity. It was deduced that the observed signal originated
from the nonlinear transmission due to the ground state occupation of
one electron-hole pair. From the maximum differential transmission of
as large as lO^4, the absorption cross section of the single quantum dot
was estimated as 0.01% of observation area. Figure 10 shows the
modulation characteristics of the sinal intensity for the pump light on
16 M. Ohtsu

Figure 7 Single quantum d ot PL spectra obseved at 8 K. The numerical value shown for
each curve represents the excitation light pow er density. The spectral lines
G, E, and B are originated from the emission from the ground-state single
exciton, single exciton in the first excited-state, and the ground-state biexciton,
respectively.

and off, by which the possibility of using the single quantum dot as a
nanometric optical switch can be confirmed.
6 PL spectroscopy of polydihexylsilane (PDHS) was carried out at UV
region. Dried PDHS has absorption and PL peaks at wavelengths of
370 nm and 3 80nm, respectively, at the room temperature. The quantum
efficiency was evaluated as high as 5%. The trans-planar-type con­
formation of PDHS was cast on the silica substrate from a very dilute
toluene solution, and the sample was dried in a vacuum. By shortening
the length of the optical loss region of the UV fiber probe, a high
Figure 8 M onochromatic PL image with an excitation pow er density o f 500 W /cm 2 (left).
Corresponding two-dimensional map indicating the origin o f PL from each sp ot
(right). G and B represents the emission by the ground-state single exciton and
the ground-state biexciton, respectively. The numbers 1,2 , 3, and 4 represents
the emission from the single exciton in the first, second, third, and fourth
excited-state, respectively.

Figure 9 Measured dependencies o f the nonlinear absorption signal intensity (closed

circles) and PL signal intensity (open circles) on the pump pow er density.
18 M. Ohtsu

Figure 10 Measured temporal variation of the signal intensity. Horizontal bars represent
the time interval in which the pump light was off.

throughput was obtained. Moreover, the protrusion part at the apex

functioned as the localized light source for the super-resolution
imaging which was indispensable to obtain local spectroscopic features
corresponding to the geometrical structure. For the optical excitation, a
351 nm line of Ar+ laser was coupled into the fiber probe. The PDHS
molecules dispersed on the silica substrate were illuminated by the
optical near field through the probe. PL from the excited molecules was
collected by a low-magnification objective lens or pure silica spherical
lens. Here, a high-magnification (large NA) lens was not available
owing to its low transmittance in the UV region. In two-dimensional
optical imaging, the collected signal (transmission of the excitation
light or PL) was detected by photomultiplier tube through the notch
and bandpass filters. A monochromator with a cooled CCD was
employed for the spectroscopic analysis of the PL signal. Figure 11
shows a PL image of a thin aggregate structure, which was obtained
under an excitation condition as low as 40 pW illumination through
the probe. At such a low excitation, fatigue of the PL signal could be
prevented. The aggregate structures was thinner than 3 nm. The back­
ground signal in the dark region was almost zero, in contrast to the
maximum counting rate of the PL signal of 50 counts per 100 ms. This
 Near field optical technologies 19

Figure 11 N ear field PL image of thin PDA aggregate structure.

implies that the fluorescence from the fiber or substrat due to the UV
excitation did not affect the measurements. The PL signal intensity
obtained agreed well with a numerical estimation using the parameters
of absorption coefficient, quantum efficiency and so on.
7 Two-dimensional near field Raman and topographic images of the
polydiacetylene(PDA) surface were measured simultaneously [37]. The
spectra (located 100 nm apart) had different spectral features. The peak
intensity ratio of two C=C peaks at 1520 and 1457 cm-1 did not cor­
relate with the topographic image and showed differences in the sub­
wavelength scale. These differences can be interpreted as spatial
differences in the number of successive bounds on the PDA surface. In
contrast, the near field Raman intensity of the C=C bond at 1457 cm-1
correlated strongly with the topographic image. This phenomenon can
be interpreted as a change in the efficiency of collecting Raman scatter­
ing light. In the case of Raman spectroscopy of Si, the desired signal
competed with the background signal of Raman scattering from the
optical fiber, which was due to its rather weak scattering efficiency and
small wavenumber. In this measurement, an optical fiber with a pure
silica core, which has been also used in UV spectroscopy, was employed.
By using this fiber, the Raman background signal from the fiber was
reduced to less than 10% compared with a fiber with a G e0 2 core.
Figure 12 shows an example of a Raman spectrum of a Si crystal using
a triple-tapered probe and short propagation of excitation light (wave­
length 532 nm) in the fiber. A sharp peak from Si is clearly seen at
520 cm-1. The broad signal around 400 cm-1 is assigned to the Raman
scattering from the S i0 2 composing the fiber. The successful acquisition
20 M. Ohtsu

Figure 12 Near field Raman spectrum of a Si crystal observed by the probe with
df = lOOnm. Black and w hite arrows represents the Stokes and anti-Stokes
spectral line o f the Raman signal, respectively. A high spectral line at the
center represents the Rayleigh singal.

of a weak Raman signal from Si is mainly attributed to a reduction of

the background Raman scattering through the careful selection of the
composition of the fiber.
8 The optical-beam-induced resistance-change-detection (OBIRCH) method
was improved by a fiber probe as the heat source in order to identify
voids and other defects in the A1 and silicide interconnects of
integrated-circuit-device chip, which is a key part of failure analysis
and process monitoring in the semiconductor industry [38]. N ot only
for improving spatial resolution, the near field OBIRCH method is
advantageous because the probe-induced resistance change caused by
heating can be observed using a metallized probe without interference
from a photocurrent created by electron-hole-pair generation. An Ar+
laser beam (488 nm and 514.5nm dual line) was introduced into the
probe. The voltage changes during scanning were introduced into an
external input terminal of a NOM system so as to produce an image of
resistance changes. A1 line of 300 nm width was employed as a sample.
The separation of a void was resolved in the near field OBIRCH image.
On the other hand, observation of 200 nm wide TiSi line showed: (a)
the OBIRCH effect caused by heating could be observed using the met­
allized probe without interference from a photocurrent effect; (b) the
photocurrent could be observed using the apertured probe, in a higher
spatial resolution than a conventional photocurrent method.
 Near field optical technologies 21

6. CHEMICAL VAPOR DEPOSITION OF ZINC BY

OPTICAL NEAR FIELD

Patterning of thin films has been traditionally performed by photolitho­

graphy. Although several works on near field optical lithography on the
photo-resist films have been reported recently [39], it is unlikely to be
employed by industry because conventional photolithography has been
well established and matured. Apart from being a complicated multistep
method, it presents an etch-damaging threat to the substrate. On the other
hand, the subwavelength deposition of metals, oxides, and semiconductors
is required for photomask repair of DRAM, nano-photonic devices, and
in situ fabrication for the needs of microelectronics and for nanoscale elec­
trochemical studies. These trends signify the near field optical-chemical
vapor deposition (NFO-CVD) as a means of overcoming diffraction limit
and etch-damaging of the substrates [40]. Expected reproducibility of
NFO-CVD for fabricating nanometric stripes and dots at desired positions
is much higher than, e.g., the conventional self-organized growth technique
of semiconductor quantum dots. Moreover, by varying a light wavelength
and appropriate parent gases, selective growth can be accomplished.
The core of the experimental setup is the illumination-mode NO M
placed inside the reaction chamber. 244 nm-wavelength UV light from a
frequency doubled Ar+ laser was coupled into the optical fiber in order to
be used for patterned prenucleation stage. For this experiment, an A1
coated fiber probe with 100 nm aperture was fabricated by a 10|im pure
silica core multimode UV fiber. Transmission loss at 244 nm for this fiber
was 1.1 dB/m, which means the throughput of the used probe was as high
as 1 x 10-4 and the power density was 1 kW/cm2. Dimethilzinc(DmZn) was
chosen as a parent gas. The same fiber probe was used to obtain a shear
force image of the deposited Zn patterns. Prior to the patterning stage, the
reaction chamber was evacuated to the pressure lO^Torr and filled with
Ar-buffered DmZn. After keeping 15 Torr pressure for 14min, the chamber
was thoroughly re-evacuated. Such a procedure produced a chemisorbed
molecular layer with a thickness of few monolayers on the substrate. Pat­
terning was performed in 1O'4 Torr vacuum by shining the area beneath the
aperture while keeping the probe in the near field region and scanning on
the substrate. As a result, surface molecules of DmZn were decomposed
selectively forming Zn nucleation centers. Second stage of final deposition
was performed using unfocused UV propagating light (193 nm-wavelength)
of a pulsed ArF excimer laser. After the reaction chamber was refilled with
1 Torr of DmZn, the prenucleated area was irradiated from the far field.
Due to the presence of constant atom flux in the vicinity of the surface, the
Zn around previously prenucleated centers was deposited and the pattern
was grown. We obtained the shear force image of the successfully written
pattern with sub-200 nm Zn stripes on a Corning glass (#7059). Quantitative
22 M. Ohtsu

verification estimated the average height of the deposited Zn to be about

300 atomic layers, which corresponds well to the expected amount of atoms
considering absorption cross section of DmZn at the used wavelength and
the total energy of laser pulses on the patterned area.
Recent experiments demonstrated the direct deposition of Zn by the UV
optical near field. Though exposing the UV optical near field for over 2-3 h
in the DmZn gas-filled reaction chamber will make the probe surface opaque
by the deposited Zn film, decreases in the throughput of the probe by the
deposited Zn was not observed while the Zn was deposited and patterned on
the glass substrate. Figure 13 shows the shear force image of the T-shape pat­
tern of the deposited Zn. The width as narrow as sub-200 nm was also
obtained, which was already about 10 times narrower than those patterned
by the conventional optical CVD. Further improvements in the deposition
parameter and in resolution of the imaging will realize sub-100 nm width.
By modifying this NFO-CVD technique, we expect to deposit several
metals such as A1 and W on a S i0 2 or Si substrate, oxide such as ZnO on a
S i0 2 or sapphire substrate, semiconductors such as GaAs, ZnSe, and ZnS
on GaAs or Si substrate, and so on. By depositing these materials, it can be
expected to fabricate light emitting dots, optical switching dots, etc., on the

Figure 13 The shear force image of the T-shape pattern of Zn deposited on a glass sub-
srate. The full width at the half maximum o f the stripe, as indicated by the tw o
black arrows, is measured to be sub-200 nm.
 Near field optical technologies 23

Figure 14 Schematic explanation o f a planar integrated nano-photonic device.

common substrate. This nano-fabrication may lead to a novel planar inte­

grated nano-photonic device, as is schematically explained by Figure 14.

7. ATOM MANIPULATION AND DEPOSITION

Precise control of atomic motion is an up-to-date and important subject not

only for atomic physics but also for the sophisticated technology of crystal
growth. An optical near field localized in a nanometric region is very suit­
able for atom manipulation with high spatial accuracy. Fabrication of a
three-dimensional atomic-scale structure is now an experimental subject
with challenge. In this section, we discuss a couple of near field optical
methods of controlling atomic motion toward realization of atomic scale
crystal growth.
We have carried out guiding of neutral Rb atoms through a hollow
optical fiber with a micron-sized hollow core by blue-detuned optical near
field [41]. Figure 15 shows a typical two-step photoionization spectrum of
the 85Rb atoms guided through a 7 Jim hollow optical fiber over a distance
of 3 cm as a function of the frequency detuning A of the optical near field
normalized to the natural linewidth T. This figure represents the long-range
dispersive properties of dipole interaction between guided atoms and
24 M. Ohtsu

Figure 15 Doppler-free tw o-step photoionization spectrum o f the 85Rb atom s in the

5S|/2» F = 3 upper ground state guided through a 7jim hollow optical fiber
over a distance o f 3 cm. A: Frequency detuning o f the optical near field with
respect to the 5S|/2, F - 3 upper ground state. T: Natural linewidth o f the
atomic dipole transition. The broken line represents the value o f the atom
flux transmitted w ithout the optical near field.

optical near field. A large enhancement factor of over 20 in the transmitted

atomic flux was obtained at optimal conditions and the total guidance
efficiency was estimated to be above 40%.
The optical potential is in proportion to the light power coupled to the
hollow fiber at a fixed blue-detuning. On the other hand, the cavity poten­
tial becomes larger as the hollow diameter becomes smaller. This indicates
that the repulsive optical potential produced by a weak blue-detuned
optical near field can be canceled by the attractive cavity potential if we
employ a small hollow fiber with a hollow diameter comparable to a wave­
length. As a consequence, atoms cannot be successfully transmitted through
the hollow fiber. This situation can be confirmed by the observation of the
threshold power in the atom guidance. For this purpose, two-step photo­
ionization experiments were carried out, in which the power of the guide
light beam was changed at a large blue-detuning. Figure 16 shows the result
in the case of a 0.3|xm hollow fiber: the two-step photoionization signal
on the 87Rb atoms in the 5S1/2? ^ = 2 upper ground state was plotted as a
function of the transmission power of the guide light. Here, the blue detuning
 Near field optical technologies 25

Figure 16 T w o-step photoionization signal o f 87Rb atom s in the 5S,/2, F= 2 upper ground
state guided through a 0.3 |im hollow optical fiber, plotted as a function o f the
transmission pow er o f the guide light.

A of + 4 GHz with respect to the 85Rb, 5S1/2>F = 3 upper ground state was
chosen so that the optical pumping between the hyperfine ground states due
to the spontaneous transition could be suppressed. In this figure, we can
find a threshold of the guiding of 87Rb atoms at a power of about 2.6 mW.
Two kinds of force contribute to the cavity potential. The van der Waals
force is dominant in a region below a wavelength, but the Casimir-Polder
force is dominant in a region above a wavelength. Since the wavelength
used here is 0.78 |im, the case with a 0.3 \im hollow fiber corresponds to the
van der Waals case. To examine the Casimir-Polder case, we can use a 1.4 |im
hollow fiber. In fact, a similar result has previously been obtained [42].
As an application, we have also demonstrated the in-line spatial separa­
tion of two stable Rb isotopes by utilizing the state- and species-selective
features of the optical near field in the hollow optical fiber with proper
frequency detunings.
To show the feasibility of fabricating nano-sized structure with nanometric
depth on a substrate, we measured the spatial distribution of the guided atom
flux with a hot-wire detector [43]. Moreover, precise control of the depos­
ition rate was estimated with a 1.4 |im hollow fiber via photoionization
26 M. Ohtsu

spectroscopy. This ratio of the guided atom flux relative to the background
transmission was enhanced up to 80-fold with a slightly tilted hollow fiber.
In order to prepare cold atoms for guiding with a bent hollow optical fiber
for atom deposition, we proposed an atomic funnel coupled with an optical
near field mirror produced in a conical hollow prism, as is schematically
explained by Figure 17 [44], The funneling of cold Rb atoms released from
a magneto-optical trap was simulated in the scheme of the optical near
field-induced Sisyphus cooling for compensating the heating by gravity. A
geometrical method of the conversion of a Gaussian light beam into a
doughnut-shaped light beam suitable for the atomic funnel was also experi­
mentally demonstrated by means of a double-cone prism. Under the
assumption of a proper optical intensity distribution over the inner surface
of a specific conical hollow prism, Monte-Carlo simulation including the
van der Waals interaction shows that half of the released Rb atoms can

Figure 17 Cross-sectional structure o f an atomic funnel utilizing the optical near field on
a conical hollow prism.
 Near field optical technologies 27

be collected and the mean temperature of the collected atoms was low
enough for the application to be guided with a bent hollow optical fiber.
We also presented two methods of controlling atomic motion using a
sharpened optical fiber with a nanometric optical near field, i.e., atom
deflection and atom trap. Deflection angle and trap potential are estimated
based on a near field intensity distribution derived from a Yukawa-type
screened potential. The manipulation techniques are useful for precise con­
trol of atoms with a spatial accuracy beyond diffraction limit, which will
lead to atomic-scale crystal growth.

8. RELATED THEORIES

Several approaches have been proposed for optical near field problems.
These have been used for analyzing experimental results as well as in trying
to understand the phenomena observed in the experiments and their under­
lying physics. As emphasized in Section 1, here one should keep in mind
that sample-probe interaction via the optical near field is essential for
NOM and spectroscopy, and that a three-dimensional treatment is essen­
tial. As pointed out in Sections 2 and 3, resolution, contrast, and sensitivity
are also very closely related to the apex size and the cone angle of the
probe, the approach distance, illumination conditions (such as the polariza­
tion of incident light), and the scanning method (such as constant-height
mode or constant-distance mode). Thus, the most desirable theoretical
approach is one that can take account of all these considerations consis­
tently, as well as provide physical insights.
Macroscopic approaches require electromagnetic boundary conditions in
order to solve the equations, but it is generally difficult in macroscopic
approaches to set boundary conditions for arbitrary three-dimensional
objects, instead of using numerical point-to-point matching. Owing to the
high cost of such approaches in computational time, they are usually
applied only to two-dimensional problems. Moreover, they cannot system­
atically provide any spectroscopic information on nanometric/mesoscopic
systems; nor can they handle quantum systems such as single atoms/mol­
ecules, quantum dots, and internal degrees of freedom such as spin/angular
momentum. Semi-microscopic and microscopic approaches, on the other
hand, can do these things, although they also require numerical com puta­
tion that takes a time which is roughly proportional to the third power of
the space to be considered.
We have proposed an intuitive model - the massive virtual photon model -
based on profound physical insight, which will provide a very instructive
and critical way of thinking for future developments of optical near field
theories. Let us therefore consider this model (with nonzero effective mass)
and discuss the physics behind it [45-48]. The model is based on the
28 M. Ohtsu

analogy of a ‘virtual particle’ or a ‘normal mode’ in quantum field theory

(see, for example, [49], which violates the usual energy conservation principle
to survive for a very short time determined by the Heisenberg uncertainty
principle. In vacuum, electromagnetic interaction governed by the Helmholtz
equation is due to the exchange of virtual photons (with mass = 0). If we
can assume the Klein-Gordon equation to be

( 1)

after renormalizing the induced source term (light-matter interaction)

empirically, we can obtain the well-known Yukawa function:

( 2)

This gives us a screened and finite-range interaction, owing to virtual

photon exchange with a nonzero mass (metf). Since an evanescent field has
a wave number parallel to a material surface (larger than J c ) and one per­
pendicular to the surface that is purely imaginary, the effective field due to
the interaction is found to be highly localized, in close proximity to a
material, and highly dependent on the size of sample or probe. From the
model, we can easily obtain the spatial distribution of the optical near field
intensity, for example, in a circular aperture with a radius smaller than the
wavelength of the light used. Moreover, the resolution and contrast of the
NOM , as well as the size-dependent signal behavior, can be discussed as
clearly as in section 2. This coincidence might be due to the resemblance
between 1/r3 (quasi-static dipole interaction) and the Yukawa function.

ACKNOWLEDGMENTS

The author would like to express his thanks to Prof. H. Hori (Yamanashi
Univ.), Dr K. Kobayashi (Ohtsu’s Localized Photon Project of ERATO
and IBM Japan Ltd.), Drs M. Ashino, H. Ito, M. Kourogi, K. Kurihara,
S. Mononobe, T. Saiki, and R. Uma Maheswari (Ohtsu’s Photon Control Pro­
ject, Kanagawa Academy of Science & Technology) for their collaboration.

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Exploring the Variety of Random
Documents with Different Content
for that glorious land which lies beyond the valley of death. Come
back, Sen-tur, to me at nights, and tell me what thou hast seen. Sen-
tur is ready, oh, beloved of the gods,” she added; “thou needst not
fear, he will not even struggle. Make haste. I wish it.”
“Dost really wish me to kill Sen-tur?” asked Hugh at last.
“Yes, really! I wish it.”
“Why?”
“Because Sen-tur has sinned grievously, and sinning, will surely
sin again. He hath tasted the blood of a slave, he liked the taste and
will wish to drink again.”
“But will it not grieve thee to see Sen-tur die?”
“More than thou canst conceive,” she replied earnestly. “Sen-tur is
my only friend, but it would grieve me even more if thou didst leave
my presence now with evil thoughts of me in thy heart.”
She looked divinely pretty, this exquisite product of a strange and
mystic land: quaint as one of those images on ancient tombs, dainty
as the lotus blossom and roses in her garden. She was—my reason
told me—flirting outrageously, desperately, with Hugh, even to the
extent of endangering the life of innocent Sen-tur. Had she but
known him as I did—the scientific enthusiast, blind even to such
beauty as hers—she would have realised how she was wasting her
time. In spite of her pretty speech, her sweet, appealing look, Hugh
was singularly unresponsive, and it was in a very matter-of-fact,
prosy way that he picked up the small dagger and gave it back to
her.
“Thou must punish Sen-tur in the way thou thinkest fit. I am no
good hand at killing beasts.”
“Thou dost confine thyself to killing women then,” she retorted with
one of those sudden changes in her mood, which to me were so
puzzling.
“Thou art too young to understand the purport of thy words,”
rejoined Hugh, who had become very pale. “The motive which led
me to kill Kesh-ta, thy slave, in the judgment-hall of Men-ne-fer, was
one for which I have not to answer to any one, least of all to thee.
But the hour is late, Princess; wilt deign to allow me to follow my
counsellor? He will wish to visit the holy Pharaoh, and I would fain
pay my respects to Queen Maat-kha.”
 And having bowed to her, Hugh took my arm and quickly led me
away from the terrace.
I wish I had been a more subtle reader of feminine character, for
then, perhaps, I could have interpreted the look with which Princess
Neit-akrit followed Hugh’s retreating figure.
 CHAPTER XVIII.
LOVE OR HATE?

Eh! you dull old Mark Emmett, what a difficult task you have set
yourself! Do you really imagine that you can convey to the minds of
strangers an adequate idea of a woman, young, exotic, voluptuous
and divinely pretty, and with it all changeable, impenetrable as the
waters of the lake?
I suppose if I had been born a woman I should have been able to
understand the various moods of Princess Neit-akrit. As a mere
straightforward male creature, I must confess that I was completely
at sea.
Of course, originally, she must have hated the idea of any man—
be he beloved of all the gods or not—coming between her and the
crown of Kamt, which already she must have looked upon as her
own.
She was so absolutely queen of this land by her beauty, her
fascination, her wonderful personality, that it must have been terribly
galling to her suddenly to see a stranger placed, in virtue of his
mystic descent, immeasurably above her in the hearts of the entire
population of Kamt.
So much I understood and appreciated. Neit-akrit was a woman;
she would have been more than human if she had not resented the
intrusion of the beloved of the gods. I suppose that she hated Hugh
at first, hated his power over the people, hated the very messenger
who knelt at his feet and brought homage to him from distant cities—
homage which in future and in his presence was denied to her.
So, womanlike, seeing that a master was placed above her, she
tried to make him her slave. Being superstitious, she had stolen the
talisman which was destined to guard him against her fascination.
Then she brought to her aid all the gifts which bountiful Nature had
lavished upon her. Her exquisite voice became more melodious and
more gentle as she whispered words of clinging, womanly humility
into his ear; her blue eyes melted into tears when they met his.
Alternately she tried to charm and to irritate him, to attract him by her
tenderness and to repulse him by her cruelty.
Poor Hugh! I wondered how long he would be adamant. Inwardly I
prayed that he might remain so always. If the beautiful Neit-akrit
succeeded in her dangerous game of capturing his heart… well!…
what could result but misery for him, since his word was pledged to
Maat-kha?
Fortunately, so far, I had detected no sign of change in his frigid
attitude towards her. She certainly seemed to have the power of
irritating him and making him say—against his will, I am sure—some
very unkind words to her.
But there! how could I guess what went on in the minds of these
two young people whom Nature in a freakish mood seemed to have
fashioned for one another? Both ardent, passionate, poetic, mystic,
both as beautiful specimens of Heaven’s handiwork as it was ever
granted to my eyes to see.
Princess Neit-akrit talked to me a great deal during the next few
days, and I was fascinated with her strange questionings, the
unaccountable and mystic longings she felt, in the midst of her
ignorance.
“Tell me of that land beyond,” she would beg, and I did not know
what to say. Was it for my clumsy hands to roughly tear asunder the
veil which fifty centuries of priest-craft had woven, thick and dark,
before the eyes of all the children of Kamt?
There was no moonlight one evening. The sky was heavily
overcast, and after the evening banquet, when we followed her on to
the terrace, Neit-akrit leaned against the marble balustrade and
spoke as if to herself.
“How strange that Isis should veil her countenance when she
might behold the beloved of the gods!”
“It is a sight she has oft witnessed, Princess,” said Hugh, with a
laugh, “and therefore, probably, it has no overpowering charm!”
“Yes, of course! I know when thou didst dwell at the foot of the
throne of the gods thou must have often seen the majesty of Isis
herself, whose image up on the vault of heaven is all we poor
mortals are allowed to see. Tell me about her.”
 “Nay, Princess, there is naught to tell thee which thou dost not
know thyself. Her beauty is all before thee in those lovely nights of
Kamt when she shines upon sleeping Nature and throws diamond
sparks upon the lake.”
She shook her head.
“Ah, then I am wiser than thou art, for I know something more
about the goddess than merely her cold image up there.”
“Wilt tell me, Princess?”
Queen Maat-kha had remained within; she said that the night
looked dark and cold, but personally I thought that she would have
been wiser to look after her own property, which was being strangely
and wilfully toyed with, and in grave danger of being stolen.
“I learnt it all in a dream,” began Neit-akrit, looking dreamily out
towards the hills. “It was just such a night as this, and I could not
rest, for the wind was whistling through the fuchsia trees, making
each bell-shaped blossom tinkle like innumerable short, sharp sighs.
It was a dream, remember! I rose from my couch and went out
beneath the solitary alleys of the park; not even Sen-tur walked by
my side. I felt unspeakably lonely and desolate, and the darkness
weighed upon me like a pall. Suddenly I felt that some one…
something took my hand, while a voice whispered, ‘Come!’ I
followed, and the unseen hand guided me over the canals and cities
of Kamt, above those hills yonder which mark the boundaries of the
living world, and right across the valley of death, where, in the
darkness, I heard the cry of the carrion and the moaning of the dying
souls.”
She stood—a quaint, rigid, infinitely graceful image—dimly
outlined in the gloom, slightly bent forward as if her eyes were trying
to meet through the darkness those of Hugh fixed upon her. I could
see his tall figure, very straight, with arms crossed over his chest,
and I longed to take him away, far from this strange and voluptuous
girl whose every motion was poetry and every word an intoxicating
charm.
“I knew that the valley of death lay at my feet,” she resumed in the
same monotonous, sing-song tone, dreamy and low. “I knew that all
round me was desolation, sorrow and waste, but I did not see it, for
my eyes sought the distance beyond, and what I saw there, far
away, was so glorious and fair, that ever since my memory has dwelt
upon that vision and my feet longed to wander there again.”
“What didst thou see?”
“I saw a bower of tangled flowers drooping beneath the sun,
whose rays I thought I had never seen so glorious and so hot, and
between the roses and the lilies, the laurel and the mimosa,
innumerable birds chirruped and sang. The ghostly hand still led me
on, and presently I stood among the flowers and saw that each little
bird had a nest, and each by his side a mate; and beneath the
tangled trees of fuchsias and acacias men and women wandered
two by two. Their heads were close together, their arms were
intertwined, even the trees above their heads mingled their branches
and bent their trunks towards each other. The air was filled with
sounds of whispers murmured low and sweet, of kisses exchanged,
of fond sighs and endearing words. Then a great sorrow filled my
heart, for I, whom men have called so fair, was all alone in this
abode of love; no one stood near me to caress me, no one was
whispering in my ear, and as I passed the young couples would
pause a moment in their love-making and gaze at me with
astonishment, whilst some of them would whisper, ‘Behold! ’tis Neit-
akrit, Princess of Kamt! Is she not fair?’ And others would add, ‘Yea!
so fair, so high and so mighty, but she knoweth not the abode of Isis!’
And all would sigh, ‘Alas! poor Neit-akrit!’ And I was so overwhelmed
with sorrow that I fell on the soft dewy grass and cried bitter tears.”
I thought that Hugh must have felt very sure of himself to dare
venture on such a subject of conversation with a woman who was
beautiful and fascinating beyond words. He could not see her, for the
night was very dark, only an outline and a warm glow round her
head, as of living gold.
“Then,” she began once more, “while I cried suddenly I felt as if
two arms encircled me, as if something undefinable and
immeasurably sweet filled the air, and I was borne through the roses
and the lilies to a bower of blossoms, which smelt more sweet than
anything on earth. And there in the deep shadows, peeped at only by
tiny eyes of birds, there dwelt the majesty of Isis herself, and
suddenly in the presence of the goddess I ceased to be Neit-akrit,
forgot all pomp and glitter, remembered only that I was young and
fair, and when the arms which bore me had laid me down on the
sweet-scented carpet, I and the owner of those arms knelt down and
worshipped before the shrine of Isis.”
She paused, and for a few moments there was deep silence in the
darkness; only the splash of the water against the marble steps
sounded at regular intervals like a faint murmur from below.
“Dost wonder that ever since I have longed to visit that spot again;
that I have begged Sen-tur to guide me there, for I believe he knows
that I have prayed sweet Death to lead me through that dark valley,
so that I might behold Isis once again and worship at her feet… with
some one else… who would be a part… nay! the whole of my life…
who would love! and yet not worship… ’tis I who would worship, who
would live for a smile, who would die for a kiss. I, who would be
coward and weak, and prouder of that weakness than of the double
crown of Kamt. But the throne of Isis is hidden from my view. It
stands before the poor and lowly. The rich princess may not enter
there.”

Hugh said nothing, and presently we heard a footfall on the

flooring, a frou-frou of silks and jewels, a last lingering sigh on the
evening air, and she was gone, leaving behind her an aroma of
exotic flowers, of delicious young ripe fruit, of voluptuous womanly
charm, which in this strange land spoke to us of country and of
home.
During the next few days the changeable and capricious girl spoke
not a single word to Hugh. She seemed altogether to ignore his very
presence, and all her charms, her fascinations were lavished with a
free hand upon the holy Pharaoh. I had become deeply interested in
my illustrious patient, and had even begun to sympathise with him in
his mental troubles. He hated Hugh, who was the person on earth to
whom I was most attached, and yet how could I help acknowledging
that he had a just cause for hatred? But now Neit-akrit seemed to
have set herself the task of making him forget every one of his
troubles, and succeeded fully by lavishing all her powers of
fascination and sweetness upon him. Once more I fell into my rôle of
gooseberry, and although the Pharaoh insisted on my presence near
him at all hours of the day, and even night, there were many
moments when I thought it more prudent to keep out of earshot. It
was a curious kind of lovemaking, and throughout those few
memorable days a strange feeling would now and then creep into my
prosy old heart at sight of the beautiful girl radiant with youth and
health, side by side with the sickly, emaciated man with one foot in
the grave.
He was as silent as ever, but the ugly frown had almost
disappeared from between his eyes, and he too avoided being near
Hugh or speaking to him.
Half that day and the next Neit-akrit sat beside him on the couch
which overlooked the lake, and prattled to him in a merry way of a
thousand nothings, which delighted him more than a chorus of
nightingales; or she would take a harp and would let her slim young
fingers glide gently along the chords, and sing to him sweet and
quaint lullabies which soothed him into quiet, dreamless sleep.
Then when he slept she still remained by his side, softly humming
her low monotonous tunes, ready to greet him with a sunny smile the
moment he opened his eyes; if then I tried to speak to her she would
place a warning finger to her mouth, and I sat and watched her while
she watched the mighty Pharaoh, and once or twice I saw great
tears rise to her eyes and trickle slowly down her cheeks. She
puzzled me. I could not bring myself to believe that she was
suddenly beginning to care for her ailing kinsman, who, but for his
rank, must have been very unattractive to a young and beautiful girl:
nor did I wish to admit to myself that I feared she was playing a cruel
game, in order to arouse jealousy in Hugh.
As for old Girlie, he was strangely reticent about the Princess, and
once or twice when I mentioned her name he very abruptly changed
the subject. I thought that the excitement, or perhaps the oppressive
air of Kamt, was beginning to tell on him. He looked strangely pale
and worn, and I knew he did not sleep at nights. His hand felt hot
and feverish, as it had done during those terrible years when he took
it upon himself to complete his father’s work, and when I seemed
anxious about him, he only laughed in a dry, sarcastic way, quite
unlike his usually bright and sunny laugh.
 Late one afternoon I at last contrived to be alone with him. He had
received many deputations, made speeches and heard others all the
morning; no wonder that he felt tired and glad mentally to quit Egypt
and wander in England for a while with me.
“Maat-kha has expressed a wish,” he said very suddenly, “that we
should be married in a month. The town of Tanis sent a deputation
to-day to say that already they are prepared to receive us. I
understand that the temple of Isis, in which the royalties of this land
are always married, is in Tanis, and I have no wish to postpone my
marriage.”
“Girlie, I wonder if you realise what a terribly earnest step you are
taking. Though the rites may be pagan, marriage is always a sacred
tie, and though you live away from your native land, your home must
always be beside your wife, whoever she may be.”
“I know, old Mark, I know. I have thought more about the matter
lately, but you must remember that there are things as sacred as
marriage, and one of these is an Englishman’s word.”
“I don’t like to hear you talk like this, Girlie. I am afraid that in this
wild adventure you are risking some of your happiness.”
“Oh, what tragedy, old Mark!” he said with a forced laugh. “My
happiness? Why, it is complete! Have I not accomplished the aim of
my life? Can I not now prove to the world that mad Tankerville and
his fool of a son were neither visionaries nor liars? Am I not virtually
king of the fairest land on earth? Why, old Mark, we came here for
the sake of science, not for such paltry objects as my happiness.”
“That is all very well, Girlie; but with all your scientific enthusiasm
you have got a great and good heart somewhere about you, and that
does not seem to me to be quite satisfied.”
“It will be satisfied presently, old chap, when all these pageants,
processions and welcomes are over and I can set to work to guide
the destinies of these picturesque people, and gradually teach them
the mysteries of an outer world. And when they have begun to
understand, and my influence over them is absolutely established,
then I can begin to destroy and pierce through those insurmountable
barriers which divide them from Europe and modern civilisation.
Then gradually we shall see my picturesque subjects take to wearing
top hats and patent leather boots, and Queen Maat-kha look superb
in a Paris gown. We shall build railways from Men-ne-fer to Tanis,
and steamboats will ply the canals. There is plenty to dream of, old
friend, never fear. My life will lack no excitement from now till its
close, and there will be no room in it for sentiment or happiness.”
We had reached one end of the terrace, and close to us we saw
the daïs, where I had left the Pharaoh asleep an hour before, with
his young cousin softly cooing to him like a pigeon, and fanning his
forehead gently with a large palm leaf. They neither of them heard
our footsteps, and we both stopped with the same instinct of curiosity
watching the strangely ill-assorted pair. The Pharaoh was awake and
speaking, but some inward emotion had made his deepset eyes
glow with unnatural brilliancy and taken every drop of blood from out
his cheeks and lips. His mouth seemed parched, and his throat half
choked as he spoke, while she, a radiant picture of youth and
beauty, with fresh colour in her cheeks, a wondering look in her blue
eyes, looked like a nymph beside a satyr.
“I do not often dream, Neit-akrit,” the Pharaoh was saying, “when
thou sittest by my side. I think Anubis chases dreams away and
renders my sleep as refreshing as death. But just now I had a
dream.”
“Wilt tell me, cousin?”
“I dreamt, Neit-akrit, that I stood within the sacred temple of Isis, at
Tanis. All round me the incense rose in great and dense clouds, so
that I could not distinguish my people, but only dimly saw Ur-tasen,
the high priest, with his shaven crown, robed in his most gorgeous
garments, standing before me, with arms outstretched, as if
pronouncing a blessing.”
“He blessed thee, Pharaoh, no doubt, for some great good thou
hadst done to thy people, now that health is once again restored to
thee.”
“So I thought at first, Neit-akrit, in my dream,” he replied, bending
his head closer to her, “but soon Ur-tasen came up to me and
whispered something which made my pulses thrill with a joy that
almost made me faint. Ur-tasen had whispered that I should take thy
hand.”
She turned her head away from him, and from where I stood I
could see that every vestige of colour had left her cheeks, and that
her lips were trembling and absolutely bloodless. I thought that we
had no right to stand where we did, or to listen any longer to a
conversation which was evidently drifting into very intimate channels,
and I had just turned to go, when something in Hugh’s face made me
stop. He, too, was gazing at the picture before us of the young girl
and the sick, almost dying man, but in his eyes there was an
expression I could not define.
“At first,” resumed the Pharaoh, in the same harsh, trembling
voice, “I hardly dared to obey Ur-tasen. That I should take thy hand,
at the foot of the throne of Isis, before all my people assembled
there, seemed to me a joy so great that death would be easier to
bear than the agony of so wild a happiness. But Ur-tasen waited,
and I turned my head, and thou, Neit-akrit, wert standing by my side.
Thy head, with its ruddy tresses, was hidden beneath the diadem
which belongs to the rulers of Kamt, and from it down to thy tiny feet
thou wast covered with a golden veil, through which I, in my dream,
could see gleaming visions of thy blue eyes, which made me swoon
with delight. Then Ur-tasen whispered again, and I took thy hand in
mine, at the foot of the throne of Isis, before all my people
assembled there… for they had come to see the mighty Pharaoh
take Neit-akrit… as his wife.”
His voice broke almost into a sob, he had glided down from the
couch on to his knees, and was lying half-fainting with the emotion
which, weak as he was, was overmastering him, while his arms
tremblingly sought to clasp the young girl. She was as pale as death.
Her blue eyes stared at him, strangely terrified, with a look which, to
me, seemed almost like loathing. But he could not see. His eyes
were half closed. I am sure he was not conscious of his acts: his
hands, trembling and clawlike, wandered round her shoulders and
her waist, while he murmured more and more inarticulately:
“Thou art beautiful, Neit-akrit… and at the throne of Isis thy hair
gleamed red and hot, and made my eyes ache with its glow: thy veil
but partly covered thee… and when I looked upon thee… it seemed
to me that I would forfeit my double crown of Kamt to be allowed to
look again, and perhaps see thee smile. And thou didst promise to
be my wife… and Isis smiled down upon me. And she whispered that
in the night… when she peeped through the fuchsia alleys… and
looked on the lilies and lotus blossoms… thou and thy loveliness
would be wholly mine.”
He had fallen, half-fainting, upon the marble floor, and clung, still
babbling inarticulate words, round her knees. Neit-akrit had stood up,
rigid as a marble image: it were impossible to describe the look of
horror and loathing with which she looked down on the unfortunate
man at her feet.
“For God’s sake take him away from her, Mark!”
It was Hugh Tankerville’s voice whispering in my ear, but I hardly
recognised it, so hoarse and choked was it. Astonished, I looked up
at him, and suddenly

He had fallen, half-fainting, upon the marble floor, and clung,… around
her knees.
a strange presentiment of some terrible trouble ahead, which as yet I
could not explain, cast a chill over my heart. On my friend’s face
there was such a look of acute mental and physical suffering, it was
so deathly pale, that instinctively I put out my arm to help him, for I
feared he would fall in a swoon; but he said quickly, with a forced
laugh:
“Only a sudden dizziness, old chap.… The heat, I think. But have
pity on her and take that moribund satyr away from her.”
“It would be needless interference, old man,” I replied, “and one for
which she would not thank me.”
And I pointed to the picture, which, to my own amazement, had
changed as if with the magic touch of a fairy wand. Neit-akrit, sweet
and smiling, with tears of pity shining in her softened blue eyes, was
bending towards the invalid, while her voice, soft and low, murmured:
“Hush, hush! cousin! remember thou art ill: thy health is precious
and thy nerves are overstrained. Canst raise thyself and sit here
beside me? See, thou canst pillow thy head upon my shoulder and I
can brush away the hair from thy burning forehead with my fingers,
which are soft and cool. Or, if thou wilt, I will play for thee upon the
harp, and thou shalt watch Sen-tur chase the ibis along the terrace.
Hush! do not speak now! Thou shalt tell me thy dream again some
other time… but not now.… Now, thou must have rest.”
And with wonderful strength and dexterity she half-lifted, half-
supported the Pharaoh and placed him once more upon the couch.
Then she sat down beside him and pillowed his head upon her
shoulder, and soothingly, as if he were some sick and wayward child,
she began to sing and coo to him a simple lullaby. I looked on
amazed, not knowing what to do or what to think. Though I watched
her closely, I never saw her eyes look anything but sweet, pitying
and loving, even though his eyes were closed and his breathing
became more and more regular, as if her song had at last rocked
him to sleep. I began to think that I must have been mistaken: it
seemed impossible to believe that the rigid statue, alive only by the
look of horror and repulsion on the stony face, could be the same
clinging, loving woman, full of tender pity and girlish compassion for
the sick man lying happy and contented in her arms.
 CHAPTER XIX.
A KISS

I somehow dared not look at Hugh. I felt his presence near me as

rigid as a statue, and once my ears caught the sound of a sigh,
which ended almost in a sob.
“Is it for the dying Pharaoh thou sighest, oh, my beloved,”
suddenly said a harsh voice close behind us, “or for her who deals
death and sorrow with so free a hand?”
It was Queen Maat-kha, who had glided noiselessly near, and now
stood beside Hugh, tall and imperious, with an ugly look of hatred
directed towards the sleeping Pharaoh and his companion. Hugh
started as from a dream. He passed his hand over his eyes, as if to
dispel some haunting vision, and turned to his handsome fiancée,
who returned his look with a curious searching expression in her
eyes.
“Thou dost not answer,” she said. “Was the sigh for her?”
“Indeed, my Queen, it is sad to see so young a girl wooed by a
man with one foot in the grave,” replied Hugh at last, speaking with a
mighty effort.
“Then thou dost not understand the girl before thee, and hast
forgotten that the man, though he have one foot in the grave, has the
other firmly planted on the throne of Kamt.”
Princess Neit-akrit must have heard every one of Maat-kha’s
words, yet she took no notice of them, and remained quietly
watching the sleeping Pharaoh.
“Thou hast also forgotten,” added the Queen, “that thou and thy
wise counsellor have decided to cure the mighty Pharaoh of his
ailments, that, anon, he will once more hold with a firm hand the
sceptre of ancient Kamt. Neit-akrit hath thought it worth her while to
smile on him again, so that he may extend his other hand, and with it
place upon her brow the diadem of a queen. Believe me, there is no
sadness in that wooing, save perhaps for a deceived and befooled
monarch.”
 “Thou speakest harsh words of a woman who hath done thee no
wrong,” said Hugh. “Art not satisfied that already by thy intended
marriage thou dost threaten to deprive her of that which thou sayest
she covets most? Wouldst add to the injustice by heaping calumny
upon her?”
“No wrong?” exclaimed the Queen, impulsively. “Dost think that I
am blind and cannot see? Dull-witted and cannot understand? Hath
she done me no wrong? Ah! that I do not know as yet. Thy face is
set and inscrutable; but the gods will open my eyes. That which they
gave me, they will not take away. And if she come like a cunning
jackal, prowling round my most precious treasure, then let her
beware, for Maat-kha is powerful and will know how to hurl
vengeance on the thief.”
“What dost thou mean?” asked Hugh, very quietly. “Take care, oh,
Queen! lest in thy blindness thou shouldst forget my dignity and thy
self-respect.”
“I forget everything,” she said, coming quite close up to him, “save
that I love thee and that thou art cold. I did not seek for thee, I did not
even ask the gods to place thee across my path; thou didst come
and didst stand before me and, with arm outstretched, didst claim
me for thy wife. Now, that which thou didst give thou dost surely take
away—thy word, thy fealty to me.”
“My Queen,” replied Hugh, gently taking her hand, “in that land
from whence I come men have but one word, one pledge. Words
such as thou dost speak, thoughts such as thou dost harbour, are an
insult; look at me, Maat-kha, and tell me if I can lie.”
She looked up at him, and I, who watched Neit-akrit, saw that she
looked too. I did not know if these two strange, impulsive women
could judge a man’s character by gazing at his face, but Hugh’s was
not a difficult nature to understand; above everything he was upright
and true, and whatever presentiments may have assailed me when
first I guessed my friend’s secret thoughts, I knew that whatever
might happen, his promised bride need have no fear of his loyalty to
her.
I thought that the Pharaoh had moved, and I was glad of an
excuse to go and attend upon him and leave Queen Maat-kha a
moment alone with Hugh. Neit-akrit still looked very pale, and I could
see in her eyes that she had been crying. I did not altogether
understand her, but there was something strangely pathetic and
appealing in the way in which she looked at me, eagerly waiting for
some reassuring words concerning the sick man.
“I will send his slaves to him,” I said; “he will need rest.”
And I went within. When I returned I found that Queen Maat-kha
had gone and that Hugh was standing beside Neit-akrit.
“I crave it of thee as a favour,” I heard him say.
“So soon?” she replied. “Art already tired of Neit-akrit’s hospitality?
Has she forgot aught that would make thy sojourn here a happy
one? Tell me, is not my palace beautiful? Are my gardens not
fragrant with scent of flowers, the air not sweet with song of birds?”
“Thy dwelling is more beautiful than aught I have ever dreamed
of.”
“And yet thou wouldst leave it?”
“I crave of thee to forgive my seeming ingratitude, for though fair
be thy palace and fragrant thy garden, I would fain leave them to-
day.”
“Leave them and me?” she said sadly.
“Ay! leave them and thee, Princess,” said Hugh, with that same icy
calm with which he responded to Neit-akrit’s fascinating ways, “lest if
I remained even one day longer, I might leave that behind me which
is more precious to me than aught else on earth.”
“What is that?” she asked. “Thou needst not fear, I will guard it for
thee, wherever thou goest.”
“Nay, a man is sole guardian of that most precious treasure;
women often do not know its worth, and I fear I am proving but a
sorry keeper myself, hence the reason why I would go.”
“Wilt say farewell to me before thou goest?”
“I will do that now with thy permission. I have promised the
inhabitants of Net-amen that I would visit them, and having gone I
will not come back, but go straight to Tanis and await there the
coming of Queen Maat-kha for our approaching marriage.”
“So soon?” she asked very quietly.
“In seventy days, Princess.”
“Farewell then, oh, beloved of the gods; thou hast indeed graced
the abode of thy kinswoman by dwelling beneath its roof.”
 “Hast forgiven me, then?”
“I to thee? What have I to forgive?”
“Everything. I came and the double crown of Kamt, which already
hovered over thy brow, was ruthlessly snatched from thee. My
presence deprived thee of a throne. It were meet that thou shouldst
seek revenge upon the intruder, instead of which thou didst bid him
welcome.”
“Nay,” she said sweetly, “I have naught to forgive, and revenge is
in the hands of the gods.” Then she added, “Farewell, oh, son of
Ra!”
He bent his tall figure before her, then turned as if to go.
“Wilt thou not kiss me?” she said. “In Kamt a kiss denotes
friendship, and if thou goest without a kiss, I shall fear that thou art
my enemy.”
“By all the gods of Kamt, I swear to thee that I am no enemy. But
wilt pardon me if I do not give thee the kiss of friendship?”
“Why? A kiss is so soon given. It has so little meaning, for it is as
swift as the flight of the bird through the air. Thou didst kiss me when
thou camest, why wilt not kiss me now?”
“Because thou art beautiful above all things on earth,” he said very
quietly, “and because in my dazed mind there is still a glimmer of
reason, which the perfume of thy hair would quickly dispel.”
She blushed suddenly as if for the first time in her life she had
been told that she was fair. How strange women are! When I told
Neit-akrit that she was more beautiful than anything on earth, she
smiled and looked pleased. When the Pharaoh fell half-fainting at
her feet she became as white and rigid as a statue carved in stone.
And now when Hugh Tankerville told her, with frigid calm, and I
thought with a singular want of conviction, that she was beautiful,
she suddenly became a thousand times more so, for she blushed
and the heightened colour became her well.
“Farewell, then, oh, thou who art of the gods beloved!” she said
once more very gently.
The next moment Hugh had gone and Neit-akrit had thrown
herself on the couch in a passionate fit of weeping.
 CHAPTER XX.
A LETTER FROM HUGH

Hugh went away that same day. He was going to Net-amen,

together with the gorgeous retinue which had, as it were, sprung up
round him and escorted him everywhere. Queen Maat-kha did not
accompany him this time: she was unprepared for the journey, she
said. She would proceed to Tanis alone, there to meet him for the
wedding ceremony.
Hugh took a very brief farewell of me. I could see that he dared not
trust himself to speak, and, even before me, he shrank from breaking
down. I could not go with him, for my patient demanded my
immediate attention. He was undoubtedly worse since this morning:
the strong emotion had done him an infinity of harm. Yet I was torn
between my affection for Hugh and my duty to the sick man. It
seemed to me that Hugh needed my care as much as the sick
Pharaoh. His sufferings were mental, but I felt that they were keen.
And did I not love him as much as my prosy nature was capable of
loving? and did I not know him, and his ardent, passionate nature,
forcibly hardened by years of dry, scientific research, all the more
ready to fall a prey to strong impressions, such as the strange and
fascinating girl had undoubtedly made upon it?
Hugh had never been in love. During his early youth he had had
no opportunity of meeting any woman who would appeal to his keen
sense of the mystic and the picturesque. Such women are rare in
Western Europe, and none had come across the recluse student’s
path. Then, suddenly, Fate and his own choosing threw him into this
land of mysticism and beauty, where the atmosphere was fragrant
and intoxicating with the scent of exotic flowers, where the air was
filled with the twitter of birds, busy in making their nests. And, framed
by these picturesque surroundings, which in themselves palpitated
with youth and with life, there was the poetic, mystic, yet intensely
feminine vision of an exquisitely beautiful woman who was irresistibly
drawn towards him, and with the artless impulse of her own
untrammelled nature showed to his enthusiastic mind visions of
ardent and reciprocated love, such as he had never dreamed of.
What wonder if for the moment Hugh forgot?—forgot that he had
pledged himself to another woman and only remembered when it
was too late?
The first few days after his departure were terribly wearisome to
me. My patient, fretful and irritable, would not allow me to leave his
bedside, and, even at night, I was forced to take what rest I could,
rolled in a rug, at the foot of his couch.
I saw little of Princess Neit-akrit, but, once or twice, when I caught
sight of Queen Maat-kha in the gardens of the palace, I was shocked
to see the change in her face. All its beauty had vanished to my
mind: it looked hard and set, nay, worse, positively evil. On the night
which followed Hugh’s departure, when I strolled out to get a breath
of fresh air, having at last soothed my patient to sleep, I saw Maat-
kha in close conversation with Ur-tasen. To me this boded no good. I
could not understand why the Queen and the high priest should
choose the hours of the night for their meeting. I could not get near
enough to them to hear what they were saying—which I should most
unblushingly have done—but in the shadows where they stood, I
could see that Queen Maat-kha had buried her face in her hands,
and that Ur-tasen seemed to tower over her as if he were dictating
some commands.
My mind, filled with thoughts of my absent friend, dwelt
persistently on fears for his safety. The high priest was his enemy, of
that I had no doubt, and I thought that he was trying to work upon the
Queen’s jealousy, for evil purposes of his own. I felt terribly helpless
to be of any use to him, and vowed that when at last I could join him
again, nothing would separate me from him. After all, the sick
Pharaoh of this modern Egypt was but a secondary consideration to
me.
Eight days after Hugh’s departure a runner came in with a letter for
me from him.

“Dear old Mark:—Thank goodness that I can write to you

and know that this letter will reach you safely. I am fagged to
death bodily and long to have you near me, to talk over some
of my wondrous experiences. The city of Net-amen is
picturesque. It lies on the side of a hill and is a city of industry:
the applied arts reign supreme, and I am looking forward to
renewing my visit to it with you later on, and showing you the
paintings and carvings on the walls and pillars of the houses,
which to my mind are as beautiful as any we have seen. This
is a wonderful country, Mark, and its people have lost none of
the mysterious powers which have astonished Europe for so
long. Will you believe me when I tell you that in the very heart
of the city a palace has been built expressly for me?—yes! for
me, the beloved of the gods!—and I have only been in the
land less than a month! And yet, there my palace stands, of
rose-coloured granite, with massive pillars and exquisite
carvings, and a figure of my sire Ra presiding in the courtyard
—all built in less than a month by a hundred thousand
workmen, who worked night and day in relays. The granite
works are just outside the city, but still think of it, Mark, and
remember how long it takes to put up a block of flats in
London.
“Still, there is the sorrowful aspect of my palace: all the hard
work was done by slaves, and these people use their slaves
shockingly. This is the ugliest trait in their character. They are
cruel, Mark, both to man and beast. The men are cruel! and
the women more so. We have seen one or two instances of
that already, but there is a thing I have learned which to me is
horrible beyond words. You know of course that the Egyptians
are monogamous—you have noticed in what high esteem
they hold their women folk; as a consequence of this, their
laws against adultery are barbarous beyond what words can
describe, and in one respect hideously unjust, for it is
invariably the woman who is punished—the man is allowed to
go scot free.
“I saw a woman in the streets of Net-amen yesterday. She
was blind, both her ears had been cut off, all her teeth drawn
out, and her hair had been pulled out by the roots. Turned out
from her home, she is obliged to live by the charity of the
passers-by, and is driven from street to street as an example
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